United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EMB Report 78-CUS-10
March 1979
Air
Arsenic
Non-Ferrous Smelters
Emission Test Report
Phelps-Dodge Copper
Smelter
Playas, New Mexico
-------
EMISSION TESTING OF PHELPS-DODGE COPPER SMELTER
PLAYAS, NEW MEXICO
TO
ENVIRONMENTAL PROTECTION AGENCY
Contract #68-02-2812
Work Assignment #15
April 20, 1979
By
Thomas Rooney
TRW
ENVIRONMENTAL ENGINEERING DIVISION
One Space Park, Redondo Beach, CA 90278
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CONTENTS
Figures iii
Tables iii
1. Introduction 1
2. Summary and Discussion of Results 2
3. Process Description 6
4. Location of Sampling Points 7
5. Sampling and Analytical Procedure 9
6. Appendices
A. Field and Laboratory Data 14
1. Traverse Point Location 14
2. Field Data Sheets 16
3. Analytical Data Sheets 23
4. Particle Sizing Analysis 27
5. Meter Box Calibration Data Sheets 34
B. Sample Calculations 36
C. Daily Activity Log 44
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FIGURES
Number Page
1 Converter fugitive emission duct schematic 3
2 Arsenic/sulfur dioxide sampling train 10
3 Brinks impactor sampling schematic 13
TABLES
Number Page
1 Converter Fugitive Emission -
Arsenic/Sulfur Dioxide Results 3
2 Particle Sizing Summary 4
3 Process Sample Analysis 5
TM
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SECTION 1
INTRODUCTION
In conjunction with the Environmental Protection Agency's Program for
developing new source performance standards, TRW performed fugitive emission
tests at the Phelps-Dodge Cooper Smelter located in Playas, New Mexico.
The test was conducted July 24-27, 1978.
The process tested was secondary converter hooding system which removed
fugitive emissions from the converter during the slag and copper blow cycles.
The testing consisted of three arsenic/sulfur dioxide tests and three
particle sizing tests which were performed during the copper and slag blow
cycles. The testing location was a seven foot duct located between the hooding
system and the stack. These tests were coordinated with a process engineer
from the Environmental Protection Agency.
This report presents the results of the testing program. The following
sections of the report contain a summary of the results, description of
sampling points, description of the process, and the sampling procedure with
the laboratory procedure. The appendices contain field data, laboratory
data, sample calculations, and the daily activity log.
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SECTION 2
SUMMARY AND DISCUSSION OF RESULTS
The results of converter hooding fugitive emission system tests are
summarized in Table 1 and Table 2. Table 1 consists of Field, Laboratory
and Emission Data. Table 2 contains particle sizing data from the three
tests.
During the testing program the following observations and problems
were noted.
For the first test, twenty-five minutes per sampling point was used to
assure that sampling was done through a complete production cycle. For
the second and the third test, twenty minutes per sampling point and a
smaller nozzle size was utilized. After 155 minutes of the third test,
TRW personnel noticed that the AP readings were abnormally low. After
checking equipment, the process engineer discovered that the plant opera-
tors inadvertently left the dampers on the system in the open position. When
the problem was corrected,the AP reading increased to the appropriate reading.
Thus, during 80 minutes of the sampling period of the third test, dilution
air entered the duct which resulted in a non-representative sample.
During the Data Reduction, the meter volume was back calculated to
account for sulfur dioxide that was removed by the three 10% hydrogen peroxide
impingers. The back calculation for sulfur dioxide was accom-
plished in the following order. First, parts per million sulfur dioxide
at standard conditions was calculated. Then parts per million was converted
to a fraction by dividing by 10^. This number was added to one and the
result multiplied by the volume of gas collected through the dry gas
meter at standard conditions. The result of multiplication yielded the true
gas volume collected at standard conditions. Since S02 removal by the peroxide
impingers does not reach the dry gas meter, corrected values for dry gas meter
volumes (at meter conditions) found on the summary sheets will be slightly
higher than those obtained from the field data sheets.
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TABLE 1 CONVERTER FUGITIVE EMISSIONS ARSENIC/S02 RESULTS
RUN NUMBER
! DATE
II STACK PARAMETERS
PST - STATIC PRESSURE, "Ho (MMHG)
Ps - STACK GAS PRESSURE, "He ABSOLUTE (MMHG)
I C02 - VOLUME J DRV
I (>2 - VOLUME !! DRY
SOj - VOLUME 1 DRY
J N2 - VOLUME X DRV
1 H20 - X MOISTURE IN STACK GAS, BY VOLUME
As - STACK AREA, FT (M*)
Mo - MOLECULAR WEIGHT OF STACK GAS, DRY BASIS
Ps - MOLECULAR HEIGHT OF STACK GAS, WET BASIS
Vs - STACK GAS VELOCITY, FT/SEC, (M/S;C)
QA - STACK GAS VOLUMETRIC FLOW AT STACK CONDITIONS, ACFI" (NM /MIN)
Qs - STACK GAS VOLUMETRIC FLOW AT STANDARD CONDITIONS, DSCFM (NM /MIN)
I EA - PERCENT EXCESS AIR
III TEST CONDITIONS
PB - BAROMETRIC PRESSURE, "He (MMHG)
DN - SAMPLING NOZZLE DIAMETER, IN. (MM)
T - SAMPLING TIME, MIN
VN - SAMPLE VOLUME, ACF (M3>
CP - PITOT TUBE COEFFICIENT
TM - AVERAGE METER TEMPERATURE °F (°C)
PM - AVERAGE ORIFICE PRESSURE DROP, "h^O (MMHnO)
VLC - CONDENSATE COLLECTED (IMPINGERS AND GEL), MLS
&p - STACK VELOCITY HEAD "I^O (MMH20)
IV TEST CALCULATIONS
V» - CONDENSED VATER VAPOR, SDCF (NM3)
VM - VOLUME OF GAS SAMPLED AT STANDARD CONDITIONS, DSCF (NM5)
? H20 " PERCENT MOISTURE, BY VOLUME
Ms - MOLECULAR WEIGHT OF STACK GAS, WET BASIS
Vs - STACK VELOCITY, FT/SEC (M/SEC)
I I - PERCENT ISOKINETIC
V ANALYTICAL DATA
A) ARSENIC FRONT HALF
PROBE (MG)
CYCLONE (MG)
FILTER (MG)
ARSENIC FRONT HALF TOTAL (MG)
PF-M, («G/M3)
''MR, (KG/HR)
B) ARSENIC - IMPINGER COLLECTION
IMPINGER #1. 2 (MG)
PPM, (MG/M3)
»/HR, (KG/HR)
IflEittsEBj!i,S,5 (MG)
PPM, MG/M3)
»/HR, (KG/HR)
C) ARSENIC - IMPINGER TOTAL (MG)
PPM, (MG/M3)
#/HR, (KG/HR)
D) TOTAL ARSENIC (MG)
PPM, (MG/M^)
#/HR, (KG/HR)
E) TOTAI SOo IMGJ
PPM
(MG/M3)
#/HR, (KG/HR)
1
ENGLISH
UNITS
7/25/78
- .24
25.60
.2
20.2
.38
79.22
216.7
1.5
35.34
28.97
28.95
49.29
104514.5
69076.1
4.7
25.84
.250
300.
221.95
12
.84
137.9
1.59
.516
2.65
169.97
1.5
28.95
49.29
85.3
-
.1272
.1026
.2832
.1921
.2832
.1921
-
.3654
.2947
-
2649.4671
METRIC
UNITS
7/25/78
-6.10
650.24
.2
20.2
.38
79.22
102.6
1.5
3.28
28.97
28.95
15.02
2960.8
1956.8
4.7
656.34
6.35
300.
6.29
.84
58.8
<0.39
13.11
.08
4.82
1.5
28.95
15.02
85.3
.71
•
1.20
1 .91
.3967
.0466
3.577
.7429
.0872
-
3.577
.7429
.0872
5.4870
1.1396
.1338
49329.6
3845.4857
10244.954
1202.6632
2
ENGLISH
UNITS
7/26/78
- .24
25.55
.2
20.2
.48
79.12
207.5
2.2
35.34
29.01
28.77
59.49
126163.4
83315.9
4.7
25.79
.185
240.
131.19
.84
104.4
.78
.756
2.43
105.98
2.2
28.83
59.44
98.6
-
.0737
.0718
.0062
.0060
.0062
.0060
.0799
.0778
•
-
4012.9187
METRIC
UNITS
7/26/78
-6.10
648.97
.2
20.2
.48
79.12
97.5
2.2
3.28
29.01
28.77
18.14
3574.0
2361 .1
4.7
655.07
4.70
240.
3.72
.84
40.2
19.81
51 .7
19.20
.07
3.00
2.2
28.83
18.12
98.6
.09
-
.60
.69
.2298
.0326
.058
.0193
.0027
.
.058
.0193
.0027
.7480
.2491
.0353
38570.4
4822.2099
12847.0950
1821.5700
3
ENGLISH
UNITS
7/26/78
- .24
25.55
.2
20.2
1.10
78.50
216.1
2.2
35.34
29.23
28.98
40.54
85957.9
56063.1
4.7
25.79
.185
240.
90.36
.84
114.0
.38
.349
1.63
71.69
2.2
29.05
40.49
99.1
-
.1231
.0807
.0242
.0158
_
-
.0242
.0158
-
.1473
.0965
-
-
6206.6644
METRIC
UNITS
7/26/78
-6.10
648.97
.2
20.2
1.10
78.50
102.3
2.2
3.28
29.23
28.98
12.36
2435.1
1588.2
4.7
655.07
4.70
240.
2.56
12.
.84
45.6
9.65
8.86
.05
2.03
2.2
29.05
12.34
99.1
03
-
.75
.78
.3841
.0366
.153
.0753
.0072
_
.153
.0753
.0072
.9330
.4594
.0438
60003.6
11090.078
29545.642
2817.3692
AVERAGE
ENGLISH
UNITS
7/26/78
- .24
25.57
.2
20.2
.65
78.95
213.4
2.0
35.34
29.07
28.90
49.77
105545.3
69495.0
4.7
25.81
.207
260.
147.83
12.
.84
118-8
.92
36.7
.540
2.24
115.88
2.0
28.94
29.74
94.3
-
.1080
.0650
.BB95
.0713
_
-
.
.0895
.0713
.1975
.1563
-
.
4289.6334
METRIC
UNITS
7/26/78
-6.10
649.39
.2
20.2
.65
78.95
100.8
2.0
3.28
29.07
28.90
15.17
2989.95
1968.7
4.7
655.49
5.25
260.
4.19
12.
.84
48.2
23.28
33.5
13.72
.07
3.28
2.0
28.94
15.16
94.3
.28
"
.85
1.1267
.3369
.0386
1 2627
.2792
.0324
_
.
1.2627
.2792
.0324
2.3894
.6160
.0710
49301.2
6585.9245
17545.897
1947.2008
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TABLE 2. PARTICLE SIZING SUMMARY
(LOCATION-PHELPS DODGE-PLAYAS, N. MEXICO)
LOCATION
CONVERTER
CONVERTER
CONVERTER
TEST
ONE
TWO
THREE
PARTICLE SIZE DISTRIBUTION %
>5p
24.0
19.0
38.0
3-5y
8.0
13.0
6.0
l-3y
19.0
32.0
14.0
< in
49.0
36.0
42.0
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TABLE 3.
PROCESS SAMPLE ANALYSIS
SAMPLE
DATE SAMPLED
AS
Flash Furnace Feed 7/26/78 - 7/27/78 .0132%
Flash Furnace Slag 7/26/78 - 7/27/78 .0032%
Flash Furnace Matte 7/26/78 - 7/27/78 .0051%
Electric Furnace Matte 7/26/78 - 7/27/78 .0088%
Electric Furnace Slag 7/27/78 - 7/27/78 .0120%
Converter Slag 7/27/78 - 7/28/78 .0072%
Converter Blister 7/27/78 - 7/28/78 .0139%
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SECTION 3
PROCESS DESCRIPTION
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SECTION 4
LOCATION OF SAMPLING POINT
Outlet from Converter Hooding System
Samples from converter hooding system were taken from a seven foot
diameter horizontal duct located approximately 70 feet above the ground.
The sampling ports on the top and side of the duct allowed for vertical
and horizontal traverses during sampling. The nearest upstream flow
disturbance was 7 duct diameters from the sampling location. The nearest
downstream flow disturbance was greater than ten duct diameters from
the sampling location, where there was a 90° bend. Twelve traverse points,
six on each traverse, were used. Sampling was done for twenty minutes per
point to provide sampling through a complete slag and copper blow cycle.
Figure 1 illustrates the cross-sectional view.
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Traverse point locations
Tra-
verse
Point
Loca-
tions
1
2 '
3
4
5
6
Fraction of
Stack I.D.
.044
.146
.296
.704
.854
.956
Distance
From Inside.
Wall (in)
3.66
12.30
24.85
59.15
71.70
80.34
Stack
From
converter
hoods
Figure 1. Converter fugitive emission duct
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SECTION 5
SAMPLING AND ANALYTICAL PROCEDURE
A. Arsenic/Sulfur Dioxide Sampling
The sampling train used for arsenic/sulfur dioxide collection consists
of an EPA method 5 train modified by adding two additional impingers in series
to the four used in the method 5 train. The first two impingers contained
150 milliliters of distilled water each, the third impinger was empty, the
fourth,fifth and sixth impingers contained 150 milliliters of 10% hydrogen
peroxide each. The seventh impinger contained 250 grams of silica gel.
Sampling train schematic is presented in figure 2.
Before each test a velocity traverse of the stack was done to determine
the average stack temperature and velocity pressure. The velocity traverse
was done according to EPA Methods 1 and 2. A grab sample of the stack gas
was taken and analyzed with a Fryite apparatus for C02. Before the first
test at each location the moisture content of the gas stream was estimated
by either condensation in impingers as in EPA Method 4, or by wet and dry
bulb thermometer if the stack gas temperature was below 1200F.
The arsenic/sulfur dioxide samples were taken at traverse points at
the center of equal areas within the stack. The number of traverse points
was determined by the number of duct diameters upstream and downstream from
the nearest flow disturbances. The sampling rate was adjusted to isokinetic
conditions using a nomograph which had been set based on the preliminary
velocity traverse data, and moisture estimate.
The sampling time per traverse point was 20-25 minutes, to assure
sampling during the whole process cycle.
Leak checks of the sampling train were done at the beginning of each
test, just before the sampling port change, and at the end of the test.
At the end of each test the sampling train was inspected for cracked or
broken glassware, and to assure that the filter remained intact.
Sample Recovery
The sampling nozzle and probe liner were rinsed with 0.1N NaOH and
brushed out with a nylon bristle brush with a teflon tubing handle. The
remainder of the sampling train was removed to the mobile laboratory. The
front half of the filter and connecting glassware were rinsed with 0.1N
NaOH and this rinse was added to the nozzle and probe rinse. The filter was
removed from the filter holder and placed in a polyethylene container, which
was labeled and sealed. The first three impinger solutions were measured and
placed in a glass sample container along with a 0.1N NaOH rinse of the im-
pingers. The contents of the fourth, fifth, and sixith impingers were measured
and placedin a separate glass sample container along with a distilled
water rinse of the impingers. The silica gel in the seventh impinger was
weighed to the nearest 0.5 grams, and regenerated.
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12
13
17
Figure 2. Arsenic sulfur dioxide train
1. Calibrated Nozzle
2. Heated Probe
3. Type S Pitot
4. Cyclone Assembly
5. Filter Holder
6. Heated Box
1. Ice Bath with Impingers
a. 150 mis H20
b 150 mis H20
KEY
c. Empty
d. 150 mis H202
e. 150 mis H202
f. 150 mis H202
g. 250 gms. Si lea Gel
12. Thermometer
13. Check Valve
14. Vacuum Line
15. Vacuum Gauge
16.
17.
18.
19.
20.
21.
22.
Main Valve
Air Tight Pump
By-Pass Valve
Dry Test Meter
Orifice
Pitot Manometer
Thermometer
10
-------
B. Analysis
The samples were analyzed for sulfur dioxide by taking an aliquot of
the hydrogen peroxide impinger solutions and titrating with barium perchlorate
solution and thorin indicator as described in EPA Method 6 (Determination of
Sulfur Dioxide Emissions from Stationary Sources).
Arsenic-Analysis
1. Filter - warm filter and loose particulate matter with 50 ml
0.1N NaOH for about 15 minutes. Add 10 ml concentrated HMOs and bring to
boil for 15 minutes. Filter solution through no. 41 Whatman paper and
wash with hot water. Evaporate filtrate, cool, redissolve in 5 ml of 1:1
HN03, transfer to a 50 ml volumetric flask and dilute.
2. Probe Wash and Impinger Solns - These should be combined and a
200 ml sample withdrawn. Add 10 ml concentrated HN03 and evaporate to a
few milliliters. Redissolve with 5 ml 1:1 HN03 and dilute to 50 mis. A
reagent blank should be carried through the same procedure. The resulting
blank solution should be used in the dilution of standards to matrix match
samples and standards.
3. All the samples prepared above should be screened by air/acetylene
flame. The filter samples may require dilution with 0.8N HNOv Impinger
solutions containing more than 25 mg/1 of arsenic should be diluted since
linearity decreases dramatically above that level.
Since an entrained hydrogen flame provides about five times as much
sensitivity as the air/acetylene flame, a matrix check of a sample in a
hydrogen flame should be carried out by the method of standard additions,
and compared with a value obtained from matrix matched standards in a
hydrogen flame. If values are comparable (+5%) the air entrained hydrogen
flame value should be used.
Due to high concentrations of copper on the filter an air/acetylene
flame should always be used to dissociate any AsCu compounds stable in
the cooler hydrogen flame.
4. For samples below the lmg/1 level, hydride generation is necessary.
An appropriate aliquot of digested sample in 0.8N HN03 containing less then
about lOug of arsenic is chosen (some screening may be necessary). Five mini-
liters of concentrated H2S04 is added to the sample which is then placed on a
hot plate until S03 fumes fill the flask. A reduction in volume to about 5 ml
or less may be necessary. This step removes HN03 which causes a violent
11
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reaction when the reducing agent is added resulting in poor reproducibility
and lowered senitivity by producing 12, N02 and possibly other species.
One millilHer of 30% KI and 1 ml of 30% SnCl2 are added to the sample,
the former to act as catalyst in hydride formation and the latter to reduce
all the arsenic to As+3. The sample is then diluted to about 15 ml, and 15 ml
of concentrated HC1 is added. Powdered Zn (or NABH4) is then added, the
reaction vessel is immediately closed and the nitrogen or argon carrier
flow initiated. A peak should be produced within a few seconds.
C. Particle Sizing
The size distribution of the particulates was estimated with a
Brinks six stage impactor. Figure 3 is a diagram of the Brinks impactor
sampling system used.
Sampling Procedure
The Brinks impactor was introduced into the gas stream through the
sampling port with the nozzle facing the flow of gas. The sampling pump
was turned on and the pressure drop across the impactor adjusted with the
by-pass valve. The pressure drop across the impactor was read from the
mercury manometer. The pressure drop is proportional to the flowrate
through the impactor, and to the particle sizing cutoffs of each stage.
Sampling time at each location varied according to grain loading in
the particular duct being sampled. The impactor plates were inspected after
each test and the sampling time altered on the succeeding test to optimize
the amount of particulate sampled. Sampling for too long results in carry-
over from one stage to the next, while sampling for too short a time can
result in insufficient particulate on one or more of the stages for accurate
analysis.
Analysis
The impactor plates and filters had been dessicated to a constant weight
before the tests, and tare weights taken. After the test the same procedure
was used to get the final weights of the impactor plates and filters. The
difference between the tare weight and final weight is the weight of parti-
culate collected.
The cummulative percentage of the total particulate catch which was
collected in each stage was plotted on semi-log graph paper against the
size cutoffs for each stage. The resulting best fit straight line is the
estimated particle size distribution of the collected particulatesJ
1 Brink, J.A. "Cascade Impactor for Adiabatic Measurements," Industrial
and Engineering Chemistry, Vol.-5, No. 4, April 1958, page 647
12
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BRINKS IMPACTOR
47 MM GLASS FIBER FILTER
SHUT OFF
VALVE
•BY PASS VALVE
MERCURY
MANOMETER
PUMP
DRY GAS
METER
ORIFICE
MANOMETER
Figure 3. Brinks impactor particle sizing system schematic
13
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