EPA 440/1-73/014
DEVELOPMENT DOCUMENT FOR
PROPOSED EFFLUENT LIMITATIONS GUIDELINES
AND NEW SOURCE PERFORMANCE STANDARDS
FOR THE
PETROLEUM REFINING
POINT SOURCE CATEGORY
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
DECEMBER 1973
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Publication Notice
This is a development document for proposed effluent limitations
guidelines and new source performance standards. As such, this report
is subject to changes resulting from comments received during the period
of public comments of the proposed regulations. This document in its
final form will be published at the time the regulations for this
industry are promulgated.
-------
DEVELOPMENT DOCUMENT
for
PROPOSED EFFLUENT LIMITATIONS GUIDELINES
and
NEW SOURCE PERFORMANCE STANDARDS
for the
PETROLEUM REFINING
POINT SOURCE CATEGORY
Russell E. Train
Administrator
Robert L. Sansom
Assistant Administrator for Air & Water Programs
Allen Cywin
Director, Effluent Guidelines Division
David L. Becker
Martin Halper
Project Officers
December, 1973
Effluent Guidelines Division
Office of Air and Water Programs
U.S. Environmental Protection Agency
Washington, D.C. 20460
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-------
ABSTRACT
Tis development document presents the findings of an extensive study of
the Petroleum Refining Industry for the purposes of developing effluent
limitation guidelines, standards of performance, and pretreatment
standards for the industry to implement Sections 304, 306 and 307 of the
Federal Water Pollution Control Act of 1972, (PL 92-500). Guidelines
and standards were developed for the overall petroleum refining
industry, which was divided into six subcategories.
Effluent limitation guidelines contained herein set forth the degree of
reduction of pollutants in effluents that is attainable through the
application of best practicable control technology currently available
(BPCTCA), and the degree of reduction attainable through the application
of best available technology economically achievable (BATEA) by existing
point sources for July 1, 1977, and July 1, 1983, respectively.
Standards of performance for new sources are based on the application of
best available demonstrated technology (BADT).
Annual costs for the petroleum refining industry for achieving BPCTCA
Control by 1977 are estimated at $244,000,000, and the additional annual
costs for attaining BATEA Control by 1980 are estimated at $250,000,000.
The estimated annual costs for BADT for new sources is $26,000,000.
Supporting data and rationale for the development of proposed effluent
limitation guidelines and standards of performance are contained in this
(velopment document.
111
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CONTENTS
Section Page
ABSTRACT ill
CONTENTS v
FIGURES x
TABLES xi
I CONCLUSIONS 1
II RECOMMENDATIONS 3
III INTRODUCTION 17
Purpose and Authority 17
Methods Used for Development of the Effluent 18
Limitation Guidelines and Standard of
Performance
General Description of the Industry 20
Storage and Transportation 25
Crude Oil and Product Storage 25
Process Description
Wastes
Trends
. Ballast Water 26
Process Description
Wastes
Treands
Crude Desalting 26
Process Description
Wastes
Trends
Crude Oil Fractionation 28
Process Description
Prefractionation and Atmospheric Distillation
(Topping or Skimming)
Vacuum Fractionation
Three Stage Crude Distillation
Wastes
Trends
Cracking 31
Thermal Cracking 31
Process Description
Wastes
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Section Page
Trends
Catalytic Cracking 32
Process Description
Wastes
Trends
Hydrocracking 34
Process Description
Wastes
Trends
Hydrocarbon Rebuilding 35
Polymerization 35
Process Description
Wastes
Trends
Alkylation 35
Process Description
Wastes
Trends
Hydrocarbon Rearrangements 36
Isomerization 36
Process Description
Wastes
Trends
Reforming 37
Process Description
Wastes
Trends
Solvent Refining 38
Process Description
Wastes
Trends
Hydrotreating 39
Process Description
Wastes
Trends
Grease Manufacture 40
Process Description
Wastes
Trends
Asphalt Production 41
Process Description
Wastes
Product Finishing 41
Drying and Sweetening 41
Process Description
Wastes
Trends
vi
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Section Page
Lube Oil Finishing 42
Process Description
Wastes
Trends
Blending and Packaging 43
Process Description
Wastes
Trends
Auxiliary Activities 44
Hydrogen Manufacture 44
Process Description
Wastes
Trends
Utilities Function 45
Refinery Distribution 48
Anticipated Industry Growth 51
IV INDUSTRY SUBCATEGORIZATION 61
Discussion of the Rationale of Subcategorization 61
Development of the Industry Subcategorization 62
Subcategorization Results 63
Analysis of the Subcategorization 63
Topping Subcategory
Low and High Cracking Subcategory
Petrochemical Subcategory
Lube Subcategory
Integrated Subcategory
Conclusion 67
V WASTE CHARACTERIZATION 69
General
Raw Waste Loads
Wastewater Flows
Basis for Effluent Limitations
VI SELECTION OF POLLUTANT PARAMETERS 79
Selected Parameters
Oxygen Demand Parameters 79
BODS
COD
TOC
TSS
vii
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Section Pag
Hexane Extractables - Oil and Grease
Ammonia as Nitrogen
Phenolic Compounds
Sulfides
Total Chromium
Hexavalent Chromium
Zinc 88
Other Pollutants
IDS
Cyanides
pH (Acidity and Alkalinity)
Temperature
Other Metallic Ions
Chlorides
Fluorides
Phosphates
VII CONTROL AND TREATMENT TECHNOLOGY 95
In-Plant Control/Treatment Techniques 95
Housekeeping
Process Technology
Cooling Towers
Evaporative Cooling Systems
Dry Cooling Systems
Wet Cooling Systems
At-Source Pretreatment
Sour Water Stripping 99
Spent Caustic Treatment
Sewer System Segregation
Storm Water Runoff
Gravity Separation of Oil
Further Removal of Oil and Solids Clarifiers 106
End-of-Pipe Control Technology
Equalization
Dissolved Air Flotation
Oxidation Ponds
Aerated Lagoon
Trickling Filter
Bio-Oxidation Tower
Activated Sludge
Physical Chemical Treatment
Flow Reduction Systems
Granular Media Filters
Activated Carbon
viii
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Section
VIII
IX
X
XI
XII
XIII
XIV
Sludge Handling and Disposal
Digestion
Vacuum Filtration
Centrifugation
Sludge Disposal
Landfilling
Incineration
COST, ENERGY, AND NON-WATER QUALITY ASPECTS
BPCTCA Treatment Systems Used For Economic Evaluation
BATEA Treatment Systems Used For Economic Evaluation
Estimated Costs of Facilities
Non-Water Quality Aspects
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY
AVAILABLE— EFFLUENT LIMITATIONS
Procedure for Development of BPCTCA Limitations
Application of Oxygen Demand Limitations
Variability Allowance for Treatment Plant Performance
BEST AVAILABLE TECHNOLOGY ECONOMICALLY ACHIEVABLE—
EFFLUENT LIMITATIONS
H9
165
173
Flow
Procedure for Development for BATEA Effluent Limitations
Statistical Variability of a Properly Designed and
Operated Waste Treatment Plant
NEW SOURCE PERFORMANCE STANDARDS
179
Procedure for Development of BADT Effluent Limitations
Variability Allowance for Treatment Plant Performance
ACKNOWLEDGEMENTS
BIBLIOGRAPHY
GLOSSARY AND ABBREVIATIONS
183
185
193
ix
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LIST OF FIGURES
Figure No. Title Page No.
1 Crude Desalting (Electrostatic Desalting) 27
2 Crude Fractionation (Crude Distillation, 30
Three Stages)
3 Catalytic Cracking (Fluid Catalytic Cracking) 33
4 Geographical Distribution of Petroleum 49
Refineries in United States
5 Hypothetical 100,000 Barrel/Stream Day 52
Integrated Refinery
6 BPCTCA - Wastewater Treatment System 141
7 BATEA - Proposed Treatment 145
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TABLES
Table No. Title Page No.
1 BPCTCA Petroleum Refining Industry Effluent Limitations 4-7
2 BATEA Petroleum Refining Industry Effluent Limitations 8-11
3 BADT New Source Performance Standards for the Petroleum 12-15
Refining Industry
4 Intermediates and Finished Products Frequently Found in 21
the Petroleum Refining Industry
5 Major Refinery Process Categories 23
6 Qualitative Evaluation of Wastewater Flow and Charac- 24
teristics by Fundamental Refinery Processes
7 Crude Capacity of Petroleum Refineries by States as of 50
January 1, 1973 (3).
8 Process Employment of Refining Processes as of 53
January 1, 1973 (3).
9 Trend in Domestic Petroleum Refining from 1967 to 1973 54
10 1972 Consumption of Petroleum Feedstocks 55
11 Sources of Supply for U. S. Petroleum Feedstocks 57
12 Characteristics of Crude Oils from Major Fields 58-60
Around the World
13 Categorization of the Petroleum Refining Industry 64
Reflecting Significant Differences in Wastewater
Characteristics
14 Median Net Raw Waste Loads from Petroleum Refining 65
Industry Categories
15 Topping Subcategory Raw Waste Load 71
16 Low Cracking Subcategory Raw Waste Load 72
17 High Cracking Subcategory Raw Waste Load 73
xi
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Table No. Title Page No.
18 Petrochemical Subcategory Raw Waste Load 74
19 Lube Subcategory Raw Waste Load 75
20 Integrated Subcategory Raw Waste Load 76
21 Wastewater Flow from Petroleum Refineries Using 3% 77
or Less once-Through Cooling Water for Heat Removal
22 Significant Pollutant Parameters for the Petroleum 80
Refining Industry
23 Metallic Ions Commonly Found in Effluents from 92
Petroleum Refineries
24 Observed Refinery Treatment Systems and Effluent 108
Loadings
25 Expected Effluents from Petroleum Treatment Processes 109
26 Typical Removal Efficiencies for Oil Refinery 110
Treatment Processes
27 Estimated Total Annual Costs for End-of-Pipe Treatment 120
Systems for the Petroleum Refining Industry (Existing
Refineries)
28 Summary of End-of-Pipe Wastewater Treatment Costs for 121
Representative Plants in the Petroleum Refinery Industry
29 Water Effluent Treatment Costs Petroleum Refining 123
Industry - Topping Subcategory
30 Water Effluent Treatment Costs Petroleum Refining 124
Industry - Topping Subcategory
31 Water Effluent Treatment Costs Petroleum Refining 125
Industry - Topping Subcategory
32 Water Effluent Treatment Costs Petroleum Refining 126
Industry - Low Cracking Subcategory
33 Water Effluent Treatment Costs Petroleum Refining 127
Industry - Low Cracking Subcategory
xii
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Table No. Title Page No.
34 Water Effluent Treatment Costs Petroleum Refining 128
Industry - Low Cracking Subcategory
35 Water Effluent Treatment Costs Petroleum Refining 129
Industry - High Cracking Subcategory
36 Water Effluent Treatment Costs Petroleum Refining 130
Industry - High Cracking Subcategory
37 Water Effluent Treatment Costs Petroleum Refining 131
Industry - High Cracking Subcategory
38 Water Effluent Treatment Costs Petroleum Refining 132
Industry - Petrochemical Subcategory
39 Water Effluent Treatment Costs Petroleum Refining 133
Industry - Petrochemical Subcategory
40 Water Effluent Treatment Costs Petroleum Refining 134
Industry - Petrochemical Subcategory
41 Water Effluent Treatment Costs Petroleum Refining 135
Industry - Lube Subcategory
42 Water Effluent Treatment Costs Petroleum Refining 136
Industry - Lube Subcategory
43 Water Effluent Treatment Costs Petroleum Refining 137
Industry - Lube Subcategory
44 Water Effluent Treatment Costs Petroleum Refining 138
Industry - Integrated Subcategory
45 Water Effluent Treatment Costs Petroleum Refining 139
industry - Integrated Subcategory
46 Water Effluent Treatment Costs Petroleum Refining 140
Industry - ^Integrated Subcategory
47 BPCTCA - End-of-Pipe Treatment System Design Summary 142
48 BATEA - End of-Pipe Treatment System Design Summary 146
49 BPCTCA - Estimated Wastewater Treatment Costs for 152
the Topping Subcategory
xiii
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Table No. Title Page No.
50 BPCTCA - Estimated Wastewater Treatment Costs for 153
the Low Cracking Subcategory
51 BPCTCA - Estimated Wastewater Treatment Costs for 154
the High Cracking Subcategory
52 BPCTCA - Estimated Wastewater Treatment Costs for 155
the Petrochemical Subcategory
53 BPCTCA - Estimated Wastewater Treatment Costs for 156
the Lube Subcategory
54 BPCTCA - Estimated Wastewater Treatment Costs/ for 157
the Integrated Subcategory
55 Estimated Additional Wastewater Treatment Costs for 158
BATEA Topping Subcategory
56 Estimated Additional Wastewater Treatment Costs for 159
BATEA Low Cracking Subcategory
57 Estimated Additional Wastewater Treatment Costs for 160
BATEA High Cracking Subcategory
58 Estimated Additional Wastewater Treatment Costs for 161
BATEA Petrochemical Subcategory
59 Estimated Additional Wastewater Treatment Costs for 162
BATEA Lube Subcategory
60 Estimated Additional Wastewater Treatment Costs for 163
BATEA Integrated Subcategory
61 Attainable Concentrations from the Application of 169
Best Practicable Control Technology Currently Available
62 BPCTCA - Petroleum Refining Industry Effluent 170
Limitations (Annual Average Daily Limits)
63 Variability Factors 171
64 Flow Basis for Developing BATEA Effluents Limitations 176
65 BATEA Reductions in Pollutants Loads Achievable by 177
Application of Activated Carbon to Media Filtration
Effluent (BPCTCA)
xiv
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Table No. Title Page No.
66 BATEA - Petroleum Refining Industry Effluent 178
Limitations (Annual Daily Limits)
67 BADT - New Source Performance Standards for the 181
Petroleum Refining Industry (Annual Average Daily
Limits)
68 Metric Units Conversion Table 182
xv
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SECTION I
CONCLUSIONS
This study covered the products included in the Petroleum Refining
Industry (SIC 2911). The 2U7 U.S. petroleum refineries currently
process 2.2 million cubic meters (14 million barrels) of crude oil per
stream day. U.S. refineries vary in complexity from the very small,
with simple atmospheric fractionation, or topping, to the very large
integrated refineries manufacturing a multitude of petroleum and
petrochemical products from a variety of feedstocks. The raw waste
water load is dependent upon the types of processes employed by the
refinery, justifying the utilization of production process groupings, as
delineated by their effects on raw waste water as the basis for the
subcategorization. The subcategories developed for the petroleum
refining industry for the purpose of establishing effluent limitations
are as follows:
Subcategory
Topping
Low-Cracking
High-Cracking
Basic Refinery Operations Included
\
Topping and catalytic reforming
Topping and cracking, with fresh feed (non-recycle)
to the cracking and hydroprocessing of less than 50
percent of the feedstock throughput.
Topping cracking, with a fresh feed (nonrecycle) to
the cracking and hydroprocessing of greater than 50
percent of the feedstock throughput.
Petrochemical Topping, cracking and petrochemicals operations.*
Lube Topping, cracking and lubes.**
Integrated Topping, cracking, lubes and petrochemicals
operations. *
* Petrochemical operations - Production of greater than 15 percent of
the feedstock throughput in first generation petrochemicals and
isomerization products (benzene, toluene, xylene, olefins, cyclohexane,
etc.) and/or production of second generation petrochemicals (cumene,
alcohols, ketones, etc.).
** Lubes - the production of less than 12 percent of the feedstock
throughput as lubes. Refineries with greater than 12 percent lubes are
being considered speciality refineries and the guidelines for these
specialty refineries will be set at a later date.
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All six subcategories generate waste waters which contain simil
constituents. However, the concentration and loading of the
constitutents, termed "raw waste load," vary between the subcategories^
Existing control and treatment technology, as practiced by the industry,
includes both end-of-pipe treatment and in-plant reductions. Many of
the individual wastewater streams, such as sour waters, have a
deleterious effect on biological treatment facilities and/or receiving
waters. Consequently, these individual streams are pretreated in-plant,
prior to discharge to waste water facilities. Current technology for
end-of-pipe treatment involves biological treatment and granular media
filtration. Biological treatment systems employed include activitated
sludge plants and aerated lagoons and stabilization pond systems.
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SECTION II
RECOMMENDATIONS
The significant waste water constituents are BOD5, COD, TOC, total
suspended solids, oil and grease, phenolic compounds, ammonia (N),
sulfides, total and hexavalent chromium and zinc. These waste water
constituents were selected to be the subject .of the effluent
limitations.
Effluent limitations commensurate with the best practical control
technology currently available are proposed for each refinery
subcategory. These limitations, listed in Table 1, are explicit
numerical values for the allowable discharges within each subcategory.
Implicit in BPCTCA in-process technology is segregation of non-contact
waste waters from process waste water. BPCTCA end-of-pipe technology is
based on the application of the existing waste water treatment processes
currently used in the Petroleum Refining Industry. These consist of
equilization and storm diversion; initial oil and solids removal (API
separators or baffle plate separators); further oil and solids removal
(clarifiers, dissolved air flotation, or filters); carbonaceous waste
removal (activated sludge, aerated lagoons, oxidation ponds, trickling
filter, activated carbon, or combinations of these); and filters (sand,
dual media; or multi-media) following biological treatment methods. The
«iability of performance of biological waste water treatment systems
been recognized in the development of the BPCTCA effluent
itations.
Effluent limitations commensurate with the best available technology
economically achievable are proposed for each subcategory. These
effluent limitations are listed in Table 2. The limitations are
explicit numerical values for the allowable discharges within each
subcategory. The primary end-of-pipe treatment proposed for BATEA
effluent limitations is activated carbon adsorption, as further treat-
ment in addition to BPCTCA control technology. Also implicit in BATEA
technology are achievable reductions in waste water flow.
New source performance standards commensurate with the best available
demonstrated technology are based on the flows achievable with BATEA
technology, and the end-of-pipe control technology achievable with
BPCTCA technology. These BADT effluent limitations are listed in Table
3. Activated carbon adsorption has not been included as BADT
technology, since the use of this technology has not been sufficiently
demonstrated, at this time, on petroleum refining waste water to insure
its applicability and reliability on secondary effluent waste waters
from refineries.
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Table 1
BPCTCA
Petroleum Refining Industry Effluent Limitations
Kilograms of Pollutants/1000 Cubic Meters of Feedstock (1) Per Stream Day
(Pounds of Pollutants/1000 BBL of Feedstock Per Stream Day)
Refinery
Subcategory
Topping
Low-Cracking
High-Cracking
Petroleum
Lube
Integrated
BODS
Monthly
Average
7.3 (2.6)
10.2 (3.6)
13.5 (4.4)
15.5 (5.4)
18.4 (6.5)
Daily
Maximum
9.0 (3.2)
12.6 (4.4)
16.7 (5.9)
19.1 (6.7)
22.7 (8.0)
COD
TOG
Monthly
Average
(10.0)
(22.1)
(38.4)
(33.6)
27.5 (9.7) 34.0 (12.0)
28.3
62.5
108.7
95.1
152.6 (53.9)
198.8 (70.2)
Daily
Maximum
31.7 (11.2)
78.1 (27.6)
135.8 (48.0)
118.9 (42.0)
190.7 (67.4)
248.5 (87.8)
Monthly
Average
Daily
Maximum
6
14
18
21
25
37
.3
.0
.4
.0
.0
.9
(2.
(4.
(6.
(7.
(8.
(13
2)
9)
5)
4)
8)
.4)
7.
17.
22.
25.
30.
46.
7
2
6
8
8
6
(2.
(6.
(8.
(9.
(10
(16
7)
1)
0)
1)
.9)
.5)
Runoff (2)
Ballast (3)
0.025
0.025
(0.21)
(0.21)
0.031(0.26)
0.031(0.26)
0.24 ( 1.6)
0.19 ( 2.0)
0.30 ( 2.0)
0.24 ( 2.5)
0.035 (0.293)0.043(0.360)
0.035 (0.293)0.043(0.360)
(1) Feedstock - crude oil and/or natural gas liquids.
(2) The additional allocation being allowed for contaminated storm runoff flow (kg/1000 liters
(lb/1000 gallons) shall be based solely on that storm flow which passes through the treatment
system. All additional storm runoff, that has been segregated from the main waste stream, shall
not show a visible sheen or exceed a TOG concentration of 15 mg/1 when discharged.
(3) This is an additional allocation, based on ballast water intake (daily average)-
per 1000 liters (per 1000 gallons)
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Table 1
BPCTCA
(continued)
Refinery
Subcategory
Topping
Low-Cracking
High-Cracking
Petrochemical
Lube
Integrated
Total
Suspended
Monthly
Average
4.6 (1
6.4 (2
8.2 (2
9.6 (3
14.1(5
17.3(6
.6)
.2)
.9)
.4)
.0)
.1)
Solids
Daily
Maximum
5
8
10
12
17
21
.8(2.
.0 (2
.2 (3
.0.(4
.6 (6
.6 (7
0
.8)
.6)
.2)
.2)
.6)
Oil
& Grease
Monthly
Average
2.
3.
4.
5.
6.
8.
2
2
0
0
9
6
(0.
(1.
(1.
(1.
(2.
(3.
8)
1)
4)
8)
4)
0)
Daily
Maximum
2.8
4.0
5.0
6.2
8.6
10.8
(1.0)
(1.4)
(1.8)
(2.2)
(3.0)
(3.8)
Phenolic Compounds
Monthly Daily
Average- Maximum
0.048 (0.017) 0.070 (0.025)
0.068 (0.024)
0.088 (0.031)
0.110 (0.039)
0.150 (0.053)
0.188 (0.066)
0.096 (0.034
0.125 (0.044)
0.156 (0.055)
0.211 (0.074)
0.266 (0.094)
Runoff (2)
Ballast (3)
0.016(0.13)
0.016(0.13)
0.020(0.17)
0.020(0.17)
0.0080(0.067)
0.0080(0.067)
0.010(0.084)
0.010(0.084)
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Table 1 (continued)
BPCTCA
Hexavalent
Refinery
Subcategory
topping 0.
Low-CTacking 0.
High-CrackingO.
PetrochemicalO .
Lube 0.
Integrated 0.
Runoff (2)
Ballast (3)
Chromium
Monthly
Average
0023
0032
0041
0045
0068
0091
(0.
(0.
(0.
(0.
(0.
(0.
__
00080)
0011)
0014)
0016)
0024)
0032)
0.
0.
0.
0.
0.
0.
Daily
Maximum
0028
0040
0051
0057
0085
Oil
(0.
(0.
(0.
(0.
(0.
(0.
0010)
0014)
0018)
0020)
0030)
0040)
Zinc
Monthly
Average
0.23
0.32
0.41
0.45
0.68
0.91
__
(.080)
(0.11)
(0.14)
(0.16)
(0.24)
(0.32)
Daily
Maximum
0.28
0.40
0.51
0.57
0.85
1.1
___
(0.10)
(0.14)
(0.18)
(0.20)
(0.30)
(0.40)
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Table 1 (continued)
BPCTCA
Ammonia (N)
Sulfide
Total Chromium
Refinery
Subcategory
Topping
Low-Cracking
High-Cracking
Petroleum
Lube
Integrated
Monthly
Average
1.5 (0.53)
3.0 (1.1)
6.9 (2.4)
10.2 (3.6)
6.9 (2.4)
10.6 (3.8)
Daily
Maximum
2.0 (0.70)
4.0 (1.4)
9.2 (3.2)
13.6 (4.8)
9.2 (3.2)
14.2 (5.0)
Monthly
Average
0.04
0.055
0.07
0.085
0.13
0.155
(0.014)
(0.020)
(0.025)
(0.029)
(0.042)
(0.055)
Daily
Maximum
0.07
0.09
0.11
0.13
0.20
0.24
(0
(0
(0
(0
(0
(0
.022)
.031)
.040)
.046)
.066)
.086)
Monthly
Average
0.
0.
0.
0.
0.
0.
115
16
20
235
35
445
(0.
(0.
(0.
(0.
(0.
(0.
040)
056)
070)
083)
123)
157)
Daily
Maximum
0.
0.
0.
0.
0.
0.
14 (0.
20 (0.
25 (0.
295 (0
435 (0
555 (0
050)
070)
088)
.104)
.154)
.196)
Runoff (2)
Ballast (3)
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Table 2
BATEA
Petroleum Refining Industry Effluent Limitations
Kilograms of Pollutants/1000 Cubic Meters of Feedstock (1) Per Stream Day
(Pounds of Pollutants/1000 BBL of Feedstock Per Stream Day)
Refinery
Subcategory
Topping
Low-Cracking
High-Cracking
Petroleum
Lube
Integrated
BODS
Monthly Daily
Average Maximum
1.4(0.50)
2.2(0.78)
2.8(0.99)
3.0(1.07)
6.1(2.16)
6.3(2.23)
1.7(0.61)
2.7(0.97)
3.5(1.22)
3.7(1.32)
7.6(2.67)
7.8(2.75)
COD
Monthly
Average
3.7(1.3)
12.7(4.5)
20.4(7.2)
11.3(4.0)
37.6(13.3)
34.0(12.0)
Daily
Maximum
4.5(1.6)
15.8(5.6)
25.5(9.0)
14.2(5.0)
47.0(16.6)
42.5(15.0)
TOC
Monthly
Average
3.1(1.1)
5.1(1.8)
6.5(2.3)
7.1(2.5)
13.9(4.9)
14.4(5.1)
Daily
Maximum
4.0(1.4)
6.2(2.2)
8.2(2.9)
8.5(3.0)
17.3(6.1)
17.5(6.2)
oo
Runoff(2) 0.0085(0.071) O.O..(0.088) 0.023(0.19)
Ballast(3) 0.0085(0.071)0.011(0.088) 0.028(0.23)
0.028(0.23)
0.035(0.29)
0.019(0.16) 0.024(0.20)
0.019(0.16) 0.024(0.20)
(1) Feedstock - crude oil and/or natural gas liquids.
(2) The additonal allocation being allowed for contaminated storm runoff flow (kg/inn.O liters
(lbs/1000 gallons) shall be based solely on that storm flow which passes through the
treatment system. All additional storm runoff, that has been seere^atfid from the main
waste stream, shall not show a visible sheen or exceed a TOC concentration of 15 mg/1 when
discharged.
(3) This is an additonal allocation, based on ballast water intake (daily average)
per 1000 liters (per 1000 gallons)
-------
T
BA'
2 (continued)
Refinery
Subcategory
Topping
Low-Cracking
High-Cracking
Petrochemical
Lube
Integrated
Total Suspended Solids
Monthly
Average
1.3(0.46)
2.1(0.74)
2.6(0.93)
2.8(1.0)
5.6(2.0)
5.9(2.1)
Daily
Maximum
1.6(0.58)
2.6(0.92)
3.3(1.2)
3.6(1.3)
7.1(2.5)
7.4(2.6)
Oil &
Monthly
Average
0.28(0.10)
0.40(0.14)
0.54(0.19)
0.59(0.21)
1.1(0.40)
1.2(0.42)
Grease
Daily
Maximum
0.34(0.12
0.51(0.18)
0.68(0.24)
0.74(0.26)
1.4 (0.50)
1.5(0.52)
Phenolic Compounds
Monthly Daily
Average- Maximum
0.0050(0.0018) 0.0073(0.0026)
0.0084(0.0030) 0.012(0.0043)
(0.0039)
(0.0042)
0.011
0.012
0.025 (0.0087)
0.0155(0.055)
0.017 (0.0060)
0.034 (0.012)
0.0255(0.0090) 0.037 (0.013)
Runoff (2)
Ballast (3)
0.0079(0.066)0.010(0.083) 0.0016(0.04)
0.0079(0.066)0.010(0.083) 0.0016(0.014)
0.0020(0.017)
0.0020(0.017)
-------
Table 2 (continued)
BATEA
Ammonia (N)
Refinery Monthly
Subcategory Average
Topping 0.34(0.12)
Low-Cracking 0.76(0.27)
High-Cracking 1.3(0.46)
Petroleum 2.5(0.87)
Lube 2.3(0.80)
Integrated 2.8(1.0)
Daily
Maximum
0.45(0.16)
1.0(0.36)
1.6(0.58)
3.3(1.2)
3.0(1.1)
3.8(1.4)
Sulfide
Total Chromium
Monthly
Average
0.024(0.0084)
0.036(0.013)
0.048(0.017)
0.075(0.027)
0.10(0.036)
0.10(0.036)
Daily
Maximum
0.037(0.013)
0.056(0.020)
0.075(0.026)
0.12(0.042)
0.16(0.057)
0.16(0.057)
Monthly
Average
Daily
Maximum
0.065(0.023) 0.085(0.030)
0.105(0.037) 0.13(0.046)
0.13(0.046) 0.16(0.058)
0.14(0.050) 0.175(0.062)
0.29(0.102) 0.36(0.128)
0.30(0.106) 0.37(0.132)
Runoff(2)
Ballast(3) —
-------
Table 2 (continued)
BATEA
Hexavalent Chromium
Zinc
Refinery
Subcategory
Topping
Low-Cracking
High-Cracking
Petrochemical
Lube
Integrated
Monthly
Average
0.
0.
0.
0.
0.
0.
0013(0.
0020(0.
0026(0.
0028(0.
0059(0.
0059(0.
00046)
00072)
00092)
00099)
0020)
0021)
0
0
0
0
0
0
Dally
Maximum
.0016(0
.0025(0
.0034(0
.0035(0
.0072(0
.0074(0
.00058)
.00090)
.00120)
.00124)
.0025)
.0026)
0.
0.
0.
0.
0.
0.
Monthly
Average
13(0.
20(0.
26(0.
28(0.
44(0.
46(0.
046)
072)
092)
099)
15)
16)
0
0
0
0
0
0
Daily
Maximum
.16(0.
.25(0.
.34(0.
.35(0.
.57(0.
.59(0.
050)
090)
120)
124)
20)
21)
Runoff (2)
Ballast (3)
-------
Table 3
BADT
Petroleum Refining Industry Effluent Limitations
Kilograms of Pollutants/1000 Cubic Meters of Feedstock (1) Per Stream Day
(Pounds of Pollutants/1000 BBL of Feedstock Per Stream Day)
BODS
COD
Refinery
Subcategory
Topping
Low-Cracking
High-Cracking
Petrochemical
Lube
Integrated
Monthly
Average
TOC
Daily
Maximum
Monthly
Average
4.3(1.5)
5.8(2.4)
8.8(3.1)
9.1(3.2)
14.9(5.3)
18.8(6.6)
5.2(1.85)
8.3(2.9)
10.8(3.8)
11.3(4.0)
18.4(6.5)
23.2(8.2)
15.0(5.3)
40.2(14.2)
75.3(25.6)
57.2(20.2)
125(44.3)
136(48.2)
Daily
Maximum
18.7(6.6)
50.4(17.8)
90.6(32.0)
71.3(25.2)
157(55.4)
170(60.2)
Monthly
Average
Daily
Maximum
3.7(1.3)
9.3(3.3)
11.9(4.2)
12.5(4.4)
20.6(7.3)
26.1(9.2)
4.5(1.6)
11.3(4.0)
14.4(5.1)
15.3(5.4)
25.5(9.0)
32.3(11.4)
Runoff(2) 0.025(0.24) 0.031(0.26) 0.91(0.76) 0.11(0.94)
Ballast(3)0.025(0.21) 0.031(0.26 0.11(0.95) 0.14(1.2)
0.023(0.19)
0.023(0.19)
0.028(0.23)
0.028(0.23)
(1) Feedstock - crude oil and/or natural gas liquids.
(2) The additional allocation being allowed for contaminated storm runoff flow (kg/1000 liters
(lbs/1000 gallons shall be based solely on that storm flow which passes through the. treatment
system. All additional storm runoff, that has been segregated from the main waste stream,
shall not show a visible sheen or exceed a TOC concentration of 15 mg/1 when discharged.
(3) This is an additional allocation, based on ballast water intake (daily average)
per 1000 liters (per 1000 gallons)
-------
Table 3 (continued)
BADT
Refinery
Subcategory
Topping
Low-Cracking
High-Cracking
Petrochemical
Lube
Integrated
Total Suspended Solids
Monthly Daily
Average Maximum
Oil & Grease
2.6(0.93)
4.2(1.5)
5.4(1.9)
5.9(2.1)
3.3(1.2)
5.2(1.8)
6.8(2.4)
7.4(2.6)
11.9(4.2) 14.7(5.2)
11.9(4.2) 14.7(5.2)
Monthly
Average
1.3(0.46)
2.1(0.74)
2.6(0.93)
2.8(1.0)
5.7(2.0)
5.9(2.1)
Daily
Maximum
1.6(0.58)
2.6(0.92)
3.3(1.2)
3.6(1.3)
7.1(2.5)
7.4(2.6)
Phenolic Compounds
Monthly Daily
Average- Maximum
0.02(0.0099)
0.045(0.016)
0.057(0.020)
0.059(0.021)
0.115(0.044)
0.130(0.046)
0.040(0.014)
0.062(0.022)
0.082(0.029)
0.085(0.030)
0.177(0.062)
0.183(0.065)
Runoff (2)
Ballast (3)
0.016(0.13)0.020(0.17)
0.016(0.13)0.020(0.17)
0.0080(0.066)
0.0080(0.066)
0.010(0.083)
0.010(0.083)
-------
Table 3 (continued)
BADT
Ammonia (N)
Sulfide
Total Chromium
Refinery
Subcategory
Topping
Low-Cracking
High-Cracking
Petrochemical
Lube
Integrated
Monthly
Average
0.85(0.30)
1.9(0.68)
4.7(1.7)
5.9(2.1)
5.7(2.0)
7.2(2.6)
Daily
Maximum
1.1(0.40)
2.5(0.90)
6.2(2.2)
7.9(2.8)
7.4(2.6)
9.6(3.4)
Monthly
Average
0.
0.
0.
0.
0.
0.
023(0.
037(0.
048(0.
051(0.
103(0.
107(0.
0081)
013)
017)
018)
026)
038X
Daily
Monthly
Maximum
0.
0.
0.
0.
0.
0.
037(0
057(0
074(0
079(0
162(0
168(0
.013)
.020)
.026)
.028)
.057)
.059)
0
0
0
0
0
0
Average
.065(0
.105(0
.13(0.
.14(0.
.29(0.
.30(0.
.023)
.037)
046)
050)
102)
106)
0.
0.
0.
0.
0.
0.
Daily
Maximum
085(0
13(0.
16(0.
175(0
36(0.
37(0.
.030)
046)
058)
.062)
128)
132)
Runoff(2)
Ballast(3) —
-------
Table 3 (continued)
BADT
Hexavalent Chromium
Zinc
Refinery
Subcategory
Topping
Low-Cracking
High-Cracking
Petrochemical
Lube
Integrated
Monthly
Average
0.
0.
0.
0.
0.
0.
0013(0
0020(0
0026(0
0028(0
0057(0
0059(0
.00046)
.00072)
.00092)
.00099)
.0020)
.0021)
0.
0.
0.
0.
0.
0.
Daily
Monthly
Maximum
0016(0
0025(0
0034(0
0035(0
0072(0
0074(0
.00058
.00090)
. 00120)
.00124)
.0025)
.0026)
0.
0.
0.
0.
0.
0.
Average
13(0
20(0
26(0
28(0
44(0
46(0
.046)
.072)
.092)
.099)
.15)
.16)
0.
0.
0.
0.
0.
0.
Daily
Maximum
16(0.
25(0.
34(0.
35(0.
57(0.
59(0.
050)
090)
120)
124)
20)
21)
Runoff (2)
Ballast (3)
-------
SECTION III
INTRODUCTION
Purpose and Authority
Section 301(b) of the Act requires the achievement by no later than July
1, 1977, of effluent limitations for point sources, other than publicly
owned treatment works, which are based on the application of the best
practicable control technology currently available as defined by the
Administrator, pursuant to section 304(b) of the Act. Section 301(b)
also requires the achievement by not later than July 1, 1983, of
effluent limitations for point sources, other than publicly owned
treatment works, which are based on the application of the best
available technology economically achievable, which will result in
reasonable further progress toward the national goal of eliminating
discharge of all pollutants, as determined in accordance with
requlations issued by the Administrator, pursuant to section 304(b) of
the Act. section 306 of the Act requires the achievement by new sources
of a Federal standard of performance providing for the control of the
discharge of pollutants which reflects the greatest degree of effluent
reduction which the Administrator determines to be achievable through
the application of the best available demonstrated technology,
processes, operative methods or other alternatives, including, where
racticable, a standard permitting no discharge of pollutants.
ction 304 (b) of the Act requires the Administrator to publish within
one year of enactment of the Act, regulations providing guidelines for
effluent limitations setting forth the degree of effluent reduction
attainable through the application of the best practicable control
technology currently available and the degree of effluent reduction
attainable through the application of the best control measures and
practices achievable including treatment techniques, process and
procedure innovations, operation methods and other alternatives. The
regulations proposed herein set forth effluent limitations guidelines
pursuant to section 304 (b) of the Act for the petroleum refining
industry source category.
Section 306 of the Act requires the Administrator, within one year after
a category of sources is included in a list published pursuant to
section 306 (b) (1) (A) of the Act, to propose regulations establishing
Federal standards of performance for new sources within such categories.
The Administrator published in the Federal Register of January 16, 1973
(38 F.R. 1624), a list of 27 source categories. Publication of the list
constituted announcement of the Administrator's intention of
establishing, under section 306, standards of performance applicable to
new sources within the petroleum refining industry source category which
was included in the list published January 16, 1973.
17
-------
Methods used for Development of the Effluent Limitations Guidelines
Standards of Performance
The Office of Air and Water Programs of the Environmental Protection
Agency has been given the responsibility for the development of effluent
limitation guidelines and new source standards as required by the Act.
In order to promulgate the required guidelines and standards, the
following procedure was adopted.
The point source category was first categorized for the purpose of
determining whether separate limitations and standards are appropriate
for different segments within a point source category. Such sub-
categorization was based upon raw materials used, products produced,
manufacturing processes employed, raw waste loads, and other factors.
This included an analysis of (1) the source and volume of water used in
the plant and the sources of waste and waste waters in the plant; and
(2) the constituents (including thermal) of all waste waters (including
toxic constituents and other constituents) which result in taste, odor,
and color in water or aquatic organisms. The constituents of waste
waters which should be subject to effluent limitations guidelines and
standards of performance were identified.
The full range of control and treatment technologies existing within
each subcategory was identified. This included an identification of
each distinct control and treatment technology, including both inplant
and end-of-pipe technologies, which are existent or capable of bein,
designed for each subcategory. It also included an identification,
terms of the amount of constituents (including ' thermal) and
chemical, physical, and biological characteristics of pollutants, of the
effluent level resulting from the application of each of the treatment
and control technologies. The problems, limitations, and reliability of
each treatment and control technology, and the required implementation
time was also identified. In addition, the nonwater quality
environmental impact (such as the effects of the applisubcation of such
technologies upon other pollution problems, including air, solid waste,
noise, and radiation) was also identified. The energy requirement of
each of the control and treatment technologies was identified, as well
as the cost of the application of such technologies.
The information, as outlined above, was then evaluated in order to
determine methods or other alternatives. In identifying such
technologies, various factors were considered. These included the total
cost of application of technology in relation to the effluent reduction
benefits to be achieved from such application, the age of equipment and
facilities involved, the processes employed, the engineering aspects of
the application of various types of control techniques, process changes,
nonwater quality environmental impact (including energy requirements)
and other factors.
18
-------
ring the initial phases of the study, an assessment was made of the
lilability, adequacy, and usefulness of all existing data sources.
on the identity and performance of waste water treatment systems
within the petroleum refining industry were known to be included in:
1. National Petroleum Refining Waste Water
Characterization Studies and the
Petroleum Industry Raw Waste Load Survey of 1972.
2. Environmental Protection Agency (Refuse Act) Permit
Application.
3. Self-reporting discharge data from various states.
4. Monitoring data on individual refineries, collected
by state agencies and/or regional EPA offices.
A preliminary analysis of these data indicated an obvious need for
additional information. Although approximately 135 refineries were
surveyed during the 1972 Raw Waste Load Survey, five activated sludge
treatment plants were subjected to intensive sampling for identification
of waste water treatment plant effluent performance. Identification of
the types of treatment facilities used by the other individual
refineries included no performance data.
jfuse Act Permit Application data are limited to identification of the
katment systems used and reporting of final concentrations (which were
Luted with cooling waters in many cases); consequently, operating
performance could not be established.
Self-reporting data was available from Texas, Illinois, and Washington.
These reports show only the final effluent concentrations and identify
the systems in use; rarely is there production information available
which would permit the establishment of unit waste loads.
Monitoring data from the individual states and/or regional EPA offices
again show only the final effluent concentrations and identify the
systems in use. Rarely is production information available to permit
the establishment of unit waste loads.
Additional data in the following areas were therefore required: 1)
currently practiced or potential in-process waste control techniques; 2)
identity and effectiveness of end-of-pipe waste control techniques; and
3) long-term data to establish the variability of performance of the
end-of-pipe waste control techniques. The best source of information
was the petroleum refineries themselves. New information was obtained
from direct interviews and inspection visits to petroleum refinery
facilities. Verification of data relative to long-term performance of
waste control techniques was obtained by the use of standard EPA
reference samples to determine the reliability of data submitted by the
19
-------
petroleum refineries, and by comparison of the refinery data v
monitoring data from the state agencies and/or regional EPA offices.
The selection of petroleum refineries as candidates to be visited was
guided by the trial categorization, which was based on the 1972 Raw
Waste Load survey. The final selection was developed from identifying
information available in the 1972 Raw Waste Load Survey, EPA Permit
Applications, state self-reporting discharge data, and contacts within
regional EPA offices and the industry. Every effort was made to choose
facilities where meaningful information on both treatment facilities and
manufacturing processes could be obtained.
Survey teams composed of project engineers conducted plant visits.
Information on the identity and performance of waste water treatment
systems were obtained through:
1. Interviews with plant water pollution control personnel.
2. Examinations of treatment plant design and historical
data (flow rates and analyses of influent and effluent).
3. Inspection of operations and analytical procedures, in-
cluding verification of reported analyses by the use of
EPA standard reference samples and by comparison of the
refinery data with monitoring data from state
agencies and/or regional EPA offices.
Information on process plant operations and associated waste wat
characteristics were obtained through:
1. Interviews with plant operating personnel.
2. Examination of plant design and operating data.
3. Inspection of in~plant waste water controls.
The data base obtained in this manner was then utilized to develop
recommended effluent limitations and standards of performance for the
petroleum refining industry. All of the references utilized are
included in Section XIII of this report. The data obtained during the
field data collection program are included in Supplement B.
General Description of the Industry
The industrial waste water profile covers the petroleum refining
industry in the United States, as defined by Standard Industrial
Classification (SIC) Code 2911 of the U.S. Department of Commerce.
Intermediates and finished products in this industry are numerous and
varied. Table 4 is a partial listing of these products. The production
of crude oil or natural gas from wells, or the production of natural
20
-------
TABLE 4
Intermediates and Finished Products
Frequently Found in the Petroleum Refining Industry
SIC 2911
Acid Oil
Alkylates
Aromatic Chemicals
Asphalt and Asphaltic Materials:
Semi-Solid and Solid
Benzene
Benzol
Butadiene
Coke (Petroleum)
Fuel Oils
Gas, Refinery or Still Oil
Gases, (LPG)
Gasoline, except natural gasoline
Greases: Petroleum, mineral jelly,
lubricative, etc.
Jet Fuels
Kerosene
Mineral Oils, natural
Mineral Waxes, natural
Naphtha
Napthenic Acids
Oils, partly refined
Paraffin Wax
Petrolatums, nonmedicinal
Road Oils
Solvents
Tar or Residuum
21
-------
gasoline and other operations associated with such production,
covered under SIC Code 1311, are not within the scope of this stud
This study also does not include distribution activities, such a
gasoline service stations. Transportation of petroleum products is
covered only to the extent that it is part of refinery pollution
control, such as the treatment of ballast water. Other activities
outside the scope of the SIC Code 2911 were included in the development
of raw waste load data, and are listed as auxiliary processes which are
inherent to an integrated refinery operation. Some of these include
soap manufacture for the production of greases, steam generation, and
hydrogen production.
A petroleum refinery is a complex combination of interdependent
operations engaged in the separation of crude molecular constituents,
molecular cracking, molecular rebuilding and solvent finishing to
produce the products listed under SIC Code 2911. The refining
operations may be divided among 12 general categories, where each
category defines a group of refinery operations. The categories are
listed in Table 5.
The characteristics of the waste water differ considerably for different
processes, considerable knowledge is available that can be used to make
meaningful qualitative interpretations of pollutant loadings from
refinery processes. Such information is presented in Table 6, a semi-
graphic outline of the major sources of pollutants within a refinery
In order to set forth the character of the waste derived from each
the industry categories established in Section IV, it is essential
study the sources and contaminants within the individual producti
processes and auxiliary activities. Each process is itself a series of
unit operations which causes chemical and/or physical changes in the
feedstock or products. In the commercial synthesis of a single product
from a single feedstock, there generally are sections of the process
associated with: the preparation of the feedstock, the chemical
reaction, the separation of reaction products, and the final
purification of the desired product. Each unit operation may have
drastically different water usages associated with it. The type and
quantity of contact waste water are therefore directly related to the
nature of the various processes. This in turn implies that the types
and quantities of waste water generated by each plant's total production
mix are junique. The processes and activities along with brief process
descriptions, trends in applications, and a delineation of waste water
sources, are as follows:
y
•
22
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TABLE 5
Major Refinery Process Categories
1. Storage and Transportation
2. Crude Desalting
3. Fractionation
4. Cracking
5. Hydrocarbon Rebuilding
6. Hydrocarbon Rearrangement
7. Solvent Refining or Extraction
8. Hydrotreating
9. Grease Manufacturing
10. Asphalt Production
11. Product Finishing
12. Auxiliary Activities (Not listed under SIC Code 2911)
23
-------
TABLE 6
Qualitative Evaluation of Wastewater Flow and Characteristics
Production
Pi ocesses
Crude Oil and
Product Storage
Crude Desalting
Crude Distill-
ation
Thermal Cracking
Catalytic Cracking
Hydrocracklng
Polymerization
Alkylatlon
Isomerlzatlon
Reforming
Solvent Refining
Asphalt Blowing
Dewaxlng
Hydrotreatlng
Drying and
Sweete Ing
Flow SOD COD
XX • X XXX
XX XX XX
XXX X X
XXX
XXX XX XX
X
X XX
XX X .X
X
X 00
X X
xxx xxx xxx
X XXX XXX
xxx
XXX XXX X
by Fundamental Refinery Processes
Emulsified Am-
Phenol Sulflde Oil Oil pH Temp. monla Chloride Acidity Alkalinity SUSP. Solids
X XXX XX 0 0 0 0 XX
x xxx x xxx : x xxx xx xxx o x axx
XX XXX .XX XXX X XX XXX X 0 X X
XXX XX XX X X 0 XX X
XXX XXX X X XXX XX XXX X 0 XXX X
XX XX XX XX
OXXOXXXX X 0 X
0 XX X 0 XX I X XX XX 0 XX
XX X OOXXO 0 0 0
X 0 X X 0 0 X
X XXX
X 0 X 0
XX 0 XX XX 0 0 X 0
XX 00 X XX 0 XO X X XX
XXX - Major Contribution, XX - Moderata Contribution. X - Minor Contribution. 0 - No Problem ,
— No Data
-------
^~ STORAGE AND TRANSPORTATION
TK CRUDE OIL AND PRODUCT STORAGE
Process Description
Crude oil, intermediate, and finished products are stored in tanks of
varying size to provide adequate supplies of crude oils for primary
fractionation runs of economical duration, to equalize process flows and
provide feedstocks for intermediate processing units, and to store final
products prior to shipment in adjustment to market demands. Generally,
operating schedules permit sufficient detention time for settling of
water and suspended solids.
Wastes
Waste waters associated with storage of crude oil and products are
mainly in the form of free and emulsified oil and suspended solids.
During storage, water and suspended solids in the crude oil separate.
The water layer accumulates below the oil, forming a bottom sludge.
When the water layer is drawn off, emulsified oil present at the oil-
water interface is often lost to the sewers. This waste is high in COD
and contains a lesser amount of BODS. Bottom sludge is removed at
infrequent intervals. Additional quantities of waste result from leaks,
spil-ls, salt "filters" (for product drying) , and tank cleaning.
ermediate storage is frequently the source of polysulfide bearing
te waters and iron sulfide suspended solids. Finished product
storage can produce high BOD5, alkaline waste waters, as weli as
tetraethyl lead. Tank cleaning can contribute large amounts of oil,
COD, and suspended solids, and a minor amount of BODS. Leaks, spills
and open or poorly ventilated tanks can also be a source of air
pollution, through evaporation of hydrocarbons into the atmosphere.
Trends
Many refineries now have storage tanks equipped to minimize the release
of hydrocarbons to the atmosphere. This trend is expected to continue
and probably accelerate. Equipment to minimize the release of
hydrocarbon vapors includes tanks with floating-roof covers, pressurized
tanks, and/or connections to vapor recovery systems. Floating-roof
covers add to the waste water flow from storage tanks. Modern
refineries impose strict Bottom Sediment and Water (BS&W) specifications
on crude oil supplies, and frequently have mixed-crude storage tanks;
consequently, little or no waste water should originate from modern
crude storage. Another significant trend is toward increased use of
dehydration or drying processes preceding product finishing. These
processes significantly reduce the water content of finished product,
thereby minimizing the quantity of waste water from finished product
storage.
25
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B. BALLAST WATER
Process Description
Tankers which are used to ship intermediate and final products generally
arrive at the refinery in ballast (approximately 30 percent of the cargo
capacity is generally required to maintain vessel stability).
Wastes
The ballast waters discharged by product tankers are contaminated with
product materials which are the crude feedstock in use at the refinery,
ranging from water soluble alcohol to residual fuels. In addition to
the oil products contamination, brackish water and sediments are
present, contributing high COD, and dissolved solids to the refinery
waste water. These waste waters are generally discharged to either a
ballast water tank or holding ponds at the refinery. In many cases, the
ballast water is discharged directly to the waste water treatment
system, and constitutes a shock load on the system.
Trends
As the size of tankers and refineries increases, the amount of ballast
waters discharged to the refinery waste water system will also increase.
The discharge of ballast water to the sea or estuary without treatment,
as had been the previous practice by many tankers, is no longer^a
practical alternative for disposal of ballast water. Consequently,
ballast water will require treatment for the removal of pollutants
to discharge. The use of larger ballast water storage tanks or ponds,
for control of flow into the waste water treatment system, should
increase as ballast water flow increases.
2. CRUDE DESALTING
Process Description
Common to all types of desalting are an emulsifier and settling tank.
Salts can be separated from oil by either of two methods. In the first
method, water wash desalting in the presence of chemicals (specific to
the type of salts present and the nature of the crude oil) is followed
by heating and gravity separation. In the second method, water wash
desalting is followed by water/oil separation under the influence of a
high voltage electrostatic field acting to agglomerate dispersed
droplets. In either case, waste water containing various removed
impurities is discharged to the waste stream, while clean desalted crude
oil flows from the upper portion of the holding tank. A process flow
schematic of electrostatic desalting is shown in Figure 1.
Wastes
26
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PROCESS
WATER
ELECTRICAL
POWER
HEATER EMULSIFIER
Figure \
Crude Desalting
(Electrostatic Desalting)
DESALTED
CRUDE
EFFLUENT
WATER
27
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\
Much of' the BSSW content in crude oil is caused by the "Load-on-r
procedure used on many tankers. This procedure can result in one
more cargo tanks containing mixtures of sea waters and crude oil, whicl
cannot be separated by decantation while at sea, and are consequently
retained in the crude oil storage at the refinery. While much of the
water and sediment are removed from the crude oil by settling during
storage, a significant quantity remains to be removed by desalting prior
to processing of the crude in the refinery.
The continuous waste water stream from a desalter contains emulsified,
and occasionally free oil, ammonia, phenol, sulfides, and suspended
solids. These pollutants produce a relatively high BOD5 and COD. This
waste water also contains enough chlorides and other dissolved materials
to contribute to the dissolved solids problem in the areas where the
waste water is discharged to fresh water bodies. There are also
potential thermal pollution problems because the temperature of the
desalting waste water often exceeds 95°C (200°F).
Trends
Electrical desalting is currently used much more than chemical
desalting. In the future, chemical methods are expected to be used only
as a supplement where the crude has a very high salt content. Two stage
electrical desalting will become a more prevelant process, as dirtier
crude feedstocks are processed in refineries. The growth in capacity of
desalting units will parallel the growth of crude oil capacity.
3. CRUDE OIL FRACTIONATION
Fractionation serves as the basic refining process for the separation of
crude petroleum into intermediate fractions of specified boiling point
ranges. The several alternative subprocesses included are
prefractionation and atmospheric fractionation, vacuum fractionation,
vacuum flashing, and three-stage crude distillation.
Process Description
Prefractionation and Atmospheric Distillation (Topping or Skimming)
Prefractionation is an optional distillation process to separate
economical quantities of very light distillates from the crude oil.
Lower temperature and higher pressure conditions are used than would be
required in atmospheric distillation. Some process water can be carried
over to the prefractionation tower from the desalting process.
Atmospheric Distillation breaks the heated crude oil as follows:
1. Light overhead products (C5 and lighter) as in the case of
prefractionation.
28
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2. Sidestream distillate cuts of kerosene, heating and gas oil can
be separated in a single tower or in a series of topping
towers, each tower yielding a successively heavier product
stream.
3. Residual or reduced crude oil.
Vacuum Fractionation
The asphaltic residuum from the atmospheric distillation amounts to 37
percent (U.S. average) of the crude charged. This material is sent to
vacuum stills, which recover additional heavy gas oil and deasphalting
feedstock from the bottoms residue.
Three Stage Crude Distillation
Three stage crude distillation, representing only one of many possible
combinations of equipment, is shown schematically in Figure 2. The
process consists of:
1. An atmospheric fractioning stage which produces lighter oils;
2. An initial vacuum stage which produces well-fractioned, lube
oil base stocks plus residue for subsequent propane de-
asphalting;
3. A second vacuum stage which fractionates surplus atmospheric
bottoms not applicable for lube production, plus surplus
initial vacuum stage residuum not required for deasphalting.
This stage adds the capability of removing catalytic cracking
stock from surplus bottoms to the distillation unit.
Crude oil is first heated in a simple heat exchanger, then in a direct-
fired crude charge heater. Combined liquid and vapor effluent flow from
the heater to the atmospheric fractionating tower, where the vaporized
distillate is fractionated into gasoline overhead product and as many as
four liquid sidestreams products:naphtha, kerosene, light and heavy
diesel oil. Part of the reduced crude from the bottom of the
atmospheric tower is pumped through a direct-*fired heater to the vacuum
lube fractionator. Bottoms are combined and charged to a third direct-
fired heater. In the tower, the distillate is subsequently condensed
and withdrawn as two sidestreams. The two sidestreams are combined to
form catalytic cracking feedstocks, with an asphalt base stock withdrawn
from the tower bottom.
Wastes
The waste water from crude oil fractionation generally comes from three
sources. The first source is the water drawn off from overhead
accumulators prior to recirculation or transfer of hydrocarbons to other
29
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Atmospheric
Fr;ict Senator
Fract ionator
To Vacuum
System
To Vacuum
System
Stabilized
Gasoline
-£TT
Catalytic
Cracker
Feed
Propane Deasphalter Feed
Crude
Petroleum
Figure 2
CRUDE FRACTIONATION
(CRUDE DISTILLATION. THREE STAGES)
-------
f
actionators. This waste is a major source of sulfides and ammonia,
pecially when sour crudes are being processed. It also contains
ignificant amounts of oil, chlorides, mercaptans and phenols.
A second waste source is discharged from oil sampling lines. This
should be separable but may form emulsions in the sewer.
A third possible waste source is the very stable oil emulsions formed in
the barometric condensers used to create the reduced pressures in the
vacuum distillation units. However, when barometric condensers are
replaced with surface condensers, oil vapors do not come in contact with
water; consequently, emulsions do not develop.
Trends
The general industry trend to larger and more complete refineries has
been reflected also in larger and more complete crude fractionation
units. Thus, simple atmospheric "topping" units are being replaced by
the atmospheric- vacuum combinations with an increasing number of
sidestream products. Installed vacuum fractionation capacity now
totals, 0.8 million cu m/day (5 million bbl/day). (3) Modern refineries
are installing surface condensers to significantly reduce waste water
loads from vacuum operations.
4. CRACKING
THERMAL CRACKING
Process Description
This fundamental process is defined in this study to include visbreaking
and coking, as well as regular thermal cracking. In each of these
operations, heavy gas oil fractions (from vacuum stills) are broken down
into lower molecular weight fractions such as domestic heating oils,
catalytic cracking stock, and other fractions by heating, but without
the use of a catalyst. Typical thermal cracking conditions are 480° -
603°C, (900° - 1100°F) and 41.6 - 69.1 atm (600-1000 psig). The high
pressures result from the formation of light hydrocarbons in the
cracking reaction (olefins, or unsaturated compounds, are always formed
in this chemical conversion) . There is also always a certain amount of
heavy fuel oil and coke formed by polymerization and condensation
reactions.
Wastes
The major source of waste water in thermal cracking is the overhead
accumulator on the fractionator, where water is separated from the
hydrocarbon vapor and sent to the sewer system. This water usually
contains various oil and fractions and may be high in BODS, COD,
ammonia, phenol, and sulfides, and may have a high alkalinity.
31
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Trends
Regular thermal cracking, which was an important process before tne
development of catalytic cracking, is being phased out. Visbreaking and
coking units are still installed but, because of product sulfur
restrictions, to a lesser extent than before. With the trends toward
dirtier crudes containing more sulfur, hydrocracking and propane
deasphalting are receiving more attention to recover salable products
with low sulfur content from the residuum.
B. CATALYTIC CRACKING
Process Description
Catalytic cracking, like thermal cracking, breaks heavy fractions,
principally gas oils, into lower molecular weight fractions. This is
probably the key process in the production of large volumes of high-
octane gasoline stocks; furnace oils and other useful middle molecular
weight distillates are also produced. The use of a catalyst permits
operations at lower temperatures and pressures than with thermal
cracking, and inhibits the formation of undesirable polymerized
products. Fluidized catalytic processes, in which the finely powdered
catalyst is handled as a fluid, have largely replaced the fixed bed and
moving bed processes, which use a beaded or pelleted catalyst. A
schematic flow diagram of fluid catalytic cracking is shown in Figure 3.
The process involves at least four types of reactions: 1)
decomposition; 2) primary catalytic reactions at the catalyst
3) secondary catalytic reactions between the primary products, and 4)
removal of polymer izable products from further reactions by absorption
onto the surface of the catalyst as coke. This last reaction is the key
to catalytic cracking because it permits decomposition reactions to move
closer to completion than is possible in simple thermal cracking.
Cracking catalysts include synthetic and/or natural silica-alumina,
treated bentonite clay, Fuller's earth, aluminum hydrosilicates and
bauxite. These catalysts are in the form of beads, pellets, and powder,
and are used in either a fixed, moving or fluidized bed. The catalyst
is usually heated, lifted into the reactor area by the incoming oil feed
which, in turn, is immediately vaporized upon contact. Vapors from the
reactors pass upward through a cyclone separator, which removes most of
the entrained catalyst. These vapors then enter the fractionator, where
the desired products are removed and heavier fractions recycled to the
reactor.
Wastes
Catalytic cracking units are one of the largest sources of sour and
phenolic wastewaters in a refinery. Pollutants from catalytic cracking
generally come from the steam strippers and overhead accumulators on
32
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GAS AND GASOLINE TO
PRESSURE
REDUCING
ORIFICE
CHAMBER
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SLURRY CHARGE
Figure 3
CATALYTIC CRACKING
(FLUID CATALYTIC CRACKING)
33
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fractionators, used to recover and separate the various hydrocarb
fractions produced in the catalytic reactors.
The major pollutants resulting from catalytic cracking operations are
oil, sulfides, phenols, cyanides, and ammonia. These pollutants produce
an alkaline waste water with high BOD5 and COD concentrations. Sulfide
and phenol concentrations in the waste water vary with the type of crude
oil being processed,\but at times are significant. Regeneration of
spent catalyst may produqe enough carbon monoxide and catalyst fines to
constitute an air pollution problem.
Trends
Recycle rates have been declining since 1968, and the trend is expected
to continue due to the development of higher activity catalysts
(molecular sieve catalysts, as opposed to high surface area silica-
alumina catalysts). The trend in subprocesses is toward greater use of
large fluid catalytic cracking in preference to moving or fixed-bed
cracking. Catalytic cracking units are also being supplanted by
hydrocracking and hydrotreating processes. During 1972, a decline of
1.4 percent in fresh feed catalytic cracking capacity was experienced in
the United states. (3)
C. HYDROCRACKING
Process Description
This process is basically catalytic cracking in the presence
hydrogen, with lower temperatures and higher pressures than fluid
catalytic cracking. Hydrocracking temperatures range from 203° - 425°C
(400° - 800°F), while pressures range from 7.8 - 137.0 atm (100 to 2000
psig). Actual conditions and hydrogen consumption depend upon the
feedstock, and the degree of hydrogenation required. The molecular
weight distribution of the products is similar to catalytic cracking,
but with the reduced formation of olefins.
Wastes
At least one waste water stream from the process should be high in
sulfides, since hydrocracking reduces the sulfur content of the material
being cracked. Most of the sulfides are in the gas products which are
sent to a treating unit for removal and/or recovery of sulfur and
ammonia. However, in product separation and fractionation units
following the hydrocracking reactor, some of the HS will dissolve in the
waste water being collected. This water from the separator and
fractionator will probably be high in sulfides, and possibly contain
significant quantities of phenols and ammonia.
Trends
34
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flrocracking has greater flexibility than catalytic cracking in
justing operations to meet changing product demands. For the last few
"ars, it has been one of the most rapidly growing refining processes.
This trend is expected to continue.
5. HYDROCARBON REBUILDING
A. POLYMERIZATION
Process Description
Polymerization units are used to convert olefin feedstocks (primarily
propylene) into higher octane polymer units. These units generally
consist of a feed treatment unit (remove H2S, mercaptans, nitrogen
compounds), a catalytic reactor, an acid removal section, and a gas
stabilizer. The catalyst is usually phosphoric acid, although sulfuric
acid is used in some older methods. The catalytic reaction occurs at
147° . 224°C (300° - 435°F), and a pressure of 11.2 - 137.0 atm (150 -
2000 psig). The temperature and pressure vary with the individual
subprocess used.
Wastes
Polymerization is a rather dirty process in terms of pounds of
pollutants per barrel of charge, but because of the small polymerization
capacity in most refineries, the total waste production from the process
small. Even though the process makes use of acid catalysts, the
e stream is alkaline, because the acid catalyst in most subprocesses
is recycled, and any remaining acid is removed by caustic washing. Most
of the waste material comes from the pretreatment of feedstock to the
reactor. The waste water is high in sulfides, mercaptans, and ammonia.
These materials are removed from the feedstock in caustic acid.
Trends
Polymerization is a marginal process, since the product octane is not
significantly higher than that of the basic gasoline blending stocks,
and does not provide much help in upgrading the overall motor fuel pool.
±n addition, alkylation yields per unit of olefin feed are much better
than polymerization yields. Consequently, the current polymerization
downtrend is expected to continue.
B. ALKYLATION
Process Description
Alkylation is the reaction of an isoparaffin (usually isobutane) and an
olefin (propylene, butylene, amylenes) in the presence of a catalyst at
carefully controlled temperatures and pressures to produce a high octane
alkylate for use as a gasoline blending component. Propane and butane
35
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are also produced. Sulfuric acid is the most widely used catalysl
although hydrofluoric acid is also used. The reactor products a(
separated in a catalyst recovery unit, from which the catalyst S
recycled. The hydrocarbon stream is passed through a caustic and water
wash before going to the fractionation section.
Wastes
The major discharge from sulfuric acid alkylation are the spent caustics
from the neutralization of hydrocarbon streams leaving the sulfuric acid
alkylation reactor. These waste waters contain dissolved and suspended
solids, sulfides, oils, and other contaminants. Water drawn off from
the overhead accumulators contains varying amounts of oil, sulfides, and
other contaminants, but is not a major source of waste in this
subprocess. Most refineries process the waste sulfuric acid stream from
the reactor to recover clean acids, use it as if for neutralization of
other waste streams, or sell it.
Hydrofluoric acid alkylation units have small acid rerun units to purify
the acid for reuse. HF units do not have a spent acid or spent caustic
waste stream. Any leaks or spills that involve loss of fluorides
constitute a serious and difficult pollution problem. Formation of
fluosilicates has caused line plugging and similar problems. The major
sources of waste material are the overhead accumulators on the
fractionator.
Trends
Alkylation process capacity is currently declining slowly, but this
trend may be reversed, as the demand for low lead, high octane gasoline
increases.
6. HYDROCARBON REARRANGEMENTS
A. ISOMERIZATION
Process Description
Isomerization is a process technique for obtaining higher octane motor
fuel by converting light gasoline stocks into their higher octane
isomers. The greatest application has been, indirectly, in the
conversion of isobutane from normal butane, for uses as feedstock for
the alkylation process. In a typical subprocess, the desulfurized
feedstock is first fractionated to separate isoparaffins from normal
paraffins. The normal paraffins are then heated, compressed, and passed
through the catalytic hydrogenation reactor which isomerizes the n-
paraffin to its respective high octane isomer. After separation of
hydrogen, the liquids are sent to a stabilizer, where motor fuel
blending stock-or synthetic isomers are rejnoved as products.
36
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«stes
omer:
somerization waste waters present no major pollutant discharge
problems. Sulfides and ammonia are not likely to be present in the
effluent. isomerization waste waters should also be low in phenolics
and oxygen demand.
Trends
The requirements for units to isomerize n-butane to isobutane will not
be as great in refineries where hydrocracking is being installed, as the
hydrocracking process yields an off -gas rich in isobutane. However, the
isomerization capacity of U.S. refiners is not expected to decrease, but
to continue to grow as the demand for motor fuel grows.
B. REFORMING
Process Description
Reforming converts low octane naphtha, heavy gasoline, and napthene-rich
stocks, to high octane gasoline blending stock, aroma tics for petro-
chemical use, and isobutane. Hydrogen is a significant by-product of
the process. Reforming is a mild decomposing process, since some
reduction occurs in molecular size and boiling range of the feedstock.
Feedstocks are usually hydrotreated for the removal of sulfur and
trogen compounds prior to charging to the reformer, since the platinum
widely used are readily poisoned.
The predominant reaction during reforming is the dehydrogenation of
naphthenes. Important secondary reactions are the isomerization and
dehydrocyclization of paraffins. All three reactions result in higher
octane products.
One subprocess may be divided into three parts: the reactor heater
section, in which the charge plus recycle gas is heated and passed over
the catalyst in a series of reactions; the separator drum, in which the
reactor effluent is separated into gas and liquid streams, the gas being
compressed for recycle; and the stabilizer section, in which the
separated liquid is stabilized to the desired vapor pressure. There are
many variations in subprocesses, but the essential, and frequently the
only, difference is the composition of the catalyst involved,
Wastes
Reforming is a relatively clean process. The volume of waste water flow
is small, and none of the waste water streams has high concentration of
significant pollutants. The waste water is alkaline, and the major
pollutant is sulfide from the overhead accumulator on the stripping
tower used to remove light hydrocarbon fractions from the reactor
effluent. The overhead accumulator catches any water that may be
37
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contained in the hydrocarbon vapors. In addition to sulfides, the
water contains small amounts of ammonia, mercaptans and oil.
Trends
Reforming capacity in the U.S. is currently growing at about the same
rate as total crude capacity. This growth rate may increase, however,
as the demand for motor fuel grows.
7. SOLVENT REFINING
Refineries employ a wide spectrum of contact solvent processes, which
are dependent upon the differential solubilities of the desirable and
undesirable feedstock components. The principal steps are: counter-
current extraction, separation of solvent and product by heating and
fractionation, and solvent recovery. Napthenics, aromatics unsaturated
hydrocarbons, sulfur and other inorganics are separated, with the
solvent extract yielding high purity products. Many of the solvent
processes may produce process waste waters which contain small amounts
of the solvents employed. However, these are ususally minimized,
because of the economic incentives for reuse of the solvents.
Process Description
The major processes include:
Solvent Deasphalting - The primary purpose of solvent deasphalting is
recover lube or catalytic cracking feedstocks from asphaltic residua
with asphalt as a by-product. Propane deasphalting is the predominant
technique. The vacuum fractionation residual is mixed in a fixed pro-
portion with a solvent in which asphalt is not soluble. The solvent is
recovered from the oil via steam stripping and fractionation, and is
reused. The asphalt produced by this method is normally blended into
fuel oil or other asphaltic residuals.
Solvent Dewaxing - Solvent dewaxing removes wax from lubricating oil
stocks by promoting crystallization of the wax. Solvents which are used
include: furfural, phenol, cresylic acid - propane (Duo-Sol), liquid
sulfur dioxide (Eleleanu process), B-B - dichloroethyl ether, methyl
ethyl ketone, nitrobenzene, and sulfur-benzene. The process yields de-
oiled waxes, wax-free lubricating oils, aromatics, and recovered
solvents.
Lube Oil Solvent Refining - This process includes a collection of
subprocesses for improving the quality of lubricating oil stock. The
raffinate or refined lube oils obtain improved temperature, viscosity,
color and oxidation resistance characteristics. A particular solvent is
selected to obtain the desired quality raffinate. The solvents include:
furfural, phenol, sulfur dioxide, and propane.
38
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€omatic Extraction - Benzene, toluene, and xylene (BTX) are formed as
-products in the reforming process. The reformed products are
actionated to give a BTX concentrate cut, which in turn is extracted
from the napthalene and the paraffinics with a glycol base solvent.
Butadiene Extraction - Approximately 15 percent of the U.S. supply of
butadiene is extracted from the C4 cuts from the high temperature
petroleum cracking processes. Furfural or cuprous ammonia acetate (CAA)
are commonly used for the solvent extraction.
Wastes
The major potential pollutants from the various solvent refining
subprocesses are the solvents themselves. Many of the solvents, such as
phenol, glycol, and amines, can produce a high BOD5. Under ideal
conditions the solvents are continually recirculated with no losses to
the sewer. Unfortunately, some solvent is always lost through pump
seals, flange leaks, and other sources. The main source of waste water
is from the bottom of fractionation towers. Oil and solvent are the
major waste water constituents.
Trends
Solvent extraction capacities can be expected to slowly increase as
quality requirements for all refinery products become more stringent, as
the demand for lube oils grows, and as the petrochemicals industry
ntinues to require increasing quantities of aromatics.
8. HYDROTREATING
Process Description
Hydrotreating processes are used to saturate olefins, and to remove
sulfur and nitrogen compounds, odor, color and gum-forming materials,
and others by catalytic action in the presence of hydrogen, from either
straight-run or cracked petroleum fractions. In most subprocesses, the
feedstock is mixed with hydrogen, heated, and charged to the catalytic
reactor. The reactor products are cooled, and the hydrogen, impurities
and high grade product separated. The principal difference between the
many subprocesses is the catalyst; the process flow is similar for
essentially all subprocesses.
Hydrotreating processes are used to reduce the sulfur content of product
streams from sour crudes by approximately 90 percent or more. Nitrogen
removal requires more severe operating conditions, but generally 80-90
percent, or better, reductions are accomplished.
The primary variables influencing hydrotreating are hydrogen partial
pressure, process temperature, and/contact time. An increase in
hydrogen pressure gives a better removal of undesirable materials and a
39
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better rate of hydrogenation. Make-up hydrogen requirements
generally high enough to require a hydrogen production unit. Exce^si
temperatures increase the formation of coke, and the contact time
to give adequate treatment without excessive hydrogen usage and/or undue
coke formation. For the various hydrotreating processes the pressures
range from 7.8 - 205.1 atm (100 to 3000 psig). Temperatures range from
less than 177°C (350°F) to as high as 450°C (850°F), with most
processing done in the range of 314°C (600°F) to U27°C (800°F).
Hydrogen consumption is usually less than 5.67 NM3 (200 scf) per barrel
of charge.
Principal hydrotreating subprocesses are used as follows:
1. Pretreatment of catalytic reformer feedstock.
2. Naphtha desulfurization.
3. Lube oil polishing.
4. Pretreatment of catalytic cracking feedstock.
5. Heavy gas-oil and residual desulfurization.
6. Naphtha saturation.
Wastes
The strength and quantity of waste waters generated by hydrotreating
depends upon the subprocess used and feedstock. Ammonia and sulfides
are the primary contaminants, but phenols may also be present, if the
feedstock boiling range is sufficiently high.
Trends
The use of hydrotreating is increasing and should continue to increase
at a greater rate than crude capacity since the process can be applied
to almost any sour feedstock, is flexible, and eliminates contaminants
of concern to the refining industry from an operating standpoint, and to
the general public from an aesthetic standpoint.
9. GREASE MANUFACTURING
Process Description
Grease manufacturing processes require accurate weight or volumetric
measurements of feed components, intimate mixing, rapid heating and
cooling, together with milling, dehydration and polishing in batch
reactions. The feed components include soap and petroleum oils, with
inorganic clays and other additives.
Grease is primarily a soap and lube oil mixture. The properties of
grease are determined in large part by the properties of the soap
component. For example, sodium metal base soaps are water soluble and
would then not be suitable for water contact service. A calcium soap
40
-------
ase can be used in water service. The soap may be purchased as a raw
erial or may be manufactured on site as an auxiliary process.
Wastes
Only very small volumes of waste water are discharged from a grease
manufacturing process. A small amount of oil is lost to the waste water
system through leaks in pumps. The largest waste loading occurs when
the batch units are washed, resulting in soap and oil discharges to the
sewer system.
Trends
Because of an increase in sealed grease fittings in automobiles and
longer lasting greases, a slight decline in grease production is
expected through 1975.
10. ASPHALT PRODUCTION
Process Description
Asphaltic feedstock (flux) is contacted with hot air at 203°C (400°F) to
280°C (550°F) to obtain desirable asphalt product. Both batch and
continuous processes are in operation at present, but the batch process
is more prevalent because of its versatility. Nonrecoverable catalytic
impounds include: Copper sulfate, zinc chloride, ferric chloride,
num chloride, phosphorous pentoxide, and others. The catalyst will
normally contaminate the process water effluent.
Wastes
Waste waters from asphalt blowing contain high concentrations of oils,
and have high oxygen demand. Small quantities of phenols may also be
present.
11. PRODUCT FINISHING
A. DRYING AND SWEETENING
Process Description
Drying and sweetening is a relatively broad process category primarily
used to remove sulfur compounds, water and other impurities from
gasoline, kerosene, jet fuels, domestic heating oils, and other middle
distillate products. "Sweetening" pertains to the removal of hydrogen
sulfide, mercaptans and thiophenes, which impart a foul odor and
decrease the tetra-ethyl lead susceptibility of gasoline. The major
sweetening operations are oxidation of mercaptans or disulfides, removal
of mercaptans, and destruction and removal of all sulfur compounds.
Drying is accomplished by salt filters or absorptive clay beds.
41
-------
Electric fields are sometimes used to facilitate separation of
product.
Wastes
The most common waste stream from drying and sweetening operations is
spent caustic. The spent caustic is characterized as phenolic or
sulfidic, depending on which is present in the largest concentration.
Whether the spent caustic is actually phenolic or sulfidic is mainly
determined by the product stream being treated. Phenolic spent caustics
contain phenol, cresols, xylenols, sulfur compounds, and some neutral
oils. Sulfidic spent caustics are rich in sulfides, but do not contain
any phenols. These spent caustics have very high BOD5 and COD. The
phenolic caustic streams are usually sold for the recovery of phenolic
materials.
Other waste streams from the process result from water washing of the
treated product and regeneration of the treating solution such as sodium
plumbite (No2 PbO2) in doctor sweetening. These waste streams will
contain small amounts of oil and the treating material, such as sodium
plumbite (or copper from copper chloride sweetening).
The treating of sour gases produces a purified gas stream, and an acid
gas stream rich in hydrogen sulfide. The H2S rich stream can be flared,
burned as fuel, or processed for recovery of elemental sulfur.
Trends
As air pollution agencies increase their efforts to control sulfur
emissions to the atmosphere, the restrictions on sulfur content in fuels
can be expected to tighten. This will generate a strong trend to
replacement of the sweetening processes by more hydrotreating
(desulfurization), because hydrotreating removes almost all sulfur
compounds and not just hydrogen sulfide, mercaptans, and elemental
sulfur. Nevertheless, on certain feedstocks sweetening will continue to
be used because it will be as effective as, and more economical than,
hydrotreating. Those processes producing high waste loads (Doctor
Sweetening, etc.) are being replaced by lower waste-producing processes.
B. LUBE OIL FINISHING
Process Description
Solvent refined and dewaxed lube oil stocks can be further refined by
clay or acid treatment to remove color-forming and other undesirable
materials. Continuous contact filtration, in which an oil-clay slurry
is heated and the oil removed by vacuum filtration, is the most widely
used subprocess.
Wastes
42
-------
Acid treatment of lubricating oils produces acid bearing wastes occuring
1 rinse waters, sludges, and discharges from sampling, leaks and
tdowns. The waste streams are also high in dissolved and suspended
ids, sulfates, sulfonates, and stable oil emulsions.
Handling of acid sludge can create additional problems. Some refineries
burn the acid sludge as fuel. Burning the sludge produces large volumes
of sulfur dioxide that can cause air pollution problems. other
refineries neutralize the sludge with alkaline wastes and discharge it
to the sewer, resulting in both organic and inorganic pollution. The
best method of disposal is probably processing to recover the sulfuric
acid, but this also produces a waste water stream containing acid,
sulfur compounds and emulsified oil.
Clay treatment results in only small quantities of waste water being
discharged to the sewer. Clay, free oil, and emulsified oil are the
major waste constituents. However, the operation of clay recovery kilns
involves potential air pollution problems of hydrocarbon and particulate
emissions. Spent clays usually are disposed of by landfill.
Trends
Acid and clay treatment of lube oils is gradually being replaced by
hydrotreating methods. Acid treatment in particular is being phased out
rather rapidly.
C. BLENDING AND PACKAGING
Description
Blending is the final step in producing finished petroleum products to
meet quality specifications and market demands. The largest volume
operation is the blending of various gasoline stocks (including
alkylates and other high-octane components) and anti-knock (tetra-ethyl
lead) , anti-rust, anti-icing, and other additives. Diesel fuels, lube
oils, and waxes involve blending of various components and/ or additives.
Packaging at refineries is generally highly-automated and restricted to
high volume, consumer-oriented products such as motor oils.
Wastes
These are relatively clean processes because care is taken to avoid loss
of product through spillage. The primary source of waste material is
from the washing of railroad tank cars or tankers prior to loading
finished products. These wash waters are high in emulsified oil.
Tetra-ethyl lead is the major additive blended into gasoline and it must
be carefully handled because of its high toxicity. Sludges from
finished gasoline storage tanks can contain large amounts of lead and
should not be washed into the wastewater system.
43
-------
Trends
There will be an increased use of automatic proportioning facilities f
product blending with a trend toward contracting out of packaging
lower-volume products that are less suitable to highly-automated
operation.
12. AUXILIARY ACTIVITIES
A. HYDROGEN MANUFACTURE
Process Description
The rapid growth of hydrotreating and hydrocracking has increased the
demand for hydrogen beyond the level of by-product hydrogen available
from reforming and other refinery processes. The most widely used
process for the manufacture of hydrogen in the refinery is steam
reforming, which utilizes refinery gases as a charge stock. The charge
is purified to remove sulfur compounds that would temporarily deactivate
the catalysts.
The desulfurized feedstock is mixed with superheated steam and charged
to the hydrogen furnace. On the catalyst the hydrocarbons are converted
to hydrogen, carbon monoxide, and carbon dioxide. The furnace supplies
the heat needed to maintain the reaction temperature.
The gases from the furnace are cooled by the addition of condensate a
steam, and then passed through a converter containing a high- or loi
temperature shift catalyst depending on the degree of carbon monoxi
conversion desired. Carbon dioxide and hydrogen are produced by the
reaction of the monoxide with steam.
The gas mixture from the converter is cooled and passes to a hydrogen
purifying system where carbon dioxide is absorbed into amine solutions
and later driven off to the atmosphere by heating the rich amine
solution into the reactivator.
Since some refining processes require a minimum of carbon oxides in the
product gas, the oxides are reacted with hydrogen in a methanation step.
This reaction takes place in the methanator over a nickel catalyst at
elevated temperatures.
Hydrocarbon impurities in the product hydrogen usually are not
detrimental to the processes where this hydrogen will be used. Thus, a
small amount of hydrocarbon is tolerable in the effluent gas.
Wastes
Information concerning wastes from this process are not available.
However, the process appears to be a relatively clean one. In the steam
44
-------
reforming subprocess a potential waste source is the desulfurization
it, which is required for feedstock that has not already been
ulfurized. This waste stream would contain oil, sulfur compounds,
phenol. In the partial oxidation subprocess free carbon is removed
by a water wash. Carbon dioxide is discharged to the atmosphere at
several points in the subprocess.
Trends
Hydrogen requirements of the rapidly growing hydrocracking and
hydrotreating processes in many instances exceed the by-product hydrogen
available from catalytic reforming units. Since hydrocracking and
hydrotreating are expected to grow more rapidly than other refinery
processes, the demand for hydrogen manufacturing units should continue
to be strong.
B. UTILITIES FUNCTION
Utility functions such as the supply of steam and cooling water
generally are set up to service several processes. Boiler feed water is
prepared and steam is generated in a single boiler house. Non-contact
steam used for surface heating is circulated through a closed loop
whereby varying quantities are made available for the specific
requirements of the different processes. The condensate is nearly
always recycled to the boiler house, where a certain portion is dis-
charged as blowdown.
three major uses of steam generated within a refinery plant are:
1. For non-contact process heating. In this application, the
steam is normally generated at pressures of 9.5 to U5.2
atm (125 to 650 psig) .
2. For power generation such as in steam-driven turbines,
compressors, and pumps associated with the process. In
this application, the steam is normally generated at
pressures of 45.2 to .103 atm (650 to 1500 psig) and
requires superheating.
3. For use as a diluent, stripping medium, or source of
vacuum through the use of steam jet ejectors. This steam
actually contacts the hydrocarbons in the manufacturing
processes and is a source of contact process waste water
when condensed. It is used at a substantially lower
pressure than the foregoing and frequently is exhaust
steam from one of the other uses.
Steam is supplied to the different users throughout the plant either by
natural- circulation, vapor-phase systems, or by forced-circulation
45
-------
liquid heat-transfer systems. Both types of systems discharge some
condensate as blowdown and require the addition of boiler make-up watej
The main areas of consideration in boiler operation are normally boii
efficiency, internal deposits, corrosion, and the required steal
quality.
Boiler efficiency is dependent on many factors. One is the elimination
of boiler-tube deposition that impedes heat transfer. The main
contributors to boiler deposits are calcium, magnesium, silicon, iron,
copper, and aluminum. Any of these can occur in natural waters, and
some can result from condensate return-line corrosion or even from make-
up water pretreatment. Modern industrial boilers are designed with
efficiencies on the order of 80 percent. A deposit of 0.32 cm (1/8
inch) in depth will cause a 2-3 percent drop in this efficiency,
depending on the type of deposit.
Internal boiler water treatment methods have advanced to such a stage
that corrosion in the steam generation equipment can be virtually
eliminated. The control of caustic embrittlement in boiler tubes and
drums is accomplished through the addition of sodium nitrate in the
correct ratio to boiler water alkalinity. Caustic corrosion in high
heat transfer boilers can also be controlled by the addition of
chelating agents. This type of solubilizing internal boiler water
treatment has been shown to be more effective than previous
precipitation treatment using phosphate.
Other factors influencing boiler efficiency include reduction of t
amount of boiler blcwdown by increasing cycles of concentration of
boiler feedwater, efficiency of the blowdown heat-recovery equipmerf
and the type of feed used.
Steam purity is of prime importance if:
1. The boilers are equipped with superheaters.
2. The boilers supply power-generation equipment.
3. The steam is used directly in a process where contamination
could affect product quality or destroy some material (such
as a catalyst) essential to the manufacture of the product.
The minimum purity required for contact steam (or contact process water)
varies from process to process. Limits for suspended solids, total
solids, and alkalinity vary inversely with the steam pressure. The
following tabulation summarizes boiler water concentration limits for a
system providing a steam purity of 0.5 - 1.0 ppm total solids, which is
required for most non-contact steam uses. It should be noted that the
boiler operation must incorporate the use of antifoam agents and steam
separation equipment for the concentrations shown to be valid.
46
-------
Boiler Water Concentration Required to
Maintain Steam Purity at 0.5 •* 1.0 ppm Total Solids
Boiler Pressure/ atm.
Parameters 21.4 21.5 - 31.6 31.7 -41.8 41.9 - 52.0
Total Solids (mg/1) 6,000 5,000 4,000 2,500
Suspended Solids (mg/1) 1,000 200 100 50
Total Alkalinity (mg/1) 1,000 900 800 750
Water conditioning or pretreatment systems are normally part of the
utilities section of most plants. From the previous discussions, it is
obvious that the required treatment may be quite extensive. Ion-
exchange demineralization systems are very widely employed, not only for
conditioning water for high-pressure boilers, but also for conditioning
various process waters. Clarification is also widely practiced and
usually precedes the ion-exchange operation.
Non-contact cooling water also is normally supplied to several processes
from the utilities area. The system is either a loop which utilizes one
or more evaporative cooling towers, or a once-through system with direct
discharge.
Cooling towers accomplish the cooling of water circulated over the tower
by moving a predetermined flow of ambient air through the tower with
large fans. The air water contact causes a small amount of the water to
* evaporated by the air. Thus, through latent heat transfer, the
ainder of the circulated water is cooled.
Approximately 252 kg cal (1,000 BTU) are removed from the total water
circulation by the evaporation of 0.454 kg (1 Ib) of water. Therefore,
if 45.4 kg (100 Ibs) of water are introduced at the tower inlet and
0.454 kg (1 Ib) is evaporated to the moving air, the remaining 44.9 kg
(99 Ibs) of water are reduced in total heat content by 252 kg cal (1,000
BTU) , of water leaving the tower have been cooled 3.24°C/kg/kg cal
(l°F/lb/BTU removed, and the exit temperature is reduced by about 5,500
(10°F). This leads to the common rule of thumb: 1 percent evaporation
loss for each 5.5°C (10°F) cooling.
Since cooling is primarily by transfer of latent heat, cooling tower
selection is based on the total heat content or enthalpy of the entering
air. At any one enthalpy condition, the wet bulb temperature is
constant. Therefore, cooling towers are selected and guaranteed to cool
a specific volume of water from a hot-water temperature to a cold-water
temperature while operating at a design wet-bulb temperature. Design
wet-bulb temperatures vary from 15.6°C (60°F) to 35°C (85°F) depending
on the geographic area, and are usually equaled or exceeded only 2.5
percent to 5 percent of the total summer operating time.
47
-------
Hot water temperature minus cold water temperature is termed cooling
range, and the difference between cold water and wet-bulb temperature is
called approach.
A closed system is normally used when converting from once-through river
cooling of plant processes. In the closed system, a cooling tower is
used for cooling all of the hot water from the processes. With the
closed system, make-up water from the river is required to replace
evaporation loss at the tower.
Two other water losses also occur. The first is drift, which is droplet
carryover in the air as contrasted to evaporative loss. The cooling
tower industry has a standarized guarantee that drift loss will not
exceed 0.2 percent of the water circulated. The second loss in the
closed system is blowdown to sewer or river. Although blowdown is
usually taken off the hot water line, it may be removed from the cold
water stream in order to comply with regulations that limit the
temperature of water returned to the stream. Blowdown from a tower
system will vary depending on the solids concentration in the make-up
water, and on the occurrence of solids that may be harmful to equipment.
Generally, blowdown will be about 0.3 percent per 5.5°C (10°F) of
cooling, in order to maintain a solids concentration in the recirculated
water of three to four times that of the make-up water.
The quantity and quality of the blowdown form boilers and cooling towers
depend on the design of the particular plant utility system. The heat
content of these streams is purely a function of the heat recovery
equipment associated with the utility system. The amounts of was4
brine and sludge produced by ion exchange and water treatment syst
depend on both the plant water use function and the intake source. No
of these utility waste streams can be related directly to specific
process units.
Quantitative limitations on parameters such as dissolved solids,
hardness, alkalinity, and temperature, therefore, cannot be allocated on
a production basis. The limitations on such parameters associated with
non-contact utility effluents should be established on the basis of the
water quality criteria of the specific receiving water body or an EPA
study of all industries, to define specific utility effluent
limitations.
Refinery Distribution
There are a total of 247 operating petroleum refineries in the United
States, as of January 1, 1973, with a combined capacity of 2.24 million
cu m/day (14 million barrels/day of) crude oil processing (see Figure 4
and Table 7). The capacity of these plants range from 32 cu m/day (200
bbl/day) to 69,000 cu m/day (434,000 bbl/day) of crude oil.
48
-------
*-
NO
Figure 4
Geographical Distribution of Petroleum
Refineries in the
United States
-------
TABLE 7
Crude Capacity of Petroleum Refineries by States as of Jan. 1, 1973 (3)
Rated
Crude Capacity
State
Alabama
Alaska
Arkansas
Cal ifornlia
Colorado
Delaware
Florida
Georgia
Hawai i
Illinois
j ndiana
Kansas
Kentucky
Louis iana
Maryland
Michigan
Minnesota
Miss iss ippi
Missouri
Montana
Nebraska
New Jersey
New Mexico
New York
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
Tennessee
Texas
Utah
Virginia
Washington
West Virginia
Wisconsin
Wyom i ng
Number of Plants
5
• 4
.4 •
3k
3
1
1
2
2
11
7
11
3
18
2
6
3
5
1
8
I
5
6
2
2
8
12
I
II
1
1
40
5
I
7
3
I
9
Cubic Me6ers/day
6,460
8,950
7,600
285,675
8,580
23,850
875
2,050
11,290
173,070
88,250
64,475
26,300
255,350 .
4,040
21,340
28,380
52,260
16,880
23,780
875
98,700
7,740
16,850
8,750
98,850
75,370
2,860
108,870
1,590
4,770
57-9,640
19,875
247
-%\ ~ ^
55,520
3,260
5,800
23,810
2,230,535
Barrels/day
40,650
56,300
47,800
1,796,700
53,950
150,000
5,500
12,900
71,000
1,088,500
555,000
405,500
165,400
1,606,200
25,400
134,190
178,500
328,700
106,200
149,575
5,500.
620,800
48,700
106,000
55,000
584,000
474,000
18,000
684,715
10,000
30,000
3,645,550
125,000
"5",000
349,200
20,500
36,500
149,750
13,991,580
50
-------
Within the United States, refineries are concentrated in areas of major
cruSe production (California, Texas, Louisiana, Oklahoma, Kansas), and
major population areas (Illinois, Indiana, Ohio, Pennsylvania, Texas,
California) .
There are an almost unlimited number of process combinations possible
within the process area, or "Battery Limits", of the typical refinery.
Selection of the processing route for the manufacture of a particular
product mix at a particular location or time is a decision based on the
particular refiner's unique situation. In order to illustrate the
diversity of operations which may be included within a refinery, Figure
5 shows the schematic flow diagram for a hypothetical 15,900 cu m/day
(100,000 bbl/day) integrated refinery. This hypothetical refinery
includes essentially all production processes previously outlined; hence
the hypothetical refinery shown in Figure 5 is completely integrated for
current U.S. refinery capacity. Inspection of Table 8 demonstrates the
general distribution of refining processes.
The trend in the petroleum refining industry is toward fewer and larger
refineries, which are integrated with satellite or companion industries.
This consolidation trend for a six-year period (1967-1973) is shown in
Table 9. Refineries with capacities over 15,900 cu m/day (100,000
bbl/day) (11.5 percent of the total) represented <*8 percent of the
domestic refinery crude capacity in 1967; in 1972, 16.6 percent of the
refineries had capacities of 15,900 cu m/day (100,000 bbl/day) or more,
and represented 58 percent of the domestic refinery crude capacity.
Growth of the large refinery was a result of the annual need for
« creased fuel capacity, and the imposed load due to the phasing out of
aller refineries. Refineries are increasing capacities for reforming,
drotreating, cracking, and isomerization processes to obtain higher
octane gasoline in lieu of adding lead. Desulfurization of heavy fuels,
longer process catalyst life requirements, and high quality, low sulfur,
light fuels and lubes are factors in the rapid growth of the hydrogen
treating process. The complexity and size of the typical refinery can
be expected to increase at a rate comparable to the period 1967 through
1972 for the near future, and no major technological breakthroughs are
expected that would drastically alter petroleum processes.
Anticipated industry Growth
The petroleum refining industry is presently facing a shortage of crude
oil. There have been scattered shortages of gasoline and fuel oil.
Since demand continues to grow and very little refinery expansion work
is under way, shortages will become more severe over the next few years.
Consumption of petroleum products will keep growing, and supplies must
be generated to satisfy these growing demands. (1972 consumption of
petroleum products, shown in Table 10, was approximately 2.56 million cu
m/day (16.1 million bbl/day). The growth rate in consumption has been
5.2 percent per year; the projected growth in consumption over the next
51
-------
FIGURE 5
HYPOTHETICAL 100,000 BARREL/STREAM DAY INTEGRATED REFINERY
52
-------
TABLE 8
Process Employment Profile of Refining Processes as of January 1, 1973 ( 3 )
Production Processes
Ol
o>
Number of Refineries
Employing a Production Process
by Crude Capacity Classification
Storage: Crude & Product
Crude Desalting
Atmospheric Distillation
Vacuum Distillation
Thermal Cracking
Catalytic Cracking
Hydrocracking
Hydretreating: Cat Reformer
and Cat Crack Feed
Middle Distillates 6 Naptha
Lubes
Heavy Oils and Residuals
Other Feedstocks
Alkylation
Isomerization
Reforming
Aromatics
Lubes
Asphalt
All
Refineries
247
247
247
175
87
141
45
129
54
13
5
57
125
30
166
35
44
111
<35
MB/SD
141
141
141
79
27
41
11
42
11
2
2
14
30
4
65
3
16
58
35 to 100
MB/SD
65
65
65
55
32
59
11
52
21
2
3
17
57
19
60
16
10
30
>100
MB/SD
41
41
41
41
28
41
23
35
22
9
-
26
38
7
41
16
18
23
Percent of Refineries
Employing a Production Process
by Crude Capacity Classification
All
Refineries
100
100
100
70
35
57
18
52
22
5
2
23
51
12
67
14
18
45
<35
MB/SD
100
100
100
56
19
29
8
30
8
1
1
10
21
3
46
2
11
41
35 to 100
MB/SD
100
100
100
85
49
91
17
80
32
3
5
26
88
29
92
25
15
46
>100
MB/SD
100
100
100
100
68
100
56
85
54
22
-
63
93
17
100
39
44
56
-------
TABLE 9
Trend in Domestic Petroleum Refining from 1967 to 1973 (3,3a)
January 1, 1967 January 1, 1973
Crude Capacity, M3/SD (bbl/SD) 1,853,618
Total Companies
Total Refineries
Refineries with Capacity J>100 Mbbl/SD
Refineries with Capacity <35 Mbbl/SD
Total Capacity of All >100 Mbbl/SD
(11,657,975)
146
269
31
159
5,597,300
2,224,661(13,991,580)
132
247
41
141
8,167,200
Percent
Change
+ 20
(- 10)
(- 8)
+ £
(- 10
+ 46
Refineries
Average Refinery Capacity, M3/SD (bbl/SD) 6890 (43,338) 9006(56,6461 + 31
54
-------
TABLE 10
1972 Consumption of Petroleum Products (63)
Products 1972 Consumption. Million Cubic Meters/Day
(Million Barrels/Day)
Motor Gasoline 1.02 (6.4)
Aviation Fuel 0.17 (1.1)
Middle Distillates 0.49 (3.1)
Residual Fuels 0.40 (2.5)
All Other Products 0.49 (3.1)
55
-------
eight years is 43 percent, or a compounded growth rate of 4.6 percent
per year.
Supplies of refinery feedstocks and products will show a rapid increas^
in imports. Table 11 indicates current and projected 1980 sources of
feedstocks and products. In 1972, imports accounted for 29 percent of
the total supply; in 1980, imports are projected at 55 percent of the
total supply.
Refinery runs of crude oil are projected to increase from 1.86 million
cu m/day (11.7 million bbl/day) in 1972 to 2.73 million cu m/day (17.2
million bbl/day) in 1980. Refinery capacity in 1972 was about 2.23
million cu m/day (14.0 million bbl/day). By 1980 the national refinery
capacity must increase to 3.18 million cu m/day (20.0 million bbl/day)
to satisfy the projected requirements. The need for 0.95 million cu
m/day (6.0 million bbl/day) of new refinery construction for real
growth, plus 0.64 million cu m/day (4.0 million bbl/day) of new
construction for replacement, indicates a total of 1.59 million cu m/day
(10.0 million bbl/day) of new refinery construction is required by 1980.
Because of crude supply limitations, most new refinery capacity will be
designed to process higher sulfur crudes. (A partial list of analyses
of crude oils from major oil fields around the world is given in Table
12.) The use of sour crude feedstock from outside the United states
will' require not only a change in processing equipment, but changes in
in-plant waste water control and treatment operations. Some refineries
currently consuming sweet crude stocks are not employing strippers t(
remove minimal amounts of ammonia and hydrogen sulfide from their *
waters. when processing sour crude within these refineries, sour watl
strippers will be required prior to discharge of the waste waters to
biological waste water treatment facilities. Two stage desalting will
become more prevalent. other changes will be required within the
refinery to minimize corrosion, treat more sour heavy bottoms, and
reduce emissions of sour gases.
56
-------
TABLE 11
Sources of Supply for U.S. Petroleum Feedstocks
Supplypillion Cubic Meters/Day(Million Barrels/Day
Source ' 1972 1980 (Projected)
Domestic Crude Oil Production 1.51 (9.5) 1.35 (8.5)
Domestic Natural Gas Liquids 0.27 (1.7) 0.24 (1.5)
Crude Oil Imports 0.35 (2.2) 1.38 (8.7)
Residual Fuel Imports 0.27 (1.7) 0.40 (2.5)
Other Imports 0.13 (0.8) 0.24 (1.5)
Miscellaneous Sources 0.06 (0.4) 0.08 (0.5)
57
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TABLE 12
Country
Abu Dhabi
Algeria
Brunei
Canada
Alberta
Bonnie Glen
Golden Spike
Judy Creek
Pembina
Swan Hills
Saskatchewan
Midale
Weyburn
Indonesia
1 ran
Iraq
Libya
Mexico
Ebano Panuco
Naranjos-Cerro-Azul
Poza Rica
Peru
Saudi Arabia
United States
Alaska
Cook Inlet
Prudhoe Bay
Swanson River
Arkansas
Smackover
Gravi ty
39.3
46 -
21 -
41 -
36 -
42 -
35 -
41
28 -
24 -
35
31 -
35 -
37 -
12
20
35
33.5
27 -
36
30.5
29-7
22.2
, API
48
37
42
39
43
42
32
33
38
36
41
- 35.5
38
Sulfur, Percent Nitrogen, Percent
0.15
0.1
0.25
0.23
0.42
0.80
1.89
2.12
0.10
1.12 - 1.66
1.97
0.23 - 0.52
5.38
3.80
1.77
0.12
1.30 - 3.03
0.0
0.16 0.203
2.10 0.080
58
-------
TABLE 12
(Continued)
Country
Californ ia
Elk Hills
Huntington Beach
Kern River =
Midway-Sunset
San Ardo
WiImlngton
Colorado
Rangely
Kansas
Bemis Shutts
Loui s iana
Bayou Sale
Cai1lou I si.
Golden Meadow
Grand Bay
Lake Barre
Lake Washington
West Bay
Bay Marchand Blk. 2
Main Pass Blk. 69
South Pass Blk. 24
South Pass Blk. 27
Timbalier Bay
West Delta Blk. 30
Miss iss ippi
Baxtervi1le
New Mexico
Vacuum
Oklahoma
Golden Trend
Texas
Anahuac
Con roe
Diamond M
East Texas
Hastings
Hawkins
Head lee
Kelly Snyder
Level land
Midland Farms
Panhandle
Seeliason
Gravity, API
22.5
22.6
12.6
22.6
11.1
22.1
34.8
34.6
36.2
35.4
37.6
35
Sulfur, Percent Nitrogen, Percent
28
32
20
30
32
35.6
34.4
27
•17.
35
33.2
37.6
45.4
39.4
31.0
26.8
51
38
31
39
40
0.68
57
19
0.94
2.25
1.44
0.56
0.57
0
41.3
0.16
0.23
18
0.31
0.14
0.37
0.27
0.46
0.25
0.26
0.18
0.33
0.33
2.71
0.95
0.11
0.2.3
0.15
0.20
0.32
0.15
2.19
<0.10
0.29
2.12
0.13
0.55
<0.10
0.472
0.048
0.604
0.913
0.073
0.162
0.040
0.02
0.146
0.071
0.098
0.068
0.069
0.081
0.09
0.111
0.075
0.041
0.02
0.076
0.083
0.066
0.136
0.080
0.067
0.014
59
-------
TABLE 12
(Continued)
Country
Tom O'Connor
Wasson
Webster
Yates
Utah
Aneth
Venezuela
Bachaquero
Boscan
Laguni1 las
Mene Grande
Tia Juana
Oficina
Los Claros
Gravity, API
31.1
31.9
29.3
30.2
4o.4
21.
10.
2k. 8
18.4
20.
21
.3
,5
.2
.4
Sulfur, Percent
0.16
0.21
0.20
,62
53
,18
,65
,49
Nitrogen, Percent
0.03
0.07
0.046
0.150
0.059
0.59
10.5
60
-------
SECTION IV
INDUSTRY SUBCATEGORIZATION
Discussion of the Rationale of Subcategorization
The goal of this study is the development of effluent limitations
commensurate with different levels of pollution control technology.
These effluent limitations will specify the quantity of pollutants which
will ultimately be discharged from a specific manufacturing facility and
will be related to the quantity of raw materials consumed and the
production methodology.
The diverse range of products and manufacturing processes to be covered
suggests that separate effluent limitations be designated for different
segments with the industry. To this end, a Subcategorization of the
Petroleum Refining Industry has been developed. The Subcategorization
is process oriented, with a delineation between subcategories based upon
raw waste load characteristics in relation to the complexity of refinery
operations.
Today's petroleum refinery is a very complex combination of
interdependent operations and systems. In the development of a
pollution profile for this industry, twelve major process categories
were listed as fundamental to the production of principal oil products
[see listing in Table 5) . As was indicated in the qualitative
iluation of refinery process flows and pollutant characteristics in
)le 5, of these processes - crude desalting, distillation, and
cracking contribute most heavily to a refinery's pollution load. It is
felt that any new method of classification must recognize at least one
of these process technologies.
The American Petroleum Institute (API) has developed a classification
system which utilizes this technology breakdown. They have tentatively
divided U.S. refineries into 5 classifications, which primarily
recognize varying degrees of processing complexity and resultant
distribution of products. The present API classification system is as
follows:
Class Process Complexity
A Crude Topping
B Topping and Cracking
C Topping, cracking, and petrochemicals
D "B" Category, and lube oils processing
61
-------
E "D" Category, and petrochemicals
Development of Industry Subcategorization
Age, size, and waste water treatability of refineries were considered
during the Subcategorization of the refining industry. However,
subcategorization by age is not necessarily useful, as additions to and
modifications of refineries are the industry's principal form of
expansion. Since most of the technology employed within the industry is
of an evoluationary nature, refinery age was not a major factor in
refinery subcategorization.
while the size of a refinery is important in terms of economical waste
water treatment, the control technology employed in smaller refineries
need not be as sophisticated a technology to achieve parity with larger
refineries within the same subcategory. Thus, size of refinery was not
used as a criterion for refinery classification.
Treatability characteristics of refinery waste waters indicate that
these waste waters are generally amenable to excellent degrees of
removal of pollutants. Since this is an industry-wide characteristic,
the proper place to evaluate the subcategorization of the industry is
with the raw waste load delivered to the refinery waste water treatment
plant. The 1972 National Petroleum Refining Waste Water
Characterization Studies of 135 refinery API separator effluents,
provides a major tool for this evaluation. Attempts to explain and
justify the differences based solely on type and method of coolin
inplant pretreatment, and housekeeping practices were also fruitle
However, generally speaking those refineries with good practices in a
these areas did have the lower waste loadings.
In an attempt to determine the effects of process technology, a further
analysis was made of the API individual or combined categories to
evaluate the raw waste load as a function of the degree of cracking
employed within the refinery. The operations included in degree of
cracking were: thermal operations, catalytic cracking and
hydroprocessing. The degree of cracking was expressed as percentage
capacity of the total feedstock processing capacity within the refinery.
The data for evaluating the net raw waste loads by this criteria was
obtained by analyzing the raw waste load surveys supplied by refineries,
literature sources, and analysis of the 1972 National Petroleum Refining
Waste Water Characterization Studies.
1. The net waste load (total raw waste load minus quality of
influent water) from the API categories, with corrections
supplied by EPA, were statistically analyzed; determining the
50 percent probability-of-occurrence loading for the key waste
water parameters (BOD5, Oil/Grease, Phenol, and Ammonia).
These parameters are representative of the major contaminants
discharged by refineries and therefore, could serve as a valid
62
-------
basis for screening correlations of variations in oil separator
performance/ housekeeping, severity of cracking, and other
factors. The 50 percent probability-of-occurrence numbers were
chosen, as they reflect the median net raw waste load
performance of the entire subcategory.
2. A subcategory-to-subcategory comparison was then made to
determine if, based upon these median levels of performance,
significant differences in waste water loadings between
subcategories of refineries existed. By comparing the median
values on a subcategory-to-subcategory basis, internal
differences in separator performance, housekeeping, and other
factors are minimized. Those subcategories which exhibited a
high degree of similarity in median net raw waste loads for the
key parameters were then combined and reanalyzed to develop
new median values for the combinations.
In an additional attempt to determine the effects of process technology,
an analysis was made of the lube oil manufacturing refineries. It was
found that these refineries split into two separate groups; (1) large,
complex refineries with a low overall percentage lube production, and
(2) small, specialty lube refineries. The first group is made up of 27
refineries, with capacities of 36,000 bbl/day and higher and lube
productions from 0.6 - 9.4 percent of the feedstock throughput. The
second group includes 18 refineries ranging in capacity from 1,000
10,400 bbl/day and lube productions from 14 - 100 per cent of feedstock
throughput.
categorization Results
Using the procedures outlined above, many trials were performed in order
to obtain a subcategorization of the petroleum refining industry which
is reflective of the net raw waste load with respect to type of refinery
(function) , process technology employed, and severity of operations.
The final subcategorization obtained from this analysis is indicated
below in Table 13. Detailed probability plots for the development of
the subcategorization are contained in supplement B.
For each of these new subcategories the parameters for the selected
median values are indicated in Table 14. A further enumeration of
overall net raw waste load characteristics is given in Section V.
In addition to the subcategorization made by raw waste load, the
splitting out of the speciality lube plants (as outlined above) is being
made because of the special nature of these plants.
Analysis of the Subcategorization
Topping subcategory
63
-------
Table 13
Subcategorization of the Petroleum Refining Industry
Reflecting Significant Differences in Wastewater Characteristics
Subcategory Basic Refinery Operations Included
Topping Topping and Catalytic reforming
Low-Cracking Topping and cracking, with fresh feed
(non-recycle) to the cracking and hydro-
processing of less than 50% of the feed-
stock throughout.
High-Cracking Topping cracking, with a fresh feed
(non-recycle to the cracking and hydro-
processing of greater than 50% of the
feedstock throughout.
Petrochemical Topping, cracking and petrochemicals
operations.*
Lube Topping, cracking and lubes.**
Integrated - Topping, cracking, lubes and petrochemicals
operations.*
* Petrochemical operations - Production of greater than 15 % of the
feedstock throughout in first generation petrochemicals and feedstock
isomerization products (BTX, olefins, cyclohexane, etc.) and/or
production of second generation petrochemicals (cumene alcohols,
ketones, etc.)
** Lubes - the production less than 12% of the feedstock throughout
as lubes. Refineries with greater than 12% lubes are being
considered speciality refineries and are to be handled on an
individual basis.
-------
ON
Ui
Subcategory
Topping
Low-Cracking
High-Cracking
Petrochemical
Lube
Integrated
* Supplement
individual
TABLE 14
Median Net Raw Waste Loads from Petroleum Refining *
Industry Categories
Median Net Raw Waste Load, kg/1000 m3 (lb/1000 BBL)
BOD,
Oil/Grease
Phenol
Ammonia
7.1 (2.5) 5.1 (1.8)
71.3 (25) 27.4 (9.6)
82.7 (29) 31.4 (11)
148.4 (52) 45.6 (16)
184.3 (65) 136.1 (U8)
215.5 (76) 131.8 (46.5) 5.1
0.029 (0.01) 1.43 (0.5)
2.85 (1.0) 10.0 (3.5)
5.1 (1.8) 32.8 (11.5)
10.3 (3.6) 34.2 (12.0)
6.2 (2.2) 22.1 (7-8)
(1.8) 35.4 (12.5)
B contains probability plots containing distributions of
parameters for each category.
-------
The topping subcategory is similar to the previous API category A.
Refineries in this subcategory are relatively simple in operation,
operating only crude oil distillation or topping units and catalytj^
reforming. These processes are common to all other subcategories.
High & low cracking subcategories
API Category B includes refineries which contain topping, reforming, and
cracking operations. Also included are all first generation
conventional refinery-associated products or intermediates, such as
benzene-toluene-xylene (BTX), alkanes, alkenes, alkynes, and other
miscellaneous items such as sulfur, hydrogen, coke, and ammonia.
Category B has been subdivided on the basis of degree of cracking. The
primary differentiation between the high and low cracking subcategories
is in the degree of cracking operations performed on the feedstock. An
analysis of all refineries for which cracking data was available was
made in order to determine if the amount of cracking employed within the
refinery had a demonstrable effect upon the net raw waste load. No
direct correlation, relating percent cracking of crude to the resultant
raw waste load, was obtained. However, a breakpoint appeared at
approximately 50 percent cracking, based on feedstock charge.
The division of API category B refineries into two subcategories, high
and low cracking, using 50 percent cracking as the breakpoint, was made
in order to more accurately reflect actual raw waste load conditions
within this portion of the petroleum refining industry. While this
division of the refineries is not the ultimate answer to s
categorization, it nevertheless recognizes the existence of an inher
difference in raw waste loads which result from the increasin
complexity of refinery operations in API category B.
Another change from the API classification, is that the inclusion of
first generation petrochemicals shall only be for those whose production
amounts to less than 15 percent of the refinery throughput.
Petrochemical subcategory
The petrochemical subcategory is similar to the API category C.
Operations included within this subcategory are topping, cracking, and
petrochemical operations. Petrochemical operations include first
generation conventional refinery-associated production, as described
under high and low cracking and category B, but only when it amounts to
greater than 15 percent of the refinery throughput. This takes into
consideration the additional cooling tower blowdown from this operation.
Intermediate chemical production, including such typical products as
cumene, phthalic anhydride, alcohols, ketones, trimer, and styrene,
shall also be considered petrochemical operations and classify a
refinery in this subcategory.
66
-------
Attempts to correlate degree of cracking data for the petrochemical
subcategory refineries were unsuccessful. Only a small data base was
for analysis, and no conclusions could be drawn from this
as to the effect of increased cracking on the petrochemical
subcategory refinery raw waste loads. The analysis is also probably
overshadowed by the presence of petrochemicals operations within these
refineries.
Lube subcategory
The new lube subcategory is the same as the API category D, except that
those refineries with greater than 12 percent of their throughput going
to lube production have been split out for separate consideration, with
limits to be set at a later date.
In the lube subcategory, the operations included under the high and low
cracking subcategories are expanded to include lube operations. Lube
operations in this subcategory require the production of lube oil
blending stocks via operations such as dewaxing, lube hydrotreating, or
clay treatment. Lube oil processing excludes formulating blended oils
and additives.
Again, for the new lube subcategory, no correlation or breakpoint for
degree of cracking was observable. This may be due in part to: the
small data base; the presence of lube operations; or the size and
complexity of refineries within this subcategory.
Integrated subcategcry
new integrated subcategory is the same as API category E, except for
the new definition of petrochemical operatons specified in the
petrochemical subcategory.
Conclusion
The subcategorization of the petroleum refinery industry presented above
allows for the definition of logical segments of the industry in terms
of factors which effect generated API separator effluent waste water
quality. It allows for rapid identification of the expected median net
raw waste loads as a basis for developing effluent guidelines for the
discharge from the individual refinery. The subcategorization
determined above is used throughout this report as the basis for
development of effluent limitations and guidelines.
.67
-------
SECTION V
WASTE CHARACTERIZATION
General
After developing an understanding of the fundamental production
processes and their inter-relationships in refinery operations,
determination of the best method of characterizing of refinery
discharges will enhance the interpretation of the industry water
pollution profile. If unit raw waste loads could be developed for each
production process, then the current effluent waste water profile could
be obtained by simply adding the components, and future profiles by
projecting the types and sizes of refineries. However, the information
required for such an approach is not available. Essentially all of the
available data on refinery waste waters apply to total API separator
effluent, rather than to effluents from specific processes.
Another factor detracting from the application of a summation of direct
subprocess unit raw waste loads, is the frequent practice of combining
specific waste water streams discharging from several units for
treatment and/or reuse. Thus, such streams as sour waters, caustic
washes, etc., in actual practice are generally not traceable to a
specific unit, but only to a stripping tower or treatment unit handling
wastes from several units. The size, sequence, and combination of
contributing processes are so involved that a breakdown by units would
extremely difficult to achieve.
view of the limitations imposed by the summation of waste water data
from specific production process, the evaluation of refinery waste loads
was based on total refinery effluents discharged through the API (Oil)
separator, which is considered an integral part of refinery process
operations for product/raw material recovery prior to final waste water
treatment.
Raw Waste I^oads
The information on raw waste loading was compiled from the 1972 National
Petroleum Refining Waste Water Characterization Studies and plant
visits. The data are considered primary source data, i.e., they are
derived from field sampling and operating records. The raw waste data
for each subcategory of the petroleum refining industry, as subcater
gorized in Section IV, have been analyzed to determine the probability
of occurrence of mass leadings for each considered parameter in the
subcategory. These frequency distributions are summarized in Tables 15
through 20 for each subcategory.
Waste water Flows
69
-------
As shown in Table 15 through 20, the waste water flows associated with
raw waste loads can vary significantly. However, the loadings of
pollutants tend to vary within fairly narrow limits, independent
flow.
Since the inter-refinery data suggest that the pollutant loading to be
expected from a refinery is relatively constant in concentration, an
examination of water use practices was made. The waste water flow
frequencies reported in Tables 15 through 20 are dry^weather flows, and
in many cases include large amounts of once-through cooling water.
Refineries with more exemplary waste water treatment systems are
probably making a greater effort to control waste loads and flows.
Conversely, refineries with very high water usages and/or raw waste
loads either do not have identifiable waste water treatment plants, or
have them under construction.
The primary methods for reduction of the waste water flows to the API
separator are either segregation of once"through cooling waters, or by
installation of recycle cooling towers and/or air coolers. In order to
estimate the flows that should be attainable in refineries with good
water practices, a statistical analysis was made of flows from
refineries in which 3 percent or less of the total heat removal load is
accomplished by once-through cooling water. Data for this analysis were
obtained from the tabulation of refinery cooling practices contained in
the 1972 National Petroleum Refining Waste Water characterization
Studies. These frequency distributions are summarized in Table 21.
Basis for Effluent Limitations
The median (50 percent probability-of-occurrence) raw waste loads
outlined in Tables 15 through 20 are reflective of the performance of
median refineries within each subcategory. At the same time, attainable
process waste water flows, as reflected by the median water usage for
refineries in which 3 percent or less of the total heat removal load is
accomplished by once-through cooling water, are indicative of equitable
process waste water loadings which require waste water treatment.
Consequently, these median (50 percent probability-of-occurrence) waste
water loadings and estimated process waste water flows were selected as
one basis for developing effluent limitations, and are used in
subsequent sections to define these effluent limitations.
70
-------
Parameter
Flow *
TABLE 15
Topping Subcategory Raw Waste Load**
Effluent from Refinery API Separator
Net Kilograms/1000 m (LB/1000 bbls) of Feedstock Throughput
Probability of Occurrence,
rei ^ei
1 0%
BOD5 0.26 (0.09)
COD
TOC
TSS
Phenol s
Ammonia
Sulfides
0.72
0.086
0.30
0.97
0.001
0.18
0.0037
0.024
(0.25)
(0.03)
(0.105)
(0.34)
(0.00035)
(0.064)
(0.0013)
(1.0)
1 L 1 tibb LI Id
n ur ei|udi L
50% (.Median)
7.1
24.0
4.9
6.6
5.1
0.029
1.43
1.57
0.53
(2.5)
(8.4)
(1.7)
(2.3)
(1.8)
(0.01)
(0.5)
(0.55)
(22)
o.
90%
286 .(100)
858 (300)
269 ( 98)
123 ( 43)
45.8 ( 16)
0.92(0.32)
11.4 (4.0)
7.2 (2.5)
12.0 (500)
* 1000 cubic meters/1000 m Feedstock Throughput (gallons/bbl)
** Probability plots are contained in Supplement B.
71
-------
TABLE 16
Lew-Cracking Subcategory ,Raw Waste Load**
Effluent from Refinery API Separator
Net Kilograms/1000 m3 (LB/1000 bbls) of Feedstock Throughput
Parameter
Probability of Occurrence,
Percent less than or equal to
10%
BOD
COD
TOC
TSS
Oil
y
Phenol s
Ammon i a
Sul
fides
15.
7.
3.
5.
0.
1.
0.
7
7
k
36
9
(5.
(19)
(2.
(1.
(l.
(0.
(0.
000^9(0.
5)
6)
3)
9)
125)
67
)
00017)
50% (Median)
71.5
200
k5.7
27
27
2.86
10.0
1.0
(25)
(70)
(16)
( 9.6)
( 9.6)
(1.0)
(3.5)
(0.35)
90%
3*0
286
200
137
22
51
22
.9
.5
(120)
(260)
(100)
(70)
(W)
(8.0)
(18)
,308(7800)
F1 ow»
0.10
t. 3)
0.79 (33)
6.
* 1000 Cubic Meters/1000 m Feedstock Throughput (gallons/bbl)
** Probability plots are contained in Supplement B.
72
-------
TABLE 17
High Cracking Subcategory Raw Waste Load
Effluent from Refinery API Separator
Net Kilograms/1000 nT (LB/1000 bbls) of Feedstock Throughput
Parameter
BOD
5 '
COD
TSS
Oil
Phenols
Ammonia
Sulfides
F1 ow»
Probability of Occurrence,
Percent less than or equal to
10%
28.0 (9.8)
45.8 (16)
7.4 (2.6)
0.054 (0.019)
6.7 (2.35)
0.57 (0.20)
6.6 (2.3)
0.0049(0.0017)
50% (Median)
82.9 (29)
260 (91)
52.9 (18.5)
32.3 (11.3)
31.4 (H.O)
5.1 (1.8)
32.8 (11.5)
1.28(0.45)
90%
235 (82)
1487 (520)
372 (130)
212 (74)
120 (42)
48.6(17)
166 (58)
315 (110)
0.12 (4.8)
0.62(26)
*|000 Cubic Meters/1000 m3; Feedstock Throughput (gallons
** Probability plots are contained in Supplement B.
48.0(2000)
73
-------
TABLE 18
Petrochemical Subcategory Raw Waste Load **
Effluent from Refinery API Separator
Net Kilograms/1000 m3 (LB/1000 bbls) of Feedstock Throughput
Parameter
COD
TOC
TSS
Oily
Phenols
Ammonia
Sulfides
Flow-1'
Probability of Occurrence,
Percent less than or equal to
10% 50% (median)
34.3
137
31.5
4.0
7.4
2.2
6.3
0.01
(12)
(48)
(ID
(1.4)
(2.6)
(0.78)
(2.2)
1(0.004)
149
372
117
44.
45.
10.
3<*.
1.
(52)
(130)
(M)
3(15.5)
8(16)
3(3.6)
3(12)
69(0.59)
90%
629
2888
443
887
315
48.
189
229
(220)
(800)
(155)
(310)
(110)
6(17)
(66)
(80)
0.11 (4.6)
0.96(40)
* 1000 Cubic Meters/1000 m3 Feedstock Throughput (gallons/bbl)
** Probability polots are contained in Supplement B.
12.0(500)
74
-------
TABLE 19
Lube Subcategory Raw Waste Load**
Effluent from Refinery API Separator
Net Kilograms/1000 m3 (LB/1000 bbls) of Feedstock Throughput
Parameters
5
Probability of Occurrence,
Percent less than or equal to
113
200
3.
U8
0.
6.
0.
0.
nnn
10%
(to)
(-71.)
U (1.2)
(17)
2 (0.07)
2 (2.2)
00017 (0.00006)
56(21*. 2)
nrt *ff**» — . <3«. ^ _ _!.. fm_. u.._.__ ^_T.
50%
187
382
79
. 136
6.2
22
1.1
(median)
(66)
(13V)
(28)
(V8)
(2.2)
(7.8) ,
(O.U)
0.91(39)
j_ / nn Ai_i_ n \
90%
311
1750
1769
396
20
79
35.0
13.0
(110)
(618)
(625)
(ito)
(7.0)
(28)
(12.U)
(560)
BOD
COD
TOC
TSS
Phenolics
Ammonia (N)
Sulfides
Flow*
* 1000 Cubic Meter
** Probability plots are contained in Supplement B.
75
-------
Parameters
TABLE 20
Integrated Subcategory Raw Waste Load**
Effluent from REfinery API Separator
Net Kilograms/1000 M^ (LB/1000 BBLs) of Feedstock Throughput
Probability of Occurrence,
Percent legs than or equal to
BOD
10% 50% (median) 90%
^ (16)
120 (1*2.1*)
0.6 (0.2)
23.8 (8.1*)
100 (0.35)
T.U (2.6)
0.00028 (0.00010)
0.23(10.0)
238
-590
29
133
6.5
35. U
1.7
1.8
(81*)
(20.8).
(10.2)
(vn
(2.3)
(12.5)
(0.6)
(79)
U13
1150
3^0
750
1*1
170
1*5
25.6
(1U6)
(1*06)
(120)
(26.5)
(lU.5)
(60)
(15.9)
(1100)
COD
TOG
TSS
Oil
Phenolics
Ammonia (N)
Sulfides
Flow*
* 1000 Cubic Meters/1000 m3 Feedstock Throughput (gallons/bbl)
** Probability plots are contained in Supplement B.
76
-------
TAi
21
Wastewater Flow from Petroleum Refineries*
Using 3 Percent or Less Once-Through
Cool ing Water for Heat Removal
1000 M3 / 1000 M3 (gallona/bbl) of Feedstock Throughput
Probability of Occurrence,
Percent Less than or Equal to
Subcategory
Topping
Low-Cracking
High-Cracking
Pet ro chemi c al
Lube
Integrated
10%
0.046 (1.9)
0.18 (7.6)
0.21 (8.8)
0.19 (8.0)
0.53 (22)
0.65 (27)
50% (median)
0.29 (12)
0.41 (1?)
0.50 (21)
0.60 (25)
0.89 (37)
1.11 (U6)
90%
2.16 (90)
1.46 (61)
5.52 (230)
1.58 (66)
1.25 (52)
8.80 (365)
* Probability plots are contained in Supplement B.
-------
SECTION VI
SELECTION OF POLLUTANT PARAMETERS
Selected Parameters
The selection of the complete list of pollutant parameters which are
discharged in significant quantities was based on a review of: the
Environmental Protection Agency permits for discharge of waste waters
from a number of refineries; reviews with personnel in regional EPA
offices; the 1972 National Petroleum Refining Waste Water
Characterization Studies; discussions with industry representatives and
consultants; and literature survey data. The results of the above
indicated the parameters shown in Table 22 are significant in describing
the physical, chemical and biological characteristics of waste waters
discharged by the petroleum refining industry, as defined in the Act.
The rationale and justification for inclusion of these parameters are
discussed below. This discussion will provide the basis for selection
of parameters upon which the actual effluent limitations were postulated
and prepared. In addition, particular parameters were selected for
discussion in the light of current knowledge as to their limitations
from an analytical as well as from an environmental standpoint.
Oxygen Demand Parameters
ree oxygen demand parameters are discussed below: BODS, COD, and TOG.
should be noted that since separate limitations are specified for
5, COD, and TOC in sections IX, X, and XI for each subcategory.
Almost without exception, waste waters from petroleum refineries exert a
significant and sometimes major oxygen demand. The primary sources are
soluble biodegradable hydrocarbons and inorganic sulfur compounds.
Crude distillation, cat cracking, and the product finishing operations,
are the major contributors of BOD5. In addition, the combination of
small leaks and inadvertent losses that occur almost continuously
throughout a complex refinery can become principal BOD_ pollution
sources.
Biochemical oxygen demand (BOD) refers to the amount of oxygen required
to stabilize biodegradable matter under aerobic conditions. The BOD5
test has been used to gauge the pollutional strength of a waste water in
terms of the oxygen it would demand if discharged into a watercourse.
Historically, the BOD5 test has also been used to evaluate the
performance of biological waste water treatment plants and to establish
effluent limitation values. However, objections to the use of the BOD5
test have been raised.
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TABLE 22
Significant Pollutant Parameters for
the Petroleum Refining Industry
Biochemical Oxygen Demand (BODS)
Chemical Oxygen Demand (COD)
Total Organic Carbon (TOG)
Oil and Grease (O&G)
Ammonia as Nitrogen (NH3-N)
Phenolic Compounds
Sulfides
Chromium
Zinc
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The major objections are as follows:
1. The standard BOD5 test takes five days before the results are
available, thereby negating its use as a day-to-day treatment
plant operational indicator.
2. At the start of the BOD5 test, seed culture (microorganisms) is
added to the BOD5 bottle. If the seed culture was not
acclimated, i.e., exposed to a similar waste water in the past,
it may not readily be able to biologically degrade the waste.
This results in the reporting of a low BOD5 value. This
situation is very likely to occur when dealing with complex
industrial wastes, for which acclimation is required in most
cases. The necessity of using "acclimated bacteria" makes it
very important to take a seed from the biological plant
treating the waste or downstream of the discharge in the
receiving waterbody.
3. The BOD5 test is sensitive to toxic materials, as are all
biological processes. Therefore, if toxic materials are
present in a particular waste water, the reported BOD5 value
may very well be erroneous. This situation can be remedied by
running a toxicity test, i.e., subsequently diluting the sample
until the BOD5 value reaches a plateau indicating that the
material is at a concentration which no longer inhibits
biological oxidation.
«ere has been much controversy concerning the use of BOD5 as a measure
pollution, and there have been recommendations to substitute some
her parameter, e.g., COD or TOG. EPA has recently pointed out that
some or all of the previously cited reasons make the BOD5 test a non-
standard test, and ASTM's Subcommittee p-19 has also recommended
withdrawal of the BOD5 test as a standard test.
However, some of the previously cited weaknesses of the BOD5 test also
make it uniquely applicable. It is the only parameter now available
which measures the amount of oxygen used by selected microorganisms in
metabolizing a waste water. The use of COD or TOC to monitor the
efficiency of BOD5 removal in biological treatment is possible only if
there is a good correlation between COD or TOC and BOD. After
consideration of the advantages, disadvantages and constraints, BOD5
will continue to be used as a pollutional indicator for the petroleum
refining industry.
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Typical raw waste load concentrations for each subcategory are listed
below:
Subcategory BOD5 RWL Range, mg/1
Topping 10-50
Low Cracking 30 - 300
High Cracking 100 - 600
Petrochemical 50 - 800
Lube 100 - 700
Integrated 100 - 800
As a matter of reference, typical BOD5 values for raw municipal waste
waters range between 100 and 300 mg/L7
COD
Chemical oxygen demand (COD) provides a measure of the equivalent oxygen
required to oxidize the materials present in a waste water sample, under
acid conditions with the aid of a strong chemical oxidant, such as
potassium dischromate, and a catalyst (silver sulfate). One major
advantage of the COD test is that the results are available normally in
less than three hours. Thus, the COD test is a faster test by which to
estimate the maximum oxygen exertion demand a waste can make on a
stream. However, one major disadvantage is that the COD test does not
differentiate between biodegradable and non-biodegradable organic
material. In addition, the presence of inorganic reducing chemicals
(sulfides, reducible metallic ions, etc.) and chlorides may interfere
with the COD test.
caT^
The slow accumulation of refractory (resistant to biologice
decomposition) compounds in watercourses has caused concern among
various environmentalists and regulatory agencies. However, until these
compounds are identified, analytical procedures developed to quantify
them, and their effects on aquatic plants and animals are documented, it
may be premature (as well as economically questionable) to require their
removal from waste water sources.
Typical raw waste load concentrations for each subcategory are listed
below:
Subcategory COD RWL Range, mg/1
Topping 50 - 150
Low Cracking 150 - 300
High Cracking 150 - 400
Petrochemical 300 - 600
Lube 400 - 700
Integrated 300 - 600
Typical COD values for raw municipal waste waters are
between 200 mg/1 and 400 mg/1.
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TOC
«tal organic carbon (TOC) is a measure of the amount of carbon in the
ganic material in a waste water sample. The TOC analyzer withdraws a
small volume of sample and thermally oxidizes it at 150°C. The water
vapor and carbon dioxide from the combustion chamber (where the water
vapor is removed) is condensed and sent to an infrared analyzer, where
the carbon dioxide is monitored. This carbon dioxide value corresponds
to the total inorganic value. Another portion of the same sample is
thermally > oxidized at 950°c, which converts all the carbonaceous
material to carbon dioxide; this carbon dioxide value corresponds to the
total carbon value. TOC is determined by subtracting the inorganic
carbon (carbonates and water vapor) from the total carbon value.
The recently developed automated carbon analyzer has provided a rapid
and simple means of determining organic carbon levels in waste water
samples, enhancing the popularity of TOC as a fundamental measure of
pollution. The organic carbon determination is free of many of the
variables which plague the COD and BOD analyses, yielding more reliable
and reproducible data. However, meaningful correlations between the
three are sometimes hard to develop.
Typical raw waste concentrations for each subcategory are presented
below:
Subcategory TOC RWL Range, mg/1
Topping 10 - 50
Low Cracking 50 - 100
High Cracking 50 - 500
Petrochemical 100 - 250
Lube 100 - 400
Integrated 50 - 500
Typical values for raw municipal waste waters range between 50 and 250
mg/L.
TSS
In refineries, major sources of suspended matter are contributed by
crude storage, alkylation, crude desalting and finishing operations.
Quenching and removal operations in the production of coke can
contribute significant amounts of suspended fines to the refinery
effluent.
Total suspended solids, when discharged to a watercourse, settle to the
bottom and can blanket spawning grounds and interfere with fish
propagation. In addition, the solids which are organic will be
metabolized and exert an oxygen demand. Total suspended solids, in
large concentrations, can impede light transmittance and interfere with
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aquatic photosynthesis, thereby affecting the oxygen content of a Joody
of water.
Typical total suspended solids raw waste concentrations for
subcategory are listed below:
Subcategory TSS RWL Range, mg/1
Topping 10 - 40
Low Cracking 10 - 70
High Cracking 20 - 100
Petrochemical 50 - 200
Lube 80 - 300
Integrated 20 •* 200
Total suspended solids concentrations for typical raw municipal waste
waters range from 100 to 300 mg/1.
Freon Extractables - Oil and Grease
No solvent is known which will directly dissolve only oil or grease,
.thus the manual "Methods for the Chemical Analysis of Water and Wastes
1971" distributed by the Environmental Protection Agency states that
their method for oil and -grease determinations includes the freon
extractable matter from waters.
In the petroleum refining industry, oils, greases, various other hydro-
carbons and some inorganic compounds will be included in the freon
extraction procedure. The majority of material removed by the procedv
in a refinery waste water will, in most instances, be of Na hydrocarl
nature. These hydrocarbons, predominately oil and grease
compounds, will make their presence felt in the COD, TOC, TOD, and
usually the BOD tests where high test values will result. The oxygen
demand potential of these freon extractables is only one of the
detrimental effects exerted on water bodies by this class of compounds.
The water insoluble hydrocarbons and free floating emulsified oils in a
waste water will affect stream ecology by interfering with oxygen
transfer, by damaging the plumage and coats of water animals and fowls,
and by contributing taste and toxicity problems. The effect of oil
spills upon boats and shorelines and their production of oil slicks and
iridescence upon the surface of waters is well known. The average freon
extractable material recorded by a refinery survey for effluent waters
from the refineries ranged from a maximum of 37 mg/1 to a minimum of U.
mg/1.
Grease is defined in "Webster's Third New International Dictionary" as a
thick lubricant. The class of refinery products known as greases are
usually included in the freon extractable portions of a water analysis.
Some thick heavy petroleum products coat the silt and sediment of a
stream bottom samples which have been contaminated by oily products over
a long period. An infrared scan of such an extract done on bottom
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sediments from the New York Harbor area compares closely to a typical 90
w automative grease. Such bottom contamination can, of course, exert
fluence upon the aquatic life of a stream, estuary, bay or other water
dy. Typical oil and grease concentrations for each subcategory are
isted below:
Freon Extractables as Oil and Grease
Subcategory RWL Range, mg/1
Topping 10 -50
Low Cracking 15 - 150
High Cracking 30 - 300
Petrochemical 20 - 250
Lube 40 - 400
Integrated 20 - 500
Ammonia as Nitrogen
Ammonia is commonly found in overhead condensates from distillation and
cracking and from desalting. It is usually found combined with sulfide
as an ammonium sulfide salt. The presence of even small amounts of
ammonia in surface waters contributes to eutrophication - the growth of
algae. Large growths of algae are unsightly, often interfere with
swimming and boating, impart tastes and odors to water, and when they
die in the early fall add a substantial organic load to the stream.
Ammonia may exert a toxic effect on aquatic life which is usually more
pronounced at a high pH value.
;monia nitrogen is also the nitrogen and energy source for autotrophic
ganisms (nitrifiers). The oxidation of ammonia to nitrite and then
nitrate has a stoichiometric oxygen requirement of approximately 4.6
times the concentration of NH3-N. The nitrification reaction is much
slower than the carbonaceous reaction and therefore, the dissolved
oxygen utilization is observed over a much longer period.
Typcial ammonia as nitrogen raw waste concentrations for each
subcategory are listed below:
Subcategory NH3 - N RWL Range, mg/1
Topping 0.05 - 20
Low Cracking 0.5 - 200
High Cracking 2 - 200
Petrochemical 4-300
Lube 1 «• 120
Integrated 1-250
Phenolic Compounds
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Catalytic cracking, crude distillation, and product finishing ^ and
treating, are the major sources of phenolic compounds. Catalytic
cracking produces phenols by the decomposition of multi-cyclicaromaticj^
such as anthracene and phenanthrene. Some solvent refining process^B
use phenol as a solvent and although it is salvaged by recovery
processes, losses are inevitable.
Phenols in waste water present two major problems: 1) at high
concentrations, phenols act as bactericides, and 2) at very low
concentrations, when disinfected with chlorine, chlorophenols are formed
producing taste and odor. Past experience has indicated that biological
treatment systems may be acclimated to phenol concentrations of 300 mg/1
or more. However, protection of a biological treatment system against
slug loads of phenol should be given careful consideration.
Typical phenolic raw waste concentrations for each subcategory are
listed below:
Subcategory Phenolics, RWL Range, mg/1
Topping 0-200
Low Cracking 0-20
High Cracking 0-100
Petroleum 0.5-50
Lube 0.1-25
Integrated 0.5-50
i
sul fides
In the petroleum refining industry, major sources of sulfide wastes
crude desalting, crude distillation and cracking processes, sulfides
cause corrosion, impair product quality, and shorten the useful catlyst
life. They are removed by caustic, diethanciamine, water or steam, or
appear as sour condensate waters in these initial processing operations.
Hydrotreating processes can be used to remove sulfides in the feedstock.
Most removed and recovered sulfide is burned to produce sulfuric acid or
elemental sulfur.
When present in water, soluble sulfide salts can reduce pH; react with
iron and other metals to cause black precipitates; cause odor problems;
and can be toxic to aquatic life. The toxicity of solutions of sulfides
to fish increases as the pH value is lowered. Sulfides also chemically
react with dissolved oxygen present in water, thereby lowering dissolved
oxygen levels.
Typical sulfide raw waste concentrations for each subcategory are listed
below:
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Subcategory Sulfide, RWL Range, mg/1
Topping 0-5
Low Cracking 0-400
High Cracking 0-20
Petroleum 0-200
Lube 0-40
Integrated 0-60
Total Chromium
Chromium may exist in water supplies in both the hexavalent and
trivalent state. Chromium salts are used extensively in industrial
processes and chromate compounds are frequently added to cooling water
for corrosion control. The toxicity of chromium salts toward aquatic
life varies widely with the species, temperature, pH, concentration, and
synergistic or antagonisitc effects of other water constituents,
especially hardness.
It appears that about 1 mg/1 of chromium is toxic to fish life in any
water. A limit of .05 mg/1 for hexavalent chromium is set by the USPHS
Drinking Water Standards of 1962. A survey of refinery effluents
sampled across the U.S. produced chromium values ranging from .02 to
1.45 mg/1. The median figure found for chromium in the effluents was
.26 mg/1.
Hexavalent Chromium
hexavalent chromium content of potable water supplies within the
U.S. has been reported to vary between 3 to 40 micrograms per liter. In
the +6 oxidation state; chromium is usually combined with oxygen in the
form of the oxide, chromium trioxide Cr03 or the Oxyanions chromate
Cr04= and dichromate Cr207. Chromates will generally be present in a
refinery waste stream when they are used as corrosion inhibitors in
cooling water.
Zinc
Zinc is an essential and beneficial element in human metabolism when its
intake to an organism is limited. At higher amounts zinc can lead to
gastrointestinal irritation and large amounts of the metal have been
reported to upset trickling filter and activated sludge waste treatment
processes.
Zinc may also affect toxicity of an effluent water through its
synergistic effects on other ions present, although research on such
effects have been limited, zinc's reported toxicity to fish varies from
about .1 to 1.0 mg/1. Calcium content of the water is said to directly
affect this toxicity.
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Zinc compounds can be used as corrosion inhibitors for cooling water.
In addition, zinc is produced in the combustion of fossil fuels and ma;
find its way into refining waters by leaching processes.
A survey of effluents from petroleum refineries across the U.S. reports
zinc concentrations of .04 to 1.84 mg/1 in the effluent waters. The
median concentration of zinc found in the effluents was .16 mg/1. -
Other Pollutants
Other pollutants which were examined in this study of refining waste
water practices included: total dissolved solids, cyanide, pH (acidity
and alkalinity), temperature, various metallic ions, chloride, fluoride
and phosphates.
It was determined that these parameters are generally found in
refineries in small enough amounts as not to warrant accross the board
treatment. Restrictions on these parameters may be required as a result
of water quality requirements.
TDS
Dissolved solids in refinery waste waters consist mainly of carbonates,
chlorides, and sulfates. U.S. Public Health Service Drinking Water
Standards for total dissolved solids are set at 500 mg/L on the basis of
taste thresholds. Many communities in the United states use water
containing from 2,000 to 4,000 mg/1 of dissolved solids. Such waters
are not palatable and may have a laxative effect on certain peopl
However, the geographic location and
-------
U.S.- Public Health service Drinking Water standards set a cyanide value
of 0.01 mg/L of CN-. Cyanides, although toxic at high concentrations,
deteriorate by bacterial action at lower concentrations.
Cyanide raw waste load data for the refining industry show median values
of 0.0 - 0.18 mg/L for the six subcategories. Only occasionally are any
values found above 1.0 mg/1. At these concentration ranges, no
inhibition is expected in biological waste facilities. Consequently,
the values are such that specific limitations are not required.
Cyanides are on the EPA toxic materials list and limitations based on
health effects will be made available at a later date.
pH (Acidity and Alkalinity)
The acidity of a waste is a measure of the quantity of compounds
contained therein which will dissociate in an aqueous solution to
produce hydrogen ions. Acidity in petroleum refining waste waters can
be contributed by both organic and inorganic compound dissociation.
Most mineral acids found in waste waters (sulfuric acid, hydrochloric
acid, nitric acid, phosphoric acid) are typically strong acids. The
most common weaker acids found include the organic acids such as
carboxyl and carbonic.
Compounds which contribute to alkalinity in waste waters are those which
dissociate in aqueous solutions to produce hydroxyl ions. Alkalinity is
often defined as the acid-consuming ability of the waste water and is
measured by titrating a given volume of waste with standard acid until
of the alkaline material has reacted to form salts. In effect,
_ talinity is the exact opposite of acidity; high alkalinities lower the
hydrogen ion concentration of a solution and raise its pH.
Most refinery waste waters are alkaline due to the presence of ammonia
and the use of caustic for sulfur removal. Cracking (both thermal and
catalytic) and crude distillation are the principal sources of alkaline
discharges. Alkylation and polymerization utilize acids as catalysts
and produce severe acidity problems.
Extreme pH values are to be avoided because of effects on emulsification
of oil, corrosion, precipitation/^ volatilization of sulfides and other
gases, etc. In streams and water courses, extreme pH levels accentuates
the adverse effects of other pollutants as well as causing toxicity
itself.
The hydrogen ion concentration in an aqueous solution is represented by
the pH of that solution. The pH is defined as the negative logarithm of
the hydrogen ion concentration in a solution. The pH scale ranges from
zero to fourteen, with a pH of seven, representing neutral conditions,
i.e., equal concentrations of hydrogen and hydroxyl ions. Values of pH
less than seven indicate increasing hydrogen ion concentration or
acidity; pH values greater than seven indicate increasing alkaline
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conditions. The pH value is an effective parameter for predicting
chemical and biological properties of aqueous solutions. It should
emphasized that pH cannot be used to predict the quantities of alkali
or acidic materials in a water sample. However, most effluent a
stream standards are based on maximum and minimum allowable pH values
rather than on alkalinity and acidity.
Since pH RWL values are not additive, it is not always possible to
predict the final pH of a process waste water made up of multiple
discharges. In addition, the individual refinery's discharge
characteristics will dictate final pH ranges, which may be kept within
the acceptable range merely by equalization, or which may require more
sophisticated neutralization facilities. However, it is recommended
that a pH range of 6.0 to 9.0 be established as the effluent limitation.
Temperature
Crude desalting, distillation, and cracking contribute substantial
thermal wasteloads.
Effluent heat loads can have adverse effects on the receiving waters.
Water temperature is important in terms of its effect on aquatic life,
the use of water for cooling purposes, and its influence on the self-
purification processes in a stream. Increased temperature reduces the
solubility of oxygen in water and speeds biological degradation
processes, thus accelerating the demand ,on oxygen resources of the
stream. Both of these phenomenon reduce the streams assimilative
capacity for waste loads. High temperatures have also been reported
intensify the effect of toxic substances.
Other Metallic Ions
Several metallic ions in addition to chormium and zinc may be found in
refinery effluents. The major sources for their presence in waste water
are from the crude itself and corrosion products. The concentration of
metallic ions varies considerably dependent upon the effectiveness of
catalyst recovery in production process. Table 23 lists those metals
which may be commonly found in petroleum refinery effluents. Dissolved
metallic ions create turbidity and discoloration, can precipitate to
form bottom sludges, and can impart taste to water.
Metallic ions such as copper, and cadmium are toxic to microorganisms
because of their ability to tie up the proteins in the key enzyme
systems of the microogranisms.
Chlorides:
chloride ion is one of the major anions found in water and produces a
salty taste at a concentration of about 250 mg/1. Concentrtations of
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1000* mg/1 may be undetectable in waters which contain appreciable
.ounts of calcium and magnesium ions.
«:
:
ter is invariably associated with naturally occurring hydrocarbons
underground and much of this water contains high amounts of sodium
chloride. The saltiest oil field waters are located in the mid-
continent region of the country where the average dissolved solids
content is 174,000 ppm; therefore, waters containing high levels of salt
may be expected.
Copper chloride may be used in a sweetening process and aluminum
chloride in catalytic isomerization. These products may also find their
ways to waste streams.
The toxicity of chloride salts will depend upon the metal with which
they are combined. Because of the rather high concentration of the
anion necessary to initiate detrimental biological effects, the limit
set upon the concentration of the metallic ion with which it may be
tied, will automatically govern its concentration in effluents, in
practically all forms except potassium, calcium, mganesium, and sodium.
Since sodium is by far the most common (sodium 75 percent, magnesium 15
percent, and calcium 10 percent) the concentration of this salt will
probably govern the amount of chlorides in waste streams from petroleum
refineries.
It is extremely difficult to pinpoint the exact amount of sodium
«oride salt necessary to result in toxicity in waters. Large
centrations have been proven toxic to sheep, swine, cattle or
poultry.
In swine fed diets of swill containing 1.5 to 2.0% salt by weight,
poisoning symptoms can be induced if water intake is limited and other
factors are met. The time interval necessary to accomplish this is
still about one full day of feeding at this level.
Since problems of corrosion, taste and quality of water necessary for
industrial or agricultural purposes occur at sodium chloride con-
centration levels below those at which toxic effects are experienced,
these factors will undoubtedly determine the amount of chlorides allowed
to escape in waste streams from refining operations. The study of
refinery effluents previously mentioned, placed net chloride levels at
values ranging from 57 to 712 mg/1. The median value was 176 mg/1.
Fluoride: HF
Alkalation units (when hydrofluoric acid is used) can contribute
fluoride ion to the plant's waste effluent. Since calcium and barium
fluoride are insoluble in water the fluorides will by necessity be
associated with other cations.
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TABLE 23
Metallic Ions Commonly Found in Effluents from Petroleum Refineries
Aluminum
Arsenic
Cadmium
Chromium
Cobalt
Copper
Iron
Lead
Mercury
Nickel
Vanadium
Zinc
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In concentrations of approximately 1 mg/1 in potable water supplies
have been found to be an effective preventer of dental
In concentrations greater than this amount, fluorides can
carree molting of tooth enamel and may be incorporated into the bones.
Natural waters can contain levels of fluorides up to 10 ppm. if these
waters are to be used for potable supplies or for certain industrial or
agricultural purposes the fluoride levels must be reduced. Since many
municipal waters are artificially fluoridated as a dental health aid,
the U.S. Public Health service has placed limits on the total amounts of
fluorides a water supply may contain. Their recommended control levels
depend upon temperature and are expressed as lower, optimum, and upper
limits. Optimum limits range from .7 to 1.2 mg/1. If values exceed two
times the optimum value, the supply must be rejected or the fluoride
content lowered. Because refinery effluents may empty into water ways
which may eventually become public supplies, the maximum permissible
limits of fluorides present in an effluent will probably be derived from
the USPHS control limits for drinking water.
Phosphate - Total
Various forms of phosphates find their way into refinery effluents.
They range through several organic and inorganic species and are usually
contributed by corrosion control chemicals. Plant cooling systems may
contain 20 to 50 mg/1 of phosphate ion.
Phosphorus is an element which is essential to growth of an organism.
at times become a growth limiting nutrient in the biological
of a water body. In these instances an over abundance of the
element contributed from an outside source may stimulate the growth of
photosynthetic aquatic macro and micro-organisms resulting in nuisance
problems, since the forms of phosphorus in waters or industrial wastes
are so varied, the term total phosphate has been used to indicate all
the phosphate present in an analyzed sample regardless of the chemical
form. Also, many phosphorus compounds tend to degrade rather readily,
and in these less complex forms phosphate may be readily utilized in the
aquatic life cycle. It is therefore reasonable to direct concern toward
the total amount of phosphorus present rather than chemical structure it
may assume, for in only very unusual cases may the form or concentration
of the element present in a waste stream be toxic. Total phosphate
values noted on a nationwide refinery survey were 9.49 mg/1 maximum and
.096 mg/1 minimum for effluents. The median value was .68 mg/1
expressed as phosphorus.
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SECTION VII
CONTROL AND TREATMENT TECHNOLOGY
Petroleum refinery waste waters vary in quantity and quality from
refinery to refinery. However, the wastes are readily treatable. The
results of the industry survey indicate, as would be expected, that
techniques for in-process control are general across the industry and
the specific application of these techniques at individual plants
determines their success. Local factors such as climate, discharge
criteria, availability of land, or other considerations may dictate the
use of different waste water treatment processes to reach an acceptable
effluent. The survey has shown that although the end-of-pipe waste
water treatment technologies used throughout the petroleum refining
industry have a marked similarity in operational steps, a considerable
variation in treatment results exist. The processes used for treating
refinery waste water, however, are similar in purpose; namely—maxi-
mizing oil recovery and minimizing the discharge of other pollutants.
The wastewater treatment technology described below is generally
applicable across all industry subcategories.
In-Plant Control/Treatment Techniques
In-plant practices are the sole determinant of the amount of waste water
to be treated. There are two types of in-plant practices that reduce
«DW to the treatment plant. First, reuse practices involving the use
water from one process in another process. Examples of this are:
ing stripper bottoms for makeup to crude desalters; using blowdown
from high pressure boilers as feed to low pressure boilers; and using
treated effluent as makeup water whereever possible, second, recycle
systems that use water more than once for the same purpose. Examples of
recycle systems are: the use of steam condensate as boiler feedwater;
and cooling towers. The reduction or elimination of a waste stream
allows the end-of-pipe processes to be smaller, provide better
treatment, and be less expensive. Since no treatment process can
achieve 100 percent pollutant removal from the individual stream,
reduction in flow allows for a smaller pollutant discharge.
Housekeeping
In addition to reuse/recycle of water streams and reduction in flows by
other in-plant techniques, another effective in-plant control is good
housekeeping. Examples of good housekeeping practices are: minimizing
waste when sampling product lines; using vacuum trucks or dry cleaning
methods to clean up any oil spills; using a good maintenance program to
keep the refinery as leakproof as possible; and individually treating
waste streams with special characteristics, such as spent cleaning
solutions.
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The use of dry cleaning, without chemicals, aids in reducing ,water
discharges to the sewer. Using vacuum trucks to clean up spills and
charging of this recovered material to slop oil tanks, reduces
discharge of both oil and water to the waste water system. The o
also be recovered for reprocessing. Process units should be curbed to
prevent the contamination of clean areas with oily storm runoff and to
prevent spills from spreading widely. Prompt cleanup of spills will
also aid in reducing discharges to the sewer systems. Additionally,
sewers should be flushed regularly to prevent the buildup of material in
the sewer, eliminating sudden surges of pollutants during heavy rains.
Collection vessels should also be provided whenever maintenance is
performed on liquid processing units, to prevent accidental discharges
to the sewers.
Operations during turnaround present special problems. Wastes generated
by cleaning tanks and equipment should be collected, rather than
draining directly to the sewer. The wastes from these holding tanks
should be gradually bled to the sewer, after first pretreating as
necessary to eliminate deleterious effects on the waste water treatment
system. An alternative method of disposal is through the use of
contract carriers.
while these are not all the examples of good housekeeping practices
which can be cited for refinery operations, it is evident that
housekeeping practices within a refinery can have substantial impact on
the loads discharge to the waste treatment facilities. The application
of good housekeeping practices to reduce waste loads requires judicious
planning, organization and operational philosophy.
Process Technology
Many of the newer petroleum refining processes are being designed or
modified with reduction of water use and subsequent minimization of
contamination as design criteria; although no major innovations in basic
refining technology are anticipated. Improvements which can be expected
to be implemented in existing refineries are: primarily dedicated to
better control of refinery processes and other operations; elimination
of marginal processing operations, and specific substitution of
processes and/or cooling techniques to reduce discharge loads to waste
treatment facilities. Examples of the possible changes which may be
implemented include:
1. Substitution of improved catalysts which have higher activity
and longer life, consequently requiring less regeneration and
resulting in lower waste water loads.
2. Replacement of barometric condensers with surface condensers
or air fan coolers, reducing a major oil-water emulsion source.
As an alternative, several refineries are using oily water
cooling tower systems, with the barometric condensers, equipped
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with oil separation/emulsion breaking auxiliary equipment.
3. Substitution of air fan coolers to relieve water cooling duties
simultaneously reduces blowdown discharges.
4. Installation of hydrocracking and hydrotreating processes will
allow generation of lower waste loadings than the units they
replace. The rapid pace at which such units are being
installed is exerting and will continue to exert a strong
influence on the reduction of waste loadings, particularly
sulfides and spent caustics.
5. Installation of automatic monitoring instrumentation, such as
TOC monitors, will allow early detection of process upsets
which result in excessive discharges to sewers.
6. Increased use of improved drying, sweetening, and finishing
procedures will minimize spent caustics and acids, water
washes, and filter solids requiring disposal.
Cooling Towers
Cooling towers eliminate large volumes of once through cooling water by
passing heated water through heat exchange equipment. By recycling the
cooling water many times, the amount of water used is greatly reduced.
The number of times cooling water can be reused is determined by the
total dissolved solids (TDS) content of the water, and the effects high
issolved solids have on process equipment, when the TDS becomes too
gh, scaling occurs and heat transfer efficiency decreases. The TDS
evel in the circulating water is controlled by discharging a portion of
the steam (blowdown) from the system. The higher the allowable TDS
level, the greater number of cycles of concentration and the less make-
up water is required (87). Installation of cooling towers will reduce
the amount of water used within the refinery by at least 90 percent
(87).
There are three types of cooling towers (106); wet or evaporative, dry,
and combined "wet-dry."
Evaporative cooling Systems
Evaporative cooling systems transport heat by transfer of the latent
heat of vaporization. This results in a temperature decrease of circu-
lating water and a temperature and humidity increase of cooling air.
Spray ponds are an evaporative cooling system using natural air currents
and forced water movement. Because of their inefficiency, spray ponds
are used less in industry than cooling towers. Cooling towers have a
higher efficiency because they provide more intimate contact between the
air and water. As the water falls over the packing, it exposes a large
97
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contact surface area. As the water heats up the air, the air can absorb
more water. The more water evaporated, the more heat is transferred
(106). Because an evaporative cooling tower is dependent on ambie
temperatures and humidity, its performance is variable throughout t'
year. There are three types of evaporative cooling towers: mecahnical
draft towers; atmospheric towers, which use. wind or natural air
currents; and natural draft towers, which use tall stacks to move air by
stack effect. Most refineries use mechanical draft towers, which have
baffles, called drift eliminators, to separate entrained water from the
air stream, thus reducing the amount of water carried into the air. The
evaporative system is the least costly of all cooling towers.
Dry Cooling Systems
There are two types of dry air cooling systems. Either system can be
used with either mechanical or natural draft cooling towers. Most
refineries use mechanical draft towers on indirect condensing systems.
The tubes used in dry cooling equipment have circumferential fins to
increase the heat transfer area. Most tube designs have an outside to
inside surface area ratio of 20:1. (106) The advantage of the dry air
system is that it requires no makeup water and there is no water
entrainment. Dry air cooling systems are being increasingly used to
reduce the amount of water discharged to the waste water treatment
plant. A disadvantage of the dry cooling process is that it has low
rates of heat transfer requiring large amounts of land and uses more
power than other cooling systems. The dry cooling tower is also more
expensive to ins'tall than evaporative systems.
Wet"Dry Systems
The wet-dry systems use an evaporative and non-evaporative cooling tower
in either series or parallel, each of which can be operated with a
mechanical or natural draft tower. The series design has the
evaporative cooling process preceeding the dry process with respect to
the air flow. This lowers the temperature of the air entering the dry
process which would mean a smaller unit could be used. The problem with
this method is that solids are deposited in the dry tower due to drift
from the wet section. The parallel process uses a dry cooling tower
upstream of the wet section, each of which has its own air supply. The
two air streams are mixed and discharged, reducing the vapor plume.
Recycle/Reuse Practices
Recycle/reuse can be accomplished either by return of the waste water to
its original use, or by using it to satisfy a lower quality demand. The
recycle/reuse practices within the refining industry are extremely
varied and only a few examples are described briefly below:
1. Reduction of once-through cooling water results in tremendously
decreased total effluents.
98
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2. Sour water stripper bottoms are being used in several
refineries as make-up water for crude desalter operations.
These sour water bottoms are initially recovered
from overhead accumulators on the catalytic cracking units.
3. Regeneration of contact process steam from contaminated
condensate will reduce the contact process waste water to a
small amount of blowdown. This scheme can be used to regener-
ate steam in distillation towers or dilution steam stripping
in pyrolysis furnaces.
4. Reuse of waste water treatment plant effluent as cooling water,
as scrubber water, or as plant make-up water, reduces total
make-up requirements.
5. Cooling tower blowdowns are frequently reused as seal water
on high temperature pump service, where mechanical seals are
not practicable.
6. Storm water retention ponds are frequently used as a source of
fire water or other low quality service waters.
Many' other conservation methods can be implemented, such as the use of
stripped sour water as low pressure (LP) boiler make-up, and LP boiler
blowdown as irake-up water for crude desalting. However, these, and the
other possible recycle/reuse cases outlined above must be examined by
; individual refinery in light of its possible
antages/disadvantages, insofar as product quality or refining process
^abilities are affected. For example, one refinery has reported that
reuse of sour water stripper bottoms for desalting resulted in a
desalted crude which was difficult to process downstream.
At-Source Pretreatment
Major at-source pretreatment processes which are applicable to
individual process effluents or groups of effluents within a refinery
are stripping of sour waters, neutralization and oxidation of spent
caustics, ballast water separation, and slop oil recovery. The
particular areas of application of these processes are discussed below.
Sour Water Stripping
Sour or acid waters are produced in a refinery when steam is used as a
stripping medium in the various cracking processes. The hydrogen
sulfide, ammonia and phenols distribute themselves between the water and
hydrocarbon phases in the condensate. The concentrations of these
pollutatns in the water vary widely depending on crude sources and
processing involved.
99
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The purpose of the treatment of sour water is to remove sulfides (as
fhydrogen sulfide, ammonium sulfide, and polysulfides) before the waste
enters the sewer. The sour water can be treated by: stripping
steam or flue gas; air oxidation to convert hydrogen
thiosulfates; or vaporization and incineration.
Sour water strippers are designed primarily for the removal of sulfides
and can be expected to achieve 85-99 percent removal. If acid is not
required to enhance sulfide stripping, ammonia will also be stripped
with the percentage varying widely with stripping temperature and pH.
If acid is added to the waste water, essentially none of the ammonia
will be removed. Thus, ammonia removals in sour water strippers vary
from 0 to 99 percent. Depending upon such conditions as waste water pH,
temperature, and contaminant partial pressure; phenols and cyanides can
also be stripped with removal as high as 30 percent. The bottoms from
the stripper usually go to the desalter where most of the phenols are
extracted and the waste water can be sent to the regular process water
treating plant. COD and BOD5 are reduced because of the stripping out
of phenol and oxidizable sulfur compounds.
The heated sour water is stripped with steam or flue gas in a single
stage packed or plate-type column. Two-stage units are also being
installed to enhance the separate recovery of sulfide streams and
ammonia streams. Hydrogen sulfide released from the waste water can be
recovered as sulfuric acid or sulfur, or may be burned in a furnace.
The bottoms have a low enough sulfide concentration to permit discharge
into the general waste water system for biological treatment. If the
waste contains ammonia, it is neutralized with acid before
stripping. The waste liquid passes down the stripping column while
stripping gas passes upward. Most refiners now incinerate th sour
stripper acid gases without refluxing the stripper. This converts the
ammonia to nitrogen with possibly traces of nitrogen oxides. Due to the
high concentrations of sulfur dioxide produced more complex processing
will probably be required in the future.
Several stripping processes are available. These include: Chevron
WWT; ammonium sulfate production; a dual burner Claus sulfur plant; and
the Howe-Baker ammonex process. Deep well injection and oxidation to
the thiosulfate are also being used, but in the future probably won't do
a good enough job.
The Chevron WWT process (37) is basically two stage stripping with
ammonia pruification, so that the hydrogen sulfide and ammonia are
separated. The hydrogen sulfide would go to a conventional Claus sulfur
plant and the ammonia can be used as fertilizer.
Ammonium sulfate can be produced by treating with sulfuric acid but a
very dilute solution is produced and concentrating it for sale as
fertilizer is expensive. Again the hydrogen sulfide goes to a
conventional Claus sulfur plant.
100
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A dual burner Claus sulfur process is generally the answer in new
plants, but adding the second burner to an existing sulfur plant is
^difficult. The second burner is required to handle the ammonia. A
»efluxed stripper is required to reduce the water vapor in the hydrogen
^sulfide-ammonia mixture and the line between the stripper and the Claus
Unit must be kept at about 150°F to prevent precipitation of ammonium
sulfide complexes.
Howe-Baker Engineers Inc. of Tyler, Texas have developed to the pilot
plant stage a process they call "Ammonex". It is a solvent extraction
process that basically is intended to complete with the Chevron WWT
process. No commercial units have been built.
Another way of treating sour water is to oxidize by aeration.
Compressed air is injected into the waste followed by sufficient steam
to raise the reaction temperature to at least 190°F. Reaction pressure
of 50-100 psig is required. Oxidation proceeds rapidly and converts
practically all the sulfides to thiosulfates and about 10 percent of the
thiosulfates to sulfates. Air oxidation, however, is much less
effective than stripping in regard to reduction of the oxygen demand of
sour waters, since the remaining thiosulfates can later be oxidized to
sulfates by aquatic microorganisms.
The stripping of sour water is normally carried out to remove sulfides
and hence, the effluent may contain 50-100 ppm of ammonia, or even
considerably higher, depending on the influent ammonia concentration.
Values of ammonia have been reported as low as 1 ppm, but generally the
ffluent ammonia concentration is held to approximately 50 ppm to
rovide nutrient nitrogen for the refinery biological waste treatment
system (2,14,33,58) .
Spent Caustic Treatment
v
•
Caustic solutions are widely used in refining. Typical uses are to
neutralize and extract:
a. Acidic materials that may occur naturally in crude oil.
b. Acidic reaction products that may be produced by various
chemical treating processes.
c. Acidic materials formed during thermal and catalytic cracking
such as hydrogen sulfide, phenolics, and organic acids.
Spent caustic solutions may therefore contain sulfides, mercaptides
sulfates, sulfonates, phenolates, naphthenates, and other similar
organic and inorganic compounds.
At least four companies process these spent caustics to market the
phenolics and the sodium hyposulfide. However, the market is limited
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and most of the spent caustics are very dilute so the cost of shipping
the water makes this operation uneconomical.
Some refiners neutralize the caustic with spent sulfuric from
refining processes, and charge it to the sour water stripper.
removes the hydrogen sulfide. The bottoms from the sour water stripper
go to the desalter where the phenolics are extracted by the crude oil.
Spent caustics usually originate as batch dumps, and the batches may be
combined and equalized before being treated and/or discharged to the
general refinery waste waters. Spent caustic solutions can also be
treated by neutralization with flue gas. In the treatment of spent
caustic solutions by flue gas, hydroxides are converted to carbonates.
Sulfides, mercaptides, phenolates, and other basic salts are converted
by the flue gas stripping. Phenols can be removed and used as a fuel or
can be sold. Hydrogen sulfide and mercaptans are usually stripped and
burned in a heater. Some sulfur is recovered from stripper gases. The
treated solution will contain mixtures of carbonates, sulfates,
sulfites, thiosulfates and some phenolic compounds. Reaction time of
16-21 hours is required for the neutralization of caustic solution with
flue gas.
The oxidation phase of spent caustic treatment is aimed at the sulfide
content of these wastes and achieves 85-99 percent sulfide removal. In
this process, sulfides are oxidized primarily to thiosulfates although
in some variations there is partial oxidation of the sulfur compounds to
sulfate. Oxidation processes are not applied to phenolic caustics, as
phenols inhibit oxidation. It should be noted that those process*
which oxidize the sulfide only to thiosulfate, satisfy half of
oxygen demand of the sulfur, as thiosulfate can be oxidized biological^
to sulfate. Neutralization of spent caustics is applied to both
phenolic and sulfidic caustic streams; the sulfidic caustics are also
steam stripped, after neutralization, to remove the sulfides. When
phenolic spent caustics are neutralized, crude acid oils or "crude
carbolates" are sprung and thus removed from the waste water. The major
part of the phenols will appear in the oil fraction, but a significant
part may remain in the waste water as phenolates.
Fluid bed incineration is also now being used. This process was
developed under an EPA demonstration grant (26) and at least two large
units are under construction. Once the incinerator is started up, the
sludge should provide the necessary heating value to keep the system
operating. Oxidizing fuels may be required when the sludge is burnt, as
ash remains in the bed of the incinerator. A constant bed level is
maintained, so the sand bed originally in the incinerator is gradually
replaced by the inert sludge ash (5) . The gasses pass through a
scrubber, so the fines and particulate matter can be recovered. The ash
and fines can be landfilled. This landfill is cleaner than a sludge
landfill, because there are no organic materials present to contaminate
ground water or run-off.
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In the past ocean dumping, deep well injection, evaporative lagoons, and
mple dilution have all been used. These methods will no longer be
Sewer System Segregation
Waste water quantity is one of the major factors that affect the cost of
waste treatment facilities most directly. Water usage in the petroleum
refining industry varies from less than 5 gallons of water per barrel of
crude charge in the newer refineries to higher than 1000 gallons of
water per barrel of crude charge in the older refineries. In order to
provide efficient treatment to the wastes originating within a refinery,
it is very important that segregation of concentrated waste streams be
considered. Segregation of waste streams frequently simplifies waste
treating problems as well as reduces treatment facility costs. Thus,
treatment of highly polluted waste streams at the source can prevent
gross pollution of large volumes of relatively clean waste water. Such
treatment is often a more economical solution of a problem than would be
possible if wastes are discharged directly to the refinery sewers.
Treatment at the source is also helpful in recovering by-products from
the wastes which otherwise could not be economically recovered when the
wastes are combined.
In areas where water supply is limited, reduced water requirements have
been 'incorporated into the design and operation, thereby reducing total
water usage.
minimize the size of the waste water treatment processes it is
ative polluted water only be treated. This can be guaranteed by
segregating the various sewer systems. There should be a sewer carrying
process and blowdown waters that are treated continuously. A polluted
storm water sewer should go to a storage area from which it can be
gradually discharged to the treatment facilities. A sewer system
containing clean storm water can be discharged directly to the receiving
water. The sanitary system should be treated separately from the
process water because of the bacteria present in this stream. Once
through cooling water should be kept separate because of the large
volumes of water involved and the low waste loadings encountered. A
connection to the treatment plant should be provided in case of oil
leaks into the system.
Storm Water Runoff
An additional source of pollution from a petroleum refinery area is
caused by rainfall runoff. Size and age of refinery site, housekeeping,
drainage areas, and frequency and intensity of rainfall are several of
the factors which compound the assignment of allowable pollutional
values.
103
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There are several measures that refiners can provide to minimize storm
water loads to their treatment system after diverting all extraneou
drainage around the refinery area. The major consideration is
separate storm water sewer and holding system.
By providing separate collection facilities for storm water runoff,
protection is afforded the operation of the separator and ancillary
treatment systems by controlling the hydraulic load to be treated.
Comingling of inorganic particles with oily waste water often times
produces an emulsion which is difficult to break in the oil-water
separator.
Design of this facility should be based on the maximum ten-year, twenty-
four-hour rainfall runoff of the refinery drainage area. Diversion of
the collected storm water runoff to the oil-water separator facilities
can be provided when hydraulic flows return to normal operations. In
the event of excessive collection due to a high intensity storm,
diversion facilities should be provided to allow for emergency bypass
capability to divert the trailing edge of the runoff hydrograph (the
leading edge normally contained the mass of pollutants in urban runoff
investigations). An oil retention baffle and an API type overflow weir
should be provided to prevent the discharge of free and floating oil.
An alternate to the separate sewer system would be the provision of a
storm surge pond that would receive the polluted waters when the flow to
the oil-water separator exceeded 15 percent of the normal hydraulic
flow. During normal periods, the collected storm water-refinery
could then be diverted to the oil-water separator (provided process
did not equal or exceed the units hydraulic capacity) .
The major cause of pollution by storm water runoff is the lack of
housekeeping within the refinery confine. Proper procedures should be
encouraged to prevent the accumulation of materials which contribute to
pollution due to rainfall runoff. Some of the more common preventive
measures are: (1) Provide curbing around process unit pads; (2) Prevent
product sample drainage to sewers; (3) Repair pumps and pipes to prevent
oily losses to the surface areas; (4) Contain spilled oil from
turnarounds; (5) Dike crude and product tank areas and valve
precipitation to the storm water sewer.
In the event the collected water needs to be released from the storm
water detention pond due to overflow, samples of the water should be
monitored for; (1) Sheen, (2) Organic analysis such as COD, TOC, or TOD.
Ballast water Separation
Ballast water normally is not discharged directly to the refinery sewer
system because the intermittent high-volume discharges. The potentially
high oil concentrations, would upset the refinery waste water treatment
facilities. Ballast waters may also be treated separately, with
104
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heating, settling, and at times filtration as the major steps„ The
settling tank can also be provided with a steam coil for heating the
t^^ contents to help break emulsions, and an air coil to provide
apHation,, The recovered oil, which may be considerable^ is generally
sent to the slop oil system.,
Slop Oil Treatment
Separator skimmings, which are generally referred to as slop oil,
require treatment before they can be reused, because they contain an
excess amount of solids and water„ Solids and water contents in excess
of about 1 percent generally interfere with processing.,
In most cases slop oils are easily treated by heating to 190°F for 12 to
14 hourso At the end of settling, three definite layers exists a top
layer of clean oil; a middle layer of secondary emulsion; and a bottom
layer of water containing soluble components, suspended solids, and oilo
In some cases, it is advantageous or even necessary to use acid or
specific chemical demulsifiers to break slop oil emulsions., The water
layer resulting from acid and heat treatment has high BOD and COD, but
also low pH, and must be treated before it can be discharged.,
Slop oil can also be successfully treated by centrifugation or
precoat filtration using diatomaceous earth as the precoato
Gravity Separation of Oil
separators remove a majority of the free oil found in refinery
waste waterso Because of the large amounts of reprocessable oils which
can be recovered in the gravity separators, these units must be
considered an integral part of the refinery processing operation and not
a waste water treatment process„ The functioning of gravity°type
separators depends upon the difference in specific gravity of oil and
watero The gravity-type separator will not separate substances in
solution, nor will it break emulsions., The effectiveness of a separator
depends upon the temperature of the water, the density and size of the
oil globules, and the amounts of characteristics of the suspended matter
present in the waste water., The msusceptibility to separation80 (STS)
test is normally used as a guide to determine what portion of the
influent to a separator is amenable to gravity separation.,
The API separator is the most widely used gravity separator., The basic
design is a long rectangular basin, with enough detention time for most
of the oil to float to the surface and be removed., Most API separators
are divided into more than one bay to maintain laminar flow within the
separator, making the separator more effective,, API separators are
usually equipped with scrapers to move the oil to the downstream end of
the separator where the oil is collected in a slotted pipe or on a drum.,
On their return to the upstream end, the scrapers travel along the
105
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bottom moving the solids to a collection trough. Any sludge which
settles can be dewatered and either incinerated or disposed of as
landfill.
The gravity separator usually consists of a pre-separator (grit chamber)
and a main separator, usually rectangular in shape, provided with
influent and effluent flow distribution and stilling devices and with
oil skimming and sludge collection equipment. It is essential that the
velocity distribution of the approach flow be as uniform as possible
before reaching the inlet distribution baffle.
Another type of separator finding increasing employment in refineries is
the parallel plate
-------
The incorporation of solids removal ahead of biological treatment is not
as important as it is in treating municipal waste waters,,
of the initial criteria used to screen refineries for the field
survey, was degree of treatment provided by their waste water treatment
facilities. Therefore, the selection of plants was not based on a
cross-section of the entire industry, but rather was biased in favor of
those segments of the industry that had the more efficient waste water
treatment facilities. Table 2k indicates the types of treatment
technology and performance characteristics which were observed during
the survey* In most of the plants analyzed, some type of biological
treatment was utilized to remove dissolved organic material<, Table 25
summarizes the expected effluents from waste water treatment processes
throughout the petroleum refining industry. Typical efficiencies for
these processes are shown in Table 26,
During the survey program, waste water treatment plant performance
history was obtained when possible., This historical data were analyzed
statistically and the individual plant°s performance evaluated in
comparison to the original design basiSo After this evaluation, a group
of plants was selected as being exemplary and these plants were
presented in Table 24„ The treatment data in Table 26 represent the
annual daily average performance (50 percent probabilityof-^occurrence) 0
There were enough plants involving only one subcategory to make the
interpretation meaningful. In preparing the economic data base,
however,, all the waste water treatment plant data ware analyzed to
Jlop a basis for subsequent capital and operating costs„
The treatment data from the exemplary plants referred to previoulsy were
analyzed to formulate the basis for developing BPCTCA effluent criteria.
The effluent limitations were based on both these treatment data, other
data included in Supplement B, and other sources as discussed in section
IXo These effluent limitations were developed for each subcategory
individually and thus no common treatment efficiency was selected as
being typical of the petroleum refining industry for use in the BPCTCA
effluent limitations„ A brief description of the various elements of
end~of°pipe treatment follows.
Equalization
The purpose of equalization is to dampen out surges in flows and
loadings. This is especially necessary for a biological treatment
plant, as high concentrations of certain materials will upset or
completely kill the bacteria in the treatment plant. By evening out the
loading on a treatment plant, the equalization step enables the
treatment plant to operate more effectively and with fewer maintenance
problems. Where equalization is not present, an accident or spill
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Observed Refinery Treatment System and Effluent Loadings
SUBCATEGORY A B-l
Type of OP AL-PP
Treatment
Refinery R32 R18
Observed Average
Effluent Loadings
Net-kg/1000 m3 of
feedstock
(lb/1000 bbl of
feedstock)
BODS 8(2.8)
COD 39(13.8)
TCC ___ _ _
O&G 2.0(0.7) 2.3(0.8)
NH3-N
Phenolic
Compounds 0.14(0.05) 0.003(0.001)
Footnotes: AL-aerated lagoon
AS-activated sludge
DAF-dlssolved air flotation
E-equallzatlon
O
oo
B-2 B-2
TABLE 24
B-2 B-2
AL-F E-DAF-AS OP DAF.AL.PP
R27 R26 R7
8.0(4.4) 5.9(2.1)
68(24) 96(34)
25(8.7) 34(12)
9(3.2) 4.0(1.4)
0.4(0.145) 0.37(0.13)
0.2(0.07) 0(0)
10(3.6) 3.7(1.3)
71(25.0) 39(13.8)
8.5(3.0) 4.2(1.5)
2.8(1.0)
4.8(1.7) 0.14(0.05)
0.05(0.018) 0.0006
(0.002)
0.03(0.010) 0.014
(0.005)
F-flltratlon A-Topplng
OP-oxldatlon pond B-l-Low cracking
FP-polishing pond B-2-Hlgh-Cracklng
TF-trlckllng filter C-Petrochemlcal
C C C
DAF.AS DAF.AS DAF.AL.PP
R20 R8 R23
13(4.6) 2.7(0.95) 2.6(0.91)
67(23.5) 54(19)
13.6(4.8) 8.5(3.0) 7(2.5)
6.5(2.3)
4.5(1.6) 2(0.7)
0.06
(0.023)
OAC __ _ _____
(0.018)
D-Lube
E-Integrated
DDE
E.TF.AS E.AS DAF.AS.PP
R24 R28 R25
7.4(2.6) 14(5.0) 17.5(6.2)
57(20) 136(48) 320(113)
12(4.3) 38(13.5) 36(12.7)
4(1.4) 7.2(2.55) 22(7.7)
1.2(0.44) 2.3(0.8)
0.17(0.06) 0.017(0.003)
_____ __ ___ o ?n f ri7 ^
— — — U. £Ul( vt J
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TABLE 25
Expected Effluents from Petroleum Treatment Processes
EFFLUENT CONCENTRATION
PROCESS
1
2
3
1»
5
6
7.
8.
9.
0.
1.
2.
. API Separator
. Clarifier
. Dissolved Air
Flotation
. Granular Media
Filter
. Oxidation Pond
. Aerated Lagoon
Activated Sludge
Trickling Filter -
Cooling Tower
Activated Carbon
Granular Media Filter
Activated Carbon
PROCESS
INFLUENT
Rav Waste
1
1
1
1
2,3,1*
2,3,1*
1
2,3,1*'
2.3.U
5-9
5-9 and 11
BOD5
250-350
1* 5-200
U5-200
l»0-170
10-60
10-50
5-50
25-50
25-50
5-100
NA
3-10
COD
260-700
130-1*50
130-1*50
100-1*00
50-300
50-200
30-200
80-350
1*7-350
30-200
NA
30-100
TOC
NA
NA
NA
NA
NA
NA
20-80
NA
70-150
NA
25-61
1-17
ss
50-200
25-60
25-60
-5-25
20-100
10-80
5-50
20-70
1*. 5-100
10-20
3-20
1-15
^ mg/L
OIL
20-100
5-35
5-20
6-20
1.6-50
5-20
1-15
10-80
20-75
2-20
3-17
0.8-2.5
PHENOL
6-100
10-1*0
10-1*0
3-35
0.01-12
0.1-25
0.01-2.0
0.5-10
.1-2.0
<1
0.35-10
0-0.1
AMMOHIA
15-150
NA
NA
NA
3-50
l»-25
1-100
25-100
1-30
10-11*0
NA
1-100
SULFIDE
NA
NA
NA
NA
0-20
0-0.2
0-0.2
0.5-2
NA
NA
NA
0-0.2
REFERENCES
7,13,30,1*1,1*9,59
3l*,l*8a,l*9
13,29,32,l»8a,l*9
17»l»l,l»8a,l*8
18,22,23,31,1»2,1»8»,
1»9,55,75,R18
31,39,l*2a,l*8a,l*9,
55,59,R7,R23,R26
13, 21* ,27, 30, 31), 35,
l*2,l»8a,l»9,6o,69,72
R8,R20,R2l*,R25,R27
R28.R29
I8,30,l*2,l*8a,l»9>
33,1*1
17 ,21,27 ,l*8,l*8a, 1*9.
53,62a
IT.W.SU
17,21,27,1*8,l*8a,l*9,
e •* ^r»_
A - Data Not Available
O
\f>
-------
TABLE 26
Typical Removal Efficiencies for Oil Refinery Treatment Processes
PROCESS
1.
2.
3.
1*.
5.
6.
7.
8.
9.
10
10.
11.
12.
API Separator
Clarifier
Dissolved Air
Flotation
Filter
Oxidation Pond
Aerated Lagoon
Activated Sludge
Trickling
Filter
Cooling Tower
Activated
Carbon
Filter
Granular Media
Activated
Carbon
PROCESS
INFLUENT BODc;
Raw Waste 5-1*0
1 ' . 30-60
1 20-70
1 1*0-70
1 1*0-95
2,3,1* -75-95
2,3,1* 80-99
1 60-85
2,3,1* 50-90
2,3,1* 70-95
5-9 NA
5-9- plus 11 91-98
REMOVAL EFFICIENCY. %
COD
5-30
20-50
10-60
20-55
30-65
60-85
50-95
30-70
1*0-90
70-90
NA
86-91*
TOC
NA
NA
NA
NA
60
NA
1*0-90
NA
10-70
50-80
50-65
50-80
SS
10-50
50-80
50-85
75-95
2"0-70
1*0-65
60-85
60-85
50-85
60-90
75-95
60-90
OIL
60-99
60-95
10-85
65-90
50-90
70-90
80-99
50-80
60-75
75-95
65-95
70-95
PHENOL
0-50
0-50
10-75
5-20
60-99
90-99
95-99+
70-98
75-99+
90-100
5-20
90-99
AMMONIA
NA
NA
NA
NA
0-15
10-1*5
33-99
15-90
60-95
7-33
NA
33-87
SULFIDE
NA
NA
NA
NA
70-100
95-100
97-100
70-100
NA
NA
NA
NA
REFERENCES
7, 13 ,30 ,1*1 ,1*9 ',59
3l*,l*8a,l»9
13,29>32>l*8a,l*9
17,ltl,l*8a,l*9
18,22,23,31,1*2,1*8
1*9 ,55 ,75 ,R18
31,39,l*2,l*8a,l*9,
55,59,R7,R23,R26
13, 21*^7,30,3!*, 35
1*2, U8a, 1*9 ,60 ,69 ,7 2
R8,R20,R2l*,R25,R2
R28,R29
I8,30,l*2,l*8a,l*9
33,1*1
17,21,27,l*8,l*8a,l*9
l*9,53,62a
17,1*8,51*
17,21,27,l*8,l*8a,
l»9,53,62a
NA - Data Hot Available
-------
within the refinery can greatly affect the effluent quality or kill the
biomass (R7, R20) .
«e equalization step usually consists of a large pond that may contain
xers to provide better mixing of the wastes. In some refineries the
equalization is done in a tank (55, R29). The equalization step can be
before or after the gravity separator but is more effective before as it
increases the overall efficiency of the separator. However, care must
be taken to prevent anaerobic decomposition in the equalization
facilities.
Dissolved Air Flotation
Dissolved air flotation consists of saturating a portion of the waste
water feed, or a portion of the feed or recycled effluent from the
flotation unit with air at a pressure of 40 to 60 psig. The waste water
or effluent recycle is held at this pressure for 1-5 minutes in a
retention tank and then released at atmospheric pressure to the
flotation chamber. The sudden reduction in pressure results in the
release of microscopic air bubbles which attach themselves to oil and
suspended particles in the waste water in the flotation chamber. This
results in agglomerates which, due to the entrained air, have greatly-
increased vertical rise rates of about 0.5 to 1.0 feet/minute. The
floated materials rise to the surface to form a froth layer. Specially
designed flight scrapers or other skimming devices continuously remove
the froth. The retention time in the flotation chambers is usually
about 10-30 minutes. The effectiveness of dissolved air flotation
Depends upon the attachment of bubbles to the suspended oil and other
which are to be removed from the waste stream. The attraction
the air bubble and particle is a result of the particle surface
and bubble-size distribution.
Chemical flocculating agents, such as salts of iron and aluminum, with
or without organic polyelectrolytes, are often helpful in improving the
effectiveness of the air flotation process and in obtaining a high
degree of clarification.
Dissolved air flotation is used by a number of refineries to treat the
effluent from the oil separator. Dissolved air flotation using
flocculating agents is also used to treat oil emulsions. The froth
skimmed from the flotation tank can be combined with other sludges (such
as those from a gravity separator) for disposal. The clarified effluent
from a flotation unit generally receives further treatment in a
biological unit, prior to discharge. In two refineries, dissolved air
flotation is used for clarification of biologically treated effluents
(29).
Oxidation Ponds
111
-------
The oxidation pond is practical where land is plentiful and cheap.g An
oxidation pond has a large surface area and a shallow depth, usually not
exceeding 6 feet. These ponds have long detention periods from 1
110 days.
The shallow depth allows the oxidation pond to be operated aerobically
without mechanical aerators. The algae in the pond produce oxygen
through photosynthesis. This oxygen is then used by the bacteria to
oxidize the wastes. Because of the low loadings, little biological
sludge is produced and the pond is fairly resistant to uspsets due to
shock loadings.
Oxidation ponds are usually used as the major treatment process. Some
refineries use ponds as a polishing process after other treatment
processes.
Aerated Lagoon
The aerated lagoon is a smaller, deeper oxidation pond equipped with
mechanical aerators or diffused air units. The addition of oxygen
enables the aerated lagoon to have a higher concentration of microbes
than the oxidation pond. The retention time in aerated lagoons is
usually shorter, between 3 and 10 days. Most aerated lagoons are
operated without final clarification. As a result, biota is discharged
in the effluent, causing the effluent to have high BOD5 and solids
concentrations. As the effluent standards become more strict, final
clarification will be increasing in use.
Trickling Filter
A trickling filter is an aerobic biological process. It differs from
other processes in that the biomass is attached to the bed media, which
may be rock, slag, or plastic. The filter works by: 1) adsorption of
organics by the biological slime 2) diffusion of air into the biomass;
and 3) oxidation of the dissolved organics. When the biomass reaches a
certain thickness, part of it sloughs off. When the filter is used as
the major treatment process, a clarifier is used to remove the sloughed
biomass.
The trickling filter can be used either as the complete treatment system
or as a roughing filter. Most applications in the petroleum industry
use it as a roughing device to reduce the loading on an activated sludge
system.
Bio-Oxidation Tower
The bio-oxidation tower uses a cooling tower to transfer oxygen to a
waste water. API (112) has called the bio-oxidation towers a modified
activated sludge process, as most of the biomass is suspended in the
112
-------
wastewater. Results from refineries indicate it is a successful process
to "treat portions or all of a refinery waste water (80, 81, 92) .
Activated Sludge
Activated sludge is an aerobic biological treatment process in which
high concentrations (1500-3000 mg/L) of newly-grown and recycled
microorganisms are suspended uniformly throughout a holding tank to
which raw waste waters are added. Oxygen is introduced by mechanical
aerators, diffused air systems, or other means. The organic materials
in the waste are removed from the aqueous phase by the microbiological
growths and stabilized by biochemical synthesis and oxidation reactions.
The basic activated sludge process consists of an aeration tank followed
by a sedimentation tank. The flocculant microbial growths removed in
the sedimentation tank are recycled to the aeration tank to maintain a
high concentration of active microorganisms. Although the
microorganisms remove almost all of the organic matter from the waste
being treated, much of the converted organic matter remains in the
system in the form of microbial cells. These cells have a relatively
high rate of oxygen demand and must be removed from the treated waste
water before discharge. Thus, final sedimentation and recirculation of
biological solids are important elements in an activated sludge system.
Sludge is wasted on a continuous basis at a relatively low rate to
prevent build-up of excess activated sludge in the aeration tank. Shock
rganic loads usually result in an overloaded system and poor sludge
ttling characteristics. Effective performance of activated sludge
cilities requires pretreatment to remove or substantially reduce oil,
sulfides (which causes toxicity to microorganisms), and phenol
concentrations. The pretreatment units most frequently used are:
gravity separators and air flotation units to remove oil; and sour water
strippers to remove sulfides, mercaptans, and phenol. Equalization also
appears necessary to prevent shock loadings from upsetting the aeration
basin. Because of the high rate and degree of organic stabilization
possible with activated sludge, application of this process to the
treatment of refinery waste waters has been increasing rapidly in recent
years.
Many variations of the activated sludge process are currently in use.
Examples include: the tapered aeration process, which has greater air
addition at the influent where the oxygen demand is the highest; step
aeration, which introduces the influent waste water along the length of
the aeration tank; and contact stabilization, in which the return sludge
to the aeration tank is aerated for 1-5 hours. The contact
stabilization process is useful where the oxygen demand is in the
suspended or colloidal form. The completely mixed activated sludge
plant uses large mechanical mixers to mix the influent with the contents
of the aeration basin, decreasing the possibility of upsets due to shock
113
-------
loadings. The Pasveer ditch is a variation of the completely m,ixed
activated sludge process that is widely used in Europe. Here brushes
are used to provide aeration and mixing in a narrow oval ditch.
advantage of this process is that the concentration of the biota
higher than in the conventional activated sludge process, and the waste
sludge is easy to dewater. There is at least one refinery using the
Pasveer ditch type system.
J1CO
The activated sludge process has several disadvantages. Because of the
amount of mechanical equipment involved, its operating and maintenance
costs are higher than other biological systems. The small volume of the
aeration basin makes the process more subject to upsets than either
oxidation ponds or aerated lagoons.
As indicated in Table 25, the activated sludge process is capable of
achieving very low concentrations of BOD5, COD, TSS, and oil, dependent
upon the influent waste loading and the particular design basis.
Reported efficiencies for BODS removal are in the range of 80 to 99
percent.
Physical-Chemical Treatment
Physical-chemical treatment refers to treatment processes that are non-
biological in nature. There are two types of physical-chemical
processes; those that reduce the volume of water to be treated (vapor
compression evaporators, reverse osmosis, etc.) , and those that reduce
the concentration of the pollutants (activated carbon) .
Physical-chemical (P-C) processes reguire less land than
processes. P-C processes are not as susceptible to upset due to
loading as are biological processes. Another advantage of P-C is that
much smaller amounts of sludge are produced.
Flow Reduction Systems
Flow reduction systems produce two effluents, one of relatively pure
water and one a concentrated brine. The pure water stream can be reused
within the refinery resulting in a smaller effluent flow. The brine is
easier to treat as it is highly concentrated. Both of the processes
described herein have been demonstrated on small flows only and at
present the costs involved are extremely high (45, 52, 93) .
In the vapor compression evaporator the waste water flows over heat
transfer surfaces. The steam generated enters a compressor where the
temperature is raised to a few degrees above the boiling point of the
waste water. The compressed steam is used to evaporate more waste water
while being condensed. The condensed steam is low in dissolved solids.
The major process costs are the costs of electrical power, which is
approximately $1.0/1000 gallons of clean water (93).
114
-------
The^everse osmosis process uses high pressures (400-800 psig) to force
water through a semi-permeable membrane. The membrane allows the water
«pass through, but contains the other constituents in the waste water.
rrently available membranes tend to foul and blind, requiring frequent
eaning and replacement. Until this problem is corrected, reverse
osmosis is not a practicable process. The operating cost for a reverse
osmosis unit is approximately 20-300/1000 gallons (45, 95).
Granular Media Filters
There are several types of granular media filters: sand, . dual media,
and multimedia. These filters operate in basically the same way, the
only difference being the filter media. The sand filter uses relatively
uniform grade of sand resting on a coarser material. The dual media
filter has a course layer, of coal above a fine layer of~-sai3d. Both
types of filters have the problem of keeping the fine particles on - the
bottom. This problem is solved by using a third very heavy, very fine
material, (usually garnet) beneath the coal and sand.
As the water passes down through a filter, the suspended matter is
caught in the pores. When the pressure drop through the filter becomes
excessive, the flow through the filter is reversed for removal of the
collected solids loading. The backwash cycle occurs approximately once
a day, depending on the loading, and usually lasts for 5-8 minutes.
Most uses of sand filters have been for removing oil and solids prior to
an activated carbon unit. There is one refinery that uses a mixed media
on the effluent from a biological system. Granular media filters
shown to be capable of consistently operated with extremely low TSS
oil effluent discharges, on the order of 5-10 mg/L.
Activated Carbon
The activated carbon (AC) process utilizes granular activated carbon to
adsorb pollutants from waste water. The adsorption is a function of the
molecular size and polarity of the adsorbed substance. Activated carbon
preferentially adsorbs large organic molecules that are non-polar.
An AC unit follows a solids removal process, usually a sand filter which
prevents plugging of the carbon pores. From the filter the water flows
to a bank of carbon columns arranged in series or parallel. As the
water flows through the columns the pollutants are adsorbed by the
carbon, gradually filling the pores. At intervals, portions of the
carbon are removed to a furnace where the adsorbed substances are burnt
off. The regenerated carbon is reused in the columns, with some makeup
added, because of handling and efficiency losses.
Activated carbon processes currently have only limited usage in the
refining industry. However, there are new installations in the planning
construction stages. The increasing use of activated carbon has occured
115
-------
because activated carbon can remove organic materials on an economically
competitive basis with biological treatment. Activated carbon
regeneration furnaces have high energy requirements.
Sludge Handling and Disposal
Digestion
Digestion is usually used preceding the other sludge concentration and
disposal methods. The purpose of digestion is to improve the dewatering
of the sludge. Digestion can occur aerobically or, anaerobically.
During digestion, bacteria decompose the organic material in the sludge
producing methane, carbon dioxide and water. At the end of the
digestion process, the sludge is stable and non-decomposable.
Vacuum Filtration
The various vacuum filters, usually a revolving drum, use a vacuum to
dewater the sludge. The revolving drum type has a vacuum applied
against a cloth. The water passes through the cloth and returns to the
influent of the treatment plant. The sludge remains on the drum until
it is scraped off with a knife.
Centrifugation
Centrifugation uses high speed rotation to separate sludge and water.
The heavier sludge moves to the outside and is conveyed to one end,
where it is collected for final disposal. The water flows out
opposite end and is returned to the treatment plant.
Sludge Disposal
From any waste water treatment plant, the sludge must be disposed of.
The methods used are landfilling, landfarming, barging to sea, and
incineration.
Landfilling
A landfill operation requires a large amount of land. Before
landfilling, the sludge should be digested to avoid odor problems. The
sludge is disposed of in an excavation site. After each batch is
disposed of, it is covered with a layer of earth. When the site is
filled to capacity it is covered with a thick layer of earth.
The largest problem of industrial landfills is the pollution to ground
and surface waters by leaching. Leaching occurs when water percolates
through the landfill. As it drains through the landfill site, the water
carries with it dissolved and suspended solids and organic matter. This
water can then contaminate underground or surface streams it comes in
contact with.
116
-------
.Incineration
«cineration is gradually complementing landfills as a method of sludge
sposal. The principal process is fluid bed incineration. In this
ocess, a bed of sand is preheated with hot air to 482-538°C (900 -
1000°F). Torch oil is then used to raise the bed temperature to 649
705°C (1200 - 1300°F). At this point waste water sludge and/or sludge
is introduced and the torch oil is stopped. The solid products of
combustion remain in the bed which is a gradually withdrawn to maintain
a constant bed height. Eventually, the bed will be composed of only
ash.
The sludge fed to the incinerator usually contains inorganic as well as
organic material. However, the sludge must contain a minimum amount of
organics to maintain the combustion process. One refinery (26) suggests
a minimum of 1,930,000 cal/cu m (29,000 Btu/gal) of sludge heating value
is necessary to maintain the combustion process.
117
-------
SECTION VIII
COST, ENEBGY, AND NON-WATER QUALITY ASPECTS
The first part of this section summarizes the costs (necessarilly
generalized) and effectiveness of end-of-pipe control technology for
BPCTCA and BATEA and BADT-NSPS effluent limitations. Treatment costs
for small, medium, and large refineries in each subcategory have been
estimated for the technologies considered. The expected annual costs
for existing plants in the petroleum refining industry in 1977
consistent with BPCTCA effluent limitations are estimated at $225
million (end-of-pi'pe treatment only) . For 1983, consistent with BATEA
effluent limitations, the estimated additional annual costs are
estimated at $250 million (end-of-pipe treatment only) . For BADT-NSPS
the annual cost is estimated at $26 million. These costs are summarized
by subcategory in Table 27.
The effect of plant size relative to annual costs can be seen in Table
28 where the annual costs are summarized for application of BPCTCA and
BATEA to small, medium, and large refineries in each subcategory. The
cost, energy, and nonwater quality aspects of in-plant controls are
intimately related to the specific processes for which they are
developed. Although there are general cost and energy requirements for
equipment items (e.g. surface air coolers), these correlations are
usually expressed in terms of specific design parameters, such as the
Juired heat transfer area. Such parameters are related to the
duction rate and specific situations that exist at a particular
production site.
There is a wide variation in refinery sizes. When these size ranges are
superimposed on the large number of processes within each subcategory,
it is apparent that many detailed designs would be required to develop a
meaningful understanding of the economic impact of process
modifications. The decision to attain the limitations through in-plant
controls or by end-of-pipe treatment should be left up to individual
manufacturers. Therefore, a series of possible designs for the end-of•»
pipe treatment models is provided.
Alternative Treatment Technologies
The range of components used or needed for either best practicable or
best available technology have been combined into five alternative
end-of-pipe treatment steps, which are as follows:
A. Initial treatment, consisting of dissolved air flotation,
equalization, neutralization, and nutrient (phosphoric acid) feed
facilities.
119
-------
TABLE 27
Estimated Total Annual Costs for End-of-Pipe Treatment
Systems for the Petroleum Refining Industry (Existing Refineries)
Sub category TotaJ Annual Cost, $ Million
1977 1983
Topping $1^.2 $16.5
•jq fl kk k
Low-Cracking ^'° HH'H
High-Cracking ^5-5 **8.l
Petrochemical 53'9 5°-°
Lube 70.1 66-. 2
Integrated 35.3 2^.8
Industry Total $255.0 $250.0
120
-------
TABLE 28
Summary of End-of Pipe Wastewater Treatment Costs for
Representative Plants in the Petroleum Refining Industry
Subcategory
Representative
Refinery Size
Annual
Level.I Costs
$/1000 m3 $/1000 gal
Annual Additional
Level 11 Costs
$/1000 m3 $/1000 gal
Topping
Low-Cracking
High Cracking
Lube
Integrated
1000 m3/day
0.318
1.11
2.4
2.4
5.09
11.9
10.18
23.8
Petrochemical 4.0
15.9
31.8
17.5
39.8
9.8
23.0
1000 BBL/day
2
7
15
15
32
75
25
6k
150
25
100
200
25
110
250
65
152
326
0.066
0.030
0.018
0.014
0.010
0.007
0.009
0.007
0.006
0.009
0.007
0.005
0.009
0.006
0.005
0.006
0.005
0.005
17.
7.
4.
3.
2.
1.
2.
1.
.31
,86
,87
,78
,53
,84
,34
,84
.62
1.32
.78
.35
J.33
.50
.25
1.6?
1.28
,1.13
0.070
0.034
0.023
0.019
0.012
0.008
0.013
0.008
0.006
0.010
0.006
0.005
0.010
0.006
0.004
0.006
0.005
0.003
18.41
9.06
5.97
4.90
3.25
2.20
3.40
2.16
1.47
2.65
1.63
1.20
2.57
1.51
0.93
1.53
1.05
0.65
121
-------
B. Biological treatment, consisting of acitvated sludge units,
thickness, digesters, and dewatering facilities.
C. Granular media filtration, consisting of filter systems
associated equipment.
D. Physical-chemical treatment facilities consisting of activated
carbon adsorption.
E. Alternative Biological treatment, consisting of aerated lagoon
facilities.
Tables 29 through 46 are summaries of the costs of major treatment steps
required to achieve different levels of technology for small, medium,
and large refineries in each subcategory; using median raw waste loads
and median "good water use" flow rates, for the end-of-pipe treatment
models.
BPCTCA Treatment Systems used for the Economic Evaluation
A general flow schematic for the BPCTCA waste water treatment facilities
is shown in Figure 6. A summary of the general design basis is
presented in Table 47 and a summary of the treatment system effluent
limitations for each subcategory is presented in Table 1.
BATEA treatment Systems Used for the Economic Evaluation
BATEA treatment facilities are basically added on to the discharge
from BPCTCA facilities. It is expected that flows will be
slightly by the application of BATEA in-plant technology, so that the
activated carbon treatment unit may treat a smaller hydraulic load.
However, the activated carbon system was sized for the same flow basis
as in BPCTCA technology in order to establish a conservative basis for
economic evaluation of proposed effluent limitations.
A general flow schematic diagram for the BATEA waste water treatment
facilities is shown in Figure 7. A summary of the general design basis
is presented in Table 48. and a summary of the treatment system
effluent limitations for each subcategory is presented in Table 2.
122
-------
TABLE 29
WATER EFFLUENT TREATMENT COSTS
PETROLEUM REFINING INDUSTRY
TOPPING SUBCATEGORY
Refinery Capacity
1000 cubic meters/day (1000 BBL/DAY)
Wastewater Flow
cubic meters/cublic metric crude oil (gal/bbl)
Treatment Plant Size
1000 cubic meters/day
Costs in $1000
Initial Investment
ANNUAL COSTS:
Capital Costs (10%)
Depreciation (20%)
Operating Costs
Energy
Total Annual Costs
Effluent Quality
0.318 (2)
0.286 (12)
0.091 (0.025)
Alternative Treatment Steps
A
183
13
155
£
52
70.5
66.7
20.8
BOD5
COD
Oil/Grease
Phenol
Sulfide
Ammonia
Suspended Solids
Raw Waste
Load ...,
Kg/1000 mj (LB/1000 BBL)
7.1 (2.5)
24.0 (8.4)
5.1 (1.8)
0.028 (0.01)
0.157 (0.055)
1.43 (0.5)
6.6 (2.5)
Resulting Effluent Levels
D
295
18.3
36.6
14.6
1.0
15.5
31.0
12.4
7.8
5.2
10.4
4.2
1.0
30
59
72.5
6.5
168.0
iBL)
4.3
16.0
2.0
0.03
0.03
1.0
5.8
£ P.
0.82
2.34
1.4 0.17
0.003
0.017
0.23
2.9 0.82
123
-------
TABLE 30
WATER EFFLUENT TREATMENT COSTS
PETROLEUM REFINING INDUSTRY
TOPPING SUBCATEGORY
Refinery Capacity
1000 cubic meters/day (1000 BBL/DAY)
Wastewater Flow
cubic meters/cubic meter crude oil (gal/bbl)
Treatment Plant Size
1000 cubic meters/day (MGD)
Costs in $1000
Initial Investment
ANNUAL COSTS:
Capital Costs (10%)
Depreciation (20%)
Operating Costs
Energy
L/bbl]
A
282
28
56
23
2
1.11
I 0.286
0.32
Alternative
B
238
24
48
19
12
(7)
(12)
(0.085)
Treatment
C
80
8
16
6
2
Steps
D
612
61
122
89
9
Total Annual Costs
109
103
32
281
Effluent Quality
Raw Waste Resulting Effluent Levels
Load Design Average Kg/1000 m^
BOD5
COD
Oil/Grease
Phenol
Sulfide
Ammonia
Suspended Solids
Kg/1000 m3
7.1 (2.5)
24.0 (8.4)
5.1 (1.8)
0.028 (0.01)
0.157 (0.055)
1.43 (0.5)
6.6 (2.3)
(LB/1000BBL)
B_ C
4.3
16.0
2.0 1.4
0.03
0.03
1.0
5.8 2/9
D
0.82
2.34
0.17
0.003
0.017
0.23
0.82
124
-------
TABLE 31
WATER EFFLUENT TREATMENT COSTS
PETROLEUM REFINING INDUSTRY
TOPPING SUBCATEGORY
Refinery Capacity
1000 cubic meters/day (1000 BBL/DAY)
Wastewater Flow
cubic meters/cubic meter crude oil (gal/bbl)
Treatment Plant Size
1000 cubic meters/day
Costs in $1000
Initial Investment
ANNUAL COSTS:
Capital Costs (10%)
Depreciation (20%)
Operating Costs
Energy
(MGD)
2.4 (15)
0.286 (12)
0.68 (0.18)
Alternative Treatment Steps
A
341
34
68
28
3
B_
318
32
64
26
19
£
114
11
23
17
2
D
' 943
94
187
101
10
Total Annual Costs
133
141
46
392
Effluent Quality
Raw Waste
Load
Resulting Effluent Levels
BOD 5
COD
Oil/Grease
Phenol
Sulflde
Ammonia
Suspended Solids
7.1 (2.5)
24.0 (8.4)
5.1 (1.8)
0.028 (0.01)
0.157 (0.055)
1.43 (0.5)
6.6 (2.3)
B
4.3
16.0
2.0
0.03
0.03
1.0
5.8
£ D
0.82
2.34
1.4 0.17
0.003
0.017
0.23
2.9 0.82
125
-------
TABLE 32
WATER EFFLUENT TREATMENT COSTS
PETROLEUM REFINING INDUSTRY
LOW CRACKING SUBCATEGORY
Refinery Capacity
1000 cubic meters/day (1000 BBL/DAY)
Wastewater Flow
cubic meters/cubic meter crude oil (gal/bbl)
Treatment Plant Size
1000 cubic meters/day
(MGD)
2.4 (15)
0.405 (17)
0.97 (0.26)
Costs in $1000
Initial Investment
ANNUAL COSTS:
Capital Costs (10%)
Depreciation (20%)
Operating Costs
Energy
Alternative Treatment Steps
Effluent Quality
BOD
COD
Oil/Grease
Phenol
Sulfide
Ammonia
Suspended Solids
A
368
37
74
29
2
£
375
38
75
30
21
£
133
13
26
11
3
£
1.164
116
233
106
10
Total Annual Costs
142
164
53
465
Raw Waste
Load-,
Resulting Effluent Levels
(Design Average Kg/1000 m3)
Kg/1000 m (LB/1000 BBL7
71 (25)
200 (70)
27.4 (9.6)
2.85 (1.0)
1.0 (0.35)
10.0 (3.5)
27.4 (9.6)
.;
B
6.0
39.1
2.8
0.04
0.03
2.0
8.0
C D
1.31
8.0
2.0 0.26
0.006
0.026
0.51
4.0 1.31
126
-------
TABLE 33
WATER EFFLUENT TREATMENT COSTS
PETROLEUM REFINING INDUSTRY
LOW CRACKING SUBCATEGORY
Refinery Capacity
1000 cubic meters/day (1000 BBL/DAY)
Wastewater Flow
cubic meters/cubic meter crude oil (gal/bbl)
Treatment Plant Size
meters/day
(MGD)
5.09 (32)
0.405 (17)
2.06 (0.54)
Costs in $1000
Initial Investment
ANNUAL COSTS:
Capital Costs (10%)
Depreciation (20%)
Operating Costs
Energy
Alternative Treatment Steps
A
487
49
98
39
3
B_
548
54
109
44
31
C
179
18
36
14
4
D
1,164
177
354
94
15
Total Annual Costs
189
238
64
640
Effluent Quality
Raw Waste Resulting Effluent Levels
Load , (Design Average Kg/lOOti m3)
Kg/1000 m 3(LB/1000 BELT
BUUc
COD
Oil/Grease
Phenol
Sulfide
Ammonia
71 (25)
200 (70)
27.4 (9.6)
2.85 (1.0)
1.0 (0.35)
10.0 (3.5)
Suspended Solids 27 A (9 6}
L;
B_
6.0
39.1
2.8
0.04
0.03
2.0
8.0
£ P_
1.31
8.0
2.0 0.26
0.006
0.026
0.51
4.0 1.31
127
-------
TABLE 34
WATER EFFLUENT TREATMENT COSTS
PETROLEUM REFINING INDUSTRY
LOW CRACKING SUBCATEGORY
Refinery Capacity
1000 cubic meters/day (1000 BBL/DAY)
Wastewater Flow
cubic meters/cubic meter crude oil (gal/bbl)
Treatment Plant Size
1000 cubic meters/day
(MGD)
11.9 (75)
0.405 (17)
4,8 (1.3 MGD)
Costs in $1000
Initial Investment
ANNUAL COSTS:
Capital Costs (10%)
Depreciation (20%)
Operating Costs
Energy
Alternative Treatment Steps
A
787
79
158
64
8
B
1062
106
212
86
59
C
231
25
50
20
7
D
2^895
290
579
152
25
Total Annual Costs
Effluent Quality
BOD 5
COD
Oil/Grease
Phenol
Sulfide
Ammonia
Raw Waste Resulting Effluent Levels
Load (Design Average Kg/1000 M3)
Kg/1000 m J(LB/1000 BBLf
71 (25)
200 (70)
27.4 (9.6)
2.85 (1.0)
1.0 (0.35)
10.0 (3.5)
Suspended Solids 27.4 (9.6)
<)
B_
6.0
39.1
2.8
0.04
0.03
2.0
8.0
C D
1.31
8.0
, 2.0 0.26
0.006
0.026
0.51
4.0 1.31
128
-------
TABLE 35
WATER EFFLUENT TREATMENT COSTS
PETROLEUM REFINING INDUSTRY
HIGH CRACKING SUBCATEGORY
Refinery Capacity
1000 cubic meters/day (1000 BBL/DAY)
Wastewater Flow
cubic meters/cubic meter crude oil (gal/bbl)
Treatment Plant Size
1000 cubic meters/day
Costs in $1000
Initial Investment
ANNUAL COSTS:
Capital Costs (10%)
Depreciation (20%)
Operating Costs
Energy
(MGD)
4.0
0.5
2.0
(25)
(21)
(0.525)
Alternative Treatment Steps
A
443
44
89
36
4
IJ
470
47
94
38
29
•c
170
17
34
13
4
D_
1,720
172
344
121
15
Total Annual Costs
173
208
68
652
Effluent Quality
Raw Waste
Resulting Effluent Levels
Load (Design Average Kg/1000 m3)
Kg/1000 m3 (LB/1000 BBfc) -
BOD
COD
Oil/Grease
Phenol
Sulfide
Ammonia
Suspended Solids
83 (29)
260 (91)
31.4 (11)
5.1 (1.8)
1.28 (0.45)
32.8 (11.5)
32.2 (11.3)
ci
:B
8.9
68.0
3.5
0.05
0.05
4.5
10.2
£ D
1.65
12.8
2.5 0.34
0.006
0.034
1.65
5.1 1.65
129
-------
TABLE 36
WATER EFFLUENT TREATMENT COSTS
PETROLEUM REFINING INDUSTRY
HIGH CRACKING SUBCATEGORY
Refinery Capacity
1000 cubic meters/day (1000 BBL/DAY)
Wastewater Flow
cubic meters/cubic meter crude oil (gal/bbl)
Treatment Plant Size
1000 cubic meters/day
Costs in $1000
Initial Investment
ANNUAL COSTS:
Capital .Costs (10%)
Depreciation (20%)
Operating Costs
Energy
(MGD)
10.18 (64)
0.500 (21)
5.09 (1.35)
Alternative Treatment Steps
A
817
82
164
67
9
B
1,105
110
221
90
59
C
261
26
52
21
8
D
2,950
295
590
155
25
Total Annual Costs
322
480
107 1,065
Effluent Quality
Raw. Waste
Load
Resulting Effluent Levels
(Design Average Kg/1000
BOD5
COD
Oil/Grease
Phenol
Sulfide
Ammonia
Suspended Solids
Kg/1000 m J(LB/1000 BBL)
83 (29)
260 (91)
31.4 (11.0)
5.1 (1.8)
1.28 (0.45)
32.8 (11.5)
32.2 (11.3)
.)
1 c.
8.0
68.0
3.5 2.5
0.51
0.05
4.5
10.2 5.1
D
1.65
12.8
0.34
0.006
0.034
0.82
1.65
130
-------
TABLE 37
WATER EFFLUENT TREATMENT COSTS
PETROLEUM REFINING INDUSTRY
HIGH CRACKING SUBCATEGORY
Refinery Capacity
- 1000 cubic meters/day (1000 BBL/DAY)
Wastewater Flow
cubic meters/cubic meter crude oil (gal/bbl)
Treatment Plant Size
1000 cubic meters/day
Costs in $1000
Initial Investment
ANNUAL COSTS:
Capital Costs (10%)
Depreciation (20%)
Operating Costs
Energy
(MGD)
23.8 (150)
0.500 (21)
11.9 (3.2)
Alternative Treatment Steps
A
1.703
140
280
119
17
B
2,763
276
553
236
113
C
3^7
37
74
31
15
D
4,"8~90
489
987
211
44
Total Annual Costs
556
1,178
157 1,722
Effluent Quality
BOD
COD
Oil/Grease
Phenol
Sulfide
Ammonia
Suspended Solids
Raw Waste Resulting Effluent Levels
Load (Design Average Kg/1000 m3)
Kg/1
83
260
31.4
5.1
1.28
32.8
32.2
OOU m~> (LB/J
(29)
(91)
(ID
(1.8)
(0.45)
(11.5)
(11.3)
LOOU BBL/
B
8'.
68.
3.
0.
0.
4.
10.
0
0
5
51
05
5
2
C D
1.65
12.8
2.5 0.34
0.006
0.034
0.82
5.1 1.65
131
-------
TABLE 38
WATER EFFLUENT TREATMENT COSTS
PETROLEUM REFINING INDUSTRY
PETROCHEMICAL SUBCATEGORY
Refinery Capacity
1000 cubic meters/day (1000 BBL/DAY)
Wastewater Flow
cubic meters/cubic meter crude oil (gal/bbl)
Treatment Plant Size
1000 cubic meters/day
Costs in $1000
Initial Investment
ANNUAL COSTS:
Capital Costs (10%)
Depreciation (20%)
Operating Costs
Energy
(MGD)
4.0 (25)
0.595 (25)
2.4 (0.625)
Alternative Treatment Steps
A
495
49
99
39
5
B
595
60
119
48
34
C
190
19
38
15
4
D
1,875
188
375
125
16
Total Annual Costs
192
261
76
604
Effluent Quality
COD
Oil/Grease
Phenol
Sulfide
Ammonia
Suspended Solids
Raw Waste Resulting Effluent Levels
Load (Design Average Kg/1000 m3)
Kg/1000 m (LB/1000 BBL}
148 (52)
371 (130)
45.6 (16)
10.3 (3.6)
1.7 (0.59)
34.2 (12)
44.2 (15.5)
.;
.B
9.1
59.5
4.3
0.065
0.06
6.8
12.0
C D
1.8
7.1
3.1 0.37
0.009
0.054
1.65
6.0 1.8
132
-------
TABLE 39
WATER EFFLUENT TREATMENT COSTS
PETROLEUM REFINING INDUSTRY
. PETROCHEMICAL SUBCATEGORY
Refinery Capacity
1000 cubic meters/day (1000 BBL/DAY)
Wastewater Flow
cubic meters/cubic meter crude oil (gal/bbl)
Treatment Plant Size
1000 cubic meters/day
Costs in $1000
Initial Investment
ANNUAL COSTS:
Capital Costs (10%)
Depreciation (20%)
Operating Costs
Energy
(MGD)
Total Annual Costs
Alternative Treatment Steps
A
1,165
117
233
98
15
B_
2,410
241
482
203
93
C
335
33
67
29
12
D_
4,200
420
840
192
38
463
1,019
141 1,490
Effluent Quality
BOD 5
COD
Oil/Grease
Phenol
Sulfide
\
Ammonia
Suspended Solids
Raw Waste Resulting Effluent Levels
Load . jDesign Average Kg/1000 m
Kg/1000 mj
148 (52)
371 (130)
45.6 (16)
10.3 (3.6)
1.7 (0.59)
34.2 (12)
44.2 (15.5)
(LB/1000 BBL)
B £
9.1
59.05
4.3 3.1
0.065
0.06
6.8
12.0 6.0
p_
1.8
7.1
0.37
0.009
0.054
1.65
1.8
133
-------
TABLE 40
WATER EFFLUENT TREATMENT COSTS
PETROLEUM REFINING INDUSTRY
PETROCHEMICAL SUBCATEGORY
Refinery Capacity
1000 cubic meters/day (1000 BBL/DAY) 31.8 (200)
Wastewater Flow
cubic meters/cubic meter crude oil (gal/bbl) 0.595 (25)
Treatment Plant Size
1000.cubic meters/day (MGD) 18.9 (5.0)
Costs in $1000 Alternative Treatment Steps
Initial Investment A _B CD
1,6"6~2 3,785 4"2~3 67220
ANNUAL COSTS:
Capital Costs (10%) 166 379 42 622
Depreciation (20%) 332- 757 85 1,244
Operating Costs 145 329 37 270
Energy 25 155 20 60
. Total Annual Costs 668 1,620 184 2,196
Effluent Quality
Raw Waste Resulting Effluent Levels
(Design Average Kg/1000
BOD5
COD
Oil/Grease
Phenol
Sulfide
Ammonia
Suspended Solids
;/100(
148
371
45.6
10.3
1.7
34.2
44.2
) mj (LB/100
(52)
(130)
(16)
(3.6)
(0.59)
(12)
(15.5)
0 BBLJ
9
59
4
0
0
6
12
B
.1,
.5
.3
.065
.06
.8
.0
£ D
1
_ 7
3.1 0
0
0
1
6.0 1
.8
.1
.37
.009
.054
.65
.8
134
-------
TABLE 41
WATER EFFLUENT TREATMENT COSTS
PETROLEUM REFINING INDUSTRY
LUBE SUBCATEGORY
Refinery Capacity
1000 cubic meters/day (1000 BBL/DAY) 4.0 (25)
Wastewater Flow
cubic meters/cubic meter crude oil (gal/bbl) 0.881 (37)
Treatment Plant Size
1000 cubic meters/day (MGD) 3.5 (0.925)
Costs in $1000 Alternative Treatment Steps
Initial Investment A B_ C D_
778 895 . 247 2,360
ANNUAL COSTS:
Capital Costs (10%) 78 90 24 236
Depreciation (20%) 156 179 49 472
Operating Costs 62 72 20 139.
Energy 6 47 5 20
Total Annual Costs 302 388 98 867
Effluent Quality
Raw Waste Resulting Effluent Levels
Load .(Design Average Kg/1000 m3)
BOD 5
COD
Oil/Grease
Phenol
Sulfide
Ammonia
spended Solids
000 m
200
382
136
6.2
1.1
227
79
54
3 (LB/1000
(66)
(134)
(38)
(202)
(0.4)
(7.8)
(28)
BBL)
_B
10.3
95.5
6.0
0.088
0.088
4.5
17.6
C D
3.6
23.5
4.3 0.7
0.015
0.073
1.5
8.8 3.55
135
-------
TABLE 42
WATER EFFLUENT TREATMENT COSTS
PETROLEUM REFINING INDUSTRY
LUBE SUBCATEGORY
Refinery Capacity
1000 cubic meters/day (1000 BBL/DAY)
Wastewater Flow
cubic meters/cubic meter crude oil (gal/bbl)
Treatment Plant Size
1000 cubic meters/day
Costs in $1000
Initial Investment
ANNUAL COSTS:
Capital Costs (10%)
Depreciation (20%)
Operating Costs
Energy
(MGD)
17.5 (110)
0.881 (37)
15.4 (4.07)
Alternative Treatment Steps
A
1,501
150
300
129
20
B
3,316
332
663
285
135
C
413
41
83
35
17
D
5,600
560
1,120
236
52
Total Annual Costs
599
1,415
176 1,968,00
Effluent Quality
Raw Waste Resulting Effluent Levels .
Load ^'Design Average Kg/1000 m^)
BOD5
COD
Oil/Grease
Phenol
Sulfide
Ammonia
Suspended Solids
m3 (LB/1000 BBL)
187
382
136
6.2
1.1
22
79
(66)
(134)
(48)
(2.2)
(0.4)
(7.8)
(28)
B C
10.3
95.5
6.0 4.3
0.088
0.088
4.5
8.8
D
3.6
23.5
0.7
0.015
0.073
1.5
3.55
136
-------
TABLE 43
WATER EFFLUENT TREATMENT COSTS
PETROLEUM REFINING INDUSTRY
LUBE SUBCATEGORY
Refinery Capacity
1000 cubic meters/day (1000 BBL/DAY) 39.8 (250)
Wastewater Flow
cubic meters/cubic meter crude oil (gal/bbl) 0.881 (37)
Treatment Plant Size
1000 cubic meters/day (MGD) 35 (9-. 25)
Costs in $1000 Alternative Treatment Steps
Initial Investment A B^ £ D
2,846 6,610 534 8,890
ANNUAL COSTS:
Capital Costs (10%) 285 661 53 889
Depreciation (20%) 570 1,322 106 1778
Operating Costs 256 595 48 370
Energy 45 245 35 95
Total Annual Costs 1,156 2,823 242 3,132
Effluent Quality
Raw Waste Resulting Effluent Levels
Load .(Design Average Kg/1000 nr)
BOD5
COD
Oil/Grease
Phenol
.Sulfide
Ammonia
Suspended Solids
000 m-
187
382
136
6.2
1.1
22
79
» (LB/1000
(70
(134)
(48)
(2.2)
(0.4)
(7.8)
(28)
BBL)
1
10.3
95.5
6.0
0.088
0.088
4.5
17.6
C D
3.6
23.5
4.3 0.7
0.015
0.073
1.5
8.8 3.55
137
-------
TABLE 44
WATER EFFLUENT TREATMENT COSTS
PETROLEUM REFINING INDUSTRY
INTEGRATED SUBCATEGORY
Refinery .Capacity
1000 cubic meters/day (1000-BBL/DAY)
Wastewater Flow
cubic meters/cubic meter crude oil (gal/bbl)
Treatment Plant Size
1000 cubic meters /day
Costs in $1000
Initial Investment
ANNUAL COSTS:
Capital Costs (10$)
Depreciation '(20/0
Operating Costs
Energy
Total Annual Costs
.(MOD)
9.8 (65)
l.l (1*6)
10.8 (3.0)
Alternative Treatment Steps
A
1,256
126
252
103
20
B
2,920
292
581*
21*3
106
£
23
1*6
21
15
D
1*,750
1*75
950
206
1*3
501
1,223
105
1,671*
Effluent Quality
Kg/1000
BOD
5
COD
Oil/Grease
Phenol
Sulfide
Ammonia
Raw Waste
Load
i3 (lb/1000 BBL)
238 (81*)
590 (208)
133 (1*7)
6.5 (2.3)
1.7 (0.6
35.1* (12.5)
Resulting Effluent Levels
(Design Average Kg/1000
Suspended Solids 29 (10.2)
B_
16.1
121+.5
8.0
0.111.
0.111
7.1
21.6
£ . D
3.7
21. g
5.1* 0.63
0.015
0.07&
1.9
10.8 3.7
138
-------
TABLE 45
WATER EFFLUENT TREATMENT COSTS
PETROLEUM REFINING INDUSTRY
INTEGRATED SUBCATEGORY
Refinery Capacity
1000 cubic meters/day (1000 BBL/DAY)
Was tew at er Flow
cubic meters/cubic meter crude oil (gal/bbl)
Treatment Plant Size
1000 cubic meters /day
Costs in $1000
Initial Investment
ANNUAL COSTS:
Capital Costs (10$)
Depreciation (20$)
Operating Costs
Energy
Total Annual Costs
(MGD)
23 (152)
1.1 (1*6)
25-5 (7.0)
Alternative Treatment Steps
A
2,2l*9
225
550
203
36
B
5,223
522
1,01*1*
1*70
(l88
C
1*18
1*2
84
38
21
D
7,600
760
1,520
329
68
2,22k
192
2,677
Effluent Quality
Kg/1000
COD
Oil/Grease
Phenol
Sulfide
Ammonia
^^ispended Solids
Raw Waste
Load
(lb/1000 BBL)
238 (84)
590 (.(808)
133 (47) '
6.5 (2.3)
1.7 (0.6)
35.4 (12.5)
29 (10.2
Resulting Effluent Levels
(Design Average Kg/1000 m3}:..
B £
16.1
124.5
8.0 5.4
0.111
0.111
7.1
21.6 10.8
D
3.7
21.3
0.63
0.015
0.073
1.9
3.7
139
-------
TABLE 46
WATER EFFLUENT TREATP-IEWT COSTS
PETROLEUM REFINING INDUSTRY
INTEGRATED SUBCATEGORY
Refinery Capacity
1000 cubic meters/day (1000 BBL/DAY)
Wastewater Flow
cubic meters/cubic meter crude oil (gal/bbl)
Treatment Plant Size
1000 cubic meters/day (MGD)
Costs in $1000
Initial Investment
ANNUAL COSTS:
Capital Costs (10$)
Depreciation (20$)
Operating Costs
Energy
Total Annual Costs
>*9 (326)
1.1 (U6)
t.O (15.0)
Alternative Treatment Steps
A
l4,2~32
1423
8^6
381
69
1,719
B
9,831
983
1,966
885
35^
it, 188
C
787
79
158
71
52
360
D
10,100
1,010
2,020
Ii39
107
3,576
Effluent Quality
Raw Waste
Load
Kg/1000 m3 (lb/1000 BBL)
.BOD
5
COD
Oil/Grease
Phenol
Sulfide
Ammonia
238
590 (208)
133 (W)
6.5 (2.3)
1.7 (0.6)
35.^ (12.5)
Resulting Effluent Levels
(Design Average Kg/1000 m3)
Suspended Solids 29 (10.2)
B C_
16.1
12U.5
8.0 5.^
•O.lll
0.111
7-1
21.6 10.8
D
3.7
21.3
0'.63
0.015
0.073
1.9
3.7
140
-------
BPCTCA - Wastewater Treatment System
MODEL SYSTEM USED FOR THE ECONOMIC EVALUATION
Wast* Wat«r
Vat
W.I I
Wat
Well
TO
l«pr«c**i tng
Slop
Oil
Treatment
Gravity
Separator
Gravity
Separator
Chemical
Feed Tank*
Sludg.
Thickening
Dissolved
Air
Flotation
EqualIzatlon
Aeration
Tank
Dissolved
Air
Flotation
EqualIzatlon
SIudqe
Recycle
Ae ra 11 on
Tank
Surge
1
f
•\
<
Granular
Media
Filter
Granular
Media
e 1 1 »_.•
\
4
Effluent
Contaminated Storm Water
Sludge
Digestion
Vacuum
Filtration
Final
Disposal
-------
TABLE 47
BPCTCA - "END OF PIPE TREATMENT SYSTEM
MODEL USE FOR THE ECONOMIC EVALUATION
DESIGN SUMMARY
Treatment ^SYStern^Hydraulic_LQading
Treatment system hydraulic loadings are sized to represent the
projected waste water flows from small, average, and large
refineries in each subcategory. The flow range used in these
estimates ranges from 95 to 38,000 m3/day (25,000 gpd to 10,000,000
gpd) .
Dissolyed_iAir_Flotation
The flotation units are sized for an overflow rate of 570 m3/day/m2
(1400 gpd/sq.ft)
§ t a t i on
Capacity to handle 200 percent of the average hydraulic flow.
Equalization
One day detention time is provided. Floating mixers are provided to
keep the contents completely mixed.
Neutralization
The two-stage neutralization basin is sized on the basis of an
average detention time of twenty minutes. The lime-handling
facilities are sized to add 1,000 Ibs. of hydrated lime per mgd of
waste water, to adjust the pH. Bulk-storage facilities (based on 15
days usage) or bag storage is provided, depending on plant size.
Lime addition is controlled by two pH probes, one in each basin.
The lime slurry is added to the neutralization basin from a lime
slurry recirculation loop. The lime-handling facilities are
enclosed in a building.
Nutrient_Addition
Facilities are provided for the addition of phosphoric acid to the
biological system in order to maintain the ratio of BOD:P at 100:1.
Aeration Basin
Platform-mounted mechanical aerators are provided in the aeration
basin. In addition, walkways are provided to all aerators for fan
142
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haccess and maintenance. The following data were used in sizing the
aerators.
Oxygen utilization
L
B
Waste water temperature
Oxygen transfer
Motor Efficiency
Minimum Basin D.O.
1.5 kg 02/kg BOD
(1.5 Ibs 02/lb. BOD) removed
0.8
0.9
20°C
1.6 kg (3.5 Ibs.) o2/hr./shaft HP at
20°C and zero D.O.
85 percent
1 mg/1
in tap water
Oxygen is monitored in the basins using D.O. probes.
Secondary Clarifiers
All secondary clarifiers are circular units. The side water depth
is 3.0 meters (10 ft.) and the overflow rate is 500 gpd/sq. ft.) .
Sludge recycle pumps are sized to deliver 50 percent of the average
flow.
Sludge_Holding Tank-Thickener
For the smaller plants, a sludge-holding tank is provided, with
sufficient capacity to hold 5 days flow from the aerobic digester.
The thickener provided for the larger plants was designed on the
basis of 29 kg/m2/day (6 Ibs./sq. ft./day) and a side water depth of
3.0 meters (10 ft.)
,-!'
Aerobic Digester
The aerobic digester is sized on the basis of a hydraulic detention
time of 20 days. The sizing of the aerator-mixers was based on
0.044HP/m3 (1.25,HP/1,000 cu.ft.) of digester volume.
Vacuum Filtration
The vacuum filters were sized on cake yield of 9.75 kg/m2/hr. (2
Ibs./sq.ft./hr) and a maximum running time of 18 hrs./day. The
polymer system was sized to deliver up to 0.005kg of polymer/kg of
day solids (10 Ibs. of polymer/ton dry solids).
Granular_Media Filters
The filters are sized on the basis of an average hydraulic loading
of 9.12m3/m2/min. (3 gpm/sq.ft.) Backwash facilities are sized to
provide rate up to 0.82m3/m2/min. (20 gpm/sq.ft.) and a backwash
cycle of up to 20 minutes duration.
143
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Fina1_s1udge_Dis20sa1
Sludge is disposed of at a sanitary landfill assumed to be 5 mil
from the waste water treatment facility.
Design Philosophy
The plant's forward flow units are designed for parallel flow, i.e:
either half of the plant can be operated independently. The sludge
facilities are designed on the basis of series flow. All outside
tankage is reinforced concrete. The tops of all outside tankage are
assumed to be 12 ft above grade.
144
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FILTER WATER
HOLDING TANK
CARBON COLUMN
FEED PUMPS
REGENERATED CARBON
STORAGE TANK
V
PLANT
EFFLUENT
CARBON
COLUMNS)
J-*
TRANSFER
TANK
FIGURE 7
DRYING TANK
4 ( ^ AIR
BLOWER
DRY STORAGE TANK
\ Hfrfr>6t>
-------
TABLE 48
BATEA - END OF PIPE TREATMENT SYSTEM
DESIGN SUMMARY
Granular Carbon_CQlumns
The carbon columns are sized on a hydraulic loading of 0.4-0.8
m3/m2/min. (10-20 gpm/sq. ft.) and a column detention time of 40
minutes. A backwash rate of (50 gpm/sq. ft.) was assumed for 40 percent
bed expansion at 70°F.
Filter-Column Decant_Sumg
Tankage is provided to hold the backwash water and decant it back to the
treatment plant over a 24-hour period. This will eliminate hydraulic
surging of the treatment units.
Regeneration Furnace
An exhaustion rate of 1 kg of COD/kg carbon (1 Ib COD/lb carbon) was
used for sizing the regeneration facilities.
Regenerated JExhausted Carbon Stgrage
Tankage is provided to handle the regenerated and exhausted carbon both
before and after regeneration.
146
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Estimated Costs of Facilities
« discussed previously, designs for the model treatment systems were
ted out in order to evaluate the economic impact of the proposed
luent. limitations. The design considerations resulted in the
generation of cost data which would be conservative. However,
relatively conservative cost numbers are preferred for this type of
general, economic analysis.
Activated sludge followed by granular media filtration was used as the
BPCTCA treatment system. The plant designs were varied to generate cost
effectiveness data within each category. Activated carbon adsorption
was used as the BATEA treatment.
Capital and annual cost data were prepared for each of the proposed
treatment systems.
The capital costs were generated on a unit process basis, e.g.
equalization, neutralization, etc. for all the proposed treatment
systems. The following ^'percent add on" figures were applied to the
total unit process costs ip order to develop the total capital cost
requirements:
Percent of Unit
Item Process Capital Cost
Electrical 12
Piping 15
Instrumentation 8
Site work 3
Engineering Design and Construction
Supervision Fees 15
Construction Contingency 15
Land costs were computed independently and added directly to the total
capital costs.
Annual costs were computed using the following cost basis:
Item Cost Allocation
Amortization 10 percent of investment.
Depreciation 5 year-straight line with zero salvage value.
Operations and Includes labor and supervision, chemicals
Maintenance sludge, hauling and disposal, insurance
and taxes (computed at 2 percent of the
capital cost), and maintenance (computed
at 4 percent of the capital cost)•
Power Based on $1.50/100 KWH for electrical power.
147
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The short term capitalization and depreciation write-off period is .that
which is presently acceptable under current Internal Revenue Service
Regulations pertaining to industrial pollution control equipment.
All cost data were computed in terms of August, 1971 dollars,
corresponds to an Engineering News Records (ENR) value of 1580.
which
The following is a qualitative as well as a quantitative discussion of
the possible effects that variations in treatment technology or design
criteria could have on the total capital costs and annual costs.
Technology or Design Criteria
1. Use aerated lagoons and sludge de-
watering lagoons in place of the
proposed treatment system.
2. Use earthern basins with a plastic
liner in place of reinforced concrete
construction, and floating aerators
versus platform-mounted aerators
with permanent-access walkways.
Capital
Cost Differential
1. The cost reduction could
be to 70 percent of the
proposed figures.
2. cost reduction could be
10 to 15 percent of the
total cost.
Place all treatment tankage above grade 3. Cost savings would depend
to minimize excavation, especially if on the individual situation.
a pumping station is required in any
case. Use all-steel tankage to min-
imize capital cost.
4. Minimize flow and maximize.concen-
trations through extensive in-plant
recovery and water conservation, so
that other treatment technologies
(e.g. incineration) may be economi-
cally competitive.
4. Cost differential would
depend on a number of items,
e.g. age of plant, accessi-
bility to process piping,
local air pollution
standards, etc.
The cost requirements for implementing BPCTCA effluent standards are
presented in Tables 49 through 54. The additional cost requirements for
implementing BATEA effluent standards are presented in Tables 55 and 60.
The following table summarizes the general ranges of sludge quantities
generated by small, medium, and large refineries in each subcategory.
148
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.Subcategory cu m/yr 1 cu_yd/yr_^
Topping 2.3-15 3-20
Low Cracking 76-380 100 - 500
High Cracking 380-2300 500 - 3000
Petrochemical 460-3800 600 - 5000
Lube 610-6900 800 - 9000
Integrated 760-9200 1000 - 12000
iWet-weight basis
Particular plants within the petrochemical, lube, and integrated
subcategories may be amenable to sludge incineration because of the
large quantities of sludge involved. For example, sludge incineration
would reduce the previous quantities by about 90 percent. Sludge cake
is 80 percent water, which is evaporated during incineration, and more
than half of the remaining (20 percent) solids are thermally oxidized
during incineration. Sludge incineration costs were not evaluated for
those specific cases, because the particular economics depend to a large
degree on the accessibility of a sanitary landfill and the relative
associated hauling costs.
The following discussion is presented to help visualize the complexities
involved in evaluating cost effectiveness data. Every treatment system
is composed of units whose design basis is primarily hydraulically
dependent, organically dependent, or a combination of the two. The
following is a list of the unit processes employed, and a breakdown of
e design basis.
Hydraulically Organically Hydraulically and
Dependent Dependent Organically Dependent
Pump station Thickener Aeration basin
API separator Aerobic Digestor Oxygen transfer equipment
Equalization Vacuum filter Air flotation Unit
Neutralization
Nutrient addition
Sludge recycle pump
Clarifier
The annual cost associated with the hydraulically dependent unit
processes is not a function of effluent level. On the other hand, the
sizing of the organically dependent units should theoretically vary in
direct proportion to the effluent level: e.g. reducing the BOD5 removal
from 95 to 85 percent should reduce the sizes of the sludge handling
equipment by approximately 10 percent. However, there are two
complicating factors: 1) only a relatively few sizes of commercially
available equipment; and 2) broad capacity ranges. These two factors,
149
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especially in regard to vacuum filters, tend to negate differentials, in
capital cost with decreasing treatment levels.
The relationship between design varying contaminant levels and
design of aeration basins and oxygen transfer equipment is somewhat more
complex. The levels are dependent on the hydraulic flow, organic
concentration, sludge settleability, and the relationship between mixing
and oxygen requirements. For example, to reach a particular effluent
level, the waste water's organic removal kinetics will require a
particular detention time at a given mixed-liquor concentration. The
oxygen transfer capacity of the aerators may or may not be sufficient to
keep the mixed liquor suspended solids in suspension within the aeration
basin. Therefore, the required horsepower would be -increased merely to
fulfill a solids mixing requirement. Alternatively, the oxygen
requirements may be such that the manufacturer's recommended minimum
spacing and water depth requirements would require that the basin volume
be increased to accommodate oxygen transfer requirements. -
Non-Water Quality Aspects
The major nonwater quality consideration which may be associated with
in-process control measures is the use of and alternative means of
ultimate disposal of either liquid or solid wastes. As the process Raw
Waste Load is reduced in volume, alternate disposal techniques such as
incineration, ocean discharge, and deep-well injection are feasible.
Recent regulations are tending to limit the applicability of ocean
discharge and deep-well injection because of the potential long-term
detrimental effects associated with these disposal procedures,
Incineration may be a viable alternative for highly concentrated was
streams. However, associated air pollution and the need for auxiliar
fuel, depending on the heating value of the waste, are considerations
which must be evaluated on an individual basis for each use. Other
nonwater quality aspects, such as noise levels, will not be perceptibly
affected. Most refineries generate fairly high noise levels (85-95
dB(A)) witHin the battery limits because of equipment such as pumps,
compressors, steam jets, flare stacks, etc. Equipment associated with
in-process or end-of-pipe control systems would not add significantly to
these levels. In some cases, substituting vacuum pumps for steam jets
would in fact reduce plant noise levels. There are no radioactive
nuclides used in the industry, other than in instrumentation. Thus no
radiation problems will be expected, compared to the odor emissions
possible from other refinery sources, odors from the waste water
treatment plants are not expected to create a significant problem.
However, odors are possible from the waste water facilities, especially
from the possible stripping of ammonia and sulfides in the air flotation
units, and from accidental anaerobic conditions in biological facilities
during upsets.
150
-------
The*extra power required for waste water treatment and control systems
negligible compared to the total power requirements of the petroleum
equipment.
151
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TABLE 49
BPCTCA ESTIMATED WASTEWATER TREATMENT COSTS FOR THE TOPPING SUBCATEGORY
( ENR 1580 - August, 1971 Costs)
Flow, innp M3/p«y (GPP)
Tota.l Capital Cost
Annual Cost
Capital Costs
Depreciat ion
Operating and
Maintenance
Energy and
Powe r
Total Annual Cost
0.091 ( 25.000 )
$390,000
$ 39,000
$ 78,000
$ 31,200
$ 9,800
0.32 ( 85.000)
$600,000
$ 60,000
$120,000
$ 1+8,000
$ 16,000
$158,000
$244,000
0.68 (180.000)
$773,000
$ 77,000
$155,000
$64,000
$ 24,000
$320,000
152
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TABLE sp .
BPCTCA ESTIMATED WASTEWATER TREATMENT COSTS FOR THE LOW-CRACKING SUBCATEGORY
( ENR 1580 - August, 1971 Costs)
Flow, 1000 M3/Day (GPD)
Total Capital Cost
Annual Cost
Capital Costs
Depreciat ion
Operating and
Maintenance
Energy and
' Power
Total Annual Cost
n 07 (260,000}
$876,000
$ 88,000
$175,000
$ 70,000
$ 26,000
$359,000
2.06 t
$1
$
$
$
$
$
540.000}
,214,000
121,000
243,000
97,000
38,000
499,000
k ft M
.300,000^
$2,100,000
$
$
$
$
$
210,000
420, 000
170,000
74,000
874,000
153
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TABLE 51
BPCTCA ESTIMATED WASTEWATER TREATMENT COSTS FOR THE HIGH-CRACKING SUBCATEGOR'.
( ENR 1580 - August, 197! Costs )
Flow, 1000 M3/Day (GPD)
Total Capital Cost
Annual Cost
Capital Costs
Depreciat ion
Operating and
Maintenance
Energy and
Power
Total Annual Cost
2-0 ( 525.000 )
$1,083,000
$ 108,000
$ 217,000
$ 87,000
$ 37,000
5.09 (1.350.000) .11-9 ( 3,200,000)
$ 449,000
$2,183,000
$ 218,000
$ 437,000
$ 178,000
$ 76,000
$ 909/000
$4,533,000
$ 453,000
$ 90 7,00
$ 386,000
$ 145,000
$1,89hOOO
154
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TABLE 88
• BPCTCA ESTIMATED WASTEWATER TREATMENT COSTS FOR PETROCHEMICAL SUBCATEGORY
( ENR 1580 - August, 1971 Costs )
Flow, 1000 M3/Day (GPD)
2.1* (625.000) 9.5 (2.500.000) 18.9 (5.000.000)
Total Capital Cost $1,280,000 $3,910,000 $5,870,000
Annual Cost
Capital Costs $ 128,000 $ 391,000 $ 587,000
Depreciation $ 256,000 $ 782,000 $1,17^,000
Operating and $ 102,000 $ 330,000 $ 511,000
Maintenance
Energy and $ 43,000 $ 120,000 $ 200,000
Powe r
Total Annual Cost . $ 52.9,000 $1,623,000 $2,^72,000
155
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TABLE 53
BPCTCA ESTIMATED WASTEWATER TREATMENT COSTS FOR THE LUBE SUBCATEGORY
( ENR 1580"- August, 1971 Costs)
Flow, 1000 M3/Day (GPD)
Total Capital Cost
Annual Cost
Capital Cost
Depreciation
Operating and
Maintenance
Energy and
Power
Total Annual Cost
3-5 (925.000) 15.^ (MOO,OOP) 35 (9,250.000)
$1,920,000 $5,230,000 $9,990,000
$ 192,000
$ 384,000
$ 154,000
$ 58,000
$ 788,000
$ 523,000
$1,046,000
$ 449,000
$ 172,000
$2,190,000
$ 999,000
$1,998,000
$ 899,000
$ 325,000
$4,221,000
156
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TABLE 54
BPCTCA ESTIMATED WASTEWATER TREATMENT COSTS FOR THE INTEGRATED SUBCATEGORY
( ENR 1580 - August, 1971 Costs)
Flow, 1000 M3/Day (GPD)
in.fi (? ,000,noo 25.5 ft.ooo.QOO) 54.0 (15.000.000)
Total Capital Cost $ 4,410,000 . :$7,890,000 $14,850,000
Annual Cost
Capital Cost $ Ul-'}00D $ 789,000 $ 1,1*85,000
Depreciation $ 882,000 $1,578,000 $ 2,970,000
Operating and $ 367,000 $ 657,000 $ 1,237,000
Maintenance
Energy and $ 141,000 $' 25^,000 $ 479,000
Power
Total Annual Cost 1,831,600' $3,278,000 $ 6,171,000
157
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TABLE 55
ESTIMATED ADDITIONAL WASTEWATER TREATMENT COSTS FOR
BATEA TECHNOLOGY _ TOPPING SUBCATEGORY
( ENR 1580 - August, 1971 Costs )
Flow, 1000 M3/Day (GPD)
Total Capital Cost
Annual Cost
Capital Cost
Depreciation
Operating and
Maintenance
Energy and
Power
Total Annual Cost
0.91 (25.000)
$295,000
$ 30,000
$ 59,000
$ 72,500
$ 6,500
0.32 (85.000)
$612,000
$ 61,000
$122,000
$89,900
$ 9,000
$168,000
$281,000
0.68.(180.000)
$9^3,000
$ 9MOO
$187,000
$101,000
$ 10,000
$392,000
158
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TABLE 56
ESTIMATED ADDITIONAL WASTEWATER TREATMENT COSTS FOR
BATEA TECHNOLOGY - LOW CRACKING SUBCATEGORY
( ENR 1580 - August, 1971 Costs )
riow. 1000 M3/Day (GPD)
0.97 (260,000) 2.06 C-^L922j U.8 ( 1.300.000)
Total Capital Cost $1,16^,00 $1,769,000 $2,895,000
Annual Cost .
Capital Cost $ 116,000 $ 177,000 $ 290,000
Depreciation $ 233,000 $ 35^,000 $ 579,000
Operating and $ 106,000 $ S'MOO $ 152,000
Maintenance
Energy and $ 10,000 $ 15,000 $ 25,000
Power ' .
Total Annual Cost $^65,000 $6^0,000 $1,0^*6,000
159
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TABLE 57
ESTIMATED ADDITIONAL WASTEWATER TREATMENT COSTS FOR
BATEA TECHNOLOGY - HIGH CRACKING SUBCATEGORY '
( ENR 1580 - August, 1971 Costs )
Flow, 1000 M3/Day (GPD)
2.0 (525.000) 5-09 (1.350.000) 11.9 (3.200.000)
Total Capital Cost $1,720,000 $2,950,000 $4,890,000
Annual Cost
Capital Cost $ 172,000 $ 295,000 $ 489,000
Depreciation $ 344,000 $ 590,000 $ 978,000
Operating and $ 121,000 $ 155,000 $ 211,000
Maintenance
Energy and $ 15,000 $ 25,000 $ 44,000
Powe r
Total Annual Cost $ 652,000 $1,065,000 $1,722,000
L60
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TABLE 58
ESTIMATED ADDITIONAL WASTEWATER TREATMENT COSTS FOR
BATEA TECHNOLOGY - Petrochemical Subcategory
( ENR 1580 - August, 1971 Costs )
Flow,
2,1* (625.000) 9.5 ( 2.500.000) 18.9( 5.000.000)
Total Capital Cost $1,875,000 $4,200,000 $6,220,000
Annual Cost
Capital Cost $ 188,000 $ 420,000 $ 622,000
Depreciation $ 375,000 $ 840,000 $1,244,000
Operating and $ 125,000 $ 192,000 $ 270,000
Mai ntenance
Energy and $ 16,000 $ 38,000 $ 60,000
Powe r ' . .
Total Annual Cost $ 604,000 $1,490,000 $2,196,000
161
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TABLE 29
ESTIMATED ADDITIONAL WASTEWATER TREATMENT COSTS FOR
BATEA TECHNOLOGY - Lube Subcategory
( ENR 1580 - August, 1971 Costs )
Flow, 1000 M3/Day (GPD)
3.5 (925.000) 15.1* (*t.OOP.OOP) 35 f9.250.OOP)
Total Capital Cost $2,360,000 $5,600,000 $8,890,OOP
Annual Cost
Capital Cost $ 236,PPP $ 560,000 $ 889,000
Depreciation $ ^72,000 $1,120,000 ' $1,778,000
Operating and $ 139,000 $ 236,000 $ 370,000
Maintenance
Energy and $ 20,000 $ 52,000 $ 95,000
Power •
Total Annual Cost $ 867,000 $1,968,000 $3,132,000
162
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TABLE $(J
ESTIMATED ADDITIONAL WASTEWATER TREATMENT COSTS FOR
BATEA TECHNOLOGY - INTEGRATED SUBCATEGORY
(ENR - August, 1971 Costs)
Total Capital Cost
Annual Cost
Total Annual Cost
Flow, 1000 M3/Day (GPP)
10.8 (3,000,000) 25-5 (7,000,000) 5^.0 (15,000,000)
$U,750 ,000 $7,600,000 • $10,100,000
Capital Cost
Depreciation
Operating and
Maintenance
Energy and
Power
$
$
$
$
1*75
950
206
U3
,000
,000
,000
,000
$
$1
' $
$
760
,520
329
68
,000
,000
,000
,000
$
$
$
$
1,010
2,020
i+39
107
,000
,000
,000
,000
$1,67^,000
$2,677,000
$ 3,576,000
163
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SECTION IX
BEST PRACTICABLE CONTROL TECHNOLOGY CURRENTLY
AVAILABLE--EFFLUENT LIMITATIONS
Based on the information contained in Sections III through VIII of this
report, effluent limitations commensurate with the best practicable
control technology currently available have been established for each
petroleum refining subcategory. The limitations, which explicitly set
numerical values for the allowable pollutant discharges within each
subcategory, are presented in Table 1. The effluent limitations specify
allowable discharges of BODS, COD, TOC, total suspended solids, oil and
grease, phenolic compounds, ammonia (N), sulfides, total and hexavalent
chromium and zinc; based upon removals which are capable of being
attained through the application of BPCTCA pollution control technology.
The best practicable control technology currently available is based on
both in-plant and end-of-pipe technology. BPCTCA in-plant technology is
based. on control practices widely used within the petroleum refining
industry, and include the following:
1. Installation of sour water strippers to reduce the sulfide and
ammonia concentrations entering the treatment plant.
2. Elimination of once-through barometric condenser water by using
surface condensers or recycle systems with oily water cooling
towers.
3. Segregation of sewers, so that unpolluted storm runoff and once-
through cooling waters are not treated normally with the process and
other polluted waters.
4. Elimination of polluted once-through cooling water, by monitoring
and repair of surface condensers or by use of wet and dry recycle
systems.
BPCTCA end-of-pipe treatment technology is based on the existing waste
water treatment processes currently used in the Petroleum Refining
Industry. These consist of equalization and storm diversion; initial
oil and solids removal (API separators or baffle plate separators);
further oil and solids removal (clarifiers, dissolved air flotation, or
filters); carbonaceous waste removal (activated sludge, aerated lagoons,
oxidation ponds, trickling filter, activated carbon, or combinations of
these); and filters (sand, dual media; or multi-media) following
biological treatment methods. It must be recognized that specific
treatability studies are required prior to the application of a specific
treatment system to the individual refinery.
165
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Granular media filtration or polishing ponds prior to final discharge
are included so that the total suspended solids and oil concentrations
in the final effluent can be generally maintained at approximately
mg/1 and 5 mg/1, respectively. The final polishing step is consider
BPCTCA for the petroleum refining industry since several refineries al
now using polishing ponds, and granular media filters are becoming
excepted technology with a few installations operating currently and
several more now under construction.
In a petroleum refinery the waste water treatment plant should be used
to treat only polluted waters. All once^through cooling water or storm
runoff which is unpolluted should be segregated as it dilutes ,the
polluted waters and requires treatment of a greater flow. Flows for
BPCTCA were based on the 50 percent probability of occurance flows for
plants practicing recycle with less than 3 percent heat removal by once-
through cooling water (on a dry weather basis). Recognizing the
additional flows and waste loads associated with rain runoff and ballast
waters, allocations for these added flows must be given based on strict
segregation of runoff and ballast waters treated.
PROCEDURE FOR DEVELOPMENT OF BPCTCA EFFLUENT LIMITATIONS
The effluent guideline limitations were determined using effluent data
from refineries visited during this project or attainable effluent
concentrations and the median flow from the refineries with 3 percent or
less of the heat removed by once-through cooling water. In some cases
the available data from the refineries visited was considered to be too
stringent to be met by the industry in general. In these cases the flj
and concentration procedure was used. The median flows are presented!
Table 21, Section V. The attainable concentrations for BPCTCA
presented in Table 61. Refinery data are presented in Tables 2Ur26,
Section VII.
flow
W
Several exceptions to this procedure were required to establish
meaningful effluent limitations in specific cases. These are as
follows:
Topping, Low Cracking, Petrochemical, Lube, and Integrated
Subcategories - Ammonia as Nitrogen
The ammonia as nitrogen effluent limitations were calculated using an 80
percent reduction from the median raw wa'ste loads in each subcategory.
Low Cracking, High Cracking, Petrochemial and Lube Subcategories
TOC
Little data is available on the reduction of TOC. Available effluent
data indicate an effluent TOC/BOD. ratio of 1.8. Using this factor,
effluent limitations for TOC, were based on BOD5 limitations. It is
recognized that this ratio (TOC/BOD) is variable between the refineries.
166
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and iprior to use, an agreed upon correlation should be developed for the
individual refinery.
Topping Subcategory - TOC
Application of the procedure outlined above yielded a TOC value of 2,7
lb/1000 bblr which is higher than the median raw waste load for the
topping subcategory. Therefore, the median .raw waste load value was
used for the topping subcategory TOC effluent limitations.
Topping Subcategory - COD
The COD effluent limitation was calculated using the COD/BOD ratio
determined from published refinery data. This ratio was applied to the
BOD_5 removal for the topping subcategory A to determine the COD removal
efficiency.
The long term (annual or design) average effluent limitations determined
are contained in table 62.
Statistical Variability of a Properly Designed and Operated Waste
Treatment Plant
The effluent from a properly designed and operated treatment plant
changes continually due to a variety of factors. Changes in production
mix, production rate and reaction chemistry influence the composition of
raw wasteload and, therefore, its treatability. Changes in biological
•tors influence the efficiency of the treatment process. A common
icator of the pollution characteristics of the discharge from a plant
is the long-term average of the effluent load, however, the long-term
(e.g., design or yearly) average is not a suitable parameter on which to
base an enforcement standard. However, using data which show the
variability in the effluent load, statistical analyses can be used to
compute short-term limits (monthly or daily) which should never by
exceeded, provided that the plant is designed and run in the proper way
to achieve the desired long-term average load. It is these short-term
limits on which make up the effluent guidelines.
In order to reflect the variabilities associated with properly designed
and operated treatment plants for each of the' parameters as discussed
above, a statistical analysis was made of plants where sufficient data
was available to determine these variances for day-to-day and month-to-
month operations. The standard deviations for day-to-day and month-to-
month operations were calculated. For the purpose of determing effluent
limitation a variability factor was defined as follows:
Standard deviation = Q
Long-term average (yearly or design) = x
Variability factor y = x+20.
167
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The annual average is multiplied by the variability factor to determine
the effluent limitation guideline for each parameter. The
limitation guideline as calculated by use of the variability
based on. two standard deviations is only exceeded 2-3 percent of the
time for a plant that is attaining the long-term average. The data used
for the variability analysis came from plants under voluntary operation.
As a result of the application of mandatory requirements, the effluent
limitation guidelines as discussed in this paragraph should never be
exceeded.by a properly designed and operated waste treatment facility.
The variability factors used are contained in Table 63. These factors
for each ' parameter except total and hexavalent chromium and zinc were
calculated from long-term refinery data. The factors for total chromium
and zinc are the same as that used for suspended solids since both of
these metallic ions are removed as insoluble salts. The variability
factor for hexavalent chromium was based on the sulfide variability.
The guidelines for BPCTCA presented in table 1 have taken into
consideration the above variability factors.
168
-------
TABLE 61
Attainable Concentrations from the Application of
Best Practicable Control Technology Currently Available
Parameter
BOD5
COD
TOC
SS
0 & G
Phenol
NH3-N
Sulfide
CrT
Ct6
Zh
Concentration mg/1
15
80
*(1.8 x BOD5)
10
5
0.1
*(80% removal)
0.1
.25
.005
.5
*See Text
169
-------
Refinery
Subcategory
Topping
Lou-Cracking
Kigh-Cracking
Petrochemical
Lube
Intergrated
Runoff(2)
BallastO)
BOD5
4.3(1.5)
6.0(2.1)
8.0(2.8)
9.1(3.2)
f
10.7(3.8)
COD
TOC
4.9(1.7)
16.0(5.6)
39.1(13.8) 10.8(3.8)
68.0(24.0) 14.4(5.0)
59.5(21.0) 16.3(5.7)'
95.5(33.7) 19.4(6.0)
16.1(5.7) 124.5(43.9) 29.1(10.3)
0.015(0.125) ,0.12(1.0) 0.027(0.225)
0.015(0.125) 0.15(1.250) 0.027(0.225)
TABLE 62
BPCTCA
mOLEUM REFINING INDUSTRY EFFLUENT LIMITATIONS
ras of Pollutants/1000 Cubic Meters Feedstock (1) Per Stream Day
lly Pounds of Pollutant/1000 BEL of Feedstock Per Stream Day)
Total
Suspended Solids
2.9(1.0)
4.0(1.4)
5.1(1.8)
6.0(2.1)
8.8(3.1)
10.8(3.8)
0.010(0.083)
0-010(0.083)
Oil 4 Grease
1.4(0.5)
2.0(0.7)
2.5(0.88)
3.1(1.10)
4.3(1.5)
5.4(1.9)
0.0050(0.042)
0.0050(0.042)
Phenolic
Compounds
0.03(0.01)
0.040(0.014)
0.051(0.018)
0.065(0.023)
0.088(0.031)
0.111(0.039)
— '
—
Ammonia (N)
1.0(0.35)
2.0(0.70)
4.5(1.60)
6.8(2.46)
4.5(1.60)
7.1(2.5)
—
—
Sulfide
0.028(0.010)
0.040(0.014)
0.050(0.018)
0.060(0.021)
0.088(0.031)
0.111(0.039)
—
—
Total
Chromium
0.071(0.025)
0.100(0.035)
0.115(0.044)
0.148(0.052)
0.219(0.077)
0.278(0.098)
—
-
Hexavalent
Chromium Zinc
0.0014(0.0005) 0.142(0.050)
0.0020(0.0007) 0.202(0.071)
0.0025(0.0009) 0. 249(0. 0£8)
0.0029(0 0010) 0.297(0.104)
0.0044(0.0015) 0.436(0.154)
0.0055(0.0020) 0.555(0.196)
(1) Feedstock -crude oil and/or natural gas liquids '
(2) The additional allocation being allowed for contaminated storm runoff flow (kg/1000 liters
(lbs/1000 gallons) shall be based solely on that storm flow which passes through the treatment
system. All additional storm runoff, that has been segregated from the main waste stream, shall
not show a visible sheen or exceed a TOC concentration of 15 mg/1 when discharged.
(3) This is an additional allocation, based on ballast water intake (daily average)
kilograms per 1000 liters (pounds per 1000 gallons)
-------
TABLE 63
VARIABILITY FACTORS BASED ON PROPERLY DESIGNED
AND OPERATED WASTE TREATMENT FACILITIES
BODi- COD TOG TSS 0 & G Phenol Ammonia Sulfide CrT Cr6 Zn_
Daily
Variability 2.1 2.0 1.6 2.0 2.0 2.1* 2.0 2.2 2.0 2.2 2.0
Monthly
Variability 1.7 1.6 1.3 1.7 1.6 1.7 1.5 I.1* 1.7 l.U 1.7
-------
SECTION X
BEST AVAILABLE TECHNOLOGY ECONOMICALLY
ACHIEVABLE ~ EFFLUENT LIMITATIONS
The application of best available technology economically achievable is
being defined as further reductions of water flows in-plant and the
addition of a physical - chemical treatment step (activated carbon),
end-of-pipe. The limitations, which set numerical values for the
allowable pollutant discharges within each subcategory for BATEA are
presented in Table 2. Although there are specific systems which can
effectively reduce the water usage from a particular process to nearly
zero, these "zero, discharge" systems cannot be uniformly applied
throughout the refinery to develop "zero discharge" criteria for the
entire refinery.
BATEA in-plant technology is based on control practices now practiced by
some plants in the petroleum refining industry, and include the
following:
(1) Use of air cooling equipment.
(2) Reuse of sour water stripper bottoms in crude desalters.
(3) Reuse of once-through cooling water as make-up to the
water treatment plant.
(U) Using waste water treatment plant effluent as cooling water,
scrubber water, and influent to the water treatment plant.
(5) Reuse of boiler condensate as boiler feedwater.
(6) Recycle of water from coking operations.
(7) Recycle of waste acids from alkylation units.
(8) Recycle of overhead water in water washes.
(9) Reuse overhead accumulator water in desalters.
(10)Use of closed compressor and pump cooling
water system.
(11)Reuse of heated water from the vacuum overhead condensers
to heat the crude. This reduces the amount of cooling water
needed.
(12)Use of rain runoff as cooling tower make-up or
water treatment plant feed.
(13)other methods.
Flow
Flow reductions proposed for BATEA effluent limitations. were derived
from further analysis of the 1972 National Petroleum Waste Water
Characterization Studies. The flows from refineries in each subcategory
meeting the BPCTCA flow basis were averaged to determine the flow basis
for establishment of BATEA effluent limitations. That these average
flows are achievable within the petroleum refining industry is readily
demonstrable, by determining the number and geographical distribution of
173
-------
refineries in the United states currently at, or lower than,» the
proposed BATEA flows. There are 3 to 5 refineries in each of the six
subcategories which have flows less than or equal to the proposed B
effluent limitations. These refineries range in size from 827,000
69,000,000 cubic meters per stream day (5,200 to 434,000 barrels per
stream day), and range in cracking capacity from 0 to 106 percent. The
geographical distribution of these refineries indicates that good water
practices, and consequently low waste water flows, are not confined to
water - short areas or cool climates, but are located throughout the
United States. Within this group of refineries with low-water usage,
there are refineries located in both high rainfall and dry areas
(Washington and New Mexico) and areas of extreme temperatures (New
Mexico and Texas to Alaska and Minnesota).
Consequently, these flows, shown in Table 64, were used as the basis for
establishment of BATEA effluent limitations. The objective of this
basis for flow is to provide inducement for in-plant reduction of both
flow and contaminant loadings prior to end-of-pipe treatment. However,
it is not the intent of these effluent limitations to specify either the
unit waste water flow which must be achieved or the waste water
treatment practices which must be employed at the individual petroleum
refinery.
The end-pf-pipe system proposed for BATEA technology is based on the
addition of activated carbon adsorption in fixed bed columns, to the
treatment system proposed as BPCTCA technology.
Procedure for Development of BATEA Effluent Limitations
The effluent limitations proposed for BATEA technology are based on
refinery pilot plant data, which indicate the percentage reductions
achievable or concentrations achievable for effluents from activated
carbon adsorption systems. These data are presented in table 65.
These concentrations were then used in conjunction with the BATEA flows
from Table 65 or the percentage reductions were applied to the BPCTCA
effluent limit. The daily annual average effluent limitations
determined are contained in Table 66.
Since these effluent limitations are based upon pilot plant data, which
have, not been fully demonstrated in full-scale installations as actual
performance data becomes available, the effluent limitations presented
in Table 2 may require revision.
Variability Allowance for Treatment Plant Performance
The effluent limitations presented . in Table 2 have taken into
consideration the variability factors, as in BPCTCA. Since there is not
enough performance data from physical - chemical treatment systems
174
-------
available at this time to determine variability, the ratios established
for'BPCTCA have been used.
175
-------
Siibcategory
Topping
Lov-Cracking
High-Cracking
Petrochemical
Lube
Integrated
TABLE 64
FLOW BASIS FOR DEVELOPING
BATEA EFFLUENT LIMITATIONS
Flow, per unit throughout
M3/M3 Gallons/BBL
0.17
0.26
0.33
0.36
0.73
0.76
7
11
\k
15
30.5
31.5
176
-------
BATEA REDUCTIONS IN POLLUTANT LOADS ACHIEVABLE BY
APPLICATION OF ACTIVATED CARBON TO
MEDIA FILTRATION EFFLUENT BPCTCA
Parameter
Type of Data
Achievable
Refinery Effluent
References
BOD
COD
TOC
TSS
on
Phenols
Ammonia
Sulfldes
Pi
Pi
Pi
Pi
Pi
Pi
Pi
No
lot
lot
lot
lot
lot
lot
lot
Plant
Plant
Plant
Plant
Plant
Plant
Plant
mq/L % Reduction
5 - 21,
75 21,
15 - 17,
5 - 31A
1-1.7 80 3iA
0.02 99 31A
60 27
27,31A,U8,62A
27, 31A, 1*7,53,<
31A,1*8,62A
JU8,53,62A
,1*8,62A
,U8,62A
,31A,62A
data
-------
TABLE 66
BATEA
Annual Average Daily Kilograns of Pollutants/1000 Cubic Meters of Feedstock (1) Per Stream Day
(Annual Average Daily Pounds of Pollutants/1000 B3L of Feedstock Per Stream Day)
Refinery
Subcategory
BODS
COD
TOC
0.82 (0.29) 2.3 (0.82) 2.5 (0.87) 0.82 (0.29)
1.31 (0.46) 8.0 (2.8) 4.0 (1.4)
5.1 (1.8)
5.4 (1.9)
Toppi-g
Low-Cracking
Kigh-Crackir.g 1.65 (0.58) 12.8 (4.5)
Petrochemical 1.80 (0.63) 7.1 (2.5)
Lube 3.59 (1.27) 23.5 (8.3) 10.8 (3.8)
Integrated 3.70 (1.31). 21.2 (7.5) 11.0 (3.9)
Runoff (2) 0.0050 (0.042) 0.014 (0.12) 0.016 (0.13) 0.0050 (0.042) 0.0010 (0.009)
Ballast (3) 0.0050 (O.C42) 0.019 (0.16) 0.016 (0.13) 0.0050 (0.042) 0.0010 (0.009)
(1) Feedstock - Crude oil and/cr natural gas liquids.
(2) The additional allocation being allowed for contaminated'storm runoff flow (kg/1000 liters
(Ibs/lOCO gallons) shall be based solely on that storm flow which passes through the treatment
system. All additional stora runoff, that has been segregated frOE the main waste stream, shall
net show a visible sheen or exceed a TOC concentration of 15 r.g/1 when discharged.
(3) This is an additional allocation, based on ballast water intake (daily average) kilograms
per 1000 liters (pounds per 1000 gallons).
Total Suspended Oil £.
Solids Grease
0.82
1.3
1.7
1.8
3.6'
3.7
(0.29)
(0.46)
(0.58)
(0.63)
(1.27)
(1.31)
0.17
0.26
0.34
0.37
0.71
0.74
(0.06)
(0.09)
(0.12)
(0.13)
(0.25)
(0.26)
Phenolic
Compounds
0.0031
0.0050
0.0060
0.0090
0.014
0.015
(0.0011)
(0.0018)
(0.0023)
(0.0025)
(0.0051)
(0.0053)
Aramonia (N)
0.23
0.51
0.82
1.65
1.50
1.94
(0.08)
(0.18)
(0.29)
(0.58)
(0.53)
(0.68)
Sulfide
0.017
0.026
0.034
0.054
0.074
0.074
(0.006)
(0.009)
(0.012)
(0.019)
(0.026)
(0.026)
Total
Chromium
0.042
0.065
0.082
0.088
0.18
0.19
(0.015)
(0.023)
(0.029)
(0.031)
(0.064)
(0.066)
Hexavalent
Chror.iun
0.00084
0.0013
0.0016
0.0018
0.0037
0.0037
(0.0003)
(0.00045)
(0.0005S)
(0.00062)
(0.00127)
(0.00131)
Zirc
0,032
0.13
0.16
0.18
0.36
0.38
(0.029)
(C.046)
(C.05S)
(0.063)
(0.127)
(0.131)
CD
-------
SECTION XI
NEW SOURCE PERFORMANCE STANDARDS
Recommended effluent limitations for new source performance standards
are based upon the application of BPCTCA control technology to the waste
water flows used as the basis for BATEA effluent limitations. The
proposed BADT effluent limitations are shown in Table 3.
The refining technology available today does not call for major
innovations in refining processes. Basically, BADT refining technology
consists of the same fundamental processes which are already in
practice, with few modifications and additions. However, a major design
criterion for new refinery capacity is reuse/ recycle of water streams
to the greatest extent possible, in order to minimize discharges to
waste water treatment facilities. Consequently, the water flow on which
new source performance standards were based is identical to the best
available technology economically achievable flow, which reflects the
best water usage as demonstrated in the petroleum refining industry.
These flows are shown in Table 65.
It should be clearly understood that no recommendations have been made,
nor are any implied, regarding the substitution of processes which
produce a lower raw waste load for others with higher raw waste load.
This is based on the consideration that the choice of a particular
«mercial route is governed largely by the availability of feedstocks
on the conditions in the product markets. Companies produce a given
of products based on their particular marketing and feedstock
position within the industry. The substitution of a cleaner process may
be possible for new producers from a technical point of view, but
completely impossible based on limited availability of the required
alternative feedstocks or on the lack of viable markets for new co-
products.
The waste water treatment technology recommended for BADT effluent
limitations is the same as called for by BPCTCA and does not include
physical - chemical treatment, because that technology has not been
sufficiently demonstrated by the petroleum refining industry.
Procedure for Development of BADT Effluent Limitations
The effluent limitations proposed for BADT technology are based on the
concentrations considered achievable by.BPCTCA and the flows from BATEA.
The daily annual average effluent limitations thus determined are con-
tained in Table 67.
179
-------
Variability Allowance for Treatment Plant Performance
The guideline numbers presented in Table .3 have taken into considerati
the variability factors, as in BPCTCA. Since the treatment technol
and process technology for BADT are the same as BPCTCA, the rati
established for BPCTCA have been used in BADT.
180
-------
TABLE 6 7
BADT
NEK SOURCE PERFORMANCE STANDARDS FOR THE PETROLEUM RT.Fi:;iNG INDUSTRY
Ar.nual Daily Kilograr.s of Pollutants/1000 Cubic Xeters of Feedstock (1) Per Stream Day
(Annual Average Daily Pounds of Pollutants/1000 BBL of Feedstock Per Streatm Day
Refinery
BODS COD TOC
2.5 (0.83) 9.4 (3.3) 2.9 (1.0)
Topping
lev-Cracking 4.0 (1.4) 25.2 (8.9) 7.1 (2.5)
Kirr.-Cracki-g 5.1 (1.8) 45.3 (16.0) 9.1 (3.2)
Petrochemical 5.4 (1.9) 35.7 (12.6) 9.7 (3.4)
Lube 8.8 (3.1) 78.7 (27.7) 15.9 (5.6)
Ir.tegrated 11.1 (3.9) 85.5 (3C.1) 20.2 (7.1)
«
sur-aff. (2) O.C14 (C.12) 0.056 (0.47) 0.017 (0.14)
Ballast (3) 0.014 (0.12) O.C72 (0.60) 0.017 (0.14)
Total Suspended
Solids
1.65 (0.5S)
2.6 (0.92)
3.4 (1.2)
3.7 (1.3)
7.1 (2.5)
7.4 (2.6)
0.011 (0.09)
0.011 (0.09)
Oil &
Grease
Phenolic
Compounds
Ar-.or.ia (N)
0.83 (0.29) 0.017 (0.0058) 0.57 (0.20)
1.32 (0.46) 0.026 (0.0092) 1.28 (0.45)
1.65 (0.58) 0.034 (0.012) 3.1 (1.1)
1.8 (0.63) 0.036 (0.0125) 4.0 (1.4)
3.5 (1.24) 0.074 (0.026) 3.7 (1.3)
3.7 (1.30) 0.077 (0.027) 4.S (1.7)
0.0050 (0.042)
0.0050 (0.042)
Sulfide
Total
Chrorciu-
0.016 (0.005S) 0.042 (0.015)
0.026 (0.0092) 0.065 (0.023)
0.034 (0.012) 0.082 (0.029)
0.037 (0.013) 0.038 (0.031)
0.072 (0.025) 0.18 (0.064)
0.077 (0.027) 0.19 (0.066)
Hexavalent
Chroniua
Zinc
0.00034 (0.0003) 0.032 (0.029)
0.0013 (0.00045) 0.13 (O.C46)
0.0016 (0.00058) 0.16 (0.05S)
0.0018 (0.00062) 0.18 (0.063)
0.0037 (0.03127) 0.36 (0.127)
0.0037 (0.00131) 0.38 (0.131)
(1) raedstccV. - Crude oil ar.d/or natural gas liquids.
(D T'r.e additional allocation being allovei! for cc.ntl-ir.atod stcrrr. runoff flow (kg/1000 liters
(Ibs.'ICCO g^llcns) shall be b;uec solely on that storr. flcv vhich passes thcurgh the treatment
syster.. All additicr.al storr. runoff, that has been segregated frcr. the r.ain v.iste stream, shall
net show a visible sheen or exceed a TCC'Concentration of 15 ;r.g/l when discharged.
(3) This is an additional allocation, based on ballast vater intake (daily average) kilograr.s
per ICjO liters (pounds per 10CC gallons).
00
-------
TABLE 68
METRIC UNITS
CONVERSION TABLE
MULTIPLY (ENGLISH UNITS) by TO OBTAIN (METRIC UNITS)
ENGLISH UNIT ABBREVIATION CONVERSION ABBREVIATION METRIC UNIT
acre ac
acre - feet ac ft
British Thermal
Unit BTU
British Thermal
Unit/pound BTU/lb
cubic feet/minute cfm
cubic feet/second cfs
cubic feet cu ft
cubic feet cu ft
cubic inches cu in
degree Fahrenheit F°
feet ft
gallon' gal
gallon/minute gpm
horsepower hp
inches in
inches of mercury in Hg
pounds Ib
million gallons/day mgd
mile mi
pound/square
inch (gauge) psig
square feet sq ft
square inches sq in
tons (short) t
yard y
* Actual conversion, not a multiplier
0.405
1233.5
. 0.252
0.555
0.028
1.7
0.028
28.32
16.39
0.555(°F-32)*
. 0.3048
3.785
0.0631
0.7457
2.54
0.03342
0.454
3,785
1.609
(0.06805 psig +1)*
0.0929
6.452
0.907
0.9144
ha
cu m
kg cal
kg cal/kg
cu m/min
cu m/min
cu m
1
cu cm
°C
m
1
I/sec
kw
cm
atm
kg
cu m/day
km
atm
sq m
sq cm
kkg ^
m
hectares
cubic meters
kilogram - calories
kilogram calories/kilogram
cubic meters/minute
cubic meters/minute
cubic meters
liters
cubic centimeters
degree Centigrade
meters
liters
liters/second
killowatts
centimeters
atmospheres
kilograms
cubic meters/day
kilometer
atmospheres (absolute)
square meters
square centimeters
metric tons (1000 kilograms)
meters
182
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SECTION XII
ACKNOWLEDGEMENT
This Development Document was prepared for the Environmental Protection
Agency by the staff of Roy F. Weston, Inc., under the direction of Clem
Vath, Project Director. The following individuals of the staff of Roy
F. Weston, Inc. made significant contributions to this effort:
David Baker, Project Manager
Michael Smith, Project Engineer
M. Jotwani, Project Engineer
David L. Becker, Project Officer and Martin Halper, Chemical Engineer,
Effluent Guidelines Division, contributed to the overall supervision of
this study, preparation of the draft report and preparation of this
Development Document. Allen Cywin, Director, Effluent Guidelines
Division, Ernst P. Hall, Deputy Director, Effluent Guidelines Division
and Walter J. Hunt, Chief, Effluent Guidelines Development Branch,
offered guidance and suggestions during this program.
•
The members of the working group/steering committee who coordinated the
internal EPA review are:
Allen Cywin, Effluent Guidelines Division
Walter J. Hunt, Effluent Guidelines Division
David Becker, Effluent Guidelines Division
Martin Halper, Effluent Guidelines Division
Leon Myers, Office of Research and Monitoring, (Ada)
William Bye, Region VIII
Robert Twitch-ell, Region III
Wayne Smith, National Field Investigation Center, (Denver)
Thomas Belk, Office of Permit Programs
John Savage, Office of Planning and Evaluation
Alan Eckert, office of General Counsel
Phillip Bobel, Region IX
Benigna Carroll, Office of Hazardous Materials Control
Ned Burleson, Region VI
Srini Vasan, Region V
Acknowledgement and appreciation is also given to the secretarial staff
of both the Effluent Guidelines Division and Roy F. Weston, Inc., for
their effort in the typing of the drafts and necessary revisions, and
the final preparation of the effluent guidelines document. The
following individuals are acknowledged for their contributions:
Kit Krickenberger, Effluent Guidelines Division
Kay Starr, Effluent Guidelines Division
Brenda Holmone, Effluent Guidelines Division
Chris Miller, Effluent Guidelines Division
183
-------
Sharon Ashe, Effluent Guidelines Division
Susan Gillmann, Roy F. Weston, Inc.
Judith Cohen, Roy F. Weston, Inc.
Appreciation is extended to staff members of EPA's Regions II, III, V,
VI, IX, and X offices and the Robert S. Kerr Laboratory for their
assistance and cooperation.
Appreciation is extended to the following State organizations for
assistance and cooperation given to this program.
California, state Water Resources Control Board
Illinois, Environmental Protection Agency
Michigan, Water Resources commission
Texas, Water Control Board
Virginia, State Water Control Board
Washington, Department of Ecology
Appreciation is extended to the following trade associations and
corporations for their assistance and cooperation given to this program.
American Petroleum Institute
Amerada Hess Corporation
American Oil Company
Ashland oil Inc.
Atlantic Richfield Company
Beacon Oil Company
BP Oil Corporation
Champlin Petroleum Company
Coastal States Petrochemical Company
Commonwealth Oil & Refining Company, Inc.
Exxon, USA
Gulf Oil Company
Kerr - McGee Corporation
Laketon Asphalt Refining, Inc.
Leonard Inc.
Lion Oil Company
Marathon Oil Company
OKC Refining Inc.
Phillips Petroleum Company
Shell Oil Company
Sun Oil Company of Pennsylvania
Texaco Inc.
Union Oil Company of California
United Refining Company
U.S. Oil and Refining Company
184
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SECTION XIII
BIBLIOGRAPHY
1. American Petroleum Institute, "Petroleum Industry Raw Waste toad
Survey," December, 1972.
2. Annessen, R. J., and Gould, G. D., "Sour Water Processing Tui^ns
Problem Into Payout," Chemical Engineering, March 22, 1971.
\
3. Annual-Refining Surveys, "Survey of Operating Refineries in the
U.S.," The Oil and Gas Journal, April 1, 1973.
3a. Annual Refining Surveys, "Survey of Operating Refineries in the
U.S.", The Oil and Gas Journal 1967.
4. Armstrong, T. A., "There's Profit in Processing Foul Water," The Oil
and Gas Journal, pp. 96-98, June 17, 1968.
5. Beavon, David K., "Add-On Process Slashes Glaus Tailgas Pollution,"
Chemical Engineering, pp. 71-73, December 13, 1971.
6. "The Beavon Sulfur Removal Process for the Purification of Sulfur
Plant Tailgas," Ralph M. Parsons Company Publication.
Benger, M., "Disposal of Liquid and Solid Effluents from Oil
Refineries," 21st Purdue Industrial Waste Conference, pp. 759-767,
1966.
8. Beychok, M. R., Aqueous Wastes from Petroleum and Petrochemical
Plants, John Wiley 6 Sons, London, 1967.
9. Beychok, M. R., "Waste water Treatment of Skelly Oil Company's El
Dorado, Kansas Refinery," 16th Purdue Industrial Waste Conference,
pp. 292-303, 1961.
10. Brown, K. M., "Some Treating and Pollution Control Process for
Petroleum Refineries," The Second INTERPETROL.Congress, Rome, Italy,
June 22-27, 1971.
11. Brownstein, Arthur M., U.S. Petrochemicals, The Petroleum Publishing
Co., Tulsa, Oklahoma, 1972.
12. Brunner, D. R., and Keller, D. J., "Sanitary Landfill Design and
Operation," U.S. Environmental Protection Agency, Washington, D.C.,
1972.
185
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13. Campbell, G. C., and Scoullar, G. R., "How Shell Treats Oakville
Effluent," Hydrocarbon Processing 6 Petroleum Refiner, 43 (5): 137-
140, May, 1964.
14. "Chevron Waste Water Treating Process," Chevron Research Company
Publication, September, 1968.
15. Cohen, J. M., "Demineralization of Waste waters," Advanced Waste
Treatment and Water Reuse Symposium, Volume 2, February 23-24, 1971.
16. Conser, R. E., "The Environmental Fuels Processing Facility," SNG
Symposium, Institute of Gas Technology, Chicago, Illinois, March 12-*
16, 1973.
17. Gulp, R. L., and Gulp, G. L., Advanced Waste water Treatment, Van
Nostrand Reinhold Company, New York, 1971.
18. Davis, R. W., Biehl, V. A., and Smith, R. M., "Pollution Control and
Waste Treatment at an Inland Refinery," 19th Purdue Industrial Waste
Conference, pp. 128-138, 1964.
19. Daniels, E. K., Latz, J. R., Castler, L. A., "Pollution Control at
Ferndale, Washington," 23rd Midyear Meeting of the American
Petroleum Instituted Division of Refining, May, 1958.
20. Denbo, R. T., and Gowdy, F. W., "Baton Rouge Waste Water Control
Program Nears End," The Oil and Gas Journal, pp. 62-65, May 29,
1972.
21. Diehl, D. S., Denbo, R. T., Bhatta, M. N., and sitman, W. D.,
"Effluent Quality Control .at a Large Refinery," Journal of the Water
Pollution Control Federation, 43 (11), November, 1971.
22. Dorris, T. C., Patterson, D., copeland, B. J., "Oil Refinery
Effluent Treatment in Ponds," 35th Meeting of the Water Pollution
Control Federation, pp. 932-939, # October 7-11, 1962.
23. Easthagen, J. H., Skrylov, V., and Purvis, A. L., "Development of
Refinery Waste water Control at Pascagbwle, Mississippi," Journal of
Water Pollution Control Federation, 37 (12): 1621-1628, December,
1965.
24. Elkin, H. F., "Activated Sludge Process Application to Refinery
Effluent Waters," Journal of Water Pollution Control Federation, 28
(9): 1122-1129, September, 1956.
25. Fair, G. M., Geyer, J. C., and Okum, D. A., Water and Waste water
Engineering, Volume 2, John Wiley 6 Sons, Inc., New York, 1968.
186
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26. ^luid Bed Incineration of Petroleum Refinery Wastes fcr the
Environmental Protection Agency, Washington, D.C., March, 1971.
12050KET
27. Ford, D. L., and Buercklin, M. A., "The Interrelationship of
Biological-Carbon Adsorption Systems for the Treatment of Refinery
and Petrochemical Waste waters," 6th International Water Pollution
Research Conference, Session 11, Hall C, June 18-23, 1972.
28. Fosberg, T. M., "Industrial Waste Water Reclamation," 74th National
Meeting American Institute of Chemical Engineers, March 11-15, 1973.
29. Franzen, A. E., Skogan, V. G., and Grutsch, J. F., "Successful
Tertiary Treatment at American," The Oil and Gas Journal, April 3,
1972.
30. Gillian, A. S., and Anderegg, F. C., "Biological Disposal of
Refinery Wastes," 14th Purdue Industrial Waste Conference, pp. 145-
154, 1959.
31. Gloyna, E. G., Brady, S. 0., and Lyles, H., "Use of Aerated Lagoons
and Ponds in Refinery and Chemical Waste Treatment," 41st Conference
of the Water Pollution Control Federation, September 22-27, 1968.
31a. Hale, J.H., and Myers, L.H., "The Agencies Removed by Carbon
Treatment of Refinery Waste waters".
Hart, J. A., "Air Flotation Treatment and Reuse of Refinery Waste
water," 25th Annual Purdue Industrial Waste Conference, May, 1970.
33. Hart, J. A., "On Improving Waste water Quality," Water, and Sewage
Works, IW 20-26, September-October, 1970.
34. Hentschel, M. L., and Cox, T. L., "Effluent Water Treating at
Charter International Oil Company's Houston Refinery," 74th National
Meeting American Institute of Chemical Engineers, March, 1973.
35. Home, W. R., and Hurse, J. E., "Biological Reduction of Phenolic
Type Industrial Wastes," Southern Engineering, January, 1965.
35a. Ingols, R.S., "The Toxicity of Chromium," $ percentSth Purdue
Industrial waste conference,$ percent pp. 86-95, 1953.
36. Kaup, E. C., "Design Factors in Reverse Osmosis," Chemical
Engineering, April 2, 1973.
37. Klett, Robert J., "Treat sour Water for Profit," Hydrocarbon
Processing, October, 1972.
187
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38. Klipple, R. W., "Pollution Control Built into Guayama Petrochemical
Complex," water and sewage Works, 116 (3): IW 2-6, March, 1969.
39. Lankin, J. C., and Sord, L. V., "American Oil Cleans up Wastes
Aerated Lagoons," Hydrocarbon Processing & Petroleum Refiner, 43
(5) : 133-136, May, 1964,
40. "Major Oil Fields Around the World," International Petroleum
Encyclopedia, 1967, Petroleum Publishing Co., Tulsa, Oklahoma.
41. Mohler, E. F. Jr., Clere, L. T., "Development of Extensive Water
Reuse and Bio-oxidation in a Large Oil Refinery," National
Conference on Complete Water Reuse, April, 1973.
42. McKinney, R. E., "Biological Treatment Systems for Refinery Wastes,"
39th Annual Conference of the Water Pollution Control Federation,
pp. 346-359, September 24-30, 1966.
43. McKinney, G. M., Ferrero, E. P., and Wenger, W. J., "Analysis of
Crude Oils from 546 Important Oil Fields in the United States,"
Report of Investigations 6819, United states Department of the
Interior.
44. McPhee, W. T., and Smith, A. R., "From Refinery Waste to Pure
Water," 16th Purdue Industrial Wastes Conference, pp. 440-448, May,
1961.
45. McWilliams, F. G., and Schuller, R. P., "SNG, Naptha and Low-Sul
Fuel Oils from Crude oils Using Commercially Proven Technolog
American Institute of Chemical Engineers, New York, November
December 2, 1972.
46. Patterson, J. W., and Minear, R. A., Waste water Treatment
Technology, for State of Illinois Institute for Environmental
Quality, 2nd, January, 1973.
47. "P. C. Treatment Gets Industrial Trial," Environmental Science and
Technology, Vol. 7, No. 3, March, 1973, pp. 200-202.
48. Peoples, R. F., Krishnan, P., and simonsery, R. N., "Nonbiological
Treatment of Refinery Waste water," Journal of the Water Pollution
Control Federation, 44 (11): 2120-2128, November, 1972.
48a. "Petroleum Refining Effluent Guidelines", for the Environmental
Protection Agency, Office of Water Programs.
49. "Petroleum Refining Industry Waste water Profile" for the Federal
Water Pollution Control Association.
188
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50. »Porges, JR., "Industrial Waste Stabilization Ponds in the United
States," Journal of the Water Pollution Control Federation, 35 (4) :
456-468, April, 1963.
51. Prather, B. V., "Effects of Aeration on Refinery Waste Water
Effluents," Western Petroleum Refiners Association Proceedings of
the Waste Disposal and Stream Pollution Conference, October 7-*-8,
1959.
52. "Pretreatment of Discharges to Publicly Owned Treatment Works,"
Federal Guidelines, E.P.A., 1973.
53. Process Design Manual for Carbon Adsorption, Environmental
Protection Agency,'Washington, D.C., October, 1971.
54. Process Design Manual for Suspended Solids Removal, Environmental
Protection Agency, Washington, D.C., 1971.
55. Purcell, W. L., and Miller, R. B., "Waste Treatment of Skelly Oil
Company's El Dorado, Kansas Refinery," 16th Purdue Industrial Waste
Conference, pp. 292-303, 1961.
56. Rambow, C. A., "Industrial Waste water Reclamation," 23rd Purdue
Industrial Waste Conference, pp. 1-9, May, 1968.
57. Reid, G. W., and Streebin, L. E., "Evaluation of Waste Waters from
Petroleum and Coal Processing," Prepared for Office of Reserach and
Monitoring U.S. Environmental Protection Agency,, Washington, D.C.,
(Contract no. EPA-R2-72-001. December, 1972).
58. Rodriguez, D. G., "Sour Water Strippers," 74th National Meeting
American Institute of Chemical Engineers, March 11-15, 1973.
59. Rose, B. A., "Water Conservation Reduces Load on Sohio's Waste
Treatment Plant," Water and Sewage Works, 116 (9): IW 4-8,
September, 1969.
60. Rose, W. L., and Gorringe, G. E., "Activated Sludge Plant Handles
Loading Variations," The Oil and Gas Journal, pp. 62-65, October,
1972.
61. Sebald, J. F., "A Survey of Evaporative and Non-Evaporative Cooling
Systems," 74th National Meeting American Institute of Chemical
Engineers, March 11-15, 1973.
62. Selvidge, C. W., Conway, J. E., and Jensen, R. H., "Deep
Desulfurization of Atmospheric Reduced Crudes by RCD isomax," Japan
Petroleum Institute Meeting, Tokyo, Japan, November 29, 1972.
189
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62a. Short, E., and Myers, L.H., "Pilot-Plant Activated Carbon Treatment
of Petroleum Refinery Waste water".
63. Skamser, Robert O., "The U.S. Refining Outlook to 1980,"
National Meeting American Institute of Chemical Engineers, March 11-
15, 1973.
64. Solid Waste Disposal Study, Technical Report Genesee County,
Michigan, U.S. Department of Health, Education and Welfare, Bureau
of Solid Waste Management, Cincinnati, 1969.
65. Standard Industrial Classification Manual, 1967, Executive Office of
the President, Bureau of the Budget.
66. Standard Methods for Examination of Water and Waste water, American
Public Health Association, American waterworks Association, water
Pollution Control Federation, 13th Edition.
67. Stern, Arthur C. , Air Pollution, Vol. Ill, Academic Press Inc.,
1968.
68. Stramberg, J. B. , "EPA Research and Development Activities with
Oxygen Aeration," Technology Transfer Design Seminar for Municipal
Waste water Treatment Facilities, February 29 and March 1-2, 1972.
69. Strong, E. R., and Hatfield, R. , "Treatment of Petrochemical Wastes
by Superactivated Sludge Process," Industrial and Engineering
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70. strother, C. w.. Vermilion, W. L. , and Conner, A. J., "UOP
Innovations in Design of Fluid Catalytic Cracking Units," Division
of Refining, 37th Midyear Meeting, New York, May 8-12, 1972.
71. stroud, P. W. , sorg, L. v., and Lamkin, J. C. , "The First Large
Scale Industrial Waste Treatment Plant on the Missouri River," 18th
Purdue Industrial Waste Conference, pp. 460-475, 1963.
72. Thompson, C. S., Stock, J. , and Mehta, P. L. , "Cost and Operating
Factors for Treatment of Oil Waste Water," The oil and Gas Journal,
pp. 53-56, November 20, 1972.
72a. U.S. Department of Health, Education and Welfare, "Public Health
Service Drinking Water Standards", PHS Publication No. 956,1962.
73. Walker, G. J., "A Design Method for Sour Water Stream Strippers,"
National Petroleum Refiners Association, March 23-26, 1969.
74. Watkins, C. H. , and Czajkowski, G. J., "Hydrodesulfurization of
Atmospheric and Vacuum Gas Oils," 68th National Meeting American
190
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Institute of Chemical Engineers, Houston, Texas, February 28-March
"4, 1971.
Wigren, A. A., and Burton, F. L., "Refinery Waste water Control,"
Journal of the Water Pollution Control Federation, 44 (1): 117-128,
January, 1972.
191
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SECTION XIV
GLOSSARY AND ABBREVIATIONS
Glossary
Acid Oil
Straight chain and cyclic hydrocarbon with carboxyl group(s) attached.
Act
The Federal Water Pollution Act Amendments of 1972.
Aerobic
In the presence of oxygen.
Alkylates
Branched paraffin hydrocarbons.
Anaerobic
Living or active in absence of free oxygen.
latic Life
All living forms in natural waters, including plants, fish, shellfish,
and lower forms of animal life.
Aromatics
Hydrogen compounds involving a 6-carbon, benzene ring structure.
Best Available Technology Economically Achievable (BATEA)
Treatment required by July 1, 1983 for industrial discharge to surface
waters as defined by section 310 (b) (2) (A) of the Act.
Best Practicable Control Technology Currently Achievable (BPCTCA)
Treatment required by July 1, 1977 for industrial discharge to surface
waters as defined by section 301 (b) (1) (A) of the Act.
Best Available Demonstrated Technology (BADT)
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Treatment required for new sources as defined by section 306 of the Act.
Biochemical Oxygen Demand
Oxygen used by bacteria in consuming a waste substance.
Blowdown
A discharge from a system, designed to prevent a buildup of some
material, as in boiler and cooling tower to control dissolved solids.
Butadiene
Synthetic hydrocarbon having two unsaturated carbon bonds.
By-Product
Material which, if recovered, would accrue some economic benefit, but
not necessarily enough to cover the cost of recovery.
Capital Costs
Financial charges which are computed as the cost of capital times the
capital expenditures for pollution control. The cost of capital is
based upon a weighted average of the separate costs of debt and equity.
Catalyst
A substance which can change the rate of a chemical reaction, but wh
is not itself involved in the reaction.
Category and Subcategory
Divisions of a particular industry which processed different traits
which affect water quality and treatability.
Chemical Oxygen Demand
Oxygen consumed through chemical oxidation of a waste.
Clarification
The process of removing undissolved materials from a liquid.
Specifically, removal of solids either by settling or filtration.
Coke Petroleum
Solid residue of 90 to 95 percent fixed carbon.
194
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Cycles of Concentration
e ratio of the dissolved solids concentration of the recirculating
er to make-up water.
Depletion or Loss
The volume of water which is evaporated, embodied in product, or
otherwise disposed of in such a way that it is no longer available for
reuse in the plant or available for reuse by others outside the plant.
Depreciation
The cost reflecting the deterioration of a capital asset over its useful
life.
Direct-Fired Heater
A heater in which heat is supplied by combustion, as distinguished from
a heat exchanger where heat is supplied by a hot liquid or gas.
Emulsion
A liquid system in which one liquid is finely dispersed in another
liquid -in such a manner that the two will not separate through the
action of gravity alone.
End-of-Pipe Treatment
of overall refinery wastes, as distinguished from treatment at
individual processing units.
Filtration
Removal of solid particles or liquids from other liquids or gas streams
by passing the liquid or gas stream through a filter media.
Fractionator
A generally cylindrical tower in which a mixture of liquid components is
vaporized and the components separated by carefully varying the
temperature and sometimes pressure along the length of the tower.
Gasoline
A mixture of hydrocarbon compounds with a boiling range between 100 o and
UOOo F.
Grease
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A solid or semi-solid composition made up of animal fats, alkali, water,
oil and various additives.
Hydrocarbon
A compound consisting of carbon and hydrogen.
Hydrogenation
The contacting of unsaturated or impure hydrocarbons with hydrogen gas
at controlled temperatures and pressures for the purpose of obtaining
saturated hydrocarbons and/or removing various impurities such as sulfur
and nitrogen.
Industrial Waste
All wastes streams within a plant. Included are contact and non-contact
waters. Not included are wastes typically considered to be sanitary
wastes.
Investment costs
The capital expenditures required to bring the treatment or control
technology into operation. These include the traditional expenditures
such as design; purchase of land and materials; ''site preparation;
construction and installation; etc., plus any additional expenses
required to bring the technology into operation including expenditures
to establish related necessary solid waste disposal.
Isomer
A chemical compound that has the same number, and kinds of atoms as
another compound, but a different structural arrangement of the atoms.
Mercaptan
An organic compound containing hydrogen, carbon, and sulfur (RSH) .
Microcrystalline Wax
A non-crystalline solid hydrogen with a melting point of about 106o to
195o F. Also known as petrolatum.
Motor Octane Number
An expression of the antiknock value of gasoline.
Naphtha
196
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I
A petroleum fraction, including parts of the boiling range of gasoline
and Tcerosine, from which solvents are obtained.
Acids
Partially oxidized naphthalenes.
New Source
Any building, structure, facility, or installation from which there is
or may be a discharge of pollutants and whose construction is commenced
after the publication of the proposed regulations.
No Discharge of Pollutants
No net increase (or detectable gross concentration if the situation
dictates) of any parameter designated as a pollutant to the accuracy
that can be determined from the designated analytical method.
Octane
The numerical rating of a gasoline's resistance to engine knock.
Olefins
Unsaturated straight-chain hydrocarbon compounds seldom present in crude
oil, but frequently in cracking processes.
ration and Maintenance
Costs required to operate and maintain pollution abatement equipment.
They include labor, material, insurance, taxes, solid waste disposal,
etc.
Overhead Accumulator
A tank in which the condensed vapors from the tops of the fractionators,
steam strippers, or stabilizers are collected.
Paraffin Wax
A crystalline solid hydrocarbon with a melting point of 105o to 1.55o F.
Petroleum
A complex liquid mixture of hydrocarbons and small quantities of
nitrogen, sulfur, and oxygen.
PH
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A measure of the relative acidity or alkalinity of water. A pH of 7.0
indicates a neutral condition. A greater pH indicates alkalinity and a
lower pH indicates acidity. A one unit change in pH indicates 10 fold
change in acidity and alkalinity.
Phenol
Class of cyclic organic derivatives with basic formula C6HOH.
Pretreatment
Treatment proved prior to discharge to a publicly owned treatment works.
Process Effluent or Discharge
The volume of water emerging from a particular use in the plant.
Plant Effluent or Discharge After Treatment
The volume of waste water discharge from the industrial plant. In this.
definition, any waste treatment device is considered part of the
industrial plant.
Raffinate
The portion of the oil which remains undissolved and is not removed by
solvent extraction.
Raw
Untreated or unprocessed.
Reduced Crude
The thick, dark, high-boiling residue remaining after crude oil has
undergone atmospheric and/or vacuum fractionation.
Secondary Treatment
Biological treatment provided beyond primary clarification.
Sludge
The settled solids from a thickener or clarifier. Generally, almost any
flocculated settled mass.
Sour
Denotes the presence of sulfur compounds, such as sulfides and
mercaptans, that cause bad odors.
198
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Spent. Caustic
ecus solution of sodium hydroxide that has been used to remove
fides, mercaptans, and organic acids from petroleum fractions.
Stabilizer
A type of fractionator used to remove dissolved gaseous hydrocarbons
from liquid hydrocarbon products.
Standard Raw Waste Loads (SRWL)
Net pollution loading produced per unit of production (or raw material)
by a refining process after separation of the separables (STS).
Stripper
A unit in which certain components are removed from a liquid hydrocarbon
mixture by passing a gas, usually steam, through the mixture.
Supernatant
The layer floating above the surface of a layer of solids.
Surface Waters
Navigable waters. The waters of the United States, including the
rritorial seas.
^?e
eet
Denotes the absence of odor^causing sulfur compounds, such as sulfides
and mercaptans.
Topping Plant
A refinery whose processing is largely confined to oil into raw products
by simple atmospheric distillation.
Total Suspended Solids (TSS)
Any solids found in waste water or in the stream which in most cases can
be removed by filtration. The origin of suspended matter .may be man-
made wastes or natural sources such as silt from erosion.
Waste Discharged
The amount (usually expressed as weight) of some residual substance
which is suspected or dissolved in the plant effluent after treatment.if
any.
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Waste Generated
The amount (usually expressed as weight) of some residual
generated by a plant process or the plant as whole and which
suspended or dissolved in water. This quantity is measured before
treatment.
Waste Loading
Total amount of pollutant substance, generally expressed as pounds per
day.
200
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Abbreviations
- Aerated Lagoon •
AS - Activated Sludge
API - American Petroleum Institute
BADT - Best Available Demonstrated Technology
BATEA - Best Available Technology Economically Achievable
BPCTCA - Best Practicable Control Technology Currently Available
bbl - Barrel
BOD - Biochemical Oxygen Demand
bpcd - Barrels per calendar day
bpsd - Barrels per stream day (operating day)
BS and W - Bottom Sediment and Water
BTX - Benzene-Toluene-Xylene mixture
- Chemical Oxygen Demand
m - cubic meter(s)
DAF - Dissolved Air Flotation
DO - Dissolved Oxygen
gpm - Gallons per minute
k - thousand(e.g., thousand cubic meters)
kg - kilogram(s)
1 - liter
Ib. - pound (s).
LPG - Liquified Petroleum Gas
M - Thousand (e.g., thousand barrels)
MBCD - Thousand Barrels per calendar day
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MBSD - Thousand Barrels per stream day
mgd - Million gallons per day
mg/L - Milligrams per liter (parts per million)
MM - Million (e.g., million pounds)
PP - Polishing pond
psig - pounds per square inch, gauge (above 1U.7 psig)
RSH - Mercaptan
sec - Second-unit of 'time
scf - Standard cubic feet of gas at 60o F and 14.7 psig
SIC - Standard Industrial Classification
SRWL - Standard Raw waste Load
ss - Suspended Solids
STS - Susceptible to Separation
.TOC - Total Organic Carbon
TSS - Total Suspended Solids
VSS - volatile Suspended Solids
202
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