United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EMB Report 78-OCM-8
Air
xvEPA
Acrylic Acid and Esters
Production
Test Report
Union Carbide
Corporation
Taft, Louisiana
-------
EMISSION TEST OF AN ACRYLIC ACID AND
ESTER MANUFACTURING PLANT
by
George W. Scheil
September 1980
FINAL REPORT
EPA Contract No. 68-02-2814, Work Assignment No. 14
EPA Project No. 78-OCM-8
MRI Project No. 4468-L(14)
For
Emission Measurement Branch
Field Testing Section
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
Attn: Mr. J. C. McCarley, Jr.
-------
PREFACE
This work was conducted by Midwest Research Institute under Environmental
Protection Agency Contract No. 68-02-2814, Work Assignment No. 14.
The project was supervised by Mr. Doug Fiscus, Head, Field Programs
Section. Dr. George Scheil served as field team leader and was assisted in
the field by Messrs. Ron Jones, Al Myers, Dan Vogel, Jeff Thomas, and Tom
Altpeter of Midwest Research Institute, and by Mr. Gary Hippie of Pollution
Control Science, Inc. Laboratory assistance was provided by Mr. Ron Jones and
Ms. Alice Shan.
Approved for:
MIDWEST RESEARCH INSTITUTE
M. P. Schrag, Director V
Environmental Systems Department
iii
-------
CONTENTS
Figures vi
Tables vii
1. Introduction 1
2. Summary and Discussion of Results 2
3. Process Description and Operation ........... 32
4. Location of Sample Points 34
5. Sampling and Analytical Procedures 39
Appendices
A. TGNMO Method Data A-l
B. Aldehyde Method Sampling Data B-l
C. Pitot Traverse Data C-l
D. Integrated Gas Sampling Data D-l
E. Moisture Train Data E-l
F. NOX Data F-l
G. Draft EPA Benzene Method G-l
H. Program Listing for Field Data Acquisition H-l
I. Program Listing for Data Filter and Printout Operations. 1-1
J. GO Analysis Data J-l
K. Program Listing for Peak Deconvolution K-l
L. Aldehyde Sample Analysis Data L-l
M. Retention Data of Known Compounds M-l
N. Sample Calculations N-l
-------
FIGURES
Number Page
1 Run 3 - Inlet chromatogram, Taft, Louisiana ....... 18
2 Run 3 - Acrylic acid off-gas gas chromatogram, Taft,
Louisiana ......... 19
3 Run 3 - Outlet chromatogram, Taft, Louisiana 20
4 Run 6 - TGNMO Tank UCO-6 chromatogram, Taft, Louisiana . 24
5 Run 5 - TGNMO Tank UCI-6 chromatogram, Taft, Louisiana . 25
6 Run 3 - Fuel gas chromatogram, Taft, Louisiana 30
7 General process diagram showing sampling points ..... 35
8 Sampling Point No. l-(AOG) acrylic acid unit off-gas . . 36
9 Incinerator layout with sampling locations 37
vi
-------
TABLES
Number Page
1 Gas Chromatography Analyses for Methane 3
2 Gas Chromatography Analyses for Ethylene . 4
3 Gas Chromatography Analyses for Acetylene ........ 5
4 Gas Chromatography Analyses for Ethane 6
5 Gas Chromatography Analyses for Propylene 7
6 Gas Chromatography Analyses for Propane ... 3
7 Gas Chromatography Analyses for Acetaldehyde . 9
8 Gas Chromatography Analyses for Butenes 10
9 Gas Chromatography Analyses for Acrolein 11
10 Gas Chromatography Analyses for Acetone 12
11 Gas Chromatography Analyses for Unknown Peak 13
12 Gas Chromatography Analyses for 1-Hexene 14
13 Gas Chromatography Analyses for 2-Hexene 15
14 Gas Chromatography Analyses for Acrylic Acid 16
15 Gas Chromatography Analyses for Total Hydrocarbons ... 17
16 Total Gaseous Nonmethane Organic (TGNMO) Sampling
Results 22
17 TGNMO Tank Samples Analyzed by Gas Chromatography .... 23
18 Aldehyde Analysis Results - Bisulfite Reaction 26
19 Composition/Flow Summary (Metric Units) 27
20 Composition/Flow Summary (English Units) 28
21 Fuel Gas Analysis (ppm as propane) 29
22 NOX Results 31
23 Summary of Sampling Conditions 32
VI. 1
-------
SECTION 1
INTRODUCTION
This report presents the results of source testing performed during the
period November 27 to December 8, 1978, by Midwest Research Institute (MRI) at
the acrylic acid facility of Union Carbide Corporation at Taft, Louisiana. The
inlet and outlet of a low temperature, long residence time fume combustor were
sampled at two different combustor temperatures. The combustor is used to
limit emissions of the process off-gases from an acrylic acid plant and an acro-
lein plant. Both units used partial oxidation of propylene to produce their
products. Most of the sampling was done with only the acrylic acid process
operating. Both processes were operating on one day and an additional gas sam-
ple was taken from the acid process off-gas before the acrolein process stream
joined the combustor feedline. A sample of the contents of the liquid knock-
out trap at the combustor inlet was also obtained.
The vapor streams were analyzed for methane, ethylene, ethane, propane,
propylene, acetaldehyde, acrolein, acetone, acrylic acid, and total hydrocar-
bons by gas chromatography (GC). Duct temperature, flow rate, oxygen, carbon
monoxide, carbon dioxide, and aldehydes were also determined by manual sampling
on all streams. The fuel gas was analyzed by GC, and NOX samples were taken
at the outlet.
The results of these tests are to be used as reference data for establish-
ing performance standards of organic fume combustors.
-------
SECTION 2
SUMMARY AND DISCUSSION OF RESULTS
The GC analysis results are shown in Table 1 through 15. The first 14
tables show results for each component observed, from methane to acrylic acid,
at the inlet and outlet to the incinerator. Table 15 shows the sum of all 14
components. All actual meausrements were made as parts per million (ppm) of
propane with the other units reported derived from the equivalent values. The
values were measured by digital inegration. The tables include any contribu-
tion from the portion of each sample which condensed in the sampling train
trap. These condensates were generally small.
The gas stream at the incinerator inlet had considerable entrained liquid.
Therefore, since samples were not taken isokinetically, the fractions shown for
the condensate fractions may not be representative of the sample streams. The
condensate sample taken from the plant knock-out trap at the inlet showed about
7 /ng/g acetaldehyde, 31.4 /Ltg/g of butenes and 120 /Lig/g of acetone (all expressed
as acetone response).
The incinerator combustion temperature for the first six runs was about
625°C. Runs 7 through 9 were made at an incinerator temperature of about 800°C.
Only during Run 3 was the acrolein process.operating. Its contribution to the
total inlet load is the difference of the 3-1 and 3-AOG concentrations. The
higher temperature during Runs 7 through 9 caused most of the compounds heavier
than propane to drop below the detection limits. No single number can be as-
signed as a detection limit due to the wide range of attenuations used, nearby
obscuring peaks, and baseline noise variations. The detection limit ranges
from about 10 ppb to 10 ppm, generally increasing during the chromatogram, and
especially near large peaks. Several of the minor peaks were difficult to
measure. However, the compounds of interest, methane, ethane, ethylene, pro-
pane, propylene, acetaldehyde, acetone, acrolein, and acrylic acid, dominate
the chromatograms (see Figure 1 through 3 for examples). Only acetic acid was
never detected in any sample.
The probable reason for negative destruction efficiencies for several
light components is generation by pyrolysis from other components. For instance,
the primary pyrolysis products of acrolein are carbon monoxide and ethylene.
Except for methane and, to a much lesser extent, ethane and propane, the fuel
gas cannot contribute hydrocarbons to the outlet samples.
-------
TABLE 1. GAS CHROMATOGRAPHY ANALYSES FOR METHANE
Propane, ppm
Methane, ppm
Carbon, ppm .
Methane, g/m ~T
Carbon, g/m ~
Methane, Ib/sec
Carbon, g/sec .
Methane, Ib/flj ^J
Carbon, Ib/ft -
Methane, Ib/hr
Carbon, Ib/hr
Propane, ppm
Methane, ppm
Carbon, ppm .
Methane, g/m *T
Carbon, g/m ~
Methane, g/sec
Carbon, g/sec .
Methane, Ib/ft "J
Carbon, Ib/ft -
Methane, Ib/hr
Carbon, Ib/hr
X Efficiency
Run No. 1-1
362
1,006
1,006
0.668
0.501
5.84
4.38
4.16 x 10
3.12 x 10
46.3
34.8
Run No. 1-0
19
53
53
0.035
0.026
0.83
0.62
2.2 x 10"^
1.6 x 10
6.6
4.9
85.1
Run No. 2-1
318
883
883
0.586
0.440
7.07
5.30
3.66 x 10
2.74 x 10
56.1
42.1
Run No. 2-0
56
156
156
0.103
0.077
2.8
2.1 ,
6.4 x 10
4.8 x 10
22
16
62.0
Run No. 3-1
490
1,361
1,361
0.904
0.678
10.87
8.15
5.64 x 10 ^
4.23 x 10
86.2
64.6
Run No. 3-0
70
194
194
0.129
0.097
3.3
2'5 ft
8.1 x 10
6.0 x 10
26
20
69.0
Run No. 3-AOC
426
1,183
1,183
0.786
0.589
8.09
6.07
4.90 x 10
3.67 x 10
64.1
48.1
Run No. 4-1
293
814
814
0.540
0.405
5.15
3.87
3.37 x 10 ^
2.53 x 10 3
40.9
30.7
Run No. 4-0
27
73
75
0.050
0.037
1.26
0.95
3.1 x 10'*
2.3 x 10
10.0
7.5
75.6
Run No. 5-1
397
1,103
1,103
0.732
0.549
6.60
4.95
4.13 x 10 ^
3.42 x 10
52.3
39.2
Run No. 5-0
26
72
72
0.048
0.036
1.20
0.90
3.0 x 10~
2.2 x 10"
9.5
7.1
81.9
Run No. 6-1
438
1,217
1,217
0.808
0.606
7.03
5.27
4.57 x 10
3.78 x 10
55.7
41.8
Run No. 6-0
33
92
92
0.061
0.046
1.47
1.10
3.8 x 10"
2.8 x 10
11.7
8.7
79.2
Run No. 7-1
367
1,019
1,019
0.677
0.508
6.08
4.56
3.83 x 10 ^
3.17 x 10
48.2
36.2
Run No. 7-0
0.80
2.2
2.2
1.5 x 10
1.1 x 10"
0.035
0.027
9.2 x 10~°
6.9 x 10"
0.28
0.21
99.4
Run No. 8-1
377
1,047
1,047
0.695
0.521
6.68
5.01
4.22 x 10 ^
3.25 x 10 5
53.0
39.8
Run No. 8-0
0.07
0.19
1.3 x 10
9.7 x 10"
3.2 x 10
2.4 x 10
8.1 x 10";
6.0 x 10
0.025
0.019
99.95
Run No. 9-1
498
1,383
1,383
0.918
0.689
8.04
6.03
5.16 x 10 •
4.30 x 10
63.8
47.8
Run No. 9-0
0.08
0.22
°-22 -4
1.5 x 10
1.1 x 10"
3.6 x 10
2.7 x 10
9.2 x 10
6.9 x 10"
0.029
0.021
99.96
oj Dry standard conditions
Note: Retention Index = 100
-------
TABLE 2. GAS CHROMATOGRAPHY ANALYSES FOR ETHYLENE
Propane,
Ethylene
Carbon,
Ethylene
Carbon,
Ethylene
Carbon,
Ethylene
Carbon,
Ethylene
Carbon,
Propane,
Ethylene
Carbon,
Ethylene
Carbon,
Ethylene
Carbon,
Ethylene
Carbon,
Ethylene
Carbon,
ppm
, ppm
ppm
, g/mf'
S/m^7
, g/sec
g/sec
, lb/ft3^
Ib/ft^7
, Ib/hr
Ib/hr
ppm
, ppm
ppm ,
8/n.f'
g/m3*7
, g/sec
g/sec
, Ib/ft3^7
Ib/ft3*'
, Ib/hr
Ib/hr
7. efficiency
Run No. l-[
208
314
629
0.365
0.313
3.20
2.74
2.28 x HP5
1.95 x 10" 5
25.3
21.7
Run No. 1-0
52
79
157
0.091
0.078
2.16
1.85
5.70 x 10~6
4.90 x 10"6
17.1
14.7
32.3
Run No. 2-1
156
236
471
0.274
0.235
3.30
2.83
1.71 x 1Q-5
1.46 x 10"5
26.2
22.4
Run No. 2-0
182
275
550
0.320
0.274
8.54
7.32
1.99 x 10~5
1.71 x 10~5
67.7
58.0
b/
Run No. 3-1
159
240
480
0.279
0.239
3.36
2.88
1.74 x 10-5
1.49 x 10'5
26.6
22.8
Run No. 3-0
192
290
580
0.337
0.289
8.63
7.40
2.10 x 10"5
1.80 x 10'5
68.4
58.7
b/
Run No. 3-AOG
174
263
526
0.305
0.262
3.14
2.70
1.91 x 10~5
1.63 x 10-5
24.9
21:4
Run No. 4-1
181
273
547
0.318
0.272
3.03
2.60
1.98 x 10"5
1.70 x 10"5
24.0
20.6
Run No. 4-0
84
127
254
0.147
0.126
3.73
3.20
9.20 x 10'6
7.90 x lO"6
29.6
25.4
b/
Run No. 5-1
178
269
538
0.312
0.268
2.82
2.41
1.95 x 10~5
1.67 x 10-5
22.3
19.1
Run No. 5-0
84
127
254
0.147
0.126
3.70
3.17
9.20 x 10~6
7.90 x 10"6
29.3
25.1, ,
b/
Run No. 6-T
162
245
490
0.284
0.244
2.48
2.12
1.77 x 10"5
1.52 x 10"5
19.6
16.8
Run No. 6-0
92
139
278
0.162
0.138
3.90
3.34
1.01 x ID"5
8.60 x 10~6
30.9
26.5 ,
b/
Run No. 7-1
187
283
565
0.328
0.281
2.95
2.53
2.05 x HT5
1.75 x 1Q-5
23.4
20.0
Run No. 7-0
0.022
0.033
0.066
3.86 x 10~5
3.31 x 10~5
9.3 x 10-*
8.0 x 10-*
2.4.x 1Q-9
2.1 x HT9
7.4 x 10"3
6.3 x 10'3
99.97
Run No. 8-1
183
277
553
0.321
0.275
3.09
2.65
2.00 x 10"5
1.72 x 10"5
24.5
21.0
Run .No. 8-0
0.051
0.077
0.154
9.0 x 10"5
7.7 x 10~5
2.2 x 10"3
1.9 x 10"3
5.6 x 10~9
4.8 x 10~9
0.018
0.015
99.93
Run No. 8-1
173
261
523
0.304
0.260
2.66
2.28
1.89 x 10"*
1.62 x 10- 5
21.1
18.1
Run No. 9-0
0.078
0.118
0.236
1.37 x 10~4
1.17 x 10"4
3.3 x 10"3
2.9 x 10~3
8.5 x KT9
7.3 x 10~9
0.026
0.023
99.9
a/ Dry standard conditions.
j>/ Negative efficiency.
Note: Retention index = 185.
-------
TABLE 3. GAS CHROMATOGRAPHY ANALYSES FOR ACETYLENE
Run Ho. 1-1 Run No. 2-1 Run No. 3-T Run No. 3-AOC Run No. 4-1 Run No. 5-1 Run No. 6-1 Run No. 7-1 Run No. 8-1 Run No. 9-1
NONE DETECTED AT IN1.F.T
Run No. 1-0 Run No. 2-0 Run No. 3-0
Run No. 4-0 Run No. 5-0 Run No. 6-0 Run No. 7-0 Run No. 8-0 Run No. 9-0
Propane, ppm
Acetylene, ppm
Carbon, ppm
Acetylene, g/m3—
Carbon, g/ra3— '
3.4
5.3
10.6
5.7 x 10-3
5.3 x ID"3
Acetylene, g/sec ND^' 0.152
Carbon, g/sec
Acetylene, lb/ft3-
Carbon, Ib/ft3^
Acetylene, Ib/hr
Carbon, Ib/hr
0.140
3.6 x 10-7
3.3 x 10-7
1.21
1.11
3.8
5.9
11.8
6.4 x lO-3
5.9 x lO"3
0.163
0.150
4.0 x lO"7
3.7 x 10"7
1.29
1.19
1.7
2.6
5.3
2.8 x 10"3
2.6 x lO-3
0.072
0.067
1.8 x 10-7
1.6 x 10' 7
0.57
0.53
1.6
2.5
5.0
2.7 x lO-3
2.5 x lO-3
0.067
0.062
1.7 x 1Q-7
1.5 x 10" 7
0.53
0.49
2.2
3.4
6.8
3.7 x 10-3
3.2 x ID'3
0.089 ND ND ND
0.082
2.3 x 10'7
2.1 x 10~7
0.71
0.65
'
a/ Dry standard conditions
b/ ND - None detected
Note: Retention Index = 195
-------
TABLE 4. GAS CHROMATOGRAPHY ANALYSES FOR ETHANE
Propane,
Ethane,
Carbon,
Ethane,
Carbon,
Ethane,
Carbon,
Ethane,
Carbon,
Ethane,
Carbon,
ppm
ppm
ppm
g/ra3^
g/m35/
g/sec
g/sec
Ib/ft!*3-'
Ib/ft3^/
Ib/hr
Ib/hr
Run No. 1-1
138
204
409
0.254
0.204
2.23
1.78
1.59 x 10-5
1.27 x ID"5
17.7
14.1
Run No. 2-1
113
167
335
0.208
0.167
2.51
2.01
1.30 x ID"5
1.04 x ID"5
19.9
15.9
Run No. 3-1
102
151
302
0.188
0.150
2.26
1.81
1.17 x 10~5
9.40 x 10"6
17.9
14.3
Run No. 3-AOG
52
77
154
0.096
0.077
0.99
0.79
6.00 x 10-6
4.80 x HT6
7.8
6.3
Run No. 4-1
118
175
350
0.218
0.174
2.04
1.63
1.36 x 10-5
1.09 x 10-5
16.1
12.9
Run No. 5-1
92
136
273
0.170
0.136
0.153
0.122
1.06 x ID"5
8.50 x 10"6
12. 1
9.7
Run No. 6-1
97
144
287
0.179
0.143
1.56
1.25
1.12 x 10-5
9.90 x 10~6
12.3
9.9
Run No. 7-1
104
154
308
0.192
0.153
1.72
1.38
1.20 x 10~5
9.60 x 10~6
13.7
10.9
Run No. 8-1
104
154
308
0.192
0.153
1.84
1.48
1.20 x ID"5
9.60 x 10~6
14.6
11.7
Run No.
Hi
169
338
0.210
0.168
1.84
1.47
1.31 x
1.05 x
14.6
11.7
9,1
10-5
10-5
Run No. 1-0 Run No. 2-0 Run No. 3-0
Run No. 4-0 Run No. 5-0 Run No. 6-0 Run No. 7-0 Run No. 8-0 Run No. 9-0
Propane, ppm 0.86 2.1 3.2
Ethane, ppm 1.27 3.1 4.7
Carbon, ppm 2.55 " 6.2 9.5
Ethane, g/m^' 1.59 x 10"3 3.9 x 10"3 5.9 x HT3
Carbon, g/m35/ 1.27 x 10"3 3.1 x 10"3 4.7 x 10"3
0.84
1.24
2.49
1.55 x 10~3
1.24 x 10"3
Ethane, g/sec 0.038 0.104 0.151 ND^' ND 0.037 ^
Carbon, g/sec ' 0.030 0.083 0.121
Ethane, Ib/ft*-' 9.90 x 10~8 2.4 x HP7 3.7 x 10~7
Carbon, lb/ft3-' 7.90 x 10~8 1.9 x 10~7 2.9 x 10~7
Ethane, Ib/hr 0.297 0.82 1.20
Carbon, Ib/hr 0.238 0.66 0.96
% efficiency 98.3 95.8 93.3
'
0.030
9.70 x 10~8
7.70 x 10~8
0.297
0.237
97.6
A A
) ND ND
»'
aj Dry standard conditions
b/ ND = None detected
Note: Retention index = 200
-------
TABLE 5. GAS CHROMATOGRAPHY ANALYSES FOR PROPYLENE
Propane, ppm
Propylene, ppm
Carbon, ppm
Propylene, g/mS3.'
Carbon, g/m3—
Propylene, g/sec
Carbon, g/sec
Propylene, lb/ft3-'
Carbon, Ib/ft3^'
Propylene, Ib/hr
Carbon, Ib/hr
Run No. 1-1
5,140
5,379
15,840
9.20
7.89
80.5
69.0
5.74 x IO"4
4.92 x 10~4
639
:5'47
Run No. 1-0
Run No. 2-1
4,650
4,780
14,330
8.32
7.13
100.4
86.0
5.19 x IO"4
4.45 x IO"4
796
682
Run No. 2-0
Run No. 3-1
4,910
5,040
15,130
8.79
7.53
105.7
90.6
5.48 x 10"4
4.70 x IO"4
838
718
Run No. 3-0
Run No. 3-AOG
5,640
5,790
17,380
10.09
8.65
103.9
89.1
6.30 x IO"4
5.40 x IO"4
824
706
Run No. 4-1
7,510
7,710
23,140
13.44
11.52
128.2
109.9
8.38 x IO"4
7.19 x IO"4
1,017
872
Run No. 4-0
Run No. 5-1
6,870
7,060
21,170
12.30
10.54
110.8
95.0
7.67 x IO"4
6.57 x IO"4
879
753
Run No. 5-0
Run No. 6-1
6,850
7,040
21,110
12.26
10.51
106.7
91.5
7.65 x IO"4
6.55 x IO"4
846
725
Run No. 6-0
Run No. 7-1
6,230
6,400
19,200
11.15
9.56
100.2
85.9
6.96 x IO"4
5.96 x IO"4
794
681
Run No. 7-0
Run No. 8-1
6,680
6,860
20,580
11.96
10.25
115.0
98.5
7.46 x IO"4
6.39 x IO"4
912
781
Run No. 8-0
Run No .
5,450
5,600
16,790
9.76
8.36
85.4
73.2
6.08 x
5.22 x
677
581
Run No.
9-1
<
10"4
9-0
NONE DETECTED AT OUTLET
a/ Dry standard conditions
Note: Retention index • 295
-------
TABLE 6. GAS CHROMATOGRAPHY ANALYSES FOR PROPANE
00
Propane,
Propane,
Carbon,
Propane,
Carbon,
Propane,
Carbon,
Propane,
Carbon,
Propane,
Carbon,
Propane,
Propane,
Carbon,
Propane,
Carbon,
Propane,
Carbon,
Propane,
Carbon,
Propane,
Carbon,
ppm
ppm
ppm ;
g/-27
g/m3"
g/sec
g/sec a;
Ib/ftST
Ib/ft^
Ib/hr
Ib/hr
ppm
ppm
PP™ .,/
~a/
g/m32
g/sec
g/sec ,
lb/fta/
Ib/ft3^
Ib/hr
Ib/hr
Z efficiency
Run No. 1-1
2,890
2,890
8,670
5.28
4.32
46.2
37.8
3.29 x 10"4
2.69 x 10"4
366
300
Run No. 1-0
12
12
36
0.022
0.018
0.52
0.42
1.40 x 10"6
1.10 x 10~6
4.1
3.4
98.9
Run No. 2-1
2,620
2,620
7,860
4.78
3.91
57.7
47.2
2.98 x 10"4
2.44 x IO"4
457
374
Run No. 2-0
63
63
189
0.115
0.094
3.1
2.5
7.20 x 10"6
5.90 x 10"6
24.4
19.9
94.7
Run No. 3-1
2,760
2,760
8,280
5.04
4. L2
60.6
49.6
3.14 x 10"4
2.57 x 10"4
480
393
Run No. 3-0
69
69
207
0.126
0.103
3.23
2.64
7.90 x IO"6
6.40 x IO"6
25.6
20.9
94.7
Run No. 3-AOR
3,170
3,170
9,510
5.79
4.74
59.6
48.8
3.61 x 10~4
2.95 x 10"4
473
387
Run No. 4-1
4,220
4,220
12,660
7.70
6.30
73.5
60.1
4.81 x 10"4
3.93 x 10"4
583
477
Run No. 4-0
39
39
117
0.071
0.058
1.80
1.47
4.40 x 10"6
3.60 x 10"6
14.3
11.7
97.5
Run No. 5-1
3,860
3,860
11,580
7.05
5.77
63.5
52.0
4.40 x lO"4
3.60 x IO"4
504
412
Run No. 5-0
36
36
108
0.066
0.054
1.65
1.35
4.10 x IO"6
3.40 x 10"6
13.1
10.7
97.4
Run No. 6-1
3,850
3,850
11,550
7.03
5.75
61.2
50.1
3.82 x IO"4
3.12 x IO"4
485
397
Run No. 6-0
33
33
99
0.060
0.049
1.46
1.19
3.80 x 10"6
3.10 x IO"6
11.5
9.4
97.6
Run No. 7-T
3,510
3,510
10,530
6.41
5.24
57.6
47.1
4.38 x IO"4
3.59 x 10"4
456
373
Run No. 7-0
0.172
0.172
0.516
3.14 x IO"4
2.57 x IO"4
7.56 x IO"3
6.18 x 10"3
1.96 x 10"8
1.60 x-10"8
0 . 060
0.049
99.99
Run No. 8-1
3,760
3,760
11,280
6.86
5.62
66.0
54.0
4.00 x IO"4
3.27 x 10"4
523
428
Run No. 8-0
0.089
0.089
0.267
1.62 x IO"4
1.33 x IO"4
4.04 x 10"3
3.31 x IO"3
1.01 x 10"8
8.30 x 10~9
0.032
0.026
99.994
Run No. 9-1
3,070
3,070
9,210
5.60
4.59
49.1
40.1
3.50 x 10"4
2.86 x 10"4
389
318
Run No. 9-0
0.056
0.056
1.68
1.02 x IO"4
8.40 x 10"5
2.50 x IO"3
2.00 x 10"3
6.40 x HT9
5.20 x IO"9
0.020
0.016
99.995
aj Dry standard conditions
Note: Retention index
300
-------
TABLE 7. GAS CHROMATOGRAPRY ANALYSES FOR ACETALDEHYDE
Propane, ppm
Acetaldehyde, ppm
Carbon, ppm
Acetaldehyde, g/m-' —
Carbon, g/m3 —
Acetaldehyde, g/sec
Carbon, g/sec .
Acetaldehyde, lb/ft3 -
Carbon, lb/ft3 il
Acetaldehyde, Ib/hr
Carbon, Ib/hr
Propane, ppm
Acetaldehyde, ppm
Carbon, ppm
Acetaldehyde, g/m — '
Carbon, g/m S.I
Acetaldehyde, g/sec
Carbon, g/sec .
Acetaldehyde, lb/ft —
Carbon, lb/ft3 Sf
Acetaldehyde, Ib/hr
Carbon, Ib/hr
7. Efficiency
Run No. 1-1
( 1Z>-'
116
314
627
0.572
0.312
5.01
3.57 x 10"'
1.95 x 10
39.7
21.7
Run No. 1-0
0.89
2.41
4.81
4.39 x 10
2.40 x 10
0.104
0.057
2.74 x 10
1.49 x 10
0.82
0.449
97.9
Run No. 2-1
5«
151
303
0.28
0.151
3.3
1.82
1.72 x 10"
9.4 x 10
26.4
14.4
Run No. 2-0
(2X>fe/
4.5
12.1
24.2
O.O221
0.0120
0.60
°'32 -6
1.38 x 10
7.6 x 10
4.7
2.53
82.4
Run No. 3-1
( 17.)V
70
189
378
0.35
0.188
4.2
2.15 x 10"^
1.18 x 10
32.9
18.0
Run No. 3-0
(2%)by
4.8
12.9
25.9
0.0237
0.0129
0.606
0.329
1.48 x 10
8.1 x 10
4.8
2.62
85.4
Run No. 3-AOG Run No. 4-1
( lZ)b/ (6%)b/
4.7 78
12.7 21
25 422
0.023 0.385
0.0126 0.210
.59 3.69
.32 2.01
1.45 x 10" 2.40 x 10"^
7.9 x 10" 1.31 x 10
4.7 29.3
2.6 16.0
Run No. 4-0
(5%)h/
1.9
5.1
10.2
9.3 x 10
5.1 x 10
0.24
0.13
5.8 x 10 '
3.2 x 10
1.9
1.0
93.8
Run No. 5-1
'(4Z)i/
69
186
373
0.340
0.186
3.05
1.66
2.12 x 10"^
1.16 x 10
24.2
13.2
Run No. 5-0
( !%)]>/
1.6
4.3
8.6
7.9 x 10
4.3 x 10
0.20
0.11
4.9 x 10 '
2.7 x 10
1.6
0.86
93.5
Run No. 6-1
63
170
341
0.311
0.170
2.71
1.48
1.94 x 10
1.06 x 10"
21.5
11.7
Run No. 6-0
(2%)fe/
1.4
3.9
7'7 -3
7.0 x 10
3.8 x 10
0.17
0. 093
4.3 x 10
2.4 x 10"
1.3
0.73
93.8
Run No. 7-1
( IDS'
76
205
411
0.375
0.205
3.37
1.84
2.34 x 10"^
1.28 x 10
26.7
14.6
Run No. 7-0
0.25
0.68
1.4 3
1.2 x 10 ,
6.7 x 10
0.030
0. 016
7.7 x 10
4.2 x 10"
0.24
0.13
99.1
Run No. 8-1
( ITL)-^
74
200
400
0.365
0.199
3.51
1.92
2.28 x 10"^
1.24 x 10
27.8
15.2
Run No. 8-0
0.058
0.157
0.31 ,
2.9 x 10
1.56 x 10
7.1 x 10
3.9 x 10
1.78 x 10
9.7 x 10
0.056
0.031
99.8
Run No
( 1*
88
238
476
0.434
0.237
3.80
2.07
2.71 x
1.48 x
30.1
16.4
Run No
0.107
0.289
0.578
5.28 x
2.88 x
.0129
7.02 x
3.29 x
1.80 x
0.102
0.056
99.7
. 9-1
ID"*
10
. 9-0
-4
10
10
-3
10 I
10
10"
£/ Dry standard conditions
by Found In condensate fraction
Note: Retention Index = 375
-------
TABLE 8. GAS CHROMATOGRAPHY ANALYSES FOR BUTENES
Propane, ppm
Butenes, ppm
Carbon, ppra
Butenes, g/m ~.
, .3 a/
Carbon, g/m —
Butenes, g/sec
Carbon, g/sec
Butenes, lb/ft3 £/
Carbon, lb/ft -'
Butenes, Ib/hr
Carbon, Ib/hr
Run No. 1-1
12.2
9.4
37.6
0.0218
0.0187
0.191
0.164
1.36 x 10~'
1.17 x 10
1.52
1.30
Run No. 2-1
13.8
10.6
42.5
0.0247
0.0212
0.298
0.255
1.54 x 10"'
1.32 x 10
2.36
2.02
Run No. 3-1
(37. >b/
15.9
12.3
48.9
0.0284
0.0243
0.341
0.293
1.78 x 10"'
1.52 x 10
2.71
2.32
Run No. 3-AOG
lst)r
14.9
11.4
46.0
0.0267
0.0229
0.275
0.236
1.66 x 10"'
1.43 x 10"
2.18
1.87
Run No. 4-1
31.4
24.2
96.9
0.0562
0.0482
0.537
0.460
3.51 x 10"'
3.00 x 10
4.26
3.65
Run No. 5-1
30.9
23.7
95-1
0.0552
0.0474
0.498
0.427
3.45 x 10"
2.96 x 10
3.95
3.38
Run No. 6-1
15.2
11.7
46.8
0.0272
0.0233
0.237
0.203
1.70 x 10"'
1.45 x 10"6
1.88
1.61
Run No. 7-1
(57. >fe'
14.9
11.5
45.9
0.0267
0.0229
0.240
0.205
1.66 x 10"'
1.43 x 10
1.90
1.63
Run No. 8-1
(207.)b/
16.0
12.3
49.3
0.0286
0.0245
0.275
0.236
1.79 x 10"'
1.53 x 10"5
2.18
1.87
Run No
(67.)
16.1
12.4
49.6
0.0288
0.0247
0.252
0.216
1.80 x
1.54 x
2.00
1.72
0/9'1
10"6
Run No. 1-0 Run No. 2-0 Run No. 3-0
Run No. 4-0 Run No. 5-0 Run No. 6-0 Run No. 7-0 Run No. 8-0 Run No. 9-0
(167.)^' (50%)by
Propane, ppm
Butenes, ppm
Carbon, ppm
Butenes, S/ty y
Carbon, g/m —
Butenes, g/sec . N
Carbon, g/sec .
Butenes, lb/ft •*'
Carbon, lb/ft -'
Butenes, Ib/hr
Carbon, Ib/hr
% Efficiency
0.14
0.11
2.5 x 10
c/ 2'1 * 10_3
r- 6.4 x 10
5.5 x 10'J
1.6 x 10
1.3 x 10"
0.51
0.044
97.8
1.4
1.1
4.4
2.59 x 10
2.2 x 10
.066
.056 •
1.6 x 10"'
1.3 x 10"
0.52
0.45
80.6
0.94
0.73
2.90
1.69 x 10
1.45 x 10"
0.043
0.037
1.05 x 10"
9.0 x 10"
0.34
0.290
92.1
0.64
0.49
1.96 .,
1.14 x 10
9.8 x 10"
0.028
0.024
7.1 x 10"
6.1 x 10"
0.23
0.194
94.3
0.38
0.29
1.17 ,
6.8 x 10
5.8 x 10"
C.I
1.64 x 10 NIT" N
1.41 x 10
4.2 x 10"
3.5 x 10"
0.130
0.116
92.8
c/
c/
r- ND-
- -. . . .
af Dry standard conditions
bf Found in condensate fraction
c/ NO - Not detected
Note: Retention index = 410
-------
TABLE 9. GAS CHROMATOGRAPHY ANALYSES FOR ACROLEIN
Propane, ppm
Acrolein, ppm
Carbon, ppm
Acroleln, g/m3^'
Carbon, g/m3J'
Acrolein, g/sec
Carbon, g/sec
Acroleln, lb/ft3^'
Carbon, Ib/ft3j'
Acrolein, Ib/hr
Carbon, Ib/hr
Propane, ppm
Acrolein, ppm
Carbon, ppm
Acroleln, g/m3!/
Carbon, g/m3-S'
Acroleln, g/sec
Carbon, g/sec
Acroleln, Ib/ft3^'
Carbon, Ib/ft3^
Acroleln, Ib/hr
Carbon, Ib/hr
1. efficiency
Run No. l-I
1,360
2,270
6,820
5.28
3.40
46.2
29.7
3.29 x 10'4
2.12 x 10'4
367
236
Run No. 1-0
0.24
0.40
1.20
9.3 x KT4
5.0 x 10"4
0.022
0.0142
5.8 x 10'8
3.7 x 10'8
0.175
0.112
99.95
Run No. 2-1
652
1,090
3,270
2.53
1.63
30.5
19.6
1.58 x ID" 4
1.02 x 10"4
242
156
Run No. 2-0
5.6
9.4
28.1
0.0218
0.0140
0.58
0.37
1.36 x 10'6
8.7 x 10'7
4.6
2.96
98.1
Run No. 3-1
909
1,520
4,560
3.53
2.27
42.5
27.3
2.20 x 10~4
1.42 x 10"4
337
216
Run No. 3-0
14.6
24.4
73.2
0.0567
0.0365
1.45
0.93
3.54 x 10'6
2.27 x HT6
11.5
7.40
96.6
Run No. 3-AOG
990
1,660
4,970
3.85
2.47
39.6
25.5
2.47 x 10"4
1.54 x 10"4
314
202
Run No. 4-1
906
1,510
4,540
3.52
2.26
33.6
21.6
2.20 x 10"4
1.41 x lO'4
266
171
Run No. 4-0
1.0
1.7
5.0
3.9 x 10"3
2.5 x UT3
0.098
0.063
2.4 x 10~7
1.6 x 10'7
0.78
0.50
99.7
Run No. 5-1
766
1,280
3,840
2.98
1.91
26.8
17.2
1.86 x 10'4
1.19 x 10~4
213
137
Run No. 5-0
0.31
0.52
1.6
1.2 x 10"3
7.7 x 10"4
0.030
0.019
7.5 x HT8
4.8 x 10'8
0.24
0.15
99.9
Run No. 6-1 Run No. 7-1 Run No. 8-1 Run No. 9-1
662 795 754 893
1,110 1,330 1,260 1,490
3,320 3,990 3,780 4,480
2.57 3.09 2.93 3.47
1.65 1.99 1.88 2.23
22.4 27.7 28.2 30.4
14.4 17.8 18.1 19.5
1.60 x lO'4 1.93 x lO'4 1.83 x 10"4 2.16 x 10'4
1.03 x 10'4 1.24 x KT4 1.17 x KT4 1.39 x 10"4
177 220 223 241
114 141 144 155
Run No. 6-0 Run No. 7-0 Run No. 8-0 Run No. 9-0
0.54 /N "
0.90
2.7
2.1 x 10"3
1.3 x 10'3
0.051 ^^/ ^>/ NDb/
0.033
1.31 x 10'7
8.4 x 10"8
0.40
0.26
99.8 V V v
'
a7 Dry standard conditions.
b7 None detected.
Note: Retention index - 495.
-------
TABLE 10. GAS CHROMATOGRAPHY ANALYSES FOR ACETONE
Propane,
Acetone,
Carbon,
Acetone,
Carbon,
Acetone,
Carbon,
Acetone,
Carbon,
Acetone,
Carbon,
Prop ane ,
Acetone,
Carbon,
Acetone,
Carbon,
Acetone,
Carbon,
Acetone,
Carbon,
Acetone,
ppm
ppm
Ppro ,
g/m3^
g/m3— '
g/sec
g/sec
Ib/ftV
Ib/hr
Ib/hr
ppm
ppm
ppm
g/sec
g/sec
Ib/ft3*/
Ib/ftV
Ib/hr
Carbon, Ib/hr
7. efficiency
Run No. 1-1
62
94
282
0.226
0.141
1.98
1.23
1.41 x 10'5
8.8 x 10"6
15.7
9.8
Run No. 1-0
0.43
0.65
1.96
1.57 x 10"3
9.7 x 10"4
0.037
0.023
9.8 x ID"8
6.1 x 10-8
0.29
0.183
98.1
Run No. 2-1
59
90
269
0.215
0.134
2.60
1.61
1.34 x 10'5
8.3 x 10~6
20.6
12.8
Run No. 2-0
(27.)V
4.1
6.2
18.6
0.0149
9.10 x 10' 3
0.40
0.25
9.3 x 10- 7
5.8 x 10"7
3.2
1.96
84.7
Run No. 3-1
82
124
375
0.301
0.186
3.62
2.25
1.87 x 10'5
1.16 x UT5
28.7
17.8
Run No. 3-0
(2%)b/
4.5
6.8
20.4
0.0164
0.0102
0.42
0.26
1.02 x 10~6
6.4 x 10"7
3.3
2.07
88.4
Run No. 3-ADG
(47. Xb/
89 •
135
407
0.327
0.203
3.36
2.09
2.03 x 10"5
1.26 x 10'5
26.6
16.5
Run No. 4-1
141
214
640
0.515
0.319
4.91
3.05
3.21 x 10"5
1.99 x 10'5
39.0
24.2
Run No. 4-0
(237. &
0.69
1.05
3.13
2.52 x lO"3
1.56 x 10"3
0.064
0.0395
1.57 x 10"7
9.8 x 10-8
0.50
0.313
98.7
Run No. 5-1
(28% )b/
124
188
565
0.453
0.282
4.08
2.54
2.82 x 10'5
1.75 x 10'5
32.4
20.1
Run No. 5-0
(37. ^
2.3
3.4
10.3
8.3 x 10"3
5.1 x 10"3
0.207
0.129
5.2 x ID' 7
3.3 x 10-7
1.64
1.02
94.9
Run No. 6-1 Run No. 7-1
128 99
194 150
583 450
0.468 0.361
0.290 0.224
4.07 3.24
2.53 2.01
2.92 x 10"5 2.25 x 10"5
1.81 x 10'5 1.40 x 10"5
32.3 25.7
20.0 16.0
Run No. 6-0
(177.}fe' Run No. 7-0
0.80 A
1.22
3.66
2.94 x 10" 3
1.82 x 10' 3
0.071 ^c/
0.044
1.82 x ID" 7
1.13 x ID"7
0.56
0.35
98.2 ^
Run No. 8-1 Run No. 9-1
117 106
178 161
534 483
0.428 0.387
0.266 0.240
4.12 3.39
2.56 2.11
2.66 x 10'5 2.41 x 10"5
1.65 x 10'5 1.50 x 10'5
32.6 26.9
20.3 16.7
Run No. 8-0 Run No. 9-0
A />
Nl>c/ upc/
\ t \ t
al Dry standard conditions.
b_/ Found In condensate fraction.
c_l None detected.
Note: Retention Index - 505.
-------
TABLE 11. GAS CHROMATOGRAPHY ANALYSES FOR UNKNOWN PEAK
Run No. 1-t Run No. 2-1 Run No. 3-1 Run No. 3-Aon Run No. 4-1 Run No. 5-1 Run No. 6-1 Run No. 7-1 Run No. 8-1 Run No. 9-1
Propane, ppm 2.0 2-2 3.0 3.9 5.0 '
Propane, ppm 2.0 2.2 3.0 3.9 5.0
Carbon, ppm 6-0 6.6 9.0 11.7 15.0
Propane, g/m3*/ 3.7 x 10~3 4.0 x 1Q-3 5.5 x 10-3 7.1 x 1Q-3 9.1 x 1Q-3
Carbon, g/m3a/ 3.0 x 10-3 3.3 x 10-3 4.5 x 10-3 5.8 x 10-3 7.5 x iQ-3
2.4 4.4 4.0 4.0
2.4 4.4 4.0 4.0
7.2 13.2 12.0 12.0
4.4 x 10~3 8.0 x 10~3 7.3 x 10~3 7.3 x 10"3
3.6 x 10-3 6.6 x 10~3 6.0 x 10"3 6.0 x 10"3
Propane, g/sec 0.032 0.048 0.066 0.073 0.087 ND^/ 0.038 0.072 0.070' 0.064
Carbon, g/sec 0.026 0.040 0.054 0.060 0.071
Propane, Ib/ft3!/ 2.3 x 10-7 2.5 x 10~7 3.4 x 1Q-7 4.4 x HT7 5.7 x 10"7
Carbon, Ib/ft3*' 1.9 x 10~7 2.0 x 10~7 2.8 x 10"7 3.6 x 10-7 4.7 x 10"7
Propane, Ib/hr 0.25 0.52 0.50 0.69
Carbon/lb/hr 0.21 0.43 0.48 0.56
0.031 0.059 0.057 0.052
2.7 x 10-7 5.0 x 10-7 4.6 x 10"7 4.6 x HT7
2.2 x 10-7 4.1 x 10-7 3.7 x 10~7 3.7 x 10"7
0.30 0.57 0.56 0.51
0.25 0.47 0.46 0.41
Run No. 1-0 Run No. 2-0 Run No. 3-0 Run No. 4-0 Run No. 5-0 Run No. 6-0 Run No. 7-0 Run No. 8.0 Run No. 9-0
Propane, ppm
Propane, ppm
Carbon, ppm
Propane, g/m3.£/
Carbon, g/m3^/
Propane, g/sec
Carbon, g/sec I
Propane, Ib/ft3£/
Carbon, Ib/ft3?/
Propane, Ib/hr
Carbon, Ib/hr
% efficiency >
1.5 /•
1.5
4.5
2.7 x 10-3
2.2 x HT3
0.070
/
A
D ND 0.057 ND ND ND 1
1.7 x 10~ 7 i
1.4 x 10"7
0.56
0.46
V \
V
f.
"D »
'
/v
D I
'
v negative
D
a_/ Dry standard conditions
b/ ND - None detected
Note: Retention index = 590
-------
TABLE 12. GAS CHROMATOGRAPHY ANALYSES FOR. 1-HEXENE
Run No. l-I Run No. 2-1 Run No. 3-1 Run No. 3-AOO Run No. 4-1 Run No. 5-1 Run No. 6-1 Run No. 7-1 Run No. 8-T Run No. 9-1
Propane, ppm 3.8 1.6 3.0 1.8 2.2 4.3 4.0 4.6 5.4 4.4
1-hexene, ppm 2.0 0.83 1.6 0.93 1.1 2.2 2.1 2.4 2.8 2.3
Carbon, ppm 11.8 5.0 9.3 5.6 6.8 13.4 12.4 14.3 16.8 13.7
1-hexene, g/ra3^' 6.9 x 10"3 2.9 x 10~3 5.4 x 10"3 3.3 x 10' 3 4.0 x 10~3 7.8 x 10~3 7.2 x 10~3 8.3 x 10~3 9.8 x 10"3 8.0 x 10~3
Carbon, g/m3^' 5.9 x 10-3 2.5 x 10'3 4.6 x lO"3 2.8 x J0~3 3.4 x 10"3 6.7 x UT3 6.2 x 10"3 7.1 x 10"3 8.4 x 10"3 6.8 x 10"3
1-hexene, g/scc 0.060 0.035 0.065 0.034 0.038 0.070 0.063 0.075 0.094 0.070
Carbon, g/sec 0.052 0.030 0.056 0.029 , 0.033 0.060 0.054 0.064 0.80 0.060
1-hexene, Ib/ft3*/ 4.3 x 10"7 1.8 x 10"7 3.4 x 10~7 2.0 x 10"7 2.5 x 10"7 4.8 x 10"7 4.5 x 10" 7 .5.2 x 10"7 6.1 x 10"7 5.0 x 10"7
Carbon, Ib/ft3!7 3.7 x 10"7 1.5 x 10~7 2.9 x 10"7 1.7 x 10~7 2.1 x 10"7 4.2 x 10"7 3.9 x 10~7 4.4 x 10~7 5.2 x 10"7 4.3 x 10"7
1-hexene, Ib/hr 0.48 0.28 0.52 0.27 0.30 0.56 0.50 0.60 0.74 0.55
Carbon, Ib/hr 0.41 0.24 0.44 0.23 0.26 0.48 0.43 0.51 0.64 0.47
Run No. 1-0 Run No. 2-0 Run No. 3-0 Run No. 4-0 Run No. 5-0 Run No. 6-0 Run No. 7-0 Run No. 8-0 Run No. 9-0
Propane, ppm
1-hexene, ppm
Carbon, ppm
1-hexene, g/ra3J!/
Carbon, g/m3?'
1-hexene, g/sec N
Carbon, g/sec
1-hexene, Ib/ft3^/
Carbon, Ib/ft3!'
1-hexene, Ib/hr
Carbon, Ib/hr
% efficiency
1.1
0.57
3.4
2.0 x 10~3
1.7 x 10-3
nk/ ND 0.051 ND ND NO ND ND ND
0.044
1.2 x KT7
1.1 x 10~7
0.40
0.35
20
ei/ Dry standard conditions
b/ ND - None detected
Note: Retention Index = 615
-------
TABLE 13. GAS CHROMATOGRAPHY ANALYSES FOR 2-HEXENE
Run No. 1-1 Run No. 2-1 Run No. 3-1 Run No. 3-AOG Run No. 4-1 Run No. 5-1 Run No. 6-1 Run No. 7-1 Run No. 8-1 Run No. 9-1
Propane, ppm
2-Hexene, ppm
Carbon, ppm .
2-Hexene, g/m .—
„ ,3 a/
Carbon, g/ra ~
2-Hexene, g/sec
Carbon, g/sec ,
2-Hexe'ne, Ib/ft -
Carbon, Ib/ft3 — '
2-Hexene, Ib/hr
Carbon, Ib/hr
11.6
6.0
36.1
0.0210
0.0180
0.184
0.157
1.31 x 10"°
1.12 x 10
1.46
1.25
6.6
3.4
20.5
0.0119
0.0102
0.144
0.123
7.4 x 10"'
6.4 x 10
1.14
0.98
1.5
7.8
47
0.027
0.023
0.33
0.28
1.7 x 10~*
1.4 x 10"
2.6
2.2
12
6.2
37
0.022
0.019
0.22
0.19
1.4 x 10"*
1.2 x 10
1.8
1.5
19
9.9
59 .
0.034
0.029
0.33
0.28
2.1 x 10"*
1.8 x 10
2.6
2.2
20
10.4
62
0.036
0.031
0.33
0.28
2.3 x 10"*
1.9 x 10
2.6
2.2
17
8.8
53
0.031
0.036
0.27
°'23 -6
1.9 x 10_6
1.6 x 10 '
2.1
1.8
21
10.9
65
0.038
0.033
0.34
0.29
2.4 x 10"
2.0 x 10"
2.7
2.3
21
10.9
65
0.038
0.033
0.36
0.31
2.4 x 10
2.0 x 10
2.9
2.5
22
11.4
68
0.040
0.034
0.35
0.30
2.5 x 10"
2.1 x 10"
2.8
2.4
Run No. 1-0 Run No. 2-0 Run No. 3-0
Run No. 4-0 Run No. 5-0 Run No. 6-0 Run No. 7-0 Run No. 8-0 Run No. 9-0
Propane," ppm
2-Hexene, ppm
Carbon, ppm .
2-Hexene, g/m —
Carbon, "g/m — '
2-Hexene,' g/sec ND
Carbon, g/sec .
2-Hexene, Ib/ft -
Carbon, Ib/ft3 *
2-Hexene, Ib/hr
Carbon, Ib/hr
7. Efficiency N
i- NC
>
^ 4.2
2.2
13.1
7.6 x 10";?
6.5 x 10" J
I- 0. 194 W
0.167
4.7 x 10"^
4.1 x 10"'
1.54
1.32
f 40 1
^ ND
f t
^ ND&' ND
'-' NI
[ t
1
i/ NDb/
\
at Dry standard conditions
b/ ND - None detected
Note: Retention index = 635
-------
TABLE 14. GAS CHROMATOGRAPHY ANALYSES FOR ACRYLIC ACID
Run No. 1-t Run No. 2-1 Run No. 3-1 Run No. 3-AOG Run No. 4-1 Run No. 5-1 Run No. 6-1 Run No. 7-1 Run No. 8-1 Run No. 9-1
Propane
Acrylic
Carbon,
Acrylic
Carbon,
Acrylic
Carbon,
Acrylic
Carbon,
Acrylic
Carbon,
, ppm
Acid, ppm
ppm
Acid, g/m3^'
g/m^/
Acid, g/sec
g/sec
Acid, Ib/ft3*/
Ib/ft3*/
Acid, Ib/hr
Ib/hr
34
53
160
0.159
0.080
1.39
0.70
9.9 x 10"6
5.0 x 10~6
11.0
5.5
28
44
132
0.131
0.066
1.58
0.79
8.2 x 10"6
4.1 x 10'6
12.5
6.3
40
63
188
0.187
0.094
2.25
1.13
1.17 x 10"5
5.8 x 10"6
17.9
8.9
48
75
226
0.225
0.112
2.31
1.16
1.40 x 10~5
7.0 x 10"6
18.4
9.2
61
96
287
0.286
0.143
2.72
1.36
1.78 x 10"5
8.9 x 10~6
21.6
10.8
61
96
287
0.286
0.143
2.57
1.29
1.78 x 10" 5
8.9 x 10"6
20.4 .
10.2
49
77
230
0.229
0..115
2.00
1.00
1.43 x 10"5
7.2 x 10"6
15.8
7.9
58
91
273
0.272
0.136
2.44
1.22
1.70 x 10" 5
8.5 x 10~6
19.3
9.7
56
88
263
0.262
0.131
2.52
1.26
1.64 x 10"5
8.2 x 10"6
20.0
10.0
57
89
268
0.267
0.133
2.34
1.17
1.66 x
8.3 x
18.5
9.3
ID"5
io-6
Run No. 1-0 Run No. 2-0 Run No. 3-0
Run No. 4-0 Run No. 5-0 Run No. 6-0 Run No. 7-0 Run No. 8-0 Run No. 9-0
Propane, ppm
Acrylic Acid, ppm
Carbon, ppm
Acrylic Acid, g/m35/
Carbon, g/m3.5/
Acrylic Acid g/sec
Carbon, g/sec K
Acrylic Acid, Ib/ftW
Carbon, Ib/ft3^
Acrylic Acid, Ib/hr
Carbon, Ib/hr
% efficiency
D^ N
18
28
85
0.084
0.042
2.2
D 1.1 P
5.3 x 10"6
2.6 x 10~6
17
8.6
3.4
D N
D ^
'
D ' ^
D N
D N
)
a/ Dry standard conditions
b/ ND - None detected
Note: Retention Index = 750
-------
b/
TABLE 15. GAS CHROMATOGRAPHY ANALYSES FOR TOTAL HYDROCARBONS-
Propane, ppm
Hydrocarbons, ppm
Carbon, ppm
Hydrocarbons, g/m3^/
Carbon, g/m3^./
Hydrocarbons, g/sec
Carbon, g/sec
Hydrocarbons ,
Carbon, Ib/ft3a/
Hydrocarbons, Ib/hr
Carbon, Ib/hr
Propane from THC
mode (column
bypass) , ppm
Propane, ppm
Hydrocarbons, ppm
Carbon, ppm
Hydrocarbons , g/nf3j!/
Carbon, g/m3£'
Hydrocarbons, g/sec
Carbon, g/sec
Hydrocarbons,
Carbon, Ib/ft32/
Hydrocarbons, Ib/hr
Carbon, Ib/hr
Propane from THC
mode (column
bypass), ppra
% efficiency
Run No. 1-1
10,340
12,540
34,530
22.1
17.2
193
150
1.38 x ID"3
1.07 x 10-3
1,530
1,190
8,990
Run No. 1-0
85
150
257
0.156
0.115
3.71
3.01
9.8 x 10~6
7.9 x 10"6
29.4
24.0
58
98.0
Run No. 2-1
8,676
10,080
27,928
17.4
13.9
209.5
592
1.08 x ID"3
8.68 x HT4
1,660
1,330
8,340
Run No. 2-0
321
530
983
0.607
0.404
16.3
13.1
3.78 x 10"5
3.1 x 10~5
129
103
205
92.3
Run No. 3-1
9,559
11,470
31,170
19.6
15.5
236.2
186.7
1.22 x 10-3
9.68 x 10~4
1,972
1,480
8,160
Run No. 3-0
388
641
1,230
0.800
0.614
20.5
15.8
5.00 x ID" 5
3.82 x 10~5
162
125
231
91.6
Run No. 3-AOG Run No. 4-1
10,630 13,566
12,390 15,263
34,481 30,918
21.6 27.0
17.2 23.6
222.2 257.8
177.0 207.0
1.34 x 10-3 1.69 x 10"3
1.07 x ID"3 1.35 x 10" 3
1,760 2,045
1,400 1,640
10,040 12,440
Run No. 4-0
160
252
473
0.288
0.234
7.26
5.96
1.80 x lO-5
1.46 x ID"5
58
47.2
97
97.1
Run No. 5- 1
12,470
14,210
39,900
24.7
19.87
221.3
177.9
1.54 x 10-3
1.24 x 10"3
1,770
1,420
10,930
Run No. 5-0
149
242
450
5.1
0.228
6.8
5.6
1.7 x 10-5
1.4 x 10-5
54.3
44.3
94
96.9
Run No. 6-1
12,340
14,070
39,250
24.2
19.5
210.8
170.2
1.45 x 10-3
1.17 x Kf3
1,670
1,350
13,240
Run No. 6-0
163
273
487
0.296
0.242
7.1
5.8
1.88 x 10-5
1.53 x 10" 5
56.5
46.3
99
96.6
Run No. 7-1
11,470
13,170
36,884
22.9
18.1
206.0
165
1.47 x HP3
1.18 x 10~3
1,630
1,310
10,480
Run No. 7-0
1.2
3.1
4.2
3.1 x 10~3
2.1 x 10"3
7.3 x 10~2
5 x 10"2
1.91 x 10" 7
1.64 x 10~7
0.59
0.4
11.3
99.97
Run No. 8-1
12,150
13,850
38,888
24.1
19.4
231.8
186
1.48 x 10-3
1.18 x 10"3
1,840
1,480
10,460
Run No. 8-0
0.27
0.51
0.92
6.7 x 10-*
4.6 x 10"4
1.65 x 10~2
1.15 x 10" 2
4.36 x 10"8
2.9 x 10~8
0.131
0.091
9.2
99.99
Run No. 9-1
10,500
12,490
34,094
21.4
19.1
187.7
149
1.34 x 10-3
1.06 x 10" 3
1,490
1,180
9,590
Run No. 9-0
0.32
0.68
2.14
9.2 x 10~4
6 x 10-4
2.23 x 10"2
2.0 x 10" 2
5.1 x 10"8
3.2 x 10"8
0.183
0.116
9.2
99.99
a/ Dry standard conditions.
b/ Measured as the sum of observed peaks.
-------
00
I I I I I I I I I I I I I I I I 1 I
01 234567
10 II 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39
Figure 1. Run 3 - Inlet chromatogram, Taft, Louisiana.
-------
9 10 II 12 13 14 15 16 17 16 19 20 21 22 23 24 25 26 27 28 29 3: 31 32 33 34 3; 36 37 38 39 40
01 234567
Figure 2. Run 3 - Acrylic acid off-gas gas chromatogram, Taft, Louisiana.
-------
IVVXI I I I I
01 234567
Figure 3. Run 3 - Outlet chromatogram, Taft, Louisiana.
-------
Table 16 shows the results of the total gaseous nonmethane organic (TGNMO)
sampling performed simultaneously with the GC integrated gas sampling. Also
included are comparison readings made by GC/FID from each tank sample on site
as well as comparison totals from the integrated gas samples. The general drop
in inlet samples between the on-site measurements and final tank analyses may
indicate that even the lighter components are unstable. Propylene polymerization
is one possibility. The outlet samples show signs of possible contamination,
especially Runs 7 through 9. There is a high probability that the true hydro-
carbon levels are close to the values reported by GC/FID integrated sampling.
Also, some of the outlet tanks showed extreme variability for successive injec-
tions. Some of the tank samples by GC/FID are averaged over 10 and 20 injec-
tions. Appendix A includes the original TGNMO sampling and analysis data.
Table 17 shows GC/FID analyses for selected tank TGNMO samples for compo-
nent identification/quantification. The sum of the peaks is in reasonable agree-
ment with the total hydrocarbon (THC) values in Table 16 except for the expected
inflated THC readings at low levels. Figures 4 and 5 show typical chromatograms
from the tank samples.
Table 18 shows the evacuated flask aldehyde sampling results with compari-
son values by GC/FID. Data sheets for the aldehyde sampling are in Appendix B.
The outlet values reported are of limited value, since the sensitivity limits
were being approached. The aldehyde method may also be responding to inter-
ferences or high molecule weight aldehydes not detectable by GC/FID.
Table 19 (metric) and 20 (English) summarize the general process parameters,
flow rates, and bulk gas compositions for the different sampling streams. Appen-
dix C includes the pitot traverse data. Appendix D contains the integrated gas
sampling data sheets, and Appendix E contains the moisture train data.
Table 21 shows the results of the fuel gas analyses by GC/FID. A typical
chromatogram is shown in Figure 6. Table 22 shows the results of the NOX
sampling. Data sheets for NOX sampling are in Appendix F.
21
-------
^ABLEJ.6. TOTAL GASEOUS NON-METHANE ORGANIC (TGNMO) SAMPLING RESULTS
Trap fraction - ppm C.
Tank fraction - ppm C.
Total - ppm C
.
UCI-1 OCI-1F UCI-2 UCI-2F UCI-3 UCI-3F UCI-4 UCI-4F UCI-5 UCI-5F UCI-6 - UCI-7 UCI-8 UC1-9
2,700 3,330 700 4,070 1,860 6,270 4,530 6,680 5,880 6,220 3,390 4,890 4,560 6,000
18,590 17,040 16,180 16,510 17,470 15,570 23,650 23,600 21,600 21,560 20,310 18,590 20,440 10,920
21,290 20,370 16,880 20,580 19,330 21,840 28,180 30,280 27,480 27,780 23,700 23,480 25,000 16,920
3,720 3,160 2,270 2,150 2,720 2,170 4,220 3,540 2,960 3,480 3,680 3,650 3,450
Total Hydrocarbon/FID mode
reading of tank ppm as
propane (as is-uncorrected for N2 dilution)
THC/FID reading of tank 31,340 28,000 22,670 22,350 23,800 22,830 33,790 32,720 29,780 29,850 30,760 29,890 28,870
N2 dilution corrected ppm
as Cj£/
GC/FID sum - ppm as carbonk/ 34,530 34,530 27,930 27,930 31,170 31,170 30,920 30,920 39,900 39,900 39,250 36,880 38,890 34,090
of integrated gas sample
Trap fraction - ppm C,
Tank fraction - ppm C,
Total - ppm C,
UCO-1F
80
56
136
UCO-3A
735
209
944
UCO-3B
520
144
664
UCO-AA
640
114
754
UCO-4B
235
91
326
UCO-5A
308
84
392
UCO-5B
513
91
604
UCO-6
329
140
469
UCO-7
234
50
284
UCO-8
219
34
253
UCO-9
c/
55
-
Total hydrocarbon/FID mode 25.7
reading of tank ppm as
propane (as is-uncorrected for N2 dilution)
THC/FID reading of tank 206
N2 dilution corrected ppm
GC/FID sum - ppm as carbonk/
of Integrated gas sample
257
101
1,090
1,230
94
1,143
1,230
47
387
473
42
297
473
52
453
450
49
447
450
33
448
487
21.4
178
4.2
12.4
105
0.92
4.8
42
2.1
aj Three times the value measured as propane. The tanks were originally at negative pressure arid pressurized on-site for the THC field readings.
]>/ Excluding methane.
cf Sample lost.
d/ Note that THC readings by column bypass tend to be high at low levels due to flame upsets and pressure changes from Injection.
-------
TABLE 17. TGNMO TANK SAMPLES ANALYZED BY GAS CHROMATOGRAPHY
Components
Methane
Ethylene
Acetylene
Ethane
Propylene
Propane
Acetaldehyde
Butenes
Acrolein
Acetone
Unknown peak
1-Hexene
2-Hexene
Acrylic acid
Total of all peaks
UCO-6
(ppm as propane)
7.6
21.0
0.33
-
-
9.6
-
-
0.11
0.78
-
-
-
-
39.4
Run
ppm as Cl
103
285
4
-
-
130
-
-
1.5
10.6
-
-
-
-
535
6
UC1-6
, • ,a
(ppm as propane)
83
56
-
34
2,455
1,505
8.0
4.8
32
17
-
-
-
-
4,195
ppm as Cl
690
470
-
280
20,500
12,600
67
40
270
140
-
-
-
-
35,100
Run 8
UCI-8
(ppm as propane)
125
64
-
36
2,220
1,360
9.0
4.8
19.8
-
-
-
-
-
3,840
Run 9
b UCO-9
ppm as GI (ppm as propane) ppm as C]b
1,040 0.051 .45
530 0.023 .20
_
300
18,500
11,300 1.0 8.8
75 -
40 -
165
-
.
_
.
.
32,000 1.1 9.6
a Not corrected for N2 dilution (as Is basis).
b These data are corrected for the N2 pressurizatlon and multiplied by three to convert from propane to Cl response.
-------
16 X 10
2 X 10
N3
.p-
I 1 "I^J I I I I I I I I \ I I I I I I I I I I I I 1 I I I I I I I I I I
0 1 2 3 4 56 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 34
Figure 4. Run 6 - TGNMO Tank UCO-6 chromatogram, Taft, Louisiana.
-------
I I ' I I I -I-
AJV
I I I I I I I I I I I I I I I I I I
01 234567
N3
Ln
9 10 II 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 36
MINUTES
Figure 5. Run 5 - TGNMO Tank UCI-6 chromatogram, Taft, Louisiana.
-------
TABLE 18. ALDEHYDE ANALYSIS RESULTS - BISULFITE REACTION
Run 1-1
Run 2-1
Run 3-1
Run 3-AOG
Run 4-1
Run 5-1
Run 6-1
Run 7-1
Run 8-1
Run 9-1
Run 1-0
Run 2-0
Run 3-0
Run 4-0
Run 5-0
Run 6-0
Run 7-0
Run 8-0
Run 9-0
Aldehyde
g/m as acrolein
6.74
3.22
4.74
5.00
3.56
2.96
2.79
3.41
3.58
3.90
0.027
0.083
0.107
0. 053
0.055
0.055
0.019
0.020
0.012
method
ppm as acrolein
2,900
1,380
2,040
2,150
1,530
1,270
1,200
.1,470
1,540
1,680
12
36
46
23
24
24
8
9
5
a/
Aldehydes- by GC
ppm total
2,680
1,330
1,830
1,810
1,940
1,650
1,460
1,680
1,640
1,890
3.5
27.7
44.1
7.8
8.2
6.0
0.7
0.16
0.29
a/ Sum of acetaldehyde, acrolein, and acetone peaks.
26
-------
TABLE 19. COMPOSITION/FLOW SUMMARY (METRIC UNITS)
Date — Time of start
Outlet:
Stack velocity, m/sec
Flow rate, dsm-Vsec
Mass flow, kg/sec
Temperature, °C
Oxygen, %
Carbon dioxide, %
Moisure, %
Carbon monoxide, ppm
Combustor:
Fuel gas flow, kg/sec
Combustion airflow, kg/sec
Combustion temperature, °C
Air preheater, °C
Inlet, combined feed:
Flow rate, dsm-Vsec
Mass flow, kg/sec —
Temperature, °C
Oxygen, %
Carbon dioxide, %
Moisture, %
Carbon monoxide, ppm
Acid off-gas:
Flow rate, dsmVsec
Mass flow, kg/sec
Oxygen, %
Carbon dioxide, %
Moisture, %
Carbon monoxide, ppm
Run No. 1
11/29—1600
21.59
23.65
31.51
211
7.5
2.7
-5S
530
0.0995
12.21
621
282
8.753
12.30
a/
0.7
1.1
_£'
12,900
Run No. 2
12/2—0900
24.99
26.73
35.67
222
6.2
3.2
16.0
7,510
0.1289
11.76
627
279
12.059
15.60
-a/
2.8
1.0
14.0
12,000
-
-
-
-
-
Run No. 3
12/2—1400
23.88
25.61
34.04
227
6.5
3.8
15.2
7,750
0.1260
11.62
627
281
12.025
15.52
63
2.0
0.8
14.0
12,000
10.300
13.29
0.25
0.75
8.0
12,800
Run No. 4
12/5—0920
22.40
25.31
33.24
202
8.1
3.8
. 14.9.
4,840
0.0980
12.36
627
265
9.539
12.89
69
2.0
2.0
18.9
12,400
Run No. 5
12/5—1500
22.25
25.06
32.95
207
7.6
3.2
14.0
5,000
0.1012
12.13
627
265
9.012
12.80
67
2.0
1.8
25.7
12,400
Run No. 6
12/6—1120
21.64
24.16
32.19
208
7.8
3.6
15.4
5,320
0.1027
11.94
627
268
8.704
12.69
68
1.6
1.9
27.4
9,000
Run No. 7
12/7—0930
21.64
24.06
33.12
221
7.2
4.4
13.0
<10
0.1180
11.98
799
281
8.983
12.12
58
2.6
2.9
18.1
12,800
Run No. 8
12/7—1230
21.39
24.86
34.95
221
7.2
5.0
8.8
<10
0.1170
11.87
799
282
9.615
12.06
57
1.4
1.9
9.5
12,000
Run No. 9
12/8—0900
21.54
24.39
31.79
223
7.6
5.4
11.3
<10
0.1255
11.94
800
282
8.756
10.98
61
1.8
2.9
20.4
12,800
a Data not obtained—assumed to be the same as next run.
b Measured by plant Annubar flow measuring device.
-------
TABLE 20. COMPOSITION/FLOW SUMMARY (ENGLISH UNITS)
NJ
00
Date — Time of start
Outlet:
Stack velocity, ft/min
Flow rate, dscf/min
Mass flow, Ib/hr
Temperature, °F
Oxygen, X
Carbon dioxide, 7,
Moisture, %
Carbon monoxide, ppm
Combustor :
Fuel gas flow, Ib/hr
Combustion airflow, Ib/hr
Combusion temperature, °F
Air preheater, °F
Inlet, combined feed:
Flow rate, dscf/min
Mass flow, Ib/hr^/
Temperature, °F
Oxygen, %
Carbon dioxide, %
Moisture
Carbon monoxide, ppm
Acid off-gas:
Flow rate, dscf/min
Mass flow, Ib/hr
Oxygen, %
Carbon dioxide, %
Moisture, %
Carbon monoxide, ppra
Run No. 1
11/29—1600
4,250
50,110
250,100
411
7.5
2.7
- -'
530
790
96,900
1,150
540
18,540
97,600
-i/
0.7
1.1
12,900
Run No. 2
12/2—0900
4,920
56,640
283,100
432
6.2
3.2
16.0
7,510
1,023
93,300
1,160
535
25,550
123,800
-*}
2.8
1.0
14.0
12,000
-
-
-
-
-
-
Run No. 3
12/2—1400
4,700
54,260
270,100
440
6.5
3.8
15.2
7,750
999
92,200
1,160
537
25,480
123,200
145
2.0
0.8
14.0
12,000
21,810
100,600
0.25
0.75
8.0
12,800
Run No. 4
12/5—0920
4,410
53,610
263,800 -
395
8.1
3.8
14.9
4,840
778
98,100
1,160
509
20,210
102,300
156
2.0
2.0
18.9
12,400
Run No. 5
12/5—1500
4,380
53,090
261,500
404
7.6
3.2
14.0
5,000
803
96,300
1,160
509
19,090
101,600
152
2.0
1.8
25.7
12,400
Run No. 6
12/6—1120
4,260
51,180
255,500
406
7.8
3.6
15.4
5,320
815
94,800
1,160
514
18,440
100,700
154
1.6
1.9
27.4
9,000
Run No. 7
12/7—0930
4,260
50,970
262,800
430
7.2
4.4
13.0
<10
936
95,100
1,470
538
19,030
96,200
136
2.6
2.9
18.1
12,800
Run No. 8
12/7—1230
4,210
52,680
277,400
430
7.2
5.0
8.8
<10
925
94,200
1,470
540
20,370
95,700
135
1.4
1.9
9.5
12,000
Run No. 9
12/8—0900
4,240
51,670
252,300
434
7.6
5.4
11.3
<10
992
94,800
1,470
540
18,550
95,500
141
1.8
2.9
20.4
12,800
a Data not obtained—assumed tr> be the same as next run.
b Measured by plant Annubar flow measuring device.
-------
TABLE 21. FUEL GAS ANALYSIS (ppm as propane)
Retention
Index
100
200
300
375
400
480
500
555
575
590
600
630
670
690
700
755
780
800
830
850
890
920
980
1020
1050
Compound
Methane^/
Ethane
Propane
losbutane
n-Butane
Branched chain C5
n-Pentane
Branched chain C6
Branched chain C6
Branched chain C6
n-Hexane
Branched chain C7
Branched chain 07
Branched chain C7
n-Heptane
C8 + above
C8 +
n-Octane
C8 +
C8 +
C8 +
C8 +
C8 +
C8 +
C8 +
Run 2
175,200
12,880
1,868
251
270
151
97
.
63
25
52
46
68
.
133
108
98
36
147
143
252
194
.
-
Run 3
179,360
12,960
1,695
331
306
159
99
11.2
60
19.3
42
18.1
36
-
36
33
4.0
13.3
4.8
8.0
27
14.3
-
.
Run 4
192,680
12,810
2,218
651
607
338
214
5.1
54
19.0
47
22
44
19.0
69
55
6.9
8.7
50
.
20
9.4
4.1
5.6
Run 5
188,700
12,650
963
235
227
135
93
6.8
63
26
41
29
67
30
116
100
101
76
13.4
25
92
59
85
43
Run 6
181,100
11,490
1,411
311
279
142
89
7.3
52
17.6
38
19.5
40
22
68
68
55
18.7
28
6.8
67
41
120
97
Run 7
192,800
11,817
1,281
316
294
179
116
10.9
66
21
48
24
22
-
53
35
2.2
14.6
11.0
5.1
45
21
51
39
Run 8
193,800
12,500
1,636
349
333
198
129
10.0
61
27
43
25
39
7.2
49
45
15.7
24.9
29.2
16.1
91
56
78
55
4.4
Run 9
190,400
12,675
1,664
442
371
175
105
8.
66
26
50
24
25
1.
49
114
11.
39
39
22
53
25
24
4.
3.
4
3
6
1
9
a Total concentration will not add to 100% after correcting for response factors due to the detector overload which
occurs during the methane peak.
-------
u>
o
10 !! 12 13 14 15 16 17 18 I? 20 21 22 23 24 25 2s
Figure 6. Run 3 - Fuel gas chromatogram, Taft, Louisiana.
-------
TABLE 22. NOX RESULTS
Run
Number
1
2
3
4
5
6
7
8
9
Ib of
1
—
4.5
-
3.3
3.9
2.8
3.1
3.6
3.4
Reported
N02/million ft
2
—
3.5
3.5
3.3
3.2
2.9
4.2
4.1
3.5
as
3, dry
3
—
3.5
3.6
3.2
3.5
2.5
4.0
3.9
4.1
standard
Avg.
—
3.8
3.6
3.3
3.5
2.7
3.8
3.9
3.7
1
—
73
-
53
63
45
Reported as
2
—
56
56
53
52
47
50 68
58
55
66
56
mg/m , dry
3
—
56
58
52
56
40
65
63
66
standard
Avg.
—
62
57
53
57
44
61
62
59
-------
SECTION 3
PROCESS DESCRIPTION AND OPERATION
The fume incinerator sampled is a John Zink horizontal cylindrical unit
averaging about 11.9 ft ID and 45.6 ft in length (5050 cu ft). The unit uses
natural gas as a fuel and is normally controlled and operated at an outlet tem-
perature of 625 to 650°C (1157 to 1202°F). The natural gas is fed into the cen-
ter of the unit through a burner assembly. Preheated combustion air at about
500°F enters the fume incinerator tangentially, forming a vortex flow pattern.
The blow-off enters the incinerator about 5 ft downstream of the combustion air
inlet, where it is mixed with the combustion air by the vortex flow pattern.
In addition to air preheat, energy is recovered from the combustion flue gas as
steam. The intent of the sampling program was to obtain inlet and outlet com-
position data for the fume incinerator used to thermally oxidize the process
waste vent gas (blow-off) from, both the acrolein and acrylic acid (AA) processes.
Because of acrolein process problems, this data could not be obtained. The ori-
ginal sampling plan was to obtain three sampling runs during operation of both
processes at constant rates at one temperature and three sampling runs for the
same process rate at a different temperature. Because of the acrolein process
problems, the original plan could not be followed. Table 23 summarizes the con-
ditions for the actual sampling program.
TABLE 23. Summary of Sampling Conditions
Date
11-29-78
12-2-78
12-5-78
12-6-78
12-7-78
12-8-78
Run
No.
1
2
3
4
5
6
7
8
9
Processes
Sampled
AA
A+AA
A+AA
AA
AA
AA
AA
AA
AA
Blow-Off Rate
(lb/hr)
97,600
123,800
123,200
102,300
101,600
100,700
96,200
95,100
95,500
Temp, of Incin.
. (°c)
624
624
625
624
625
624
800
800
800
32
-------
Runs 4 through 9 are the data runs which are used for the study. Nine sam-
pling runs were performed rather than six because of the acrolein process problems.
Sampling of the AA process only was started on November 29 after being told by UCC
that the acrolein process would be down for about a week. On November 30, just
before the second sampling run was about to start, the AA production rate dropped
by about 30%. At noon on November 30, UCC informed the sampling team that the
acrolein process would be brought back on line during the night. The decision
was then made by the sampling team and Bob Weber to wait until the acrolein pro-
cess was at steady state and then to start .sampling both processes as originally
planned. On December 2 two sampling runs were made on the fume incinerator with
both processes operating. On December 3, the acrolein plant was again shut down
due to acrolein quality problems of an unknown origin and full crude storage tanks.
Since it appeared that the acrolein process would be down for a number of days,
the decision was made by EPA to stay an additional week and try to make additional
sampling runs for the acrylic acid process only at two different temperatures.
These runs were made between December 5 and December 8 as shown in Table 23.
33
-------
SECTION 4
LOCATION OF SAMPLE POINTS
Figure 7 shows a general diagram of the process with the sampling points
marked. The sampling points are some distance from one another. Point No. 1,
the. acrylic acid off-gas, is at about 70°C, and a few pounds per square inch
positive pressure, so that no sampling pump is necessary. The sampling point
is at an existing tap about 5 m above the grating on the third level of the
unit. A 1/4-in. stainless steel insulated sampling line was run to near deck
level. A diagram of the sample train setup is shown in Figure 8. The sampling
probe was inserted to the center of the duct. The location is near a flow dis-
turbance but only gas samples were taken.
Figure 9 shows the general layout of the incinerator with the remaining
sample points shown.
Point No. 2, the combined inlet flow to the combustor, is slightly above
ambient temperature, again, at positive pressure, and a 1/4-in. stainless steel
line at the top of a 20-ft scaffold was used for sampling. The sample probe
enters the top of the duct between two horizontal bends in the duct. A fixed,
single-axis flow measuring device (Annubar) is installed in a straight section
of the pipe, a few feet downstream from Point No. 2. The Annubar was mounted
the required distances from the nearest flow disturbances. A thermocouple
well is installed in the main duct downstream from the horizontal bend. The
sample at both inlet, and outlet was split three ways with two TGNMO trains and
one integrated gas sample for GC analysis run simultaneously. A condensate
knockout trap was located downstream from Point 2, since entrained liquid is
present in this duct. A sample of this knockout trap contents was obtained
and analyzed.
Point No. 3, the incinerator outlet, was used for all sampling at the out-
let except for volumetric flow and temperature, which were measured at the stack
ports (Point No. 4). Sample Point No. 3 had to be used due to the difficulty
of hoisting equipment to Point No. 4, and the limited room on the scaffolding
at Point No. 4. The sample stream was split three ways as at the inlet. This
was the only sampling point which required a pump and gas box for integrated
gas sampling. Point No. 3 was an existing sample point located in an expansion
zone near the incinerator exhaust. No detailed information of the duct internal
dimensions was obtainable from the plant except that the probe end was well away
from the walls.
34
-------
Ul
Acrylic Acid
Unit
Acrolein
Unit
Stack
AOG
i
(2)
Inlet
I
Incinerator
Outlet
Outlet
at Stack
,
Fuel Gas
Figure 7. General process diagram showing sampling points.
-------
Flow
=4=®=
20"
Shut-Off Valve
Condenser
Water
Bath
Needle Valve
Reducer
Figure 8. Sampling Point No. l-(AOG) acrylic acid unit off-gas.
36
-------
U)
Ports for
Pitot Traverse® StacU
i /
I
6
i
^
4'
i
»
^
\
/
\
/
\
12'
s
/
^
/
s
•4
Scaffold -
i
2
1
^-65
T
I
® ,GN
14i
Integrated
TGNMC © /a
^4^.. I/"""'
MO
Incinerator
- i 1
/
Thermo - ;
Well ;
\
Integrated
Gas
150'
^ — 1
\ T 1
-A 30" 20'
\ }
Scaffold
Figure 9. Incinerator layout with sampling locations.
-------
Point No. 5, fuel gas, was taken at the main plant natural gas distribution
center. Small Tedlar bags were flushed and then filled directly from the line.
38
-------
SECTION 5
SAMPLING AND ANALYTICAL PROCEDURES
The integrated gas samples were obtained according to the September 27,
1977, EPA draft benzene method (Appendix G). Seventy-liter aluminized Mylar
bags were used at an approximate sampling rate of 0.5 liter/min for 1 hr. A
glass vacuum trap immersed in water of ambient temperature was used as a conden-
ser ahead of each bag. The contents of the condensers were measured by weight
difference and stored for later GC analysis. No heating of the sample bags was
used.
At the inlet and absorber off-gas sampling points, the duct pressure was
sufficient to fill the bags directly from the duct without pumps or sample
boxes. A needle valve was inserted on the sample tap to control the sampling
rate. The sampling rate was set initially by connecting a rotameter in place
of the bag. The rotameter was then removed and the bag connected for sampling.
At the end of each run the flow rate was again checked.
Each integrated gas sample was analyzed on a Varian Model 2400 gas chroma-
O
tograph with FID, and a heated Carle gas sampling valve with matched 2 cm sample
loops. A valved capillary bypass is used for THC analyses and a 2 m, 1/8 in. OD
nickel column with Porapak P-S, 80-100 mesh packing used for component analyses.
The .column was programmed from 20 to 225°C at 6°/min with temperature hold at
upper limits. Nominal running time is 35 min. THC readings were obtained by
peak height ratios for standards (99 ppm propane is the primary standard for all
analyses) and samples.
Peak area measurements were used for the individual component analyses. A
Tandy TRS-80, 48K floppy disk computer interfaced via the integrator pulse output
of a Linear Instruments Model 252A recorder acquired, stored, and analyzed the
chromatograms. The computer is programmed in BASIC. The program listed in
Appendix H was used for data acquisition and preliminary field data analyses.
The stored data were later reanalyzed using the more comprehensive program
listed in Appendix I. The latter program allows noise filtering, graphic peak
display, and a printed listing of the results. Except for a few chromatograms
which were accidentally lost from the storage disks, (single runs for 3-AOG,
6-OUT, 8-IN, 9-IN and all of run 7) all results presented are from the filtered
39
-------
output of the second program. The destroyed chromatograms use the field reported
values. Duplicate runs were made for all samples unless the primary peak areas
did not agree within approximately 10%, in which case, further runs were necessary.
The higher temperature outlet runs were conducted at least three times due to the
very low sample concentration.
Normal sampling used a 3-sec integration interval with about 700 points
recorded for each chromatogram. A count rate of 6,000 counts/min was used (1 mv
reference) with integrator overload occurring at 2.3 mv and integrator resolution
of about 3 fjiv (1 count/3 sec) with normal accuracy of about 6 //v overall including
the conversion accuracy of the recorder.
Programming allows appropriate descriptions of each chromatogram, selectable
sampling interval, maximum chromatogram length of 1,000 data points, and on-line
entry of attenuation changes via the keyboard. The programs sense peaks by two
consecutive readings which increase by more than a selectable noise factor. The
baseline is measured as a straight line from before peak start to peak end.
Merged peaks are split by a vertical line through the minimum between them with
an overall baseline factor. Both programs have difficulty giving accurate re-
sults for small slowly rising peaks due to the effect of counting noise. Con-
centrations are reported using a single external calibration factor (99 ppm
propane standard) using the average of pre- and post-test standard runs (a mini-
mum of six standard peaks total). The GC detector response is linear (within
+ 5%) over wide concentration ranges (10-2000 ppm propane) but irreversible
adsorption by the column can occur with reactive compounds which may cause low
results for compounds such as acrylic acid. The program result printouts are
in Appendix J.
The propylene/propane peaks are not resolvable on the column used. The sin-
gle observed peak was artifically split using the program in Appendix K, which
compares the peak with a pure reference peak and uses a two equation, two unknown
solution, assuming that both components have a shape similar to the reference
and that the superimposition observed is additive (no interaction between the
two components). A limited iteration range is used with the final values taken
for the solution with a minimal sum of the squared residuals. Sample peaks from
the inlet and AOG showed propane as 38% (± 3%) of the composite peak, with no
significant variation with sample run or site. The outlet sample peaks are pure
propane. No propylene component was observable at the outlet.
The GC data use no temperature or pressure corrections due to the use of a
thermostated (+ 1°C) valve and negligible barometric pressure changes during a
normal analysis day.
The integrated gas samples were analyzed for oxygen and carbon dioxide by
duplicate Fyrite readings. Carbon monoxide concentrations were obtained using
a Beckman Model 215A nondispersive infrared (IR) analyzer using the integrated
40
-------
samples. A three-point calibration (1,000, 3,000 and 10,000 ppm CO standards)
was used with a linear-log curve fit.
The integrated gas samples were also analyzed for total aldehydes using 2-
liter evacuated flasks according to the Los Angeles method given in Appendix B.
The aldehyde titration gave a very unstable endpoint on the inlet samples. The
inlet samples were finally titrated for the first persistent blue color (stable
for 1 to 2 sec in a well-stirred flask). This endpoint is reproducible to i 5%.
The cause of the poor endpoint is still unknown. Analytical log sheets for this
procedure are in Appendix L.
The residual bag volume was measured and an estimate of the sample volumes
withdrawn was made to calculate the gas phase concentrations of the organics
found in the condensates. The condensates were injected directly in 2 /Hi liquid
portions using the conditions, established for the gas sampling, but with injec-
tion through a septum onto the column. Concentrations were calculated by peak
area (height x width at 1/2 height) using a 2,000 /u,g/g acetone standard in water.
Stack traverses for outlet flow rate were made using EPA Method 1 through
4 (midget impingers) and NOX was sampled at the outlet using EPA Method 7.
Total organic carbon was sampled from T-fittings at the inlet and outlet
using the tentative EPA procedure given in Appendix A. THC readings via the
field GC were made from each volatile fraction tank after pressurization with
nitrogen which had been cleaned with molecular sieves. A few tanks were also
analyzed for individual components by GC. The tanks and traps were then shipped
to Pollution Control Science for analysis.
Single GC chromatogratns were run for plant fuel gas samples taken during
each run. Column conditions and analyses are identical to those used for organic
component identification and quantification. No detailed analysis was made for
the many observed peaks. Refer to Appendix M for a listing of all compound reten-
tion indices measured on the analytical column.
Sample calculations for the various methods used are listed in Appendix N.
41
------- |