«>EPA
United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EMB Report 79-CUS-15
August 1979
Air
Arsenic
Non-Ferrous Smelter
(No. 2 Converter Duct)
Emission Test Report
ASARCO
Tacoma, Washington
-------
EMISSIONS TESTING OF ASARCO COPPER SMELTER
TACOMA, WASHINGTON
TO
ENVIRONMENTAL PROTECTION AGENCY
Contract #68-02-2812
Work Assignment #45
August 22, 1979
D. J. Powell, T. Rooney and D. C. Ringwald
TRW
ENVIRONMENTAL ENGINEERING DIVISION
One Space Park, Redondo Beach, Ca 90278
i
-------
TABLE OF CONTENTS
Page
Introduction 1
Summary and Discussion of Results 2~3
Process Description (EPA) IQ
Location of Sampling Points
Sampling and Analysis Procedures 15
Sampli ng procedures • 15
Sampl e recovery 17
Sample preparation 18
Analysis 18
S02 analysis 18
Appendices
A. Field and laboratory data 20
B. Sample calculations 95
C. Daily activity log • 103
ii
-------
LIST OF FIGURES
Number Page
1 Converter number two off-gas ducting schematic 12
2 Converter off-gas duct sampling location 13
3 Converter off-gas ducting schematic 14
4 Arsenic sulfur dioxide sampling train 1g
n
-------
LIST OF TABLES
Number page
1 Converter Ful 1 Cycl e Resul ts 4
2 Converter Copper Blow Results 5
3 Converter Fugitive Results (east train) c
4 Converter Fugitive Results (middle train) 7
5 Converter Fugitive Results (west train) 8
6 Process Sample Analysis Results 9
IV
-------
INTRODUCTION
A test crew from TRW Environmental Engineering Division performed emission
tests for arsenic and sulfur dioxide at the Asarco copper smelter in Tacoma,
Washington between May 8 and 15th, 1979. These tests were performed on an
individual converter in an attempt to achieve a mass balance for arsenic over
a converter cycle. The test results will be used to support the EPA in esta-
blishing performance standards for the primary copper industry.
The tests were performed in two locations. One location was in the pri-
mary converter off-gas duct. This location was after a settling chamber and
multiclone and before the common plenum where emissions from the four con-
verters mix before going to the sulfuric acid plant. The second location was
directly above the converter, where three sampling trains were positioned to
sample the fugitive emission plume of the converter.
The tests were run over complete converter cycles, with fugitive samples
and off-gas duct samples taken simultaneously. In addition one sample was
taken in the off-gas duct only during the copper blow. Tests were performed
during each of three converter cycles.
This report presents the results of the sampling and analysis effort at
the Asarco copper smelter in Tacoma, Washington. The following sections of
the report contain a summary of the results, descriptions of the sampling
locations, descriptions of the sampling and analysis procedures, and appendices
containing field and laboratory data and example calculations.
-------
SUMMARY & DISCUSSION OF RESULTS
The results of the testing program are summarized in tables
1-6. Data from testing of the converter off-gas during the
full cycle are presented in Table 1. Data of testing done during
the copper blow are presented in Table 2. Data from fugitive
sampling above the converter are presented in Tables 3-5. The
arsenic concentrations of the process samples collected are
summarized in Table 6.
The results of the full cycle testing show a much higher
concentration* of arsenic than those of the Copper blow test.
The average arsenic concentration for the full cycle was 1116.4
mg/m^, 18 times as high as the average arsenic concentration
found during the copper blow (61.7mg/m3). This indicates that
most of the arsenic in the matte is volatilized early in the
converter cycle.
The emissions of sulfur dioxide were more variable than those
of arsenic. The S02 concentration of the off-gas during the
copper blow were two to three times higher than for the full
cycle for the first two tests, but only one fifth as high for
the third test. A large number of scrap anodes were added to
the converter late in the cycle during the third test which
may have acted to dilute S02 emissions during the copper blow.
The mass emission rates for arsenic and sulfur dioxide shown
in Tables 1 through 5 represent emissions during the 8 to 10
hour converter cycle. Since converting is a batch operation
rather than a continuous one, the mass emission rate averaged
over a 24 hour period would be considerably lower than the
rates shown.
Samples were also taken of the converter fugitive emissions.
Three sampling trains were positioned in the fugitive plume
and operated throughout the converter cycle. The concentration
of arsenic in the plume averaged 6 mg/m* at the center of the
plume and 3 mg/m3 eleven feet to each side of the plumes center.
Since the air 1n the converter building was quiescent the
fugitive plume rose vertically up, buoyed by the lower density
of the hot gases leaving the converter. A diffusion model was
applied to the data to estimate the mass emission rate of
Arsenic in the fugitive plume. The model assumes a Gaussian
(Normal) distribution of pollutants across the plume. The extra-
-------
polation back to the emission rate was accomplished by sub-
stituting the measured downwind concentration into the disper-
sion formula used:
=JL JL
TT Us by bz exp - 2 bx2
Where: X = down wind Concentration (gm/m3)
Q = pollutant emission rate (gm/sec)
bz by = Horizontal & vertical plume standard deviation (m)
Os = mean wind speed at height of stack (M/sec.)
h = effective stack heights (m)
x = downwind distance (m)
y = crosswind distance (m)
The effective stack height was assumed to be zero, and the atmospheric
stability was assumed to be high due to the lack of turbulent mixing and
cross drafts. The average mass emission rate for the three tests was
calculated to be 13.95 pounds per converter cycle.
-------
TABLE 1. CONVERTER FULL CYCLL
RUN NUMBER
1 EkTE
1! STACK PARAHETERS
Ps - STACK GAS PRESSURE, "HG ABSOLUTE (mHe) •
Z C02 - VOLUME Z DRY
% 0? - VOLUME \ DRY
1 CO - VOLUME X DRY
I N2 - VOLUME Z DRY
Ts - AVERAGE STACK TEMPERATURE °F (°C)
I H20 - Z MOISTURE IN STACK GAS, BY VOLUME
As - STAC AREA, FT (ir)
No - MOLE ULAR WEIGHT OF STACK GAS, DRY BASIS
Ms - MOLE ULAR WEIGHT OF STACK GAS, WET BASIS
Vs - STAC GAS VELOCITY, FT/SEC, (M/SEC)
Qs - STAC GAS VOLUMETRIC FLOW AT STANDARD CONDITIONS, DSCFM (NM'/MIN)
Z EA - PE CENT EXCESS AIR
III TEST CONDITIONS
PB - BAROMETRIC PRESSURE, "He (MMHG)
DN - SAMPLING NOZZLE DIAMETER, IN. (MM)
T - SAMPLING TIME/ MIN
VM - SAMPLE VOLUME, flCF (M3)
NP - NET SAMPLING POINTS
CP - PITOT TUBE COEFFICIENT
TM - AVERAGE METER TEMPERATURE °F (°C)
PM - AVERAGE ORIFICE PRESSURE DROP, "H^O (MMHoO)
VLC - CONDENSATE COLLECTED (iMPINGERS AND GEL), MLS
AP - STACK VELOCITY HEAD "H20 (MMH20)
IV TEST CALCULATIONS
Vw - CONDENSED WATER VAPOR, SDCF (NM3) ,
VM - VOLUME OF GAS SAMPLED AT STANDARD CONDITIONS, DSCF CfJMJ)
I }\2® - PERCENT MOISTURE, BY VOLUME
Ms - MOLECULAR WEIGHT OF STACK GAS, WET BASIS
Vs - STACK VELOCITY, FT/SEC (M/SEC)
1 I - PERCENT ISOKINETIC
V ANALYTICAL DATA
A) ARSENIC 'fiwir HALF
PROBE to)
CYCLONE (MS)
FILTER (MS)
ARSENIC Ron- KALF TOTAL (ME)
GRS/SDCF, (MVM3)
#/HR, KG/HR)
. B) ARSENIC BACK HALF
(MG) 7
CRs/SnCF, (fcAr)
M*, TKG/HRT
ToTALAesENic (HG)
WS&^flj&P)
fito, (KE/HR;
C) TOTAL SC? (HB)
PPM
(MG/M?)
#/HR, (KG/HR
D) TOTAL WATER DROPLET VomnE COLLECTED (MS)
X WATER DROPLETS
MLS/DSCF
ENGLISH
UNITS
5/8/79
-0.3
29.58
0.2
19.56
1.23
79
658.8
2.3
13.64
29.26
29.00
129.4
105694
48220
29.88
0.250
184
110. 46
24
0.84
83
1.28
2.49
2.54
107.585
2.3
29.00
129.4
47.7
631.79
261.50
3.78
1.56
635.56
263.07
12291
14266.0
S904.8
1
METRIC
UNITS
S/8/79
-7.62
751.33
0.2
19.56
1.23
79
348.25
2.3
0.39
29. Z6
29.00
39.4
2993
1366
758.9
6.35
184
3.13
24
0.84
28
32.5
55.1
63.25
0.07
3.05
2.3
29.00
39.4
47.7
1898.33
2512.50
4410.83
1447.66
118.62
26.367
8.6S
0.79
4437.20
1456.32
119.33
99598.4
12291
32688.8
2678.4
ENGLISH
UNITS
5/10/79
-0.37
29.90
0.2
18.32
2.44
79
666.2
4.4
13.64
29.66
29.14
120.0
97995
43925
30.27
0.125
156
40.57
24
0.84
85
0.199
2.16
1.79
39.777
4.4
29.14
120.0
91.3
487.68
183.88
5.64
2.13
493.32
186.01
24397
28317.7
10677.1
2
METRIC
UNITS
5/10/79
-9.34
759.5
0.2
18.32
2.44
79
352.36
4.4
0.39
29.66
29.14
36.6
2775
1244
768.9
3.18
156
1.15
24
0.84
29
5.06
40
54.86
0.05
1.13
4.4
29.14
36.6
91.3
548.83
710.00
1258.83
1117.47
83.41
14.56
12.92
0.96
1273.39
1130.40
84.37
73095.0
24397
64B87.1
4843.1
ENGLISH
UNITS
5/15/79
-0.3
29.57
0.2
15.99
4.62
79
695.5
10.0
13.64
30.40
29.16
140.4
1 1 4621
46620
29.87
0.125
111
35.18
24
0.84
88
0.275
2.85
3.52
33.856
10.0
29.16
140.4
102.9
325.90
130.42
6.83
2.73
332.72
133.15
46251
53683.3
21482.7
METRIC
UNITS
5/15/79
-7.62
751.08
0.2
15.99
4.62
79
368.6
10.0
0.39
30.40
29.16
42.8
3246
1320
758.7
3.18
111
1.0
24
0.84
31
82
72.39
0.10
0.96
10.0
29.16
42.8
102.9
216.00
500.00
716.00
746.75
59.16
15.00
15.64
1.24
731.00
731 .00
762.39
60.40
1179*3.0
46251
123008.3
9744.5
A\
ENGLISH
UNITS
29.68
0.2
17.96
2.76
79
673.5
5.6
13.64
29.77
29.10
133.1
46255
30.01
0.167
150
62.07
24
0.84
85
0.585
2.5
2.62
60.406
5.6
29.10
133.1
80.6
481 .79
191.93
5.42
2J4
"
487.20
194.08
27647
32089.0
12688.2
/e.
METRIC
UNITS
753.97
0.2
17.96
2.76
79
356.4
5.6
0.39
29.77
29.10
39.6
1310
762.2
4.24
150
1.76
24
C.84
29
14.85
59
(3.50
0.074
1.71
5.6
T9.10
?9.6
fO.6
f 87 . 72
U40.8
2128.55
1U3.96
T7.06
18.64
12.40
1 .00
' 2147.2
1116.37
88.03
96878.8
27647
73528.1
5755. 3
-------
TABLE 2. CONVERTER COPPER BLOW CYCLE
RUN NUMBER
I DATE
11 STACK PARAMETERS
PST - STATIC PRESSURE, "He (MMHG)
Ps - STACK GAS PRESSURE, "He ABSOLUTE (MMHG)
C02 - VOLUME X DRY
0? - VOLUME X DRY
CO - VOLUME X DRY
N2 - VOLUME X DRY
s - AVERAGE STACK TEMPERATURE °F (°C)
H20 - X MOISTURE IN STACK GAS, BY VOLUME
As - STACK AREA, FT (M^)
Mo - MOLECULAR WEIGHT OF STACK GAS, DRY BASIS
Ms - MOLECULAR WEIGHT OF STACK GAS, WET BASIS
Vs - STACK GAS VELOCITY, FT/SEC, (M/SEC)
Os - STACK GAS VOLUMETRIC FLOW AT STANDARD CONDITIONS, DSCFM (NMVMIN)
III TEST CONDITIONS
PB - BAROMETRIC PRESSURE, "He (MMHG)
DN - SAMPLING NOZZLE DIAMETER, IN. (MM)
T - SAMPLING TIME, MIN
VM - SAMPLE VOLUME, ACF (M^)
NP - NET SAMPLING POINTS
CP - PITOT TUBE COEFFICIENT
PM - AVERAGE ORIFICE PRESSURE DROP, "H20 (MnH20)
VLC - CONDENSATE COLLECTED (IMPINGERS AND GEL), MLS
CiP - STACK VELOCITY HEAD "H20 (MMH20)
IV TEST CALCULATIONS
Vw - CONDENSED WATER VAPOR, SDCF (NM3)
VM - VOLUME OF GAS SAMPLED AT STANDARD CONDITIONS, DSCF (NMJ)
X H20 - PERCENT MOISTURE, BY VOLUME
Ms - MOLECULAR WEIGHT OF STACK GAS, WET BASIS
Vs - STACK VELOCITY, FT/SEC CM/SEC)
X I - PERCENT ISOKINETIC
V ANALYTICAL QATA
A) ARSENIC FRONT HALF
PROBE (TO)
CYCLONE (MS)
FILTER (MG)
ARSENIC FRONT HALF TOTAL (ws) '
GRS/SDCF, (MG/M?)
#/HH, KG/NR)
B) ARSENIC PACK HALF
GRs/SDCFj (MG/H^)
wHRy TKG/HR)
TOTAL ARSENIC (fee)
«W^
0 TOTAL SOz (MG)
TPM
(MG/M3)
#/HR, (KG/HR
1
ENGLISH
UNITS
5/8/79
-0.30
29.58
0.2
17.21
3.42
76.82
734
4.5
13.64
29.29
28.79
119.9
97972
40948
29.88
0.125
112
31.14
24
0.84
0.24
1.99
1.39
30.535
4.5
28.79
119.9
104,7
18.34
6.45
4.01
1.41
22.35
7.85
34326
39842.2
14003.8
METRIC
UNITS
-7.62
751.33
0.2
17.21
3.42
76.82
390
4.5
1.27
29.29
28.79
36.56
2775
1160
758.95
3.175
112
0.88
24
0.04
6.10
31.2
50.55
0.040
0.665
4.5
28.79
36.56
104.7
16.99
19.35
36.34
42.02
2.92
7.94
9.18
0.64
44.28
51.20
3.56
78947.5
34326
91291.8
6352.1
2
ENGLISH
UNITS
5/10/79
-0.37
29.90
0.2
15.49
4.9
76.58
654
4.1
13.64
29.62
29.14
108.4
88493
40204
30.27
0.125
135
32.67
24
0.84
0.18
1.78
1.35
32.031
4.1
29.14
108.4
92.8
40.85
14.10
6.94
2.39
47.79
16.49
49177
57079.8
19698.9
METRIC
UNITS
-9.34
759.46
0.2
15.49
4.9
76.58
346
4.1
1.27
29.62
29.14
33.03
2506
1139
768.86
3.175
135
0.93
24
0.84
4.57
30
45.21
0.038
0.907
4.1
29.14
33.03
92.6
43.47
41.45
84.92
93.61
6.39
14.42
15.90
1.09
99.34
109.51
7.48
118645.3
49177
130791.0
8935.3
3
ENGLISH
UNITS
-0.30
29.57
0.2
19.90
0.9
82.91
671
3.9
13.64
30.25
29.76
123.5
1 00852
44718
29. B7
0.125
129
38.69
24
0.84
0.23
2.30
1.52
38.064
3.9
29.76
123.5
103.8
10.85
4.16
0.02
0.009
10.87
4.17
9639
10378.8
3984.0
METRIC
UNITS
-7.62
751.08
0.2
19.90
0.9
82.91
355
3.9
1.27
30.25
29.76
37.64
28S6
1266
758.70
3.175
129
1.10
24
0.84
24
5.84
34.0
58.42
0.043
1.078
3.9
29.76
37.64
103.8
11.30
15.50
26.8
24.86
1.89
0.055
0.05
0.004
26.86
24.92
" 1.89
25636.4
9639
23781.9
1807.1
Ave.
ENGLISH
UNITS
-0.32
29.68
0.2
17.53
3.07
78.77
686
4.2
13.64
29.72
29.23
117.3
95772
41957
30.01
0.125
125
34.17
24
0.84
80
0.22
•2.02
1.42
33.54
4.2
29.23
117.3
100.4
23.35
8.24
3.66
"9:5?
31047
35767
12562.2
METRIC
UNITS
-8. 9
753.Q6
0.2
17.53
3.07
70. 7
36
4.
1. 7
29. 2
29. 3
35. 4
271
1188
762.17
3.175
125
0.97
24
0.84
26
5.50
•1 .7
51.39
0.040
r.95
1.2
?9.23
35.74
1T0.4
23.92
25.43
49.35
53.50
3.73
7.47
8.38
56.83
61.88
4.31
74409.7
31047
B1954.9
5698.2
-------
TABLE 3. CONVERTER FUGITIVE #1(E)
RUN NUMBER
I DATE
1 1 STACK PARAMETERS
PST - STATIC PRESSURE, "He (MMHG)
Ps - STACK GAS PRESSURE, "Ho ABSOLUTE (MMHG)
Z C02 - VOLUME I DRY
Z Oo - VOLUME Z DRY
X CO - VOLUME Z DRY
X f^2 - VOLUME Z DRY
Ts - AVERAGE STACK TEMPERATURE °F (°C)
Z H20 - Z MOISTURE IN STACK GAS, BY VOLUME
As - STACK AREA, FT2 (MZ)
Pto - I*OLECULAR WEIGHT OF STACK GAS, DRY BASIS
!*s - MOLECULAR WEIGHT OF STACK GAS, WET BAS.IS
Vs - STACK GAS VELOCITY, FT/SEC, (M/SCC)
QA - STACK GAS VOLUMETRIC FLOW AT STACK CONDITIONS, ACFP (NV/Mia)
Os - STACK GAS VOLUMETRIC FLOW AT STANDARD CONDITIONS, DSCFM (NMVMIH)
I EA - PERCENT Excess AIR
II! TEST CONDITIONS
PB - BAROMETRIC PRESSURE, "HG (MMHG)
UN - SAMPLING NOZZLE DIAMETER, IN. (MM)
T - SAMPLING TIME, MIN
VM - SAMPLE VOLUME, ACF (M3)
HP - NET SAMPLING POINTS
CP - PITOT TUBE COEFFICIENT
TM - AVERAGE METER TEMPERATURE °F (°C)
PM - AVERAGE ORIFICE PRESSURE DHOP, "(^O (MM^O)
VLC - CONDENSATE COLLECTED (IwPINGERS AND GEL), MLS
AP - STACK VELOCITY HEAD "I^O (Mnf^O)
IV TEST CALCULATIONS
Vw - CONDENSED VATER VAPOR, SDCF (NM3)
VM - VOLUME OF GAS SAMPLED AT STANDARD CONDITIONS, DSCF (NM3)
Z H20 - PERCENT MOISTURE, BY VOLUME
Ms - MOLECULAR WEIGHT OF STACK GAS, WET BASIS
Vs - STACK VELOCITY, FT/SEC (M/SEC)
Z I - PERCENT ISOKINETIC
V ANALYTICAL DATA
A) ARSENIC FRONT HALF
PROBE (MG)
CYCLONE (MG)
FILTER (MG)
ARSFNIC FRONT HALF TOTAL (MG)
PPM, (MG/M^)
ff/HR, (KG/HR)
B) ARSENIC - IMPINGER COLLECTION
I-BPJMEB.J!L_2 (MG)
PPM, (MG/M3)
#/HR, (KG/HR)
lttPiHGERj^..t*,5 (MG)
PPM, MG/M^)
ti/HR, (KG/HR)
C) ARSENIC - IMPINGER TOTAL (HG)
PPM, (MG/M3)
#/HR, (KG/HR)
D) TOTAL ARSENIC (MG)
PPM, (MG/M*)
#/HR, (KG/HR)
E) iDIALjiQj \MG) !
PPM |
(MG/M3)
f/m, (KG/HR)
1
ENGLISH
UNITS
0.00
29.88
0.0
20.98
.02
79.0
104
0.0
314.16
28.85
28.85
4.0
75280.7
70318.9
29.88
.5
508
87.291
1
118.8
Z.5
0.0
629.98
0.00
28.85
4.0
407.1
2.0439
1.6781
.0249
.0205
.
.
.0249
.0205
.
2.0688
1.698E
-
124.229
METRIC
UNITS
0.00
758.95
0.0
20.98
.02
79.0
40
0.0
Z9.21
28.85
28.85
1.22
2132.6
1992.04
758.95
12.70
508
19.47
1
48.2
63.50
0.0
-
0.0
17.85
0.00
28.85
1.22
4071 .
8.382
.
105.375
113.757
6.3742
.7617
1.388
.0778
.0093
.
1.388
.0778
.0093
115.1450
6.4520
.7710
8421 .4
177.12
471.881
56.391
2
ENGLISH
UNITS
0.00
30.27
0.0
20.99
.01
79.0
83
0.0
314.16
28.84
28.84
4.5
84730.4
83353.5
30.27
.5
584
809.040
1
120.5
2.5
0.0
749.00
0.00
28.84
4.5
354.7
.6836
.6653
.0013
.0012
.
.
.0013
.0012
.6849
.6666
47.504
METRIC
UNITS
0.00
768.86
0.0
20.99
.01
79.0
28
0.0
29.21
28.84
28.84
1.38
2400.3
2361.3
768.86
12.70
58.4
22.92
1
49.2
63.50
0.0
0.0
21.22
0.00
28.24
1.38
354.7
9.438
35.800
45.238
2.1320
.3020
.084
.0040
.0006
.084
.0040
.0006
45.3220
2.1360
.3026
32Z9.9
57.14
152.224
21.563
3
ENGLISH
UNITS
0.00
29.87
0.0
20.99
.01
79.0
84
0.0
314.16
28.84
28.84
4.5
84698.7
82070.2
29.87
.5
575
658.126
1
126.9
2.5
0.0
594.73
0.00
28.84
4.5
290.5
.2417
.2316
.002
.0002
.0002
.0002
.2419
.2318
.
54.444
METRIC
UNITS
0.00
758.70
0.0
20.99
.01
79.0
29
0.0
29.21
28.84
28.84
1.38
2399.4
2324.9
758.70
12.70
575
18.64
1
.
52.7
63.50
0.0
0.0
16.85
0.00
28.84
1.38
209.5
.700
.
12.00
12.7000
.7538
.1051
.012
.0007
.0001
.012
.0007
.0001
12.712
.7545
.1052
2985.3
66.510
177.192
24.714
AVERAGE
ENGLISH
UNITS
0.00
30.01
0.0
20.99
.01
79.0
90
0.0
314.16
28.84
28.84
4.33
21569.9
78580.9
30.01
.5
555
718.15
1
_
122.1
2.5
0.0
647.9
0.00
28.84
4.33
209.5
.
.
.9897
.8584
.0088
.0073
.0088
.0073
.9985
.8557
75.392
METRIC
UNITS
0.00
762.17
0.0
20.99
.01
79.0
32
0.0
29.21
28.84
28.84
3.98
2310.7
1226.1
762.12
12.70
555
20.34
1
50.0
63.50
0.0
0.0
18.64
0.00
28.84
3.98
350.7
6.173
51 .058
57.231
3.0867
.3895
.4947
.0275
.0032
.4947
.0275
.0033
57.7263
3.1142
.3929
4878.9
100.257
267.099
34.223
-------
TABLE 4. CONVERTER FUGITIVE #2(M)
RUN NUMBER
I DATE
1 1 STACK PARAMETERS
PST - STATIC PRESSURE, "HG (MMHG)
Ps - STACK GAS PRESSURE, "Ho ABSOLUTE (MMHG)
X C02 - VOLUME X DRV
X Ch - VOLUME X DRY
X CD - VOLUME I DRY
X \\2 - VOLUME X DRY
Ts - AVERAGE STACK TEMPERATURE °F (°C)
1 H20 - 7, MOISTURE IN STACK GAS, BY VOLUME
As - STACK AREA, FT^ (M*-)
MD - MOLECULAR WEIGHT OF STACK GAS, DRY BASIS
fs - MOLECULAR WEIGHT OF STACK GAS, WET BASIS
Vs - STACK GAS VELOCITY, FT/SEC, (M/S:C)
OA - STACK GAS VOLUMETRIC FLOW AT STACK CONDITIONS, ACFM (NM /HIM)
Os - STACK GAS VOLUMETRIC FLOW AT STANDARD CONDITIONS, DSCFM (NM /MIN)
% EA - PERCENT EXCESS AIR
III TEST CONDITIONS
DN - SAMPLING NOZZLE DIAMETER, IN, (MM)
T - SAMPLING TIME, MIN
VM - SAMPLE VOLUME, ACF (M5)
NP - NET SAMPLING POINTS
CP - PITOT TUBE COEFFICIENT
TM - AVERAGE METER TEMPERATURE °F (°C)
PM - AVERAGE ORIFICE PRESSURE DROP, "^0 (MMH20)
VLC - CONDENSATE COLLECTED UMPINGERS AND GEL), MLS
£JP - STACK VELOCITY HEAD "f^O (MMH20)
IV TEST CALCULATIONS
Vw - CONDENSED V'ATER VAPOR, SDCF (NM3)
VM - VOLUME OF GAS SAMPLED AT STANDARD CONDITIONS, DSCF (NM5)
X H20 - PERCENT MOISTURE, BY VOLUME
Ms - MOLECULAR WEIGHT OF STACK GAS, WET BASIS
Vs - STACK VELOCITY, FT/SEC (M/SEC)
X I - PERCENT ISOKINETIC
V ANALYTICAL DATA
A) ARSENIC FRONT HALF
PROBE (MG)
CYCLONE (MG)
FILTER (MG)
ARSENIC FRONT HALF TOTAL (MG)
PPM, (M6/n3)
#/HR, (KG/HR)
B) ARSENIC - IMPINGER COLLECTION
1 MP-1NGER HI, 1 ( MG )
PPM,
-------
TABLE 5. CONVERTER FUGITIVE #3(W)
RUN NUMBER
1 DATE ' •
1 1 STACK PARAI«ETERS
PST - STATIC PRESSURE, "Ho (MMHG)
Ps - STACK GAS PRESSURE, "He ABSOLUTE (MMHG)
J C02 - VOLUME Z DRV
I Oi - VOLUME Z DRV
I CO - VOLUME Z DRV
Z N2 - VOLUME Z DRV
1 HjO - I MOISTURE IN STACK GAS, BY VOLUME
As - STACK AREA, FT^ (M^)
MD - MOLECUUR WEIGHT OF STACK GAS, DRY .BASIS
Ps - MOLECULAR WEIGHT OF STACK GAS, WET BASIS
OA - STACK GAS VOLUMETRIC FLOW AT STACK CONDITIONS, ACFM (NM-VMIN)
Os - STACK GAS VOLUMETRIC FLOW AT STANDARD CONDITIONS, DSCFM (NM'/MIN)
% CA - PERCENT EXCESS AIR
[I! TEST CONDITIONS
PB - BAROMETRIC PRESSURE, "H$ (MMHG)
T - SAMPLING TIME, MIN
VM - SAMPLE VOLUME, ACF
NP - NET SAMPLING POINTS
CP - PITOT TUBE COEFFICIENT
TM - AVERAGE METER TEMPERATURE °F (°C)
PM - AVERAGE ORIFICE PRESSURE DROP, "f^O (MM^O)
VLC - CONDENSATE COLLECTED UMPINGERS AND GEL), MLS
£jp - STACK VELOCITY HEAD "H20 (MMH20)
IV TEST CALCULATIONS
VM - VOLUME OF GAS SAMPLED AT STANDARD CONDITIONS, DSCF (Nn )
1 H20 - PERCENT MOISTURE, BY VOLUME
Vs - STACK VELOCITY, FT/SEC (M/SEC)
V ANALYTICAL DATA
A) ARSENIC FRONT HALF
PROBE (MG)
CYCLONE (MG)
FILTER (MG)
ARSENIC FRONT HALF TOTAL (MG)
PPM, (MG/M3)
fan, (KG/MR)
8) ARSENIC - IMPINGER COLLECTION :
IMPINGER #1. 2 (MG)
PPM, (MG/M^)
#/HR, (KG/HR)
IttpjN.GERj^L.U.,5 (MG)
PPM, MG/M3)
Mm, (KG/HR)
C) ARSENIC - IMPINGER TOTAL (MG)
PPM, (MG/M')
#/HR, (KG/HR)
D) TOTAL ARSENIC (MG)
PPM, (MG/M^)
#/HR, (KG/HR)
E) TOTAL SO^ IMG)
PPM
(MG/M3)
f/HR, (KG/HR)
1
ENGLISH
UNITS
0.0
29.88
0.0
20.99
.01
79.00
0.0
314.16
28.84
28.84
75108.7
70220.5
29.88
5
508
788.068
1
112.33
3.0
-
0 00
731.42
0.0
28.84
1.0
472.7
_
.9739
.7985
.0023
.0019
.0023
.0019
.9762
.8004
_
49.399
METRIC
UNITS
0.0
758.95
0.0
20.99
.01
79.00
0.0
29.21
23.84
28.84
2127.7
1989.3
758.95
12 70
508
22.32
1
44.6
76.20
0.0
0.00
20.72
0.00
28.84
1.22
472.7
7.181
55.750
62.9310
3.0372
.3624
.150
.0072
.0009
.150
.0072
.0009
63.810
3.0444
.3633
3893.4
70.53
187.904
22.424
2
ENGLISH
UNITS
0.0
30.27
0.0
20.99
.01
79.00
0.0
314.16
28.84
28.84
85616.4
83549.2
30.27
.5
584
696300
1
111.4
3.0
.
0.00
655.68
0.00
28.84
4.5
309.8
1 .4972
1 .4606
.0480
.0468
.
.0480
.0468
1.5453
1.5074
-
.
5.386
METRIC
UNITS
0.0
768.86
0.0
20.99
.01
79.00
0.0
29.21
28.84
28.84
2397.1
2366.8
768.86
12 70
584
19.73
1
44.1
76.20
0.0
0 00
18.57
0.00
28.84
1.37
309.8
7.483
79 . 250
86.7330
4.6695
.6630
2.788
.1498
.0213
2.788
.1498
.0213
89.5150
4.8192
.6843
319.8
6.46
17.217
2.445
3
ENGLISH
UNITS
0.0
29,87
0.0
20.98
.02
79
0.0
314.16
28.85
28.85
85407.5
8276.9
29.87
5
575
586.974
1
113
3.0
_
0.00
543.96
0.00
28.85
4.5
263.5
_
.3288
.3177
.0006
.0006
.
.0006
.0006
.3293
.3182
.
129.883
METRIC
UNITS
0.0
758.70
0.0
20.98
.02
79.00
0.0
29.21
28.85
28.85
2419.5
2344.4
758.70
12.70
575
16.63
1
45.0
76.20
0.0
0.00
15.41
0.00
28.85
1.37
263.5
1.300
14.500
15.8000
1.0253
.1442
.028
.0018
.0003
-
.028
.0018
.0003
15.8280
1 .0271
.1445
6459.8
157.35
419.205
58.957
AVERAGE
ENGLISH
UNITS
0.0
30.0!
0.0
20.99
.01
79
0.0
314.16
28.84
28.84
8170.9
78842.2
30.01
.5
555
690.45
1
112.2
3.0
0.00
643.69
0.00
28.84
4.33
848.67
.
.9333
.8589
.0170
.0164
-
-
.0170
.0164
.9503
.8754
,
61.556
METRIC
UNITS
0.0
762.t7
0.0
20.99
.01
79
0.0
29.21
28.84
28.84
2314.7
2233.5
762.17
12.72
555
19.56
I
-
44.6
75.20
0.0
0.00
18.23
0.00
28.84
1.32
348.67
5.3213
49.833
55.1545
2.9107
.3899
.9867
.0529
.6075
-
.9867
.0529
.0075
56.1413
2.9636
.3973
3557.7
78.115
208.109
27.942
-------
TABLE 6. PROCESS SAMPLE ANALYSIS RESULTS
Sample Description Charge No. Date Sampled Date Analyzed Arsenic Concentrat
(*)
Blister Copper #2 anode pies 183 5/14/79 5/22/79 0.40
Copper Slag 0.50
Anode Slag 0.81
Finish Copper Slag 0.96
Converter Flux . 0.68
Converter Slag 0.38
Roaster Charge 4.50
Converter Matte 0.67
Cyclone Dust 2.60
Roaster Calcine 4.21
Balloon Flue Dust 1.62
Crushed Reverts 11.5
Fine Metal from Copper Slag 0.27
Metal from Crushed Reverts 5.62
Converter Slag 185 5/15/79 5/22/79 0.33
Roaster Calcine 1.73
Converter Finish Slag 0.72
Converter Crushed Reverts 7.44
Converter Flux 0.72
Converter Matte 0.29
Cyclone Dust 0.79
Anode Pies 0.25
Balloon Flue Dust 0.51
Roaster Calcine 1.90
Copper Slag 0.37
Roaster Feed 2.85
Roaster Feed 2.73
Aisle Reverts 190 5/16/79 5/22/79 0.51
Roaster Charge 2.34
Roaster Calcine 2.06
Blister Copper 0.24
Girder Grab over #2 . 0.56
Fugitive Metallic Dust 0.043
Fugitive Dust above #2 0.55
Background Contamination Dust 17.9yg
Converter Slag 0.33
Roaster Calcine 3.44
Finish Slag 0.73
Crushed Reverts 7.5
Converter Flux 0.40
Converter Matte 0.51
Finish Slag 0.56
Cyclone Dust 2.00
Roaster Charge 3.33
Anode Slag 1.09
Balloon Flue Dust 0.66
-------
SECTION 3
PROCESS DESCRIPTION
(By EPA)
10
-------
LOCATION OF SAMPLING POINTS
1) Primary converter off-gas duct - The duct carrying emissions from
the converter to the acid plant goes from the converter hooding
to a balloon flue section, to a multiclone, to a common plenum,
and then to the acid plant. The emissions in this duct were
sampled at a point between the multiclone and the plenum. The
duct at this point has an inside diameter of 50 inches. The
sampling location is 21 feet (5 diameters) downstream from the
nearest bend and approximately 40 feet (9.6 diameters) downstream
from the multiclone. The sampling point is 7 feet 9 inches (1.9
diameters) upstream from a damper. Figure 1 is a diagram of this
location.
2) Fugitive emissions from the converter - When the converter is rolled
out to charge, or to pour slag or matte, fugitive emissions rise
in a plume from the converter pour hole. Three sampling trains
were placed above the converter with their nozzles positioned
at the center and at two sides of the plume. The sampling
nozzles were positioned 12 feet apart and 35 feet above the con-
verter pour hole. Fiaure 2 is a diagram of this sampling loca-
tion.
11
-------
Fugitive Emission
Sampling Location
t
Off-gas Duct
Sampling
Location
To Acid
Plant
Common
Manifold
Multiclones
Figure 1. Converter number two off-gas ducting schematic
12
-------
Traverse Point Locations
Traverse
Point
Number
1
2
3
4
5
fi
7
8
9
10
11
1?
Percentage
of
Stack I.D.
2.1
6.7
11.8
17.7
25.0
35.fi
64 4
75.0
82.3
88.2
93.3
97.9
Distance
from
Inside WaV
(in.1)
1.1
3.4
5.9
8.9
12.5
17.8
32 2
37.5
41.2
44.1
46.7
49.0
Figure 2. Converter off-gas duct sampling location
13
-------
.
— To Aci
Comincm Ma
J
Multi clones
00
Balloon Flue
Converter
«3
Figure 3. Converter off-gas ducting schematic
14
-------
SAMPLING AND ANALYSIS PROCEDURES
Sampling Procedures
Arsenic/sulfur dioxide sampling was done in accordance with EPA Method
108, "Reference Method for Determination of Participate and Gaseous Arsenic
Emission from Non-Ferrous Smelters." This method entails isokinetic sampling
of emissions, and collection of arsenic on a glass fiber filter and in dis-
tilled water.
The sampling train consists of a heated probe, heated filter,
and six impingers in series in an ice bath. Figure 4 is a diagram
of the sampling train. The first two impingers each contain
150 milliliters of distilled water. The third, fourth, and fifth
impingers contained 150 ml each of 15% hydrogen peroxide (rather
than 10% in method specification) to collect sulfur dioxide which
was present in large quantities.
Sampling in the primary converter off-gas duct was done at twenty-four
traverse points. Heavy grain loading encountered in the first test made it
necessary to unclog the nozzle once and change filters twice.* In subsequent
tests a smaller nozzle was used to allow a lower sampling rate, and sampling
on for two minutes and off (with the nozzle turned away from the
flow) for three minutes was done to allow a representative sample
of the complete cycle without gaps for filter changes.
During the converter copper blow a second sampling train was operated
simultaneously with the full cycle train. This was accomplished by running
one train in each of the two sampling ports. The copper blow train was
operated for a full five minutes per traverse point. This was made possible
by a much lower particulate loading during the copper blow than during the
slag blow.
When the converter rolled out to recieve charge or to pour slag or matte,
a damper closed off the gas flow through the duct. The converter would remain
rolled out for 15 to 30 minutes. Port changes and filter changes were done
during these periods of no flow. Since the converter roll-out seldom coin-
cided with completion of a traverse, it was sometimes necessary to change ports
before completing the traverse, or to continue sampling at points of average
velocity until roll-out occurred.
In order to sample the fugitive arsenic emissions of the converter, three
sampling trains were placed above the converter. The sampling trains were
positioned so that the nozzles were in the fugitive plume. The nozzles were
twelve feet apart, with the center nozzle in the center of the plume and the
15
-------
2.
3.
4.
5.
6.
7.
12.
13.
Figure 4. Arsenic/Sulfur Dioxide Sampling Train
KEY
Calibrated Nozzle
Heated Probe
Reverse Type Pitot
Cyclone Assembly
Filter Holder
Heated Box
Ice Bath with Impingers
Thermometer
Check Valve
14. Vacuum Line
15. Vacuum Gauge
16. Main Valve
17. Air Tight Pump
18. By-Pass Valve
19. Dry Test Meter
20. Orifice
21. Pi tot Manometer
22. Thermometer
16
-------
other two nozzles positioned at the outer edges of the plume.
The air flow up from the-converter averaged approximately 3.5 feet per
second when the converter was rolled in, and approximately 10 feet per second
when it rolled out. The velocity was too low to be measured accurately with
a conventional pi tot tube so a Gill Propeller Anemometer was used. The ane-
mometer gives an analog direct current output porportional to the wind velocity.
The anemometer was linked to a strip chart recorder so that the air speed could
be recorded continuously during the tests. A velocity traverse of the air
coming up from the converter was done before the test to see how it varied
across the plume. The anemometer was placed on the center probe approximately
6 inches from the nozzle during the tests.
The fugitive sampling trains were started at the beginning of the converter
cycle and ran continuously throughout the cycle. Sampling parameters were
recorded at hourly intervals. The sampling trains were run at their maximum
sampling rate to assure that sufficient arsenic was collected for analysis.
The EPA process engineer observed the magnitude and direction of the plume
during the cycle as well. The plume was primarily vertical although it did
deviate 5 to 10 feet from one side to the other due to drafts coming through
the open doors of the converter building.
Sample Recovery
After completion of each test the probe was removed from the sampling
train and rinsed at the sampling location. The probe and nozzle were rinsed
with 0.1 N NaOH and brushed out with a nylon brush attached to a flexible
polypropylene handle. The probe wash was placed in a glass sample container
with a teflon liner.
The filter holder and impingers were returned to the mobile laboratory
for sample recovery. In the laboratory the filter was removed from the filter
holder and placed in a teflon sample container. The NaOH rinse of the front
half of the filter holder was placed into the orobe wash container.
The contents of the first two impingers (containing
distilled water) were placed in a separate glass container.
The NaOH rinse of these, impingers, connecting glassware, and
the back half of the filter holder were also placed in this
container.
The impinger solutions from impingers three, four, and
five were placed in a nalgene container along with a water
'rinse of the impingers and connecting glassware.
The silica gel from the sixth impinger was weighed to within 0.5 grams to
determine the change of weight. This silica gel was then regenerated in an
oven for reuse.
After recovery of the samples the containers were inventoried, lids were
sealed with tape, and packed for transport to TRW's Redondo Beach laboratory
for analysis.
17
-------
The following procedure was used to analyze the samples for arsenic:
Sample "Preparation
1. Filter - Warm filter and loose parti cul ate matter with 50 ml of 0.1 N
NaOH for 15 minutes. Add 5 ml concentrated HN03 and heat to boiling
for 15 minutes. Filter solution through Whatman No. 41 filter paper
and wash with hot distilled water. Evaporate filtrate, cool, redis-
solve in 25 ml of 0.1N HNOa. Transfer to a 50 ml volumetric flask
and dilute to volume with distilled water.
2. Probe Wash and Impinger Solutions - These should be analyzed separ-
arately using 50 ml of sample. Add 1 ml of concentrated HN03 and
evaporate to a few milliliters. Redissolve with 25 ml of 0.1N HN03
and dilute to 50 ml 1n a volumetric flask. A reagent blank should be
carried through this procedure. The resulting blank solution is used
in the dilution of standards to matrix match samples and standards.
Analysis
1. All samples prepared above are screened by N20/acetylene flame. The
filter samples may require dilution with 0.1N HN03. Impinger solu-
tions containing more than 26 mg/1 arsenic are diluted because the
linearity of atomic absorption decreases dramatically above this
level. Due to the high concentrations of copper in the filtered
particulates a ^/acetylene flame is used to dissociate any AsCu
compounds stable in the cooler hydrogen flame.
2. For sample solutions below 1 mg/1 arsenic the graphite furnace
atomizer is used. The sample solution is diluted 1:1 with 200 ppm
Ni solution. The excess nickel forms a stable nickel arsenide when
heated to 750-1 000°C in the ash cycle of the graphite atomizer.
Atomization occurs at approximately 2200°C. The detection limit
using the graphite atomizer is 200 picograms in samples with low
background interference. The detection limit increases rapidly with
increasing background signal. Deuterium arc background correction is
essential for all determinations in both the flame and graphite
furnace atomizer.
SOo Analysis
A 10 ml aliquot of the solutions from impingers three,
four and five was pipetted into a one liter volumetric
flask and brought to volume with distilled water. One
hundred ml of this solution was then placed in a 250 ml
erlenmyer flask. One ml of isopropanol and 2 to 4 drops
of thorin indicator were then added to this aliquot, and
the solution was titrated to a pink endpoint with 0.0100
N barium perchlorate. The titration was repeated with
a second aliquot of the sample. A blank was prepared from
100 ml of 80% isopropanol with 2-4 drops of thorin in-
18
-------
dicator added. The blank was titrated with 0.0100 N
barium perchlorate and the amount used was subtracted
from the amount of titrant used for the sample.
During the Data Reduction, the meter volume was back
calculated to account for sulfur dioxide that was removed by
the three 15% hydrogen peroxide impingers. The back calcula-
tion for sulfur dioxide was accomplished in the following
order. First, parts per million sulfur dioxide at standard
conditions was calculated. Then parts per million was con-
verted 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
peroxi.de 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.
19
------- |