United Statw
E nvtron rnontnl Protection
Agency
Office of Water Regulations
and Standards (WH-552)
Industrial Technology Division
Washington, DC 20460
EPA 440/1-89-019.6
May 1989
Office of Water
FINAL
Development
Document for
Effluent Limitations
Guidelines and
Standards for the
Nonferrous Metals
Manufacturing
Point Source
Category
Volume VI
Primary Tungsten
Secondary Tungsten and Cobalt
Primary Molybdenum and
Rhenium
Secondary Molybdenum and
Vanadium
-------
ORGANIZATION OF THIS DOCUMENT
This development document for the nonferrous metals manufacturing
category consists of a general development document which
considers the general and overall aspects of the regulation and
31 subcategory specific supplements. These parts are organized
into 10 volumes as listed below.
The information in the general document and in the supplements is
organized by sections with the same type of information reported
in the same section of each part. Hence to find information on
any specific aspect of the category one would need only look in
the same section of the general document and the specific
supplements of interest.
The ten volumes contain contain the following subjects:
Volume I
Volume II
Volume III
Volume IV
Volume V
Volume VI
Volume VII
General Development Document
Bauxite Refining
Primary Aluminum Smelting
Secondary Aluminum Smelting
Primary Copper Smelting
Primary Electrolytic Copper Refining
Secondary Copper Refining
Metallurgical Acid Plants
Primary Zinc
Primary Lead
Secondary Lead
Primary Antimony
Primary Precious Metals and Mercury
Secondary Precious Metals
Secondary Silver
Secondary Mercury
Primary Tungsten
Secondary Tungsten and Cobalt
Primary Molybdenum and Rhenium
Secondary Molybdenum and Vanadium
Primary Beryllium
Primary Nickel and Cobalt
Secondary Nickel
Secondary Tin
Volume VIII Primary Columbium and Tantalum
Secondary Tantalum
Secondary Uranium
Volume IX Primary and Secondary Titanium
Primary Zirconium and Hafnium
Volume X Primary and Secondary Germanium and Gallium
Primary Rare Earth Metals
Secondary Indium
-------
DEVELOPMENT DOCUMENT
for
EFFLUENT LIMITATIONS GUIDELINES AND STANDARDS
for the
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
VOLUME VI
Primary Tungsten
Secondary Tungsten and Cobalt
Primary Molybdenum and Rhenium
Secondary Molybdenum and Vanadium
William K. Reilly
Administrator
Rebecca Hanmerf Acting
Assistant Administrator for Water
Martha Prothro, Director
Office of Water Regulations and Standards
Thomas P. O'Farrell, Director
Industrial Technology Division
Ernst P. Hall, P.E., Chief
Metals Industry Branch
and
Technical Project Officer
May 1989
U.S. Environmental Protection Agency
Office of Water
Office of Water Regulations and Standards
Industrial Technology Division
Washington, D. C. 20460
-------
11
-------
TABLE OP CONTENTS
Supplement Page
Primary Tungsten 2925
Secondary Tungsten and Cobalt 3161
Primary Molybdenum and Rhenium 3341
Secondary Molybdenum and Vanadium 3487
For detailed contents see detailed contents list in
individual supplement.
111
-------
-------
NONFERROOS METALS MANUFACTURING POINT SOURCE CATEGORY
DEVELOPMENT DOCUMENT SUPPLEMENT
for the
Primary Tungsten Subcategory
William K. Reilly
Administrator
Rebecca Hanmer
Acting Assistant Administrator for Water
Martha Prothro, Director
Office of Water Regulations and Standards
Thomas P. O'Farrell, Director
Industrial Technology Division
Ernst P. Hall, P.E., Chief
Metals Industry Branch
and
Technical Project Officer
May 1989
U.S. Environmental Protection Agency
Office of Water •;
Office of Water Regulations and Standards
Industrial Technology Division
:.. Washington D. C. 20460
2925
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2926
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PRIMARY TUNGSTEN SUBCATEGQRY
TABLE OF CONTENTS
Section
I SUMMARY 2935
II CONCLUSIONS • 2937
III SOBCATEGORY PROFILE 2963
Description of Primary Tungsten Production 2963
Raw Materials 2963
Leaching of Ore Concentrates 2963
Purification to Ammonium Paratungstate 2964
Reduction to Metal 2965
Process Wastewater Sources 2965
Other Wastewater Sources 2966
Age, Production and Process Profile 2966
IV SUBCATEGORIZATION 2975
Factors Considered in Subdividing the Primary 2976
Tungsten Subcategory
Other Factors 2977
Production Normalizing Parameters 2980
V WATER USE AND WASTEWATER CHARACTERISTICS 2979
Wastewater Flow Rates 2980
Wastewater Characteristics Data 2981
Data Collection Portfolios 2981
Field Sampling Data 2981
Wastewater Characteristics and Flows by 2983
Subdivision
Tungstic Acid Rinse Water 2983
Acid Leach Wet Air Pollution Control 2984
Alkali Leach Wash 2984
Ion-Exchange Raffinate 2985
Calcium Tungstate Precipitation Wash 2985
Crystallization and Drying of Ammonium 2985
Paratungstate
Ammonium Paratungstate Conversion to Oxides 2986
Wet Air Pollution Control
Reduction to Tungsten Wet Air Pollution Control 2987
Reduction to Tungsten Metal Water of Formation 2987
2927
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PRIMARY TUNGSTEN SUBCATEGORY
Section
VII
TABLE OP CONTENTS (Continued)
SELECTION OP POLLUTANT PARAMETERS
Conventional and Nonconventional Pollutants
Parameters
Conventional and Nonconventional Pollutant
Parameters Selected
Toxic Pollutants
Toxic Pollutants Never Detected
Toxic Pollutants Never Pound Above Their
Analytical Quantification Limit
Toxic Pollutants Present Below Concentrations
Achievable by Treatment
Toxic Pollutants Detected in a Small Number
of Sources
Toxic Pollutants Selected for Purther
Consideration in Limitations and Standards
CONTROL AND TREATMENT TECHNOLOGIES
Current Control and Treatment Practices
Tungstic Acid Rinse Water
Acid Leach Met Air Pollution Control
Alkali Leach Wash
Ion-Exchange Raffinate
Calcium Tungstate Precipitation Wash
Crystallization and Drying of Ammonium
Paratungstate
Ammonium Paratungstate Conversion to Oxides
Wet Air Pollution Control
Reduction to Tungsten Wet Air Pollution
Control
Reduction to Tungsten Water of Formation
Control and Treatment Options
Option A
Option B
Option C
Option E
Option P
3049
3049
3049
3050
3051
3054
3063
3063
3063
3063
3064
3064
3064
3064
3065
3065
3066
3066
3066
3067
3067
3068
3068
2928
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PRIMARY TUNGSTEN SUBCATEGORY
Section
TABLE OP CONTENTS (Continued)
VIII
IX
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS 3069
Treatment Options Costed for Existing Sources 3069
Option A 3069
Option B 3069
Option C 3069
Nonwater Quality Issues 3071
Energy Requirements 3071
Solid Waste 3071
Air Pollution 3072
BEST PRACTICABLE TECHNOLOGY CURRENTLY AVAILABLE 3075
Technical Approach to BPT 3075
Industry Cost and Pollutant Reduction Benefits 3077
BPT Options Selection 3077
Wastewater Discharge Rates 3079
Tungstic Acid Rinse Water 3080
Acid Leach Wet Air Pollution Control 3081
Alkali Leach Wash 3081
Ion-Exchange Raffinate 3082
Calcium Tungstate Precipitate Wash 3083
Crystallization and Drying of Ammonium 3083
Paratungstate
Ammonium Paratungstate Conversion to Oxides 3084
Wet Air Pollution Control
Reduction to Tungsten Wet Air Pollution Control 3085
Reduction to Tungsten Water of Formation 3086
Regulated Pollutant Parameters 3086
Effluent Limitations 3087
BEST AVAILABLE TECHNOLOGY ECONOMICALLY 3099
ACHIEVABLE
Technical Approach to BAT 3099
Option A 3099
Option B 3100
Option C 3101
Option E
Option P
Industry Cost and Pollutant Reduction Benefits 3102
Pollutant Reduction Benefits 3102
Compliance Costs 3102
BAT Option Selection 3103
Wastewater Discharge Rates 3105
Regulated Pollutant Parameters 3106
Effluent Limitations 3107
2929
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PRIMARY TUNGSTEN SUBCATEGORY
TABLE OP CONTENTS (Continued)
Section
XI NEW SOURCE PERFORMANCE STANDARDS 3123
Technical Approach to BDT 3123
Option A 3123
Option B 3123
Option C 3124
BDT Option Selection 3124
Regulated Pollutant Parameters 3125
New Source Performance Standards 3125
XII PRETREATMENT STANDARDS 3135
Technical Approach to Pretreatment 3135
Industry Cost and Pollutant Reduction Benefits 3136
Pretreatment Standards for Existing Sources 3136
Option A 3136
Option B 3136
Option C 3136
PSNS and PSES Options Selection 3137
Regulated Pollutant Parameters 3137
Pretreatment Standards 3138
XIII BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY 3157
2930
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PRIMARY TUNGSTEN SUBCATEGORY
LIST OP TABLES
Page
INITIAL OPERATING YEAR (RANGE) SUMMARY OF PLANTS 2968
IN THE PRIMARY TUNGSTEN SUBCATEGORY BY DISCHARGE
TYPE
III-2 PRODUCTION RANGES FOR THE PRIMARY TUNGSTEN 2969
SUBCATEGORY
II1-3 TREATMENT LEVEL SUMMARY FOR THE PRIMARY TUNGSTEN 2969
INDUSTRY
III-4 SUMMARY OF SUBCATEGORY PROCESSES AND ASSOCIATED 2970
WASTE STREAMS
III-5 PRODUCTION PROCESSES UTILIZED BY THE PRIMARY 2971
TUNGSTEN INDUSTRY (10 PLANTS)
III-6 TREATMENT PROCESSES UTILIZED BY THE PRIMARY 2972
TUNGSTEN SUBCATEGORY (10 PLANTS)
V-l WATER USE AND DISCHARGE RATES FOR TUNGSTIC 2988
ACID RINSE WATER
V-2 WATER USE AND DISCHARGE RATES FOR ACID LEACH 2988
WET AIR POLLUTION CONTROL
V-3 WATER USE AND DISCHARGE RATES FOR ALKALI 2989
LEACH WASH
V-4 WATER USE AND DISCHARGE RATES FOR ION EXCHANGE 2989
RAFFINATE
V-5 WATER USE AND DISCHARGE RATES FOR CALCIUM 2990
TUNGSTATE PRECIPITATE WASH
V-6 WATER USE AND DISCHARGE RATES FOR AMMONIUM 2991
PARATUNGSTATE CRYSTALLIZATION AND DRYING
V-7 WATER USE AND DISCHARGE RATES FOR APT CONVERSION 2992
TO OXIDES WET AIR POLLUTION CONTROL
V-8 WATER USE AND DISCHARGE CHARACTERISTICS FOR APT 2993
CONVERSION TO OXIDES WATER OF FORMATION
V-9 WATER USE AND DISCHARGE RATES FOR REDUCTION TO 2994
TUNGSTEN WET AIR POLLUTION CONTROL
V-10 WATER USE AND DISCHARGE RATES FOR REDUCTION 2995
TO TUNGSTEN WATER OF FORMATION
2931
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PRIMARY TUNGSTEN SUBCATEGORY
LIST OF TABLES (Continued)
Table No. Page
V-ll WATER OSE AND DISCHARGE RATES FOR TUNGSTEN 2995
POWDER ACID LEACH AND WASH
V-12 PRIMARY TONGSTEN SAMPLING DATA TUNGSTIC ACID 2996
RINSE RAW WASTEWATER
V-13 PRIMARY TUNGSTEN SAMPLING DATA ION-EXCHANGE 3003
RAFFINATE RAW WASTEWATER
V-14 PRIMARY TUNGSTEN SAMPLING DATA SYNTHETIC 3011
SCHEELITE FILTRATE RAW WASTEWATER
V-15 PRIMARY TUNGSTEN SAMPLING DATA OXIDES REDUCTION 3015
FURNACE SCRUBBER RAW WASTEWATER
V-16 PRIMARY TUNGSTEN SAMPLING DATA REDUCTION TO 3017
TUNGSTEN WATER OF FORMATION RAW WASTEWATER
V-17 PRIMARY TUNGSTEN SAMPLING DATA TREATMENT PLANT 3021
SAMPLES - PLANT B
V-18 PRIMARY TUNGSTEN SAMPLING DATA TREATMENT PLANT 3024
SAMPLES - PLANT C
V-19 PRIMARY TUNGSTEN SAMPLING DATA TREATMENT PLANT 3032
SAMPLES - PLANT E
VI-1 FREQUENCY OF OCCURRENCE OF TOXIC POLLUTANTS 3057
PRIMARY TUNGSTEN RAW WASTEWATER
VI-2 TOXIC POLLUTANTS NEVER DETECTED 3061
2932
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PRIMARY TUNGSTEN SUBCATEGORY
LIST OF TABLES (Continued)
Table No. Page
VIII-1 COST OP COMPLIANCE FOR THE PRIMARY TUNGSTEN 3073
SUBCATEGORY DIRECT DISCHARGERS
VIII-2 COST OF COMPLIANCE FOR THE PRIMARY TUNGSTEN 3073
SUBCATEGORY INDIRECT DISCHARGERS
IX-1 BPT WASTEWATER DISCHARGE RATES FOR THE 3088
PRIMARY TUNGSTEN SUBCATEGORY
IX-2 BPT EFFLUENT LIMITATIONS FOR THE PRIMARY 3090
TUNGSTEN SUBCATEGORY
X-l CURRENT RECYCLE PRACTICES WITHIN THE PRIMARY 3108
TUNGSTEN SUBCATEGORY
X-2 POLLUTANT REDUCTION BENEFITS FOR DIRECT 3109
DISCHARGERS
X-3 BAT WASTEWATER DISCHARGE RATES FOR THE 3110
PRIMARY TUNGSTEN SUBCATEGORY
X-4 BAT EFFLUENT LIMITATIONS FOR THE PRIMARY 3112
TUNGSTEN SUBCATEGORY
XI-1 NSPS WASTEWATER DISCHARGE RATES FOR THE 3126
PRIMARY TUNGSTEN SUBCATEGORY
XI-2 NSPS FOR THE PRIMARY TUNGSTEN SUBCATEGORY 3128
XII-1 POLLUTANT REDUCTION BENEFITS FOR INDIRECT 3139
DISCHARGERS
XII-2 PSES AND PSNS WASTEWATER DISCHARGE RATES FOR 3140
THE PRIMARY TUNGSTEN SUBCATEGORY
XII-3 PSES FOR THE PRIMARY TUNGSTEN SUBCATEGORY 3142
XI1-4 PSNS FOR THE PRIMARY TUNGSTEN SUBCATEGORY 3149
2933
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PRIMARY TUNGSTEN SUBCATEGORY
LIST OP FIGURES
Figure No. Page
III-l PRIMARY TUNGSTEN PRODUCTION PROCESS 2973
111-2 GEOGRAPHIC LOCATIONS OF THE PRIMARY TUNGSTEN 2974
SUBCATEGORY PLANTS
V-l SAMPLING SITES AT PRIMARY TUNGSTEN PLANT A 3038
V-2 SAMPLING SITES AT PRIMARY TUNGSTEN PLANT B 3039
V-3 SAMPLING SITES AT PRIMARY TUNGSTEN PLANT C 3040
V-4 SAMPLING SITES AT PRIMARY TUNGSTEN PLANT D 3041
V-5 SAMPLING SITES AT PRIMARY TUNGSTEN PLANT E 3042
V-6 SAMPLING SITES AT PRIMARY TUNGSTEN PLANT F 3043
IX-1 BPT TREATMENT SCHEME FOR PRIMARY TUNGSTEN 3097
SUBCATEGORY
X-l BAT TREATMENT SCHEME FOR OPTION A 3119
X-2 BAT TREATMENT SCHEME FOR OPTION B 3120
X-3 BAT TREATMENT SCHEME FOR OPTION C 3121
2934
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PRIMARY TUNGSTEN SUBCATEGORY SECT - I
SECTION I
SUMMARY
This document provides the technical basis for promulgating
effluent limitations based on best practicable technology (BPT)
and best available technology (BAT) for existing direct
dischargers, pretreatment standards for existing indirect
dischargers (PSES), pretreatment standards for new indirect
dischargers (PSNS), and standards of performance for new source
direct dischargers (NSPS) for plants in the primary tungsten
subcategory.
The primary tungsten subcategory consists of 17 plants. Four
plants discharge directly to rivers, lakes, or streams; six
discharge to publicly owned treatment works (POTW); and seven
achieve zero discharge of process wastewater.
EPA first studied the primary tungsten subcategory to determine
whether differences in raw materials, final products,
manufacturing processes, equipment, age and size of plants, water
usage, required the development of separate effluent limitations
and standards for different segments of the subcategory. This
involved a detailed analysis of wastewater discharge and treated
effluent characteristics, including (1) the sources and volume of
water used, the processes used, and the sources of pollutants and
wastewaters in the plant; and (2) the constituents of
wastewaters, including toxic pollutants.
Several distinct control and treatment technologies (both in-
plant and end-of-pipe) applicable to the primary tungsten
subcategory were identified. The Agency analyzed both historical
and newly generated data on the performance of these
technologies, including their nonwater quality environmental
impacts and air quality, solid waste generation, and energy
requirements. EPA also studied various flow reduction techniques
reported in the data collection portfolios (dcp) and plant
visits.
Engineering costs were prepared for each of the control and
treatment options considered for the subcategory. These costs
were then used by the Agency to estimate the impact of
implementing the various options on the subcategory. For each
control and treatment option that the Agency found to be most
effective and technically feasible in controlling the discharge
of pollutants, the number of potential closures, number of
employees affected, and impact on price were estimated. These
results are reported in a separate document entitled The Economic
Impact Analysis of Effluent Standards and Limitations Guidelines
and Standards for the Nonferrous Smelting and Refining Industry.
Based on consideration of the above factors, EPA identified
various control and treatment technologies which formed the basis
2935
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PRIMARY TUNGSTEN SUBCATEGORY SECT - I
for BPT and selected control and treatment appropriate for each
set of standards and limitations. The mass limitations and
standards for BPT, BAT, NSPS, PSES, and PSNS are presented in
Section II.
After examining the various treatment technologies, the Agency
has identified BPT to represent the average of the best existing
technology. Metals removal based on lime precipitation and
sedimentation technology is the basis for the BPT limitations.
Steam stripping was selected as the technology basis for ammonia
limitations. To meet the BPT effluent limitations based on this
technology, the primary tungsten subcategory is expected to incur
a capital cost of $0.115 million (1982 dollars) and an annual
cost of $0.168 million (1982 dollars).
For BAT, the Agency has built upon the BPT technology basis by
adding in-process control technologies which include recycle of
process water from air pollution control waste streams.
Filtration is added as an effluent polishing step to the end-of-
pipe treatment scheme. To meet the BAT effluent limitations
based on this technology, the primary tungsten subcategory is
estimated to incur a capital cost of $0.773 million (1982
dollars) and an annual cost of $1.0 million (1982 dollars).
BDT, which is the technical basis of NSPS, is equivalent to BAT.
In selecting BDT, EPA recognizes that new plants have the
opportunity to implement the best and most efficient
manufacturing processes and treatment technology. As such, the
technology basis of BAT has been determined as the best
demonstrated technology.
The technology basis for PSES is equivalent to BAT. To meet the
pretreatment standards for existing sources, the primary tungsten
subcategory is estimated to incur a capital cost of $0.445
million (1982 dollars) and an annual cost of $0.568 million (1982
dollars). For PSNS, the Agency selected end-of-pipe treatment
and ' in-process flow reduction control techniques equivalent to
NSPS.
After promulgation of the final rule, AMAX, Inc. with GTE
Products Corp., as an intervenor filed a petition for review of
the final rule. After a full review of the technical problems and
new data, the Agency agreed in a settlement agreement to amend
the regulation in three respects: increase the ammonia limitation
for uncomingled ion exchange raffinate, add a building block for
alkali leach condensate, and revise the PNP, to the element
tungsten rather than specific salts. EPA proposed these
amendments to the Primary Tungsten Subcategory regulation on
January 22, 1987 (52 FR 2480), and promulgated these amendments
on January 21, 1988 (53 FR 1704). Details of the settlement can
be found at 52 FR 2480.
2936
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PRIMARY TUNGSTEN SUBCATEGORY SECT - II
SECTION II
CONCLUSIONS
EPA has divided the primary tungsten subcategory into 14
subdivisions for the purpose of effluent limitations and
standards. These subdivisions are:
(a) Tungstic acid rinse,
(b) Acid leaching wet air pollution control,
(c) Alkali leach wash,
(d) Alkali leach wash condensate,
(e) Ion exchange raffinate, (commingled with other process and
nonprocess streams)
(f) Ion .exchange raffinate (not commingled with other process
and nonprocess streams),
(g) Calcium tungstate precipitate wash,
(h) Crystallization and drying of ammonium paratungstate,
(i) Ammonium paratungstate conversion to oxides wet air
pollution control,
(j) Ammonia paratungstate conversion to oxides water
of formation,
(k) Reduction to tungsten wet air pollution control,
(1) Reduction to tungsten water of formation,
(m) Tungsten powder acid leach and wash, and
(n) Molybdenum sulfide precipitation wet air pollution control.
BPT is promulgated based on the performance achievable by the
application of chemical precipitation and sedimentation (lime
and settle) technology, along with preliminary treatment
consisting of ammonia steam stripping for selected waste
streams. The following BPT effluent limitations are
promulgated:
(a) Tungstic Acid Rinse BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W) produced
Lead 17.230 8.205
Zinc 59.900 25.030
Ammonia (as N) 5,469.000 2,404.000
TSS 1,682.000 800.000
pH Within the range of 7.0 to 10.0 at all times
2937
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PRIMARY TUNGSTEN SUBCATEGORY
SECT - II
(b) Acid Leach Wet Air Pollution Control BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W) produced
Lead
Zinc
Ammonia (as N)
TSS
pH
15.040 7.162
52.280 21.840
4,773.000 2,098.000
1,468.000 698.300
Within the range of 7.0 to 10.0 at all times
(c) Alkali Leach Wash BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Majcimum for
Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Lead
zinc
Ammonia (as N)
TSS
pH Within the range of
(d) Alkali Leach Wash Condensate BPT
0.000
0.000
0.000
0.000
7.0 to
0.000
0.000
0.000
0.000
10.0 at all times
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Lead
Zinc
Ammonia (as N)
TSS
pH
8.057 3.837
28.011 11.700
2,557.000 1,124.000
786.200 374.100
Within the range of 7.0 to 10.0 at all times
2938
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PRIMARY TUNGSTEN SUBCATEGORY
SECT - II
(e) Ion-Exchange Raff inate (commingled with other Process
or Nonprocess waters) BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units
English Units
Zinc
Ammonia (as N)
TSS
pH
mg/kg of ammonium tungstate (as W) produced
Ibs/million Ibs of ammonium tungstate (as W)
produced
37.160 17.700
129.200 53.970
11,790.000 5,185.000
3,627.000 1,726.000
Within the range of 7.0 to 10.0 at all times
(f ) Ion-Exchange Raffinate _J_ Not Commingled with other Process
or Nonprocess waters) BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of ammonium tungstate (as W) produced
English Units - Ibs/million Ibs of ammonium tungstate (as W) produced
Lead
Zinc
Ammonia (as N)
TSS
pH
37.160
192.200
11,790.000
3,627.000
Within the range of 7.0 to
17.700
53.970
5,185.000
1,726.000
10.0 at all times
(g) Calcium Tungstate Precipitate Wash BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of calcium tungstate (as W) produced
English Units - Ibs/million Ibs of calcium tungstate (as W) produced
Lead
Zinc
Ammonia (as N)
TSS
pH
31.000 14.760
107.800 45.020
9,838.000 4,325.000
3,026.000 1,439.000
Within the range of 7.0 to 10.0 at all times
2939
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PRIMARY TUNGSTEN SUBCATEGORY SECT - II
(h) Crystallization and Drying of Ammonium Paratungstate BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium paratungstate (as W) produced
English Units - Ibs/million Ibs of ammonium paratungstate
(as W) produced
Lead
Zinc
Ammonia (as N)
TSS
pH
0.000
0.000
0.000
0.000
Within the range of 7.0 to
0.000
0.000
0.000
0.000
10.0 at all times
(i) Ammonium Paratungstate Conversion to Oxides Wet Air
Pollution Control BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Lead 11.600 5.523
Zinc 40.320 16.850
Ammonia (as N) 3,681.000 1,618.000
TSS 1,132.000 538.500
pH Within the range of 7.0 to 10.0 at all times
(j) ' Ammonium Paratungstate Conversion to Oxides Water of
Formation BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Lead
Zinc
Ammonia (as N)
TSS
pH
0.026
0.092
8.398
2.583
Within the range of 7.0 to
0.013
0.038
3.692
1.229
10.0 at all times
2940
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PRIMARY TUNGSTEN SOBCA$EGORY SECT -II
(k) Reduction to Tungsten Wet Air Pollution Control BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Lead 12.940 6.161
Zinc 44.970 18.790
Ammonia (as N) 4,106.000 1,805.000
TSS 1,263.000 600.700
pH Within the range of 7.0 to 10.0 at all times
(1) Reduction to Tungsten Water of Formation BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal reduced
English Units - Ibs/million Ibs of tungsten metal reduced
Lead 0.205 0.098
Zinc 0.714 0.298
Ammonia (as N) 65.190 28.660
TSS 20.050 9.536
pH Within the range of 7.0 to 10.0 at all times
(m) Tungsten Powder Acid Leach and Wash BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English units - Ibs/million Ibs of tungsten metal produced
Lead 1.008 0.480
Zinc 3.504 1.464
Ammonia (as N) 319.900 140.700
TSS 98.400 46.800
pH Within the range of 7.0 to 10.0 at all times
2941
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - II
(n) Molybdenum Sulfide Precipitation Wet Air Pollution
Control BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Lead 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
TSS 0.000 0.000
pH Within the range of 7.0 to 10.0
at all times
BAT is promulgated based on the performance achievable by the
application of chemical precipitation, sedimentation, and
multimedia filtration (lime, settle, and filter) technology
and in-process flow reduction methods, along with preliminary
treatment consisting of ammonia steam stripping for selected
waste streams. The following BAT effluent limitations are
promulgated:
(a) Tungstic Acid Rinse BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W)
produced
Lead 11.490 5.333
Zinc 41.850 17.230
Ammonia (as N) 5,469.000 2,404.000
2942
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - II
(b) Acid Leach Wet Air Pollution Control BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W)
produced
Lead 1.003 0.466
Zinc 3.653 1.504
Ammonia (as N) 477.400 209.900
(c) Alkali Leach Wash BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Lead 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
(d) Alkali Leach Wash Condensate BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Lead 5.372 2.494
Zinc 19.570 8.057
Ammonia (as N) 2,557.000 1,124.000
2943
-------
PRIMARY TUNGSTEN SUBCATEGORY
SECT - II
(e) Ion-Exchange Raffinate (Commingled with other Process
or Nonprocess Waters) BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units
English Units
Lead
Zinc
Ammonia (as N)
mg/kg of ammonium tungstate (as W) produced
Ibs/million Ibs of ammonium tungstate (as W)
produced
24.780
90.240
11,790.000
11.500
37.160
5,185.000
(f) Ion-Exchange Raffinate (Not Commingled with other Process
or Nonprocess Waters)1 BAT
Maximum for
Monthly Average
Pollutant or
Pollutant Property
Maximum for
Any One Day
Metric Units
English Units
Lead
Zinc
Ammonia (as N)
mg/kg of ammonium tungstate (as W) produced
Ibs/million Ibs of ammonium tungstate (as W)
produced
24.780
90.240
11,790.000
11.500
37.160
5,185.000
1The effluent limitation for this pollutant does not apply if
(a) the mother liquor feed to the ion exchange process or the
raffinate from the ion exchange process contains sulfates at
concentrations exceeding 1000 mg/1; (b) this mother liquor or
raffinate is treated by ammonia steam stripping; and (c) such
mother liquor or raffinate is not commingled with any other
process or nonprocess waters prior to steam stripping for ammonia
removal.
2944
-------
PRIMARY TUNGSTEN SOBCATEGORY SECT - II
(g) Calcium Tungstate Precipitate Wash BAT
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of calcium tungstate (as W) produced
English Units - Ibs/million Ibs of calcium tungstate (as W)
produced
Lead 20.670 9.594
Zinc 75.280 31.000
Ammonia (as N) 9,838.000 4,325.000
(h) Cr ys talli zat ion and Drying of Ammonium Par a tungstate BAT
pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Onits - mg/kg of ammonium paratungstate (as W) produced
English Units - Ibs/million Ibs of ammonium paratungstate
(as W) produced
Lead 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
(i) Ammonium Paratungstate Conversion to Oxides Wet Air
Pollution Control BAT
OT Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Lead 0.773 0.359
Zinc 2.817 1.160
Ammonia (as N) 368.200 161.900
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - II
(j) Ammonium Paratungstate Conversion to Oxides Water of_
Formation BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Lead 0.018 0.008
Zinc 0.064 0.026
Ammonia (as N) 8.398 3.692
(k) Reduction to Tungsten Wet Air Pollution Control
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Lead 0.862 0.400
Zinc 3.142 1.294
Ammonia (as N) 410.600 180.500
(1) Reduction to Tungsten Water of Formation BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal reduced
English Units - Ibs/million Ibs of tungsten metal reduced
Lead 0.137 0.064
Zinc 0.499 0.205
Ammonia (as N) 65.190 28.660
2946
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - II
*
(m) Tungsten Powder Acid Leach and Wash BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Lead 0.672 0.312
Zinc 2.448 1.008
Ammonia (as N) 319.900 140.700
(n) Molybdenum Sulfide Precipitation Wet Air Pollution
Control BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal
produced
Lead 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
NSPS are promulgated based on the performance achievable by
the application of chemical precipitation, sedimentation, and
multimedia filtration (lime, settle, and filter) technology,
and in-process flow reduction control methods, along with
preliminary treatment consisting of ammonia steam stripping
for selected waste streams. The following effluent standards
are promulgated for new sources:
(a) Tungstic Acid Rinse NSPS NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W) produced
Lead 11.490 5.333
Zinc 41.850 17.230
Ammonia (as N) 5,469.000 2,404.000
TSS 615.400 492.300
pH Within the range of 7.0 to 10.0 at all times
2947
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - II
(b) Acid Leach Wet Air Pollution Control NSPS NSPS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W) produced
Lead 1.003 0.466
Zinc 3.653 1.504
Ammonia (as N) 477.400 209.900
TSS 53.720 42.970
pH Within the range of 7.0 to 10.0 at all times
(c) Alkali Leach Wash NSPS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Lead
Zinc
Ammonia (as N)
TSS
pH
0.000
0.000
0.000
0.000
Within the range of 7.0 to 10.0
0.000
0.000
0.000
0.000
at all times
(d) Alkali Leach Wash Condensate NSPS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Lead 5.372 2.494
Zinc 19.570 8.057
Ammonia (as N) 2,557.000 1,124.000
TSS 287.800 229.600
pH Within the range of 7.0 to 10.0 at all times
OO/IQ
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - II
(e) Ion-Exchange Raffinate (Commingled with other Process
or_ Nonprocess Waters) NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium tungstate (as W) produced
English Units - Ibs/million Ibs of ammonium tungstate (as W)
produced
Lead 24.780 11.500
Zinc 90.240 37.160
Ammonia (as N) 11,790.000 5,185.000
TSS 1,327.000 1,062.000
pH Within the range of 7.0 to 10.0 at all times
(f) Ion-Exchange Raffinate (Not Commingled with other Process
or Nonprocess Waters)1 NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium tungstate (as W) produced
English Units - Ibs/million Ibs of ammonium tungstate (as W)
produced
Lead 24.780 11.500
Zinc 90.240 37.160
Ammonia (as N) 11,790.000 5,185.000
TSS 1,327.000 1,062.000
pH Within the range of 7.0 to 10.0 at all times
new source standard for this pollutant does not apply if
(a) the mother liquor feed to the ion exchange process or the
raffinate from the ion exchange process contains sulfates at
concentrations exceeding 1000 mg/1; (b) this mother liquor or
raffinate is treated by ammonia steam stripping; and (c) such
mother liquor or raffinate is not commingled with any other
process or nonprocess waters prior to steam stripping for ammonia
removal.
2949
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - II
(g) Calcium Tungstate Precipitate Wash NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of calcium tungstate (as W) produced
English Units - Ibs/million Ibs of calcium tungstate (as W)
produced
Lead 20.670 9.594
Zinc 75.280 31.000
Ammonia (as N) 9,838.000 4,325.000
TSS 1,107.000 885.600
pH Within the range of 7.0 to 10.0 at all times
(h) Crystallization and Drying of Ammonium Paratungstate NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium pafatungstate (as W) produced
English Units - Ibs/million Ibs of ammonium paratungstate
(as W) produced
Lead
Zinc
Ammonia (as N)
TSS
pH
0.000
0.000
0.000
0.000
Within the range of 7.0 to
0.000
0.000
0.000
0.000
10.0 at all times
(i) Ammonium Paratungstate Conversion to Oxides Wet Air
Pollution Control NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Lead 0.773 0.359
Zinc 2.817 1.160
Ammonia (as N) 368.200 161.900
TSS 41.430 33.150
pH Within the range of 7.0 to 10.0 at all times
2950
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - II
(j) Ammonium Paratungstate Conversion to Oxides Water of
Formation NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Lead 0.018 0.008
Zinc 0.064 0.026
Ammonia (as N) 8.398 3.692
TSS 0.945 0.756
pH Within the range of 7.0 to 10.0 at all times
(k) Reduction to Tungsten Wet Air Pollution Control NSP.S
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Lead 0.862 0.400
Zinc 3.142 1.294
Ammonia (as N) 410.600 180.500
TSS 46.200 36.960
pH Within the range of 7.0 to 10.0 at all times
(1) Reduction to Tungsten Water of Formation NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Lead 0.137 0.064
Zinc 0.499 0.205
Ammonia (as N) 65.190 28.660
TSS 7.335 5.868
pH Within the range of 7.0 to 10.0 at all times
2951
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - II
(m) Tungsten Power Acid Leach and Wash NSPS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Lead 0.672 0.312
Zinc 2.448 1.008
Ammonia (as N) 319.900 140.700
TSS 36.000 28.800
pH Within the range of 7.0 to 10.0 at all times
(n) Molybdenum Sulfide Precipitation Wet Air Pollution
Control NSPS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Lead
Zinc
Ammonia (as N)
TSS
pH
0.000
0.000
0.000
0.000
Within the range of 7.0 to 10.0
0.000
0.000
0.000
0.000
at all times
PSES are promulgated based on the performance achievable by
the application of chemical precipitation, sedimentation, and
multimedia filtration (lime, settle, and filter) technology,
and in-process flow reduction control methods, along with
freliminary treatment consisting of ammonia steam stripping
or selected waste streams. The following pretreatment
standards are promulgated for existing sources:
(a) Tungstic Acid Rinse PSES
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W) produced
Lead 11.490 5.333
Zinc 41.850 17.230
Ammonia (as N) 5,469.000 2,404.000
2952
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - II
(b) Acid Leach Wet Air Pollution Control PSES
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W) produced
Lead
Zinc
Ammonia (as N)
1.003
3.653
477.400
0.466
1.504
209.900
(c) Alkali Leach Wash PSES
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of sodium tungstate produced
English Units - Ibs/million Ibs of sodium tungstate produced
Lead 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
(d) Alkali Leach Wash Condensate PSES
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Lead 5.372 2.494
Zinc 19.570 8.057
Ammonia (as N) 2,557.000 1,124.000
2953
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - II
(e) Ion-Exchange Raffinate (Commingled with Other Process
or Nonprocess Water) PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium tungstate (as W) produced
English Units - Ibs/million Ibs of ammonium tungstate (as W)
produced
Lead
Zinc
Ammonia
(as N)
24.780 11.500
90.240 37.160
11,790.000 5,185.000
(f) Ion-Exchange Raffinate (Not Commingled with Other Process
or Nonprocess Water)1 PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium tungstate (as W) produced
English Units - Ibs/million Ibs of ammonium tungstate (as W)
produced
Lead 24.780 11.500
Zinc 90.240 37.160
Ammonia (as N) 11,790.000 5,185.000
1The pretreatment"^standard for this pollutant does not apply
if (a) the mother liquor feed to the ion exchange process or the
raffinate from the ion exchange process contains sulfates at
concentrations exceeding 1000 mg/1; (b) this mother liquor or
raffinate is treated by ammonia steam stripping; and (c) such
mother liquor or raffinate is not commingled with any other
process or nonprocess waters prior to steam stripping for ammonia
removal.
(g) Calcium Tungstate Precipitate Wash PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of calcium tungstate (as W) produced
English Units - Ibs/million Ibs of calcium tungstate (as W)
produced
Lead 20.570 9.594
Zinc 75.280 31.000
Ammonia (as N) 9,333.000 4,325.000
2954
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - II
(h) Crystallization and Drying of Ammonium Paratungstate PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium paratungstate (as W) produced
English Units - Ibs/million Ibs of ammonium paratungstate
(as W) produced
Lead 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
(i) Ammonium Paratungstate Conversion to Oxides Wet Air
Pollution Control PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Lead 0.773 0.359
Zinc 2.817 1.160
Ammonia (as N) 368.200 161.900
(j) Ammonium Paratungstate Conversion to Oxides Water of
Formation PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Lead 0.018 0.008
Zinc 0.064 0.026
Ammonia (as N) 8.398 3.692
2955
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - II
(k) Reduction to Tungsten Wet Air Pollution Control PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Lead 0.862 0.400
Zinc 3.142 1.294
Ammonia (as N) 410.600 180.500
(1) Reduction to Tungsten Water of Formation PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Lead 0.137 0.064
Zinc 0.499 0.205
Ammonia (as N) . 65.190 28.660
(m) Tungsten Powder Acid Leach and Wash PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Lead 0.672 0.312
Zinc 2.448 1.008
Ammonia (as N) 319.900 140.700
2956
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - II
(n) Molybdenum Sulfide Precipitation Wet Air Pollution
Control PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal
produced
Lead
Zinc
Ammonia (as N)
0.000
0.000
0.000
0.000
0.000
0.000
PSNS are promulgated based on the performance achievable by
the application of chemical precipitation, sedimentation, and
multimedia filtration (lime, settle, and filter) technology,
and in-process flow reduction control methods, .along with
preliminary treatment consisting of ammonia steam stripping
for selected waste streams. The following pretreatment
standard are promulgated for new sources:
(a) Tungatic Acid Rinse PSNS
Pollutant or"Maximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W)
produced
Lead
Zinc
Ammonia (as N)
11.490
41.850
5,469.000
5.333
17.230
2,404.000
(b) Acid Leach Wet Air Pollution Control PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W)
produced
Lead 1.003 0.466
Zinc 3.653 1.504
Ammonia (as N) 477.400 209.900 '
2957
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - II
(e) Alkali Leach Wash PSNS
Pollutant or Maximum "Tor Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Lead 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
(d) Alkali Leach Wash Condensate PSNS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Lead . 5.372 2.494
Zinc 19.570 8.057
Ammonia (as N) 2,557.000 1,124.000
(e) Ion-Exchange Raf f inate ( Commi ngl ed with Other Process
or Nonprocess Waters) PSNS
or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium tungstate (as W) produced
English Units - Ibs/million Ibs of ammonium tungstate (as W)
produced
Lead 24.780 11.500
Zinc 90.240 37.160
Ammonia (as N) 11,790.000 5,185.000
2958
-------
PRIMARY TUNGSTEN SUBCATEGORY
SECT - II
(f) Ion-Exchange Raffinate (Not Commingled with Other Process
or Nonprocess Waters) PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units
English Units
Lead
Zinc
Ammonia (as N)
mg/kg of ammonium tungstate (as W) produced
Ibs/million Ibs of ammonium tungstate (as W)
produced
24.780
90.240
11,790.000
11.500
37.160
5,185.000
•"•The pretreatment standard for this pollutant does not apply
if (a) the mother liquor feed to the ion exchange process or the
raffinate from the ion exchange process contains sulfates at
concentrations exceeding 1000 mg/1; (b) this mother liquor or
raffinate is treated by ammonia steam stripping; and (c) such
mother liquor or raffinate is not commingled with any other
process or nonprocess waters prior to steam stripping for ammonia
removal.
(g) Calcium Tungstate Precipitate Wash
PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units
English Units
Lead
Zinc
Ammonia
(as N)
mg/kg of calcium tungstate (as W) produced
Ibs/million Ibs of calcium tungstate (as W)
produced
20.670
75.280
9,838.000
9.594
31.000
4,325.000
(h) Crystallization and Drying of Ammonium Paratungstate PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of ammonium paratungstate (as W) produced
English Units - Ibs/million Ibs of ammonium paratungstate
(as W) produced
Lead
Zinc
Ammonia (as N)
0.000
0.000
0.000
0.000
0.000
0.000
2959
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - II
(i) Ammonium Paratungstate Conversion to Oxides Wet Air
Pollution Control PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Lead 0.773 0.359
Zinc 2.817 1.160
Ammonia (as N) 368.200 161.900
(j) Ammonium Paratungstate Conversion to Oxides Water of
Formation PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Lead 0.018 0.008
Zinc 0.064 0.026
Ammonia (as N) 8.398 3.692
(k) Reduction to Tungsten Wet Air Pollution Control PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungoten metal produced
Lead 0.862 0.400
Zinc 3.142 1.294
Ammonia (as N) 410.600 180.500
2960
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - II
(1) Reduction to Tungsten Water of Formation PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Lead 0.137 0.064
Zinc 0.499 0.205
Ammonia (as N) 65.190 28.660
(m) Tungsten Powder Acid Leach and Wash PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Lead 0.672 0.312
Zinc 2.448 1.008
Ammonia (as N) 319.900 140.700
(n) Molybdenum Sulfide Precipitation Wet Air Pollution
Control PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal
produced
Lead 0.000 0.000
Zinc 0.000 0.000
Ammonia (as N) 0.000 0.000
2961
-------
PRIMARY TUNGSTEN SU1CATEGORY SECT - II
THIS PAGE INTENTIONALLY LEFT BLANK
2962
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - III
SECTION III
SUBCATEGORY PROFILE
This section of the primary tungsten supplement describes the raw
materials and processes used in producing primary tungsten, and
presents a profile of the primary tungsten plants identified in
this study.
In the early 1780's, tungstic acid was first isolated from
scheelite and wolframite and/ shortly thereafter, tungsten was
obtained by both carbon and hydrogen reduction of wolframite
{(Fe,Mn)WC>4) • Hydrogen reduction is still a key step in the
production of tungsten powder from which other finished products
are derived. From the mid-nineteenth century through the first
third of this century, tungsten was used chiefly as an alloying
agent in steel. During the last 30 years, however, tungsten uses
have increased to include production of carbides and alloys. The
1974 production use breakdown was 68 percent carbide, 15 percent
pure metal, and 15 percent alloy. Another 2 percent was used to
manufacture various metal compounds.
DESCRIPTION OF PRIMARY TUNGSTEN PRODUCTION
The production of tungsten metal can be divided into three
distinct stages - leaching of ore concentrates, purification to
ammonium paratungstate (APT), and the reduction of APT to metal.
The actual processes used in each stage vary with the type and
purity of the raw material used. The primary tungsten production
process is presented schematically in Figure III-l (Page 2973)
and described below.
RAW MATERIALS
The principal domestic ores used to produce ammonium
paratungstate and tungsten metal powder are ferberite (FeWO4),
wolframite ((Fe,Mn)WO4), and scheelite (CaWO4). These ores are
mined principally in California and Colorado.
LEACHING OF ORE CONCENTRATES
Scheelite ores of high quality (i.e., low concentrations of
molybdenum and complexing elements such as phosphorus, arsenic,
and silicon) are usually leached with hot hydrochloric acid
(HC1). An insoluble tungstic acid intermediate (H2WO4) is
formed. Subsequently, the tungstic acid is filtered and washed.
The acidic tungstic acid rinse water and HC1 fume control
scrubber water are wastewater sources.
Lower quality scheelite ores and some wolframite ores, (Fe,Mn)WO4
may be digested using a soda-autoclave leach process that uses
high temperature steam and soda ash in quantities greater than
stoichiometric amounts to produce a sodium tungstate intermediate
2963
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - III
(Na2WC>4). The sodium tungstate solution is usually filtered to
remove calcium carbonate (CaCC>3) and silica solids which are the
contaminants in largest concentrations in the ore. If molybdenum
impurities are present, the sodium tungstate solution is reacted
with sodium hydrosulfide (NaHS) to precipitate molybdenum
trisulfide (MoSs). The molybdenum trisulfide solids are removed
with a filter and the sodium tungstate solution is further
processed. A wet scrubber is used on the precipitation step to
control hydrogen sulfide (H2S) gaseous emissions. The spent
scrubber liquor is a possible source of wastewater.
Higher quality wolframite ores are processed using an alkaline
leaching method. This method, which also produces a sodium
tungstate intermediate, involves digestion with a strong caustic
solution, usually sodium hydroxide (NaOH). The sodium tungstate
solution is filtered to remove insoluble impurities, which are
washed and discarded. Sodium tungstate is crystallized from the
filtrate and the remaining caustic solution and wash water are
recycled, evaporated, or discharged. The alkali leach wash
condensate may also be discharged. Alternately, the filtrate
is sent to the solvent extraction process for tungsten recovery
(discussed below).
PURIFICATION TO AMMONIUM PARATUNGSTATE
Purification of the tungstic acid intermediate (H2VK>4) is more
direct than that for sodium tungstate. After filtering and
washing to remove soluble calcium chloride (CaCl2)r the tungstic
acid is dissolved in ammonium hydroxide (NH4OH) to form ammonium
tungstate ((NH4)6W7024 * 6H20) in solution. Ammonium
paratungstate (5(NH4)2O * 12W03 • 5H2O) is obtained by
crystallization from the ammonium tungstate solution. Ammonia
evolved during crystallization is usually recovered and recycled.
Spent mother liquor from the crystallization is either recycled
or discarded. The APT is filtered and dried to drive off
residual mother liquor. Baghouses are used to capture
particulate APT from drying furnace off-gases.
The purification of the sodium tungstate intermediate can follow
two basic routes. The classical approach is to precipitate
calcium tungstate (synthetic scheelite) from the sodium tungstate
solution by adding calcium chloride. The solution is filtered to
mostly sodium chloride, is discharged. The calcium tungstate
(CaW04) can then be digested with hydrochloric acid (HC1). Prom
this point, the purification is the same as described above for
the purification of tungstic acid intermediate - dissolution with
ammonia followed by crystallization.
Synthetic scheelite is also prepared from recycled process
solutions and cleanup water, such as spent crystallization liquor
and floor wash, that may contain tungsten values. The calcium
tungstate is precipitated with calcium chloride and can be
processed as described above. Alternatively, the calcium
tungstate may be sent through solvent extraction instead of
digested with hydrochloric acid.
2964
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - III
The second approach for purifying the sodium tungstate
intermediate is a n^wer solvent extraction method. The sodium
tungstate solution is converted to ammonia tungstate solution in
a liquid ion-exchange system. The sodium tungstate solution is
contacted countercurrently with an organic solvent, which removes
the tungstate ions from solution. The ion-exchange raffinate, or
waste solution, is a process wastewater source. The organic
solvent is washed with water to remove impurities and recycled.
Wash water is discharged with the raffinate. The ammonium
tungstate solution is fed to a crystallizer where APT crystals
are formed. The APT crystals are filtered and dried as described
above.
APT CONVERSION TO OXIDE
Dried APT is calcined in rotary furnaces heated indirectly to
drive off ammonia and produce tungsten oxides (WOX). The type of
oxide produced is a function of furnace atmosphere (N2r &2' etc.)
and temperature. Blue tungsten oxide (W2Os), brown tungsten
oxide (WO2)r or yellow tungstic oxide (WC>3) are possible
products. The calciners are often equipped with wet scrubbers
whose wastewaters contain treatable concentrations of ammonia.
Water of formation may also be collected and discarded.
REDUCTION TO METAL
Tungsten oxides are reduced to metal powder in high temperature
(>700°C) furnaces. The reducing agent is typically hydrogen
(H2>. Powders of various particle sizes are produced by varying
furnace reaction time, temperature gradient, hydrogen flow, and
layer thickness. Water of formation and scrubber wastewater may
be generated in this step.
Tungsten powder used in high-purity application is leached with
acids (e.g., hydrochloric or hydrofluoric), rinsed with water and
dried. The spent acid and rinse water are discharged to
wastewater treatment.
TUNGSTEN CARBIDE PRODUCTION
Tungsten carbide (WC) is formed by reducing APT or tungsten
oxides in the presence of carbon. Tungsten ores may also be
reduced and carburized in a single reaction. In the latter
process, impurities are leached with acid from the furnace
product to yield tungsten carbide crystals. Acids used are
hydrochloric, sulfuric, and hydrofluoric. Wastewater generated
consists of spent acid, rinse water, and spent liquor from a
scrubber on the leaching step.
PROCESS WASTEWATER SOURCES
Although a variety of processes are involved in primary tungsten
production, the process wastewater sources can are subdivided as
2965
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - III
follows:
1. Tungstic acid rinses,
2. Acid leaching wet air pollution control,
3. Alkali leach wash,
4. Alkali leach wash condensate
5. Molybdenum sulfide precipitation wet air pollution
control,
6. Ion-exchange raffinate, (commingled with other process
and nonprocess streams)
7. Ion-exchange raffinate (not commingled with other
process and nonprocess streams)
8. Calcium tungstate precipitate wash,
9. Crystallization and drying of ammonium paratungstate,
10. Ammonium paratungstate conversion to oxides wet air
pollution control,
11. Ammonia paratungstate conversion to oxides water of
formation,
12. Reduction to tungsten wet air pollution control,
13. Reduction to tungsten water of formation, and
14. Tungsten powder acid leach and wash.
OTHER WASTEWATER SOURCES
There are other wastewater streams associated with the primary
tungsten subcategory. These streams may include stormwater
runoff, Maintenance and cleanup water, tungsten carbide acid
leach and rinse, tungsten carbide acid leach wet air pollution
control, and acid rinse of alkali intermediates. These wastewater
streams are not considered as a part of this rulemaking. EPA
believes that the flows and pollutant loadings associated with
these waste streams are insignificant relative to the waste
streams selected, and are best handled by the appropriate permit
authority on a case-by-case basis under authority of Section 402
of the CWA.
One plant in the subcategory reported the tungsten carbide acid
leach and associated scrubber waste streams. This plant is a
zero discharger through evaporation in ponds. The Agency
believes these wastewater streams are unique and do not warrant a
national effluent limitation.
One plant generates a tungstic acid rinse water from an acid
leaching step. This stream was considered unique because an
alkali leaching product, not ore concentrates, was leached, and
the tungstic acid produced was more thoroughly rinsed and dried
in preparation for sale as a by-product.
AGE, PRODUCTION, AND PROCESS PROFILE
Figure III-2 (Page 2974) shows the location of the 17 primary
tungsten plants operating in the United States. Thirteen of the
17 plants are located in states east of the Mississippi River
around the Great Lakes while one is located in California, one in
Iowa, and two in Nevada. All but the plants in California and
2966
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - III
Nevada are in net precipitation areas.
Table III-l (Page 2973} shows the relative age and discharge
status of the tungsten plants and illustrates that many plants
were built around the time of World War II. The average plant
age is between 20 and 30 years. From Table III-2 (Page 2969), it
can be seen that five plants produce over 1,000 kkg/yr of metal,
three produce between 250 and 1,000 kkg/yr, and nine others
produce less than 250 kkg/yr. Mean production is about 480
kkg/yr.
Table III-3 (page 2969) shows a summary of the existing treatment
level of plants in the primary tungsten subcategory. Table III-4
(Page 2970) provides a summary of the number of plants generating
wastewater for the waste streams associated with various
processes and the number of plants with the process. Table III-5
(page 2971) relates the production processes used in the
subcategory with the number of plants using the process.
Finally,Table III-6 (page 2972) displays the treatment processes
used by the various types of dischargers in the primary tungsten
subcategory.
2967
-------
Table III-1
INITIAL OPERATING YEAR (RANGE) simRY OF PLANTS
IN THE mmm TUNGST^ SUBCATEGGRY BY DISCHAIGE TYPE
Initial Operating Year (Range)
1983-
1974
Type of Plant (0-10)
Direct 1
w Indirect 1
vo
00
Zero 3_
Total 5
1973-
1969
(11-15)
0
0
2
2
1968-
1959
(16-25)
0
0
1
1
(Plant A&<
1958-
1949
(26-35)
1
1
0
2
> in Years;
1948-
1939
(36-45)
2
2
J_
4
»
1938-
1929
(46-55)
0
0
0
0
1928-
1919
(56-65)
0
1
0
1
Before
1919
(65*) Total
0 4
1 6
0 _7
1 17
s
H
K
Q
OT
m
2S
m
G
w
0
M
Q
0
*
m
m
o
i
H
-------
PRIMARY TUNGSTEN SUBCATEGORY
SECT - III
TABLE III-2
PRODUCTION RANGES FOR THE
PRIMARY TUNGSTEN INDUSTRY
Production Ranges
for 1976
tons/year)
0 - 1,000
1,001 - 5,000
5,000 +
Insufficient Data
Number of Plants
4
3
2
1
TABLE III-3
TREATMENT LEVEL SUMMARY FOR
THE PRIMARY TUNGSTEN INDUSTRY
Discharge
Type
Direct
Indirect
Zero
Totals
No
Treatment
0
0
1
Level A*
2
2
2.
6
Level B
1
1
0_
2
Total
3
3
3
9
*The levels of treatment have been defined ass
Level A - Physical separation of solids, cooling or
neutralization only.
Level B - Removal of dissolved metals by chemical
precipitation followed by coagulation/
flocculation, settling and/or filtration.
2969
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - III
TABLE II1-4
SUMMARY OF SDBCATEGORY PROCESSES AND ASSOCIATED
WASTEWATER STREAMS
Number of plants Number of Plants
Wastewater Stream with Process Generating Wastewater
Tungstic Acid Rinse 2 2
Acid Leaching Air Pollution Control 2 2
Alkali Leach Wash 4 • 4
Alkali Leach Wash Condensate 1 1
Molybdenum Sulfide Precipitation 2 2
Air Pollution control
Ion-Exchange Raffinate (Commingled and 4 4
Not Commingled With Other Process or
Nonprocess Streams)
Calcium Tungstate Precipitate Wash 6 6
Crystallization and Drying of Ammonium 5 5
Paratungstate
Ammonium Paratungstate Conversion to 2 2
Oxides Air Pollution control
Ammonium Paratungstate Conversion to 2 2
Oxides Water of Formation
Reduction to Tungsten Air Pollution 7 7
Control
Reduction to Tungsten Water of 6 6
Formation
Tungsten Powder Acid Leach and Wash 2 2
NOTE: Through reuse or evaporation practices, a plant may
generate a wastewater from a particular process but may not
discharge it.
2970
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - III
TABLE III-5
PRODUCTION PROCESSES UTILIZED BY THE
PRIMARY TUNGSTEN SUBCATEGORY (10 PLANTS)
Number of Plants
Production Process With Process
Fusion or Concentrate 2
Leaching 4
Precipitation 4
Filtration 4
APT Drying 6
Reduction 7*
•Identification of the use of a reduction process, at one
plant which produces metal from APT, was indeterminable
due to insufficient data.
2971
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - III
TABLE III-6
TREATMENT PROCESSES UTILIZED BY THE
PRIMARY TUNGSTEN SUBCATEGORY (10 PLANTS)
Direct Indirect Zero Total
Treatment Processes Dischargers Dischargers Dischargers Subcatego
Number of Plants
Ammonia Stripping
Lime
Polymer
Cooling
Evaporation
Settling
Filtration
NO Treatment
3
2
3
1
1
0
3
3 ' '
0
3
1
1
1
0
1
3
1
0
3
1
0
0
1
1
2
2
1
9*
4
4
2
2
2
8
6
1
*Method of wastewater discharge was indeterminable for one plant
due to insufficient data.
2972
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - III
HUM Cr*d«
Or* Concincr»c«« 5ch»«lic« Or*
<«i
-------
K)
VD
e>
IIWTM
D-Direct Process WaStewater Discharge Plants
I-Indlrect Wastewater Discharge Plants
Z-Zero Wastewater Discharge Plants
Figure III-2
GEOGRAPHIC LOCATION OF PRIMARY TUNGSTEN PLANTS
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IV
SECTION IV
SDBCATEGORIZATION
This section summarizes the factors considered during the
designation of the primary tungsten subcategory and its related
subdivisions. Production normalizing parameters for each
subdivision are also discussed.
FACTORS CONSIDERED IN SUBDIVIDING THE PRIMARY TUNGSTEN
SUBCATEGORY
The factors listed for general subcategorization were each
evaluated when considering subdivision of the primary tungsten
subcategory. In the discussion that follows, the factors will be
described as they pertain to this particular subcategory.
The rationale for considering segmentation of the primary
tungsten subcategory is based primarily on differences in the
production processes and raw materials used. Within this
subcategory, a number of different operations are performed,
which may or may not have a water use or discharge, and which may
require the establishment of separate effluent limitations. While
primary tungsten is considered a single subcategory, a more
thorough examination of the production processes has illustrated
the need for limitations and standards based on a specific set of
waste streams. Limitations are based on specific flow allowances
for the following subdivisions or building blocks:
1. Tungstic acid rinse,
2. Acid leach wet air pollution control,
3. Alkali leach wash,
4. Alkali leach wash condensate
5. Molybdenum sulfide precipitation wet air pollution
control,
6. Ion-exchange raffinate, (commingled with other process
and nonprocess streams)
7. Ion-exchange raffinate (not commingled with other
process and nonprocess streams)
8. Calcium tungstate precipitate wash,
9. Crystallization and drying of ammonium paratungstate,
10. Ammonium paratungstate conversion to oxides wet air
pollution control,
11. Ammonium paratungstate conversion to oxides water of
formation,
12. Reduction to tungsten wet air pollution control,
13. Reduction to tungsten water of formation, and
14, Tungsten powder acid leach and wash.
These subdivisions follow directly from differences within the
three distinct production stages of primary tungsten; leaching
of ore concentrates, purification to APT, and reduction to metal.
Generally, a specific plant will either process ore to APT,
2975
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IV
reduce APT to metal, or utilize all three stages of production
and process ore concentrate all the way to tungsten metal.
Leaching of ore concentrates gives rise to the first four
building blocks. The acidic rinses of insoluble tungstic acid
are a major source of wastewater directly attributable to
leaching with HC1. Wastewaters from scrubbers which are used to
control HC1 fumes may also be significant sources of pollutants.
If the alkali leaching process is used/ the decantation of sodium
tungstate may produce waste streams.
Differences in methods of purifying the two intermediates—sodium
tungstate and tungstic acid—into APT resulted in the fifth,
sixth, seventh, eight and ninth building blocks. If sodium
tungstate is the intermediate from leaching, calcium tungstate
(synthetic scheelite) may be precipitated by adding calcium
chloride, CaCl2« The filtrate from this process is a wastewater
which contains sodium chloride, NaCl. Molybdenum sulfide
impurities also may be precipitated from sodium tungstate
solution, resulting in wastewater from a scrubber on this step.
If the liquid ion-exchange route is chosen to convert sodium
tungstate to APT, a raffinate stream is a potential discharge.
Plants which produce APT crystallize it from solution.
Consequently the spent mother liquor may create another discharge
situation. Some plants use a combination of recycle or
evaporation if it is feasible for this process. An ammonia
recovery system is commonly economically viable for this waste
stream.
The final production stage, reduction of APT to metal, also has
three subdivisions associated with it. The decomposition of APT
to tungsten oxides drives off ammonia which is usually contained
with some type of wet scrubbing system. "Water of formation" may
also be generated. This water may pass in a vapor phase through
the scrubber system or may be condensed separately; consequently,
a separate subdivision has been included to account for this
potential discharge. The reduction of oxides to tungsten metal
in reduction furnaces will also require a wet scrubber to clean
the reduction furnace off-gases. The reduction of WO3 to
tungsten metal in a hydrogen atmosphere will also produce a
"water of formation." The final subdivision is for spent acid
and wash for leaching of tungsten powder.
OTHER FACTORS
The other factors considered in this evaluation were shown to be
inappropriate bases for subdivision. Air pollution control
methods, treatment costs, and total energy requirements are
functions of the selected segmentation factors—metal product,
raw materials, and production processes. Therefore, they are not
independent factors and do not affect the segmentation which has
been applied.
2976
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IV
PRODUCTION NORMALIZING PARAMETERS
As discussed previously, the effluent limitations and standards
developed in this document establish mass limitations on the
discharge of specific pollutant parameters. To allow these
regulations to be applied to plants with various production
capacities, the mass of pollutant discharged must be related to a
unit of production. This factor is known as the production
normalizing parameter (PNP).
In general, for each production process which has a wastewater
associated with it, the actual mass of the element tungsten in
the tungsten product or intermediate produced will be used as the
PNP. Using the elemental tungsten produced or processed as a
production normalizing parameter rather than a chemical compound
makes the production basis clear and unanbiguous. Thus, the PNPs
for the 14 subdivisions are as follows:
1. Tungstic acid rinse
2. Acid leach wet air pollution
control
3. Alkali wash leach
4. Alkali leach wash condensate
5. Molybdenum sulfide
precipitation wet air
pollution control
6. Ion-exchange raffinate
(commingled with other
process and nonprocess
streams)
7. Ion-exchange raffinate
(not commingled with
other process and
nonprocess streams)
8. Calcium tungstate precipitate
wash
9. Crystallization and drying
of ammonium paratungstate
10. Ammonium paratungstate con-
version to oxides wet air
pollution control
11. Ammonium paratungstate
conversion to oxides water
of formation
12. Reduction to tungsten wet
air pollution control
13. Reduction to tungsten water
of formation
14. Tungsten powder leach and
wash
kkg of tungstic acid (as W)
produced
kkg of tungstic acid (as W)
produced
kkg of sodium tungstate
produced
kkg of sodium tungstate
(as W) produced
kkg of tungsten metal
produced
kkg of ammonium tungstate
(as W) produced
kkg of ammonium tungstate
(as W) produced
kkg of calcium tungstate
(as W) produced
kkg of ammonium paratungstate
(as W) produced
kkg of tungstic oxide (as W)
produced
kkg of tungstic oxide (as W)
produced
kkg of tungsten produced
kkg of tungsten produced
kkg of tungsten produced
2977
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IV
Other PNPs were considered. The use of production capacity
instead of actual production was eliminated from consideration
because the mass of the pollutant produced is more a function of
true production than of installed capacity. The use of some
common intermediate (i.e., ammonium paratungstate or tungsten
metal) as a basis for PNPs for all processes was rejected since
not all plants follow the same production path to get to the
specific end-product. Additionally, some plants divert part of
their intermediate products (e.g., sodium tungstate and tungsten
acid) and sell them as by-products instead of processing all
input raw materials to one final product. If an "end-product"
were chosen as the PNP, plants that had these upstream diversions
would be allowed to discharge more per mass of product than their
competitors who did not.
2978
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - V
SECTION V
WATER USE AND WASTEWATER CHARACTERISTICS
This section describes the characteristics of the wastewaters
associated with the primary tungsten subcategory. Water use and
discharge rates are explained and then summarized in tables at
the end of this section. Data used to characterize the
wastewaters are presented. Finally, the specific source, water
use and discharge flows, and wastewater characteristics for each
separate wastewater source are discussed.
Two . principal data sources were used in the development of
effluent limitations and standards for this subcategory: data
collection portfolios (dcp) and field sampling results. Data
collection portfolios contain information regarding wastewater
flows and production levels.
In order to quantify the pollutant discharge from primary
tungsten plants, a field sampling program was conducted. A
complete list of the pollutants considered and a summary of the
techniques used in sampling and laboratory analyses are included
in Section V of Vol. I. Wastewater samples were collected in two
phases: screening and verification. The first phase, screen
sampling, was to identify which toxic pollutants were present in
the wastewaters from production of the various metals. Screening
samples were analyzed for 125 of the 126 toxic pollutants and
other pollutants deemed appropriate. Because the analytical
standard for TCDD was judged to be too hazardous to be made
generally available, samples were never analyzed for this
pollutant. There is no reason to expect that TCDD would be
present in nonferrous metals manufacturing wastewater. A total
of six plants were selected for sampling in the primary tungsten
subcategory; one for screening, five for verification. In
general, the samples were analyzed for three classes of
pollutants: toxic organic pollutants, toxic metal pollutants,
and criteria pollutants (which includes both conventional and
nonconventional pollutants).
Two of these verification sampling efforts were conducted between
proposal and promulgation because EPA believed additional process
and wastewater data were needed to correctly characterize the
primary tungsten subcategory.
As described in Section IV of this supplement, the primary
tungsten subcategory has been divided into 14 subdivisions or
wastewater sources, so that the proposed regulation contains mass
discharge limitations and standards for 14 unit processes
discharging process wastewater. Differences in the wastewater
characteristics associated with these subdivisions are to be
expected. For this reason, wastewater streams corresponding to
each subdivision are addressed separately in the discussions that
follow. These wastewater sources are:
2979
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - V
1. Tungstic acid rinse water,
2. Acid leach wet air pollution control,
3. Alkali leach wash,
4. Alkali leach wash condensate
5. Molybdenum sulfide precipitation wet air pollution
control,
6. Ion-exchange raffinate, (commingled with other process
and nonprocess streams)
7. Ion-exchange raffinate (not commingled with other
process and nonprocess streams)
8. Calcium tungstate precipitate wash,
9. Crystallization and drying of ammonium paratungstate,
10. Ammonium paratungstate conversion to oxides
wet air pollution control,
11. Ammonium paratungstate conversion to oxides water of
formation,
12. Reduction to tungsten wet air pollution control,
13. Reduction to tungsten water of formation, and
14. Tungsten powder acid leach and wash.
WASTEWATER FLOW RATES
Data supplied by dcp responses were evaluated, and two flow-to-
production ratios, water use and wastewater discharge flow, were
calculated for each stream. The two ratios are differentiated by
the flow value used in calculation. Water use is defined as the
volume of water or other fluid required for a given process per
mass of product and is therefore based on the sum of recycle and
make-up flows to a given process. Wastewater flow discharged
after pretreatment or recycle (if these are present) is used in
calculating the production normalized flow—the volume of
wastewater discharged from a given process to further treatment,
disposal, or discharge per mass of tungsten produced. Differences
between the water use and wastewater flows associated with a
given stream result from recycle, evaporation, and carry-over on
the product. The production values used in calculation
correspond to the production normalizing parameter, PNP, assigned
to each stream, as outlined in Section IV. As an example, acid
leaching scrubber water flow is related to the production of the
tungstic acid intermediate. As such, the discharge rate is
expressed in liters of scrubber water per metric ton of tungsten
in the tungstic acid produced (gallons of scrubber water per ton
of tungsten in the tungstic acid).
The production normalized discharge flows were compiled and
statistically analyzed by stream type. These production
normalized water use and discharge flows are presented by
building block in Tables V-l through V-ll (page 2988 - 2995).
Where appropriate, an attempt was made to identify factors that
could account for variations in water use and discharge rates.
These variations are discussed later in this section by
subdivision. A similar analysis of factors affecting the
wastewater flows is presented in Sections X, XI, and XII where
2980
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - V
representative BAT, BPT, and pretreatment flows are selected for
use in calculating the effluent limitations. The water use and
discharge rates shown do not include nonprocess wastewater, such
as rainfall runoff and noncontact cooling water.
After proposal, EPA identified nine primary tungsten plants that
were previously not included in the subcategory data base.
Wastewater flow rates and production data were solicited from
these plants through dcp. Some data from plants already in the
Agency's data base were updated and revised because of comments
received concerning the proposed regulation. This information
was collected by telephone contacts. The new data were used to
revise production normalized -flow rates and recalculate
regulatory flow allowances where appropriate (see Section IX).
WASTEWATER CHARACTERISTICS DATA
Data used to characterize the various wastewaters associated with
primary tungsten production come from two sources—data
collection portfolios and analytical data from field sampling
trips.
DATA COLLECTION PORTFOLIOS
In the data collection portfolios, the tungsten plants that
discharge wastewater were asked to specify the presence or
absence of toxic pollutants in their wastewater. In all cases,
the plants indicated that the toxic organic pollutants were
believed to be absent. However, nearly all of the plants stated
that they either knew the metals to be present or they believed
the metals to be absent. The responses for the metals are
summarized below: (Two plants which produce tungsten metal have
been omitted due to lack of data.)
Known Believed Believed Known
Pollutant Present Present Absent Absent
Antimony .1 1 4 1
Arsenic 3 0 3 1
Asbestos 0061
Beryllium 0061
Cadmium 2041
Chromium 3121
Copper 4120
Cyanide 1051
Lead 3031
Mercury 2131
Nickel 1231
Selenium 0061
Silver 3130
Thallium 00 7 0
Zinc 4 1 20
2981
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - V
FIELD SAMPLING DATA
In order to quantify the concentrations of pollutants present in
wastewater from primary tungsten plants, wastewater samples were
collected at six plants, which represents one-third of the
primary tungsten plants in the United States. Diagrams
indicating the sampling sites and contributing production
processes are shown in Figures V-l through V-6 (pages 3038 -
3043).
Raw wastewater data are summarized in Tables V-12 through V-16
(pages 2996 - 3017). Analytical results for tungstic acid rinse
water, ion-exchange raffinate, calcium tungstate precipitate
wash, oxides reduction furnace scrubber water and reduction to
metal furnace scrubber water, and reduction to metal water of
formation are given in Tables V-12, V-13, V-14, V-15, and V-16,
respectively. Table V-17 presents data on tungstic acid rinse
water after lime and settle treatment. Tables V-18 and V-19
present treatment plant samples for plant C and E, respectively.
Note that the stream numbers listed in the tables correspond to
those given in individual plant sampling site diagrams, Figures
V-l through V-6. Where no data are listed for a specific day of
sampling, the wastewater samples for the stream were not
collected. If the analyses did not detect a pollutant in a waste
stream, the pollutant was omitted from the table.
The data tables include some samples measured at concentrations
considered not quantifiable. The base-neutral extractable, acid
extractable, and volatile organics generally are considered not
quantifiable at concentrations equal to or less than 0.010 mg/1.
Below this concentration, organic analytical results are not
quantitatively accurate; however, the analyses are useful to
indicate the presence of a particular pollutant. The pesticide
fraction is considered not quantifiable at concentrations equal
to or less than 0.005 mg/1. Nonquantifiable results are
designated in the tables with an asterisk (double asterisk for
pesticides).
These detection limits shown on the data tables are not the same
in all cases as the published detection limits for these
pollutants by the same analytical methods. The detection limits
used were reported with the analytical data and hence are the
appropriate limits to apply to the data. Detection limit
variation can occur as a result of a number of laboratory-
specific, equipment-specific, and daily operator-specific
factors. These factors can include day-to-day differences in
machine calibration, variation in stock solutions, and variation
in operators.
2982
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - V
The statistical analysis of data includes some samples measured
at concentrations considered not quantifiable. Data reported as
an asterisk are considered as detected but below quantifiable
concentrations, and a value of zero is used for averaging. Toxic
organic, nonconventional, and conventional pollutant data
reported with a "less than" sign are considered as detected, but
not further quantifiable. A value of zero is also used for
averaging. If a pollutant is reported as not detected, it is
excluded in calculating the average. Finally, toxic metal values
reported as less than a certain value were considered as not
detected, and a value of zero is used in the calculation of the
average. For example, three samples reported as ND, *, and 0.021
mg/1 have an average value of 0.010 mg/1.
Appropriate tubing or background blank and source water
concentrations are presented with the summaries of the sampling
data. The method by which each sample was collected is indicated
by number, as follows:
1 one-time grab
2 24-hour manual composite
3 24-hour automatic composite
4 48-hour manual composite
5 48-hour automatic composite
6 72-hour manual composite
7 72-hour automatic composite
WASTEWATER CHARACTERISTICS AND FLOWS BY SUBDIVISION
Since primary tungsten production involves 14 principal sources
of wastewater and each has potentially different characteristics
and flows, the wastewater characteristics and discharge rates
corresponding to each subdivision will be described separately. A
brief description of why the associated production processes
generate a wastewater and explanations for variations of water
use within each subdivision will also be discussed.
TUNGSTIC ACID RINSE WATER
Both plants that leach scheelite ores or calcium tungstate
(synthetic scheelite) with hydrochloric acid to produce tungstic
acid (H2WO4) also use water to rinse the insoluble H2WO4. The
spent rinse water is discharged. The production normalized water
use and discharge rates for tungsten acid rinses are given in
Table V-l (page 2988) in liters per metric ton of tungstic acid
produced.
Table V-12 (page 2996) summarizes the field sampling data for
spent tungsten acid rinse water from two plants. From this data,
it can be seen that tungsten acid rinses can be characterized by .
acidic pH, treatable concentrations of many metals including lead
and zinc, and treatable concentrations of suspended solids.
2983
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - V
ACID LEACH WET AIR POLLUTION CONTROL
Plants that acid leach use wet scrubbing systems for the control
of HC1 fumes. One plant reuses this water as tungstic acid rinse
water and the other discharges all of it. Table V-2 (page 2988)
presents the production normalized water use and discharge flows
for acid leach scrubber water in liters per metric ton of
tungstic acid produced.
The Agency did not specifically sample this wastestream, but the
stream's major characteristics should be very similar to the raw
wastewater data from tungstic acid rinse water, Table V-10 (page
2998). That is, the scrubber water is expected to be acidic (pH
of approximately 2).
ALKALI LEACH WASH
Four plants reported using water for an alkali leaching step in
which wolframite type ores, (Fe,Mn)WO4 are digested in a caustic
solution to produce sodium tungstate, N32WO4. N32WO4 is filtered
from the digestion-wash liquor and the filtrate may be evaporated
or reused. Table V-3 (page 2989) presents the production
normalized water use and discharge flows for alkali leach wash
water in liters per metric ton of sodium tungstate produced.
Although this waste stream was not sampled, it is assumed that
many of the impurities that were leached away in the acid
leaching process will also be present in the alkali leach wash
since both start from ore concentrates. Consequently, treatable
concentrations of metals and suspended solids are expected.
Wastewater characteristics for acid leaching are shown in Table
V-10 (page 2995).
ALKALI LEACH WASH CONDENSATE
This building block was originally omitted from the promulgated
rule • because the Agency believed this condensate would be
accounted for through other building blocks, primarily the
raffinate building block. The petitioners presented data
indicating that the alkali lf;.-.-ch wash condensate is a discrete
process stream which was not covered by the raffinate building
block. EPA is including this building block in the regulation
and the flow basis for the limitations is the flow data provided
for this unit operation.
MOLYBDENUM SULFIDE PRECIPITATION WET AIR POLLUTION CONTROL
Three plants report a precipitation step to remove molybdenum
trisulfide (MoS3) from the sodium tungstate solution. Two plants
use wet scrubbers over the precipitation tanks to control
hydrogen sulfide fumes. Water use and production data were not
reported for one of the plants. Production data were not
reported for the second plant. However, both of these plants
reuse all of the spent scrubber liquor in the tungsten process.
No discharge of wastewater was reported for this wastewater
2984
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - V
stream. Although this wastewater was not sampled, it is expected
to be acidic and contain captured particulates.
ION-EXCHANGE RAFFINATE (COMMINGLED AND NOT COMMINGLED WITH OTHER
PROCESS AND NONPROCES3 STREAMS)
Four plants use a liquid ion exchange (solvent extraction)
process for producing ammonium tungstate from sodium tungstate.
The wastewater discharge consists of ion-exchange raffinate and
wash water used for cleansing the organic solvent. Table V-4
(page 2989) presents the production normalized water use and
discharge flows for this waste stream. These flows are given in
liters per metric ton of ammonium tungstate produced.
Table V-13 (page 3003) presents field sampling data for ion
exchange raffinate and wash from two plants. This stream is
acidic (pH of approximately 3.0) ' and contains treatable
concentrations of toxic metals, suspended solids, and ammonia.
Since an organic solvent is used in the process, this stream has
measurable concentrations of organics such as acenaphthene,
naphthalene, phenol, and fluorene. These organics may be present
directly as solvents or as? ;~purities in the solvents used.
CALCIUM TUNGSTATE PRECIPITATION WASH
Six plants report a flow associated with calcium tungstate
(synthetic scheelite) precipitation. In this intermediate step,
sodium tungstate is converted to calcium tungstate by mixing with
a calcium chloride solution. The calcium tungstate crystals are
allowed to settle, and the waste sodium chloride supernatant can
be decanted or the precipitate recovered by filtration. Some
plants also rinse the precipitate. No plants reported recycling
this wastewater. The production normalized water use and
discharge flows are reported in Table V-5 (page 2990) as liters
per metric ton of calcium tungstate produced.
Table V-14 (page 3011) presents the sampling data for this
wastewater at one plant. This waste stream is basic (pH of 11)
and contains treatable concentrations of ammonia and oil and
grease.
CRYSTALLIZATION AND DRYING OF AMMONIUM PARATUNGSTATE
Five plants which produce ammonium paratungstate (APT) report
that wastewater is associated with the crystallization and drying
step. APT crystals are precipitated and filtered from an aqueous
mother liquor. This mother liquor is usually recycled or
evaporated after ammonia recovery. Baghouses are used on drying
furnaces to control particulate APT in furnace off-gases. Water
produced during drying is usually evaporated to the atmosphere.
Table V-6 (page 2991) presents the production normalized water
use and discharge flows for this subdivision in liters per metric
ton of APT produced.
The most significant pollutant characteristic associated with
2985
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - V
this stream is the concentration of ammonia. Although the Agency
did not specifically sample APT drying scrubber water or mother
liquor, the metal constituents present should be similar to those
given in the sampling data in Table V-15 (page 3015). This table
gives data for scrubber water from a reduction furnace.
AMMONIUM PARATUNGSTATE CONVERSION TO OXIDES WET AIR POLLUTION
CONTROL
Six plants report using water in converting APT to tungsten
oxides (WOX). In all cases a wet scrubbing system is used to
control the ammonia which is driven off when APT is calcined to
oxides in rotary furnaces. One plant reported recycling 100
percent of the scrubber liquor but did not report water use. To
calculate production normalization factors, all oxides were
assumed to be the common "yellow" oxide, WO3. In the proposed
development document, this parameter was incorrectly listed as
"blue" oxide. The production normalized water use and discharge
flows are presented as liters of water per metric ton of
"tungstic" oxide (WO3) in Table V-7 (page 2992).
Table V-15 (page 3016) summarizes the field sampling data for the
pollutants detected in a stream which should be representative of
APT reduction scrubber water with regard to toxic pollutants.
Additionally, treatable concentrations of ammonia and suspended
solids, and an alkaline pH are characteristic of this wastewater.
The ammonia is present in the wastewater from this scrubber
because it evolves as the APT is converted to an oxide. The
presence of ammonia causes the pH to be elevated.
AMMONIUM PARATUNGSTATE CONVERSION TO OXIDES WATER OF FORMATION
Two plants report generating water of formation during the
conversion of APT to oxide. This water is usually condensed in a
gas recovery system for the hydrogen or nitrogen gas used for
reduction furnace atmosphere. In some plants this water may be
recondensed in the APT conversion to oxides scrubber system.
Production normalized water use and discharge flows for one plant
are presented in Table V-8 (page 2993) in liters per metric ton
of tungstic oxide (WO3) produced. The second plant did not
report the water of formation flow. It should be noted that
since this is water of formation, no water is actually used in
this process.
The wastewater characteristics for this stream should be very
similar to those for the scrubber waters from APT conversion to
oxides furnaces as described above. Table V-15 (page 3015) is
the sampling data associated with this stream.
REDUCTION TO TUNGSTEN WET AIR POLLUTION CONTROL
Seven plants that reduce tungsten oxides to tungsten metal report
using water in a wet scrubbing system. The scrubbing system is
used to control particulates from the furnace operation, although
some plants also use a hydrogen recovery system. Table V-9 (page
2986
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - V
2994) gives production normalized water use and discharge flows
in liters per metric ton of tungsten metal for the seven plants
which use water. As shown in Table V-9, three plants use a total
recycle of this stream.
Particulates and soluble salts from fluxes used in the reduction
furnaces will characterize this waste stream. Treatable
concentrations of ammonia and an alkaline pH are also found.
Table V-15 (page 3015) presents field sampling data for samples
taken from two different reduction furnace scrubber waters. One
sample contains wastewater combined with APT conversion to oxides
scrubber water.
REDUCTION TO TUNGSTEN METAL WATER OF FORMATION
Plants that reduce oxides to tungsten metal in a hydrogen
atmosphere may generate a water of formation as generalized by
the following reaction:
WOX -i- H2 > W + H2O
In some plants this water may be recondensed in the reduction
furnace scrubber system. Production normalized water use and
discharge flows for this subdivision are presented in Table V-9
(page 2994) in liters per metric ton of tungsten metal. It
should be noted that since this is a water of formation, no water
is actually used in this process.
Wastewater sampling data for this stream are presented in Table
V-16 (page 3017). This wastewater is basic (pH of approximately
9.6) and contains treatable concentrations of ammonia and
suspended solids.
TUNGSTEN POWDER ACID LEACH AND WASH
Two plants report leaching tungsten powder with acids to produce
a high-purity product. Both plants discharge the spent acid and
wash water. The production normalized water use and discharge
rates are presented in Table V-ll (page 2995) in liters per
metric ton of tungsten produced.
Although the Agency did not sample tungsten powder acid leach and
wash wastewater, it is expected to be very acidic (pH of
approximately 1 to 2) and contain suspended solids.
2987
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT -
TABLE V-l
WATER OSS AND DISCHARGE RATES FOR TUNGSTIC ACID
RINSE WATER
(10^ 1/kkg of Tungstic Acid Produced)
Plant Code
Percent
Recycle
Production
Normalized
water use
Production
Normalized
Discharge
Flow
9011
9014
0
0
57.6
2.78
57.6
2.78
TABLE V-2
WATER USE AND DISCHARGE RATES FOR ACID LEACH
WET AIR POLLUTION CONTROL
1/kkg of Tungstic Acid Produced)
Percent
Recycle
0
100
Production
Normalized
Wate_£ Use
37.7
15.0
Production
Normalized
Discharge
Flow
37.7
0*
*100 percent reuse as tungstic acid rinse water,
2988
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - V
TABLE V-3
WATER USE AND DISCHARGE RATES FOR ALKALI LEACH WASH
(103 1/kkg of Sodium Tungstate Produced)
Production
Production
Normalized
Plant Code
9011
9012
9017
9030
Percent
Recycle
0
0
0
0
Normalized
Water Use
24.4
NR
82.6
303.0
Discha:
Flow
0*
0*
0*
0*
TABLE ¥-4
HATER USE AND DISCHARGE RATES FOR ION-EXCHANGE
RAFFINATE
(103 1/kkg of Ammonium Tungstate Produced)
Plant Code
9012
9017
9030
9031
Percent
Recycle
0
0
21
0
Production
Normalized
Water Use
Production
Normalized
Discharge
Flow
76.06
47.9
256.0
28.16
76.06
47.9
203.0
28.16
NR - Present but data not reported in dcp.
*Zero discharge through 100 percent evaporation or reuse in other
processes.
2989
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - V
TABLE V-5
WATER USE AND DISCHARGE RATES FOR CALCIUM TUNGSTATE
PRECIPITATE WASH
(10^ 1/kkg of Calcium Tungstate Produced)
Percent
Recycle
0
0
0
0
0
0
Production
Normalized
Water Use
21.0
40,5
65.8
24.7
385.0
83.7
Production
Normalized
Discharge
Flow
21.0
40.5
65.8
24.7
385.0
83.7
2990
-------
PRIMARY TUNGSTEN SDBCATEGORY SECT - V
TABLE V-6
WATER USE AND DISCHARGE RATES FOR AMMONIUM PARATUNGSTATE
CRYSTALLIZATION AND DRYING
(103 1/kkg of Ammonium Paratungstate Produced)
Plant Code
9011
9012
9014
9017
9030
Percent
Recycle
0
100
100
NR
0
Production
Normalized
Water Use
3.03
NR
NR
68.6
54.5
Production
Normalized
Discharge
Flow
2.93 (a)
0 (b)
0 (c)
0 (d)
0 (e)
NR - Present but data not reported in dcp.
(a) Partial evaporation.
(b) Recycled in ammonia recovery system.
(c) Crystallization wastewater recycled in ammonia recovery
system; water from drying is 100 percent evaporated.
(d) 100 percent evaporation.
(e) 100 percent reuse.
2991
-------
PRIMARY TUNGSTEN SUBCATEGORY
SECT -
TABLE V-7
WATER USE AND DISCHARGE RATES FOR APT CONVERSION
TO OXIDES WET AIR POLLUTION CONTROL
(1Q3 l/kkg of Tungstic Oxide (^03) Produced)
Percent
Recycle
0
0
100
0
0
0
Production
Normalized
Water Use
36.8
7.43
NR
28.4
17.54
19.4
Production
Normalized
Discharge
Flow
36.8
7.43
0
28.4
17.54
19.4
NR - Present but data not reported in dcp.
2992
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - V
TABLE V-8
WATER USE AND DISCHARGE CHARACTERISTICS FOR
APT CONVERSION TO OXIDES WATER OP FORMATION
(103 1/kkg of Tungstic Oxide (WO3) Produced)
Plant Code
9011
9010
Percent
Recycle
0
0
Production
Normalized
Water Use
0.05
NR
Production
Normalized
Discharge
Flow
0
0
(a)
(b)
(a) 100 percent evaporation.
(b) Contract hauled.
NR - Present but data not reported in dcp.
2993
-------
PRIMARY TUNGSTEN SUBCATEGORY
SECT - V
TABLE V-9
WATER USE AND DISCHARGE RATES FOR REDUCTION TO
TUNGSTEN WET AIR POLLUTION CONTROL
(103 1/kkg of Tungsten Produced)
Production
Plant Code
9012
9014
9015
9016
9018
9024
9029
Percent
Recycle
0
0
100
100
0
100
0
Normalized
Water
426.
9.
NR
939.
65.
358.
17.
Use
0
1
0
9
0
4
Production
Normalized
Discharge
Flow
426.0
9.1
0
0
65.9
0
17.4
NR - Present but data not reported in dcp.
2994
-------
PRIMARY TUNGSTEN SUBCATEGORY
SECT - V
TABLE V-10
WATER USE AND DISCHARGE RATES FOR REDUCTION TO
TUNGSTEN WATER OF FORMATION
{103 1/kkg of Tungsten Produced)
Production
Production
Normalized
Plant Code
9010
9011
9014
9025
9026
9028
Percent
Recycle
NR
0
NR
0
0
0
Normalized
Water Dse
0
0
0
0
0
0
Discharg
Flow
NR
0*
NR
0.440
0.208
1.043
TABLE V-ll
WATER OSE AND DISCHARGE RATES FOR TUNGSTEN
Plant Code
9011
9029
POWDER ACID LEACH AND WASH
1/kkg of Tungsten Produced)
Percent
Recycle
0
0
Production
Normalized
Water Use
3.2
1.6
Production
Normalized
Discharge
Flow
3.2
1.6
NR - Present but data not reported in dcp.
*100 percent evaporation or reuse; 267 1/kkg generated,
2995
-------
fable V-12
PRIMARY TUNGSTEN SAMPLING DATA
TUNGSTIC ACID RINSE
RAH WASTEWATER
Concentrations ("g/1, except as noted)
1.
4.
eo
V0
^ *
O.
8.
10.
14.
15.
23.
25.
29.
Pollutant
Toxic Pollutants (a)
acenaphthene
benzene
carbon tetrachloride
1 , 2 ,4-trichlorobenzene
1 ,2-dlchloroethane
1 ,1 ,2-trichloroethane
1,1,2, 3-te trachloroethane
chlorofom
I ,2-dichlorobenzene
1 , 1-dichloroethylene
Stream
Code
220
64
220
64
64
64
220
220
220
64
220
64
64
220
Sample
Type t
1
2
2
2
7
2
2
2
2
2
2
7
2
2
Source
*
*
ND
ND
ND
ND
ND
ND
*
.075
*
ND
ND
ND
Day 1
ND
*
*
ND
ND
ND
ND
ND
*
.025
ND
ND
ND
ND
Day 2 Day 3 Average
* * *
* *
ND ND
ND ND
ND
ND
* *
.017 .043 .028
ND
ND .019 .019
ND
H
S
K;
H
O
w
w
25
W
a
w
o
M
a
o
s
to
w
o
t-3
1
<
38* ethylbenzene
220
ND
ND
ND
-------
Table V-12 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
TUNGSTIC ACID RINSI
RAH WASTEWATER
Concentrations (mg/1, except as noted)
44.
47.
48.
NJ
VO
-1 51.
55.
56,
66.
68.
69.
70.
71.
76.
Pollutant
nethylene chloride
bromofom
di chlorobronome thane
chlorodlbromome thane
naphthalene
nitrobenzene
bis(2-ethylhexyl) phthalate
di-n-butyl phthalate
dl-n-octyl phthalate
diethyl phthalate
dimethyl phthalate
chrysene
Stream
Code
220
220
64
220
220
64
220
64
64
220
64
64
64
64
64
Saaple
Type t
2
2
2
2
2
7
1
2
1
1
7
7
7
7
7
Source
ND
ND
ND
ND
ND
ND
*
ND
0.06
O.OS8
0.011
0.037
ND
ND
ND
Day 1 Day 2 Day 3 Average
ND ND
ND ND
ND ND ND
ND ND
ND ND
* ~ *
ND
ND
0.94 0.94
* *
0.035 0.035
0.038 0.038
ND
ND
0.024 0.024
'RIMARY TUNGSI
«~3
W
55
SUBCA1
*^3
1
to
O
I
-------
Table V-12 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
TUNGSTIC ACID RINSE
RAH WASTEWATER
Concentrations (ng/1, except as noted)
03
77.
78.
81.
80.
84.
85.
86.
87.
89.
95.
96.
06.
Pollutant
acenaphthylene
anthracene (b)
phenanthrene (b)
fluorene
pyrene
tetrachloroethylene
toluene
trichloroethylene
aldrin
al p ha- endo sul fan
be ta-endosul fan
PCB-1242 (c)
Stream
Code
220
64
220
220
64
64
220
220
64
220
220
220
220
220
Sample
Type t
1
7
1
1
7
2
2
2
2
2
1
1
I
1
Source
ND
ND
<0.016
*
*
*
*
ND
<0.043
ND
ND
ND
ND
**
Day 1 Day 2 Day 3 Average
ND
<0.014 <0.014
ND
* *
* *
* * * *
0.012 * 0.006
* * *
* ND <0.02 <0.015
* * *
ND
ND
ND
** **
M
S
3
t-3
G
25
Q
W
M
2
CO
CO
O
H3
W
8
K;
CO
B
n
i
<
107. PCB-1254 (c)
108. PCB-1221 (c)
-------
Table V-12 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
TUNGSTIC ACID RINSE
RAH WASTEWATER
Concentrations (ng/1, except as noted)
109.
110.
111.
112.
N> 11*.
vo
iO
« 115.
117.
118.
119.
120.
121.
122.
Pollutant
PCB-1232 (d)
PCB-1248 (d)
PCB-1260 (d)
PCB-1016 (d)
antimony
arsenic
beryllium
cadmium
chromlua
-
copper
cyanide
lead
Stream
Code
220
220
64
220
64
64
220
64
220
64
220
64
220
64
220
Sample
Type t
1
1
7
1
7
7
1
7
1
7
1
7
1
7
I
Source
**
<0.l
<0.01
<0.01
<.001
0.008
<0.002
<0.005
HI
M
55
w
a
w
o
S
ra
Q
1
OT
W
O
^
I
<
-------
Table V-12 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
TUKGSTIC ACID RINSE WATER
RAW HASTEWATER
Concentrations (ag/1.
as noted)
Pollutant
123. mercury
124. nickel
UJ
g 125. selenium
o
126. silver
127. thallium
128. zinc
Nonconventionals
aluminum
' ammonia
chemical oxygen demand
(COD)
Strean
Code
64
220
64
220
220
64
220
64
220
64
220
64
64
64
220
Sample
Type t
7
1
7
1
1
7
1
7
1
7
1
7
2
2
2
Source
<0.0001
<0.0001
<0.005
<0.005
<0.01
<0.02
<0.0l
<0.1
0.08
0.1
<0.050
Day 1 Day 2
0.0011
0.0005
1.0
<0.05
<0.01
0.29
<0.02
0.7
<0.1
2.0
0.6
3.0
3.1 3.4
323
22
Day 3 Average
0.0011
0.0005
1.0
<0.05
<0.0l
0.29
<0.02
0.7
<0.01
2.0
0.6
3.0
3.2 3.233
323
22
H
I
K
Hi
sz;
Q
HJ
W
5!
W
§
n
*•:.*
.1
O
21
w
w
o
HI
i
<
cobalt
64
<0.005 4.0
4.0
-------
Table V-12 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
TUNCSTIC ACID RINSE
RAH WASTEWATER
Concentrations (ng/1, except as noted)
Pollutant
iron
manganese
w chloride
o
o
H
phenols (total; by 4-AAP
method)
total organic carbon
(TOC)
Convent lonals
oil and grease
total suspended solids
(TSS)
pH (standard units)
Streaa
Code
64
64
64
220
64
220
64
220
64
220
64
220
64
220
Sample
Type t
7
7
2
2
2
2
2
2
2
2
7
2
1
1
Source Day 1
<0.02 50.0
<0.005 2.0
25,700
16,600
0.023
0.029
6
4
6
1
209
19
0.85
1.80
*•*" mm
Day 2 Day 3 Average
50.0
2.0
25,700
16,600
0.024 0.221 0.0893
0.029
6
4
2 11 6
3 2
209
19
0.6 1.0
1.80
H
3
g
K
§
O
to
to
§
O
Ml
O
O
a
w
o
^
1
-------
Table V-12 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
TUNGSTIC ACID RINSE
RAH WASTEWATER
(a) One sample from each stream was analyzed for acid extractable toxic organic pollutants; ^
none was reported above its analytical quantification concentration. ^
S
(b), (c), (d) Reported together. §
^3
tSample type. Note: These numbers also apply to subsequent sampling data tables in this section. £l
ss
1 ~ one-time grab in
2 - 24-hour manual composite t|
3 - 24-hour automatic composite ^
w 4 - 48-hour manual composite w
o 5 - 48-hour automatic composite a
*° 6 - 72-hour manual composite P
7 - 72-hour automatic composite t|
Q
^Indicates less than or equal to 0.01 mg/1. >d
**Indicates less than or equal to 0.005 mg/1. ^
en
w
o
-------
Table V-13
PRIMARY TUNGSTEN SAMPLING DATA
ION-EXCHANGE RAFFINATE
RAW WASTEWATER
Concentrations (rag/1, except as noted)
Pollutant
Stream
Code
Sample
Type
Source
Day 1
Day 2
Day 3 Average
Toxic Poilutants(a)
1.
4.
10.
u>
o
S 14.
15.
23.
29.
38.
44.
47.
48.
acenaphthene
benzene
1 ,2-dichloro-
ethane
1,1 ,2-trl-
chloroethane
1.1,2,2-tetra-
chioroethane
chloroform
1 , 1 -dichloro-
ethylene
ethylbenzene
methylene
chloride
bromoform
dichlorobromo-
219
219
219
219
219
219
219
219
219
219
219
7
2
2
2
2
2
2
2
2
2
2
*
ND
ND
ND
*
*
ND
ND
ND
ND
ND
0.111
*
*
ND
<0.043
0.014
ND
0.011
ND
ND
ND
ND
ND
ND
*
*
ND
ND
ND
0.036
ND
0.111
ND *
* *
ND
* <0.021
0.036 0.017
ND
* 0.0055
ND
0.053 0.0445
ND
50
H
K
3
Q
C/l
W
iz;
CA
W
O
H)
PI
Q
O
K
W
O
HI
I
<
methane
-------
Table V-13 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
ION-EXCHANGE RAFFINATE
RAW VASTEWATER
Concentrations (mg/1,
as noted)
o
o
*»
Stream
Pollutant Code
51.
54.
55.
65.
66.
68.
69.
70.
71.
77.
7tt.
chlorodibro-
raome thane
isophorone
naphthalene
phenol
bis(2-ethyl-
hexyl) phthalate
di-n-butyl
phthalate
di-n-octyl
phthalate
diethyl phthalate
dimethyl
phthalate
acenaphthylene
anthracene (b)
219
311
219
311
311
219
311
311
311
311
311
219
219
Sample
Type
2
3
7
3
3
7
3
3
3
3
3
7
7
Source
ND
ND
*
ND
ND
0.058
ND
0.00172
ND
ND
ND
ND
<0.016
Day 1
0.038
ND
1.078
0.00732
0.0718
0.016
0.00382
0.00522
ND
0.00274
0.00670
0.112
<0.325
Day 2
ND
ND
0.00576
0.0654
0.00204
0.00284
0.00155
0.00181
ND
Day 3
ND
0.00816
0.00818
0.067
ND
0.00430
ND
ND
ND
Averapo
0.038
0.00816
1.078
0.00708
0.0680
0.016
0.0029
0.0041
0.00155
0.00220
0.00670
0.112
<0.325
•M
H
s
s
I
Q
in
M
25
en
G
ro
o
S
M
K
OT
W
a
n
i
<
-------
Table V-13 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
ION-EXCHANGE RAFFINATE
RAW WASTEWATER
Concentrations (rag/i, except as noted)
Pol
81
80
85
w 86
0
o
Ul
87
89
95
96
106
107
108
109
110
111
lutant
. phenanthrene
. fluorene
. tetrachloro-
ethylene
. to luene
. trichloro-
ethylene
. aldrin
. alpha-endo-
sulfan
. beta-endo-
sulfan
. PCB-1242 (c)
. PCB-1254 (c)
. PCB-1221 (c)
. PCB-1232 (d)
. PCB-1248 (d)
. PCB-1260 (d)
Stream
Code
(b)
219
219
219
311
219
219
219
219
219
219
Sample
Type
7
2
2
3
2
7
7
7
7
7
Source
*
*
ND
ND
ND
ND
ND
ND
**
**
Day 1
0.06
<0.053
0.046
ND
*
ND
**
ND
**
**
w
Day 2 Day 3 Average H
Mj
0.06 a
2
0
0.026 0.037 <0.021 »
M
0.020 * 0.022 g
0.005 ND 0.005 »
ND ND * ^
1
*
**
W
M
O
1
<
**
**
112. PCB-1016 (d)
-------
Table V-13 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
ION-EXCHANGE RAFPINATE
WASTEUATER
Concentrations (mg/1, except as noted)
Pollutant
114.
115.
w 117.
o
° 118.
119.
120.
121.
122.
123.
antimony
arsenic
beryllium
cadmium
chromium
copper
cyanide
lead
mercury
Stream
Code
219
311
219
311
311
219
311
219
311
219
311
219
311
219
311
219
311
Sample
Type
7
3 .
7
3
3
7
3
7
3
7
3
7
3
7
3
7
3
Source
<0.1
0.0020
<0.01
0.0050
<0.01
<0.002
<0.05
<0.005
<0.1
0.01
<0.01
0.29
<0.02
<0.1
<0.0001
<0.0010
Day 1 Day 2
<0.1
0.031 0.035
0.22
0.041 0.050
<0.01 <0.01
<0.02
<0.05 <0.05
<0.05
<0.1 <0.1
0.1
<0.01 <0.01
0.002 0.003
0.055
<0.2
<0.1 <0.1
0.0003
<0.0010 <0.0010
Pay 3 Average
<0.1
0.0080 0.025
0.22
0.060 0.0503
<0.01 <0.01
<0.02
<0.05 <0.05
<0.05
<0.1 <0.1
0.1
0.03 0.01
0.002 0.002
0.05.1)
<0.2
<0.1 <0.1
0.0003
0.0013 0.0004
50
H
•<
(-3
O
to
^3
W
53
to
r-t
§
vW
O
w
8
K
M
O
(-3
<
-------
Table V-13 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
ION-EXCHANGE RAFFINATE
RAW WASTEWATER
Concentrations (mg/1, except as noted)
Pollutant
124. nickel
125. selenium
126. silver
U)
o 127. thallium
*4
128. zinc
Nonconventionals
acidity
alkalinity
aluminum
ammonia
barium
Stream
Code
219
311
219
311
219
311
219
311
219
311
311
311
219
311
219
311
311
Sample
Type
7
3
7
3
7
3
7
3
7
3
3
3
2
3
2
3
3
Source
<0.005
<0.1
<0.01
<0.01
<0.02
<0.007
<0.1
K|
Hi
O
W
25
W
C
a
n
5
w
o
o
K
w
M
O
I
<
-------
Table V-13 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
ION-EXCHANGE RAFFINATE
RAW WASTEWATER
Concentrations (mg/1, except as noted)
Stream
Pollutant
boron
calcium
chemical oxygen
demand (COD)
o
° chloride
cobalt
fluoride
iron
magnesium
manganese
molybdenum
phenols (total;
by 4-AAP method)
Code
311
311
219
311
311
219
311
311
219
311
311
219
311
311
219
311
Sample
Type
3
3
2
3
3
2
3
3
2
3
3
2
3
3
2
3
Source
<0.100
63.5
<1
20
<0.005
<0.1
0.68
<0.2
0.230
15.6
<0.005
0.090
<0.01
<0.005
Day 1
2.50.
29.4
127
140
41
<0.05
<0.1
350
<2.0
5.90
7.10
0.2
0.16
<0.01
0.002
0.064
Day 2
0.740
38.4
140
51
<0.1
130
4.76
11.6
0.12
<0.01
0.065
0.064
Day 3
1.06
46.2
150
50
<0.1
160
7.80
16.4
<0.010
<0.01
0.051
0.080
Average
1.4
38.0
127
143
47
<0.05
<0.1
21
<2.0
6.15
11.7
0.2
0.093
<0.01
0.03933
0.069
PU
H
§
K
i-3
Q
W
1-3
M
21
W
C
W
O
H3
w
Q
o
I
w
M
O
H3
i
-------
Table V-13 (Continued)
o
o
Stream
Pollutant Code
phosphate
sodium
aulfate
tin
titanium
total dissolved
solids (TDS)
total organic
carbon (TOG)
total solids (TS)
vanadium
yttrium
311
311
311
311
311
311
219
311
311
311
311
Sample
Type Source
3
3
3
3
3
3
2
3
3
3
3
5
17 18
75 60
<0.2
<0.02,
430 86
-------
Table V-13 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
ION-EXCHANGE RAFFINATE
RAW WASTEWATER
Concentrations (rag/1, except as noted)
u>
o
M
O
Pollutant
Convent ionals
oil and grease
total suspended
solids (TSS)
pH (standard
units)
(a) For stream 219,
pollutants; none
Stream Sample
Code Type Source
219 2
311 3 <1 1
219 2
311 3 3
219 1
311 3 6.00
one sample was analyzed for th
was reported above its analyt
Day 1
5
20
43
33
2.4
3.60
Day 2 Day 3 Average
3137
<1 <1 40
43
3 9.7 15.2
2.5 2.5
3.98 2.79
\*
H
3
§
|
Q
M
53
CO
s
*J»
n
K3
M
Q
O
W
W
n
e acid extractable toxic organic **
ical quant
ification concentration.
1
<
(b), (c), (d) Reported together for stream 219.
*Less than or equal to 0.01 mg/1.
**Less than or equal to 0.005 mg/1.
For stream 311, three samples were analyzed for the acid extractable, base-neutral
'
-------
Table V-14
PRIMARY TUNGSTEN SAMPLING DATA
SYNTHETIC SCHEELITE FILTRATE
RAW WASTEWATER
Concentrations (rag/1, except as noted)
O
M
Stream
Pollutant Code
11.
55.
65.
66.
68.
69.
73.
79.
82.
114.
115.
117.
118.
Toxic Pollutants (a)
1,1,1 -trichloroethane
naphthalene
phenol
bis(2-ethylhexyl)
phthalate
di-n-butyl phthalate
di-n-octyl phthalate
benzo(a)pyrene
benzo(ghi)perylene
d i ben zo (a, h) anthracene
antimony
arsenic
beryllium
cadmium
312
312
312
312
312
312
312
312
312
312
312
312
312
Sample
Type
1
1
1
1
1
1
1
1
1
1
1
1
1
Source Day
ND
ND
ND
ND
0.00172
ND
ND
ND
ND
<0.0020
<0.0050
<0.010
<0.050
1 Day 2 Daj
0.020
0.0588
0.118
0.0876
ND
0.048
0.120
0.139
0.108
<0.0020
<0.0050
<0.010
<0.050
? _ 3 Average
0.020
0.0588
0.118
0.0876
0.048
0.120
0.139
0.108
<0.0020
<0.0050
<0.010
<0.050
RIMARY TUNGSTEN
SUBCATEGC
%
w
M
O
1
<
-------
Table V-14 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
SYNTHETIC SCHEELITE FILTRATE
RAM WASTEWATER
Concentrations (rag/1, except as noted)
u>
o
M
tO
Pollutant
119.
120.
121.
122.
123.
124.
125.
126.
127.
128.
chromium (total)
copper
cyanide (total)
lead
mercury
nickel
selenium
silver
thallium
zinc
Nonconventional
acidity
alkalinity
aluminum
Stream
Code
312
312
312
312
312
312
312
312
312
312
Pollutants
312
312
312
Sample
Type
1
1
1
1
1
1
1
1
1
1
1
1
1
tf
Source Day 1 Day 2 . Day 3 Average H
<0.100
<0.010
0.29
<0.100
— •
1
t-3
Q
W
m
c
a
o
HI
w
Q
O
S-
in
m
o
i
<
-------
Table V-14 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
SYNTHETIC SCHEELITE FILTRATE
RAW WASTEWATER
Concentrations (mg/1, except as noted)
U)
o
Pollutant
ammonia
barium
boron
calcium
chemical oxygen demand
(COD)
chloride
cobalt
fluoride
Iron
magnesium
manganese
molybdenum
phenoltcs
Stream
Code
312
312
312
312
312
312
312
312
312
312
312
312
312
Sample
Type
1
1
1
1
1
1
1
1
1
1
1
1
1
Source
0.75
0.2
<0.!0
63.5
-------
Table V-14 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
SYNTHETIC SCHEELITE FILTRATE
RAW WASTEWATER
H*
*»
Stream
Pollutant Code
phosphate
sodium
tin
titanium
total dissolved solids
(TDS)
total organic carbon
(TOG)
total solids (TS)
vanadium
ytrrium
Conventional Pollutants
oil and grease
total suspended solids
312
312
312
312
312
312
312
312
312
312
312
Sample
Type
1
1
1
1
1
1
1
1
1
1
1
Source Day 1 Day 2
5
17
0.321
<0.020
430
0
500
<0.01
0.056
o
3
<4
2,000
<0.200
<0.02
9,240
27
9,300
<0.01
<0.020
26
3
(TSS)
pH (standard units)
312
Concentrations (rag/1, except as noted)
Day 3 Average
<4
2,000
<0.200
<0.02
9,240
27
9,300
<0.01
<0.020
26
3
6.00
11.08
50
M
3
o
w
w
i
o
%
K
C
7.
K
W
m
o
(a) For stream 312, the acid extractable, base-neutral extractable, and volatile organic
pollutant fractions were analyzed for in one sample.
-------
Table V-15
PRIMARY TUNGSTEN SAMPLING DATA
OXIDES REDUCTION FURNACE SCRUBBER AND REDUCTION TO TUNGSTEN FUKNACE SCRUBBER
RAW WASTEWATER
Concentrations (rag/l,
noted)
CO
o
Pollutant
S t ream
Code
Sample
Type
Source
Day 1 Day 2
Day 3 Average
w
»
H
... . , , „ ,,..-. y
Toxic Pollutants(a) X
114.
115.
118.
119.
122.
123.
124.
125.
126.
127.
antimony
arsenic
cadmium
chromium
lead
mercury
nickel
selenium
silver
thallium
130
221
130
221
130
130
130
130
221
130
130
221
130
221
130
221
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
-------
Table V-15 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
OXIDES REDUCTION FURNACE SCRUBBER AND REDUCTION TO TUNGSTEN FURNACE SCRUBBER
RAM WASTEWATER
Concentrations (rag/I, except as noted)
Pollutant
Toxic Pollutants (Continued)
128. zinc
Nonconventionals
aluminum
ammonia
chemical oxygen demand (COD)
cobalt
iron
manganese
total organic carbon (TOC)
Convent ionals
total suspended solids (TSS)
pH (standard units)
Stream
Code
(a)
130
221
130
130
130
130
130
130
130
130
130
Sample
Type
1
1
1
1
1
1
1
1
1
1
1
Source
<0.065
0.1
0.100
0.5
<0.005
0.400
0.020
Day 1 Day 2
<0.06
0.06
0.080
435
0.48
0.020
0.200
0.010
12
74
12
Day, 3 Average
<0.06
0.06
0.080
435
0.48
0.020
0.200
0.010
12
74
s
H
H
1
i-3
s
as
en
w
55
CO
g
W
O
o
w
w
M
a
?
<
(a) Stream 221 was analyzed only for the toxic metal pollutants; only mercury and zinc were
detected.
-------
u>
o
Table V-16
PRIMARY TUNGSTEN SAMPLING DATA
REDUCTION TO TUNGSTEN WATER OF FORMATION
RAW WASTEWATER
Concentrations (mg/1, except as noted)
Stream Sample
jr» .1 m . <•* . vx 4 v% t\ r^ 1
Pollutant (a)
1
1
1
1
1
1
1
1
1
1
1
1
1
14.
15.
17.
ia.
19.
20.
22.
23.
24.
25.
26.
27.
28.
Toxic Pollutants
antimony
arsenic
beryllium
cadmium
chromium (total)
copper
lead
mercury
nickel
selenium
silver
thallium
zinc
Code
301
301
301
301
301
301
301
301
301
301
301
301
301
Type
1
1
1
1
1
1
1
1
1
1
1
1
1
Source
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
<0
0
.01
.01
.005
.02
.02
.05
.05
.0002
.5 (b)
.01
.01
.01
.08
Day 1 Day 2
<0
<0
<0
<0
<0
0
<0
<0
<0
<0
<0
<0
0
.01
.02 (b)
.005
.02
.02
.25
.05
.000?
.0!> (b)
.01
.01
.01
.14
Day 3 Average
<0
<0
<0
<0
<0
0
-------
Table V-16 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
REDUCTION TO TUNGSTEN WATER OF FORMATION
RAW WASTEHATER
u
o
itant (a)
Nonconvent ional
acidity
alkalinity
aluminum
ammonia
barium
boron
calcium
chemical oxygen
(COD)
chloride
cobalt
fluoride
iron
magnesium
Stream
Code
Pollutants
301
301
301
301
301
301
301
demand 301
301
301
301
301
301
Sample
Type
1
1
1
1
1
1
1
1
1
1
1
1
1
•4kJ"Ur*l*Mr*M>IBV» k «
Source
<1
40
0.2
2.0
<0.05
<0.1
25.7
110
11
<0.05
0.64
<0.5 (b)
4.5
A«<»^*'!lt? \ i**f»j 1 *• f 1*» ** «•">*• £*
Day 1 Day 2
0
500
<0.1
180
<0.05
3.8
<0.1
50
87
<0.05
86
0.7 (c)
<0.1
\~ «» HUt*t.*J/
Day 3 Average
o
500
<0.1
180
<0.05
3.8
<0.1
50
87
<0.05
86
0.7
<0.1
ftf
H
K
|
Q
W
tn
c;
n
w
Q
o
3
en
w
n
H
1
<
-------
Table V-16 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
REDUCTION TO TUNGSTEN WATER OF FORMATION
RAW WASTEWATER
U)
o
Pollutant (a)
manganese
molybdenum
phosphate
sodium
sulfate
tin
titanium
total dissolved
solids (TDS)
total organic carbon
(TOO
total solids (TS)
vanadium
ytrrium
S t ream
Code
301
301
301
301
301
301
301
301
301
301
301
301
Sample
Type
1
1
1
1
1
1
1
1
1
1
1
1
WWK**** **•*» 1* *-
Source
<0.05
<0.05
0.82
4.5
590 2
<0.05
<0.05
175
<1
250
<0.05
<0.05
cji «. JL. «^ K i ^ n
Day 1
<0.05
<0.05
0.76
<0.1
,200
<0.05
<0.05
140
51
200
<0.05
<0.05
tf^f %* **.-*** *i*|»r ft*. **** KIW L. *~U X
Day 2 Day 3 Average
<0.05
<0.05
0.76
<0. 1
2,200
<0.05
<0.05
140
51
200
<0.05
<0.05
t)
H
%
G
a
o
H
w
a
M
C
to
o
w
0
3
M
W
O
^
1
<
-------
Table V-16 (Continued)
. PRIMARY TUNGSTEN SAMPLING DATA
REDUCTION TO TUNGSTEN WATER OP FORMATION
RAW WASTEWATER
u>
o
tv>
O
Stream
Pollutant (a) Code
Conventional Pollutants
oil and grease 301
total suspended solids 301
(TSS)
pH (standard units) 301
Concentrations (mg/1, except as noted)
Sample
Type Source Day 1 Day 2 Day 3
Average
19
7.60
62
62
9.64
Q
M
M
g
O
S
M
(a) Toxic organic pollutants were not analyzed for this waste stream
(b) Detection limit raised because of interference
(c) Sample was redigested and reanalyzed due to high blanks
w
M
O
Hi
-------
Table V-17
PRIMARY TUNGSTEN SAMPLING DATA
TREATMENT PLANT SAMPLES - PLANT B
Concentrations (mg/1, except as noted)
O
(O
Stream
Pollutant Code
4.
10.
23.
29.
48.
66.
68.
69.
87.
Toxic Pollutants
benzene
1 ,2-dichloro-
ethane
chloroform
1 ,1 -dichloro-
ethylene
dlchlorobrorao-
methane
bls(2-ethyl-
hexyl) phthalate
di-n-butyl
phthalate
dl-n-octyl
phthalate
trichloro-
65
65
65
65
65
65
65
65
65
Sample
Type
2
2
2
2
2
7
7
7
2
Source
*
ND
0.075
ND
ND
0.06
0.011
0.037
<0.043
Day 1 Day 2
<0.017 *
0.015 ND
0.031 0.041
ND 0.02
0.012 *
0.797
0.078
0.08
<0.088 <0.045
Day 3 Average
* <0.022
0.029 0.022
0.083 0.052
ND 0.02
* 0.004
0.797
0.078
0.08
<0.03 <0.054
s
1-4
1
Hj
Q
W
HI
W
"Z
W
G
»
O
Hi
W
Q
O
Kj
W
W
O
H
I
ethylene
-------
Table V-17 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
TREATMENT PLANT SAMPLES - PLANT B
Concentrations (mg/1, except as noted)
Pollutant
1
1
1
1
1
1
1
I
1
1
15.
18.
19.
20.
21.
22.
24.
I'ft.
27.
28.
arsenic
cadmium
chromium
copper
cyanide
lead
nickel
silver
thallium
zinc
Stream
Code
65
65
65
65
65
65
65
65
65
65
Sample
Type
7
7
7
7
7
7
7
7
7
7
Source
<0
0
<0
0
0
<0
<0
<0
<0
0
.01
.008
.005
.01
.05
.02
.005
.02
.1
.08
Day 1 Day 2
0
0
<0
0
0
<0
0
0
0
<0
.08
.08
.0543
.07
.004 0.006
.2
.1
.03
.9
.6
Day 3 Average
0
0
<0
0
0.001 0
<0
0
0
0
-------
Table V-17 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
TREATMENT PLANT SAMPLES - PLANT B
UJ
O
to
Pollutant
phenols (total; by
4-AAP method)
total organic
carbon (TOC)
Conventionals
Stream
Code
65
65
Sample
Type
solids (TSS)
pH (standard units)
65
Concentrations (mg/1, except as noted)
Source Day1 Day 2 Day 3 Average
1.55 1.17 0.62 1.11
10
oil and grease
total suspended
65
65
1
2
2
151
8.5
8.1
10
5.8
10
5
151
H
3
i
Q
Cfl
01
c
»
o
M
O
O
M
W
Q
I
<
-------
o
to
Pollutant
Toxic Pollutant
1. acenaphthene
4. benzene
6. carbon tetrachloride
8. 1,2,4-trichlorobenzene
10. 1,2-dichloroethane
14. 1,1,2-trichloroethane
15. 1,1,2,3-tetrachloroethane
23. chloroform
25. 1,2-dichlorobenzene
Table V-18
PRIMARY TUNGSTEN SAMPLING DATA
TREATMENT PLANT SAMPLES - PLANT C
Concentrations (tag/1, except as noted)
Stream Sample
Code Type Source Day 1 Day 2 Day 3 Average
H
9
9
10
11
11
11
9
10
11
9
10
9
10
9
10
11
11
7
1
1
1
1
7
1
1
1
1
1
1
1
1
1
1
7
ND
*
*
*
ND
0.011
*
0.017
ND
ND
ND
ND
ND
0.142
0.342
1.933
0.011
ND
<0.012
<0.020
ND
0.15
0.097
0.065
ND
ND
ND
*
0.024
0.54
0.073
<0.117
<0.017
ND
0.022
ND
ND
ND
0.043
0.011
ND
<0.011
0.044
0.045
0.058
<0.064
<0,013
<0.0i
0.022
0.011
0.075
0.057
0.065
0.043
0.011
<0.011
0.07
0.309
0.688
O.Oll
H
Q
W
t-3
M
as
en
a
tu
9
8
M
i<
CO
w
a
i
<
-------
Table V-18 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
TREATMENT PLANT SAMPLES - PLANT C
Concentrations (ng/1, except as noted)
50
Pollutant
29. 1,1-dlchloroethylene
38. ethylbenzene
10
o
to
44. methylene chloride
47. bromoform
48. dichlorobromooetLaite
51. chlorodibromomethane
55. naphthalene
56. nitrobenzene
66. bls(2-ethylhexyl)phthalate
Strean
Code
9
10
11
9
10
9
9
9
10
11
9
10
9
11
11
9
10
11
Sample
Type
1
1
1
1
1
1
1
1
1
1
1
1
7
7
7
7
7
7
Source Day 1
0.013
0.051
0.048
ND
0.011
0.018
ND
ND
ND
ND
ND
ND
ND
0.032
0.011
0.03
0.014
0.034
Day 2
0.05
0.04
ND
*
*
ND
ND
ND
0.012
0.012
ND
ND
Day 3
ND
ND
ND
ND
*
ND
ND
0.117
0.022
0.048
0.146
0.034
Average
0.03
0.05
0.048
*
0.0037
0.018
0.117
0.017
0.03
0.146
0.034
0.032
0.011
0.03
0.014
0.034
H
50
1-3
§
O
w
25
M
W
O
^
n
8
50
M
o
H
1
-------
Table V-18 (Continued)
PRIMARY TUNGSTEN- SAMPLING DATA
TREATMENT PLANT SAMPLES - PLANT C
OJ
o
en
Pollutant
68. dl-n-butyl phthalate
69. dl-n-octyl phthalate
70. diethyl phthalate
71. dimethyl phthalate
76. chrysene
77. acenaphthylene
78. anthracene (b)
81. phenanthrene (b)
80. fluorene
84. pyrene
85. tetrachloroethylene
Concentrations (ag/l« except as noted)
Stream
Code
11
10
11
11
11
11
9
9
11
9
11
9
10
11
Sample
Type
7
7
7
7
7
7
7
7
7
7
7
1
1
I
Source Day 1
0.013
0.025
ND
0.016
0.23
ND
ND
ND
0.016
ND
0.015
0.012
0.078
0.02
Day 2 Day 3 Average
0.013
0.025
0.016
0.23
0.016
0.015
ND ND 0.012
* * 0.026
* ND 0.01
•tJ
H
J3
K-
1-3
Q
Hi
W
G
td
P
i
el
Q
K
W
M
O
I
-------
Table V-18 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
TREATMENT PLANT SAMPLES - PLANT C
Concentrations (ng/1, except as noted)
Pollutant
86.
87.
U)
o
^4 89.
95.
96.
106.
107.
108.
109.
110.
112.
114.
115.
toluene
trichloroethylene
aldrln
alpha-endosulfan
beta-endosulfan
PCB-1242.
PCB-1254
PCB-1221
PGB-1232
PCB-1248
PCB-1016
antimony
arsenic
(c)
(0
(c)
(d)
(d)
(d)
Stream
Code
9
10
9
10
U
9
9
9
9
10
9
10
9
9
11
Sample
Type Source Day 1 Day 2
1
1
1
1
1
7
7
7
7
7
7
7
1
7
7
* ND
0.011
* ND
0.045 <0.064
* <0.093
0.007
0.03
0.03
<0.012
X0.009
<0.015
<0.013
0.8
0.02
0.018
Day 3 Average
* *
* 0.0055
<0.162 <0.086
<0.07 0.015
ND <0.0515
0.007
0.03
0.03
<0.012
<0.009
<0.015
<0.013
0.8
0.02
0.018
•d
$0
H
3
IS
1
p
M
M
2!
W
a
w
o
M
a
o
K!
W
M
D
1
<
-------
Pollutant
o
CO
oa
117. beryllium
118. cadmium
119. chromium
120. copper
121. cyanide
122. lead
123. mercury
Table V-18 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
TREATMENT PLAHT SAMPLES - PLANT C
Stream
Code
11
Sample
Type
9
10
11
9
10
11
9
10
11
9
10
11
9
10
11
9
10
11
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
Concentrations (ag/1, except as noted)
Source
<0.002
Average
<0.002
H
<0.02
<0.02
<0.02
0.044
<0.024
0.0443
0.115
0.148
0.064
0.159 0.179
0.6 0.001
0.014 0.021
0.242
0.219
0.14
0.003
0.0002
0.0006
<0.02
<0.02
<0.02
0.044
<0.024
0.0443
0.115
0.148
0.064
0.096 0.1447
0.516 0.3723
0.286 0.106
0.242
0.219
0.14
0.003
0.0002
0.0006
Q
w
w
55
w
G
O
•>
s
M
I
•<
W
w
o
H
r Jl
1
<
-------
Table V-18 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
TREATMENT PLANT SAMPLES - PLANT C
Concentrations (og/1, except as noted)
U)
o
KJ
Pollutant
124. nickel
125. selenium
126. silver
127. thallium
128. zinc
Nonconventionals
aluminum
ammonia
Stream
Code
9
10
11
9
10
9
9
10
11
9
10
11
Sample
Type
7
7
7
7
7
7
7
7
7
7
7
7
Source Day 1 Day 2
0.092
0.108
<0.05
1
0.09
ND
0.2
0.224
ND
0.248
0.239
0.083
Day 3 Average
0.042
0.108
<0.05
1
0.09
0.2
0.224
0.248
0.239
0.083
H
S
t<
Hi
O
tfl
H
Si
W
G
W
O
8
w
o
Hj
w
w
n
H
1
<
9
10
11
1
1
1
10.0
2,250
1,150
6.8
10.0
950
775
210
1,630
1,480
700
1,610
1,135
300
-------
fable V-18 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
TREATMENT PLANT SAMPLES - PLANT C
Concentrations (ng/1, except as noted)
Pollutant
chemical oxygen deaand
(COD)
cobalt
to iron
o
to
° manganese
total organic carbon
(TOG)
phenols (total; by 4-AAP
method)
Convent i ona 1 a
oil and grease
pH (standard units)
Strea*
Code
9
10
11
9
9
9
9
10
11
9
10
11
9
10
11
9
10
11
Sample
Type
1
7
1
7
7
7
1
7
1
1
1
1
1
1
1
I
1
1
Source Day 1
881
242
100
0.045
30.0
10.0
269
61
33
0.076
0.007
0.011
9
6
9
10.4
3.6
8.2
Day 2
0.018
0.016
0.01
23
8
6
8.6
8.5
9.2
Day 3
0.021
0.007
0.013
20
18
16
9.5
8.0
7.3
Average
881
242
100
0.045
30.0
10. 0
269
61
33
0.038
0.01
0.011
17
11
10
H
K)
HI
§
Q
W
W
ss
W
a
w
o
>
n
w
»
K
in
M
n
H
i
<
-------
Table V-18 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
TREATMENT PLANT SAMPLES - PLANT C
u>
o
u>
Pollutant
total suspended solids
(TSS)
Stream
Code
9
10
11
Concentrations (ag/1, except as noted)
Sample
Type
1
1
7
Source
Day I
6,714
374
91
Day 2 Day 3
Average
6,714
374
91
s
0
CO
^
M
CO
C
tn
M
S
(a) One sample from each stream vas analyzed for acid extractable toxic organic pollutants; none
was reported above Its analytical quantification concentration.
(b), (c), (d) Reported together.
*Lesa than or equal to 0.01 ng/1.
**Lesa than or equal to 0.005 mg/1.
en
w
O
I
<
Source water samples were not taken at this plant.
-------
Table V-19
PRIMARY TUNGSTai SAMPLING DATA
TfiEATMOT PWNT SAMPIfiS - PWNT E
Concentrations (ng/1, except as noted)
U)
o
U)
to
54.
65.
66.
68.
70.
114.
115.
117.
118.
119.
•
Pollutant (a)
Toxic Pollutant
isophorone
phenol
bi s (2-ethy lhexyl)phthalate
di-n-butyl phthalate
diethyl phthalate
antimony
arsenic
beryllium
cadmium
chromLun (total)
Stream
Code
316
315
315
316
315
316
316
315
316
315
316
315
316
315
316
315
316
Sample
Type
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Source
0.040
0.040
*
*
ND
<0.01
<0.01
<0.005
<0.02
<0.02
Day 1
ND
*
*
ND
*
*
*
<0.002
<0.002
0.058
0.019
<0.010
<0.01
<0.050
<0.05
0.12
<0.1
Day 2
*.
*
ND
0.208
*
*
ND
<0.002
<0.002
0.324
0.446
<0.010
<0.01
<0.050
0.05
0.22
<0 1
Day 3
ND
*
ND
ND
*
ND
<0.002
<0.002
0.076
0.022
<0.010
<0.01
<0.050
0.05
0.10
<0 1
Average
*
*
*
0.208
*
*
*
<0.002
<0.002
0.152
0.162
<0.010
<0.01
<0.050
0.03
0.14
<0 1
W
H
Kj
1
Q
W
1
25
W
5
o
I
W
Q
O
a
en
a
a
'
-------
U)
o
U)
U)
120. copper
122. lead
123. mercury
124. nickel
125. selenium
126. silver
127. thallium
128. zinc
Table V-19 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
TREATMENT PLANT SAMPLES - PLANT E
Concentrations (rag/1, except as noted)
Stream
Pollutant (a) Code
ir 315
316
de (total) 315
316
315
316
iry 315
316
1 315
316
ium 315
316
r 315
316
ium 315
316
315
316
Sample
Type
3
3
1
1
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Source
<0.05
<0.02
<0.05
<0.001
<0.05
<0.05
<0.01
<0.01
0.06
Day 1
0.015
<0.01
0.082
0.23
<0.100
<0.0010
<0.001
0.202
<0.10
(b) 0.528
0.044
<0.002
<0.002
<0.005
<0.005
0.11
0.05
Day 2
<0.010
0.015
<0.100
<0.0010
0.100
<0.10
0.016
0.059
0.002
<0.002
<0.005
0.005
0.30
0.05
Day 3
<0.010
0.013
<0.100
<0.0010
<0.001
0.100
0.15
0.050
0.085
<0.(J02
0.006
<0.005
0.005
0.18
0.05
Average
0.005
0.009
0.082
0.23
<0.100
<0.0010
<0.001
0.134
0.05
0.198
0.062
0.001
0.002
<0.005
0.003
0.19
0.05
PRIMARY TU
a
Q
Ul
H
Ul
§
n
w
o
o
Q
Ul
M
n
i
-------
Table V-19 (Continued)
PRIMARY TUNGSTEN SAMPLING IttTA
TREATMQff PLANT SAMPIES - PLANT E
Concentrations (rug/1, except as noted)
Pollutant (a)
Nonconventional Pollutants
acidity
alkalinity
o
^ aluminum
*>>
ammonia
barium
boron
calcium
chemical oxygen demand (COD)
chloride
Stream
Code
315
316
315
316
315
316
315
316
315
316
315
316
315
316
315
316
316
Sample
Type
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Source Day 1
73
164
<0.10 2
.5
0.13
<1
460
<0.05 0
0
<0.10 0
0
37.2 620
347
<1
120
5 140
.10
.075
.54
.24
Da
160
0
0
740
390
0
0
<0
0
839
328
150
67
140
y 2
.38
.29
.060
.080
.10
.30
Da
160
3
0
660
650
0
0
0
0
645
122
100
90
130
Li-
.5
.13
.0120
.040
.44
.26
A
161
2
0
700
500
s/erage
.1
.18
H3
H
K;
TUNGSTEN SI
a
V*J
O
M
Q
O
3
0.057
0
0
0
701
265
125
92
136
.065
.32
.26
w
w
o
1-3
1
<
-------
Table V-19 (Continued)
PRIMARY TUNGSTEN SAMPLING C&TA
PLANT SAMPLES - PLANT E
Concentrations (rag/1, except as noted)
Pollutant (a)
cobalt
fluoride
w iron
o
en
magnesium
manganese
molybdenum
phenolics
phosphate
sodium
Stream
Code
315
316
315
316
315
316
315
316
315
316
315
316
315
316
315
316
315
316
Sample
Type
3
3
3
3
3
3
3
3
3
3
3
3
1
1
3
3
3
3
Source
<0.05
0.1
0.30
5.50
<0.05
<0.05
<0.005
Oo26
4.10 2,
2,
Day 1
<0.10
180
47
10.0
0.11
11.1
17.9
1.89
0.63
0.30
0.890
0.019
<0.005
8.0
750 5
450 3
Day 2
<0.10
0.185
135
18.8
0.14
32.5
13.8
1.24
0.43
0.35
1.79
0.013
<0.005
<4
<4
,020 5
,000 2
Day 3
<0.10
120
52
31.2
0.14
33.2
18.6
1.19
0.50
1.00
1.54
<0.005
<0.005
<8
<4
,500 4
,850 2
Average
<0.10
100
78
20
O.J3
25.6
16.7
1.44
0.52
0.55
1.40
0.010
<0.005
<6
2
,400
,766
RIMARY
1
0
in
w
53
cn
c
03
o
M
o
K
w
0
1
-------
Table V-19 (Continued)
PRIMARY TUNGSTEN SAMPLING MTA
TREATMENT PLANT SAMPIES - PLAOT E
Concentrations (rag/1, except as noted)
Pollutant (a)
sulfate
tin
w titanium
0
10
en
total dissolved solids (TDS)
total organic carbon (TOC)
total solids (TS)
vanadium
yttrium
Conventional Pollutants
oil and grease
Stream
Code
315
316
315
316
315
316
316
315
316
316
315
316
315
316
315
316
Sample
Type
3
3
3
3
3
3
3
3
3
3
3
3
3
3
1
1
Source
36
12
0.50
<0.05
189 14
3
200 14
<0.05
<0.05
3
Day 1
,000 12,
<0.200
<0.200
0.042
<0.02
,000 14,
6.3
,000 14,
<0.10
<0.1
0.026
0.10
9.0
2.4
Da
000
<0
<0
<0
<0
700
30
5
500
-------
Table V-19 (Continued)
PRIMARY TUNGSTEN SAMPLING DATA
TREATMENT PLANT SAMPLES - PLANT E
Concentrations (mg/1, except as noted)
(a)
(b)
Pollutant (a)
total suspended solids (TSS)
pH (standard units)
All toxic organic pollutants
Detection limit raised due to
Stream
Code
Sample
Type
315 3
316 3
315 3
316 3
except the pesticide
interference.
Source Day
1 Day 2 Day 3 Average
(c) (c) (c)
1 6 18 7 10
6 10
-------
PRIMARY TUNGSTEN SUBCATEGQRY
SECT - V
APT
CONVERSION
TO OXIDES
SCRUIiERS
213
some!
MATER
VOA BLANK
DISCHARGE
0.0039 MGD
CYAH1DS
TREATMENT
tfXTH
HfFOCHLORITE
ISCHARGE
Figure V-1
SAMPLING SITES-AT PRIMARY TUNGSTEN PLANT A
3038
-------
PRIMARY TUNbSTEN SUBCATEGORY SECT - V
i i
TUNCSTIC !
' ACID
RINSE -
: WATER
LIKE
VOA BLANK
0.03&36 MGD
0.034 MGD
DISCHARGE
Figure V-2
SAMPLING SITES AT PRIMARY TUNGSTEN PLANT B
3039
-------
PRIMARY TUNGSTEN SUBCATEGORY
SECT - V
TUKGSTIC
ACID
LEACH
SCRUBBER
LIOUOE
APT
CRYSTAL-
LI7ATIQN
SCRUBBER
LIQUOR
FINAL
TUNGSTIC
ACID
RINSEWATER
COOLING
SLOWDOWN I
HYDROGEN
RECYCLING
WASHWATER
GRAPHITE
LUBRICANf
FROM
DRAWING
DOPING
OPERATION
WASTE
WIRE
WASHWATER
"DISCHARGE
LIME
TANK &
BATCH SETTLE
009
EQUALIZATION
SUMP
HYDROCHLORIC ACID
0.2^02 MGD
QU
|0,681 MGD
DISCHARGE
Figure V-3
SAMPLING SITES AT PRIMARY TUNGSTEN PLANT C
3040
-------
PRIMARY TUNGSTEN 'SUBCATEGORY SECT - V
123 VOA BLANK
APT
CONVERSION
TO OXIDES
SCRUBBER
OXIDES
REDUCTION
FOTHACE
SCRUBBERS
0,0177 KGO
DISCHARGE
Figure V-4
SAMPLING SITES AT PRIMARY TUNGSTEN PLANT D
3041
-------
PRIMARY TUNGSTEN SUBCATEGORY
SECT - V
ION
EXCHANGE
RAFFINATE
0.0
311
TION AND
FILTRATION
DISCHARGE
Figure V-5
SAMPLING SITES AT PRIMARY TUNGSTEN PLANT 1
3042
-------
PRIMARY TUNGSTEN SUBCATEQORY
SSCT - V
301
WAftlQF
FORMATION
DISCHARGE
0.000057 MOT
Figure V-6
SAMPLING SITES AT PRIMARY TUNGSTEN PLANT F
3043
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - V
THIS PAGE INTENTIONALLY LEFT BLANK
Pages 3045 and 3046 are omitted.
3044
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - VI
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
This section examines chemical analysis data presented in Section
V and discusses the selection or exclusion of pollutants for
potential limitation. The discussion that follows describes the
analysis that was performed to select or exclude pollutants for
further consideration for limitations and standards. Pollutants
will be considered for limitation if they are present in
concentrations treatable by the technologies considered in this
analysis. The treatable concentrations used for the toxic metals
were the long-term performance values achievable by lime
precipitation, sedimentation, and filtration. The treatable
concentrations used for the toxic organics were the long-term
performance values achievable by carbon adsorption.
As discussed in Section V, EPA collected additional wastewater
sampling data after proposal in an attempt to further
characterize the primary tungsten subcategory. As a result of
the new data, the Agency revised its selection of pollutant
parameters as The Agency has selected seven additional pollutants
for further consideration in establishing limitations and
standards. These pollutants are:
11. 1,1,1-trichloroethane,
65. phenol,
73. benzo(a)pyrene,
79. benzo(ghi)perylene,
82. dibenzo(a,h)anthracene
124. nickel, and
126. silver.
All of these pollutants are present above the concentrations
considered achievable by the technologies considered in this
analysis. Additionally, four pollutants were removed from further
consideration for limitation. These are:
1, acenaphthene
77. acenaphthylene
80. fluorene
125. selenium
The raw wastewater data show that selenium was not detected in
each of the 10 samples analyzed from three plants. At proposal,
partially treated wastewater was used in the selection of
selenium. The selection or removal of the other pollutants is
discussed below.
After proposal, the Agency also re-evaluated the treatment
performance of activated carbon adsorption to control toxic
organic pollutants. The treatment performance for the acid
extractable, base-neutral extractable, and volatile organic
3047
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - VI
limit of O.OiO tng/1. The analytical quantification limit for
pesticides and total phenols (by 4-AAP method) is 0.005 mg/lf
which is below the 0.010 mg/1 accepted for the other toxic
organics. However, to be consistent, the treatment performance
of 0.010 mg/1 is used for pesticides and total phenols. The
0.010 mg/1 concentration is achievable, assuming enough carbon is
used in the column and a suitable contact time is allowed. The
frequency of occurrence for 36 of the toxic pollutants has been
redetermined based on the revised treatment performance value.
As a result.- the following pollutants, which were not selected at
proposal, have been selected for further consideration for
limitation:
85. tetrachloroethylene
86. toluene
A full discussion of pollutant selection is presented below.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS
This study examined samples from the primary tungsten subcategory
for three conventional pollutant parameters (oil and grease,
total suspended solids, and pH) and four nonconventional
pollutant parameters (ammonia, chemical oxygen demand, total
organic carbon, and total phenols).
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS SELECTED
The conventional and nonconventional pollutants or pollutant
parameters selected for limitation in this subcategory are:
ammonia
total suspended solids (TSS)
pH
Ammonia is the only nonconventional pollutant parameter selected
for consideration in establishing limitations for this
subcategory. Ammonia was found in all 12 raw waste samples
analyzed for this subcategory in concentrations ranging from 3.1
to 1,790 mg/1. Nine of the values recorded are well above the
32.2 mg/1 concentration attainable by the available treatment
technology. The ammonia is used, as a process reagent.
Additionally, ammonia concentrations above the treatable
concentration (up to 2,250 mg/1) were found in three partially
treated wastewaters where there was no raw waste data available.
Consequently, ammonia is selected for limitation in this
subcategory.
TSS concentrations ranging from 3 to 209 mg/1 were observed in
the nine raw wastewater samples analyzed for this study. All
three concentrations are above the 2.6 mg/1 treatable
concentration. In one partially treated sample, TSS was measured
at 6,714 mg/1. Furthermore, most of the specific methods used to
remove toxic metals do so by converting these metals to
precipitates, and these toxic-metal-containing precipitates
3048
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - VI
should not be discharged. Meeting a limitation on total
suspended solids helps ensure that removal of these precipitated
toxic metals has been effective. For these reasons, total
suspended solids are selected for limitation in this subcategory.
The 15 pH values observed during this study ranged from 0.6 to
12.0. Nine of the 15 values were equal to or less than 3.98, and
three others were above the 7.0 to 10.0 range considered
desirable for discharge to receiving waters. Many deleterious
effects are caused by extreme pH values or rapid changes in pH.
Also, effective removal of toxic metals by precipitation requires
careful control of pH. Since pH control within the desirable
limits is readily attainable by available treatment, pH is
selected for limitation in this subcategory.
TOXIC POLLUTANTS
The frequency of occurrence of the toxic pollutants in the raw
wastewater samples taken is presented in Table VI-1 (page 3057).
Table VI-1 is based on the raw wastewater data from streams 64,
130, 219, 220, 221, 301, 311, and 312 (see Section V). These
data provide the basis for the categorization of specific
pollutants, as discussed below. Treatment plant samples were not
considered in the frequency count.
TOXIC POLLUTANTS NEVER DETECTED
The toxic pollutants listed in Table VI-2 (page 3061) were not
detected in any raw wastewater samples from this subcategory;
therefore, they are not selected for consideration in
establishing limitations.
TOXIC POLLUTANTS NEVER FOUND ABOVE THEIR ANALYTICAL
QUANTIFICATION CONCENTRATION
The toxic pollutants listed below were never found above their
analytical quantification concentration in any raw wastewater
samples from this subcategory; therefore, they are not selected
for consideration in establishing limitations.
4. benzene
10. 1,2-dichloroethane
15. 1,1,2,2-tetrachloroethane
78. anthracene (a)
81. phenanthrene (a)
84. pyrene
87. trichloroethylene
95. alpha endosulfan
106. PCB-1242 (b)
107. PCB-1254 (b)
108. PCB-1221 (b)
109. PCB-1232 (c)
110. PCB-1248 (c)
111. PCB-1260 (c)
112. PCB-1016 (C)
3049
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - VI
(a) Reported together for three samples, as a combined value
(b), (c) Reported together, as a combined value
TOXIC POLLUTANTS PRESENT BELOW CONCENTRATIONS ACHIEVABLE BY
TREATMENT
The pollutants listed below are not selected for consideration in
establishing limitations because they were not found in any raw
wastewater samples from this subcategory above concentrations
considered achievable by existing or available treatment
technologies. These pollutants are discussed individually
following the list.
54. isophorone
70. diethyl phthalate
71. dimethyl phthalate
114. antimony
117. beryllium
123. mercury
Isophorone was detected in only one of the seven raw wastewater
samples for which it was analyzed. This one concentration of
0.008 mg/1 is well below the 0.010 mg/1 concentration considered
achievable by identified treatment technology. Therefore,
isophorone is not selected for limitation.
Diethyl phthalate was measured in two of seven samples. Both
concentrations were above its treatable concentration (0.010
mg/1). This compound is a plasticizer in many products and is
not considered a pollutant specific to this subcategory. Also,
in the dcp, the responding primary tungsten plants indicated that
this pollutant was believed to be absent. Therefore, diethyl
phthalate is not selected for limitation.
Dimethyl phthalate was detected in only one of seven samples
analyzed. This one concentration is above its treatable
concentration (0.010 mg/1). This compound is a plasticizer
commonly used in laboratory and field sampling equipment, and is
not considered a pollutant specific to this subcategory. Also,
in the dcp, the responding primary tungsten plants indicated that
this pollutant was believed to be absent. Therefore, dimethyl
phthalate is not selected for limitation.
Antimony was found in three of 10 samples analyzed, at
concentrations ranging from 0.008 mg/1 to 0.035 mg/1. Since all
of these are below the treatable concentration (0.47 mg/1),
antimony is not selected for limitation.
Beryllium was detected in only one of the 10 raw waste samples.
This one concentration of 0.03 mg/1 is below the 0.20 mg/1
concentration considered achievable by available treatment.
Therefore, beryllium is not selected for limitation.
3050
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - VI
Mercury was found in seven of 10 samples analyzed, at
concentrations ranging from 0.0002 mg/1 to 0.004 mg/1. Since all
of these are below the treatable concentration (0.036 mg/1),
mercury is not selected for limitation.
TOXIC POLLUTANTS DETECTED IN A SMALL NUMBER OF SOURCES
The following pollutants were not selected for limitation on the
basis that they were detectable in the effluent from only a small
number of sources within the subcategory and are uniquely related
to only those sources:
1. acenaphthene
23. chloroform
29. 1,1-dichloroethylene
38. ethylbenzene
47. bromoform
51. chlorodibromomethane
66. bis(2-ethylhexyl) phthalate
68. di-n-butyl phthalate
69. di-n-octyl phthalate
76. chrysene
77. acenaphthylene
80. fluorene
115. arsenic
120. copper
121. cyanide
Although these pollutants were not selected for limitation in
establishing nationwide regulations, it may be appropriate, on a
case-by-case basis, for the local permit issuing authority to
specify effluent limitations.
Acenaphthene was detected in one of the five raw wastewater
streams for which it was analyzed. That sample, the ion-exchange
raffinate, exhibited a concentration of 0.111 mg/1, which is
above the concentration attainable by treatment (0.010 mg/1).
This result is site-specific since acenaphthene was not detected
in any of the three samples of ion-exchange raffinate from
another plant. For this reason, acenaphthene is not selected for
limitation.
Chloroform was detected in six of 12 samples. Five of the
samples had concentrations ranging from 0.014 to 0.036 mg/1,
which are above the treatable concentration (0.010 mg/1). All
six samples containing chloroform were taken from two streams at
two plants. Chloroform is a common laboratory solvent and the
site-specific results suggest sample contamination. Also, all
primary tungsten plants responding in the dcp indicated that this
pollutant was believed to be absent. Therefore, chloroform is
not selected for limitation.
Concentrations of 1,1-dichloroethylene were above treatable
concentration (0.010 mg/1) in only one of seven samples analyzed.
The sample measured 0.019 mg/1. This site-specific result cannot
3051
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - VI
be generalized as characteristic of the entire subcategory,
therefore, 1,1-dichloroethylene is not selected for limitation.
Ethylbenzene was detected in two of the 12 raw wastewater
samples. Only one of these samples (0.011 mg/1) contained
ethylbenzene above its analytical quantification concentration
(0.010 mg/1). Because this concentration is slightly above that
attainable by identified treatment technology (0.010 mg/1),
ethylbenzene is not selected for limitation.
Bromoform was detected in two of 12 raw wastewater samples. The
concentrations were above the treatable concentration of 0.010
mg/1, with values of 0.036 mg/1 and 0.053 mg/1. Both samples
were taken from ion-exchange raffinate at one plant. Bromoform
was not detected in 10 other samples, including three samples of
ion-exchange raffinate at a different plant from the treatable
samples. Since such a small number of sources indicate that
bromoform is present, bromoform is not selected for limitation.
Chlorodibromomethane was detected in only one of the 12 raw waste
samples. This one concentration of 0.038 mg/1 is above the 0.010
mg/1 concentration considered achievable by identified treatment
technology. Since only one source indicates Chlorodibromomethane
is present, it is not selected for limitation.
Bis(2-ethylhexyl) phthalate was found above its treatable
concentration (0.010 mg/1) in three of seven samples analyzed for
it. This compound is a plasticizer commonly used in laboratory
and field sampling equipment, and is not used or formed as a by-
product in this subcategory. Also, in the dcp, the responding
primary tungsten plants indicated that this pollutant was
believed to be absent. Therefore, bis(2-ethylhexyl) phthalate is
not selected for limitation.
Di-n-butyl phthalate was detected above its treatable
concentration (0.010 mg/1) in only one of seven samples analyzed.
This compound is a plasticizer commonly used in laboratory and
field sampling equipment, and is not considered a pollutant
specific to this subcategory. Also, in the dcp, the responding
primary tungsten plants indicated that this pollutant was
believed to be absent. Therefore, di-n-butyl phthalate is not
selected for limitation.
Di-n-octyl phthalate occurred above its treatable concentration
(0.010 mg/1) in two of seven samples. This compound is a
plasticizer used in many products and is not considered a
pollutant specific to this subcategory. Also, in the dcp, the
responding primary tungsten plants indicated that this pollutant
was believed to be absent. Therefore, di-n-octyl phthalate is
not selected for limitation.
Chrysene concentrations were above treatable concentration (0.010
mg/1) in only one of seven samples analyzed. The sample measured
0.024 mg/1. This site-specific result cannot be generalized as
characteristic of the entire subcategory, therefore, chrysene is
3052
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - VI
not selected for limitation.
Acenaphthylene was detected in one of the seven raw wastewater
samples analyzed. That sample, ion-exchange raffinate, exhibited
a concentration of 0.112 mg/1 which is above the concentration
attainable by treatment (0.010 mg/1). This result is site-
specific since no other ion-exchange raffinate samples were
identified to contain acenaphthylene. Therefore, this compound
is not selected for limitation.
Fluorene was detected in one of five raw wastewater streams. That
sample, ion exchange raffinate, exhibited a concentration of 0.06
mg/1, which is above its treatable concentration (0.010 mg/1).
Three samples of ion-exchange raffinate from another plant were
not found to contain fluorene. This result is site-specific/ so
fluorene is not selected for limitation.
Arsenic was detected above its treatable concentration (0.34
mg/1) in only one of the 10 samples analyzed. The Agency has no
reason to believe that treatable arsenic concentrations should be
present in primary tungsten wastewaters, and it believes that
this one value found at one plant is not representative of the
subcategory. For these reasons, arsenic is not selected for
limitation.
Copper was found at 5 mg/1 in one sample, but the other nine
samples analyzed contained copper at 0.25 mg/1 or less, which is
below its treatable concentration of 0.39 mg/1. The Agency has
no reason to believe that treatable copper concentrations should
be present in primary tungsten wastewaters, and it believes that
this one value found at one plant is not representative of the
subcategory. Thus, copper is not selected for limitation.
Cyanide was found above its treatable concentration (0.047 mg/1)
in two of nine samples analyzed. The samples measured 0.055 and
0.064 mg/1. The Agency has no reason to believe that treatable
cyanide concentrations should be present in primary tungsten
wastewaters, and it believes that these two values are not
representative of the subcategory. For these reasons, cyanide is
not selected for limitation.
TOXIC POLLUTANTS SELECTED FOR FURTHER CONSIDERATION IN
ESTABLISHING LIMITATIONS AND STANDARDS
The toxic pollutants listed below are selected for further
consideration in establishing limitations and standards for this
subcategory. The toxic pollutants selected for further
consideration for limitation are each discussed following the
list.
11. 1,1,1-trichloroethane
55. naphthalene
65. phenol
73. benzo(a)pyrene
79. benzo(ghi)perylene
3053
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - VI
82. dibenzo(a,h)anthracene
85. tetrachloroethylene
86. toluene
118. cadmium
119. chromium
122. lead
124. nickel
126. silver
127. thallium
128. zinc
1,1,1-Trichloroethane was measured above its treatable
concentration (0.010 rag/1) in one of the five raw wastewater
streams for which it was analyzed. That sample, synthetic
scheelite filtrate, exhibited a concentration of 0.02 mg/1.
Since this waste stream may contain toxic organic pollutants,
1,1,1-trichloroethane is selected for further consideration for
limitation.
Naphthalene was found in four of the five raw wastewater streams
analyzed. Two of these four streams are from ion-exchange
raffinate and one is from synthetic scheelite filtrate, both of
which are expected to contain toxic organic pollutants. Two of
seven samples from the five wastewater streams have naphthalene
concentrations above its treatable concentration (0.010 mg/1).
For these reasons, naphthalene is selected for further
consideration for limitation.
Phenol was measured above its treatable concentration (0.010
mg/1) in four of seven samples with concentrations ranging from
0.0654 to 0.118 mg/1. The treatable concentrations were found in
ion-exchange raffinate and synthetic scheelite filtrate, both of
which may contain toxic organic pollutants because of the organic
solvents used.
Benzo(a)pyrene was detected above its treatable concentration
(0.010 mg/1) in one of the five raw wastewater streams for which
it was sampled. That sample, synthetic scheelite filtrate,
exhibited a concentration of 0.120 mg/1. Since this stream may
contain toxic organic pollutants, benzo(a)pyrene is selected for
further consideration for limitation.
Benzo(ghi)perylene was detected above its treatable concentration
(0.010 mg/1) in one of five raw wastewater streams sampled. That
sample, synthetic scheelite filtrate, exhibited a concentration
of 0.139 mg/1. Since this stream may contain toxic organic
pollutants, 'benzo(ghi)perylene is selected for further
consideration for limitation.
Dibenzo(a,h)anthracene was measured above its treatable
concentration (0.010 mg/1) in one of five raw wastewater streams.
A concentration of 0.108 was found in a synthetic scheelite
filtrate sample. Since this stream may contain toxic organic
pollutants, dibenzo(a,h)anthracene is selected for further
consideration for limitation.
3054
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - VI
Tetrachloroethylene was detected in eight of the 12 raw waste
samples. Three of these samples have tetrachloroethylene
concentrations above its treatable concentration (0.010 mg/1).
Two of the three samples are from the ion-exchange raffinate.
This stream may contain toxic organic pollutants because of the
organic solvent used. For these reasons, this compound is
selected for further consideration for limitation.
Toluene was found in five of the 12 raw waste sample of which two
of the concentrations are above its treatable concentration
(0.010 mg/1). These two samples are from the ion-exchange
raffinate which may contain toxic organic pollutants because of
the organic solvent used. For these reasons, toluene is selected
for further consideration for limitation.
Cadmium was detected above its treatable concentration (0.049
mg/1) in one of eight raw wastewater streams sampled. The
treatable concentration was detected in tungstic acid rinse
water, which may contain cadmium from the ore concentrates.
Therefore, cadmium is selected for further consideration for
limitation.
Chromium was detected above its treatable concentration of 0.07
mg/1 in both tungstic acid rinse water samples before treatment.
The highest concentration was 2.0 mg/1. One sample from a third
stream indicated that chromium was present at a concentration
quantifiable but below the treatable concentration. Therefore,
chromium is selected for further consideration for limitation.
Lead was detected in one raw waste stream at a concentration of
20.0 mg/1 which is well above the 0.08 mg/1 attainable by
identified treatment technology. This concentration wab observed
in tungstic acid rinse water which may contain toxic metals from
ore concentrates. Although no raw waste data is available,
sampling data at a second plant indicated that lead
concentrations above the treatable concentration were present in
the treated wastewater. For these reasons, lead is selected for
further consideration for limitation.
Nickel was found in one raw waste stream at a concentration of
1.0 mg/1 which is above the 0.22 mg/1 attainable by identified
treatment technology. This concentration was observed in
tungstic acid rinse water which may contain toxic metals from ore
concentrates. Therefore, nickel is selected for further
consideration for limitation.
Silver was detected in five of ten wastewater samples. Two of
the samples contained concentrations of 0.1 and 0.29 mg/1, which
can be treated to the 0.07 mg/1 attainable by identified
treatment technology. Therefore, silver is selected for further
consideration for limitation.
3055
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - VI
Thallium was detected in one of the eight raw wastewater streams
sampled at a concentration above its treatable concentration of
0.34 mg/1. The treatable concentration was observed in raw
tungstic acid rinse water at 0.70 mg/1. Therefore, thallium is
selected for further consideration for limitation.
Zinc was detected in four of the ten samples for which it was
analyzed above its treatable concentration of 0.23 mg/1. The
highest concentration found was 2.0 mg/1. Treated wastewater
sampling data from one plant also indicated that concentrations
above treatability remained even after lime and settle treatment
had been applied to a stream. Accordingly, zinc is selected for
further consideration for limitation.
3056
-------
Table VI-1
FREQUENCY OF OCCURRENCE OF TOXIC POLLUTANTS
PRIMARY TUNGSTEN
RAW WASTEWATER
ui
o
Ul
-J
Pollutant
I. acenaphthene
2. acroleln
3. acrylonHrlle
4. bensene
5. benztdine
6. carbon cetrachlorlde
7. chlorabenzene
8. 1,2.4-trlchlorobentene
9. hexadilorobeniane
10. I 2-dtehloroethane
II. I 1,1-trldiloroetiune
12. hexadlloroethane
I). I 1-dtchloroethane
14. I 1.2-trtchlaro*thane
15. I 1,2,2-tetrachloroethane
16. chloroe thane
17. bU(chloronethyl) ether
18. bla(2-chloroethyl) ether
19. 2-chloroethyl vinyl ether
20. 2-chlorona(ihthal«»e
21. 2,4,fc-trlchlorop»ienol
22. parachloraKta crecol
21. chloroform
24. 2-chlorophenol
25. I,2-dlchlorobenzen*
26. 1,3-dlchlorQbemene
27. I,4-dlchlorobeniene
28. 3,3'-dlchIon*enildine
29. 1,1-dlchloroethylene
30. 1.2-tranfl-dlchlorocthylene
31. 2.4-arafroKfhenoi
32. 1,2-dlchloropropane
33. 1.3-dlchloroprqpylene
34. 2,4-di«ethylpoenol
3), 2,4-dlnltrotolume
J6. 2,6-dlnltrotoluene
37. 1,2-dlphenylhydrailne
Analytical
Quantification
Concentration
Ow/l> (a)
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
o.oso
0.0)0
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.0 10
0.010
0.010
0.010
0.010
0.010
0.010
0.010
Treatable
Concentration
<*l/l) (b)
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0,010
0.010
0.010
0.010
0.010
0.010
0.010
o.oto
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
o.oto
0.010
0.010
0.010
O.OIU
0.010
o.otu
0.010
0.010
Huafcer of
Stream
Ana ly led
5
5
5
&
S
5
S
5
i
5
i
5
S
5
5
5
5
5
5
5
$
5
5
5
S
5
5
S
5
5
5
5
5
5
$
5
5
NMbec of
S«4>lea
Analyzed
7
12
12
12
7
12
12
7
7
12
12
7
12
12
12
12
12
7
12
7
7
1
12
7
7
7
7
J
12
12
7
12
12
7
7
7
7
ttoc
Detected
6
12
12
6
7
12
12
7
7
10
11
7
12
12
8
12
12
7
12
7
7
7
6
7
7
7
7
7
II
12
7
12
12
7
7
7
7
Detected Below
Quantification
Concentration
0
0
0
6
0
0
0
0
0
2
0
0
0
0
4
0
0
0
0
0
0
0
1
0
0
0
u
0
0
0
(1
0
0
0
0
0
u
Detected
Below
Treatable
Concent rat too
U
0
0
0
0
0
0
0
0
0
0
0
u
0
0
0
u
0
0
0
0
0
0
0
0
0
0
0
0
u
0
0
u
0
0
u
0
Ifetected
AUove
Treatable
Concentration
I
0
0
0
0
0
0
0
u
0
1
0
0
u
0
0
u
0
u
0
0
0
5
0
0
u
0
0
1
0
0
u
u
0
0
0
u
t-3
G
21
Q
W
W
G
OB
n
w
Q
O
C/l
M
n
I
H
-------
Table VI-1 (Continued)
FREQUENCY OF OCCURRENCE OF TOXIC POLLUTANTS
PRIMARY TUNGSTEN
RAW WASTEUATER
OJ
o
en
oo
I
Pollutant
18. ethylbenzene
39. fluoranthcne
40. 4-chlorophenyl phenyl ether
41. 4-bruouuhenyl phenyl ether
42. bla(2-chlorolBOprcpyl) ether
43. bla(2-chloroetnoxy) •ethane
44. aethylene chloride
45. Methyl chloride
46. -ethyl bromide
47. broBOtbna
48. dlchlorabroiaaethane
49. trldilorofluoraaethane
SO. dtchlorodlfluoroaethane
51. chlorodibroatMethane
52. hexachlorobutadiene
5). hexachlorocyclopcntadlene
54. laoohorooe
55. naphthalene
56. nitrobenzene
57. 2-nitrophenol
58. 4-nltrophenol
59. 2.4-dlnitrophenol
60. 4.6-dinitro-o-<:re«oi
61. N-nitroaodiHethylaaUne
62. N-nitroaodiphenylaalne
63. N-nitrosodi-n-propylamlne
64. pentachlorophenol
65. phenol
66. bia(2-ethylhexyl) phthaUte
67. butyl benzyl phthalate
68. di-n-butyl phthaUte
69. dl-n-octyl phthalate
70. diethyl phthaUte
71. dimethyl phthalate
72. benzo(a)authracene
73. benzo(a>pyrene
74. 3.4-benzofluoranthene
Analytical
{uantlCication
Concentration
(an/D (a)
0.010
0.010
0.010
0.010
0.010
0.010
0.0)0
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
o.oio
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.0 W
0.010
0.010
0.010
Treatable
Concentration
(an/1) (b)
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
o.ow
0.010
0.010
0.010
0.010
0.010,
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.0 W
0.010
O.OIO
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
Nuaber ot
Streaaa
Analyzed
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
Huafcer of
Saiplea
Analyzed
12
7
7
7
7
7
12
12
12
12
12
12
12
12
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
Not
Detected
10
7
;
7
7
7
12
12
12
10
12
12
12
II
7
7
6
1
7
7
7
7
7
7
7
7
7
3
1
7
3
4
5
6
7
6
7
Detected Below
Quantification
Concentration
,
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
1
0
0
0
0
0
0
0
0
Detected
below
Treatable .
Concentration
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
3
0
0
0
0
0
0
0
0
0
0
2
0
3
1
2
1
0
0
0
Detected
Above
Treatable
Concentration
,'
0
0
0
0
0
0
0
0
2
0
0
0
1
0
0
0
2
0
0
0
0
0
0
0
0
0
4
3
0
1
i
0
0
0
1
0
OT
W
n
-------
Table VI-1 (Continued)
FREQUENCY OF OCCURRENCE OF TOXIC POLLUTANTS
PRIMARY TUNGSTEN
RAW WASTEWATER
Pollutant
75. benza(k)fluarimthene
76. chrysene
77. acenafihthylene
78. anthracene (c)
79. benzo(gil)perylaM
80. fluorene
81. phavanthrow (c)
82. dlhenza(a,h)anthracene
83. lndeno(l.2.3-cd)pyrene
84. pyrene
85. tetradiloroethylane
86. toluene
U> 87. trlchloroethylene
0 88. vinyl chloride
J£ 89. aldrln
^ 90. dleldrln
91. chlordane
92. 4,4'-DOT
91. 4.4'-DOE
94. 4,4'-H»
95. alpha-endoBulfan
96. beta-endoaulfan
97. endoaulfan sulfate
98. endrln
99. endrln aldehyde
100. heptachlor
101. heptachlor epoxtda
102. alpha BHC
103. beta-BHa
104. gaima-BHC
105. delta-BHC
106. PCB-1242 (d)
107. tCB-1254 (d)
11)6. PCB-I22I (d)
109. PCB-1232
110. PCtt-1248
111. KB-1260
112. FCH-1016
(e)
(*)
(e)
Analytical
Quantification
Concentration
<«/!> (a)
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.005
O.OOS
0,005
O.OOS
O.OOS
0.005
0.005
0.005
0.005
O.OOS
0.005
O.OOS
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
O.OOS
0.005
0.005
0.005
Treatable NMber of limber at
Concentration Streams Samples
(««/l) (b) Analyzed Analysed
0.010 S J
0.010 S 7
0.010 5 7
0.010 5 7
0.010 S 1
0.010 S 1
0.010
0.010
0.010
0.010
0.010
o.o to
0.010
0.010
0.010
0.010
o.oio
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
1
1
7
7
12
12
12
12
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
0.010 3 3
0.010 3 a
0.010 3 3
0.010 3 3
0.010 3 3
0.010 3 3
fot
Detected
1
6
6
S
6
5
5
6
;
6
it
6
7
12
3
3
3
3
3
3
3
3
3
1
Detected Below
Quantification
Concent rat ton
u
0
0
2
0
1
I
0
0
1
5
3
5
0
U
0
0
0
0
0
1
0
u
0
0
0
0
0
0
0
0
2
2
2
2
2
2
2
Detected
Below
Treatable
Concentration
0
0
0
0
0
0
u
0
0
0
0
1
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
LfctecttO
About
Treatable
Concentration
0
1
1
0
I
I
0
1
0
u
J
2
0
U
u
u
0
0
u
0
0
0
0
0
u
0
u
0
0
u
0
0
0
0
0
u
0
u
W
M
O
H
-------
Table VI-1 (Continued)
FREQUENCY OF OCCURRENCE OF TOXIC POLLUTANTS
PRIMARY TUNGSTEN
RAW WASTEWATER
oo
o
a\
o
Pollutant
113. toxaphene
114. antUony
IIS. arsenic
116. tubcaloa
117. berylllin
118. cadnlin
119. chroBliM
120. copper
121. cyanide
122. lead
123. Mercury
124. nickel
123. selenliw
126. silver
127. thalllui
128. zinc
129. 2.3.7,8-tetrachlorodlbenzo-
p-dloxln (TCDD)
Analytical
Quantification
Concentration
ta/1) (a)
0.005
0.100
0.010
IOMFL
0.010
0.002
0.005
0.009
0.02(f)
0.020
0.0001
0.005
0.01
0.02
0.100
0.050
0.005
Treatable
Concentration
(ag/1) (b)
0.010
0.470
0.340
lOHfL
0.200
0.049
0.070
0.390
0.047
0.080
0.036
0.220
0.200
0.070
0.340
0.230
Nuber of
Stream
Analyzed
3
•
8
2
8
8
8
a
5
8
8
8
a
8
8
8
(tutor of
Saqplea
Analyzed
3
10
10
4
10
10
10
10
9
Mt
10
to
to
10
10
10
Not
Detected
3
7
4
4
9
8
7
4
1
9
3
9
10
5
9
4
Detected Below
Quantification
Concentration
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Detected
Below
Treatable
Concent ration
0
3
5
1
1
1
5
6
0
7
0
0
3
0
2
Delected
Above
Treatable
Concentration
0
0
1
0
1
2
1
2
1
0
1
0
2
1
4
Nat Analyzed
H
H
i
to
a
to
o
B
w
a
o
(a) Analytical quantification concentration waa reported with the data (aee Section V).
(b) Treatable concentrations are based on performance of llae precipitation, aedlaentatlon, and filtration for toxic a>etal pollutants anJ activated
carbon adsorption for toxic organic pollutants.
(c) Reported together for three sacaplea.
(d).(e) Reported together.
(f) Analytical quantification concentration for EPA Method 335.2. Total Cyanide Method* for Chmlcal Analysis of
Uater and Uaatea. EPA-600/4-79-020. March 1979.
W
O
-------
PRIMARY :• JNGSTEN SUBCATEGORY SECT - VI
TABLE VI-2
TOXIC POLLUTANTS NEVER DETECTED
2. acrolein
3. acrylonitrile
5. benzidine
6. carbon tetrachloride
7. chlorobenzene
8. lr2,4-trichlorobenzene
9. hexachlorobenzene
12. hexachloroethane
13. 1,1-diehloroethane
14. 1,1,2-trichloroethane
16. chloroethane
17. DELETED
18. bis(2-chloroethyl) ether
19. 2-chloroethyl vinyl ether
20. 2-chloronaphthalene
21. 2,4,6-trichlorophenol
22. parachlorometa cresol
24. 2-chlorophenol
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
28. 3,3'-dichlorobenzidine
30. 1,2-trans-dichloroethylene
31. 2,4-dichlorophenol
32. 1,2-dichloropropane
33. 1,3-dichloropropylene
34. 2 f 4-dintethylphenol
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. lf2-diphenylhydrazine
39. fluoranthene
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl)ether
43. bis(2-chloroethoxy)methane
44. methylene chloride
45. methyl chloride (chloromethane)
46. methyl bromide (bromomethane)
48. dichlorobromomethane
49. DELETED
50. DELETED
52. hexachlorobutadiene
53. hexaehlorocyclopentadiene
56. nitrobenzene
57. 2-nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
3063
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - VI
TABLE VI-2 (Continued)
TOXIC POLLUTANTS NEVER DETECTED
60. 4,6-dinitro-o-cresol
61. N-nitrosodimethylamine
62. N-nitrosodiphenylamine
63. N-nitrosodi-n-propylamine
64. pentachlorophenol
67. butyl benzyl phthalate
72. benzo(a)anthracene
74. 3,4-benzofluoranthene
75. benzo(k)fluoranthene
83. indeno (1,2,3-cd)pyrene
88. vinyl chloride
89. aldrin
90. dieldrin
91. chlordane
92. 4,4'-DDT
93. 4,4'-DDE
94. 4,4'-ODD
96. beta-endosulfan
97. endosulfan sulfate
98. endrin
99. endrin aldehyde
100. heptachlor
101. heptachlor epoxide
102. alpha-BHC
103. beta-BHC
104. ganuna-BHC
105. delta-BHC
113. toxaphene
116. asbestos
125. selenium
129. 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
3062
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - VII
SECTION VII
CONTROL AND TREATMENT TECHNOLOGIES
The preceding sections of this supplement discussed the sources,
flows, and characteristics of the wastewaters from primary
tungsten plants. This section summarizes the description of
these wastewaters,indicates the treatment technologies which are
currently practiced in the primary tungsten subcategory for each
wastewater stream and presents the control and treatment
technology options which were examined by the Agency for possible
application to the primary tungsten subcategory.
CURRENT CONTROL AND TREATMENT PRACTICES
Wastewater associated with the primary tungsten subcategory is
characterized by the presence of the toxic metal pollutants and
suspended solids. This analysis is supported by the raw
(untreated) wastewater data presented for specific sources as
well as combined wastewater streams in Section V. Generally,
these pollutants are present in each of the streams at treatable
concentrations, so these wastewaters are commonly combined for
treatment. Construction of one wastewater treatment system for
combined treatment allows plants to take advantage of economic
scale and in some instances to combine streams of different
alkalinity to reduce treatment chemical requirements. Four
plants in this subcategory currently have lime precipitation and
sedimentation treatment. Three of these plants operate this
treatment on combined wastewater. No plants in the subcategory
currently operate lime, settle, and filter treatment. As such,
three options have been selected for consideration for BPT, BAT,
and BDT, and pretreatment based on combined treatment of these
compatible waste streams.
TUNGSTIC ACID RINSE WATER
Tungstic acid is prepared by leaching ore concentrates with
hydrochloric acid and then rinsing the insoluble tungsten acid
with water. The two plants using this process practice lime and
settle treatment to precipitate metals before discharging the
rinse water. A third plant which produces a tungsten acid
intermediate by reacting HC1 with sodium tungstate neutralizes
the rinse water along with other wastes and then coagulates with
polymers and practices sedimentation.
ACID LEACH WET AIR POLLUTION CONTROL
Plants that acid leach use wet scrubbing systems for the control
of hydrochloric acid fumes. One plant discharges this acidic
wastewater after lime and settle treatment while a second
recycles the entire stream for use as tungsten acid rinse water.
3063
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PRIMARY TUNGSTEN SUBCATEGORY SECT - VII
ALKALI LEACH WASH
The four plants which use an alkali ore leaching process, such as
caustic digestion or a soda autoclave, generate a waste from the
decant washing of the sodium tungstate intermediate. None of the
plants discharge this waste stream. Two plants have reduced this
flow to zero by filtering the insoluble impurities and using a
combination of evaporation and recycle. Two plants discharge
this and all other wastes to a settling pond where the water
either evaporates or percolates into the ground.
MOLYBDENUM SULFIDE PRECIPITATION WET AIR POLLUTION CONTROL
Two plants use wet air pollution scrubbers on precipitation steps
that remove molybdenum impurities from sodium tungstate solution.
Neither plant discharges this wastewater. Both plants recycle
the spent scrubber liquor back to the process to recover any
tungsten captured.
ION-EXCHANGE RAFFINATE (COMMINGLED AND NOT COMMINGLED WITH OTHER
PROCESS AND NONPROCESS STREAMS)
When a liquid ion-exchange process is used to convert sodium
tungstate to ammonium tungstate, a raffinate stream is generated.
Of the four plants which utilize this process, one is a zero
discharge plant because it pumps all of its wastes, including the
ion-exchange raffinate, to a settling pond where the water
evaporates. Two plants, direct dischargers, treat this
wastewater with a lime and settle process; one of these plants
also adds polymer as a coagulant. The third plant recycles 50
percent of its wash water and discharges the remainder along with
the raffinate to an evaporation pond.
CALCIUM TUNGSTATE PRECIPITATION WASH
Calcium tungstate, also referred to as synthetic scheelite, is
precipitated when sodium tungstate crystals are dissolved and
then reacted with calcium chloride solution. The precipitated
crystals are allowed to settle, and the waste sodium chloride
supernatant can be decanted or the precipitate recovered by
filtration. Some plants also wash the precipitate. Of the six
plants which precipitate calcium tungstate, two have achieved
zero discharge status. These plants discharge all the wastes to
settling ponds. Three plants treat this wash water. Two use
lime and settle, and the third adds coagulation with polymers to
a lime and settle treatment. The sixth plant discharges this
waste without treatment.
CRYSTALLIZATION AND DRYING OF AMMONIUM PARATUNGSTATE
Ammonium paratungstate 'crystals are precipitated from a mother
liquor which will contain ammonia and possibly tungsten. For
this reason, three plants completely recycle and reprocess the
filtrate after recovering the ammonia for reuse. One plant
currently discharges the mother liquor to central lime and settle
3064
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PRIMARY TUNGSTEN SUBCATEGORY SECT - VII
treatment. If heating is used to dry the crystals, a baghouse is
used to contain particulates while the water vapor is evaporated
to the atmosphere. A fifth plant recycles and reuses some of.
this scrubber water, but discharges the majority of it to an
evaporation pond.
AMMONIUM PARATUNGSTATE CONVERSION TO OXIDES WET AIR POLLUTION
CONTROL
When ammonium paratungstate (APT) is converted to tungsten oxides
(WOX), ammonia is evolved. Most plants use a wet scrubbing
system to contain the fumes, and some use an ammonia recovery
system. Of the six plants which reported using this process and
generating a waste stream, one has reduced the flow to zero. This
is accomplished by recycle to a cooling tower and reuse. The
following treatment schemes are currently in place in the rest of
the subcategory:
1. No treatment of scrubber water, direct discharge - one
plant;
2. No treatment of scrubber water, indirect discharge - two
plants;
3. Lime and settle treatment of scrubber water with polymer
addition; and
4. Off-gases run through bubbling tank, fine particles
of tungsten material settle out, overflow from settling
tanks is indirectly discharged - one plant.
AMMONIUM PARATUNGSTATE CONVERSION TO OXIDES WATER OF FORMATION
The conversion of APT to oxides generates water of formation. In
some plants this water is recondensed in the APT conversion to
oxides scrubber system. Two plants condense this water in a
recovery system for the reduction furnace atmospheric gas. One
plant collects the water in drums and has it contract hauled. The
other plant evaporates 100 percent to the atmosphere.
REDUCTION TO TUNGSTEN WET AIR POLLUTION CONTROL
Tungsten oxides (WOX) are reduced to tungsten metal in rotary
reduction furnaces, usually under a hydrogen atmosphere. Seven
plants report using a wet scrubbing system to control particulate
emissions from these furnaces. The following treatment schemes
are currently in place:
1. No treatment of scrubber water, direct discharge - one
plant;
2. No treatment of scrubber water, indirect discharge - two
plants;
3. Lime and settle treatment with polymer addition - one
3065
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - VII
plant;
4. 100 percent recycle with cooling tower - two plants? and
5. 100 percent recycle with holding tank - one plant.
REDUCTION TO TUNGSTEN WATER OP FORMATION
Plants that reduce oxides to tungsten metal in a hydrogen
atmosphere may generate a water of formation as generalized by
the following reaction:
WOX + H2 -> W + H2O
The following treatment schemes are currently in place:
1. No treatment, direct discharger - three plants;
2. No treatment, indirect discharger - one plant;
3. 100 percent evaporation or reuse - one plant; and
4. Settle in sump, tungsten solids returned to furnace,
indirect discharger - one plant.
TUNGSTEN POWDER LEACH AND WASH
Two plants leach the tungsten powder product with acid to produce
a higher purity product. The wastewater consists of spent acid
and wash water. One plant neutralizes this wastewater with soda
ash, settles the solids for drying and recycle, and discharges to
a POTW. The other plant discharges this waste stream to a POTW
'without treatment.
CONTROL AND TREATMENT OPTIONS
The 'Agency examined three control and treatment technology
options between proposal and promulgation that are applicable to
the primary tungsten subcategory. The options selected for
evaluation represent a combination of in-process flow reduction,
preliminary treatment technologies applicable to individual waste
streams, and end-of-pipe treatment technologies. The
effectiveness of these technologies is presented in Section VII
of Vol. I.
Examination of the raw wastewater data does not show any arsenic
or selenium at or above treatable concentrations. Also, these
pollutants are not characteristic of the raw materials and
processing agents used in this subcategory. Therefore, Option D,
which includes activated aluminum adsorption, was not considered
as an appropriate treatment technology for this subcategory.
OPTION A
Option A for the primary tungsten subcategory requires control
3066
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PRIMARY TUNGSTEN SUBCATEGORY SECT - VII
and treatment technologies to reduce the discharge of wastewater
volume and pollutant mass.
The Option A treatment scheme consists of chemical precipitation
and sedimentation technology. Specifically, lime or some other
alkaline compound is used to precipitate toxic metal ions as
metal hydroxides. The metal hydroxides and suspended solids
settle out and the sludge is collected. Vacuum filtration is
used to dewater sludge.
Preliminary treatment consisting of ammonia steam stripping for
waste streams containing treatable concentrations of ammonia is
also included in Option A. Steam stripping is an efficient
method for reducing the ammonia concentrations, as well as for
recovering ammonia as a by-product. Steam stripping also
prevents the transfer of ammonia to the air.
Oil skimming is added as a preliminary step to remove oil and
grease from calcium tungstate (synthetic scheelite) precipitate
wash.
OPTION B
Option B for the primary tungsten subcategory consists of the
Option A (ammonia steam stripping, oil skimming, lime
precipitation and sedimentation) treatment scheme plus flow
reduction techniques to reduce the discharge of wastewater
volume.. In-process changes which allow for water recycle and
reuse are the principal control mechanisms for flow reduction.
OPTION C
Option C for the primary tungsten subcategory consists of all
control and treatment requirements of Option B (in-process flow
reduction, ammonia steam stripping, oil skimming, lime
precipitation and sedimentation) plus multimedia filtration
technology added at the end of the Option B treatment scheme.
Multimedia filtration is used to remove suspended solids,
including precipitates of metals, beyond the concentration
attainable by gravity sedimentation. The filter suggested is of
the gravity, mixed-media type, although other forms of filters,
such as rapid sand filters or pressure filters would perform
satisfactorily. The addition of filters also provides consistent
removal during periods of time in which there are rapid increases
in flows or loadings of pollutants to the treatment system.
LIMITATIONS TO TREATMENT OPTIONS
Streams with sulfate concentrations exceeding 1000 mg/1 may
interfere with stream stripping performance by plugging the
stripper column. This may necessitate more frequent column
cleaning and downtime than the Agency anticipated in the
promulgated rule. As a result, the treatment effectiveness
concentrations for ammonia presented in Section VII of Vol. I may
not be achievable for the high sulfate waste streams in the
3067
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PRIMARY TUNGSTEN SUBCATEGORY SECT - VII
primary tungsten subcategory. The only wastewater stream in the
primary tungsten subcategory which is expected to have the high
sulfate concentration is the ion exchange raffinate. The
ramifications of this are discussed in Section 10 of this
document.
CONTROL AND TREATMENT OPTIONS REJECTED
Two additional control and treatment options were considered
prior to proposing effluent limitations for this subcategory.
Activated carbon adsorption technology is not necessary since
toxic organic pollutants are not limited in this subcategory (see
discussion on regulated pollutant parameters in Section X).
Reverse osmosis technology was rejected because it is not
demonstrated in the nonferrous metals manufacturing category, nor
is it clearly transferable.
OPTION E
Option E for the primary tungsten subcategory consists of Option
C (in-process flow reduction, ammonia steam stripping, oil
skimming, lime precipitation and sedimentation) with the addition
of granular activated carbon technology at the end of the Option
C treatment scheme. The activated carbon process is utilized to
^control the discharge of toxic organics.
OPTION P
Option P for the primary tungsten subcategory consists of all of
the control and treatment requirements of Option C (in-process
flow reduction, ammonia steam stripping, oil skimming, lime
precipitation and sedimentation) plus reverse osmosis and
multiple-effect evaporation technology added at the end of the
Option C treatment scheme. Reverse osmosis is provided for the
complete recycle of the treated water by controlling the
concentration of dissolved solids concentrations. Multiple-
effect evaporation is used to dewater brines rejected from
reverse osmosis.
3068
-------
PRIMARY TUNGSTEN SUBCATEGORY
SECT - VIII
SECTION VIII
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS
This section describes the method used to develop the costs
associated with the control and treatment technologies of Options
A, B, and C discussed in Section VII for wastewaters from primary
plants. Plant-by-plant compliance costs for these
were revised following proposal. These revisions
incremental costs, above treatment already in place,
to comply with these effluent limitations and
The energy requirements of the considered options as
solid waste, and air pollution aspects are also
tungsten
options
calculate
necessary
standards.
well as
discussed.
TREATMENT OPTIONS COSTED FOR EXISTING SOURCES
Three treatment options have been considered for existing primary
tungsten sources. The options are summarized below and
schematically presented in Figures X-l through X-3 (pages 3119-
3121).
OPTION A
Option A consists of preliminary ammonia steam stripping
treatment and lime precipitation and sedimentation end-of-pipe
technology. Oil skimming is added as a preliminary step to
remove oil and grease from calcium tungstate (synthetic
scheelite) precipitate wash.
OPTION B
Option B consists of in-process flow reduction measures,
preliminary ammonia steam stripping and oil skimming treatment,
and lime precipitation and sedimentation end-of-pipe technology.
The in-process flow reduction measure consists of the recycle of
acid leach scrubber water, APT conversion to oxides scrubber
water, and reduction to tungsten scrubber water through holding
tanks.
OPTION C
Option C requires the in-process flow reduction measures of
Option B, preliminary ammonia steam stripping and oil skimming
treatment, and end-of-pipe treatment technology consisting of
lime precipitation, sedimentation, and multimedia filtration.
Cost Methodology
A detailed discussion of the methodology and the major
assumptions used to develop the compliance costs is presented in
Section VIII of Vol. I. However, each subcategory contains a
unique set of waste streams requiring certain subcategory-
3069
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PRIMARY TUNGSTEN SUBCATEGORY SECT - VIII
specific assumptions to develop compliance costs. Six major
assumptions are discussed briefly below. A comparison of the
costs developed for proposal and the revised costs for the final
regulation are presented in Tables VIII-1 and VIII-2 (page 3073)
for the direct and indirect dischargers, respectively.
(1) For ammonia steam stripping, the design value for pH
is 11.5 and the design effluent concentration of
ammonia is 32.0 mg/1.
(2) Ammonia steam stripping requirements may exceed the
excess steam generation capacity at any given plant.
Therefore, a steam generation unit is included in the
steam stripping costs.
(3) The lime dosage to the ammonia steam stripping process
is based on the influent pH and the concentration of
ammonia.
(4) Costs for plants discharging less than 50 gallons per
week of total flow are based on contract hauling of
the entire discharge.
(5) Costs for ammonia removal for streams with flow rates
below 50 liters per hour (none of which are air
pollution streams) are estimated using an air stripping
system. Ammonia steam stripping is not considered
feasible due to insufficient hydraulic loading in the
stripping column (given the minimum column diameter of
2 feet used in cost estimation). The chemical
precipitation tank is used for the air stripping
operation. Chemical precipitation is always operated in
the "low flow" batch treatment mode with a five day
holdup due to the low flow rate . An air sparger is
incorporated into the reactor tank. The influent is
sparged while the tank fills with wastewater, i.e.,
over the entire five day holdup period. A hood is
placed over the tank to capture any ammonia-laden
vapors.
Direct capital costs for the ammonia air stripping
system include a blower, a sparger system, and a
ventilation hood. Direct annual costs are assumed to
consist solely of blower operation and maintenance
costs. These are assumed to be 5 percent of the
blower capital cost.
(6) Recycle of air pollution control scrubber liquor is
based on recycle through holding tanks. Annual costs
associated with maintenance and sludge disposal are
included in the estimated compliance costs. If a
plant currently recycles scrubber liquor, capital
costs of the recycle equipment (piping and holding
3070
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - VIII
tanks) were not included in the compliance costs.
NONWATER QUALITY ASPECTS
Nonwater quality impacts specific to the primary tungsten
subcategory, including energy requirements, solid waste and air
pollution are discussed below.
ENERGY REQUIREMENTS
The methodology used for determining the energy requirements for
the various options is discussed in Section VIII of the General
Development Document. Energy requirements for the three options
considered are estimated at 6.32 mwh/yr, 5.48 mwh/yr and 5.55
mwh/yr for Options A, B, and C respectively. Option B energy
requirements decrease over those for Option A because less water
is being treated, thus saving energy costs for lime and settle
treatment. Option C represents roughly one percent of a typical
plant's electrical usage. It is therefore concluded that the
energy requirements of the treatment options considered will have
no significant impact on total plant energy consumption. Option
C, which includes filtration, is estimated to increase energy
consumption over Option B by approximately 1 percent.
SOLID WASTE
Sludge generated in the primary tungsten subcategory is due to
the precipitation of metal hydroxides and carbonates using lime.
Sludges associated with the primary tungsten subcategory will
necessarily contain additional quantities (and concentrations) of
toxic metal pollutants. Wastes generated by primary smelters and
refiners are currently exempt from regulation by Act of Congress
(Resource Conservation and Recovery Act (RCRA), Section 3001(b)),
as interpreted by EPA. Consequently, sludges generated from
treating primary industries' wastewater are not presently subject
to regulation as hazardous wastes. If a small excess (5-10%) of
lime is added during treatment, the Agency does not believe these
sludges would be identified as hazardous under RCRA in any case.
(Compliance costs include this amount of lime.)
Although it is the Agency's view that solid wastes generated as a
result of these guidelines are not expected to be hazardous,
generators of these wastes must test the waste to determine if
the wastes meet any of the characteristics of hazardous waste
(see 40 CFR 262.11).
If these wastes should be identified or are listed as hazardous,
they will come within the scope of RCRA's "cradle to grave"
hazardous waste management program, requiring regulation from the
point of generation to point of final disposition. EPA's
generator standards would require generators of hazardous
nonferrous metals manufacturing wastes to meet containerization,
labeling, recordkeeping, and reporting requirements; if plants
dispose of hazardous wastes off-site, they would have to prepare
a manifest which would track the movement of the wastes from the
3071
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - VIII
generator's premises to a permitted off-site treatment, storage,
or disposal facility. See 40 CFR 262.20 45 FR 33142 (May 19,
1980), as amended at 45 FR 86973 (December 31, 1980). The
transporter regulations require transporters of hazardous wastes
to comply with the manifest system to assure that the wastes are
delivered to a permitted facility. See 40 CFR 263.20 45 FR 33151
(May 19, 1980), as amended at 45 FR 86973 (December 31, 1980).
Finally, RCRA regulations establish standards for hazardous waste
treatment, storage, and disposal facilities allowed to receive
such wastes. See 40 CFR Part 464 46 FR 2802 (January 12, 1981),
47 FR 32274 (July 26, 1982).
Even if these wastes are not identified as hazardous, • they still
must be disposed of in compliance with the Subtitle D open
dumping standards, implementing 4004 of RCRA. See 44 FR 53438
(September 13, 1979). The Agency has calculated as part of the
costs for wastewater treatment the cost of hauling and disposing
of these wastes. For more details, see Section VIII of the
General Development Document. EPA estimates that implementation
of lime, settle, and filter technology will produce approximately
1,212 tons per year of sludge at 20 percent solids. Multimedia
filtration technology will not result in any significant amount
of sludge over that generated from lime precipitation.
AIR POLLUTION
There is no reason to believe that any substantial air pollution
problems will result from implementation of ammonia steam
stripping, chemical precipitation, sedimentation, and multimedia
filtration. These technologies transfer pollutants to solid
waste and are not likely to transfer pollutants to air.
At three primary tungsten plants, streams with treatable
concentrations of ammonia having flows less than 50 1/hr were
treated with air stripping for design and cost determination.
None of the waste streams were air pollution control streams.
The air stripping is accomplished by aeration and agitation in
the chemical precipitation batch tank, which includes a
ventilation hood. Air stripping is not a model treatment
technology because it simply transfers the ammonia from one
medium to another, whereas steam stripping allows for ammonia
recovery, and if desired, reuse. Air stripping was used in cost
estimation instead of steam stripping because at such low flow,
continuous operation of steam strippers is not feasible.
Therefore, the treatable concentration for ammonia would be
difficult to attain. The Agency does not believe that under
these circumstances (low flow, non-air pollution control streams)
that air stripping will create an air quality problem.
3072
-------
PRIMARY TUNGSTEN SQBCATEGORY SECT - VIII
TABLE VIII-1
COST OF COMPLIANCE FOR THE PRIMARY TUNGSTEN SUBCATEGORY
DIRECT DISCHARGERS
(March, 1982 Dollars)
Proposal Costs Promulgation Costs
Option Capital Cost Annual Cost Capital Cost Annual Cost
A
B
C
0
458000
608000
0
74800
262000
619000
647000
773000
1008000
943000
1008000
TABLE VIII-2
COST OF COMPLIANCE FOR THE PRIMARY TUNGSTEN SUBCATEGORY
INDIRECT DISCHARGERS
(March, 1982 Dollars)
Proposal Costs Promulgation Costs
Option Capital Cost Annual Cost Capital Cost Annual Cost
A
B
C
575000
777000
538000
272000
302000
447000
529000
504000
568000
485000
407000
445000
3073
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - VIII
THIS PAGE INTENTIONALLY LEFT BLANK
3074
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PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY
CURRENTLY AVAILABLE
This section defines the effluent characteristics attainable
through the application of best practicable control technology
currently available (BPT). BPT reflects the existing performance
by plants of various sizes, ages, and manufacturing processes
within the primary tungsten subcategory, as well as the
established performance of the recommended BPT systems.
Particular consideration is given to the treatment already in
place at plants within the data base.
The factors considered in identifying BPT include the total cost
of applying the technology in relation to the effluent reduction
benefits from such application, the age of equipment and
facilities involved, the manufacturing processes used, nonwater
quality environmental impacts (including energy requirements),
and other factors the Administrator considers appropriate. In
general, the BPT level represents the average of the existing
performances of plants of various ages, sizes, processes, or
other common characteristics. Where existing performance is
uniformly inadequate, BPT may be transferred from a different
subcategory or category. Limitations based on transfer of
technology are supported by a rationale concluding that the
technology is, indeed, transferable, and a reasonable prediction
that it will be capable of achieving the prescribed effluent
limits (see Tanner *s Council of America v. Train, 540 P.2d 1188)
(4th Cir. 1976). BPT focuses on end-of-pipetreatment rather
than process changes or internal controls, except where such
practices are common industry practice.
TECHNICAL APPROACH TO BPT
The Agency studied the nonferrous metals category to identify the
processes used, the wastewaters generated, and the treatment
processes installed. Information was collected from industry
using data collection portfolios, and specific plants were
sampled and the wastewaters analyzed. Some of the factors which
must be considered in establishing effluent limitations based on
BPT have already been discussed. The age of equipment and
facilities, processes used, and raw materials were taken into
account in subcategorization and subdivision and are discussed
fully in Section IV. Nonwater quality impacts and energy
requirements are considered in Section VIII.
The primary tungsten subcategory has been subdivided into 14
potential wastewater sources. Since the water use, discharge
rates, and pollutant characteristics of each of these wastewaters
is potentially unique, effluent limitations will be developed fo.r
each of these building blocks.
3075
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PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
For each of the subdivisions, a specific approach was followed
for the development of BPT mass limitations. To account for
production and flow variability from plant to plant, a unit of
production or production normalizing parameter (PNP) was
determined for each waste stream which could then be related to
the flow from the process to determine a production normalized
flow. Selection of the PNP for each process element is discussed
in Section IV. Each process within the subcategory was then
analyzed to determine whether or not operations included
generated wastewater, specific flow rates generated, and the
specific production normalized flows for each process. This
analysis is discussed in detail in Section V. Nonprocess
wastewater such as rainfall runoff and noncontact cooling water
is not considered in the analysis.
Normalized flows were analyzed to determine which flow was to be
used as part of the basis for BPT mass limitations. The selected
flow (sometimes referred to as a BPT regulatory flow or BPT
discharge flow) reflects the water use controls which are common
practices within the industry. The BPT normalized flow is based
on the average of all applicable data. Plants with normalized
flows above the average may have to implement some method of flow
reduction to achieve the BPT limitations. In most cases, this
will involve-improving housekeeping practices, better maintenance
to limit water leakage, or reducing excess flow by turning down a
flow valve. It is not believed that these modifications would
incur any costs for the plants.
For the development of effluent limitations, mass loadings were
calculated for each wastewater source or subdivision. This
calculation was made on a stream-by-stream basis, primarily
because plants in this category may perform one or more of the
operations in various combinations. The mass loadings
(milligrams of pollutant per metric ton of production unit
mg/kkg) were calculated by multiplying the BPT normalized flow
(1/kkg) .by the treatability concentration using the BPT treatment
system (mg/1) for each pollutant parameter to be limited under
BPT.
The Agency usually establishes wastewater limitations in terms of
mass rather than concentration. This approach prevents the use
of dilution as a treatment method (except for controlling pH).
The production normalized wastewater flow (1/kkg) is a link
between the production operations and the effluent limitations.
The pollutant discharge attributable to each operation can be
calculated from the normalized flow and effluent, concentration
achievable by the treatment technology and summed';to derive an
appropriate limitation for each subcategory.
<».
BPT effluent limitations are based on the .average of the
discharge flow rates for' each source; consequently, the treatment
technologies which are currently used by the lowest' dischargers
will be the treatment technologies most likely required to meet
BPT limitations. Section VII discusses the various treatment
technologies which are currently in place for feach wastewater
3076
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
source. In most cases, the current treatment technologies
consist of chemical precipitation and sedimentation (lime and
settle technology) and a combination of reuse and recycle to
reduce flow. Ammonia steam stripping is added to streams
containing treatable concentrations of ammonia. Oil skimming is
added to remove oil and grease from calcium tungstate (synthetic
scheelite) wash. Consequently, the typical BPT treatment scheme
will consist of ammonia steam stripping (if needed), oil skimming
(if needed), chemical precipitation, and sedimentation. This BPT
treatment scheme is presented schematically in Figure IX-1 (page
3097).
The overall effectiveness of end-of-pipe treatment for the
removal of wastewater pollutants is improved by the application
of water flow controls within the process to limit the volume of
wastewater requiring treatment. The controls or in-process
technologies recommended under BPT include only those measures
which are commonly practiced within the subcategory and which
reduce flows to meet the production normalized flow for each
operation.
In making technical assessments of data, reviewing manufacturing
processes, and assessing wastewater treatment technology options,
both indirect and direct dischargers have been considered as a
single group. An examination of plants and processes did not
indicate any process differences based on the type of discharge,
whether it be direct or indirect.
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
In balancing costs in relation to pollutant removal estimates,
EPA considers the volume and nature of existing discharges, the
volume and nature of discharges expected after application of
BPT, the general environmental effects of the pollutants, and the
cost and economic impacts of the required pollution control
level. The Act does not require or permit consideration of water
quality problems attributable to particular point sources or
industries, or water quality improvements in particular water
quality bodies. Accordingly, water quality considerations were
not the basis for selecting the proposed BPT. See Weyerhaeuser
Company v. Costle, 590 F.2d 1011 (D.C. Cir. 1978).
The methodology for calculating pollutant removal estimates and
plant compliance costs is discussed in Section X. The pollutant
removal estimates have been revised since proposal based on
comments and on new data. Table X-2 (page 3109) shows the
pollutant removal estimates for each treatment option.
Compliance costs for direct dischargers are presented in Table
VIII-1 (page 3073).
BPT OPTION SELECTION
The technology basis for the BPT limitations is Option A,.
chemical precipitation and sedimentation technology to remove
metals and solids from combined wastewaters and to control pH,
3077
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
ammonia steam stripping preliminary treatment to remove ammonia,
and oil skimming preliminary treatment to remove oil and grease
(if necessary). The promulgated technology is equivalent to the
proposed technology, with the exception of oil skimming. Lime
and settle technology is currently demonstrated at three of the
four direct discharging plants in this subcategory. The BPT
treatment scheme is presented in Figure IX-l(page 3088).
Ammonia steam stripping is demonstrated in the nonferrous metals
manufacturing category, including three primary tungsten plants.
As discussed in detail in Section VII of Vol. I, EPA believes
that performance data from the iron and steel manufacturing
category provide a valid measure of this technology's performance
on nonferrous metals manufacturing category wastewater because
raw wastewater concentrations of ammonia are of the same order of
magnitude in the respective raw wastewater matrices.
Chemical analysis data were collected of raw waste (treatment
influent) and treated waste (treatment effluent) from one coke
plant of the iron and steel manufacturing category. A contractor
for EPA, using EPA sampling and chemical analysis protocols,
collected data paired samples in a two-month period. These data
are the data base for determining the effectiveness of ammonia
steam stripping technology and are contained within the
administrative record supporting this document. Ammonia
treatment at this coke plant consisted of two steam stripping
columns in series with steam injected countercurrently to the
flow of the wastewater. A lime reactor for pH adjustment
separated the two stripping columns.
The raw untreated wastewater samples from the coke facility
contained ammonia concentrations of 599, 226, 819, 502, 984, and
797 mg/1. The raw untreated wastewater from the primary tungsten
subcategory contained treatable ammonia concentrations ranging
from 134 to 1,790 mg/1.
The iron and steel data are supported by ammonia steam stripping
performance data from a well-operated zirconium-hafnium plant in
the nonferrous metals manufacturing category. The long-term mean
and variability of the data collected in a one year period agree
with the coke plant data.
As discussed in Section VII of this document, steam stripping may
not achieve the treatment effectiveness concentrations for
ammonia for the ion exchange raffinate if this stream contains
high concentrations of sulfates. Sulfate concentrations
exceeding 1000 mg/1 may interfere with steam stripping
performance by plugging the stripper column, resulting in
frequent cleaning and downtime. As a result of the litigation
settlement, EPA has proposed suspending, under limited
circumstances, the ammonia treatment effectiveness concentration
value for the ion-exchange raffinate building block. These
circumstances are: (a) where the influent (called "mother
liquor") to or effluent (called "raffinate") from this process
contains sulfates at concentrations exceeding 1000 mg/1 ("high
3078
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
sulfate influent or effluent"); (b) where the high sulfate
influent or effluent is treated by ammonia steam stripping; and
(c) where this high sulfate raffinate or mother liquor is not
commingled with other wastestreams before treatment for steam
stripping for ammonia removal.
In the event a plant satisfies these conditions, mass limitations
will be established on a Best Professional Judgment ("BPJ") basis
by a permit writer pursuant to 40 CFR 125.3(c)(2) and (3) using
the regulatory flows used as the basis for the promulgated
effluent limitation guidelines and standards established in this
proceeding and treatment effectiveness concentration values
determined by the permit writer.
Oil skimming is added to remove oil and grease from calcium
tungstate (synthetic scheelite) precipitate wash. Although oil
and grease is not limited under this regulation, oil skimming is
needed for BPT to ensure proper metals removal. Oil and grease
interfere with the chemical addition and mixing required for
chemical precipitation treatment.
Implementation of the promulgated BPT limitations will remove an
estimated 4,800 kg/yr of toxic metals, 141,000 kg/yr of ammonia,
and 50,300 kg/yr of TSS from raw wastewater. EPA projects
$115,000 (March, 1982 dollars) in capital costs and $168,000
(March, 1982 dollars) in annual costs for achieving the
promulgated BPT. These costs represent wastewater treatment
equipment not in place.
WASTEWATER DISCHARGE RATES
A BPT discharge rate is calculated for each subdivision based on
the average of the flows of the existing plants, as determined
from analysis of dcp. The discharge rate is used with the
achievable treatment concentrations to determine BPT effluent
limitations. Since the discharge rate may be different for each
wastewater source, separate production normalized discharge rates
for each of the 14 wastewater sources are discussed below and
summarized in Table IX-1 (page 3088). The discharge rates are
normalized on a production basis by relating the amount of
wastewater generated to the mass of the intermediate product
which is produced by the process associated with the waste stream
in question. As a result of the litigation settlement, EPA is
proposing to modify the production basis for determining the
amount of pollutant which may be discharged to the amount of the
element tungsten produced or processed. As discussed in Section
V, in the final regulation, EPA used the chemical salt form of
tungsten which was believed appropriate for the processing step
or building block being regulated. However, petitioners stated
that the chemical formulas were incorrect and confusing. Using
the element tungsten produced or processed as a production
normalizing parameter rather than a chemical compound makes the
production basis clear and unambiguous. This change will affect.
all of the building blocks except for 8421.102(i) through (k),
8421.103(i) through (k), 8421.104(i) through (k), 8421.105(i)
3079
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
through (k), and 8106(i) through (k), which were already based on
the amount of elemental tungsten produced. This change will
affect the regulatory flows for these building blocks, which are
based on the production normalizing parameter. These production
normalizing parameters, or PNPs, are also listed in Table IX-1.
After proposal, EPA became aware of nine primary tungsten plants
which were not previously included in the subcategory.
Wastewater flow- rates and production data were solicited from
these plants through dcp. Some data from plants already in the
Agency's data base were updated and revised because of comments
received concerning the proposed regulation. This information
was collected by telephone contacts. The new data were used to
revise production normalized flow rates and recalculate
regulatory flow allowances where appropriate.
Section V of this document further describes the discharge flow
rates and presents the water use and discharge flow rates for
each plant by subdivision in Tables V-l through V-ll (pages 2989-
2996).
TUNGSTIC ACID RINSE WATER
The BPT wastewater discharge rate at proposal for tungstic acid
rinse water was 47,600 1/kkg (11,400 gal/ton) of tungstic acid
produced. This rate was allocated only for those plants which
acid leach ore concentrates and then rinse the insoluble tungstic
acid with water. Two plants leached ore concentrates in this
manner and generated 57,600 and 37,600 1/kkg of wastewater.
A third plant generated a tungstic acid rinse water from an acid
leaching step, but this production normalized flow was much
larger than the other flows in this subdivision and was not
included in the calculations. This stream was considered unique
because an alkali leaching product, not ore concentrates, were
leached, and the tungstic acid produced was more thoroughly
rinsed and dried in preparation for sale as a by-product.
Consequently, the BPT flows at proposal were based on data from
the first two plants while the third one mentioned above should
be considered unique and regulated on a case-by-case basis.
The BPT wastewater discharge rate at promulgation for tungstic
acid rinse was 30,190 1/kkg (7,240 gal/ton) of tungstic acid
produced. After proposal, plant 9014 updated its flow for this
waste stream by submitting a revised dcp. The revised flow is
2,780 1/kkg. The two other plants have not changed their
processes. Consequently, the BPT flow is based on the average of
the discharge from plants 9011 and 9014. As a result of the
change in production normalizing parameter in the litigation
settlement, the final BPT wastewater discharge rate is 41,030
1/kkg (9,839 gal/ton) of tungstic acid (as W) produced. Water
use and wastewater discharge rat^s are presented in Table V-l
(page 2989).
3080
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
ACID LEACH WET AIR POLLUTION CONTROL
The BPT wastewater discharge rate at proposal for acid leach
scrubber water was 37/700 1/kkg (9,040 gal/ton) of tungstic acid
produced. This rate was allocated only for those plants which
acid leach ore concentrates and use a wet scrubbing system to
control the fumes. Two plants which treated ore concentrates in
this manner use water for emission control. Water use and
wastewater discharge rates are presented in the proposed primary
tungsten supplement. One plant reported a once-through flow of
37,700 1/kkg while the second reported no generation of
wastewater due to total recycle. Extensive recycle may be
possible for this stream, but zero discharge may not be
technically feasible unless a recycle system controls dissolved
solids build-up, the wastewater is evaporated, or there is a
production operation which can accept the quality of treated
wastewater. Some of these zero discharge possibilities are site
specific and, hence, may not apply to all plants. For this
reason, the BPT flow at proposal was based on the non-zero
discharger flows only, and in this case, there was only one non-
zero discharger.
The BPT wastewater discharge rate at promulgation for acid leach'
wet air pollution control was 26,350 1/kkg (6,319 gal/ton) of
tungstic acid produced. Plant 9014 reuses its scrubber water as
tungstic acid rinse water. At proposal the Agency considered
this zero discharge and did not include the flow in the
calculation of the regulatory allowance. However, the Agency
believes this reuse practice is site specific and should not
preclude the use of this scrubber data in the calculation of a
flow allowance. The acid leach scrubber flow allowance is based
on the scrubber water use, not the discharge. Therefore, the BPT
flow is the average production normalized water use at the two
plants. As a result of the change in the final PNPs, the final
BPT wastewater discharge rate is 35,810 1/kkg (8,587 gal/ton) of
tungstic acid (as W) produced. Water use and discharge rates for
this stream are shown in Table V-2 (page 2989).
ALKALI LEACH WASH
The BPT wastewafcer discharge rate at proposal for alkali leach
wash was 46,700 1/kkg (11,200 gal/ton) of sodium tungstate
produced. It was the average of two plants generating this
wastewafcer. This rate was allocated only for those plants which
use an alkaline leaching step to process ore concentrates
followed by a filtering or wash/decant step. Of the four plants
which alkali leach, only two reported generating a wastewater, at
rates of 10,700 1/kkg and 82,600 1/kkg. The two plants which
report zero discharge from the alkali leaching step were not
considered in the regulatory flow since zero discharge is
feasible in only a few site-specific applications as explained
above.
No wastewater discharge allowance for alkali leach wash will be
provided for the promulgated BPT. New data received by the
3081
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
Agency show that one of the four plants with this waste stream at
proposal no longer practices alkali leaching while another plant
added to the data base after proposal reports generating this
wastewater. Water use and discharge rates are presented in Table
V-3 (page 2990). Analysis of the data shows that all four plants
with this stream evaporate this wastewater by either artificial
means or evaporation ponds. Since zero discharge of alkali leach
wash is practiced at all four plants/ no discharge allowance is
necessary.
ALKALI LEACH WASH CONDENSATE
As a result of data provided after the promulgation of this
regulation, EPA has proposed a BPT discharge allowance based on
a wastewater discharge rate for alkali leach wash condensate of
19,180 1/kkg (4,599 gal/ton) of sodium tungstate (as W) produced.
This flow is based on the flow rate at the sole plant which
provided data.
MOLYBDENUM SULFIDE PRECIPITATION WET AIR POLLUTION CONTROL
No BPT wastewater discharge allowance will be provided for
molybdenum sulfide precipitation wet air pollution control. Two
plants added to the subcategory since proposal report the use of
wet scrubbing systems to control hydrogen sulfide fumes evolved
during precipitation of molybdenum impurities from sodium
tungstate solution. Therefore, the Agency added this subdivision
to the subcategory for promulgation. Water use and production
data submitted were incomplete for both plants; however, both
plants completely reuse this wastewater in the primary tungsten
process. Since this practice is demonstrated in both plants in
the subcategory with this waste stream, no flow allowance is
necessary.
ION-EXCHANGE RAFFINATE (COMMINGLED AND NOT COMMINGLED WITH OTHER
PROCESS AND NONPROCESS STREAMS)
The BPT wastewater discharge rate at proposal for ion-exchange
raffinate was 51,200 1/kkg (12,300 gal/ton) of ammonium tungstate
produced. This rate was allocated only to those plants which use
a liquid ion-exchange process. The two plants operating ion-
exchange processes at proposal generated raffinate streams at
flows of 29,800 1/kkg and 72,500 1/kkg. Water use and wastewater
discharge rates are presented in the proposed primary tungsten
supplement. These values were averaged to calculate the
regulatory flow. The plant which generated the 72,500 1/kkg of
wastewater is a zero discharge plant, but this flow was still
included in the calculation since its ability to achieve zero
discharge through an end-of-pipe treatment (evaporation and
percolation from a settling pond) is site-specific.
The BPT wastewater discharge allowance at promulgation for ion-
exchange raffinate was 50,707 1/kkg (12,160 gal/ton) of ammonium
tungstate produced. The two plants with this stream at proposal
updated their flows and production. Two other plants were added
3082
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
to the data base because of new data submittals. Water use and
discharge rates are presented in Table V-4 (page 2990). The BPT
flow is based on the average discharge from three of the four
plants. One plant was not used in the average because its data
were collected during plant startup and reflected extremely high
water use. The Agency does not believe this plant's data are
representative of a normal operating ion-exchange process. As a
result of the change in production normalizing parameter the
final BPT wastewater discharge rate is 88,480 1/kkg (21,220
gal/ton) of ammonium tungstate (as W) produced.
CALCIUM TUNGSTATE PRECIPITATE WASH
The BPT wastewater discharge rate at proposal for calcium
tungstate precipitate wash was 37,200 1/kkg (8,920 gal/ton) of
calcium tungstate produced. This rate was allocated only to
those plants which precipitate calcium tungstate from a sodium
tungstate solution by adding calcium chloride. The filtrate or
rinses of the precipitate make up this wastewater. At proposal,
all four plants which precipitate calcium tungstate report
generating a wastewater, although the data was insufficient to
quantify the flow from one plant. The BPT flow rate was the
average of the remaining three flows, which ranged from 21,000
1/kkg to 65,800 1/kkg. The plant inside this range was actually
a zero discharge plant, but its flow generation rate is still
used in calculation since its ability to achieve zero discharge
status is site-specific.
The BPT wastewater discharge allowance at promulgation was 47,140
1/kkg (11,305 gal/ton) of calcium tungstate produced. Data were
collected from the plant that reported insufficient data at
proposal. Two additional plants were included based on new dcp
submittals. The data from one of these plants (# 9030) were
collected during plant startup and reflected extremely high water
use. The Agency does not believe these data are representative
of a normal operating ion-exchange process. The BPT flow is
based on the average of five plants excluding plant 9030. As a
result of the change in production normalizing parameter the
final BPT wastewater discharge rate is 73,810 1/kkg (17,700
gal/ton) of calcium tungstate (as W) produced. Water use and
discharge rates are presented in Table V-5 (page 2991).
CRYSTALLIZATION AND DRYING OF AMMONIUM PARATUNGSTATE
No BPT wastewater discharge rate was provided for the
crystallization and drying of ammonium paratungstate at proposal.
Of the four plants which crystallized and then dried ammonium
paratungstate, three were direct dischargers which had reduced
the flow of this wastewater to zero through a combination of
reuse and recycle. The fourth plant was a zero discharge plant
which pumped its wastes to a settling pond. Water use and
discharge rates are presented in the proposed primary tungsten
supplement. Since the plants in this category demonstrated the
ability to reduce the flow of this stream to zero, it was
considered appropriate that the BPT regulatory flow should be
3083
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
zero.
Ho BPT wastewater discharge rate is provided for promulgation of
the crystallization and drying of ammonium paratungstate stream.
One plant was added to the data base based on a new dcp
submittal. This plant achieves 100 percent reuse of the water
using a settling pond. Three plants achieve zero discharge
through combinations of ammonia recovery, recycle, and
evaporation. The fifth plant practices partial evaporation and
has an ammonia recovery system which is currently not operating.
Since the plants with this stream have demonstrated the ability
or have the capacity to reduce the flow to zero, it is
appropriate that the BPT regulatory flow be zero. The water use
and discharge rates are presented in Table V-6 (page 2992).
AMMOKIUM PARATUNGSTATE CONVERSION TO OXIDES WET AIR POLLUTION
CONTROL
The BPT wastewater discharge rate at proposal for the APT
conversion to oxides step was 20,900 1/kkg (5,010 gal/ton) of
"blue" oxide (WO3) produced. This rate was allocated only to
those plants which calcined APT to drive off ammonia and produce
tungsten oxides (assumed to be WO3). Most plants used a wet
scrubbing system to contain the fumes, and some used an ammonia
recovery system. Of the six plants which reported using this
process and generating a waste stream, two reduced this flow to
zero through combinations of recycle, reuse, and evaporation.
These two plants were not considered in the BPT flow calculations
since zero discharge was feasible in only a few site-specific
applications. Water use and wastewater discharge rates are
presented in the proposed primary tungsten supplement. The flow
rates from the four direct and indirect dischargers which were
averaged to develop the production normalized BPT flow allowance
range from 7,430 1/kkg to 36,800 1/kkg.
The BPT wastewater discharge rate at promulgation for APT
conversion to oxides wet air pollution control was 21,900 1/kkg
(5,252 gal/ton) of tungstic oxide (WO3> produced. Since proposal
the Agency has determined that the wastewater reported at two
plants for this stream is actually APT conversion to oxide water
of formation. A separate building block was created for this
wastewater (see below). Two additional plants were included
based on new dcp submittals. Since recycle of this wastewater is
not currently practiced, the BPT rate is based on the average
discharge from the five plants discharging from this process. As
a result of the change in production normalizing parameter, the
final BPT wastewater discharge rate is 27,620 1/kkg (6,623
gal/ton) of tungstic oxide (as W) produced. Water use and
discharge rates are presented in Table V-7 (page 2993).
AMMONIUM PARATUNGSTATE CONVERSION TO OXIDES WATER OP FORMATION
The BPT wastewater discharge rate at promulgation for APT
conversion to oxides water of formation was 50 1/kkg (12 gal/ton)
of tungstic oxide (WO3) produced. As a result of the change in
3084
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
production normalizing parameter in the litigation settlement,
the final BPT wastewater discharge rate is 63 1/kkg (15 gal/ton)
of tungstic oxide (as W) produced.
As discussed above, the Agency determined that for two plants,
the wastewater reported at proposal for APT conversion to oxides
wet air pollution control was actually water of formation.
Therefore, a new subdivision was created in the primary tungsten
subcategory after proposal. One of the plants collects the
wastewater in drums and disposes of it by contract hauling. This
plant did not report flow information. The second plant
evaporates all of the water. Since complete evaporation may be
site-specific to the one plant, and is not demonstrated in the
other plant, an allowance is provided. The allowance is equal to
the discharge flow from the plant reporting complete flow and
production data. Water use and discharge rates are shown in
Table V-8 (page 2994).
REDUCTION TO TUNGSTEN WET AIR POLLUTION CONTROL
The BPT wastewater discharge rate at proposal for reduction to
tungsten metal scrubber water was 73,200 1/kkg (17,500 gal/ton)
of tungsten produced. This rate was allocated only to those
plants which use a wet air pollution control system to control
particulate emissions from furnaces used to reduce tungsten
oxides (WOX) to tungsten metal. Five of the seven reporting
plants that produce tungsten metal in this manner used a wet
scrubbing system. Two of these five claimed to have reduced this
flow to zero through 100 percent recycle. Extensive recycle was
demonstrated for this stream, but a zero discharge may not be
technically feasible unless a recycle system controls dissolved
solids build-up, the wastewater is evaporated, or there is a
production operation which can accept the quality of the treated
wastewater. Some of these zero discharge possibilities were
site-specific and, hence, are not applicable on a nationwide
basis. For this reason, BPT flow was based on the non-zero
discharger flows only. Of the three dischargers, one had a flow
which was six times greater than the others. Since there was no
technical basis for this, it was not considered when the two
other flows, at 80,500 1/kkg and 65/900 1/kkg, were averaged.
The BPT wastewater discharge rate at promulgation for reduction
to tungsten wet air pollution control is 30,802 1/kkg (7,387
gal/ton) of tungsten metal produced. Two plants were added to
the data base for this stream because of new dcp submittals.
Plant 9014 revised its flow data to reflect current practice.
Three plants practice 100 percent recycle of this wastewater. All
three of these plants are extremely high water users and all are
zero discharging plants. These plants were not included in the
calculation of the regulatory flow. One plant, which does not
practice recycle, reports a flow which is over 10 times the
average flow of the other dischargers. The Agency believes there
is no technical basis for this variation and this flow was not
included in the calculation. The BPT flow is based on the
average water use at plants 9014, 9018, and 9029. Water use and
3085
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
discharge rates are presented in Table V-9 (page 2995).
REDUCTION TO TUNGSTEN WATER OP FORMATION
The BPT wastewater discharge rate at proposal for water of
formation from the reduction of tungsten oxides was 19,400 1/kkg
(4,650 gal/ton) of tungsten produced. Of the seven plants which
reduce tungsten oxides to tungsten metal, only two report
wastewaters that are not associated with wet air pollution
control devices or noncontact cooling. Water use and wastewater
discharge rates are presented in the proposed primary tungsten
supplement. Water of formation is generated when WOX is reduced
to tungsten metal in a hydrogen atmosphere. The BPT wastewater
discharge rate was based on the discharge rate of one of the
plants. The other plant did not discharge this wastewater and
was not considered in calculating the discharge allowance.
The BPT wastewater discharge rate at promulgation for reduction
to tungsten water of formation is 489 1/kkg (117 gal/ton) of
tungsten metal produced. This allowance is based on updated data
received after proposal from several different plants rather than
the one used at proposal. Plant 9010, on which the proposed BPT
flow was based, revised its flow but did not provide production
data, which does not allow use of the new data. Data from three
new plants and one existing plant were received through dcp
submittals and telephone contacts. The BPT flow is based on the
average water of formation generated at these four plants. Water
use and discharge rates are presented in Table V-10 (page 2996).
In plants which use wet scrubbing systems, this water of
formation is most likely vaporized upon formation and then
recondensed in the scrubber system. Consequently, plants with
wet scrubbing systems on their reduction furnaces do not report a
separate water of formation waste stream. For this reason, this
BPT flow rate should be allocated only to those plants which
reduce oxides to metal, but do not use a wet air pollution
control system.
TUNGSTEN'POWDER ACID LEACH AND WASH
The BPT wastewater discharge rate at promulgation for tungsten
powder acid leach and wash is 2,400 1/kkg (576 gal/ton) of
tungsten produced. This waste stream was not considered at
proposal. Through a new dcp submittal and telephone contacts, the
Agency determined that two plants in the subcategory generated
wastewater from leaching tungsten powders with acid. The BPT
flow is based on the average discharge from the two plants.
Table V-ll (page 2996) presents water use and discharge rates for
this stream.
REGULATED POLLUTANT PARAMETERS
The raw wastewater concentrations from individual operations and
the subcategory as a whole were examined to select certain
pollutant parameters for limitation. This examination and
3086
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PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
evaluation was presented in Section VI of the proposed primary
tungsten supplement. A total of six pollutants or pollutant
parameters were selected for limitation under proposed BPT and
are listed below:
122. lead
125. selenium
128. zinc
ammonia
TSS
pH
Analytical data gathered since proposal at two primary tungsten
plants have demonstrated that selenium is not found on a
subcategory-wide basis. Therefore, selenium is eliminated as a
control parameter. Based on the evaluation and examination
presented in Section VI of this document, the pollutants or
pollutant parameters selected for limitation under promulgated
BPT are:
122. lead
128. zinc
ammonia
TSS
pH
EFFLUENT LIMITATIONS
The treatable concentrations achievable by application of the
promulgated BPT are discussed in Section VII of Vol. I and
summarized there in Table VII-21 (page 248). With the exception
of ammonia, these treatable concentrations (both one day maximum
and monthly average values) are multiplied by the BPT normalized
discharge flows summarized in Table IX-1 to calculate the mass of
pollutants allowed to be discharged per mass of product. The
results of these calculations in milligrams of pollutant per
kilogram of product represent the BPT effluent limitations and
are presented in Table IX-2 (page 3090) for each individual waste
stream.
3087
-------
PRIMARY TUNGSTEN SUBCATEGORY
SECT - IX
TABLE IX-1
BPT WASTEWATER DISCHARGE RATES FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
Wastewater Stream
Tungstic Acid
Rinse Water
BPT Normalized
Discharge Rate
1/kkg gal/ton
41,030
9,839
Production
Normalizing
Parameter
Tungstic acid
(as W) produced
Acid Leach Wet Air
Pollution Control
Alkali Leach
Wash
Alkali Leach Wash
Condensate
Ion-Exchange
Raffinate
(commingled
and not
commingled
with other
process and
nonprocess
streams)
Calcium Tungstate
Precipitate Wash
Crystallization
and Drying of
Ammonium Para-
tungstate
Ammonium Paratung-
state Conversion
to Oxides Wet
Air Pollution
Control
Ammonium Paratung-
state Conversion
to Oxides Water
of Formation
35,810 8,587
19,180 4,599
88,480 21,220
73,810
0
27,620
63
17,700
0
6,623
15
Tungstic acid
(as W) produced
Sodium tungstate
(as W) produced
Sodium Tungstate
(as W) produced
Ammonium tungstate
(as W) produced
Calcium tungstate
(as W) produced
Ammonium paratung-
state (as W)
produced
Tungstic oxide
(as W) produced
Tungstic oxide
produced
3088
-------
PRIMARY TUNGSTEN SDBCATEGORY SECT - IX
TABLE IX-1 (Continued)
BPT WASTEWATER DISCHARGE RATES FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
BPT Normalized Production
Discharge Rate Normalizing
Wastewater Stream 1/kkg gal/ton Parameter
Reduction to 30,802 7,387 Tungsten metal
Tungsten produced
Air Pollu-
tion Control
Reduction to 489 117 Tungsten metal
Tungsten produced
Water of
Formation
Tungsten Powder Acid 2,400 576 Tungsten metal
Leach and Wash produced
Molybdenum Sulfide 0 0 Tungsten metal
Precipitation Wet produced
Air Pollution
Control
3089
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
TABLE IX-2
BPT EFFLUENT LIMITATIONS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(a) Tungstic Acid Rinse BPT
Pollutant or '• Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W) produced
Cadmium 10.270 4.529
Chromium 13.280 5.434
*Lead 17.230 8.205
Nickel 57.970 38.340
Silver 12.380 5.132
Thallium 61.890 27.470
*Zinc 59.900 25.030
*Ammonia (as N) 5,469.000 2,404.000
*TSS 1,682.000 800.000
*pH Within the range of 7.0 to 10.0 at all times
(b) Acid Leach Wet Air Pollution Control BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W) produced
Cadmium 8.959 3.953
Chromium 11.590 4.743
*Lead 15.040 7.162
Nickel 50.590 33.470
Silver 10.800 4.480
Thallium 54.020 23.980
*Zinc 52.280 21.840
*Ammonia (as N) 4,773.000 2,098.000
*TSS 1,468.000 698.300
*pH Within the range of 7.0 to 10.0 at all times
*Regulated Pollutant
3090
-------
PRIMARY TUNGSTEN SUBCATEGORY
SECT - IX
TABLE IX-2 (Continued)
BPT EFFLUENT LIMITATIONS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(c) Alkali Leach Wash BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
* Ammonia (as N)
*TSS
*pH
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
Within the range of 7.0 to 10.0 at
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
all times
(d) Alkali Leach Wash Condensate BPT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
*Ammonia (as N)
*TSS
*pH
8.057
28.011
2,557.000
786.200
3.837
11.700
1,124.000
374.100
Within the range of 7.0 to 10.0 at all times
*Regulated Pollutant
3091
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
TABLE IX-2 (Continued)
BPT EFFLUENT LIMITATIONS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(e) Ion-Exchange Raffinate (commingled with other Process
or Nonprocess waters) BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium tungstate (as W) produced
English Units - Ibs/million Ibs of ammonium tungstate (as W)
produced
Cadmium 17.240 7.606
Chromium 22.310 9.127
*Lead 37.160 17.700
Nickel ' 97.360 64.400
Silver 20.790 8.620
Thallium 103.900 46.140
*Zinc 129.200 53.970
*Ammonia (as N) 11,790.000 5,185.000
*TSS 3,627.000 1,726.000
*pH Within the range of 7.0 to 10.0 at all times
(f) Ion-Exchange Raffinate £ Not Commingled with other Process
or Nonprocess waters) BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium tungstate (as W) produced
English Units - Ibs/million Ibs of ammonium tungstate (as W)
produced
Cadmium
Chromium
*Lead 37.160 17.700
Nickel
Silver
Thallium
*Zinc 192.200 53.970
*Ammonia (as N) 11,790.000 5,185.000
*TSS 3,627.000 1,726.000
*pH Within the range of 7.0 to 10.0 at all times
^Regulated Pollutant
3092
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
TABLE IX-2 (Continued)
BPT EFFLUENT LIMITATIONS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(g) Calcium Tungstate Precipitate Wash BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of calcium tungstate (as W) produced
English Units - Ibs/million Ibs of calcium tungstate (as W)
produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
*Ammonia (as N)
*TSS
*pH
16.030
20.740
31.000
90.510
19.330
96.640
107.800
9,838.000
3,026.000
Within the range of 7.0 to 10.0
7.071
8.485
14.760
59.870
8.014
42.900
45.020
4,325.000
1,439.000
at all times
(h) Crystallization and Drying of Ammonium Paratungstate BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium paratungstate (as W) produced
English Units - Ibs/million Ibs of ammonium paratungstate
(as W) produced
Cadmium 0.000 0.000
Chromium 0.000 0.000
*Lead 0.000 0.000
Nickel 0.000 0.000
Silver 0.000 0.000
Thallium 0.000 0.000
*Zinc 0.000 0.000
*Ammonia (as N) 0.000 0.000
*TSS 0.000 0.000
*pH Within the range of 7.0 to 10.0 at all times
(i) Ammonium Paratungstate Conversion to Oxides Wet Air
Pollution Control BPT
Pollutant orMaximum forMaximum for"
Pollutant Property Any One Day Monthly Average
3093
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Cadmium 7.446 3.285
Chromium 9.636 3.942
*Lead 11.600 5.523
Nickel 42.050 27.810
Silver 8.979 3.723
Thallium 44.900 19.930
*Zinc 40.320 16.850
*Ammonia (as N) 3,681.000 1,618.000
*TSS 1,132.000 538.500
*pH Within the range of 7.0 to 10.0 at all times
(j) Ammonium Paratungstate Conversion to Oxides Water of
Formation BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Cadmium 0.017 0.008
Chromium 0.022 0.009
*Lead 0.026 0.013
Nickel 0.096 0.064
Silver 0.021 0.009
Thallium 0.103 0.046
*Zinc 0.092 0.038
*Ammonia (as N) 8.398 3.692
*TSS 2.583 1.229
*pH Within the range of 7.0 to 10.0 at all times
*Regulated Pollutant~
3094
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
TABLE IX-2 (Continued)
BPT EFFLUENT LIMITATIONS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(k) Reduction to Tungsten Wet Air Pollution Control BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Cadmium 10.470 4.620
Chromium 13.550 5.544
*Lead 12.940 6.161
Nickel 59.140 39.120
Silver 12.630 5.236
Thallium 63.140 28.030
*Zinc 44.970 18.790
*Ammonia (as N) 4,106.000 1,805.000
*TSS 1,263.000 600.700
*pH Within the range of 7.0 to 10.0 at all times
(1) Reduction to Tungsten Water of Formation BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal reduced
English Units - Ibs/million Ibs of tungsten metal reduced
Cadmium 0.166 0.073
Chromium 0.215 0.088
*Lead 0.205 0.098
Nickel 0.939 0.621
Silver 0.200 0.083
Thallium 1.002 0.445
*Zinc 0.714 0.298
*Ammonia (as N) 65.190 28.660
*TSS 20.050 9.536
*pH Within the range of 7.0 to 10.0 at all times
*Regulated Pollutant~~
3095
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
TABLE IX-2 (Continued)
BPT EFFLUENT LIMITATIONS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(m) Tungsten Powder Acid Leach and Wash BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Cadmium 0.816 0.360
Chromium 1.056 0.432
*Lead 1.008 0.480
Nickel 4.608 3.048
Silver 0.984 0.408
Thallium ' 4.920 2.184
*Zinc 3.504 1.464
*Amraonia (as N) 319.900 140.700
*TSS 98.400 46.800
*pH Within the range of 7.0 to 10.0 at all times
(n) Molybdenum Sulfide Precipitation Wet Arr Pollution
ControlBPT
pollutanj. or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal
produced
Cadmium 0.000 0.000
Chromium 0.000 0.000
*Lead 0.000 0.000
Nickel 0.000 0.000
Silver 0.000 0.000
Thallium 0.000 0.000
*Zinc 0.000 0.000
*Ammonia (as N) 0.000 0.000
*TSS 0.000 0.000
*pH Within the range of 7.0 to 10.0 at all times
*Regulated Pollutanti
3096
-------
Alkali Leach Wash Condenjate
Ammonium Pargtungstate Conv«oitoft
to Oxides Water of Formation
Ammonium Paratungstate Conversion
to Oxides Scrubber Liquor
Ion —Exchange Raffinate
Reduction to Tungsten Scrubber Uquor
Reduction to Tungsten
Water of Formation
Calcium Tyngstate Precipitate Wash
•*•*
i
,
on
Skimming
9
/ v
E^uaUjroUon
Tank
*•
Recovery
A
§§^§§
Ammonia
Steam
Stripping
^y
Removal
of Oil and
Graax
lungitlc Acid Rinsa
Tungsten Po«« in Tunftten Process
Chemical
Addition
Chemical
Precipitation
Sedimentation
Oi>chor9«
Sludge R«eycl«
Vacuum Filtrate
Sludge
Sludge
Dewatering
Sludae to
Disposal
JO
M
3
5
Q
W
H
W
55
W
§
n
w
a
o
w
n
I
H
FIGURE IX-1. BPT TREATMENT SCHEME PRIMARY TUNGSTEN SUBCATEGORY
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - IX
THIS PAGE INTENTIONALLY LEFT BLANK
3098
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - X
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
These BAT effluent limitations are based on the best control and
treatment technology used by a specific point source within the
industrial category or subcategory, or by another category from
which it is transferable. Emphasis is placed on additional
treatment techniques applied at the end of the treatment systems
currently used, as well as reduction of the amount ofi water used
and discharged, process control, and treatment technology
optimization.
The factors considered in assessing best available technology
economically achievable (BAT) include the age of equipment and
facilities involved, the process usedr process changes, nonwater
quality environmental impacts (including energy requirements),
and the costs of application of such technology. BAT represents
the best available technology economically achievable at plants
of various ages, sizes, processes, or other characteristics. BAT
may be transferred from a different subcategory or category. BAT
may include feasible process changes or internal controls, even
when not in common industry practice.
The required assessment of BAT considers costs, but does not
require a balancing of costs against effluent reduction benefits
(see Weyerhaeuser v. Costle, 590 F.2d 1011 (D.C. Cir. 1978)).
However, in assessing BAT, the Agency has given substantial
weight to the economic achievability of the technology.
TECHNICAL APPROACH TO BAT
The Agency reviewed a wide range of technology options and
evaluated the available possibilities to ensure that the most
effective and beneficial technologies were used as the basis of
BAT. To accomplish this, the Agency examined five technology
options prior to proposing mass limitations which could be
applied to the primary tungsten subcategory as alternatives for
the basis of BAT effluent limitations and which would represent
substantial progress toward reduction of pollutant discharges
over and beyond progress achieved by BPT. Three of these
treatment technologies were re-evaluated between proposal and
promulgation.
r^-
The treatment technologies considered for BAT are summarized
below:
Option A (Figure X-l page 3119) is based on:
I •
o Preliminary treatment with oil skimming (where required)
o Preliminary treatment with ammonia steam stripping
(where required)
o Lime precipitation and sedimentation
3099
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - X
Option B (Figure X-2 page 3120) is based on:
o Preliminary treatment with oil skimming (where required)
o Preliminary treatment with ammonia steam stripping
(where required)
o Lime precipitation and sedimentation
o In-process flow reduction of acid leach, ammonium
paratungstate conversion to oxides, and reduction to
tungsten scrubber liquor
Option C (Figure X-3 page 3121) is based on:
o Preliminary treatment with oil skimming (where required)
o Preliminary treatment with ammonia steam stripping
(where required)
o Lime precipitation and sedimentation
o In-process flow reduction of acid leach, ammonium
paratungstate conversion to oxides, and reduction to
tungsten scrubber liquor
o Multimedia filtration
The three options examined for BAT are discussed in greater
detail on the following pages. The first option considered
(Option A) is the same as the BPT treatment and control
technology which was presented in the previous section. The last
two options each represent substantial progress toward the
reduction of pollutant discharges above and beyond the progress
achievable by BPT.
OPTION A
Option A for the primary tungsten subcategory is equivalent to
the control and treatment technologies which were analyzed for
BPT in Section IX (see Figure X-l). The BPT end-of-pipe
treatment scheme includes lime precipitation and sedimentation,
with ammonia steam stripping preliminary treatment of wastewaters
containing treatable concentrations of ammonia and oil skimming
preliminary treatment (if required). Oil skimming is added to
remove oil and grease from calcium tungstate (synthetic
scheelite) precipitate wash. Although oil and grease is not
limited under this regulation, oil skimming is needed for BAT to
ensure proper metals removal. Oil and grease interferes with the
chemical addition and mixing required for chemical precipitation
treatment. The discharge rates for Option A are equal to the
discharge rates allocated to each stream as a BPT discharge flow.
OPTION B
Option B for the primary tungsten subcategory achieves lower
pollutant discharge by building upon the Option A end-of-pipe
treatment technology. Flow reduction measures are added to the
Option A treatment scheme which consists of lime precipitation
and sedimentation, with ammonia steam stripping preliminary
treatment of the wastewaters containing treatable concentrations
of ammonia and oil skimming preliminary treatment (see Figure X-
3100
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - X
2). These flow reduction measures, including in-process changes,
result in the elimination of some wastewater streams and the
concentration of pollutants in other effluents. As explained in
Section VII of the General Development Document, treatment of a
more concentrated effluent allows achievement of a greater net
pollutant removal and introduces the possible economic cost-
effectiveness associated with treating a lower volume of
wastewater.
The method used in Option B to reduce process wastewater
generation and discharge rates is recycle of water used in wet
air pollution control. There are three wet air pollution control
wastewater sources regulated under these effluent limitations for
which recycle is considered feasible:
- Acid leach wet air pollution control,
Ammonium paratungstate conversion to oxides wet air
pollution control, and
Reduction to metal wet air pollution control.
Table X-l (page 3108) presents the number of plants reporting
wastewater use with these sources, the number of plants
practicing recycle of scrubber liquor, and the range of recycle
values being used. Although four plants report total recycle of
their scrubber water, some blowdown or periodic cleaning is
likely to be needed to prevent the build-up of dissolved and
suspended solids since the water picks up particulates and fumes
from the air.
Reduction of flow through recycle or reuse represents the best
available technology economically achievable for these streams.
Acid leaching scrubber water may be reused in the scrubber with
periodic blowdown or as rinse water for insoluble tungstic acid.
Scrubber water from wet air pollution control systems on furnaces
which reduce ammonium paratungstate to oxides or reduce tungsten
oxides to metal may also be recycled through the scrubber with
periodic blowdown as several plants have demonstrated. Holding
tanks are the technology selected (and considered in developing
compliance costs) for scrubber water recycle. The tanks allow
for settling of particulates in the wastewater before recycle.
OPTION C
Option C for the primary tungsten subcategory consists of all
control and treatment requirements of Option B (flow reduction,
ammonia steam stripping, oil skimming, lime precipitation and
sedimentation) plus multimedia filtration technology added at the
end of the Option B treatment scheme (see Figure X-3). Multi-
media filtration is used to remove suspended solids, including
precipitates of toxic metals, beyond the concentrations
attainable by gravity sedimentation. The filter suggested is of
the gravity, mixed media type, although other forms of filters,
such as rapid sand filters or pressure filters, would perform
satisfactorily.
3101
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - X
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
As one means of evaluating each technology option/ EPA developed
estimates of the pollutant reduction benefits and the compliance
costs associated with each option. The methodologies are
described below.
POLLUTANT REMOVAL ESTIMATES
A complete description of the methodology used to calculate the
estimated pollutant reduction, or benefit, achieved by the
application of the various treatment options is presented in
Section X of Vol. I. The pollutant removal estimates have been
revised from proposal based on comments and new data, however,
the methodology for calculating pollutant removals was not
changed. The data used for estimating removals are the same as
those used to revise the compliance costs.
Sampling data collected during the field sampling program were
used to characterize the major waste streams considered for
regulation. At each sampled facility, the sampling data were
production normalized for each unit operation (i.e., mass of
pollutant generated per mass of product manufactured). This
value, referred to as the raw waste, was used to estimate the
mass of toxic pollutants generated within the primary tungsten
subcategory. By multiplying the total subcategory production for
a unit operation times the corresponding raw waste value, the
mass of pollutant generated for that unit operation was
estimated.
The volume of wastewater discharged after the application of each
treatment option was estimated for each operation at each plant
by comparing the actual discharge to the regulatory flow. The
smaller of the two values was selected and summed with the other
plant flows. The mass of pollut'-^t discharged was then estimated
by multiplying the achievable concentration values attainable by
the -option (mg/1) by the estimated volume of process wastewater
discharged by the subcategory. The mass of pollutant removed is
simply the difference between the estimated mass of pollutant
generated within the subcategory and the mass of pollutant
discharged after application of the treatment option. The
pollutant removal estimates for direct discharges in the primary
tungsten subcategory are presented in Table X-2 (page 3109).
Pollutant removal estimates for indirect dischargers are shown in
Section XII.
COMPLIANCE COSTS
Compliance costs presented at proposal were estimated using cost
curves, which related the total costs associated with
installation and operation of wastewater treatment technologies
to plant process wastewater discharge. EPA applied these curves
on a per plant basis, a plant's costs — both capital, and
operating and maintenance — being determined by what treatment
it has in place and by its individual process wastewater
3102
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - X
discharge (from dcp). The final step was to annualize the. capital
costs, and to sum the annualized capital costs, and the operating
and maintenance costs, yielding the cost of compliance for the
subcategory.
Since proposal, the cost estimation methodology has been changed
as discussed in Section VIII of this document and in Section VIII
of the General Development Document. A design model and plant-
specific information were used to size a wastewater treatment
system for each discharging facility. After completion of the
design, capital and annual costs were estimated for each unit of
the wastewater treatment system. Capital costs rely on vendor
quotes, while annual costs were developed from the literature.
The revised compliance costs for direct dischargers are presented
in Table VIII-1 (page 3073).
BAT OPTION SELECTION - PROPOSAL
EPA selected Option C for the proposed BAT, which includes flow
reduction, lime precipitation, sedimentation, and multimedia
filtration, with ammonia steam stripping preliminary treatment of
wastewaters containing treatable concentrations of ammonia.
Activated carbon technology (Option E) was also considered,
however this technology is not necessary since toxic organic
pollutants are not limited in this subcategory (see discussion on
Regulated Pollutant Parameters at the end of this section).
Reverse osmosis and multiple-effect evaporation (Option P) was
considered for the purpose of achieving zero discharge of process
wastewater; however, the Agency ultimately rejected this
technology because it was determined that its performance for
this specific purpose was not adequately demonstrated in this
category nor was it clearly transferable from another category.
BAT OPTION SELECTION - PROMULGATION
After proposal and in response to comments, EPA gathered data
through special requests, dcp submittals, and telephone contacts.
Nine additional plants were included in the subcategory. The new
data were used to revise regulatory flow allowances as well as
compliance costs. Additional sampling data were also collected
by the Agency at two primary tungsten plants. These data were
used for recalculating pollutant removal estimates and for
revising compliance costs.
EPA is promulgating BAT limitations for this subcategory based on
ammonia steam stripping, lime precipitation and sedimentation,
in-process flow reduction, and multimedia filtration. Plow
reductions are based on 90 percent recycle of scrubber effluent
through holding tanks. The end-of-pipe and pretreatment
technology basis for BAT limitations being promulgated is the
same as that for the proposed limitations. In addition, the
treatment performance concentrations, upon which the mass
limitations are based, are equal to values used to calculate the
proposed mass limitations, except for lead. Ammonia steam
3103
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - X
stripping is demonstrated at three primary tungsten facilities.
Filtration is not demonstrated within the subcategory; however,
it is demonstrated in six nonferrous metals manufacturing
subcategories at 23 plants. Recycle of the scrubber effluent
through holding tanks is demonstrated in the nonferrous metals
category, including one primary tungsten plant.
Implementation of the promulgated BAT limitations will remove
annually an estimated 5,140 kg of toxic pollutants, which is 318
kg of toxic metals over the estimated BPT discharge. Ammonia
steam stripping is estimated to remove 2,280 kg/yr of ammonia
over estimated BPT discharges and 144,000 kg/yr of the ammonia
generated.
The estimated capital cost for achieving promulgated BAT is
$0.773 million (March, 1982 dollars), and the estimated annual
cost is $1.0 million.
The Agency has developed BAT limitations and costs assuming that
wastewater will be treated with ammonia stripping, where
appropriate, followed' by central treatment with lime, settle, and
multimedia filtration for metals. It is possible that several
plants could achieve more stringent limits and save compliance
costs by removing metals first from tungsten acid rinse and acid
leach wet air pollution control and then combining these streams
with any other process streams for ammonia removals. Since the
mass of metals discharged is equal to the product of the
treatable concentrations and the flow, a lower flow to central
•treatment would result in less mass of metals discharged. (The
Agency believes that the treatable concentrations can be achieved
with the identified treatment technology for all flow rates.) By
assuming that waste streams will not be mixed in a central
treatment system until after metals are removed, individual
permits may be able to eliminate allowances for metals in the six
waste streams not containing metals, and' thus allow less mass of
pollutants to be discharged. The elimination of flow to central
treatment would also eliminate the cost of lime, settle, and .
filter technology for those six processes.
FINAL AMENDMENTS TO THE REGULATION
For the Primary Tungsten Subcategory, EPA promulgated amendments
on January 21, 1988, (53 FR 1704) to the regulations promulgated
on March 8, 1984 (48 FR 8742) concerning three topics, which are
briefly described here.
EPA amended the BPT and BAT effluent limitations and NSPS, PSES
and PSNS for ammonia in the ion exchange raffinate building
block, when ammonia is treated under a specific set of
circumstances. These circumstances are when raffinate contains
high sulfate concentrations (greater than 1000 mg/1), and when
the raffinate is not commingled with any other waste streams and
then is treated by ammonia steam stripping.
EPA added a new building block for alkali leach condensate. This
3104
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - X
building block was omitted from the promulgated rule because the
Agency believed this condensate would be accounted for through
other building blocks.
EPA modified the production basis for determining the amount of
pollutant which may be discharged to the amount of element
tungsten produced or processed. This was done to avoid any
confusion over the chemical formula for the salt form of
tungsten.
WASTEWATER DISCHARGE RATES
A BAT discharge rate was calculated for each subdivision based
upon the flows of the existing plants, as determined from
analysis of the data collection portfolios. The discharge rate
is used with the achievable treatment concentrations to determine
BAT effluent limitations. Since the discharge rate may be
different for each wastewater source, separate production
normalized discharge rates for each of the 14 wastewater sources
were determined and are summarized in Table X-3 (page 3110). The
discharge rates are normalized on a production basis by relating
the amount of wastewater generated to the mass of the
intermediate product which is produced by the process associated
with the waste stream in question. EPA modified the production
basis for determining the amount of pollutant which may be
discharged to the amount of the element tungsten produced or
processed. As discussed in Section IV, in the final regulation,
EPA used the chemical salt form of tungsten which was believed
appropriate for the processing step or building block being
regulated. However, the chemical formulas may have been
incorrect and were confusing. Using the element tungsten
produced or processed as a production normalizing parameter
rather than a chemical compound makes the production basis clear
and unambiguous. This change will affect all of the building
blocks except for 8421.102(i) through (k), 8421.103(i) through
(k), 8421.104(i) through (k), 8421.105(i) through (k), and
8421.106(i) through (k), which were already based on the amount
of. elemental tungsten produced. This change will affect the
regulatory flows for these building blocks, which are based on
the production normalizing parameter. These production
normalizing parameters, or PNPs, are also listed in Table X-3.
The BAT discharge rates are the same as the BPT rates except for
three scrubber streams for which flow reduction can be achieved.
The BAT discharge rates are based on 90 percent recycle of the
scrubber effluent. Consequently, the BAT discharge allowance for
acid leach wet air pollution control is 3581 1/kkg (859 gal/ton)
of tungstic acid (as W) produced. The BAT discharge allowance
for ammonium paratungstate conversion to oxides wet air pollution
control is 2762 1/kkg (662 gal/ton) of tungstic oxide (as W)
produced. Finally, the BAT discharge allowance for reduction to
tungsten wet air pollution control is 3,080 1/kkg (739 gal/ton)
of tungsten metal produced.
The BAT discharge rates reflect the flow reduction requirements
3105
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - X
of the selected BAT option. For this reason, the three scrubber
waters which were targeted for flow reduction through recycle for
BAT have lower flow rates than the corresponding BPT flows. Since
several plants have demonstrated sufficient ability to achieve
substantial recycle of these three wastewaters, lower flow
allowances for these streams represent the best available
technology economically achievable.
REGULATED POLLUTANT PARAMETERS
The raw wastewater concentrations from individual operations and
the subcategory as a whole were examined to select certain
pollutants and pollutant parameters for limitation. This
examination and evaluation was presented in Section VI. The
Agency, however, has chosen not to regulate all 17 toxic
pollutants selected in this analysis.
The Agency believes that the toxic organic pollutants in the
primary tungsten subcategory are present only in trace (deminimus
quantities) and are neither causing nor likely to cause toxic
effects. Therefore, the following toxic organic pollutants are
excluded from regulation:
11. 1,1,1-trichloroethane
55. naphthalene
65. phenol
73. benzo(a)pyrene
79. benzo(ghi)perylene
82. dibenzo(a,h)anthracene
85. tetrachloroethylene
86. toluene
The cost associated with analysis for toxic metal pollutants has
prompted EPA to develop an alternative method for regulating and
monitoring toxic pollutant discharges from the nonferrous metals
manufacturing category. Rather than developing specific effluent
mass limitations and standards for each of the toxic metals found
in treatable concentrations in the raw wastewater from a given
subcategory, the Agency is promulgating effluent mass limitations
only for those pollutants generated in the greatest quantities as
shown by the pollutant removal estimates. The pollutants
selected for specific limitation are listed below:
122. lead
128. zinc
ammonia (as N)
By establishing limitations and standards for certain toxic metal
pollutants, discharges will attain the same degree of control
over toxic metal pollutants as they would have been required to
achieve had all the toxic metal pollutants been directly limited.
This approach is justified technically since the treatable
concentrations used for lime precipitation and sedimentation
technology are based on optimized treatment for concomitant
3106
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - X
multiple metals removal. Thus, even though metals have somewhat
different theoretical solubilities, they will be removed at very
nearly the same rate in a lime precipitation and -sedimentation
treatment system operated for multiple- . metals removal.
Filtration as part of the technology basis is likewise justified
because this technology removes metals non-preferentially.
The toxic metal pollutants selected for specific limitation in
the primary tungsten subcategory to control the discharges of
toxic metal pollutants are lead and zinc. Ammonia is also
selected for limitation since the methods used to control lead
and zinc are not effective in the control of ammonia.: - The
following toxic metal pollutants are excluded from limitation on
the basis that they are effectively controlled by the limitations
developed for lead and zinc: ... -
118. cadmium ^
119. chromium (Total)
124. nickel
126. silver , - ,,,.:. •
127. thallium
In the proposed limitations, selenium was also selected for
control. Analytical data gathered since proposal at two primary
tungsten plants have demonstrated that selenium is not a toxic
pollutant found on a subcategory-wide basis (see Section VI).
Therefore, selenium is eliminated as a control parameter.
EFFLUENT LIMITATIONS
The concentrations achievable by application of BAT are discussed
in Section VII of Vol. I and summarized there in Table VII-21
(page 248). The treatable concentrations both one day maximum
and monthly average values are multiplied by the BAT normalized
discharge flows summarized in Table X-3 to calculate the mass of
pollutants allowed to be discharged per mass of product. The
results of these calculations in milligrams of pollutant per
kilogram of product represent the BAT effluent limitations and
are presented in Table X-4 (page 3112) for each waste stream.
The regulatory tables displayed in Sections IX through XII
contain the potential limitations which would have been
established if the Agency had elected to regulate all of the
significant pollutants found at levels above the treatment
effectiveness of the model technology. The pollutants actually
regulated are marked (*) in each table. The potential regulatory
levels of the unregulated (unmarked) pollutants may be used by
the permitting authority when it finds the regulation of these
pollutants to be necessary.
3107
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - X
TABLE X-l
CURRENT RECYCLE PRACTICES WITHIN THE
PRIMARY TUNGSTEN SUBCATEGORY
Number of Number of
Plants Plants Range of
with Wastewater Practicing Recycle Recycle
Acid Leach Wet Air 2 0
Pollution Control
Ammonium Paratungstate 6 1 100
Conversion to Oxides
Wet Air Pollution
Control
Reduction to Metal 7 3 100
Wet Air Pollution
Control
3108
-------
Table x-z
POLLUTANT REMOVAL ESTIMATES FOR PRIMARY TUNGSTEN DIRECT DISCHARGERS
o
ID
POLLWANT
Cfdmlum
ChcoaliM
Lead
Nickel
Silver
Thai 11 u»
Zinc
TOTAL TOXIC METALS
Aluminum
Aamonla
Fluoride
Iron
TOTAL NONCONVKNTIONALS
TSS
Oil & Gr**ie
TOTAL CONVENT IONAI.S
TOTAL POLLUTANTS
FLOW
24.0
25.5
16.5
204.4
30.4
142.9
100.3
564.1
681.0
9,728.0
4,408.0
124.6
14.941.6
3.648.0
2.805.3
6.4S3.3
21,958.9
304.000.000
OPTION A
REMOVED
(kg/yr)
16.8
386.1
4,052.7
0.0
41.2
0.0
324.0
4.820.S
63.5
141. 322.1
19.964.1
10,490.1
171,839.8
50,261.8
0.0
50.261.8
226,922.4
OPTION 8
DISCHARGED
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - X
TABLE X-3
BAT WASTEWATER DISCHARGE RATES FOR THE
PRIMARY TUNGSTEN SUBCATSGORY
Wastewater Stream
Tungstic Acid
Rinse Water
BAT Normalized
Discharge Rate
1/kkg gai./ton
41,030
9,839
Production
Normalization
Parameter
Tungstic acid
(as W) produced
Acid Leach Wet Air
Pollution Control
Alkali Leach
Wash
Alkali Leach Wash
Condensate
Ion-Exchange
Raffinate
(commingled
and not
commingled
with other
process and
nonprocess
streams)
Calcium Tungstate
Precipitate Wash
Crystallization
and Drying of
Ammonium Para-
tungstate
Ammonium Paratung-
state Conversion
to Oxides Wet
Air Pollution
Control
Ammonium Paratung-
state Conversion
to Oxides Water
of Formation
3,581
0
73,810
0
2,762
63
859
0
19,180 4,599
88,480 21,220
17,700
0
662
15
Tungstic acid
(as W) produced
Sodium tungstate
(as W) produced
Sodium Tungstate
(as W) produced
Ammonium tungstate
(as W) produced
Calcium tungstate
(as W) produced
Ammonium paratung-
state (as W)
produced
Tungstic oxide
(as W) produced
Tungstic oxide
(WO3) produced
3110
-------
PRIMARY TONGSTEN SUBCATEGORY
SECT - X
TABLE X-3 (Continued)
BAT WASTEWATER DISCHARGE.'RATES FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
Wastewater Stream
Reduction to 3,800
Tungsten
Air Pollu-
tion Control
Reduction to 489
Tungsten
Water of
Formation
.Tungsten Powder Acid 2,400
Leach and Wash
Molybdenum Sulfide 0
Precipitation Wet
Air Pollution
Control
BAT Normalized
Discharge Rate
1/kkg gal/ton
739
117
576
Production
Normali zat ion
Parameter,
Tungsten metal
produced
Tungsten metal
produced
Tungsten metal
produced
Tungsten metal
produced
3111
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT
TABLE X-4
BAT EFFLUENT LIMITATIONS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(a) Tungstic Acid Rinse BAT
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W) produced
Cadmium 6.038 2.415
Chromium 11.170 4.529
*Lead 11.490 5.333
Nickel 16.610 11.170
Silver 8.755 3.623
Thallium 42.270 18.420
*Zinc 41.850 17.230
*Ammonia (as N) 5,469.000 2,404.000
(b) Acid Leach Wet Air Pollution Control BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W) produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zihc
*Ammonia (as N)
0.527
0.975
1.003
1.449
0.764
3.689
3.653
477.400
0.211
0.395
0.466
0.975
0.316
1.607
1.504
209.900
*Regulated Pollutant
3112
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - X
TABLE X-4 (Continued)
BAT EFFLUENT LIMITATIONS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(c) Alkali Leach Wash BAT
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
* Ammonia (as N)
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
o.ooo
0.000
(d) Alkali Leach Wash Condensate BAT
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Cadmium
Chromium
*Lead 5.372 2.494
Nickel
Silver
Thallium
*Zinc 19.570 8.057
*Ammonia (as N) 2,557.000 1,124.000
*Regulated Pollutant
3113
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - X
TABLE X-4 (Continued)
BAT EFFLUENT LIMITATIONS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(e) Ion-Exchange Raffinate (Commingled with other Process
or Nonprocess Waters) BAT
Pollutant or '. Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium tungstate (as W) produced
English Units - Ibs/million Ibs of ammonium tungstate (as W)
produced
Cadmium 10.140 4.057
Chromium 18.760 7.606
*Lead 24.780 11.500
Nickel 27.890 18.760
Silver 14.710 6.085
Thallium 70.990 30.930
*Zinc 90.240 37.160
*Ammonia (as N) 11,790.000 5,185.000
(f) Ion-Exchange Raffinate (Not Commingled with other Process
or Nonprocess Waters)1 BAT
Pollutant or"Maximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium tungstate (as W) produced
English Units - Ibs/million Ibs of ammonium tungstate (as W)
produced
Cadmium
Chromium
*Lead 24.780 11.500
Nickel
Silver
Thallium
*Zinc 90.240 37.160
*Ammonia (as N) 11,790.000 5,185.000
*Reguiated Pollutant
1The effluent limitation for this pollutant does not apply if
(a) the mother liquor feed to the ion exchange process or the
raffinate from the ion exchange process contains sulfates at
concentrations exceeding 1000 mg/1; (b) this mother liquor or
raffinate is treated by ammonia steam stripping; and (c) such
mother liquor or raffinate is not commingled with any other
process or nonprocess waters prior to steam stripping for ammonia
removal.
3114
-------
PRIMARY TUNGSTEN SUBCATEGORY
SECT - X
TABLE X-4 (Continued)
BAT EFFLUENT LIMITATIONS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(g) Calcium Tungstate Precipitate Wash BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of calcium tungstate (as W) produced
English Units - Ibs/million Ibs of calcium tungstate (as W)
produced
Cadmium
Chromium
*Lead
Nickel
"Silver
Thallium
*Zinc
*Ammonia (as N)
9.428
17.440
20.670
25.930
13.670
66.000
75.280
9,838.000
3.771
7.071
9.594
17.440
5.657
28.760
31.000
4,325.000
(h) Crystallization and Drying of Ammonium Paratungstate BAT
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of ammonium paratungstate (as W) produced
English Units - Ibs/million Ibs of ammonium paratungstate
(as W) produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
*Ammonia (as N)
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
*Regulated Pollutant
3115
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - X
TABLE X-4 (Continued)
BAT EFFLUENT LIMITATIONS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(i) Ammonium Paratungstate Conversion to Oxides Wet Air
Pollution Control BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
* Ammonia (as N)
0.438
0.810
0.773
1.205
0.635
3.066
2.817
368.200
0.175
0.329
0.359
0.810
0.263
1.336
1.160
161.900
(j) Ammonium Paratungstate Conversion to Oxides Water of
Forma ti'o'n BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
* Ammonia (as N)
0.010
0.019
0.018
0.028
0.015
0.070
0.064
8.398
0.004
0.008
0.008
0.019
0.006
0.031
0.026
3.692
* RegulatedPolIutant
3116
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - X
TABLE X-4 (Continued)
BAT EFFLUENT LIMITATIONS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(k) Reduction to Tungsten Wet Air Pollution Control
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
* Ammonia (as N)
0.616
1.140
0.862
1.694
0.893
4.312
3.142
410.600
0.246
0.462
0.400
1.140
0.370
1.879
1.294
180.500
(1) Reduction to Tungsten Water of Formation BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - rag/kg of tungsten metal reduced
English Units - Ibs/million Ibs of tungsten metal reduced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
* Ammonia (as N)
0.098
0.181
0.137
0.269
0.142
0.685
0.499
65.190
0.039
0.073
0.064
0.181
0.059
0.298
0.205
28.660
*Regulated Pollutant
3117
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - X
TABLE X-4 (Continued)
BAT EFFLUENT LIMITATIONS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(m) Tungsten Powder Acid Leach and Wash BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Cadmium
Chromium
*Lead
Nickel
Siilver
Thallium
*Zinc
*Ainmonia (as N)
0.480
0.888
0.672
1.320
0.696
3.360
2.448
319.900
0.190
0.360
0.312
0.888
0.288
1.464
1.008
140.700
(n) Molybdenum Sulfide Precipitation Wet Air Pollution
Control BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal
produced
Cadmium 0.000 0.000
Chromium 0.000 0.000
*Lead 0.000 0.000
Nickel 0.000 0.000
Silver 0.000 0.000
Thallium 0.000 0.000
*Zinc 0.000 0.000
*Ammonia (as N) 0.000 0.000
*Regulated Pollutant
3118
-------
Alkali Leach Wash CondeiMate
Ammonium Paratungatate Conversion
to Oxides Water of Formation
Ammonium Poratungstots Conversion
to Oxides Scrubber Uquor
Ion—Exchange Raffinate
Reduction to Tungsten Scrubber Uquor
Reduction to Tungsten
Water of Formation
To Ammonia
Recovery
/ =
Equalization
Ammonia
Steam
Stripping
Steam
Calcium Tungstate Precipitate Wash
Tungstk Acid Rinse
Tungsten PowdAf Acid Leach and Wash
Acid Uoch Scrubber Uquor
Oiicharge
Alkali Leach Wa»h
Uoiybdenum Surflde Precipitation
Scnibber Uquor
Complete Evaporation
Complete Reuse In Tungsten Proctw
Qyitalltstatlon and Drying of
Amman! um. Parotungatote Dro»tt«oter
Complete Recycle or Evaporation
Sludge to
Disposal
FIGURE X-1. BAT TREATMENT SCHEME OPTION A PRIMARY TUNGSTEN SUBCATEGORY
•o!
s
CO
a
w
o
w
w
-------
Ammonium Parofurigstate Conv*r»Jon
to Oxides Scrubber liquor _
Reduction to Tungjlen Scrubber UQOOT ^
Attccl! teach Wash Condensate _
Ammonium Parotungslate Conversion
19 Oxides Water of Formation ^
ion— Exchange Rafftnate __
Reduction to Tungsten
Water of Formation
OH
Calcium Tungitate Precipitate Wash __ g,jmn
u> 1*
Hofdfdg
Tank
Sludge ^-1
Removal
\
I
ting
M *
Removal
of Oil and
Tungitic Acid Rinse __ Create
Tungsten Powder Acid Leach and Wash
Add Leech Scrubber Liquor
Alkali Leach Wash
9
Uolybdtii.."n Sulfide Precipitation
Scruhhi! i *'iJOr
CfystaHUotH«< jnd Drying of
Ammonium Paratungatote *aste*ater
Recycle •
V
«„.*"
Tank
Complete Cvapor
To Ammonia 2
Recovery tj
p t i
1 T? \ «
* 1 — /"~L~\ 1-3
i Equalization ~~] f \ Cj
°'°°"k 8888^ ^
, CO
Ammonia 1-3
.^ Steom Steam Jr}
Stripping "^ 2|
338888 Chemical S2
\ / Addition §
^T^ I °
0 lp §
/ V /V V g
1 ~ ChemicoT ~ Oi,chorge 5
n Equolixation — T~T»» _ , ' 7 »> Sedimentation »•> 73
D" .Tank n/i Precipitation ^
^^^^
y Studae . 0]
Sludge (r]
Removal ("J
Sludge Recycle 1-3
otion ' '
/C\ (Jj .
Complete Reuwi in Tunatten Proceii Vacuum Wrote "^\^~f^~7 Sludae to ^
Ammonia
^* Recovery
^
^"^^^^ Disposal
Sludge
Denaturing 1 r
] i i
•••
-------
Ammonium Porotungstote Conversion
to Oxides Scrubber Liquor ^__ \7
Reduction to Tungsten Scrubber Uqyor Tank
*• L_ M
Alkali Leach Wash Candensate Sludge ^J
Ammonium Parotungetate Conversion Removal
to Proles Water of Formation J
lon-Exchonqe Rolfinate _ _'
Reduction to Tungsten
Water of Formation
Oil
taicium lungssote Precipitate wosn ^ Skimming
T
Removal
af Oil and
Tungttic Acid Rinse ^__ Crease
To Amrnonia (— j
Recovery 3
f * 1 ^
i Equalization ~] ( \ §
**°l""k ^S^ CT
Ammonia ^
fc Steam Steam H
Stripping ^
RXXXXX> Chemical CS
AdHiiion backwash (jj
o Ip 1
/ V / V V Cl
Tungsten Po*der Acid Leach and Woth 1 ''^/ /«. ' i T" 1 r u. i.:™.,:,, re—i,-™. S
Recycle *
V
Acid Leach Scrubber Liquor Holding
Tank
Alkali Leach Wash Complete Evopor
Molybdenum Sulfide Precipitation
Scrubber liquor Complete Reuse i
Crystollization and Drying al
Ammonium Paralungstate Wastewater Ammonia
~ -—• »> Recovery
' ^" Cauoliiation •• l> miwnn.ni ^ Sedimiintation • Ht «.—..«.,- ,»,
^_^ i i """Tank i i ^ Precipitation """ "" "" nitroUan ~~ K
| 1 t^^m^^^^—^ppp^
^f Sludge Backwaeh W
Sludge Q
R«mawal Sludge Recycle H
sMon ' ' .
T , D Vacuum nitrate *\ Vp^~r4~' „.,'"*
^ Disposal
Sludge '
Dewatering .L
n i
Complete Recycle or Evaporation -^ —
X-3. BAT TREATMENT SCHEME OPTION C PRIMARY TUNGSTEN SUBCATEGORY
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - X
THIS PAGE INTENTIONALLY LEFT BLANK
3122
-------
PRIMARY TUNGSTEN SUBCATEGORY
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
This section describes the technologies for treatment of
wastewater from new sources and presents mass discharge standards
for regulatory pollutants for NSPS in the primary tungsten
subcategory, based on the selected treatment technology. The
basis for new source performance standards (NSPS) under Section
306 of the Act is the best available demonstrated technology
(BDT). New plants have the opportunity to design the best and
most efficient production processes and wastewater treatment
technologies without facing the added costs and restrictions
encountered in retrofitting an existi-ng plant.
TECHNICAL APPROACH TO BDT
The best available demonstrated technology (BDT) for new source
performance standards is equivalent to the best available
technology (BAT) selected for currently existing primary tungsten
plants. This result is a consequence of careful review by the
Agency of a wide range of technical options for new source
treatment systems. This review of the primary tungsten
subcategory found no new, economically feasible, demonstrated
technologies which could be considered an improvement over those
chosen for consideration for BAT. Additionally, there was
nothing found to indicate that the wastewater flows and
characteristics of new plants would not be similar to those from
existing plants, since the processes used by new sources are not
expected to differ from those used at existing sources.
Consequently, BAT production normalized discharge rates, which
are based on the best existing practices of the subcategory, can
also be applied to new sources. These rates are presented in
Table XI-1 (page 3126).
Treatment technologies considered for the BDT options are
identical to the treatment technologies considered for the BAT
options. These options are:
OPTION A
o Preliminary treatment with oil skimming (where required)
o Preliminary treatment with ammonia steam stripping
(where required)
o Lime precipitation and sedimentation
OPTION B
o Preliminary treatment with oil skimming (where required)
o Preliminary treatment witji ammonia steam stripping
(where required)
o Lime precipitation and sedimentation
o In-process flow reduction of acid leach, ammonium para-
3123
-------
PRIMARY TUNGSTEN SUBCATEGORY
tungstate conversion to oxides, and reduction to tungsten
scrubber liquor
OPTION C
o Preliminary treatment with oil skimming (where required)
o Preliminary treatment with ammonia steam stripping
(where required)
o Lime precipitation and sedimentation
o In-process flow reduction of acid leach, ammonium para-
tungstate conversion to oxides, and reduction to tungsten
scrubber liquor
o Multimedia filtration
BDT OPTION SELECTION - PROPOSAL
EPA proposed that the best available demonstrated technology for
the primary tungsten subcategory be equivalent to Option C (flow
reduction, ammonia steam stripping, lime precipitation,
sedimentation, and multimedia filtration).
The wastewater flow rates for BDT were the same as the BAT flow
rates. Further flow reduction measures for BDT were not
considered feasible, because dry scrubbing was not demonstrated
for controlling emissions from acid leaching, APT conversion to
oxides, and tungsten reduction furnaces. The nature of these
emissions (acid fumes, hot particulate matter) technically
precluded the 'use of dry scrubbers. Therefore, EPA included an
allowance from this source at BDT equivalent to that proposed for
BAT. EPA also did not believe that new plants could achieve any
additional flow reduction beyond the 90 percent scrubber effluent
recycle proposed for BAT.
Activated carbon technology (Option E) was also considered,
however this technology was not necessary since toxic organic
pollutants were not limited in this subcategory. Reverse osmosis
in conjunction with multiple-effect evaporation (Option F) was
considered for the purpose of achieving zero discharge of process
wastewater; however, the Agency ultimately rejected this
technology because it was determined that its performance for
this specific purpose was not adequately demonstrated in this
category nor was it clearly transferable from another category.
BPT OPTION SELECTION - PROMULGATION .
EPA is promulgating best available demonstrated technology for
the primary tungsten subcategory equivalent to Option C (flow
reduction, oil skimming, ammonia steam stripping, lime
precipitation, sedimentation, and multimedia filtration).The
wastewater flow rates for BDT are the same as the BAT flow rates.
The BDT flow rates are presented in Table XI-1 (page 3126).
Additional flow reduction and more stringent treatment
technologies are not demonstrated or readily transferable to the
primary tungsten subcategory for the reasons stated at proposal..
3124
-------
PRIMARY TUNGSTEN SUBCATEGORY
REGULATED POLLUTANT PARAMETERS
The Agency has no reason to believe that the pollutants that will
be found in treatable concentrations in processes within new
sources will be any different than with eKisting sources.
Accordingly, pollutants and pollutant parameters selected for
limitation under NSPS, in accordance with the rationale of
Sections VI and X, are identical to those selected for BAT. The
conventional pollutant parameters TSS and pH are also selected
for limitation.
NEW SOURCE PERFORMANCE STANDARDS
The NSPS discharge flows for each wastewater source are the same
as the discharge rates for BAT and are shown in Table XI-1 (page
3126). The mass of pollutant allowed to be discharged per mass
of product is calculated by multiplying the appropriate treatment
performance concentration (mg/1) by the production normalized
wastewater discharge flows (1/kkg). The results of these
calculations are the production-based new source. performance
standards. These standards are presented in Table XI-2 (page
3128).
3125
-------
PRIMARY TUNGSTEN SUBCATEGORY
TABLE XI-1
NSPS WASTEWATER DISCHARGE RATES FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
Wgatewater Stream
Tungstie Acid
Rinse Water
NSPS Normalized
Discharge Rate
1/kkg gal/ton
41,030 9,839
Production
Normalizing
Parameter
Tungstic acid
(as W) produced
Acid Leach Wet Air
Pollution Control
Alkali Leach
Wash
Alkali Leach Wash
Condensate
Ion-Exchange
Raffinate
(commingled
and not
commingled
with other
process and
nonprocess
streams)
Calcium Tungstate
Precipitate Wash
Crystallization
and Drying of
Ammonium Para-
tungstate
Ammonium Paratung-
state Conversion
to Oxides Wet
Air Pollution
Control
Ammonium Paratung-
state Conversion
to Oxides Water
of Formation
3,581
859
19,180 4,599
88,480 21,220
73,810
0
2,762
63
17,700
0
662
15
Tungstic acid
(as W) produced
Sodium tungstate
(as W) produced
Sodium Tungstate
(as W) produced
Ammonium tungstate
(as W) produced
Calcium tungstate
(as W) produced
Ammonium paratung-
state (as W)
produced
Tungstic oxide
(as W) produced
Tungstic oxide
(WO3) produced
3126
-------
PRIMARY TUNGSTEN SUBCATEGORY
TABLE XI-1 (Continued)
NSPS WASTEWATER DISCHARGE RATES FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
NSPS Normalized Production
Discharge Rate Normalization
Wastewater Stream 1/kkg gal/ton Parameter
Reduction to 3,800 739 Tungsten metal
Tungsten produced
Air Pollu-
tion Control
Reduction to 489 117 Tungsten metal
Tungsten produced
Water of
Formation
Tungsten Powder Acid 2,400 576 Tungsten metal
Leach and Hash produced
Molybdenum Sulfide 0 0 Tungsten metal
Precipitation Wet produced
Air Pollution
Control
3127
-------
PRIMARY TUNGSTEN SUBCATEGORY
TABLE IX-2
NSPS FOR THE PRIMARY
TUNGSTEN SUBCATEGORY
(a) Tungstic Acid Rinse NSPS NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W) produced
Cadmium 6.038 2.415
Chromium 11.170 4.529
*Lead 11.490 5.333
Nickel 16.610 11.170
Silver 8.755 3.623
Thallium 42.270 18.420
*Zinc 41.850 17.230
*Ammonia (as N) 5,469.000 2,404.000
*TSS 615.400 492.300
*pH .Within the range of 7.0 to 10.0 at all times
(b) Acid Leach Wet Air Pollution Control NSPS NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W) produced
Cadmium . 0.527 0.211
Chromium 0.975 0.395
*Lead 1.003 0.466
Nickel 1.449 0.975
Silver 0.764 0.316
Thallium 3.689 1.607
*Zinc 3.653 1.504
*Ammonia (as N) 477.400 209.900
*TSS 53.720 42.970
*pH Within the range of 7.0 to 10.0 at all times
*Regulated Pollutant
3128
-------
PRIMARY TUNGSTEN SUBCATEGORY
TABLE IX -2 (Continued)
NSPS FOR THE PRIMARY
TUNGSTEN SUBCATEGORY
(c) Alkali Leach Wash NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Cadmium 0.000 0.000
Chromium 0.000 0.000
*Lead 0.000 0.000
Nickel 0.000 0.000
Silver 0.000 0.000
Thallium 0.000 0.000
*Zinc 0.000 0.000
*Ammonia (as N) 0.000 0.000
*TSS 0.000 0.000
*pH Within the range of 7.0 to 10.0 at all times
(d) Alkali Leach Wash Condensate NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Cadmium
Chromium
*Lead 5,372 2.494
Nickel
Silver
Thallium
*Zinc 19.570 8.057
*Ammonia (as N) 2,557.000 1,124.000
*TSS 287.800 229.600
*pH Within the range of 7.0 to 10.0 at all times
*Regulated Pollutant~
3129
-------
PRIMARY TUNGSTEN SUBCATEGORY
TABLE IX-2 (Continued)
NSPS FOR THE PRIMARY
TUNGSTEN SUBCATEGORY
(e) Ion-Exchange Raffinate (Commingled with other Process
or Nonprocess Waters) NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium tungstate (as W) produced
English Units - Ibs/million Ibs of ammonium tungstate (as W)
produced
Cadmium 10.140 4.057
Chromium 18.760 7.606
*Lead 24.780 11.500
Nickel 27.890 18.760
Silver 14.710 6.085
Thallium 70.990 30.930
*Zinc 90.240 37.160
*Ammonia (as N) 11,790.000 5,185.000
*TSS 1,327.000 1,062.000
*pH Within the range of 7.0 to 10.0 at all times
(f) Ion-Exchange Raffinate (Not Commingled with other Process
or Nonprocess Waters)1 NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium tungstate (as W) produced
English Units - Ibs/million Ibs of ammonium tungstate (as W)
produced
Cadmium
Chromium
*Lead 24.780 11.500
Nickel
Silver
Thallium
*Zinc 90.240 37.160
*Amraonia (as N) 11,790.000 5,185.000
*TSS 1,327.000 1,062.000
*pH Within the range of 7.0 to 10.0 at all times
*Regulated Pollutant
1The new source standard for this pollutant does not apply if
(a) the mother liquor feed to the ion exchange process or the
raffinate from the ion exchange process contains sulfates at
concentrations exceeding 1000 mg/1; (b) this mother liquor or
raffinate is treated by ammonia steam stripping; and (c) such
mother liquor or raffinate is not commingled with any other
process or nonprocess waters prior to steam stripping for ammonia
removal.
3130
-------
PRIMARY TUNGSTEN SUBCATEGORY
TABLE IX-2 (Continued)
NSPS FOR THE PRIMARY TUNGSTEN SUBCATEGORY
(g) Calcium Tungstate Precipitate Wash NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of calcium tungstate (as W) produced
English Units - Ibs/million Ibs of calcium tungstate (as W)
produced
Cadmium . 9.428 3.771
Chromium 17.440 7.071
*Lead 20.670 9.594
Nickel 25.930 17.446
Silver 13.670 5.657
Thallium 66.000 28.760
*Zinc 75.280 31.000
*Ammonia (as N) 9,838.000 4,325.000
*TSS 1,107.000 885.600
*pH Within the range of 7.0 to 10.0 at all times
(h) Crystallization and Drying of Ammonium Paratungstate NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium paratungstate (as W) produced
English Units - Ibs/million Ibs of ammonium paratungstate
(as W) produced
Cadmium 0.000 0.000
Chromium 0.000 0.000
*Lead 0.000 0.000
Nickel 0.000 0.000
Silver 0.000 0.000
Thallium 0.000 ^ 0.000
*Zinc 0.000 0.000
*Ammonia (as N) 0.000 0.000
*TSS 0.000 0.000
*pH Within the range of 7.0 to 10.0 at all times
*Regulated Pollutant
3131
-------
PRIMARY TUNGSTEN SUBCATEGORY
TABLE XI-2 (Continued)
NSPS FOR THE PRIMARY
TUNGSTEN SUBCATEGORY
(i) Ammonium Paratungstate Conversion to Oxides Wet Air
Pollution Control NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Cadmium 0.438 0.175
Chromium 0.810 0.329
*Lead 0.773 0.359
Nickel 1.205 0.810
Silver 0.635 0.263
Thallium 3.066 1.336
*Zinc 2.817 1.160
*Ammonia (as N) 368.200 161.900
*TSS 41,430 33.150
*pH Within the range of 7.0 to 10.0
at all times
{j) Ammonium Paratungstate Conversion to Oxides Water of
Formation NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide {as W)
produced
Cadmium 0.010 0.004
Chromium 0.019 0.008
*Lead 0.018 0.008
Nickel 0.028 0.019
Silver 0.015 0.006
Thallium 0.070 0.031
*Zinc 0.064 0.026
*Ammonia {as N) 8.398 3.692
*TSS 0.945 0.756
*pH Within the range of 7.0 to 10.0 at all times
^Regulated Pollutant
3132
-------
PRIMARY TUNGSTEN SUBCATEGORY
TABLE IX-2 (Continued)
NSPS FOR THE PRIMARY
TUNGSTEN SUBCATEGORY
(k) Reduction tc) Tungsten Wet Air Pollution Control NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Cadmium 0.616 0.246
Chromium 1.140 0.462
*Lead 0.862 0.400
Nickel 1.694 1.140
Silver 0.893 0.370
Thallium 4.312 . 1.879
*Zinc 3.142 1.294
*Ammonia (as N) 410.600 180.500
*TSS 46.200 36.960
*pH Within the range of 7.0 to 10.0
at all times
(1) Reduction to Tungsten Water of Formation NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
*Ammonia (as N)
*TSS
*pH Within the
0.098
0.181
0.137
0.269
0.142
0.685
0.499
65.190
7.335
range of 7.0 to 10.0
0.039
0.073
0.064
0.181
0.059
0.298
0.205
28.660
5.868
at all times
*Regulated Pollutant
3133
-------
PRIMARY TUNGSTEN SUBCATEGORY
TABLE IX-2 (Continued)
NSPS FOR THE PRIMARY
TUNGSTEN SUBCATEGORY
(m) Tungsten Power Acid Leach and Wash NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Cadmium 0.480 0.192
Chromium 0.888 0.360
*Lead 0.672 0.312
Nickel 1.320 0.888
Silver 0.696 0.288
Thallium 3.360 1.464
*Zinc 2.448 1.008
*Ammonia (as N) 319.900 140.700
*TSS 36.000 28.800
*pH Within the range of 7.0 to 10.0 at all times
(n) Molybdenum Sulfide Precipitation Wet Air Pollution
ControlNSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal
produced
Cadmium 0.000 0.000
Chromium 0.000 0.000
*Lead 0.000 0.000
Nickel 0.000 0.000
Silver 0.000 0.000
Thallium 0.000 0.000
*Zinc 0.000 0.000
*Ammonia (as N) 0.000 0.000
*TSS 0.000 0.000
*pH Within the range of 7.0 to 10.0
at all times
^Regulated Pollutant
3134
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - XII
SECTION XII
PRETREATMENT STANDARDS
This section describes the control and treatment technologies for
pretreatment of process wastewaters from existing sources and new
sources in the primary tungsten subcategory. PSES are designed
to prevent the discharge of pollutants which pass through,
interfere with, or are otherwise incompatible with the operation
of publicly owned treatment works (POTW). The Clean Water Act of
1977 requires pretreatment for pollutants, such as toxic metals,
that limit POTW sludge management alternatives. Section 307(c)
of the Act requires EPA to promulgate pretreatment standards for
new sources (PSNS) at the same time that it promulgates NSPS.
New indirect discharge facilities, like new direct discharge
facilities, have the opportunity to incorporate the best
available demonstrated technologies, including process changes,
in-plant controls, and end-of-pipe treatment technologies, and to
use plant site selection to ensure adequate treatment system
installation. Pretreatment standards are to be technology based,
analogous to the best available technology for removal of toxic
pollutants. Pretreatment standards for regulated pollutants are
presented based on the selected control and treatment technology.
TECHNICAL APPROACH TO PRETREATMENT
Before proposing and promulgating pretreatment standards, the
Agency examines whether the pollutants discharged by the industry
pass through the POTW or interfere with the POTW operation or its
chosen sludge disposal practices. In determining whether
pollutants pass through a well-operated POTW achieving secondary
treatment, the Agency compares the percentage of a pollutant
removed by POTW with the percentage removed by direct dischargers
applying the best available technology economically achievable. A
pollutant is deemed to pass through the POTW when the average
percentage removed nationwide by well-operated POTW meeting
secondary treatment requirements, is less than the percentage
removed by direct dischargers complying with BAT effluent
limitations guidelines for that pollutant. (See generally, 46 PR
at 9415-16 (January 28, 1981).)
This definition of pass through satisfies two competing
objectives set by Congress: (1) that standards for indirect
dischargers be equivalent to standards for direct dischargers
while at the same time, (2) that the treatment capability and
performance of the POTW be recognized and taken into account in
regulating the discharge of pollutants from indirect dischargers.
The Agency compares percentage removal rather than the mass or
concentration of pollutants discharged because the latter would
not take into account the mass of pollutants discharged to the
POTW from non-industrial sources or the dilution of the
pollutants in the POTW effluent to lower concentrations due to
the addition of .large amounts of non-industrial wastewater.
3135
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - XII
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
The industry cost and pollutant removal estimates of each
treatment option were used to determine the most cost-effective
option. The methodology applied in calculating pollutant removal
estimates and plant compliance costs is discussed in Section X.
Table XII-1 (page 3939) shows the estimated pollutant removal
estimates for indirect dischargers. Compliance costs for
indirect dischargers are presented in Table VIII-2 (page xxxx).
PRETREATMENT STANDARDS FOR EXISTING AND NEW SOURCES
Options for pretreatment of wastewaters from both existing and
new sources are based on increasing the effectiveness of end-of-
pipe treatment technologies. All in-plant changes and applicable
end-of-pipe treatment processes have been discussed previously in
Sections X and XI. The options for PSNS and PSES, therefore, are
the same as the BAT options discussed in Section X.
A description of each option is presented in Section X, while a
more detailed discussion, including pollutants controlled by each
treatment process is presented in Section VII of the General
Development Document.
Treatment technologies considered for the PSNS and PSES options
are:
OPTION A
o Preliminary treatment with ammonia steam stripping
(where required)
o Lime precipitation and sedimentation
OPTION B
o Preliminary treatment with ammonia steam stripping
(where required)
o Lime precipitation and sedimentation
o In-process flow reduction of acid leach, ammonium para-
tungstate conversion to oxides, and reduction to tungsten
scrubber liquor
OPTION C
o Preliminary treatment with ammonia steam stripping
(where required)
o Lime precipitation and sedimentation
3136
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - XII
o In-process flow reduction of acid leach, ammonium para-
tungstate conversion to oxides, and reduction to tungsten
scrubber liquor
o Multimedia filtration
PSNS AND PSES OPTION SELECTION
Option C (flow reduction, ammonia steam stripping, lime
precipitation, sedimentation, and multimedia filtration) has been
selected as the regulatory approach for pretreatment standards
for new and existing sources (PSNS and PSES). Option C prevents
pass-through and is equivalent to BAT treatment for direct
dischargers. Additionally, Option C removes incremental amounts
of toxic pollutants. Ammonia steam stripping is demonstrated at
three primary tungsten facilities. Filtration is not
demonstrated within the subcategory; however, it is demonstrated
in six nonferrous metals manufacturing subcategories at 23
plants.
The wastewater discharge rates for both PSES and PSNS are
identical to the BAT discharge rates for each waste stream. The
PSES and PSNS discharge rates are shown in Table XII-2 (page
3140).
Implementation of the promulgated PSES limitations would remove
annually an estimated 3,400 kg/yr of toxic pollutants and 63,320
kg/yr of ammonia over raw discharge. The final PSES effluent
mass limitations will remove 91 kg/yr of toxic metals over the
intermediate PSES option considered, which lacks filtration. Both
options are economically achievable. The Agency believes the
incremental removal justifies selection of filtration as part of
PSES model technology. The estimated capital cost for achieving
promulgated PSES is $0.568 million (March, 1982 dollars) and the
estimated annual cost is $0.445 million.
The wastewater discharge rates for both PSES and PSNS are
identical to the BAT discharge rates for each waste stream. The
PSES and PSNS discharge rates are shown in Table XII-3 (page
3142).
REGULATED POLLUTANT PARAMETERS
Pollutants selected for limitation, in accordance with the
rationale of Sections VI and X, are identical to those selected
for limitation for BAT. It is necessary to promulgate PSES and
PSNS to prevent the pass-through of lead, zinc, and ammonia,
which are the limited pollutants. Limitations for selenium,
although proposed, have not been promulgated because analytical
data gathered since proposal at two primary tungsten plants have
demonstrated that selenium is not found on a subcategory-wide
basis (see Section VI).
3137
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - XII
PRETREATMENT STANDARDS
Pretreatment standards are based on the treatment performance
concentrations from the selected treatment technology, (Option
C), and the discharge rates determined in Section X for BAT. A
mass of pollutant per mass of product (mg/kg) allocation is given
for each subdivision within the subcategory. This pollutant
allocation is based on the product of the treatable concentration
from the promulgated treatment (mg/1) and the production
normalized wastewater discharge rate (1/kkg). The achievable
treatment concentrations for BAT are identical to those for PSES
and PSNS. These concentrations are listed in Table XII-21 of the
General Development Document. PSES and PSNS are presented in
Tables XII-3 and XII-4 (pages 3142 and xxxx).
3138
-------
Table XII-1
POLLUTANT REMOVAL ESTIMATES FOR PRIMARY TUNGSTEN INDIRECT DISCHARGERS
Ul
M
Ul
POLLUTANT
Cadmium
Chromium
Lead
Nickel
Silver
Thalllu*
Zinc
TOTAL TOXIC HETALS
TOTAL
Alualnum
Amonla
Fluoride
Iron
KONCONVENTIONALS
TSS
Oil 4 Crease
TOTAL CON VENT IONALS
TOTAL POLLUTANTS
FLOW (1/yr)
TOTAL
RAW HASTE
26.7
268.2
2,674.9
133.7
38.8
93.5
267.5
3,503.3
SOI. 4
66. 577. 1
397.8
6,741.6
74.117.9
29,576.1
3,279.9
32,856.0
110,577.2
OPTION A
DISCHARGED
(kg/yr)
14.8
15.8
22.5
133.7
18.8
93.5
61.9
360.9
420.2
6,003.2
397.8
76.9
6,898.1
2,251.2
1,876.0
4,127.2
11,386.3
187.600.000
OPTION A
REMOVED
11.9
252.5
2.652.4
0.0
20.0
0.0
205.6
3.142.3
81.1
60,573.9
0.0
6,664.7
67,319.8
27,324.9
1,403.9
28,728.8
99,190.9
OPTION B
DISCHARGED
(kg/yr)
8.0
8.5
12.2
75.3
10.2
50.9
33.6
198.6
227.8
3,254.4
397.8
41.7
3,921 .7
1.220.4
1.017.0
2,237.4
6,357.7
101,700,000
OPTION B
REMOVED
(kg/yr)
18.7
259.7
2.662.7
58.5
28.6
42.6
233.9
3.304.7
273.6
63.322.7
0.0
6,699.9
70,296.2
28.355.7
2.262.9
30,618.6
104,219.5
OPTION C
DISCHARGED
(kg/yr)
5.0
7.1
8.1
22.4
7.1
34.6
23.4
107.7
151.5
3.254.4
397.8
28.5
3.832.2
264.4
1,017.0
1,281.4
5.221.3
IOI.7UO.OOO
OPTION C
REMOVED
(kg/yr)
21.7
261.1
2,666.8
III. 3
31.7
58.9
244.1
3,395.6
349.8
63,322.7
0.0
6,713.2
70,385.7
29, .111. 7
2,262.9
31,574.6
105,355.9
NOTE: TOTAL TOXIC HETALS - Cadi»lu* * Chromium * Lead «• Nickel + Silver + Thallium + Zinc
TOTAL NONCOHVENTIONALS - Aluminum * Ammonia * Fluoride * Iron
TOTAL OONVENT10NALS - TSS + Oil k Crease
TOTAL POLLUTANTS - Total Toxic Hetals + Total Honconventlonals + Total Conventional*
OPTION A - AaMonla Steal Stripping, Line Precipitation, and Sedimentation
OPTION 8 - Option A, plus In-Process Flow Reduction
OPTION C - Option B, plus Multimedia nitration
t)
»
H
S
Q
in
M
M
G
w
o
M
8
W
O
M
M
-------
PRIMARY TUNGSTEN SUBCATEGORY
SECT - XII
TABLE XI1-2
PSES AND PSNS WASTEWATER DISCHARGE RATES FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
Wastewater Stream
Tungstic Acid
Rinse Water
PSES and PSNS
Normalized
Discharge Rate
1/kkg gal/ton
41,030
9,839
Production
Normalizing
Parameter
Tungstic acid
(as W) produced
Acid Leach Wet Air
Pollution Control
Alkali Leach
Wash
Alkali Leach Wash
Condensate
Ion-Exchange
Raffinate
(commingled
and not
commingled
with other
process and
nonprocess
streams)
Calcium Tungstate
Precipitate Wash
Crystallization
and Drying of
Ammonium Para-
tungstate
Ammonium Paratung-
state Conversion
to Oxides Wet
Air Pollution
Control
Ammonium Paratung-
state Conversion
to Oxides Water
of Formation
3,581
859
19,180 4,599
88,480 21,220
73,810
2,762
63
17,700
0
662
15
Tungstic acid
(as W) produced
Sodium tungstate
(as W) produced
Sodium Tungstate
(as W) produced
Ammonium tungstate
(as W) produced
Calcium tungstate
(as W) produced
Ammonium paratung-
state (as W)
produced
Tungstic oxide
(as W) produced
Tungstic oxide
(WO3) produced
3140
-------
PRIMARY TUNGSTEN SUBCATEGORY
SECT - XII
TABLE XII-2 (Continued)
PSES AND PSNS WASTEWATER DISCHARGE RATES FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
Wastewater Stream
Reduction to
Tungsten
Air Pollu-
tion Control
Reduction to
Tungsten
Water of
Formation
Tungsten Powder Acid
Leach and Wash
Molybdenum Sulfide
Precipitation Wet
Air Pollution
Control
PSES AND PSNS
Normalized
Discharge Rate
gal/ton
739
489
2,400
117
576
Production
Normalizing
Parameter
Tungsten metal
produced
Tungsten metal
produced
Tungsten metal
produced
Tungsten metal
produced
3141
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT -XII
TABLE XI1-3
PSES FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(a) Tungstic Acid Rinse PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W)
produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
* Ammonia (as N)
6.038
11.170
11.490
16.610
8.755
42.270
41.850
5,469.000
2.415
4.529
5.333
11.170
3.623
18.420
17.230
2,404.000
(b) Acid Leach Wet Air Pollution Control PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W)
produced
Cadmium 0.527 0.211
Chromium 0.975 0.395
*Lead 1.003 0.466
Nickel 1.449 0.975
Silver 0.764 0.316
Thallium 3.689 1.607
*Zinc 3.653 1.504
*Ammonia (as N) 477.400 209.900
*Regulated Pollutant~~~
3142
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - XII
TABLE XII-3 (Continued)
PSES FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(c) Alkali Leach Wash PSES
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of sodium tungstate produced
English Units - Ibs/million Ibs of sodium tungstate produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
* Ammonia (as N)
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
(d) Alkali Leach Wash Condensate PSES
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Cadmium
Chromium
*Lead 5.372 2.494
Nickel
Silver
Thallium
*Zinc 19.570 8.057
*Ammonia (as N) 2,557.000 1,124.000
*Regulated Pollutant
3143
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - XII
TABLE XII-3 (Continued)
PSES FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(e) Ion-Exchange Raf f inate (Commingled with Other Process
or Nonprocess Water) PSES
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium tungstate (as W) produced .
English Units - Ibs/million Ibs of ammonium tungstate (as W)
produced
Cadmium 10.140 4.057
Chromium 18.760 7.606
*Lead 24.780 11.500
Nickel 27.890 18.760
Silver 14.710 6.085
Thallium 70.990 30.930
*Zinc 90.240 37.160
*Ammonia (as N) 11,790.000 5,185.000
(f ) Ion-Exchange Raf f inate (Not Commingled with Other Process
or Nonprocess Water)1 PSES
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium tungstate (as W) produced
English Units - Ibs/million Ibs of ammonium tungstate (as W)
produced
Cadmium
Chromium
*Lead 24.780 11.500
Nickel
Silver
Thallium
*Zinc 90.240 37.160
*Ammonia (as N) 11,790.000 5,185.000
*Regulated Pollutant ~~ ~~
pretreatment standard for this pollutant does not apply
if (a) the mother liquor feed to the ion exchange process or the
raffinate from the ion exchange process contains sulfates at
concentrations exceeding 1000 mg/1; (b) this mother liquor or
raffinate is treated by ammonia steam stripping; and (c) such
mother liquor or raffinate is not commingled with any other
process or nonprocess waters prior to steam stripping for ammonia
removal .
3144
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - XII
TABLE XII-3 (Continued)
PSES FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(g) Calcium Tungstate Precipitate Wash PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of calcium tungstate (as W) produced
English Units - Ibs/million Ibs of calcium tungstate (as W)
produced
Cadmium 9.428 3.771
Chromium 17.440 7.071
*Lead 20.670 9.594
Nickel 25.930 17.440
Silver 13.670 5.657
Thallium 66.000 28.760
*Zinc 75.280 31.000
*Ammonia (as N) 9,838.000 4,325.000
(h) Crystallization and Drying of Ammonium Paratungstate PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium paratungstate (as W) produced
English Units - Ibs/million Ibs of ammonium paratungstate
(as W) produced
Cadmium 0.000 0.000
Chromium 0.000 0.000
*Lead 0.000 0.000
Nickel 0.000 0.000
Silver 0.000 0.000
Thallium 0.000 0.000
*Zinc 0.000 0.000
*Ammonia (as N) 0.000 0.000
*Regulated Pollutant
3145
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - XII
TABLE XII-3 (Continued)
PSES FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(i) Ammonium Paratungstate Conversion to Oxides Wet Air
Pollution Control PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
*Ammonia (as N)
0.438
0.810
0.773
1.205
0.635
3.066
2.817
368.200
0.175
0.329
0.359
0.810
0.263
1.336
1.160
161.900
(j) Ammonium Paratungstate Conversion to Oxides Water of
Formation PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Cadmium 0.010 0.004
Chromium 0.019 0.008
*Lead 0.018 0.008
Nickel 0.028 0.019
Silver 0.015 0.006
Thallium 0.070 0.031
*Zinc 0.064 0.026
*Ammonia (as N) 8.398 3.692
*Regulated Pollutant
3146
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - XII
TABLE XII-3 (Continued)
PSES FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(k) Reduction t£ Tungsten Wet Air Pollution Control PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
*Ammonia (as N)
0.616
1.140
0.862
1.694
0.893
4.312
3.142
410.600
0.246
0.462
0.400
1.140
0.370
1.879
1.294
180.500
(1) Reduction to Tungsten Water of Formation PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Cadmium 0.098 0.039
Chromium 0.181 0.073
*Lead 0.137 0.064
Nickel 0.269 0.181
Silver 0.142 0.059
Thallium 0.685 0.298
*Zinc 0.499 0.205
*Ammonia (as N) 65.190 28.660
*Regulated Pollutant
3147
-------
PRIMARY TUNGSTEN SUBCATEGOR¥ SECT - XII
TABLE XI1-3 (Continued)
PSES FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(m) Tungsten Powder Acid Leach and Wash PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/raillion Ibs of tungsten metal produced.
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
* Ammonia (as N)
0.480
0.888
0.672
1.320
0.696
3.360
2.448
319.900
0.190
0.360
0.312
0.888
0.288
1.464
1.008
140.700
(n) Molybdenum Sulfide Precipitation Wet Air Pollution
ControlPSES
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal
produced
Cadmium 0.000 0.000
Chromium 0.000 0.000
*Lead 0.000 0.000
Nickel 0.000 0.000
Silver 0.000 0.000
Thallium 0.000 0.000
*Zinc 0.000 0.000
*Ammonia (as N) 0.000 0.000
3148
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - XII
TABLE XI1-4
PSNS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(a) Tungstic Acid Rinse PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W)
produced
Cadmium 6.038 2.415
Chromium 11.170 4.529
*Lead 11.490 5.333
Nickel 16.610 11.170
Silver 8.755 3.623
Thallium 42.270 18.420
*Zinc 41.850 17.230
*Ammonia (as N) 5,469.000 2,404.000
(b) Acid Leach Wet Air Pollution Control PSNS
Pollutant or"Maximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic acid (as W) produced
English Units - Ibs/million Ibs of tungstic acid (as W)
produced
Cadmium 0.527 0.211
Chromium 0.975 0.395
*Lead 1.003 0.466
Nickel 1.449 0.975
Silver 0.764 0.316
Thallium 3.689 1.607
*Zinc 3.653 1.504
*Ammonia (as N) 477.400 209.900
*Regulated Pollutant
3149
-------
PRIMARY TUNGSTEN SUBCATEGORY
SECT - XII
TABLE XII-4 {Continued)
PSNS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(c) Alkali Leach Wash
PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
*Aramonia (as N)
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
(d) Alkali Leach Wash Condensate PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of sodium tungstate (as W) produced
English Units - Ibs/million Ibs of sodium tungstate (as W)
produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
*Ammonia (as N)
5.372
19.570
2,557.000
2.494
8.057
1,124,000
*Regulated Pollutant
3150
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - XII
(e) Ion-Exchange Raffinate (Commingled with Other Process
or Nonprocess Waters) PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of ammonium tungstate (as W) produced
English Units - Ibs/million Ibs of ammonium tungstate (as W)
produced
Cadmium 10.140 4.057
Chromium 18.760 7.606
*Lead 24.780 11.500
Nickel 27.890 18.760
Silver . 14.710 6.085
Thallium 70.990 30.930
*Zinc 90.240 37.160
*Ammonia (as N) 11,790.000 5,185.000
(f) Ion-Exchange Raffinate (Not Commingled with Other Process
or Nonprocess Waters) PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric units - mg/kg of ammonium tungstate (as W) produced
English Units - Ibs/million Ibs of ammonium tungstate (as W)
produced
Cadmium
Chromium
*Lead 24.780 11.500
Nickel
Silver
Thallium
*Zinc 90.240 37.160
*Ammonia (as N) 11,790.000 5,185.000
*Regulated Pollutant
1The pretreatment standard for this pollutant does not apply
if (a) the mother liquor feed to the ion exchange process or the
raffinate from the ion exchange process contains sulfates at
concentrations exceeding 1000 mg/1; (b) this mother liquor or
raffinate is treated by ammonia steam stripping; and (c) such
mother liquor or raffinate is not commingled with any other
process or nonprocess waters prior to steam stripping for ammonia
removal.
3151
-------
PRIMARY TUNGSTEN SUBCATEGORY
SECT - XII
TABLE XII-4 (Continued)
PSNS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(g) Calcium Tungstate Precipitate Wash PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of calcium tungstate (as W) produced
English Units - Ibs/million Ibs of calcium tungstate (as W)
produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
*Ammonia (as N)
9.428
17.440
20.670
25.930
13.670
66.000
75.280
9,838.000
3.771
7.071
9.594
17.440
5.657
28.760
31.000
4,325.000
(h) Crystallization and Drying of_ Ammonium Paratungstate PSNS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
Metric Units - mg/kg of ammonium paratungstate (as W) produced
English Units - Ibs/million Ibs of ammonium paratungstate
(as W) produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
*Ammonia (as N)
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
*Regulated Pollutant
3152
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - XII
TABLE XII-4 (Continued)
PSNS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(i) Ammonium Paratungstate Conversion to Oxides Wet Air
Pollution Control PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
* Ammonia (as N)
0.438
0,810
0.773
1.205
0.635
3.066
2.817
368.200
0.175
0.329
0.359
0.810
0.263
1.336
1.160
161.900
(j) Ammonium Paratungstate Conversion to Oxides Water of
Formation PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungstic oxide (as W) produced
English Units - Ibs/million Ibs of tungstic oxide (as W)
produced
Cadmium 0.010 0.004
Chromium 0.019 0.008
*Lead 0.018 0.008
Nickel 0.028 0.019
Silver 0.015 0.006
Thallium 0.070 0.031
*Zinc 0.064 0.026
*Ammonia (as N) 8.398 3.692
*Regulated Pollutant
3153
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - XII
TABLE XI1-4 (Continued)
PSNS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(k) Reduction to Tungsten Wet Air Pollution Control PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
*Ammonia (as N)
0.616
1.140
0.862
1.694
0.893
4.312
3.142
410.600
0.246
0.462
0.400
1.140
0.370
1.879
1.294
180.500
(1) Reduction to Tujngsten Water of Formation PSNS
or ; Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Cadmium 0.098 0.039
Chromium 0.181 0.073
*Lead 0.137 0.064
Nickel 0.269 0.181
Silver 0.142 0.059
Thallium 0.685 0.298
*Zinc 0.499 0.205
*Ammonia (as N) 65.190 28.660
*Regulated Pollutant
3154
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT -XII
TABLE XII-4 (Continued)
PSNS FOR THE
PRIMARY TUNGSTEN SUBCATEGORY
(m) Tungsten Powder Acid Leach and Wash PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
* Ammonia (as N)
0.480
0.888
0.672
1.320
0.696
3.360
2.448
319.900
0.190
0.360
0.312
0.888
0.288
1.464
1.008
140.700
(n) Molybdenum Sulfide Precipitation Wet Air Pollution
Control PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Metric Units - mg/kg of tungsten metal produced
English Units - Ibs/million Ibs of tungsten metal
produced
Cadmium
Chromium
*Lead
Nickel
Silver
Thallium
*Zinc
* Ammonia (as N)
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
*Regulated Pollutant
3155
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - XII
THIS PAGE INTENTIONALLY LEFT BLANK
3156
-------
PRIMARY TUNGSTEN SUBCATEGORY SECT - XIII
SECTION XIII
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY
EPA is not promulgating best conventional pollutant control
technology (BCT) for the primary tungsten subcategory at this
time.
3157
-------
THIS PAGE INTENTIONALLY LEFT BLANK
Pages 3159 and 3160 are omitted,
3158
-------
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
DEVELOPMENT DOCUMENT SUPPLEMENT
for the
Secondary Tungsten and Cobalt Subcategory
William K. Reilly
Administrator
Rebecca Hanmer
Acting Assistant Administrator for Water
Martha Prothro, Director
Office of Water Regulations and Standards
USf)
Thomas P. O'Farrell, Director
Industrial Technology Division
Ernst P. Hall, P.E., Chief
Metals Industry Branch
and
Technical Project Officer
May 1989
U.S. Environmental Protection Agency
Office of Water
Office of Water Regulations and Standards
Industrial Technology Division
Washington, D. C. 20460
3161
-------
3162
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORI
TABLE OF CONTENTS
Section
I SUMMARY 3171
II CONCLUSIONS 3173
III SUBCATEGORY PROFILE 3193
Description of Secondary Tungsten and Cobalt 3193
Production
Raw Materials 3193
Tungsten Recovery From Scrap 3193
Synthetic Scheelite Production 3194
Tungsten Carbide Recovery Prom Scrap 3194
Cobalt Recovery From Sludges and Solutions 3195
Cobalt Production Via Cobalt Hydroxide 3195
Cobalt Dichloride Production 3195
Cobalt Production From Cobalt Oxylate 3196
Process Wastewater Sources 3196
Other Wastewater Sources 3196
Age, Production, and Process Profile 3196
IV SUBCATEGORIZATION 3205
Factors Considered in Subdividing the Secondary 3205
Tungsten and Cobalt Subcategory
Other Factors 3206
Production Normalizing Parameters 3206
V WATER USE AND WASTEWATER CHARACTERISTICS 3209
Wastewater Flow Rates 3210
Wastewater Characteristics Data 3211
Data Collection Portfolios 3211
. Field Sampling Data 3211
Wastewater Characteristics and Flows by 3213
Subdivision
Tungsten Detergent Wash and Rinse 3213
Tungsten Leaching Acid 3213
Tungsten Post-Leaching Wash and Rinse 3213
Synthetic Scheelite Filtrate 3213
Tungsten Carbide Leaching Wet Air Pollution 3214
Control
Tungsten Carbide Wash Water 3214
Cobalt Sludge Leaching Wet Air Pollution 3215
Control
Crystallization Decant 3215.
Acid Wash Decant 3215
Cobalt Hydroxide Filtrate 3216
Cobalt Hydroxide Filter Cake Wash 3216
3163
-------
SECONDARY TUNGSTEN AND COBALT SDBCATEGORY
Section
VI
TABLE OF CONTENTS (Continued)
SELECTION OP POLLUTANT PARAMETERS
Conventional and Nonconventional Pollutant
Parameters Selected
Toxic Priority Pollutants
Toxic Pollutants Never Detected
Toxic Pollutants Present Below Concentrations
Achievable by Treatment
Toxic Pollutants Detected in a Small Number of
Sources
Toxic Pollutants Selected for Further
Consideration in Limitations and Standards
3260
3261
3261
3261
3262
VII
VIII
CONTROL AND TREATMENT TECHNOLOGIES 3269
Current Control and Treatment Practices 3269
Tungsten Detergent Wash and Rinse 3269
Tungsten Leaching Acid 3269
Tungsten Post-Leaching Wash and Rinse 3270
Synthetic Scheelite Filtrate 3270
Tungsten Carbide Leaching Wet Air Pollution 3270
Control
Tungsten Carbide Wash Water 3270
Cobalt Sludge Leaching Wet Air Pollution 3270
Control
Crystallization Decant 3270
Acid Wash Decant 3271
Cobalt Hydroxide Filtrate 3271
Cobalt Hydroxide Filter Cake Wash 3271
Control and Treatment Options 3271
Option A 3271
Option C 3272
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS 3273
Treatment Options for Existing Sources 3273
Option A 3273
Option C 3273
Cost Methodology 3273
Energy Requirements 3274
Solid Waste 3274
Air Pollution 3275
3164
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY.
TABLE OF CONTENTS (Continued)
Section Page
IX BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY 3279
AVAILABLE
Technical Approach to BPT 3279
Industry Cost and Pollutant Removal Estimates 3279
BPT Option Selection 3279
Wastewater Discharge Rates 3281
Tungsten Detergent Wash and Rinse 3281
Tungsten Leaching Acid 3281
Tungsten Post-Leaching Wash and Rinse 3281
Synthetic Scheelite Filtrate 3281
Tungsten Carbide Leaching Wet Air Pollution 3282
Control
Tungsten Carbide Wash Water 3282
Cobalt Sludge Leaching Wet Air Pollution 3282
Control
Crystallization Decant 3282
Acid Wash Decant 3282
Cobalt Hydroxide Filtrate 3283
Cobalt Hydroxide Filter Cake Wash 3283
Regulated Pollutant Parameters 3283
Effluent Limitations 3283
X BEST AVAILABLE TECHNOLOGY ECONOMICALLY 3293
ACHIEVABLE
Technical Approach to BAT 3293
Option A 3294
Option C 3294
Industry Costs and Pollutant Removal Estimates 3294
Pollutant Removal Estimates 3294
Compliance Costs 3295
BAT Option Selection - Proposal 3295
BAT Option Selection - Promulgation 3296
Amended Regulation 3296
Wastewater Discharge Rates 3297
Regulated Pollutant Parameters 3297
Effluent Limitations 3299
XI NEW SOURCE PERFORMANCE STANDARDS 3311
Technical Approach to NSPS 3311
NSPS Option Selection 3312
Regulated Pollutant Parameters 3312
New Source Performance Standards 3312
3165
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TABLE OF CONTENTS (Continued)
Section Page
XII PRETREATMENT STANDARDS 3321
Technical Approach to Pretreatment 3321
Pretreatment Standards for New Sources 3321
PSNS Option Selection 3322
Regulated Pollutant Parameters 3322
Pretreatment Standards 3323
XIII BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY 3339
3166
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
LIST OP TABLES
Title Page
Initial Operating Year (Range) Summary of 3198
Plants in the Secondary Tungsten and Cobalt
Subcategory By Discharge Type
III-2 Production Ranges for the Secondary Tungsten 3199
and Cobalt Subcategory
III-3 Summary of Secondary Tungsten and Cobalt 3200
Subcategory Associated Waste Streams
V-l Water Use and Discharge Rate for 3217
Tungsten Detergent Wash and Rinse
V-2 Water Use and Discharge Rate for 3217
Tungsten Leaching Acid
V-3 Water Use and Discharge Rate for 3217
Tungsten Post-Leaching Wash and Rinse
V-4 Water Use and Discharge Rate for 3218
Synthetic Scheelite Filtrate
V-5 Water Use and Discharge Rate for Tungsten 3218
Carbide Leaching Wet Air Pollution Control
V-6 Water Use and Discharge Rate for 3218
Tungsten Carbide Wash Water
V-7 Water Use and Discharge Rate for Cobalt 3219
Sludge Leaching Wet Air Pollution Control
V-8 Water Use and Discharge Rate for 3219
Crystallizer Decant
V-9 Water Use and Discharge Rate for 3219
Acid Wash Decant
V-10 Water Use and Discharge Rate for 3220
Cobalt Hydroxide Filtrate
V-ll Water Use and Discharge Hate for 3220
Cobalt Hydroxide
V-12 Secondary Tungsten and Cobalt Subcategory 3221
Tungsten Detergent Wash and Rinse
Raw Wastewater Sampling Data
3167
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
LIST OF TABLES (Continued)
Table Title Page
V-13 Secondary Tungsten and Cobalt Subcategory 3226
Tungsten Leaching Acid
Raw Wajtewater Sampling Data
V-14 Secondary Tungsten and Cobalt Subcategory 3230
Tungsten Post-Leaching Wash and Rinse
Raw Wastewater Sampling Data
V-15 Secondary Tungsten and Cobalt Subcategory 3234
Wastewater Storage - Crystallization and Acid
Wash Decants, and Cobalt Sludge Leaching Wet Air
Pollution Control Raw Wastewater Sampling Data
V-16 Secondary Tungsten and Cobalt Subcategory 3236
Crystallization Decant
Raw Wastewater Sampling Data
V-17 Secondary Tungsten and Cobalt Subcategory 3238
Acid Wash Decant
Raw Wastewater Sampling Data
V-18 Secondary Tungsten and Cobalt Subcategory 3243
Cobalt Hydroxide Filtrate
Raw Wastewater Sampling Data
V-19 Secondary Tungsten and Cobalt Subcategory 3245
Cobalt Hydroxide Filter Cake Wash
Raw Wastewater Sampling Data
V-20 Secondary Tungsten and Cobalt Subcategory 3247
Treatment Plant Sampling Data - Plant A
V-21 Secondary Tungsten and Cobalt Subcategory 3252
Treatment Plant Sampling Data - Plant B
VI-1 Frequency of Occurrence of Toxic Pollutants 3264
Secondary Tungsten and Cobalt Subcategory
VI-2 Toxic Pollutants Never Detected 3265
VIII-1 Cost of Compliance for the Secondary Tungsten 3276
and Cobalt Subcategory Direct Dischargers
VIII-2 Cost of Compliance for the Secondary Tungsten 3276
and Cobalt Subcategory Indirect Dischargers
3168
-------
SECONDARY TUNGSTEN AND COBALT SU1CATEGORY
LIST OF TABLES (Continued)
Title Page
BPT Wastewater Discharge Rates for the 3285
Secondary Tungsten and Cobalt Subcategory
IX-2 BPT Mass Limitations for the Secondary 3286
Tungsten and Cobalt Subcategory
X-l Pollutant Removal Estimates for Direct 3308
Dischargers in the Secondary Tungsten and
Cobalt Subcategory
X-2 Cost of Compliance for the Secondary Tungsten 3301
and Cobalt Subcategory Direct Dischargers
X-3 BAT Wastewater Discharge Rates for the Secondary 3302
Tungsten and Cobalt Subcategory
X-4 BAT Limitations for the Secondary Tungsten 3305
and Cobalt Subcategory
XI-1 NSPS Wastewater Discharge Rates for the 3313
Secondary Tungsten and Cobalt Subcategory
XI-2 NSPS for the Secondary Tungsten and Cobalt 3314
Subcategory
XII-1 PSES and PSNS Wastewater Discharge Rates for the 3324
Secondary Tungsten and Cobalt Subcategory
XII-2 Cost of Compliance for the Secondary Tungsten 3325
and Cobalt Subcategory Indirect Dischargers
XI1-3 FSNS for the Secondary Tungsten and Cobalt 3326
Subcategory
XII-4 PSNS for the Secondary Tungsten and Cobalt 3332
Subcategory
3169
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
LIST OF FIGURES
Figure Title
III-l Secondary Tungsten and Cobalt Production 3201
Processes
III-2 Geographic Locations of Secondary Tungsten 3204
and Cobalt Subcategory Plants
IX-1 BPT Treatment Scheme for the Secondary Tungsten 3292
and Cobalt Subcategory
X-l BAT Treatment Scheme for Option A 3309
X-2 BAT Treatment Scheme for Option C 3310
3170
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - I
SECTION I
SUMMARY
This document provides the technical basis for promulgating
effluent limitations based on best practicable technology (BPT)
and best available technology (BAT) for existing direct
dischargers, standards of performance for new source direct
dischargers (NSPS), pretreatment standards for existing indirect
dischargers (PSES), and pretreatment standards for new indirect
dischargers (PSNS) for plants in the secondary tungsten and
cobalt subcategory.
The secondary tungsten and cobalt subcategory consists of six
plants. Four of the six plants discharge directly to rivers,
lakes or streams, and one plant achieves zero discharge of
process wastewater. One plant in this subcategory discharges to
a publicly owned treatment works.
EPA first studied the secondary tungsten and cobalt subcategory
to determine whether differences in raw materials, final
products, manufacturing processes, equipment, age and size of
plants, or water usage required the development of separate
effluent limitations and standards for different segments of the
subcategory. This involved a detailed analysis of wastewater
discharge and treated effluent characteristics, including the
sources and volume of water used, the processes used, the sources
of pollutants and wastewaters in the plant, and the constituents
of wastewaters, including priority pollutants. As a result, 11
subdivisions or building blocks have been identified for this
subcategory that warrant separate effluent limitations. These
include:
1. Tungsten detergent wash and rinse,
2. Tungsten leaching acid,
3. Tungsten post-leaching wash and rinse,
4. Synthetic scheelite filtrate,
5. Tungsten carbide leaching wet air pollution control,
6. Tungsten carbide wash water,
7. Cobalt sludge leaching wet air pollution control,
8. Crystallization decant,
9. Acid wash decant,
10. Cobalt hydroxide filtrate, and
11. Cobalt hydroxide filter cake wash.
EPA also identified several distinct control and treatment
technologies (both in-plant and end-of-pipe) applicable to the
secondary tungsten and cobalt subcategory. The Agency analyzed
both historical and newly generated data on the performance of
these technologies, including their nonwater quality
environmental impacts and air quality, solid waste generation',
and energy requirements. EPA also studied various flow reduction
techniques reported in the data collection portfolios (dcp) and
plant visits.
3171
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - I
Engineering costs were prepared for each of the control and
treatment options considered for the subcategory. These costs
were then used by the Agency to estimate the impact to
implementing the various options on the subcategory. For each
control and treatment option that the Agency found to be most
effective and technically feasible in controlling the discharge
of pollutants, we estimated the number of potential closures,
number of employees affected, and impact on price. These results
are reported in a separate document entitled "The Economic Impact
Analysis of Effluent Limitations and Standards for the Nonferrous
Metals Manufacturing Industry."
After examining the various treatment technologies, the Agency
has identified BPT to represent the average of the best existing
technology. Metals removal based on chemical precipitation and
sedimentation technology is the basis for the BPT limitations.
Steam stripping was selected as the technology basis for ammonia
limitations. Oil skimming was selected as the technology basis
for oil and grease limitations. To meet the BPT effluent
limitations based on this technology, the secondary tungsten and
cobalt subcategory is estimated to incur a capital cost of
$42,900 and an annual cost of $173,000.
For BAT, the Agency has built upon the BPT technology basis by
adding filtration. Filtration is added as an effluent polishing
step to the end-of-pipe treatment scheme. To meet the BAT
effluent limitations based on this technology, the secondary
tungsten and cobalt subcategory is estimated to incur a capital
cost to $60,900 and an annual cost of $182,700.
NSPS is equivalent to BAT. In selecting NSPS, EPA recognizes
that new plants have the opportunity to implement the best and
most efficient manufacturing processes and treatment technology.
As such, the technology basis of BAT has been determined as the
best demonstrated technology. The technology basis for PSES is
equivalent to BAT. To meet the pretreatment standards for
existing sources, the secondary tungsten and cobalt subcategory
is estimated to incur a capital cost of $16,300 and an annual
cost of $8,800. For PSNS, the Agency selected end-of-pipe
treatment and in-process flow reduction control techniques
equivalent to NSPS.
The best conventional technology (BCT) replaces BAT for the
control of conventional pollutants. BCT is not being promulgated
because the methodology for BCT has not yet been finalized.
The mass limitations and standards for BPT, BAT, NSPS, PSES and
PSNS are presented in Section II.
3172
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - II
SECTION II
CONCLUSIONS
EPA has divided the secondary tungsten and cobalt subcategory
into 11 subdivisions for the purpose of effluent limitations
and standards. These subdivisions are:
(a) Tungsten detergent wash and rinse,
(b) Tungsten leaching acid,
(c) Tungsten post-leaching wash and rinse,
(d) Synthetic scheelite filtrate,
(e) Tungsten carbide leaching wet air pollution control,
(f) Tungsten carbide wash water,
(g) Cobalt sludge leaching wet air pollution control,
(h) Crystallization decant,
(i) Acid wash decant,
(j) Cobalt hydroxide filtrate, and
(k) Cobalt hydroxide filter cake wash.
BPT is promulgated based on the performance achievable by the
application of chemical precipitation and sedimentation (lime and
settle) technology, along with preliminary treatment consisting
of ammonia steam stripping and oil skimming for selected waste
streams. The following BPT effluent limitations are promulgated:
(a) Tungsten Detergent Wash and Rinse BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tungsten scrap washed
Copper 0.371 0.195
Nickel 0.374 0.248
Ammonia (as N) 25.990 11.430
Cobalt 0.768 0.337
Tungsten 1.357 0.542
Oil and Grease 3.900 2.340
Total Suspended 7.995 3.803
Solids
pH Within the range of 7.5 to 10.0
at all times
3173
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - II
(b) Tungsten Leaching Acid BPT
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
rag/kg (Ib/million Ibs) of tungsten produced
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
Oil and Grease
TSS
pH
(c) Tungsten
4.885
4.937
342.700
10.130
17.890
51.420
105.400
Within the range of 7
Post-Leaching Wash and
2.571
3.265
150.700
4.448
7.147
30.850
50.140
.5 to 10.0 at all times
Rinse BPT
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
rag/kg (Ib/million Ibs) of tungsten produced
Copper 9.772 5.143
Nickel 9.875 6.532
Ammonia (as N) 685.600 301.400
Cobalt 20.263 8.897
Tungsten 35.800 14.300
Oil and Grease 102.900 61.720
TSS 210.900 100.300
pH Within the range of 7.5 to 10.0 at all times
(d) Synthetic Scheelite Filtrate BPT
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
rag/kg (Ib/million Ibs) of synthetic scheelite produced
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
Oil and Grease
TSS
pH Within
31.660
31.990
2,221.000
65.644
116.000
333.200
683.100
the range of 7.5
16.660
21.160
976.300
28.824
46.320
200.000
324.900
to 10.0 at all
times
3174
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGQRY SECT - II
(e) Tungsten Carbide Leaching Wet Air Pollution Control BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg
Copper
Nickel
Ammonia (as
Cobalt
(Ib/million Ibs) of
3
3
N) 233
6
Tungsten 12
Oil and Grease 35
TSS
PH
71
Within the range
tungsten
,327
,362
.400
.899
.190
.020
.790
of 7.5 to
carbide scrap
1.751
2.224
102.600
3.029
4.868
21.010
34.150
10.0 at all
leaded
times
Tungsten Carbide Wash Water BPT
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
Oil and Grease
TSS
pH Within the
Ibs) of tungsten
15.830
16.000
1,111.000
32.832
58.000
166.700
341.700
range of 7.5 to
carbide produced
8.333
10.580
488.300
14.416
23.170
100.000
162.500
10.0 at all times
Cobalt Sludge Leaching Wet Air Pollution Control BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cobalt produced from cobalt slud
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
Oil and Grease
TSS
pH Within
67.990
68.700
4,770,000
140,977
249,000
715,600
1,467.000
the range of 7.5
35.780
45.440
2,097.000
61.901
99.470
429.400
697.700
to 10.0 at all times
3175
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - II
(h) Crystallization Decant BPT
Pollutant ^>rMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cobalt produced
Copper 79.140 41.650
Nickel 79.970 52.900
Ammonia (as N) 5,552.000 2,441.000
Cobalt 164.101 72.055
Tungsten 289.900 115.800
Oil and Grease 833.000 499.800
TSS 1,708.000 812.200
pH Within the range of 7.5 to 10.0 at all times
(i) Acid Wash Decant BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cobalt produced
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
Oil and Grease
TSS
pH Within
( j J Cobalt Hydroxide
36.220
36.600
2,541.000
75.104
132.700
381.300
781.600
the range of 7.5
Filtrate BPT
19.060
24.210
1,117.000
32.977
52.990
228.800
371.700
to 10.0 at all times
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
Oil and Grease
TSS
pH Within the
107.600
108.800
7,551.000
223.189
394.300
1,133.000
2,323.000
range of 7.5
cobalt produced
56.650
71.940
3,320.000
97.999
157.500
679.800
1,105.000
to 10.0 at all
times
3176
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT -II
(k) Cobalt Hydroxide Filter Cake Wash BPT
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
Oil and Grease
TSS
pH Within the
207.200
209.400
14,530.000
429.598
758.900
2,181.000
4,471.000
range of 7.5
cobalt produced
109.100
138.500
6,389.000
188.631
303.100
1,309.000
2,126.000
to 10.0 at all times
BAT is promulgated based on the performance achievable by the
application of chemical precipitation, sedimentation, and
multimedia filtration (lime, settle, and filter) technology along
with preliminary treatment consisting of ammonia steam stripping
and oil skimming for selected waste streams. The following BAT
effluent limitations are promulgated:
(a) Tungsten Detergent Wash and Rinse BAT
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tungsten scrap washed
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
0.250
0.107
25.990
0.538
0.679
0.119
0.072
11.430
0.236
0.302
(b) Tungsten Leaching Acid BAT
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tungsten produced
Copper 3.291 1.569
Nickel 1.414 0.951
Ammonia (as N) 342.700 150.700
Cobalt 7.096 3.111
Tungsten 8.947 3.985
3177
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - II
(c) Tungsten Post-Leaching Wash and Rinse BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tungsten produced
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
(d) Synthetic Scheelite
•
6.583
2.829
685.600
14.197
17.900
Filtrate BAT
3.137
1.903
301.400
6.223
7.972
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of synthetic scheelite produced
Copper 21.330 10.170
Nickel 9.164 6.165
Ammonia (as N) . 2,221.000 976.300
Cobalt 45.984 20.160
Tungsten 57.980 25.82O
(e) Tungsten Carbide Leaching Wet Air Pollution Control BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tungsten carbide scrap leached
Copper 2.241 1.068
Nickel 0.963 0.648
Ammonia (as N) 233.400 102.600
Cobalt 4.833 2.119
Tungsten 6.093 2.714
3178
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - II
(f) Tungsten Carbide Wash Water BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tungsten carbide produced
Copper 10.670 5.083
Nickel 4.583 3.083
Ammonia (as N) 1,111.000 488.300
Cobalt 22.999 10.083
Tungsten 29.000 12.920
(g) Cobalt Sludge Leaching Wet Air Pollution Control BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg ( Ib/mi 1 1 ion
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
(h) Crystallization
Ibs) of cobalt
45.800
19.680
4,769.000
98.756
124.500
Decant BAT
produced from cobalt slud
21.830
13.240
2,097.000
43.295
55.460
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cobalt produced
Copper 53.310 25.410
Nickel 22.910 15.410
Ammonia (as N) 5,552.000 2,441.000
Cobalt 114.954 50.397
Tungsten 144.900 64.560
3179
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - II
(i) Acid Wash Decant BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cobalt produced
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
24.400
10.490
2,541.000
52.611
66.340
11.630
7.053
1,117.000
"23.065
29.550
(j) Cobalt Hydroxide Filtrate BAT
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cobalt produced
Copper 72.510 34.560
Nickel 31.160 20.960
Ammonia (as N) 7,551.000 3,320.000
Cobalt . 156.346 68.543
Tungsten 197.100 87.800
(k) Cobalt Hydroxide Filter Cake Wash BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cobalt produced
Copper 139.600 66.510
Nickel 59.970 40.340
Ammonia (as N) 14,530.000 6,389.000
Cobalt 300.094 131.932
Tungsten 379.400 169.000
NSPS are Promulgated based on the performance achievable by
the application of chemical precipitation, sedimentation, and
multimedia filtration (lime, settle, and filter) technology,
along with preliminary treatment consisting of ammonia steam
stripping and oil skimming for selected waste streams. The
following effluent standards are promulgated for new sources:
3180
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - II
(a) Tungsten Detergent Wash and Rinse 'NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
Copper
Nickel
Ammonia
Cobalt
Tungsten
Oil and
TSS
pH
rog/kg (Ib/million Ibs) of tungsten
0.250
0.107
(as N) 25.990
0.538
0.679
Grease 1.950
2.925
Within the range of 7.5 to 10.0
scrap washed
0.119
0.072
11.430
0.236
0.302
1.950
2.340
at all times
(b) Tungsten Leaching Acid NSPS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
nig/kg (Ib/million Ibs) of tungsten produced
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
Oil and Grease
TSS
pH Within the
3.291
1.414
342.700
7.096
8.947
25.710
38.570
range of 7.5
1.569
0.951
150.700
3.111
3.985
25.710
30.850
to 10.0 at all times
(c) Tungsten Post-Leaching Wash and Rinse NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
Oil and Grease
TSS
Ibs) of
6.583
2.829
685.600
14.194
17.900
51.430
77.150
pH Within the range of 7.
tungsten produced
3.137
1.903
301.400
6.223
7.972
51.430
61.720
5 to 10.0 at all times
3181
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - II
(d) Synthetic Scheelite Filtrate NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
Oil and Grease
TSS
pH Within the
Ibs) of synthetic
21.330
9.164
2,221.000
45.984
57.980
166.600
249.900
range of 7.5 to
scheelite produced
10.170
6.165
976.300
20.160
25.820
166.600
200.000
10.0 at all times
(e) Tungsten Carbide Leaching Wet Air Pollution Control NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
Oil and Grease
TSS
pH Within the
Ibs) of tungsten
2.241
0.963
233.400
4.833
6.093
17.510
26.270
range of 7.5 to
carbide scrap leache
1.068
0.648
102.600
2.119
2.714
17.510
21.010
10.0 at all times
(f) Tungsten Carbide Wash Water NSPS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tungsten carbide produced
Copper 10.670 5.083
Nickel 4.583 3.083
Ammonia (as N) 1,111.000 488.300
Cobalt 22.999 10.083
Tungsten 29.000 12.920
Oil and Grease 83.330 83.330
TSS 125.000 100.000
pH Within the range of 7.5 to 10.0 at all times
3182
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - II
(g) Cobalt Sludge Leaching Wet Air Pollution Control NSPS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
Oil and Grease
TSS
pH Within the
Ibs) of cobalt produced
45.800
19.680
4,769.000 2,
98.756
124.500
357.800
536.700
range of 7.5 to 10.0 at
from cobalt
21.830
13.240
097.000
43.295
55.460
357.800
429.400
all times
sludge
(h) Crystallization Decant NSPS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cobalt produced
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
Oil and Grease
TSS
pH Within the
53.310
22.910
5,552.000
114.954
144.900
416.500
624.800
range of 7.5 to
25.410
15.410
2,441.000
50.397
64.560
416.500
499.800
10.0 at all times
(i) Acid Wash Decant NSPS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cobalt produced
Copper 24.400 11.630
Nickel 10.490 7.053
Ammonia (as N) 2,541.000 1,117.000
Cobalt 52.611 23.065
Tungsten 66.340 29.550
Oil and Grease 190.600 190.600
TSS 286.000 228.700
pH Within the range of 7.5 to 10.0 at all times
3183
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
SECT - II
(j) Cobalt Hydroxide Filtrate NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of cobalt produced
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
Oil and Grease
TSS
72.510
31.160
7,551.000
156.346
197.100
566.500
849.700
34.560
20.960
3,320.000
68.543
87.800
566.500
679.800
pH
Within the range of 7.5 to 10.0 at all times
(k) Cobalt Hydroxide Filter Cake Wash NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
nig/kg (Ib/million Ibs) of cobalt produced
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
Oil and Grease
TSS
139.600
59.970
14,530.000
300.094
379.400
1,091.000
1,636.000
66.510
40.340
6,389.000
131.932
169.000
1,091.000
1,309.000
pH
Within the range to 7.5 to 10.0 at all times
PSES are promulgated based on the performance achievable by
the application of chemical precipitation, sedimentation, and
multimedia filtration (lime, settle, and filter) technology,
along with preliminary treatment consisting of ammonia steam
stripping and oil skimming for selected waste streams. The
following pretreatment standards are promulgated for existing
sources:
3184
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - II
(a) Tungsten Detergent Wash and Rinse PSES
PollutantorMaximum forMaximumfor
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tungsten scrap washed
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
0.250
0.107
25.990
0.538
0.679
0.119
0.072
11.430
0.236
0.302
(b) Tungsten Leaching Acid PSES
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
rag/kg (Ib/million Ibs] of tungsten produced
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
3.291
1.414
342.700
7.096
8.947
1.569
0.951
150.700
3.111
3.985
(c) Tungsten Post-Leaching Wash and Rinse PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tungsten produced
Copper 6.583 3.137
Nickel 2.829 1.903
Ammonia (as N) 685.600 301.400
Cobalt 14.194 6.223
Tungsten 17.900 7.972
3185
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - II
(d) Synthetic Scheelite Filtrate PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tungsten produced
Copper 21.330 10.170
Nickel 9.164 6.165
Ammonia (as N) 2,221.000 976.300
Cobalt 45.984 20.160
Tungsten 57.980 25.820
(e) Tungsten Carbide Leaching Wet Air Pollution Control PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (
Copper
Nickel
Ammonia (as
Cobalt
Tungsten
Ib/million Ibs)
N)
(f) Tungsten Carbide Wash
of tungsten
2.241
0.963
233.400
4.833
6.093
Water PSES
carbide
1
0
102
2
2
scrap leached
.068
.648
.600
.119
.714
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tungsten carbide produced
Copper 10.670 5.083
Nickel 4.583 3.083
Ammonia (as N) 1,111.000 488.300
Cobalt 22.999 10.083
Tungsten 29.000 12.920
3186
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT -II
(g) Cobalt Sludge Leaching Wet Air Pollution Control PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cobalt produced from cobalt sludge
Copper 45.800 21.830
Nickel 19.680 13.240
Ammonia (as N) 4,770.000 2,097.000
Cobalt 98.756 43.295
Tungsten 124.500 55.460
(h) Crystallization Decant PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
rag/kg (Ib/million Ibs) of
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
(i) Acid Wash Decant
53.310
22.910
5,552.000
114.954
144.900
PSES
cobalt produced
25.410
15.410
2,441.000
50.397
64.560
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cobalt produced
Copper 24.400 11.630
Nickel 10.490 7.053
Ammonia (as N) 2,541.000 1,117.000
Cobalt 52.611 23.065
Tungsten 66.340 29.550
3187
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - II
(j) Cobalt Hydroxide Filtrate PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cobalt produced
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
72.510
31.160
7,551.000
156.346
197.100
34.560
20.960
3,320.000
68.543
87.800
(k) Cobalt Hydroxide Filter Cake Wash PSES
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/milllon Ibs) of cobalt produced
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
139.600
59.970
14,530.000
300.094
379.400
66.510
40.340
6,389.000
131.932
169.000
PSNS are promulgated based on the performance achievable by
the application of chemical precipitation, sedimentation, and
multimedia filtration (lime, settle, and filter) technology,
along with preliminary treatment consisting of ammonia steam
stripping and oil skimming for selected wastewater streams. The
following pretreatment standards are promulgated for new sources:
(a) Tungsten Detergent Wash and Rinse PSNS
Pollutant or"Maximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
(Ib/million Ibs) of
0.250
0.107
25.990
0.538
0.679
tungsten scrap washed
0.119
0.072
11.430
0.236
0.302
3188
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - II
(b) Tungsten Leaching Acid PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of tungsten produced
Copper 3.291 1.569
Nickel 1.414 0.951
Ammonia (as N) 342.700 150.700
Cobalt 7.096 3.111
Tungsten 8.947 3.985
(c) Tungsten Post-Leaching Wash and Rinse PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg {Ib/million Ibs) of tungsten produced
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
6.583
2.829
685.600
-14.194
17.900
3.137
1.903
301.400
6.223
7.972
(d) Synthetic Scheelite Filtrate PSNS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of synthetic scheelite produced
Copper 21.330 10.170
Nickel 9.164 6.165
Ammonia (as N) 2,221.000 976.300
Cobalt 45.984 20.160
Tungsten 57.980 25.82O
3189
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - II
(e) Tungsten Carbide Leaching Wet Air Pollution Control PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
rog/kg (lb/million
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
(f) Tungsten Carbide
Ibs) of tungsten carbide scrap leached
2.241
0.963
233.400
4.833
6.093
Wash Water PSNS
1.068
0.648
102.600
2.119
2.714
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (lb/million Ibs
Copper
Nickel
Ammonia (as N) 1,
Cobalt
Tungsten
(g) Cobalt Sludge Leaching
) of tungsten
10.670
4.583
111.000
22.999
29.000
carbide produced
5.083
3.083
488.300
10.083
12.920
Wet Air Pollution Control PSNS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (lb/million Ibs) of cobalt produced from cobalt sludge
Copper 45.800 21.830
Nickel 19.680 13.240
Ammonia (as N) 4,770.000 2,097.000
Cobalt 98.756 43.295
Tungsten 124.500 55.460
3190
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - II
(h) Crystallization Decant PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cobalt produced
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
(i) Acid Wash Decant
53.310
22.910
5/552.000
114.954
144.900
PSNS
25.410
15.410
2,441.000
50.397
64.560
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cobalt produced
Copper
Nickel
Ammonia (as N)
Cobalt
Tungsten
(i) Cobalt Hydroxide
24.400
10.490
2,541.000
52.611
66.340
Filtrate PSNS
11.630
7.053
1,117.000
23.065
29.550
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cobalt produced
Copper 72.510 34.560
Nickel 31.160 20.960
Ammonia (as N) 7,551.000 3,320.000
Cobalt 156.346 68.543
Tungsten 197.100 87.800
3191
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - II
(k) Cobalt Hydroxide Filter Cake Wash PSNS
Pollutant orMaximum forMaximumfor
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of cobalt produced
Copper 139.600 66.510
Nickel 59.970 40.340
Ammonia (as N) 14,530.000 6,389.000
Cobalt 300.094 131.932
Tungsten 379.400 169.000
EPA is not promulgating BCT for this subcategory at this time.
3192
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - III
SECTION III
SUBCATEGORY PROFILE
This section of the secondary tungsten and cobalt supplement
describes the raw materials and processes used in smelting and
refining secondary tungsten and cobalt and presents a profile of
the secondary tungsten and cobalt plants identified in this
study.
DESCRIPTION OF SECONDARY TUNGSTEN AND COBALT PRODUCTION
Secondary tungsten is produced from tungsten carbide scrap and
other tungsten bearing scrap. Secondary cobalt is recovered as a
co-product of the tungsten carbide recovery process. Cobalt is
used as a binder alloy in the manufacture of tungsten carbide
parts. The hydrometallurgical processing used -to recover
secondary tungsten, secondary tungsten carbide/ and secondary
cobalt can be divided into several steps: tungsten recovery f-rom
scrap (non-tungsten carbide), synthetic scheelite production,
tungsten carbide recovery from scrap, cobalt recovery from
sludges and solutions, and cobalt produced from cobalt oxylate.
Not all of these processes are present at each plant. The
secondary tungsten and cobalt subcategory production processes
are presented schematically in Figure III-l (page 3201) and
described below.
RAW MATERIALS
The raw materials used for secondary tungsten and cobalt are
tungsten carbide scrap, other tungsten bearing scrap, cobalt
sludge, and cobalt oxylate. Tungsten scrap consists mostly of
oily machine turnings, and brazed-tungsten alloy scrap. The
major impurities in this type of scrap are copper, nickel,
silver, and zinc. Tungsten carbide scrap is comprised of
recycled drilling bits and other mining tools, machinery parts,
die casts, and other hard surfacing materials. The major
impurities in this type of scrap are cobalt and other metals.
Tungsten scrap may contain more than 90 percent tungsten, and
tungsten carbide scrap generally contains 10 to 40 percent
cobalt, with more than 90 percent of the remainder being tungsten
carbide.
TUNGSTEN RECOVERY FROM SCRAP
Tungsten may be recovered from scrap by leaching, as shown in
Figure III-l. The tungsten bearing scrap is washed with detergent
and rinsed with water prior to the leaching to remove surface
oils from the scrap.
Scrap is washed in either a mixing vessel or in a screw-conveyer
apparatus. Detergent solution is added to break up oil and
grease particles, and then rinse water is added and continuously
3103
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - III
removed until the scrap is cleaned. Clean scrap is easier to
leach and requires less leaching time. The detergent wash and
rinse water are discharged as a wastewater stream.
Acid leaching is the major purification step in secondary
tungsten production. Tungsten bearing raw materials are leached
in an agitated vessel with hydrochloric acid and other chemicals.
Tungsten is leached in order to remove copper, nickel, silver,
zinc and other impurities. Leaching is generally operated
batchwise, and may be repeated several times in order to increase
product purity. Following the leaching operation is a liquid-
solid separation step, which is either done by filtration or
decantation. When tungsten scrap is acid leached, the spent
leaching solution is discharged.
After leaching impurities away from tungsten, the purified metal
is washed with acid and base, and rinsed with water. Washing
neutralizes and removes any traces of impurities and leaching
acid from the tungsten product. The washing solutions are
discharged as a wastewater stream.
SYNTHETIC SCHEELITE PRODUCTION
Both tungsten and tungsten carbide scrap may be used to produce
synthetic scheelite as shown in Figure III-l (page 3201).
Synthetic scheelite (CaWO4) is used in primary tungsten
production as a supplemental feedstock along with natural
scheelite ore.
Tungsten scrap may be purified with an acid leaching process
prior to entering the smelting or roasting furnace where it is
oxidized. No wastewater is associated with this process.
Tungsten oxide is digested with caustic, in order to dissolve the
tungsten oxide. Undissolved impurities are filtered away, and
the solution is reacted with calcium chloride or other chemicals
to produce synthetic scheelite. The liquid waste is filtered
away from the synthetic scheelite and is discharged. If tungsten
carbide issued as a raw material, the final filtrate contains
cobalt values which are recovered prior to discharge by a
hydroxide precipitation and filtration process.
TUNGSTEN CARBIDE RECOVERY FROM SCRAP
As shown in Figure III-l, tungsten carbide is recovered from
scrap by acid leaching. After preliminary cleaning with
detergent and water, tungsten carbide scrap is leached with acid
and other chemicals to remove impurities. Cobalt is the major
impurity removed. Tungsten carbide powder is washed with water
and then crushed and ground to specification. One plant reported
discharging the post-leaching wash water as a wastewater stream.
Other plants leaching tungsten carbide scrap reported reuseing
their spent solutions in a cobalt recovery process.
One plant leaching tungsten carbide scrap reported a wet scrubber
to control acid fumes from the leaching vessel. There is a
3194
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - III
wastewater discharge from this scrubber.
COBALT RECOVERY FROM SLUDGES AND SOLUTIONS
The cobalt-laden solutions and filtrates produced in the tungsten
carbide recovery process, along with cobalt-laden solutions
produced by leaching cobalt sludge, may be routed to a cobalt
recovery circuit. Cobalt hydroxide, which may be reduced to
cobalt powder is most commonly produced, although other chemical
compounds of cobalt may be produced. These processes are shown
in Figures III-l.
One plant leaching cobalt sludge reported a wet scrubber to
control acid fumes from the leaching vessel. There is a
wastewater discharge from this scrubber.
Cobalt Production Via Cobalt Hydroxide
The first step in the production of cobalt is to crystallize the
cobalt in solution as a complex cobalt salt. Most commonly, this
is an ammonium complex, but other systems may be used. The
crystals settle out, and the resultant supernatant liquor is
decanted and discharged as a process wastewater. The cobalt
crystals are washed with hydrochloric acid and water to remove
impurities. The acid wash water is also decanted and discharged
as a wastewater stream.
The purified crystals are then dissolved in sodium fluoride
solution, and the cobalt precipitated as cobalt hydroxide
(Co(OH)2)« The slurry is filtered, and the filtrate discharged
as a wastewater stream. The Co(OH)2 filter cake is then washed
with water. The wash water is also discharged as a wastewater
stream. Cobalt hydroxide is dried and reduced in a furnace under
a hydrogen atmosphere to pure cobalt powder. Reduction to the
metal is a dry operation.
Cobalt Bichloride Production
Cemented tungsten carbide scrap can also be processed to yield a
tungsten carbide product and cobalt dichloride (CoCl2). This
process does not generate a process wastewater discharge based on
complete recycle of the wastewater.
COBALT PRODUCTION FROM COBALT OXYLATE
Cobalt powder is produced from cobalt oxylate by reducing it in a
hydrogen furnace, as shown in Figure III-l. There is no process
wastewater associated with this reduction process.
PROCESS WASTEWATER SOURCES
Although a variety of processes are involved in secondary
tungsten and cobalt production, the significant wastewater
sources that are associated with the subcategory can be
designated as follows:
3195
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - III
1. Tungsten detergent wash and rinse,
2. Tungsten leaching acid,
3. Tungsten post-leaching wash and rinse,
4. Synthetic scheelite filtrate,
5. Tungsten carbide leaching wet air pollution control,
6. Tungsten carbide wash water,
7. Cobalt sludge leaching wet air pollution control,
8. Crystallization decant,
9. Acid wash decant,
10. Cobalt hydroxide filtrate, and
11. Cobalt hydroxide filter cake wash.
OTHER WASTEWATER SOURCES
Other waste streams associated with the secondary tungsten and
cobalt subcategory include stormwater runoff, maintenance and
cleanup water, and noncontact cooling water. These streams are
not considered as a part of this rulemaking. EPA believes that
the flows and pollutant loadings associated with these streams
are insignificant relative to the waste streams selected and are
best handled by the appropriate permit authority on a case-by-
case basis under authority of Section 403 of the Clean Water Act.
AGE, PRODUCTION, AND PROCESS PROFILE
Figure III-2 (page 3204) shows the locations of the six secondary
tungsten and cobalt plants operating in the United States. All
are located east of the Mississippi River, concentrated near
industrial centers.
Table III-l (page 3198) illustrates the relative age and
discharge status of the secondary tungsten and cobalt plants
operating in the United States. One plant was built prior to
World War I, two plants were built during World War II, and only
two have been built in the last 17 years.
From Table III-2 (page 3199) it can be seen that of the six
facilities which produce secondary tungsten and cobalt, mean
tungsten product production is about 100 tons/year and mean
cobalt product production is also about 100 tons/year.
Table III-3 (page 3200) provides a summary of the number of
plants generating wastewater for the waste streams associated
with the various processes and the number of plants with the
process.
3196
-------
u>
M
(D
-4
Table III-1
INITIAL OPERATING YEAR (RANGE) SUMMARY OF PLANTS
IN THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY BY DISCHARGE TYPE
Initial Operating Year(Range) (PlantAge in Years)
w
M
n
o
S3
O
Type of Plant
Direct
Indirect
Zero
Dry
Total
Present-
1966
(0-17
1
0
0
1
2
1965-
1946
(15-35)
0
0
0
0
0
1945-
1926
(35-55)
2
0
0
0
2
1925-
1906
(55-75)
0
0
0
0
0
1905-
1885
(75-100)
1
0
0
0
1
Total «
4 w
t-3
w
1 55
0 g
1 o
6 ^
w
g
o
Q
O
W
n
o
1-3
H
H
H
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - III
TABLE II1-2
PRODUCTION RANGES FOR THE SECONDARY TUNGSTEN
AND COBALT SUBCATEGORY
Tungsten Products
Production Ranges for 1982
(Tons/Year)(a) Number of Plants
0-10 2
10-100 3
100-500 1
Total
Cobalt Products
Production Ranges for 1982
(Tons/Year)(b) Number of Plants
0-10 2
10-100 0
100-500 1
Total
(a) Based on production reported in dcp.
(b) Cobalt production was unavailable from one plant.
3198
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
SECT - III
TABLE II1-3
SUMMARY OF SECONDARY TUNGSTEN AND COBALT SUBCATEGORY PROCESSES
AND ASSOCIATED WASTE STREAMS
Process or Waste Stream
Tungsten or tungsten
carbide recovery
Tungsten detergent wash
and rinse
Tungsten leaching acid
Tungsten post-leaching
wash and rinse
Synthetic scheelite
filtrate
Tungsten carbide leaching
air pollution control
Tungsten carbide wash
water
Cobalt recovery
Cobalt sludge leaching
air pollution control
Crystallization decant
Acid wash decant
Cobalt hydroxide filtrate
Cobalt hydroxide filter
cake wash
Number of Tungsten
and Cobalt Plants
with Process or
Waste Stream
Number of
Plants Reporting
Generation of
Wastewater*
2
1
4
1
1
1
1
1
1
1
3
1
1
1
1
1
1
*Through reuse or evaporation practices, a plant may "generate" a
wastewater from a particular process but not discharge it.
3199
-------
<1) Tungsten Production
w
w
O
§
U>
ro
O
o
Detergent
Tungsten ^_ Waah and
Scrap * Water *"
ftinae
1©
(11) Synthetic ScheelHe Production
Solids
4
Liquid to
Further
Processing
Acid Wish and Screen and Hydrogen
Leach "~ ~~ * Rln»e *• Hill **• Reduction
Tun|Sten
*• Ponder
Product
1© ©
f f Tungsten Oxide
*~ Powder Product
tCaCl2
or Othrr
Settling NaOH, IUO Chenlcal
Chamber I 1
t ..i 1
**" Or - (iJOTHllon •. Filter M Reactor
Koiitt ^ " ^ p
A
^ Filler - Synthetic
"" Srheellte
Product
il C.iHO, nr
|© .-A
Filter Clke Cither niscliarite
Solid Unite nr Further Recovery
M Cobalt as Hydroxide
K;
n
O
w
O
O
w
§
o
I
Q
O
s
w
o
n
Figure III-l
SECONDARY TUNGSTEN AND COBALT PRODUCTION PROCESSES
H
M
M
-------
OJ
NJ
O
Cail.-il Ir
Solution *
UC Scrap
C.IIIHI It-
Solution *"
Cn Sludgi* — —
(Iw) Tutigstifn
Cemented ^
UC Scrap
UC 1*ni li Wl'I
Mr I'ul lut Inn
Ctmt rol
t
Acid
~* l-encli
t
-^r
KiUev iind .^^ ToMiler
U'tsli Product
Filtrale I (b)
Unsli W.tcr
Cobnlt Sludge
Leach Wet Air
Pollution
Control
t
Acid
""* Uach
Cnrbltle and
IJO1^ of AiMNiiiiluM ««f> Acid mm.,::ff, 01 a«t* 1 at ion «-,.,,0, filler »*.—.•> tn iij
^ Cobalt Cc»p1** *-'urnace
^"i f 1 1 1 v r ^n^nmnn^nn^p rrct, i pi t •!. it*u
Kit rat* ' -[••" | | " | j _
1 * 1© *® ^^
| MM. 1^ Acid F1U"" "l!"',:i">e
Filter Cake Crystallization Uashe* Hils
Dec am Derint
Cobult Dlchlorlde Production
Fret inlnary
C.eanln,
<•> Cr 1 nd
OT
W
(1
i
Product
-»
Holding
Tank
p ^ iecyrle F*Cl3 Solution
j
i
Recycle to
Leach
BUcd
Strean
Evaporator.
Fitter
fJ
O
§
(0
i
Q
§
U
W
n
Figure III-1 (Continued)
SECONDARY TUNGSTEN AND COBALT PRODUCTION PROCESS
N
N
N
-------
Figure III-l (Continued)
SECONDARY TUNGSTEN AND COBALT PRODUCTION PROCESSES
en
M
O
o
25
O
(v) Cobalt Powder Produced From Cobalt Oxylate
u>
to
o
to
Cobalt Oxylate
(Purchased
Intermediate)
Reduction
in H2
Furnace
•Cobalt Product
Q
en
(-3
W
25
a
a
o
en
a
w
o
en
W
o
-------
u>
K)
O
I - Indirect Process Wastewater Discharge Plant
D - Direct Process Mastewater Discharge Plants
Dry - No Process Wastewater
Figure III-2
GEOGRAPHIC LOCATIONS OF SECONDARY TUNGSTEN
AND COBALT SUBCATEGORY PLANTS
pi
o
i
d
k
Hi
o
w
1-3
I
d
o
o
HI
W
O
>
HI
w
O
o
ft
Hi
I
H
H
H
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGOEY SECT - III
THIS PAGE INTENTIONALLY LEFT BLANK
3204
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - IV
SECTION IV
SUBCATEGORIZATION
This section summarizes the factors considered during the
designation of the subdivisions or building blocks of the
secondary tungsten and cobalt subcategory and its related
subdivisions. Production normalizing parameters for each
subdivision are discussed.
FACTORS CONSIDERED IN SUBDIVIDING THE SECONDARY TUNGSTEN AND
COBALT SUBCATEGORY
The factors listed previously for general subcategorization were
each evaluated when considering subdivision of the secondary
tungsten and cobalt subcategory. In the discussion that follows,
the factors will be described as they pertain to this particular
subcategory.
The rationale for considering subdivision of the
secondary tungsten and cobalt subcategory is based primarily on
differences in the production processes and raw materials used.
Within this subcategory, a number of different operations are
performed, which may or may not have a water use or discharge,
and which may require the establishment of separate effluent
limitations. Secondary tungsten and cobalt is considered a single
subcategory, however, a thorough examination of the production
processes has illustrated the need for limitations and standards
based on wastewater streams. Limitations will be based on
specific flows for the following subdivisions:
1. Tungsten detergent wash and rinse,
2. Tungsten leaching acid,
3. Tungsten post-leaching wash and rinse,
4. Synthetic scheelite filtrate,
5. Tungsten carbide leaching wet air pollution control,
6. Tungsten carbide wash water,
7. Cobalt sludge leaching wet air pollution control.
8. Crystallization decant,
9. Acid wash decant,
10. Cobalt hydroxide filtrate, and
11. Cobalt hydroxide filter cake wash.
These subdivisions follow directly from differences between the
processing steps of secondary tungsten and cobalt production.
Tungsten recovery from scrap, synthetic scheelite production,
tungsten carbide recovery from scrap, and cobalt recovery from
sludges and solutions each have various steps which may generate
wastewaters.
Refining tungsten scrap into pure tungsten metal powder
establishes a need for the first three subdivisions — tungsten
detergent wash and rinse, tungsten leaching acid, and tungsten
post-leaching wash and rinse. Tungsten scrap may be washed,
3205
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - IV
leached, and washed again to produce a pure tungsten product.
Separate subdivisions are necessary because some plants do not
use all these processes.
The fourth subdivision, synthetic scheelite filtrate, is needed
for plants which produce synthetic scheelite from scrap and
discharge the wastewater generated by the process.
The fifth and sixth subdivisions are necessary for plants which
recover tungsten carbide from scrap, and discharge post-leaching
wash water, or leaching scrubber liquor.
The seventh through eleventh subdivisions are needed for plants
which refine cobalt found in tungsten carbide scrap or other
secondary materials into pure cobalt powder. This is a wet
chemistry purification and there are several wastewater sources.
OTHER FACTORS
The other factors considered in this evaluation were shown to be
inappropriate bases for subdivision. Air pollution control
methods, treatment costs, and total energy requirements are
functions of the selected subcategorization factors — metal
product, raw materials, and production processes. As discussed
in Section IV of the General Development Document, certain, other
factors, such as plant age, plant size, and the number of
employees, were also evaluated and determined to be inappropriate
for use as bases for subdivision of this nonferrous metals
subcategory.
PRODUCTION NORMALIZING PARAMETERS
As discussed previously, the effluent limitations and standards
developed in this document establish mass limitations for the
discharge of specific pollutants or pollutant parameters. To
allow these regulations to be applied to plants with various
production capacities, the mass of pollutant discharged must be
related to a unit of production. This factor is known as the
production normalizing parameter (PNP). The PNPs for the 11
subdivisions or building blocks are as follows:
Building Block PNP
1. Tungsten detergent wash and rinse tungsten scrap washed
2. Tungsten leaching acid tungsten produced
3. Tungsten post-leaching wash and tungsten produced
rinse
4. Synthetic scheelite filtrate synthetic scheelite
produced
5. Tungsten carbide leaching wet air tungsten carbide scrap
pollution control leached
3206
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - IV
6. Tungsten carbide wash water tungsten carbide
produced
7. Cobalt sludge leaching wet air cobalt produced from
pollution control cobalt sludge
8. Crystallization decant cobalt produced
9. Acid wash decant cobalt produced
10. Cobalt hydroxide filtrate cobalt produced
11. Cobalt hydroxide filter cake cobalt produced
wash
Other production normalizing parameters were considered. The use
of production capacity . instead of actual production was
eliminated because wastewater flow is more closely related to
production than to rated capacity.
The amount of scrap washed was selected as the normalizing
parameter for the pre-leaching detergent wash and rinse waste
stream instead of the amount of tungsten produced because not all
the tungsten scrap is washed prior to leaching. Non-oily scrap
is leached without preliminary washing, and, if it were included
in the production used to calculate a flow allowance, it would
upset the flow-to-production relation inherent in this
regulation.
3207
-------
SECONDARY TUNGSTfiN AND COBALT SUBCAT1GORY SECT - IV
THIS PAGE INTENTIONALLY LEFT BLANK
3208
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - V
SECTION V
WATER USE AND WASTEWATER CHARACTERISTICS
This section describes the characteristics of the wastewaters
associated with the secondary tungsten and cobalt subcategory.
Water use and discharge rates are explained and then summarized
in tables at the end of this section. Data used to characterize
the wastewaters are presented. Two principal data sources were
used: data collection portfolios (dcp) and field sampling
results. Data collection portfolios contain information
regarding wastewater flows and production levels. Finally, the
specific source, water use and discharge flows, and wastewater
characteristics for each separate wastewater source are
discussed.
In order to quantify the pollutant discharge from secondary
tungsten and cobalt plants, a field sampling program was
conducted. A complete list of the pollutants considered and a
summary of the techniques used in sampling and laboratory
analyses are included in Section V of Vol. I. Samples were
analyzed for 124 of the 126 priority pollutants and other
pollutants deemed appropriate. (Because the analytical standard
for TCDD was judged to be too hazardous to be made generally
available, samples were never analyzed for this pollutant.
Samples were also never analyzed for asbestos. There is no
reason to expect that TCDD or asbestos would be present in
nonferrous metals manufacturing wastewater.) Specific plants
were selected for sampling in the secondary tungsten and cobalt
subcategory. In general, the samples were analyzed for two
classes of pollutants: toxic metal pollutants, and criteria
pollutants (which includes both conventional and nonconventional
pollutants).
One additional plant was identified following proposal based on
information supplied in an industry comment. This facility
manufactures synthetic scheelite and is an indirect discharger of
synthetic scheelite filtrate.
Since proposal, EPA gathered additional wastewater sampling data
for two of the subdivisions in this subcategory. These data were
acquired through a self-sampling program which was conducted at
the specific request of EPA. The data include analyses for the
toxic metals arsenic, beryllium, cadmium, chromium, copper, lead,
nickel, silver, and zinc. The data also include analyses for the
nonconventional pollutants ammonia, cobalt, and tungsten. These
data support the assumptions which EPA had made concerning the
presence and concentration to pollutants in those subdivisions
where we did not have analytical data for specific pollutants.
For this reason, the selection of pollutant parameters for
limitation in this subcategory (Section VI) has not been revised
based on these new data.
3209
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - V
As described in Section IV of this supplement, the secondary
tungsten and cobalt subcategory has been divided into 11
subdivisions or building blocks, so that the promulgated
regulation contains mass discharge limitations and standards for
11 unit processes discharging process wastewater. Differences in
the wastewater characteristics associated with these subdivisions
are to be expected. For this reason, wastewater streams
corresponding to each subdivision are addressed separately in the
discussions that follow. These wastewater sources are:
1. Tungsten detergent wash and rinse,
2. Tungsten leaching acid,
3. Tungsten post-leaching wash and rinse,
4. Synthetic scheelite filtrate,
5. Tungsten carbide leaching wet air pollution control,
6. Tungsten carbide wash water,
7. Cobalt sludge _eaching wet air pollution control,
8. Crystallization decant,
9. Acid wash decant,
10. Cobalt hydroxide filtrate, and
11. Cobalt hydroxide filter cake wash.
WASTEWATER FLOW RATES
Data supplied by dcp responses were evaluated, and two flow-to-
production ratios were calculated for each stream. The two
ratios, water use and wastewater discharge flow, are
differentiated by the flow value used in calculation. Water use
is defined as the volume of water required for a given process
per mass of tungsten and cobalt product and is therefore based on
the sum of recycle and make-up flows to a given process.
Wastewater flow discharged after pretreatment or recycle (if
these are present) is used in calculating the production
normalized flow — the volume of wastewater discharged from a
given process to further treatment, disposal, or discharge per
mass of tungsten or cobalt produced. Differences between the
water use and wastewater flows associated with a given stream
result from recycle, evaporation, and carry-over on the product.
The production values used in calculation correspond to the
production normalizing parameter, PNP, assigned to each stream,
as outlined in Section IV. As an example, tungsten leaching acid
wastewater flow is related to tungsten production. As such, the
discharge rate is expressed in liters of leaching acid wastewater
discharged per metric ton of tungsten produced.
The production normalized flows were compiled and statistically
analyzed by stream type. These production normalized water use
and discharge flows are presented by subdivision in Tables V-l
through V-ll (pages 3217 - 3220). Where appropriate, an attempt
was made to identify factors that could account for variations in
water use. This information is summarized in this section. A
similar analysis of factors affecting the wastewater values is
presented in Sections IX, X, XI, and XII where representative
BPT, BAT, NSPS, and pretreatment discharge flows are selected for
use in calculating the effluent limitations and standards.
3210
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - V
WASTEWATER CHARACTERISTICS DATA
Data used to characterize the various wastewaters associated with
secondary tungsten and cobalt production come from two sources —
data collection portfolios and analytical data from field
sampling.
DATA COLLECTION PORTFOLIOS
In the data collection portfolios,, the secondary tungsten and
cobalt plants were asked to indicate whether or not the priority
pollutants were present in their effluent. All of the
discharging plants indicated that priority organic pollutants
were believed to be absent from their effluent. Three plants
stated that some of the priority metals were known or believed to
be present in their effluent. The responses for the priority
metals and cyanide are summarized below:
Known Believed
Pollutant Present Present
Antimony 0 1
Arsenic 1 0
Beryllium 0 0
Cadmium 0 1
Chromium 2 2
Cyanide 2 2
Copper 0 0
Lead 1 0
Mercury 1 1
Nickel 1 2
Selenium 0 0
Silver 0 1
Thallium 0 0
Zinc 1 2
FIELD SAMPLING DATA
In order to quantify the concentrations of pollutants present in
wastewater from secondary tungsten and cobalt plants, wastewater
samples were collected at discharging plants.
The sampling data for the secondary tungsten and cobalt
subcategory are presented in Tables V-12 through V-19 (pages 3221
3245). Table V-20 (page 3247) presents sampling data for
influent and effluent from treatment for secondary tungsten and
cobalt. Table V-21 (page 3252) presents partially treated
wastewater data. The stream codes displayed in Tables V-12
through V-21 (pages 3221 - 3252) may be used to identify the
location of each of the samples on process flow diagrams in
Figures V-l and V-2. Where no data are listed for a specific day
of sampling, the wastewater samples for the stream were not
3211
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - V
collected. If the analysis did not detect a pollutant in a waste
stream, the pollutant was reported as not detected (or ND), and a
value of zero was used in averaging.
Toxic organic pollutants were not measured in this subcategory.
Wastewater samples collected at plants in this subcategory were
analyzed for all priority metal pollutants, cyanide, and several
conventional and nonconventional pollutants.
The detection limits shown on the data tables for toxic
pollutants and conventional and nonconventional pollutants are
not the same in all cases as the published detection limits for
these pollutants by the same analytical methods. The detection
limits used were reported with the analytical data and hence are
the appropriate limits to apply to the data. Detection limit
variation can occur as a result of a number of laboratory-
specific, equipment-specific, and daily operator-specific
factors. These factors can include day-to-day differences in
machine calibration, variation in stock solutions, and variation
in operators.
The statistical analysis of data includes some samples measured
at concentrations considered not quantifiable. For data
considered as detected but below quantifiable concentrations, a
value of zero is used for averaging. Nonconventional and
conventional pollutant data reported with a "less than" sign are
considered as detected, but not further quantifiable. A value of
zero is also used for averaging. If a pollutant is reported as
not detected, it is assigned a value of zero in calculating the
average. Finally, priority metal values reported as less than a
certain • value were considered as not quantifiable, and
consequently were assigned a value of zero in the calculation of
the average. The average values were not used in the selection
of pollutants or pollutant parameters for regulation.
Appropriate source water concentrations are presented with the
summaries of the sampling data. The method by which each sample
was collected is indicated by number, as follows:
1 - One-time grab
2 - Manual composite during intermittent process operation
3 - 8-hour manual composite
4 — 8-hour automatic composite
5 - 24-hour manual composite
6 - 24-hour automatic composite
WASTEWATER CHARACTERISTICS AND FLOWS BY SUBDIVISION
Since secondary tungsten and cobalt production involves 11
principal sources of wastewater and each has potentially
different characteristics and flows, the wastewater
characteristics and discharge rages corresponding to each
3212
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - V
subdivision will be described separately. A brief description of
why the associated production processes generate a wastewater and
explanations for variations of water use within each subdivision
will also be discussed.
TUNGSTEN DETERGENT WASH AND RINSE
Tungsten scrap is washed with detergent and rinsed with water in
order to clean surface oils from the scrap. The water use and
discharge rates for tungsten detergent wash and rinse are
reported in Table V-l (page 3217). Tungsten detergent wash and
rinse sampling data are presented in Table V-12 (page 3221).
Samples were taken of both the wash and the rinse, and the data
are shown in Table V-12. This wastewater stream is characterized
by the presence of treatable concentrations of cadmium, chromium,
cobalt, copper, nickel, oil and grease, and suspended solids.
TUNGSTEN LEACHING ACID
Tungsten scrap is leached with acid in order to remove impurities
from the tungsten metal. After leaching, the spent acid is
discharged. The water use and discharge rates are presented in
Table V-2 (page 3217). Tungsten leaching acid sampling data 'are
presented in Table V-13 (page 3226). This wastewater stream is
characterized by the presence of treatable concentrations of
arsenic, cadmium, chromium, cobalt, copper, nickel, silver, zinc,
suspended solids, and an acidic pH.
TUNGSTEN POST-LEACHING WASH AND RINSE
After leaching tungsten scrap with acid, the tungsten product may
be washed with acid and rinsed with water in order to further
purify the product. The water use and discharge rates for this
wastewater stream are presented in Table V-3 (page 3217).Sampling
data for tungsten post-leaching wash and rinse water is presented
in Table V-14 (page 3230). Treatable concentrations of arsenic,
cadmium, chromium, cobalt, copper, nickel, silver, zinc,
suspended solids, and an acidic pH characterize this waste
stream.
SYNTHETIC SCHEELITE FILTRATE
Both tungsten and tungsten carbide scrap can be processed into
synthetic scheelite, which can then be used as a raw material in
a primary tungsten refinery. After producing synthetic
scheelite, wastewater is filtered away from the product and may
be discharged. Table V-4 (page 3218) shows the water use and
discharge rates for plants producing synthetic
scheelite.
Although this waste stream was not sampled, it is believed to
have similar characteristics to the cobalt hydroxide filtrate
sampling data is shown in Table V-18 (page 3243). These streams
are expected to be similar because both processes are
precipitating products from a caustic solution which generally
3213
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - V
come from the same raw material. This stream is characterized by
treatable concentrations of antimony, arsenic, cadmium, cyanide,
nickel, silver, zinc, and suspended solids. Ammonia is not
expected to be present in synthetic scheelite filtrate.
TUNGSTEN CARBIDE LEACHING WET AIR POLLUTION CONTROL
Scrap tungsten carbide may be leached with hydrochloric acid to
solubilize cobalt, which is used as the binder alloy in the
tungsten carbide. Off-gasses from leaching may be controlled
with a wet scrubber, which uses a caustic solution as the
scrubbing medium. Three plants reported a tungsten carbide
leaching operation but only one controls off-gasses. The water
use and discharge rates for these plants are presented in Table
V-5 (page 3218).
Although tungsten carbide leaching wet air pollution control was
not sampled prior to proposal, raw wastewater data were available
from a cobalt sludge leaching scrubber presented as a combined
wastewater sample in Table V-15 (page 3234). This combined
sample contains scrubber liquor, and crystallization and acid
wash decant wastewater. The wastewater characteristics for the
two scrubbers are expected to be similar because of the
similarities in the raw materials and processes used. The
wastewater sample collected from the analogous wet scrubber
stream contains treatable concentrations of toxic metals,
ammonia, and suspended solids, and an acidic pH.
Following proposal, sampling data for this subdivision were
acquired through a self-sampling effort made at the specific
request of EPA. These data (shown in Table V-22, page 3257) show
treatable concentrations of chromium and lead, thus corroborating
the data used at proposal.
TUNGSTEN CARBIDE WASH WATER
After leaching, tungsten carbide is washed with water in order to
remove any traces of acid and other contaminants. The wash water
may be discharged or further processes to recover dissolved
metals such as cobalt and then recycled to the leaching step.
Table V-6 (page 3218) presents the water use and discharge rates
for these two plants.
Although tungsten carbide wash water was not sampled prior to
proposal, raw wastewater data were available from a secondary
tungsten post-leaching wash water. The wastewater
characteristics for the two wash waters were expected to be
similar due to the similarities in the raw materials and
processes used. The wastewater sample collected from the
analogous wash water stream (shown in Table V-14, page 3230),
contains toxic metals and suspended solids above treatable
limits.
Following proposal, sampling data for this subdivision were
acquired through a self-sampling effort at the specific request
3214
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - V
of EPA. These data (presented in Table V-22, page 3257) show
treatable concentrations of chromium, cobalt and tungsten, thus
corroborating the data used at proposal.
COBALT SLUDGE LEACHING WET AIR POLLUTION CONTROL
When cobalt sludges are leached with acid, off-gasses are
controlled with a wet air pollution control device. The scrubber
uses a dilute caustic solution as the scrubbing medium which
neutralizes the acidic off-gasses and removes contaminants. The
water use and discharge rates for this wastewater stream are
presented in Table V-7 (page 3219).
Combined wastewater sampling data including cobalt sludge
leaching wet air pollution control is presented in Table V-15
(page 3234). This wastewater stream is characterized by the
presence of treatable concentrations of cadmium, chromium,
cobalt, copper, lead, nickel, silver, zinc, ammonia, and
suspended solids, as well as an acidic pH.
CRYSTALLIZATION DECANT
After leaching cobalt sludge and tungsten carbide scrap with acid
and filtering away the tungsten and undissolved impurities,
cobalt is crystallized as an ammonium cobalt intermediate
product. The excess crystallization liquor is decanted off and
discarded. The water use and discharge rates for this
wastewater stream are presented in Table V-8 (page 3219).
Sampling data for crystallization decant is presented in Table V-
16 (page 3236). This wastewater stream is characterized by the
presence of treatable concentrations of arsenic, cadmium,
chromium, cobalt, copper, lead, nickel, silver, thallium, zinc,
ammonia, and suspended solids, as well as an acidic pH.
ACID WASH DECANT
The ammonium cobalt crystals produced from cobalt sludge and
scrap tungsten carbide are washed with dilute hydrochloric acid
to remove all traces of ammonia, and to further purify the
crystals. After washing the crystals, the acid is decanted off,
and discharged. One plant reported generating this waste stream,
and its water use and discharge rates are presented in Table V-9
(page 3219).
Sampling data for acid wash decant are presented in Table V-17
(page 3238). This waste stream is characterized by the presence
of treatable concentrations of cadmium, chromium, cobalt, copper,
lead, nickel, silver, zinc, ammonia, and suspended solids, as
well as an acidic pH.
COBALT HYDROXIDE FILTRATE
After purifying the ammonium cobalt crystals, they are dissolved
using various chemical systems and cobalt is precipitated as the
3215
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - V
hydroxide. The cobalt hydroxide precipitate is filtered and the
filtrate is discharged. The water use and discharge rates for
this stream are shown in Table V-10 (page 3220).
Sampling data for cobalt hydroxide filtrate show an alkaline pH
and elevated concentrations of antimony, arsenic, cyanide, lead,
nickel, silver, zinc, ammonia, and suspended solids. These data
are presented in Table V-18 (page 3243). Although not
analytically determined, fluoride is expected to be present in
this wastewater.
COBALT HYDROXIDE FILTER CAKE WASH
The cobalt hydroxide filter cake is washed with water in order to
remove any residual alkalinity or other impurities and the wash
water discharged. The water use and discharge rates for this
wastewater stream are presented in Table V-ll (page 3220).
The sampling data for cobalt hydroxide filter cake wash water is
presented in Table V-19 (page 3245). This wastewater stream is
characterized by the presence of treatable concentrations of
lead, nickel, zinc, and ammonia.
3216
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
SECT - V
Plant
Code
TABLE V-l
WATER USE AND DISCHARGE RATES FOR
TUNGSTEN DETERGENT WASH AND RINSE
(1/kkg of tungsten scrap washed)
Recycle or
Reuse {%)
0
Production Normalized
Water Use Flow
195
Production normalized
Discharge Flow
195
TABLE V-2
WATER USE AND DISCHARGE RATES FOR
TUNGSTEN LEACHING ACID
(1/kkg of tungsten produced)
Plant Recycle or Production Normalized
Code Reuse (%) Water Use Flow
0
100*
2571
NR
Production normalized
Discharge Flow
2571
0
* 100% reuse of process effluent in secondary silver recovery
operation
TABLE V-3
WATER USE AND DISCHARGE RATES FOR
TUNGSTEN POST-LEACHING WASH AND RINSE
(1/kkg of tungsten produced)
Plant
Code
Recycle or
Reuse {%)
0
Production Normalized
Water Use Flow
5143
Production normalized
Discharge Flow
5143
3217
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
SECT
Plant
Code
TABLE V-4
WATER USE AND DISCHARGE RATES FOR
SYNTHETIC SCHEELITE FILTRATE
(1/kkg of synthetic scheelite produced)
Recycle or Production Normalized Production normalized
Reuse {%) Water Use Flow Discharge Flow
0
0
0
16661
NR
6532
16661
NR
6532
TABLE V-5
WATER USE AND DISCHARGE RATES FOR
TUNGSTEN CARBIDE LEACHING WET AIR POLLUTION CONTROL
(1/kkg of tungsten carbide scrap leached)
Plant Recycle or Production Normalized
Code Reuse _(%)_ Water Use Flow
>90
NR
Production normalized
Discharge Flow
1751
TABLE V-6
WATER USE AND DISCHARGE RATES FOR
TUNGSTEN CARBIDE WASH WATER
(1/kkg of tungsten carbide produced)
Plant Recycle or Production Normalized
Code Reuse (%) Water Use Flow
100
0
NR
8333
Production normalized
Discharge Flow
0
8333
3218
-------
SECONDARY" TUNGSTEN AND COBALT SUBCATEGORY
SECT - V
Plant
Code
TABLE V-7
WATER USE AND DISCHARGE RATES FOR
COBALT SLUDGE LEACHING WET AIR POLLUTION CONTROL
(1/kkg of cobalt produced from cobalt sludge)
Recycle or
Reuse (%)
>90
Production Normalized
Wa te r Use Flow
NR
Production normalized
Discharge Flow
35718
Plant
Code
TABLE V-8
WATER USE AND DISCHARGE RATES FOR
CRYSTALLIZATION DECANT
Recycle or
Reuse {%)
(1/kkg of cobalt produced)
Production Normalized
Water Use Flow
41650
Production normalized
Discharge Flow
41650
TABLE V-9
WATER USE AND DISCHARGE RATES FOR
ACID WASH DECANT
(1/kkg of cobalt produced)
Plant Recycle or Production Normalized
Code Reuse (%) Water Use Flow
0 19062
Production normalized
Discharge Flow
19062
3219
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT
TABLE V-10
WATER USE AND DISCHARGE RATES FOR
COBALT HYDROXIDE FILTRATE
(1/kkg of cobalt produced)
Plant Recycle or Production Normalized Production normalized
Code Reuse (%) Water Use Flow Discharge Flow
0 56647 56647
TABLE V-ll
WATER USE AND DISCHARGE RATES FOR
COBALT HYDROXIDE FILTER CAKE WASH
(1/kkg of cobalt produced)
Plant Recycle or Production Normalized Production normalized
Code Reuse {%) Water Use Flow Discharge Flow
0 109035 109035
3220
-------
Table V-12
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
to
Pollutant:
Toxic Pollutants
114. antimony
115. arsenic
117. beryllium
118. cadmium
119. chromium (total)
120. copper
122. lead
123. mercury
124. nickel
WASH At
.MPLING
Sample
Typet
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
-------
Table V-12 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TUNGSTEN DETERGENT WASH AND RINSE
KJ
Kt
Pollutant
Toxic Pollutants (continued)
125. selenium
126. silver
127. thallium
128. zinc
Nonconventional Pollutants
Acidity
Alkalinity
Aluminum
Ammonia Nitrogen
.MPLING DATA
Sample Concentrations (mg/1)
Typet
1
2
1
2
1
2
1
2
2
1
2
1
2
1
2
Source
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.08
0.08
.
XI
<1
40
40
0.2
0.2
2.0
2.0
Day 1 Day 2
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<2
<0.5
S 1
\l
<]
590
200
30
1.7
2.1
1.6
Day 3
<0.1
U
n
o
CD
t-i
H
c
03
O
M
Q
O
K
cn
w
o
1
<
-------
Table V-12 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEUORY
TUNGSTEN DETERGENT WASH ANU RINSE
u>
to
N)
U)
Pollutant
Nonconventional Pollutants (continued)
Barium
Boron
Calcium
Chemical Oxygen Demand (COD)
Chloride
Cobalt
Fluoride
Iron
Magnes ium
UPLING
Sample
Typet
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
DATA
Concentrat
Source Day
<0.05
<0.05
<0.1
<0.1
25.7
25.7
110
110
11
1 1
<0.05
<0.05
0.64
0.64
<0.5
<0.5
4.5
4.5
ions (mR/1)
1 Day 2
<1
W
§
a
C/i
w
o
H
1
<
-------
Table V-12 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TUNGSTEN DETERGENT WASH AND RINSE
u>
to
to
Pollutant
Nonconventional Pollutants (continued)
Manganese
Molybdenum
Phosphate
Sodium
Sulfate
Tin
Titanium
Total Organic Compound (TOC)
nritjii ruiu i\.Lri>ji^
.MPLING DATA
Sample Concentrations (mg/1)
Typet
1
2
1
2
1
2
1
2
1
2
1
2
1
2
1
2
Source
<0.05
<0.05
<0.05
<0.05
0.82
0.82
4.5
4.5
590
590
<0.05
<0.05
<0.05
<0.05
<1
<1
Day 1 Day 2
7
0.4
<5
<0.5
630
150
196
88.9
1,700
1,400
<1 0
<0.1
<1
<0.5
390
14
Day 3
5
0.15
<5
<0.5
3,300
13
350
46.5
3,700
80
<1 0
<0.5
<5
<0.05
710
16
SECONDAI
Kj
M
1-3
W
g
O
0
o
a
t-i
M
G
O
M
1
K
M
W
0
1-3
I
-------
Table V-12 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
NJ
Ul
Pollutant
Nonconventional Pollutants (continued)
Total Solids (TS)
Vanadium
Yttrium
Conventional Pollutants
Oil and Grease
Total Suspended Solids (TSS)
pH (standard units)
tSample Type Code: 1 - One-time grab
2 - Manual composite during Intermittent process operation
WASH AJNU K1N5E
M»LING DATA
Sample Concentrations (mg/1)
Typet
1
2
1
2
1
2
1
1
1
2
1
2
Source
250
250
<0.05
<0.05
<0.05
<0.05
<1
<1
19
19
7.60
7.60
Day 1 Day 2
52,000 53
3,300 1
<1
<0.05
-------
Table V-13
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TUNGSTEN LEACHING ACID
U)
to
K3
Pollutant
Toxic Fo1lu t an t s
114. antimony
115. arsenic
117. beryllium
118. cadmium
119. chromium (total)
120. copper
122. lead
123. mercury
124. nickel
125. selenium
126. silver
127. thallium
128. zinc
, 4.1^V> jTfc ** *
.MPLINU
Sample
Typet
1
1
1
1
1
1
1
1
1
1
1
DATA
Concentrat
Source Day
<0.01
<0.01
<0.0005
<0.02
<0.02
<0.05
<0.05
<0.0002
0.5
<0.()1
<0.01
ions (mft/1)
I Day 2 Day :
<0.1
1.8
<0.5
6
38
2,890
<500
<0.0002
13,900
<0.05
1 .4
SECONDA]
i
i K
Q
W
Hi
W
Z
I
O
o
o
oa
tr"
(n
§
o
S
w
Q
O
K
cn
w
o
0.08
108
-------
Table V-13 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TUNGSTEN LEACHING ACID
U)
(O
to
Pollutant
N on convent i on a1 P o 1 lu tan t s
Acidity
Alkalinity
Aluminum
Ammonia Nitrogen
Barium
Boron
Calcium
Chemical Oxygen Demand (COD)
Chloride
Cobalt
Fluoride
Iron
Magnesium
Manganese
,MPLING
Sample
Typet
1
1
1
1
1
1
1
1
1
1
1
1
1
1
DATA
Concentrat
Source Day
<1
40
0.2
2.0
<0.05
<0.-1
25.7
110
11
<0.05
0.64
<0.5
4.5
<0.05
ions (mg/1)
I Day 2
1 ,000
<1
70
2.0
<5
<50
90
13,000
61 ,000
445
1.0
25,900
,<10
220
V
W
1
Day 3 K
o
en
M
£2
•*-(
O
8
Cfl
3
w
§
o
H
C3
O
JO
K
t/1
M
O
1
<
-------
Table V-13 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TUNGSTEN LEACHING ACID
10
NJ
00
Pollutant
Nonconventlonal Pollutants (continued)
Molybdenum
Phosphate
Sodium
Sulfate
Tin
Titanium
Total Organic Carbon (TOC)
Total Solids (TS)
Vanadium
Yttrium
Conventional Pollutants
Oil and Grease
Total Suspended Solids (TSS)
.MPLING
Sample
Typet
1
1
1
1
1
1
1
1
1
1
1
1
DATA
Concentrations
Source Day 1
<0.05
0.82
4.5
590
<0.05
<0.05
<1
250
<0.05
<0.05
<1
19
(mg/D
Day 2
<25
39,000
20
240
<25
<5
43
200,000
5
<5
<1
50,000
w
n
8
1
Day 3 3
a
en
g
o
o
§
5
en
§
o
1
i
W
M
O
<
-------
Table V-13 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TUNGSTEN LEACHING ACID
RAW WASTEWATER SAMPLING DATA
Pollutant
Conventional Pollutants (continued)
pH (standard units)
Sample
Typet
Concentrations (mg/1)
Source
7.60
0.89
in
M
8
55
O
s
0
in
t-3
n
55
co
to
VO
tSample Type Code;
1 - One-time grab
2 - Manual composite during intermittent process operation
3 - 8-hour manual composite
4 - 8-hour automatic composite
5 - 24-hour manual composite
6 - 24-hour automatic composite
o
o
w
c!
to
8
w
n
-------
Table V-14
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TUNGSTEN POST-LEACHING WASH AND RINSE
CO
w
w
o
Pollutant
Toxic Pollutants
114. antimony
1 S 5. arsenic
117. beryllium
118. cadmium
119. chromium (total)
120. copper
122. lead
123. mercury
124. nickel
125. selenium
126. silver
127. thallium
128. zinc
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TUNGSTEN POST-LEACHING WASH AND RINSE
Pollutant
Nonconventional Pollutants.
Acidity
Alkalinity
Aluminum
Ammonia Nitrogen
Barium
Boron
Calcium
Chemical Oxygen Demand (COD)
Chloride
Cobalt
Fluoride
I ron
Magnesium
Manganese
MPLING
Sample
Typet
2
2
2
2
2
2
2
2
2
2
2
2
2
2
DATA
Concentrat
Source Day
<1
40
0.2
2.0
<0.05
<0.1
25.7
1 10
11
<0.05
0.64
<0.5
4.5
<0.05
ions (mg/1)
1 Day 2 Day
190
<1
30
1 .4
<5
10
70
75
27,000
165
0.36
7,650
<10
65
SECONDS
-1 K
i-i
G
55
O
W
w
25
O
O
0
w
fl
^a
G
W
a
S
HI
W
8
KJ
*^S(
01
M
O
1
-------
Table V-14 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TUNGSTEN POST-LEACHING WASH AND RINSE
U)
K5
U>
Pollutant
Nonconventional Pollutants (continued)
Molybdenum
Phosphate
Sodium
Sulfate
Tin
Titanium
Total Organic Carbon (TOC)
Total Solids (TS)
Vanadium
Yttrium
Conventional Pollutants
Oil and Grease
Total Suspended Solids (TSS)
.MPLING
Sample
Typet
2
2
2
2
2
2
2
2
2
2
1
2
DATA
Concentrations
Source Day 1
<0.05
0.82
4.5
590
<0.05
<0.05
<1
250
<0.05
<0.05
<1
19
(mg/1)
Day 2
10
39,000
4,050
12
<5
<5
9
61 ,000
<5
<5
3
14,000
w
M
o
o
55
O
Day 3 |
Q
w
w
as
o
0
o
m
3
c
0)
o
s
w
o
o
K
W
M
O
H
<
-------
Table V-14 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TUNGSTEN POST-LEACHING WASH AND RINSE
RAW WASTEWATER SAMPLING DATA
Pollutant
ConventionalPollutants (continued)
pH (standard units)
Sample
Typet
Concentrations (tng/1)
Source
7.60
Day 3
1.31
n
o
£
O
5
Q
OT
H
W
9S
OJ
o
o
w
tSample Type Code;
1 - One-time grab
2 - Manual composite during intermittent process operation
3 - 8-hour manual composite
4 - 8-hour automatic composite
5 - 24-hour manual composite
6 - 24-hour automatic composite
W
Q
O
M
O
-------
Table V-15
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
WASTEWATER STORAGE TANK - CRYSTALLIZATION AND ACID WASH DECANTS, AND
u>
to
Pollutant
Toxic Pollutants
114. antimony
115. arsenic
117. beryllium
118. cadmium
119. chromium (total)
120, ,opper
121. cyanide (total)
122. lead
123. mercury
124. nickel
1?';. selenium
126. silver
127. thallium
128. zinc
K.LK, rut
04PLING
Sample
Typet
1
• t ,
1
1
1
1
1
1
1
1
1
1
1
1
•JUUilUM UUMiRUl.
DATA
Concentrations (mg/1)
Source
0.023
0.001
<0.001
<0.001
0.018
0.070
0.003
<0.0002
0.17
0.011
0.008
<0.001
420
Day 1 Day 2
0.20
<0.001
0.006
7.5
6.6
640
10
0.010
2,000
<0.001
7.0
0.55
320
w
m
o
o
as
o
Day 3 «!
n
o
^
M
525
O
O
O
tfl
tr"
Kl
M
G
ro
w
o
Hj
w
o
H3
<
-------
Table V-15 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
U)
K>
U>
lr
Pollutant
Nonconyenttonal Pollutants
Amroonia Nitrogen
Chloride
Cobalt
Iron
Phenolics
Titanium
Total Solids (TS)
Conventional Pollutants
Oil and Grease
Total Suspended Solids (TSS)
pH (standard units)
.TION AND ACID WASH DECANTS, AND
AIR POLLUTION CONTROL
.MPLING DATA
Sample Concentrations (mg/1)
Typet
1
1
1
1
1
1
1
1
1
Source
0.07
<1
0.24
0.30
<0.001
0.10
16
11
<4
7.1
Day 1 Day 2
6,500
83,000
2,000
620
0.014
7.0
100,000
6.1
900
0
SECONDARY
Day 3 Hj
55
en
1
O'
o
o
03
1
c
o
>
W
Q
O
Hj
W
W
o
hi
I
tSample Type Code: 1 - One-time grab
-------
Table V-16
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
CRYSTALLIZATION DECANT
U)
N)
U)
CT.
Pollutant
Toxic Pollutants
114. antimony
115. arsenic
117. beryllium
118. cadmium
119. chromium (total)
120. copper
1 21 . cyanide (total)
122. lead
123. mercury
124. nickel
125. selenium
126. silver
127. thallium
128. zinc
'11 UAJ^rul
.MPLING
Sample
Typet
1
1
1
1
1
1
1
1
1
1
1
1
1
DATA
Concentrations (mg/1)
Source
0.023
0.001
<0.001
<0.001
0.018
0.070
0.003
<0.0002
0.17
0.011
0.008
<0.001
420
Day 1 Day 2
<0.001
3.4
0.16
1.4
1.1
470
5.4
0.0005
7,600
<0.001
6.5
1.9
1 ,200
w
w
n
s
o
g
Day 3 3
Q
W
M
g
O
n
8
s
en
g
n
w
1
CO
w
n
H
<
-------
Table V-16 (Continued)
KJ
UJ
-J
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
CRYSTALLIZATION DECANT
RAW WASTEWATER SAMPLING DATA
to
Pollutant
Nonconventional Pollutants
Ammonia Nitrogen
Chloride
Cobalt
Iron
Phenolics
Titanium
Total Solids (TS)
Convent tonal Pollutants
Oil and Grease
Total Suspended Solids (TSS)
pH (standard units)
tSample Type Code: 1 - One-time grab
Sample
Typet
jn.
Concentrations (mg/1)
Source
0.07
<1
0.24
0.30
<0.001
0.10
16
11
<4
7.1
Day 1 Day 2
26,000
160,000
1,100
1,200
0.019
7.5
280,000
<1
160
0.1
a
o
§
pay 3 "S
Ci
1
g
9
o
C0
s
J"3
i
o
1
o
M
m
n
^
i
<
-------
Table V-17
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
ACID WASH DECANT
RAW WASTEWATER SAMPLING DATA
Pollutant
Sample
Typet
Concentrations (mg/1)
Source
Dl
M
8
a
o
3*
K)
OJ
Toxic Pollutants
114. antimony
115. arsenic
117. beryllium
118. cadmium
119. chromium (total)
0.023
0,023
0.023
0.023
0.001
0.001
0.001
0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
0.018
0.018
0.018
0.018
<0.001
0.74
0.04
NA
<0.001
0.18
0.15
NA
0.003
0.12
<0.001
<0.001
8.3
6.3
4.8
5.4
2.1
0.86
0.73
0.68
Q
OT
H
w
55
O
8
G
W
o
w
Q
O
W
M
O
HI
-------
Table V-17 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
ACID WASH DECANT
RAW WASTEWATER SAMPLING DATA
U)
Pollutant
Nonconventional Pollutants
120. copper
122. lead
123. mercury
124. nickel
125. selenium
Sample
Typet
Concentrations (mg/1)
Source
0.070
0.070
0.070
0.070
0.003
0.003
0.003
0.003
<0.0002
<0.0002
<0.0002
<0.0002
0.17
0.17
0.17
0.17
0.011
0.011
0.011
0.011
920
710
7.1
67
15
9.0
8.8
9.1
0.058
<0.0002
<0.0002
<0.0002
3,000
1,000
220
66
<0.001
<0.001
0.18
NA
to
KJ
1
§
OT
a
a
o
CO
a
w
o
>
El
Q
I
OT
M
i
<
-------
Table V-17 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
ACID WASH DECANT
RAW WASTEWATER SAMPLING DATA
u>
M
Pollutant
Toxic Pollutants (continued)
126. silver
127. thallium
128. zinc
Nonconventional Pollutants
Ammonia Nitrogen
Chloride
Sample
Typet
Source
0.008
<0.001
420
Concentrations (mg/1)
0.07
5.5
2.5
0.3
0.78
0.56
0.05
<0.001
<0.001
460
100
78
46
10,000
3,400
700
150
120,000
83,000
74,000
76,000
en
w
o
1
0
en
o
8
en
S
o
I
0
en
M
O
i
<
-------
Table V-17 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
ACID WASH DECANT
RAW WASTEWATER SAMPLING DATA
Pollutant
Nonconyenttonal Pollutants (continued)
Cobalt
u> Iron
PhenolIcs
Titanium
Total Solids (TS)
Sample
Typet
Concentrations (mg/1)
Source
0.24
0.24
0.24
0.24
0.30
0.30
0.30
0.30
<0.001
<0.001
<0.001
<0.001
0.10
0.10
0.10
0.10
16
16
16
16
Day 1
1 ,100
1 ,000
360
150
590
300
70
20
<0.001
0.440
0.003
0.490
13
6.0
1.7
0.9
80,000
5,800
10,000
4,300
w
w
o
i
o
to
o
o
o
i
in
w
8
<
-------
Table V-17 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
ACID WASH DECANT
RAW WASTEWATER SAMPLING DATA
u>
Pollutant
Conventional Pollutants
Oil and Grease
Total Suspended Solids (TSS)
pH (standard units)
Sample
Typet
Concentrations (mg/1)
Source
11
11
11
11
<4
<4
<4
7.1
7.1
7.1
7.1
5.7
940
71
17
<4
0
0
0
0
w
M
o
o
z
a
§
Q
CO.
(-3
M
55
O
O
8
Hi
W
§
o
w
a
o
K
w
w
n
H3
tSaraple Type" Code: 1 - One-time grab
-------
Table V-18
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
COBALT HYDROXIDE FILTRATE
u»
ro
Pollutant
Toxic Pollutants
114. antimony
115. arsenic
117. beryllium
118. cadmium
119. chromium (total)
120. copper
121. cyanide (total)
122. lead
123. mercury
124. nickel
125. selenium
126. silver
127. thallium
128. zinc
.MFLING
Sample
Typet
1
1
1
1
1
1
1
1
1
1
\
1
1
1
DATA
Concentrations (mg/1)
Source
0.023
0.001
<0.001
<0.001
0.018
0.07.0
0.009
0.003
<0.0002
0.17
0.01 1
0.008
<0.001
420
Day 1 Day 2
0.5
0.7
<0.001
0.18
<0.001
0.19
0.31
1.4
<0.0002
1.4
0.2
1.5
0.24
0.72
tn
W
J
Day 3 »
Q
Vt
m
25
1
n
1
OT
«
(0
0
S
m
Q
O
JO
W
a
n
i
-------
LU
Table V-18 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
COBALT HYDROXIDE FILTRATE
Pollutant
Nonconventional Pollutants
Ammonia Nitrogen
Chloride
Cobalt
Iron
Molybdenum
Titanium
Total Solids (TS)
Conventional Pollutants
Oil and Grease
Total Suspended Solids (TSS)
pH (standard units)
' iu i i. iJt *. &vra J. o
MPLING DATA
Sample Concentrations (rag/1)
Typet
1
1
1
1
1
1
1
1
1
Source
0.07
<1
0.24
0.30
0.75
0.10
16
11
<4
7.1
Day 1 Day 2
14,000
42,000
2.8
0.63
0.006
0.15
86,000
3.9
66
12.7
to
W
O
O
Day 3 §
O
to
1
i
o
o
to
§
§
o
s
M
1
K
to
M
O
HI
tSample Type Code: 1 - One-time grab
-------
Table V-19
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
COBALT HYDROXIDE FILTER CAKE WASH
OJ
to
it*
en
Pollutant
Toxic Pollutants
114. antimony
115, arsenic
117. beryllium
118. cadmium
119. chromium (total)
120, copper
121. cyanide (total)
122. lead
123. mercury
124. nickel
125. selenium
126. silver
127. thallium
128. zinc
I_t J. t^ l\ \jC*
.MPL1NG
Sample
Typet
2
2
2
2
2
2
2
2
2
2
2
2
2
2
INLJ vim~»*
DATA
Concentrations i.mg/1)
Source
0.023
0.001
<0.001
<0.001
0.018
0.070
0.009
0.003
<0.0002
0.17
0.011
0.008
<0.001
420
Day 1 Day 2
0.007
0.009
<0.001
0.010
<0,001
0.10
0.015
0.98
<0.0002
1.3
<0.001
0.05
-------
tO
Table V-19 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
COBALT HYDROXIDE FILTER CAKE WASH
Pollutant
Nonconventional Pollutants
Ammonia Nitrogen
Chloride
Cobalt
Phenolics
Titanium
Total Solids (TS)
Con ven t lona 1 Po 1 lu tan t s
Oil and Grease
Total Suspended Solids (TSS)
pH (standard units)
iMPLING DATA
Sample Concentrations (mg/1)
Typet
2
2
2
2
2
2
2
1
2
2
Source Day 1 Day 2
0.07 220
<1 <1
0.24 0.18
0.30 0.19
<0.001 <0.001
0.10 <0.'lO
16 <1
11 11
<4 <4
7.1 9.7
w
w
o
o
Day 3 I
K;
G
W
M
55
O
O
w
S
w
§
o
S
Hi
W
Q
O
pa
K«
w
w
9
tSaraple Type Code: 2 - Manual composite during intermittent process operation
-------
Table V-20
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TREATMENT PLANT SAMPLING DATA - PLANT A
Pollutant
Toxic Pollutants
114. antimony
115. arsenic
oo 117. beryllium
£>.
1 18. cadmium
119. chromium (total)
120. copper
122. lead
123. mercury
124. nickel
l^ V^ LSt* M. 4
Sample
Typet
3
6
3
6
3
6
3
6
3
6
3
6
3
6
3
6
3
6
Concentrations (mR/1)
Source
<0.01
<0.01
<0.01
<0.01
<0.0005
<0.0005
<0.02
<0.02
<0.02
<0.02
<0.05
<0.05
<0.05
<0.05
<0.0002
<0.0002
0.5
0.5
Day 1
<0.01
0.13
<0.01
<0.01
<0.005
<0.005
0.04
<0.02
0.32
<0.02
71.7
0.35
2.35
<0.5
<0.0002
<0.0002
145 2
5.35
Day 2
<0.1
<0.01
<0.09
<0.01
<0.05
<0.005
0.8
<0.02
6.2
<0.02
950
0.7
73.5
<0.3
<0.0002
<0.0002
,130
4,6
Day 3
<0.05
<0.01
<0.1
<0.01
<0.05
<0.005
0.6
<0.02
6.4
<0.02
518
<0.05
<10
<0.5
0.011
<0.0002
955
1.85
SECONI
\H/
i
B
Q
to
§
%,
O
O
0
tu
g
to
G
tB
O
S
M
g
s
en
M
^
1
<
-------
Table V-20 (continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TREATMENT PLANT SAMPLING DATA - PLANT A
Pollutant
Toxic Pollutants (Cont'd)
125, selenium
126. silver
127. thallium
oo
*j 128. zinc
Noneonventional Pollutants
Acidity
Alkalinity
Aluminum
Ammonia Nitrogen
Barium
Boron
Sample
Typet
3
6
3
6
3
6
3
6
3
6
3
6
3
6
3
6
3
6
3
6
Concentrations (mg/1)
Source
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
0.08
0.08
<1
XI
40
4U
0.2
0.2
2.0
2.0
<0.05
<0.05
<0.1
<0.1
Day 1
<0.01
<0.01
0.04
<0.02
<0.05
<0,02
15.4
1.46
10 1
XI
~3
W
8
*<
Vt
W
n
^
i
-------
Table V-20 (continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TREATMENT PLANT SAMPLING DATA - PLANT A
to
£*
U3
Pollutant
Nonconventional Pollutants (Cont'd)
Calcium
Chemical Oxygen Demand (COD)
Chloride
Cobalt
Fluoride
Iron
Magnesium
Manganese
Molybdenum
Phosphate
Sample
Typet
3
6
3
6
3
6
3
6
3
6
3
6
3
6
3
6
3
6
3
6
Concentrations (rog/1)
Source
25.7
25.7
110
110
11
11 1
<0.05
<0.05
0.64
0.64
<0.5
<0.5
4.5
4.5
<0.05
<0.05
<0.05
<0.05
0.82
0.82
Day
31.6
745
56
160
310
.100
5.75
4.25
0.21
5.8
150
0.15
7.4
2.0
4.5
2.5
<0.5
<0.05
860
15
JL Day 2
41
762
4,300
120
8,300
240
75.5
2.9
0.72
4.9
3,440
1 .35
8
1.9
59.5
2.35
<5
<0.05
16,000
8.4
Day 3
38
808
6,140
130
4,200
1,200
37
1.3
0.52
0.67
1,300
<0.15
8
1.8
28
1.45
<0.5
<0.05
6,600
39
SECONI
g
K;
HI
O
w
n
i
§
o
o
w
f
w
a
w
a
8
M
1
S
w
w
o
n
1
<;
-------
Table V-20 (continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TREATMENT PLANT SAMPLING DATA - PLANT A
Pollutant
Nonconventional Pollutants (continued)
Sodium
Sulfate
u> Tin
NJ
Ul
O
Titanium
Total Organic Carbon (TOC)
Total Solids (TS)
Vanadium
Yttrium
* * *-* *-*» *»»*.*
Sample
Typet
3
6
3
6
3
6
3
6
3
6
3
6
3
6
3
6
*. A-l**l* A. **
Concentrations
Source
4.5
4.5
590
590
<0.05
<0.05
<0.05
<0.05
<1
<1
250
250
<0.05
<0.05
<0.05
<0.05
Day 1
9.3
14.7
470
670 1
6.15
<0.05
<0.05
<0.05
13
15
2,000 25
4,000 3
<0.05
<0.05
<0.05
<0.05
(mg/1)
Day 2
33
15.7
93
,200 7
9
<0.1
<0.5
<0.05
47
8.4
,000 13
,500 3
0.5
0.05
0.5
0.05
Day 3
610
21.2
91
,600
<0.5
<0.1
<0.5
<0.05
78
39
,000
,400
<0.5
<0.05
<0.5
<0.05
SECONI
*-*
yo
K
Q
W
W
25
§
O
O
O
a
3
W
a
03
O
Jj
W
Q
O
K
Cfl
M
O
t-3
i
-------
Table V-20 (continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
K)
U1
Pollutant
Conventional Pollutants
Oil and Grease
Total Suspended Solids (TSS)
pH (standard units)
INU IJA1A
Sample
Typet
1
1
3
6
3
6
- fLAWl A
Concentrations (rag/1)
Source
-------
Table V-21
Pollutant
Toxic Pollutants
114. antimony
115. arsenic
u>
to
117, beryllium
118. cadmium
119. chromium (total)
120, copper
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TREATMENT PLANT SAMPLING DATA - PLANT B
Sample
Typet
1
1
2
2
1
1
2
2
1
1
2
2
1
1
2
2
1
1
2
2
1
1
2
2
Concentrations (mg/1)
Source
0.023
0.023
0.023
0.023
0.001
0.001
0.001
0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
0.018
0.018
0.018
0.018
0.070
0.070
0.070
0.070
Day 1 Day 2
0.93
8.0
0.014 10
0.41
<0.001
0.040
<0.001 1.0
0.27
<0.001
0.005
0.004 <0.001
0.08
4.3
2.6
2.9 3.4
1.1
<0.001
0.21
0.06 <0.001
0.084
24
52
42 62
53
Day 3
0.18
1.4
<0.001
2.1
0.059
32
en
w
o
o
Q
02
§
g
8
I
W
M
O
n
-------
Table V-21 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TREATMENT PLANT SAMPLING DATA - PLANT B
U)
Pollutant
Toxic Pollutants (Cont'd)
121. cyanide (total)
122. lead
123, mercury
124. nickel
125. selenium
126. silver
Stream
Code
Sample
Typet
'j>
rt
o
o
Concentrations (rog/1) g
Source Day 1 Day 2 Day 3 >
1
1
2
2
1
1
2
2
1
1
2
2
1
1
2
2
1
1
2
2
Source
0.009
0.009
0.009
0.009
0.003
0.003
0.003
0.003
<0.0002
<0.0002
<0.0002
<0.0002
0.17
0.17
0.17
0.17
0.011
0.011
0.011
0.011
0.008
0.008
0.008
0.008
Day 1 Day 2
0.033
0.43
0.68 0.16
0.41
0.47
2.2
<0.001 0.23
2.2
<0.0002
<0.0002
<0.0002 <0.0002
<0.0002
420
290
242 540
150
0.93
0.073
1.3 0.27
0.042
0.25
1.9
3.8 2.6
3.6
Pay 3
0.16
0.02
<0.002
380
<0.001
0.18
n
I
o
§
CO
tt>
o
w
Cft
o
i
<
-------
Table V-21 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TREATMENT PLANT SAMPLING DATA - PLANT B
Ul
Pollutant
Toxic Pollutants (Cont'd)
127. thallium
128. zinc
Nonconventional Pollutants?
Ammonia Nitrogen
Calcium
Chloride
Cobalt
Sample
Typet
1
1
2
2
1
1
2
2
1
1
2
2
2
1
1
2
2
1
1
2
2
Concentrations (ing/1)
Source
<0.001
<0.001
<0.001
<0.001
420
420
420
420
0.07
0.07
0.07
0.07
0.36
<1
<1
<1
<1
0.24
0.24
0.24
0.24
Day 1 Day 2 Day 3
0.62
0.45
0.68 0.60 0.43
1.1
240
1 .8
76 540 160
36
23,000
13,000
13,000 16,000 14,000
160
490
88,000
66,000
66,000 64,000
40,000
16
46
30 12
22
SECON:
a
K
H3
55
W
1-3
M
55
a
n
o
w
H3
c!
W
>
W
g
K
cn
w
9
•
<
-------
Table V-21 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TREATMENT PLANT SAMPLING DATA - PLANT B
Pollutant
Nonconventional Pollutants (Cont' d)
Iron
Magnesium
Phenolics
ui
Sulfate
Titanium
Total Solids (TS)
Sample
Typet
1
1
2
2
1
1
2
2
1
1
2
2
Concentrations (mg/1)
Source
0.30
0.30
0.30
0.30
0.009
<0.001
<0.001
<0.001
<0.001
2.0
0.10
0.10
0.10
0.10
16 61
16 80
16 110
16 140
Day 1 Day 2 Day 3
0.35
3.4
0.23 1.5 0.52
24
5.6
<0.001
<0.001
<0.001 <0.001 <0.001
0.016
11 28
0.10 ,
0.40
0.30 0.20
3.6
,000
,000
,000 120,000 110,000
,000
n
m
o
O
2*
O
CS
25
Q
OT
^
W
Z
O
o
s
OT
C5
tfl
O
w
n
3
w
ft]
I
<
-------
Table V-21 (Continued)
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
TREATMENT PLANT SAMPLING DATA - PLANT B
U)
to
Ul
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - V
TABLE V-22
SECONDARY TUNGSTEN AND COBALT SAMPLING DATA
RAW WASTEWATER SELF SAMPLING DATA
Pollutant Wastewater Pollutant Concentration (mg/1)
Sample No. 88145 88146
Toxic Pollutants
115. arsenic 0.022 <0.010
117. beryllium <0.050 <0.050
118. cadmium 0.040 <0.050
119. chromium 0.120 0.100
120. copper <0.100 <0.100
122. lead 0.480 <0.200
124. nickel <0.200 <0.200
126. silver ,030 <0.050
Nonconventional Pollutants
aluminum <0.500 <0.500
anunonia-N <0,02 0.21
cobalt <0.500 14.500
fluoride 0.03 0.03
iron 2.250 0.390
manganese 0.060 <0.050
molybdenum <0.050 <0.050
tin 13.0 (5.000
titanium <0.200 <2.000
tungsten <86.0 3.6
vanadium 2.800 <1.000
No. 88145 - Tungsten carbide leaching wet air pollution control
No. 88146 - Tungsten carbide wash water
3257
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - V
THIS PAGE INTENTIONALLY LEFT BLANK
3258
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - VI
SECTION VI
SELECTION OF POLLUTANTS
Section V of this supplement presented data from secondary
tungsten and cobalt plant sampling visits and subsequent chemical
analyses. This section examines that data and discusses the
selection or exclusion of toxic pollutants for potential
limitation. Also, this section discusses the selection or
exclusion of conventional and nonconventional pollutants for
limitation.
Each pollutant selected for potential limitation is discussed in
Section VI of Vol. I. That discussion provides information about
the nature of the pollutant (i.e., whether it is a naturally
occurring substance, processed metal, or a manufactured
compound); general physical properties and the form of the
pollutant; toxic effects of the pollutant in humans • and other
animals; and behavior of the pollutant in POTW at the
concentrations expected in industrial discharges.
The discussion that follows describes the analysis that was
performed to select or exclude toxic pollutants for further
consideration for limitations and standards. The data from 14
wastewater samples from tungsten and cobalt plants are considered
in this analysis. All 14 samples are raw wastewater. The
samples are from streams numbered 468, 484, 470, 471, 064, 053,
056, 068, and 071. Pollutants will be selected for further
consideration if they are present in concentrations treatable by
the technologies considered in this analysis. In Section X, a
final selection of the pollutants to be limited will be made
based on relative factors.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS
This study examined samples from secondary tungsten and cobalt
plants for three conventional pollutant parameters (oil and
grease, total suspended solids, and pH) and three nonconventional
pollutant parameters (ammonia, cobalt and tungsten).
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS SELECTED
The conventional and nonconventional pollutants or pollutant
parameters selected for limitation in this subcategory are:
ammonia oil and grease
cobalt total suspended solids (TSS)
tungsten pH
Ammonia was found in eight of 14 samples analyzed at
concentrations exceeding the concentration achievable by
treatment (32 mg/1). The treatable concentrations ranged from
3259
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - VI
150 mg/1 to 26,000 mg/1. Ammonia was found in treatable
concentrations, and is used extensively in tungsten and cobalt
processing, and therefore ammonia is selected for limitation in
this subcategory.
Cobalt was found in 13 of 14 samples above its treatable
concentration of 0.667 mg/1. The treatable concentrations ranged
from 2.8 mg/1 to 2,000 mg/1. Cobalt is a product in this
subcategory, and is soluble in solutions at the pH values of
several waste streams, and is therefore expected 1:o be present in
the wastewater. For these reasons, cobalt is selected for
limitation in this subcategory.
Tungsten was determined in two samples of raw wastewater from
this subcategory in a self-sampling effort conducted at the
specific request of EPA. Tungsten was detected at 3.6 mg/1, which
is greater than the 0.85 mg/1 concentration achievable with
treatment. In addition, it is expected to be present in the raw
wastewaters from this subcategory based of its presence in the
raw materials and production processes, and also because of its
solubility in the various acids and bases used in these
hydrometallurgical processes. For these reasons, tungsten is
selected for limitation in this subcategory.
Oil and grease was observed above its treatable concentration
(10.0 mg/1) in three of the 14 samples analyzed. The three
treatable concentrations found are 11.0 mg/1, 18 mg/1, and 240
mg/1 s. Two of these samples with high oil and grease
concentrations are samples of the water used to remove oils from
the raw material prior to tungsten leaching and would be
predicted to have high oil and grease concentrations. Therefore,
oil and grease is a pollutant parameter selected for limitation
in this subcategory.
Total suspended solids (TSS) concentrations were found above the
2.6 mg/1 concentration considered achievable by identified
treatment technology in 12 of the 14 samples analyzed. Treatable
concentrations ranged from 17 mg/1 to 50,000 mg/1. Furthermore,
most of the technologies used to remove toxic metals do so by
converting these metals to precipitates. A limitation on total
suspended solids helps ensure that sedimentation to remove
precipitated toxic metals is effectively operating. For these
reasons, total suspended solids is a pollutant parameter selected
for limitation in this subcategory.
The pH values observed ranged from zero to 12.7. Five wastewater
streams have pH values between zero and 1.31. Effective removal
of toxic metals by precipitation requires careful control of pH.
Therefore, pH is selected for limitation in this subcategory.
PRIORITY POLLUTANTS
The frequency of occurrence of the priority pollutants in the raw
wastewater samples considered in this analysis is presented in
Table VI-1. These data provide the basis for the categorization
3260
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - VI
of specific pollutants, as discussed below. Table VI-1 (page
3264) is based on the raw wastewater sampling data from streams
468, 470, 471, 487, 053, 056, 064, 068, and 071. The stream
codes correspond to sample locations in Figures V-l and V-2.
Combined and treated vastewater data, streams 479, 473, 069, 062,
061, and 058 were not: used in the frequency count.
TOXIC POLLUTANTS NEVER DETECTED
The toxic pollutants listed in Table VI-2 (page 3265) were not
detected in any raw wastewater samples from this subcategory;
therefore, they are not selected for consideration in
establishing limitations:
TOXIC POLLUTANTS PRESENT BELOW CONCENTRATIONS ACHIEVABLE BY
TREATMENT
The pollutants listed below are not selected for consideration in
establishing limitations and standards because they were not
found in any wastewater samples from this subcategory above
concentrations considered achievable by existing or available
treatment technologies. These pollutants are discussed
individually following the list.
117. beryllium
125. selenium
Beryllium was detected above its analytical quantification limit
in two of the 14 samples. The observed concentrations were 0.12
mg/1 and 0.16 mg/1. Both of these values are below the 0.20 mg/1
concentration considered achievable by identified treatment
technology. Therefore, beryllium is not considered for
limitation.
Selenium was detected above its analytical quantification limit
in two of the 13 samples. The observed concentrations were 0.18
mg/1 and 0.2 mg/1. Neither of these values are above the 0.2
mg/1 concentration considered achievable by identified treatment
technology. For this reason, selenium is not selected for
limitation.
PRIORITY POLLUTANTS DETECTED IN A SMALL NUMBER OF SOURCES
The following pollutants were not selected for limitation because
they were detected in the effluent from only a small number of
sources within the subcategory and they are uniquely related to
only those sources.
114. antimony
121. cyanide
123. mercury
127. thallium
Antimony was detected above its analytical quantification limit
3261
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - VI
in three of the 13 samples considered in the analysis. Two of
the three values (0.5 mg/1, 0.74 mg/1) are above the 0.47 mg/1
concentrations considered achievable by identified treatment
technology. Antimony was not detected above its quantification
limit in the other samples. Since antimony was only detected at
one plant, it is not selected for limitation.
Cyanide was detected above its analytical quantification limit in
only one sample analyzed. This value (0.31 mg/1) is above the
0.047 mg/1 concentration considered achievable by identified
treatment technology. However, cyanide is not expected to be
present in the wastewater based on the raw materials and
production processes involved. Therefore, cyanide is not
selected for limitation.
Mercury was detected above its analytical quantification limit in
four of the 14 samples considered in the analysis. One of the
four values (0.058 mg/1) is above the 0.036 mg/1 concentration
considered achievable by identified treatment technology. Mercury
was not detected in the other 10 samples. Since mercury was
detected at treatable levels in only sample, it is not selected
for limitation.
Thallium was detected above its analytical quantification limit
in four of the 12 samples considered in the analysis. Three of
the four values are above the 0.34 mg/1 concentration considered
achievable by identified treatment technology. Thallium was not
detected in the other samples. Since thallium was detected at
treatable levels at only one plant, it is not selected for
limitation.
TOXIC POLLUTANTS SELECTED FOR FURTHER CONSIDERATION IN
ESTABLISHING LIMITATIONS AND STANDARDS
The toxic pollutants listed below are selected for further
consideration in establishing limitations and standards for this
subcategory. The toxic pollutants selected are each discussed
following the list.
115. arsenic
118. cadmium
119. chromium
120. copper
122. lead
124. nickel
126. silver
128. zinc
Arsenic was detected above its treatable concentration (0.34
mg/1) in five of 13 samples. The quantifiable concentrations
ranged from 0.14 to 3.4 mg/1. Since arsenic was present in
concentrations exceeding the concentration achievable by
identified treatment technology, it is selected for consideration
for limitation.
3262
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - VI
Cadmium was detected above its treatable concentration (0.049
mg/] ) in 12 to 14 samples. The quantifiable concentrations
ranged from 0.01 to 8.3 mg/1. Since cadmium was present in
concentrations exceeding the concentration achievable by
identified treatment technology, it is selected for consideration
for limitation.
•-htomium was detected above its treatable concentration. (0.07
ing/1) in 12 of 14 samples. The quantifiable concentrations
imaged from 0.68 to 38 mg/1. Since chromium was present in
concentrations exceeding the concentration achievable by
identified treatment technology, it is selected for consideration
for limitation.
Copper was detected above its treatable concentration (0.39 mg/1)
in 12 of 14 samples. The quantifiable concentrations ranged from
C.i to 2,890 mg/1. Since copper was present in concentrations
exceeding the concentration achievable by identified treatment
technology, it is selected for consideration for limitation.
Lead was detected above its treatable concentration (0.08 mg/1)
in eight of 14 samples. The quantifiable concentrations ranged
-from 0.98 to 15 mg/1. Since lead was present in concentrations
exceeding the concentration achievable by identified treatment
technology, it is selected for consideration for limitation.
Nickel was detected above its treatable concentration (0.22 mg/1)
in all of the 14 samples. The quantifiable concentrations ranged
from 1.3 to 13,900 mg/1. Since nickel was present in
concentrations exceeding the concentration achievable by
identified treatment technology, it is selected for consideration
for limitation.
Silver was detected above its treatable concentration (0.07 mg/1)
in nine to 14 samples. The quantifiable concentrations ranged
from 0.05 to 7.0 mg/1. Since silver was present in
concentrations exceeding the concentration achievable by
identified treatment technology, it is selected for consideration
for limitation.
Zinc was detected above its treatable concentration (0.23 mg/1)
in 10 of 14 samples. The quantifiable concentrations ranged from
0.4 to 1,200 mg/1. Since zinc was present in concentrations
exceeding the concentration achievable by identified treatment
technology, it is selected for consideration for limitation.
3263
-------
U)
K5
a\
Table VI-1
FREQUENCY OF OCCURRENCE OF PRIORITY POLLUTANTS
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
Polluiani
114,
115.
116.
117.
118,
119.
120.
121.
122.
123.
124.
125.
126.
127.
128.
ant iinuny
arsenic
asbestos
beryl 1 liis
cadmium
chruniiin
copper
cyanide (e)
lead
mercury
nickel
seletiliw
silver
thai It in
zinc
Amnonia
Oil and Crease
Total Suspended Solids (TSS)
Analytical
Quantification
Concentration
(wg/l)(a)
0.100
0.010
10MFL
0.010
0.002
0.005
0.009
0.02
0.020
0.0001
.005
0.01
0.02
0.100
0.050
5.0
1.0
Treatable
Concentra-
tion
0.47
0.34
10 MFL
0.20
0.049
0.07
0.39
0.047
0.08
0.036
0.22
0.20
0.07
0.34
0.23
32
10.0
2.6
Nunber of
Streams
Analyzed
8
8
8
8
8
8
2
8
8
8
8
8
6
8
8
8
8
Nuaber of
Samples
Analyzed
13
13
14
14
14
14
2
14
14
14
13
14
12
14
14
14
14
Detected Below
Quantification
Concentration
10
5
12
0
2
0
1
6
10
0
11
4
8
4
NA
9
2
Detected
Below Treat-
able Concen-
tration
1
3
2
2
0
2
0
0
3
0
2
1
1
0
6
2
0
Detected
Above Treat-
able Concen-
tration
2
5
0
12
12
\2
1
tf
1
14
0
9
3
10
8
3
12
(a) Analytical quantification concentration was reported with the data (see Section V).
fh) Treatable concentrations are based on performance of line precipitation, sedimentation, and filtration.
(c) Analytical quantification concentration for EPA Method 335.2, Total Cyanide Methods for Chemical Analysts of Water and Wastes, EPA 600/4-7V-020,
March 1979.
W
M
O
O
2!
z;
Q
to
1-3
w
25
O
o
o
a
c
CO
o
M
Q
O
to
M
O
I
<
-------
SECONDARY TPNP-STEN AND COBALT SUBCATEGORY SECT - VI
TABLE VI-2
PRIORITY POLLUTANTS NEVER DETECTED
1. acenaphthene*
2. acrolein*
3. acrylonitrile*
4. benzene*
5. benzidine*
6. carbon tetrachloride (tetrachloromethane)*
7. chlorobenzene*
8. 1,2f4-trichlorobenzene*
9. hexachlorobenzene*
10. 1,2-dichloroethane*
11. Ijlf1-trichloroethane*
12. hexachloroethane*
13. lf1-dichloroethane*
14. 1,1,2-triehloroethane*
15. 1,1,2,2-tetrachloroethane*
16. ehloroethane*
17. bis (chloromethyl) ether (DELETED)*
18. bis (2-chloroethyl) ether*
19. 2-chloroethyl vinyl e'<.fter (mixed)*
20. 2-chloronaphthalene*
21. 2,4,6-trichlorophenol*
22. parachlorometa cresol*
23. chloroform (trichlororaethane)*
24. 2-chlorophenol*
25. If 2 dichlorobenzene*
26. 1,3-dichlorobenzene*
27. If4-dichlorobenzene*
28. 3,3"-dichlorobenzidine*
29. 1,1-dichloroethylene*
30. 1,2-trans-dichloroethylene*
31. 2,4-dichlorophenol*
32. 1,2-dichloropropane*
33. 1,2-dichloropropylene (1,3-diehloropropene)*
34. 2,4-dimethylphenol*
35, 2,4-dinitrotoluene*
36. 2,6-dinitrotoluene*
37. 1,2-diphenylhydrazine*
38. ethylbenzene*
39. fluoranthene*
40. 4-chlorophenyl phenyl ether*
41. 4-bromophenyl phenyl ether*
42. bis(2-chloroisopropyl) ether*
43. bis(2-choroethoxy) merhane*
rnethylene chloride (dichloromethane) *
45. methyl chloride (chloromethane)*
46. methyl bromide (bromomethane)*
47. bromoform (tribromomethane)*
3265
-------
SECONDARY TUNGSTEN.AND COBALT SUBGATEGORY SECT - VI
TABLE VI-2 (Continued)
PRIORITY POLLUTANTS NEVER DETECTED
48. dichlorobromomethane*
49. trichlorofluoromethane (DELETED)*
50. dichlorodifluoromethane (DELETED)*
51. chlorodibromomethane*
52. hexachlorobutadiene*
53. hexachlorocyclopentadiene*
54. isophorone*
55. naphthalene*
56. nitrobenzene*
57. 2-nitrophenol*
58. 4-nitrophenol*
59. 2,4-dinitrophenol*
60. 4,6-dinitro-o-cresol*
61. N-nitrosodimethylamine*
62. N-nitrosodiphenylamine*
63. N-nitrosodi-n-propylamine*
64, pentachlorophenol*
65. phenol*
66. bis{2-ethylhexyl) phthalate*
67. butyl benzyl phthalate*
68. di-n-butyl phrhalate*
69. di-n-octyl phthalate*
70. diethyl phthalate*
71. dimethyl phthalate*
72. benzo (a)anrhracene (1,2-benzanthracene)*
73. benzo (a)pyrene (3,4-benzopyrene)*
74. 3,4-benzofluoranthene*
75. benzo(k)fluoranthane {11,12-benzofluoranthene)*
76. chrysene*
77. acenaphthylene*
78. anthracene*
79. benzo(ghi)perylene (1,11-benzoperylene)*
80. fluorene*
81. phenanthrene*
82. dibenzo (a,h)anthracene (1,2,5,6-dibenzanthracene)*
83. indeno (1,2,3-cd)pyrene (w,e,-o-phenylenepyrene)*
84. pyrene*
85. tetrachloroethylene*
86. toluene*
87. trichloroethylene*
88. vinyl chloride (chloroethylene)*
89. aldrin*
90. dieldrin*
91. chlordane (technical mixture and metabolites)*
92. 4,4'-DDT*
93. 4,4'-DDE(p,p'DDX)*
94. 4'4f-DDD(p,p'TDE)*
3266
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - VI
TABLE VI-2 (Continued)
PRIORITY POLLUTANTS NEVER DETECTED
95. Alpha-endosulfan*
OS. Beta-endosulfan*
£'; . endosulfan sulfate*
98. endrin*
99. endrin aldehyde*
100. heptachlor*
101. heptachlor epoxide*
102. Alpha-BHC*
103. Beta-BHC*
t04. Gamma-BHC (lindane)*
105. Delta-3HC*
106. PCB-1242 (Arochlor 1242)*
IU7. PCB-1254 (Arochlor 1254)*
108. PCB-1221 (Arochlor 1221)*
109. PCB-1232 (Arochlor 1232)*
UO. PCB-1248 (Arochlor 1248)*
111. PCB-1260 (Arochlor 1260)*
112. PCB-1016 (Arochlor 1016)*
113. toxaphene*
116. asbestos (Fibrous)
129. 2,3,7,8-tetra chlorodibenzo-p-dioxin (TCDD)
*We did not analyze for these pollutants in samples of raw
wastewater from this subcategory. These pollutants are not
believed to be present based on the Agency's best engineering
judgment which includes consideration of raw materials and
process operations.
3267
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGQRY SECT - VI
THIS PAGE INTENTIONALLY LEFT BLANK
3268
-------
SECONDARY TUNGSTEN AND COBALT SUBCATKGORy bKCT - VII
SECTION VII
CONTROL AND TREATMENT TECHNOLOGIES
The preceding sections of this supplement discussed the sources,
flows, and characteristics of the wastewaters from secondary
tungsten and cobalt plants. This section summarizes the
description of these wastewaters and indicates the treatment
technologies which are currently practiced in the secondary
tungsten and cobalt subcategory for each waste stream. Secondly,
this section presents the control and treatment options which
were examined by the Agency for possible application to the
secondary tungsten and cobalt subcategory.
CURRENT CONTROL AND TREATMENT PRACTICES
Control and treatment technologies are discussed in Section VII
of Vol. I, and the basic principles of these technologies and the
applicability to wastewater similar to that found in this
subcategory are presented there. This section presents a summary
of the control and treaLirent technologies that are currently
being applied to each ot the sources generating wastewater in
this subcategory. As discussed in Section V, wastewater
associated with the secondary tungsten and cobalt subcategory is
characterized by the presence of the toxic metal pollutants,
ammonia, oil and grease and suspended solids. This analysis is
supported by the raw (untreated) wastewater data presented for
specific sources as well as combined waste streams in Section V.
Generally, these pollutants are present in each of the waste
streams at concentrations above treatability, and these waste
streams are commonly combined for treatment. Construction of one
wastewater treatment system for combined treatment allows plants
to take advantage of economic scale and in some instances to
combine streams of different alkalinity to reduce treatment
chemical requirements. Three plants in this subcategory
currently have combined wastewater treatment systems. One plant
has no treatment. All three treatment schemes consist of
chemical precipitation and sedimentation with adding ammonia
steam stripping preliminary treatment. Two options have been
selected for consideration for BPT, BAT, NSPS, and pretreatment
based on combined treatment of these compatible waste streams.
TUNGSTEN DETERGENT WASH AND RINSE
^".ngst^n s-.rrap may be prop^r.-1^ fVr leaching by washing it with
detergent and then rinsing it with water. The wastewater from
this process is treated by lime and settle treatment of combined
wastewater to precipitate metals before discharging the wash and
rinse water.
TUNGSTEN LEACHING ACID
Tungsten scrap is leached with acid in order to remove impurities
3269
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - VII
from tungsten. The acid leachate contains significant
concentrations of toxic metals. This wastewater stream, may be
treated it in a combined wastewater system with lime and settle
treatment technology to precipitate metals before discharge or
alternatively, it may be routed to further processing to recover
metals prior to treatment and discharge.
TUNGSTEN POST-LEACHING WASH AND RINSE
After leaching tungsten scrap the tungsten product may be washed
with acid and rinsed with water in order to remove any traces of
acid, and to further purify it. After using this process, lime
and settle treatment of the combined wastewater is used to
precipitate metals before discharging.
SYNTHETIC SCHEELITE FILTRATE
Both tungsten and tungsten carbide scrap may be processed into
synthetic scheelite for use in a primary tungsten process. After
oxidizing tungsten and dissolving the oxide in caustic, the
scheelite is precipitated and the wastewater filtered away. The
filtrate is discharged to lime and settle treatment of combined
wastewater prior to discharge.
TUNGSTEN CARBIDE LEACHING WET AIR POLLUTION CONTROL
Hydrochloric acid fumes from the acid leaching of tungsten
carbide scrap are controlled with a wet scrubber system. The wet
scrubber process water is extensively recycled but produces a
blowdown wastewater stream. This wastewater stream is treated
with lime and settle prior to discharge.
TUNGSTEN CARBIDE WASH WATER
After leaching away the cobalt and impurities, tungsten carbide
powder may be washed with water in order to remove any traces of
acid. This wastewater stream may be discharged to a lime and
settle system prior to discharge or recycled for further use in
the carbide wash operation.
COBALT SLUDGE LEACHING WET AIR POLLUTION CONTROL
During the acid leaching of cobalt sludge, a wet scrubbing system
may be used to control hydrochloric acid fumes. This wastewater
stream is extensively recycled and the blowdown is treated with
ammonia steam stripping, chemical precipitation and sedimentation
prior to discharge.
CRYSTALLIZATION DECANT
After leaching tungsten carbide scrap with acid and filtering
away the undissolved impurities, cobalt is crystallized as an
ammonium cobalt intermediate. The excess crystallization liquor
is decanted off, and discharged following treatment. Treatment
for this wastewater stream consists of ammonia steam stripping
3270
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - VII
preliminary treatment, followed by chemical precipitation and
sedimentation of a combined waste stream. The sludge from the
clarifier is reacted with excess lime and then filtered using a
filter press.
ACID WASH DECANT
"•he ammonium cobalt crystals may be washed several times with
dilute hydrochloric acid. After washing the crystals, the acid is
decanted off and discharged to treatment. This wastewater is
combined with the crystallization decant water, and treated with
ammonia steam stripping, chemical precipitation and
sedimentation.
COBALT HYDROXIDE FILTRATE
After purifying the ammonium cobalt crystals, they are dissolved
and cobalt is precipitated as the hydroxide. The cobalt
hydroxide precipitate is filtered and the filtrate is discharged.
This wastewater stream is combined with crystallization and acid
wash decant wastewater and is treated with ammonia steam
stripping and chemical precipitation and sedimentation.
COBALT HYDROXIDE FILTER CAKE WASH
The cobalt hydroxide filter cake may be washed with water in
order to remove any traces of caustic or other impurities. It is
discharged after treating it with chemical precipitation and
sedimentation of a combined waste stream.
CONTROL AND TREATMENT OPTIONS
The Agency examined two control and treatment technology options
that are applicable to the secondary tungsten and cobalt
subcategory. The options selected for evaluation represent a
combination of in-process flow reduction, preliminary treatment
technologies applicable to individual waste streams, and end-of-
pipe treatment technologies.
Option B was eliminated from consideration for promulgation
because the two subdivisions identified for possible flow
reduction were determined as being extensively recycled
currently. Therefore, flow reduction beyond that considered in
Option A is not applicable in this subcategory.
OPTION A
Option A for the secondary tungsten and cobalt subcategory
requires control and treatment technologies to reduce the
discharge to wastewater volume and pollutant mass. The Option A
treatment scheme consists of chemical precipitation and
sedimentation technology. Specifically, lime or some other
alkaline compound is used to precipitate metal ions as metal
hydroxides. The metal hydroxides and suspended solids settle out
and the sludge is collected. Vacuum filtration is used to
3271
-------
SKCONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - VII
dewater sludge.
Preliminary treatment consisting of ammonia steam stripping for
waste streams containing treatable concentrations of ammonia is
nlso included in Option A. Steam stripping is an efficient
method for reducing the ammonia concentrations as well as
recovering ammonia as a by-product. Steam stripping also
prevents the transfer of ammonia to the air. Preliminary
treatment for Option A also includes oil skimming, for waste
streams containing treatable concentrations of oil and grease.
Oil skimming is ah efficient method for reducing the oil and
grease concentration.
OPTION C
Option C for the secondary tungsten and cobalt subcategory
consists of all control and treatment requirements of Option A
(ammonia steam stripping, oil skimming, chemical precipitation
and sedimentation) plus multimedia filtration technology added to
the end of the Option A treatment scheme. Multimedia filtration
is used to remove suspended solids, including precipitates of
metals, beyond the concentration attainable by gravity
sedimentation. The filter suggested is of the gravity,
mixed media type, although other forms of filters, such as rapid
sand filters or pressure filters would perform satisfactorily.
The addition of filters also provides consistent removal during
periods of time in which there are rapid increases in flows or
loadings of pollutants to the treatment system.
3272
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - VIII
SECTION VIII
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS
This section presents a summary of compliance costs for the
secondary tungsten and cobalt subcategory and a description of
the treatment options and subcategory-specific assumptions used
to develop these estimates. Together with the estimated
pollutant reduction performance presented in Sections IX, X, XI,
and XII of this supplement, these cost estimates provide a basis
for evaluating each regulatory option. These cost estimates are
also used in determining the probable economic impact to
regulation on the subcategory at different pollutant discharge
levels. In addition, this section addresses nonwater quality
environmental impacts of wastewater treatment and control
alternatives, including air pollution, solid waste, and energy
requirements, which are specific to the secondary tungsten and
cobalt subcategory.
TREATMENT OPTIONS FOR EXISTING SOURCES
As discussed in Section VII, two treatment options have been
developed for existing secondary tungsten and cobalt sources. The
options are summarized below and schematically presented in
Figures X-l and X-2.
OPTION A
Option A consists of ammonia steam stripping and oil-water
separation preliminary treatment and chemical precipitation and
sedimentation end-of-pipe technology.
OPTION C
Option C consists of ammonia steam stripping and oil-water
separation preliminary treatment, and end-of-pipe treatment
technology consisting of chemical precipitation, sedimentation,
and multimedia filtration.
COST METHODOLOGY
Plant-by-plant compliance costs for the nonferrous metals
manufacturing category have been revised as necessary following
proposal. These revisions calculate incremental costs, above
treatment already in-place, necessary to comply with the
promulgated effluent limitations and standards. The costs
developed for the final regulation are presented in Table VIII-1
(page 3276) for the direct dischargers, and in Table VIII-2 (page
3276) for the indirect dischargers.
Each of the general assumptions used to develop compliance costs
is presented in Section VIII of Vol. I. Each subcategory contains
a unique set of waste streams requiring certain subcategory-
specif ic assumptions to develop compliance costs. For the
3273
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - VIII
secondary tungsten and cobalt subcategory, only one assumption
was made, namely that all chromium pollutant data are assumed to
measure trivalent chromium. Therefore, chromium reduction is not
required in the treatment scheme.
ENERGY REQUIREMENTS
Energy requirements for the two options considered are estimated
at 1.15 x 106 kwh/yr and 1.185 x 106 kwh/yr for Options A and C,
respectively. Option C, which includes filtration, is estimated
to increase energy consumption over Option A by less than one
percent. Option C represents roughly 15 percent of a typical
plant's electrical energy usage. It is therefore concluded that
the energy requirements of the treatment options considered will
not have a significant impact on total plant energy consumption.
SOLID WASTE
Sludge generated in the secondary tungsten and cobalt subcategory
is due to the precipitation of metal hydroxides and carbonates
using lime or other chemicals. Sludges associated with the
secondary tungsten and cobalt subcategory will necessarily
contain quantities of toxic metal pollutants. Wastes generated
by secondary metal industries can be regulated as .hazardous.
However, the Agency examined the solid wastes that wculd be
generated at secondary nonferrous metals manufacturing plants by
the suggested treatment technologies and believes they are not
hazardous wastes under the Agency's regulations implementing
Section 3001 of the Resource Conservation and Recovery Act. The
one exception to this is solid wastes generated by cyanide
precipitation. These sludges are expected to be hazardous and
this judgment was included in this study. None of the non-
cyanide wastes are listed specifically as hazardous. Nor are
they likely to exhibit a characteristic of hazardous waste. This
judgment is made based on the recommended technology of chemical
precipitation and filtration. By the addition of a small excess
(5 - 10%) of lime during treatment, similar sludges, specifically
toxic metal bear-ing sludges, generated by other industries such
as the iron and steel industry passed the Extraction Procedure
(EP) toxicity test. See 40 CFR .8261.24. Thus, the Agency
believes that the wastewater sludges will similarly noi-. be? EP
toxic if the recommended technology is applied.
Although it is the Agency's view that solid wastes generated as a
result of these guidelines are not expected to be hazardous,
generators of these wastes must test the waste to determine if
the wastes meet any of the characteristics of hazardous waste
(see 40 CFR $262.11) .
If these wastes identified should be or are listed as hazardous,
they will come within the scope of RCRA's "cradle to grave
hazardous waste management program, requiring regulation from the
point of generation to point of final disposition. EPA's
generator standards wouid require generators of hazardous
nonferrous metals manufacturing wastes to meet containeri-sation,
3274
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - VIII
labeling, recordkeeping, and reporting requirements; if plants
dispose off hazardous wastes off-site, they would have to prepare
a manifest which would track the movement of the wastes from the
'^enoratoi ' s premises to a permitted off-site treatment, storage,
or disposal facility. See 40 CFR S262.20 (45 FR 33142 (May 19,
1980), as amended at 45 FR 86973 (December 31, 1980)). The
transporter regulations require transporters of hazardous waste
to comply with the manifest system to assure that the wastes are
delivered to a permitted facility. See 40 CFR 0263.20 (45 FR
33151 (May 19, 1980), as amended at 45 FR 86973 (December 31,
1980)). Finally, RCRA regulations establish standards for
hazardous waste treatment, storage, and disposal facilities
allowed to receive such wastes. See 40 CFR Part 464 (46 FR 2802
(January 12, 1981), 47 FR 32274 (July 26, 1982)).
Even if these wastes are not identified as hazardous, they still
must be disposed of in compliance with the Subtitle D open
dumping standards, implementing 84004 of RCRA. See 44 FR 53438
(September 13, 1979). The Agency has calculated as part of the
costs for wastewater treatment the cost of hauling and disposing
of these wastes.
The Agency estimates that the BPT regulation for secondary
tungsten and cobalt manufacturing facilities will generate 563
metric tons of solid wastes (wet basis) in 1982 as a result of
wastewater treatment. BAT for this subcategory should not
increase sludge generation.
AIR POLLUTION
There is no reason to believe that any substantial air pollution
problems will result from implementation of ammonia steam
stripping, oil-water separation, chemical precipitation,
sedimentation, and multimedia filtration. These technologies
transfer pollutants to solid waste and are not likely to transfer
pollutants to air.
3275
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT
TABLE VIII-1
COST OF COMPLIANCE FOR THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
Direct Dischargers
Total Required Total
Capital Cost Annual Cost
Option (1982 Dollars) (1982 Dollars)
A 42,900 173,000
B NA NA
C 60,900 182,700
NA - Not applicable, i.e., Option B eliminated for final
regulation.
Table VII1-2
COST OF COMPLIANCE FOR THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
Indirect Dischargers
Total Required Total
Capital Cost Annual Cost
Option (1982 Dollars) (1982 Dollars)
A 8,500 5,300
C 16,300 8,800
3276
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - IX
SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY
CURRENTLY AVAILABLE
This section defines the effluent characteristics attainable
through the application of best practicable control technology
currently available (BPT). BPT reflects the existing performance
by plants of various sizes, ages, and manufacturing processes
within the secondary tungsten and cobalt subcategory, as well as
the established performance of the model BPT treatment systems.
Particular consideration is given to the treatment already in
place at plants within the data base.
The factors considered in identifying .BPT include the total cost
of applying the technology in relation to the effluent reduction
benefits from such application, the age of equipment and
facilities involved, the manufacturing processes used, nonwater
quality environmental impacts (including enargy requirements),
and other factors the Administrator considers appropriate. In
general, the BPT level represents the average of the existing
performances of plants of various ages, sizes, processes, or
other common characteristics. Where existing performance is
uniformly inadequate, BPT may be transferred from a different
subcategory or category. Limitations based on transfer of
technology are supported by a rationale concluding that the
technology is, indeed, transferable, and a reasonable prediction
that it will be capable of achieving the prescribed effluent
limits (see Tanner s» Council of America v. Train, 540 P.2d 1188
(4th Cir. 1976). BPT focuses on end-of-pipe treatment rather
than process changes or internal controls, except where such
practices are common industry practice.
TECHNICAL APPROACH TO BPT
The Agency studied the secondary tungsten and cobalt subcategory
to identify the processes used the wastewaters generated and
the treatment processes installed. Information was collected
from the category using data collection portfolios, and specific
plants were sampled and the wastewaters analyzed. In making
technical assessments of data, reviewing manufacturing processes,
and assessing wastewater treatment technology options, both
indirect and direct dischargers have been considered as a single
group. An examination of plants and processes did not indicate
any process differences based on the type of discharge, whether
it be direct or indirect.
As explained in Section IV, the secondary tungsten and cobalt
subcategory has been subdivided into 11 potential wastewater
sources. Since the water use, discharge rates, and pollutant
characteristics of each of these wastewaters is potentially
unique, effluent limitations will be developed for each of the 11
subdivisions.
3277
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - IX
For each of the subdivisions, a specific approach was followed
for the development of BPT mass limitations. The first
requirement to develop limitations is to account for production
and flow variability from plant to plant. Therefore, a unit of
production or production normalizing parameter (PNP) was
determined for each wastewater stream which could then be related
to the flow from the process to determine a production normalized
flow. Selection of the PNP for each process element is discussed
in Section IV. Each plant within the subcategory was then
analyzed to determine which subdivisions were present, the
specific flow rates generated for each subdivision and the
specific production normalized flows for each subdivision. This
analysis is discussed in detail in Section V. Nonprocess
wastewaters such as rainfall runoff and noncontact cooling water
are not considered in the analysis.
Production normalized flows for each subdivision were then
analyzed to determine the flow to be used as part of the basis
for BPT mass limitations. The selected flow (sometimes referred
to as the BPT regulatory flow or BPT discharge rate) reflects the
water use controls which are common practices within the
subcategory. The BPT regulatory flow is based on the average of
all applicable data. Plants with normalized flows above the
average may have to implement some method of flow reduction to
achieve the BPT limitations.
The second requirement to calculate mass limitations is the set
of concentrations that are achievable by application of the BPT
level of treatment technology. Section VII discusses the various
control and technologies which are currently in place for each
wastewater source. In most cases, the current control and
treatment technologies consist of chemical precipitation and
sedimentation (lime and settle technology) and a combination of
reuse and recycle to reduce flow. Ammonia steam stripping is
applied to streams with treatable concentrations of ammonia. Oil
skimming is applied to streams with treatable concentrations of
oil and grease.
Using these regulatory flows and the achievable concentrations,
the next step is to calculate mass loadings for each wastewater
source or subdivision. This calculation was made on a stream-by-
stream basis, primarily because plants in this subcategory may
perform one or more of the operations in various combinations.
The mass loadings (milligrams of pollutant per metric ton of
production - mg/kkg) were calculated by multiplying the BPT
regulatory flow (1/kkg) by the concentration achievable by the
BPT level of treatment technology (mg/1) for each pollutant
parameter to be limited under BPT. These mass loadings are
the BPT effluent limitations.
The mass loadings which are allowed under BPT for each plant will
be the sum of the individual mass loadings for the various
wastewater sources or building blocks which are found at
particular plants. Accordingly, all the wastewater generated
3278
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SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - IX
within a plant may be combined for treatment in a single or
common treatment system, but the effluent limitations for these
combined wastewaters are based on the various wastewater sources
which actually contribute to the combined flow. This method
accounts for the variety of combinations of wastewater sources
and production processes which may be found at secondary tungsten
and cobalt plants.
The Agency usually establishes wastewater limitations in terms of
mass rather than concentrations. This approach prevents the use
of dilution as a treatment method (except for controlling pH).
The production normalized wastewater flow (1/kkg) is a link
between the production operations and the effluent limitations.
The pollutant discharge attributable to each operation can be
calculated from the normalized flow and effluent concentration
achievable by the treatment technology and summed to derive an
appropriate limitation for each plant.
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
In balancing costs in relation to pollutant removal estimates,
EPA considers the volume and nature of existing discharges, the
volume and nature of discharges expected after application of
BPT, the general environmental effects of the pollutants, and the
cost and economic impacts of the required pollution control
level. The Act does not require or permit consideration of water
quality problems attributable to particular point sources or
industries, or water quality improvements in particular water
quality bodies. Accordingly, water quality considerations were
not the basis for selecting the proposed BPT. See Weyerhaeuser
Company v. Costle, 590 F.2d 1011 (D.C. Cir. 1978).
The methodology for calculating pollutant removals and plant
compliance costs is discussed in Section X. Tables X-l (page
3300) and XII-1 (page 3324) show the pollutant removal estimates
for each treatment option for direct and indirect dischargers,
respectively. Compliance costs for this subcategory are
presented in Tables VIII-1 and VIII-2 (page 3276).
BPT OPTION SELECTION
The technology basis for the BPT limitations is Option A,
chemical precipitation and sedimentation technology to remove
metals and solids from combined wastewaters and to control pH,
oil skimming to remove oil and grease, and ammonia steam
stripping to remove ammonia. Chemical precipitation and
sedimentation technology is already in-place at three direct
dischargers in the subcategory. The pollutants specifically
proposed for regulation at BPT are copper, nickel, cobalt,
tungsten, ammonia, oil and grease, TSS, and pH.
Implementation of the BPT limitations will remove annually an
estimated 150,656 kg of toxic metals, and 186,400 kg of ammonia.
Capital cost of achieving BPT is estimated at 442,900, with
annual cost estimated at 460,900.
3279
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - IX
More stringent technology options were not selected for BPT since
they require in-process changes or end-of-pipe technologies less
widely practiced in the subcategory, and, therefore, are more
appropriately considered under BAT.
The BPT treatment scheme is presented in Figure IX-1 (page 3285).
Ammonia steam stripping is demonstrated at six facilities in the
nonferrous metals manufacturing category. These facilities are
treating ammonia bearing wastewaters associated with the
production of primary tungsten, primary columbium and tantalum,
primary molybdenum, secondary tungsten and cobalt, and primary
zirconium and hafnium. EPA believes that performance data from
the iron and steel manufacturing category provide a valid measure
of this technology's performance on nonferrous metals
manufacturing category wastewater because raw wastewater
concentrations of ammonia are of the same order of magnitude in
the respective raw wastewater matrices.
Chemical analysis data were collected of raw wastewater
(treatment influent) and treated wastewater (treatment effluent)
from one coke plant of the iron and steel manufacturing category.
A contractor for EPA, using sampling and chemical analysis
protocols, collected six paired samples in a two-month period.
These data are the data base for determining the effectiveness of
ammonia steam stripping technology and are contained within the
public record supporting this document. Ammonia treatment at
this coke plant consisted of two steam stripping columns in
series with steam injected countercurrently to the flow of the
wastewater. A lime reactor for pH adjustment separated the two
stripping columns.
The Agency has verified the proposed steam stripping performance
values using steam stripping data collected at a primary
zirconium-hafnium plant which has raw ammonia levels as high as
any in the nonferrous metals manufacturing category. Data
collected by the plant represent almost two years of daily
operations, and support the long-term mean used to establish
treatment effectiveness.
In addition, data submitted by a primary columbium-tantalum
plant, which also has significant raw ammonia levels, verify the
promulgated steam stripping performance values.
Oil skimming is demonstrated in the nonferrous metals
manufacturing category. Although no secondary tungsten and
cobalt plants have oil skimming in place, it is necessary to
reduce oil and grease concentrations in the discharge from this
subcategory.
WASTEWATER DISCHARGE RATES
A BPT discharge rate is calculated for each subdivision based on
the average of the flows of the existing plants, as determined
3280
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - IX
from analysis of dcp. The discharge rate is used with the
achievable treatment concentrations to determine BPT effluent
limitations. Since the discharge rate may be different for each
wastewater source, separate production normalized discharge rates
for each of the 11 wastewater sources are discussed below and
summarized in Table TX-1 (page 3285). The discharge rates are
normalized on a production basis by relating the amount of
wastewater generated to the mass of the intermediate product
which is produced by the process associated with the waste stream
in question. These production normalizing parameters, or PNPs,
are also listed in Table IX-1.
Section V of this document further describes the discharge flow
rates and presents the water use and discharge flow rates for
each plant by subdivision in Tables V-l through V-ll.
TUNGSTEN DETERGENT WASH AND RINSE
The proposed and promulgated BPT wastewater discharge rate for
tungsten detergent wash and rinse is 195 liters/kkg of tungsten
scrap washed. This rate is allocated only for those plants which
wash and rinse oily tungsten scrap before leaching it with acid.
Water use and wastewater discharge rates are presented in Table
V-l. The BPT flow is based on the only water use rate reported.
TUNGSTEN LEACHING ACID
The proposed and promulgated BPT wastewater discharge rate for
tungsten leaching acid is 2,571 liters/kkg to tungsten produced.
This rate is allocated only for those plants which leach
impurities away from tungsten scrap. Water use and wastewater
discharge rates are presented in Table V-2 (page 3217). The BPT
flow is based on the only water use rate reported.
TUNGSTEN POST-LEACHING WASH AND RINSE
The BPT wastewater discharge rate for tungsten post-leaching wash
and rinse is 5,143 liters/kkg of tungsten produced This rate is
allocated only for those plants which wash and rinse tungsten
powder after purifying it with a leaching operation. Water use
and wastewater discharge rates are presented in Table V-3 (page
3217). The BPT flow is based on the only water use rate
reported.
SYNTHETIC SCHEELITE FILTRATE
The BPT wastewater discharge rate proposed and promulgated for
synthetic scheelite filtrate is 16,661 liters/kkg of synthetic
scheelite produced. This rate is allocated only for those plants
which manufacture synthetic scheelite from tungsten or tungsten
carbide scrap. Water use and wastewater discharge rates are
presented in Table V-4 (page 3218). The BPT flow is based on the
only wdter use rate reported.
3281
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SECONDARY TUNGSTEN AND COBALT SDBCATEGORY SECT - IX
TUNGSTEN CARBIDE LEACHING WET AIR POLLQTION CONTROL
The BPT wastewater discharge rate proposed and promulgated for
tungsten leaching wet air pollution control is 1,751 liters/kkg
of tungsten carbide scrap leached. This rate is allocated only
for those plants which control acid fumes from a tungsten carbide
scrap leaching operation with a wet scrubber. Water use and
wastewater discharge rates are presented in Table V-5 (page
3218). The BPT flow is based on the reported water use rate
which includes extensive recycle of the scrubber liquor,
TUNGSTEN CARBIDE WASH WATER
The BPT wastewater discharge rate for tungsten carbide wash water
is 8,333 liters/kkg of tungsten carbide produced. This rate is
allocated only for those plants which produce tungsten carbide by
leaching tungsten carbide scrap, and then wash the product with
water. Water use and wastewater discharge rates are presented in
Table V-6 (page 3218). The BPT flow is based on the reported
water use rate.
COBALT SLUDGE LEACHING WET AIR POLLUTION CONTROL
The BPT wastewater discharge rate proposed and promulgated for
cobalt sludge leaching wet air pollution control " is 35,781
liters/kkg of cobalt produced from sludge. This rate is
allocated only for those plants which leach cobalt sludge as a
preliminary step in the recovery of cobalt, and control acid
fumes with a wet scrubber. Water use and wastewater discharge
rates are presented in Table V-7 (page 3219). The BPT flow of
35,781 liters/kkg is based on the reported water use rate and
includes extensive recycle of the scrubber liquor.
CRYSTALLIZATION DECANT
The BPT wastewater discharge rate proposed and promulgated for
crystallization decant is 41,650 liters/kkg of cobalt produced.
This rate is allocated only for those plants which use an
ammonium-cobalt crystallization process to recover cobalt from
secondary sources such as cobalt sludges and tungsten carbide
scrap. Water use and wastewater discharge rates are presented in
Table V-8 (page 3219).
ACID WASH DECANT
The BPT wastewater discharge rate proposed and promulgated for
acid wash decant is 19,062 liters/kkg to cobalt produced. This
rate is allocated only for those plants which wash cobalt
crystals with acid to recover cobalt from secondary sources such
as sludges and tungsten carbide scrap. Water use and wastewater
discharge rates are presented in Table V-9 (page 3219). The BPT
flow is based on the reported water use rate.
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - IX
COBALT HYDROXIDE FILTRATE
The BPT wastewater discharge rate proposed and promulgated for
cobalt hydroxide filtrate is 56,647 liters/kkg to cobalt'
produced. This rate is allocated only for those plants which
recover cobalt as cobalt hydroxide from secondary sources such as
sludges and tungsten carbide scrap. Water use and wastewater
discharge rates are presented in Table V-10 (page 3220). The BPT
flow is based on the reported water use rate.
COBALT HYDROXIDE FILTER CAKE WASH
The BPT wastewater discharge rate proposed and promulgated for
cobalt hydroxide filter cake wash is 109,035 liters/kkg of cobalt
produced. This rate is allocated only for those plants which
recover cobalt hydroxide from secondary sources such as sludges
and tungsten carbide scrap and wash the cobalt hydroxide filter
cake with water. Water use and wastewater discharge rates are
presented in Table V-ll (page 3220). The BPT flow is based on
the reported water use rate.
REGULATED POLLUTANT PARAMETERS
The raw wastewater concentrations from individual operations and
the subcategory as a whole were examined to select certain
pollutant parameters for limitation. This examination and
evaluation was presented in Section VI. A total of eight
pollutants or pollutant parameters are selected for limitation
under BPT and are listed below:
120. copper
124. nickel
ammonia
cobalt
tungsten
oil and grease
TSS
PH
EFFLUENT LIMITATIONS
The treatable concentrations achievable by application of the
promulgated BPT are discussed in Section VII of Vol. I and
summarized there in Table VII-21 (page 248), with one exception.
The exception is the cobalt treatment effectiveness value. EPA
promulgated the cobalt treatment effectiveness value based upon
data from the porcelain enameling category. Petitioners
indicated that the wastewater streams from the tungsten-cobalt
subcategory cannot be treated to the same level as in the
porcelain enameling category because they contain higher
concentrations of complexed cobalt than were found in the
porcelain-enameling category. In response to these concerns, the
Agency reviewed and analyzed new data supplied by the petitioner
on cobalt treatment effectiveness at levels found in the effluent
-------
SECONDARY TUNGSTEN AND COBALT SDBCATKGORY SECT - IX
from the tungsten-cobalt subcategory. EPA is revising the long
term mean treatment effectiveness value from 0.03 mg/1 to 0.667
mg/1. This corresponds to a one day maximum of 2.76 mg/1 and a
monthly average of 1.21 mg/1.
These treatable concentrations (both one day maximum and monthly
average values) are multiplied by the BPT normalized discharge
flows summarized in Table IX-1 (page 3285) to calculate the mass
of pollutants allowed to be discharged per mass of product. The
results of these calculations in milligrams of pollutant per
kilogram of product represent the BPT effluent limitations and
are presented in Table IX-2 (page 3286) for each individual waste
stream.
3284
-------
Table IX-1
BPT WASTEWATEK DISCHARGE RATES FOK THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
OJ
Wastewater Stream
Tungsten detergent wash
and rinse
Tungsten leaching acid
Tungsten post-leaching wash
Synthetic scheelite filtrate
Tungsten carbide leaching wet
air pollution control
Tungsten carbide wash water
Cobalt sludge leaching wet
air pollution control
Crystallization decant
Acid wash decant
Cobalt hydroxide filtrate
Cobalt hydroxide filter cake
wash
BPT Normalized
Discharge Rate
(1/kkR)
195
2,571
5,143
16,661
1 ,751
8,333
35,781
41 ,650
19,062
56,647
109,035
(gal/ton)
47
618
1,235
4,002
421
2,002
8,595
10,004
4,579
13,607
26,190
Production Normalizing
Parameter
tungsten scrap washed
tungsten produced
tungsten produced
synthetic scheelite produced
tungsten carbide scrap leached
tungsten carbide produced
cobalt produced from cobalt sludge
cobalt produced
cobalt produced
cobalt produced
cobalt produced
en
w
n
o
C
53
§
o
n
8
w
G
W
o
I
w
n
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SECONDARY TUNGSTEN AND COBALT SDBCATEGORY SECT - IX
TABLE IX-2
BPT MASS LIMITATIONS FOR THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(a) Tungsten Detergent: Wash and Rinse BPT
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten scrap washed
Arsenic ' 0.408 0.181
Cadmium 0.066 0.029
Chromium 0.086 0.035
*Copper 0.371 0.195
Lead 0.082 0.039
*Nickel 0.374 0.248
Silver 0.080 0.033
Zinc 0.285 0.119
*Ammonia 25.990 11.430
*Cobalt 0.768 0.337
*Tungsten 1.357 0.542
*Oil and Grease 3.900 2.340
*TSS . 7.995 3.803
pH Within the range of 7.5 to 10.0 at all times
Tungsten Leaching Acid BPT
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg {Ib/million Ibs) of tungsten produced
Arsenic 5.373 2.391
Cadmium 0.874 0.386
Chromium 1.131 0.463
*Copper 4.885 2.571
Lead 1.080 0.514
*Nickel 4.936 3.265
Silver 1.054 0.437
Zinc 3.754 1.568
*Ammonia 342.700 150.700
*Cobalt 10.130 4.448
*Tungsten 17.890 7.147
*Oil and Grease 51.420 30.850
*TSS 105.400 50.130
*pH Within the range of 7.5 to 10.0 at all times
*Regulated Pollutant
3286
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - IX
TABLE IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(c) Tungsten Post-Leaching Wash BPT
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten produced
Arsenic 10.750 4.783
Cadmium 1.749 0.771
Chromium 2.263 0.926
*Copper 9.772 ' 5.143
Lead 2.160 1.029
*Nickel 9.875 6.532
Silver 2.109 0,874
Zinc 7.509 3.137
*Ammonia 685.600 301.400
*Cobalt 20.263 8.847
*Tungsten 35.800 14,300
*0il and Grease 102.900 61.720
*TSS 210.900 100.300
*pH Within the range of 7.5 to 10.0 at all times
(d) Synthetic Scheelite Filtrate BPT
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of synthetic scheelite produced
Arsenic 34.820 15.490
Cadmium 5.665 2.499
Chromium 7.331 2.999
*Copper 31.660 16.660
Lead 6.998 3.332
*Nickel 31.990 21.160
Silver 6.831 2.832
Zinc 24.330 10.160
*Ammonia 2,221.000 976.300
*Cobalt 65.644 28.824
*Tungsten 116.000 46.320
*Oil and Grease 333.200 199.900
*TSS 683.100 324.900
*pH Within the range of 7.5 to 10.0 at all times
*Regulated Pollutant
3287
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - IX
TABLE IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(e) Tungsten Carbide Leaching Wet Air Pollution Control BPT
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten carbide scrap leached
Arsenic 3.660 1.628
Cadmium 0.595 0.263
Chromium 0.770 0.315
*Copper 3.327 1.751
Lead 0.735 0.350
*Nickel 3.362 2.224
Silver 0.718 0.298
Zinc 2.556 1.068
*Amraonia 233.400 102.600
*Cobalt 6.899 3.029
*Tungsten 12.190 4.868
*Oil and Grease 35.020 21.010
*TSS . 71.790 34.140
*pH Within the range of 7.5 to 10.0 at all times
(f) Tungsten Carbide Wash Water BPT
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
nig/kg (Ib/million Ibs) of tungsten carbide produced
Arsenic 17.420 7.750
Cadmium 2.833 1.250
Chromium 3.667 1.500
*Copper 15.830 8.333
Lead 3.500 1.667
*Nickel 16.000 10.580
Silver 3.417 1.417
Zinc 12.170 5.083
*Ammonia If111.000 488.300
*Cobalt 32.832 14.416
*Tungsten 58.000 23.170
*0il and Grease 166.700 100.000
*TSS 341.700 162.500
*pH Within the range of 7.5 to 10.0 at all times
*Regulated Pollutant
3288
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - IX
TABLE IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(g) Cobalt Sludgta Leaching Wet Air Pollution Control BPT
Pollutantor'MaximumforMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of cobalt produced from cobalt sludge
Arsenic 74.780 33.280
Cadmium 12.170 5.367
Chromium 15.740 6.441
*Copper 67.980 35.780
Lead 15.030 7.156
*Nickel 68.700 45.440
Silver 14.670 6.083
Zinc 52.240 21.830
*Ammonia 4,770.000 2,097.000
*Cobalt 140.977 61.901
*Tungsten 249.000 99.470
*Oil and Grease 715.600 429.400
*TSS 1,467.000 697,700
*pH Within the range of 7.5 to 10.0 at all times
(h) Crystall izat ion Decant BPT
PollutantorMaximum forMaximum for
pollutant property any one day monthly average
mg/kg {Ib/million Ibs) of cobalt produced
Arsenic 87.050 38.730
Cadmium 14.160 6.248
Chromium 18.330 7.497
*Copper 79.140 41.650
Lead 17.490 8.330
*Nickel 79.970 52.900
Silver 17.080 7.081
Zinc 60.810 25,410
*Ammonia 5,552.000 2,441.000
*Cobalt 164.101 72.055
*Tungsten 289.900 115.800
*Oil and Grease 833.000 499.800
*TSS 1,708.000 812.200
*pH Within the range of 7.5 to 10.0 at all times
*Regulated Pollutant ~~~~
3289
-------
SECONDARY TONGSTEN AND COBALT S0BCATEGORY
SECT
IX
TABLE IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(i) Acid Wash Decant BPT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of cobalt produced
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
*0il and Grease
*TSS
*pH Within the range
39.840
6.481
8.387
36.220
8.006
36.600
7.815
27.830
2,541.000
75.104
132.700
381.200
781.500
of 7.5 to 10.0
17.730
2.859
3.431
19.060
3.812
24.210
3.241
11.630
1,117.000
32.977
52.990
228.700
371.700
at all times
(j) Cobalt Hydroxide Filtrate BPT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of cobalt produced
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
*0il and Grease
*TSS
*pH Within the
118.400
19.260
24.920
107.600
23.790
108.800
23.230
82.700
7,551.000
223.189
394.300
1,133.000
2,323.000
range of 7.5 to 10.0
52.680
8.497
10.200
56,650
11.330
71.940
9.630
34.550
3,320.000
97.999
157.500
679.800
1,105.000
at all times
*Regulated Pollutant
3290
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
SECT - IX
TABLE IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(k) Cobalt Hydroxide Filter Cake Wash BPT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg {Ib/million Ibs) of cobalt produced
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
*Oil and Grease
*TSS
*pH Within the
227.900
37.070
47.980 .
207.200
45.790
209.300
44.700
159.200
14,530.000
429.598
758.900
2,181.000
4,470.000
range of 7.5 to 10
101.400
16.360
19.630
109.000
21.810
138.500
18.540
66.510
6,389.000
188.631
303.100
1,308.000
2,126.000
,0 at all times
3291
-------
o,. ,
/ /
Tungaten Detergent U«»h and Rlnf* fc
P
W „,,
SUa-lnt
Removal of
Oil and Greaae
Tungsten Leaching Acid «^
Tunesten Patt-LeachlnK Uaih ^_
Tungsten Carbide Leaching wet air pollution control^
Tungsten Carbide Wash Water ^
Cobalt Sludge Leaching vet air pollution control ^
U)
NJ
VO
W
To AtMonia Recovery
Crystallization Decant ^ 1
j^^~~*^.
ArM Hfl?h Dersnt ^ pT^
Cobalt Hydroxide rtltraie h
m
nonia
Stea*
Cobalt Hydroxide Filter Cake Uaah ___ Stripping
DOOCXXf* Steaa
~_-^
*
w
w
o
o
as
Q
ChcMlcal Addltlcm CO
uZ, ull, u_^ !
1 — 1 — — Ulsi-liiiriu' *-*
' Equalization ^ Chemical ^sedimentation •** Q
/ Precipitation Q
Sludgf *^
CO
G
f ^ _C I
Vacuum Filtrate l_a>. ^ f l—( ) «,...,... ,.. Wl
\ ^^-^ / Disposal W
Sludge f S
Deurtterlng
m
o
Figure IX-1
BPT TREATMENT SCHKME FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
-------
SECONDARAY TUNGSTEN AND COBALT SUBCATEGORY SECT - X
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
These effluent limitations are based on the best control and
treatment technology used by a specific point source within the
industrial category or subcategory, or by another category from
which it is transferable. Emphasis is placed on additional
treatment techniques applied at the end of the treatment systems
currently used, as well as reduction of the amount of water used
and discharged, process control, and treatment technology
optimization.
TECHNICAL APPROACH TO BAT
The Agency reviewed a wide range of technology options and
evaluated the available possibilities to ensure that the most
effective and beneficial technologies were used as the basis of
BAT. To accomplish this, the Agency elected to examine two
technology options whicn could be applied to the secondary
tungsten and cobalt subcategory as alternatives for the basis of
BAT effluent limitations.
For the development of BAT effluent limitations, mass loadings
were calculated for each wastewater source or subdivision in the
subcategory using the same technical approach as described in
Section IX for BPT limitations development. The differences in
the mass loadings for BPT and BAT are due to increased treatment
effectiveness achievable with the more sophisticated BAT
treatment technology and reductions in the effluent flows
allocated to various waste streams.
The treatment technologies considered for BAT are summarized
below:
Option A (Figure X-l, page 3300) is based on:
o Preliminary treatment with oil skimming (where required)
o Preliminary treatment with ammonia steam stripping
(where required)
o Chemical precipitation and sedimentation
Option C (Figure X-2, page 3301) is based on:
o Preliminary treatment with oil skimming (where required)
o Preliminary treatment with ammonia steam stripping
(where required)
o Chemical precipitation and sedimentation
o Multimedia filtration
The two options examined for BAT are discussed in greater detail
on the following pages. The first option considered (Option A)
3293
-------
SECONDARAY TUNGSTEN AND COBALT SUBCATEGORY SECT - X
is the same as the BPT treatment and control technology which was
presented in the previous section. The other option represents
substantial progress toward the reduction of pollutant discharges
above and beyond the progress achievable by BPT.
OPTION A
Option A for the secondary tungsten and cobalt subcategory is
equivalent to the control and treatment technologies which were
analyzed for BPT in Section IX (see Figure X-l, page 3300). The
BPT end-of-pipe treatment scheme includes chemical precipitation
and sedimentation, with ammonia steam stripping and oil skimming
preliminary treatment of wastewaters containing treatable
concentrations of ammonia and oil and grease (see Figure IX-1,
page 3285). The discharge rates for Option A are equal to the
discharge rates allocated to each stream as a BPT discharge flow.
OPTION C
Option C for the secondary tungsten and cobalt subcategory
consists of all control and treatment requirements of Option A
(ammonia steam stripping, oil skimming, chemical precipitation
and sedimentation) plus multimedia filtration technology added at
the end of the Option A treatment scheme (see Figure X-2, page
3301). Multimedia filtration is used to remove suspended solids,
including precipitates of toxic metals, beyond the concentrations
attainable by gravity sedimentation. The filter suggested is of
the gravity, mixed media type, although other forms of filters,
such as rapid sand filters or pressure filters, would perform
satisfactorily.
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
As one means of evaluating each technology option, EPA developed
estimates of the pollutant removals and the compliance costs
associated with each option. The methodologies are described
below.
POLLUTANT REMOVAL ESTIMATES
A complete description of the methodology used to calculate the
estimated pollutant removal, or benefit, achieved by the
application of the various treatment options is presented in
Section X of the General Development Document. The pollutant
removal estimates have been revised from proposal based on
comments and on new data; however, the methodology for
calculating pollutant removals has not changed. The data used
for estimating removals are the same as those used to revise the
compliance costs.
Sampling data collected during the field sampling program were
used to characterize the major waste streams considered for
regulation. At each sampled facility, the sampling data were
production normalized for each unit operation (i.e., mass of
3294
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SECONDARAY TUNGSTEN AND COBALT SUBCATEGORY SECT - X
pollutant generated per mass of product manufactured). This
value, referred to as the raw waste, was used to estimate the
mass of toxic pollutants generated within the secondary tungsten
and cobalt subcategory. The pollutant removal estimates were
calculated for each plant by first estimating the total mass of
each pollutant in the untreated wastewater. This was calculated
by first multiplying the raw waste values by the corresponding
production value for that stream and then summing these values
for each pollutant for every stream generated by the plant.
Next, the volume of wastewater discharged after the application
of each treatment option was estimated for each operation at each
plant by comparing the actual discharge to the regulatory flow.
The smaller of the two values was selected and summed with the
other plant flows. The mass of pollutant discharged was then
estimated by multiplying the achievable concentration values
attainable with the option (mg/1) by the estimated volume of
process wastewater discharged by the subcategory. The mass of
pollutant removed is the difference between the estimated mass of
pollutant generated within the subcategory and the mass of
pollutant discharged after application of the treatment option.
The pollutant removal estimates for direct dischargers in the
secondary tungsten and cobalt subcategory are presented in Table
X-l (page 3300).
COMPLIANCE COSTS
In estimating subcategory-wide compliance costs, the first step
was to develop a cost estimation model, relating the total costs
associated with installation and operation of wastewater
treatment technologies to plant process wastewater discharge.
EPA applied the model to each plant. The plant's investment and
operating costs are determined by what treatment it has in place
and by its individual process wastewater discharge flow. As
discussed above, this flow is either the actual or the BAT
regulatory flow, whichever is lesser. The final step was to
annualize the capital costs, and to sum the annualized capital
costs, and the operating and maintenance costs for each plant,
yielding the cost of compliance for the subcategory. These costs
were used in assessing economic achievability.
Table X-2 (page 3301) shows a comparison of the costs developed
for proposal and the revised costs for promulgation for direct
dischargers in the secondary tungsten and cobalt subcategory. A
similar comparison of compliance costs for indirect dischargers
is presented in Table XII-2 (page 3325).
BAT OPTION SELECTION - PROPOSAL
Our proposed BAT limitations for this subcategory were based on
Option C, (BPT technology - chemical precipitation and
sedimentation, oil skimming and ammonia steam stripping, plus in-
process wastewater reduction, and filtration). Flow reductions
were based on 90 percent recycle of scrubber effluent, which is
the rate reported by the only existing plant with a scrubber.
3295
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SECONDARAY TUNGSTEN AND COBALT SUBCATEGORY SECT - X
Implementation of the proposed BAT limitations would remove
annually an estimated 150,700 kg of priority pollutants which is
44 kg greater than proposed BPT. Capital costs for achieving
proposed BAT were estimated at $135,150 with annual costs of
?442,500.
BAT OPTION SELECTION - PROMULGATION
EPA selected Option C as the basis for promulgating BAT
limitations. BAT is based on chemical precipitation,
sedimentation and filtration end-of-pipe treatment, along with
preliminary treatment consisting of oil-water separation and
ammonia steam stripping. This is different from the proposed
BAT, since flow reduction is no longer included as part of the
treatment train. Following proposal, EPA learned that the two air
pollution streams targeted for flow reduction already were
operated with greater than 90 percent recycle.
The pollutants specifically limited under BAT are cobalt, copper,
nickel, and ammonia. The priority pollutants arsenic, cadmium,
chromium, lead, silver, and zinc were also considered for
regulation because they were found at treatable concentrations in
the raw wastewaters from this subcategory. These pollutants were
not selected for specific regulation because they will be
effectively controlled when the regulated priority metals are
treated to the levels achievable by the model BAT technology.
Implementation of the promulgated BAT limitations will remove
annually an estimated 150,700 kg of toxic pollutants, which is 44
kg greater than promulgated BPT. Capital costs for achieving
promulgated BAT are estimated at $60,900, with annual costs of
$182,700.
AMENDMENT TO THE REGULATION
In response to a petition for review of this regulation and new
data supplied by the petitioner, EPA agreed to a settlement
agreement to propose to amend this regulation and to take final
action on the proposal. EPA agreed to propose to revise the long
term average cobalt treatment effectiveness value from 0.03 mg/1
to 0.667 mg/1. The 0.03 mg/1 value used at promulgation was
based on data from the porcelain enameling category. The new
long term average is based on data from treatment of cobalt
wastewaters and takes into account the higher concentrations of
complexed cobalt found in the secondary tungsten • and cobalt
subcategory. The new long term average treatment effectiveness
value results in a one day maximum value of 2.76 mg/1 and a
monthly average value of 1.21 mg/1. These new values have been
used in calculating the limitations for this supplement.
WASTEWATER DISCHARGE RATES
A BAT discharge rate was calculated for each subdivision based
upon the flows of the existing plants, as determined from
3296
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SECONDARAY TUNGSTEN AND COBALT SUBCATEGORY SECT - X
analysis to the data collection portfolios. The discharge rate
is used with the achievable treatment concentrations to determine
BAT effluent limitations. Since the discharge rate may be
different for each wastewater source, separate production
normalized discharge rates for each of the 11 wastewater sources
were determined and are summarized in Table X-3 (page 3302). The
discharge rates are normalized on a production basis by relating
the amount of wastewater generated to the mass of the
intermediate product which is produced by the process associated
with the waste stream in question. These production normalizing
parameters, or PNPs, are also listed in Table X-3.
The BAT discharge rates are equivalent to the BPT discharge
rates. Further flow reduction, beyond BPT rates, is not
considered achievable in this subcategory.
At proposal subdivisions 5 and 7 were targeted for additional
flow reduction beyond that considered for BPT. However, through
industry comments on the proposed rulemaking, EPA learned that
the one plant operating these two processes currently practices
extensive (>90 percent) recycle. Therefore, the BPT flow rates
promulgated for subdivisions 5 and 7 include recycle, and it is
no longer necessary to include additional flow reduction for
these two subdivisions at BAT.
REGULATED POLLUTANT PARAMETERS
In implementing the terms of the Consent Agreement in NRDC v.
Train, Op. Cit., and 33 U.S.C. 1314(b)(2)(A and B) (1976), the
Agency placed particular emphasis on the priority pollutants. The
raw wastewater concentrations from individual operations and the
subcategory as a whole were examined to select certain pollutants
and pollutant parameters for limitation. This examination and
evaluation was presented in Section VI. The Agency, however, has
chosen not to regulate all eight priority pollutants selected in
this analysis.
The high cost associated with analysis for priority metal
pollutants has prompted EPA to develop an alternative method for
regulating and monitoring priority pollutant discharges from the
nonferrous metals manufacturing category. Rather than developing
specific effluent mass limitations and standards for each of the
priority metals found in treatable concentrations in the raw
wastewater from a given subcategory, the Agency is proposing
effluent mass limitations only for those pollutants generated in
the greatest quantities as shown by the pollutant removal
estimates. The pollutants selected for specific limitation are
listed below:
120. copper
124. nickel
ammonia (as N)
cobalt
tungsten
3297
-------
SECONDARAY TUNGSTEN AND COBALT SUBCATEGORY SECT - X
By establishing limitations and standards for certain priority
metal pollutants, discharges will attain the same degree of
control over priority metal pollutants as they would have been
required to achieve had all the priority metal pollutants been
directly limited.
This approach is technically justified since the treatment
effectiveness concentrations used for chemical precipitation and
sedimentation technology are based on optimized treatment for
concomitant multiple metals removal. Thus, even though metals
have somewhat different theoretical solubilities, they will be
removed at very nearly the same race in a chemical precipitation
and sedimentation treatment system operated for multiple metals
removal. Filtration as part of the technology basis is likewise
justified because this technology removes metals non-
preferential ly.
The priority metal pollutants selected for specific limitation in
the secondary tungsten and cobalt subcategory to control the
discharges of toxic metal pollutants are copper and nickel.
Ammonia is also selected for limitation since the methods used to
control copper and nickel are not effective in the control of
ammonia. Cobalt and tungsten are also selected for limitation, as
was shown in Section VI. The following priority metal pollutants
are excluded from limitation on the basis that they are
effectively controlled by the limitations developed for copper
and nickel:
3298
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SECONDARAY TUNGSTEN AND COBALT SUBCATEGORY SECT - X
115. arsenic
118. cadmium
119. chromium (total)
122. lead
126. silver
128. zinc
EFFLUENT LIMITATIONS
The concentrations achievable by application of BAT are discussed
in Section VII of Vol. I and summarized there in Table VII-21
(page 248), with the exception of the cobalt treatment
effectiveness value. See Section IX for a discussion of the
cobalt treatment effectiveness value. The treatable
concentrations both one day maximum and monthly average values
are multiplied by the BAT normalized discharge flows summarized
in Table X-3 (page 3302) to calculate the mass of pollutants
allowed to be discharged per mass of product. The results of
these calculations in milligrams of pollutant per kilogram of
product represent the BAT effluent limitations and are
represented in Table X-4 (page 3303) for each waste stream.
3299
-------
Table X-l
POLLUTANT REMOVAL ESTIMATES FOR DIRECT DISCHARGERS IN THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
Pollutant
Antimony
Arsenic
Cadmium
Chromium (total)
Copper
Cyanide (total)
Lead
Hercury
Nickel
Selenium
Silver
Thallium
u> Zinc
U)
° TOTAL PRIORITY
0 POLLUTANTS
Ammonia
Cobalt
TOTAL NONCOHVENTIONALS
TSS
Oil and Crease
TOTAL CON VENT IONALS
TOTAL POLLUTANTS
Total
Raw Waste
(kR/yr)
61.07
10.57
36.70
48.67
82,961.17
2.27
26,287.16
0.06
25,470.35
3.76
137.75
5.28
15,717. 94
150,742.75
187,060
9,457.09
196,517
109,061.98
1,045.28
110,107.26
457,367
Option A
Discharge
(kR/yr)
16.97
9.85
2.06
2.12
13.90
1.74
3.51
0.04
19.00
2.58
2.92
3.59
8.59
86.86
672
1.46
673
350.53
626.11
976.64
1,737
Option A
Removed
(kg/yr)
44.10
0.72
34.64
46.54
82,947.27
0.54
26,283.65
0.02
25,451.35
1.18
134.83
1.69
15,709.35
150,655.89
186,388
9.455.64
195,844
108,711.45
419.17
109,130.62
455,630
Option C
Discharge
(kR/yr)
7.26
5.78
0.91
1.15
5.86
1.54
1.60
0.04
4.40
2.12
1.40
2.95
4.13
39.14
672
0.68
673
52.00
510.28
562.27
1,274
Option C
Removed
(kR/yr)
53.81
4.80
35.79
47.51
82,955.31
0.73
26,285.56
0.02
25,465.95
1.64
136.35
2.34
15,713.81
150,703.61
186,388
9,456.41
195,844
109,009.98
535.00
109,544.98
456,093
Option A - Oil skimming, ammonia steam stripping, chemical precipitation and sedimentation
Option B - Oil skimming, ammonia steam stripping, chemical precipitation, and sedimentation
Option C - Oil skimming, ammonia steam stripping, chemical precipitation, sedimentation, and filtration
W
W
O
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W
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o
§
W
w
-------
SECONDARAY TUNGSTEN AND COBALT SUBCATEGORY
SECT - X
TABLE X-2
COST OP COMPLIANCE FOR THE
SECONDARY TUNGSTEN AND COBALT SDBCATEGORY
Direct Dischargers
Option
A
B
C
Total Required
Capital Cost
(1982 Dollars)
42,900
NA
60,900
Total
Annual Cost
(1982 Dollars)
173,000
NA
182,700
NA - Not applicable, i.e., Option B eliminated for final
regulation.
-------
Table X-3
BAT WASTEWATER DISCHARGE RATES FOR THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
BAT Normalized
Discharge Rate
Production Normalizing
cutt
Wastewater Stream
Tungsten detergent wash and rinse
Tungsten leaching acid
Tungsten post-leaching wash
Synthetic scheelite filtrate
Tungsten carbide leaching wet
air pollution control
Tungsten carbide wash water
U/kkgJ
195
2,
5,
16,
1,
8,
571
143
661
751
333
(gal/ ton)
47
618
1,235
4,002
42
2,002
Parameter
tungsten
tungsten
tungsten
scrap washed
produced
produced
synthetic scheelite
produced
tungsten carbide scrap
leached
tungsten
carbide
Cobalt sludge leaching wet air 35,781
pollution control
Crystallization decant 41,650
Acid wash decant 19,062
Cobalt hydroxide filtrate 56,647
Cobalt hydroxide filter cake 109,035
wash
produced
860 cobalt produced from
cobalt sludge
10,004 cobalt produced
4,579 cobalt produced
13,607 cobalt produced
26,190 cpfcalt produced
to
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t-3
-------
SECONDARAY TUNGSTEN AND COBALT SUBCATEGORY SECT - X
TABLE X-4
BAT MASS LIMITATIONS FOR THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(a) Tungsten Detergent Wash and Rinse BAT
Pollutant orMaximum for"Maximum for
pollutant property any one day monthly average
nig/kg (Ib/million Ibs) of tungsten scrap washed
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel .
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
0.271
0.039
0.072
0.250
0.055
0.107
0.057
0.199
25.990
0.538
0.679
0.121
0.016
0.029
0.119
0.025
0.072
0.023
0.082
11.430
0.236
0.302
(b) Tungsten Leaching Acid BAT
Pollutant or Maximum for Maximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten produced
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
3.574
0.514
0.951
3.291
0.720
1.414
0.746
2.622
342.700
7.096
8.947
1.594
0.206
0.386
1.568
0.334
0.951
0.309
1.080
150.700
3.111
3.985
*Regulated Pollutant
3303
-------
SECONDARAY TUNGSTEN AND COBALT SUBCATEGORY SECT - X
TABLE X-4 (Continued)
BAT MASS LIMITATIONS FOR THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(c) Tungsten Post-Leaching Wash BAT
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten produced
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
7.149
1.029
1.903
6.583
1.440
2.829
1.491
5.246
685.600
14.194
17.900
3 . 189
0.411
0.771
3.137
0.669
1.903
0.617
2.160
301.400
6.223
7.972
(d) Synthetic Scheelite Filtrate BAT
Pollutant or Maximum for Maximum for
pollutant property any one day monthly average
rug/kg (Ib/million Ibs) of synthetic scheelite produced
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
* Ammonia
*Cobalt
*Tungsten
23.160
3.332
6.165
21.330
4.665
9.164
4.832
16.990
2,221.000
45. -984
57.980
10.330
1.333
2.499
10.160
2.166
6.165
1.999
6.998
976.300
20.160
25.820
*Regulated Pollutant
-------
SECONDARAY TUNGSTEN AND COBALT SUBCATEGORY SECT - X
TABLE X-4 (Continued)
BAT MASS LIMITATIONS FOR THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(e) Tungsten Carbide Leaching Wet Air Pollution Control BAT
Pollutant orMaximumforMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten carbide scrap leached
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
* Ammonia
*Cobalt
*Tungsten
2.434
0.350
0.648
2.241
0.490
0.963
0.508
1.786
233.400
4.833
6.093
1.086
0.140
0.263
1..068
0.228
0.648
0.210
0.735
102.600
2.119
2.714
(f) Tungsten Carbide Wash Water BAT
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten carbide produced
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
* Ammonia
*Cobalt
*Tungsten
11.580
1.667
3.083
10.670
2.333
4.583
2.417
8.500
1,111.000
22.999
29.000
5.166
0.667
1.250
5.083
1.083
3.083
1.000
3.500
488.300
10.083
12.920
*Regulated Pollutant
3305
-------
SECONDARAY TUNGSTEN AND COBALT SUBCATEGORY
SECT - X
TABLE X-4 (Continued)
BAT MASS LIMITATIONS FOR THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(g) Cobalt Sludge Leaching Wet Air Pollution Control BAT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of cobalt produced from cobalt sludge
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
49.740
7.156
13.240
45.800
10.020
19.680
10.380
36.500
4,770.000
98.756
124.500
22.180
2.862
5.367
21.830
4.652
13.240
4.294
15.030
2,097.000
43.295
55.460
(h) Crystallization Decant BAT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of cobalt produced
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
57.890
8.330
15.410
53.310
11.660
22.910
12.080
42.480
5,552.000
114.954
144.900
25.820
3.332
6.248
25.410
5.415
15.410
4.998
17.490
2,441.000
50.397
64.560
*Regulated Pollutant
3306
-------
SECONDARAY TUNGSTEN AND COBALT SUBCATEGORY SECT - X
TABLE X-4 (Continued)
BAT MASS LIMITATIONS FOR THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(i) Acid Wash Decant BAT
Pollutant orMaximum forMaximum for~
pollutant property any one day monthly average
rog/kg {lb/million Ibs) of cobalt produced
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
* Cobalt
*Tungsten
26.500
3.812
7.053
24.400
5.337
10.480
5.528
19.440
2,541.000
52.611
66.340
11.820
1.525
2.859
11.630
2 478
7.053
2.287
8.006
1,117.000
23.065
29.550
(j) Cobalt Hydroxide Filtrate BAT
Pollutant or Maximum for Maximum for
pollutant property any one day monthly average
mg/kg {lb/million Ibs) of cobalt produced
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
78.740
11.330
20.960
72.510
15.860
31.160
16.430
57.780
7,551.000
156.346
197.100
35.120
4.532
8.497
34.550
7.364
20.960
6.798
23.790
3,320.000
68.543
87.800
*Regulated Pollutant
3307
-------
SECONDARAY TUNGSTEN AND COBALT SUBCATEGORY SECT - X
TABLE X-4 (Continued)
BAT MASS LIMITATIONS FOE THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(k) Cobalt Hydroxide Filter Cake Wash
PollutantorMaximum forMaximumfor
pollutant property any one day monthly average
mg/kg (Ib/mlllion Ibs) of cobalt produced
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
* Ammonia
*Cobalt
*Tungsten
151.600
21.810
40.340
139.600
30.530
59.970
31.620
111.200
14,530.000
300.094
379.400
67.600
8.723
16.360
66 510
14.170
40.340
13.080
45.790
6,389.000
131.932
169.000
*Regulated Pollutant
3308
-------
Q, ..... ,P
I / l^y
• i ... » - ou w
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Removal of
Oil and Crease
Tungsten Leaching Acid ^_
Tunusten Post-Le.ichinK Wash «_
Sy^fhpT^C Srhfi*! 4f*» filtrate fr,
Tungsten Carbide Leaching wet air pollution control^ ""
Tungsten Carbide Wash Water ^_
Cobalt Sludge Leaching wet air pollution control ^
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O
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Crystallization Decant ^_ 1
x^*^*^
Acid Hash Decant j^, p^VytX™
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BAT TREATMENT SCHIiMK i?'OR OPTION A
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f ttogatCB ro«t-L«achlB| W«h ^
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-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XI
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
This section describes the technologies for treatment .of
wastewater from new sources and presents mass discharge standards
for regulated pollutants for NSPS in the secondary tungsten and
cobalt subcategory, based on the selected treatment technology.
New plants have the opportunity to design the best and most
efficient production processes and wastewater treatment
technologies without facing the added costs and restrictions
encountered in retrofitting an existing plant. Therefore, BAT
considers the best demonstrated process changes, in-plant
controls, and end-of-pipe treatment technologies which reduce
pollution to the maximum extent feasible.
TECHNICAL APPROACH TO NSPS
New source performance standards are equivalent to the best
available technology (BAT) selected for currently existing
secondary tungsten and cobalt plants. This result is a
consequence of careful review by the Agency of a wide range of
technical options for new source treatment systems which is
discussed in Section XI of Vol. I. Additionally, there was
nothing found to indicate that the wastewater flows and
characteristics of new plants would not be similar to those from
existing plants, since the processes used by new sources are not
expected to differ from those used at existing sources.
Consequently, BAT production normalized discharge rates, which
are based on the best existing practices of the subcategory, can
also be applied to new sources. These rates are presented in
Table XI-1 (page 3313).
Treatment technologies considered for the NSPS options are
identical to the treatment technologies considered for the BAT
options. These options are:
OPTION A
o Preliminary treatment with oil skimming (where required)
o Preliminary treatment with ammonia steam stripping (where
required)
o Chemical precipitation and sedimentation
3311
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XI
OPTION C
o Preliminary treatment with oil skimming (where required)
o Preliminary treatment with ammonia steam stripping (where
required)
o Chemical precipitation and sedimentation
o Multimedia filtration
NSPS OPTION SELECTION
We have proposed and are promulgating that NSPS be equal to BAT.
We do not believe that new plants could achieve any flow
reduction beyond the allowances promulgated for BAT. Because
NSPS is equal to BAT we believe that the proposed and promulgated
NSPS will not pose a barrier to the entry of new plants into this
subcategory. Promulgated NSPS are equivalent to promulgated BAT.
At proposal, subdivisions 5 and 7 were targeted for additional
flow reduction beyond that considered for BPT. However, through
industry comments on the proposed rulemaking, EPA learned that
the one plant operating these two processes currently practices
extensive (>90 percent) recycle. Therefore, the BPT flow rates
promulgate for subdivisions 5 and 7 include recycle, and it is no
longer necessary to include additional flow reduction for these
two subdivisions at BAT or NSPS.
REGULATED POLLUTANT PARAMETERS
The Agency has no reason to believe that the pollutants that will
be found in treatable concentrations in processes within new
sources will be any different than with existing sources.
Accordingly, pollutants and pollutant parameters selected for
limitation under NSPS, in accordance with the rationale of
Sections VI and X, are identical to those selected for BAT. The
conventional pollutant parameters oil and grease, TSS, and pH are
also selected for limitation.
NEW SOURCE PERFORMANCE STANDARDS
The NSPS discharge flows for each wastewater source are the same
as the discharge rates for BAT and are shown in Table XI-1 (page
3313). The mass of pollutant allowed to be discharged per mass
of product is calculated by multiplying the appropriate treatable
concentration (mg/1) by the production normalized wastewater
discharge flows (1/kkg). The treatable concentrations are listed
in Table VII-21 (page 248) of Vol. I, with the exception of the
cobalt treatment effectiveness values. See Section IX of this
supplement for a discussion of cobalt treatment effectiveness
values. The results of these calculations are the production-
based new source performance standards. These standards are
presented in Table Xl-2 (page 3314).
3312
-------
Table XI-1
NSPS WASTEWATER DISCHARGE RATES FOR THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
Wastewater Stream
NSPS Normalized
Discharge Rate
U/kkg)(gal/ton)
Tungsten detergent wash and rinse 195 47
Tungsten leaching acid 2,571 618
Tungsten post-leaching wash 5,143 1,235
Synthetic scheelite filtrate 16,661 4,002
Tungsten carbide leaching wet 1,751 42
air pollution control
Tungsten carbide wash water 8,333 2,002
Cobalt sludge leaching wet air 35,781 860
pollution control
Crystallization decant 41,650 10,004
Acid wash decant 19,062 4,579
Cobalt hydroxide filtrate 56,647 13,607
Cobalt hydroxide filter cake 109,035 26,190
wash
Production Normalizing
Parameter
tungsten scrap washed
tungsten produced
tungsten produced
synthetic scheelite
produced
tungsten carbide scrap
leached
tungsten carbide
produced
cobalt produced from
cobalt sludge
cobalt produced
cobalt produced
cobalt produced
cobalt produced
g
o
o
Q
W
g
en
o
8
w
8
a
Dd
a
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XI
TABLE XI-2
NSPS FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(a) Tungsten Detergent Wash and Rinse NSPS
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten scrap washed
Arsenic 0.271 0.121
Cadmium 0.039 0.016
Chromium 0.072 0.029
*Copper 0.250 0.119
Lead 0.055 0.025
*Nickel 0.107 0.072
Silver 0.057 0.023
Zinc 0.199 0.082
*Ammonia 25.990 11.430
*Cobalt 0.538 0.236
*Tungsten 0.679 0.302
*Oil and Grease 1.950 1.950
*TSS 2.925 2.340
*pH Within the range of 7.5 to 10.0 at all times
(b) Tungsten Leaching Acid NSPS
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten produced
Arsenic 3.574 1.594
Cadmium 0.514 0.206
Chromium 0.951 0.386
*Copper 3.291 1.568
Lead 0.720 0.334
*Nickel 1.414 0.951
Silver 0.746 0.309
Zinc 2.622 1.080
*Ammonia 342.700 150.700
*Cobalt 7.096 3.111
*Tungsten 8.947 3.985
*Oil and Grease 25.710 25.710
*TSS 38.570 30.850
*pH Within the range of 7.5 to 10.0 at all times
*Regulated Pollutant
3314
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XI
TABLE XI-2 (Continued)
NSFS FOR THE SECONDARY TUNGSTEN AND COBALT SDBCATEGORY
Cc) Tungsten Post-Leaching Wash NSPS
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten produced
Arsenic 7.149 3.189
Cadmium 1.029 0.411
Chromium 1.903 0.771
*Copper 6.583 3.137
Lead 1.440 0.669
*Nickel . 2.829 1.903
Silver 1.491 0.617
Zinc 5.246 2.160
*Ammonia 685.600 301.400
*Cobalt 14.194 6.223
*Tungsten 17.900 7.972
*Oil and Grease 51.430 51.430
*TSS 77.150 61.720
*pH Within the range of 7.5 to 10.0 at all times
(d) Synthetic Scheelite Filtrate NSPS
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of synthetic scheelite produced
Arsenic 23.160 10.330
Cadmium 3.332 1.333
Chromium 6.165 2.499
*Copper 21.330 10.160
Lead 4.665 2.166
*Nickel 9.164 6.165
Silver 4.832 1.999
Zinc 16.990 6.998
*Ammonia 2,221.000 976.300
*Cobalt 45.984 20.160
*Tungsten 57.980 25.820
*Oil and Grease • 166.600 166.600
*TSS 249.900 199.900
*pH Within the range of 7.5 to 10.0 at all times
*Regulated Pollutant
3315
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XI
TABLE XI-2 (Continued)
NSPS FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(e) Tungsten Carbide Leaching Wet Air Pollution Control NSPS
Pollutant or Maximum for Maximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten carbide scrap leached
Arsenic 2.434 1.086
Cadmium 0.350 0.140
Chromium 0.648 0.263
*Copper 2.241 1.068
Lead 0.490 0.228
*Nickel 0.963 0.648
Silver 0.508 0.210
Zinc 1.786 0.735
*Ammonia 233.400 102.600
*Cobalt 4.833 2.119
*Tungsten 6.093 2.714
*Oil and Grease 17.510 17.510
*TSS 26.270 21.010
*pH Within the range of 7.5 to 10.0 at all times
(f) Tungsten Carbide Wash Water NSPS
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten carbide produced
Arsenic 11.580 5.166
Cadmium 1.667 .667
Chromium 3.083 1.250
*Copper 10.670 5.083
Lead 2.333 1.083
*Nickel 4.583 3.083
Silver 2.417 1.000
Zinc 8.500 3.500
*Ammonia 1,111.000 488.300
*Cobalt 22.999 10.083
*Tungsten 29.000 12.920
*Oil and Grease 83.330 83.330
*TSS 125.000 100.000
*pH Within the range of 7.5 to 10.0 at all times
*Regulated Pollutant
3316
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XI
TABLE XI-2 (Continued)
NSPS FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEG0R1T
(g) Cobalt Sludge Leaching Wet Air Pollution Control NSPS
Pollutant orMaximum forMaximum for"
Pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of cobalt produced from cobalt sludge
Arsenic 49.740 22.180
Cadmium 7.156 2.852
Chromium 13.240 5.367
*Copper 45.800 21.830
Lead 10.020 4.652
*Nickel 19.680 13.240
Silver 10.380 4.294
Zinc 36.500 15.030
*Ammonia 4,770.000 2,097.000
*Cobalt 98.756 43.295
*Tungsten 124.500 55.460
*Oil and Grease 357.800 357.800
*TSS 536,700 429.400
*pH Within the range of 7.5 to 10.0 at all times
(h) Crystallization Decant NSPS
Pollutant or'Maximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of cobalt produced
Arsenic 57.890 25.820
Cadmium 8.330 3.332
Chromium 15.410 6.248
*Copper 53.310 25.410
Lead 11.660 5.415
*Nickel 22.910 15.410
Silver 12.080 4.998
Zinc 42.480 17.490
*Ammonia 5,552.000 2f441.000
*Cobalt 114.954 50.397
*Tungsten 144.900 64.560
*Oil and Grease . 416.500 416.500
*TSS 624.800 499.800
*pH Within the range of 7.5 to 10.0 at all times
*Regulated Pollutant
3317
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
SECT - XI
TABLE XI-2 (Continued)
NSPS FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(i) Acid Wash Decant NSPS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
(Ib/million Ibs) of cobalt produced
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
*0il and Grease
*TSS
*pH Within the range
26.500
3.812
7.053
24.400
5.337
10.480
5.528
19.440
2,541.000
52.611
66.340
190.600
285.900
of 7.5 to 10
11.820
1.525
2.859
11.630
2.478
7.053
2.287
8.006
1,117.000
23.065
29.550
190.600
228.700
0 at all times
(j) Cobalt Hydroxide Filtrate NSPS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of cobalt produced
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
*0il and Grease
*TSS
*pH Within the
78.740
11.330
20.960
72.510
15.860
31.160
16.430
57.780
7,551.000
156.346
197.100
566.500
849.700
range of 7.5 to 10.0
35.120
4.532
8.497
34.550
7.364
20.960
6.798
23.790
3,320.000
68.543
87.800
566.500
679.800
at all times
*Regulated Pollutant
3318
-------
SECONDARY TUNGSTEN AND COBALT SDBCATEGORY SECT - XI
TABLE XI-2 (Continued)
NSPS FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(k) Cobalt Hydroxide Filter Cake Wash NSPS
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of cobalt produced
Arsenic 151.600 67.600
Cadmium 21.810 8.723
Chromium 40.340 16.360
*Copper 139.600 66.510
Lead 30.530 14.170
*Nickel 59.970 40.340
Silver 31.620 13.080
Zinc 111.200 45.790
*Ammonia 14,530.000 6,389.000
*Cobalt 300.094 131.932
*Tungsten 379.400 169.000
*Oil and Grease 1,090.000 1,090.000
*TSS 1,636.000 1,308.000
*pH Within the range of. 7.5 to 10.0 at all times
*Regulated Pollutant
3319
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XI
THIS PAGE INTENTIONALLY LEFT BLANK
3320
-------
SECONDARY TUNGSTEN AND COBALT SOBCATEGORY SECT - XII
SECTION XII
PRETREATMENT STANDARDS
This section describes the control and treatment technologies for
pretreatment of process wastewaters in the secondary tungsten and
cobalt subcategory. Pretreatment standards for regulated
pollutants are presented based on the selected control and
treatment technology.
TECHNICAL APPROACH TO PRETREATMENT
Before promulgating pretreatment standards, the Agency examines
whether the pollutants discharged by the industry pass through
the POTW or interfere with the POTW operation or its chosen
sludge disposal practices. In determining whether pollutants
pass through a well-operated POTW achieving secondary treatment,
the Agency compares the percentage of a pollutant removed by POTW
with the percentage removed by direct dischargers applying the
best available technology economically achievable. A pollutant
is deemed to pass through the POTW when the average percentage
removed nationwide by well-operated POTW meeting secondary
treatment requirements is less than the percentage removed by
direct dischargers complying with BAT effluent limitations
guidelines for that pollutant.
*
This definition of pass through satisfies two competing
objectives set by Congress: (1) that standards for indirect
dischargers be equivalent to standards for direct dischargers
while at the same time, (2) that the treatment capability and
performance of the POTW be recognized and taken into account in
regulating the discharge of pollutants from indirect dischargers.
The Agency compares percentage removal rather than the mass or
concentration of pollutants discharged because the latter would
not take into account the mass of pollutants discharged to the
POTW from non-industrial sources or the dilution of the
pollutants in the POTW effluent to lower concentrations due to
the addition of large amounts of non-industrial wastewater.
PRETREATMENT STANDARDS FOR NEW SOURCES
Options for pretreatment of wastewaters from new sources are
based on increasing the effectiveness of end-of-pipe treatment
technologies. All in-plant changes and applicable end-of-pipe
treatment processes have been discussed previously in Sections X
and XI. The options for PSNS are the same as the BAT and NSPS
options discussed in Sections X and XI, respectively.
A description of each option is presented in Section X, while a
more detailed discussion, including pollutants controlled by each
treatment process is presented in Section VII of the General
Development Document,
3321
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XII
Treatment technologies considered for the PSNS options are:
OPTION A
o Preliminary treatment with ammonia steam stripping (where
required)
o Preliminary treatment with oil skimming (where required)
o Chemical precipitation and sedimentation
OPTION C
o Preliminary treatment with ammonia steam stripping (where
required)
o Preliminary treatment with oil skimming (where required)
o Chemical precipitation and sedimentation
o Multimedia filtration
PSES AND PSNS OPTION SELECTION
We are promulgating PSES and PSNS equal to NSPS and BAT (Option
C) for this subcategory. It is necessary to promulgate PSES and
PSNS to prevent pass-through of copper, nickel, cobalt, and
ammonia. These toxic pollutants are removed by a well-operated
POTW achieving secondary treatment at an average of 26 percent,
while the NSPS and BAT level technology removes approximately 97
percent.
The technology basis for PSES and PSNS thus is chemical
precipitation and sedimentation, oil skimming, ammonia steam
stripping, and filtration. The achievable concentration for
ammonia steam stripping is based on iron and steel manufacturing
category data, as'explained in the discussion of BPT for this
subcategory. The PSES and PSNS discharge rates are shown in
Table XII-1 (page 3324).
Capital cost for achieving PSES is estimated as $16,300, with
annual costs of $8,800. These costs are not considered
prohibitive. Costs for indirect dischargers are shown in Table
XII-2 (page 3325).
We believe that the promulgated PSNS are achievable, and that
they are not a barrier to entry of new plants into this
subcategory,
REGULATED POLLUTANT PARAMETERS
Pollutants selected for limitation, in accordance with the
rationale of Sections VI and X, are identical to those selected
for limitation for BAT. It is necessary to promulgate PSES and
PSNS to prevent the pass-through of copper, nickel, ammonia,
cobalt, and tungsten.
3322
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XII
PRETREATMENT STANDARDS
Pretreatment standards are based on the treatable concentrations
from the selected treatment technology, (Option C). and the
discharge rates determined in Sections X and XI for BAT and NSPS,
respectively, A mass of pollutant per mass of production (mg/kg)
allocation is given for each subdivision within the subcategory.
This pollutant allocation is based on the product of the
treatable concentration from the proposed treatment (mg/1) and
the production normalized wastewater discharge rate (1/kkg). The
achievable treatment concentrations for BAT are identical to
those for PSES and PSNS. These concentrations are listed in
Table VII-21 (page 248) of Vol. I, with the exception of the
cobalt treatment effectiveness value. See Section IX for a
discussion of the cobalt treatment effectiveness value. PSES and
PSNS are presented in Tables XII-3 and XII-4 (pages 3326 and
3332), respectively.
3323
-------
Table XII-1
PSES AND PSNS WASTEWATER DISCHARGE RATES FOR THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
to
Wastewater Stream
PSNS Normalized
Discharge Rate
(1/kkg)(gal/ton)
Tungsten detergent wash and rinse 195 47
Tungsten leaching acid 2,571 618
Tungsten post-leaching wash 5,143 1,235
Synthetic scheelite filtrate 16,661 4,002
Tungsten carbide leaching wet 1,751 42
air pollution control
Tungsten carbide wash water 8,333 2,002
Cobalt sludge leaching wet air 35,781 860
pollution control
Crystallization decant 41,650 10,004
Acid wash decant 19,062 4,579
Cobalt hydroxide filtrate 56,647 13,607
Cobalt hydroxide filter cake 109,035 26,190
wash
Production Normalizing
Parameter
tungsten scrap washed
tungsten produced
tungsten produced
synthetic scheelite
produced
tungsten carbide scrap
leached
tungsten carbide
produced
cobalt produced from
cobalt sludge
cobalt produced
cobalt produced
cobalt produced
cobalt produced
w
W
o
P
Q
M
H
I
n
o
en
S
o
Q
I
to
X
H
H
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGQRY SECT - XII
TABLE XII-2
COST OF COMPLIANCE FOR THE
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
Indirect Dischargers
Total Required Total
Capital Cost Annual Cost
Option (1982 Dollars) (1982 Dollars)
A 8,500 5,300
C 16,300 8,800
3325
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XII
TABLE XI1-3
PSES FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(a) Tungsten Detergent Wash and Rinse PSES
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten scrap washed
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
0.271
0.039
0.072
0.250
0.055
0.107
0.057
0.199
25.990
0.538
0.679
0.121
0.016
0.029
0.119
0.025
0.072
0.023
0.082
11.430
0.236
0.302
(b) Tungsten Leaching Acid PSES
Pollutant or Maximum for Maximum for
pollutant property any one day monthly average
mg/kg {Ib/million Ibs) of tungsten produced
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
3.574
0.514
0.951
3.291
0.720
1.414
0.746
2.622
342.700
7.096
8.947
1.594
0.206
0.386
1.568
0.334
0.951
0.309
1.080
150.700
3.111
3.985
*Regulated Pollutant
3326
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XII
TABLE XII-3 (Continued)
PSES FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(c) Tungsten Post-Leaching Wash PSES
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten produced
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
7.149
1.029
1.903
6.583
1.440
2.829
1.491
5.246
685.600
14.194
17.900
3.189
0.411
0.771
3.137
0.669
1.903
0.617
2.160
301.400
6.223
7.972
(d) Synthetic Scheelite Filtrate PSES
Pollutant or Maximum for Maximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of synthetic scheelite produced
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
23.160
3.332
6.165
21.330
4.665
9.164
4.832
16.990
2,221.000
45.984
57.980
10.330
1.333
2.499
10.160
2.166
6.165
1.999
6.998
976.300
20.160
25.820
*Regulated Pollutant
3327
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XII
TABLE XII-3 (Continued)
PSES FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(e) Tungsten Carbide Leaching Wet Air Pollution Control PSES
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten carbide scrap leached
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
*Amraonia
*Cobalt
*Tungsten
2.434
0.350
0.648
2.241
0.490
0.963
0.508
1.786
233.400
4.833
6.093
1.086
0.140
0.263
1.068
0.228
0.648
0.210
0.735
102.600
2.119
2.714
(f) Tungsten Carbide Wash Water PSES
Pollutant or Maximum for Maximum for
pollutant property any one day monthly average
(Ib/million Ibs) of tungsten carbide produced
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
11.580
1.667
3.083
10.670
2.333
4.583
2.417
8.500
1,111.000
22.999
29.000
5.166
0.667
1.250
5.083
1.083
3.083
1.000
3.500
488.300
10.083
12.920
*Regulated Pollutant
3328
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
SECT - XII
TABLE XII-3 (Continued)
PSES FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(g) Cobalt Sludge Leaching Wet Air Pollution Control PSES
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of cobalt produced from cobalt sludge
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
* Ammonia
*Cobalt
*Tungsten
49.740
7.156
13.240
45.800
10.020
19.680
10.380
36.500
4,770.000
98.756
124.500
22.180
2.862
5.367
21.830
4.652
13.240
4.294
15.030
2,097.000
43.295
55.460
(h) Crystallization Decant PSES
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
nig/kg (Ib/million Ibs) of cobalt produced
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
* Ammonia
*Cobalt
*Tungsten
57.890
8.330
15.410
53.310
11.660
22.910
12.080
42.480
5,552.000
114.954
144.900
25.820
3.332
6.248
25.410
5.415
15.410
4.998
17.490
2,441.000
50.397
64.560
"Regulated Pollutant
3329
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XII
Table XII-3 (Continued)
PSES FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(i) Acid-Wash Decant PSES
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
. mg/kg (Ib/million Ibs) of cobalt produced
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
26.500
3.812
7.053
24.400
5.337
10.480
5.528
19.440
2,541.000
52.611
66.340
11.820
1.525
2.859
11 630
2.478
7.053
2.287
8.006
1,117.000
23.065
29.550
(j) Cobalt Hydroxide Filtrate PSES
Pollutant or Maximum for Maximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of cobalt produced
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
* Ammonia
*Cobalt
*Tungsten
78.740
11.330
20.960
72.510
15.860
31.160
16.430
57.780
7,551.000
156.346
197.100
35.120
4.532
8.497
34.550
7.364
20.960
6.798
23.790
3,320.000
68.543
87.800
*Regulated Pollutant
3330
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XII
Table XII-3 (Continued)
PSES FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
PSES
Secondary Tungsten and Cobalt
(k) Cobalt Hydroxide Filter Cake Wash PSES
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of cobalt produced
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
* Ammonia
*Cobalt
*Tungsten
151.600
21.810
40.340
139.600
30.530
59.970
31.620
111.200
14,530.000
300.094
379.400
67.600
8.723
16.360
66.510
14.170
40.340
13.080
45.790
6,389.000
131.932
169.000
*Regulated Pollutant
3331
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XII
TABLE XII-4
PSNS FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(a) Tungsten Detergent Wash and Rinse PSNS
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten scrap washed
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
0.271
0.039
0.072
0.250
0.055
0.107
0.057
0.199
25.990
0.538
0.679
0.121
0.016
0.029
0.119
0.025
0.072
0.023
0.082
11.430
0.236
0.302
(b) Tungsten Leaching Acid PSNS
Pollutant or Maximum for Maximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten produced
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
* Ammonia
*Cobalt
*Tungsten
3.574
0.514
0.951
3.291
0.720
1.414
0.746
2.622
342.700
7.096
8.947
1.594
0.206
0.386
1.568
0.334
0.951
0.309
1.080
150.700
3.111
3.985
^Regulated Pollutant
3332
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XII
Table XII-4 (Continued)
PSNS FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(c) Tungsten Post-Leaching Wash PSNS
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten produced
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
* Ammonia
*Cobalt
*Tungsten
7.149
1.029
1.903
6.583
1.440
2.829
1.491
5.246
685.600
14.194
17.900
0.189
0.411
0.771
3.137
0.669
1.903
0.617
2.160
301.400
6.223
7.972
(d) Synthetic Scheelite Filtrate PSNS
Pollutant or Maximum for Maximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of synthetic scheelite produced
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
* Ammonia
* Cobalt
*Tungsten
23.160
3.332
6.165
21.330
4.665
9.164
4.832
16.990
2,221.000
45.984
57.980
10.330
1.333
2.499
10.160
2.166
6.165
1.999
6.998
976.300
20.160
25.820
"Regulated Pollutant
3333
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XII
TABLE XII-4 (Continued)
PSNS FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(e) Tungsten Carbide Leaching Wet Air Pollution Control PSNS
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten carbide scrap leached
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
2.434
0.350
0.648
2.241
0.490
0.963
0.508
1.786
233.400
4.833
6.093
1.086
0.140
0.263
1.068
0.228
0.648
0.210
0.735
102.600
2.119
2.714
(f) Tungsten Carbide Wash Water PSNS
Pollutant or Maximum for Maximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of tungsten carbide produced
V
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
11.580
1.667
3.083
10.670
2.333
4.583
2.417
8.500
1,111.000
22.999
29.000
5.166
0.667
1.250
5.083
1.083
3.083
1.000
3.500
488.300
10.083
12.920
*Regulated Pollutant
3334
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
SECT - XII
TABLE XI1-4 (Continued)
PSNS FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(g) Cobalt Sludge Leaching Wet Air Pollution Control PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of cobalt produced from cobalt sludge
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
*Ammonia
*Cobalt
*Tungsten
49.740
7.156
13.240
45.800
10.020
19.680
10.380
36.500
4,770.000
98.756
124.500
22.180
2.862
5.367
21.830
4.652
13.240
4.294
15.030
2,097.000
43.295
55.460
(h) Crystallization Decant PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of cobalt produced
Arsenic
Cadmium
Chromium
* Copper
Lead
*Nickel
Silver
Zinc
*Anunonia
*Cobalt
*Tungsten
57.890
8.330
15.410
53.310
11.660
22.910
12.080
42.480
5,552.000
114.954
144.900
25.820
3.332
6.248
25.410
5.415
15.410
4.998
17.490
2,441.000
50.397
64.560
*Regulated Pollutant
3335
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
SECT - XII
TABLE XII-4 (Continued)
PSNS FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
(i) Acid Wash Decant PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of cobalt produced
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
* Ammonia
*Cobalt
*Tungsten
26.500
3.812
7.053
24.400
5.337
10.480
5.528
19.440
2,541.000
52.611
66.340
11.820
1.525
2 859
11.630
2.478
7.053
2.287
8.006
1,117.000
23.065
29.550
PSNS
Secondary Tungsten and Cobalt
(j) Cobalt Hydroxide Filtrate
PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of cobalt produced
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
* Ammonia
*Cobalt
*Tungsten
78.740
11.330
20.960
72.510
15.860
31.160
16.430
57.780
7,551.000
156.346
197.100
35.120
4.532
8.497
34.550
7.364
20.960
6.798
23.790
3,320.000
68.543
87.800
*Regulated Pollutant
Table XII-4 (Continued)
PSNS FOR THE SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
3336
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XII
Ck) Cobalt Hydroxide Filter Cake Wash PSNS
Pollutant or'Maximum forMaximumfor
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of cobalt produced
Arsenic
Cadmium
Chromium
*Copper
Lead
*Nickel
Silver
Zinc
* Ammonia
*Cobalt
*Tungsten
151.600
21.810
40.340
139.600
30.530
59.970
31.620
111.200
14,530.000
300.094
379.400
67.600
8.723
16.360
66.510
14.170
40.340
13.080
45.790
6,389.000
131.932
169.000
*Regulated Pollutant
3337
-------
SECONDARY TUNGSTEN AND COBALT SOBCATEGORY SECT - XII
THIS PAGE INTENTIONALLY LEFT BLANK
3338
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XII
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY
SECTION XIII
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY
EPA is not promulgating best conventional pollutant control
technology (BCT) for the secondary tungsten and cobalt
subcategory at this time.
3339
-------
SECONDARY TUNGSTEN AND COBALT SUBCATEGORY SECT - XII
THIS PAGE INTENTIONALLY LEFT BLANK
3340
-------
NONFERROUS METALS MANUFACTURING POINT SOURCE CATEGORY
DEVELOPMENT DOCUMENT SUPPLEMENT
for the
Primary Molybdenum and Rhenium Subcategory
William K. Reilly
Administrator
Rebecca Hanmer
Acting Assistant Administrator for Water
Martha Prothro, Director
Office of Water Regulations and Standards
Thomas P. O'Farrell, Director
Industrial Technology Division
Ernst P. Hall, P.E., Chief
Metals Industry Branch
and
Technical Project Officer
May 1989
U.S. Environmental Protection Agency
Office of Water
Office of. Water Regulations and Standards
Industrial Technology Division
Washington, D. C. 20460
3341
-------
3342
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
TABLE OF CONTENTS
Section
I SUMMARY
II CONCLUSIONS
III SUBCATEGORY PROFILE 3363
Description of Primary Molybdenum and Rhenium 3363
Production
Raw Materials 3363
Molybdenum Sulfide Roasting 3364
Production of Pure Molybdic Oxide 3364
Production of Ammonium Molybdate Compounds 3364
Reduction to Molybdenum Metal 3364
Recovery of Rhenium 3364
Process Wastewater Sources 3365
Other Wastewater Sources 3365
Age, Production, and Process Profile 3365
IV SUBCATEGORIZATION 3372
Factors Considered in Subdividing the Primary 3372
Molybdenum and Rhenium Subcategory
Other Factors 3373
Production Normalizing Parameters 3373
V WATER USE AND WASTEWATER CHARACTERISTICS 3375
Wastewater Flow Rates 3376
Wastewater Characterization Data 3377
Data Collection Portfolios
Field Sampling Data 3377
Wastewater Characteristics and Flows .by 3379
Subdivision
Molybdenum Sulfide Leachate 3379
Roaster 803 Scrubber 3379
Molybdic Oxide Leachate 3380
Hydrogen Reduction Furnace Scrubber 3381
Depleted Rhenium Scrubbing Solution 3381
3343
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
TABLE OF CONTENTS (Continued)
Section
VI
VII
VIII
SELECTION OP POLLUTANT PARAMETERS
Conventional and Nonconventional Pollutant
Parameters
Conventional and Nonconventional Pollutant
Parameters Selected
Toxic Pollutants
Toxic Pollutants Never Detected
Toxic Pollutants Never Pound Above Their
Analytical Quantification Concentration
Toxic Pollutants Present Below Concentrations
Achievable by Treatment
Toxic Pollutants Detected in a Small Number
of Sources
Toxic Pollutants Selected for Further
Consideration in Establishing Limitations and
Standards
CONTROL AND TREATMENT TECHNOLOGIES
Current Control and Treatment Practices
Molybdenum Sulfide Leachate
Roaster SO2 Scrubber
Molybdic Oxide Leachate
Hydrogen Reduction Furnace Scrubber
Depleted Rhenium Scrubbing Solution
Control and Treatment Options
Option A
Option B
Option C
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS
Treatment Options for Existing Sources
Option A
Option B
Option C
Cost Methodology
Nonwater Quality Aspects
Energy Requirements
Solid Waste
Air Pollution
3429
3419
3419
3419
3419
3420
3420
3429
3429
3429
>
3430
3430
3430
3431
3431
3431
3431
3433
3433
3433
3433
3433
3433
3434
3434
3434
3636
3344
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
TABLE OP CONTENTS (Continued)
Section Pag_e
IX BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY 3439
AVAILABLE
Technical Approach to BPT 3439
Industry Cost and Pollutant Removal Estimates 3441
BPT Option Selection 3441
Wastewater Discharge Rates 3442
Molybdenum Sulfide Leachate 3443
Roaster SO2 Scrubber 3443
Molybdic Oxide Leachate 3443
Hydrogen Reduction Furnace Scrubber 3444
Depleted Rhenium Scrubbing Solution 3444
Regulated Pollutant Parameters 3445
Effluent Limitations 3445
X BEST AVAILABLE TECHNOLOGY ECONOMICALLY 3451
ACHIEVABLE
Technical Approach to BAT 3451
Option A 3452
Option B 3452
Option C 3453
Industry Cost and Pollutant Removal Estimates 3453
Pollutant Removal Estimates 3453
Compliance Cost 3453
BAT Option Selection - Proposal 3453
BAT Option Selection - Promulgation 3454
Wastewater Discharge Rates 3455
Hydrogen Reduction Furnace Scrubber 3456
Regulated Pollutant Parameters 3456
Effluent Limitations 3457
XI NEW SOURCE PERFORMANCE STANDARDS 3469
Technical Approach to NSPS 3469
NSPS Option Selection - Proposal 3470
NSPS Option Selection - Promulgation 3470
Regulated Pollutant Parameters 3470
New Source Performance Standards 3471
3345
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
TABLE OP CONTENTS (Continued)
Section Page
XII PRETREATMENT STANDARDS 3477
Technical Approach to Pretreatment 3477
Pretreatment Standards for New Sources 3478
PSNS OPTION Selection 3478
Regulation Pollutant Parameters 3479
Pretreatment Standards for New Sources 3479
XIII BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY 3485
3346
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
LIST OF TABLES
Title Page
Initial Operating Year (Range) Summary of Plants 3366
in the Primary Molybdenum and Rhenium
Subcategory by Discharge Type
III-2 Production Ranges for Primary Molybdenum Plants 3367
Molybdenum Production Ranges for 1982
III-3 Production Ranges for Primary Rhenium Plants 3368
Rhenium Production Range for 1982
III-4 Summary of Primary Molybdenum and Rhenium 3369
Subcategory Processes and Associated Waste
Streams
V-l Water Use and Discharge Rates for Molybdenum 3382
Sulfide Leachate
¥-2 Water Use and Discharge Rates for Roaster SOj 3383
Scrubber
V-3 Water Use and Discharge Rates for Molybdic Oxide 3384
Leachate
V-4 Water Use and Discharge Rates for Hydrogen 3385
Reduction Furnace Scrubber
V-5 Water Use and Discharge Rates for Depleted 3386
Rhenium Scrubbing Solution
¥-6 Primary Molybdenum and Rhenium Subcategory Acid 3387
Plant Slowdown Raw Wastewater Sampling Data
V-7 Primary Molybdenum and Rhenium Subcategory H2 3395
Reduction Furnace Scrubber Raw Wastewater
Sampling Data
V-8 Primary Molybdenum and Rhenium Subcategory 3398
Molybdic Oxide Leachate Raw Wastewater
Sampling Data
V-9 Primary Molybdenum and Rhenium Subcategory Acid 3401
Plant Slowdown After Sulfide Precipitation and
Filtration Wastewater Sampling Data
V-10 Primary Molybdenum and Rhenium Subcategory Acid 3405
Plant Slowdown Commingled Wastewater
Sampling Data
3347
-------
PRIMARX MOLXBDENUM AND RHENIUM SUBCATEGORY
LIST OP TABLES (Continued)
Table Title
V-ll Primary Molybdenum and Rhenium Subcategory Acid 3409
Plant Slowdown Treated Wastewater Sampling Data
V-12 Primary Molybdenum and Rhenium Subcategory 3413
Molybdic Oxide Leachate Raw Wastewater
Self Sampling Data
VI-1 Frequency of Occurrence of Priority Pollutants 3422
Primary Molybdenum and Rhenium Subcategory Raw
Wastewater
VIII-1 Cost of Compliance for the Primary Molybdenum 3437
and Rhenium Subcategory Direct Dischargers
IX-1 BPT Wastewater Discharge Rates for the Primary 3446
Molybdenum and Rhenium Subcategory
IX—2 BPT Mass Limitations for the Primary Molybdenum 3447
and Rhenium Subcategory
X-l Current Recycle Practices Within the Primary 3459
Molybdenum and Rhenium Subcategory
X-2 Pollutant Removal Estimates for Direct 3460
Dischargers Primary Molybdenum and Rhenium
Subcategory
X-3 Cost of Compliance for the Primary Molybdenum 3461
and Rhenium Subcategory Direct Dischargers
X-4 BAT Wastewater Discharge Rates for the Primary 3462
Molybdenum and Rhenium Subcategory
X-5 BAT Mass Limitations for the Primary Molybdenum 3463
and Rhenium Subcategory
XI-1 NSPS Wastewater Discharge Rates for the Primary 3472
Molybdenum and Rhenium Subcategory
XI-2 NSPS for the Primary Molybdenum and Rhenium 3473
Subcategory
XII-1 PSNS Wastewater Discharge Rates for the Primary 3480
Molybdenum and Rhenium Subcategory
XII-2 PSNS for the Primary Molybdenum and Rhenium 3481
Subcategory
3348
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
LIST OF PIGDRES
Figure Title ' Page
I3JI-1 Primary Molybdenum and Rhenium Production 3370
Processes
III-2 Geographic Locations of the Primary Molybdenum ,3371
and Rhenium Subcategory Plants
V-l Sampling Sites at Primary Molybdenum Plant B 3414
V-2 Sampling Sites at Primary Molybdenum Plant C 3415
V-3 Sampling Sites at Primary Molybdenum Plant D 3416
IX-1 BPT Treatment Scheme for the Primary Molybdenum 3450
and Rhenium Subcategory
X-l BAT Treatment Scheme for Option A 3466
X-2 BAT Treatment Scheme for Option B 3467
X-3 BAT Treatment Scheme for Option C 3468
3349
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
THIS PAGE INTENTIONALLY LEFT BLANK
3350
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - I
SECTION I
SUMMARY
This document provides the technical basis for promulgating
effluent limitations based on best practicable technology (BPT)
and best available technology economically achievable (BAT) for
existing direct dischargers, pretreatment standards for new
indirect dischargers (PSNS), and standards of performance for new
source direct dischargers (NSPS) for plants in the primary
molybdenum and rhenium subcategory.
The primary molybdenum and rhenium subcategory consists of 13
plants. Four of these 13 plants operate molybdenum metallurgical
acid plants. Of the 13 plants, four discharge directly to
rivers, lakes, or streams and nine achieve zero discharge of
process wastewater.
EPA first studied the primary molybdenum and rhenium subcategory
to determine whether differences in raw materials, final
products, manufacturing processes, equipment, age and size of
plants, and water usage required the development of separate
effluent limitations and standards for different segments of the
subcategory. This involved a detailed analysis or wastewater
discharge and treated effluent characteristics, including the
sources and volume of water used, the processes used, the sources
of pollutants and wastewaters in the plant, and the constituents
of wastewaters, including toxic priority pollutants. As a
result, five subdivisions have been identified for this
subcategory that warrant separate effluent limitations. These
include:
o Molybdenum sulfide leachate,
o Roaster S02 scrubber,
o Molybdic oxide leachate,
o Hydrogen reduction furnace scrubber, and
o Depleted rhenium scrubbing solution.
EPA also identified several distinct control and treatment
technologies (both in-plant and end-of-pipe) applicable to the
primary molybdenum and rhenium subcategory. The Agency analyzed
both historical and newly generated data on the performance of
these technologies, including their nonwater quality
environmental impacts and air quality, solid waste generation,
and energy requirements. EPA also studied various flow reduction
techniques reported in the data collection portfolios (dcp) and
plant visits.
Engineering costs were prepared for each plant for each of the
control and treatment options considered for the subcategory.
These costs were then used by the Agency to estimate the impact
of implementing the various options in the subcategory. For each
control and treatment option that the Agency found to be most
effective and technically feasible in controlling the discharge
3351
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - I
of pollutants, we estimated the number of potential closures,
number of employees affected, and impact on price. These results
are reported in a separate document entitled "The Economic Impact
Analysis of Effluent Limitations and Standards for the Nonferrous
Metals Manufacturing Industry."
After examining the various treatment technologies being operated
in the subcategory, the Agency has identified BPT to represent
the average of the best existing technology. Metals removal
based on chemical precipitation and sedimentation technology is
the basis for the BPT limitations. Steam stripping was selected
as the technology basis for ammonia limitations. Iron
coprecipitation was selected as the basis for molybdenum
limitations. To meet the BPT effluent limitations based on this
technology, the primary molybdenum and rhenium subcategory is
estimated to incur a capital and an annual cost. These cost
figures cannot be presented here because the data on which they
are based have been claimed to be confidential.
For BAT, the Agency has built upon the BPT technology basis by
adding in-process control technologies which include recycle of
process water from air pollution control waste streams.
Filtration is added as an effluent polishing step to the end-of-
pipe treatment scheme. To meet the BAT effluent limitations
based on this technology, the primary molybdenum and rhenium
subcategory is estimated to incur a capital and an annual cost.
These cost figures cannot be presented here because the data on
which they are based have been claimed to be confidential.
For BAT, the Agency has built upon the BPT technology basis by
adding in-process control technologies which include recycle of
process water from air pollution control waste streams.
Filtration is added as an effluent polishing step to the end-of-
pipe treatment scheme. To meet the BAT effluent limitations
based on this technology, the primary molybdenum and rhenium
subcategory is estimated to incur a capital and an annual cost.
These cost figures cannot be presented here because the data on
which they are based have been claimed to be confidential.
NSPS is equivalent to BAT. In selecting NSPS, EPA recognizes
that new plants have the opportunity to implement the best and
most efficient manufacturing processes and treatment technology.
However, no such processes or treatment technology were
considered to meet the NSPS criteria. Therefore, the technology
basis of BAT has been determined as the best demonstrated
technology.
The mass limitations and standards for BPT, BAT, NSPS, and PSNS
are presented in Section II.
3352
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - II
SECTION II
CONCLUSIONS
EPA has divided the primary molybdenum and rhenium subcategory
into five subdivisions for the purpose of effluent limitations
and standards. These subdivisions are:
(a) Molybdenum sulfide leachate,
(b) Roaster SO2 scrubber.
(c) Molybdic oxide leachate,
(d) Hydrogen reduction furnace scrubber, and
(e) Depleted rhenium scrubbing solution.
BPT is promulgated based on the performance achievable by the
application of chemical precipitation and sedimentation (line
and settle) technology, along with preliminary treatment
consisting of ammonia steam stripping and iron co-
precipitation for selected waste streams. The following BPT
effluent limitations are promulgated:
(a) Molybdenum Sulfide Leachate BPT
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum sulfide leached
Arsenic 0.968 0.431
Lead 0.195 0.093
Nickel 0.889 0.588
Selenium 0.570 0.255
Fluoride 16.210 9.214
Molybdenum Reserved Reserved
Ammonia (as N) 61.720 27.130
TSS 18.980 9.029
pH Within the range of 7.5 to 10.0 at all times
3353
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - II
(b) Roaster SOa Scrubber BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
rag/kg (Ib/million Ibs) of molybdenum sulfide roasted
Arsenic 3.509 1.561
Lead 0.705 0.336
Nickel 3.224 2.133
Selenium 2.065 0.924
Fluoride 58.770 33.410
Molybdenum Reserved Reserved
Ammonia (as N) 223.800 98.390
TSS 68.840 32.740
pH Within the range of 7.5 to 10.0 at all times
(c) Molybdic Oxide Leachate BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/raillion Ibs) of molybdenum contained in
molybdic oxide leached
Arsenic 24.210 10.770
Lead 4.865 2.317
Nickel 22.240 14.710
Selenium 14.250 6.371
Fluoride 405.400 230.500
Molybdenum Reserved Reserved
Ammonia (as N) 1,544.000 678.800
TSS 474.900 225.900
pH Within the range of 7.5 to 10.0 at all times
3354
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - II
(d) Hydrogen Reduction Furnace Scrubber
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum metal powder produced
Arsenic 47.860 21.300
Lead 9.617 4.580
Nickel 43.970 29.080
Selenium 28.170 12.600
Fluoride 801.400 455.700
Molybdenum Reserved Reserved
Ammonia (as N) 3,052.000 1,342.000
TSS 938.800 446.500
pH Within the range of 7.5 to 10.0 at all times
(e) Depleted Rhenium Scrubbing Solution
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum sulfide roasted
Arsenic 1.497 0.666
Lead . 0 301 0.143
Nickel 1.375 0.909
Selenium 0.881 0.394
Fluoride 25.060 14.250
Molybdenum Reserved Reserved
Ammonia (as N) 95.440 41.960
TSS 29.360 13.960
pH Within the range of 7.5 to 10.0 at all times
BAT is promulgated based on the performance achievable by the
application of chemical precipitation, sedimentation and
multimedia filtration (lime, settle and filter) technology and
in-process flow reduction methods, along with preliminary
treatment consisting of ammonia steam stripping and iron co-
precipitation for selected waste streams. The following BAT
effluent limitations are promulgated:
3355
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - II
(a) Molybdenum Sulfide Leachate BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum sulfide leached
Arsenic 0.644 0.287
Lead 0.130 0.060
Nickel 0.255 0.171
Selenium 0.380 0.171
Fluoride 16.210 9.214
Molybdenum Reserved Reserved
Ammonia (as N) 61.720 27.130
(b) Roaster SO? Scrubber BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum sulfide roasted
Arsenic 2.334 1.041
Lead 0.470 0.218
Nickel 0.924 0.621
Selenium 1.377 0.621
Fluoride 58.770 33.410
Molybdenum Reserved Reserved
Ammonia (as N) 223.8QO 98.390
(c) Holybdic Oxide Leachate BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/raillion Ibs) of molybdenum contained in
molybdic oxide leached
Arsenic 16.100 7.182
Lead 3.244 1.506
Nickel 6.371 4.286
Selenium 9.499 4.286
Fluoride 405.400 230.500
Molybdenum Reserved Reserved
Ammonia (as N) 1,544.OQO 678.800
3356
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - II
(d) Hydrogen Reduction Furnace Scrubber BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum metal powder produced
Arsenic 3.183 1.420
Lead 0.641 0.298
Nickel 1.260 0.847
Selenium 1.878 0.847
Fluoride 80.150 45.570
Molybdenum Reserved Reserved
Ammonia (as N) 305.300 134.200
(e) Depleted Rhenium Scrubbing Solution BAT
Pollutant orMaximum forMaximum for"
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum sulfide roasted
Arsenic 0.995 0.444
Lead 0.201 0.093
Nickel 0.394 0.265
Selenium 0.587 0.265
Fluoride 25.060 14.250
Molybdenum Reserved Reserved
Ammonia (as N) 95.440 41.960
NSPS is based on the performance achievable by the application of
chemical precipitation, sedimentation and multimedia filtration
(lime, settle and filter) technology, and in-process flow
reduction control methods, along with preliminary treatment
consisting of ammonia steam stripping and iron co-precipitation
for selected waste streams. The following effluent standards are
promulgated for new sources:
3357
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - II
(a) Molybdenum Sulfide Leachate NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of molybdenum sulfide leached
Arsenic
Lead
Nickel
Selenium
Fluoride
Molybdenum
Ammonia (as N)
TSS
pH
0.644
0.130
0.255
0.380
16.210
Reserved
61.720
6.945
0.287
0.060
0.171
0.171
9.214
Reserved
27.130
5.556
Within the range of 7.5 to 10.0 at all times
(b) Roaster SO? Scrubber NSPS
Pollutant or
Pollutant Property
Maximum for
Any One Day
Maximum for
Monthly Average
mg/kg (Ib/million Ibs) of molybdenum sulfide roasted
Arsenic
Lead
Nickel
Selenium
Fluoride
Molybdenum
Ammonia (as N)
TSS
pH
2.334
0.470
0.924
1.377
58.770
Reserved
223.800
25.190
1.041
0.218
0.621
0.621
33.410
Reserved
98.390
2O.150
Within the range of 7.5 to 10.0 at all times
3358
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - II
(c) Molybdic Oxide Leachate NSPS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum contained in
molybdic oxide leached
Arsenic
Lead
Nickel
Selenium
Fluoride
Molybdenum
Ammonia (as N)
TSS
pH
(d) Hydrogen
16.100
3.244
6.371
9.499
405.400
Reserved
If544.000
173.800
Within the range of 7.5
Reduction Furnace Scrubber
7.182
1.506
4.286
4.286
230.500
Reserved
678.800
139.000
to 10.0 at all times
NSPS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
rog/kg (Ib/million Ibs) of molybdenum metal powder produced
Arsenic 3.183 1.420
Lead 0.641 0.298
Nickel 1.260 0.847
Selenium 1.878 0.847
Fluoride 80.150 45.570
Molybdenum Reserved Reserved
Ammonia (as N) 305.300 134.200
TSS 34.350 27.480
pH Within the range of 7.5 to 10.0 at all times
3359
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - II
(e) Depleted Rhenium Scrubbing Solution
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum sulfide roasted
Arsenic 0.995 0.444
Lead 0.201 0.093
Nickel 0.394 0.265
Selenium 0.587 0.265
Fluoride 25.060 14.250
Molybdenum Reserved Reserved
Ammonia (as N) 94.440 41.960
TSS 10.740 8.592
pH Within the range of 7.5 to 10.0 at all times
EPA is not promulgating pretreatment standards for
existing sources (PSES) for the primary molybdenum and
rhenium subcategory.
PSNS are promulgated based on the performance achievable
by the application of chemical precipitation, sedimentation
and multimedia filtration lime, settle and filter)
technology, and in-process flow reduction control
methods, along with preliminary treatment consisting of
ammonia steam stripping and iron co-precipitation for
selected waste streams. The following pretreatment
standards are promulgated for new sources:
(a) Molybdenum Sulfide Leachate PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum sulfide leached
Arsenic 0.644 0.287
Lead 0.130 0.060
Nickel 0.255 0.171
Selenium 0.380 0.171
Fluoride 16.210 9.214
Molybdenum Reserved Reserved
Ammonia (as N) 61.720 27.130
3360
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - II
(b) Roaster SO? Scrubber PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum sulfide roasted
Arsenic 2.334 1.041
Lead 0.470 0.218
Nickel 0.924 0.621
Selenium 1.377 0.621
Fluoride 58.770 33.410
Molybdenum Reserved Reserved
Ammonia (as N) 223.800 98.390
(c) Molybdic Oxide Leachate PSNS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum contained in
molybdic oxide leached
Arsenic 16.100 7.182
Lead 3.244 1.506
Nickel 6.371 4.286
Selenium 9.499 4.286
Fluoride 405.400 230.500
Molybdenum Reserved Reserved
Ammonia (as N) 1,544.000 678.800
3361
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - II
(d) Hydrogen Reduction Furnace Scrubber PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum metal powder produced
Arsenic 3.183 1.420
Lead 0.641 0.298
Nickel 1.260 0.847
Selenium 1.878 0.847
Fluoride 80.150 45.570
Molybdenum Reserved Reserved
Ammonia (as N) 305.300 134.200
(e) Depleted Rhenium Scrubbing Solution PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum sulfide roasted
Arsenic 0.995 0.444
Lead 0.201 0.093
Nickel 0.394 0.265
Selenium 0.587 0.265
Fluoride 25.060 14.250
Molybdenum Reserved Reserved
Ammonia (as N) 95.440 41.960
EPA is not promulgating best conventional pollutant control
technology (BCT) limitations at this time.
3362
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - III
SECTION III
SUBCATEGORY PROFILE
This section of the primary molybdenum and rhenium supplement
describes the raw materials and processes used in the production
of primary molybdenum and rhenium, and presents a profile of the
primary molybdenum and rhenium subcategory plants identified in
this study.
Molybdenum is used primarily in steel production as an alloying
agent which results in improved hardness, strength, and
resistance to corrosion and high temperatures. It is produced
primarily as technical grade molybdic oxide (MoO3), most of which
is sold directly to steel producers. Approximately 28 percent of
technical grade molybdic oxide produced is further processed to
metal powder, pure molybdic oxide, ammonium molybdate, and a
variety of other chemical forms.
Rhenium is recovered as a by-product from the roasting of
molybdenum sulfide concentrates. Less than 10 metric tons per
year of rhenium is produced domestically, 90 percent of which is
used in bimetallic platinum rhenium reforming catalysts. These
catalysts are used in the petroleum refining industry to produce
low lead and lead free high octane gasolines.
DESCRIPTION OF PRIMARY MOLYBDENUM AND RHENIUM PRODUCTION
The production of molybdenum products can be divided into four
general processes — roasting of molybdenum sulfide concentrates,
production of pure molybdic oxide, production of ammonium
molybdate compounds, and reduction of pure molybdic oxide or
ammonium molybdate to produce molybdenum metal powder.
Rhenium is recovered from molybdenum roaster flue gases as crude
ammonium perrhenate which can subsequently be purified and
reduced to rhenium metal. The primary molybdenum and rhenium
production processes are presented schematically in Figure III-l
and described below.
RAW MATERIALS
The primary source of molybdenum is a molybdenum sulfide (MoS2)
ore called molybdenite. Most domestic molybdenite is mined and
comes from a mine in New Mexico. Molybdenite is also recovered
as a by-product from concentrating porphyry copper ores. Rhenium
is produced only from molybdenite which is associated with copper
mining operations.
MOLYBDENUM SULFIDE ROASTING
Molybdenite concentrates, which are typically 90 percent
molybdenum disulfide (MoS2), are roasted in multiple hearth
3363
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - III
furnaces at temperatures of 500 to 650°C. The product of
roasting is technical grade molybdic oxide consisting of 90 to 95
percent Mo03- The flue gases contain products of combustion, •
sulfur dioxide, and rhenium heptoxide (Re407) when molybdenite
concentrates from copper mining operations are roasted. Sulfur
dioxide emissions are controlled with either a caustic scrubber
or a sulfuric acid plant. One plant reported leaching of the
molybdenite concentrates with nitric acid as a preliminary
treatment step prior to roasting. Leaching at this stage in the
process reduces alkali concentrations in the concentrates.
PRODUCTION OF PURE MOLYBDIC OXIDE
Pure molybdic oxide can be produced from technical grade molybdic
oxide through sublimation and condensation or by leaching. In
sublimation, the tech oxide is heated to approximately 1,100°C in
a muffle type furnace. The oxide is vaporized and carried in a
stream of forced air through cooling ducts and the condensed
oxide particles are collected in a fabric filter. The purified
oxide contains greater than 99.5 percent
Technical grade oxide may also be purified by leaching with a
hydrochloric acid-ammonium chloride solution. The impurities are
dissolved and separated from the solid molybdic oxide by
filtration. The pure oxide may be sold as a product, reduced to
molybdenum metal powder, or used to produce various molybdenum
chemicals.
PRODUCTION OF AMMONIUM MOLYBDATE COMPOUNDS
Technical grade molybdic oxide is dissolved in ammonium hydroxide
solution and recrystallized as pure ammonium molybdate compounds.
The ammonium molybdate may be sold as a product, calcined to form
pure molybdic oxide, or reduced to form molybdenum metal powder.
REDUCTION TO MOLYBDENUM METAL
Either pure molybdic oxide or ammonium molybdate may be reduced
in a hydrogen atmosphere to produce molybdenum metal powder. The
reduction of molybdic oxide to molybdenum metal is typically a
two stage process carried out in two separate furnaces. In the
first stage, molybdic oxide, MoO3, is reduced to brown molybdenum
dioxide, MoOo/ under a hydrogen atmosphere at 1,100°F. In the
second stage furnace, molybdenum dioxide is reduced to molybdenum
metal at 2,000°F. The second stage hydrogen reduction furnace
may be equipped with a wet scrubber to clean and cool the
hydrogen gas prior to reuse.
RECOVERY OF RHENIUM
When molybdenite concentrates from copper mining operations are
roasted at approximately 600°C, rhenium present in the
concentrate is volatilized as rhenium heptoxide (Re207). The
rhenium heptoxide is water soluble and is removed from the flue
gas by wet scrubbing. The efficiency with which rhenium is
3364
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - III
recovered from the flue gas is approximately 64 percent. Hoc
electrostatic precipitators or baghouses are used upstream from
the rhenium recovery scrubber in order to minimize the amount of
impurities in the scrubber solution. Impurities in the scrubber
liquor, particularly molybdenum and other base metals, are
removed by precipitation and filtration. The rhenium is then
recovered from the scrubber liquor via selective ion exchange or
solvent extraction. Rhenium is stripped from the resin or
solvent with aqueous ammonia and crude ammonium perrhenate,
NH4ReO4, is crystallized from the resulting solution. The crude
ammonium perrhenate may be sold as a product, further purified
prior to reduction to rhenium metal, or used in the manufacture
of various rhenium chemicals. The reduction to metal is a dry
process.
PROCESS WASTEWATER SOURCES
Although a variety of processes are involved in primary
molybdenum and rhenium production, the process wastewater sources
can be subdivided as follows:
1. Molybdenum sulfide leachate,
2. Roaster SO2 scrubber,
3. Molybdic oxide leachate,
4. Hydrogen reduction furnace scrubber, and
5. Depleted rhenium scrubber solution.
OTHER WASTEWATER SOURCES
There may be other wastewater streams associated with the primary
molybdenum and rhenium subcategory. These streams include
noncontact cooling water, stormwater runoff, and maintenance and
cleanup water. These wastewater streams are not considered as a
part of this rulemaking. EPA believes that the flows and
pollutant loadings associated with these wastewaters are
insignificant relative to the waste streams selected, and are
best handled by the appropriate permit authority on a case-by-
case basis under authority of Section 403 of the Clean Water Act,
AGE, PRODUCTION, AND PROCESS PROFILE
Table III-l(page 3366) shows the relative age and discharge
status of the molybdenum and rhenium plants. The average plant
age is between 25 and 35 years. The plant age distribution is
generally uniform with the plant ages ranging from eight to 67
years. Tables 111-2 and III-3 (page 3367) show the 1982
production ranges for primary molybdenum and rhenium,
respectively. Table III-4 (page 3369} provides a summary of the
number of plants generating wastewater streams associated with
the various primary molybdenum and rhenium processes and the
number of plants with the process. Figure 111-2 (page 3370)
shows the geographic locations of the primary molybdenum and
rhenium facilities in the United States by discharge status.
3365
-------
Table III-l
INITIAL OPERATING YEAR (RANGE) SUMMARY OF PLANTS IN THE
u>
u>
1982-
1973
Discharge
Type (0-10)
Direct 1
Indirect 0
Zero 1
Dry 1
Total 3
PRIMARY MOLYBDENUM AND RHENIUM
Initial Operating
(Plant Age
1972- 1967- 1957-
1968 1958 1948
(11-15) (16-25) (26-35)
Oil
000
110
£ £ i
122
SUBCATEGORY BY DISCHARGE TYPE
Year (Range)
in Years)
1947- 1937- 1927- Before
1938 1928 1918 1918
(36-45) (46-55) (56-65) (65+) Total
10004
00000
00115
£^£04
1 2 1 1 13
PRIMARY MC
f
K
W
O
W
25
1
O
§
M
2!
H
w
CJ
W
O
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(-3
W
O
O
»
K
tn
w
o
t-3
1
H
H
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U!
uj
o\
Discharge Type
Direct
Indirect
Zero
Dry
Total
Tabie 111-2
PRODUCTION RANGES FOR PRIMARY MOLYBDENUM PLANTS
MOLYBDENUM PRODUCTION RANGES FOR 1982
0-1,000 kkg/yr
2
0
1
3
6
1 .000-10,000 kkg/yr
1
0
4
0
5
10.000-20,000 kkg/yr Total
1 4
0 0
0 5
0 _3
1 12*
H
3
g
3
o
M
to
g
W
Q
*Twelve of the 13 plants in this subcategory produce molybdenum.
en
w
n
H
H
H
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - III
TABLE III-3
PRODUCTION RANGES FOR PRIMAARY RHENIUM PLANTS
RHENIUM PRODUCTION RANGE FOR 1982
Discharge type
Direct
Indirect
Zero
Total
* Three of the 13 plants in this subcategory produce rheniun
0-1 kkg/yr
0
0
I
2
1-5 kkg/yr
0
0
I
1
Total
0
0
£
3*
3368
-------
u>
en
vo
Table II1-4
SUMMARY OF PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
AND ASSOCIATED WASTE STREAMS
- Hydrogen Reduction Furnace Scrubber
Rhenium Recovery
Rhenium Scrubbing Solution
ti
Process or Waste Stream
Molybdenum Sulfide Roasting
- Molybdenum Sulfide Leachate
Roaster S02 Scrubber
- Sulfuric Acid Plant
Sublimation
Molybdic Oxide Leaching
- Molybdic Oxide Leachate
Ammonium Molybdate Production
Reduction to Molybdenum Metal
Number
of Plants
With Process
7
1
3
4
3
6
Number
of Plants
Reporting
Generation
of Wastewater*
1
3
3
3
§
»
KJ
3!
t^
3
W
s
§
o
w
25
i
CO
a
td
o
1
I* J
a
o
w
*Through reuse or evaporation practices, a plant may "generate" wastewater from a
particular process but not discharge it.
-------
Sl)j Si rubber
or
Acid flant
Uiatevater
Molybdenum
Sul Mde »
Convent rate
HolybdeniM
Siilflde
Concentrate
W»alew»ler
Uaatevater
Figure lll-l
PRIMARY MOLYBDENUM AND RHENIUM PRODUCTION PROCESSES
g
0
n
iz:
§
W
w
G
dd
o
w
Q
§
K
W
W
O
-------
U)
D - Direct Process Wastewater Discharge Plants
I - Indirect Process Wastewater Discharge Plants
Z - Zero Process Wastewater Discharge Plants
Dry - Plants With No Process Wastewater Generate*1
o
n
25
s
M
as
w
§
o
Q
O
CO
M
o
H
Figure III-2
GEOGRAPHIC LOCATIONS OF THE PRIMARY MOLYBDENUM
AND RHENIUM SUBCATEGORY PLANTS
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - IV
SECTION IV
SUBCATEGORIZATION
This section summarizes the factors considered during the
designation of the related subdivisions of primary molybdenum
and rhenium subcategory.
FACTORS CONSIDERED JEN SUBDIVIDING THE PRIMARY MOLYBDENUM AND
RHENIUM SUBCATEGORY
The factors listed previously for general subcategorization were
each evaluated when considering subdivision of the primary
molybdenum and rhenium subcategory. In the discussion that
follows, the factors will be described as they pertain to this
particular subcategory.
The rationale for considering further subdivision of the primary
molybdenum and rhenium subcategory is based primarily on
differences in the production processes and raw materials used.
Within this subcategory, a number of different operations are
performed, which may or may not have a water use or discharge,
and which may require the establishment of separate effluent
limitations. While primary molybdenum and rhenium is still
considered a single subcategory, a more thorough examination of
the production processes has illustrated the need for limitations
and standards based on a specific set of waste streams.
Limitations will be based on specific flow allowances for the
following subdivisions:
1. Molybdenum sulfide leachate,
2. Roaster SO2 scrubber,
3. Molybdic oxide leachate,
4. Hydrogen reduction furnace scrubber, and
5. Depleted rhenium scrubbing solution.
These subdivisions follow directly from differences within the
five distinct production stages of primary molybdenum and rhenium
production: production of technical grade molybdic oxide,
production of pure molybdic oxide, production of ammonium
molybdate, production of molybdenum metal powder, and rhenium
recovery.
The production of technical grade molybdic oxide gives rise to
the first and second subdivisions. If the molybdenum sulfide is
leached with nitric acid to remove excess alkali prior to
roasting spent leachate and rinse water are the resultant waste
streams. The control of sulfur dioxide emissions from roaster
flue gases results in an SO2 scrubber blowdown waste stream.
The production of pure molybdenum via sublimation and
condensation is a dry process and does not result in the
generation of any wastewater.
3372
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PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - IV
The third subdivision results from the leaching of molybdic oxide
prior to either dissolution and crystallization of ammonium
molybdate, or production of pure molybdic oxide. Spent nitric or
hydrochloric acid leachate and rinse water comprise the
wastewater associated with this operation.
The reduction of either pure molybdic oxide or ammonium molybdate
to molybdenum metal powder gives rise to the fourth subdivision.
Hydrogen gas, which is used to maintain a reducing atmosphere in
the reduction furnace, may be scrubbed with water prior to being
recycled to the reduction furnace. The scrubber liquor blowdown
may be discharged as a wastewater stream.
The recovery of rhenium from molybdenite roaster flue gases as
crude ammonium perrhenate results in the fifth subdivision. Prior
to SO2 scrubbing, the flue gases are scrubbed with water to
recover rhenium. When the rhenium is recovered via solvent
extraction or ion exchange, the depleted scrubber solution is
discarded as a wastewater stream.
OTHER FACTORS
The other factors considered in this evaluation either support
the establishment of the five subdivisions or were shown to be
inappropriate bases for subdivision. Air pollution control
methods, treatment costs, and total energy requirements are
functions of the selected subcategorization factors — metal
product, raw materials, and production processes. Therefore,
they are not independent factors and do not affect the
subcategorization which has been applied. As discussed in
Section IV of the General Development Document, certain other
factors, such as plant age, plant size, and the number of
employees, were also evaluated and determined to be inappropriate
for use as bases for subdivision of nonferrous metals plants.
PRODUCTION NORMALIZING PARAMETERS
As discussed previously, the effluent limitations and standards
developed in this document establish mass limitations on the
discharge of specific pollutant parameters. To allow these
regulations to be applied to plants with various production
capacities, the mass of pollutant discharged must be related to a
unit of production. This factor is known as the production
normalizing parameter (PNP).
in general, for each production process which has a wastewater
associated with it, the actual mass of molybdenum or rhenium
product, intermediate or raw material processed will be used as
the PNP. Thus, the PNPs for the five subdivisions are as
follows:
3373
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
SECT - IV
Building Block
PNP
1. Molybdenum sulfide leachate
2. Roaster SO2 scrubber
3. Molybdic oxide leachate
Hydrogen reduction furnace
scrubber
Depleted rhenium scrubbing
solution
kkg of molybdenum sulfide
leached
kkg of molybdenum sulfide
roasted
kkg of molybdenum contained
in molybdic oxide leached
kkg of molybdenum metal powder
produced
kkg of molybdenum sulfide
roasted
At proposal the PNP for Subdivision 3, molybdic oxide leachate,
was kkg of ammonium molybdate produced. For promulgation, this
PNP is revised to kkg of molybdenum contained in the molybdic
oxide leached. As discussed in Sections V and IX, this change
does not affect the mass limitations promulgated for any plant in
this subcategory. The change was made to more accurately reflect
actual manufacturing processes.
3374
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PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - V
SECTION V
WATER USE AND WASTEWATIR CHARACTERISTICS
This section describes the characteristics of the wastewaters
associated with the primary molybdenum and rhenium subcategory.
Water use and discharge rates are explained and then summarized
in tables at the end of this section. Data used to characterize
the wastewaters are presented. Finally, the specific source,
water use and discharge flows, and wastewater characteristics for
each separate wastewater source are discussed.
The two principal data sources used are the data collection
portfolios (dcp) and field sampling results. Data collection
portfolios contain information regarding wastewater flows and
production levels.
In order to quantify the pollutant discharge from primary
molybdenum and rhenium plants, a field sampling program was
conducted. Samples were analyzed for 124 of the 126 priority
pollutants and other pollutants deemed appropriate. Because the
analytical standard for TCDD was judged to be too hazardous to be
made generally available, samples were never analyzed for this
pollutant. There is no reason to expect that TCDD would be
present in nonferrous metals manufacturing wastewater. Asbestos
was not analyzed for, nor is there any reason to expect that
asbestos would be present in primary molybdenum and rhenium
wastewater. A total of four plants were selected for sampling in
the primary molybdenum and rhenium subcategory. In general, the
samples were analyzed for three classes of pollutants: organic
priority pollutants, metal priority pollutants, and criteria
pollutants (which includes both conventional and nonconventional
pollutants).
Following proposal, additional wastewater characteristics and
flow and production data were obtained through industry comments
and a field sampling episode. These data were used to confirm
assumptions made at proposal. These data are contained in the
administrative record for this rulemaking.
After proposal, EPA gathered additional wastewater sampling data
for one of the subdivisions in this subcategory through a self-
sampling program initiated at the specific request of the Agency.
The data include analyses for the priority metals arsenic,
beryllium, cadmium, chromium, copper, lead, nickel, selenium, and
zinc. The data also include analyses for the nonconventional
pollutants ammonia and molybdenum. These data show pollutant
concentrations similar to those indicated by the data which EPA
had acquired for these subdivisions prior to proposal (see Table
V-9, page 3401} For this reason, the selection of pollutant
parameters for limitation in this subcategory (Section VI) has
not been revised based on this new data.
3375
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - V
As described in Section IV of this supplement, the primary
molybdenum and rhenium subcategory has been divided into five
subdivisions or building blocks/ so that the promulgated
regulation contains mass discharge limitations and standards for
five unit processes discharging process wastewater. Differences
in the wastewater characteristics associated with these
subdivisions are to be expected. For this reason, wastewater
streams corresponding to each subdivision are addressed
separately in the discussions that follow. These wastewater
sources are:
1. Molybdenum sulfide leachate,
2. Roaster SC>2 scrubber,
3. Molybdic oxide leachate,
4. Hydrogen reduction furnace scrubber, and
5. Depleted rhenium scrubbing solution.
WASTEWATER FLOW RATES
Data supplied by dcp responses were evaluated, and two flow-to-
production ratios, water use and wastewater discharge, were
calculated for each stream. The two ratios are differentiated by
the flow value used in calculation. Water use is defined as the
volume of water or other fluid required for a given process per
mass of molybdenum product and is therefore based on the sum of
recycle and make-up flows to a given process. Wastewater flow
discharged after pretreatment or recycle (if these are present)
is used in calculating the production normalized flow—the volume
of wastewater discharged from a given process to further
treatment, disposal, or discharge per mass of molybdenum
produced. Differences between the water use and wastewater flows
associated with a given stream result from recycle, evaporation,
and carry-over on the product. The production values used in
calculation correspond to the production normalizing parameter,
PNP, assigned to each stream, as outlined in Section IV. As an
example, hydrogen reduction furnace scrubber water flow is
related to the production of molybdenum metal powder. As such,
the discharge rate is expressed in liters of scrubber water per
metric ton of molybdenum metal powder produced (gallons of
scrubber water per ton of molybdenum powder).
The production normalized discharge flows were compiled and
statistically analyzed by stream type. These production
normalized water use and discharge flows are presented by
subdivision in Tables V-l through V-5 (pages 3382 - 3386). Where
appropriate, an attempt was made to identify factors that could
account for variations in water use and discharge rates. These
variations are discussed later in this section by subdivision. A
similar analysis of factors affecting the wastewater flows is
presented in Sections X, XI, and XII where representative BAT,
NSPS, and pretreatment flows are selected for use in calculating
the effluent limitations.
The water use and discharge rates shown do not include nonprocess
wastewater, such as rainfall runoff and noncontact cooling water.
3376
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - V
WASTEWATER CHARACTERIZATION DATA
Data used to characterize the various wastewaters associated with
primary molybdenum and rhenium production comes from three
sources — data collection portfolios, analytical data from field
sampling trips, and through industry comments or responses to
data requests made under authority of Section 308 of the Clean
Water Act.
DATA COLLECTION PORTFOLIOS
in the data collection portfolios, the molybdenum and rhenium
plants that discharge wastewater were asked to specify the
presence or absence of priority pollutants in their wastewater.
The responses are summarized below:
Pollutant Known Present Believed Present
phenol 1 -
bis(2-ethylhexyl) phthalate 1
antimony - 1
arsenic 4 -
cadmium 2 1
chromium 2
copper 6 2
lead 5 1
mercury 1 1
nickel 4 -
selenium 4 -
silver 3 -
zinc 4 -
The other pollutants were never recorded as known or believed
present by any facility.
FIELD SAMPLING DATA
In order to quantify the concentrations of pollutants present in
wastewater from primary molybdenum and rhenium plants, wastewater
samples were collected at four plants, which represents
approximately one fourth of the primary molybdenum and rhenium
plants in the United States. Diagrams indicating the sampling
sites and contributing production processes are shown in Figures
V-l through V-3 (page 3414 - 3416).
One plant (primary molybdenum plant D) was sampled following
proposal and the data obtained from this sampling episode are
presented in Table V-8(page 3398). One grab sample of molybdic
oxide leachate was taken at this plant.
Raw wastewater data are summarized in Tables V-6 through V-8
(page 3389 - 3398). Analytical results for acid plant blowdown
and hydrogen reduction furnace scrubber water are given in Tables
3377
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - V
V-6 and V-7, respectively. Additional data for hydrogen
reduction furnace scrubber water is contained in the confidential
record. Note that the stream numbers listed in the tables
correspond to those given in individual plant sampling site
diagrams, Figures V-l through V-3. Where no data are listed for
a specific day of sampling, the wastewater samples for the stream
were not collected. Tables V-9 through V-ll (pages 3401 - 3409)
show analytical data for samples of treated and partially treated
acid plant wastewater.
Acid plant blowdown data for molybdenum metallurgical acid plants
are presented in this document - see Tables V-6, V-9, V-10. and
V-ll. EPA believes that these data for acid plant blowdown
provide a good measure of the wastewater characteristics of
several of the primary molybdenum and rhenium subcategory
subdivisions. This is discussed further later in this section.
Several points regarding these tables should be noted. First,
the data tables include some samples measured at concentrations
considered not quantifiable. The base-neutral extractable, acid
extractable, and volatile organics generally are considered not
quantifiable at concentrations equal to or less than 0.010 mg/1.
Below this concentration, organic analytical results are not
quantitatively accurate; however, the analyses are useful to
indicate the presence of a particular pollutant. The pesticide
fraction is considered not quantifiable at concentrations equal
to or less than 0.005 mg/1.
Second, the detection limits shown on the data tables for metals
and conventional and nonconventional pollutants are not the same
in all cases as the published detection limits for these
pollutants by the same analytical methods. The detection limits
used were reported with the analytical data and hence are the
appropriate limits to apply co the data. Detection limit
variation can occur as a result of a number of laboratory-
specific, equipment-specific, and daily operator-specific
factors. These factors can include day-to-day differences in
machine calibration, variation in stock solutions, and variation
in operators.
Third, the statistical analysis of data includes some samples
measured at concentrations considered not quantifiable. For data
considered as detected but below quantifiable concentrations, a
value of zero is used for averaging. Priority organic,
nonconventional, and conventional pollutant data reported with a
"less than" sign are considered as detected, but not further
quantifiable. A value of zero is also used for averaging. If a
pollutant is reported as not detected, it is assigned a value of
zero in calculating the average. Finally, metal values reported
as less than a certain value were considered as not quantifiable,
and consequently were assigned a value of zero in the calculation
of the average.
Finally, appropriate source water concentrations are presented
with the summaries of the sampling data. The method by which
3378
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - V
each sample was collected is indicated by number, as follows:
1. one-time grab
2. manual composite during intermittent process operation
3. 8-hour manual composite
4. 8-hour automatic composite
5. 24-hour manual composite
6. 24-hour automatic composite
WASTEWATER CHARACTERISTICS AND FLOWS BY SUBDIVISION
Because primary molybdenum and rhenium production involves five
principal sources of wastewater and each has different
characteristics and flows, the wastewater characteristics and
discharge rates corresponding to each subdivision will be
described separately. A brief description of why the associated
production processes generate wastewater and explanations for
variations of water use within each subdivision will also be
discussed.
MOLYBDENUM SULFIDE LEACHATE
The first step in the production of primary molybdenum is the
roasting of molybdenum sulfide concentrates to produce technical
grade molybdic oxide. One primary molybdenum producer indicated
that a portion of the molybdenum sulfide was leached with nitric
acid and water prior to roasting in order to remove excess
alkali. This facility also produces molybdenum chemicals from
molybdic oxide. Presumably, the excess alkali would be an
impurity in the chemical production processes. The spent
leachate and rinsewater are then discharged as a waste stream.
Water use and discharge rates are shown in liters per metric ton
of molybdenum sulfide leached in Table V-l(page 3382).
Wastewater sampling data for priority metals in this waste stream
were supplied by the facility. Treatable levels of copper,
cadmium, and selenium are present. Based on the fact that this
is an acid leaching process, it can be assumed that this
wastewater has an acidic pH. It can also be assumed that
treatable concentrations of suspended solids are present. The
facility which reported this waste stream discharges it to an on-
site evaporation pond and contract hauls a portion of the
contents of the pond periodically, thereby achieving zero
discharge.
ROASTER SO2 SCRUBBER
When molybdenum sulfide concentrates are roasted to produce
technical grade molybdic p.XuidjJj^th.e sulfur is carried off in the
flue gas as sulfur dioxide. Four"facilities reported the use of
caustic scrubbers to control SO2 emissions. Slowdown streams
from these scrubbers constitute a significant, wastewater stream.
Water use and discharge rates are shown in liters per metric ton
of molybdenum sulfide roasted in Table V-2 (page 3383).
3379
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - V
All four of the facilities reporting this stream achieve zerc
discharge through evaporation ponds, lagoon disposal or treatment
and reuse in other plant processes. One facility uses this
stream as a raw material to a fertilizer plant which produces
ammonium sulfate. No EPA field-sampling analytical data are
available for this stream; however, it is expected to have an
alkaline pH, and contain treatable levels of suspended solids,
and priority metals, which are absorbed or entrained from the
roaster flue gas. Data submitted by one of the facilities in its
dcp indicates that treatable concentrations of lead, selenium,
copper, cadmium, and arsenic are present.
MOLYBDIC OXIDE LEACHATE
Technical grade molybdic oxide is leached in order to produce
pure molybdic oxide, or as a preliminary step in the production
of ammonium molybdate compounds. One plant leaches molybdic oxide
with hydrochloric acid and ammonium chloride in order to produce
pure molybdic oxide. The leachate and rinsewater are discharged
as a wastewater stream.
Ammonium molybdate is produced from technical grade molybdic
oxide by dissolution in an aqueous ammonia solution followed by
crystallization. The ammonium molybdate is either sold as a
product, or further processed to molybdenum metal, pure molybdic
oxide, or other molybdenum chemicals. Prior to dissolving in
aqueous ammonia, the technical grade molybdic oxide may be
leached with nitric acid, aqueous ammonia, or water to remove
impurities. The spent leachate and rinse water constitute a
wastewater stream. Water use and discharge rates are shown in
liters per metric ton of molybdenum contained in the molybdic
oxide leached in Table V-3 (page 3384).
Of the three facilities reporting this wastewater stream, one is
a direct discharger, after treatment by ammonia stripping,
chemical precipitation and sedimentation. Another facility
achieves zero discharge through the use of evaporation ponds and
contract hauling. The third facility achieves zero discharge
through the use of contract hauling.
Analytical data for this waste stream are presented in Table V-9
(page 3401). These data show treatable concentrations of arsenic,
cadmium, chromium, copper, lead, nickel, zinc, ammonia, fluoride,
molybdenum and TSS, along with an acidic pH. At proposal, this
stream was listed as having not been sampled, but expected to
contain toxic metals, an acidic pH. and treatable concentrations
of TSS. Also, it was expected to contain ammonia if ammonia
compounds were used for leaching. The analytical data presented
in Table V-8 (page 3398) support these expectations.
Following proposal, sampling data for this subdivision were
acquired through a self-sampling effort undertaken at the
specific request of EPA. These data are presented in Table V-12
(page 3413) and show treatable concentrations of ammonia,
cadmium, chromium, copper, lead, nickel, zinc, and molybdenum,
3380
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - V
thus corroborating the data used at proposal.
HYDROGEN REDUCTION FURNACE SCRUBBER
High purity molybdenum metal powder is produced by reducing pure
molybdic oxide or ammonium molybdate. Reduction is accomplished
in a tube furnace with a hydrogen atmosphere. At two plants, the
hydrogen gas is scrubbed with water prior to reuse in the
reduction furnaces. Both of these facilities reported a
discharge of hydrogen gas scrubber water. Water use and
discharge rates are shown in liters per metric ton of molybdenum
metal powder produced in Table V-4 (page 3385).
Both of the facilities which reported this wastewater stream
discharge it to surface waters with no treatment. Table V-7
(page 3396) presents raw wastewater sampling data for priority
and selected conventional and nonconventional pollutants.
Additional data for this stream is contained in the confidential
record. Treatable concentra-tions of toxic metals are present
including lead, nickel, and zinc.
DEPLETED RHENIUM SCRUBBING SOLUTION
Two facilities reported recovery of rhenium from molybdenite
roaster flue gases. Rhenium is absorbed from the flue gas into
an aqueous ammonia solution through the use of wet scrubbers.
After the rhenium has been recovered from the solution through
solvent extraction or selective ion exchange, the depleted
solution is discharged as a wastewater stream. Water use and
discharge rates are shown in liters per metric ton of molybdenum
sulfide roasted in Table V-5 (page 3386). The amount of
molybdenum sulfide roasted was chosen as the production
normalizing parameter for depleted rhenium solution since the
amount of water generated in the scrubber is directly related to
the volume of flue gases produced, which is, in turn, directly
related to the quantity of molybdenum sulfide roasted.
Both of the facilities reporting this wastewater stream achieve
zero discharge through treatment and reuse to other plant
processes or through the use of evaporation ponds and contract
hauling. No analytical data are available for this wastewater
stream; however, data supplied by one of the facilities reporting
this wastewater indicate that treatable concentrations of
selenium are present as well as high concentrations of molybdenum
and iron. Priority organics may also be present when solvent
extraction is used to recover rhenium from the solution.
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - V
TABLE V-l
WATER USE AND DISCHARGE RATES FOR
MOLYBDENUM SULFATE LEACHATE
(1/kkg of molybdenum sulfide leached)
Production Production
Normalized Normalized
Plant Percent Water Discharge
Code Recycle Use Rate
1064 0 463 463
3382
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - V
TABLE V-2
WATER USE AND DISCHARGE RATES FOR
ROASTER SO2 SCRUBBER
(1/kkg of molybdenum sulfide roasted)
Production Production
Normalized Normalized
Plant Percent Water Discharge
Code Recycle Use Rate
1086 0 181 181
1064 0 3117 3117
1174 96 392525 15701
1107 NR MR NR
3383
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - V
TABLE V-3
WATER USE AND DISCHARGE RATES FOR
MOLYBDIC OXIDE LEACHATE
(1/kkg of molybdenum contained in molybdic oxide leached)
Production Production
Normalized Normalized
Plant Percent Water Discharge
Code Recycle Use Rate
1146 0 25122 25122
1064 0 6020 6020
1099 0 3609 3609
3384
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - V
TABLE V-4
WATER USE AND DISCHARGE RATES FOR
MOLYBDENUM SULFATE LEACHATE
(1/kkg of molybdenum sulfide leached)
Production Production
Normalized Normalized
Plant Percent Water Discharge
Code Recycle Use Rate .
1182 99 2000 20
1146 0 43795 43795
3385
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - V
TABLE V-5
WATER USE AND DISCHARGE RATES FOR
DEPLETED RHENIUM SCRUBBING SOLUTION
(1/kkg of molybdenum sulfide leached)
Production Production
Normalized Normalized
Plant Percent Water Discharge
Code Recycle Use Rate
1107 0 637 637
1064 0 794 794
3386
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
ACID PLANT SLOWDOWN
RAW WASTEWATER SAMPLING
Toxic
114.
115.
117.
w MB.
00
^ 119.
120.
121.
122.
123.
124.
125.
126.
Pollutant
Pollutants
antimony
arsenic
beryll lum
cadmium
chromium (total)
j
copper
cyan Ide (total )
lead
•
mercury
n i eke 1
se 1 en I urn
si Iver
Stream
Code
781
781
781
781
781
781
781
781
781
781
781
781
Sample
Typet
6
6
6
6
6
6
1
6
6
6
6
6
DATA
Concentrations (mg/l)
Source
<0.0020
0.00500
0.010
<0.050
<0.10
<0.010
0.29
<0.100
<0.0010
<0.0100
-------
Table V-6 (Continued)
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
ACID PLANT SLOWDOWN
RAW WASTEWATER SAMPLING DATA
Pollutant
Toxic Pollutants (Continued)
127. thai MUM
120. zinc
Noncon ven t 1 ona 1 Po 1 1 u tan t s
w acidity
u»
£ alkalinity
aluminum
ammonia nitrogen
barium
boron
calciuM
chemical oxygen demand (COD)
chloride
cobalt
fluoride
Stream
Code
781
781
781
781
781
781
781
781
781
781
781
781
781
Sample
Typet
6
6
6
6
6
6
6
6
6
6
6
6
6
H
3
*W
tf
Concentrations (mg/l) £!
Source
<0.005
<0.0500
<,
200
0.00370
0.75
0.20
-------
Table V-6 (Continued)
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
ACID PLANT SLOWDOWN
RAM WASTEWATER SAMPLING DATA H
Pollutant
Nonconventional Pol
iron
magnesium
manganese
uj molybdenum
to
00
^> phenol I cs
phosphate
sodium
•
sui fate
tin
1 1 tan 1 urn
total dissolved sol
Stream
Code
lutants (Continued)
781
781
781
781
781
781
781
781
781
781
ids (TDS) 781
total organic carbon (TOC) 781
total solids (TS)
vanadium
yttrium
781
781
781
Sample
Typet
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
Source
0.230
15.6
0.090
<0.02
<0.005
5
17
75
0,321
<0.020
430
-------
Table V-6 (Continued)
PRIMARY MOLYBDENUM AND RHENIUM SUBCATE60RY
ACID PLANT SLOWDOWN
RAW WASTEWATER SAMPLING DATA
H
u>
UD
Pol lutant
Stream Sample Concentrations (mg/l)
Code Typet Source Day 1 Day 2 Day 3
Conventional Pollutants (Continued)
o 1 1 and grease
total suspended solids
pH (standard units)
t Sample Type Code:
NA - Not analyzed.
781 - 1 <1 7.7 NA NA
(TSS) 781 6 3 87 NA 38
781 6 6.00 1.20 NA 1.24
1 - One-time grab
2 - Manual composite during Intermittent process operation
3 - 8-hour manual composite
4 - 8-hour automatic composite
5 - 24-hour manual composite
6 - 24-hour automatic composite
«;
1
Ft
3
O
m
z;
§
8
M
55
H
i
W
c
a
o
w
o
o
8
M
M
O
HI
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
ACID PLANT SLOWDOWN (DUPLICATE)
RAW WASTEWATER SAMPLING DATA
Stream SampI a
Concentrations (mg/l)
Toxic
114.
115.
117.
-. 118.
,o
0
a 119.
120.
121.
122.
123.
124.
125.
126.
Pol lutant
Pollutants
antimony
arsenic
bar y 1 1 1 urn
cadmium
chromium (total )
copper
cyanide (total )
lead
mercury
nickel
se 1 en 1 urn
s i 1 ver
Code
781
781
781
781
781
781
781
781
781
781
781
781
Typet
6
6
6
6
6
6
1
6
6
6
6
6 ;
Source
<0.0020
<0.0050
H3
M
Q
o
-------
Table V-6 (Continued)
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
ACID PLANT SLOWDOWN (DUPLICATE)
RAW NASTEWATER SAMPLING DATA
H
VD
Po 1 i utant
Toxic Pollutants (Continued)
127. thallium
128. zinc
Nonconventlonal Pollutants
acidity
alkalinity
a 1 urn i num
ammonia nitrogen
bar 1 um
boron
calcium
chemical oxygen demand (COD)
chloride
coba 1 t
f 1 uor i do
Stream
Code
781
781
781
781
781
781
781
781
781
781
781
781
781
Sample
Typet
6
6
6
6
6
6
6
6
6
6
6
6
6
Concentrations
Source
<0.005
<0.050
<1 19,
200
0.037
0.75
0.20
<0. 100
63.5
<»
20
<0.1
0.68
(mq/l)
Day 1
<0.005
0.050
000
<1
1.76
1.28
0.098
3.68
72
86
53
<0.1
720
3
a
W
-------
U)
Table V-6 (Continued)
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
ACID PLANT SLOWDOWN (DUPLICATE) ^
RAN NASTEWATER SAMPLING DATA 3
I
s
1
Pollutant
Noncon vent 1 ona 1 Po 1 1 utants
iron
mag n as i urn
manganese
molybdenum
phenol ics
phosphate
sod i urn
sul fate.
tin
t i tan 1 urn
Stream
Code
(Continued)
781
781
781
781
781
781
781
781
781
781
total dissolved solids (TDS) 781
total organic carbon (TOC)
total solids (TS)
vanad i urn
yttrium
781
781
781
781
Sample
Typet
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
Concentrations
Source
0.230
15.6
0.090
<0.02
<0.005
5
17
75 48.
<0.2
<0.02
430
<1
500 52,
<0.01
0.056
(mq/l)
Day 1
35.8
19.6
1.3
1.86
<0.005
5.2
19
000
<0.2
<0.02
NR
15
000
<0.01
0.064
w
§
n
s
w
8
H
W
w
o
I
<
-------
Table V-6 (Continued)
PRIMARY MOLYBDENUM AND RHENIUM SU8CATEGORY
ACID PLANT SLOWDOWN (DUPLICATE)
RAW WASTEWATER SAMPLING DATA
H
u>
u>
Pol lutant
Conventional Pollutants
olI and grease
total suspended solids (TSS)
pH (standard units)
Stream
Code
Sample
Typet
Concentrations (mg/l)
Source Day 1
tSample Type Code:
NA - Not analyzed,
781
781
781
1
6
6
-------
Table V-7
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
H2 REDUCTION FURNACE SCRUBBER
RAW WASTEWATER SAMPLING DATA
u>
U)
vo
Ul
Pollutant
Toxic Pollutants
114. antimony
115. arsenic
117. beryllium
118. cadmium
119. chromium (total)
120. copper
121. cyanide (total)
122. lead
123. mercury
124. nickel
125. selenium
126. silver
Stream
Code
55
55
55
55
55
55
55
55
55
55
55
55
Sample
Typet
1
1
1
1
1
1
1
1
1
1
1
1
Concentrations (mg/1) K
Source
0.023
0.001
<0.001
<0.001
0.018
0.070
0.009
0,003
<0.0002
0.17
<0.001
0.008
Day 1
<0.001
0.006
<0.001
<0.001
0.005
0.64
0.01
0.026
<0.0002
2.8
<0.001
0.014
Day 2
0.024
0.024
0.005
<0.001
0.006
0.54
0.01
0.17
<0.0002
0.66
<0.001
0.001
Day 3 %
O
1
0.002 g
0.002 ^
<0.001 w
<0.001 1
0.001 |
0.004 G
CO
o
0.01 g
w
<0.001 o
<0.0002
0.024 in
m
0.001 "3
1
<0.001 <
-------
Table V-7 (Continued)
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
H2 REDUCTION FURNACE SCRUBBER
RAW WASTEWATER SAMPLING DATA
Pollutant
Toxic Pollutants (Continued)
127. thallium
128. zinc
Nonconventional Pollutants
Alkalinity
Ammonia Nitrogen
Calcium
Chloride
Magnesium
Phenolics
Sulfate
Total Dissolved Solids (TDS)
Total Solids (TS)
Stream
Code
55
55
55
55
55
55
55
55
55
55
55
Sample
Typet
1
1
1
1
1
1
1
1
1
1
1
Concentrations (ng/1)^
Source
<0.001
420
2.8
0.07
0.36
<1
0.009
<0.001
2
<10
16
Day 1
<0.001
0.58
120
3.3
53
2.7
0.005
25
310
310
Day 2
<0.001
0.63
120
11
29
2.7
0.004
95
350
350
Day 3
<0.001
0.51
120
14
37
<0.001
23
Kj
g
O
a
a
M
g
M
H
3
i
o
1-3
W
§
H!
M
m
o
i
<
-------
Table V-7 (Continued)
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
H2 REDUCTION FURNACE SCRUBBER
RAW WASTEWATER SAMPLING DATA
Pollutant
Conventional Pollutants
Oil and Grease
Total Suspended Solids (TSS)
pH (standard units)
Stream
Code
55
55
55
Sample
Typet
1
1
1
Concentrations
Source
11
<4
7.1
Day 1
24
<4
8.8
(mR/i)
Day 2
<4
8.2
Hj
Day 3 3
o
1
o
1
3
UJ
u>
H
tSample Type Code: 1 - One-time grab
2 - Manual composite during Intermittent process operation
3 . g-hour manual composite
4 - 8-hour automatic composite
5 - 24-hour manual composite
6 - 24-hour automatic composite
A - Anticipated quality if new process implemented.
(a),(b),(c) Reported together
m
G
to
1
Q
en
w
o
i
<
-------
Table V-8
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGOHY
MOLYBDIC OXIDE LEACHATE
U)
Pollutant
Toxic Pollutants
114. antimony
1 15, arsenic
1 18. cadmium
119. chromium (total)
00 120. copper
122. lead
123. mercury
124. nickel
125. selenium
126. silver
128. zinc
Nonconventional Pollutants
Acidity
Alkalinity
iSTEMATEl
Stream
Code
001
001
001
001
001
001
001
001
001
001
001
001
55
I SAMPLING
Sample
Typet
1
1
1
1
1
1
1
1
1
1
1
1
1
DATA
Concentrations (mg/1)
Source
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
N.A. >1
N.A.
Day 1 Day 2
<0.03
0.48
0.71
1.4
130
110
<0.0002
10
<0.002
<0.2
120
,000
-------
v-o
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
MOLYBDIC OXIDE LEACHATE
RAW UASTEWATER SAMPLING DATA
Pollutant
Nonconventional Pollutants (Continued)
Ammonia Nitrogen
Barium
Chemical Oxygen Demand (COD)
Chloride
CA)
U>
S Fluoride
Iron
Manganese
Molybdenum
Phosphate
Sulfate
Total Dissolved Solids (TDS)
Total Organic Carbon (TOG)
Total Solids (TS)
Stream
Code
001
001
001
001
001
001
001
001
001
001
001
001
001
Sample
Typet
1
1
1
1
1
1
1
1
1
1
1
1
1
Concentrations (mg/1) 22
Source
N.A.
N.A.
N.A.
N.A. 1
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
N.A. 44
N.A.
N.A. 46
Day 1
3,400
3.3
200
6,000
42
2,500
19
440
0.16
170
,600
3
,000
Day 2 Day 3 J)
Q
Ki
3
o
w
25
i
1
X
M
525
M
CO
G
O
t-1
M
8
Jd
Hj
en
o
<
-------
Table V-8 (Continued)
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
MOLYBDIC OXIDE LEACHATE
RAW WASTEWATER SAMPLING DATA
Pollutant
Conventtonal Pollutants
Total Suspended Solids (TSS)
pH (standard units)
Stream
Code
001
001
Sample
Typet
Concentrations (mg/l)
Source Day 1
Day 3
N.A.
N.A.
82
<2
3
§
U>
O
O
tSample Type Code:
1 - One-time grab
2 - Manual composite during intermittent process operation
3 - 8-hour manual composite
4 - 8-hour automatic composite
5 - 24-hour manual composite
6 - 24-hour automatic composite
A - Anticipated quality if new process implemented.
en
G
to
O
5
w
8
a
CO
M
o
-------
Table V-9
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
ACID PLANT SLOWDOWN AFTER SULFIDE PRECIPITATION AND FILTRATION
WASTEWATER SAMPLING DATA
Stream Sample
Concentrations (mg/l)
Toxic
68.
114.
115.
117.
10
g 118.
119.
120.
121.
122.
123.
124.
125.
126.
Pollutant
Pol lutants
dl-n-butyl phthalate
antimony
arsenic
bery 1 1 1 urn
cadm 1 urn
chrom 1 urn ( tota 1 )
copper
cyanide (total )
lead
mercury
nickel
se 1 en 1 urn
s 1 1 ver
Code
782
782
782
782
782
782
782
782
782
782
782
782
782
Typet
6
6
6
6
6
6
6
1
6
6
6
6
6
Source
0.00172
<0.0021
<0.005
<0.010
<0.050
<0. 100
-------
Table V-9 (Continued)
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
ACID PLANT SLOWDOWN AFTER SULFIDE PRECIPITATION AND FILTRATION
WASTEWATER SAMPLING DATA
H
Pollutant
Toxic Pollutants (Continued)
127. thallium
128. zinc
Noncon vent 1 ona 1 Poll utant s
acidity
Ui '
*>. <
g alkalinity
aluminum
ammonia nitrogen
bar i urn
boron
calcium
chemical oxygen demand (COD)
chloride
coba 1 t
f luoride
Stream
Code
782
782
782
782
782
782
782
782
782
782
782
782
782
Sample
Typet
6
6
6
6
6
6
6
6
6
6
6
6
6
Concentrations (mg/l)
Source
<0.005
<0.050
<,
200
0.037
0.75
0.20
<0. 100
63.5
<1
20
<0.100
0.68
Day 1
<0.005
<0.050
1,000
<1
2.01
1.24
0.085
4.77
63
230
510
<0.100
1,050
Day 2
<0.005
<0.050
1,500
-------
UJ
Table V-9 (Continued)
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORf
ACID PLANT SLOWDOWN AFTER SULFIDE PRECIPITATION AND FILTRATION
WASTEWATER SAMPLING DATA
H
Pol lutant
Nonconvent lonal Pol
Iron
magnesium
manganese
mol ybdenum
phenol Ics
phosphate
sod 1 urn
sul fate
tin
t i tan i urn
total dissolved sol
Stream
Code
lutants (Continued)
782
782
782
782
782
782
782
782
782
782
Ids (IDS) 782
total organic carbon (TOG) 782
total solids (TS)
vanadium
yttrium
782
782
782
Sample
Typet
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
Concentrations (mg/l) g
Source
0.230
15.6
0.090
<0.0200
<0.005
5
17
75
0.321
<0.020
4.30
<1
500
<0.010
0.056
Day 1
9.90
17.8
0.40
1.70
0.089
6.0
19
45,000
<0.200
<0.020
2,940
15
55,000
<0.010
0.064
Day 2
7.20
17.5
0.24
4.22
NA
<4
11
45,000
<0.200
<0.020
27,600
65
66,000
<0.010
0.070
Day 3
6.60
23.6
0.24
1.95
NA
9.2
27
39,000
<0.200
<0.020
8,000
HO
37,000
<0.010
0.076
K
SS
O
d
w
55
§
|
§
M
a
H
i
w
c
w
O
1
3
w
M
o
HI
1
<
-------
Table V-9 (Continued)
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
ACID PLANT SLOWDOWN AFTER SULFIDE PRECIPI TAT(ON AND FILTRATION
WASTEWATER SAMPLING DATA
H
Pollutant
Convent 1 ona 1 Po i 1 utan ts
oil and grease
total suspended solids
-------
Table V-IO
PRIMARY MOLYBDENUM AND RHENIUM SU8CATEGORY
ACID PLANT SLOWDOWN
Toxic
65.
66.
68.
Ul
o 114.
en
115.
117.
118.
119.
120.
121.
122.
123.
124.
Pol lutant
Pollutants
phenol
bls(2-ethylhexyl)
phthalate
d 1 -n-oct y 1 phtha 1 ate
antimony
arsenic
beryllium
cadmium
chromium (total)
copper
cyanide (total)
lead
mercury
nickel
CO!
Stream
Code
67
67
67
67
67
67
67
67
67
67
67
67
67
4MINGLED W
Sample
Typet
6
6
6
6
6
6
6
6
6
1
6
6
6
ASTEWATER SAMPL
ING DATA
»
H
3
3*
JO
Concentrations (mg/l) K
Source
0.00172
<0.002
<0.0050
<0.010
<0.050
<0.10
<0.010
0.29
<0. 100
<0.00!0
<0.0100
Day 1
0.0101
0.00382
0,00382
<0.002
0.058
<0,010
<0.050
0.12
0.015
0.082
-------
Table V-10 (Continued)
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
ACID PLANT SLOWDOWN
COMMINGLED WASTEWATER SAMPLING DATA
Pollutant
Toxic Pol lutants
125. selenium
126. silver
127. thallium
128. zinc
*>
O
m Nonconventional Pollutants
acidity
alkalinity
al uminum
ammonia nitrogen
bar i um
boron
calcium
chemical oxygen demand (COD)
Stream
Code
67
67
67
67
67
67
67
67
67
67
67
67
Sample
Typet
6
6
6
6
6
6
6
6
6
6
6
6
Concentrations (mg/l)
Source
<0.010
<0.002
<0.005
<0.050
<•
200
0.037
0.75
0.20
-------
Table V-IO (Continued)
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
ACID PLANT BLOWDOWN
COMMINGLED WASTE WATER SAMPLING DATA
Pollutant
Nonconventional Pol
chloride
goba 1 t
f luorlde
Iron
u>
•1*.
3 magnes i um
manganese
molybdenum
phenol ics
phosphate
sod i um
sul fate
tin
t i tan i um
total dissolved sol
Stream
Code
lutants (Continued)
67
67
67
67
67
67
67
67
67
67
67
67
67
ids (TDS) 67
Samp 1 e
Typet
6
6
6
6
6
6
6
6
6
6
6
6
6
6
Concentrations (mg/i)
Source
20
<0.10
0.68
0.230
15.6
0.0900
<0.020
<0.005
5
17
75
0.321
<0.020
430
Day 1
NA
<0.10
180
10.0
It. 1
1.89
0.30
0.019
NA
2,750
NA
<0.200
0.042
NA
Day 2
NA
<0.10
0.185
18.8
32.5
1.24
0.35
0.013
<4
5,020
<0.200
<0.020
NA
Day 3
NA
<0.10
120
31.2
33.2
1.19
1.00
<0.005
<8
5,500
<0.200
0.090
NA
PRIMA
8
*^t
3
O
§
d
a
2
i
o
M
55
M
W
o
w
Q
O
K
W
W
O
I
-------
o
00
Table V-IO (Continued)
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
ACID PLANT SLOWDOWN
.COMMINGLED WASTEWATER SAMPLING DATA
H
«
Stream Sample Concentrations (mg/l)
Pol lutant
Noncon vent 1 ona 1 Po 1 1 utants
total organic carbon (TOG)
total solids (TS)
vanadium
yttrium
Conventional Pollutants
oi 1 and grease
Code
(Continued)
67
67
67
67
67
total suspended solids (TSS) 67
pH (standard units)
tSample Type Code: 1 -
2 -
3 -
67
One-time grab
Typet Source
6 <1
6 500
6
w
NA §
^
w
w
o
4 - 8-hour automatic composite
5 - 24-hour manual composite
6 - 24-hour automatic composite
NA - Not analyzed.
*TSS was not analyzed because the sample was taken from the lime pit. Lime had already been added to the
wastewater.
-------
Table V-ll
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
ACID PUNT SLOWDOWN
TREATED WASTEWATER SAMPLING DATA
U)
o
VD
Toxic
54.
66.
68.
70.
114.
115.
117.
118.
119.
120.
121.
122.
123.
124.
Pollutant
Pol lutants
1 sophorone
bls(2-ethylhexyl)
phthalate
di-n-butyl phthalate
di ethyl phthalate
antimony
arsen 1 c
ber y 1 1 1 urn
cadmium
chromium (total)
copper
cyanide (total)
lead
mercury
nickel
Stream
Code
68
68
68
68
68
68
68
68
68
68
68
68
68
68
Sample
Typet
6
6
6
6
6
6
6
6
6
6
1
6
6
6
a
Concentrations (mg/l) jp
Source
0.00172
<0.002
< 0.0050
H
M
0.05 §
K
0.013 M
w
NA 8
i
<0*' <
-------
Table V-1! (Continued)
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
AGIO PLANT SLOWDOWN
TREATED WASTEHATER SAMPLING DATA
Pol lutant
Toxic Pollutants (Continued)
125. selenium
126. silver
127. thallium
128. zinc
CO
1 i
b Nonconventional Pollutants
acidity
alkalinity
aluminum
amroon 1 a n 1 trogen
bar i uni
boron
ca 1 c 1 um
chemical oxygen demand (COD)
cMor ide
Stream
Code
68
68
68
68
68
68
68
68
68
68
68
68
68
Sample
Typet
6
6
6
6
6
6
6
6
6
6
6
6
6
5
Concentrations (mg/l) j>
Source
<0.010
<0.002
<0.005
<0.05
<1
200
0.037
0.75
0.20
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATE60RY
ACID PLANT SLOWDOWN
TREATED WASTEWATER SAMPLING DATA
Pollutant
Nonconventlonal Pollutants
cobalt
f luoride
Iron
magnesium
oo
*; manganese
molybdenum
phenol Ics
phosphate
sod 1 urn
sulfate
tin
1 1 tan 1 urn
total organic carbon (TOG)
Stream
Code
(Continued)
68
68
68
68
68
68
68
68
68
68
68
68
68
Sample
Typet
6
6
6
6
6
6
6
6
6
6
6
6
6
Concentrations (mg/l) i>
Source
<0. 1
0.68
0.23
15.6
0.090
<0.0200
<0.005
5
17
75
0.321
<0.02
-------
Table V-11 (Continued)
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
riVnf i t-r • *-*«* • fe'tM.xfnh'wniv
TREATED WASTEWATER SAMPLING DATA
Pollutant
Noncon ven t 1 ona 1 Po 1 1 utant s
total, solids (TS)
vanadium
yttrium
Convent 1 ona 1 Po 1 1 utants
ol 1 and grease
Stream
Code
(Continued)
68
68
68
68
total suspended solids (TSS) 68
pH (standard units)
tSample Type Code; 1 -
2 -•
3 -
4 -
5 .
68
One- time grab
Sample Concentrations (mg/l)
Typet Source Day 1 Day 2 Day 3
6 500 14,000 14,500 14,000
6 <0.0i <0.1 <0.1 <0.1
6 0.056 0.10 0.043 0.077
1
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - V
TABLE V-12
PRIMARY MOLYBDENUM AND RHENIUM SAMPLING DATA
MOLYBDIC OXIDE LEACHATE
RAW WASTEWATER SELF-SAMPLING DATA
Pollutant
Concentration (mg/1)
115. arsenic 0.218
117. beryllium <0.050
118. cadmium 0.180
119. chromium 1.380
120. copper 125.000
122. lead 9.490
124. nickel 1.900
125. selenium <0.010
128. zinc 7.500
Npncpnyen tiona1 Pollutants
Aluminum 370.000
Ammonia - N 22000.000
Cobalt <0.500
Iron 880.000
Fluoride 0.020
Manganese 11.000
Molybdenum 206.000
Tin 8.000
Titanium 6.400
Vanadium <1.000
3413
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - V
Source Water
Acid
Plant
Slowdown
Other
NFM Wastewater
69
781
H2S
Lime.
NaOH
Rainfall '
Non-Scope
Streams
Pressure
Filter
Molybdenum
to Roaster
Pressure
Filter
.^Selenium
to Storage
782
Lime Pit
XN
67
Settling
Ponds
68
Discharge
co Creek
Figure V-1
SAMPLING SITES AT PRIMARY MOLYBDENUM PLANT B
3414
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
SECT - V
Source Water
54
Reduceion
Furnace
Scrubber
.Water
55
(Discharge
'to River
Figure V-2
SAMPLING SITES AT PRIMARY MOLYBDENUM PLANT C
3415
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - V
HC1, NHCl
1
Technical Grade
Holybdic Oxida
Leaching
Filter Press
Pure
Molybdic
Oxide
Contract
Hauling
Figure V-3
SAMPLING SITES AT PRIMARY MOLYBDENUM PLANT D
3416
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - VI
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
Section V of this supplement presented data from primary
molybdenum and rhenium plant sampling visits and subsequent
chemical analyses. This section examines that data and discusses
the selection or exclusion of pollutants for potential
limitation.
Raw wastewater characteristics data obtained following proposal
were not included in the pollutant selection analysis. The data
obtained following proposal were useful in supporting the
proposed pollutant selection because the priority pollutants
selected for further consideration at proposal were all detected
in excess of their treatable concentration in the new data, with
the exception of selenium. In addition, the new data show the
two conventional pollutant parameters selected for Limitation in
this subcategory (total suspended solids and pH) and the three
nonconventional pollutants analyzed for and selected for
limitation (ammonia, fluoride and molybdenum), in excess of their
treatable concentrations.
The discussion that follows presents and briefly discusses the
selection of conventional and nonconventional pollutants for
effluent limitations. Also described is the analysis that was
performed to select or exclude priority pollutants for further
consideration for limitations and standards. Pollutants will be
considered for limitation if they are present in concentrations
treatable by the technologies considered in this analysis. The
treatable concentrations used for the priority metals were the
long-term performance values achievable by chemical
precipitation, sedimentation, and filtration. The treatable
concentrations used for the priority organics were the long-term
performance values achievable by carbon adsorption.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS
This study examined samples from the primary molybdenum and
rhenium subcategory for three conventional pollutant parameters
(oil and grease, total suspended solids, and pH) and the
nonconventional pollutant parameters ammonia, fluoride, and
molybdenum.
On March 18, 1984, the Agency published a Notice of Data
Availability which stated that EPA was considering regulating the
nonconventional metal pollutant rhenium in this subcategory. For
promulgation, EPA has decided not to regulate rhenium because it
will be effectively controlled by the limitations developed for
the selected priority metal pollutants and the nonconventional
metal pollutant molybdenum.
3417
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - VI
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS SELECTED
The conventional and nonconventional pollutants or pollutant
parameters selected for limitation in this subcategory are:
ammonia
fluoride
molybdenum
total suspended solids (TSS)
pH
Treatable levels of ammonia are known to be present in
wastewaters resulting from ammonium molybdate production. Data
obtained during a post proposal sampling episode at a primary
molybdenum plant show an ammonia concentration in molybdic oxide
leachate of 3,400 mg/1. This value is in excess of the 32.2 mg/1
considered achievable by treatment technology. Ammonia is
therefore selected for limitation in this subcategory.
At proposal, the Agency stated that it was considering limiting
fluoride in this subcategory, and solicited comments from
industry. Following review of these comments, the Agency has
decided to limit fluoride based on its presence in the raw
wastewater from this subcategory. Effluent limitations for
fluoride are based on treatment effectiveness concentrations of
19.9 mg/1 for the monthly average and 35 mg/1 for the daily
maximum.
Molybdenum was found in four of four raw waste samples ranging
from 1.69 mg/1 to 29 mg/1. In addition, post-proposal sampling
data show molybdenum detected in molybdic oxide leachate at 440
mg/1. Because molybdenum was detected in excess of its treatable
concentration, it is selected for limitation in this subcategory.
Total suspended solids (TSS) concentrations ranging from less
than 1 to 87 mg/1 were observed in the six raw waste samples
analyzed for this study. Four of the concentrations are above
the 2.6 mg/1 treatable concentration. Most of the specific
methods used to remove priority metals do so by converting these
metals to precipitates, and these metal-containing precipitates
should not be discharged. Meeting a limitation on total
suspended solids helps ensure that removal of these precipitated
toxic metals has been effective. For these reasons, total
suspended solids are selected for limitation in this subcategory.
The six pH values observed during this study ranged from 0.72 to
9.6. Three of the six values were equal to or less than 1.24.
Many deleterious effects are caused by extreme pH values or rapid
changes in pH. Also, effective removal of toxic metals by
precipitation requires careful control of pH. Since pH control
within the desirable limits is readily attainable by available
treatment, pH is selected for limitation in t..--.-. ? subcategory
3418
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - VI
TOXIC PRIORITY POLLUTANTS
The frequency of occurrence of the priority pollutants in the raw
wastewater samples taken is presented in Table VI-1 {page 3422).
Table VI-1 is based on the raw wastewater data from streams 55
and 781 (see Section V) and data contained in the confidential
record. It is not based on data received after proposal. These
data provide the basis for the categorization of specific
pollutantSf as discussed below. Treatment plant samples were not
considered in the frequency count.
TOXIC POLLUTANTS NEVER DETECTED
The toxic pollutants listed in Table Vl-2 (page 3426) were not
detected in any raw wastewater samples from this subcategory.
Therefore, they are not selected for consideration in
establishing limitations.
TOXIC POLLUTANTS NEVER FOUND ABOVE THEIR ANALYTICAL
QUANTIFICATION CONCENTRATION
The toxic pollutants listed below were never found above their
analytical quantification concentration in any raw wastewater
samples from this subcategoryj therefore, they are not selected
for consideration in establishing limitations.
44. methylene chloride
104. gamma-BBC
114. antimony
127. thallium
TOXIC POLLUTANTS PRESENT BELOW CONCENTRATIONS ACHIEVABLE BY
TREATMENT
The pollutants listed below are not selected for consideration in
establishing limitations because they were not found in any raw
wastewater samples from this subcategory above concentrations
considered achievable by existing or available treatment
technologies. These pollutants are discussed individually
following the list.
117. beryllium
118. cadmium
121. cyanide
123. mercury
Beryllium was detected above quantification concentrations in
three out of eight raw wastewater samples. All three values were
0.01 mg/1 which is significantly below the concentration
considered achievable by identified treatment technology (0.20
mg/1). Beryllium is therefore not selected for limitation.
Cadmium was detected above quantification concentrations in only
one out of eight raw wastewater samples. The observed
concentration is 0.040 mg/1, which is below the concentration
3419
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - VI
considered achievable by identified treatment technology (0.049
mg/1). Cadmium is therefore not selected for limitation.
Cyanide was detected above quantification concentrations in two
out of six raw wastewater samples. The observed concentrations
were 0.032 mg/1 and 0.033 mg/1. Because both of these values are
below the concentration considered achievable by available
treatment technology, 0.047 mg/1, cyanide is not selected for
limitation.
Mercury was detected above quantification concentrations in three
out of eight raw wastewater samples at concentrations of 0.0088
mg/1, 0.0180 mg/1, and 0.0045 mg/1. Because all three of these
values are below the concentration considered achievable by
identified treatment technology, mercury is not selected for
regulation.
TOXIC POLLUTANTS DETECTED IN A SMALL NUMBER OP SOURCES
The following pollutant was not selected for limitation on the
basis that it is detectable in the effluent from only a small
number of sources within the subcategory and it is uniquely
related to only those sources.
126. silver
Although this pollutant was not selected for limitation in
establishing nationwide regulations, it may be appropriate, on a
case-by-case basis, for the local permit authority to specify
effluent limitations.
Silver was detected above the treatable level for silver (0.07
mg/1) in only one out of eight raw waste samples. The observed
concentration is 0.18 mg/1. The silver concentrations observed
in the other seven samples analyzed were all below the analytical
quantification level. The Agency has no reason to believe that
treatable silver concentrations should be present in primary
molybdenum wastewaters and believes that this one value is not
representative of the subcategory. Silver is therefore not
selected for limitation.
TOXIC POLLUTANTS SELECTED FOR FURTHER CONSIDERATION IN
ESTABLISHING LIMITATIONS AND STANDARDS
The toxic pollutants listed below are selected for further
consideration in establishing limitations and standards for this
subcategory. The priority pollutants selected for further
consideration for limitation are each discussed following the
list.
115. arsenic
119. chromium
120. copper
122. lead
124. nickel
3420
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - VI
125. selenium
128. zinc
Arsenic was detected above the level considered achievable by
identified treatment technology (0.34 mg/1) in four out of eight
raw wastewater samples. The treatable concentrations observed
range from 0.517 mg/1 to 12.4 mg/1. Arsenic may be present as an
impurity in molybdenite ore concentrates. For these reasons,
arsenic is selected for further consideration for limitation.
Chromium was detected above the level considered achievable by
identified treatment technology (0.07 mg/1) in four out of eight
raw wastewater samples. The treatable concentrations observed
range from 3.08 mg/1 to 13.0 mg/1. Because of the treatable
levels observed and because chromium may be present as an
impurity in molybdenite ore concentrates, chromium is selected
for further consideration for limitation.
Copper was detected above its treatability level of 0.07 mg/1 in
three of eight raw wastewater samples. The treatable
concentrations ranges in value from 0.54 mg/1 to 2.92 mg/1.
Copper is therefore selected for further consideration for
limitation.
Lead was detected above the treatability level of O.Q8 mg/1 in
six out of eight raw wastewater samples. The observed values
ranged from 0.17 mg/1 to 9.4 mg/1. Lead is therefore selected
for further consideration for limitation.
Nickel was detected above the treatable level of 0.22 mg/1 in six
out of eight raw wastewater samples. The observed values ranged
from 0.66 mg/1 to 4.60 mg/1. Nickel is therefore selected for
further consideration for limitation.
Selenium was detected above the level considered achievable by
available technology in four out of eight raw wastewater samples.
The treatable concentrations observed ranged from 0.784 to 61.2
mg/1. Because of the treatable concentrations observed and
because selenium may be present as an impurity in the molybdenite
ore concentrate, selenium is selected for further consideration
for limitation.
Zinc detected above its treatable level of 0.23 mg/1 in five out
of eight raw wastewater samples. The observed values ranged from
0.51 to 8.2 mg/1. Zinc is therefore selected for further
consideration for limitation.
3421
-------
Table Vl-l
tv)
FREQUENCY OF OCCURRENCE OF PRIORITY POLLUTANTS
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
RAW WASTEWATER
Pollutant
I . aceiiaphthene
2. acroleln
1. acrylonltrlle
'.».
b.
7.
H.
9.
10.
II.
12.
13.
14.
IS.
16.
U.
la.
13.
22.
2).
24.
25.
26.
27.
28.
29.
3ft.
31.
32.
33.
34.
carbon CeCrachloride
chlorubenzene
I ,2,4-trlchlorobanzene
hcxachlorobenzene
1,2-dtchloroethane
1,1,1-trlchloroethane
hexachloroethane
1,1-dtchloroethane
1,1,2-trlchloroethane
1,1,2,2-tetrachLoroethane
chloroethane
.M3(chlororaethyl) ether
Did(2-chloroediyl) ether
2-chloroethyl vinyl ether
2-chluronapntlialene
.1,4,6-crlchloraphenol
parechlororaeta cresol
chlurofom
2-chlorophenul
2-dLchlorubenzene
3-dlchlorubenzene
4~dlchlorobenzene
3,3'-dk'hlorobenztdlne
, 1 -dichloroethylene
, 2-trana-dtchloroethy lene
2,4-dichlorophenol
,2-dtchLoropropane
,3-dIdilorupropylene
2,4-dlaethylphenul
Analytical
Quant IClcac ion
Concent radon
(oR/l)(a)
0.010
0.010
0.010
0.010
o.oto
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
Treatable
Concentra-
tion
(ns/lKb)
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.0 1
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.0)
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
H
3
Nuaber of
Stream
Analyzed
timber of
Saoplea
Analyzed
Detected Below
Quantification
Concentration
Detected
Below Treat-
able Concen-
tration
Detected
Above Treat-
able Concert-
tratlon
«
§
'
D
M
55
g
M
55
H
en
a
o
M
Q
O
a
cn
M
O
-------
Table VI-1 (Continued)
FREQUENCY OF OCCURRENCE OF PRIORITY POLLUTANTS
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
RAW MASTEWATER
H
3
LO
*k
W
U)
Pollutant
35. 2,4-dlnltrotoluene
36. 2.6-dinltrotolueoe
.37. l,2-dlphenylhydra*lne
38. ethylbenzene
39. fluoranthene
40. 4-ehlorophenyl phenyl ether
41. 4-brou»phenyi phenyl ether
42. bls(2-chloroi8Opropyl) etlier
43. bis(2-ehloroethoxy) oechane
44. nethylene chloride
45. methyl chloride
46. methyl bromide
47. bruaofora
48. dichlorobronoBethane
49. trlehlorofluoronethane
50. dlchlorodtfluarotKthane
51. chlorodlbrowodethane
52. hexachiorobutadlaite
53. hexaehloroeyclopentadiene
54. isophorone
55. naphthalene
56. nitrobenzene
57. 2-nitrophenol
58. 4-nltrophenol
59. 2,4-dlnitrophenol
60. 4,6-dlnltro-o-creaol
61. N-nltroaodlnethylaraine
62. N-nltrosodlphenylaralne
63. N-nitroaodi-n-propylamine
64. pentach loroptienol
65. phenol
66. bia(2-ethylhexyl) phthalate
67. butyl benzyl phthalate
68. dl-n-butyl ptithalate
Analytical
Quantification
Concentrat ion
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
Treatable
Concentra-
tion
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
Ntnber of
Stream
Analyzed
NuMber of
Saraplea
Analyzed
NO
Detected Below
Quantification
Concent ration
Detected
Below Treat-
able Concen-
tration
Detected
Above Treat-
able Concen-
tration
8
M
a
M
55
M
C
W
Q
O
a
w
w
o
H
-------
Table VI-1 (Continued)
FREQUENCY OF OCCURRENCE OF PRIORITY POLLUTANTS
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
RAW WASTEWATER
U)
J*
K>
*«.
Pollutant
69. dl-n-octyi phthalate
70. dlethyl plithalate
71. dimethyl phthalate
72. benzo(a)anthrac{r)e
73. beruo(a)py rents
74. 3,4-benzofluoranthene
75. benzo(k)fluoranchene
76. chrysene
77. acenaphthylene
78. enthracwa (c>
79. benzo(ghl)perylene
80. fluorene
81. phenanthrene (c)
82. dtbenzo(a,h)anthraccne
83. tndeno(l,2,3-cd)pyrene
84. pyrene
85. tetrachloroethylene
86. toluene
87. trichloroethylene
88. vinyl chloride
89. aldrln
90. dieldrln
91. chlordane
92. 4.4'-DOT
93. 4.4"-DEE
94. 4,4'-ODD
95. alpha-endosulfan
96. beta-endosulfan
97. endosulfan sulfate
98. endrln
99. endrln aldehyde
100. heptachlor
101. heptachlor epoxide
102. alpha-BHC
103. beta-BHC
Analytical
Quantification
Concentration
(•R/lKa)
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.010
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
Treatable
Concentra- Nwber of NuAer of
tlon Strew Samples
(m/I)(b) Analyzed Analyzed
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.0!
I
ND
Detected Below
Quantification
Concentration
Detected
Below Treat-
able Concen-
tration
Detected
Above Treat-
able Concen-
tration
25
H
W
G
CO
O
5
w
Q
O
H
w
M
O
H
-------
Table VI-1 (Continued)
FREQUENCV OF OCCURRENCE OF PRIORITY POLLUTANTS
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
RAW WASTEMATER
H
3!
Pollutant
104. gai«ua-BHC
105. delta-lilt,'
106. KJB-1242
10?. KB-1254
1U&. fCB-1221
109. HUB -1232
;io. rca-1248
III. WB-1260
112. WB-IOI6
113. toxaphene
ijj 114. antimony
ifc. 115. arsenic
w 116. asbestos
^117. berylllun
118. cadtplum
119. chroDiug
120. copper
121. cyanide
122. lead
123. mercury
124. nickel
125. selenium
126. silver
127. thallium
128. zinc
129. 2,3, ?,8-tet
(d)
(«>
(-1)
(e)
(e)
(e)
(e)
(i)
:racn
I»-dioxin (TCUU)
Analytical
(^jantiCication
Concentration
JaLVSsL...
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.100
0.010
10 rlFL
0.010
0.002
0.005
0.00V
0.02
0.020
0.0001
0.005
0.01
0.02
0.100
0.050
Nut Analyzed
Treatable
Concentra-
tion
(Bfc/lMb)
a 01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.01
0.47
0.34
10MKL
0.20
a 049
0.07
0.39
0.047
0.08
0.036
0.22
0.20
0.07
0.34
a 23
Niooer of
Streams
Analyzed
3
3
3
3
3
3
3
3
3
3
3
3
3
3
Number of
Saiiples
Analyzed
8
8
8
8
8
8
6
8
8
8
8
8
8
ND
Detected Below
quantification
Concentration
U; tected
He low 'it-eat-
able Concen-
tration
Detected
Above Treat-
able Concen-
tration
8
2
5
7
1
4
I
5
4
7
a
2
.3
1
3
4
2
1
3
2
4
3
b
4
1
(a) Analytical quantification concentration was reported with the data (see Section*/).
(b) Treatable concentrations are based on performance of chemical precipitation, sedimentation, and filtration.
(e), (ti), (e) Keported together.
(t) Analytical quantification concentration for Elft cfctnod 335.2, 'local Cyanide tfethods for Chemical Analysis of oiattic aid Pastes tin «JU/«»-?9-020
1979,
8
w
2!
H
w
a
w
o
I
o
o
»
K
w
w
o
H
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - VI
TABLE VI-2
TOXIC POLLUTANTS NEVER DETECTED
1. acenaphthene
2. acrolein
3. acrylonitrile
4. benzene
5. benzidene
6. carbon tetrachloride (tetrachloromethane)
7. chlorobenzene
8. 1,2,4-trichlorobenzene
9. hexachlorobenzene
10. 1,2-dichloroethane
11. 1,1,1-trichloroethane
12. hexachloroethane
13. 1,1-dichloroethane
14. 1,1,2-trichloroethane
15. l,lf2,2-tetrachloroethane
16. chloroethane
17. bis (chloromethyl) ether (DELETED)
18. bis (2-chloroethyl) ether
19. 2-chloroethyl vinyl ether (mixed)
2O. 2-chloronaphthalene
21. 2,4,6-trichlorophenol
22. parachlorometa cresol
23. chloroform (trichloromethane)
24. 4-chlorophenol
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. If4-dichlorobenzene
28. 3,3,-dichlorobenzidine
29. 1,1-dichloroethylene
30. 1.2-trans-dichloroerhylene
31. 4i-dichlorophenol
32. 1,4-dichloropropane
33. 1,2-dichloropropylene (1,3-dichloropropene)
34. 2,4-dimethylphenol
35. 4,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. 1,2-diphenylhydrazine
38. ethylbenzene
39. fluoranthene
40. 4-chlorophenol phenyl ether
41. 4-bromophenyl phenol ether
42. bis(2-chloroisopropyl) ether
43. bis{2-choroethoxyl) methane
45. methyl chloride (chloromethane)
46. methyl bromide (bromomethane)
47. bromoform (tribromomethane)
48. dichlorobromomethane
49. trichlorofluoromethane (DELETED)
3426
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - VI
TABLE VI-2 (Continued)
TOXIC POLLUTANTS NEVER DETECTED
50. dichlorodifluoromethane (DELETED)
51. chlorodibromomethane
52. hexaehlorobutadiene
53. hexachlorocyclopentadiene
54. isophorone
55. naphthalene
56. nitrobenzene
57. 2-nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 2,6-dinitro-o-cresol
61. N-nitrosodimethylamine
62. N-nitrosodiphenylamine
63. N-nitrosodi-n-propylamine
64. pentaehlorophenol
65. phenol
66. bis(2-ethylhexyl) phthalate
67. butyl benzyl phthalate
68. di-n-butyl phthalate
69. di-n-octyl phthalate
70. diethyl phthalate
71. dimethyl phthalate
72. benzo (a)anthracene (1,2-benzanthracene)
73. benzo (a)pyrene (3,4-benzopyrene)
74. 3f4-benzofluoranthene
75. benzo(k)fluoranthene (11,12-benzofluoranthene)
76. chrysene
77. acenaphthylene
78. anthracene
79. benzo(ghi)perylene (1,11-benzoperylene)
80. fluorene
81. phenanthrene
82. dibenzo (a,h)anthracene (1,2,4,6-dibenzanthracene)
83. indeno (l,2,3-cd)pyrene (,w,e,-o-phenylenepyrene)
84. pyrene
85. tetrachloroethylene
86. toluene
87. trichloroethylene
88. vinyl chloride (chloroethylene)
89. aldrin
90. dieldrin
91. chlordane (technical mixture and metabolites)
92. 4-DDT
93. 4,4'
94. 4,4'-DDE(p,p'DDX)
95. 4,4'-DDD(p,p'TDE)
96. a-endosulfan-Alpha
97. b-endosulfan-Beta
98. endosulfan sulfate
99. endrin
3427
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PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - VI
TABLE VI-2 (Contiued)
TOXIC POLLUTANTS NEVER DETECTED
100. endrin aldehyde
101. heptachlor
102. heptachlor epoxide
103. a-BHC-Alpha
104. b-BHC-Beta
105. c-BHC-Delta
106. PCB-1242 (Arochlor 1242)
107. PCB-1254 {Arochlor 1244)
108. PCB-1221 (Arochlor 1221)
109. PCB-1232 (Arochlor 1242)
110. PCB-1248 (Arochlor 1248)
111. PCB-1260 (Arochlor 1260)
112. PCB-1016 (Arochlor 1016)
113. toxaphene
116. asbestos
129. 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)
3428
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGOK* SECT - VII
SECTION VII
CONTROL AND TREATMENT TECHNOLOGIES
The preceding sections of this supplement discussed the sources,
flows, and characteristics of the wastewaters generated in the
primary molybdenum and rhenium subcategory. This section
summarizes the description of these wastewaters and indicates the
level of treatment which is currently practiced for each
wastewater stream. Secondly, this section presents the control
and treatment technology options which were examined by the
Agency for possible application to the primary molybdenum and
rhenium subcategory.
CURRENT CONTROL AND TREATMENT PRACTICES
This section presents a summary of the control and treatment
technologies that are currently applied to each of the sources
generating wastewater in this subcategory. As discussed in
Section V, wastewater associated with the primary molybdenum and
rhenium subcategory is characterized by the presence of the metal
priority pollutants, ammonia, fluoride, molybdenum, and suspended
solids. This analysis is supported by the raw (untreated)
wastewater data in Section V. Generally, these pollutants are
present in each of the waste streams at concentrations above
treatability, and these waste streams are commonly combined for
treatment. Construction of one wastewater treatment system for
combined treatment allows plants to bake advantage of economies
of scale, and in some instances, to combine streams of differing
alkalinity to reduce treatment chemical requirements. Three
plants in this subcategory currently have combined wastewater
treatment systems, consisting of chemical precipitation and
sedimentation. One of these three plants also practices ammonia
stripping. Three options have been selected for consideration
for BPT, BAT, NSPS, and pretreatment standards in this
subcategory, based on combined treatment of these compatible
waste streams.
MOLYBDENUM SULFIDE LEACHATE
One of the facilities surveyed reported the practice of leaching
and rinsing a portion of the molybdenite concentrate raw material
prior to roasting. The concentrate is leached with nitric acid
and rinsed with water to remove excess alkali. The leachate and
rinsewater are then discharged as a wastewater stream. This
waste stream has an acidic pH, and treatable levels of priority
metals and suspended solids. The one facility which reported
this waste stream discharges it to an on-site evaporation pond
and contract hauls a portion of the contents of the pond
periodically, thereby achieving zero discharge.
ROASTER SO2 SCRUBBER
Four facilities reported the use of caustic scrubbers to control
3429
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PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - VII
SO2 emissions from molybdenum sulfide roasting operations. The
blowdown from the caustic scrubber has an alkaline pH, and
treatable concentrations of suspended solids and priority metals.
All four facilities reporting this waste stream achieve zero
discharge through evaporation ponds, lagoon disposal, or
treatment and reuse in other plant processes. The specific
practices reported by the four facilities are:
1. Lime addition and sedimentation, recycle to other plant
processes;
2. Neutralization, permanent lagoon disposal (no recycle);
3. Use as feedstock for fertilizer plant; and
4. Tailings pond (96 percent recycle).
MOLYBDIC OXIDE LEACHATE
Technical grade molybdic oxide may be leached with nitric acid,
hydrochloric acid, aqueous ammonia, ammonium chloride, and water
either prior to dissolving and recrystallization to produce
ammonium molybdate or to produce pure molybdic oxide. The
leachate and rinsewater contain treatable levels of toxic metals,
suspended solids, and ammonia. For the three plants generating
this stream, the reported treatment practices for this waste
stream are as follows:
1. Ammonia steam stripping, lime addition, and sedimenta-
tion; and
2. Evaporation ponds and contract hauling - two plants.
HYDROGEN REDUCTION FURNACE SCRUBBER
Hydrogen gas from the reduction furnaces used to produce
molybdenum metal powder may be quenched or scrubbed with water
prior to reuse in the furnaces. Treatable concentrations of
toxic metals are present in the water discharged from the
scrubbing system. Of the two facilities reporting this wastewater
stream, one practices extensive recycle (>99 percent) and the
other practices no recycle. Both plants are direct dischargers
of this waste stream with no wastewater treatment practiced.
DEPLETED RHENIUM SCRUBBING SOLUTION
Rhenium is absorbed into solution from molybdenite roaster off-
gases in a wet scrubbing system. After the rhenium is recovered
from solution, the barren scrubber liquor is discharged as a
wastewater stream. Treatable concentrations of toxic metals,
particularly selenium, are present in this waste stream. Both of
the facilities reporting this waste stream achieve zero
discharge. The specific practices reported by these facilities
are:
1. Lime addition and sedimentation, total reuse in other
plant processes; and
2. Evaporation ponds and contract hauling.
3430
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PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - VII
CONTROL AND TREATMENT OPTIONS
The Agency examined three control and treatment technology
alternatives that are applicable to the primary molybdenum and
rhenium subcategory. The options selected for evaluation
represent a combination of in-process flow reduction,
pretreatment technology applicable to individual waste streams,
and end-of-pipe treatment technologies. These options are
discussed below.
OPTION A
The Option A treatment scheme consists of ammonia steam stripping
preliminary treatment applied to molybdic oxide leachate
wastewater. Also included is preliminary treatment consisting of
iron co-precipitation to reduce molybdenum concentrations. Iron
co-precipitation is applied to the combined stream of steam
stripper effluent, molybdenum sulfide leachate, roaster SO2
scrubber, hydrogen reduction furnace scrubber wastewater, and
depleted rhenium scrubbing solution. Preliminary treatment is
followed by chemical precipitation and sedimentation applied to
the iron co-precipitation effluent. Chemical precipitation is
used to remove metals by the addition of lime followed by gravity
sedimentation. Suspended solids are removed by this process.
OPTION B
Option B for the primary molybdenum and rhenium subcategory
consists of all treatment requirements of Option A (ammonia steam
stripping, iron co-precipitation, chemical precipitation, and
sedimentation) plus control technologies to reduce the discharge
of wastewater volume. Water recycle of hydrogen reduction
furnace scrubber liquor is the principal control mechanism for
flow reduction.
OPTION C
Option C for the primary molybdenum and rhenium subcategory
consists of all control and treatment requirements of Option B
(ammonia steam stripping, iron co-precipitation, in-process flow
reduction, chemical precipitation, and sedimentation) plus
multimedia filtration technology added at the end of the Option B
treatment scheme. Multimedia filtration is used to remove
suspended solids, including precipitates of metals, beyond the
concentration attainable by gravity sedimentation. The filter
suggested is of the gravity, mixed media type, although other
forms of filters such as rapid sand filters or pressure filters
would perform as well. The addition of filters also provides
consistent removal during periods in which there are rapid
increases in flows or loadings of pollutants to the treatment
system.
3431
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PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT -VII
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3432
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PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - VIII
SECTION VIII
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS
This section presents a summary of compliance costs for the
primary molybdenum and rhenium subcategory and a description of
the treatment options and subcategory-specific assumptions used
to develop these estimates. Together with the estimated
pollutant reduction performance presented in Sections IX, X, XI,
and XII of this supplement, these cost estimates provide a basis
for evaluating each regulatory option. These cost estimates are
also used in determining the probable economic impact of
regulation on the subcategory at different pollutant discharge
levels. In addition, this section addresses nonwater quality
environmental impacts of wastewater treatment and control
alternatives, including air pollution, solid wastes, and energy
requirements, which are specific to the primary molybdenum and
rhenium subcategory.
TREATMENT OPTIONS FOR EXISTING SOURCES
As discussed in Section VII, three treatment options have been
developed for existing primary molybdenum and rhenium sources.
The treatment schemes for each option are summarized below and
schematically presented in Figures X-l through X-3 (pages 3459
3461).
OPTION A
Option A consists of ammonia steam stripping and iron co-precipi-
tation preliminary treatment, and chemical precipitation and
sedimentation end-of-pipe technology.
OPTION B
Option B consists of in-process flow reduction measures, ammonia
steam stripping and iron co-precipitation preliminary treatment,
and chemical precipitation and sedimentation end-of-pipe
technology. In-process flow reduction consists of the recycle of
hydrogen reduction furnace scrubber water through holding tanks.
OPTION C
Option C requires the in-process flow reduction measures of
Option B, ammonia steam stripping and iron co-precipitation
preliminary treatment, and end-of-pipe treatment technology
consisting of chemical precipitation, sedimentation, and
multimedia filtration.
COST METHODOLOGY
A detailed discussion of the methodology used to develop the
compliance costs is presented in Section VIII of Vol. I. Plant-
3433
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PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - VIII
by-plant compliance costs for the nonferrous metals manufacturing
category have been revised as necessary following proposal.
These revisions calculate incre-mental costs, above treatment
already in place, necessary to comply with the promulgated
effluent limitations and standards, and are presented in the
administrative record supporting this regulation. A comparison
of the costs developed for proposal and the revised costs for the
final regulation are presented in Table VIII-1 (page 3437) for
the direct dischargers in the primary molybdenum and rhenium
subcategory.
Each of the general assumptions used to develop compliance costs
is presented in Section VIII of the General Development Document.
Each subcategory also contains a unique set of waste streams
requiring certain subcategory specific assumptions to develop
compliance costs. The major assumptions specific to the primary
molybdenum and rhenium subcategory are discussed briefly below.
(1) Cost for the removal of molybdenum are included in
the treatment system costs. Molybdenum treatment
effectiveness concentrations, based on iron co-
precipitation, are estimated to be 1.83 and 1.23 mg/1 for
iron co-precipitation and iron co-precipitation with
filtration, respectively.
(2) Costs for plants having total flows of less than 100
1/hr were based on the general guidelines established
for low flows.
ENERGY REQUIREMENTS
Energy requirements for Option A are estimated at 103,000 kwh/yr.
Option B energy requirements decrease over those for Option A
because less water is being treated, thus saving energy costs for
lime and settle treatment. Option C, which includes filtration,
is estimated to increase energy consumption over Option B by
approximately 1 percent. Further, the total energy requirement
for Option C is approximately 1 percent of the estimated total
plant energy usage. It is therefore concluded that the energy
requirements of the treatment options considered will have no
significant impact on total plant energy consumption. Iron co-
precipitation is not expected to significantly increase the
energy requirements in this subcategory.
SOLID WASTE
Sludges associated with the primary molybdenum and rhenium
subcategory will necessarily contain quantities of metal priority
pollutants. Wastes generated by primary smelters and refiners
are currently exempt from regulation by Act of Congress (Resource
Conservation and Recovery Act (RCRA), Section 3001(b)), as
interpreted by EPA. Consequently, sludges generated from
treating primary molybdenum and rhenium wastewater, including
metallurgical acid plants wastewater, are not presently subject
to regulation as hazardous wastes.
3434
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PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - VIII
The technology basis for the metallurgical acid plants includes
sulfide precipitation for the control of various toxic metals.
The Agency believes sludge generated through sulfide
precipitation (and sedimentation or pressure filtration) will be
classified as hazardous under RCRA. The costs of hazardous waste
disposal were considered in the economic analysis for this
subcategory (in spite of the current statutory and regulation
exemption) because sulfide will not form metal hydroxides that
resist leaching. The costs of hazardous waste disposal were
determined to be economically achievable. However, lime sludges
are not expected to be hazardous. This judgment is based on the
results of Extraction Procedure (EP) toxicity tests performed on
similar sludges (toxic metal-bearing sludges) generated by other
industries such as the iron and steel industry. A small amount
of excess lime was added during treatment, and the sludges
subsequently generated passed the toxicity test. See 40 CFR Part
261.24. Thus, the Agency believes that the wastewater sludges
will similarly not be EP toxic if the recommended technology is
applied.
If these wastes should be identified or are listed as hazardous,
they will come within the scope of RCRA's "cradle to grave"
hazardous waste management program, requiring regulation, from
the point of generation to point of final disposition. EPA's
generator standards would require generators of hazardous
nonferrous metals manufacturing wastes to meet containerization,
labeling, recordkeeping, and reporting requirements; if plants
dispose of hazardous wastes off-site, they would have to prepare
a manifest, which would track the movement of the wastes from the
generator's premises to a permitted off-site treatment, storage,
or disposal facility. See 40 CFR 262.40, 44 FR 33144 (May 19,
1980), as amended at 45 FR 86974 (December 31, 1980). The
transporter regulations require transporters of hazardous
wastes to comply with the manifest system to assure that the
wastes are delivered to a permitted facility. See 40 CFR
263.20, 45 33151 (May 19, 1980), as amended at 45 FR 86973
(December 31, 1980). Finally, RCRA regulations establish
standards for hazardous waste treatment, storage, and disposal
facilities allowed to receive such wastes. See 40 CFR Part
464, 46 FR 2802 (January 12, 1981), and 47 FR 32274 (July 26,
1982).
Even if these wastes are not identified as hazardous, they still
must be disposed of in compliance with the Subtitle D open
dumping standards, implementing Section 4004 of RCRA. (See 44 FR
54438, September 13, 1979). The Agency has calculated as part of
the costs for wastewater treatment the cost of hauling and
disposing of these wastes. For more details, see Section VIII of
the general development document.
It is estimated that 109 kkg/yr of sludge will be generated as a
result of these promulgated regulations for the primary
molybdenum and rhenium subcategory.
3435
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PRIMARY MOLYBDEN0M AND RHENIUM SUBCATEGORY SECT - VIII
AIR FOLL0TIOH
There is no reason to believe that any substantial air pollution
problems will result from implementation of ammonia steam
stripping, iron co-precipitation, chemical precipitation,
sedimentation and multimedia filtration. Ammonia steam
stripping yields an aqueous ammonia product stream. The other
technologies transfer pollutants to solid waste and are not
likely to transfer pollutants to air.
3436
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - VIII
TABLE VIII-1
COST OF COMPLIANCE FOR THE PRIMARY MOLYBDENUM
AND RHENIUM SUBCATEGORY
DIRECT DISCHARGERS
Compliance costs for this subeategory cannot be presented here
because the data on which they are based have been claimed to be
confidential.
3437
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - VIII
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3438
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - IX
SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY AVAILABLE
This section defines the effluent characteristics attainable
through the application of best practicable control technology
currently available (BPT). BPT reflects the performance by
existing plants of various sizes, ages/ and manufacturing
processes within the primary molybdenum and rhenium subcategory,
as well as the established performance of the recommended BPT
systems. Particular consideration is given to the treatment
already in place at existing plants.
The factors considered in identifying BPT include the total cost
of applying the technology in relation to the effluent reduction
benefits from such application, the age of equipment and
facilities involved, the manufacturing processes used, nonwater
quality environmental impacts (including energy requirements),
and other factors the Administrator considers appropriate. In
general, the BPT level represents the average of the existing
performances of plants of various ages, sizes, processes, or
other common characteristics. Where existing performance is
uniformly inadequate, BPT may be transferred from a different
subcategory or category. Limitations based on transfer of
technology are supported by a rationale concluding that the
technology is indeed transferable, and a reasonable prediction
that it will be capable of achieving the prescribed effluent
limits. BPT focuses on end-of-pipe treatment rather than process
changes or internal controls except where such practices are
common industry practice.
TECHNICAL APPROACH TO BPT
The Agency studied the nonferrous metals category to identify the
processes used, the wastewaters generated, and the treatment
processes installed. Information was collected from the category
using data collection portfolios, and specific plants were
sampled and the wastewaters analyzed. In making technical
assessments of data, reviewing manufacturing processes, and
assessing wastewater treatment technology options, both indirect
and direct dischargers have been considered as a single group.
An examination of plants and processes did not indicate any
process differences based on the type of discharge, whether it be
direct or indirect.
As explained in Section IV, the primary molybdenum and rhenium
subcategory has been subdivided into five potential wastewater
sources. Since the water use, discharge rates, and pollutant
characteristics of each of these wastewaters is potentially
unique, effluent limitations will be developed for each of the
five subdivisions
For each of the subdivisions, a specific approach was followed
for the development of BPT mass limitations. The first
3439
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PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - IX
requirement to calculate these limitations is to account for
production and flow variability from plant to plant. Therefore,
a unit of production or production normalizing parameter (PNP)
was determined for each waste stream which could then be related
to the flow from the process to determine a production normalized
flow. Selection of the PNP for each process element is discussed
in Section IV. Each plant within the subcategory was then
analyzed to determine which subdivisions were present, the
specific flow rates generated for each subdivision, and the
specific production normalized flows for each subdivision. This
analysis is discussed in detail in Section V. Nonprocess
wastewaters such as rainfall runoff and noncontact cooling water
are not considered in the analysis.
Production normalized flows for each subdivision were then
analyzed to determine the flow to be used as part of the basis
for BPT mass limitations. The selected flow (sometimes referred
to as the BPT regulatory flow or BPT discharge rage) reflects the
water use controls which are common practices within the
category. The BPT regulatory flow is based on the average of all
applicable data. Plants with normalized flows above the average
may have to implement some method of flow reduction to achieve
the BPT limitations.
The second requirement to calculate mass limitations is the set
of concentrations that are achievable by application of the BPT
level of treatment technology. Section VII discusses the various
control and treatment technologies which are currently in place
for each wastewater source. In most cases, the current control
and treatment technologies consist of chemical precipitation and
sedimentation (lime and settle technology) and a combination of
reuse and recycle to reduce flow. Ammonia steam stripping is
applied to streams with treatable concentrations of ammonia.
Iron co-precipitation is applied to streams with treatable
concentrations of molybdenum.
Using these regulatory flows and the achievable concentrations,
the next step is to calculate mass loadings for each wastewater
source or subdivision. This calculation was made on a stream-by-
stream basis, primarily because plants in this subcategory may
perform one or more of the operations in various combinations.
The mass loadings (milligrams of pollutant per metric ton of
production - mg/kkg) were calculated by multiplying the BPT
regulatory flow (1/kkg) by the concentration achievable by the
BPT level of treatment technology (mg/1) for each pollutant
parameter to be limited under BPT. These mass loadings are
published in the Federal Register and in CFR Part 421 as the
effluent limitations guidelines.
The mass loadings which are allowed under BPT for each plant will
be the sum of the individual mass loadings for the various
wastewater sources which are found at particular plants.
Accordingly, all the wastewater generated within a plant may be
combined for treatment in a single or common treatment system,
3440
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - IX
but the effluent limitations for these combined wastewaters are
based on the various wastewater sources which actually contribute
to the combined flow. This method accounts for the variety of
combinations of wastewater sources and production processes which
may be found at primary molybdenum and rhenium plants.
The Agency usually establishes wastewater limitations in terms of
mass rather than concentration. This approach prevents the use
of dilution as a treatment method (except for controlling pH).
The production normalized wastewater flow (1/kkg) is a link
between the production operations and the effluent limitations.
The pollutant discharge attributable to each operation can be
calculated from the normalized flow and effluent concentration
achievable by the treatment technology and summed to derive an
appropriate limitation for each plant.
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
In balancing costs in relation to pollutant removal benefits, EPA
considers the volume and nature of existing discharges, the vol-
ume and nature of discharges expected after application of BPT,
the general environmental effects of the pollutants, and the cost
and economic impacts of the required pollution control level. The
Act does not require or permit consideration of water quality
problems attributable to particular point sources or industries,
or water quality improvements in particular water quality bodies.
Accordingly, water quality considerations were not the basis for
selecting the proposed or promulgated BPT. See Weyerhaeuser
Company v. Costle, 590 F.2d 1011 (D.C. Cir. 1978).
The methodology for calculating pollutant removal estimates and
plant compliance costs is discussed in Section X. The pollutant
removal estimates have been revised since proposal based on com-
ments. Table X-2 show the estimated pollutant removal estimates
for each treatment option for direct dischargers. Compliance
costs for each option are presented in Table X-3.
BPT OPTION SELECTION
The technology basis for the promulgated BPT limitations is
chemical precipitation and sedimentation technology to remove
metals and solids from combined wastewaters and to control pH,
and ammonia steam stripping and iron co-precipitation preliminary
treatment. Ammonia stripping, chemical precipitation and
sedimentation technologies are already in-place at one of the two
dischargers in the subcategory. The best practicable technology
is presented in Figure IX-1. The BPT treatment is equivalent to
Option A described in Section VII.
Ammonia steam stripping is demonstrated at six facilities in the
nonferrous metals manufacturing category. These facilities are
treating ammonia bearing wastewaters associated with the produc-
tion of primary tungsten, primary columbium and tantalum, primary
molybdenum, secondary tungsten and cobalt, and primary zirconium
and hafnium. EPA believes that performance data from the iron
3441
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PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - IX
and steel manufacturing category provide a valid measure of this
technology performance on nonferrous metals manufacturing
category wastewater because raw wastewater concentrations of
ammonia are of the same order of magnitude in the respective raw
wastewater matrices.
Chemical analysis data were collected of raw waste (treatment
influent) and treated waste (treatment effluent) from one coke
plant of the iron and steel manufacturing category. A contractor
for EPA, using EPA sampling and chemical analysis protocols,
collected six paired samples in a two-month period. These data
are the data base for determining the effectiveness of ammonia
steam stripping technology and are contained within the public
record supporting this document. Ammonia treatment at this coke
plant consisted of two steam stripping columns in series with
steam injected countercurrently to the flow of the wastewater. A
lime reactor for pH adjustment separated the two stripping
columns.
The Agency has verified the proposed and promulgated steam strip-
ping performance values using steam stripping data collected at a
zirconium-hafnium plant, which has raw ammonia levels as high as
any in the nonferrous metals manufacturing category. Data
collected by the plant represent almost two years of daily
operations, and support the long-term mean used to establish
treatment effectiveness.
In addition, data submitted by a primary columbium-tantalum
plant, which also has significant raw ammonia levels, verifies
the promulgated steam stripping performance values.
Implementation of the promulgated BPT limitations will remove
annually an estimated 73,631 kg of priority metals, 736 kg of
molybdenum, 63,443 kg of ammonia, and 51,529 kg of TSS over
estimated current discharge. While both discharging plants have
the equipment in-place to comply with BPT, we do not believe that
the plants are currently achieving the BPT mass limitations. The
estimated capital and annual cost for achieving the promulgated
BPT cannot be presented here because the data on which they are
based have been claimed to be confidential.
More stringent technology options were not selected for BPT since
they require in-process changes or end-of-pipe technologies less
widely practiced in the subcategory, and, therefore, are more
appropriately considered under BAT.
WASTEWATER DISCHARGE RATES
A BPT discharge rate is calculated for each subdivision based on
the average of the flows of the existing plants, as determined
from analysis of dcp. The discharge rate is used with the
achievable treatment concentration to determine BPT effluent
limitations. Since the discharge rate may be different for each
wastewater source, separate production normalised discharge rates
for each of the five wastewater sources are discussed below and
3442
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PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - IX
summarized in Table IX-1 (page 3446). The discharge rates are
normalized on a production basis by relating the amount of
wastewater generated to the mass of the product which is produced
by the process associated with the waste stream in question.
These production normalizing parameters, or PNPs, are listed in
Table IX-1.
Section V of this document further describes the discharge flow
rates and presents the water use and discharge flow rates for
each plant by subdivision.
MOLYBDENUM SULFIDE LEACHATE
The BPT wastewater discharge rate for proposal and promulgation
for molybdenum sulfide leaching is 463 1/kkg (112 gal/ton) of
molybdenum sulfide concentrate leached prior to roasting. This
rate is allocated only to facilities which leach molybdenum
sulfide concentrates to remove excess alkali, prior to roasting.
One of the seven plants which roasts molybdenite practices
leaching prior to roasting. The water use and discharge rate are
presented in Table V-l. This facility currently achieves zero
discharge of this stream through the use of evaporation ponds and
contract hauling. The possibility for achieving zero discharge
of this stream in this manner is site-specific and therefore not
applicable on a nationwide basis. The leaching and rinsing flow
reported by this facility was used as the basis for the BPT flow
allowance for this stream.
ROASTER SO2 SCRUBBER
The BPT wastewater discharge rate for proposal and promulgation
for molybdenite roaster SO2 scrubber wastewater is 1,679 1/kkg
(404 gal/ton) of molybdenum sulfide roasted. This rate is
allocated only to those plants which use scrubbers to control SO2
emissions from molybdenum sulfide roaster flue gases. Four of
the seven plants which roast molybdenum sulfide concentrates use
scrubbers to control SO2 emissions. Three of these facilities
use caustic scrubbers and achieve zero discharge through the use
of tailings ponds or permanent impoundments. One facility uses
an ammonia scrubbing solution and achieves zero discharge by
using the scrubber liquor as feed material to a fertilizer plant.
One of the four facilities did not report actual flow rates for
this stream. The BPT flow rate was based on the production
normalized flows from two facilities which reported flow rates
for scrubbing systems. The production normalized flow reported
by plant 1174 was not used because the reported water use was
inordinately high, and not characteristic of effective wet air
pollution control systems.
MOLYBDIC OXIDE LEACHATE
The BPT wastewater discharge rate at promulgation for molybdic
oxide leachate is 11,584 1/kkg (2,782 gal/ton) of molybdenum
contained in the molybdic oxide leached. This rate is not
equivalent to the proposed BPT rate of 7,630 1/kkg of ammonium
3443
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - IX
molybdate product. This rate was revised following proposal
based on additional flow and production data obtained by the
Agency through a field sampling effort at plant 1099. In
additionf the flows for plants 1146 and 1064 have been revised in
Table V-3 based on the fact that 49 percent of ammonium molybdate
(by weight) is molybdenum.
The promulgated rate is applicable only to those plants which
leach molybdic oxide to increase its purity. This practice is
often associated with the production of ammonium molybdate
compounds. The water use and discharge rates for three of the
facilities which practice molybdic oxide leaching are presented
in Table V-3. The remaining plant which leaches molybdic oxide
uses an evaporator in the process and generates no wastewater. A
representative for the facility, however, indicated that they
plan to change from the evaporative process and will need to
discharge wastewater in the near future. The BPT regulatory flow
was based on the average production normalized water use of the
three plants which reported discharging this wastewater (plants
1099, 1146, and 1064). One of the three plants which generates
process wastewater from the ammonium molybdate process achieves
zero discharge through the use of an evaporation pond and
contract hauling. The possibility for achieving zero discharge
in this manner is site-specific and therefore not applicable on a
nationwide basis.
HYDROGEN REDUCTION FURNACE SCRUBBER
The BPT wastewater discharge rate at proposal and promulgation
for hydrogen reduction furnace scrubbing is 22,898 1/kkg (5,505
gal/ton) of molybdenum metal powder produced. This rate is
applicable only to those plants which practice wet scrubbing of
hydrogen gas used in reduction furnaces. Two of the four plants
which use reduction furnaces to produce molybdenum metal powder
from either pure molybdic oxide or ammonium molybdate reported
the use of wet scrubbing. The water use and discharge rates are
presented in Table V-4 (page 3385). The BPT flow rate is based
on the average of the water use at these two facilities. One of
the facilities reported 0 percent recycle. The other facility
reported recycle but did nou specify the recycle ratio. The
recycle ratio at this facility was assumed to be 99 percent and
the water use was calculated from the discharge rate by dividing
the discharge flow by 0.01, yielding a water use of 2,000 1/kkg.
The water use and discharge flow rates for the facility which
practices no recycle are the same. This facility reported a
reduction furnace scrubber flow rate of 43,795 1/kkg. The BPT
flow rate is based on the average of the water use rates at these
two facilities.
DEPLETED RHENIUM SCRUBBING SOLUTION
The BPT wastewater discharge rate at proposal and promulgation
for depleted rhenium scrubbing solution is 716 1/kkg (173
gal/ton) of molybdenum sulfide roasted. This rate is applicable
only to those facilities which recover crude ammonium perrhenate
3444
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - IX
from molybdenite roaster flue gases. Two of the seven plants
which roast molybdenite concentrates reported that they recover
rhenium from roaster flue gases. The water use and discharge
rates are presented in Table V-5 (page 3386). Both of the
facilities which practice rhenium recovery achieve zero discharge
through the use of evaporation ponds, contract hauling or recycle
to other plant processes. The possibility of achieving zero
discharge in this manner is site-specific and therefore not
applicable on a nationwide basis. The BPT flow rate is based on
the average of the production normalized water use rates reported
by the two facilities reporting this stream. The production
normalized flow rates used in the average are 637 1/kkg and 794
1/kkg.
REGULATED POLLUTANT PARAMETERS
The raw wastewater concentrations from individual operations and
the subcategory as a whole were examined to select certain
pollutant parameters for limitation. This examination and
evaluation was presented in Section VI. A total of nine
pollutants or pollutant parameters were selected for limitation
and are listed below:
115. arsenic
122. lead
124. nickel
125. selenium
EFFLUENT LIMITATIONS
ammonia
fluoride
molybdenum
total suspended solids
pH
The treatment effectiveness concentrations achievable by
application of the promulgated BPT treatment are explained in
Section VII of Vol. I and summarized there in Table VII-21 (page
248), with one exception. This exception is the molybdenum
treatment effectiveness value. As a part of the settlement
agreement, EPA agreed to propose to suspend the molybdenum
limitations in the previously promulgated BPT and BAT
limitations, NSPS and PSNS for this subcategory. EPA would then
recommend interim limits for use in permits on a Best
Professional Judgment (BPJ) basis. These values would be
recommended to be effective until after iron co-precipitation
treatment is installed and evaluated.
The achievable treatment concentrations for all regulated
pollutants (both one day maximum and monthly average values) are
multiplied by the BPT normalized discharge flows summarized in
Table IX-1 (page 3446) to calculate the mass of pollutants
allowed to be discharged per mass of product. The results of
these calculations in milligrams of pollutant per kilogram of
product represent the BPT effluent limitations and are presented
in Table IX-2 (page 3447) for each individual waste stream.
3445
-------
00
*.
Table IX-1
BPT WASTEWATER DISCHARGE RATES FOR THE
. PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
Wastewater Stream
Molybdenum Sulfide Leachate
Roaster S02 Scrubber
Molybdic Oxide Leachate
Hydrogen Reduction Furnace
Scrubber
Depleted Rhenium Scrubbing
Solution
BPT Normalized
Discharge Rate
1/kkg gal/ton
463 112
1,679 404
11,584 2.782
22.898
716
5,505
173
Production
Normalizing Parameter
Molybdenum aulfide leached
Molybdenum sulfide roasted
Molybdenum contained in
molybdic oxide leached
Molybdenum powder produced
Molybdenum sulfide roasted
H
I
Kj
8
w
ss
H
CO
G
CD
O
w
Q
I
03
o
i
H
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
SECT - IX
Table IX-2
BPT MASS LIMITATIONS FOR THE PRIMARY
MOLYBDENUM AND RHENIUM SUBCATEGORY
(a) Molybdenum Sulfide Leachafae BPT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of molybdenum sulfide leached
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
*Ammonia
*Pluoride
*Molybdenum
Rhenium
*TSS
0,
0,
0,
,968
,204
,880
0.194
0.889
0.569
0.676
61.720
16.210
Reserved
3.060
18.980
0.431
0.083
0.463
0.093
0.588
0.255
0.282
27.130
9.214
Reserved
1.583
9.029
Within the range of 7.5 to 10.0 at all times
(b) Roaster 803 Scrubber BPT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of molybdenum sulfide roasted
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
*Ammonia
*Fluoride
*Molybdenum
Rhenium
*TSS
3.509
0.739
3.190
0.705
3.224
,065
,451
,800
,770
• 2,
2,
223,
58,
Reserved
11.100
68.840
1.
0,
1,
0.
2,
0,
1,
98.
.561
,302
,679
,336
,132
,923
,024
,390
33.410
Reserved
5.742
32.740
Within the range of 7.5 to 10.0 at all times
*Regulated Pollutant
3447
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - IX
Table IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE PRIMARY
MOLYBDENUM AND RHENIUM SUBCATEGORY
(c) Molybdic Oxide Leachate BPT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of molybdenum contained
in molybdic oxide leached
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
*Ammonia
*Fluoride
*Molybdenura
Rhenium
*TSS
24.210
5.097
22.010
4.865
22.240
14.250
16.910
1,544.000
405.400
Reserved
76.570
474.900
pH
Within the range of 7.5 to 10.0 at
10.770
2.085
11.580
2.317
14.710
6.371
7.066
678.800
230.500
Reserved
39.620
225.900
all times
(d) Hydrogen Reduction Furnace Scrubber BPT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
(Ib/million Ibs) of molybdenum powder produced
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
*Ammonia
*Fluoride
*Molybdenum
Rhenium
*TSS
*pH Within the range
47.860
10.080
43.510
9.617
43.960
28.160
33.430
3,052.000
801.400
Reserved
151.400
938.800
of 7.5 to 10.0
21.300
4.122
22.900
4.580
29.080
12.590
13.970
1,342.000
455.700
Reserved
78.310
446.500
at all times
*Regulated Pollutant
3448
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - IX
Table IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE PRIMARY
MOLYBDENUM AND RHENIUM SUBCATEGORY
(e) Depleted Rhenium Scrubbing Solution BPT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of molybdenum sulfide roasted
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
*Ammonia
*Pluoride
*Molybdenuitt
Rhenium
*TSS
1.496
0.315
1.360.
0.301
1.375
0.881
1.045
95.440
25.060
Reserved
4.733
29.360
0.666
0.129
0.716
0.143
0.909
0.394
0.437
41.960
14.250
Reserved
2.449
13.960
Within the range of 7.5 to 10.0 at all times
*Regulated Pollutant
-------
U)
1i> Arwuuli.l Kurnvvrv
Hulybdlc Oxide Leachate
A*win IJ
Si IMS.
Stripping
Clie.lcal Addition Chemical Addition
H
K:
tr1
Mulybileiiun SulUJc LeacKatA
Roaster SO? Scrubber
Reduction Kurnace Scrubber
Rhenium Scrubbing Solution
1»
v />
Equalization
<£
1»
v'/
Precipitation
1
»
Js
Chealcal
Precipitation
Sludge Recycle
V
* SedlMCntation
Isiudge
Vacuiw Filtrate ^*\( ^
• Olacliarge
cj
S
Sludge Dewaterlng
H
Figure IX-1
BPT TREATMENT SCHEME FOR THE PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - X
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
These effluent limitations are based on the best control and
treatment technology used by a specific point source within the
industrial category or subcategory, or by another industry where
it is readily transferable. Emphasis is placed on additional
treatment techniques applied at the end of the treatment systems
currently used, as well as reduction of the amount of water used
and discharged, process control, and treatment technology
optimization.
The factors considered in assessing best available technology
economically achievable (BAT) include the age of equipment and
facilities involved, the manufacturing process used, process
changes, nonwater quality environmental impacts (including energy
requirements), and the costs of application of such technology
BAT technology represents the best available technology at plants
of various ages, sizes, processes, or other characteristics. BAT
may be transferred from a different subcategory or category and
BAT may include feasible process changes or internal controls,
even when not in common industry practice.
The statutory assessment of BAT considers costs, but does not
require a balancing of costs against pollutant removal benefits.
However, in assessing the proposed and promulgated BAT, the
Agency has given substantial weight to the economic achievability
of the selected technology.
TECHNICAL APPROACH TO BAT
The Agency reviewed a wide range of technology options and
evaluated the available possibilities to ensure that the most
effective and beneficial technologies were used as the basis of
BAT. To accomplish this, the Agency elected to examine three
technology options which could be applied to the primary
molybdenum and rhenium subcategory as treatment options for the
basis of BAT effluent limitations.
For the development of BAT effluent limitations, mass loadings
were calculated for each wastewater source or subdivision in the
subcategory using the same technical approach as described in
Section IX for BPT limitations development. The differences in
the mass loadings for BPT and BAT are due to increased treatment
effectiveness achievable with the more sophisticated BAT
treatment technology and reductions in the effluent flows usually
achieved by recycle and reuse technologies.
In summary, the treatment technologies considered for BAT are
presented below:
3451
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - X
Option A (Figure X-l, page 3466) is based on
o Preliminary treatment with ammonia steam stripping
o Preliminary treatment with iron co-precipitation
o Chemical precipitation and sedimentation
Option B (Figure X-2, page 3467) is based on
o Preliminary treatment with ammonia steam stripping
o Preliminary treatment with iron co-precipitation
o Chemical precipitation and sedimentation
o In-process flow reduction
Option C (Figure X-3, page 3458) is based on
o Preliminary treatment with ammonia steam stripping
o Preliminary treatment with iron co-precipitation
o Chemical precipitation and sedimentation
o In-process flow reduction
o Multimedia filtration
The three options examined for BAT are discussed in greater
detail below. The first option considered is the same as the BPT
treatment which was presented in the previous section. The last
two options each represent substantial progress toward the
prevention of polluting the environment above and beyond the
progress achievable by BPT.
OPTION A
Option A for the primary molybdenum and rhenium subcategory is
equivalent to the control and treatment technologies which were
analyzed for BPT in Section IX. The BPT end-of-pipe treatment
scheme includes chemical precipitation, sedimentation, with
ammonia steam stripping and iron co-precipitation preliminary
treatment (see Figure X-l). The discharge rates for Option A are
equal to the discharge rates allocated to each stream at a BPT
discharge flow.
OPTION B
Option B for the primary molybdenum and rhenium subcategory
achieves lower pollutant discharge by building upon the Option A
end-of-pipe treatment technology, which consists of ammonia steam
stripping, iron co-precipitation, chemical precipitation, and
sedimentation. Flow reduction measures are added to Option A
treatment (see Figure X-2). These flow reduction measures,
including in-process changes, result in the elimination of some
wastewater streams and the concentration of pollutants in other
effluents. Treatment of a more concentrated effluent allows
achievement of a greater net pollutant removal and introduces the
possible economic benefits associated with treating a lower
volume of wastewater.
The method used in Option B to reduce process wastewater
3452
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - X
generation or discharge rates is recycle of water used in wet air
pollution control. There are two wastewater sources associated
with wet air pollution control or gas cleaning and quenching
prior to recycle which are regulated under these effluent
limitations:
—Roaster SO2 scrubber, and
—Hydrogen reduction furnace scrubber.
Table X-l presents the number of plants reporting wastewater use
with these sources, the number of plants practicing recycle of
scrubber water, and the range of recycle values being used.
The BAT regulatory flow for hydrogen reduction furnace scrubbers
is based on recycle of scrubber liquor as discussed liter in this
section, and represents the best available technology
economically achievable for this stream. The BAT regulatory flow
for roaster S(>2 scrubbers will not be flow reduced because the
Agency believes that flow reduction beyond the BPT regulatory
flow is not warranted.
OPTION C
Option C for the primary molybdenum and rhenium subcategory
consists of all control and treatment requirements of Option B
(ammonia steam stripping, iron co-precipitation, in-process flow
reduction, chemical precipitation, and sedimentation) plus multi-
media filtration technology added at the end of the Option B
treatment scheme (see Figure X-3). Multimedia filtration is used
to remove suspended solids, including precipitates of toxic
metals, beyond the concentrations attainable by gravity
sedimentation alone. The filter suggested is of the gravity,
mixed media type, although other filters, such as rapid sand
filters or pressure filters, would perform as well.
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
As one means of. evaluating each technology option, EPA developed
estimates of the pollutant removal estimates and the compliance
costs associated with each option. The methodologies are
described below.
POLLUTANT REMOVAL ESTIMATES
A complete description of the methodology used to calculate the
estimated pollutant removal, achieved by the application of the
various treatment options is presented in Section X of the
General Development Document. The pollutant removal estimates
have been revised since proposal based on industry comments on
the proposed rulemaking; however, the methodology for calculating
pollutant removals was not changed. The data used for estimating
removals are the same as those used to revise the compliance cost
estimates.
In short, sampling data collected during the field sampling
3453
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - X
program were used to characterize the major waste streams
considered for regulation. At each sampled facility, the
sampling data was production normalized for each unit operation
(i.e., mass of pollutant generated per mass of product
manufactured). This value, referred to as the raw waste, was
used to estimate the mass of priority pollutants generated within
the primary molybdenum and rhenium subcategory. The pollutant
removal estimates were calculated for each plant by first
estimating the total mass of each pollutant in the untreated
wastewater. This was calculated by first multiplying the raw
waste values by the corresponding production value for that
stream and then summing these values for each pollutant for every
stream generated by the plant.
Next, the volume of wastewater discharged after the application
of each treatment option was estimated for each operation at each
plant by first comparing the actual discharge to the regulatory
flow. The smaller of the two values was selected and summed with
the other plant flows. The mass of pollutant discharged was then
estimated by multiplying the achievable concentration values
attainable with the option (mg/1) by the estimated volume of
process wastewater discharged by the subcategory. Finally, the
mass of pollutant removed is the difference between the estimated
mass of pollutant generated by each plant in the subcategory and
the mass of pollutant discharged after application of the
treatment option. The pollutant removal estimates for direct
dischargers in the primary molybdenum and rhenium subcategory are
presented in Table X-2.
COMPLIANCE COST
In estimating subcategory-wide compliance costs, the first step
was to develop a cost estimation model, relating the total costs
associated with installation and operation of wastewater
treatment technologies to plant process wastewater discharge.
EPA applied the model to each plant. The plant's investment and
operating costs are determined by what treatment it has in place
and by its individual process wastewater discharge flow. As
discussed above, this flow is either the actual or the BAT
regulatory flow, whichever is lesser. The final step was to
annualize the capital costs, and to sum the annualized capital
costs, and the operating and maintenance costs for each plant,
yielding the cost of compliance for the subcategory (see Table X-
3). These costs were used in assessing economic achievability.
BAT OPTION SELECTION - PROPOSAL
EPA selected Option C for the proposed BAT which included in-
process flow reduction, ammonia steam stripping, chemical
precipitation, sedimentation and multimedia filtration. There
was a capital and annual cost associated with the proposed BAT;
however, these costs could not be presented because they were
based on data which was claimed to be confidential,
Implementation of the proposed BAT was estimated to remove 73,655
kg of priority metals annually.
3454
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - X
EPA proposed to expand the applicability of the promulgated BAT
limitations for the metallurgical acid plants subcategory to
include molybdenum acid plants. The proposed limits were based
on flow reduction, sulfide precipitation, chemical precipitation,
sedimentation and filtration. Compliance costs were not
presented because they were based on confidential information.
BAT OPTION SELECTION - PROMULGATION
After proposal, EPA received comments concerning the removal of
molybdenum in a lime and settle treatment system. For
promulgation, EPA is adding iron co-precipitation to the proposed
BAT technology in order to effectively remove molybdenum from the
raw wastewater. The promulgated BAT is equivalent to Option C
discussed in Section VII of this document, which includes ammonia
steam stripping, flow reduction, iron'co-precipitation, chemical
precipitation, sedimentation and multimedia filtration. With the
exception of molybdenum, the treatment performance concentrations
used to calculate the promulgated mass limitations are equal to
the values used to calculate the proposed mass limitations.
Iron co-precipitation is an effective method for removing
molybdenum from process wastewater. This technology is
demonstrated industries. The treatment effectiveness
concentration used for molybdenum at promulgation was based on
data from that facility. However, petitioners questioned the
data on which the treatment effectiveness concentration for
molybdenum removal is based. As a part of the settlement
agreement, the petitioners would agree to install iron
coprecipitation, as. the model technology, on all of the
molybdenum-bearing wastestreams at their facilities included in
the Primary Molybdenum and Rhenium subcategory and to provide
operating data to the Agency. EPA agreed to consider these data
in any rulemaking to propose new molybdenum limits. In the
interim, EPA would propose to suspend the molybdenum limitations
in the previously promulgated BPT and BAT limitations, NSPS and
PSNS for this subcategory. EPA would then recommend two sets of
interim limits for use in permits on a Best Professional Judgment
(BPJ) basis. See Section IX of this document for further
discussion of the molybdenum treatment effectiveness
concentration.
Implementation of the promulgated BAT limitations would remove
annually an estimated 73,655 kg of priority metals and 737 kg of
molybdenum. No additional ammonia is removed at BAT. The
estimated capital and annual cost for achieving the promulgated
BAT cannot be presented here because the data on which they are
based have been claimed to be confidential.
We are promulgating filtration as part of the BAT technology
because this technology is demonstrated in the nonferrous metals
manufacturing category (25 facilities presently have filters),
and results in additional removal of toxic metals. In addition,
filtration adds reliability to the treatment system by making it
3455
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - X
less susceptible to operator error and to sudden changes in raw
wastewater flows and concentrations.
FINAL AMENDMENTS TO THE REGULATION
For the primary molybdenum and Rhenium Subcategory, EPA prepared
a settlement agreement in June 1987, to amend the regulations
promulgated on September 20, 1985 (50 FR 38276). The settlement
agreement concerns one topic, namely, molybdenum limitations,
which is fully described in Sections IX and X of this document.
EPA has proposed this amendment (54 FR 18412), and after
reviewing comments will take final action.
WASTEWATER DISCHARGE RATES
A BAT discharge rate was calculated for each subdivision based
upon the flows of the existing plants, as determined from
analysis of the dcp. The discharge rate is used with the
achievable treatment concentration to determine BAT effluent
limitations. Since the discharge rate may be different for each
wastewater source, separate production normalized discharge rates
for each of the six wastewater sources were determined and are
summarized in Table X-4 (page 3462). The discharge rates are
normalized on a production basis by relating the amount of
wastewater generated to the mass of the product which is produced
by the process associated with the waste stream in question.
These production normalizing parameters (PNP) are also listed in
Table X-4.
The BAT wastewater discharge rate used at promulgation is the
same as the wastewater discharge rate used at proposal for four
of the five wastewater streams in the primary molybdenum and
rhenium subcategory. Based on the available data, the Agency did
not find that further flow reduction would be feasible for these
wastewater sources. The rationale for determining the regulatory
flows for these four streams was previously presented in Section
IX. -The wastewater streams for which BAT discharge rates differ
from BPT is discussed below.
HYDROGEN REDUCTION FURNACE SCRUBBER
The BAT wastewater discharge rate used at proposal and
promulgation for hydrogen reduction furnace scrubber water is
2,290 1/kkg (550 gal/ton). This rate is allocated only to those
plants which practice water scrubbing of recirculating hydrogen
gas from reduction furnaces. The BAT discharge rate is based on
90 percent recycle of the average water use of the two plants
reporting this stream. One facility currently practices
extensive recycle (assumed to be greater than 99 percent as
discussed in Section IX) and the other currently practices no
recycle. Water use and discharge rates are presented in Table V-
4 (page 3386) .
REGULATED POLLUTANT PARAMETERS
3456
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - X
The Agency placed particular emphasis on the priority pollutants.
The raw wastewater concentrations from individual operations and
the subcategory as a whole were examined to select certain
pollutants and pollutant parameters for limitation. This
examination and evaluation was presented in Section VI. The
Agency, however, has chosen not to regulate all nine toxic
pollutants selected in this analysis.
The high cost associated with analysis for toxic metal pollutants
has prompted EPA to develop an alternative method for regulating
and monitoring priority pollutant discharges from the nonferrous
metals manufacturing category. Rather than developing specific
effluent mass limitations and standards for each of the metals
found in treatable concentrations in the raw wastewater from a
given subcategory, the Agency is promulgating effluent mass
limitations only for those pollutants generated in the greatest
quantities as shown by the pollutant removal estimate analysis.
The pollutants selected for specific limitation are listed below:
114. arsenic
122. lead
123. nickel
124. selenium
ammonia (as N)
fluoride
molybdenum
By establishing limitations and standards for certain metal
pollutants, dischargers will attain the same degree of control
over metal pollutants as they would have been required to achieve
had all the metal pollutants been directly limited.
This approach is technically justified since the treatable
concentrations used for chemical precipitation and sedimentation
technology are based on optimized treatment for concomitant
multiple metals removal. Thus, even though metals have somewhat
different theoretical solubilities, they will be removed at very
nearly the same rate in a chemical precipitation and
sedimentation treatment system operated for multiple metals
removal.
Filtration as part of the technology basis is likewise justified
because this technology removes metals non-preferentially.
The priority metal pollutants selected for specific limitation in
the primary molybdenum and rhenium subcategory to control the
discharges of metal pollutants are arsenic, lead, nickel, and
selenium. Ammonia is also selected for limitation since the
methods used to control the regulated priority pollutants are not
effective in the control of ammonia. Fluoride and molybdenum are
included because they are valuable as indicator pollutants for
properly operated chemical precipitation and sedimentation
systems. The following priority pollutants are excluded from
limitation on the basis that they are effectively controlled by
the limitations developed for arsenic, lead, nickel, and
3457
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT
selenium:
119. chromium (Total)
120. copper
128. zinc
The priority metal pollutants arsenic, lead, nickel, and
selenium, as well as the nonconventional metal pollutant
molybdenum, are specifically limited to ensure the control of the
excluded priority metal pollutants. These pollutants are
indicators of the performance of the treatment technology.
EFFLUENT LIMITATIONS
The concentrations achievable by application of BAT are discussed
in Section VII of Vol. I and summarized there in Table VII-21
(page 248). With the exception of the molybdenum treatment
effectiveness concentration. See Section IX of this document for
further discussion of the molybdenum treatment effectiveness
concentration. The treatability concentrations including both one
day maximum and monthly average values are multiplied by the BAT
normalized discharge flows summarized in Table x-4 (page 3466) to
calculate the mass of pollutants allowed to be discharged per
mass of product. The results of these calculations in milligrams
of pollutant, per kilogram of product represent the promulgated
BPT effluent limitations and are presented in Table X-4 for each
waste stream.
3458
-------
Table X-1
CURRENT RECYCLE PRACTICES yiTHIN THE PRIHARY MOLYBDENUM AND RHENIUM SUBCATEGORY
Roaster S02 Scrubber
Hydrogen Reduction Furnace Scrubber
Number of Plants
Mastewater
4
2
Number of Plants
Pyact icing Recycle
Range
of Recycle
Values (%)
0 - 96
0 - 99
«
5
o
Ul
vo
M
2!
H
CO
§
O
8
M
Q
i
w
-------
Table X-2
• POLLUTANT REMOVAL ESTIMATES
FOR DIRECT DISCHARGERS
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
Pollutant
Antimony
Arsenic
Cadnlun
Chroraiu* (Total)
Copper
Cyanide (Total)
Lead
Mercury
Nickel
Selenium
Stiver
Thai Hun
Zinc
TOTAL PRIORITY
POLLUTANTS
Ammonia
Cobalt
Fluoride
Molybdenum
TOTAL NONCQNVENTIONALS
TSS
Oil and Grease
TOTAL CONVENTIONALS
TOTAL POLLUTANTS
Total
Raw Waste
(kR/yr)
30.15
5,61
18.39
23.21
40,440.83
1.52
12.818.33
0.03
12,530.39
1.79
67.36
2.54
7,731.11
73,671.24
Option A
Discharge
(kR/yr)
8.23
4.57
0.93
1.07
6.82
0.75
1.41
0.02
8.70
1.19
1.18
1.68
3.88
40.41
Option A
Removed
(kR/yr)
21.93
1.04
17,46
22.13
40,434.01
0.77
12,816.91
0.01
12,521.69
0.60
66.19
0.86
7.727.23
73.630.83
Option B
Discharge
(kR/yr)
5.15
3.90
0.58
0.70
4.27
0.66
0.88
0.02
5.45
0.99
0.73
1.40
2.43
27.17
Option B
Removed
(kR/yr)
25.00
1.71
17.80
22.50
40,436.56
0.86
12,817.44
0.01
12.524.94
0.80
66.63
1.13
7,728.68
73,644.07
Option C
Discharge
(kR/yr)
3.32
2.50
0.35
0.58
2./6
0.65
0.57
0.02
1.55
0.95
0.50
• 1.35
1.63
16.73
Option C
• Removed
(kR/vr)
26.83
3.11
18.04
22.63
40.438.07
0.86
12,817.76
0.01
12,528.83
0.84
66.87
1.19
7,729.48
73,654.51
S
O
5
a
O
w
25
3
!?•
S
PC
H
C
S
w
§
n
69.495.70
4,791.44
0.25
739.02
6,052.39
0.60
0.16
2.97
63.443.30
4,790.85
0.08
736.06
6,052.39
0.38
0.14
2.97
63.443.30
4,791.07
0.11
736.06
6,052.39
0.25
0.13
1.99
63,443.30
4,791.19
0.12
737.03
M
a
0
75,026.41 6.056.12
68.970.29 6,055.88
68,970.54 6,054.76
68,971.64
51.669.76
2,147.07
53,816.83
202.514.48
141.05
336.20
477.25
6.573.78
51.528.71
1.810.87
53.339.58
195.940.70
88.30
266.79
375.09
6,458.14
51.581.46
1,660.28
53,441.74
196.056.35
18.39
277.33
295.71
6,367.20
51,651.37
1,869.74
53,521.12
196,147.27
w
M
O
1-3
-------
PRIMARY MOLYBDENUM AND RHENIUM SOBCATEGORY SECT - X
TABLE X-3
COST OP COMPLIANCE FOR THE PRIMARY MOLYBDENUM
AND RHENIUM SUBCATEGORY
DIRECT DISCHARGERS
Compliance costs for this subcategory cannot be presented here
because the data on which they are based have been claimed to be
confidential.
3461
-------
Table X-4
BAT WASTEWATER DISCHARGE RATES FOR THE PRIMARY MOLYBDENUM
AND RHENIUM SUBCATEGORY
WastewaterStream
Molybdenum Sulflde Leachate
Roaster S02 Scrubber
Molybdtc Oxide Leachate
Hydrogen Reduction Furnace
Scrubber
Depleted Rhenium Scrubbing
Solution
BAT Production
Normalized
Discharge Rate
1/kkggal/ton
463 112
1,679 404
11,584 2,782
2,290
716
551
173
Production Normalizing Parameter
Molybdenum sulfide leached
Molybdenum sulfide roasted
Molybdenum contained in
molybdic oxide leached
Molybdenum powder produced
Molybdenum sulfide roasted
H
3
O
§
O
M
25
G
S
M
53
M
W
§
O
n
I
to
M
o
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - X
TABLE X-5
BAT MASS LIMITATIONS FOR THE
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
(a) Molybdenum Sulfide Leachate BAT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of molybdenum sulfide leached
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
* Ammonia
*Fluoride
*Molybdenum
Rhenium
0.644
0.171
0.593
0.130
0.255
0.380
0.472
61.720
16.210
Reserved
2.329
0.287
0.070
0.282
0.060
0.171
0.171
0.194
27.130
9.214
Reserved
1.032
(b) Roaster SO? Scrubber BAT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
rog/kg (Ib/million Ibs) of molybdenum sulfide roasted
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
*Ammonia
*Fluoride
*Molybdenum
Rhenium
2.334
0.621
2.149
0.470
0.923
1.377
1.713
223.800
58.770
Reserved
8.445
1.041
0.252
1.024
0.218
0.621
0.621
0.705
98.390
33.410
Reserved
3.744
^Regulated Pollutant
3463
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - X
TABLE X-S (Continued)
BAT MASS LIMITATIONS FOR THE
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
(c) Holybdic Oxide Leachate BAT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of molybdenum
contained in molybdic oxide leached
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
*Ammonia
*Fluoride
*Molybdenum
Rhenium
16.100
4.286
14.830
3.244
6.371
9.499
11.820
1,544.000
405.400
Reserved
58.270
7.182
1.738
7.066
1.506
4.286
4.286
4.865
678.800
230.500
Reserved
25.830
(d) Hydrogen Reduction Furnace Scrubber BAT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of molybdenum powder produced
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
* Ammonia
*Fluoride
*Molybdenum
Rhenium
3.183
0.847
2.931
0.641
1.260
1.878
2.336
305.300
80.150
Reserved
11.520
1.420
0.344
1.397
0.298
0.847
0.847
0.962
134.200
45.570
Reserved
5.107
*Regulated Pollutant
3464
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - X
TABLE X-5 (Continued)
BAT MASS LIMITATIONS FOR THE
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
Depleted Rhenium Scrubbing Solution BAT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of molybdenum sulfide roasted
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
*Ammonia
*Fluoride
*Molybdenum
Rhenium
0.995
0.265
0.916
0.200
0.394
0 . 587
0.730
95.440
25.060
Reserved
3.601
0.444
0.107
0.437
0.093
0.265
0.265
0.301
41.960
14.250
Reserved
1.597
*Regulated Pollutant
3465
-------
H
CO
its.
In Anmml.i KiTiiverv
HnlybJIc Oxide teachate
Stf.l.ii
Strlpplnp
Clieaical Addition Clie«lc«l Addition
MnlvbJuiiun Sullliie Leachate
Klienlnm Si.rubuliiK Solution
Figure X-1
BAT TREATMENT SCHEME FQR OPTION A
-------
To Amnmia Recovery
MolybdK Oxide I.eachale
HoiybdeniM Sulflde Uachate
U>
Scrubber
-------
To AMKH ScfubUr ^
Uieulun Scrubbing Solution
r«
V /^
_ >
I«u*liz*tlon
06
Figure X-3
BAT TRgATMENT SCHEME FOR OPTION C
H
Hj
O
1
M
55
H
K
n
o
c/i
w
o
i
X
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBGATEGORY SECT - XI
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
This section describes the technologies for treatment of
wastewater from new sources and presents mass discharge standards
for regulatory pollutants for NSFS in the primary molybdenum and
rhenium subcategory, based on the selected treatment technology.
New plants have the opportunity to design the best and most
efficient production processes and wastewater treatment
technologies without facing the added costs and restrictions
encountered in retrofitting an existing plant. Therefore, EPA
has considered the best demonstrated process changes, in-plant
controls, and end-of-pipe treatment technologies which reduce
pollution to the maximum extent feasible.
TECHNICAL APPROACH TO
New source performance standards are equivalent to the best
available technology (BAT) selected for currently existing
primary molybdenum and rhenium plants. This result is a
consequence of careful review by the Agency of a wide range of
technical options for new source treatment systems. Additionally,
there was nothing found to indicate that the wastewater flows and
characteristics of new plants would not be similar to those from
existing plants, since the processes used by new sources are not
expected to differ from those used at existing sources.
Consequently, BAT production normalized discharge rates, which
are based on the best existing practices of the subcategory, can
also be applied to new sources. These rates are presented in
Table XI-1 (page 3472).
Treatment technologies considered for the NSPS options are
identical to the treatment technologies considered for the BAT
options. These options are:
OPTION A
o Preliminary treatment with ammonia steam stripping
(where required)
o Preliminary treatment with iron co-precipitation
o Chemical precipitation and sedimentation
OPTION B
o Preliminary treatment with ammonia steam stripping
(where required)
o Preliminary treatment with iron co-precipitation
o Chemical precipitation and sedimentation
o In-process flow reduction of hydrogen reduction furnace
scrubber liquor
3469
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - XI
OPTION C
o Preliminary treatment with ammonia steam stripping
(where required)
o Preliminary treatment with iron co-precipitation
o Chemical precipitation and sedimentation
o In-process flow reduction of hydrogen reduction furnace
scrubber liquor
o Multimedia filtration
NSPS OPTION SELECTION - PROPOSAL
EPA proposed that the best available demonstrated technology for
the primary molybdenum and rhenium subcategory be equivalent to
Option C (ammonia steam stripping, flow reduction, chemical
precipitation, sedimentation and multimedia filtration).
The wastewater flow rates for NSPS were the same as the proposed
BAT flow rates. EPA did not believe that further flow reduction
beyond BAT flow rates was feasible for this Subcategory.
EPA also proposed to expand the applicability of the existing
NSPS regulation for metallurgical acids plants to include acid
plants associated with primary molybdenum roasting operations.
NSPS OPTION SELECTION - PROMULGATION
EPA is promulgating best available demonstrated technology for
the primary molybdenum and rhenium subcategory equivalent to
Option C (ammonia steam stripping, flow reduction, iron co-
precipitation, chemical precipitation, sedimentation and
multimedia filtration). This differs from the proposed NSPS in
that it includes iron co-precipitation treatment, which is
necessary for effective molybdenum removal.
The wastewater flow rates for NSPS are the same as the BAT flow
rates. The NSPS flow rates are presented in Table XI-1.
Additional flow reduction and more stringent treatment
technologies beyond BAT are not demonstrated or readily
transferable to the primary molybdenum and rhenium subcategory,
for the reasons stated at proposal.
REGULATED POLLUTANT PARAMETERS
The Agency has no reason to believe that the pollutants that will
be found in treatable concentrations in processes within new
sources will be any different than with existing sources.
Accordingly, pollutants and pollutant parameters selected for
limitation under NSPS, in accordance with the rationale of
Sections VI and X, are identical to chose selected for BAT. The
conventional pollutant parameters, TSS and pH are also selected
for limitation.
3470
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - XI
NEW SOURCE PERFORMANCE STANDARDS
The NSPS discharge flows for each wastewater source are the same
as the discharge rates for BAT and are shown in Table XI-1. The
mass of pollutant allowed to be discharged per mass of product is
calculated by multiplying the appropriate treatable concentration
(mg/1) by the production normalized wastewater discharge flows
(1/kkg). The achievable concentrations are listed in Table VII-
21 (page 248) of Vol. I. With the exception of the molybdenum
treatment effectiveness concentration. See Section IX of this
document for discussion of the molybdenum treatment effectiveness
concentration. The results of these calculations are the
production-based new source performance standards. These
standards are presented in Table XI-2 (page 3473).
3471
-------
to
Table XI-1
NSPS WASTEWATER DISCHARGE RATES FOR THE PRIMARY MOLYBDENUM
AND RHENIUM SUBCATEGORY
Wastewater Stream
Molybdenum SulfIde Leachate
Roaster S02 Scrubber
Molybdlc Oxide Leachate
Hydrogen Reduction Furnace
Scrubber
Depleted Rhenium Scrubbing
Solution
NSPS Production
Normalized
Discharge Rate
1/kkggal/ton
463 112
1.679 404
11,584 2,782
2,290
716
551
173
Production Normalizing Parameter
Molybdenum sulfide leached
Molybdenum sulfide roasted
Molybdenum contained in
molybdic oxide leached
Molybdenum powder produced
Molybdenum sulfide roasted
hi
»
H
I
w
H
C/l
g
o
Q
O
a
M
i
H
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - XI
TABLE XI-2
NSPS FOR THE PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
(a) Molybdenum Sulfide Leachate NSPS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/Jcg (Ib/million Ibs) of molybdenum sulfide leached
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
*Ammonia
*Pluoride
*Molybdenum
Rhenium
*TSS
*pH Within the
0.644
0.171
0.593
0.130
0.255
0.380
0.472
61.720
16.210
Reserved
2.329
6.945
range of 7.5 to 10.0 at all
0.287
0.070
0.282
0.060
0.171
0.171
0.194
27.130
9.214
Reserved
1.032
5.556
times
(b) Roaster SO? Scrubber NSPS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of molybdenum sulfide roasted
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
*Ammonia
*Pluoride
*Molybdenum
Rhenium
*TSS
2.
0,
2,
0.
0,
.334
,621
,149
,470
,923
1.377
1.713
223.800
58.770
8.445
Reserved
25.190
,041
,252
,024
.218
,621
,621
,705
98.390
33.410
3.744
Reserved
20.150
1,
0.
1.
0.
0,
0.
0.
*pH
Within the range of 7.5 to 10.0 at all times
*Regulated Pollutant
3473
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - XI
TABLE XI-2 (Continued)
NSPS FOR THE PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
(c) Molybdic Oxide Leachate NSPS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of molybdenum
contained in molybdic oxide leached
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
* Ammonia
*Fluoride
*Molybdenum
Rhenium
*TSS
*pH Within the
16.100
4.286
14.830
3.244
6.371
9.499
11.820
1,544.000
405.400
Reserved
58.270
173.800
range of 7.5 to 10.0 at all
7.182
1.738
7.066
1.506
4.286
4.286
4.865
678.800
230.500
Reserved
25.830
139.000
times
(d) Hydrogen Reduction Furnace Scrubber NSPS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of molybdenum powder produced
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
* Ammonia
*Fluoride
*Molybdenum
Rhenium
*TSS
*pH Within the
3.183
0.847
2.931
0.641
1.260
1.878
2.336
305.300
80.150
Reserved
11.52C
34.35L
range of 7.5 to 10.0 at all
1.420
0.344
1.397
0.298
0.847
0.847
0.962
134.200
45.570
Reserved
5.107
27.480
times
*Regulated Pollutant
3474
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
SECT
XI
TABLE XI-2 (Continued)
NSPS FOR THE PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
(e) Depleted Rhenium Scrubbing Solution NSPS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of molybdenum sulfide roasted
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
*Ammonia
*Fluoride
*Molybdenum
Rhenium
*TSS
0,
0,
0,
0,
0,
0,
.995
,265
.916
,200
.394
.587
0.730
95.440
25.060
Reserved
3.601
10.740
0.444
0.107
0.437
0.093
0.265
0.265
0.301
41.960
14.250
Reserved
1.597
8.592
Within the range of 7.5 to 10.0 at all times
*Regulated Pollutant
3475
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - XI
THIS PAGE INTENTIONALLY LEFT BLANK
3476
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - XII
SECTION XII
PRETREATMENT STANDARDS
This section describes the control and treatment technologies for
pretreatment of process wastewaters from new sources in the
primary molybdenum and rhenium subcategory. PSES are designed to
prevent the discharge of pollutants which pass through, interfere
with, or are otherwise incompatible with the operation of
publicly owned treatment works (POTW). The Clean Water Act
requires pretreatment for pollutants, such as toxic metals, that
limit POTW sludge management alternatives. New indirect
discharge facilities, like new direct discharge facilities, have
the opportunity to incorporate the best available demonstrated
technologies, including process changes, in-plant controls, and
end-of-pipe treatment technologies; and to use plant site
selection to ensure adequate treatment system installation.
Pretreatment standards are to be technology based, analogous to
the best available or best demonstrated technology for removal of
toxic pollutants.
EPA is not promulgating pretreatment standards for existing
sources at this time because there are currently no indirect
discharging facilities in this subcategory. Pretreatment
standards for regulated pollutants are presented based on the
selected control and treatment technology.
TECHNICAL APPROACH TO PRETREATMENT
Before proposing and promulgating pretreatment standards, the
Agency examines whether the pollutants discharged by the industry
pass through the POTW or interfere with the POTW operation or its
chosen sludge disposal practices. In determining whether
pollutants pass through a well-operated POTW achieving secondary
treatment, the Agency compares the percentage of a pollutant
removed by POTW with the percentage removed by direct dischargers
applying the best available technology economically achievable.
A pollutant is deemed to pass through the POTW when the average
percentage removed nationwide by well-operated POTW meeting
secondary treatment requirements, is less than the percentage
removed by direct dischargers complying with BAT effluent
limitations guidelines for that pollutant.
This definition of pass-through satisfies the two competing
objectives set by Congress that standards for indirect
dischargers be equivalent to standards for direct dischargers
while at the same time the treatment capability and performance
of the POTW be recognized and taken into account in regulating
the discharge of pollutants from indirect dischargers.
The Agency compares percentage removal rather than the mass or
concentration of pollutants discharged because the latter would
not take into account the mass of pollutants discharged to the
POTW from non-industrial sources or the dilution of the
3477
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - XII
pollutants in the POTW effluent to lower concentrations due to
the addition of large amounts of non-industrial wastewater.
PRETREATMENT STANDARDS FOR NEW SOURCES
Options for pretreatment of wastewaters from new sources are
based on increasing the effectiveness of end-of-pipe treatment
technologies. All in-plant changes and applicable end-of-pipe
treatment processes have been discussed previously in Sections X
and XI. The options for PSNS, therefore1 are the same as the BAT
options discussed in Section X. The description of each option is
presented in Section X.
Treatment technologies considered for the PSNS options are:
OPTION A
o Preliminary treatment with ammonia steam stripping
(where required)
o Preliminary treatment with iron co-precipitation
o Chemical precipitation and sedimentation
OPTION B
o Preliminary treatment with ammonia steam stripping
(where required)
o Preliminary treatment with iron co-precipitation
o Chemical precipitation and sedimentation
o In-process flow reduction of hydrogen furnace reduction
scrubber liquor
OPTION C
o Preliminary treatment with ammonia steam stripping
(where required)
o Preliminary treatment with iron co-precipitation
o Chemical precipitation and sedimentation
o In-process flow reduction of hydrogen furnace reduction
scrubber liquor
o Multimedia filtration
PSNS OPTION SELECTION
We are promulgating PSNS equal to NSPS and BAT for this
subcategory. It is necessary to promulgate PSNS to prevent pass-
through of arsenic, lead, nickel, selenium, fluoride, molybdenum,
rhenium and ammonia. These priority pollutants are removed by a
well-operated POTW achieving secondary treatment at an average of
13 percent, while the NSPS and BAT level technology removes
approximately 79 percent.
We believe that the promulgated PSNS are achievable, and that
they are not a barrier to entry of new plants into this
subcategory.
3478
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - XII
The wastewater discharge rates for PSNS are identical to the BAT
discharge rates for each waste stream. The PSNS discharge rates
are shown in Table XII-1.
REGULATED POLLUTANT PARAMETERS
Pollutants selected for limitation, in accordance with the
rationale of Sections VI and X, are identical to those selected
for limitation for BAT.
PRETREATMENT STANDARDS FOR NEW SOURCES
Pretreatment standards for new sources are based on the treatable
concentrations from the selected treatment technology, (Option
C), and the discharge rates determined in Section X for BAT. A
mass of pollutant per mass of product (mg/kg) allocation is given
for each subdivision within the subcategory. This pollutant
allocation is based on the product of the treatable concentration
from the promulgated treatment (mg/1) and the production
normalized wastewater discharge rate (1/kkg). The achievable
treatment concentrations for BAT are identical to those for PSNS.
See Section IX of this document for a discussion of the
molybdenum treatment effectiveness concentration.
3479
-------
00
o
Table XII-1
PSNS WASTEWATER' DISCHARGE RATES FOR THE PRIMARY MOLYBDENUM
AND RHENIUM SUBCATEGORY
Wastewater Stream
Molybdenum Sulfide Leachate
Roaster S02 Sdrubber
Molybdic Oxide Leachate
Hydrogen Reduction Furnace
Scrubber
Depleted Rhenium Scrubbing
Solution
PSNS Production
Normalized
Discharge Rate
1/kkggal/ton
463 112
1,679 404
11,584 2,782
2,290
716
551
173
Production Normalizing Parameter
Molybdenum sulfide leached
Molybdenum sulfide roasted
Molybdenum contained in raolybdic
oxide leached
Molybdenum powder produced
Molybdenum sulfide roasted
H
g
g
a
M
2!
25
H
§
O
w
S
0)
w
o
H
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - XII
TABLE XI1-2
PSNS FOR THE PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
(a) Molybdenum Sulfide Leachate PSNS
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of molybdenum sulfide leached
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
*Ammonia
*Pluoride
*Molybdenum
Rhenium
0.644
0.171
0.593
0.130
0.255
0.380
0.472
61.720
16.210
Reserved
2.329
0.287
0.070
0.282
0.060
0.171
0.171
0.194
27.130
9.214
Reserved
1.032
(b) Roaster SO? Scrubber PSNS
Pollutant or Maximum for Maximum for
pollutant property any one day monthly average
(Ib/million Ibs) of molybdenum sulfide roasted
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
* Ammonia
*Fluoride
*Molybdenum
Rhenium
2.334
0.621
2.149
0.470
0.923
1.377
1.713
223.800
58.770
Reserved
8.445
1.041
0.252
1.024
0.218
0.621
0.621
0.705
98.390
33.410
Reserved
3.744
*Regulated Pollutant
3481
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - XII
TABLE XI1-2 (Continued)
PSNS FOR THE PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
(c) Molybdic Oxide Leachate PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of molybdenum
contained in molybdic oxide leached
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
* Ammonia
*Fluoride
*Molybdenum
Rhenium
16.100
4.286
14.830
3.244
6.371
9.499
11.820
1,544.000
405.400
Reserved
58.270
7.182
1.738
7.066
1.506
4.286
4.286
4.865
678.800
230.500
Reserved
25.830
(d) Hydrogen Reduction Furnace Scrubber PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of molybdenum powder produced
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
*Ammonia
*Fluoride
*Molybdenum
Rhenium
3.183
0.847
2.931
0.641
1.260
1.878
2.336
305.300
80.150
Reserved
11.520
1.420
0.344
1.397
0.298
0.847
0.847
0.962
134.200
45.570
Reserved
5.107
*Regulated Pollutant
3482
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - XII
TABLE XI1-2 (Continued)
PSNS FOR THE PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY
(e) Depleted Rhenium Scrubbing Solution PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
ing/kg (Ib/million Ibs) of molybdenum sulfide roasted
*Arsenic
Chromium
Copper
*Lead
*Nickel
*Selenium
Zinc
*Ammonia
*Fluoride
*Molybdenum
Rhenium
0.995
0.265
0.916
0.200
0.394
0.587
0.730
95.440
25.060
Reserved
3.601
0.444
0.107
0.437
0.093
0..265
0.265
0.301
41.960
14.250
Reserved
1.597
*Regulated Pollutant
3483
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGORY SECT - XII
THIS PAGE INTENTIONALLY LEFT BLANK
3484
-------
PRIMARY MOLYBDENUM AND RHENIUM SUBCATEGpRY SECT - XIII
SECTION XIII
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY
EPA is not promulgating best conventional pollutant control
technology (BCT) limitations for the primary molybdenum and
rhenium subcategory at this time.
3485
-------
PRIMARY MOLYBDENUM AND RHENIOM SU8CATEGORY SECT - XIII
THIS PAGE INTENTIONALLY LEFT BLANK
3486
-------
NONFERROOS METALS MANUFACTURING POINT SOURCE CATEGORY
DEVELOPMENT DOCUMENT SUPPLEMENT
for the
Secondary Molybdenum and Vanadium Subcategory
William K. Reilly
Administrator
Rebecca Hanmer
Acting Assistant Administrator for Water
Martha Prothro, Director
Office of Water Regulations and Standards
Thomas P. O'Farrell, Director
Industrial Technology Division
Ernst P. Hall, P.E., Chief
Metals Industry Branch
and
Technical Project Officer
May 1989
U.S. Environmental Protection Agency
Office of Water
Office of Water Regulations and Standards
Industrial Technology Division
Washington, D. C. 20460
3487
-------
3488
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
TABLE OF CONTENTS
Section Page
I SUMMARY 3497
II CONCLUSIONS 3501
III SUBCATEGORY PROFILE 3511
Description of Secondary Molybdenum and 3511
Vanadium Production
Raw Materials 3511
Roasting 3512
Leaching 3512
Vanadium Recovery 3512
Molybdenum Recovery 3513
Solvent Extraction 3513
Process Wastewater Sources 3513
Other Wastewater Sources 3513
Age, Production, and Process Profile 3514
IV SUBCATIGORIZATION 3517
Factors Considered in Subdividing the Secondary 3517
Molybdenum and Vanadium Subcategory
Other Factors 3518
Production Normalizing Parameters 3518
V WATER USE AND WASTEWATER CHARACTERISTICS 3521
Wastewater Flow Rates 3522
Wastewater Characteristics Data 3522
Data Collection Portfolios 3523
Field Sampling Data 3523
Wastewater Characteristics and Flows by 3524
Subdivision
Leach Tailings 3524
Molybdenum Filtrate Solvent Extraction Raffinate 3524
Vanadium Decomposition Wet Air Pollution Control 3525
Molybdenum Drying Wet Air Pollution Control 3525
Pure Grade Molybdenum 3525
3489
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
Section
VI
VII
VIII
TABLE OP CONTENTS (Continued)
SELECTION OP POLLUTANTS
Conventional and Nonconventional Pollutant
Parameters
Conventional and Nonconventional Pollutant
Parameters Selected
Toxic Priority Pollutants
Toxic Pollutants Never Detected
Toxic Pollutants Never Found Above Their
Analytical Quantification Limit
Toxic Pollutants Present Below Concentrations
Achievable by Treatment
Toxic Pollutants Detected in a Small Number
of Sources
Toxic Pollutants Selected for Further
Consideration in Establishing Limitations
and Standards
CONTROL AND TREATMENT TECHNOLOGIES
3539
3539
3539
3540
3541
3541
3541
3542
3543
3549
Current Control and Treatment Practices 3547
Leach Tailings 3549
Molybdenum Filtrate Solvent Extraction Raffinate 3548
Vanadium Decomposition Wet Air Pollution Control 3548
Molybdenum Drying Wet Air Pollution Control 3548
Pure Grade Molybdenum 3548
Control and Treatment Options 3548
Option A 3548
Option C 3549
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS
Treatment Options for Existing Sources
Option A
Option C
Cost Methodology
Nonwater Quality Aspects
Energy Requirements
Solid Waste
Air Pollution
3551
3551
3551
3551
3551
3552
3552
3552
3553
3490
-------
Section
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
TABLE OF CONTENTS (Continued)
IX BEST PRACTICABLE CONTROL TECHNOLOGY 3557
CURRENTLY AVAILABLE
Technical Approach to BPT 3557
Industry Cost and Pollutant Removal Estimates 3559
BPT Option Selection 3559
Wastewater Discharge Rates 3560
Leach Tailings 3560
Molybdenum Filtrate Solvent Extraction Raffinate 3561
Vanadium Decomposition Wet Air Pollution Control 3561
Molybdenum Drying Wet Air Pollution Control 3561
Pure Grade Molybdenum 3561
Regulated Pollutant Parameters 3562
Effluent Limitations 3562
X BEST AVAILABLE TECHNOLOGY ECONOMICALLY 3571
ACHIEVABLE
Technical Approach to BAT 3571
Option A 3572
Option C 3572
Industry Cost and Pollutant Removal Estimates 3573
Pollutant Removal Estimates 3573
Compliance Costs 3573
BAT Option Selection-Proposal 3573
BAT Option Selection-Promulgation 3574
Final Amendments to the Regulation 3574
Wastewater Discharge Rates 3574
Regulated Pollutant Parameters 3575
Effluent Limitations 3575
XI NEW SOURCE PERFORMANCE STANDARDS 3587
Technical Approach to NSPS 3587
NSPS Option Selection Proposal 3588
NSPS Option Selection Promulgation 3588
Regulated Pollutant Parameters 3588
New Source Performance Standards 3588
3491
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
TABLE OF CONTENTS (Continued)
Section Page
XII PRETREATMENT STANDARDS 3595
Technical Approach to Pretreatment 3595
Pretreatment Standards for New Sources 3596
PSNS Option Selection 3596
Regulated Pollutant Parameters 3597
Pretreatment Standards for New Sources 3597
XIII BIST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY 3603
3492
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
LIST OF TABLES
Table Title
Page
V-l Water Use and Discharge Rates for Leach Tailings 3526
V-2 Water Use and Discharge Rates for Molybdenum 3526
Filtrate Solvent Extraction Raffinate
V-3 Water Use and Discharge Rates for Vanadium 3526
Decomposition Wet Air Pollution Control
V-4 Water Use and Discharge Rates for Molybdenum 3527
Drying Wet Air Pollution Control
V-5 Water Use and Discharge Rates for 3527
Pure Grade Molybdenum
V-6 Secondary Molybdenum and Vanadium Subcategory 3528
Leach Tailings Raw Wastewater Sampling Data
V-7 Secondary Molybdenum and Vanadium Subcategory 3528
Molybdenum Filtrate Solvent Extraction Raffinate
Raw Wastewater Sampling Data
V-8 Secondary Molybdenum and Vanadium Subcategory 3528
Molybdenum Filtrate Raw Wastewater Sampling Data
V-9 Secondary Molybdenum and Vanadium Subcategory 3528
Pond Water Solvent Extraction Raffinate Raw
Wastewater Sampling Data
V-10 Secondary Molybdenum and Vanadium Subcategory 3544
Sedimentation Effluent Treated Wastewater
Sampling Data
VI-1" Toxic Pollutants Never Detected 3544
Secondary Molybdenum and Vanadium Subcategory
Raw Wastewater
VIII-1 Cost of Compliance for the Secondary Molybdenum 3536
and Vanadium Subcategory Direct Dischargers
3493
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
LIST OP TABLES (Continued)
Table Title Page
IX-1 BPT Wastewater Discharge Rates for the Secondary 3563
Molybdenum and Vanadium Subcategory
IX-2 BPT Mass Limitations for the Secondary 3564
Molybdenum and Vanadium Subcategory
X-l Pollutant Removal Estimates for Direct 3577
Dischargers Secondary Molybdenum and
Vanadium Subcategory
X-2 Cost of Compliance for the Secondary Molybdenum 3578
and Vanadium Subcategory Direct Dischargers
X-3 BAT Wastewater Discharge Rates for the Secondary 3579
Molybdenum and Vanadium Subcategory
X-4 BAT Mass Limitations for the Secondary 3580
Molybdenum and Vanadium Subcategory
XI-1 NSPS for the Secondary Molybdenum and 3590
Vanadium Subcategory
XII-1 PSNS for the Secondary Molybdenum and 3598
Vanadium Subcategory
3494
-------
SECONDARY MOLYBDENUM AND VANADIUM SDBCATEGORY
LIST OP FIGURES
Figure Title Page
III-l Secondary Molybdenum and Vanadium
Production Process
IX-1 BPT Treatment Scheme for Secondary Molybdenum
and Vanadium Subcategory
X-l BAT Treatment Scheme for Option A
X-2 BAT Treatment Scheme for Option C
3495
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
THIS PAGE INTENTIONALLY LEFT BLANK
3496
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - I
SECTION I
SUMMARY
This document provides the technical basis for promulgating
effluent limitations based on best practicable technology
(BPT) and best available technology (BAT) for existing direct
dischargers, pretreatment standards for new indirect
dischargers (PSNS), and standards of performance for new source
direct dischargers (NSPS) for plants in the secondary molybdenum
and vanadium subcategory.
After promulgation of the final effluent limitations and
standards for this subcategory (September 20, 1985, 50 FR 38276),
industry filed a petition for judicial review of the secondary
molybdenum and vanadium subcategory. Industry presented new data
and information which formed the basis for a settlement agreement
with EPA resolving issues raised by the petitioner. EPA agreed to
propose amendments specified in the Settlement Agreement, and
after reviewing comments, take final action on these amendments.
This settlement agreement concerns the treatment effectiveness
values for molybdenum and ammonia, a new building block for pure
grade molybdenum, and revised flow allowances for two building
blocks. The settlement is detailed in the preamble to the
proposed amendment (54 FR 18412, April 28, 1989). This supplement
incorporates the changes of the proposal.
Industry requested that information describing their production
processes, raw wastewater characteristics and economic data be
considered as confidential. Therefore, this supplement does not
include much of the technical data upon which the effluent
limitations and standards for secondary molybdenum and vanadium
are based.
The secondary molybdenum and vanadium subcategory consists of two
plants. One plant discharges its process wastewaters directly to
a surface water. (EPA has recently learned of the existence of
two additional secondary molybdenum and vanadium plants. No
information was obtained regarding the discharge status or
operations at these additional plants.)
EPA first studied the secondary molybdenum and vanadium
subcategory to determine whether differences in raw materials,
final products, manufacturing processes, equipment, age and size
of plants, or water usage, required the development of separate
effluent limitations and standards for different segments of the
subcategory. This involved a detailed analysis of wastewater
discharge and treated effluent characteristics, including the
sources and volume of water used, the processes used, the
sources of pollutants and wastewaters in the plant, and the
constituents of wastewaters, including priority pollutants. As a
result, five subdivisions or building blocks have been identified
in this subcategory that warrant separate effluent limitations.
3497
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - I
These are listed below.
(a) Leach tailings,
(b) Molybdenum filtrate solvent extraction raffinate,
(c) Vanadium decomposition wet air pollution control,
(d) Molybdenum drying wet air pollution control, and
(e) Pure grade molybdenum
Several distinct control and treatment technologies (both
in-plant and end-of-pipe) applicable to the secondary
molybdenum and vanadium subcategory were identified. The
Agency analyzed both historical and newly generated data
on the performance of these technologies, including their
nonwater quality environmental impacts and air quality,
solid waste generation, and energy requirements. EPA also
studied various flow reduction techniques reported in the
data collection portfolios (dcp) and plant visits.
Engineering costs were prepared for each of the control and
treatment options considered for the subcategory. These costs
were then used by the Agency to estimate the impact of
implementing the various options on the subcategory. For each
control and treatment option that the Agency found to be most
effective and technically feasible in controlling the discharge
of pollutants, the number of potential closures, number of
employees affected, and impact on price were estimated. These
results are reported in a separate document entitled "The
Economic Impact Analysis of Effluent Limitations and Standards
for the Nonferrous Metals Manufacturing Industry."
After examining the various treatment technologies, the Agency
has identified BPT to represent the average of the best existing
technology. Metals removal based on iron co-precipitation,
chemical precipitation and sedimentation technology is the basis
for the BPT limitations. Air stripping was selected as the
technology basis for ammonia limitations.
For BAT, the Agency has built upon the BPT technology basis . by
adding filtration as an effluent polishing step to the end-of-
pipe treatment scheme.
NSPS is equivalent to BAT. In selecting NSPS, EPA recognizes
that new plants have the opportunity to implement the best and
most efficient manufacturing processes and treatment technology.
As such, the technology basis of BAT has been determined as the
best demonstrated technology.
PSES is not being promulgated for this subcategory because there
are no existing indirect dischargers in the secondary molybdenum
and vanadium subcategory. For PSNS, the Agency selected
pretreatment and end-of-pipe treatment techniques equivalent to
BAT.
The best conventional technology (BCT) replaces BAT for the
control of conventional pollutants. BCT was not promulgated at
3498
-------
SECONDARY MOI/2BDEITOM AND VANADIUM SOBCATEGORY SECT - I
the time the regulation was promulgated because the iduthodology
for BCT has not been finalized at that time.
The mass limitations and standards for BPT, BAT, NSPS, and PSNS
are presented in Section II.
3499
-------
SECONDARY MOLYBDENUM AHD VANADIUM SUBCATEGORY SECT -
THIS PAGE INTENTIONALLY LEFT BLANK
3500
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - II
SECTION II
CONCLUSIONS
EPA has divided the secondary molybdenum and vanadium subcategory
into five subdivisions or building blocks for the purpose of
effluent limitations and standards. These subdivisions are:
(a) Leach tailings,
(b) Molybdenum filtrate solvent extraction raffinate,
(c) Vanadium decomposition wet air pollution control,
(d) Molybdenum drying wet air pollution control, and
(e) Pure grade molybdenum.
BPT is promulgated based on the performance achievable by the
application of ammonia air stripping pretreatment for removal
of ammonia, followed by iron co-precipitation, chemical
precipitation and sedimentation technology. The following BPT
effluent limitations are promulgated:
(a) Leach Tailings BPT
Pollutant or''Maximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of technical grade molybdenum plus
vanadium plus pure grade molybdenum produced
Arsenic 40.778 18.145
Chromium 8.585 3.512
Lead 8.195 3.902
Nickel 37.460 24.779
Iron 23.410 11.902
Molybdenum Reserved Reserved
Ammonia (as N) 8078.000 3551.000
TSS 799.950 380.460
pH Within the range of 7.5 to 10.0 at all times
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - II
(b) Molybdenum Filtrate Solvent Extraction Raffinate BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs)of technical grade molybdenum plus
vanadium plus pure grade molybdenum produced
Arsenic
Chromium
Lead
Nickel
Iron
Molybdenum
Ammonia (as N)
TSS
PH
(c) Vanadium
121.720
25.625
24.460
111.819
69.887
Reserved
24114.000
2387.800
Within the range
Decomposition Wet Air
54.162
10.483
11.648
73.964
35.526
Reserved
10600.000
1135.660
of 7.5 to 10.0 at
Pollution Control
all times
BPT
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg(Ib/million Ibs)of vanadium produced by decomposition
Arsenic 0.000 0.000
Chromium 0.000 0.000
Lead 0.000 0.000
Nickel 0.000 0.000
Iron 0.000 0.000
Molybdenum 0.000 0.000
Ammonia (as N) 0.000 0.000
TSS 0.000 0.000
pH Within the range of 7.5 to 10.0 at all times
(d) Molybdenum Drying Wet Air Pollution Control BPT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum produced
Arsenic 0.000 0.000
Chromium 0.000 0.000
Lead 0.000 0.000
Nickel 0.000 0.000
Iron 0.000 0.000
Molybdenum 0.000 0.000
Ammonia (as N) 0.000 0.000
TSS 0.000 0.000
pH Within the range of 7.5 to 10.0 at all times
3502
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - TJ
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - II
(b) Molybdenum Filtrate Solvent Extraction Raffinate BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of technical grade molybdenum
plus vanadium plus pure grade molybdenum produced
Arsenic 80.952 36.108
Chromium 21.548 8.736
Lead 16.306 7.571
Nickel 32.031 21.548
Iron 69.887 35.526
Molybdenum Reserved Reserved
Ammonia 24114.000 10600.000
(c) Vanadium Decomposition Wet Air Pollution Control BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of vanadium produced by decomposition
Arsenic
Chromium
Lead
Nickel
Iron
Molybdenum
Ammonia (as N)
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
(d) Molybdenum Drying Wet Air Pollution Control BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum produced
Arsenic
Chromium
Lead
Nickel
Iron
Molybdenum
Ammonia (as N)
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
3504
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - II
(e) Pure Grade Molybdenum BAT
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of pure molybdenum produced
Arsenic 32.359 14.434
Chromium 8.614 3.492
Lead 6.518 3.026
Nickel 12.804 8.614
Iron 27.936 14.201
Molybdenum Reserved Reserved
Ammonia (as N) 9638.000 4237.000
NSPS are promulgated based on the performance achievable by the
application of ammonia air stripping, iron co-
precipitation/ chemical precipitation, sedimentation, and
multimedia filtration technology. The following effluent
standards are promulgated for new sources:
(a) Leach Tailings NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg(Ib/million Ibs) of technical grade molybdenum plus
vanadium plus pure grade molybdenum produced
Arsenic 27.120 12.097
Chromium 7.210 2.927
Lead 5.463 2.536
Nickel 10.731 7.219
Iron 23.413 11.902
Molybdenum Reserved Reserved
Ammonia (as N) 8078.000 3551.000
TSS 292.665 234.132
pH Within the range of 7.5 to 10.0 at all times
3505
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - II
(b) Molybdenum Filtrate Solvent Extraction Raff inate NSPS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of technical grade molybdenum plus
vanadium plus pure grade molybdenum produced
Arsenic
Chromium
Lead
Nickel
Iron
Molybdenum
Ammonia (as N)
TSS
pH
(c) Vanadium
80.952
21.548
16.308
32.031
69.887
Reserved
24114.000
873.585
Within the range of
Decomposition Wet Air
36.108
8.736
7.571
21.548
35.526
Reserved
10600.000
698.868
7.5 to 10.0 at all
Pollution Control
times
NSPS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of vanadium produced by decomposition
Arsenic 0.000 0.000
Chromium 0.000 0.000
Lead 0.000 0.000
Nickel 0.000 0.000
Iron 0.000 0.000
Molybdenum 0.000 0.000
Ammonia (as N) 0.000 0.000
TSS 0.000 0.000
pH Within the range of 7.5 to 10.0 at all times
(d) Molybdenum Drying Wet Air Pollution Control NSPS
Pollutant or Maximum for Maximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum produced
Arsenic 0.000 0.000
Chromium 0.000 0.000
Lead 0.000 0.000
Nickel 0.000 0.000
Iron 0.000 0.000
Molybdenum 0.000 0.000
Ammonia (as N) 0.000 0.000
TSS 0.000 0.000
pH Within the range of 7.5 to 10.0 at all times
3506
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - II
(e) Pure Grade Molybdenum NSPS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (pounds per million pounds) of pure molybdenum produced
Arsenic 32.359 14.434
Chromium 8.614 3.492
Lead 6.518 3.026
Nickel 12.804 8.614
Iron 27.936 14.201
Molybdenum Reserved Reserved
Ammonia (as N) 9638.000 4237.000
TSS 349.200 279.360
pH With the range of 7.5 to 10.0 at all times
PSES are not being promulgated for this subcategory at this time
because there are no existing indirect dischargers in the
secondary molybdenum and vanadium subcategory.
PSNS are promulgated based on the performance achievable by the
application of ammonia air stripping, iron co-precipitation,
chemical precipitation, sedimentation, and multimedia
filtration technology. The following pretreatment standards
are promulgated for new sources:
(a) Leach Tailings PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of technical grade molybdenum plus
vanadium plus pure grade molybdenum produced
Arsenic 27.120 12.097
Chromium 7.219 2.927
Lead 5.463 2.536
Nickel 10.731 7.219
Iron 23.413 11.902
Molybdenum Reserved Reserved
Ammonia (as N) 8078.000 3551,000
3507
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - II
(b) Molybdenum Filtrate Solvent Extraction Raffinate PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of technical grade molybdenum
plus vanadium plus pure grade molybdenum produced
Arsenic 80.952 36.108
Chromium 21.548 ' 8.736
Lead 16.306 7.571
Nickel 32.031 21.548
Iron 69.887 35.526
Molybdenum Reserved Reserved
Ammonia (as N) 24114.000 10600.000
(c) Vanadium Decomposition Wet Air Pollution Control PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million
Arsenic
Chromium
Lead
Nickel
Iron
Molybdenum
Ammonia (as N)
Ibs) of vanadium produced by decomposition
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
(d) Molybdenum Drying Wet Air Pollution Control PSNS
Pollutant orMaximum forMaximum for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs) of molybdenum produced
Arsenic
Chromium
Lead
Nickel
Iron
Molybdenum
Ammonia (as N)
o.ooo
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
3508
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - II
(e) Pure Grade Molybdenum PSNS
Pollutant or Maximum for Maximum "'for
Pollutant Property Any One Day Monthly Average
mg/kg (Ib/million Ibs'j of pure molybdenum produced
Arsenic 32.359 14.434
Chromium 8.614 3.492
Lead 6.518 3.026
Nickel 12.804 8.614
Iron 27.936 14.201
Molybdenum Reserved Reserved
Ammonia (as N) 9638.000 4237.000
EPA is not promulgating BCT at this time for the secondary
molybdenum and vanadium subcategory.
3509
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - II
THIS PAGE INTENTIONALLY LEFT BLANK
3510
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - III
SECTION III
SUBCATEGORY PROFILE
This section of the secondary molybdenum and vanadium supplement
describes the raw materials and processes used in refining
secondary molybdenum and vanadium and presents a profile of the
secondary molybdenum and vanadium plants identified in this
study.
Molybdenum is used primarily as an alloying agent in steel and
in other metallurgical applications. Molybdenum's predominant
use in metallurgy stems from its high hot strength and
corrosion resistant characteristics. Molybdenum in steel,
ferroalloys, and nonferrous alloys increases wear resistance,
strength, and toughness much like other common alloying elements,
however, it also imparts the unique properties of hot strength
and corrosion resistance as well. Molybdenum compounds are
widely used in applications as principal catalysts, in the
manufacture of colored pigments for dyeing and ceramics glazing,
and as lubricants and soluble corrosion inhibitors for aqueous
and select organic solutions.
Like molybdenum, the most important use of vanadium is as an
alloying agent in steel. The addition of vanadium increases
hardenability and grain refinement in steel which yields
greater toughness and impact resistance. High temperature
strength and wear resistance are also favorable properties
imparted by vanadium. Such alloys are used for aircraft engines
and turbine blades where high-temperature creep resistance is a
requirement; these properties are also increasing interest in
vanadium as a fuel-element cladding for fast-breeder reactors.
Vanadium compounds are key industrial catalysts for both organic
and inorganic reactions. Oxides of vanadium added to glass in
small quantities filter harmful ultraviolet radiation from
natural light.
DESCRIPTION OF SECONDARY MOLYBDENUM AND VANADIUM PRODUCTION
Secondary molybdenum and vanadium production involves five basic
process steps: roasting, leaching, vanadium recovery, molybdenum
recovery, and solvent extraction. The five basic processes are
shown schematically in Figure III-l (page 3515) and are described
below.
RAW MATERIALS
Spent hydrodesulfurization (HDS) catalysts are used as raw
materials for secondary molybdenum and vanadium production. The
catalysts become spent or inactive when they are exhausted
through extended use or contaminated with impurities, or some
combination of both factors. Impurities which may contaminate or
deactivate HDS catalysts include heavy metals such as lead,
3511
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - III
nickel, vanadium or other metals depending on the specific
catalyst and its use.
HDS catalysts are generally composed of a substrate such as sand
(silicates) or zeolite, coated with active substances such as
molybdenum, precious metals, and others. Catalysts are used for
different applications and each application requires a specific
catalytic composition. The mass of molybdenum and vanadium in a
spent catalyst is usually small (<12 percent) compared with the
total mass of the catalyst.
ROASTING
The first step in recovering molybdenum and vanadium from spent
HDS catalysts is to roast the catalysts in a furnace. Sodium
carbonate (Na2C03) may be added to the furnace. Off-gases from
the roasting furnace, containing dust and particulates, are
controlled by an electrostatic precipitator prior to discharging
to the atmosphere. The solids collected in the precipitator may
be returned to the roaster.
Catalysts are roasted to burn off carbonaceous material, such
as residual oil, sulfur and other combustible residues
remaining on the catalysts. Roasting converts the molybdenum and
vanadium metals to their sodium salts.
LEACHING
After roasting, the calcine is quenched, ground and leached with
water. The leaching process produces a pregnant liquor
containing molybdenum and vanadium values which is sent on
for further processing. The barren leach tailings are
separated from the solution by countercurrent decantation and
discharged as a waste stream to a tailings pond for additional
settling. The supernatant from the tailings pond is recovered
and routed to solvent extraction.
VANADIUM RECOVERY
The initial step of vanadium recovery is removal of phosphorus
by precipitation as insoluble magnesium phosphates. Aluminum, if
it is present in solution, is removed as the hydroxide by
acidification followed by filtration. Vanadium is then
precipitated as ammonium metavanadate (AMV) with excess NH4C1,
and is separated from the liquid phase by filtration. Molybdenum
does not precipitate and the molybdenum-rich filtrate is routed
to the molybdenum recovery process.
The ammonium metavanadate produced by the NH^jCl precipitation is
calcined and fused to produce vanadium pentoxide. Other vanadium
products include a solution of sodium ammonium vanadate and
potassium metavanadate solutions both of which are used in the
preparation of new catalysts. The off-gases from the calcine
furnace are controlled with a dry baghouse which recovers the
dust and particulates. In series with the baghouse is a wet
3512
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - III
scrubber employing a dilute hydrochloric acid solution as the
scrubbing medium. The scrubber liquor is routed to the ammonia
recovery and reuse system. There are no wastewater streams
discharged from the vanadium products manufacturing processes.
MOLYBDENUM RECOVERY
Molybdenum is recovered from the pregnant solution by heating and
acidification to produce molybdic acid (H2MoO4), using
hydrochloric acid and steam. Molybdic acid solids are recovered
on a filter and washed with dilute hydrochloric acid. The
filtrate from this step is returned to the process.
Both technical grade and high purity molybdic oxide are produced
from molybdic acid. Molybdic acid is calcined to produce
technical grade molybdic oxide (93-96 % MoO3). There is a
scrubber controlling off-gases from this kiln. Spent liquor from
this scrubber is returned to the process.
Pure (99.8 percent) molybdic oxide is also produced from molybdic
acid. Molybdic acid is dissolved in ammonia water, purified,
reprecipitated and calcined to pure oxide containing a minimum of
99.8 percent MoO3.
SOLVENT EXTRACTION
Molybdenum filtrate and supernatant from the tailings pond
(containing leach tailings as well as stormwater runoff) are
routed through solvent extraction to recover molybdenum and
vanadium values prior to discharge to treatment. In the solvent
extraction process a reagent containing fatty quarternary amines
and kerosene is used to effect this recovery. The molybdenum and
vanadium-rich stream from this recovery step is returned to
the main process just prior to precipitating the vanadium from
solution. The molybdenum filtrate and pond water raffinates
from the solvent extraction process are discharged to wastewater
treatment.
PROCESS WASTEWATER SOURCES
The significant wastewater sources associated with the secondary
molybdenum and vanadium subcategory are as follows:
1. Leach tailings,
2. Molybdenum filtrate solvent extraction raffinate,
3. Vanadium decomposition wet air pollution control,
4. Molybdenum drying wet air pollution control, and
5. Pure grade molybdenum.
OTHER WASTEWATER SOURCE
There are other wastewater stream associated with the production
of secondary molybdenum and vanadium. These streams may include
maintenance and cleanup water, and stormwater runoff. These
wastewaters are not considered as part of this rulemaking. EPA
3513
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
SECT - III
believes that the flow and pollutant loadings associated with
these streams are insignificant relative to the waste
streams selected and are best handled by the appropriate permit
authority on a case-by—case basis
403(a) of the Clean Water Act.
AGE, PRODUCTION, AND PROCESS PROFILE
appropriate
under authority of Section
One secondary molybdenum and vanadium plant in the United
States is located in southern Texas. It is a direct discharge
facility, and was built in 1973. The production of molybdenum is
slightly less than 1000 tons per year contained in the
Ho03 product, and production of vanadium is less than -500
tons per year contained in V20g product.
After concluding the settlement agreement for this subcategory,
EPA learned of the probable existence of two additional
molybdenum and vanadium recovery facilities. No substantial
technical information is available on these facilities.
3514
-------
U)
Ol
SPENT
CATALYST
1
SODA ASH
ROASTING
1
GRINDING
LEACHING
«i
!
CCD
•Oi
\
TAILINGS
n
0
fO
NH4CI ^
. |
_ , , , T m
. ^-
•
^
SOLUTION
PURIFICATION
VANADIUM
PRECIPITATION
O
CALCINATION v o • @
**" FUSION •- * *» d
3
t HCI 1 f „ |
P.AI.Mg 1 4 1 3 <
-*•
SX
OF MoV
MOLYBDENUM
PRECIPITATION
L >
"^ 0
—p CALC,NAT,0N MC03 J
»? . «s
I 1
RECOVERY
WATER
TREATMENT
O
fc BARREN §
" SOLUTION K!
*W
3
NH4CI ,
H
FIGURE III-l H
SECONDARY MOLYBDENUM AND VANADIUM PRODUCTION PROCESSES
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - III
THIS PAGE INTENTIONALLY LEFT BLANK
3516
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - IV
SECTION IV
SUBCATEGORIZATION
This section summarizes the factors considered during the
designation of the subdivisions or building blocks in the
secondary molybdenum and vanadium subcategory.
FACTORS CONSIDERED IN SUBDIVIDING THE SECONDARY MOLYBDENUM AND
VANADIUM SUBCATEGORY
The factors listed for general subcategorization were each
evaluated when considering subdivision of the secondary
molybdenum and vanadium subcategory. In the discussion that
follows, the factors will be described as they pertain to this
particular subcategory.
The rationale for considering segmentation of the secondary
molybdenum and vanadium subcategory is based primarily on
differences in the production processes and raw materials used.
Within this subcategory, a number of different operations are
performed, which may or may not have a water use or discharge,
and which may require the establishment of separate effluent
limitations. While secondary molybdenum and vanadium is
considered a single subcategory, a more thorough examination of
the production processes has illustrated the need for limitations
and standards based on specific flow allowances for the following
subdivisions:
(a). Leach tailings,
(b). Molybdenum filtrate solvent extraction raffinate,
(c). Vanadium decomposition wet air pollution control,
(d). Molybdenum drying wet air pollution control, and
(e). Pure grade molybdenum.
These subdivisions follow directly from differences within
several of the production stages of secondary molybdenum and
vanadium: leaching of calcined raw material, and recovery and
purification of molybdenum and vanadium products. The other
production stages, roasting of spent catalysts and vanadium
recovery, do not generate a need for subdivisions because no
process wastewater is generated.
Leaching of calcined raw material gives rise to the first
subdivision, leach tailings. The calcined raw material is
leached with water, and the solution containing molybdenum and
vanadium is sent on for further processing. The inerts and other
impurities are discharged to a tailings pond. The tailings pond
overflow is discharged as a waste stream after solvent extraction
for molybdenum and vanadium recovery.
Recovery and purification of molybdenum and vanadium products
creates the need for the remaining four subdivisions: molybdenum
3517
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - IV
filtrate solvent extraction raffinate, vanadium decomposition
scrubber, molybdenum drying scrubber, and pure grade molybdenum
wastewater.
The vanadium precipitate produced in the molybdenum-vanadium
separation process may be decomposed to vanadium oxide in a
decomposition furnace. The wet air pollution control associated
with this furnace creates the need for the vanadium decomposition
scrubber subdivision.
OTHER FACTORS
The other factors considered in this evaluation were shown to be
inappropriate bases for subdivision. Air pollution control
methods, treatment costs, and total energy requirements are
functions of the selected subcategorization factors — metal
product, raw materials, and production processes. Therefore,
they are not independent factors and do not affect the
subcategorization which has been applied.
PRODUCTION NORMALIZING PARAMETERS
As discussed previously, the effluent limitations and standards
developed in this document establish mass limitations on the
discharge of specific pollutant parameters. To allow these
regulations to be applied to plants with various production
capacities, the mass of pollutant discharged must be related to a
unit of production. This factor is known as the production
normalizing parameter (PNP).
In general, for each production process which has a wastewater
associated with it, the actual mass of molybdenum and vanadium
product or intermediate produced will be used as the PNP. Thus,
the PNPs for the five subdivisions are as follows:
Building Block
1. Leach tailings
2. Molybdenum filtrate solvent
extraction raffinate
3. Vanadium decomposition wet
air pollution control
4. Molybdenum drying wet air
pollution control
PNP
kkg of technical grade
molybdenum plus vanadium
plus pure grade molybdenum
produced
kkg of technical grade
molybdenum plus vanadium
plus pure grade molybdenum
produced
kkg of vanadium produced by
decomposition
kkg of molybdenum produced
3518
-------
SECONpRR? MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - IV
5. Pure grade molybdenum kkg of pure molybder..-w, produced
Other PNPs were considered. The use of production capacity or
raw material processed instead of actual production w&.-.
eliminated from consideration because the mass of the pollutant
produced is more a function of true production than of installed
capacity or raw material processed.
3519
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - IV
THIS PAGE INTENTIONALLY LEFT BLANK
3520
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - V
SECTION V
WATER USE AND WASTEWATER CHARACTERISTICS
This section describes the characteristics of wastewater
associated with the secondary molybdenum and vanadium
subcategory. Data used to quantify wastewater flow and pollutant
concentrations are presented, summarized, and discussed. The
contribution of specific production processes to the overall
wastewater discharge from secondary molybdenum and vanadium
plants is identified whenever possible.
The two principal data sources .used are data collection
portfolios (dcp) and field sampling results. Data collection
portfolios, completed for one of the secondary molybdenum and
vanadium plants, contained information regarding wastewater flows
and production levels.
In order to quantify the pollutant discharge from secondary
molybdenum and vanadium plants, a field sampling program was
conducted. The field sampling program was conducted following
proposal. A complete list of the pollutants considered and a
summary of the techniques used in sampling and laboratory
analyses are included in Section V of the General Development
Document. Samples were analyzed for 124 of the 126
priority pollutants and other pollutants deemed appropriate.
Because the analytical standard for TCDD was judged to be too
hazardous to be made generally available, samples were never
analyzed for this pollutant. There is no reason to expect
that TCDD would be present in nonferrous metals manufacturing
wastewater. Asbestos was not analyzed for, nor is there any
reason to expect that asbestos would be present in
secondary molybdenum and vanadium wastewater. In general, the
samples were analyzed for three classes of pollutants:
priority organic pollutants, priority metal pollutants and
criteria pollutants (which includes conventional and
nonconventional pollutants).
Additional wastewater characteristics and flow and production
data were obtained by the Agency following proposal through a
field sampling visit to one facility. As described in Section
IV of this supplement, secondary molybdenum and vanadium
plants have been subdivided into five subdivisions or
wastewater sources, so that the promulgated regulation
contains mass discharge limitations and standards for five
building blocks discharging process wastewater. Differences in
the wastewater characteristics associated with these
subdivisions are to be expected. For this reason, wastewater
streams corresponding to each subdivision are addressed
separately in the discussions that follow. These wastewater
sources are:
3521
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - V
(a). Leach tailings,
(b). Molybdenum filtrate solvent extraction raffinate,
(c). Vanadium decomposition wet air pollution control,
(d). Molybdenum drying wet air pollution control, and
(e). Pure grade molybdenum.
WASTEWATER FLOW RATES
Data supplied by data collection portfolio responses were
evaluated, and two flow-to-production ratios were calculated
for each stream. The two ratios, water use and wastewater
discharge flow, are differentiated by the flow value used in
calculation. Water use is defined as the volume of water or
other fluid (e.g., emulsions, lubricants) required for a given
process per mass of molybdenum and vanadium product and is
therefore based on the sum of recycle and make-up flows to a
given process. Wastewater flow discharged after pretreatment or
recycle (if these are used) is used in calculating the production
normalized flow—the volume of wastewater discharged from a
given process to further treatment, disposal, or discharge per
mass of molybdenum and vanadium produced. Differences between
the water use and wastewater flows associated with a given
stream result from recycle, evaporation, and carry-over on
the product. The production values in calculation correspond to
the production normalizing parameter, PNP, assigned to each
stream/ as outlined in Section IV.
As an example, molybdenum filtrate solvent extraction raffinate
wastewater flow is related to the production of molybdenum and
vanadium. As such, the discharge rate is expressed in liters of
molybdenum filtrate solvent extraction raffinate per metric ton
of technical grade molybdenum plus vanadium plus pure grade
molybdenum produced (gallons of molybdenum filtrate solvent
extraction raffinate wastewater per ton of technical grade
molybdenum plus vanadium plus pure grade molybdenum produced).
The production normalized flows were compiled by stream type
The reported water use and discharge rates for the
identified secondary molybdenum and vanadium wet operations are
given in Tables V-l through V-5 (pages 3526 - 3527). Where
appropriate, an attempt was made to identify factors that could
account for variations in water use and discharge rates. This
information is summarized in this section. A similar
analysis of factors affecting the wastewater values is
presented in Sections IX, X, XI, and XII, where
representative BPT, BAT, NSPS, and pretreatment discharge flows
are selected for use in calculating the effluent
limitations and standards.
The water use and discharge rates shown do not include nonprocess
wastewater, such as rainfall runoff and noncontact cooling water.
WASTEWATER CHARACTERISTICS DATA
Data used to characterize the various wastewaters associated with
3522
-------
SECONDMIY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - V
secondary molybdenum and vanadium production come from two
sources — data collection portfolios and analytical data
from field sampling.
DATA COLLECTION PORTFOLIOS
In the data collection portfolios, plants were asked to specify
the presence of any of the priority pollutants in their
effluent. None of the plants that responded to this
portion of the questionnaire indicated the presence of priority
organic pollutants.
The responses for the priority metals are shown below.
Known Believed
Pollutant Present . Present
Antimony 1 0
Arsenic 1 0
Beryllium 1 0
Cadmium 1 0
Chromium 1 0
Copper 1 0
Lead 1 0
Mercury 0 0
Nickel 1 1
Selenium 0 0
Silver 0 0
Thallium 0 0
Zinc 1 0
FIELD SAMPLING DATA
in order to quantify the concentrations of pollutants present in
wastewater from secondary molybdenum and vanadium plants,
wastewater samples were collected at one plant.
Raw wastewater data (Tables V-6 through V-9) are not presented in
this document because they have been claimed confidential by the
sampled facility. The treated wastewater sampling data for the
facility are presented in Table V-10 (page 3536). Where no data
are listed for a specific day of sampling, the wastewater samples
for the stream were not collected.
Several points regarding the data tables should be noted. First,
the detection limits shown on the data tables for priority
metals and conventional and nonconventional pollutants are not
the same in all cases as the published detection limits
for these pollutants by the same analytical methods. The
detection limits used were reported with the analytical data and
hence are the appropriate limits to apply to the data.
Detection limit variation can occur as a result of a number
of laboratory- specific, equipment-specific, and daily
3523
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - V
operator-specific factors. These factors can include day-to-day
differences in machine calibration, variation in stock
solutions, and variation in operators.
Second, the statistical analysis of data includes some samples
measured at concentrations considered not quantifiable. For data
considered as detected but below quantifiable concentrations, a
value of zero is used for averaging. Nonconventional and
conventional pollutant data reported with a "less than" sign
are considered as detected, but not further quantifiable. A
value of zero is also used for averaging. If a pollutant is
reported as not detected, it is assigned a value of zero in
calculating the average. Finally, priority metal values reported
as less than a certain value were considered as not
quantifiable, and consequently were assigned a value of zero in
the calculation of the average.
Appropriate source water concentrations are presented with the
summaries of the sampling data.
WASTEWATER CHARACTERISTICS AND FLOWS BY SUBDIVISION
Since the secondary molybdenum and vanadium subcategory has been
divided into five subdivisions, and the waste stream from each
subdivision has potentially different characteristics and
flows, the wastewater characteristics and discharge rates
corresponding to each subdivision will be described separately.
LEACH TAILINGS
The calcined product from the roasting furnace is quenched,
ground and leached with water to dissolve molybdenum and
vanadium. The product from leaching is a solution containing
molybdenum and vanadium. Leaching also creates tailings which
are discharged to a tailings pond. The overflow from the
tailings pond is discharged as a waste stream after solvent
extraction. One plant generates a leach tailings waste
stream, and its water use and discharge rates are presented in
Table V-l (page 3526), based on data reported in the dcp.
The data for leach tailings are not presented in this document
because their have been claimed confidential by the sampled
facility.
MOLYBDENUM FILTRATE SOLVENT EXTRACTION RAFFINATE
After vanadium precipitation and filtration, molybdenum may be
recovered from the vanadium free solution by precipitation as
molybdic acid. The depleted solution is filtered away and the
molybdic acid solids are washed with water. The combined
depleted solution and wash water is treated with solvent
extraction to recover additional product. One plant generates
a molybdenum filtrate solvent extraction raffinate waste
stream, and its water use and discharge rates are presented
in Table V-2 (page 3526), based on data gathered during a
3524
-------
SL'CONDARX MOLYBDENUM AND VANADIUM SUBCATEGORX SECT - V
sampling visit.
The date for molybdenum filtrate solvent extraction raffinate are
not presented in this document because they have been claimed
confidential by the sampled facility.
VANADIUM DECOMPOSITION WET AIR POLLUTION CONTROL
Vanadium solids produced in the molybdenum-vanadium separation
step may be decomposed in a furnace to vanadium oxide.
Off-gases from the decomposition furnace may be controlled with
a scrubber with a wastewater discharge. One plant reported
having a scrubber, but reuses all of the scrubber liquor in a
co-product recovery operation. The water use and discharge
rates for vanadium decomposition wet air pollution control are
presented in Table V-3 (page 3526).
The date for vanadium decomposition wet air pollution control is
not presented in this document because they have been claimed
confidential by the sampled facility.
MOLYBDENUM DRYING WET AIR POLLUTION CONTROL
Molybdic acid produced in the molybdenum recovery operation may
be converted to technical grade molybdenum trioxide in a drying
furnace. A wet scrubber may be used to control emissions from
this process, and the scrubber liquor reused in the
manufacturing process. The water use and discharge rates for
molybdenum drying wet air pollution control are presented in
Table V-4 (page 3527).
The chemical analysis date for molybdenum drying wet air
pollution control are not presented in this document because they
have been claimed confidential by the sampled facility.
PURE GRADE MOLYBDENUM
As a result of new information made available after promulgation
of the regulation, EPA agreed to establish a new building block
for pure grade molybdenum wastewater for this subcategory. This
building block was not included in the promulgated rule because
the wastewater from this operation was included as part of the
flow from the molybdenum filtrate solvent extraction building
block. The new information indicated that the pure grade
molybdenum process and the molybdenum solvent extraction
operations are not directly linked as the Agency had believed.
This new building block would apply to the production of pure
grade molybdenum from commercial grade molybdenum and as shown in
Table V-5 (page 3527) is based on a production normalized flow of
23,280 1/kkg of pure molybdenum produced.
3525
-------
SECONDARY MOLYBDENUM AND VANADIUM SU1CATEGORY SECT - V
TABLE V-l
WATER OSE AND DISCHARGE RATES FOR LEACH TAILINGS
(1/kkg of technical grade molybdenum plus
pure grade molybdenum plus vanadium produced)
Plant Code
1119
Percent Recycle
or Reuse
0
Production
Normalized
Water Use Flow
19511
Production
Normalized
Discharge Flow
19511 -
TABLE V-2
WATER USE AND DISCHARGE RATES FOR
MOLYBDENUM FILTRATE SOLVENT EXTRACTION RAFFINATE
(1/kkg of technical grade molybdenum plus
pure grade molybdenum plus vanadium produced)
Plant Code
Percent Recycle
or Reuse
Production
Normalized
Water Use Flow
Production
Normalized
Discharge Flow
1119
58239
58239
Table V-3
WATER USE AND DISCHARGE RATES FOR
VANADIUM DECOMPOSITION WET AIR POLLUTION CONTROL
(1/kkg of vanadium produced by decomposition)
Plant Code
Percent Recycle
or Reuse
Production
Normalized
Water Use Flow
Production
Normalized
Discharge Flow
1119
100
27900
3526
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - V
TABLE V-4
WATER USE AND DISCHARGE RATES FOR
MOLYBDENUM DRYING WET AIR POLLUTION CONTROL
(1/kkg of molybdenum produced)
Plant Code
Percent Recycle
or Reuse
Production Production
Normalized Normalized
Water Use Flow Discharge Flow
1119
100
629
0
TABLE V-5
WATER USE AND DISCHARGE RATES FOR
PURE GRADE MOLYBDENUM
(1/kkg of pure grade molybdenum produced)
Plant Code
Percent Recycle
or Reuse
Production
Normalized
Water Use Flow
Production
Normalized
Discharge Flow
1119
23280
23280
3527
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORX SECT - V
TABLE V-6
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
' RAW WASTEWATER SAMPLING DATA
LEACH TAILINGS
Stream Sample Concentrations (mg/1)
Pollutant Code Type Source Day-1 Day-2 Day-3
These data have been claimed as
confidential business information.
TABLE V-7
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
RAW WASTEWATER SAMPLING DATA
MOLYBDENUM FILTRATE SOLVENT EXTRACTION RAPFINATE
Stream Sample Concentrations (mg/1)
Pollutant Code Type Source Day-1 Day-2 Day-3
These data have been claimed as
confidential business information.
TABLE V-8
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
RAW WASTEWATER SAMPLING DATA
MOLYBDENUM FILTRATE
Stream Sample Concentrations (mg/1)
Pollutant Code Type Source Day-1 Day-2 Day-3
These data have been claimed as
confidential business information.
T.-BLE V-9
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
RAW WASTEWATER SAMPLING DATA
POND WATER SOLVENT EXTRACTION RAFFINATE
Stream Sample Concentrations (mg/1)
Pollutant Code Type Source Day-1 Day-2 Day-3
These data have been claimed as
confidential business information.
3528
-------
TABLE V-10
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
SEDIMENTATION EFFLUENT
Ui
U1
10
Pollutant
Toxic Pollutants
1. acenaphthene
2. acroleln
3. acrylonltrile
4. benzene
5. benzidine
6. carbon tetrachloride
7. chlorobenzene
8. 1,2,4-trlchlorobenzene
9. hexachlorobenzene
10. 1,2-dichloroethane
11. 1,1,1-trlchloroethane
12. hexachloroethane
13. 1,1-dichloroethane
14. 1,1', 2- trichloroe thane
WASTEWATER SAMPLI
Stream Sample
Code Typet
388
388
388
388
388
388
388
388
388
388
388
388
388
388
6
1
1
1
6
1
1
6
6
1
1
6
1
1
NG DATA |
o
§
Concentrations (mg/1) >
Source
ND
ND
ND
ND
ND
0.003 .
ND
ND
ND
ND
ND
ND
ND
ND
Day 1
ND
ND/ND
ND/ND
ND/ND
ND
ND/ND
ND/ND
ND
ND
ND/ND
ND/ND
ND
ND/ND
ND/ND
Day 2 Day 3 3
i
1
I
^
i
i
M
§
en
i
n
1-3
w
o
K
0)
w
0
4
-------
TABLE V-10 (Continued)
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
SEDIMENTATION EFFLUENT
CO
Pollutant
Toxic Pollutants (Continued)
15. 1,1 ,2,2-tetrachloroethane
r
1 6. chloroethane
17. b is (chloromethyl) ether
18. bis(2-chloroethyl)ether
19. 2-chloroethyl vinyl ether
20. 2-chloronaphthalene
21. 2,4,6-trichlorophenol
22. p-ehloro-m-cresol
23. chloroform
24. 2 -chloro phenol
25. 1 ,2-diehlorobenzene
26. 1 ,3-dichlorobenzene
27. 1 ,4-dichlorobenzene
28. S.S'-dichlorobenzidine
WASTEWATER SAMPLING DATA g
SJ
i
Stream Sample Concentrations (mg/1) g
Code
338
388
388
388
388
388
388
388
388
388
388
388
388
388
Typet
1
1
1
6
1
6
6
6
1
6
6
6
6
6
Source
ND
ND
ND
ND
ND
ND
ND
ND
0.094
ND
ND
ND
ND
ND
Day 1
ND/ND
ND/ND
ND/ND
ND
ND/ND
ND
ND
ND
ND/ND
ND
ND
ND
ND
ND
Day 2 Day 3
1
o
m
s
o
1
§
H
s
w
a
w
o
w
65
O
R
w
w
n
H
•
<
-------
TABLE V-10 (Continued)
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
SEDIMENTATION EFFLUENT
TREATED WASTEWATER
LO
Ul
Pollutant
Toxic Pollutants (Continued)
29. 1,1-dIchloroethylene
30. 1,2-trana-dIchloroethylene
31. 2,4-dichlorophenol
32. 1,2-d ichloropropane
33. 1,3-dichloropropene
34. 2,4-dimethylphenol
35. 2,4-dinltrotoluene
36. 2,6-dlnltrotoluene
37. 1,2-dlphenylhydrazlne
38. ethylbenzene
39. fluoranthene
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. bis(2-chloroisopropyl)ether
Stream
Code
388
388
388
388
388
388
388
388
388
388
388
388
388
388
Sample
Typet
1
1
6
1
1
6
6
6
6
1
6
6
6
6
o
Q
Concentrations (mg/1) §
Source
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Day 1
ND/ND
ND/ND
ND
ND/ND
ND/ND
ND
ND
ND
ND
ND/ND
ND
ND
ND
ND
Day 2 Day 3 g
K
S
O
r1
ti
O
1
B
o
1
8
H
W
§
O
B
Q
O
a
w
w
(1
1
^
-------
TABLE V-10 (Continued)
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
SEDIMENTATION EFFLUENT
Ul
Pollutant
Toxic Pollutants (Continued)
43. bis(2-ehoroethoxy)raethane
44. raethylene chloride
45. methyl chloride (chloromethane)
46. methyl bromide (broraomethane)
47. bromoform (tribromoraethane)
48. dichlorobroraoraethane
49. trichlorofluoromethane
50. dichlorodifluororaethane
51. chlorodibroraoraethane
52. hexachlorobutadiene
53. hexachlorocyclopentadiene
54. isophorone
55. naphthalene
56. nitrobenzene
WASTEWATER SAMPLING DATA
Stream Sample Concentrations (mg/1)
Code Typet
388
388
388
388
388
388
388
388
388
388
388
388
388
388
6
1
1
1
1
1
1
1
1
6
6
6
6
6
Source
ND
ND
NO
ND
0.006
0.038
ND
ND
0.030
ND
ND
ND
ND
ND
Day 1 Pay 2
ND
14.00/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND/ND
ND
ND
ND
0.027
ND
en
W
O
o
Day 3 q
o
1
D
. |
g
O
B
H
W
§
n
>
o
K
tn
w
o
i
-------
TABLE V-10 (Continued)
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
SEDIMENTATION EFFLUENT
en
u>
Pollutant
Toxic Pollutants (Continued)
57. 2-nltrophenol
58, 4-nitrophehol
59. 2,4-dlnitrophenol
60. 4,6-dinttro-o-eresol
61. N-nitrosodiraethylanilne
62. N-nitrosodiphenylamine
63. N-nttrosodt-n-propylamtne
64. pentachlocophenol
65. phenol
66. bis(2-ethylhexyl) phthalate
67. butyl benzyl phthalate
68. di-n-butyl phthalate
69. di-n-octyl phthalate
70. die thy 1 phthalate
WASTEWATER SAMPLING DATA w
o
§
Stream Sample Concentrations (ma/1) g
Code
388
388
388
388
388
388
388
388
388
388
388
388
388
388
Typet
6
6
6
6
6
6
6
6
6
6
6
6
6
6
Source
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Day 1
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Day 2 Day 3 £
3
O
d
1
§
<
s
H
i
CO
a
o
§
M
a
o
Kj
w
m
3
i
<
-------
TABLE V-10 (Continued)
Pollutant
Toxic Pollutants (Continued)
71. dimethyl phthalate
72. benzo (a) anthracene
73. benzo(a)pyrene
u» 74. benzo (b)fluoranthene
75. benzo (k)fluoran thane
76. ehrysene
77. acenaphthylene
78. anthracene (a)
79. benzo (ghi)perylene
80. fluorene
81. phenanthrene (a)
82. dibenzo (a, h) anthracene
83. indeno (1,2, 3-c ,d)pyrene
84. pyrene
>L>ijuuri r\nu vnutnui.wi <•
HMENTATION EFFLUENT
WASTEWATER SAMPLING
Stream Sample
Code Typet
388
388
388
388
388
388
388
388
388
388
388
388
388
388
6
6
6
6
6
6
6
6
6
6
6
6
6
6
Hju\jni.ij\3\jL\i.
DATA
Concentrations (rag/1)
Source
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
Day 1 Day 2
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
w
w
n
|
Day 3 3
o
IT*
s
o
1
K
o
g
8
H
W
CS
to
1-3
W
5
01
w
o
i
<
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
Ul
U)
Pollutant
Toxic Pollutants (Continued)
85. tetrachloroethylene
86. toluene
87. trichloroethylene
88. vinyl chloride (chloroethylene)
114. antimony
115. arsenic
117. beryllium
118. cadmium
119. chromium (total)
120. copper
121. cyanide (total)
122. lead
123. mercury
124. nickel
i inc.r< in 1 1 UH c,r r LI«J E.W i
WASTEWATER SAMPLING DATA
Stream Sample Concentrations (rag/1)
Code
388
388
388
388
388
388
388
388
388
388
388
388
388
388
Typet
1
1
1
1
6
6
6
6
6
6
1
6
6
6
Source
ND
ND
ND
ND
0.032
0.32
<0.02
<0.03
0.14
<0.05
<0.01
0.16
<0.005
<0.05
Day 1
ND/ND
ND/ND
ND/ND
ND/ND
0.038
0.010
<0.02
<0.03
<0.10
<0.05
<0.01
0.058
<0.005
<0.05
Day 2
0.084
0.0049
<0.01
<0.03
<0. 10
0.31
0.04
0.041
0.0063
0.30
Day 3
0.066
0.0060
<0.02
<0.03
<0.10
0.50
<0.01
0.065
0.0074
0.25
SECOND AK
K«
3
O
1
8
M
3
g
a
1
s
H
i
C
tfl
o
g
g
o
w
n
n
i
<
-------
TABLE V-10 (Continued)
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
SEDIMENTATION EFFLUENT
Pollutant
Toxic Pollutants (Continued)
125* selenium
126. silver
127, thallium
u> 128. zinc
in
w
** NonconventionalPollutants
Acidity
Alkalinity
Aluminum
Ammonia Nitrogen
Barium
Boron
Calcium
Chemical Oxygen Demand (COD)
Chloride
WASTEWATER SAMPLING DATA
Stream Sample Concentrations (mg/1)
Code Typet
388
388
388
388
388
388
388
388
388
388
388
388
388
6
6 .
6
6
6
6
6
6
6
6
6
6
6
Source
0.0045
<0.0005
<0.001
<0.10
20
123 1,
0.29
0.07 2,
<0.01
0.045
54.00
20
310 43,
Day 1
0.042
0.001
0.087
<0.10
<1
080 1
<0.25
400 1
<0.01
0.58
24.00
10
000 >19
Day 2
0.057
0.0013
0.085
<0.10
<10
,330 1.
0.97
,800 1,
<0.01
2.40
15.00
125
,000 >19»
Day 3
0.067
0.0016
0.067
0.20
<10
950
0.96
600
<0.01
2.20
11.5
850
000
SECONDARY MOI
i. '
a
o
1
1
1
H
§
w
§
/•"•*
:ATEGORY
W
0
1
<
-------
TABLE V-10 (Continued)
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
SEDIMENTATION EFFLUENT
TREATED
OJ
Ul
Pollutant
Nonconyen t ional Po 1 lutan t s (Continued)
Cobalt
Fluoride
Iron
Magnesium
Manganese
Molybdenum
Germanium
Phosphate
Sodium
Suifate
Tin
Titanium
Total Dissolved Solids (TDS)
Total Organic Carbon (TOC)
WAarnwAJ
Stream
Code
388
388
388
388
388
388
388
388
388
388
388
388
388
388
LE.K »AMfL.IWlJ UATA
Sample Concentrations (rag/L)
Typet
6
6
6
6
6
6
6
6
6
6
6
6
6
6
Source
0.17
0.4
0.33
18.00
0.017
0.94
0.74
0.70
52.00 22,
16 1,
<0.25
<0.25
430 62,
<10
Day 1
<0.03
1.0
0.34
130.00
0.22
12.00
0;55
2.0
000 10.
200 2,
<0.25
<0.25
000 130,
31
Day 2
2.70
1.8
0.35
120.00
0.16
52.00
0.78
7.9
000 13,
100 1,
<0.25
<0.25
000 90,
77
Day 3
2.10
1.4
0.31
140.00
22.0
57.00
0.76
9.0
000
700
<0.25
<0.25
000
280
SECOND
%
Nj
3
O
tr1
i
1
w
1
g
i
Cfl
§
n
i-i
m
Q
o
n
m
m
i
-------
TABLE V-10 (Continued)
ouviwiiuniM iiv>L>i.iJt/u»uri ni.iv vm.Tni7j.uri uuuvsnJLEiWvxJ.
SEDIMENTATION EFFLUENT
TREATED WASTEWATER SAMPLING DATA
Pollutant
Nonconventional Pollutants (Continued)
Total Solids (TS)
Vanadium
Yttrium
00
J2 Conventional Pollutants
00
Oil and Grease
Total Suspended Solids (TSS)
pH (standard units)
Stream
Code
388
388
388
388
388
388
Sample
Typet
6
6
6
1
6
Concentrations ^rag/1)
Source
490 66,
0.46
<0.13
8
<1
Day 1
000 89,
17.00
<0.13
23
56
7.0
Day 2
000 96,
20.00
<0.13
11
280
8.0
Day 3
000
22.00
<0.13
14
170
8.0
SECONDAI
Kj
&
O
tr1
S3
0
1
g
i
I
§
H
W
O
•M
Q
O
W
O
tSample Type Code: 1 - One-time grab i
6 - 24-hour automatic composite <
(a) Reported together.
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - VI
SECTION VI
SELECTION OF POLLUTANTS
This section examines chemical analysis data presented in
Section V and discusses the selection or exclusion of pollutants
for potential limitation. The discussion that follows presents
and briefly discusses the selection of conventional and
nonconventional pollutants for effluent limitations. Also
described is the analysis that was performed to select
or exclude priority pollutants for further consideration for
limitations and standards. Pollutants will be considered
for limitation if they are present in concentrations
treatable by the technologies considered in this analysis.
The treatable concentrations used for the priority
metals were the long-term performance values achievable
by chemical precipitation, sedimentation, and filtration.
The treatable concentrations used for the priority organics
were the long-term performance values achievable by carbon
adsorption.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS
As part of this study, the Agency examined samples for two
conventional pollutant parameters (total suspended solids and pH)
and several nonconventional pollutant parameters. On March 18,
1985, the Agency published a notice of data availability which
stated that the Agency was considering regulating the
nonconventional pollutants aluminum, ammonia, boron, cobalt,
germanium, iron, manganese, molybdenum, tin, titanium, and
vanadium in this subcategory. For promulgation, the Agency has
decided to regulate only the nonconventional pollutants ammonia,
iron and molybdenum. The remaining pollutants (aluminum, boron,
cobalt, germanium, manganese, tin, titanium and vanadium) are not
selected for limitation because they will be effectively
controlled by the limitations established for the selected
priority metal pollutants and the nonconventional metal
pollutants iron and molybdenum.
CONVENTIONAL AND NONCONVENTIONAL POLLUTANT PARAMETERS SELECTED
The conventional and nonconventional pollutants or pollutant
parameters selected for limitation in this subcategory are:
ammonia
molybdenum
iron
total suspended solids (TSS)
pH
Ammonia was measured in the raw wastewater at concentrations well
above the 32.2 mg/1 considered achievable with steam stripping
3539
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - VI
treatment and the 100 mg/1 achievable with air stripping
treatment. In addition, ammonia is expected to be present in
the wastewater based on the raw materials (NH4C1) used during
processing. For these reasons, ammonia is selected for
limitation in this subcategory.
Molybdenum was detected in the raw wastewater in concentrations
above the concentration considered achievable by treatment,
1.23 mg/1. Molybdenum was detected in all 8 raw
wastewater samples analyzed. For this reason and because it is
a principal metal produced in this subcategory, molybdenum is
selected for limitations in this subcategory.
Iron was detected in the raw wastewater in concentrations
exceeding the concentration considered achievable with treatment,
0.28 mg/1. iron was detected in all 8 raw wastewater samples
analyzed. In addition, iron is expected to be present in
the wastewater because of its use as a raw material in the iron
co-precipitation wastewater treatment system. For these
reasons, iron is selected for limitation in this subcategory.
TSS was measured in all 8 raw wastewater samples above the
treatable concentration of 2.6 mg/1. Although the pH of leach
tailings was measured at 9, which is within the 7.5 to 10 range
considered acceptable, the pH of molybdenum filtrate solvent
extraction raffinate was measured outside the acceptable range.
Most of the technologies used to remove priority metals do so
by carefully controlling pH, and converting the priority metals
to precipitates. Priority-metal-containing precipitates should
not be discharged. Meeting a limitation on total suspended
solids also ensures that sedimentation to remove
precipitated priority metals has been effective. For these
reasons, both total suspended solids and pH are
selected for limitation in this subcategory.
TOXIC PRIORITY POLLUTANTS
The frequency of occurrence of the priority pollutants in
the wastewater samples taken was computed but has been claimed
confidential by the one facility that was sampled. These data
provide the basis for the categorization of specific
pollutants, as discussed below. The frequency of occurrence
analysis is based on the raw wastewater data from streams
884 and 387 (see Section V). These sampling data are from
leach tailings and molybdenum filtrate solvent extraction
raffinate raw wastewaters.
TOXIC POLLUTANTS NEVER DETECTED
The toxic pollutants listed in Table VI-1 (page 3544) were not
detected in any wastewater samples from this subcategory;
therefore, they are not selected for consideration in
establishing limitations.
3540
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - VI
TOXIC POLLUTANTS NEVER
QUANTIFICATION LIMIT
FOUND ABOVE
THEIR
ANALYTICAL
The toxic pollutants listed below were never found above
their analytical quantification concentration in any wastewater
samples from this subcategory; therefore, they are not
selected for consideration in establishing limitations.
23. chloroform
126. silver
127. thallium
TOXIC POLLUTANTS PRESENT BELOW CONCENTRATIONS ACHIEVABLE BY
TREATMENT
The toxic pollutants listed below are not selected for
consideration in establishing limitations because they were
not found in any wastewater samples from this subcategory
above concentrations considered achievable by existing or
available treatment technologies. These pollutants are
discussed below.
114. antimony
117. beryllium
118. cadmium
121. cyanide
123. mercury
125. selenium
Antimony was detected
concentration
concentration
technology (0.47 mg/1.
for limitation.
above its analytical quantification
in 4 of 8 samples. These values are below the
considered achievable by identified treatment
Therefore, antimony is not considered
Beryllium was detected above its analytical quantification
concentration in 4 of 8 samples. These values are below the
concentration considered achievable by identified treatment
technology (0.2 mg/1. Therefore, beryllium is not considered
for limitation.
Cadmium was detected above its analytical quantification
concentration in 1 of 8 samples. This value is below the
concentration considered achievable by identified treatment
technology (0.049 mg/1). Therefore, cadmium is not considered
for limitation.
Cyanide was detected above its analytical quantification
concentration in 2 of 6 samples. These values are below the
concentration considered achievable by identified treatment
technology (0.047 mg/1). Therefore, cyanide is not considered
for limitation.
Mercury was detected above its analytical quantification
concentration in 6 of 8 samples. These values are below the
3541
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - VI
concentration considered achievable by identified treatment
technology (0.036 mg/1). Therefore, mercury is not considered
for limitation.
Selenium was detected above its analytical quantification
concentration in 4 of 8 samples. These values are below the
concentration considered achievable by identified treatment
technology (0.2 mg/1. Therefore, selenium is not considered for
limitation.
TOXIC POLLUTANTS DETECTED IN A SMALL NUMBER OF SOURCES
The following pollutants were not selected for limitation on the
basis that they are detectable in the effluent from only a small
number of sources within the subcategory and they are uniquely
related to only those sources.
44. methylene chloride
45. methyl chloride
55. naphthalene
70. diethyl phthalate
Although these pollutants were not selected for consideration in
establishing nationwide limitations, it may be appropriate, on a
case-by-case basis, for the local permitter to specify effluent
limitations.
Methylene chloride was found above its treatable concentration
(0.01 mg/1) in 2 of 3 raw wastewater samples. This
compound is not attributable to specific materials or processes
associated with the secondary molybdenum and vanadium
subcategory; however it is a common solvent used in analytical
laboratories. Since the possibility of sample contamination is
likely, methylene chloride is not considered for limitation.
Methyl chloride was found above its treatable concentration (0.01
mg/1) in 3 of 3 raw wastewater samples. This compound is not
attributable to specific materials or processes associated with
this subcategory; however, it is a common solvent used in
analytical laboratories. Since the possibility of sample
contamination is likely, methyl chloride is not considered for
limitation.
Naphthalene was found above its treatable concentration (0.01
mg/1) in 2 of 3 samples analyzed. This compound is not
attributable to specific materials or processes used in this
subcategory. In addition, very little removal can be expected for
naphthalene based on its low concentration in the raw waste. For
these reasons, naphthalene is not considered for limitations.
Diethyl phthalate was found above its treatable concentration
(0.01 mg/1) in one of 3 samples analyzed. This compound is not
attributable to specific materials or processes used in this
subcategory, but is commonly used as a plasticizer in laboratory
and field sampling equipment. For these reasons, diethyl
3542
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - VI
phthalate is not considered for limitations.
TOXIC POLLUTANTS SELECTED FOR FURTHER CONSIDERATION
IN ESTABLISHING LIMITATIONS AND STANDARDS
The pollutants listed below were selected for further
consideration in establishing limitations and standards for this
subcategory. These pollutants are discussed individually
following the list.
115. arsenic
119. chromium
120. copper
122. lead
124. nickel
128. zinc
Arsenic was detected above its treatable concentration (0.34
mg/1) in 4 of 8 samples. Because arsenic is present in
concentrations exceeding the concentration achievable by
identified treatment technology, it is selected for consideration
for limitation.
Chromium was detected above its treatable concentration (0.07
mg/1) in 4 of 8 samples analyzed. Because chromium is present in
concentrations exceeding the concentration achievable by
identified treatment technology, it is selected for consideration
for limitation.
Copper was detected above its treatable concentration (0.39 mg/1)
in 7 of 8 samples analyzed. Because copper is present in
concentrations exceeding the concentration achievable by
identified treatment technology, it is selected for consideration
for limitation.
Lead was detected above its treatable concentrations (0.08 mg/1)
in 5 of 8 samples analyzed. Because lead was present in
concentrations exceeding the concentration achievable by
identified treatment technology, it is selected for consideration
for limitation.
Nickel was detected above its treatable concentration (0.22 mg/1)
in 5 of 8 samples analyzed. Concentrations ranged from 1.2 to 19
mg/1. Because nickel is present in concentrations exceeding the
concentration achievable by identified treatment technology, it
is selected for consideration for limitation.
Zinc was detected above its treatable concentration (0.23 mg/1)
in 2 of 8 samples analyzed. Because zinc is present in
concentrations exceeding the concentration achievable by
identified treatment technology, it is selected for consideration
for limitation.
3543
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - VI
TABLE VI-1
TOXIC POLLUTANTS NEVER DETECTED
1. Acenaphthene
2. Acrolein
3. Acrylonitrile
4. Benzene
5. Benzidine
6. Carbon tetrachloride {tetrachloromethane)
7. Chlorobenzene
8. 1,2,4-trichlorobenzene
9. Hexachlorobenzene
10. 1,2-diehloroethane
11. 1,1,1-trichlorethane
12. Hexachloroethane
13. 1,1-dichloroethane
14, 1,1,2-trichloroethane
15, 1,1,2,2-tetrachloroethane
16. Chloroethane
17. Bis (chloromethyl) ether (Deleted)
18. Bis (2-chloroethyl) ether
19. 2-chloroethyl vinyl ether (mixed)
20. 2-chloronaphthalene
21. 2,4,6-trichlorophenol
22. Farachlorometa cresol
24. 2-chlorophenol
25. 1,2-dichlorobenzene
26. 1,3-dichlorobenzene
27. 1,4-dichlorobenzene
28. 3,3-dichlorobenzidine
29. 1,1-dichloroethylene
30. 1,2-trans-dichloroethylene
31. 2,4-dichlorophenol
32. 1,2-dichloropropane
33. 1,2-dichloropropylene (1,3-diehloropropene)
34. ' 2,4-dimethylphenol
35. 2,4-dinitrotoluene
36. 2,6-dinitrotoluene
37. 1,2-diphenylhydrazine
38. Ethylbenzene
39. Fluoranthene
40. 4-chlorophenyl phenyl ether
41. 4-bromophenyl phenyl ether
42. Bis (2-chloroisopropyl) ether
43. Bis (2-chloroethoxy) methane
46. Methyl bromide (bromomethane)
47. Bromoform (tribromomethane)
48. Dichlorobromomethane
49. Trichlorofluoromethane (Deleted)
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - VI
TABLE VI-1 (Continued)
TOXIC POLLUTANTS NEVER DETECTED
50. Dichlorodifluoromethane (Deleted)
51. Chlorodibromomethane
52. Hexachlorobutadiene
53. Hexachloromyclopentadiene
54. Isophorone
56. Nitrobenzene
57. Nitrophenol
58. 4-nitrophenol
59. 2,4-dinitrophenol
60. 4,6-dinitro-o-cresol
61. N-nitrosodimethylaraine
62. N-nitrosodiphenylamine
63. N-nitrosodi-n-propylamine
64. Pentachlorophenol
65. Phenol
66. Bis (2-ethylhexyl) phthalate
67. Butyl benzyl phthalate
68. Di-n-butyl phthalate
69. Di-n-octyl phthalate
71. Dimethyl phthalate
72. Benzo(a)anthracene
73. Benzo(a)pyrene
74. 3,4-benzofluroanthene
75. Benzo(k)fluoranthene (11, 12-benzofluoranthene)
76. Chrysene
77. Acenaphthylene
78. Anthracene
79. Benzo(ghi)perylene (1, 12-benzoperylene)
80. Fluorene
81. Phenanthrene
82. Dibenzo(a,h)anthracene
83. Indeno (l,2,-cd)pyrene (2,3-o-phenylenepyrene)
84. Pyrene
85. Tetrachloroethylene
86. Toluene
87. Trichloroethylene*
88. Vinyl chloride (chloroethylene)
89. Aldrin*
90. Dieldrin*
91. Chlordane (technical mixture and metabolities)*
92. 4,4'-DDT
93. 4,4'-DDE(p,p'DDX)*
94. 4,4'-DDD(p,p'TDE)*
95. A-endosulfan-Alpha*
96. B-endosulfan-Beta*
97. Endosulfan sulfate*
98. Endrin*
99. Endrin aldehyde*
3545
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
SECT - VI
TABLE VI-1 {Continued}
TOXIC POLLUTANTS NEVER DETECTED
100. Heptachlor*
101. Heptachlor epoxide*
102. Alpha-BHC
103. Beta-BHC
104. Gamma-BHC
105. Delta-BBC
106. PCB-1242 (Arochlor 1242)*
107. PCB-1254 {Arochlor 1254}*
108. PCB-1221 (Arochlor 1221)*
109. PCB-1232 {Arochlor 1232)*
110. PCB-1248 {Arochlor 1248)*
111. PCB-1260 (Arochlor 1260)*
112. PCB-1016 (Arochlor 1016)*
113, Toxaphene*
116. Asbestos (Fibrous)
129. 2,3r7,8-tetra chlorodibenzo-p-dioxin (TCDD)
*We did not analyze for these pollutants in samples of raw
wastewater from this subcategory. These pollutants are not
believed to be present based on the Agency's best engineering
judgement which included consideration of raw materials and
process operations.
3546
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - VII
SECTION VII
CONTROL AND TREATMENT TECHNOLOGIES
The preceding sections of this supplement discussed the sources,
flows, and characteristics of the wastewaters from secondary
molybdenum and vanadium plants. This section summarizes the
description of these wastewaters and indicates the treatment
technologies which are currently practiced in the secondary
molybdenum and vanadium subcategory for each waste stream.
Secondly, this section presents the control and treatment
technology options which were examined by the Agency for possible
application to the secondary molybdenum and vanadium subcategory.
CURRENT CONTROL AND TREATMENT PRACTICES
This section presents a summary of the control and treatment
technologies that are currently being applied to each of the
sources generating wastewater in this subcategory. As discussed
in Section V, wastewater associated with the secondary
molybdenum and vanadium subcategory is characterized by the
presence of ammonia, iron, molybdenum, toxic metal pollutants
and suspended solids. This analysis is supported by the
wastewater data presented for 2 raw waste streams in Section V.
Generally, these pollutants are present in each of the
waste streams at concentrations above treatability, and these
waste streams are commonly combined for treatment. Combined
treatment allows plants to take advantage of economic scale and
in some instances to combine streams of different alkalinity
to reduce treatment chemical requirements. The one plant in
this subcategory currently has a combined wastewater treatment
system, consisting of ammonia air stripping, caustic
precipitation and sedimentation. The two options selected
for consideration for BPT, BAT, NSPS, and pretreatment based on
combined treatment of these compatible waste streams will be
summarized toward the end of this section.
LEACH TAILINGS
The calcined product from the roasting furnace is quenched,
ground and leached with water in order to remove inerts and
other impurities and solubilize molybdenum and vanadium. The
pregnant liquor from leaching is a solution containing the
molybdenum and vanadium values. Leaching also produces
tailings which may be discharged as a waste stream after
solvent extraction. The one plant in this subcategory generates
a leach tailings wastewater stream, and treats it along with the
molybdenum filtrate solvent extraction raffinate wastewater
stream with chemical precipitation and sedimentation.
The wastewater is directly discharged after treatment.
3547
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - VII
MOLYBDENUM FILTRATE SOLVENT EXTRACTION RAFFINATE
Treatment of molybdenum filtrate solvent extraction raffinate
consists of chemical precipitation and sedimentation, along with
preliminary treatment consisting of ammonia air stripping. The
wastewater is directly discharged after treatment.
VANADIUM DECOMPOSITION WET AIR POLLUTION CONTROL
Emissions from a vanadium decomposition furnace are controlled
with a wet scrubber. The scrubber liquor is reused in the
process so there is no discharge from the air pollution control
operation.
MOLYBDENUM DRYING WET AIR POLLUTION CONTROL
Molybdic acid produced in the molybdenum recovery operation is
converted to molybdenum trioxide in a calcining furnace. The one
plant in this subcategory uses a wet scrubber to control
emissions from the molybdenum drying furnace, but reuses all
of the scrubber liquor in the molybdic acid process. No
wastewater is discharged from the scrubber.
PURE GRADE MOLYBDENUM
As discussed in Section V, EPA established a new building block
for pure grade molybdenum wastewater. Pure grade molybdenum is
produced from molybdic acid. Wastewater from this process is
discharged after treatment.
CONTROL AND TREATMENT OPTIONS
The Agency examined two control and treatment technology options
that are applicable to the secondary molybdenum and vanadium
subcategory. The options selected for evaluation represent a
combination of preliminary treatment technologies applicable to
individual waste streams, and end-of-pipe treatment
technologies. The effectiveness of these treatment technologies
are discussed in Section VII of Vol. I.
OPTION A
Option A for the secondary molybdenum and vanadium subcategory
requires control and treatment technologies to reduce the
discharge of wastewater pollutant mass.
The Option A treatment scheme consists of chemical precipitation
and sedimentation technology. Specifically, lime or some other
alkaline compound is used to precipitate priority metal ions as
metal hydroxides. The metal hydroxides and suspended solids
settle out and the sludge is collected. Vacuum filtration is used
to dewater sludge.
Preliminary treatment consisting of ammonia air stripping for
waste streams containing treatable concentrations of ammonia is
3548
-------
SECONDARY MUliXBDENUM AND VANADIUM SUBCATJSGOEi: SECT - VJLI
also included in Option A. Air stripping is an effective
method for reducing ammonia concentrations.
Also included is treatment consisting of iron (ferric chloride
or ferrous sulfate) co-precipitation to reduce molybdenum
concentrations. Iron co-precipitation is an effective
treatment step for molybdenum removal.
OPTION C
Option C for the secondary molybdenum and vanadium subcategory
consists of all control and treatment requirements of Option A
(ammonia air strippingr iron co-precipitation, chemical
precipitation and sedimentation) plus multimedia filtration
technology added at the end of the Option A treatment scheme.
Multimedia filtration is used to remove suspended solids,
including precipitates of metals, 'beyond the concentration
attainable by gravity sedimentation. The filter suggested is of
the gravity, mixed-media type, although other forms of filters,
such as rapid sand filters or pressure filters would perform
satisfactorily. The addition of filters also provides consistent
removal during periods of time in which there are rapid increases
in flows or loadings of pollutants to the treatment system.
3549
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCAT1GORY SECT - VII
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3550
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - VIII
SECTION VIII
COSTS, ENERGY, AND NONWATER QUALITY ASPECTS
This section presents a summary of compliance costs for the
secondary molybdenum and vanadium subcategory and a description
of the treatment options and subcategory-specific assumptions
used to develop these estimates. Together with the estimated
pollutant removal performance presented in Section X of this
supplement, these cost estimates provide a basis for evaluating
each regulatory option. These cost estimates are also used in
determining the probable economic impact of regulation on the
subcategory at different pollutant discharge levels. In
addition, this section addresses nonwater quality environmental
impacts of wastewater treatment and control alternatives,
including air pollution, solid wastes, and energy requirements,
which are specific to the secondary molybdenum and vanadium
subcategory.
TREATMENT OPTIONS FOR EXISTING SOURCES
As discussed in Section VII, two treatment options have been
developed for existing secondary molybdenum and vanadium sources.
The treatment schemes for each option are summarized below and
schematically presented in Figures X-l and X-2 (pages 3585 and
3586).
OPTION A
The Option A treatment scheme includes preliminary treatment
consisting of ammonia air stripping for waste streams
containing treatable concentrations of ammonia, iron
co-precipitation, and chemical precipitation and sedimentation
end-of-pipe treatment technology.
OPTION C
Option C consists of Option A (ammonia air stripping, iron
co-precipitation, and chemical precipitation and
sedimentation) plus multimedia filtration technology added at
the end of the Option A treatment scheme.
COST METHODOLOGY
A detailed discussion of the methodology used to develop the
compliance costs is presented in Section VIII of the General
Development Document. Plant-by-plant compliance costs for the
nonferrous metals manufacturing category have been revised as
necessary following proposal. These revisions calculate
incremental costs, above treatment already in place, necessary to
comply with the promulgated effluent limitations and standards
and are presented in the administrative record supporting this
3551
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - VIII
regulation. The costs developed for the final regulation are
presented in Table VIII-1 (page 3556) for the one direct
discharger in this subcategory.
Each of the general assumptions used to develop compliance costs
is presented in Section VIII of the General Development Document.
Each subcategory contains a unique set of waste streams requiring
certain subcategory-specific assumptions to develop compliance
costs. Three major assumptions relevant to the secondary
molybdenum and vanadium subcategory are discussed briefly below.
(1) Only the molybdenum filtrate solvent extraction raff incite
will be treated for ammonia removal.
(2) The plant has a chemical precipitation and gravity settling
system currently in-place.
(3) For costing purposes, ammonia air stripping performance data
is transferred to this subcategory from a plant in the primary
beryllium subcategory.
NONWATER QUALITY ASPECTS
Nonwater quality impacts specific to the secondary molybdenum
and vanadium subcategory, including energy requirements, solid
waste and air pollution are discussed below.
ENERGY REQUIREMENTS
The methodology used for determining the energy requirements for
the various options is discussed in Section VIII of the General
Development Document. Energy requirements for Option A are
estimated at 1,000,000 kwh/yr, and for Option C the estimated
requirement is 1,023,000 kwh/yr. Both options require large
amounts of energy because ammonia air stripping is an energy
intensive technology. Option C energy requirements increase over
those for Option A because filtration is being added as an
end-of-pipe treatment technology. Both Option A and Option C
energy requirements represent approximately ten percent of the
energy usage in the secondary molybdenum and vanadium industry.
Although this is a large percentage increase, the added costs
will be partially offset by the additional ammonia values
recovered by the facility.
SOLID WASTE
Sludge generated in the secondary molybdenum and vanadium
subcategory is due to the precipitation of metal hydroxides and
carbonates using lime or other chemicals. Sludges associated
with the secondary molybdenum and vanadium subcategory will
necessarily contain quantities of priority metal pollutants.
Wastes generated by secondary metal industries can be
regulated as hazardous. However, the Agency examined the
solid wastes that would be generated at secondary nonferrous
metals manufacturing plants by the suggested treatment
3552
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - VIII
technologies and believes they are not hazardous wastes
under the Agency's regulations implementing Section 3001 of
the Resource Conservation and Recovery Act. The one
exception to this is solid wastes generated by cyanide
precipitation. These sludges are expected to be hazardous
and this judgment was included in this study. None of the
non cyanide wastes are listed specifically as hazardous.
Nor are they likely to exhibit a characteristic of hazardous
waste. This judgment is made based on the recommended
technology of chemical precipitation sedimentation, and
filtration. By the addition of a small excess of lime during
treatment, similar sludges, specifically priority metal
bearing sludges, generated by other industries such as the iron
and steel industry passed the Extraction Procedure (EP)
toxicity test. See 40 CFR 261.24« Thus, the Agency believes
that the wastewater sludges will similarly not be EP
toxic if the recommended technology is applied.
Although it is the Agency's view that solid wastes generated as a
result of these guidelines are not expected to be hazardous,
generators of these wastes must test the waste to determine if
the wastes meet any of the characteristics of hazardous waste
(see 40 CFR 262.11).
If these wastes should be identified or are listed as hazardous,
they will come within the scope of RCRA's "cradle to grave"
hazardous waste management program, requiring regulation from the
point of generation to point of final disposition. EPA's
generator standards would require generators of hazardous
nonferrous metals manufacturing wastes to meet containerization,
labeling, recordkeeping, and reporting requirements; if plants
dispose of hazardous wastes off-site, they would have to prepare
a manifest which would track the movement of the wastes from the
generator's premises to a permitted off-site treatment, storage,
or disposal facility. See 40 CFR 262.20 45 FR 33142 (May 19,
1980), as amended at 45 FR 86973 (December 31, 1980). The
transporter regulations require transporters of hazardous wastes
to comply with the manifest system to assure that the wastes are
delivered to a permitted facility. See 40 CFR 263.20 45 FR 33151
(May 19, 1980), as amended at 45 FR 86973 (December 31, 1980).
Finally, RCRA regulations establish standards for hazardous waste
treatment, storage, and disposal facilities allowed to receive
such wastes. See 40 CFR Part 464. 46 FR 2802 (January 12, 1981),
47 FR 32274 (July 26, 1982).
Even if these wastes are not identified as hazardous, they still
must be disposed of in compliance with the Subtitle D open
dumping standards, implementing 4004 of RCRA. See 44 FR 53438
(September 13, 1979). EPA estimates that 850 metric tons of
sludge will be generated annually as a result of the wastewater
treatment operations on this subcategory.
3553
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - VIII
AIR POLLUTION
There is no reason to believe that any substantial air pollution
problems will result from implementation of ammonia air
stripping, iron co-precipitation, chemical precipitation,
sedimentation, and multimedia filtration. Ammonia air stripping
as presently practiced at the one plant in this subcategory
yields an aqueous ammonium salt by-product stream. The
other technologies transfer pollutants to solid waste and
are not likely to transfer pollutants to air.
3554
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - VIII
Table VIII-1
The cost of compliance data are not presented here because the
data on which they are based have been claimed to be
confidential.
3555
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - VIII
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3556
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SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - IX
SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY
CURRENTLY AVAILABLE
This section defines the effluent characteristics attainable
through the application of best practicable control technology
currently available (8PT). BPT reflects the existing
performance by plants of various sizes, ages, and
manufacturing processes within the secondary molybdenum and
vanadium subcategory, as well as the established performance of
the recommended BPT systems. Particular consideration is given
to the treatment already in place at plants within the data base.
The factors considered in identifying BPT include the total cost
of applying the technology in relation to the efflue.nt reduction
benefits from such application, the age of equipment and
facilities Involved, the manufacturing processes used, nonwater
quality environmental impacts (Including energy requirements),
and other factors the Administrator considers appropriate. In
general, the BPT level represents the average of the existing
performances of plants of various ages, sizes, processes, or
other common characteristics. Where existing performance is
uniformly inadequate, BPT may be transferred from a different
subcategory or category. Limitations based on transfer of
technology are supported by a rationale concluding that the
technology is, indeed, transferable, and a reasonable prediction
that it will be, capable of achieving the prescribed effluent
limits. BPT focuses on end-of-pipe treatment rather than
process changes or internal controls, except where such
practices are common industry practice.
TECHNICAL APPROACH TO BPT
The Agency studied the nonferrous metals category to identify the
processes used, the wastewaters generated, and the treatment
processes installed. Information was collected from industry
using data collection portfolios, and specific plants were
sampled and the wastewaters analyzed. In making technical
assessments of data, reviewing manufacturing processes, and
assessing wastewater treatment technology options, both indirect
and direct dischargers have been considered as a single group.
An examination of plants and processes did not indicate any
process differences based on the type of discharge, whether it be
direct or indirect.
As explained in Section IV, the secondary molybdenum and vanadium
subcategory has been subdivided into five potential wastewate'r
sources. Since the water use, discharge rates, and pollutant
characteristics of each of these wastewaters is potentially
unique, effluent limitations will be developed for each of the
3557
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SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - IX
five building blocks.
For each building block, a specific approach was followed for
the development of BPT mass limitations. The first requirement to
calculate these limitations is to account for production and flow
variability from plant to plant. Therefore, a unit of production
or production normalizing parameter (PNP) was determined for each
waste stream which could then be related to the flow from the
process to determine a production normalized flow. Selection of
the PNP for each process element is discussed in Section IV.
Each plant within the subcategory was then analyzed to
determine which building blocks were present, the specific flow
rates generated for each subdivision, and the specific production
normalized flows for each subdivision. This analysis is
discussed in detail in Section V. Nonprocess wastewaters such as
rainfall runoff and noncontact water are not considered in the
analysis. Production normalized flows for each subdivision were
then analyzed to determine the flow to be used as part of the
basis for BPT mass limitations. The selected flow (sometimes
referred to as the BPT regulatory flow or BPT discharge
rate) reflects the water use controls which are common practices
within the category. The BPT regulatory flow is based on the
average of all applicable data. Plants with normalized flows
above the average may have to implement some method of flow
reduction to achieve the BPT limitations.
The second requirement to calculate mass limitations is the set
of concentrations that are achievable by application of the BPT
level of treatment technology. Section VII discusses the various
control and treatment technologies which are currently in place
for each wastewater source. In most cases, the current control
and treatment technologies consist of chemical precipitation and
sedimentation (lime and settle technology) and a combination of
reuse and recycle to reduce flow. Ammonia air stripping is
applied to streams with treatable concentrations of ammonia.
Iron co-precipitation, is applied to streams with treatable
concentrations of molybdenum.
Using these regulatory flows and the achievable concentrations,
the next step is to calculate mass loadings for each wastewater
source or subdivision. This calculation was made on a
stream-by-stream basis, primarily because plants in this
subcategory may perform one or more of the operations in various
combinations. The mass loadings (milligrams of pollutant per
metric ton of production (mg/kkg) were calculated by multiplying
the BPT regulatory flow (1/kkg) by the concentration achievable
by the BPT level of treatment technology (mg/1) for each
pollutant parameter to be limited under BPT. These mass loadings
are published in the Federal Register and in 40 CFR Part 421 as
the BPT effluent limitations.
The mass discharge loadings which are allowed under BPT for each
plant will be the sum of the individual mass loadings for
the various wastewater sources which are found at
particular plants. Accordingly, all the wastewater generated
3558
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - IX
within a plant may be combined for treatment in a single or
common treatment system, but the effluent limitations for
these combined wastewaters are based on the various wastewater
sources which actually contribute to the combined flow. This
method accounts for the variety of combinations of wastewater
sources and production processes which may be found at secondary
molybdenum and vanadium plants.
The Agency usually establishes wastewater limitations in terms of
mass rather than concentration. This approach prevents the use
of dilution as a treatment method (except for controlling pH).
The production normalized wastewater flow (1/kkg) is a link
between the production operations and the effluent limitations.
The pollutant discharge attributable to each operation can be
calculated from the regulatory (normalized) flow and effluent
concentration achievable by the treatment technology. These
discharges may be summed to derive an appropriate limitation
for each plant.
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
In balancing costs in relation to pollutant removal estimates,
EPA considers the volume and nature of existing discharges, the
volume and nature of discharges expected after application of
BPT, the general environmental effects of the pollutants, and the
cost and economic impacts of the required pollution control
level. The Act does not require or permit consideration of water
quality problems attributable to particular point sources or
industries, or water quality improvements in particular water
quality bodies. Accordingly, water quality considerations were
not the basis for selecting the proposed or promulgated BPT.
The methodology for calculating pollutant removal estimates and
plant compliance costs is discussed in Section X. The pollutant
removal estimates have been revised based on new data obtained
since proposal. The pollutant discharge and removal estimates
for the secondary molybdenum and vanadium subcategory are shown
in Table X-l (page 3577). Compliance costs for the direct
discharger are presented in Table X-2 (page 3578).
BPT OPTION SELECTION
The technology basis for the BPT limitations is Option A,
chemical precipitation and sedimentation technology to remove
metals and solids from combined wastewaters and to control pH,
ammonia air stripping preliminary treatment to remove
ammonia, and iron co-precipitation to reduce molybdenum
concentrations. The Agency believes that these technologies are
economically achievable.
The promulgated technology is based on air stripping instead
of steam stripping for ammonia as had been proposed because the
economic impact analysis showed that the costs of steam stripping
may cause the only facility in the subcategory to close.
3559
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - IX
Therefore, the Agency concluded that steam stripping technology
is not practicable for this subcategory and decided to rely on
air stripping which is already in place. The Agency is also
adding iron coprecipitation to the BPT model treatment technology
for this subcategory for molybdenum removal. Ammonia air
stripping and chemical precipitation and sedimentation
technology is in-place at the discharger in this subcategory.
The BPT treatment scheme is presented in Figure IX-1 (page
3563).
Ammonia air stripping is currently practiced in the
subcategory, and by other plants in the nonferrous metals
manufacturing category. Air stripping is an effective
method for reducing ammonia concentrations. The secondary
molybdenum facility recovers ammonia values in a by-product
ammonium chloride recovery system, thus preventing ammonia
discharge to the atmosphere.
Iron co-precipitation is not currently practiced in this
subcategory, however, it is transferred to this subcategory
because existing treatment for molybdenum removal is inadequate.
Iron co-precipitation is an effective method for reducing
molybdenum concentrations in wastewater.
Implementation of the control and treatment technologies of
Option A would remove annually an estimated 319 kilograms of
toxic metals and 28,000 kilograms of TSS over estimated
current discharge.
WASTEWATER DISCHARGE RATES
A BPT discharge rate is calculated for each subdivision based on
the average of the flows of the existing plants, as determined
from analysis of dcp. The discharge rate is used with the
achievable treatment concentrations to determine BPT effluent
limitations. Since the discharge rate may be different for each
wastewater sources, separate production normalized discharge
rates for each of.the five wastewater sources are discussed below
and summarized in Table IX-1 (page 3563). The discharge
rates are normalized on a production basis by relating the
amount of wastewater generated to the mass of the
intermediate product which is produced by the process associated
with the waste stream in question. These production normalizing
parameters, or PNPs, are also listed in Table IX-1.
Section V of this document further describes the discharge flow
rates and presents the water use and discharge flow rates by
subdivision in Tables V-l through V-5 (pages 3526 - 3527).
LEACH TAILINGS
The BPT wastewater regulatory flow rate at proposal and at
promulgation for leach tailings was 12,540 1/kkg (3,012
gal/ton) of molybdenum and vanadium produced, EPA has agreed to
revise the leach tailing regulatory flow from 12,540 to 19,511
3560
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - IX
1/kkg of technical grade molybdenum plus vanadium plus pure
grade molybdenum produced. This change reflects a recalculation
of the average flows for this building block and the
incorporation of new data. This rate is allocated only for those
plants which leach calcined spent catalysts, in order to
extract molybdenum and vanadium. Water use and wastewater
discharge rates are presented in Table V-l (page 3526).
MOLYBDENUM FILTRATE SOLVENT EXTRACTION RAPPINATE
The BPT wastewater discharge rate promulgated for molybdenum
filtrate solvent extraction raffinate was 60,548 1/kkg (14,544
gal/ton) of molybdenum and vanadium produced. EPA has agreed
to revise the molybdenum filtrate solvent extraction raffinate
regulatory flow from 60,548 to 58,239 1/kkg of technical grade
molybdenum plus vanadium plus pure grade molybdenum produced.
This change reflects the establishment of a new building block
for pure grade molybdenum. The BPT rate is allocated to only
those plants recovering molybdenum and vanadium from spent
catalysts by a dissolution and precipitation process.
Water use and discharge rates are shown in Table V-2 (page
3526). These rates are based on data gathered during a post-
proposal sampling visit.
VANADIUM DECOMPOSITION WET AIR POLLUTION CONTROL
The BPT wastewater discharge rate at proposal and at
promulgation for vanadium decomposition wet air pollution
control is 0.1/kkg of vanadium produced by decomposition. This
rate is based on the 100 percent reuse practiced within
this operation. The water use and discharge rates are
presented in Table V-3 (page 3526).
MOLYBDENUM DRYING WET AIR POLLUTION CONTROL
The BPT wastewater discharge rate proposed and promulgated for
molybdenum drying wet air pollution control is 0 1/kkg of
molybdenum produced. This rate is based on the 100 percent reuse
practiced by the only plant with this operation. The water use
and discharge rates are presented in Table V-4 (page 3527).
PURE GRADE MOLYBDENUM
EPA has established a pure grade molybdenum building block for
this subcategory. As discussed in Section V, this building block
was not included in the promulgated rule because the wastewater
from this operation was included as part of the flow from the
molybdenum filtrate solvent extraction raffinate building block.
Information made available after promulgation indicated that the
pure grade molybdenum and the solvent extraction operations are
not as closely linked as the Agency had believed. This building
block would apply to the production of pure grade molybdenum from
commercial grade molybdenum and is based on a production
normalized flow of 23,280 1/kkg of pure molybdenum produced.
3561
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - IX
REGULATED POLLUTANT PARAMETERS
The raw wastewater concentrations from individual operations and
the subcategory as a whole were examined to select certain
pollutant parameters for limitation. This examination and
evaluation is presented in Sections VI and X. A total of nine
pollutants or pollutant parameters were selected for limitation
under BPT and are listed below:
115. arsenic
119. chromium
122. lead
124. nickel
ammonia
molybdenum
iron
TSS
PH
EFFLUENT LIMITATIONS
The concentrations achievable by application of the BPT
technology are discussed in Section VII of Vol. I and
summarized there in Table VII-21 (page 248) with the
exception of the ammonia and molybdenum treatment effectiveness
concentrations. The treatment effectiveness for ammonia air
stripping is not shown in Table VII-21 and the molybdenum
treatment effectiveness values are being reserved pending the
development of new treatment effectiveness data specifically
applicable to this subcategory. These treatment effectiveness
values (both one-day maximum and monthly average values) are
multiplied by the BPT normalized discharge flows summarized in
Table IX-1 (page 3563) to calculate the mass of pollutants
allowed to be discharged per mass of product. The results of
these calculations in milligrams of pollutant per kilogram of
product represents the BPT effluent limitations and are presented
in Table IX-2 (page 3564) for each individual building block.
3562
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - IX
TABLE IX-1
BPT REGULATORY FLOW ALLOWANCES FOR THE
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
Building Block
1. Leach tailings
BAT Regulatory
Flow Allowance
(1/kkg) (gal/ton)
19511
2. Molybdenum filtrate 58239
solvent extraction
raffinate
3. Vanadium decompoai- 0
tion wet air pollu-
tion control
4. Molybdenum drying 0
wet air pollution
control
5. Pure grade molyb- 23280
denum
4687
13989
5592
PNP
kkg of technical grade
molybdenum plus vana-
dium plus pure grade
molybdenum produced
kkg of technical grade
molybdenum plus vana-
dium plus pure grade
molybdenum produced
kkg of vanadium pro-
duced by decomposition
kkg of molybdenum pro-
duced
kkg of pure molybdenum
produced
3563
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - IX
TABLE IX-2
BPT MASS LIMITATIONS FOR THE
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
(a) Leach Tailings BPT
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
rag/kg(IB/million Ibs)of technical grademolybdenum plus
vanadium plus pure grade molybdenum produced
*Arsenic
*Chromium
Copper
*Lead
*Nickel
Zinc
Aluminum
*Ammonia
Boron
Cobalt
Germanium
*Iron
Manganese
*Molybdenum
Tin
Titanium
Vanadium
*TSS
*pH Within
40.778
8.585
37.077
8.195
37.460
28.489
125.452
8078.000
35.895
4.097
8.585
23.410
13.267
Reserved
7.414
18.344
1.951
799.950
the range of 7.5
18.145
3.512
19.511
3.902
24.779
11.902
62.438
3551.000
16.384
1.757
3.S12
11.902
5.659
Reserved
4.293
7.999
380.460
to 10.0 at all times
*Regulated Pollutant
3564
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCAfEGORY SECT - IX
TABLE IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
(b) Molybdenum Filtrate Solvent Extraction Raffinate BPT
Pollutant orMaximum forMaximum for[
pollutant property any one day , monthly average
mg/kg (Ib/million Ibs) of technical grade molybdenum plus
vanadium plus pure grade molybdenum produced
*Arsenic
*Chromium
Copper
*Lead
*Nickel
Zinc
Aluminum
* Ammonia
Boron
Cobalt
Germanium
*Iron
Manganese
*Molybdenum
Tin
Titanium
Vanadium
*TSS
*pH Within
121.720
25.625
110.610
24.460
111.820
85.029
374.454
24114.000
107.152
12.235
25.624
69.887
39.600
Reserved
22.133
54.749
5.824
2387.800
the range of 7.5
54.162
10.483
58.241
11.648
73.964
35.522
186.410
10600.000
48.920
5.241
10.484
35.526
16.890
Reserved
12.817
23.873
1135.660
to 10.0 at all times
*Regulated Pollutant
3565
-------
SECONDARY MOLYBDENUM AND VANADIUM SOBCATEGORY SECT - IX
TABLE IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
(c) Vanadium Decomposition Wet Air Pollution Control BPT
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of vanadium produced by decomposition
*Araenic
*Chromium
Copper
*Lead
*Nickel
Zinc
Aluminum
* Ammonia
Boron
Cobalt
Germanium
*Iron
Manganese
*Molybdenum
Tin
Titanium
Vanadium
*TSS
*pH Within
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
the range of 7.5
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
to 10.0 at all times
*Regulated Pollutant
3566
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - IX
TABLE IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
(d) Molybdenum Drying Wet Air Pollution Control BPT
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of molybdenum produced
*Arsenic 0.000 0.000
*Chromium 0.000 0.000
Copper 0.000 • 0.000
*Lead 0.000 0.000
*Nickel 0.000 0.000
Zinc 0.000 0.000
Aluminum 0.000 0.000
*Ammonia 0.000 0.000
Boron 0.000 0.000
Cobalt 0.000 0.000
Germanium 0.000 0.000
*Iron 0.000 0.000
Manganese 0.000 0.000
^Molybdenum 0.000 0.000
Tin 0.000 0.000
Titanium 0.000 0.000
Vanadium 0.000
*TSS 0.000 0.000
*pH Within the range of 7.5 to 10.0 at all times
*Regulated Pollutant
3567
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - IX
TABLE IX-2 (Continued)
BPT MASS LIMITATIONS FOR THE
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
(e) Pure Grade Molybdenum BPT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (pounds per million pounds) of pure molybdenum produced
*Arsenic
*Chromium
Copper
*Lead
*Nickel
Zinc
Aluminum
*Aramonia (as N)
Boron
Cobalt
Germanium
*Iron
Manganese
*Molybdenum
Tin
Titanium
Vanadium
*TSS
*pH
48.655
10.243
44.232
9.778
44.698
33.990
149.700
9638.000
42.840
4.889
10.240
27.936
15.830
Reserved
8.846
21.880
2.329
954.480
21.650
4.190
23.280
4.656
29.566
14.200
74.500
4239.000
19.500
2.095
4.190
14.201
6.751
Reserved
5.122
9.545
453.960
Within the range of 7.5 to 10.0 at all times
3568
-------
UJ
tn
CTl
Molybdenum
Filtrat* Solvent
Extraction
Raftlnata
Pure Gratia
Molybdenum
Leach Tailings
To Ammonia
(Ucovory
Ammonia
Air
Stripping
Vanadium DecompoiKion Wat
Air Pollution Control
Molybdenum Drying Wat
Air Pollution Control
Complete R*uu
->»• Complete fttutt
Ch*mteal
Addition
Chemical
Addition
Sludge to
Ddpoial
M
W
O
i
I
F
M
M
Q
I
m
m
a
FIGURE IX-1. BPT TREATMENT SCHEME FOR SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
H
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - IX
THIS PAGE INTENTIONALLY LEFT BLANK
3570
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - X
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE
These effluent limitations are based on the best control and
treatment technology used by a specific point source within the
industrial category or subcategory, or by another category from
which it is transferable. Emphasis is placed on additional
treatment techniques applied at the end of the treatment systems
currently used, as well as reduction of the amount of water used
and discharged, process control, and treatment technology
optimization.
The factors considered in assessing best available technology
economically achievable (BAT) include the age of equipment and
facilities involved, the process used, process changes, nonwater
quality environmental impacts (including energy requirements),
and the costs of application of such technology. BAT
represents the best available technology economically
achievable at plants of various ages, sizes, processes, or
other characteristics. BAT may be transferred from a
different subcategory or category and BAT may include
feasible process changes or internal controls, even when not in
common industry practice.
The statutory assessment of BAT considers costs, but does not
require a balancing of costs against pollutant removals.
However, in assessing the proposed and promulgated BAT, the
Agency has given substantial weight to the economic
achievability of the technology.
TECHNICAL APPROACH TO BAT
The Agency reviewed a wide range of technology options and
evaluated the available possibilities to ensure that the most
effective and beneficial technologies were used as the basis of
BAT. To accomplish this, the Agency elected to examine two
technology options which could be applied to the secondary
molybdenum and vanadium subcategory as alternatives for the basis
of BAT effluent limitations.
For the development of BAT effluent limitations, mass loadings
were calculated for each wastewater source or subdivision in the
subcategory using the same technical approach as described in
Section IX for BPT limitations development. The differences in
the mass loadings for BPT and BAT are due to increased treatment
effectiveness achievable with the more sophisticated BAT
treatment technology.
The treatment technologies considered for BAT are summarized
below:
3571
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - X
Option A (Figure X-l page 3585) is based on:
o Preliminary treatment with ammonia air stripping
(where required)
o Iron coprecipitation
o Chemical precipitation and sedimentation
Option C (Figure X-2 page 3586) is based on:
o Preliminary treatment with ammonia air stripping
(where required)
o Iron coprecipitation
o Chemical precipitation and sedimentation
o Multimedia filtration
The two options examined for BAT are discussed in great detail on
the following pages. The first option considered (Option A) is
the same as the BPT treatment and control technology which was
presented in the previous section. The second option represents
substantial progress toward the reduction of pollutant discharges
above and beyond the progress achievable by BPT.
OPTION A
Option A for the secondary molybdenum and vanadium subcategory is
equivalent to the control and treatment technologies which were
analyzed for BPT in Section IX (see Figure X-l). The BPT
end-of-pipe treatment scheme includes chemical precipitation
and sedimentation, with ammonia air stripping preliminary
treatment of wastewaters containing treatable concentrations of
ammonia and iron co-precipitation to control molybdenum (see
Figure IX-1, page 3563). The discharge rates for Option A are
equal to the discharge rates allocated to each stream as a BPT
discharge flow.
OPTION C
Option C for the secondary molybdenum and vanadium subcategory
consists of all control and treatment requirements of Option A
(ammonia air stripping, iron co-precipitation, chemical
precipitation and sedimentation) plus multimedia filtration
technology added at the end of the Option A treatment scheme (see
Figure X-2, page 3586). Multimedia filtration is used to remove
suspended solids, including precipitates of metals, beyond the
concentrations attainable by gravity sedimentation. The filter
suggested is of the gravity, mixed media type, although other
forms of filters, such as rapid sand filters or pressure
filters, would perform satisfactorily.
3572
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - X
INDUSTRY COST AND POLLUTANT REMOVAL ESTIMATES
As one means of evaluating each technology option, EPA developed
estimates of the pollutant removals and the compliance costs
associated with each option. The methodologies are described
below.
POLLUTANT REMOVAL ESTIMATES
A complete description of the methodology used to calculate the
estimated pollutant reduction, or benefit, achieved by the
application of the various treatment options is presented in
Section X of Vol. I. The pollutant removal estimates have
been revised since proposal based on new data; however, the
methodology for calculating pollutant removals was not changed.
Next, the volume of wastewater discharged after the application
of each treatment option was estimated for each operation at each
plant by first comparing the actual discharge to the regulatory
flow. The smaller of the two values was selected and summed with
the other plant flows. The mass of pollutant discharged was then
estimated by multiplying the achievable concentration values
attainable with the option (mg/1) by the estimated volume of
process wastewater discharged by the subcategory. Finally, the
mass of pollutant removed is the difference between the estimated
mass of pollutant generated by each plant in the subcategory and
the mass of pollutant, discharged after application of the
treatment option. The pollutant removal estimates for the direct
discharger in the secondary molybdenum and vanadium subcategory
are presented in Table X-l (page 3563).
COMPLIANCE COSTS
In estimating subcategory-wide compliance costs, the first step
was to develop a cost estimation model, relating the total costs
associated with installation and operation of wastewater
treatment technologies to plant process wastewater discharge.
EPA applied the model to each plant. The plant's investment and
operating costs are determined by what treatment it has in place
and by its individual process wastewater discharge flow. As
discussed above, this flow is either the actual or the BAT
regulatory flow, whichever is lesser. The final step was to
annualize the capital costs, and to sum the annualized capital
costs, and the operating and maintenance costs for each plant,
yielding the cost of compliance for the subcategory.
The costs developed for promulgation are presented in Table X-2
(page 3578) for the direct discharger in the secondary molybdenum
and vanadium subcategory. These costs were used in assessing
economic achievability.
BAT OPTION SELECTION-PROPOSAL
EPA selected Option C for the proposed BAT which includes
chemical precipitation, sedimentation, and multimedia filtration,
with ammonia steam stripping preliminary treatment of wastewaters
3573
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - X
containing treatable concentrations of ammonia.
BAT OPTION SELECTION-PROMULGATION
After proposal, EPA collected additional data during a sampling
episode at one facility in this subcategory. These data
include flow and production information, raw wastewater pollutant
loadings, and treatment in-place information. These data were
used to calculate production normalized flow rates and regulatory
flow allowances. These data were also used for recalculating
pollutant removal estimates and for revising compliance costs.
EPA promulgated BAT limitations for this subcategory based on
iron coprecipitation, chemical precipitation, sedimentation and
multimedia filtration, with preliminary treatment consisting of
ammonia air stripping. The end-of-pipe technology basis for
the BAT limitations being promulgated is the same as that for the
proposed limitations with the addition of iron coprecipitation to
control molybdenum. In addition, the treatment performance
concentrations for toxic metals, upon which the mass
limitations are based, are equal to the values used to calculate
the proposed mass limitations.
EPA is promulgating multimedia filtration as part of the
BAT technology because this technology is demonstrated in
the nonferrous metals manufacturing industry, and results
in additional removal of priority metals. In addition,
filtration adds reliability to the treatment system by making it
less susceptible to operator error and to sudden changes in raw
wastewater flow and pollutant concentrations.
Implementation of the control and treatment technologies of
Option C would remove annually an estimated 395 kilograms of
priority metal pollutants, which is 75 kilograms of priority
metal pollutants over the estimated BPT removal. The ammonia
air stripping technology of Option C would remove annually
an estimated 569,296 kilograms of ammonia. Iron
coprecipitation would remove annually an estimated 18,532 kg
of molybdenum.
WASTEWATER DISCHARGE RATES
A BAT discharge rate was calculated for each subdivision based
upon the flows of the existing plants, as determined from
analysis of the data collection portfolios. The discharge rate
is used with the achievable treatment concentrations to determine
BAT effluent limitations. Since the discharge rate may be
different for each wastewater source, separate production
normalized discharge rates for each of the five wasfcewater
sources were determined and are summarized in Table X-3 (page
3579). The discharge rates are normalized on a production
basis by relating the amount of wastewater generated to the
mass of the intermediate product which is produced by the
process associated with the waste stream in question. These
production normalizing parameters, or PNPs, are also listed in
3574
-------
SECONDARY MOLSTBDENUM AND VANADIUM SUBCATEGORY SECT - X
Table X-3.
The promulgated BAT discharge rates are equal to the promulgated
BPT discharge rates.
REGULATED POLLUTANT PARAMETERS
The raw wastewater concentrations from individual operations and
the subcategory as a whole were examined to select certain
pollutants and pollutant parameters for limitation. This
examination and evaluation was presented in Section VI. The
Agency, however, has chosen not to regulate all six toxic
pollutants selected in this analysis.
The high cost associated with analysis for toxic metal
pollutants has prompted EPA to develop an alternative method for
regulating and monitoring priority'pollutant discharges from
the nonferrous metals manufacturing category. Rather than
developing specific effluent mass limitations and standards
for each of the toxic metals found in treatable concentrations in
the raw wastewater from a given subcategory, the Agency is
promulgating effluent mass limitations only for those
pollutants generated in the greatest quantities as shown by
the pollutant removal analysis. The pollutants selected for
specific limitation are listed below:
115. arsenic
119. chromium
122. lead
124. nickel
ammonia (as N)
molybdenum
iron
By establishing limitations and standards for selected toxic
metal pollutants, dischargers will attain the same degree of
control over priority metal toxic as they would have been
required to achieve had all the priority metal toxic been
directly limited.
This approach is technically justified since the treatable
concentrations used for chemical precipitation and sedimentation
technology are based on optimized treatment for concomitant
multiple metals removal. Thus, even though metals have somewhat
different theoretical solubilities, they will be removed at very
nearly the same rate in a chemical precipitation and
sedimentation treatment system operated for multiple metals
removal. Filtration as part of the technology basis is likewise
justified because this technology removes metals
non-preferentially.
The toxic metal pollutants selected for specific limitation in
the secondary molybdenum and vanadium subcategory are
arsenic, chromium, lead, and nickel. Ammonia, molybdenum
and iron are also selected for limitation since the methods
3575
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - X
used to control arsenic, chromium, lead, and nickel are not
effective in the control of ammonia, molybdenum and iron. The
following toxic metal pollutants are excluded from
limitation on the basis that they are effectively controlled by
the limitations developed for arsenic, chromium, lead, and
nickel:
120. copper
128. zinc
EFFLUENT LIMITATIONS
The concentrations achievable by application of BAT are discussed
in Section VII of Vol. I and summarized there in Table VII-21
(page 248), with the exception of the treatment effectiveness
concentrations for ammonia and molybdenum, which are discussed in
Section IX of this supplement. The achievable concentrations,
both one day maximum and monthly average values, are multiplied
by the BAT normalized discharge flows summarized in Table X~3
to calculate the mass of pollutants allowed to be discharged
per mass of product. The results of these calculations in
milligrams of pollutant per kilogram of product represent the
promulgated BAT effluent limitations and are presented in
Table X-4 (page 3580) for each wastewater stream.
3576
-------
Table X-1
POLLUTANT REMOVAL ESTIMATES FOR DIRECT DISCHARGERS
Pollutant
Antimony
Arsenic
Cadmium
Chromium (Total)
Copper
Cyanide (Total)
Lead
Mercury
w Nickel
^ Selenium
Silver
Thallium
Zinc
TOTAL PRIORITY POLLUTANTS
Ammonia
Iron
Molybdenum
Vanadium
TOTAL NONCONVENTIONALS
TSS
TOTAL .CONVENT IONALS
TOTAL POLLUTANTS
Raw Waste
(kg/yr)
8.42
69.69
0
6.88
44.89
1.63
231.14
0.36
142.27
5.25
0.18
3.62
2.81
517.14
572,210
117
18,643
8,869
599,839
29,222
29,222
629,578
ONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
Raw Waste
(kg/yr)
8.42
69.69
0
6.88
44.89
1.63
231.14
0.36
142.27
5.25
0.18
3.62
2.81
Option A
Discharge
(kg/yr)
8.42
46.16
0
6.88
44.89
1.63
10.86
0.36
66.97
5.25
0.18
3.62
2.81
Option A
Removed
(kg/yr)
0
23.53
0
0
0
0
220.28
0
75.3
0
0
0
0
Option C
Discharge
(kg/yr)
8.42
30.77
0
6.34
35.30
1.63
7.24
0.36
19.91
5.25
0.18
3.62
2.81
Option C
Removed
(kg/yr)
0
38.92
0
0.54
9.59
0
223.9
0
122.36
0
0
0
0
SSCON
O
j<
2
8
§
o
w
55
3
s
«£«
o
<
£»
g
M
s
198.03
319.11
121.83
395.31
572,210
117
18,643
8,869
599,839
29,222
29,222
629,578
2,914
37
166
23
3,140
1,086
1,086
4,424
569,296
80
18,477
8,846
596,699
28,136
28,136
625,154
2,914
25
111
23
3,073
235
235
3,430
569,296
92
18,532
8,846
596,766
28,987
28,987
626,148
TEGORY
m
1
X
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - X
TABLE X-2
COST OF COMPLIANCE FOR THE
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
DIRECT DISCHARGERS
The cost of compliance data are not presented here because the
data on which they are based have been claimed to be
confidential« EPA determined that the benefits justify the costs
for this subcategory.
3578
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - X
TABLE X-3
BAT REGULATORY PLOW ALLOWANCES FOR THE
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
Building Block
1. Leach tailings
BAT Regulatory
Flow Allowance
(1/kkg) (gal/ton)
19511
2. Molybdenum filtrate 58239
solvent extraction
raffinate
3, Vanadium decomposi- 0
tion wet air pollu-
tion control
4. Molybdenum drying 0
wet air pollution
control
5. Pure grade molyb- 23280
denum
4687
13989
5592
PNF
kkg of technical grade
molybdenum plus vana-
dium plus pure grade
molybdenum produced
kkg of technical grade
molybdenum plus vana-
dium plus pure grade
molybdenum produced
kkg of vanadium pro-
duced by decomposition
kkg of molybdenum pro-
duced
kkg of pure molybdenum
produced
3579 -
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - X
TABLE X-4
BAT MASS LIMITATIONS FOR THE
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
(a) Leach Tailings BAT
Pollutant or
pollutant property
Maximum for
any one clay
Maximum for
monthly average
mg/kg (Ib/million Ibs) of technical grade molybdenum plus
vanadium plus pure grade molybdenum produced
*Arsenic
* Chromium
Copper
*Lead
*Nickel
Zinc.
Aluminum
* Ammonia
Boron
Cobalt
Germanium
*Iron
Manganese
*Molybdenum
Tin
Titanium
Vanadium
27.120
7.219
24.972
5.463
10.731
19,900
119.210
8078.000
35.895
2.732
7.219
23.413
5.853
Reserved
7.414
10.341
1.951
12.097
2.927
11.901
2.536
7.219
8.195
52.870
3551.000
16.380
1.366
2.927
11.902
4.487
Reserved
4.293
4.487
""*"* " u -••-
*Regulated Pollutant
3580
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT
TABLE X~4 (Continued)
BAT MASS LIMITATIONS FOR THE
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
(b) Molybdenum Filtrate Solvent Extraction Raffinate BAT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
rag/kg (Ib/million Ibs) of technical grade molybdenum plus
vanadium plus pure grade molybdenum produced
*Arsenic
* Chromium
Copper
*Lead
*Nickel
Zinc
Aluminum
* Ammonia
Boron
Cobalt
Germanium
*Iron
Manganese
*Molybdenum
Tin
Titanium
Vanadium
80.452
21.548
74.540
16.306 -
32.031
59.400
355.800
24114.000
107.200
8.154
21.550
69.887
17.470
Reserved
22.130
30.870
5.824
36.108
8.736
35.520
7.571
21.548
24.460
157.800
10600.000
48.920
4.076
8.736
35.526
13.400
Reserved
12.810
13.400
___
*Regulated Pollutant
3581
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT
TABLE X-4 (Continued)
BAT MASS LIMITATIONS FOR THE
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
(c) Vanadium Decompos ition Wet Air Pollution Control BAT
Pbllutantfor Maximum for Maximum for
pollutant property any one day monthly average
mg/kg {Ib/millionIbs) ofvanadium produced by decomposition
*Arsenic 0.000 0.000
*Chromium 0.000 0.000
Copper 0.000 0.000
*Lead 0.000 0.000
*Nickel 0.000 0.000
Zinc 0.000 0.000
Aluminum 0.000 0.000
*Ammonia 0.000 0.000
Boron 0.000 0.000
Cobalt 0.000 0.000
Germanium 0.000 0.000
*Iron 0.000 0.000
Manganese 0.000 0.000
*Molybdenum 0.000 0.000
Tin 0.000 0.000
Titanium 0.000 0.000
Vanadium 0.000
*Regulated Pollutant
3582
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - X
TABLE X-4 (Continued)
BAT MASS LIMITATIONS FOR THE
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
(d) Molybdenum Drying Wet Air Pollution Control BAT
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of molybdenum produced
*Arsenic
*Chromium
Copper
*Lead
*Nickel
Zinc
Aluminum
*Ammonia
Boron
Cobalt
Germanium
*Iron
Manganese
*Molybdenum
Tin
Titanium
Vanadium
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
w^v^
*Regulated Pollutant
3583
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - X
TABLE X-4 (Continued)
BAT MASS LIMITATIONS FOR THE
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
(e) Pure Grade Molybdenum BAT
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (pounds per million pounds) of pure molybdenum produced
*Arsenic
*Chromium
Copper
*Lead
*Nickel
Zinc
Aluminum
*Ammonia (as N)
Boron
Cobalt
Germanium
*Iron
Manganese
*Molybdenum
Tin
Titanium
Vanadium
32.359
8.614
29.798
6.518
12.804
23.746
142.200
9038.000
42.830
3.259
8.614
27.936
6.984
Reserved
8.846
12.340
2.328
14.434
3.492
14.200
3.026
8.614
9.778
63.090
4237.000
19.560
1.630
3.492
14.201
5.354
Reserved
5.122
5.354
3584
-------
To Ammonia
Recovery
Air
-~ Stripping ^ Chemical
JWW..V Addition
Pure Grade VvvvVV 1 /"*"*!
Molybdenum JQQQQQfiJ .. /J
*^T^ / v */C
£ U«* Tailing, | Equa(I£,Uo7 », lron C°-^-
01 " "i" """ " cj^alion j
Air Pollution Control ^
Ualybdenutn Drying Wat
Air Pollution Contra)
Ch«mka)
Addition
I n
\ y
»/o.
Chemical -odimcntatian Di"=har08
;J^ Precipitation * -edlmtntatlan ».
ot»
Sludge Recycle
M ^r^
Vacuum Filtrate *\ M^^7 ~ Sludge
Dispos
Sludge
Dewatering 1 '
-^ Complete Reuie
cn
W
1
I
o
w
FIGURE X-1. BAT TREATMENT SCHEME FOR OPTION A
-------
u>
Ul
00
en
To Ammwia
Molybdenum $888v8v
Extraction Ammonia
Rofflnate Air ^jr
* stripping ^ Chemical
^^^^^^ Addition
Pure Grade XXJOuuC 1
Molybdenum A / fl JrH
^V^x7 V ?y
J^ 1 \7 /V
Chemical
AHHilinn Backwash
1^7 \7
Uoch Tailings | ^ r ' «- !«"> Co-pre- Chemical V ^ „ ,. Multimedia 0
a
s
I
D
D
G
03
El
Q
I
w
o
FIGURE X-2. BAT TREATMENT SCHEME FOR OPTION C
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - XI
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
This section describes the technologies for treatment of
wastewater from new sources and presents mass discharge standards
for regulated pollutants for NSPS in the secondary molybdenum and
vanadium subcategory, based on the selected treatment technology.
New plants have the opportunity to design the best and most
efficient production processes and wastewater treatment
technologies without facing the added costs and restrictions
encountered in retrofitting an existing plant. Therefore, EPA has
considered the best demonstrated process changes, in-plant
controls and end-of-pipe treatment technologies which reduce
pollution to the maximum extent feasible as the basis for NSPS.
TECHNICAL APPROACH TO NSPS
New source performance standards are equivalent to the best
available technology (BAT) selected for currently existing
secondary molybdenum and vanadium plants. This result is a
consequence of careful review by the Agency of a wide range of
technical options for new source treatment systems which is
discussed in Section XI of Vol. I. Additionally/ there was
nothing found to indicate that the wastewater flows and
characteristics of new plants would not be similar to those
from existing plants, since the processes used by new sources
are not expected to differ from those used at existing sources.
Consequently, BAT production normalized discharge rates,
which are based on the best existing practices of the
subcategory, can also be applied to new sources. These rates
are presented in Table X-3 (page 3579).
Treatment technologies considered for the NSPS options are
identical to the treatment technologies considered for the BAT
options. These options are:
OPTION A
o Preliminary treatment with ammonia air stripping
(where required)
o Iron co-precipitation
o Chemical precipitation and sedimentation
3587
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - XI
OPTION C
o Preliminary treatment with ammonia air stripping
(where required)
o Iron co-precipitation
j Chemical precipitation and sedimentation
o Multimedia filtration
NSPS OPTION SELECTION-PROPOSAL
EPA proposed that the technology basis for NSPS for the secondary
molybdenum and vanadium subcategory be equivalent to Option c
(chemical precipitation, sedimentation, and multimedia
filtration, with preliminary treatment consisting of ammonia
steam stripping).
The wastewater flow rates for NSPS were the same as the proposed
BAT flow rates. Flow reduction measures for NSPS and BAT were
not considered feasible because no new demonstrated technologies
existed within the subcategory that improved on present water use
practices in the subcategory. Therefore, EPA concluded that flow
reduction beyond the allowances proposed for BPT or BAT was
unachievable, and NSPS flow rates should be equal to those for
BPT and BAT.
NSPS OPTION SELECTION-PROMULGATION
EPA is promulgating NSPS for the secondary molybdenum and
vanadium subcategory equivalent to Option C (iron
coprecipitation, chemical precipitation, sedimentation, and
multimedia filtration, with preliminary treatment consisting of
ammonia air stripping).
The wastewater flow rates for NSPS are the same as the BAT flow
rates. The NSPS flow rates are presented in Table X-3
(page 3579) . Additional flow reduction and more
stringent treatment technologies are not demonstrated in the
secondary molybdenum and vanadium subcategory.
REGULATED POLLUTANT PARAMETERS
The Agency has no reason to believe that the pollutants that will
be found in treatable concentrations in processes within new
sources will be any different than with existing sources.
Accordingly, pollutants and pollutant parameters selected for
limitations under NSPS, in accordance with the rationale of
Sections VI and X, are identical to those selected for BAT. The
conventional pollutant parameters TSS and pH are also selected
for limitation.
NEW SOURCE PERFORMANCE STANDARDS
The NSPS discharge flows for each wastewater source are the same
as the discharge rates for BAT and are shown in Table IX-1 (page
3563). The mass of pollutant allowed to be discharged per mass of
3588
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - XI
product is calculated by multiplying the appropriate treatment
effectiveness concentration (mg/1) by the production normalized
wastewater discharge flows (1/kkg). See Section X for . a
discussion of the use of treatment effectiveness concentrations.
The results of these calculations are the mass-based production-
related new source performance standards. These promulgated
standards are presented in Table XI-1 (page 3590).
3589
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - XI
TABLE XI-1
NSPS FOR THE SECONDARY MOLYBDENUM
AND VANADIUM SUBCATEGORY
(a) Leach Tailings NSPS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg(Ib/million Ibs) of technical grade molybdenum plus
vanadium plus pure grade molybdenum produced
*Arsenic
*Chromium
Copper
*Lead
*Nickel
Zinc .
Aluminum
* Ammonia
Boron
Cobalt
Germanium
*Iron
Manganese
*Molybdenum
Tin
Titanium
Vanadium
*TSS
*pH
27.120
7.219
24.970
5.463
10.731
19.900
119.200
8078.000
35.895
2.732
7.219
23.413
5.853
Reserved
' 7.414
10.340
1.951
292.665
Within the range of
12.097
2.927
11.900
2.536
7.219
8.195
52.870
3551.000
16.384
1.366
2.927
11.902
4.487
Reserved
4.293
4.487
234.132
7.5 to 10.0 at all times
*Regulated Pollutant
3590
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - XI
TABLE XI-1 (Continued)
NSPS FOR THE SECONDARY MOLYBDENUM
AND VANADIUM SUBCATEGORY
(b) Molybdenum Filtrate Solvent Extraction Raffinate NSPS
Pollutant orMaximumforMaximum for
pollutant property any one day monthly average
mg/kg(Ib/million Ibs) of technical grade molybdenum plus
vanadium plus pure grade molybdenum produced
*Arsenic
*Chromium
Copper
*Lead
*Nickel
Zinc
Aluminum
*Ammonia
Boron
Cobalt
Germanium
*Iron
Manganese
*Molybdenum
Tin
Titanium
Vanadium
*TSS
*pH Within
80.952
21.548 .
74.540
16.306
32.031
59.400
355.800
24144.000
107.200
8.154
21.550
69.887
17.470
Reserved
22.130
30.870
5.824
873.585
the range of 7.5
36.108
8.736
35.520
7.571
21.548
24.460
157.800
10600.000
48.920
4.076
8.736
35.526
13.400
Reserved
12.810
13.400
698.868
to 10.0 at all times
*Regulated Pollutant
3591
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - XI
TABLE XI-1 (Continued)
NSPS FOR THE SECONDARY MOLYBDENUM
AND VANADIUM SUBCATEGORY
(c) Vanadium Decomposition Wet Air Pollution Control NSPS
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg(ib/million Ibs) ofvanadium produced by decomposition
*Arsenic
*Chromium
Copper
*Lead
*Nickel
Zinc
Aluminum
*Amraonia
Boron
Cobalt
Germanium
*Iron
Manganese
*Molybdenum
Tin
Titanium
Vanadium
*TSS
*pH Within
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
the range of 7.5
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
— ._
0.000
to 10.0 at all times
*Regulated Pollutant
3592
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - XI
TABLE XI-1 (Continued)
NSPS FOR THE SECONDARY MOLYBDENUM
AND VANADIUM SUBCATEGORY
Molybdenum Drying Wet Air Pollution Control NSPS
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mgfkg(Ib/millionIbs) of molybdenum produced
*Arsenic
*Chromium
Copper
*Lead
*Nickel
Zinc
Aluminum
*Aramonia
Boron
Cobalt
Germanium
*Iron
Manganese
*Molybdenum
Tin
Titanium
Vanadium
*TSS
*pH Within
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
the range of
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
7.5 to 10.0 at all times
*Regulated Pollutant
3593
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - XI
TABLE XI-1 (Continued)
NSPS MASS LIMITATIONS FOR THE SECONDARY MOLYBDENUM
AND VANADIUM SUBCATEGORY
(e) Pure Grade Molybdenum NSPS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (pounds per million pounds) of pure molybdenum produced
*Arsenic
*Chromium
Copper
*Lead
*Nickel
Zinc
Aluminum
*Ammonia (as N)
Boron
Cobalt
Germanium
*Iron
Manganese
*Molybdenum
Tin
Titanium
Vanadium
TSS
*pH Within
32.359
8.614
29.798
6.518
12.804
23.746
142.200
9638.000
42.830
3.259
8.614
27.936
6.984
Reserved
88.460
12.340
2.328
349.200
the ranae of 7.5
14,434
3.492
14.200
3.026
8.614
9.778
63.090
4237.000
19.560
1.630
3.492
14.201
5.354
Reserved
5.122
5.354
279.360
to 10.0 at all times
*Regulated Pollutant
3594
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - XII
SECTION XII
PRETREATMENT STANDARDS
This section describes the control and treatment technologies for
pretreatment of process wastewaters from new sources in the
secondary molybdenum and vanadium subcategory. PSES are designed
to prevent the discharge of pollutants which pass through,
interfere with, or are otherwise incompatible with the operation
of publicly owned treatment works (POTW). The Clean Water Act
also requires pretreatment for pollutants, such as toxic metals,
that limit POTW sludge management alternatives. New indirect
discharge facilities, like new direct discharge facilities, have
the opportunity to incorporate the best available demonstrated
technologies, including process changes, in-plant controls, and
end-of-pipe treatment technologies, and to use -plant site
selection to ensure adequate treatment system function.
Pretreatment standards are to be technology based, and analogous
to the best available or best demonstrated technology for
removal of toxic pollutants. Pretreatment standards for regulated
pollutants are presented based on the selected control and
treatment technology.
PSES is not being promulgated for the secondary molybdenum and
vanadium subcategory because there are no existing indirect
dischargers in this subcategory. However, pretreatment standards
for new sources (PSNS) are promulgated.
TECHNICAL APPROACH TO PRETREATMENT
Before proposing and promulgating pretreatment standards, the
Agency examines whether the pollutants discharged by the industry
pass through the POTW or interfere with the POTW operation or its
chosen sludge disposal practices. In determining whether
pollutants pass through a well-operated POTW achieving secondary
treatment, the Agency compares the percentage of a pollutant
removed by POTW with the percentage removed by direct dischargers
applying the best available technology economically achievable.
A pollutant is deemed to pass through the POTW when the average
percentage removed nationwide by well-operated POTW meeting
secondary treatment requirements, is less than the percentage
removed by direct dischargers complying with BAT effluent
limitations guidelines for that pollutant. (See generally, 46 FR
at 9415-16 (January 28, 1981).)
This definition of pass through satisfies two competing
objectives set by Congress that standards for indirect
dischargers be equivalent to standards for direct dischargers
while at the same time, the treatment capability and
performance of the POTW be recognized and taken into account in
regulating the discharge of pollutants from indirect dischargers.
3595
-------
SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - XII
The Agency compares percentage removal rather than the mass or
concentration of pollutants discharged because the latter would
not take into account the mass of pollutants discharged to the
POTW from non-industrial sources or the dilution of the
pollutants in the POTW effluent to lower concentrations due to
the addition of large amounts of non-industrial wastewater.
PRETREATMENT STANDARDS FOR NEW SOURCES
Options for pretreatment of wastewaters from new sources are
based on increasing the effectiveness of end-of-pipe treatment
technologies. All in-plant changes and applicable end-of-rpipe
treatment processes have been discussed previously in Sections X
and XI. The options for PSNS, therefore, are the same as the BAT
options discussed in Section X. A description of each option is
presented in Section X.
Treatment technologies considered for the PSNS options are:
OPTION A
o Preliminary treatment with ammonia air stripping
(where required)
o Iron co-precipitation
o Chemical precipitation and sedimentation
OPTION C
o Preliminary treatment with ammonia air steam stripping
(where required)
o Iron co-precipitation
o Chemical precipitation and sedimentation
o Multimedia filtration
PSNS OPTION SELECTION
Option C (ammonia air stripping, iron co-precipitation,
chemical precipitation, sedimentation, and multimedia filtration)
has been selected as the regulatory approach for pretreatment
standards for new sources (PSNS). Option C prevents
pass-through and is equivalent to BAT treatment for direct
dischargers. In addition, Option C achieves effective removal of
priority pollutants by incorporating filtration which
is demonstrated in the nonferrous metals manufacturing category
at 25 plants, and will not result in adverse economic impacts.
The wastewater discharge rates for the promulgated PSNS are
identical to the promulgated BAT discharge rates for each waste
stream. The PSNS regulatory flow rates are identical to the BAT
rates and are shown in Table X-2 (page 3579). No flow reduction
measures are feasible over the BAT regulatory flow rates because
the scrubbers for the vanadium decomposition furnace and the
molybdenum drying furnace presently operate at 100 percent water
reuse. EPA does not believe that new plants should achieve flow
3596
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SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - XII
reduction in any other wastewater streams regulated in this
subcategory.
REGULATED POLLUTANT PARAMETERS
Pollutants are selected for limitation in accordance with
the rationale of Sections VI and X and are identical to those
selected for limitation for BAT. It is necessary to promulgate
PSNS to prevent the pass-through of arsenic, chromium, lead,
nickel, molybdenum, iron, and ammonia, which are the limited
pollutants. These priority pollutants are removed by a well-
operated POTW achieving secondary treatment at an average of 23
percent while the NSPS and BAT level technology removes
approximately 90 percent.
PRETREATMENT STANDARDS FOR NEW SOURCES
Pretreatment standards for new sources are based on the pollutant
concentrations achievable from the selected treatment
technologies, (Option C), and the regulatory flow rates
determined in Section X for BAT (see Table X-2, page 3579). A
mass of pollutant per mass of product (rag/kg) allocation is given
for each subdivision witnin the subcategory. This pollutant
allocation is based on the product of the achievable
concentration from the selected model treatment (mg/1) and
the production normalized wastev/ater discharge rate
(1/kkg). The achievable treatment concentrations for PSNS are
identical to those of BAT and are discusses in Section X. PSNS
are presented in Table XII-1 (page 3598).
3597
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SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGQRY
SECT - XII
TABLE XII-1
PSNS FOR THE SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
(a) Leach Tailings PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of technical grade molybdenum plus
vanadium plus pure grade molybdenum produced
*Arsenic
* Chromium
Copper
*Lead
*Nickel
Zinc
Aluminum
*Ammonia
Boron
Cobalt
Germanium
*Iron
Manganese
*Molybdenum
Tin
Titanium
Vanadium
27.120
7.219
24.972
5.463
10.731
19.900
114.210
8078.000
35.895
2.732
7.219
23.413
5.583
Reserved
7.414
10.341
1.951
12.097
2.927
11.901
2.536
7.219
8.195
52.870
3551.000
16.380
1.366
2.927
11.902
4.487
Reserved
4.293
4.487
*"""""™" ****
*Regulated Pollutant
3598
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SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - XII
TABLE XII-1 (Continued)
PSNS FOR THE SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
(b) Molybdenum Filtrate Solvent Extraction Raffinate PSNS
Pollutant or
pollutant property
Maximum for
any one day
Maximum for
monthly average
mg/kg (Ib/million Ibs) of technical grade molybdenum
plus vanadium plus pure grade molybdenum produced
*Arsenic
*Chromium
Copper
*Lead
*Nickel
Zinc
Aluminum
* Ammonia
Boron
Cobalt
Germanium
*Iron
Manganese
*Molybdenum
Tin
Titanium
Vanadium
80.952
21.548
74.540 .
16.306
32.031
59.400
355.800
24114.000
107.200
8.154
21.550
69.887
17.470
Reserved
22.130
30.870
5.824
36.108
8.736
35.520
7.571
21.548
24.460
157.800
10600.000
48.920
4.076
8.736
35.526
13.400
Reserved
12.810
13.400
"*""""""""""*
*Regulated Pollutant
3599
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SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - XII
TABLE XII-1 (Continued)
PSNS FOR THE SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
(c) Vanadium Decomposi t i on Wet Air Pollution Control NSPS
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg(Ib/million Ibs) of vanadium produced by decomposition"
*Arsenic 0.000 0.000
*Chromium 0.000 0.000
Copper 0.000 0.000
*Lead 0.000 0.000
*Nickel 0.000 0.000
Zinc 0.000 0.000
Aluminum 0,000 0.000
*Ammonia 0.000 0.000
Boron 0.000 0,000
Cobalt 0.000 0.000
Germanium 0,000 0.000
*Iron 0.000 0.000
Manganese 0.000 0.000
*Molybdenum 0,000 0.000
Tin 0.000 0.000
Titanium 0.000 0.000
Vanadium 0.000
*Regulated Pollutant
3600
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SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - XII
TABLE XII-1 (Continued)
PSNS FOR THE SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
(d) Molybdenum Drying Wet Air Pollution Control PSNS
Pollutant orMaximum forMaximum for
pollutant property any one day monthly average
mg/kg (Ib/million Ibs) of molybdenum produced
*Arsenic 0.000 0.000
*Chromium 0.000 0.000
Copper 0.000 0.000
*Lead 0.000 0.000
*Nickel 0.000 . 0.000
Zinc 0.000 0.000
Aluminum 0.000 0.000
*Ammonia 0.000 0.000
Boron 0.000 0.000
Cobalt 0.000 0.000
Germanium 0.000 0.000
*Iron 0.000 0.000
Manganese 0.000 0.000
*Molybdenum 0.000 0.000
Tin 0.000 0.000
Titanium 0.000 0.000
Vanadium 0.000
*Regulated Pollutant
3601
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SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - XII
TABLE XII-1 (Continued)
PSNS FOR THE SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY
Ce) Pure Grade Molybdenum PSNS
Pollutant or Maximum for Maximum for
pollutant property any one day monthly average
mg/kg ( Ib/million Ibs ) of pure molybdenum produced
*Arsenic 32.359 14.434
*Chromium 8.614 3,492
Copper 29.798 14.200
*Lead 6.518 3.026
*Nickel 12.804 8.614
Zinc 23.746 9.778
Aluminum 142.200 63.090
*Ammonia (as N) 4638.000 4237.000
Boron • 42.830 19.560
Cobalt , 3.259 1.630
Germanium 8.614 3.492
*Iron 27.936 14.201
Manganese 6.984 5.354
*Molybdenum Reserved Reserved
Tin 8.846 5.122
Titanium 12.340 5.354
Vanadium 2.328 ---
*Regulated
3602
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SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - XIII
SECTION XIII
BEST CONVENTIONAL POLLUTANT CONTROL TECHNOLOGY
EPA is not promulgating best conventional pollutant control
technology (BCT) for the secondary molybdenum and vanadium
subcategory at this time.
3603
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SECONDARY MOLYBDENUM AND VANADIUM SUBCATEGORY SECT - XIII
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