&EPA
United States
Environmental Protection
Agency
Industrial Environmental Research EPA-600/2-78-065b
Laboratory March 1978
Cincinnati OH 45268
Research and Development
Trace Element
Study at a Primary
Copper Smelter
Volume II
Report Appendix
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-78-065b
March 1978
TRACE ELEMENT STUDY AT A
PRIMARY COPPER SMELTER
Volume II: Report Appendix
by
Klaus Schwitzgebel, Richard T. Coleman
Robert V. Collins, Robert M. Mann,
and Carol M. Thompson
Radian Corporation
Austin, Texas 78766
Contract No. 68-01-4136
Project Officers
Margaret J. Stasikowski and John 0. Burckle
Metals and Inorganic Chemistry Branch
Industrial Environmental Research Laboratory
Cincinnati, Ohio 45268
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has "been reviewed by the Industrial Environmental Research
Laboratory, Cincinnati, U.S. Environmental Protection Agency, and approved
for publication. Approval does not signify that the contents necessarily
reflect the vievs and policies of the U.S. Environmental Protection Agency,
nor does mention of trade names or commercial products constitute endorse-
ment or recommendation for use.
ii
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FOREWORD
When energy and material resources are extracted, processed,
converted, and used, the related pollutional impacts on our environment
and even on our health often require that new and increasingly more
efficient pollution control methods be used. The Industrial Environmental
Research Laboratory - Cincinnati (lERL-Ci) assists in developing and
demonstrating new and improved methodologies that will meet these needs
both efficiently and economically.
This report presents the findings of an investigation of air
pollutant emissions from the reverberatory furnace pollution control
system at a primary copper smelter. The study was performed to assess
the degree of particulate emissions control and control problems
associated with the application of electrostatic precipitators in the
nonferrous metals production industry. The results are being used within
the Agency's Office of Research and Development as part of a larger
effort to define the potential environmental impact of emissions from
this industry segment and the need for improved controls. The findings
will also be useful to other Agency components and the industry in
dealing with environmental control problems. The Metals and Inorganic
Chemicals Branch of the Industrial Pollution Control Division should be
contacted for any additional information desired concerning this program.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
iii
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ABSTRACT
This project was undertaken to explore the distribution of trace elements
in environmental emissions from a primary copper smelter. The efforts were
concentrated on the reverberatory furnace and the electrostatic precipitator
controlling emissions from the reverberatory furnace. The following major
conclusions were reached: (1) the electrostatic precipitator effectively
controls all particulate emissions at its design efficiency rating (about 96%)
at the operating gas temperature of 600 degrees F; (2) appreciable material
composed of toxic trace elements pass through the precipitator in the vapor
state at the ESP operating temperature and condense to form particulate upon
cooling. Arsenic trioxide was a major constituent of the emissions passing
the ESP from the reverberatory furnace. The following elements were examined:
Al, As, Ba, Be, Ca, Cd, Cr, Cu, F, Fe, Hg, Mo, Ni, Pb, Sb, Se, Si, V, Zn.
This report was submitted in fulfillment of Contract No. 68-01-4136 by
Radian Corporation under the sponsorship of the U.S. Environmental Protection
Agency. This report covers a period from July 1976 to December 1976, and
work was completed as of May 1977.
iv
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CONTENTS
Section Page
1 Introduction , .., 1
Smelter Minor Element Flow 3
Arsenic Sampling 4
ESP Performance 5
2 Plant Description 7
Material Flow 7
Reverberatory Furnace 15
Reverberatory Furnace ESP 16
Plant Operation During Sampling , 16
3 Description of Sampling Points. 18
Precipitator Inlet 18
Precipitator Outlet , 18
Precipitator Dust *. . 18
Concentrate , 21*
Matte and Slag ,. ,.. 21
4 Sampling Procedures 22
Evaluation of the Precipitator Performance 22
5 Electrostatic Precipitator Material Balance Samples ,. 32
Precipitator Inlet and Outlet 32
Precipitator Dust 34
6 Reverberatory Furnace Samples and Flows. 35
7 Reverberatory ESP Flow Rates 37
8 Sample Analysis 38
Sample Preparation 42
Analytical Procedures , 42
9 Data Evaluation 46
Material Balances 46
Error Propagation 47
10 Analytical Results and Material Balances Around the
Reverberatory Furnace Electrostatic Precipitator,, , 51
11 Reverberatory Furnace Material Balance 57
12 X-Ray Fluorescence and SSMS Analyses of Material
Condensed in Impingers , 63
13 Identification of Major Crystalline Species 67
14 Analytical Results of Vapor Train Sampling 87
15 Arsenic Sampling 90
Equipment Description 90
Sampling Methodology , 92
Results 93
REFERENCES . 118
TABLE OF CONVERSION FACTORS 12Q
v
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FIGURES
Figure Page
2-1 Schematic Diagram of Primary Copper Smelter ................... 8
2-2 Reverberatory Furnace Feed Preparation ........................ 9
2-3 Reverberatory Furnace Flow Diagram ............................ 11
2-4 Converters and Anode Furnace .................................. 13
2-5 Converter Dust Recovery and R2SO^ Plant ........... ............ 14
2-6 Electrostatic Precipitator and Dust Handling System
for Reverberatory Furnace Gases ............................ 17
3-1 Schematic Diagram of Inlet Ducts .............................. 19
3-2 Schematic Diagram of Outlet Duct .............................. 20
4-1 Cross Section and Sample Point Identification of
East Duct at ESP Inlet ..................................... 23
4-2 Cross Section and Sample Point Identification of
West Duct at ESP Inlet ..................................... 24
4-3 Cross Section and Sample Point Identification in
Exit Duct .................................................. 25
4-4 Velocity Profile of East Duct Precipitator Inlet
(July 7 , 1976) ............................................. 27
4-5 Velocity Profile of West Duct, Precipitator Inlet
(July 7, 1976) ........................... . ................. 28
4-6 Outlet Velocity Profile (Velocities in ESP)
(July 7 , 1976) ............................................. 29
5-1 .Wet Electrostatic Precipitator ................................ 33
8-1 Dissolution and Analytical Scheme of a WEP Slurry ............. 39
8-2 Analytical Scheme of an Impinger Liquor Sample ................ 40
VI
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FIGURES (Cont'd)
Figure Page
8-3 Dissolution and Analytical Scheme of Solid Samples 41
13-1 X-Ray Powder Diffraction Pattern - Reverberatory
Furnace Feed Concentrate (Collected July 13, 1976,
11:10 pm "C" Shift) . .. . 68
13-2 X-Ray Powder Diffraction Pattern - Dust Hopper
(Collected July 11, 1976) 73
13-3 X-Ray Powder Diffraction Pattern - Collected at
ESP Outlet on In-Stack Filter (Collected July 10,
1976, from 6:30 to 8:14 am) 76
13-4 X-Ray Diffraction Pattern - Condensed Particulate
Collected at ESP Outlet on Out~of-Stack Filter
(July 15, 1976 from 8:50 to 10:20 am) 80
13-5 X-Ray Powder Diffraction Pattern - Condensed Particulate
Collected at ESP Inlet on Out-of-Stack Filter
(July 15, 1976 from 1:00 to 2:20 pm) 82
13-6 X-Ray Powder Diffraction Pattern for Material Condensed
in Impingers (Composite Sample) 84
14-1 Schematic of the Vapor-Phase Trace Element
Sampling Train . 87
15-1 Arsenic Sampling Train (Modified ESP-5 Train) 91
Vll
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TABLES
Table Page
1-1 A Summary of the Sampling Effort (July 7
through July 16, 1976) 2
4-1 Equipment Used for Monitoring Precipitator Performance.. 26
4-2 Gas Composition 31
5-1 Impinger Solutions Used for ESP Material Balance 34
6-1 Reverberatory Furnace Flow Rates 36
7-1 Gas Flow Rate in ACFM 37
9-1 Flow Rates for Streams of the Reverberatory
Furnace ESP 48
9-2 Averaged Reverberatory Furnace Flow Rates 49
9-3 Estimated Error Limits of Chemical Analyses 50
10-1 Analytical Results from Inlet and Outlet Sampling
Trains and Precipitator Dust (July 11, 1976) 52
10-2 Elemental Content of Incoming and Outgoing ESP-Streams
(July 11, 1976) 53
10-3 Elemental Flow Rates in ESP Inlet and Outlet
Streams (July 11, 1976) 54
10-4 Survey Analysis of the Outlet WEP Sample By Spark
Source Mass Spectrometry (July 11, 1976) 55
10-5 Survey Analysis of the Precipitator Dust by Spark
Source Mass Spectrometry (July 11-13, 1976) 56
11-1 Analytical Results from Streams Around the Reverberatory
Furnace (July 11-14, 1976) 58
11-2 Element Flow Rates in the Feed and Discharge Streams of
the Reverberatory Furnace (July 11-14, 1976) 59
viii
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TABLES (Cont'd)
Table
3,1-3 Survey Analysis of the Reverberatory Furnace Feed
by SSMS (July 12-14, 1976)
60
11-4 Survey Analysis of Matte by Spark Source Mass
Spectrometry (July 12-14, 1976) ..... . . ................ 61
11-5 Survey Analysis of Reverberatory Furnace Slag* by
SSMS (July 12-14, 1976) ........ . .......................... 62
12-1 X-Ray Fluorescence Intensities for Elements of Interest ...... 64
12-T-2 Survey Analysis of the Condensibles by Spark Source
Mass Spectrometry .................... ...... .......... 66
13-1 X-Ray Powder Diffraction Pattern - Reverberatory
Furnace Feed Concentrate (Collected July 13, 1976,
11:10 pm "C" Shift) ....... . ................. ........ ---- 69
13r-2 X-Ray Powder Diffraction Pattern - Dust Hopper
(Sample #806) ............................... . ............. 74
13-3 X-Ray Powder Diffraction Pattern - Collected at ESP
Outlet on In-Stack Filter (Collected July 10, 1976
frpm 6:30 to 8:14 am) ........... . ...... ................... 77
13-4 X-Ray Powder Diffraction Pattern - Condensed Particulate
Collected at ESP Outlet on Out-of-Stack Filter
(July 15, 1976, from 8:50 to 10:20 am) .................. . . 81
13-5 X-Ray Powder Diffraction Pattern - Condensed Particulate
Collected at ESP Inlet on Out-of-Stack Filter
(Jtjly 15, 1976, from 1:00 to 2:20 pm) ---- . ---- . ......... 83
13-6 X-Ray Powder Diffraction Pattern for Material
Condensed in Impingers (Composite Sample) ..... . ........... 85
13-7 Summary of Crystalline Species Identified by X-Ray
Diffraction ...................... .... ..................... 86
14-1 Analytical Results from Vapor Train Sampling ....... . . ......... 88
14-2 Flow Ra,tes of Gaseous Emissions ............................... 89
15- J. Summary of Calibration Data ................................... 92
15-2 Summary of Arsenic Emission Data from the Reverberatory
Electrostatic Precipitator ............. . ................... 94
15-3 Summary of Arsenic Sampling Data Reverberatory
Fiarnace Electrostatic Precipitator Inlet ................... 95
15r4 Summary of Arsenic Sampling Data Reverberatory
Furnace Electrostatic Precipitator Outlet .................. 96
ix
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SECTION 1
INTRODUCTION
Volume I summarizes all major findings. The present Volume II gives
more details concerning sampling, sample analysis and data evaluation.
The primary copper smelter studied in this report started production
about 25 years ago. Gas cleaning facilities were added in the early seven-
ties to treat the off-gases from the converters. Waste heat boilers and
electrostatic precipitators (ESP) are currently used to generate steam and
remove particulates from both reverberatory furnace and converter gas
streams. The cleanup and cooling of converter gases is achieved in a
humidifier, cooler, wet electrostatic precipitator arrangement followed by
a contact sulfuric acid plant.
The primary goal of the present study was to evaluate the performance
of the electrostatic precipitator (ESP) collecting particulate matter es-
caping the reverberatory furnace. Several sampling techniques were chosen
to determine:
gas flow rate,
e gas composition,
grain loading at the inlet duct,
grain loading at the outlet duct,
particle size distribution,
0 electrical performance of the ESP,
trace element material balance,
o trace element flow rates as vapor,
the amount of material condensible between the gas
temperature of 600°F and the EPA recommended cool-off
point of 250°F, and
arsenic emission rates using an EPA suggested sampling
device.
The sampling effort was conducted from July 8 through July 16, 1976. A
detailed sampling schedule is presented in Table 1-1.
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TABLE 1-1. A SUMMARY OF THE SAMPLING EFFORT (JULY 7 THROUGH JULY 16, 1976)
Date
Location/Stream Sampled
Parameter
Evaluate Reverb ESP performance:
7-8 to 7-10
7-10
7-8 to 7-10
7-10
7-10
ESP Outlet
ESP Outlet
ESP Inlet
ESP Inlet
ESP Control Room
Complete a material balance around Reverb ESP:
7-11
7-11
7-11 to 7-13
ESP Outlet
ESP Inlet
ESP Dust
grain loading
particle size distribution
grain loading
particle size distribution
electrical performance
trace element flow rates
trace element flow rates
trace element flow rates
Complete an approximate material balance around the Reverb furnace:
7-13
7-12 to 7-14
7-11 to 7-13
7-12 to 7-14
7-12 to 7-14
ESP Outlet
Reverb feed
ESP Dust
Reverb Slag
Matte
trace element flow rates
trace element flow rates
trace element flow rates
trace element flow rates
trace element flow rates
Collect participate by particle size for trace element analysis:
7-16 ESP Outlet paniculate by size fraction
Collect vapor phase emissions:
7-16 ESP Outlet
trace element flow rates
as vapor
Determine amount of condensiblc material and SO emitted:
7-15
7-15
ESP Outlet
ESP Outlet
condensed material
(between 600°F--250°F)
and SOj-SOj concentrations
condensed material
and SOj-
concentrations
Determine arsenic emission rates:
7-13 to 7-14
7-13 to 7-14
ESP Outlet
ESP Inlet
arsenic emission rate
arsenic emission rate
Technique
in-stack filter
Andersen cascade inipactor (SRI)
instack filter
Brinks cascade impactor (SRI)
monitor operating parameters (SRI)
integral WEP
integral WEP
periodic grab sample
integral WEP
compositing slinger bin catches at the
end of each shift
periodic grab sample
periodic grab sample
periodic grab sample *
3 out of stack cyclones in series
plus filter
filter at duct temperature followed
by impingers
EPA 5 train with in-stack filters
EPA 5 train with in-stack filters
modified EPA Method 5 train
modified EPA Method 5 train
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Plant management released composites of the following samples:
concentrate (reverberatory furnace feed),
matte, and
reverberatory furnace slag.
In addition, all critical flow rates were released to Radian, A complete
material balance around the reverberatory furnace was still not possible
because compositions for the following streams are not known:
converter slag
dust collected in the converter waste heat
boiler, the balloon flue, and the converter
ESP, and
material condensed on the surface of the
reverberatory furnace waste heat boiler.
The main findings of the study are presented below.
SMELTER MINOR ELEMENT FLOW
1) Titanium, potassium, magnesium, and sodium*enter the smelter
as major components besides the elements of importance ip. the
smelting operation itself (Cu, Fe, Si, Ca, and Al).
2) Minor elements of environmental concern are:
arsenic,
cadmium,
molybdenum,
lead,
antimony,
selenium,
zinc, and
fluorine.
3) The rest of the elements surveyed enter in the low ppm con-
centration range or were not detected by spark source mass
spectrometry analysis.
4) Molybdenum entering the reverberatory furnace with the
concentrate is almost completely discharged in the reverberatory
furnace slag.
5) Nearly 50 percent of the selenium and 30 percent of the fluorine
are discharged together with the reverberatory furnace off-gases.
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6) Nearly all of the fluorine escapes in the gaseous state.
ARSENIC SAMPLING
The arsenic flows found by Radian have been repeated by Smelter person-
nel during the periods of February 28 through March 4, 1977. In addition,
integral arsenic balances were established for the months of January and
March 1977. The findings are incorporated in this report.
1) Approximately 50 percent of the arsenic entering the
smelter leaves in the reverberatory furnace off-gas based
on both plant and Radian sampling data.
2) Data gathered during this study indicate that as much as
90 percent of the arsenic entering the reverberatory furnace
ESP may leave with the off-gas.
3) Arsenic and selenium escaping the electrostatic
precipitator are partly in the vapor state.
4) The arsenic concentration in the reverberatory furnace
feed varies within a few days from 700 ppm to 7000 ppm. This
variation is not only a function of the arsenic concentration
in the orey but also depends on the amount of electrostatic
precipitator dust recycled.
5) The following arsenic rates were determined at the ESP
outlet:
140 Ib/hr
76 Ib/hr
54 Ib/hr
45 Ib/hr
51 Ib/hr
45 Ib/hr
40 Ib/hr
25 Ib/hr
34 Ib/hr
49 Ib/hr
July 11, 1976
July 13, 1976
July 13, 1976
July 14, 1976
July 14, 1976
January, 1977
March, 1977
March 1, 1977
March 2, 1977
March 3, 1977
- Radian, direct measurement
- Radian, direct measurement
- Radian, direct measurement
- Radian, direct measurement
- Radian, direct measurement
- Smelter, balance difference
- Smelter, balance difference
- Smelter, direct measurement
- Smelter, direct measurement
- Smelter, direct measurement
6) The arsenic detected was present as arsenolite,
This was determined by X-ray diffraction.
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ESP PERFORMANCE
1) ESP temperature (600°F) and gas flow rate (160,000 acfm)
correspond to design parameters.
2) ESP inlet grain loading determined at duct temperature is
0.60 grains/scf, and the outlet grain loading is 0.020 grains/scf.
The overall particulate collection efficiency is calculated to
be 96.7%. Design efficiency was 96.8%.
3) The amount of condensibles between duct temperature 600°F
and 250°F (EPA recommended) accounts for material corresponding
in mass to an additional 1.60 grains/scf at the inlet and 1.0
grains/scf at the outlet.
4) The element flow at the reverberatory furnace ESP outlet
measured July 11, 1976 is as follows:
Sulfur 2260 Ibs/hr
Arsenic 140 Ibs/hr
Fluorine 7.8 Ibs/hr
Copper 1.0 Ibs/hr
Selenium 0.97 Ibs/hr
Antimony 0.33 Ibs/hr
Molybdenum 0.2 Ibs/hr
Nickel 0.1 Ibs/hr
Lead 0.1 Ibs/hr
Zinc 0.1 Ib's/hr
5) Good material balance closure around the ESP was established
for:
Arsenic Nickel
Beryllium Sulfur
Chromium Antimony
Copper Selenium
Fluorine Vanadium
Mercury Zinc
Molybdenum
The balance for cadmium is marginal. The balance for barium and lead
did not close due to precipitation of insoluble sulfates in the
collection device.
6) Cadmium, lead, and zinc entering the smelter are transported
with the matte to the converters. Cadmium most likely leaves the
smelting circuit with the converter off-gases. Some of the zinc
and lead will be volatilized in the converter. Some will also be
returned to the reverb in the converter slag.
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The study was performed in parallel with an effort by Southern Research
Institute, Birmingham, Alabama (SRI). SRI determined the electrical charac-
teristics of the ESP during the sampling period and also determined the par-
ticle size distribution at the inlet and outlet using Brink's impactors.
Details of these investigations can be found in SRI's report: "Performance
Evaluation of an Electrostatic Precipitator Installed on a Copper Reverber-
atory Furnace," SORI-EAS-76-511, EPA Order #CA-6-99-2980-J.
The following sections present the detailed results of this study.
The important conclusions were summarized in Volume I. A general plant
description and a more detailed discussion of the reverberatory furnace are
presented in Section 2. Sections 3 through 15 discuss the sampling and
analytical procedures. The results of individual sampling efforts are in-
cluded in these sections.
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SECTION 2
PLANT DESCRIPTION
Thi? section first covers the material flow in the smelter. The rever-
beratory furnace, the hot electrostatic precipitator and the plant operation
sampling are described next.
MATERIAL FLOW
The copper smelting facility sampled can be divided into the following
process steps (see Figure 2-1) :
mining ,
concentrate preparation,
reverberatory furnace feed preparation,
matte production in the reverberatory furnace,
reverberatory furnace off-gas cleaning by hot
electrostatic precipitation,
production of blister copper in the converters
and copper refining in the anode furnace, and
cleaning of the converter off-gases with sulfuric
acid production.
An open pit mine feeds the smelter. Typical copper concentrations in the ore
range from 0.5 to 1.0%. All ore with less than 0.3% copper content is
rejected as waste rock.
The flow of the copper ore is depicted in Figure 2-2. Several trains
transport the pre from the mine to the crushing and grinding unit. The first
step is the reduction of the larger boulders in a gyratory crusher. Next,
continuous reduction of the rock size is achieved in cone crushers. The
final step in size reduction of the ore occurs in wet ball mills.
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oo
I Reformed Gas
Anode
Furnace
Anode
Copper
/ Reverb Slag
\ to Slag Dumpy
Concentrate and
Flux Material
Natural Gas, Diesel Oil
and/or No. 6 Fuel Oil
One Reverberatory
Furnace
Three Converters,
One Great Falls
Oxidizing Furnace
Stack
HumidifyingX
Tower /
Slowdown /
Figure 2-1. Schematic Diagram of Primary Copper Smelter.
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Ore from
Open Pit
Mine
Water
and
Flotation Reagents
Calcium Carbonate
Quartz
FEED STREAMS
Refuse to
Tailings
Pile
Reverb Furnace
Feed
PRODUCT STREAMS
Figure 2-2. Reverberatory Furnace Feed Preparation.
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Water and flotation reagents are added to the ball mill effluent stream
and the slurry is aerated. Copper bearing particles adhere to the ascending
air bubbles. The "froth" is skimmed from the surface. Solid-liquid separa-
tion is achieved next by vacuum filtration. The aqueous phase is recycled,
and the concentrate containing 20% or more copper goes to storage.
The particulates low in copper ore sink to the bottom in the flotation
step and are pumped as a slurry to the tailings pond. Again, supernatant
water from this pond is recycled to the ore enrichment facility.
The ore and concentrate are analyzed for copper, and major constituents.
Calcium carbonate and quartz are mixed with the concentrate to produce an
optimum reverberatory furnace feed.
The major steps in operating the reverberatory furnace are shown in
Figure 2-3. The purpose of this furnace is to reduce the sulfur and iron in
the concentrate to the point where FeS and Cu2S are present in approximately
stoichiometric amounts. This mixture is called matte. Excess iron sulfide
is converted in an exothermic reaction to FeO and SOa. Iron oxide combines
with silica to form a slag of lower density than the matte. The slag layer
is removed from the reverberatory furnace and transported in a slag train to
the slag dumping site. The off-gases contain sulfur dioxide, particulate
matter and metal fumes. Heat is recovered in two waste heat boilers.
Particulates are removed in two waste heat boilers and in a hot electro-
static precipitator. The collected dusts are recycled to the reverberatory
furnace feed preparation area. The gas leaving the reverb ESP is discharged
through the stack.
Streams entering the reverberatory furnace in addition to the concentrate
(reverb furnace feed) are (1) converter slag, (2) converter dusts collected
in both the balloon flue and the ESP treating the converter off-gases, and
(3) reverb ESP and reverb waste heat boiler dusts.
10
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c
Reverb Furnace \
Feed l~
Natural Gas,
JDiesel Oil and/o
No. 6 Fuel 01
Converter Slag
Converter &
Reverb Dust
FEED STREAMS
Reverb
Furance
Two Waste
Heat Boilers
Dry Electrostatic
Precipitator
PROCESSING STEPS
y' Matte to \
*^*\. Converters /
/ Slag
N. Dump
to
PRODUCT STREAMS
Figure 2-3. Reverberatory Furnace Flow Diagram.
11
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Three Fierce-Smith converters process the matte produced in the
reverberatory furnace. The schematic of the material flow is shown in
Figure 2-4. Charging of the matte to the converters is a batch process
using ladles transported by an overhead crane. In the converter, iron
sulfide is oxidized to FeO and SO-. Quartz addition to the converter binds
the FeO in the form of a silicate slag (4% Cu) which is recycled to the
reverb. Again, the operation is discontinuous and is carried out using
ladles and the overhead crane. "White metal" consisting of Cu-S is left
after the removal of the iron. At this stage, the copper blowing cycle
starts. Copper sulfide is converted to a 98% pure copper called "blister
copper." Cold copper-containing scrap is added periodically to absorb the
heat of the exothermic overall reaction.
The blister copper is transported to the anode furnace using ladles.
Air blowing serves to remove the Cu_S left in the blister copper. Copper
containing Cu-0 as an impurity is tne result of this processing step. The
copper oxide Is then reduced with reformed natural gas. The resulting copper
with a purity of 99+% is ready for the anode pouring step which is done once
a day. An anode casting wheel is used. The anodes weigh about 750 Ibs
apiece and are shipped for electrolytic refining. Output of the plant is
180-200 tons of anode copper a day.
Sulfur dioxide off-gas, dust and metal fumes are the result of the Cu-S
and FeS oxidation in the converters. The converter dust collection and gas
cleaning steps are shown in Figure 2-5. The SO- concentration of the con-
verter off-gases is much higher than that of the reverberatory furnace and
typically varies between 4 and 8% and as such is amenable to the manufactur-
ing of sulfuric acid using the contact process. The off-gases from the con-
verter are first cooled in waste heat boilers. Particulate removal is
achieved in an electrostatic precipitator. The dust collected in the balloon
flue and the electrostatic precipitator is recycled to the reverberatory
furnace. Dust from the waste heat boilers is fed back to the converters.
Gas cooling and cleaning is the first step in sulfuric acid production.
A humidifier, a cooler and a wet electrostatic precipitator are used to cool
and clean the gas.. The humidifying tower has a blowdown stream consisting of
dilute sulfuric acid containing the particulate matter escaping the ESP, as
well as condensable fumes. The H-SO, plant consists of drying towers, a
vanadium pentoxide catalytic bed, and SO- absorption towers. Heat exchangers
remove the heat of the exothermic SO- oxidation process. The product of the
sulfuric acid plant is a 93% H-SO, acid stream and a tail gas with low con-
centrations of contaminants.
12
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Macce
f Silica j-
I Scrap V-
f Reformed Gas V-
Air
Three
Feirce-
Smith
Converters
Anode
Furnace
Anode
Casting
Wheel
Converter Slag
to Reverb
Converter Gas
And Dus t
Anode Furnace Gases
To"Atmosphere
Anodes to Electrolytic
v Refining ,
FEED STREAMS
PROCESSING STEPS
PRODUCT STREAMS
Figure 2-4. Converters and Anode Furnace.
13
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:\
Converter \
Gas & Dust /
Makeup l
L Water J
FEED STREAMS
t,
PR
Three Wa
Boi
^
Balloon
ste Heat
lers
r
Flue
Collection
System
i
Electros
Precipit
i
r
tatic
ator
r
Gas Cooling
Cleaning
^
r
Contact
Sulfuric
Acid
Plant
OCESSING
STEPS
^/ Dust of
"^\ Converters
I ,/
j^ ^\ Dust to Reverb
/ \
^/ Humidifying
^v Tower Slowdown
/ N
,^/ Q^X Sulfuric
^\ Acid
/ "\
~/ Clean Gas to
\ Atmosphere
\ /
PRODUCT STREAMS
Figure 2-5. Converter Dust Recovery and RzSOn Plant.
14
-------
REVERBERATORY FURNACE
The single reverberatory furnace, 30 feet wide and 100 feet long
(inside dimensions), fired with burners which are capable of burning natural
gas, diesel oil and/or No. 6 fuel oil, processes concentrates from the
milling and flotation plant. The concentrates, which comprise over 90%
of the furnace charge are received from the filter plant and dryer by
conveyor or from stock piles by truck. Each charge is weighed on scales and
is carried by overhead crane to a charge point above and to the side of the
furnace. Six charge ports are provided, three on each side of the furnace.
A concrete bin of approximately 1600 tons capacity is used for surge
storage of concentrates. When necessary, the concentrates are reclaimed
by clamsheill from the storage bin.
The bath smelting reverberatory furnace was designed for wet smelting.
The crucible of the furnace is constructed in sections of rammed periclase.
The top and sides of the furnace crucible are cooled by copper water jackets.
The working bottom of the furnace is magnetite accretions fused in place.
The bath smelt ing furnace requires reaction between the new charge and the
liquid bath to cause spreading of the new charge. When calcines are
smelted, charging them through an inclined pipe imparts sufficient velocity
to allow a reaction with the liquid bath to cause spreading of the new
charge. This gravity charging method cannot be used with wet concentrates,
however, since they will not flow through an inclined pipe as will calcines.
Considerable research was necessary to develop proper charging equipment. It
is necessary to charge the wet concentrates to the furnace at a considerable
velocity and at a relatively flat angle. This enables the wet concentrate
to penetrate the liquid bath sufficiently to start the spreading reaction
a,nd prevents the concentrate from piling up in one place.
A high-speed belt slinger was developed for this operation and has
performed well. Six slingers are provided, three on each side of the fur-
nace. Each has a port through the sidewall covered with a vertically movable
door when not in use When charging begins, the door is raised by an air
cylinder, the slinger started, and the concentrates drop onto the slinger
from the charge can overhead. The slinger angle is adjustable both hori-
zontally and vertically. Belt speeds are variable allowing the charging
rate to range from 1.5 to 2 tons/min for each slinger. Furnace charging is
done by one man and is controlled by visual inspection.
The reverb is of the sprung silica arch type. The brickwork is main-
tained by silica slurry hot patching. The silicious material of over 90%
SiOa is ground wet in a ball mill and pumped to a storage tank above the
furnace from which it is blown and sprayed onto the interior surface of the
brickwork. A curtain damper has been used successfully in the furnace and
its use has resulted in better working conditions and decreased maintenance
expense in and around the boiler uptakes and flues. The curtain damper
15
-------
sections are made of cast refractory supported by loops of water-cooled steel
tubing and are maintained by slurry patching.
REVERBERATORY FURNACE ESP
Gases from the reverberatory furnace enter two waste heat boilers in
parallel. The boilers cool the gas to approximately 600°F and remove some
particulate and condensable material. Steam produced by the boilers is used
to generate either electricity or low-pressure air for the converters. Gases
exiting the waste heat boiler enter a plenum chamber for mixing prior to
treatment in an electrostatic precipitator (ESP).
The reverberatory furnace electrostatic precipitator consists of two
independent horizontal parallel units designed to handle a total 160,000 acfm
(600°F and 13.8 psia). Gas treatment time is 6 seconds; pressure drop across
the precipitator is 0.5 inches w.c. maximum. Collecting surfaces are plates;
the discharge electrodes are spring steel wires. The transformer-rectifiers
are silicon full wave for 45KV (DC) average; there is an automatic voltage
control system to maintain the optimum precipitator operating efficiency.
Dust collected is transported via screw conveyor and chain drag to a storage
bin from which it is pneumatically conveyed to the charge mixing area for the
reverberatory furnace by a fluid flow automatic pump. This pump can handle
20,000 pounds per hour when supplied with 280 scfm compressed air at 30 psig.
The electrostatic precipitator and dust handling system are shown schemati-
cally in Figure 2-6.
An induced draft fan was installed to draw the reverberatory gases from
the reverberatory furnace through the waste heat boilers, the flue system, and
the electrostatic precipitator. This fan can handle 160,000 acfm @ 600°F with
a suction of -1.75" H20 and a discharge of 3.25" HaO. All of the gases can be
discharged to the 360-foot concrete stack or part of the gases can go to the
stack and part to the SOa absorption plant. A remotely controlled damper in
the flue going to the stack controls the total volume of gas removed from the
reverberatory furnace and the distribution of the gas. The SOa absorption
plant did not operate during the sampling period.
PLANT OPERATION DURING SAMPLING
The reverberatory furnace operated continuously during the entire
sampling program. One upset in the ESP operation was recorded on July 12.
This upset was attributed to wet concentrate charged to the furnace. The
concentrate dryer was repaired that day and no further upsets were recorded.
High dust loadings were noted during the periods when the reverberatory fur-
nace was being charged. This, however, is normal operation.
16
-------
ESP Outlet
Sampling Ports
I
Electrostatic
Preclpitator
n n n n n n
Dust Hopper
ESP Inlet
Sampling Ports
Figure 2-6. Electrostatic Precipitator and Dust Handling System
for Reverberatory Furnace Gases.
-------
SECTION 3
DESCRIPTION OF SAMPLING POINTS
PRECIPITATOR INLET
The duct configuration at the inlet is depicted in a three-dimensional
sketch, Figure 3-1. Both the west and the east ducts are 4 feet deep and 6
feet wide. Each of them is equipped with six 3-inch sampling ports with male
threads. The angle between the vertical faces of the mixing chamber and the
incoming duct is slightly smaller than 135 degrees. The sampling ports are
accessible from two platforms, each 6 ft by 6 ft.
PRECIPITATOR OUTLET
The sampling conditions at the outlet duct are almost ideal. A three-
dimensional sketch of the sampling location is shown in Figure 3-2. The
outlets of the two ESP's join far enough upstream of the sampling ports that
uniform flow and particle distribution can be expected. The diameter of the
common duct is six feet. Three sample ports are provided three feet above
the sampling platform. The south and west port are three inches and the
north port is four inches in diameter. All sampling ports have female
threads in contrast to the inlet ports which have male threads.
PRECIPITATOR DUST
Dust collected in the electrostatic precipitators is conveyed to a
storage bin by a screw conveyor and a chain drag. From here it is transported
back to the charge mixing area of the reverberatory furnace by a fluid flow
automatic pump. The rating of the pump is 20,000 pounds per hour. Operation
of the pump is intermittent. Individual samples were conveniently obtained
through a port on top of the chain drag. An integral sample could then be
accumulated during the sampling periods at the inlet and outlet ducts.
Measurements of the dust level in the storage bin were made by using
a chain-secured bucket. The storage bin was emptied prior to the sampling
run. The bucket was lowered periodically through the port on top of the
storage bin to measure the dust level. The dimensions of the storage bin
were obtained from blueprints. This allowed the mass of dust accumulated
to be calculated from the average level increase, the dust density and the
18
-------
SAMPLING PORTS
(3". MALE)
W
Figure 3-1. Schematic Diagram of Inlet Cucts.
-------
N3
o
N-
W
Figure 3-2. Schematic Diagram of Outlet Duct.
-------
storage bin dimensions. Dust flow rates determined in this fashion varied
widely. A flow rate obtained by difference of the grain loading at the ESP
inlet and outlet was therefore used for the material balance calculations.
CONCENTRATE
The furnace is charged with concentrate by slingers. A small amount
of concentrate adheres to the slinger belt during charging. To prevent
this material from being scattered in the furnace work area, bins the
width of the belt are placed so that they catch this small amount of
concentrate. The bins are emptied at the end of each shift; the combined
catch from all six slingers is 100-200 pounds. An integral concentrate
sample was obtained by emptying the bins into a barrel at the end of the
shift. A representative sample was taken from the barrel, thus giving a
concentrate sample which was made up of concentrate from each of the six
slingers integrated over the duration of the shift.
MATTE AND SLAG
Smelter personnel routinely sample the furnace matte and slag for
analysis to provide operational data. Composite samples from each shift of
these two streams were provided by the plant for July 12 through 14. These
were a portion of their routine samples.
Converter slag and recycle dust from the converter waste heat boilers,
the converter balloon flues and the converter ESP could not be obtained. A
complete material balance around the reverberatory furnace was, therefore
not possible.
21
-------
SECTION 4
SAMPLING PROCEDURES
The location and configuration of the ESP inlet sampling ports were
described in Section 3. The cross sections of both inlet ducts (east and
west) at the test plane were divided into 18 equal area segments designated
as shown in Figure 4-1 and 4-2. The characterization of a given parameter
for the inlet gas stream can be expressed as the average of that parameter
for each of the 36 equal area segments. The selection of 36 points for
the inlet test plane was made based on:
the expected poor flow distribution caused by the
immediate termination of the two ducts into the
mixing chamber, and
the number of existing sampling ports.
EPA criteria as documented in Method 1, however, could not be met.
Off-gas exiting the precipitator was sampled from the single 6-foot
circular outlet duct. The location and configuration of sampling ports were
described earlier. The gas flow is downward and there are no disturbances
up or downstream of the test plane close enough to cause an uneven flow distri-
bution. For the precipitator outlet, the cross section of the duct was
divided into 12 equal area segments, the center of each area being a sampling
point. The sampling points and their designation are shown in Figure 4-3.
EVALUATION OF THE PRECIPITATOR PERFORMANCE
The measurements and equipment listed in Table 4-1 were used to collect
data for an evaluation of the electrostatic precipitator. Each of the
experiments performed as a part of the characterization is described in
subsequent chapters.
Temperature-Velocity
Initial velocity and temperature traverses were made on July 7 using
S-type pitot tubes and thermocouples for both inlet ducts and at the outlet.
22
-------
7%'
;
3
2
1
I
E
E
E
i
1
J
1
I
_ _L_
I
I
I
I
!
I
!
I
I
12"
j
S ;
61
51
41
«
t
!
1
I
1
1
1
1
1
1
!
i
!
-1
!
1
1
12"
i
9
8
7
E
E
E
1
..12."..
3
12E
HE
10E
*_.!_»
*- -»
1
i
i
1
1
1
__ L .
i
1
i
I
i
_^^JI j ._.., ^_
I
!
1.
12"
$
!
15E
14E
13E
__|_
1
1
1
I
1
_
1
f ~~
1
L2"
|
1
8E
7E
6E
-
7%"
1
\
1
8"
i
__L
3" Openings
Male Threads
Figure 4-1. Cross Section and Sample Point Identification of East Duct at ESP Inlet.
-------
7%'
31
21
11
rf
4
J
_ _
r -
,
0"
1
6W
5W
W
I
I
1
1
1
i
1
1
1
I
1
1
i
I
-r-
l
i
i
IT 1 °"
j \
91
8\
1\
tJ
rf
7
-i on
F i
12W
11W
10W
1
«- -+*
.
-1 OTI
1.
li
i:
5W
*w
5W
--
1
-
1
-
1
otr
t
8W
7W
5W
-
7%"
j
T
8"
_L
3" Openings
Male Threads
Figure 4-2. Cross Section and Sample Point Identification of West Duct at ESP Inlet.
-------
NORTH PORT
4", FEMALE
K3
Ul
6'
WEST PORT
3", FEMALE THREAD
SAMPLE POINT
SOUTH PORT
3", FEMALE
N-
W
DISTANCE FROM
INSIDE WALL
i,r
2,8
3,9
4,10
5,11
6,12
3.1"
10.6"
1'9"
4'2.8"
5'1"
5'8.9"
Figure 4-3. Cross Section and Sample Point Identification in Exit Duct.
-------
TABLE 4-1. EQUIPMENT USED FOR MONITORING PRECIPITATOR PERFORMANCE
Parameter Monitored Equipment
Velocity and temperature profile Inlet and outlet: calibrated S-type
pitot and thermocouple
Grain loading Inlet and outlet: in-stack glass-
fiber filter, followed by impingers
Particle size distribution* Inlet and outlet: Brinks cascade
impactor used in-stack
Flue gas composition Inlet and outlet: Orsat gas analyzer
Resistivity of precipitator dust* Resistivity electrode set
* These measurements were performed by personnel of the Southern Research
Institute, Birmingham, Alabama. Results are described in "Performance
Evaluation of an Electrostatic Precipitator Installed on a Copper
Reverberatory Furnace". (SORI-EAS-76-511)
This data provided preliminary information about the gas streams. The
velocity profiles as determined on the 7th for the inlet east, inlet west
and outlet ducts are shown in Figure 4-4, 4-5, and 4-6, respectively.
The temperature and velocity traverses were repeated periodically during the
sampling effort.
Measurements taken July 9 through July 10 gave an average velocity at
the inlet of 57 fps west and 55 fps east. The average velocity at the out-
let was 114 fps. The gas temperatures were 633°F (inlet) and 598°F (outlet)
during the same period. These velocity measurements were used along with
the grain loadings measured on July 9 and 10 to calculate mass flow rates
used to evaluate the ESP performance.
Grain Loading
The particulate grain loading was determined for each duct. Determina-
tions at the inlet were initially made using an alundum thimble with a glass-
fiber filter as a backup. However, the use of the thimbles even when
packed with glass wool did not significantly increase sampling times before
plugging occurred. Thus, all grain loading determination were made using
only Gelman class A/E glass-fiber filters housed in 47 mm filter holders.
26
-------
44.2 45.3 42.0 41.7 42.0 42
43.9 43.5 42.8 41.3 41.3 40.9
43.1 42.8 40.5 40.1 38.5 39.7
38.9 31.8 34.6 31.3 30.8 36.8
7,,, 7%"
^ * Jg ^ I ^ ___^_ i n H . ^ j ^ -I o " j^,- _f 1 O" <* 1 _r 12" ^u ] _^- 1 9 ' 1- -^ "* i ...*-
1 1 ; . I ' ' ' .'
I 1 1 ' 1 i
-
7-7-76
Avg. 40.0 fps
T
8"
_L
3" OpeninRs
Figure 4-4. Velocity Profile of East Duct Precipitator Inlet (July 7, 1976)
-------
NJ
00
41.8 42.8 43.4 40.3 41.1 41.2
40.5
40.1 41.1 40.3 39.5 40.4
37.2 37.5 39.4 39.3 38.1 39.0
35.1
29.6 34.4 33.9 27.2 35.2
12" I-- 12" -I 12" -112"
1.2'1
7-7-76
Avg. 38.3 fps.
T
8"
3" Openings
Male Threads
Figure 4-5. Velocity Profile of West Duct, Precipitator Inlet (July 7, 1976).
-------
NORTH PORT
4", FEMALE
6'
WEST PORT
3", FEMALE THREAD
SAMPLE POINT
SOUTH PORT
3", FEMALE
N-
w
DISTANCE FROM
INSIDE WALL
1.7
2,8
3,9
4,10
5,11
6,12
3.1"
10.6"
1'9"
4'2.8"
5'1"
5'8.9"
Figure 4-6. Oulet Velocity Profile (Velocities in ESP)(July 7, 1976) .
-------
As indicated above, problems were encountered due to the sticky or
tacky nature of the particulates which tended to plug filtering media more
quickly than would normally be expected at these grain loadings. This
problem was also experienced at the ESP outlet buf to a lesser extent.
Due to the method used to charge the reverberatory furnace, the ESP
inlet grain loading was quite variable. The dust loading could change from
light to very heavy back to light all within a few minutes. This was
apparently a function of furnace charging.
On July 9 and 10, two grain loading determinations per day were made at
each duct to coincide with the particle size determinations performed by
Southern Research Institute (SRI) personnel using Brinks cascade impactors.
Each determination consisted of a minimum of one hour sampling in each duct.
An 18-point traverse was used in each of the inlet ducts, three points in
each of six ports. A six-point traverse was used across one diameter of the
outlet duct.
Flue Gas Composition
Samples for analysis were collected at the ESP inlet and outlet using
a pump and a flexible bag. Gas from the bag was analyzed for carbon
dioxide, oxygen and carbon monoxide using an Orsat gas analyzer. The gas
analysis and the moisture content of the gas were used to calculate a gas
density. The S02 and SO3 concentrations were determined using EPA Method
8. Table 4-2 summarizes the flue gas analyses.
Measurement of Precipitator Dust Resistivity
Southern Research Institute needed the resistivity of the precipitator
dust for their ESP evaluation. The samples used for these measurements were
obtained during grain loading measurements. The actual resistivity deter-
minations were made at SRI's facilities in Birmingham, Alabama.
-30-
-------
TABLE 4-2. GAS COMPOSITION
Parameter
H20
02
CO 2
S02
S03
Method
Condensation-sorption
with silica gel
Or sat
Orsat
Sorption in 6%
H202-titration
July 15^1977
Run #1 0845-0855
Run #2 0930-0943
Run #3 1015-1028
Sorption in 80%
IPA- tit rat ion
July 15. 1977
Run #1 0845-0855
Run #2 0930-0943
Run #3 1015-1028
3.43 scf
4.32 scf
4.40 scf
AVG.
3.43 scf
4.32 scf
4.40 scf
AVG
Inlet
13.2%
10.7%
6.0%
0.35%
0.21%
0.44%
0.33%
0.005%
0.004%
0.009%
0.006%
Results
July 15, 1977
0850-0190 3.98 scf
0925-0945 4.22 scf
1000-1020 4.01 scf
AVG.
July 15, 1977
0850-0910 3.98 scf
0925-0945 4.22 scf
1000-1020 4.01 scf
AVG.
Xi
Outlet
12.3%
9.5%
6.5%
0.27%
0.16%
1.26%
0.56%
0.017%
0.006%
0.014%
0.012%
-------
SECTION 5
ELECTROSTATIC PRECIPITATOR MATERIAL BALANCE SAMPLES
Samples of particulates and vapors from the gas stream entering and
exiting the reverberatory furnace electrostatic precipitator were collected
July 11 using a small wet electrostatic precipitator followed by a series of
eight impingers. Dust removed by the reverberatory furnace electrostatic
precipitator was sampled periodically as it was conveyed to the precipitator
dust hopper. Dust hopper accumulations were monitored July 11 through 13.
PRECIPITATOR INLET AND OUTLET
The wet electrostatic precipitator (WEP) was used to capture all parti-
culate trace elements except mercury.
Samples for characterization of the gas stream with respect to
chemical composition were collected at both the precipitator inlet and
outlet. These samples were collected isokinetically from points of average
velocity and grain loading. Samples were drawn through a pyrex sampling
nozzle and probe and then through the WEP via teflon tubing. In the WEP,
shown in Figure 5-1, gas bubbles through the circulating electrolytic
reservoir then passes up through a cylindrical chamber, the walls of which
are wetted with the electrolyte (5% H2SOit) . Collection of particulates
and mist is achieved in this area by the 12 KVDC potential across the center
plantinum electrode and the wetted outer wall which will induce electrostatic
collection. The gas stream then exits at the top of the WEP. After the
gas has passed through the WEP, the particulates are contained in the electro-
lyte.
Vapors not collected in the WEP were absorbed by a series of eight
impingers. The contents of each impinger is given in Table 5-1.
Elemental mercury in the vapor phase was collected using a gold amal-
gamation technique. The gas is passed through 6% hydrogen peroxide to remove
SOz, then through a quartz tube containing a plug of very fine gold wire.
Mercury vapor is collected on the gold surface. The mercury is later
thermally desorbed and analyzed using a flameless atomic absorption technique.
32
-------
Sample
Outlet
Peristaltic
Pump
Platinum Electrode
Falling Film of Electrqlyte
Circulating
Electrolyte
Reservoir
Figure 5-1. Wet Electrostatic Precipitator,
33
-------
TABLE 5-1. IMPINGER SOLUTIONS USED FOR ESP MATERIAL BALANCE
Impinger
Number Solutions
1,2 1:1: sulfuric acid, nitric acid, deionized water in
a Smith-Greenburg impinger
3,7 dry modified Smith-Greenburg impingers
4,5 20% potassium hydroxide in a Smith-Greenburg impinger
6 hydrogen peroxide in a Smith-Greenburg impinger
8 preweighed silica gel in a modified Smith-Greenburg
impinger
PRECIPITATOR DUST
The flow rate of the precipitator catch was derived from the difference
in grain loadings at the ESP inlet and outlet. The direct determination by
measuring the level increase in the storage silo showed too wide variations.
An integral sample for analysis was conveniently obtained through a
sampling port. This port provided easy access to the dust carried by the
drag chain into the silo.
34
-------
SECTION 6
REVERBERATORY FURNACE SAMPLES AND FLOWS
On July 13, hopper dust and an integral WEP at the ESP outlet sample
were collected as described in Section 5. Composite matte and slag samples
were obtained by plant personnel for the period July 12 through July 14.
The concentrate sample was taken from the bins under the belt slinger.
At the end of each shift, July 12 through 14, the concentrate from each
of the slinger bins was combined in a barrel. A composite sample was
finally collected for analysis.
Operating data (flow rates, temperatures, furnace level, etc.) are
recorded daily. These data were made available to Radian. Table 6-1
summarizes these values. A complete material balance around the rever-
beratory furnace could not be completed. Samples of converter slag and
converter dust were not available.
35
-------
TABLE 6-1. REVERBERATORY FURNACE FLOW RATES
1. Concentrate Feed Rate:
July 11 569 tons
July 12 600 tons
July 13 628 tons
July 14
July 15
610 tons
605 tons
2. Matte Production Rate:
July 11 504 tons
July 12 504 tons
July 13 504 tons
July 14
July 15
530 tons
473 tons
3. Reverberatory Furnace Slag Production Rate:
July 11 420 tons July 14 525 tons
July 12 403 tons July 15 455 tons
July 13 420 tons
4. Converter Slag Production Rate:
July 11 305 tons July 14
July 12 377 tons July 15
July 13 348 tons
421 tons
377 tons
5. Copper Production Rate:
July 11 188 tons
July 12 209 tons
July 13 221 tons
July 14
July 15
180 tons
213 tons
6. Converter Slag Sample for July 11-15:
No longer available
7. Anode Copper Sample for July 11-15:
No longer available.
36
-------
SECTION 7
REVERBERATOR! ESP FLOW RATES
Gas and particulate flow rates were determined by traversing the inlet
and outlet ducts using S-type pitot tubes and in-duct Gelman filters.
Both the velocity distribution and the grain loading fluctuation
were much more pronounced at the inlet than at the outlet. The gas flow
rate was therefore derived from the flow measurements at the outlet. This
assumes no air leakage of the ESP. Table 7-1 shows a summary of the data.
The average grain loading at the ESP inlet was 0.60 grains/scf and at the
outlet 0.02 grains/scf. The efficiency of the ESP is therefore 96.7%.
A dust collection rate of 330 Ibs/hr is calculated from these values using
a total gas flow rate of 78,400 scfm.
TABLE 7-1. GAS FLOW RATE IN ACFM
Date
Inlet,
East
Inlet,
West
Inlet,
Total
Outlet,
Total
7-7-76
7-8-76
7-9-76
7-10-76
84000
81800
86400
81800
80500
81900
79300
79900
80700
78500
67500
78000
163300
161700
167100
160300
148000
159900
160400
178400
170800
162800
Stack Temp
Stack Press
^28.2" HG
37
-------
SECTION 8
SAMPLE ANALYSIS
The elements of interest in the present study are:
Arsenic Copper Lead
Barium Fluorine Sulfur
Beryllium Mercury Antimony
Cadmium Molybdenum Selenium
Chromium Nickel Vanadium
Zinc
Sample analysis consists of two major steps:
sample dissolution and
chemical analysis.
Sample dissolution techniques included acid reflux digestion, perchloric
acid digestion and lithium borate fusion.
The techniques used for the quantitative determinations of trace
elements in samples collected from the copper smelter were based on:
atomic absorption,
ion selective electrode, and
fluorometry.
Figures 8-1 through 8-3 summarize the dissolution and analytical pro-
cedures used for the trace element determinations. The various dissolution
and analytical procedures are described in the remainder of this section.
38
-------
Flue gas.
Wet Electrostatic Precipitator (WEF) Liquor
All.
-Hg
Solids by
PAD
.Be, Mo
HGA-AA.
SA/DCS.
. AA.
. HGA-AA.
HGA-AA.
SA/DCS
_Em±ssion
_Fluorometry
SIE
-Sb, Cd
Ni, Pb
_Cr, Cu
Zn
.As
_Ba
.Se
atomic absorption, flame
aci4 reflux digestion
double capillary system
flameless atomic absorption
heated graphite analyzer of the atomic absorption spectrophotometer
inorganic cpmplex extraction
organic extraction
perchloric acid digestion
standard additions
specific ipn electrode
figure 8-1, Dissolution and Analytical Scheme of a WEP Slurry,
39
-------
LIQUOR
SAMPLE
-Impinger Solution
IMPINGER SOLUTIONS
KMnO., Oxid.
.FAA,
AA.
HGA-AA.
HGA-AA.
HGA-AA.
Emission-
Fluorometry.
.Titrimetry.
Figure 8-2. Analytical Scheme of an Impinger Liquor Sample.
.Hg
.Be,
Mo
. Sb, Cd,
Ni, Pb
.Cr, Cu
Zn
, As
.Ba
.Se
» J-rai
AA:
ARD:
DCS:
FAA:
HGA-AA:
ICE:
OE:
PAD:
SA:
SIE:
atomic absorption, flame
acid reflux digestion
double capillary system
flameless atomic absorption
heated graphite analyzer of AA
inorganic complex extraction
organic extraction
perchloric acid digestion
standard additions
specific ion electrode
Acid Impinger:
1:1:1 HNOs: H2SO^: H20
Basic Impinger:
20% KOH
H202 Impinger:
5% H202
40
-------
HOPPER DUST
Sample
ARD
aqua regla
cig
'-*So, Cfl
. 4s
-Mo
AA: atomic absorption, flame
ARD: acid reflux digestion
DCS: double capillary system
HGA-AA: heated graphite analyzer of the atomic absorption spectrophotometer
HGA: heated graphite analyzer
ICE: inorganic complex extraction
OE: organic extraction
PAD: perchloric acid digestion
SA: standard additions
SIE: specific ion electrode
Figure 8-3. Dissolution and Analytical Scheme of Solid Samples.
41
-------
SAMPLE PREPARATION
The dissolution techniques applied to the samples were:
Acid Reflux Digestion - Solid samples are dissolved
by refluxing with a mixture of nitric acid, sulfuric
acid, and perchloric acid. Silicates are not
attacked by this procedure.
Perchloric Acid Digestion - The first step is a
treatment using nitric and hydrofluoric acid. Per-
chloric acid is added for final oxidation of the
sample. A small amount of hydrochloric is added
to insure complete dissolution.
Lithium Borate Fusion - A small amount of sample
is fused with lithium borate. The cooled melt is
dissolved in hydrochloric acid and hot water. Most
elements present in higher concentrations were
analyzed from this digestion. Elements present in
trace concentrations are, in general, determined
from solutions derived from the acid reflux or
the perchloric acid digestion.
ANALYTICAL PROCEDURES
The analytical procedures used were originally developed for the
determination of trace elements in coal, coal ashes, sludges and plant and
animal tissues. The drastic change in the matrix observed in samples col-
lected at the copper smelter necessitated screening of the procedures for
accuracy and reliability. This task was accomplished using the method of
standard addition and interference studies.
Mercury (KA-086, DI-043, OG-004)
Mercury is probably present in the copper ore in the form of
mercury sulfide. The sulfide is roasted in the oxidizing atmosphere of the
reverberatory furnace. Mercury oxide decomposes at approximately 750°F,
which is well below the furnace temperature. The gold amalgamation tech-
nique was therefore chosen to collect mercury vapor in the inlet and outlet
ducts of the ESP. The ultimate check of this approach was the closure of the
material balance.
Gas samples are drawn through a plug of gold wool. Deamalgamation is
accomplished by heating the gold wool. The released mercury is purged
through the absorption cell of an atomic absorption spectrophotometer (AA).
42
-------
Precipitator dust is analyzed for mercury by weighing a sample into a
platinum boat and heating the sample slowly in a chamber. The off-gases
containing elemental mercury are purged through a gold plug. Deamalgamation
and determination by AA follow the same procedure as described above.
Liquid samples are acidified and then the mercury is oxidized with
potassium permanganate. Hydroxylamine hydrochloride and stannous chloride
are used to reduce the mercury to the metallic state. Air is bubbled through
the solution. The mercury entrained in air is passed through the absorption
cell of an AA.
Beryllium (BO-027)
Beryllium in aqueous solutions is complexed with 2,4-pentanedione.
EDTA is used to mask interfering ions. The beryllium complex is extracted
into methyl-isobutyl-ketone (MIBK) and aspirated into the nitrous oxide-
acetylene flame of the AA.
Molybdenum (KI-092)
Molybdenum is complexed with thiocyanate, extracted into MIBK, and
aspirated into the nitrous oxide-acetylene flame of the AA. Ascorbic acid
and sodium fluoride mask interferences from iron and titantium. Solids are
dissolved using the acid reflux digestion.
Lead and Cadmium (JO-012, KI-085)
Lead and cadmium are extracted simultaneously with MIBK from the WEP
liquor, impinger solutions, and the perchloric acid digestion of the hopper
dust. The double complexing agent of ammonium pyrrolidine dithiocarbamate
and diethylammonium diethyldithiocarbamate chelates lead and cadmium. The
extracted sample is injected into the graphite furnace attachment to the AA.
Antimony (BU-136, HE-094, ED-027)
Antimony is extracted as the iodide into a mixture of tributylphosphate
and MIBK. Extraction is performed on the WEP liquor, impinger solutions and
the perchloric acid digestion. Sulfamic acid is added to the acid impinger
solution to remove the nitrates. Peroxide impinger solutions are boiled to
decompose the HaOa. The extracted solution is injected into a graphite tube
of the AA which has been coated with ammonium molybdate.
43
-------
Nickel (JO-012)
Nickel is extracted from the WEP liquor, impinger solutions, and acid
reflux digestion of the solids. Diethyldithiocarbamate is used to chelate
the nickel and extract it into MIBK. The extracted sample is injected into
the graphite furnace and analyzed by AA.
Chromium, Copper and Zinc (RA-155, PE-114, RU-079)
The three metals are analyzed by atomic absorption using the air-
acetylene flame. The double capillary system is utilized to carry out the
method of standard additions on the samples. The WEP liquor, impinger solu-
tions and the acid reflux digestion of the solids are analyzed by this method.
Arsenic RA-147, ED-027)
The WEP liquor, impinger solutions and the perchloric acid digestion of
the solids are used for the arsenic determination. Arsenic is complexed,
in acidic medium, as the heteropoly acid of molybdenum. The aqueous complex
is injected into the heated graphite analyzer (HGA) attachment to the atomic
absorption spectrophotometer. A charring temperature of 1200°C is used to
remove any interferences in the HGA.
Vanadium (CI-002)
Vanadium is determined by the method of standard additions with the
graphite furnace on the AA. Samples used are the WEP liquor, impinger solu-
tions, and the acid reflux digestion of the solid. There is no sample pre-
concentration needed for the determination.
Barium (DE-218, RU-079)
Samples from the WEP liquor, impinger solutions, and the perchloric
acid digestion are coprecipitated with lead as the dichromate and separated
from the solution. The precipitate is dissolved and aspirated into the
nitrous oxide-acetylene flame of the AA. The method of standard additions
is utilized with the double capillary system. Most interfering species are
removed by the coprecipitation procedure.
Selenium (LE-068)
Solid samples are digested in a Teflon bomb with nitric acid and per-
chloric acid. Following the bomb digestion, the sample is heated with
dilute hydrochloric acid. WEP liquors and impinger solutions are also heated
with HC1. Extraction procedures for all samples are the same from this
44
-------
point forward. Following stabilization with formic acid, hydroxylamine, and
EDTA, the samples are complexed with 2,3-diaminonaphthalene. The selenium
complex is extracted into cyclohexane and read on a fluorometer.
Fluorine (BA-131, BA-137)
Solid samples are fused with sodium carbonate and the melt dissolved in
deionized water. WEP liquors and impinger solutions are run direct. Final
determination is done with a fluoride specific ion electrode utilizing the
method of known additions to remove the effects of any interfering ions.
Sulfur (DO006)
Solid samples are dissolved in a solution of hydrochloric acid and
hydrogen peroxide. Solutions from the solid dissolution and the H202 impin-
gers are boiled to remove excess peroxide. The solutions are then eluted
through a cation exchange resin to convert the sulfate to sulfuric acid.
Volatile acids are removed by heating and the sulfuric acid is titrated with
a standard base.
The analytical accuracies of these techniques are summarized in Section
9. These values are derived by comparing analytical results with standard
reference materials where available, recovery studies, and/or precision
values. The estimated 95% confidence intervals are the result of these
analytical studies.
45
-------
SECTION 9
DATA EVALUATION
Flow rates and chemical analyses are used to calculate the transport
rates of the elements of interest to the electrostatic precipitator and their
discharge in the two effluent streams. Closure of the material balance en-
hances the validity of the individual measurements. Experimental errors are
inherent in both the flow rate and analytical measurements. An error pro-
pagation analysis was applied to bracket the uncertainties in the final re-
sults. Those material balance results for which the inlet value and the sum
of the two outlet streams overlap within these limits are considered^ too
close.
MATERIAL BALANCES
The following expression is obtained by equating the total elemental
flows entering and exiting the ESP:
FoXo(j) + MoXWo(j) (9-1)
where,
F = the volumetric flow rate of furnace off -gas
entering the ESP (scfh) ,
F = the volumetric flow rate of furnace off-gas
° exiting the ESP (scfh) ,
M = the mass flow rate of precipitator dust from
° the ESP, (Ib/h)
X (j) = concentration of element j in the inlet flue
gas, (Ib/scf),
X (j) = concentration of element j in the outlet flue
° gas (Ib/scf),
XW (j) = the weight fraction of the element j in the
0 collected ESP dust.
Closure of the balance verifies the sampling and analytical techniques
employed in this study.
46
-------
ERROR PROPAGATION
An error propagation analysis was used to establish error limits for the
calculated total in^et and outlet flow rates for each element. The values
indicate the degree of variance to be expected due to random errors.
A 95% confidence interval of 2S(Q) is calculated for a given value Q
according to the following defined expression:
S2(Q) = I |S- S2(q±) (9-2)
where,
S2(Q) = the variance in Q,
Q - the mass flow rate of a given element
j.nt° or out of the ESP,
q. - the i independent measured value
(stream flow rate or elemental con-
centration) , and
S2(q.)f the variance in q..
The errpr limits for the flow rates and analytical results used in Equation
9-^-2 are summarized in Tables 9-1, 9-2, and 9-3.
47
-------
TABLE 9-1. FLOW RATES FOR STREAMS OF THE REVERBERATORY FURNACE ESP
Stream
Flow Rate
Error
Limit
Method Used For
Flow Determinations
Furnace Off-Gas
Outlet Dust (in-
stack measurement)
4.7xl06 scfh
Inlet Dust (in-
stack measurement) 340 Ibs/hr
13 Ibs/hr
Precipitator Dust 330 Ibs/hr
±20% Measured with velocity
traverses of the outlet
duct.
±21% Based on the inlet gas flow
rate and inlet grain
loading.
±21% Based on the outlet gas
flow rate and outlet grain
loading.
±22% Determined from the dif-
ference in the inlet and
outlet dust flow rates.
48
-------
TABLE 9-2. AVERAGED REVERBERATORY FURNACE FLOW RATES
Stream
Flow Rate
Estimated Data
Error Limits Source
Concentrate Feed 5.OxlO^lbs/hr
Matte
4.2xl01)-lbs/hr
±2.4% *
±2.4%
*
Reverb Slag
3.7xlOIflbs/hr
±8.2%
*
Converter Slag
3.0xlOlflbs/hr
±8.6% *
Copper
±7.2% *
Furnace Off-Gas
4.7xl06scfh
±20% **
Precipitator Dust 330 Ibs/hr
±22% **
NOTE:
1 - Letter from plant personnel 2/1/77, five day average
2 - Radian estimate
* - Calculated from fluctuations
** - Radian estimate
49
-------
TAB1E 9-3. ESTIMATED ERROR LIMITS OF CHEMICAL ANALYSES
Element
As
Ba
Be
Cd
Cr
Cu
F
Hg
Mo
Ni
Pb
S
Sb
Se
V
Zn
WEP Liquor
and Impingers
±15%
±20%
±10%
±12%
±10%
±10%
± 8%
±20%
±12%
±15%
±20%
±10%
±10%
± 8%
±12%
±15%
Dust
±10%
± 5%
±10%
±10%
±15%
±10%
±20%
±15%
±15%
±15%
± 5%
± 5%
±15%
±20%
±10%
±15%
50
-------
SECTION 10
ANALYTICAL RESULTS AND MATERIAL BALANCES AROUND THE REVERBERATORY
FURNACE ELECTROSTATIC PRECIPITATOR
The quantitative analyses results using the dissolution procedures and
analytical methods discussed in Section 8 are listed in Table 10-1. Approxi-
mately 87 scf* of flue gas were collected at the inlet WEP train (sampling
time July 11, 1976, 8:40 am - 11:40 am) and about 95 scf at the outlet WEP
train (sampling time July 11, 1976, 8:42 am - 11:42 am). The weights of
the WEP sample solution as well as those of the acid and alkaline impinger
solutions were determined. The analytical results in Table 10-1 have the
dimensions yg of element j per gram of WEP (impinger) solution and yg of
element j per gram of ESP dust.
Table 10-2 relates the analytical findings to the element content in
10 scf of flue gas. This unit was selected for convenience regarding the
numerical values. From these data and the flow rates of ESP dust, incoming
and outgoing gas, the elemental flow rates in the three streams can be cal-
culated. The results are shown in Table 10-3. Again, the contributions from
the wet electrostatic precipitator and the acid and basic impingers are listed
separately. The final columns show the total flows to and from the ESP.
The error limits were calculated from the estimated errors in the flow rate
determinations and the errors inherent in the analytical method using error
propagation calculations as shown in Section 9. The balances are considered
to close when the mass flow rates of a given element in and out of the ESP
agree within the calculated error limits.
The survey analysis of the outlet WEP sample by spark source mass spec-
trometry is shown in Table 10-4. The analysis of ESP dust by the same method
is shown in Table 10-5. This technique is not a suitable method for certain
elements. The elements in question are marked with the symbol "ND". If no
numerical value for the concentration of an element is given the concentra-
tion was found to be below the detection limit of the SSMS technique, which
is about 0.1-1 ppm for solids and 1-10 ppb for liquids. Elements present
as major components (>1000 ppm) are marked "MC".
* scf is the gas volume at 760 mm Hg and 60°F on a dry basis.
51
-------
TABLE 10-1.
ANALYTICAL RESULTS FROM INLET AND OUTLET SAMPLING TRAINS AND PRECIPITATOR
DUST (JULY 11, 1976)
Element
Sample No.
Sample Wt.
As
Ba
Be
Cd
Cr
Cu
F
Hg
Mo
Ni
Pb
S
Sb
Se
V
Zn
INLET SAMPLES
WEP
liquor
790
698. Og
2250
<.l
.15
3.4
.33
680
89
.013
110
1.1
11
9.8
11
.49
52
1st 2nd 1st 2nd
acid acid basic basic
impinger impinger impinger impinger
792 793 794 795
631. 5g 631. Ig 559. 9g 568. 8g
.47 .079 <.02 2.6
<.l <.l <.l <.l
.001 <.001 <.001 <.001
.009 <.0001 <.0001 <.0001
<.01 <.01 <.01 <.01
.072 .10 .13 .27
3.0 .38 .32 .17
.034 .078 .010 <.001
.008 <.001 <.001 <.001
<.01 <.01 <.01 <.01
.03 .01 <.001 <.001
.0013 .0020 <.0002 <.0002
<.lppb <.lpp 1.3ppb 12ppb
.48 .14 .06 .12
.09 .09 .05 <.01
OUTLET SAMPLES
WEP
liquor
797
1120g
1100
<.l
.087
.13
.092
8.3
62
.0071
1.4
.70
.62
2.7
8.0
.38
.59
}st 2nd 1st 2nd
acid acid basic basic
impinger impinger impinger impinger
799 800 801 802
594. 8g 567. 8g 442. 7g 510. If
.13 .031 <.02 .10
<.l <.l <.l <.l
<.001 <.001 <.001 <.001
<.0001 .0013 <,0001 <.0001
<.01 <.01 <.01 <.01
.086 <.01 .16 .14
4.6 .20 .40 .30
.021 .044 .015 <.001
.028 <.001 <.001 <-001
<.01 <.01 <.01 <.01
.05 <.001 <.001 <.001
<.0002 <.0002 <.0002 <.00<)2-
<.lppb <.lppb l.Sppb l.'Oppb
<.l <.l .45 .64
.10 .05 <.01 <.01
Precip-
itator
dust
806
9. OX
70
1.2
2200
55
18.71
98
.46
2.0TL
180
1.6Z
9.0Z
3900
480
32
1.391
Ul
All values expressed in yg element/g of sample unless noted otherwise
-------
TABLE 10-2. ELEMENTAL CONTENT OF INCOMING AND OUTGOING ESP-STREAMS
(July 11, 1976)
Element
As
Ba
Be
Cd
Cr
Cu
F
Hg
Mo
Ni
Pb
S
Sb
Se
V
Zn
Inlet
Integral
WEP1
39
<.0018
0.0025
0.061
0.0057
12
1.6
0.0022
1.8
0.020
0.19
2903
0.19
0.19
0.021
0.91
Outlet
Integral
WEP1
28
<.0026
0.0022
0.0035
0.0024
.22
1.7
0.0012
0.035
0.018
0.016
5003
0.069
0.21
0.013
0.017
Precipitator
Dust2
9.0%
70
1.2
2200
55
18.7
98
0.46
2.0%
180
1.6%
9.0%
3900
480
32
1.4%
1Integral WEP values represent the total catch of the WEP plus the train of
four sample collecting impingers a,nd expressed in lhs/10s scf ,
n i
Expressed in yg element per g of dust.
Sulfur values based on SOa-SOs concentration in flue gas and the sulfur
content of the flue dust which were determined independently of the WEP
samples .
53
-------
TABLE 10-3. ELEMENTAL FLOW RATES IN ESP INLET AND OUTLET STREAMS (JULY 11, 1976)
Element
Arsenic
Barium
Beryllium
Cadmium
Chromium
Copper
Fluorine
Mercury
Molybdenum
Nickel
Lead
Sulfur
Antimony
Selenium
Vanadium
Zinc
INLET
(Ib/hr)
inlet 1st 2nd 1st 2nd
WEP acid acid basic basic
liquor impinger impinger impinger impinger
190 .036 .0060 ND 1.8
ND ND ND ND ND
.013 1.2xlO~7 ND ND ND
.29 .00068 ND ND ND
.027 ND ND ND ND
56 .0054 .0075 .0086 .018
7.4 .23 .029 .021 .0012
.0011 .0025 .0059 .00066 ND
8.7 .00060 ND ND ND
.092 ND ND ND ND
.92 .0023 .00072 ND ND
(1320 Ib/hr S as S02l 30 Ib/hr S as S03, 30 Ib/hr
in flue dust)
.81 9.8xlO~s .00025 ND ND
.91 ND ND 8.6xlO~5 .00078
.041 .036 .011 .0039 .0081
4.3 .0068 .0068 .0033 ND
E in
(Ib/hr)
190 ± 95
<.0085 ± .005
.013 ± .006
.29 ± .13
.027 ± .012
56 ± 25
7.6 ± 3.2
.010 ± .006
8.7 ± 4.0
.09 ± .05
.92 ± .52
1400 ± 640
.81 ± .36
.91 ± .34
.099 ± .046
4.3 ± 2.2
OUTLET
(Ib/hr)
outlet 1st 2nd 1st 2nd
WEP acid acid basic basic
liquor impinger impinger impinger impinger
140 .0084 .0016 - .0055
ND ND ND ND ND
.011 ND ND ND ND
.016 ND 8.1xlO~5 ND ND
.011 ND ND ND ND
1.0 .0055 ND .0077 .0077
7.5 .29 .012 .020 .016
.00087 .0013 .0027 .00072 ND
.16 .0018 ND ND ND
.085 ND ND ND ND
.075 .0035 ND ND ND
(2210 Ib/hr S as S02 , 50 Ib/hr S as S03, 1.2 Ib/hr
in flue dust)
.33 ND ND ND ND
.97 ND ND 7.2xlO~5 5.5xlO~5
.0047 ND ND .022 .035
.072 .0064 .0032 ND ND
precipi-
tator
dust
30
.023
.00040
.74
.018
62
.032
.00015
6.6
.059
5.3
30
1.3
.16
.011
4.6
I out
(Ib/hr)
170 ± 84
<.035 ± .016
.011 ± .005
.74 ± .34
.029 ± .007
63 ± 28
7.8 ± 3.4
.006 ± .003
6.8 ± 3.4
.14 ± .07
5.4 ± 2.2
2290 ± 1040
1.6 ± .80
1.1 ± .5
.073 ± .032
4.7 ± 2.3
Ul
-p-
-------
TABLE 10-4. SURVEY ANALYSIS OF THE OUTLET WEP SAMPLE BY SPARK SOURCE
MASS SPECTROMETRY (JULY 11, 1976)
CONCENTRATION IN u9/ml
ELEMENT CONC.
Uranium
Thorium
Bismuth 0=02
Lead 0.1
Thallium
Mercury NR
Gold
Platinum
Iridiura
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbium
Thulium
Erbium
Hoi mi urn
Dysprosium
ELEMENT CONC.
Terbium
Gadol inium
Europium
Samarium
Neodymi urn
Praseodymium
Cerium 0.01
Lanthanum 0.02
Barium 0.2
Cesium ±0.003
Iodine
Tellurium
Antimony 0.04
Tin
Indium STD
Cadmium
Silver 0.02
Palladium
Rhodi urn
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
CONC.
2
0.03
0.002
2
MC
0.01
<0.005
0.4
9
0.04
0.002
0.8
0.009
0.05
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
CONC!
0.004
0.2
<0.001
MC
9
0.4
4
0.5
1
0.7
0.8
4
=0.06
MR
NR
NR
0.02
0.008
NR
NR. - SSMS technique is not suitable.
No value listed: Element concentration is below the detection limit of
SSMS (0.1-1 ppm for solids, 1-10 ppb for liquids)
MC - Major component.
55
-------
TABLE 10-5. SURVEY ANALYSIS OF THE PRECIPITATOR DUST BY SPARK SOURCE
MASS SPECTROMETRY (JULY 11-13, 1976)
CONCENTRATION IN PPM WEIGHT
ELEMENT CONC.
^. ... M I, .pj. . . , .
Uranium <2
Thorium <3
Bismuth 650
Lead MC
Thallium 15
Mercury NR
Gold
Platinum
Iridium
Osmium
Rhenium
Tungsten <2
Tantalum
Hafnium
Lutetium
Ytterbium
Thulium
Erbium
Holmium
Dysprosium
ELEMENT
Terbium
Gadolinium
Europium
Samarium
Neodymi um
Praseodymi um
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmi um
Silver
Palladium
Rhodium
CONC.
0.3
0.8
0.5
2
1
0.8
8
4
36
5
2
110
MC
250
STD
330
140
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobal t
Iron
Manganese
Chromium
CONC.
MC
1
10
2
22
39
7
410
MC
31
5
MC
MC
100
21
MC
38
31
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodi um
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryl 1 i um
Lithium
Hydrogen
CONC.
6
MC
2
MC
MC
38
MC
MC
MC
>340
MC
MC
=95
NR
NR
NR
8
0.5
12
NR
NR - SSMS technique is not suitably.
No value listed: Element concentration is below the detection limit of
SSMS (0.1-1 ppm for solids, 1-10 ppb for liquids)
MC - Major component.
56
-------
SECTION 11
REVERBERATORY FURNACE MATERIAL BALANCE
The quantitative analysis results for the samples collected arpiind
the reverberatory furnace are given in Table 11-1. Approximately 131
cubic feet (at 60°F and 29.92" Hg on a dry basis) of furnace off-gas were
collected at the electrostatic precipitator outlet on July 13, 1976 be-r
tween 06:35 and 10:28 am. At the completion of sampling the weights of
the analytical solutions, the WEP liquor and five impinger solutions were
recorded. The analytical results for each solution reported in Table 11-1
have units of Jig of element j per gram of analytical solution unless nofed
otherwise.
The electrostatic precipitator dust was collected by Radian personnel
during the period July 11-13, 1976. The other solid samples, matte, slag,
and feed were composites of six shift samples supplied by plant personnel,
Analytical values for these samples are also expressed in yg/gram unless
otherwise noted.
TabJ.e 11-2 gives the elemental flow rates for each stream. The
summation of the elemental flow rates of all incoming and outgoing streams
are also given. It should be noted that samples of the converter slag,
the converter dust, and the reverberatory furnace waste heat boiler dust were
not available.
Survey analysis of the reverb feed, matte, and reverb slag by SSMS
are given in Tables 11-3, 11-4 and 11-5.
57
-------
TABLE 11-1. ANALYTICAL RESULTS FROM STREAMS AROUND THE REVERBERATORY FURNACE (JULY 11-14, 1976)
Al
As
Ba
Be
Ca
Cd
Cr
Cu
F
Fe
Hg
Mo
Ni
Pb
Sb
Se
Si
V
Zn
INCOMING STREAMS
Reverb Converter Converter
Feed Slag Dust
8000
w w
0.39% ^ ^
620 « pa
1.4 ^ *
1.5% H w
1200 * *
15.0
-------
TABLE 11-2. ELEMENT FLOW RATES IN THE FEED AND DISCHARGE STREAMS OF THE REVERBERATORY FURNACE
(JULY 11-14, 1976)
U1
Element
Al
As
Ba
Be
Ca
Cd
Cr
Cu
F
Fe
Hg
Mo
Ni
Pb
Sb
Se
Si
V
Zn
Reverb
Feed
400
190
31
0.072
770
59
0.076
1.6x10"
3.4
1.0x10*
0.018
79
0.70
49
6.0
10
1100
. 0.92
42
Incoming Streams
Converter Converter
Slag Dust
J J
« pa
iJ iJ
M H
> >
< <
(-1 H
0 0
W b3
Oj -On
s s
M CO
Total
>400
>190
>31
>0.072
>770
>59
>0.076
>1.6xlO*
>3.4
>1.0xlO*
>0.018
>79
>0.70
>49
>6.0
>10
>1100
>0.92
*2
Outgoing Streams
Matte
<17
48
33
4.1xlO~3
12
37
0.64
1.8x10*
0.012
1.1x10*
0.020
8.5
2.0
84
4.6
0.17
<42
0.33
31
Slag
700
48
43
0.032
1.9xl03
0.33
3.8
2.2xl02
2.2
1.2x10*
9.1xlO~3
89
0.76
13
3.4
5.5
4. 8x10 3
0.86
30
Flue
Outlet
0.10
76
0.64
3.4xlO~3
0.011
.076
0.044
1.8
9.4
0.55
0.033
0.17
0.011
0.38
0.030
0.65
1.7
0.027
0.22
ESP* Waste Heat*
Catch Boiler Dust
1.1
30
0.023
4.0x10"" "
2.1 M
0.74 _,
0.018 H
a
62 &
0.032 *
42.6 s_
1.5x10"" o
6.6
O.O59 M
5-3 £
1.3 S
0-16 ^
1.7
0.011
4.6
Total
700
200
76.2
0.039
2000
46
4.5
1.8x10*
12
2.3x10*
0.062
100
29
100
9.4
6.5
4800
1.2
66
* These streams were not recycled during the time of ESP sampling.
-------
TABLE 11-3. SURVEY ANALYSIS OF THE REVERBERATORY FURNACE FEED BY SSMS
(JULY 12-14, 1976)
CONCENTRATION IN PPM WEIGHT
ELEMENT CONC.
Uranium 2
Thorium 4
Bismuth 80
Lead 910
Thallium 250
MC
>600
=160
NR
NR
NR
2
<0.1
1
NR
NR - SSMS technique is not suitable.
No value listed: Element concentration is below the detection limit of
SSMS (0.1-1 ppm for solids, 1-10 ppb for liquids)
MC - Major component, (>1000 ppm).
* - Heterogeneous
60
-------
TABLE 11-4. SURVEY ANALYSIS OF MATTE BY SPARK SOURCE MASS SPECTROMETRY
(JULY 12-14, 1976)
CONCENTRATION IN PPM WEIGHT
ELEMENT CONC.
Uranium £3
Thorium 13
Bismuth 120
Lead MC
Thallium 3
Mercury NR
Gold 3
Platinum
Iridium
Osmium
Rhenium
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbium
Thulium
Erbium
Hoi mi urn
Dysprosium
ELEMENT CONC.
Terbi urn
Gadolinium
Europium
Samarium
Neodymium
Praseodymium 0.4
Cerium 0.7
Lanthanum 0.9
Barium 36
Cesium 0.2
Iodine
Tellurium 6
Antimony 180
Tin 30
Indium STD
Cadmi urn 50
Silver 110
Palladium
Rhodium
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
CONC.
170
5
2
14
3
1
410
MC
0,2
MC
MC
60
57Q
MC
34
15
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryllium
Lithium
Hydrogen
CONC.
1
26
^1.4
MC
MC
19
MC
6
470
>350
15
MC
=25
NR
NR
NR
0.4
1
NR
NR - SSMS technique is not suitable.
No value listed: Element concentration is below the detection limit of
SSMS (0.1-1 ppm for solids, 1-10 ppb for liquids)
MC - Major component , (>1000 ppm).
* - Heterogeneous
61
-------
TABLE 11-5. SURVEY ANALYSIS OF REVERBERATORY FURNACE SLAG BY SSMS
(JULY 12-14, 1976)
CONCENTRATION IN PPM WEIGHT
ELEMENT
Uranium
Thorium
Bismuth
Lead
Thallium
Mercury
Gold
Platinum
Iridium
Osmium
Rheni urn
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbium
Thulium
Erbium
ttol mi urn
Dysprosium
CONC.
9
24
5
370
NR
4
3
0.3
1
0.3
1
1
5
ELEMENT
Terbium
Gadolinium
Europium
Samarium
Neodymium
Praseodymi urn
Cerium
Lanthanum
Barium
Cesium
Iodine
Tellurium
Antimony
Tin
Indium
Cadmium
Silver
Palladium
Rhodi urn
CONC.
0.5
3
1
10
12
10
65
50
270
4
160
15
STD
4
1
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttri urn
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
CONC.
MC
10
130
18
130
44
2
25
MC
0.6
8
MC
MC
14
38
MC
260
120
1
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Silicon
Aluminum
Magnesium
Sodium
Fluorine
Oxygen
Ni trogen
Carbon
Boron
Beryl 1 i urn
Lithium
Hydrogen
CONC.
15
MC
4
MC
MC
95
MC
MC
MC
>250
MC
>640
=60
NR
NR
NR
2
0.2
2
NR
NR- SSMS technique is not suitable. ' -
No value listed: Element concentration is belqw the detection limit of
SSMS (0.1-1 ppm for solids, 1-10 ppb for liquids)
MC - Major component, (>1000 ppm).
* - Heterogeneous
62
-------
SECTION 12
X-RAY FLUORESCENCE AND SSMS ANALYSES OF MATERIAL CONDENSED IN IMPINGERS
The cumulative material condensed in the impingers during in-duct,
out-of-duct grain loading determination was mixed in an approximate ratio
of 1:4 with boric acid and compressed into a pellet. This pellet was
qualitatively analyzed for most elements heavier than iron using X-ray
fluorescence in the scanqing mode. A Siemens Sequential X-Ray Spectrometer
was used. Scanning conditions included:
e chromium target tube, 50 Kv, 48 ma,
LiF(lOO) crystal,
scintillation counter,
© pulse height discriminator settings:
baseline 0.56 volts
window width 0.90 volts,
scanning rate 2°/minute,
» chart speed 20 cm/minute, and
* scanning range 20 = 9 to 57°.
The scanning range indicated covers Ka lines for elements cobalt (atomic
No. 27) through promethium (61) and La lines for elements dysprosium (66)
through uranium (92).
Table 12-1 lists the elements of interest in the present study. Comments
indicate which elements would not have been detected by X-ray fluorescence
under the conditions used. For those elements with K or L lines within the
scanning range, the positions of analytical lines are listed with net peak
intensities above background for the sample pellet and for a pellet of pure
boric acid.
The peak Intensities listed in Table 12-1 indicate that arsenic and
selenium are the predominant heavy elements in this sample. The presence
of a smaller amount of z^nc is indicated. Small amounts of copper and lead
may also be present although the observed increases in peak intensities are
near experimental detectabilities. Other fluctuations in peak intensities
are within experimental error.
63
-------
TABLE 12-4. X-RAY FLUORESCENCE INTENSITIES FOR ELEMENTS OF INTEREST
Element
Symbol
As
Atomic Analytical
Number line
33 Ka
K
PI , 3
20 for LiF(lOO)
crystal (degrees)
34.00
30.45
Fluorescent
Intensity
for H3B03
(counts/sec)
<100
<100
Fluorescent
Intensity for
Condensate Sample
(counts/sec)
5900
1280
Ba 56 K 11.02 <120 <120
Be 4 Too light for X-ray fluorescence determination
Cd 48 K 15.31 <160 <160
Cr 24 K 69.36 Not in scanning range used
Cu
F
Hg
Mo
Ni
Pb
S
Sb
Se
29
9
80
4?
28
82
16
51
34
Ka 45'°3
KQ ' 40.46
PI, 3
Too light for X-ray fluorescence
L 35.91
K 20.33
K 48.67
L 33.93
Oil
Lg 28.26
Not in range of LiF(lOO) crystal
K 13.42
011,2
K 31.89
K0 ' 28.54
1120*
260*
determination
<80
<100
160*
<100
<120
<200
<80
<80
1380
360
<80
<120
160
(5900)**
240
<150
1120
250
V 23 K 76.94 Not in scanning range used
Oil , 2
Zn 30 K 41.80 740* 1120
KR''2 37.53 160* 260
* Some net peak intensity is always observed for Ni, Cu, Zn. These intensities
derive from materials of construction of the X-ray spectrometer.
** This line is not resolved from the As K line at 20 = 34.00 degrees. The intensities
of the As K, line and the Pb L0 line indicate that the major portion of this
PI i 3 ' PI
peak should be assigned to arsenic.
64
-------
The results of a survey analysis by spark source mass spectrospopy are
shown In Table 12-2. Again, arsenic and selenium are indicated to be present
as major species. Species found in smaller concentrations are lead, rheniunj
and zinc.
65
-------
TABLE 12-2. SURVEY ANALYSIS OF THE CONDENSIBLES BY SPARK SOURCE MASS
SPECTROMETRY
CONCENTRATION IN PPM WEIGHT
ELEMENT CONC.
Uranium
Thorium
Sismuth
Lead 15
Thallium
Mercury NR
Gold
Platinum
Iridium
Osmium
Rhenium 370
Tungsten
Tantalum
Hafnium
Lutetium
Ytterbium
Thulium
Erbium
Holmium
Dysprosium
ELEMENT CONC.
Terbium
Gadolinium
Europium
Samarium
Neodymi urn
Praseodymi urn
Cerium 4
Lanthanum 8
Barium 16
Cesium
Iodine 40
Tellurium
Antimony 7
Tin 7
Indium STD
Cadmium <6
Silver 6
Palladium
Rhodium
ELEMENT
Ruthenium
Molybdenum
Niobium
Zirconium
Yttrium
Strontium
Rubidium
Bromine
Selenium
Arsenic
Germanium
Gallium
Zinc
Copper
Nickel
Cobalt
Iron
Manganese
Chromium
CONC.
25
10
3
5
0.7
10
MC
MC
3
100
MC
35
1
770
6
97
ELEMENT
Vanadium
Titanium
Scandium
Calcium
Potassium
Chlorine
Sulfur
Phosphorus
Sil icon
Al uminum
Magnesium
Sodium
Fluorine
Oxygen
Nitrogen
Carbon
Boron
Beryl 1 ium
Lithium
Hydrogen
CONC.
2
100
<0.9
MC
420
130
700
260
MC
340
MC
870
=50
NR
NR
NR
2
1
NR
NR - SSMS technique is not suitable.
No value listed: Element concentration is below the detection limit of
SSMS (0.1-1 ppm for solids, 1-10 ppb for liquids)
MC - Major component, C>100° PPm)
* - Heterogeneous
66
-------
SECTION 13
IDENTIFICATION OF MAJOR CRYSTALLINE SPECIES
In an effort to determine the major chemical compounds present in the
emissions from the reverberatory furnace, six samples were studied using
X-ray diffraction:
reverberatory furnace feed concentrate (collected
July 13, 1976, 11:10 pm "C" shift),
dust collected by the electrostatic precipitator
(taken from screw conveyor, July 11, 1976),
particulate, collected at the ESP outlet using an
in-stack filter (July 10, 1976, from 6:30 to 8:14 am),
condensed particulate - collected at the ESP outlet at
250 F preceded by an in-stack filter at 600°F
(July 15, 1976, from 8:50 to 10:20 am),
condensed perticulate - collected at the ESP inlet
at 250°F preceded by an in-stack filter at 600°F;
this filter was unusual in that the collected material
was black while that on all other filters used in this
manner was very light in color (July 15, 1977, 1:00 pm
to 2:20 pm), and
material which condensed in the glassware following the
filter oven during modified EPA Method 5 sampling
(composite sample).
Copper Ka radiation was used in the X-ray studies.
Most of the pattern obtained for the reverberatory furnace feed con-
centrate is reproduced in Figure 13-1. Table 13-1 lists most of the
recpgnizable peaks and the crystalline species which have been assigned to
account for them. Two crystalline phases have been identified in the
reverberatory furnace feed concentrate: Chalcopyrite (CuFeSa) and
OMJuartz (SiOa). These two species dominate the pattern. Several small
peaks remain unassigned and may represent a complex mixture of minor crystal-
line components.
67
-------
CO
TWO THETA ANGLE (DEGREES!
Figure 13-1. X-Ray Powder Diffraction Pattern - Reverberatory Furnace Feed Concentrate (Collected
July 13, 1976, 11:10 pm "C" Shift).
-------
i-O
TABLE 13-1. X-RAY POWDER DIFFRACTION PATTERN - REVERBERATORY FURNACE FEED CONCENTRATE
(COLLECTED JULY 13, 1976, 11:10 PM "C" SHIFT)
OBSERVED PEAj
29
Degrees
I
Counts/Sec
FS
d
Angstroms
ASSIGNMENT OF CRYSTALLINE SPECIES
a-Quartz
Si02
d
Angstroms
7.5 11 11.7
8.6 16 10.2
9.4 12 9.36
I/I > 6
o
Chalcopyrite
CuFeSz
d
Angstroms
I/I0 > 5
d
Angstroms
T/Io >-
d I/I >
Angstroms
11.4
11.6
17.5
17.8
18.2
18.85
20.9
21.0
25.8
26.1
26.6
27.6
29.4
31.2
32.6
32.8
33.1
33.9
34.45
35.2
35.5
36.1
36.6
37.1
38.0
38.2
38.4
13
14
12
10
10
10
21
12
13
10
145
26
900
17
9
17
32
38
25
11
14
14
11
13
9
10
13
7.73
7.60
5.05
4.97
4.86
4.71
4.24 4.26 35
4.22
3.447
3.408
3.345 3.343 100
3.226
3.033 3.03 100
2.862
2.743
2.726
2.702
2.640 2.63 5
2.603
2.546
2.525
2.485
2.452 2.458 12
2.420
2.365
2.353
2.341
(Continued)
-------
TABLE 13-1. X-RAY POWDER DIFFRACTION PATTERN - REVERBERATORY FURNACE FEED CONCENTRATE
(COLLECTED JULY 13, 1976, 11:10 PM "C" SHIFT)
40.8
42.4
43.2
43.3
44.5
45.8
46.1
47.0
47.55
47.8
48.6
49.0
50.1
51.4
51.6
54.0
54.8
55.7
[56.3
1.56.4
57.85
58.6
59.2
59.3
59.5
59.85
60.3
_OESERVED PEAKS
29
I
fmmt-ta/^pr
d
Anestrdms
ASSIGNMENT OF CRYS
a-Quartz
Si02
d
Angstroms
39.2 11 2.295
39.5 12 2.279 . 2.282
40.3 6 2.235 2.237
I/I > 6
o
Chalcopyrite
CuFeS2
d
Angstroms
I/I > 5
o
FALLINE SPECIES
d
Angstroms
^o >~
d I/I0 >
Angstroms
12
6
15
5
12
12
8
8
8
16
28
26
120
240
12
8
4
10
6
11
60 (15)
35 (11)
115
70
45
20
12
9
15 (B)
2.209
2.129
2.092
2.087
2.034
1.979
1.967
1.931
1.912
1.901
1.872
1.857
1.819
1.776
1.770
697
,674
.649
.633"!
,630j
1.594
1.574
1.560
1.557
1.552
1.545
1.534
2.128
1.980
1.865 40
1.854 80
1.817
1.672
17
1.591 60
1.573 20
1.541
15
-------
TABLE 13-1. X-RAY POWDER DIFFRACTION PATTERN - REVERBERATORY FURNACE FEED CONCENTRATE
(COLLECTED JULY 13, 1976, 11:10 PM "C" SHIFT)
OBSERVED PEAKS
26
Degrees
I
Counts/Sec
d
Angstroms
ot-Quartz
. Si02
d
Angstroms
60.9 18 1.520
61.1 12 1,516
61-7 21 1.502
I/I > 6
o
ASSIGNMENT OF CRYS
Chalcopyrite
CuFeSa
d
Angstroms
1.518
I/IoT5
CALLINE SPECIES
d
Angstroms
5
mo >
^ i/i0 >
Angstroms
61.85
64.95
66.7
67.8
68.1
68.3
71.25
72.5
75.3
78.9
79.5
79.8
13
13
7
17
30
25
26
12
12
22
28
22
1.500
1.436
1.401
1.381 1.382 7
1.376 1.375 11
1.372 1.372 9
1.3234
1.302
1.2613
1.2126
1.2050
1.2012
1.323 10
1.303 5
1.214 10
1.205 30
The source for the standards was the X-Ray Powder Diffraction Data File.
Card Number 5-490 and that for Chalcopyrite on Card Number 9-423.
The pattern for silica is listed on
-------
The powder diffraction patterns of the five solids obtained from
effluent gases all contained Arsenolite (As203). Significant portions of
the patterns are presented in Figures 13-2 through 13-6. Peak identifica-
tions and assignments are listed in Tables 13-2 through 13-6.
In complex patterns such as those obtained for material from the dust
hopper and material collected on the in-stack filter, it is often.not possi-
ble to identify more than three or four species with a high degree of
confidence. The degree of confidence in peak assignments generally decreases
as one goes to the right in the tables. The first three species listed for,
the dust hopper, a-Quartz, Arsenolite and Chalcocyanite can, quite assuredly,
be said to be present. The presence of the remaining species is not so
certain. However, the peak assignments are reasonable and consistent with
what is presently known of the elemental composition of the sample. For the
material collected on the in-stack filter, hydrates of copper sulfate share
predominance with the arsenolite. The material collected on the in-stack
filter was a bright blue color. Unidentified peaks remain on both these
patterns.
Material collected on the out-of-stack filters had passed through the
in-stack filter at 315°C (600°F), presumably in the gas phase, and was
collected at 120°C (250°F). The crystalline portion of this material is
almost pure As203. Very little difference was observed between the X-ray
patterns for material which was almost white and that which was black.
As filtered gas was passed through the sampling train, some material
condensed on the surfaces of the lines leading to the first impinger. This
material was initially highly colored and oily in appearance. As time passed,
this material lost much of its color and seemed to become more crystalline.
Two major peaks appear on the pattern for this aged material in addition to
the patterns for Arsenolite, These peaks have not yet been assigned.
Table 3-17 summarizes the crystalline materials identified in the six
samples discussed above. The persistent presence of Arsenolite (As203) in
materials leaving the reverberatory furnace is striking. The blue color of
the material collected on the in-stack filter can be attributed to the
presence of copper sulfate pentahydrate.
72
-------
TWO THETA ANQLE (DEGREES)
eo
TWO THETA ANQLE (OEQREES)
Figure 13-2. X-Ray Powder Diffraction Pattern - Dust Hopper (Collected July 11, 1976)
-------
TABLE 13-2. X-RAY POWDER DIFFRACTION PATTERN - DUST HOPPER (SAMPLE #806)
26
13.8
14.9
17.3
C t'/S
d
35 6.39
22 5.93
30 5.11
ct-Ouartz 1] Arsenolite
Sin, II AszOa
d
I/I i 6 d
6.39
I/I i 10
CuSOn
d
63
i/io > 10
CuSO<,'H20
d
l/io ; 20
a-Fe203 CuO
d I/I0 i 25 1 d I/Io ^ 20
Angstroms II Angstroms
34.25
34.75
[35.3
35.6
[35.7
36.6
45
30
48
125
113
35
18.0
18.2
18.6
20.0
20.8
21.2
24.2
25.0
25.7
25.8
[26.3
26.6
27.4
27.9
28.5
28.6
29.6
30.15
31.3
32.4
33.2
30
SO
60
35
65
45
33
45
42
70
45
140
22
57
38
50
28
33
27
35
35
4.91
4.86
4.76
4.43
4.26
4.18
3.67
3.555
3.466
3.446
3.379]
3.345
3.249
3.192
3.124
3.116
3.013
2.964
2.853
2.759
2.694
2.618
2.581
2.537]
2.518
2.509]
2.452
4.26
35
3.343
100
4.187 75
3.549 100
3.195 100
2.768 28
2.541 38
.6161
4.87
4.79
3.46
3.43
3.38
3.14
30
40
30
100
80
80
2.58 35
3.66 25
2.69 100
2.51 50
|~2.530 49")
[2.523 lOOJ
2.458 12
-------
Ul
38.1
38.6
38.9
39.1
39.5
39.8
40.2
41.1
42.4
44.7
45.8
46.05
46.2
48.8
49.5
50.1
51.6
54.1
54.8
55.0
57.0
57.6
58.2
58.4
59.5
60.1
61.5
TABLE 13-2. X-RAY POWDER DIFFRACTION PATTERN - DUST HOPPER (SAMPLE #806)
29
Degrees
I
Counts/ Sec
d
Angstroms
Si02
Angstroms^
' 0
Arsenolite
AssOg
d
Angstroms
37.2 30 2. All
I/I £ 10
o
Chalcocyanite
CuSOu
A t
I/I £ 10
Copper Sulfate Hydrate
d I/I > 20
Hematite
d I/lo > 25
IT"
i
22
20
18
17
35
7
38
20
12
35
22
32
11
17
15
20
10
25
30
35
42
7
25
15
5
15
10
2.359
2.328
2.310
2.299
2.279
2.262
2.240
2.192
2.132
2.025
1.979
1.969
1.957
1.863
1.838
1.8i9
1.768
1.692
1.668
1.614
1.599
1.583
1.578
1.551
1.538
1.505
[2.421]
[2.416]
Tenorite
CuO
I/I > 20
2.282
2.237
2.128
1.980
1.817
1.672
12
6
9
6
2.301
2.262 12
2.132 17
1.957 27
1.670 21
1.599 10
1.971
1.963
1.775
1.674
1.584
1.581
1.541
15
50
10
10
16
30
12
12
10
2.323 96
2.312 30
2.26
1.866
25
60
1.505
] indicate unresolved peaks.
for the standard patterns was the X-Ray Powder Diffraction Data File. The following cards were used:
Chemical Formula Card No.
SiOj
As 20 3
CuSO»
CuSOfHzO
Ot-Fe203
CuO
5-490
4-566
15-775
12-782
13-534
-------
30 25
TWO THETA ANGLE (DEGREES)
35 20
TWO THETA ANGLE IDEQREESI
Figure 13-3.
X-Ray Powder Diffraction Pattern - Collected at ESP Outlet on In-Stack Filter
(Collected July 10, 1976, from 6:30 to 8:14 am).
-------
TABLE 13-3.
X-RAY POWDER DIFFRACTION PATTERN - COLLECTED AT ESP OUTLET ON IN-STACK FILTER
(COLLECTED JULY 10, 1976 FROM 6:30 TO 8:14 AM)
OBSERVED PEAKS
20
Degrees
I
Counts/Sec
d
Angstroms
=========_====__
Arsenolite
As203
Angstroms
I/I > 10
Copper Sulfate Pentahydrate
CuSO,, 5H20
d
Angstroms
7-° 16 12.6
14-1 48 6.27 6.394 63
I/I > 20
jj
LINE SPECIES
Bonatite
CuSO,, 3H,0
d
Angstroms
I/I > 19
Angstroms Iflo >
15.6
16.3
17.2
17.45
18.4
18.9
20.2
20.9
21.0
21
22
24.
24.4
25.2
26.0
26.7
27.2
27.5
28.1
29.2
29.5
30.1
30.3
30.6
31.3
20
37
11
36
29
38
30
22
12
55
85
10
35
52
50
20
40
20
35
40
26
5.68
5.43
5.15
5.08
4.82
4.69
4.39
4.27
4.23
4.13
3.97
3.70
3.65
3.53
3.42
3.336
3.276
3.241
3.173 3.195 100
3.056
3.025
2.966
2.948
2.919
2.855
5.73
(_5.68
5.48
5.15
j"4.73
[4.66
3.99
3.71
3.54
3.30
3.26
3.05
35
20J
55
25
ioo"|
20 J
60
85
20
60
20
30
5.09
4.83
4.69
4.40
1.96
3.65
1.42
3.24
3.18
3.00
2.97
65
35
19
100
35
55
50
£5
35
40
20
=
(Continued)
-------
00
TABLE 13-3.
X-RAY POWDER DIFFRACTION PATTERN - COLLECTED AT ESP OUTLET ON IN-STACK FILTER
(COLLECTED JULY 10, 1976 FROM 6:30 TO 8:14 AM)
ASSIGNMENT OF CRYSTALLINE SPECIES
31.6
32.1
32.5
32.8
33.8
34.4
35.0
35.4
35.6
35.8
36.0
36.65
37.1
37.35
37.
39.
39.
40.
40.
41.
42.4
42.9
43.85
45.0
46.1
46.3
47.3
c
28
BSERVED PEAKS
I
d
Angstroms
Arsenolite
AsaOi
d
Angstroms
i/io > 10
Copper Sulfate Pentahydrate
CuSOi, 5H20
d
Angstroms
I/I > 20
o -
Bonatlte
CuSOt, 3H20
d
Angstroms
I/Io > 19
d
Angstroms
^0^
j
33
15
62
48
16
7
11
2f>
27
2S
5
10
20
9
9
7
6
14
10
11
13
12
16
9
8
10
2.829
2.786
2.753
2.728
2.649
,605
561
,533
,520
.506
2.493
.450
.421
.406
.383
2.279
2.262
2.249
2.204
2.189
2.130
.106
.062
2.012
1.966
1.958
1.919
2.768
2.541
28
38
2.824
2.788
2.749
.2.662
40
20
50
40
2.814 45
2.743 25
2.418
40
2.494
2.275
35
2.262
2.132
1.958
12
17
27
(Continued)
-------
vo
TABLE 13-3. X-RAY POWDER DIFFRACTION PATTERN - COLLECTED AT ESP OUTLET ON IN-STACK FILTER
(COLLECTED JULY 10, 1976 FROM 6:30 TO 8:14 AM)
OBSERVED PEAKS
26
Degrees
I
Counts/Sec
Arsen
As
Angstroms Angstroms
48.2 20 1.886
48.8 13 1.864
49.3 15 1.846
49.8 16 1.829
50.1 10 1.819
50.4 11 1.809
ASSIGNMENT OF CRYSTALL
olite Copper Sulfate Pentahydrate
2°3 CuSOu
I/I > 10 d
o - Angstroms
5H20
I/I > 20
o
INE SPECIES
Bonatlte
CuSOt
d
Angstroms
3H20
I/ I > 19
Angstrom '/'>
The Source for the Standard Patterns was the X-Ray Powder Diffraction File. The following cards were used:
Chemical Formula Card No.
As203 4-566
CuSO,, 5H20 11-646
CuSOi, 3H20 12-262
-------
08
OT
C
US
I pi
o <:
Hi
I O
Cfl H'
rt iti
P> MI
O H
fS^ PJ
O
'Tj ft
H- e-
)_. o
rt 3
(a
/-^ rt
CH rt
C (D
M i-i
O
P
CO
Hi (D
H P<
O
3 ^
P)
oo K
o o
O P»
rt
M (D
O
O
N5 O
O M
^
P> (D
3 o
^^ rt
(D
a.
Pd
CO
O
C
rt
t-1
(D
O
3
X-RAY INTENSITY (COUNTS/SECOND)
X-RAY INTENSITY COUNTS/SECOND)
-------
TABLE 13-4. X-RAY POWDER DIFFRACTION PATTERN -
CONDENSED PARTICULATE COLLECTED AT ESP OUTLET
ON OUT-OF-STACK FILTER (JULY 15, 1976, FROM
8:50 TO 10:20 AM)
OBSERVED PEAKS
20
Degrees
I
Counts/Sec
d
Angstroms
CRYSTALLINE SPECIES
Arsenolite*
As203
d
Angstroms
I/I > 5
o
13.95
28.0
32.4
35.4
39.8
42.5
46.4
48.9
49.4
54.9
108
135
25
32
6
12
21
4
8
8
6.34
3.18
2.761
2.533
2.262
2.125
1.954
1.860
1.842
1.670
6.39
3.195
2.768
2.541
2.262
2.132
1.957
1.873
1.846
1.670
63
100
28
38
12
17
27
6
5
21
*Source: X-Ray Powder Diffraction Data File,
Card No. 4-566.
81
-------
100
40
35
30 25
TWO THETA ANGLE (DEGREES)
20
15
oo
ho
2501
g200-
W
§
O
16(H
«0
?. 100
50
250-1
200
150
100
50
100
80-
60
40
20
27
13
60
55
50
45
Figure 13-5.
TWO THETA ANGLE (DEGREES)
X-Ray Powder Diffraction Pattern - Condensed Particulate Collected at ESP Inlet on
Out-of-Stack Filter (July 15, 1976 from 1:00 to 2:20 pm) .
-------
TABLE 13-5. X-RAY POWDER DIFFRACTION PATTERN - CONDENSED
PARTICULATE COLLECTED AT ESP INLET ON OUT-OF-
STACK FILTER (JULY 15, 1976, FROM 1:00 TO 2:00 PH)
29
Degrees
13
28
32
35
39
42
46
48
49.
55.
57.
59.
.9
.0
.4
.4
.9
.5
5
8
3
1
7
6
OBSERVED PEAKS
I
Counts/Sec
105
125
26
33
8
12
18
4
2
13
6
11
d
Angstroms
6.36
3.18
2.761
2.533
2.257
2.125
1.951
1.864
1.846
1.666
1.597
1.550
CRYSTALLINE SPECIES
Arsenolite*
AsaOs
d
Angstroms
6.39
3.195
2.768
2.541
2.262
2.132
1.957
1.873
1.846
1.670
1.599
1.551
I/I £ 5
63
100
28
38
12
17
27
6
5
21
10
22
*Source: X-Ray Powder Diffraction Data File,
Card No. 4-566.
83
-------
00
-p-
TWO THETA ANGLE IDEGREESI
-------
TABLE 13-6. X-RAY POWDER DIFFRACTION PATTERN FOR
MATERIAL CONDENSED IN IMPINGERS
(COMPOSITE SAMPLE)
20
Degrees
14.0
20.3
22.4
23.7
24.3
24.6
26.8
28.0
32.5
35.45
40.0
42.5
46.5
48.7
49.3
55.1
57.8
59.1
59.7
64.6
64.8
OBSERVED PEAKS
I
Counts/Sec
260
215
30
70
135
140
18
280
92
85
20
32
50
10
10
33
15
6
28
14
15
d
Angstroms
6.32
4.372
3.966
3.751
3.660
3.617
3.324
3.184
2.753
2.5295
2.252
2.125
1.951
1.867
1.846
1.666
1.594
1.561
1.547
1.441
1.438
CRYSTALLINE
SPECIES
Arsenolite
As203
d
Angstroms
6.394
3.195
2.768
2.541
2.262
2.132
1.957
1.873
1.846
1.670
1.599
1.551
1.442
I/Io > 5
63
100
28
38
12
17
27
6
5
21
10
22
12
85
-------
oo
TABLE 13-7. SUMMARY OF CRYSTALLINE SPECIES IDENTIFIED BY X-RAY DIFFRACTION
Sample
Designation
Reverberatory
Furnace
Feed Concentrate
Dust Hopper
In-Stack Filter
(Outlet)
Copper
Sulfate
Copper
Sulfate
tr
present
present
present
present
present
present
present
probably -probably
present present
present
present
Out-of-Stack Filter
(Outlet, White Color)
present
Out-of-Stack Filter
(Inlet, Run #2, Black
Color)
present
Material Condensed in
Impinger (Inlet/Outlet
Composite)
present
-------
SECTION 14
ANALYTICAL RESULTS OF VAPOR TRAIN SAMPLING
The temperature of matte and slag in a reverberatory furnace ranges
typically from 1950-2300°F. Certain chemical compounds are vaporized at
this temperature. The temperature of the flue gas is lowered to 600°F in
waste heat boilers.
The vapor train shown in Figure 14-1 was built to determine which com-
pounds are still in the flue gas as vapors at this temperature. This train
was used to collect a vapor sample as the outlet of the electrostatic pre-
cipitator on July 16, 1977. A pyrex nozzle was attached to a pyrex-lined,
heat traced probe. The probe was connected to an out-of-stack oven kept at
duct temperature. The oven housed a cyclone followed by a filter. The
impinger train following the out-of-stack oven was the same as that used for
the integral WEP tfrain. The cyclone-filter arrangement retained particulates.
The impinger train collected species condensable between 600°F and 32°F.
Acid Impingers
Caustic Impingers
Pyrex Pytex Lined
Nozzle Probe
-Filter
Ilydrof.cnper oxide
Impinger
Cyclone
Oven
Ice Bath
Dry
Impingers
Silca Gel
Impinger
Fine
Adjustment Valve
Coarse
Adjustment Valve
Pump
Figure 14-1. Schematic of the Vapor-Phase Trace Element Sampling Train.
87
-------
Approximately 129 cubic feet (at 60°F, 29.92" Hg and dry) were collected
using the vapor phase sampling train. After trapping all particulate matter
at stack temperature, the remaining vapors were condensed in the series of
five impinger solutions. Table 14-1 gives the analytical results for each
element in units of yg/gram of analytical solution.
TABLE 14-1. ANALYTICAL RESULTS FROM VAPOR TRAIN SAMPLING
As
Ba
Be
Cd
Cr
Cu
F
Fe
'Hg)
. .-"''
Mo
Ni
Pb
Sb
Se
V
Zn
1st acid
Impinger
61
1-1
<.02
0.0010
0.11
14
55
1.1
0.45
0.025
0.085
0.058
0.039
1080 ppb
0.095
0.17
2nd acid
Impinger
150
1.4
<.02
0.0010
0.17
38
120
1.3
0.62
0.039
0.13
0.097
0.018
1590 ppb
0.099
0.16
1st basic
Impinger
24
1.4
<.02
<.001
0.18
0.19
13
0.69
0.61
0.0080
0.074
<.001
<.01
550 ppb
0.13
0.20
2nd basic
Impinger
41
1.5
<.02
<.001
0.22
0.24
8.9
0.74
<.001
0.0065
0.071
<.001
<.01
580 ppb
0.045
0.22
Peroxide
Impinger
29
<.5
<.02
<.001
0.16
0.20
0.42
<.01
<.001
0.0080
0.016
<.001
0.026
630 ppb
0.058
0.025
Note: all values in Ug/g unless otherwise noted
Table 14-2 gives the elemental flow rates as vapor or non-particulate based
on the results in Table 14-1.
88
-------
TABLE 14-2. FLOW RATES OF GASEOUS EMISSIONS
Element
As
Ba
Be
Cd
Cr
Cu
F
Fe
Flow Rate
Ib/hr
15
0.27
<4xlO~3
1.1x10"""
0.036
2.94
11.0
0.196
Element
Hg
Mo
Nl
Pb
Sb
Se
V
Zn
Flow Rate
Ib/hr
. - "
(0.062 J <-
0.016
0.031
8.7xlO~3
3.0xlO~3
0.21
0.020
0.036
89
-------
SECTION 15
ARSENIC SAMPLING
The sampling methodology and equipment used were specified by the
Environmental Protection Agency Office of Air Quality Planning and Standards.
This section describes details of the approach used to collect the samples
for arsenic determination.
EQUIPMENT DESCRIPTION
A modified EPA Method 5 sampling train, shown schematically in
Figure 15-1, was used for this sampling effort. The front half of the train
was conventional and consisted of a stainless steel nozzle, pyrex-lined
probe, cyclone, and filter holder with a glass-fiber filter. The back half
of the train was different from that normally used for EPA Method 5 sampling.
It consisted of six impingers; the first, second, third, and sixth impingers
had straight or modified tips while the fourth and fifth were standard
Smith-Greenburg impingers. The first three impingers contained 250 ml of
10% hydrogen peroxide solution. Impingers 4 and 5 contained 250 ml of O.lN
sodium hydroxide. The sixth impinger which removed moisture from the gas
stream contained dry preweighed silica gel.
Lear Siegler Inc. Model PM/100 manual stack samplers were used. The
control console of this equipment contains all controls, temperature and
pressure indicators. The vacuum pump contained in the control console is a
two cylinder diaphragm pump rated at three acfm at fifteen inches of mercury.
The pressure differential across the flow rate metering orifice, AH, is
measured with a 0-10" H20 magnehelic gauge. The pressure differential
generated by the S-type pitot is measured with a 0-5" H20 magnehelic gauge
or a 0-0.5" H20 inclined manometer. The stack temperature was monitored
using Type K, chromel-alumel, thermocouples and a digital indicating pyro-
meter.
The glassware was as specified by EPA Method 5; however, to minimize
clean-up time the cyclone was not used prior to the filter at the ESP
outlet.
90
-------
ICYCLONE
STACK TEMPERATURE T.C
IMPINGERS
PROBE TEMPERATURE T.C.
lA-\\\\\\\ \
REV. TYPE
PITOT
PITOT AP
MAGNEHELIC
FINE ADJUSTMENT
BY PASS VALVE
VACUUM
GAGE
ORIFICE AP
MAGNEHELIC GAGE'
DRY TEST METER
-COARSE
ADJUSTMENT
AIRTIGHT VALVE
VACUUM
PUMP
Figure 15-1. Arsenic Sampling Train (Modified EPA-5 Train).
Note: Six impingers were used.
VACUUM
LINE
-------
The dry gas meters, the flow rate orifice, and the S-type pitot of each
sampling train were calibrated by Lear Siegler's manufacturing agent, Napp
Inc. of Austin, Texas. A summary of these calibration results is presented
in Table 15-1.
TABLE 15-1. SUMMARY OF CALIBRATION DATA
Unit
D313
D314
Calibration Date 6-11-76
Dry gas meter correction factor y 1,0011
(ratio of standard flow to dry gas
meter flow)
6-11-76
0.9955
AH@ (orifice pressure drop @ .75
cfm, 29.92" Hg, 70°F)
1.86
1.82
Pitot tube correction factor
0.85
0.85
SAMPLING METHODOLOGY
Three runs were made sampling simultaneously at the inlet and outlet
of the electrostatic precipitator servicing the reverberatory furnace, using
methodology described by EPA Method 5.
Prior to sampling, the: trains were thoroughly cleaned then rinsed
with dilute ultra-high purity nitric acid. The reagents used in the train
clean-up and impinger solutions were reagent grade.
The sample was recovered after each run and stored in five segments
as follows:
1 - filter plus 50 ml of O.lN NaOH,
2 - probe and filter holder washings, deionized
water and O.lN Ultrex, HNOs,
3 - contents of impingers 1 through 3, (10% HaOa) ,
92
-------
4 - contents of impinger 4, (O.lN NaOH), and
o 5 - contents of Impinger 5, (O.lN NaOH).
The specified clean-up procedure, an initial rinse with deionized water
followed by a second rinse with O.lN nitric acid, did not remove all of the
sample collected. A red substance, oily in appearance, condensed in the
sample line downstream of the filter oven. The majority of this substance
was contained in the glass connector prior to the first impinger. However, it
was also visible on the down spout and walls of the first impinger.
Subsequent attempts to recover this condensed residue using deionized
water and nitric acid were unsuccessful. As specified in instructions from
EPA/OAQPS, no acetone was used in the attempted sample recovery.
A decision was made after consultation with EPA/OAQPS to allow the
condensed residue not removed by the specified sample recovery scheme to
accumulate in the glassware and to recover it if possible at the completion
of the three sampling runs.
The quantity of condensed residue which was collected at the ESP inlet
appeared to be significantly less than that collected at the outlet. For
this reason, the; residue collected by the inlet train was used to determine
which sample recovery methods would be most effective and thus was not
completely recovered.
The recovered condensed residue from the outlet sampling train was
returned to the. laboratory in a polyethylene bottle together with the reagents
used in the recovery attempts. A nylon bristled brush was found to be the
most efficient in the recovery of the residue. However, it too became
coated with the material and as a result was also included in the sample which
was returned to the laboratory for analysis. Recovery of the condensed
residue was not quantitative.
RESULTS
The results for each of the six arsenic sampling runs are in Table 15-2.
The emission rates are based on sampling data collected by Radian personnel
and the arsenic concentration of the analytical samples, as reported by
Battelle, Columbus Laboratories, Columbus, Ohio. The analytical results were
received by Radian Corporation through EPA/IERL in February, 1977.
The quantity of arsenic present in the condensed residue recovered
from the glassware following the. filter oven of the outlet sampling train
93
-------
TABLE 15-2. SUMMARY OF ARSENIC EMISSION DATA FROM THE REVERBERATORY ELECTROSTATIC PRECIPITATOR
Run
Date
INLET DUCT
Time Gas Flow Rate Arsenic Flow
(rain) (acfm) Rate (Ibs/hr)
7-13-76 0930-1226 155200
59.3
OUTLET DUCT
Time Gas Flow Rate ftrsenic Flow
(min) (acfm) Rate (Ibs/hr)
0951-1336 170700
53.7
7-14-76 0555-0907 156000
72.9
0610-0855 168900
44.8
7-14-76 1132-1505 157900
75.4
1130-1415 166500
51.3
Average
156400
69.2
168700
49.9
-------
was determined by Radian Corporation. This was accomplished by acid dis-
solution and direct aspiration into the flame of an atomic absorption
instrument. The quantity of arsenic present in the recovered residue was
0.1441 g.
The average arsenic emission rate from the electrostatic precipitator
was determined from these tests to be 49.9 Ibs/hr. Arsenic entered the ESP
at a rate of 69.2 Ibs/hr. The difference, 19.3 Ibs/hr, is the amount col-
lected by the ESP in the form of dust. This value compares with 30 Ibs/hr
arsenic collection rate determined in the ESP element balance attempt
(July 11, 1976).
All pertinent data measured and calculated follow.
TABLE 15-3. SUMMARY OF ARSENIC SAMPLING DATA REVERBERATORY FURNACE
ELECTROSTATIC PRECIPITATOR INLET
2 3
7-13-76 7-14-76 7-14-76
. 0930-1226 0555-0907 1132-1505
Duration, (mm) 120 120 12Q
Metered volume, (ft3) 42.66 42.31 4263
Corrected metered volume, (ft3) 42.47 42^2 42°44
Average meter temperature, (°R) 577 572 539
Average stack temperature, (°R) 1082 1062 1099
Barometric pressure, (in. Hg) 28.20 28.20 2820
Stack pressure, (in. Hg) 28.12 28 13 28*13
Moisture collected, (gm) 167.3 171 9 144 ]_
Dry gas fraction 0.823 0.814 0.840
Average molecular weight, (gm/gm-mole) 27.48 27.38 27.68
Average (APXTg)% 20.62 20.69 21 Q6
Average gas velocity, (ft/sec) 53.90 54 17 54 84
Flue gas flow rate, (acfm) 155232 156004 157931
Nozzle area, (ft2) 1.623x10-" 1.623x10-* 1.623x10^
bample volume @ stack conditions, (ft3) 97.04 96 31 94 51
Percent of isokinetic, (%) 154 152
Arsenic collected, (gm) Q.280 0.340 0.341
Arsenic flow rate, (Ibs/hr) 59.25 72.85 75.40
95
-------
TABLE 15-4. SUMMARY OF ARSENIC SAMPLING DATA REVERBERATORY FURNACE ELECTRO-
STATIC PRECIPITATOR OUTLET
Run
Date
Time
Duration, (min)
Metered volume, (ft )
Corrected metered volume, (ft )
Average meter temperature, (QR)
Average stack temperature, ( R)
Barometric pressure, (in. Hg)
Stack pressure, (in. Hg)
Moisture collected, (gm)
Dry gas fraction
Average molecular weight, (gm/gm-mole)
Average (APxTg)%, (in. H20-°R)2
Average gas velocity, (ft /sec)
Flue gas flow rate, (acfm)
9
Nozzle area, (ft )
Sample volume @ stack conditions, (ft )
Percent of isokinetic, (%)
Arsenic collected, (gm)
Arsenic collected as condensed
residue, (gm)
Total arsenic collected
Arsenic emission rate (Ibs/hr)
1
7-13-76
0951-1336
120
76.80
76.88
572
1055
28.20
28.02
255.4
.847
27.84
38.15
99.25
170720
1.623x10 "
168.49
145
.352
.049
.401
53.74
2
7-14-76
0610-0855
120
75.96
76.04
574
1070
28.20
28.02
254.6
.846
27.31
37.38
98.18
168880
1.623x10 "
168.63
147
.289
.049
.338
44.78
3
7-14-76
1130-1415
120
71.65
71.73
563
1040
28.20
28.02
""
.865
28.05-
37.35
96.80
166506
«." IL
1.623x10 u
154.17
136
.313
.046
.359
51.29
96
-------
TRAVERSE POINTS LAYOUT FOR REVERBERATORY ELECTROSTATIC PRECIPITATOR
OUTLET FOR ARSENIC SAMPLING
Point No.
1
2
3
4
5
6
7
8
9
Distance from
Inside Wall
Point No.
1.02"
3.19"
5.44"
7.90"
10.59"
13.63"
17.11"
20.52"
27.70"
/-"
10
11
12
13
14
15
16
17
18
* Iff^--^^^
>c 14
* 13
v 12
x 11
Distance from
Inside Wall
44.81"
51.04"
55.39"
58.87"
61.92"
64.60"
67.06"
69.31"
71.49"
north
11 12 13 14 15 17
North port extention = 5.25"
West port extention = 5.25"
Inside diameter = 72.5'
97
-------
TRAVERSE POINTS LAYOUT FOR REVERBERATORY ELECTROSTATIC PRECIPITATOR
INLET
Point Numbers
1, 4, 7, 10, 13, & 16
2, 5, 8, 11, 14, & 17
3, 6, 9, 12, 15, & 18
Distance from Port Wall
8"
24"
40"
Note: ports are on 12" centers only
only points denoted with an "x" were sampled during*'
arsenic test
ports are on 12* centers
West duct 4* x 6'
East duct 4' x 6'
West Duct
East Duct
3. 6x 9. 12. 15 * 18.
2. 5*, 8. 11. 14 / 17.
1 . 4 X 7 . 10 . 13 x 16-
in
3. 6x 9.
2. 5X 6.
1. 4X 7.
nnnnr in i
12. 15* 18-
11. 14 X 17-
10. 13>c 16
98
-------
FIELD SAMPLING DATA
Plant
Cu-Smelter
Date July
Sample No.
Meter No.
Nozzle No.
Nozzle Area
13, 1976
As #1
E-313
3/16
1.632xlO~4
Filter No.
Bar. Press. "He" 28.20
Stack Press. "H,0" 28 r 02
Orifice Constants: *
At, 1.25 AH 0.89
Oper. Rohlack
_ Probe No.
- PTCF
K
6 ft.
.85
.708
(in. H20)
Pt.
17
17
16
16
15
15
14
13
12
11
10
9
8
/
6
b
^WM
4
3
MMBMMM
Total
Clock
Time
0951
0954
0957
1000
1003
1096
1009
1012
1015
-LUIS
1021
1024
1027
1030
1033
1036
1039
1042
Dry Gas
Meter
Reading
172.1
173.90
175.86
178.20
189.21
182.23
184.25
186.33
188.43
190.51
192.62
194.71
196.80
198.88
200.96
203.00
204.95
206.92
APn
in.
H20
1.25
1.25
1.30
1.30
1.35
1.38
1.45
1.50
1.55
1.55
1.50
1.48
1.40
1.35
1.30
1.25
1.20
1.10
AHn in. H20
Desired
0.89
0.89
0.93
0.93
0.97
0.99
1.04
1.07
1.11
1.11
1.07
1.06
1.00
0.97
0.93
0.89
0.86
0.79
Actual
0.89
0.89
0.93
0.93
0.97
0.99
1.04
1.07
1.11
1.11
1.07
1.06
1.00
0.97
0.93
0.89
0.86
0.79
Dry Gas Meter
Temperature
Inlet
110
112
116
117
120
120
120
120
120
121
121
120
120
120
120
121
122
123
Outlet
99
98
98
98
98
98
98
99
100
1QQ
101
101
101
101
1Q1
101
101
101
Sample Time 120 Min r,*^
L. Vac.
In He-
Gauge
14.0
13.8
13.8
13.8
13.8
14.8
15.3
15.8
15.8
16.2
16.8
16.7
16.8
16.8
16. S
15.1
15.1
15.1
Box
Temp
OF
250
250
250
250
250
250
250
250
250
250
250
250
250
250
Stack
Temp
OF
580
579
573
616
616
615
615
615
602
615
Avg. Meter Temp.
Avg. Stack Temp. _
112
595
at Meter Conditions
( 76.80 ) x ( 1.001 i
(NetVol) (D.G.M.C.F.)
_76.88 .ft"
99
-------
FIELD SAMPLING DATA
nato Julv 13. 1976
«5amnlp No As #1 (Contd)
(ft2)
Filtpr No.
Rar PfPSS. "Hfr" IMI. _,
fJtpnlr PrPSS "H.O",. .,._
Ap AH
(in. H20)
Oper.
Probe
PTCF
K
Rohlack
Nn
Pt.
15
14
11
10
Clock
Time
1045
1048
1241
1306
1312
1318
1324
1330
1336
Dry Gas
Meter
Reading
208.85
210.65
216.45
232.45
236.08
239.60
245.98
248.96
MM^MMMH^H
APn
H20
0.85
Q.8Q
1.50
1.46
1.49
1.50
1 . 55
1.65
1.65
1.60
1.60
1.55
AHn in. H20
Desired
0.61
0.57
Actual
0.61
0.57
Dry Gas Meter
Temperature
Inlet
124
127
115
118
120
123
125
124
122
129
119
119
Outlet
101
102
no
107
108
108
inq
110
110
110
110
110
L. Vac.
In.Hg
Gauge
11.2
11.0
18.0
18.0
18.0
18.4
18. 8
20.0
20.0
29.9
29.5
21.0
Box
Temp
op
250
250
2 SO
250
250
25tt_
?sn
250
250
250
250
250
Stack
Temp
OF
615
615
)fi4
580
582
,-?82
S86
593
607
611
6.12.
$15
1
Total Sample Time
Avg. Meter Temp..
Avg. Stack Temp. _
Min.
op
Corrected Sample Vol.
at Meter Conditions
(__ ) x (
(Net Vol)
(D.G.M.C.F.:
_Jt3
100
-------
Sample No. As-1-0
Iinpinger No.
#1
#2
Solution Usacf
10% H?Do
10% H202
10% HaOa
Q.1N NaOH
Q.1N NaOH
Silica gel
Imp. Tip
Configuration
_st
st
st
st
Weight (grams)
Final 858.5
Initial 695.6
Wt. gain 162.9
Final 767.8
Initial 700.9
Wt. gain 66.9
Final 683.4
Initial 677.8
Wt. gain 5.6
Final 697.5
Initial 696.0
Wt. gain 1.5
Final 672.9
Initial JS77.9
Wt. gain -5.0 *
Final 664.8
Initial 641.3
Wt. gain 23.5
TOTAL WEIGHT GAIN OF IMPINGERS ( grams ) 255.4
* indicates that part of the impinger solution was entrained into the
next impinger.
ORSAT ANALYSIS RESULTS
Data:
Time;
Gas Fractional Part
CO-
°2
CO
101
-------
FIELD SAMPLING DATA
ESP Inlet East
Plant M"° OU. ^...^o-L-v-.*-
nato Julv 13. 1976
^amplp No AS Trl
Motor TSJr» F 31 4
PflT- PrPBB "Hpr" 28.20
Stark Proes "N.O" 28, 12
Orifice Constants: ,
Ap .30 AH
Oper. Fuchs
Prnhe No.., 6 ft. _
- PTCF
ST
(ft2)
(in. H20)
M^V*
Pt.
13
13
14
14
15
A
C
C
6
6
Clock
Time
0930
Q935
0940
0945
0950
0955
1000
1006
1016
1021
1026
1031
1036
Dry Gas
Meter
Reading
304.26
305.74
307.30
309.29
311.28
313. 29
315.31
317.92
319.83
321.94
324.0
326.2
APn
H20
0.30
0.30
0.30
0.48
0.48
0.51
0.51
0.25
0.25
0.25
0.53
0.53
0.55
0.55
AHn in. H20
Desired
0.25
0.25
0.25
0.40
0.40
0.42
0.42
0.20
Dr20
0.20
0.44
0.44
0.46
0.46
Actual
0.25
0.25
0.25
0.40
0.40
0.42
0.42
0.20
0.20
0.20
0.44
0.44
0.46
0.46
Dry Gas Meter
Temperature
Inlet
114
121
126
129
131
137
131
123
134
131
129
128
Outlet
96
97
98
100
101
107
105
110
106
104
105
106
L. Vac.
In. Hg
Gauge
4.2
4.0
5.1
5.3
6.0
6.5
5.3
7.1
14.7
15.0
17.0
17.3
Box
Temp
°F
250
250
250
250
250
250
250
250
250
250
250
250
Stack
Temp
OF
539
538
564
578
597
595
60Q
610
618
614
632
641
J 1
Total Sample Time
Avg. Meter Temp. _
Avg. Stack Temp. _
120 Min.
117 °F
622 op
Corrected Sample Vol.
at Meter Conditions
t 42.66 > x ( 0.9955)
(Net Vol) (D.G.M.C.F.)
42.47 ft3
102
-------
FIELD SAMPLING DATA
Plant
Date July 13 ? 1976
Sample No. As #1 (Contd)
Meter No.
Nozzle No.
Nozzle Area
(ft2)
Filter No.
Bar. Press. "Kg"
Stack Press. "H20"
Ap AH
(in. H,0>
Oper. Fuchs
1 PTCF
K
Pt.
13
13
14
14
15
15
4
4
5
5
6
6
Clock
Time
am
1125
1130
1135
1140
1145
_H5_0,
1156
,J,2j31_
1206
1211
1216
1221
_J22£
Dry Gas
Meter
Reading
-376*2J
327.53
328.84
330.72
332.66
334.68
^2^22
_336>L72
33jvd
^j^g^is
340.94
342.84
344.86
«JHiL22J
APn
in.
H20
0.17
0.17
0.17
0,45
0.45
0.49
JLALj
0.19
J).20
0.20
0.44
0.44
0.49
JL.4JL,
AHn in, H20
Desired
0.14
0.14
0.14
0.37
0.37
0.41
LJL11_,
0.16
0.165
>_p_ii65_
0.36
0.36
0.41
0 41
Actual
_JLH.
0.14
0,14
0.37
0.37
0.41
0.41
0.16
0.165
0.165
0.36
0.36
__ (L41J
0.41
Dry Gas Meter
Temperature
Inlet
125
129
132
134
135
135
132
133
L 136
__14pJ
141
-JM.
Outlet
103
103
103
103
104
104
105 I
105
106
108
109
109
L. Vac.
In. Hg
Gauge
3.5
3.5
4.9
4.9
5.3
5.3
3.5
3.5
5.0
5.0
6.0
6.0
Box
Temp
°F
250
250
250
250
250
250
250
250
250
250
250
250
Stack
Temp
op
640
635
657
664
683
672
624
614
646
650
669
656
STOP
Total Sample Time
Avg. Meter Temp..
Avg. Stack Temp. _
_ Min.
op
Corrected Sample Vol.
at Meter Conditions
( ) x (_.
(Net Vol)
(D.G.M.C.F.
_ft3
103
-------
Sample No.As-1-I
Impinger No.
#1
Solution Used
10%
10% H202
10% HzOz
0.1N NaOH
0.1N NaOH
Silica gel
Imp. Tip
Configuranion
_s£_
st
st
sg
st
Weighc (grains)
Final 762.9
Initial 663.7
Wt. gain 99.5
694.9
Final
Initial 663.7
Wt. gain 31.2,
Final
Initial 661.9
Wt. gain 20.4
Final 679.8
Initial 677.3
Wt. gain 2.5
674.4
Final _______
Initial 676.0
Wt. gain -1.6 *
Final .659.1
Initial 643.8
Wt. aain 15.3
TOTAL WEIGHT GAIN OF IHPI^IGZRS ( grams ) 167.3
* indicates that part of the impinger solution was entrained into the
next impinger.
ORSAT ANALYSIS RESULTS
Oats:
Tiae;
co2
°2
CO
2
Gas Fractional ?atr
104
-------
Plant Nam* Cu-Smelter
FIELD SAMPLING DATA
ESP Outlet
Date July 14, 1976
Sample No. As #2
Meter No. E-313
Nozzle No. 3/16
Nozzle Area 1 . 63 2xlO~ "*
Filter No.
Bar. Press. "He" 28.20
Stack Press. "H.O" 28.02
AD 1.20 AH .85
Oper. Rohlack
Probe No. 6 f t .
- PTCF
K .708
(in. H,0)
Pt.
17
17
16
16
15
.I,1?
14
13
.12
1]
10
9
8
7
ft
5
4
3
Clock
Time
J2£UL
0613
0616
061?
0622
0625
06.28.
0631
,,P634
0637
06.40
0643
0645
0649
065.2
06.^
0658
0701
Dry Gas
Meter
Reading
248.96
250.90
252.80
254.695
256.56
258.425
260.^
262.29
264.26
266.27
2&3L33L.
270.29
272.25
274.21
276.17
278, 11
80.025
81.97
*Pn
in.
H20
1.20
1.18
1.25
1.2.5
1.35
1.35
1.40
1.45
1.50
1.55
1,50,,.
1.45
1.38
1.33
1,30
1.28
1.18
1.04
AHn in. H20
Desired
0.85
0.84
0.89
0.89
0.96
0.96
1.00
1.03
1.07
1.10
1.07
1.03
0.98
0.95
0.93
0.91
0.84
0.74
Actual
0.85
0.84
0.89
0.89
0.96
0.96
1.00
1.03
1.07
1.10
1.07
1.03
0.98
0.95
0.93
0.91
0.84
0.74
Dry Gas Meter
Temperature
Inlet
98
103
106
107
110
111
111
111
111
110
109
110
110
112
112
114
115
115
Outlet
89
89
89
89
89
90
90
90
91
91
91
91
91
92
92
93
94
94
L. Vac.
In He-
Gauge
13.7
13.4
13.4
13.4
13.4
14.2
16,0
16.0
17.2
17.2
17.2
17.2 -
16.8
16.8
16.5
16.3
16.3
__ 16. 1_
Box
Temp
oF
250
250
250
250
250
250
250
250
250
250
250
250
250
250
250
250
250
250
^MMBB^m
Stack
Temp
op
554
555
556
555
558
557
559
561
564
590
593
594
595
595
596
590
Total Sample Time
Avg. Meter Temp. _
Avg. Stack Temp. _
120 Min
103
Corrected Sample Vol.
at Meter Conditions
(75.96 ) x ( 1.001
580
(Net Vol) (D.G.M.C.F.
76.04 ft.a
105
-------
FIELD SAMPLING DATA
ESP Outlet
Plant Name_
Date July
(ft2)
14, 1976 Filte-N«
As #2 (Contd)Bar. PI-MS "Hp-"
Ap - AH
(in. H20)
Oper.
,_ Prohf> No. _
PTCF
W
Pt.
1
17
17
16
15
15
11
10
9
\-
L
HM^H«i^H«MH
Clock
Time
Q7Q4
0707
0755
0758
0801
0807
0810
0813
0822
0825
0828
Dry Gas
Meter
Reading
83,83
85.64
87.43
89.40
91.27
293.18
295.12
297.045
298.975
302.76
304.62
306.50
308.35
APn
H20
1,04
1.04
1.35
1.35
1.35
1.35
1.35
1.35
1.35
1.35
1,48
1.55
1.55
1.55
AHn in. H20
Desired
0.74
0.74
0.96
0.96
0.96
Q,96
0.96
0.96
0.96
0,96 ,
1 .05
1.10
1.10
1.10
Actual
0.74
0.74
0.96
0.96
0.96
0.96
0.96
0.96
0.96
0.96
1.05
1.10
1.10
1.10
Dry Gas Meter
Temperature
Inlet
116
116
108
108
106
105
106
106
107 ,
108
10SL_
110
111
112
Outlet
94
94
100
99
98
97
97
97
97
97
98
98
98
99
L. Vac.
In. Hg
Gauge
15.8
15.8
16.9
19.5
19.7
19.8
19.8
19.8
19.8
19.8
19.8
19.8
19.9
19.9
Box
Temp
op
250
250
250
250
250
250
250
250
250
250
250
250
250
250
Stack
Temp
OF
590
590
566
566
570 ..
567
566
566
566
572
572
576
596
601
^^^IMH^^M
Total Sample Time .
Avg. Meter Temp..
Avg. Stack Temp. _
_ Min.
op
op
Corrected Sample Vol.
at Meter Conditions
( ) x (
(Net Vol)
(D.G.M.C.F.)
_ft3
106
-------
Sample No. As-2-0
Impinger No.
#1
Solueion Used.
10%
Imp. Tip
Configuration
st
Weight (grams)
Final 897.8
Initial 702.9
WC. gainl94.9
10% H202
10% H20a
0.1N NaQH
st
Final 716.7
Initial 683.1
WC. gain 33.6
st
Final 686.3
Initial 682.3
We. gain 4.0
Final 670.3
Initial 671.0
WC. gain -0.7
0.1N NaOH
sg-
Final 698.2
Initial 696.2
We. gain 2.0
Silica gel
st
Final 706.0
Initial 685.2
Wt. gain 20.8
TOTAL WEIGHT GAIN OF IMPIIJCERS ( grass ) 254.6
* indicates that part of the impinger solution was entrained into the
next impinger.
ORSAT ANALYSIS RESULTS
Date:
Tiae :
Gas Fractional Parr
CO-
CO
107
-------
FIELD SAMPLING DATA
Cu-Smelter
Stack Name_J£P_^nlet_Wes_t_
Date July 14. 1976
Samplp Nn A.S #2
Mptpr Nn 314
Nn7?lp No 3/16
l\J,w,lo Arpa 1.632x10"
Rar Press. "Hg" 28.20
fStflnU Prp«« "H.0',',,-,-90
3. ~
Orifice Constants: h _
Ap 1.00 AH -82
Oper. Fuchs
M 6 f t .
PTCF 0.85
v .82
(ft2)
(in. H20)
Pt.
4
4
6
13
13
13
14
14
15
15
Clock
Time
0555
0600
0605
0610
0615
0620
0630
0635
0640
0645
0650
0731
0741
Dry Gas
Meter
Reading
347.47
348.66
349.90
351.70
i 353. 60
355 64
357.65
358.90
360.18
361.70
363.69
363.81
367.85
APn
in
H20
0.19
0 22
0 22
0.45
0.45
0 52
0.52
0.22
0.22
0.22
0.48
0.48
0.50
0.50
0.50
AHn in. H20
Desired
0.16
0.18
0.18
0.37
0.37
0.44
0.44 .
0.18
0.18
0.18
0.40
0.40
0.41
0,41
0.41
Actual
0.16
0.18
0.18
0.37
0.37
0.44
0.44
0.18
0.18
0.18
0.40
0.40
0.41
0.41
0.41
Dry Gas Meter
Temperature
Inlet
112
116
120
122
124
124
118
118
116
111
119
124
Outlet
90
90
91
91
92
93
94
93
93
94
95
95
L. Vac.
In. Hg
Gauge
3.0
3.0
4.5
4.5
5.3
10.0
12.0
7.5
16.8
21.0
4.3
4.3
Box
Temp
OF
250
250
250
250
250
250
250
250
250
250
250
250
Stack
Temp
op
594
586
608
605
635
630
616
623
636
631
656
654
Total Sample Time .
Avg. Meter Temp. _
Avg. Stack Temp. _
120 Min.
112 °F
602
Corrected Sample Vol.
at Meter Conditions
(. 42.31 ) x L0.9955)
(Net Vol) (D.G.M.C.F.)
42.12ft.
108
-------
Plant Namp Cu-Smelter
FIELD SAMPLING DATA
ESP Inlet East
Date July 14
Sample No. As
Meter No.
Nozzle No.
Nozzle Area
(ft2)
,1976 Filter No.
#2 (ContcDRar Press. "He"
Stark Press. "H,O"
______ Orifice Constants- a
AD AH
(in. H20)
Oper. Fuchs
...._. Prr>be No.
~ - PTCF
K
Pt.
4
4
5
5
6
6
13
13
13
14
14
15
15
Clock
Time
0801
0806
0811
0816
0821
0826
0831
0837
0842
0847
0852
0857
0902
0907
Dry Gas
Meter
Reading
367.85
369.27
370.65
372.58
374.65
376.74
378.86
378.86
380.30
381.73
383.66
385.64
387.71
389.78
APn
in.
H20
0.27
0.27
0.27
0.53
0.53
0.55
0.56
0.28
0.28
0.28
0.49
0.49
0.53
0.53
AHn in. H20
Desired
0.22
0.22
0.27
0.44
0.44
0.45
0.47
0.23
0.23
0.23
0.405
0.405
0.44
0.44
Actual
0.22
0.22
0.22
0.44
0.44
0.45
0.47
0.23
0.23
0.23
0.405
0.405
0.44
0.44
Dry Gas Meter
Temperature
Inlet
123
126
130
132
133
134
132
134
135
137
136
131
Outlet
99
99
100
100
101
102
105
104
105
106
106
106
L. Vac.
In He
Gauge
3.2
3.2
4.4
4.5
4.8
5.1
3.8
3.8
5.0
5.5
12.1
16.0
Box
Temp
°F
250
250
250
250
250
250
250
250
250
250
250
250
Stack
Temp
°F
583
581
599
596
617
632
531
528
573
558
587
581
STOP
Total Sample Time .
Avg. Meter Temp. _
Avg. Stack Temp. _
Min.
Corrected Sample Vol.
at Meter Conditions
( ) x (
(Net Vol)
(D.G.M.C.F.)
109
-------
Sample No. As-2-I
Impinger No.
#1
Solucion Used
Imp. Tip
Configuration
10% H202
10% HzOz
st
st
Q.1N NaOH
Q.1N NaOH
sg
Silica gel
st
TOTAL WEIGHT GAIN OF IXPINGERS ( grams ) 171.9
Weight (grams)
Hinal 803.1
Initial _648.1
Wt. gain
Final 714.4
Initial 681.4
WC. gain ^.n.
Final 696'7
Initial 697.9
Wt. gain -1.2
Final 826.5
Initial 688.0
Wt. gain T3R. *5._
Final 538.0
Initial 671.8
Wt. zain-133.8
667.7
Final
Initial 651.3
WC. gain 16.4
* indicates that part of the mpinger solution was entrained into the
next impinger.
ORSAT ANALYSIS RESULTS
Data:
Time;
Gas Fractional Part
2
CO
110
-------
FIELD SAMPLING DATA
Northport
(Fig.4-6)
Plant Name_
Date Jul;
Sample No.
Meter No.
Nozzle No.
Nozzle Area
/Vi21
Cu-Smelter
y 14, 1976
As #3
E-313
3/16
1.632x10-"
. ____ Stack Nam p
Filter No.
Bar. Press. "Hg" 28.20
Stack Press. "H,0" 28.02
Orifice Constants: j*
Ap 1.35 AH .96
ESP Outlet
Oper. Rohlack
Probe No. 6 ft.
PTCF 0.85
K .71
(in. H.O)
Total Sample Time
Avg. Meter Temp. _
Avg. Stack Temp. _
120
Min.
114
610
Corrected
at Meter
( 71.65
(Net Vol)
Sample Vol.
Conditions
) x ( l.OQl
(D.G.M.C.FJ
Pt.
17
Jl
16
16
15
15
14
13
12
-LL
10
9
8
7
_JL
5.
_J_
?
Clock
Time
1130
1133
1136
1139
1142
1145
1148
1151
-HSiJ
.JJJiL
1200
1203
1206
1209
_L212_
1215
iinan !! linn
-12JJL
1221
Dry Gas
Meter
Reading
324.92
326.82
328.68
330.50
332.36
B34_._20_
336.06
337.90
212^ZiJ
^i*H_
343.40
345.22
347.04
348.87
ISJLHL
352.70
54.375
56.15
APn
in.
H20
1.35
1.35
.1.38
1.38
1.38
i^lLj
1.40
1.40
J^SJL.
J*5i_
1.55
1.52
1.55
1.55
-L-5JL.
1.48
1.40
1.30
AHn in. H20
Desired
0.96
0,96
0.98
0.98
0.98
0.98
1.00
1.00
__mzJ
1,IQ
1.10
1.08
1.10
1.10
1.07
1.05
1.00
0.93
Actual
0.96
0.96
0.98
0.98
0.98
0.98
1.00
1.00
-iuO_7__
i,;o
1.10
1.08
1.10
1.10
1.07
1.05
1.00
0.93
Dry Gas Meter
Temperature
Inlet
109
109
111
112
113
114
115
115
_!!&_
116
117
117
119
__119
-JL22.
120
120
119
Outlet
105
105
105
106
106
105
106
106
106
106
106
106
106
108
108
108
108
108
L. Vac.
In He-
Gauge
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
Box
Temp
op
250
250
250
250
250
250
250 1
250
250
250
250
250
250
^(^M^^
250
250
250
250
"IH^^HB^HHBH
Stack
Temp
Op
588
589
589
591
594
604
623
628
627
628
M^ WMH^^
629
628
626
624
ill
-------
FIELD SAMPLING DATA
Stack Name_fS^Outlet_
n,tp July 14, 1976
«amnlp Nn As #3 (Contd)
(ft2)
Filter No.
Bar. Press.
Orifice Con
An
oiacK. i^aui
"H,r"
, "H.O"
AH
(in. H20)
Oppr. Rohlack
Probe No.
PTCF
«
Westport
(Fig. 4-6^
Pt.
17
17
16
16
T>
1
in
1
h
Clock
Time
1315
1318
1321
1330
1351
1354
1 -55
1400
Dry Gas
Meter
Reading
57.915
359.67
61.46
63.30
65.075
366.90
368.69
370.37
372.11
37-3 ftfi
r rv
384.39
386 19
387.90
APn
H20
0.95
1.25
1.25
1.30
i 1.30
1.33
1.33
1.42
1 .50
1.50
1.55
1 .50
1 38
1.30
1.18
1.10
AHn in. H20
Desired
0.68
0.89
0.89
0.93
0.93
0.95 .
0.95
1.01
1 ,Q7
_JLr07
1.10
J.07
1 ,Q3
0.98
0.98
masmmaiiHH * i urn-Mi
_a*M_
0.78
Actual
0.68
0.89
0.89
0.93
0.93
0.95
0.95
1.01
1.07
1.07
1.10
1.07
1 m
0.98
0.98
1 Ill IIMII 1
Jk84
0.78
Dry Gas Meter
Temperature
Inlet
118
120
117
117
116
115
115
115
116
119
120
122
124
174
125
125
__12lL,
126
i iiilimiiih il i IB n m
Outlet
108
108
112
111
110
109
109
109
109
110
11,0
111
112
_J_L3_
113
s_U4__
,__lli_
114
HdraSaKZJBSBEESSHESli
L. Vac.
In. Hg
Gauge
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
9n.n
20.0
20.0
mm l ' HI
20.0
20.0
Box
Temp
op
250
250
250
250
250
250
250
250
250
250
250
250
250
750
250
250
250
250
Stack
Temp
op
625 1
625 1
586
586
588
589
593
596
596
604
603
609
622
6?,?,
623
624
624
628
Total Sample Time _
Avg. Meter Temp. _
Avg. Stack Temp, __
. Min.
op
°F
Corrected Sample Vol.
at Meter Conditions
) x (
(Net Vol)
(D.G.M.C.F.)
112
-------
Plant Nam* Cu-Smelter
FIELD SAMPLING DATA
ESP Outlet
Date July 14, 1976 Filter No
Sample No. As #3 (Contd)Rar
Meter No. ,. staM
Nozzle No. Orifi!
Nozzle Area /\p
(ft2)
Press. "He"
c Press. "H,O"
ccCon-Unl a
AH
(in. H20)
Oper. Rohlack
.,..._ Prr>be No
PTCF
K
Pt.
4
-
2
1
^^^MH
^HH
Clock
Time
1403
1406
1409
.,1412
1415
^^BMHOM
Dry Gas
Meter
Reading
389.70
391.40
393.07
394.90
396.57
APn
in.
H20
1.10
1.10
0.95
0.70
HBBMBMMM
AHn in. H20
Desired
0.78
0.78
0.68
0.50
Actual
0.78
0.78
0.68
0.50
Dry Gas Meter
Temperature
Inlet
126
125
125
124
Outlet
114
115
116
114
L. Vac.
In He-
Gauge
20.0
20.0
20.0
20.0
Box
Temp
OF
250
250
250
^-^^^
Stack
Temp
op
628
629
630
STOP
Total Sample Time
Avg. Meter Temp. _
Avg. Stack Temp. _
_ Min.
_oF
op
Corrected Sample Vol.
at Meter Conditions
( ) x (
(Net Vol)
(D.G.M.C.F.)
__ft3
113
-------
Sample No. As-3-0
Impinger Mo.
n
Imp. Tip
Solution Used Configuracion
10%
10% H202
10% H202
0.1N NaOH
0.1N NaOH
Silica gel
st_
st
st
sg
sg
st
Weight (grams)
Final ~ . t
Initial 681.89
Wt. gain .
Final 737.0
Initial 703.6
WC. gain 33.4,
687.7
Final
Initial 684.1
Wt. gain 3.6
Final "
Initial 690.0
Wt. gain
Final _ 685-7
Initial
Wt. gain
684.2
1.5
696.0
Final
Initial 672.9
Wt. gain 23.1
TOTAL WEIGHT GAIN OF IMPI-SGEXS (
t Faulty sample
Data:
Tiaie t
CO-
ORSAT ANALYSIS RESULTS
Gas Fractional ?art
CO
2
114
-------
FIELD SAMPLING DATA
Plant
Cu-Smelter
Date Julv 14. 1976
Sample No.
Meter No.
Nozzle No.
Nozzle Area
As #3
E-314
3/16
1.632x10"'*
Filter No.
Bar. Press. "He" 2? , 2
Stack Press. "H,0" -1.0
_ AD J--UO AH -82
Oper.
_ Probe
- PTCF
K
Fuchs
No. 6 ft.
.85
.82
(in. H20)
Pt.
13
13
14
14
15
15
4
4
5
5
6
6
fi
6
6
MMiMH
Clock
Time
1132
1137
1142
1147
1152
1157
1202
1205
1210
1215
1221
1225
1229
1235
nnn
1303
1306
Dry Gas
Meter
Reading
389.91
391.43
392.96
395.08
396.98
399.01
401.10
401.10
402.48
403.84
406.29
408.02
409.26
409.96
410.48
411.78
APn
in.
H20
0.30
0.30
0.30
0.50
0.50
0.52
0.52
0.25
0.25
0.25
0.54
0.54
0.54
0.54
O.S4
0.54
0.54
AHn in. H20
Desired
0.25
0.25
0.25
0.41
0.41
0.42
0.42
0.21
0.21
0.21
0.45
0.45
0.45
0.45
.JL.45
0.45
0.45
Actual
0.25
0.25
0.25
0.41
0.41
0.42
0.42
0.21
0.21
0.21
0.45
0.45
0.45
0.45
n.4S
0.45
0.45
Dry Gas Meter
Temperature
Inlet
130
138
140
141
142
144
142
143
142
144
132
136
140
Outlet
112
112
112
112
114
114
116
116
116
116
114
114
115
L. Vac.
In He
Gauge
3.2
3.2
4.2
4 2
4.3
4.3
3.7
3.5
10.0
17.0
23.0
4.5
4.3
Box
Temp
OF
250
250
250
250
250
250
250
250
250
250
250
250
250
250
Stack
Temp
Op
570
561
590
591
624
636
627
625
641
650
675
656
Total Sample Time
Avg. Meter Temp. _
Avg. Stack Temp. _
120
129 oF
639 °F
Corrected Sample Vol.
at Meter Conditions
( 42.63 I x ( 0.99551
(Net Vol) (D.G.M.C.F.;
_ 42.32ft..
115
-------
Plant M Cu-Smelter
FIELD SAMPLING DATA
Stack Name_ESP_InleLl££t_
TW. July 14. 1976
Sample No. As #3 (Contd) Bar. Press. "Hg^
Meter No.. Stack Press. "H201
Nozzle No.
Oper._
Probe
PTCF
Nozzle Area^
(ft2)
Ap.
AH_
(in. H20)
^MBMI
1 Pt.
T
13
13
14
14
i 5
15
4
r
5
c
6
Clock
Time
1320
1325
1330
1335
1340
1345
1350
1400
1410
1445
1450
1455
1500
1505
Dry Gas
Meter
Reading
11.78
13.01
14.19
16.07
18.02
419.97
422.09
422.09
424.59
424.59
426.47
428.40
430.50
APn
H20
0.20
0.20
0.20
0.47
0.47
[0.48
0,48
Q.22
0.22
0.43
0.44
0.44
0.41
0.51
AHn in. H20
Desired
0.16
0.16
0.16
0.38
0.38
0.40
0.40
OjJ-85
_0.1RS
0.185
0.36
0.37
0.37
0.42
0.42
Actual
0.16
0.16
0.16
0.38
0.38
0.40
0.40
0.185
O.IRS
0.185
0.37
0.37
0.42
0.42
Dry Gas Meter
Temperature
Inlet
136
139
144
145
148
149
142
140
142
144
146
148
Outlet
114
113
115
116
116
116
1?0
119
121
120
120
120
L. Vac.
In. Hg
Gauge
3.0
3.0
5.2
11.2
14.0
11,0
15.3
3.9
3.9
4.2
4.2
Box
Temp
oF
250
250
250
250
250
750
250
250
250
250
250
Stack
Temp
oF
653
672
682
688
6.88
ft?,1)
625
633
633
651
652
STOP
Total Sample Time
Avg. Meter Temp. .
Avg. Stack Temp. _
Min.
°F
op
Corrected Sample Vol.
at Meter Conditions
116
-------
Sample Ho. As-3-I
Impinger No.
#1
n
Solution Osed-
10% H?0o
10% H202
10% H202
0.1N NaOH
Imp. Tip
Configuracion
_s±_
st
st
O.IK NaOH
Silica gel
st
TOTAL WEIGHT GAIN OF IHPINGERS ( grams )
144.1
Weight (grams)
Final
812.0
Initial
697.8
Wt. gain 114-2
680.2
Final
Initial 667.3
Wt. gain 12-9
Final
704.8
Initial 678.2
Wt. gain 26.6
846.2
Final
Initial 672.7
Wt. gain 173.5
Final
482.1
Initial 679.8
Wt. gain
Final 683.5
Initial 668^
Wt. gain 14.6
* indicates that part of the impinger solution was entrained into the
next impinger.
ORSAT ANALYSIS RESULTS
Date:
Gas Fractional Part
CO-
°2
CO
N2
117
-------
REFERENCES
BA-131
BA-137
BO-027
BU-136
CI-002
DE-218
DI-043
DO-006
ED-027
HE-094
Baker R L. , "Determination of Fluoride in Vegetation Using the
Ion Electrode," Anal1_ChenK 44(7), 1326 (1972).
JO-012
KA-086
Baumann, Elizabeth W. , "Trace Fluoride Determination with Specific
Ion Electrode," Anal. Chem. Acta 42. 127-32 (1968).
Bokowski D. L., "Rapid Determination of Beryllium by a Direct-
Reading Atomic Absorption Spectrophotometer ," Am. Ind. Hyg. Assoc.
£29(5), 474-81 (1968).
Burke Keith E., "Determination of Microgram Amounts of Antimony,
Bismuth, Lead and Tin in Aluminum, Iron and Nickel-Base Alloys by
Non-Aqueous Atomic-Absorption Spectroscopy, Analyst 9/. iy-/o
(1972).
Cioni, R., F. Innocenti, and R. Mazzuoli, "The Determination of
Vanadium In Silicate Rocks with the HGA-70 Graphite Furnace,
Atomic Absorption Newsletter 11(5) . 102 (1972).
Dean, John A. and Theodore C. Rains, Eds., Flame Emission and Atom-
ic Absorption Spectrometry, Volume 3, Elements and Matrices. N.Y. ,
Marcel Dekker, 1975.
Diehl R C. pf- al.. Fate of Trace Mercury in the Combustion of
Coal.' TPR - 54. Pittsburgh, Pa., Pittsburgh Energy Research
Cntr. , 1972.
Dollman, G. W. , Environmental Science and Technology 2, 1027-1029
(1968).
Ediger, Richard, "Atomic Absorption Analysis with the Graphic Fur-
nace Using Matrix Modification," Atomic Absorption Application
Study No. 584. Perkin-Elmer , 1975.
Headridge, J. B. and D. Risson Smith, "Determination of Trace
Amounts of Antimony in Mild Steels by Solvent Extraction Followed
by Atomic Absorption Spectrophotometry ," Lab. Practice 20 (4),
312 (1971).
Joyner, T. , et al, Env. Sci. and Tech 1, 417 (1967).
Kalb G. Wm. and Charles Baldeck, The Development of the Gold Amal-
gamation Sampling and Analytical Procedure for Investigation of
Mercury in Stack Gases. PB 210 817. Columbus, Ohio, TraDet, Inc.,
1972.
118
-------
REFERENCES
(Cont'd)
KI-085 Kinrade, John D. and Jon C. Van Loon, "Solvent Extraction for Use
with Flame Atomic Absorption Spectrometry," Anal. Chem. 46 (13)
1894-8 (1974).
KI-092 Kim, C. H., C. M. Ownes, and L. E. Smyth, "Determination of Traces
of Mo in Soils and Geological Materials by Solvent Extraction of
the Molybdenum-Thiocyanate Complex and Atomic Absorption," Talanta
21, 445-54 (1974).
LE-068 Levesque, M. and E. D. Vendette, "Selenium Determination in Soil
and Plant Materials," Can. J. Soil Sci. 51, 85-93 (1971).
OG-004 O'Gorman, J. V., N. H. Suhr, and P. L. Walker, Jr., "The Determina-
tion of Mercury in Some American Coals," Applied Spectroscopy 26
(1), 44 (1972). K ^
PE-114 Perkin-Elmer, Analytical Methods for Atomic Absorption Spectro-
photometry. Norwalk, Conn., 1973.
RA-147 Ramakrishna, T. V., J. W. Robinson, and Philip W. West, "Determina-
tion of Phosphorous, Arsenic or Silicon by Atomic Absorption
Spectrometry of Molybdenum Heteropoly Acids." Anal. Chim. Acta
45, 43-49 (1969).
RA-155 Rains, Theodore C. and Oscar Menis, "Determination of Submicrobram
Amounts of Mercury in Standard Reference Materials by Flameless
Atomic Absorption Spectrometry," J. Assoc. Offie. Anal. Chem. 55
(6) 1339-1344 (1972). ~
RU-079 Rubeska, I., M. Miksovsky, and M. Huka, "A Branched Capillary for
Buffering in Flame Spectrometry," Atomic Absorpt. Newsl 14 (1)
28 (1975). ~ ' '
119
-------
TABLE OF CONVERSION FACTORS
Multiply
English Unit
by
Conversion
To Obtain
Metric Unit
acres
acre-feet
barrel, oil
British Thermal Unit
British Thermal Unit/pound
cubic feet/minute
cubic feet/second
cubic feet
cubic feet
cubic inches
degree Fahrenheit
feet
gallon
gallon/minute
horsepower
inches
inches of mercury
pounds
million gallons/day
mile
pound/square inch (gauge)
square feet
square inches
tons (short)
yard
0.
1233.
158.
0.
0.
0.
1.
0.
28.
16.
Q.555(°F-
0,
3,
0
0
2
0
0
3785
1
(0.06805
0
6
0
(a)
405
5
97
252
555
028
7
028
,32
,39
-32)
,3048
.785
.0631
.7457
.54
.03342
.454
.609
psig+1)
.0929
.452
.907
(a)
0.9144
hectares
cubic meters
liters
kilogram-calories
kilogram calories/kilogram
cubic meters/minute
cubic meters/minute
cubic meters
liters
cubic centimeters
degree Centigrade
meters
liters
liters/second
kilowatts
centimeters
atmospheres
kilograms
cubic meters/day
kilometer
atmospheres (absolute)
square meters
square centimeters
metric tons (1000
kilograms)
meters
(a) Actual conversion, not a multiplier.
120
-------
TECHNICAL REPORT DATA
(t 'lease read Instructions on the reverse before completing)
EPA-600/2-78-065b
4. TITLE AND SUBTITLE
TRACE ELEMENT STUDY AT A PRIMARY COPPER SMELTER
Volume II: Report Appendix
Schwitzgebel, K. , R. T. Coleman, R. V. Collins
R. M. Mann, and C. M. Thompson
9. PEKI-UHMING ORGANIZATION NAME AND ADDRESS
Radian Corporation
8500 Shoal Creek Blvd.
Austin, Texas 78766
It. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Laboratory - Cin. , OH
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio k^26Q
3. RECIPIENT'S ACCESSION1 NO.
5. REPORT DATE
'March 1978 issuing date
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
1 AB 60^
11. CONTRACT/GRANT NO.
68-01-4136
13. TYPE OF REPORT AND PERIOD COVERED
Final
4. SPONSORING AGENCY CODE
EPA/600/12
Project Officers: Margaret J. Stasikowski and John 0. Burckle
This project was undertaken to explore the distribution of trace elements in
environmental emissions from a primary copper smelter. The efforts vere
concentrated on the reverberatory furnace and the electrostatic precipitator
controlling emissions from the reverberatory furnace. The following maior
conclusions were reached: (l) the electrostatic precipitator effectively
controls all particulate emissions at its design efficiency rating (about 96%}
at the operating gas temperature of 600 degrees F; (2) appreciable material
composed of toxic trace elements pass through the precipitator in the vapor
state at the ESP operating temperature and condense to form particulate upon
°°0lS' Arsenlc trioxide was a major constituent of the emissions passing
the ESP from the reverberatory furnace. The following elements were examined:
Al, As, Ba, Be, Ca, Cd, Cr, Cu, F, Fe, Hg, Mo, Hi, Pb, Sb, Se, Si, V, Zn
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Exhaust emissions
Smelting
Trace elements
Pollution
13. DISTRIBUTION STATEMENT
Release Unlimited
EPA Form 2220-1 (9-73)
b.lDENTIFIERS/OPEN ENDED TERMS
19. SECURITY CLASS (ThisReport)
Unclassified
!0. SECURITY CLASS (Thispage)
Unclassified
c. COS AT l Field/Group
13B
21. NO. OF PAGES
131
121
22. PRICE
* U.S. GOVERNMENT PRINTING OFFICE: 1978 7 57 -140 /1406
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