xvEPA
United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EMB Report 78-CUS-11
March 1979
Air
Arsenic
Non-Ferrous Smelters
Emission Test Report
(Acid Plant)
Phelps-Dodge Copper
Smelter
Ajo, Arizona
-------
EMISSION TESTING OF PHELPS-DODGE COPPER SMELTER
AJO, ARIZONA
TO
ENVIRONMENTAL PROTECTION AGENCY
Contract 68-02-2812
Work Assignment #15
January 12, 1978
By
Thomas Rooney
TRW
ENVIRONMENTAL ENGINEERING DIVISION
One Space Park, Redondo Beach, CA 90278
-------
CONTENTS
Pase_
Figures ii
Tables 11
1. Introduction 1
2. Summary and Discussion of Results 2
3. Process Description 8
4. Location of Sampling Points 9
5. Sampling and Analytical Procedure 14 '
Appendices
A. Field and Laboratory Data 18
1. Traverse Point Location 18
2. Field Data Sheets 22
3. Analytical Data Sheets. 45
4. Meter Box Calibration 57
B. Sample Calculations 64
C. Daily Activity Log 71
-------
FIGURES
Number Page
1 ESP inlet sampling locations. . . . 10
2 Acid plant outlet location H
3 ESP outlet/acid plant inlet sampling location 12
4 Acid plant schematic 13
5 Arsenic/sulfur dioxide sampling train 15
TABLES
Number Page
1 ESP Inlet #1 Arsenic/Sulfur Dioxide Results 3
2 ESP Inlet #2 Arsenic/Sulfur Dioxide Results 4
3 ESP Outlet/Acid Plant Inlet Arsenic/Sulfur Dioxide Results. ... 5
4 Acid Plant Outlet Arsenic/Sulfur Dioxide Results 6
5 Process Sample Analytical Results 7
11
-------
SECTION 1
INTRODUCTION
In conjunction with the Environmental Protection Agency's program for
implementing new source performance standards, TRW personnel conducted a
testing program at the PhelpsrDodqe copper smelter, located in Ajo, Arizona.
Testing was performed June 12 through June 16, 1978.
Due to large amounts of sulfur dioxide emitted during the smelting
operation, a sulfuric acid plant is attached to the copper smelter to
control emissions by converting sulfur dioxide to sulfuric acid. The hot
gases from the smelting operation pass through a single contact sulfuric
acid plant and then the gases exit through a commom stack.
The testing program required four locations to be tested simultaneously
at the acid plant. These locations were the following: two at the ESP
inlet, one at the ESP outlet/acid plant inlet and one at the acid plant
outlet. TRW personnel performed three arsenic sulfur dioxide tests at each
location.
This report presents the results of the testing program. The following
sections of the report contain: summary of results, description of samp-
ling points, description of Process, and sampling and analytical procedure.
The appendices contain: field data, laboratory data, summary calculations
and daily activity log.
-------
SECTION 2
SUMMARY AND DISCUSSION OF RESULTS
The results of the testing program are summarized in Tables 1-5. The
ESP inlet test results are presented in Tables 1 and 2. The ESP outlet test
results are summarized in Table 3 while the acid plant outlet test results
are in Table 4. The results include the following information: stack para-
meters, test conditions, analytical data, and emission data. The process
sample analysis data are listed in Table 5.
Due to high ambient temperature (116°F) and high sulfur dioxide concen-
tration at the testing locations, sampling was performed under adverse con-
ditions.
Test no. 2 at the north acid plant inlet was aborted because TRM
personnel inadvertently pointed the nozzle downstream. Because of the
ensuing mechanical problems at the plant, the TRW crew could not repeat
test no. 2, the reason being that the plant was going down on Friday to
repair a 1 quart per minute leak from the acid plant condensate tower.
During the third day, the TRW personnel noted significantly higher
amounts of sulfur dioxide being emitted around the seals in the ducting
that enters the acid plant.
The results indicated that approximately 4.2% sulfur dioxide enters the
ESP while the average concentration of sulfur dioxide at the ESP outlet is
2.7%. The acid plant outlet shows an average of 0.14% sulfur dioxide. The
arsenic concentration indicated 0.0133 Ibs. of arsenic per hour entering the
ESP while the ESP outlet indicates and average of 0.0090 Ibs. of arsenic per
hour. The acid plant outlet shows an average of 0.0022 Ibs. of arsenic per
hour.
During the data reduction, the meter volume was back calculated to
account for sulfur dioxide that was removed by the impingers containing 10%
hydrogen peroxide. The back calculation 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 converted to a frac-
tion by dividing by 10°. This number was added to one and the result multi-
plied by the volume of gas collected through the dry gas meter at standard
conditions. The resutt of multiplication yielded the actual gas volume
collected at standard conditions.
-------
TABLE 1
ESP Inlet #1 Arsenic/Sulfur Dioxide Results
RUN NUMBER
1 DATE
11 STACK PARAMETERS
PST - STATIC PRESSURE, "He (MMHG)
Ps - STACK GAS PRESSURE, "He ABSOLUTE (MMHG)
I C02 - VOLUME Z DRY
I 02 - VOLUME Z DRY
£ SCb - Vtu*E S Dm
t Nj"- VOLUME Z DRY
Is - AVERAGE STACK TEMPERATURE °F (°C)
Z ^0 - Z MOISTURE IN STACK GAS, BY VOLUME
As - STACK AREA, FT2 (n2}
MD - MOLECULAR WEIGHT OF STACK GAS, DRY BASIS
fs - MOLECULAR WEIGHT OF STACK GAS, WET BASIS
Vs - STACK GAS VELOCITY, FT/SEC, (H/S:C)
OA - STACK GAS VOLUMETRIC FLO* AT STACK CONDITIONS, ACFP (NM'/MIH)
Os - STACK GAS VOLUMETRIC FLOW AT STANDARD CONDITIONS, DSCFP (NM*/MIN)
Z EA - PERCENT EXCESS AIR
III TEST CONDITIONS
PB - BAROMETRIC PRESSURE, "He (HF*G)
DM - SAMPLING NOZZLE DIAMETER, IN, (MM)
T - SAMPLING TIME, MIN
VM - SAMPLE VOLUME, ACF (M*>
NP - NET SAMPLING POINTS
CP - PHOT TUBE COEFFICIENT
TM - AVERAGE MITER TEMPERATURE °F (°C)
PM - AVERAGE ORIFICE PRESSURE DROP, "I^O (wfljO)
VLC - CONDENSATE COLLECTED UMPINGEHS AND GEL), MLS
&p - STACK VELOCITY HEAD "H^O (MMH20)
IV TEST CALCULATIONS
Vw - CONDENSED VATER VAPOR, SDCP _(NM5>
VM ' VOLUME OF GAS SAMPLED AT STANDARD CONDITIONS, DSCF (Nn'l
I H^O - PERCENT MOISTURE, BY VOLUME
Ms * MOLECULAR WEIGHT OF STACK GAS, WET BASIS
Z I - PERCENT ISOKINETIC
V ANALYTICAL DATA
A) ARSENIC FRONT HALF
PROBE (NO)
CYCLONE (MG)
FILTER (MG)
ARSENIC FRONT HALF TOTAL (MG)
rfn, (MG/H')
I/HR, (KG/HR)
B) ARSENIC - IMPIKGER COLLECTION
iMPINGEft fl. 1
*/HH, (KG/HR)
PPM, MG/N!)
*/HR, (KG/MB)
C) ARSENIC - INPINGER TOTAL
-------
TABLE 2
ESP Inlet #2 Arsenic/Sulfur Dioxide Results
RUN NUMBER
1 DATE
II STACK PARArtTERS
PST - STATIC PRESSURE, "He (MMHG)
Ps - STACK GAS PRESSURE, "He ABSOLUTE (MMHG)
X CO? - VOLUME X DRV
X 07 - VOLUME X DRY
X S% - touje Z Ttw
X »2 - VOLUME X DRV
Ts - AVERAGE STACK TEMPERATURE °F (°C)
I H20 - I MOISTURE IN STACK GAS, BY VOLUME
As - STACK AREA, FT (M*>
MD - MOLECULAR HEIGHT OF STACK GAS, DRY BASIS
K.s - MOLECULAR HEIGHT OF STACK GAS, HET BASIS
Vs - STACK GAS VELOCITY, FT/SEC, (M/S:C)
QA - STACK GAS VOLUMETRIC FLOW AT STACK CONDITIONS, ACFC (NM'/MIN)
Os - STACK GAS VOLUMETRIC FLOW AT STANDARD CONDITIONS, DSCFM (NM'/MIN)
X EA - PERCENT EXCESS AIR
III TEST CONDITIONS
PB - BAROMETRIC PRESSURE, "He (MMHG)
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, "HjO (MMHjO)
VLC - CONDENSATE COLLECTED (1MPINGERS AND GEL/, MLS
£p^- STACK VELOCITY HEAD "H^ (mH20)
IV TEST CALCULATIONS
VM - CONDENSED PATER VAPOR, SDCF (N*5)
VM - VOLUME OF GAS SAMPLED AT STANDARD CONDITIONS, DSCF (Nn5)
X H20 - PERCENT MOISTURE, BY VOLUME
Ms - MOLECULAR HEIGHT OF STACK GAS, HET BASIS
Vs - STACK VELOCITY, FT/SEC (M/SEC)
X 1 - PERCENT ISOKIHETIC
V ANALYTICAL DATA
A) ARSENIC FRONT HALF
PROBE (MG)
CYCLONE (MG)
FILTER (MG)
ARSENIC FRONT HALF TOTAL (MG)
PM* (MG/M'J
*/H», (KG/US)
B) ARSENIC - IMPINGER COLLECTION
IMPIHGER Fl. 2 (MG)
PPM, (MG/M3)
0/HR, (KG/HR)
PPM, MG/M3)
HR, KG HR
C) ARSENIC - IMPINGER TOTAL (MG>
PPM, (MG/M^)
0/HR, (KG/HR)
D) TOTAL ARSENIC (MG)
PPM, (MG/M*)
0/HR, (KG/KB)
E) I0IAL_SQj (MG)
PPM
(MG/MJ)
0/HR, (KG/HR)
1
ENGLISH
UNITS
6/13/78
-.15
27.95
0.0
20.0
2.59
77.41
389.4
0.30
SS.49
29,73
29.69
17.78
59162
34282
4.735
28.10
.319
144
73.23
48
.84
127.0
.86
O.dO
0.18
61.65
0.30
ID. 69
17.78
123.2
—
0.0241
0.0095
...
0.0007
0.0002
...
0.0007
0.0002
0.0248
0.0097
...
7531.7
METRIC
UNITS
6/13/78
-3.81
709.93
0.0
20.0
2.59
77.41
198.6
0.30
5.16
29.73
29.69
5.42
1675.5
970.9
""
711.74
8.1
144
2.07
48
.84
52.8
21.84
4.0
1.524
0.0052
1.75
0.30
29.69
5.42
123.2
0.126
0.0033
0.1293
0.0739
0.0043
0.0037
0.0021
0.0001
0.0037
0.0021
0.0001
0.1330
0.076
0.0044
120066.34
25931.20
68609
3411.8
2
ENGLISH
UNITS
6/14/78
-.15
27.90
0.0
20.0
3.02
76.98
358.1
0.79
SS.49
29.89
92.80
14.24
47372
28312
4.735
28.05
.319
144
45.23
48
.84
123.65
.89
0.40
o-.ar
38.17
0.79
29.80
14.24
92.1
...
...
...
...
0.0080
0.0026
0.0017
0.0007
...
0.001?
0.0007
...
0.0097
0.0031
...
8922.9
METRIC
UNITS
6/14/78
-3.81
708.66
0.0
20.0
3.03
76.98
181.2
0.79
S.1C
29.89
29.80
4.34
1341.6
801.8
—
712.47
8.1
144
1.28
48
.84
50.9
7.37
6.6
1.016
0.0086
1.08
0.79
29.80
4.34
92.1
0.0045
0.022
0.0265
0.0245
0.0012-
0.0057
0.0053
0.0003
.0057
.0053
.0003
.0322
.0298
.0014
87900.68
30290.87
81390
4047.4
3
ENGLISH
WITS
6/15/78
-.IS
27.91
0.0
20.0
7.59
72.41
404.28
0.0
55.49
31.53
31.53
15.42
51298.
29265
4.735
28.06
.319
144
49.73
48
.84
118.38
.30
0.047
0.0
42.37
OCO
31.53
15.42
99.0
—
0.0034
0.0011
0.0072
0.0024
...
0.0072
0.0024
0.0085
0.0029
...
. 21442
METRIC
UNITS
6/15/78
-3.81
708.91
0.0
20.0
7.59
72.41
206.8
0.0
5.16
31.53
31.53
4.70
1452.8
828.8
...
712.72
8.1
144
1.41
48
.84
' 84.0
7.62
0.0
1.194
0.00
1.ZO
0.0
31.53
4.70
99.0
0.0026
...
0.0098
0.0124
0.0103
0.0005
0.0265
0.0221
0.00)1
0.0265
0.0221
0.0011
0.0309
0.026
0.0013
234702.97
75960.29
19S5B6
9726.1 •
AVERAGE
ENGLISH
UNITS
-.15
27.92
0.0
20.0
4.4
75.60
383.9
0.36
SS.49
30.38
30.34
15.81
52612 .
30621
4.735
28.07
.319
144
56.07
48
,84
123.01
0.48
0.049
0.16
47.40
0.36
30.34
15.81
106.6
—
...
0.0118
0.0044
...
0.0032
0.0011
0.0032
0.0011
...
0.0069
0.0053
—
12629
METRIC
UNITS
-3.81 .
709.17
0.0
20.0
4.4
75.60
195.5
0.36
5.16
30.38
30.34
4.82
1490.0
367.?
—
713.16
8.1
144
1.59
48
.84
50.6
3.53
1.245
.0046
1.34
0.36
30.34
4.82
106.6
0.0444
...
0.0117
O.OS61
0.0362
0.0020
0.0120
0.0098
0.0005
...
0.0120
0.0098
0.000$'
0.0654
0.211
0.0024
147536.65
44061 . 01
115195
5728.4
-------
TABLE 3
ESP Outlet/Acid Plant Inlet Arsenic/Sulfur Dioxide Results
RUN NUMBER
'
1 DATE
II STACK PARAMETERS
PsT - STATIC PRESSURE, "He (MNHG)
PS - STACK GAS PRESSURE, "Ho ABSOLUTE (MKHG)
I C02 - VOLUME Z DRY
X Oj - VOLUME X DRV
Z N2 - VOLUME Z DRY
Ts - AVERAGE STACK TEMPERATURE °F (°C>
Z H20 - Z MOISTURE IN STACK GAS, BY VOLUME
As - STACK AREA, FT2 (n2)
MD - COLECULAH WEIGHT OF STACK GAS, DRV BASIS
Ps - MOLECULAR WEIGHT OF STACK GAS, VET BASIS
Vs - STACK GAS VELOCITY, FT/SEC, (M/S;C)
QA - STACK GAS VOLUMETRIC FLOW AT STACK CONDITIONS, ACFJ* (NM'/MIN)
Os - STACK GAS VOLUMETRIC FLOW AT STANDARD CONDITIONS, DSCFP" (NM'/MIN)
Z EA - PERCENT EXCESS AIR
Ml TEST CONDITIONS
PB - BAROMLIRIC PRESSURE, "He (wHc)
T - SAMPLING TIME, MIN
VM - SAMPLE VOLUME, ACF
NP ' NET SAMPLING POINTS
CP - PITOT TUBE COEFFICIENT
TM - AVERAGE HETEB TEMPERATURE °F (°C)
PM * AVERAGE ORIFICE PRESSURE DROP, "H^O (MMH^O)
VLC - CONDENSATE COLLECTED (IMPINGERS AND GEL), MLS
fip - STACK VELOCITY HEAD "H20 3
29.82
29.56
11.89
1873.4
1IOS.1
4.753
712.5
111
1.78
36
.84
49.1
20.8
26.2
7.62
.034
1.51
29. 5C
11.89
108.1
0.025
-"
0.0081
0.0331
0.0219
0.0015
0.0056
0.0037
0.0002
...
0.0056
0.0037
0.0002
0.0387
0.0256
0.0017
114485.11
28306.17
75818
5027. Z
3
ENGLISH
UNITS
6/15/78
-.07
27.99
20.0
3.99
76.01
342.1
28.27
30.24
29.77
29. SO
500)3
29692
4. 735
28.06
.248
109
48.011
36
.84
109.0
.48
.175
1.60
41.7135
29.77
29.50
106.8
...
...
0.0422
0.0042
...
0.0130
0.0062
0.0180
0.0062
0.0302
0.0104
:::
11554
METRIC
UNITS
6/15/78
-1.7E
7)1.0
20.0
3.99
76.01
172.3
2.63
30.24
29.77
8.99
1416.4
840.9
4.735
712.7
109
1.36
36
.84
42.8
12.2
34.9
4.43
.045
1.18
29.77
8.99
IDS. 8
0.0072
...
0.037
0.0442
0.0375
0.0019
0.065
0.0551
0.0028
0.065
0.0551
0.0028
0.1092
0.092S
0.0047
122570.97
39900.57
103874
5240.9
AVERAGE
ENGLISH
UNITS
-.07
28.00
HJ.O
3.93
76.07
358.5
28.27
30.22
29.85
3s.ua
62460
36578
4.735
28.07
108.7
57.74
36
.04
116.33
0.74
...
.275
1.49
94.53
29.85
38.88
103.4
...
...
0.0148
0.0064
0.0068
0.0024
...
0.0068
0.0024
0.0215
0.0088
...
14358
METRIC
UNITS
-1.78
711.2
20.0
3.93
76.07
131.4
2.63
30.22
29.05
11.24
1768.9
1035.9
4.735
713.0
108.7
1.64
36
.04
46.9
10.7
32.4
6.99
.042
1.40
29.85
11.24
103.4
0.0481
0.0160
0.0641
0.04S2
0.0029
0.0253
0.0208
0.0011
...
0.0253
0.0208
0.0011
0,0894
0.0659
0.0040
145968
39348
104235
6512.8
-------
TABLE 4
Acid Plant Outlet Arsenic/Sulfur Dioxide Results
RUN NUMBER
1 DATE
1 1 STACK PARAMETERS
PST - STATIC PRESSURE, 'He (MMHG)
Ps - STACK GAS PRESSURE, "He ABSOLUTE (MMHG)
X CO? - VOLUME X DRY
X 0? - VOLUME X DRV
« SH2 - Wauft £ Dm
X N2 - VOLUME X DRV
Ts - AVERAGE STACK TEMPERATURE °F (°C)
X HoO - X MOISTURE IN STACK GAS, BY VOLUME
As - STACK AREA, FTZ (M2)
No • MOLECULAR WEIGHT OF STACK GAS, DRV BASIS
Ms - MOLECULAR WEIGHT OF STACK GAS, WET BASIS
Vs - STACK GAS VELOCITY, FT/SEC, (M/S^C)
QA - STACK GAS VOLUMETRIC FLOW AT STACK CONDITIONS, ACFM (NMVMIN)
Os - STACK GAS VOLUMETRIC FLOW AT STANDARD CONDITIONS, DSCFM (NM'/NIH)
X EA - PERCENT EXCESS AIR
III TEST CONDITIONS .
PB - BAROMETRIC PRESSURE, "Ho (MMHG)
DN - SAMPLING NOZZLE DIAMETER, IN. (MM)
T - SAMPLING TIME, MI*
VM - SAMPLE VOLUME, ACF
NP - NET SAMPLING POINTS
CP * PITOT TUBE COEFFICIENT
TM - AVERAGE METER TEMPERATURE °F (°C)
PM - AVERAGE ORIFICE PRESSURE DROP, '^0 (MMH^O)
VLC - CONDENSATE COLLECTED (IMPINGERS AND GEuTj MLS
fip - STACK VELOCITY'HEAD "H^ (MMH^)
IV TEST CALCULATIONS
Vw - CONDENSED HATER VAPOR, SDCF (KM3)
VM - VOLUME OF GAS SAMPLED AT STANDARD CONDITIONS, DSCF (NH^)
X H20 - PERCENT MOISTURE, Bv VOLUME
Ms - MOLECULAR WEIGHT OF STACK GAS, MET BASIS
Vs - STACK VELOCITY, FT/SEC (M/SEC)
X 1 - PERCENT ISOKINETIC
V ANALYTICAL DATA
A) ARSENIC FRONT HALF
PROBE (MG)
FILTER (MG)
ARSENIC FRONT HALF TOTAL' (MG)
PPM, IH&/I?)
»/HR, (KS/HS)
B) ARSENIC - IHPIHGER COLLECTION
IMPINGER 11. 2 (MG)
PPM, (MG/M')
#/HR, (KG/HR)
inpmcEB H.n.S (MG)
PPM, MG/M3)
I/HR, (KG/HR)
C) ARSENIC - IMPINGER TOTAL (MG)
PPM, (MG/H?)
I/HR, (KG/HR)
D) TOTAL ARSENIC (NG)
PPN, (NG/M?)
I/HR, (KG/HR)
E) IfliAL_S02 IKS'
(MG/M3)
I/HR, ( KG/HR)
1
ENGLISH
UHITS
6/1 V78
.13
27.98
0.0
20.0
0.24
79.76
140
15.61
28.89
28.76
58399
47556
4.735
2B.Z3
.185
108
73.377
12
120.0
1.82
1.02
0.75
62.757
1.18
28.76
62.5
100.6
—
0.0016
0.0009
0.0008
0.0004
—
0.0008
0.0004
—
0.0024
0.0013
1154.8
METRIC
UNITS
6/13/78
3.30
710.7
0.0
20.0
0.24
79.76
60
1.45
28.89
28.76
1653.9
1346.8
4.735
717. M
4.7
108
2.08
12
48.8
46.2
16.4
25.9
O.K1
1.78
1.18
28.76
19.04
1UO.G
0.0066
0.002
0.0086
0.0048
0.0004
0.0042
0.0024
0.0002
...
0.0042
0.0024
0.0002
0.0128
0.0072
0.0006
11538.07
I4B0.51
6U2.1
523.8
2
ENGLISH
UNITS
6/14/78
.13
27.93
0.0
20.0
0.12
79.88
164.3
15.61
28.84
28.83
55514
43862
4.735
28.18
.185
108
66.115
12
wjjT
1.10
—
.88
0.275
56.304
0.49
28.83
59.4
97.4
...
...
0.0020
0.0011
0.0010
0.0004
...
0.0010
0.0004
0.0031
0.0015
:::
546.5
METRIC
UNITS
6/14/78
3.30
709.4
0.0
20.0
0.12
79.68
73.5
1.45
28.84
28.83
1572.2
1242.2
4.735
715.77
4.7
108
1.87
12
49.0
27.9
6
22.4
0.0078
1.59
0.49
28.83
18.10
97.4
0.0089
0.001
0.0099
6.0062
0.0005
0.0050
0.0031
0.0002
—
0.0050
0.0031
0.0002
0.0149
0.0094
0.0007
928B.BS
1235.31
3325.8
247.9
3
ENaiSH
UNITS
6/15/78
.13
27.94
0.0
20.0
0.08
79.92
127.5
15.61
28.83
28.83
42849
36016
4.735
28.14
.185
108
53.182
12
113.6
.70
—
.56
0.0
45.782
0.0
28.83
45.8
97.0
...
...
0.0082
0.0033
0.0011
0.0004
—
...
0.0011
0.0004
0.0094
0.0040
283.5
METRIC
UNITS
6/15/78
3.30
709.7
0.0
20.0
0.08
79.92
53
1.45
28.83
28.83
1213.5
1020.0
4.735
716.03
4.7
108
1.50
12
45.3
17.78
0
14.2
0.0
1.30
0.0
28.83
13.97
97.0
0.0017
0.031
0.0327
0.0252
0.0015
0.0046
0.0035
0.0002
...
—
0.0046
0.0035
0.0002
0.0373
0.0287
0.0018
1730.77
790.71
1100.6
128.6
AVERAGE
ENGLISH
UNITS
.13
27.95
0.0
20.0
O.TS
79.85
143.9
15.61
28.85
28.81
55.9
52255
42478
4.735
28.20
.185
108
64.3
12
117.9
1.21
.82
0.35
S5.08
0.56
28.85
55.9
98.3
— .
0.0039
0.0018
0.0010
0.0004
—
...
0.0010
0.0004
0.0049
0.0022
...
...
661.6
METRIC
UNITS
3.30
709.9
0.0
20.0
0.15
79.85
62.2
0.56
1.45
28.85
28.81
17.04
1479.9
1203.0
4.735
716.28
4.7
108
1.82
12
47.7
30.6
7.5
20.8
.0098
1.56
0.56
28.85
17.04
98.3
0.0057
0.0113
0.0168
O.T21
0.0008
0.0046
0.0030
0.0002
0.0046
0.0030
0.0002
0.0226
0.151
.0.0010
6518:96
1482.09
3969.5
300.1
-------
TABLE 5.
PROCESS SAMPLE ANALYTICAL RESULTS
(PHELPS-DODGE, AJO, ARIZONA)
SAMPLE
Liquid HLSO, Acid
Liquid lUSO, Acid
Liquid H_SO, Acid
Acid Plant Purge Water
Acid Plant Purge Water
Acid Plant Purge Water
Anode Copper
Anode Copper
Anode Copper
Converter Slag
Converter Slag
Converter Slag
Converter Matte
Converter Matte
Converter Matte
DATE
SAMPLED
6/13/78
6/14/78
6/15/78
6/13/78
6/14/78
6/15/78
6/14/78
6/15/78
6/16/78
6/13/78
6/14/78
6/15/78
6/13/78
6/14/78
6/15/78
AS
0 . 14ppm
0 . 12ppm
0 . lOppm
0.21ppm
0 . 06ppm
0 . 14ppm
0.0070%
0.0090%
0.0071%
0.11%
0.11%
0.19%
0.11%
0.16%
0.27%
-------
SECTION 3
PROCESS DESCRIPTION
(By EPA)
-------
SECTION 4
LOCATION OF SAMPLING POINTS
Inlet to ESP
Sampling was performed through a vertical rectangular duct which mea-
sured 94"x85". The sampling position was located approximately 80 feet
above the ground. Sampling ports consisted of six ports evenly distributed
across the west side of the duct. Sampling ports enabled TRW personnel to
sample with horizontal traverses. The nearest upstream disturbance was
located 10 feet (1% duct diameters) from the sampling position. The flow
disturbance occurs where the rectangular duct attaches to the circular duct
at a 90° angle,to the flow of gases. The nearest downstream disturbance is
located 7 feet (1 duct diameter) from the sampling points where the gases
enter the acid plant. Forty eight sampling points were utilized with eight
points on each of six traverses. Figure 1 is a schematic of the sampling
location.
Acid Plant Outlet
Samples were taken from a 53.5 inch horizontal duct which was located
approximately 70 feet above the ground. The sampling ports were located
on the side and top enabling horizontal and vertical traverses. The nearest
upstream disturbance was located greater than 36 feet ( 8 duct diameters)
from the sampling point. Figure 2 is a schematic of the sampling location.
ESP Outlet/Acid Plant Inlet
Sampling was performed through a horizontal circular duct that was lo-
cated approximately 25 feet above the ground. Sampling ports were positioned
on the bottom and side of the duct to allow vertical and horizontal sampling.
The nearest upstream disturbance was located 12 feet ( 2 duct diameters)
from the sampling positions. The nearest downstream flow disturbance was
at least 30 feet (5 duct diameters) away from the sampling position. Thirty
six traverse points were selected with eighteen points on each traverse.
Figure 3 is a diagram of the sampling location.
-------
»F1gure 1 Esp Inlet sampling locations
85"
85'
94"
i
94"
I
Distance of sampling point
from port
Traverse
point
ESP
Inlet
North
ESP
Inlet
South
6
7
8
Distance
from
inside
wall (in)
5.88
17.63
29.38
41.13
52.88
64.63
76.38
88.13
From
converter
building
t
Sampling points
Side view
Acid plant
bypass
sampling pointsDamper
10
-------
Traverse
point
locations
Fraction of
stack I.D.
Distance
from Inside
wall (1n)
1
2
3
4
5
:6
.044
.146
.296
.704
.854
.956
2.35
7.91
15.98
38.02
46.09
51.65
54"
Figure 2 Add plant outlet location
11
-------
Traverse
point
locations
Fraction of
stack I.D.
Distance
from 1n$1de
wall (In)
72"
1
2
3
4
5
6 *
7
8
9
10
11
12
13
14
15
16
17
18
0.014
0.044
0.075
0.109
0.146
0.188
0.236
0.246
0.382
0.618
0.704
0.764
0.812
0.854
0.891
0.925
0.956
0.986
1.01
3.14,
5.41
7.86
10.54
13.55
17.03
21.30
27.51
44.49
50.70
54.97
58.45
61.46
64.14
66.59
68.86
70.99
fTo
add plant.
Figure 3 ESP outlet/add plant Inlet sampling location
12
-------
STACK
•..
.'<*>'.
ACID PLANT OUTLET
ESP OUTLET
ESP
ACID
PLANT.
COMPLEX
ESP INLETS
CONVERTER BUILDING
Figure 4
Acid plant schematic
Phelps-Dodge, Ajo, Arizona
13
-------
SECTION 5 °
SAMPLING AND ANALYTICAL PROCEDURE
4 . 1
(A) Arsenic/Sulfur Dioxide Sampling
The sampling train used for arsenic/sulfur dioxide collection consisted of
an EPA Method 5 train modified by adding three additional impingers in series
to the four used in the Method 5 train. The first two impingers contained
150 mis of distilled water each, the third was empty, the fourth, fifth, and
sixth impingers contained 150 mis of 10% hydrogen peroxide each. The seventh
limpinger contained 250 grams of silica gel.
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 Fryrite 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 120°F.
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 3-9 minutes depending upon
the sampling location. 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 polyethlene container,
which was labeled and sealed. The first two impinger solutions were measured
and placed in a glass sample container along with a 0.1N NaOH rinse of the
impingers. The contents of the third, fourth and fifth impingers were mea-
14
-------
12
13
b c. d. e f g
Figure 5. Arsenic sulfur dioxide train
1. Calibrated Nozzle
2. Heated Probe
3. Type S Pi tot
4. Cyclone Assembly
5. Filter Holder
6. Heated Box
7. 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
Pi tot Manometer
Thermometer
15
-------
and placed in a separate glass sample container along with a distilled
water rinse of the impingers. The silica gel in the sixth impinger was
weighed to the nearest 0.5 gram, and regenerated.
(B) Analysis
Analysis-Sulfur Dioxide
i
n
The samples were analyzed for sulfur dioxide by taking an aliquot
of the hydrogen peroxide impinger solutions and titrating with; barium per-
chlorate solution and thorin indicator as described in EPA Method 6 (Deter-
mination of Sulfur Dioxide Emissions from Stationary Sources).
Analysis-Arsenic
1. Filter-warm filter and loose particulate matter with 50ml 0.1N
NaOH for about 15 minutes. Add 10ml concentrated HN03 and bring to boil for
15 minutes. Filter solution through no. 41 Whatman paper and wash with hot
water. Evaporate filtrate, cool, redissolve in 5ml of 1:1 HN03» transfer to
a 40ml volumetric flask and dilute.
2. Probe Wash and Impinger Solutions- These should be combined and a
100ml sample withdrawn. Add lOriil concentrated HN03 and dilute to 50mls. 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
flamer The filter samples may require dilution with 0.8N HNOs. Impinger
solutions containing more than 26 mg/1 of arsenic should be diluted since
linearity decreased 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 hydro-
gen 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 1 mg/1 level, hydride generation is necessary.
An appropriate aliquot of digested sample in 0.8N HN03 containing less than
about lOtig of arsenic is chosen (some screening may be necessary). Five mis
of concentrated H2S04 is added to the sample which is then placed on a hot
plate until $03 fumes fill the flask. A reduction in volume to about 5ml
or less may be necessary. This step removes HNth which causes a violent
reaction when the reducing agent is added resulting in poor reproducibility
and lowered sensitivity by producng 13. N02 and possible other species.
16
-------
One ml of 30% KI and 1ml of 30% SnCl2 are added to the sample, the
former to act as a catalyst in hydride formation and the latter to reduce
all the arsenic to As+3. The sample is then diluted to about 15ml and 15ml
of concentrated HC1 is added. Powdered Zn(or NaBH4) is then added, the
reaction vessel is immediately clbsed and the nitrogen or argon carrier
flow initiated. A peak should be produced within a few seconds.
17
-------
APPENDIX A
1. Traverse Point Location
18
------- |