v>EPA
United States
Environmental Protection
Agency
Office of Air Quality
Planning and Standards
Research Triangle Park NC 27711
EMB Report 78-OCM-9
Air
Acrylic Acid and
Esters Production
Emission Test Report
Rohm and Haas
Company
Deer Park, Texas
-------
EMISSION TEST OF AN ACRYLIC ACID AND
ESTER MANUFACTURING PLANT
by
George.W. Scheil
FINAL REPORT
August 1980
EPA Contract No. 68-02-2814, Work Assignment No. 16
EPA Project No. 78-OCM-9
MRI Project No. 4468-L(l6)
For
Emission Measurement Branch
Field Testing Section
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
Attn: Mr. J. McCarley, Jr.
-------
PREFACE
This work was conducted by Midwest Research Institute under Environmental
Protection Agency Contract No. 68-02-2814, Work Assignment No. 16.
The project was supervised by Mr. Doug Fiscus, Head, Field Programs Sec-
tion. Dr. George Scheil served as field team leader and was assisted in the
field by Messrs. Ron Jones, Robert Stultz, Dan Vogel, Jeff Thomas, and Mark
Hansen of Midwest Research Institute. Laboratory assistance was provided by
Mr. Tom Walker.
Approved for:
MIDWEST RESEARCH INSTITUTE
M. P. Schrag, Director
Environmental Systems Department
August 1980
111
-------
CONTENTS
Figures vi
Tables . vii
1. Introduction 1
2. Summary and Discussion of Results 3
3. Process Description and Operation 37
4. Location of Sample Points 41
5. Sampling and Analytical Procedures 47
Appendices
A. TGNMO method data A-l
B. Aldehyde sampling and CO data B-l
C. Pitot traverse data C-l
D. Integrated gas sampling data sheets D-l
E. Moisture data sheets E-l
F. NO 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. GC analysis data J-l
K. Program listing for peak deconvolution K-l
L. Aldehyde sample analysis data L-l
M. GC data program - averaging peak sensor M-l
N. Retention data of known compounds N-l
0. Sample calculations 0-1
-------
FIGURES
Number
1 Suction vent gas chromatogram for Run No. 8 ESED
file
2 Process off-gas chrmotogram for Run No. 8 ESED
file
3 Outlet chromatogram for Run No. 8 25
4 TGNMO tank gas chromatogram (outlet) for Run No. 8. ... 30
5 Fuel gas chromatogram for Run No. 8 35
6 Acrylic ester process schematic 38
7 General process diagram 42
8 Process off-gas sampling location 43
9 Suction vent sampling Icoation 44
10 Incinerator outlet and stack 45
VI
-------
TABLES
Number Page
1 Gas Chroraatography Analyses for Methane 4
2 Gas Chroraatography Analyses for Ethylene 5
3 Gas Chromatography Analyses for Acetylene 6
4 Gas Chromatography Analyses for Ethane 7
5 Gas Chromatography Analyses for Propylene ESED
file
6 Gas Chromatography Analyses for Propane 9
7 Gas Chromatography Analyses for Propyne and Methanol. . . 10
8 Gas Chromatography Analyses for Acetaldehyde 11
9 Gas Chromatography Analyses for Butenes 12
10 Gas Chromatography Analyses for Unknown Peaks No. 1
and 2 ESED
file
11 Gas Chromatography Analyses for Acrolein ESED
file
12 Gas Chromatography Analyses for Acetone 15
13 Gas Chromatography Analyses for Methyl Acrylate 16
14 Gas Chromatography Analyses for Unknown Peak No. 3. ... 17
15 Gas Chroraatography Analyses for Unknwon Peak No. 4. ... 18
16 Gas Chromatography Analyses for Acrylic Acid 19
17 Gas Chromatography Analyses for Ethyl Acrylate 20
18 Gas Chromatography Analyses for Propyl and Butyl
Acrylate 21
19 Gas Chroraatography Analyses for Total Hydrocarbons. ... 22
vii
-------
TABLES (continued)
Number
20 Total Gaseous Nonmethane Organic (TGNMO) Sampling
Results 27
21 TGNMO Tank Samples Analyzed by Gas Chromatography .... 29
22 Aldehyde Analysis Results - Bisulfite Reaction ESED
file
23 Composition/Flow Summary (Metric Units) 32
24 Composition/Flow Summary (English Units) 33
25 Fuel Gas Analysis (ppm as Propane) 34
26 NO Results 36
x
Vlll
-------
SECTION 1
INTRODUCTION
This report presents the results of source testing performed during
the period February 8 to March 15, 1979, by Midwest Research Institute (MRI)
at the acrylic acid facility of Rohm and Haas Corporation at Deer Park, Texas.
The inlet and outlet of a high temperature, short residence time fume combus-
tor 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 a storage tank area. The acrylic acid unit uses partial oxidation of
propylene to produce its product.
The vapor streams were analyzed for methane, ethylene, ethane, propane,
propylene, acetaldehyde, acrolein, acetone, acrylic acid, methyl-butyl acry-
lates, and total hydrocarbons by gas chromatography (GC). Duct temperature,
flow rate, oxygen, carbon monoxide, carbon dioxide, and aldehydes were also
determined by manual sampling of all streams. The fuel gas was analyzed by
GC, and NO 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 Tables 1 through 19. The first
18 tables show results for each component observed, from methane to butyl
acrylate, at the inlet and outlet to the incinerator. Table 19 shows the
sum of all components. All actual measurements were made as parts per million
(ppm) of propane (by volume) with the other units reported derived from the
propane equivalent response. The tables include any contribution from the
portion of each sample which condensed in the sampling train trap. Only
acetaldehyde and acetone were found in the condensate. All results were
measured by digital integration. Data for propylene, acrolein, and two un-
known compounds (Tables 5, 10, and 11) were obtained, considered confidential
by Rohm and Haas, and were removed from the final report and stored in the
EPA Emissions Standards and Engineering Division's (ESED) files.
The incinerator combustion temperature for the first four runs was at
normal combustion temperature. Runs 5 through 8 were made at an elevated
incinerator temperature. During Run 5 the combustion conditions were not
optimized—apparently insufficient oxygen was present for proper combustion.
Run 9 was completed during the firing of liquid wastes to the incinerator,
again at high temperature. The higher temperature runs caused many of the
compounds heavier than propane to drop below the detection limits. No single
number can be assigned as a detection limit due to the wide range of attenua-
tions used, nearby obscuring peaks, and baseline noise variations. The detec-
tion 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, propane, propylene, acetaldehyde, acetone, acrolein, and
acrylic acid, dominate the chromatograms (see Figures 1 through 3 for exam-
ples). The suction vent and process off gas chromatograms (Figures 1 and
2) are in the ESED files. Acetic acid was never detected in any sample.
Methyl, ethyl, propyl, and butyl acrylates were observed in large quantities
in the suction vent. Several minor peaks were found, some of which have
probable identifications.
The probable reason for negative destruction efficiencies for several
light components is generation by pyrolysis from other components. For in-
stance, the primary pyrolysis products of acrolein are carbon monoxide and
ethylene. Except for methane and, to a much lesser extent, ethane and pro-
pane, the fuel gas cannot contribute hydrocarbons to the outlet samples.
-------
TABLE 1. GAS CHROMATOGRAPHY ANALYSES FOR METHANE
Suction vent
ppm as Propane
ppm as Methane
ppm as Carbon .
G/Mlas Methane?
3 a/
G/M as Carbon—
G/sec as Methane
G/sec, as Carbon .
3 a/
Ib/ft as Mothanii?
Ib/ft as Carboif
Ib/hr as Methane
Ib/hr as Carbon
Process off-gas
ppm as Propane
ppm as Methane
ppm as Carbon .
G/M as Methancy
C/Mas Carbon2
G/sec as Methane
G/sec as Carbon .
lb/ft^as Methaney
Ib/tt as Carbon—
Ib/hr as Methane
Ib/hr as Carbon
Outlet
ppm as Propane
ppm as Methane
ppm as Carbon .
G/M. as Methaner
G/M as Carbon—
G/sec as Methane
G/sec as Carbon .
Ib/ft as MethanCJ
Ib/ft as Carbotf
Ib/hr as Methane
Ib/hr as Carbon
% Efficiency
Note: All compounds
Run 2
0.70
1.94
1.94
1.29 x 10,
-4
9.68 x 10
7.59 x 10~
5.69 x 10"
8.05 x 10"
6.04 x 10
0.06
0.05
46.5
129.0
129.0
0.09
O.U6
1.75
1.32
5.35 x 10"*
4.01 x 10
13.91
10.43
87.0
240.0
240.0
0.17
0.12
6.2
4'7 -5
1.00 x 10
7.5 x 10"6
49.0
37.0
b/
wore measured as ppm of pi
Run 3
0.65
1.81
1.81
1.20 x 10,
-4
8.99 x 10
7.06 x 10"
5.30 x 10"^
7.48 x 10"
5.61 x 10
0.06
0.04
44.0
122.0
122.0
0.08
0.06
1.53
1.14
5.06 x 10"°
3.80 x 10"
12.10
9.08
79.0
219.0
219.0
0.147
O.H
5.6
4.2
9.1 x 10
6.8 x 10"
45.0
33.0
b/
Run 4
0.72
2.0
2.0
1.33 x
9.96 x
. 7.79 x
5.85 x
8.28 x
6.21 x
0.06
0.05
45.5
126.0
126.0
0.08
0.06
1.61
1.21
5.23 x
3.93 x
12.74
9.56
53.0
149.0
149.0
0.092
0.074
3.8
2.8
6.1 x
4.6 x
30.0
23.0
b/
ropane. Other units shown
Run 5
1.54
4.28
4.28
10" 2.84 x 10"
to".* 2.13 x 10
10" 0.02
10" 0.01
-8 - 7
10 " 1.77 x 10 '
10" 1.33 x 10"
0.13
0.10
68.0
189.0
189.0
0.13
0.09
2.35
, 1.76
10 ° 7.82 x 10
10 5.87 x 10
18.63
13.98
30.0
83.0
83.0
0.06
0.04
1.85
, 1.39
10~ 3.45 x 10"
10"° 2.59 x 10
14.70
11.02
22.0
are derived from the
Run 6
1.27
3.53
3.53
2.34 x
1.76 x
0.01
0.01
1.46 x
1.10 x
0.11
0.08
50.0
139.0
139.0
0.09
0.07
1.71
1.28
5.75 x
4.31 x
13.56
10.12
10.6
29.0
29.0
0.02
0.01
0.73
0.55
1.22 x
9.14 x
5.81
4.36
57.0
propane
Run 7
0.74
2 06
10"' 1.36 x I0~l
-3 -3
10 1.02 x 10 ^
8.02 x 10~
6.02 x 10"
10"' 8.51 x 10""
10" 6.38 x 10"
0.06
0.05
41.0
114.0
114.0
0.08
0.06
1.40
, 1.05
10 4.72 x 10 °
10 3.54 x 10
11.09
8.31
8.4
23.0
23.0
0.02
0.01
0.58
fi °'*4 7
10"° 9.66 x 10 '
10 7.25 x 10
4.61
3.45
59.0
response.
Run 8
0.45
1.25
l'" -4
8.30 x 10
6.22 x 10
5.01 x 10":*
3.76 x 10";:
-8
5.18 x 10 °
3.88 x 10
0.04
0.03
52.0
144.0
144.0
0. 10
0.07
1.78
1.33
5.98 x 10";"
4.49 x 10
14.08
10.56
10.0
28.0
28.0
0.02
0.01
0.67
°-5° -6
1.15 x 10
8.63 x 10
5.34
4.00
62.0
Run 9
0.97
2.69
2.69
1.79 x
1.34 x
0.01
8.04 x
1.12 x
8.37 x
0.08
0.06
54.0
150.0
150.0
0.10
0.07
1.81
1.36
6.21 x
4.66 x
14.39
10.79
2.0
5.5
5.5
3.69 x
2.77 x
0.14
0.10
2.30 x
1.73 x
1.10
0.82
92.4
-3
10
io"3
10 fl
io"8
io"6
-3
10 •*
10
-7
io"7
Note: Retention index
100
_a/ Dry standard conditions.
Jj/ Negative efficiency.
-------
TABLE 2. GAS CHROMATOGRAPHY ANALYSES FOR ETHYLENE
Suction Vent
ppra as Propane
ppm as Cchylene
ppm as Carbon
S/m3*/ as Ethvlene
7 »
g/m i' as Carbon
g/sec as Echylene
g/sec as Carbon
Ib/fc3a/ as Echylene
Ib/fc3£/ as Carbon
Ib/hr as Echylene
Ib/hr as Carbon
Process Off-Gas
ppra as Propane
ppm as Echylene
ppm as Carbon
g/m3<>/ as Echylene
g/nr£/ as Carbon
g/sec as Echylene
g/sec as Carbon
Ib/fc3£/ as Echylene
Ib/fc3£/ as Carbon
Ib/hr as Echylene
Ib/hr as Carbon
due let
ppra as Propane
ppra as Echylene
ppm as Carbon
g/m3a/ as Echylene
g/ra3£/ as Carbon
g/sec as Echylene
g/sec as Carbon
Ib/fc3a/ as Echylene
Ib/fc3£/ as Carbon
Ib/hr as Echylene
Ib/hr as Carbon
" Efficiency
, Run 2
0.97
1.47
2.93
1.70 x 1CT3
1.46 x 10"3
0.0100
8.6 x 10'3
1.06 x 1C*7
9.1 x 10'8
0. 0794
0.0681
108
163
326
0.190
0.163
3.88
3.32
1.18 x 1C'5
1.01 x 10"5
30.7
26.4
369
558
1,116
0.649
0.556
25.2
21.6
4.04 x 10'5
3.41 x lO'5
199
170
b/
Run 3
1.31
1.98
3.96
2.30 x 10*3
1.97 x ID"3
0.0135
0.0116
1.43 x 10"7
1.23 x 10"7
0.107
0.0921
100
151
302
0.176
0.150.
3.30
2.83
1.09 x ID"5
9.38 x 10"6
26.2
22.4
342
517
1,030
0.602
0.515
23.2
19.9
3.75 x ID'5
3.22 x ID"5
183
157
b/
Run 4
1.49
2.25
4.50
2.62 x 10"3
2.24 x 10"3
0.0154
0.0132
1.63 x ID*7
1.40 x lO*7
0.122
0.104
102
154
308
0.179
0.153
3.43
2.94
1.12 x 10"5
9.57 x lO'6
27.2
23.3
346
523
1,050
0.607
0.501
23.4
20.1
3.79 x 10'5
3.24 x ID"5
186
159
b/
Run 5
1.21
1.83
3.66
2.2 x 10*3
1.82 x 10'3
0.0124
0.0107
1.32 x lO"7
1.14 x ID" 7
0.0985
0.0845
96
145
290
0.169
0.144
3.16 .
2.71
1.05 x 10°
9.01 x lO"6
25.0
21.5
114
172
345
0.200
0.172
6.70
5.75
1.25 x 10'5
1.07 x lO'5
53.2
45.6
b/
Run 6
1.03
1.56
3.11
1.81 x 10"3
1.55 x 10'3
0.0106
9.05 x 10'3
1.13 x 10*7
9.67 x I0'a
0.0837
0.0718
104
157
314
0.183
0.156
3.38
2.90
1.14 x 10*5
9.76 x 10"6
26.8
23.0
34.7
52.4
105
0.0609
0. 0522
2.28
1.96
3.80 x 10"°
3.26 x ID"6
18.1
15.5
33
1.
1.
3.
1.
1.
0.
8.
1.
9.
0.
0.
Run 7
00
51
02
76 x 10"3
50 x 10'3
0103
85 x 10'3
09 x 10'7
38 x 10-7
106
0908
100
151
302
0.
0.
3.
2.
1.
9.
25
22
26
39
79
0.
0.
1.
1.
2.
2.
13
11
47
176
150
25
78
09 x 10-S
38 x 10'6
.7
.1
.3
.7
.5
0462
0396
73
48
88 x 10'6
47 x 10'6
.7
.8
1.
1.
3.
2.
1.
0.
0.
1.
1.
0.
0.
97
Run 8
3
9
8
2 x 10"3
9 x 10'3
013
Oil
38 x 10-7
18 x 10"7
11
091
147
293
0.
0.
3.
2.
1.
9.
25
21
32
48
96
0.
0.
2.
1.
3.
3.
16
13
35
170
146
15
70
06 x 10"5
10 x 10"5
.0
.4
.4
.7
0562
0481
05
76
50 x 10"6
00 x lO"6
.3
.9
Run
1.4
2.0
4.1
2.4 x
2.0 x
0. 0142
0. 0122
1.5 x
1.3 x
0.11
0. 0965
99
150
299
0.174
0.149
3.17
2.71
1.08 x
9.29 x
25.1
21.5
9.1
13.8
27.5
0.0160
0.0137
0.601
0.515
9.96 x
8.54 x
4.76
4.08
81
9
io-3
io-3
io-7
io-7
101
io-6
io-7
io-7
Note: All compounds were originally measured as ppm of propane. Other unics shown are derived from the propane response.
Retention Index =185
a/ Dry scandard condicions.
b/ Negacive efficiency.
-------
TABLE 3. GAS CHROMATOGRAPHY ANALYSES FOR ACETYLENE
Outlet
ppm us Propane
ppm as Acetylene
ppm^as Carbon .
G/M as Acetylene—
G/M as Carbon—
G/sec as Acetylene
G/sec as Carbon .
Ib/ft as Acetylene—
Ib/ft as Carbon—
Ib/hr as Acetylene
Ib/hr as Carbon
Run 2
9.9
15.4
30.7
0.0166
0.0152
0.64
0.59
10.3 x 10~°
9.6 x 10
5.0
4.7
Run 3
12.1
18.8
37.7
0.0204
0.0188
0.79
0.72
1.27 x 10"°'
1.18 x 10
6.3
5.7
None Detected
Run 4
8.5
13.2
26.3
0.0143
0.0131
0.55
0.50
8.8 x 10"
8.1 x 10
4.4
4.0
at Suction
Run 5 Run 6
5.8
9.0
18.0
9.7 x 10
9.0 < 10
0.33
0.30
6.1 x 10"'
5.6 x 10
2.6
2.4
Vent or Process Off-Gas
Run 7 Run 8 Run 9
0.90
1.4
2.8
1.5 x 10
1.4 x 10
0.057
0.052
9.4 x 10"
8.7 x 10
0.45
0.41
Note: All compounds were originally measured as ppm of propane. Other units shown are derived from the propane response.
Note: Retention index = 195
_a/ Dry standard conditions.
-------
TABLE 4. GAS CHROMATOGRAPHY ANALYSES FOR ETHANE
Suction Vent
Process Off-Gas
ppm as Propane
ppm as Ethane
ppra as Carbon
g/m^af as Ethane
g/m £.' as Carbon
g/sec as Ethane
g/scc as Carbon
lb/ft3S/ as Ethane
Ib/ft3£/ as Carbon
Ib/lir as Ethane
Ib/hr as Carbon
Outlet
ppra as Propane
ppm as Ethane
ppra as Carbon
g/m 3.' as Ethane
g/m 2.' as Carbon
g/sec as Ethane
g/sec as Carbon
Ib/ft3a/ as Ethane
Ib/ft3*/ as Carbon
Ib/hr as Ethane
Ib/hr as Carbon
% Efficiency
Run 2
Run 3
Run 4
NONE DETECTED AT SUCTION
35
52
104
0.0645
0.0516
1.32
1.06
4.0 x lO"6
3.2 x lO'6
10.5
8.37
686
1,015
2,040
1.265
1.011
49.1
39.2
7.89 x lO-5
6.31 x 10-5
389
312
b/
20.5
30.4
60.7
0.0378
0.0302
0.711
0.569
2.36 x !0-6
1.89 x 10-6
5.64
4.51
646
957
1,910
1.19
0.953
45.8
36.6
7.43 x 10-5
5.94 x lO-5
364
291
b/
24
35.5
71.1
0.0443
0.0354
0.848
0.678
2.76 x 10-°
2.21 x 10-°
6.72
5.38
703
1,040
2,080
1.30
1.038
49.9
39.9
8.08 x 10-5
6.48 x 10-5
396
316
k/
Run 5
VENT
29
43.0
85.9
0.0535
0.0428
1.00
0.802
3.34
2.67
7.95
6.36
121
179
359
0.223
0.179
7.48
5.98
1.39 x 10-5
1.11 x lO-5
59.3
47.4
b/
Run 6
36
53.3
107
0.0664
0.0531
1.23
0.985
4.14 x 10-6
3.31 x 10-°
9.76
7.81
208
308
616
0.384
0.307
7.11
5.69
2.39 x lO-5
1.91 x lO-5
56.4
45.1
b/
Run 7
23
34.1
68.1
0.0424
0.0340
0.784
0.627
2.65 x tO-6
2.12 x ID'6
6.22
4.98
13.7
20.3
40.6
0.0253
0.0202
0.467
0.374
1.58 x lO'6
1.26 x ID'6
3.70
2.96
41
Run 8
19
28.1
56.3
0.0350
0.0280
0.649
0.519
2.19 x lO'6
1.75 x lO-6
5.15
4.12
1.2
1.8
3.6
2.2 x lO"3
1.8 x ID"3
0.0410
0.0328
1.38 x 10"7
1.10 x 10-7
0.32
0.26
93.7
Run 9
47
69.6
139
0.0867
0.0693
1.58
1.26
5.41 x 10-°
4.32 x lO-6
12.5
10
0.30
0.44
0.89
5.5 x 10"A
4.4 x 10-*
0.0101
8.1 x 10"3
3.5 x 10-"
2.8 x 10-8.
0.080
0. Oft4
99.4
Note: All compounds were originally measured as ppm of propane. Other units shown are derived from the propane response.
Retention Index = 200
a/ Dry standard conditions.
b/ NcgatIve efficiency.
-------
Table 5 is in the ESED Confidential Data Files
-------
TABLE 6. GAS CHROMATOGRAPHY ANALYSES FOR PROPANE
Suction Vent
ppro as Propane
ppm as Carbon
g/m3jl/ as Propane
g/m3a/ as Carbon
g/sec as Propane
g/sec as Carbon
Ib/ft3a/ as Propane
Ib/ft3£/ as Carbon
Ib/hr as Propane
Ib/hr as Carbon
Process Off-Gas
ppm as Propane
ppm as Carbon
g/m3j»/ as Propane
g/m3a/ as Carbon
g/sec as Propane
g/sec as Carbon
Ib/ft3a/ as Propane
Ib/ft3a/ as Carbon
Ib/hr as Propane
Ib/hr as Carbon
Outlet
ppm as Propane
ppm as Carbon
g/m3a/ as Propane
g/ra3j>/ as Carbon
g/sec as Propane
g/sec as Carbon
Ib/ft3a/ as Propane
Ib/ft3a/ as Carbon
Ib/hr aa Propane
Ib/hr as Carbon
X Efficiency
Run 2
2.7
8.1
4.9 x 1
-------
TABLE 7. GAS CHROMATOGRAPHY ANALYSES FOR PROPYNE AND METHANOL
Process off-gas
ppm as Propane .
ppm as Propyne—
ppm as Carbon .
G/M as Propyney1-
G/M as Carboll" .
G/sec as Propyne—
G/sec as Carbon .
Ib/ft as Propyney1—
Ib/ft as Carboir" .
Ib/hr as Propyne—
Ib/hr as Carbon
Note: Retention index = 330
Suction vent
ppm as Propane , ,
ppra as Methanol—
ppm as Carbon .
G/M^as Methanol51-
G/H as Carbon5 .
G/s«c as Methanol—
G/sec as Carbon .
lb/ft^as Methanol5*^
Ib/ft as Carbon5 .
Ib/hr as Methanol-
Ib/hr as Carbon
Note: Retention index = 370
Run 2 Run 3
2.8
2.9
4.8 x 10"^
4.3 x 10"
ND£' 0.0907
0.0816
3.0 x 10"
2.7 x 10"
0.72
0.65
Not
85.9 - 54.1
514.0 323.0
514.0 323.0
0.682 0.429
0.25G 0.161
4.00 2.53
1.503 0.949
4.25 x 10"^ 2.68 x 10"
1.60 x 10 I. 00 x 10
31.8 20.1
11.92 7.52
Not
Run 4
2.8
2.9
4.8 x 10"^
4.3 x 10
0.0924
0.0831
3.0 x 10~'
2.7 x 10
0.73
0.66
Detected at
13.4
80.1
80.1
0.106
0.0399
0.624
0.234
6.63 x 10
2.49 x 10
4.95
1.86
Detected at
Run 5 Run 6 Run 7 Run 8 Run 9
3.1 3.2 3.9 2.6
3.2 3.3 4.0 2.7
9.7 1.0 12.1 8.1
5.3 x 10~;~ 5.5 x 10~;j 6.7 x 10"^ 4.5 x 10"^
4.8 x 10 5.0 x 10" 6.0 x 10 4.0 x 10
0.100 0.102 0.12 ND 0.0816
0.0900 0.0920 0.111 0.0734
3.3 x in" 3.4 x 10" 4.2 x 10" 2.8 x 10"
3.0 x 10 3.1 x 10" 3.8 x 10" 2.5 x 10"
0.79 0.81 0.98 0.65
0.71 0.73 0.89 0.58
Other locations
ND ND ND ND ND
6
Other Locations
Note: All compounds were originally measured as ppra o£ propane. Other units shown are derived from the propane response.
al Dry standard conditions*
jj/ Identification is uncertain; the peak may be this compound.
c/ Nl) - None detected.
J
-------
TABLE 8. GAS CHROMATOGRAPHY ANALYSES FOR ACETALDEHYDE
Stiction vent
ppm as Propane
ppm as Acetaldehyde
ppm. as Carbon .
C/M as Acetaldehyde^
G/M as Carbon2
G/sec as Acetaldehyde
G/sec as Carbon
Ib/ft as Acetaldyhyde—
Ib/ft as Carbocr
Ib/hr as Acetaldchyde
Ib/lir as Carbon
Process off-eas
ppm as Propane
ppm as Acetaldehyde
ppm. as Carbon .
G/M. as Acetaldyhydc—
G/M as Carboir
G/suc as Acetaldehyde
fj/sec as Carbon .
Ib/ft, as Acetalduhyde—
Ib/ft as Carbon—
Ib/hr as Acetaldehyde
Ib/hr as Carbon
Outlet
ppm as Propane
ppin as Acetaldehyde
ppm. as Carbon
C/M as Acetaldehyde2
G/M as Carbon—
G/sec as Acetaldehyde
G/sec as Carbon .
lb/ft^as Acetaldehyde^
Ib/ft as Carboir-
Ib/hr as Acetaldehyde
Ib/hr as Carbon
7. Efficiency
Run 2
6.2
16.8
33.5
0.0306
0.0167
0.180
0.0981
1.91 x 10"
1.04 x 10
1.43
0.778
(24%)k/
36.5
98.8
198.0
0.18
0.094
3.69
2.01
1.12 x 10" ;"
6.13 x 10
29.24
15.95
(4-/. )k/
14.2
44.5
76.9
0.070
0.038
2.72
4.38 x 10"^
2.39 x 10
21.6
11.8
29.0
Run 3
1.5
4.05
a. 11
7.40 x 10
4.04 x 10
0.0436
0.0238
4.62 x 10"
2.52 x 10"
0.346
0.189
(26%)k/
39.4
108.7
217.4
0.199
0.108
3.73
2.04
1.24 x 10";"
6.75 x 10
29.61
16.15
(297.)k/
25.0
67.5
135.0
0.123
0.0681
4.75
2.59
7.69 x 10
4.20 x 10"
37.7
20.5
c/
Run 4
2.9
7.84
15.7
0.0143
7.81 x 10
0.0840
0.0458
8.92 x 10
4.87 x 10
0.667
0.363
(25Z)k/
38.8
105.0
210.0
0.192
0.104
3.67
2.0
1.20 x 10~*
6.52 x 10
29.10
15.87
(Ml.)-7
16.0
43.0
86.0
0.079
0.043
3.0
1.66
4.9 x 10";
2.7 x 10"6
24.1
13.2
79.0
Run 5
3.2
8.65
17.3
0.0158
8.61 x 10
0.0924
O.U504
9.85 x 10"'
5.37 x 10
0.732
0.400
(22%)k/
35.6
96.2
192. 31
0.176
0.096
3.23
1.79
1.10 x lO"""
5.97 x 10"
26.1
14.23
(NO)
4.2
11.4
22.7
0.0207
0.0113
0.694
0.379
1.29 x 10"
7.05 x 10"
5.51
3.00
79.0
Run 6
1.46
3.95
7.89
7.20 x 10
3.93 x 10~J
0.0421
0.0229
4.49 x 10"'
2.45 x 10
0.334
0.182
(19%)k/
43.4
117.3
235.0 -
0.214
0.117
3.97
2.17
1.34 x 10 "^
7.29 x 10"
31.48
17.17
(Nl»
1.1
2.97
5.95
5.43 x 10"^
2.46 x 10"
0.204
0.111
3.39 x 10"
1.85 x 10
1.61
0.880
95.0
Run 7
1.65
4.46
8.92
8.14 x 10"^
4.44 x 10"
0.0479
0.0261
5.08 x 10"'
2.77 x 10
0.380
0.207
(16%)k/
37.0
100.0
200.0
0.183
0.10
3.38
1.84
1.14 x 10~^
6.21 x 10
26.77
14.60
(Nil)
0.45
1.22
2.43
2.22 x 10";"
1.21 x 10
0.0833
0.0454
1.38 x 10"
7.55 x 10
0.660
0.360
97.6
Run 8
2.7
7.30
14.6
0.0133
7.27 x 10
0.0805
0.0439
8.31 x 10"^
4.53 x 10
0.638
0.348
(9X)k/
35.2
95.1
190.3
0.174
0.095
3.22
1.75
1.08 x 10~*
5.91 x 10"6
25.51
13.91
(ND)
0.63
1.70
3.41
3.11 x 10
1.70 x 10" J
0.113
0.0619
1.94 x 10"'
1.06 x 10
0.900
0.491
96.5
Run 9
4.5
12.2
24.3
0.0222
0.0121
0.133
0.0725
1.38 x 10~*
7.55 x 10
1.05
0.575
(177. )k/
41.1
111.2
222.4
0.203
0.111
3.70
2.02
1.27 x 10"^
6.91 x 10"6
29.33
16.0
Ml)
NoLe; All compounds were originally measured as ppm of piropuuu. Ochar units shoim arc derived from the propane response.
Note; Retention index — 39U
±1 Dry standard conditions.
b_/ Kraction found in condtmsate•
cj Negative uf fietuney *
d/ Nonu
-------
TABLE 9. GAS CHROMATOGRAPHY ANALYSES FOR BUTENES
Suecion Venc
ppm as Propane
ppm as Bucenes
ppm as Carbon
g/m3£/ as Bucenes
g/ra3*' as Carbon
g/sec as Bucenes
g/sec as Carbon
Ib/ft3a/ as Bucenes
Ib/fc3*/ as Carbon
Ib/hr as Bucenes
Ib/hr as Carbon
Process Off-Gas
ppm as Propane
ppm as Bucenes
ppm as Carbon
g/md' as Bucenes
3/ra3£/ as Carbon
g/sec as Bucenes
g/sec as Carbon
Ib/fe3a/ as Bucenes
Ib/fc3^/ as Carbon
Ib/hr as Bucenes
Ib/hr as Carbon
Ouclec
ppm as Propane
ppm as Bucenes
ppm as Carbon
g/m3a/ as Bucenes
g/m3£' as Carbon
g/sec as Bucenes
g/sec as Carbon
Ib/fc3^/ as Bucenes
lb/fc3JL/ as Carbon
Ib/hr as Bucenes
Ib/hr as Carbon
7. Efficiency
2.
I.
7.
4.
3.
0.
0.
2.
2.
0.
0.
5.
L.
17
0.
3.
0.
0.
6.
5.
1.
1.
7 .
2.
3.
4.
4.
0.
0.
3.
2.
1.
1.
Run 2
5
9
7
5 x ID'3
3 x ID'3
026
023
3 x IO-7
4 x 10"7
21
IS
7
4
.6
0102
7 x IO-3
21
13
4 x IO-7
5 x 10-7
7
4
7
1
4
9 x 10-3
3 x 10-3
20
17
0 x 10-"
6 x 10-7
50
29
Run 3
2.6
2.0
3.0
4.7 x ID'3
4.0 x 10*3
0.027
0.0235
2.9 x IO-7
2.5 x 10"7
0.22
0.19
5.6
4.3
17.3
0.0100
3.6 x 10-3
0.19
0.16
6.3 x IO-7
5.4 x 10-'
1.5
1.3
NDJL/
20
Run 4
3.7
2.9
11
6.6 x 10*3
5.7 x IO-3
0.039
0.033
4.1 x ID"7
3.5 x 10"7
0.31
0.26
5.5
4.2
16.9
9.3 x 10'3
3.4 x 10-3
0.19
0.16
6.1 x IO-7
5.3 x 10-'
1.5
1.3
2.5
2.0
7.9
4.6 x 10-3
3.9 x 10-3
0.173
0.152
3.0 x IO-7
2.4 x 10-7
1.4
1.2
23
Run
2.5
1.9
7.7
4.5 x
3.8 x
0.026
0.022
2.8 x
2.4 x
0.21
0.13
5.3
4.1
16.3
9.5 x
3.1 x
0.13
0.15
5.9 x
5.1 x
1.4
1.2
1.0
0.77
3.1
1.3 x
1.5 x
0.0600
0.0514
1.1 x
9.6 x
0.48
0.41
70
5
ID'3
io-3
io-7
lO"7
ID'3
10-3
io-7
io-7
10-3
10-3
io-7
10-3
Run 6
3.4
2.6
10.5
6.1 x ID'3
5.2 x IO-3
0.0355
0.0305
3.3 x IO-7
3.3 x IO"7
0.23
0.24
3.9
3.0
12
7.0 :< 10'3
5.0 x 10-3
0.13
0.11
4.4 x IO-7
3.7 x IO-7
1.0
0.38
ND°/
Run 7
4.1
3.2
12.6
7.3 x 10-3
6.3 x ID"3
0.043
0.037
4.6 x 10-7
3.9 x IO"7
0.34
0.29
4.3
3.7
14.3
3.6 x 10"3
7.4 x 10-3
0.16
0.14
5.4 x IO-7
4.5 x 10-7
1.3
1.1
\j]jb_/
Run 3
2.8
2.2
3.6
5.0 x IO-3
4.3 x 10-3
0.030
0.026
3.1 x 10-7
2.7 x 10'7
0.24
0.21
5.6
4.3
17.3
0.0100
3.5 x 10-3
0.19
0.16
5.3 x IO-7
5.4 x 10-7
1.5
1.3
;-T)b_/
Run
3.7
2.9
11
6.6 x
5.7 x
0.040
0.034
4.1 x
3.5 x
0.31
0.27
5.2
4.0
16
9.3 x
3.0 x
0.17
0.15
5.3 x
5.0 x
1.3
1.2
NB2/
9
10-3
10-3
io-7
io-7
10"3
10-3
10-"
10-"
MoCe: All compounds were originally measured as ppm of propane. OCher unics shown are derived from Che propane response.
Recencion Index = 410
a_/ Dry standard conditions.
b/ None dececced.
12
-------
Table 10 is in the ESED Confidential Data Files
13
-------
Table 11 is in the ESED Confidential Data Files
14
-------
TABLE 12. GAS CHROMATOGRAPHY ANALYSES FOR ACETONE
Suction vent
ppm a Propane
ppn a Acetone
ppoja Carbon ^
G/M a AcetoneT
C/M Carbon2
G/Bec a Acetone
C/aec a Carbon .
Ib/ft a Acetones
Ib/ft a Carbon2
Ib/hr a Acetone
Ib/hr a Carbon
Proccaa off-saa
ppn aa Propane
ppm aa Acetone
ppn aa Carbon .
C/H~aa Acetone2
G/Maa Carbon2
C/aec aa Acetone
C/aec aa Carbon .
Ib/ft'aa Acetone*
Ib/ft aa Carbon1
Ib/hr aa Acetone
Ib/hr aa Carbon
Run 2
57. 0
66. 5
259.0
0.208
0.129
1.22
0.759
1.3 x 10
8.06 > 10
9.7
6.02
(19l)V
140.0
212.0
637.0
0.512
0.918
10.5
6.49
3.19 x 10 \
1.98 x 10
83.0
51.5
Dun 3
68.0
103.0
310.0
0.248
0.154
1.46
0.908
1.55 « 10"*
9.61 x 10
11.60
7.20
(19*)^'
175.0
265.0
796.0
0.638
0.396
12.0
7.45
3.98 » 10 '
2.47 » 10
95.2
59.1
Run 4
67.0
102.0
305.0
0.245
0.152
1.44
0.891
1.53 x 10"*
9.47 x 10
11.4
7.07
(I9l)f
155.0
236.0
705.0
0.566
0.351
10.8
6.73
3.53 x 10 '
2.19 x 10
85.9
53.3
Run 5
61.0
93.0
278.0
0.223
0.138
1.30
0.809
1.39 x 10"*
8.62 « 10"6
10.3
6.41
(I7l)k/
151.0
229.0
688.0
0.552
0.343
10.3
6.42
3.44 * 10
2.14 i 10
82.1
50.9
Run 6
64.0
97.0
291.0
0.234
0.145
1.36
0.647
1.46 x
9.05 x
10.8
6.72
(16*)*'
164.0
249.0
747.0
0.600
0.372
U.I
6.90
3.74 x
2.32 x
88.2
54.7
Run 7
77.0
117.0
150.0
0.281
0.175
1.65
-5 '-°3 -5
10 ' 1.75 x 10 '
10 1.09 x 10
13.1
8.14
(4l)b/
1,279.0
1,940.0
5,820.0
4.67
2.90
86.4
-5 "•' -4
10 ' 2.91 x 10 *
10"5 1.81 x 10"*
684.0
425.0
Run 8
67.0
102.0
105.0
0.245
0.152
1.48
0.917
1.53 x
9.47 x
11.7
7.27
y
709.0
1,076.0
3,228.0
2.59
1.61
47.2
-5 29'3 -4
10 J 1.62 x 10
10 1.0 x 10
374.0
232.0
Outlet
ppn aa Propane
ppn aa Acetone
ppm aa Carbon .
C/HLaa Acetone2
C/M aa Carbon2
C/aec
C/aec
Ib/ft,
Ib/ft
Ib/hr
Ib/hr
I Effl
Acetone
Carbon .
Acetone2
Propane~
Acetone
Carbon
ency
10.0
15.2
45.6
0.035
0.023
1.42
0.88
2.3 , 10"'
1.4 x 10
11.3
7.0
88.0
7.7
11.7
35.0
0.028
0.0174
1.08
0.67
1.75 x 10"°
1.09 x 10
8.6
5.3
92.0
7.0
10.6
32.0
0.026
0.0158
0.98
- 0.61
1.59 x 10"
9.9 x 10
7.8
4.8
92.0
1.4
2.12
6.37
5.11 x 10 *
3.17 x 10
0.171 an-1
0.106
3.19 x 10~'
1.98 x 10
1.16
0.84
98.5
0.28
0.425
1.27
1.02 x 10 ^
6.35 x 10"
ttlf' 0.037
0.023
6.38 x 10 °
3.96 x 10"
0.296
0.18
99.7
0.39
0.592
1.78
1.42 x 10";
8.84 x 10"
0.054
0.033
8.88 x 10"'
5.51 x 10""
0.425
0.26
99.9
Note: Retention Index - 510.
a/ Dry standard conditions.
h/ Fraction found in mndentiate.
c/ N«n«- detected.
-------
TABLE 13. GAS CHROMATOGRAPHY ANALYSES FOR METHYL ACRYLATE
Suction Vent
ppm as Propane
ppm as Methyl Acrylate
ppm as Carbon
g/m3a/ as Methyl
Acrylate
g/m3ay as Carbon
g/sec as Methyl
Acrylate
g/sec as Carbon
Ib/ft3a/ as Methyl
Acrylate
Ib/Et3a/ as Carbon
Ib/hr as Methyl
Acrylate
Ib/hr as Carbon
Process Off-Gas
ppm as Propane
ppm as Methyl Acrylate
ppm as Carbon
g/nA/ as Methyl
Acrylate
g/m3a/ as Carbon
g/sec as Methyl
Acrylate
g/sec as Carbon
Ib/ft3a/ as Methyl
Acrylate
Ib/ft3a/ as Carbon
Ib/hr as Methyl
Acrylate
Ib/hr as Carbon
Outlet
ppm as Propane
ppm as Methyl Acrylate
ppm as Carbon
g/m3a/ as Methyl
Acrylate
g/m3a/ as Carbon
g/sec as Methyl
Acrylate
g/sec as Carbon
Ib/ft3a/ as Methyl
Acrylate
Ib/ft3ji/ as Carbon
Ib/hr as Methyl
Acrylate
Ib/hr as Carbon
X Efficiency
Run 2
28
34
140
0.12
0.0680
0.72
0.40
7.6 x 10"6
4.2 x 10~6
5.7
3.2
1.7
2.1
8.3
7.4 x 10-3
4.1 x 10-3 .
0.15
0.0843
4.6 x 10-7
2.6 x 10-7
1.2
0.67
5.0
6.1
24
0.022
12.2 x 10-3
0.85
0.47
1.35 x 10-6
7.6 x 10 -7
6.7
3.8
-0-
Run 3
36
44
180
0.16
0.0873
0.92
0.51
9.8 x ID'6
5.4 x 10"6
7.3
4.1
1.5
1.8
7.3
6.5 x 10-3
3.6 x 10-3
0.12
0.0685
4.1 x 10-7
2.3 x ID"7
0.97
0.54
NBk/
Run 4 Run 5 Run 6 Run 7 Run 8 Run 9
35 34 39 39 40 34
43 41 48 48 49 41
170 170 190 190 190 170
0.15 0.15 0.17 0.17 0.17 0.15
0.0849 0.0825 0.0946 0.0946 0.0970 0.0825
0.89 0.86 1.0 1.0 1.1 0.89
0.50 0.48 0.55 0.56 0.57 0.49
9.5 x 10"6 9.2 x 1Q-6 1.1 x 10"5 1.1 x 10"5 1.1 x 10~5 9.2 x 10~6
5.3 x 10"6 5.1 x 10"6 5.9 x 10"6 5.9 x 10~6 6.1 x 10~6 5.1 x 10"6
7.1 6.9 7.9 7.9 8.3 7.0
4.0 3.8 4.4 4.4 4.6 3.9
3.3 2.9
ND.b/ NRh_/ 4.0 3.5 NDk/ N'Dk/
16 14
0.0143 0.0126
8.0 x 10-3 7.0 x 1Q-3
0.27 0.23
0.15 0.13
8.9 x ID'7 7.9 x 10-7
5.0 x ID'7 4.4 x 10-7
2.1 1.8
1.2 1.0
NUk/ NUk/ NDk/ 0.95 NDk/ NDk/
1.15
4.6
4.1 x ID'3
2.30 x ID'3
0.155
0.0864
2.57 x ID"7
1.44 x ID"7
1.23
0.69
98.3
Note: All compounds were originally measured as ppm of propane. Other units shown are derived from the propane
response.
Note: Retenclon index > 520
a/ Dry standard conditions
b/ None detected.
16
-------
TABLE 14. GAS CHROMATOGRAPHY ANALYSES FOR UNKNOWN PEAK NO. 3
Not Detected at Suction Vent
Process off-eas
ppm as Propane
ppm as Propane
ppm as Carbon .
G/M as Propaner
C/M as Carboir"
G/sec as Propane
G/sec. as Carbon .
Ib/ft as Propane"7
Ib/ft as Carbon—
Ib/hr as Propane
Ib/hr as Carbon
Run 2
8.4
8.4
25.2
0.0153
0.0125
0.31
0.26
9.6 x 10~'
7.8 x 10
2.49
2.03
Run 3
8.6
8.6
25.8
0.0157
0.0128
0.30
0.24
9.8 x 10"
8.0 x 10~
2.34
1.92
Run 4
8.8
8.8
26.4
0.0161
0.0131
0.31
0.25
1.0 x 10~*
8.2 x 10
2.44
2.0
Not Detected
Run 5
8.2
8.2
24.6
0.0150
0.0125
0.28
0.23
9.3 x 10~
7.6 x 10
2.2
1.8
at Outlet
Run 6
8.4
8.4
25.2
0.0153
0.0125
0.28
0.23
9.6 x 10
7.8 x 10~
2.3
1.8
Run 7
9.6
9.6
28.8
0.0175
0.0143
0.32
0.27
i.ixio^
8.9 x 10
2.6
2.1
Run 8
9.0
9.0
27.0
0.0164
0.0134
0.30
0.25 ,
1.0 x 10
8.4 x 10
2.4
2.0
Run 9
10.0
10.0
3.0
0.0183
0.0150
0.33
0.27
1.1 x NT
9.3 x 10
2.6
2.2
Note: All compounds were originally measured as ppm of propane* Other units shown are derived from the propane response*
Note: Retention Index = 640
£/ Dry standard conditions*
-------
TABLE 15. GAS CHROMATOGRAPHY ANALYSES FOR UNKNOWN PEAK NO. 4
oo
Suction Vent
Process Off-Gas
ppm as Propane
ppm as Propane
ppm as Carbon .
G/M as Propaner
G/M as CarboiT"
G/ sec as Propane
G/ sec as Carbon .
Ib/ft as Propane"?
Ib/ft as Carbon—
Ib/hr as Propane
Ib/hr as Carbon
Outlet
ppm as Propane
ppm as Propane
ppm as Carbon .
G/M~as Propane"?
G/M as Carbon—
G/sec as Propane
G/ sec as Carbon .
Ib/ft as Propaner
Ib/ft as Carbon—
Ib/hr as Propane
Ib/hr as Carbon
% Efficiency
Run 2 Run 3
2.5
2.5
4.6 x 10"3
3.7 x 10
0.0859
0.0702
2.8 x 10~
2.3 x 10"7
0.68
0.56
1.8
1.8
3.3 x 10"3
2.8 x 10
0.13
0.11
2.0 x 10"'
1.7 x 10"'
1.03
0.85
£/
Run 4
None Detected
2.1
2.1
6.3
3.8 x 10"3
3.1 x 10
0.0734
0.0601
2.4 x 10"7
2.0 x 10"7
0.58
0.48
12.9
12.9
38.6
0.0236
0.0193
0.90
0.74
1.47 x 10~£
1.20 x 10
7.2
5.9
£/
Run 5 ' Run 6
b/
at Suction Venf
6.6
6.6
19.8
0.120
9.9 x 10~
NDi/ 0.22
0.183
7.5 x 10"7
6.1 x 10
1.8
1.4
1.2
1.2
2.2 x 10"3
1.8 x 10"3
0.0734 Nul/
0.0600
1.4 x 10"
1.2 x 10"
0.58
0.48
Run 7
3.0
3.0
5.5 x 10"3
4.5 x 10
0.10
0.0829
3.4 x 10* 7
2.8 x 10"
0.80
0.66
1.2
1.2
2.2 x 10"3
1.8 x 10"3
0.0822
0.0672
1.4 x 10"7
1.1 x 10
0.65
0.53
20.0
Run 8
2.8
2.8
8.4
5.1 x 10 J
4.2 x 10
0 0947
0.0775
3.2 x 10"7
2.6 x 10
0.75
0.61
Nil!/
Run 9
5.2
5.2
15.6
9.5 x 10"3
7.8 x 10"
0.17
0.14
5.9 x 10"7
4.8 x 10"7
1.4
1.1
4.1
4.1
12.3
7.5 x 10"3
6.1 x 10
0.28
0.23
4.7 x 10"
3.8 x 10"
2.2
1.8
s.1
Note: All compounds were originally measured as ppm of propane. Other units shown are derived from the propane response.
Note: Retention index = 685
SL/ Dry standard conditions.
b/ Peak present at suction vent, but is assumed to be the shifted acrylic acid peak.
£/ Negative efficiency.
tl/ None detected.
-------
TABLE 16. GAS CHROMATOGRAPHY ANALYSES FOR ACRYLIC ACID
Suction Venc^/
ppm as Propane
ppm as Acrylic Acid
ppm as Carbon
g/mlk/ as Acrylic Acid
g/m3H' as Carbon
g/sec as Acrylic Acid
g/sec as Carbon
Ib/ft3£/ as Acrylic Acid
Ib/ft3-' as Carbon
Ib/hr as Acrylic Acid
Ib/hr as Carbon
Process Off-gas
ppm as Propane
ppm as Acrylic Acid
ppm as Carbon
g/m3k/ as Acrylic Acid
b/m3Jl/ as Carbon
g/sec as Acrylic Acid
g/sec as Carbon
lb/ft3V as Acrylic Acid
Ib/fc3b./ as Carbon
Ib/hr as Acrylic Acid
Ib/hr as Carbon
Ouclec
ppm as Propane
ppm as Acrylic Acid
ppm as Carbon
g/m3V as Acrylic Acid
S/ml—' as Carbon
g/sec as Acrylic Acid
g/sec as Carbon
Ib/£t3£/ as Acrylic Acid
Ib/fc3^' as Carbon
Ib/hr as Acrylic Acid
Ib/hr as Carbon
Z Efficiency
Run 2
832
1,300
3,910
3.89
1.95
22.9
11.5
2.43 x KT*
1.21 x 10"*
182
90.8
60.0
94.0
280
0.281
0.140
5.74
2.9
1.75 x 10-5
8.76 x 10'6
45.5
22.8
8.8
13.8
41
0.041
0.021
1.60
0.81
2.57 x lO"6
1.29 x 10"6
12.8
6.4
94.4
Run 3
948
1,490
4,460
4.44
2.22
26.1
13.1
2.77 x 10-*
1.38 x 10-*
207
104
60
94
280
0.28
0.140
5.3
2.6
1.8 x 10-5
8.8 x 10"6
42
21
3.3
5.2
16
0.015
7.7 x 10"3
0.59
0.29
9.8 x 10"7
4.8 x 10"7
4.8
2.4
98
Run 4
899
1,410
4,230
4.21
2.10
24.7
12.4
2.62 x 10-*
1.31 x 1Q-*
196
97.9
60
94
280
0.28
0.140
5.4
2.7
1.8 x 10-5
8.8 x 1Q-*
43
21
2.8
4.4
13
0.013
6.4 x 10"3
0.50
0.26
8.1 x lO"7
4.0 x 10"7
3.9
2.0
98.4
Run 5
1,120
1,750
5,260
5.24
2.62
30.7
15.3
3.27 x 10-*
1.64 x 10-*
243
122
64
100
300
0.30
0.150
5.6
2.8
1.9 x 10-5
9.3 x 10~6
45
22
0.75
1.17
3.5
3.5 x 10~3
1.8 x lO"3
0.118
0.0588
2.19 x 10'7
1.09 x ID"7
0.93
0.47
99.7
Run 6
1,020
1,600
4,790
4.77
2.39
27.9
13.9
2.98 x 10-*
1.49 x 10-*
221
111
65
100
310
0.30
0.152
5.6
2.8
1.9 x 10-5
9.5 x 10~5
45
22
36.2
56.7
170
0.169
0.0847
6.35
3.18
1.06 x 10"5
5.28 x 10"5
50.4
25.2
81
Run 7
1,130
1,770
5,310
5.29
2.64
31.1
15.6
3.30 x 1Q-*
1.65 x 10-*
247
123
59
92
280
0.28
0.138
5.1
2.6
1.7 x 10-5
8.6 x ID'6
40
20
2.2
3.4
10.3
0.0103
5.1 x 10"3
0.39
0.19
6.4 x ID"7
3.2 x 10"7
3.1
1.5
99.0
Run 8
991
1,550
4,660
4.64
2.32
28.0
14.0
2.89 x 10-*
1.45 x 10'*
222
111
57
89
270
0.27
0.133
4.9
2.5
1.7 x 10-5
8.3 x lO"6
39
20
1.4
2.2
6.6
6.6 x 10"3
3.3 x KT3
0.24
0.12
4.1 x 10"7
2.0 x 10"7
1.9
0.95
99.3
Run
865
1,360
4,070
4.05
2.02
24.3
12.1
2.53 x
1.26 x
192
96.2
64
100
300
0.30
0.149
5.5
2.7
1.9 x
9.3 x
43
22
1.2
1.9
5.6
5.6 x
2.8 x
0.21
0.11
3.5 x
1.8 x
1.7
0.84
99.3
9
10-*
10-*
10-5
ID"6
ID"3
ID'3
lo:7
10 '
:iote: All compounds were originally measured as ppm of propane. Other units shown are derived from the propane response.
Note: Retention Index a 710
a/ Acrylic Acid peak appears to have shifted on top of unknown peak No. 4 at suction vent.
]>/ Dry standard conditions
19
-------
TABLE 17. GAS CHROMATOGRAPHY ANALYSES FOR ETHYL ACRYLATE
Suction vent
ppm as Propane
ppm as Ethyl acrylate
ppm as Carbon ,
G/M as Ethyl acrylate—
G/M as Carbon—
G/sec as Ethyl acrylate
G/sec as Carbon .
Ib/ft as Ethyl acrylate—
Ib/ft as Carbon—
Ib/hr as Ethyl acrylate
Ib/hr as Carbon
Process oft'-Ras
ppm as Propane
ppm as Ethyl acrylate
ppm as Carbon .
G/M as Ethyl acrylate-
G/M as Carbon^
G/sec as Ethyl acrylate
G/sec as Carbon ,
Ib/ft as Ethyl acrylate—
Ib/ft as Carbon—
Ib/hr as Ethyl acrylate
Ib/hr as Carbon
Run 2 Run 3
439 474
386 417
1,930 2,090 2
1.60 1.73
0.96 1.04
9.43 10.19
5.66 6.12 /
10. 0 x 10"^ 1.08 x 10" '
6.0 x 10 6.48 x 10"5
74.7 80.8
44.8 48.5
5.2
4.6
22.9
0.02
0.01
Nil-' 0.36
°'21 -6
1.18 x 10
7.1 x 10
2.83
1.70
Run 4
481
423
,120 1
1.76
1.05
10.31
1.10 x 10"^!
6.57 x 10'J
81.8
49.0
2.6
2.3
11.44
9.49 x 10
5.70 x 10
0.18
0.11
5.9 x 10
3.6 x 10
1.44
0.86
None Detected
Run 5
364
320
,600 2
1.33
0.80
7.78
4.67
8.29 x 10
4.97 x 10
61.7
37.0
Nil1-1-'
at Outlet
Run 6
492
433
,16(1
1.80
1.08
10.49
6.29
1.20 x
6.72 x
83.1
49.9
b/
ttlP-'
Rim 7
447
393
1.970
1.63
0.98
9.60
10~* 1.02 x
10 6.11 x
76.1
45.7
5.3
4.7
23.3
0.02
0.01
0.36
0.21
1.21 x
7.24 x
2.84
1.70
Run 8
486
428
2,140 2
1.775
1.065
10.43
6.26
10"^ I. 11 x 10"^
10 6.64 x 10
82.7
49.6
6.1
5.3
26.8
0.02
0.01
0.41
-6 °'25 -6
10 1.39 x 10
10" 8.3 x 10"
3.27
1.96
Run 9
517
455
,270
1.89
1.13
11.31
6.78
1.18 x 10"
7.06 x 10
89.7
53.8
2.1
1.8
9.2
7.7 x 10
4.6 x 10"
0.14
0.08
4.8 x 10
2.9 x 10"
1.11
0.66
Note: All compounds were originally measured as ppm of propane. Other units shovm arc derived from the propane response.
Nol.e: Retention index = 730
t
^/ Dry standard conditions.
b/ None detected.
-------
TABLE 18. GAS CHROMATOGRAPHY ANALYSES FOR PROPYL AND BUTYL ACRYLATE
Suction vent
ppra as Propane
ppra as Propyl acrylate
ppra as Carbon
G/M3 as Propyl acrylate^'
G/M3 as Carbon^/
G/sec as Propyl acrylate
G/sec as Carbon
lb/ft3 as Propyl acrylate^'
lb/ft3 as Carbon^.'
Ib/hr as Propyl acrylate
Ib/hr as Carbon
Run 2
243
167
1,000
0.792
0.500
4.66
2.94
4.94 x ID"5
3.12 x ID'5
35.9
23.3
Run 3
318
219
1,320
1.04
0.655
6.11
3.86
6.47 x 10"5
4.08 x ID'5
48.4
30.6
Run 4
304
210
1,260
0.991
0.626
5.82
3.67
6.18 x ID'5
3.90 x 10*5
46.1
29.1
Run 5
390
269
1,610
1.27
0.803
7.44
4.70
7.93 x ID'5
5.01 x ID"5
59.0
37.3
Run 6
362
249
1,500
1.18
0.745
6.89
4.35
7.36 x ID"5
4.65 x ID'5
54.7
34.5
Run 7
418
288
1,730
1.36
0.861
8.01
5.06
8.50 x ID'5
5.37 x ID"5
63.5
40.1
Run 7
342
236
1,410
1.12
0.704
6.73
4.25
6.95 x ID"5
4.39 x ID*5
53.5
33.7
Run
328
226
1,360
1.07
0.675
6.41
4.05
6.67 x
4.21 x
50.8
32.1
8
10-5
10-5
Notei Retention index = 845
aj Dry standard conditions.
None detected at outlet or process off-gas locations.
K)
ppm as Propane
ppm as Butyl acrylate
ppra
-------
TABLE 19. GAS CHROMATOGRAPHY ANALYSES FOR TOTAL HYDROCARBONS^-'
to
ppm rtft Propane
ppm us Hydrocarbon*
ppn a a Carbon
C/H1 as Hydrocarbons^'
C/H1 no Carbon?-'
C/3*e as Itydrocatbuii*.
C/scc as Carbon
Ib/ft1 n« Hy.lrocarhon.-'V
Ib/rr1 -9 Carbon*'
Ib/hr as llydrncarbnna
Ib/hr as Cirhon
Propane (ron UK, mode
(column tiyp.ifis) p|»
FfoccBB ofl-aas
ppm aa Propane
ppM SB Itydrocarlmns
ppn as Carbon
C/HJ as Hydrocaibonai'
C/H3 as Carbon"/
C/sec an Hydrocarbons
C/sec as Carbon
lb/ft3 as Hydrocarbons^'
lb/ft J AS Carbon-
Ib/hr as Hydrocarbons
Ib/hr as Carbon
Prop tii' f rna THC mnde
(column bypass) ppta
Out tut
Pi . ».....•
l>pM -*» llydruC'iiiKMift
ppm as Carbon
C/H1 JS Hydrocarbons^/
C/H' as CarUmft/
C/sec as Hydrocarbons
C/sec as Carbon
Ib/fl1 • *» Hydrocarbons^/
lb/€t3 us Carbun£/
Ib/hr a a Hydrocarbons
Ib/hr J« Carbuu
Propane from UK ..vude
(coliatan byprtfic) ppn
1 Kl.iclency
^/ Ucy •.tandjid cundll lutis.
fcm2
1,820.0
2,620.0
8,150.0
7.74
4.16
45.5
24.5
4.ai x
162.0
191.0
740.0s
1 1 , 160.0
12,010.0
35,460.0
28.)
17.6
438.0
161.0
1.14 a
1.42 «
3,490.0
2,860.0
11,300.0
1,890.0
2,610.0
5,780.0
2.91
1)8.0
112.0
2.40 a
1,090.0
942.0
505.0
69.1
Run 3
2,050.0
2,730.0
9,290.0
8.51
4.62
50. 0
27.1
10" 5.29 a
in"4 2.7« .
396.0
216.0
3,670.0
10,780.0
11,460.0
33,810.0
20.3
16. a
386.0
316.0
10"' 1.28 .
10 1.05 a
3,050.0
2,510.0
11,500.0
1 ,690.0
2,450.0
5,350.0
3.30
2.67
127.0
101.0
10"' 2.06 a
10 1.67 a
1. 010.0
814.0
519.0
70.1
Run 4
1,952.0
2,402.0
8,760.0
7.91
6.35
46.4
25.7
III"'' 4.91 „
I0~ 2.71 >
368.0
201.0
3,910.0
11,170.0
11,8)0.0
25,580.0
21.1
17.4
404.0
1)3.0
ID"' 1.32 «
10 1.08 «
3,210.0
2,640.0
12,200.0
1,870.0
2,5)0.0
5.670.0
3.45
2.82
132.0
109.0
10"* 2.15 a
10 1.76 a
1,060.0
860.0
539.0
69.8
Rim 5
2,140.0
2,6)0.0
9.6/1. U
8.74
4.80
51.2
26.0
10"* 5.45 «
10" 1.00 a
405. 0
221.0
), 550.0
10,660.1)
11,330.0
31,290.6
21.2
16.6
)78.0
311.0
ID"? 33.4
10 26.7
3.010.0
2,660.0
12,500.0
374.0
582.0
1.210.0
7.45 a
0.601
24.7
10"' 4.61 a
10" 4.28 a
198.0
160.0
290.0
94.0
Run 6
2,5)0.0
9,590.0
8.61
4.78
50.9
28. 1
10" 5.47 •
III" 2.98 .
4m. o
225.0
1,270.0
11,160.0
11,820.0
34,890.0
21.2
17.4
191.0
122.0
1.12 .
1.09 >
1,110.0
2,560.0
11,100.0
128.0
4)6.0
1,010.0
10 0.691
0.498
20.50
13.0
10 ' 4.31 a
10 3.1) a
148.0
105.0
72.1
96.2
Run 7
2,170.0
2,700.0
9,980.0
8.91
4.81
53.0
29. 3
10"* 5.57 a
III" ' 3.06 >
421.0
2)7.0
), 610.0
12,060.0
1), 260.0
19.340.O
24.8
19.5
458.0
162.0
10"' 1.55 »
III" 1.22 «
), 630.0
2,8)0.0
12,600.0
67.8
105.0
2O9.0
0.137
0.135
4.80
3.49
10 , 8.24 a
10 6.49 a
19.4
27. »
73.3
99.1
Bun 8
1,7110.0
2,500.0
9, 4HO.O
8.47
4.68
51.2
28. 3
10"* 5.29 ,
10 2.91 »
399.0
2)1.0
3,265.0
14, 650. O
15,420.0
45,7)0.0
17.4
22.8
508.0
422.0
10 "J 1.71 a
10" 1.42 a
4,020.0
3,:i50.0
11,600.0
62.4
99.8
191.0
0.120
9.13 «
4.26
10"' 7.35 «
10 5.91 *
13.9
27.2
77. J
99.2
Run 9
2,020.0
2,410.0
9.0W.O
8.06
4.49
48. A
27.4
-4
10 " 5.51 a
10 1.02 >
386.0
217.0
1,190.0
11,490.0
12,380.0
16,760.0
72.8
18.3
417.0
264.0
10~ 1.43 «
10"' 1.14 a
1,1110.0
2.64O.O
12,100.0
21.1
30.6
65.8
, 4.20 «
10 3.29 »
1.56
10"' 2.62 a
10 4.68 a
12.5
9.69
23.8
99.7
I"-*
10"'
III"'
-2
:.-'
io"6
li, pyrolybl*. pr..tjltly <
red balnea del «.:C loit.
-------
Figure 1 is in the ESED Confidential Data Files
23
-------
Figure 2 is in the ESED Confidential Data Files
24
-------
ro
t_n
8 X \0~
(k.
4 X 10"
I I
I I I I I I I I I
I I I I I I I I I I I I I
9 10 II 12 13 14 15 16 17 18 19 20 21 22 23 24 25 24 27 28 29
MINUTES
Figure 3. Outlet chromatogram for Run No. 8.
-------
The identification of the acrylic acid peak in the suction vent samples
is uncertain. The peak which is assumed to be acrylic acid is about 30 sec
early and lies where a small unidentified peak occurs in the outlet and pro-
cess off-gas samples. Without further information from the plant it is as-
sumed that the acrylic acid peak was shifted due to high loading and the
effect of nearby large peaks.
A continuous total hydrocarbon analyzer was used initially for monitor-
ing concentration variations at the suction vent. Two days of operation
showed that the total hydrocarbon levels were stable, with no observable
variations.
Then the analyzer was moved to the outlet breeching for the remainder
of the test. The outlet showed extremely high variability at all times vary-
ing by a factor of 2 to 10 over 5 sec or less. This monitor was then used
to measure the general hydrocarbon levels for adjusting the incinerator con-
trols and detecting process upsets. A condensate trap was necessary on the
inlet of the analyzer to prevent blockage of the instrument pressure regulator
which responded very slowly (later traced to blockage of the gauge capillary).
The difficulties with the pressure gauge readings and the. extreme variability
of the sample concentrations limited the instrument to general trends. An
attempted traverse of the breeching ports with the THC monitor indicated
that the hydrocarbon content may be higher near the west wall at the breech-
ing although the general variability makes this uncertain.
The probe used for the integrated gas sampling had an air leak through
its outer sheath which caused the outlet hydrocarbon C02 and CO readings to
be low and oxygen to read correspondingly high for the first three runs.
The leak was finally found and sealed and no further difficulty occurred
during sampling. For the three leaking runs the observed oxygen and C02
readings were corrected back to the values from Run 4 after the leak was
fixed to obtain an average measurement of the degree of dilution, which was
then applied to the CO, C02, and 02 and hydrocarbon readings for these runs.
The apparent dilution factors were 1.52 for Run 2, 1.84 for Run 3, and 1.84
for Run 4 (all ± 15%).
Grab samples taken simultaneously from the outlet integrated gas sampling
port and the upper stack ports showed that hydrocarbon levels were within
10% at the two locations.
Table 20 shows the results of the total gaseous nonmethane organic (TGNMO)
sampling performed simutaneously 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 gen-
eral drop in the tank samples between the on-site measurements and final
tank analyses may indicate that some components are unstable. Propylene
polymerization is one possibility. Some samples show signs of possible con-
tamination, especially Runs 7 through 9. There is a high probability that
the true hydrocarbon levels are close to the values reported by GC/FID inte-
grated sampling. Appendix A includes the TGNMO sampling and analysis data.
26
-------
TABLE 20. TOTAL GASEOUS NONMETHANE ORGANIC (TGNMO) SAMPLING RESULTS
Trap fraction - ppm GI
Tank fraction - ppm Cj
Total - ppm C}
Total hydrocarbon/FID mode
reading of tank - ppm as
propane (as is)
TUG/FID reading of tank, N2
dilution corrected, ppm
as Clk/
GC/F10 sum - ppm as
carbonS/ of integrated
gas sample
8110-lA
1,240
3,160
4,400
684
4,570
"
RIIO-1B
1,080
3,810
4,890
656
5,430
RHO-2A
1.840
2,780
4,620
644
4,070
5,540
RHO-2B
1,140
2,340
3,480
585
5,120
5,540
RHO-3A
970
3,180
4,150
686
4,220
5,130
RHO-3B
1,970
2,670
4,640
573
4,390
5,130
RHO-4A
400
3,550
3,950
d/
d/
5,520
RHO-4B
890
3,800
4,690
725
5,100
5,520
RHO-5A
1,030
373
1,403
115
1,060
1,130
RIIO-5B
1,480
700
2,180
80
2,000
1,130
RIIO-6A
900
115
1,015
30.2
289
980
RHO-6B
1,660
151
1,811
27.1
307
980
RHO-7A
220
123
343
23.8
209
186
RIIO-7B
330
123
453
25.8
190
186
RHO-8A -'
855
133
988
63.6
377
163
RHO-9A
330
118
448
6.8
73
60
RMO-9B
400
123
523
7.9
69
60
•_/ Single sample due to shortage of equipment.
b/ Three times the value measured as propane. The tanks were originally at negative pressure and pressurized on-slte for the THC field readings.
£/ Excluding methane.
Al Not analyzed.
-------
Table 21 shows GC/FID analyses for selected tank TGNMO samples for com-
ponent identification/quantification. The sum of the peaks is in reasonable
agreement with the total hydrocarbon (THC) values in Table 20. Figure 4
shows a typical chromatogram from the tank samples.
Table 22 shows the evacuated flask aldehyde sampling results with com-
parison values by GC/FID and is on file at ESED. 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 interferences or high molecule aldehydes not detect-
able by GC/FID.
Tables 23 (metric) and 24 (English) summarize the general process param-
eters, flow rates, and bulk gas compositions for the different sampling streams.
Appendix C includes the pitot traverse data. Appendix D contains the integrated
gas sampling data sheets, and Appendix E contains the moisture train data.
The carbon monoxide measurements are included as part of Appendix B. The
water knockout trap for the continuous THC analyzer was used for moisture
measurements for the last runs. The higher sample volume allowed a much
more accurate moisture measurement. Process off-gas moisture was assumed
at 20% based upon measurements found at a similar facility. The moisture
readings measured at the process off-gas line are too low due to problems
with the physical construction of the sampling ports. Much of the condensa-
tion ran back into the duct before it could enter the sample train.
Table 25 shows the results of the fuel gas analyses by GC/FID. A typical
chromatogram is shown in Figure 5. Table 26 shows the results of the NO
sampling. Data sheets for NO sampling are in Appendix F. The high NO
readings for some runs is prooably caused by ambient ammonia entering in
the combustion air supply. A strong odor of ammonia was sometimes noted in
the general process area.
28
-------
TABLE 21. TGNMO TANK SAMPLES ANALYZED BY GAS CHROMATOGRAPHY
Run 4 - RHO-4A Run 4 - RIIO-4B Run 5 - RHO-5A Run 5 - RHO-5B
Component
Methane
Ethyl ene
Acetylene
Ethane
Propylene/propane
Acetaldehyde
Acrolein
Acetone
Total of all peaks
ppm as ,
propane—
41
144
7.4
6.4
232
4.8
2.1
1.8
440
ppd as — Ppm as
C[ propane—
240
852
44
38
1,370
28
12
11
2,600
35.8
158
5.5
6.5
456
5.5
-
-
667
ppm as— ppm as
Cj propane*"
252
1,110
39
46
3,210
39
-
-
4,700
10.3
37.6
1.6
1.0
41.9
0.9
-
-
93
ppm as— ppm as . ppm as—
GI propane— Cj
95 4.8 120
347 16.5 412
15
9
386 18.0 450
8
-
.
860 39 980
Run 8 - RHO-8A
propane—
6.3
18.8
0.9
0.4
10.2
-
-
-
37
ppm as^'
cl
37
111
5
2
60
-
-
-
215
Run 9 - RIIO-9A
PP"> as
propane—
0.8
2.8
0.07
-
1.26
-
-
-
4.9
Run 9 -
ppm as— ppm as .
Cj propane—
9
30
0.8
-
13.5
-
-
-
53
0.9
3.3
0.14
0.06
1.48
0.06
-
-
5.9
RHO-9B
ppm as^'
7.9
29
1.2
0.5
12.9
0.5
-
-
52
at Not corrected for ^ dilution (as is basis).
W These data are corrected for the N2 pressurization and multiplied by three to convert from propane to Cj response.
-------
u>
o
8 X 10
l/x
4X 10
I
I
I
4 X 10""
10 11 12
MINUTES
13
14
15
16
17
18 19 20 21
22
Figure 4. TGNMO tank gas chromatogram (outlet) for Run No. 8.
-------
Table 22 is in the ESED Confidential Data Files
31
-------
TABLE 23. COMPOSITION/FLOW SUMMARY (METRIC UNITS)
OJ
Outlet
Stack velocity m/sec
Flow rate dscm/scc
Mass flow kg/sec
Temperature C
Oxygen %
Carbon dioxide %
Moisture 7.
Carbon monoxide ppra
Combustor
Fuel gas flow m-Vsec
Combustion air flow m-Vsec
Combustion temperature °C
Suction Vent
Flow rate dscm/sec
Mass flow kg/sec
Temperature °C
Oxygen %
Carbon dioxide %
Moisture %
Carbon monoxide ppm
Acid Off Cas I/
Flow rate dscm/scc
Mass flow kg/sec
Oxygen %
Moisture 7.
Carbon monoxide ppm
Temperature °C
Rim No. 1 Run No. 2
10.67
38.8
47.5
201.1
3t 1
5.5~
2.6
5,5302'
0.364
10.03
-
5.88
7.03
9
21
0
0
10
20.43s'
28.0
4.95
20C/
9,640
77.8
Run No. 3
10.31
38.5
51.8
193.9 ,
6<3a/
6.4"
1.1
3.5502'
0.356
10.46
-
5.89
7.05
20
21
0
0
10
18.81£/
26.0
5.65
20£/
9,910
85.6
Run No. 4
10.31
38.5
46.7
193.9
4.8s'
5.8—
1.1
5,540a/
0.352
10.40
-
5.87
7.03
20
21
0
0
10
19.13s'
26.4
5.7
20£./
10,200
85.6
Run No. 5
9.40
33.5
42.2
193.9
4.05
7.5
5.3
1,960
0.378
8.87
-
5.85
7.00
26
21
0
0
10
18.74s'
26.1
5.8
20£./
10,200
86.1
Run No. 6
10.82
37.5
47.0
204.4
5.1
6.0
5.6
1,000
0.426
11.93
-
5.84
6.99
25
21
0
0
10
18.54s'
25.6
5.4
20£/
9,970
83.3
Run No. 7
10.82
37.5
47.3
204.4
4.5
7.0
5.6
600
0.425
11.96
-
5.88
7.04
32
21
0
0
10
18.49s'
25.5
4.55
20£/
9,970
86.7
Run No. 8
11.07
36.5
47.0
201.1
4.45
6.0 .
10. S6'
980
0.441
12.0
-
6.04
7.23
27
21
0
0
10
18.52s'
25.5
4.5
20£/
10,400
86.1
Run No. 9
11.33
37.6
48.6
207.8
4.25
6.75
9.6^
340
0.343
11.81
-
5.99
7.17
26
21
0
0
10
18.22s'
25.1
4.4
20£/
10,300
86.7
a/ Corrected for dilution.
b/ Preferred value.
c/ Assume 20% moisture.
d/ Carbon dioxide content Is in the ESED confidential data files.
-------
TABLE 24. COMPOSITION/FLOW SUMMARY (ENGLISH UNITS)
OJ
Outlet
Stack velocity ft/mln
Flow rate dscf/mln
Mass flow Ib/hr
Temperature F
Oxygen %
Carbon dioxide TL
Moisture Z
Carbon monoxide ppm
Combustor
Fuel gas flow scf/mln
Combustion air flow scf/min
Combustion temperature °F
Suction Vent
Mass flow Ib/hr
Temperature F
Oxygen %
Carbon dioxide X
Moisture 7.
Carbon monoxide ppm
Acid Off Gas ^/
Flow rate dscf/min
Mass flow Ib/hr
Oxygen '/.
Moisture %
Carbon monoxide ppm
Temperature F
Run No. 2
2,100
82,200
377,000
394 a/
5.5—
2.6
5.5302/
772
21,260
-
12,450
55,760
48
21
0
0
10
43.330C/
222,000
4.95
2£/
10,200
187
Run No. 6
2,130
79,500
373,000
400
5.1
6.0
5.6
1,000
902
25,280
~
12,380
55,440
77
21
0
0
10
39,270£/
203,000
5.4
20£/
9,970
182
Run No. 7
2,130
79,500
375,000
400
4.5
7.0
5.6
600
900
25,340
~
12,460
55,820
90
21
0
0
10
39,180£/
202,000
4.55
209-/
9,970
188
Run No. 8
2,180
77,400
375,000
394
4.45
6.0L.
10. 5^'
980
934
25,420
'
12,800
57,330
80
21
0
0
10
39,240£/
202,000
4.5
209J
10,400
187
Run No. 9
2,230
79,700
386,000
406
4.25
6.75
9.6J2/
340
727
25,010
*
12 690
56,830
79
21
0
0
10
38,600£/
199,000
4.4
20£/
10,300
188
a/ Corrected for dilution.
b/ Preferred value.
cj Assume 20% moisture.
d/ Carbon dioxide content is in the ESED confidential data files.
-------
TABLE 25. FUEL GAS ANALYSIS
(ppm as propane)
RI
100
200
300
375
400
480
500
555
575
590
600
630
670
700
755
780
790
800
830
890
Methane
Ethane
Propane
Isobutanc
n-Butane
Branched chain C5
n-Pentane
Branched chain C6
Branched chain C6
Branched chain C6
n-Hexane
Branched chain C7
Branched chain G7
n- Heptane
C8 and above
C8 and above
CS and above
n-Octane
C8 and above
C8 and above
Run No. 2
188,000
21,200
7,700
2,130
2,190
1,110
732
37.1
196
21.2
194
142
160
242
187
.
18.8
17.1
53.0
-
Run No. 3
_
15,800
6,800
2,080
1,990
1,070
693
7.66
347
99
274
ao.i
167
135
223
25.6
.
23
72.7
-
Run No. 4
194,000
18,800
6,990
1,940
2,110
1,080
697
40
248
44.8
205
133
158
232
211
80.2
-
18.2
41.2
-
Run No. 5
193,000
18,300
6,700
1,900
1,880
960
617
41. 2
240
44.8
176
124
139
220
193
26.6
.
6.36
15.7
-
Run No. 6
184,000
18,200
7,320
2,230
2,110
1,100
763
12.6
343
121
267
132
156
238
171
8.08
-
19.1
26.3
-
Run No. 7
136,000
18,500
7,710
2,330
2,230
1,200
802
41.9
379
132
294
171
196
352
246
17.1
37.4
105
-
-
Run No. 8
_
18,100
7,580
2,290
2,250
1,150
764
44.9
371
133
298
154
171
-
216
16.2
-
46.1
92.8
-
Run No. 9
_
18,200
7,040
2,070
1,990
1,030
682
36.5
331
124
267
139
164
280
251
22.1
.
31.8
-
9.71
-------
Ln
0 1 2 3 4 5 61 7 6 9 10 II 12 13 14 IS 16 17 18 19 20 21 22 23 24 25 126 27 28 29 30 31 32 33 34
Figure 5. Fuel gas chromatogram for Run No. 8.
-------
TABLE 26. NOV RESULTS^/
CO
Reported as
Run
No.£/
3
4
5
6
7
8
Ib
1
5.1
4,940
7.5
28.3
15.7
4
of NO? /mi 11 ion
2
4
6,400
247
16.9
4
6.3
ft3, dry
3
4
1,210
15.7
24.9
1,120
4
standard
Average
4
4,200
90
23
380
5
Reported
1
83
80,100 104
122 4
460
255
65
as rag An3
2
65
,000
,010
275
65
102
, dry
3
65
19,600
255
405
18,200
65
standard
Average
70
68,000
1,500
370
6,200
80
a/ Strong odor of ammonia in the general area during several runs.
b/ No sampling during Runs 1 and 2. Samples for Run 9 lost during analysis.
-------
SECTION 3
PROCESS DESCRIPTION AND OPERATION
Acrylic esters are produced using propylene, air and alcohols, with
acrylic acid being produced as an intermediate.
Acrylic acid is produced directly from propylene by a vapor phase cata-
lytic air oxidation process. The reactions take place in two steps both in
the presence of steam as a diluent. Propylene is first oxidized to acrolein
which is then oxidized to acrylic acid according to the following equations:
1. CH2 = CHCH3 + 02 " CH2 = CHCHO + H20 + Heat
Propylene Oxygen (Air) Acrolein + Water
2. CH2 = CHCHO + 1/2 02 CH2 = CHCOOH + Heat
Acrolein Oxygen (Air) Acrylic Acid
A small amount of acetic acid is produced as a by-product. The reactions
take place in fixed-bed multi-tubed reactors which operate at high temperatures
and atmospheric pressure. The heat of reaction is removed through indirect
heat exchange with a cooling medium in the shell side of the reactors. This
heat is then converted to steam in a boiler. There are two trains for the
reaction step. Reactor effluent gas is sent to absorbers where acrylic acid
is recovered in an aqueous solution. The acrylic acid is then extracted
from the aqueous stream in an extraction system common to both trains. Acrylic
acid suitable for esterification with the desired alcohol is available after
solvent recovery. Butyl, ethyl, and methyl esters are produced in a liquid
phase reaction using a catalyst.
The following equation represents the esterification reaction:
H+
CH2 = CHCOOH + ROH CH2 = CHCOOR + H20
Acrylic Acid Alcohol Acrylic Ester Water
Monomer
The reaction product is purified in subsequent refining operations.
Excess alcohol is recovered and heavy end by-products are incinerated.
The attached process schematic shows the general flow scheme of the
process in a block diagram (Figure 6).
37
-------
Atmosphere
I
Incinerator
Boiler
Absorber Gas
Suction Vent Header
CO
co
Propylene.
Air.
Steam •
Waste Organ ics
Oxidation
Section
Separation
Section
Alcohols
Acid
Esterification
Section
Water
Waste
Treatment
Section
n
Products
to Storage
Treated
Effluent
to Sewer
Acid Wastes
to Existing
_ , Recovery Plant
Dewatered
Sludge to
Landfill
Figure 6. Acrylic ester process schematic.
-------
The waste incinerator is designed to burn the off-gas from the two absorb-
ers. In addition, process vents (from extractors, vent condensers and tanks)
which might be a potential source of gaseous emissions are collected in a
suction vent system and normally sent to the incinerator. An organic liquid
stream generated in the process is also burned intermittently providing part
of the fuel requirement. A separate natural gas line supplies the remainder.
Air is added to an amount to produce about 6% 02 in the effluent.
39
-------
SECTION 4
LOCATION OF SAMPLE POINTS
Figure 7 shows a general diagram of the process with the sampling points
marked. Point No. 1, the process off-gas, is at about 70°C, and at 4 in.
mercury positive pressure, so that no sampling pump is necessary. A diagram
of the sampling location is shown in Figure 8. A purged miniture S-type
pitot welded inside a 1/2 in. stainless steel sheath was inserted through
the packing glands and gate valve for sampling and flow traverses. The samp-
ling trains were simply connected to one leg of the pitot. After each run
a two-axis traverse was made.
Point No. 2, the suction vent (shown in Figure 9), is slightly above
ambient temperature, again at positive pressure near ground level with a
1/4 in. valve and fitting used for sampling. This sample is dry ambient
air plus vapors from several storage tanks in the area. No condensation
occurred at ice temperature.
Point No. 3, the incinerator outlet (shown in Figure 10), was used for
all sampling at the outlet except for volumetric flow and temperature, which
were measured at the stack ports (Point No. 4). Sample Point No. 3 was used
due to the difficulty of hoisting equipment to Point No. 4. The integrated
gas sample was run simultaneously with the TGNMO method using separate probes.
Then the moisture train was connected. This was the only sampling point
which required a pump and gas box for integrated gas sampling.
Point No. 5, fuel gas, was taken from a tap near the incinerator. Small
Tedlar bags were flushed and then filled directly from the line.
41
-------
Stack
t
Acrylic Acid Process
Offgas
Sampling Point
Storage Tanks
& Miscellaneous Vents
Suction Vent
Sampling
Points
#3 & #4
Incinerator
Sampling Point "2
Fan
Figure 7. General process diagram.
-------
.7'-4".
Stack I.D.=42"
Flow
10-;
Figure 8. Process off-gas sampling location.
43
-------
2m
Tap for
Sampling
•Flow
Figure 9. Suction ve,nt sampling location.
44
-------
T
27'
40'
ISO1
L
•*-9' I.D.
Port
Sampled
40'
Figure 10. Incinerator outlet and stack.
45
-------
SECTION 5
SAMPLING AND ANALYTICAL PROCEDURES
The integrated gas samples were obtained according to a modified version
of the September 27, 1977, EPA draft benzene method (Appendix G). Seventy-
liter aluminized Mylar or Tedlar 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 condenser ahead of the bag at the outlet
and process off-gas. No condenser was needed at the suction vent. The con-
tents of the condensers were measured by weight difference and stored for
later GC analysis. No heating of the sample bags was used.
At the suction vent and process off-gas sampling points, the duct pres-
sure 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 rota-
meter in place of the bag. The rotameter was then removed and the bag con-
nected 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 chro-
matograph with FID, and a heated Carle gas sampling valve with matched 2
cm3 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°C/
min with temperature hold at upper limit. Nominal running time is 35 min.
THC readings were obtained by peak areas (99 ppm propane is the primary stan-
dard for all analyses).
Peak area measurements were used for the individual component analyses.
A Tandy TRS-80, 48K floppy disc 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 pro-
gram listed in Appendix I. The latter program allows noise filtering, graphic
peak display, and a printed listing of the results. All results presented
are from the filtered output of the second program. Duplicate runs were
made for all samples unless the primary peak areas did not agree within ap-
proximately 10%, in which case further runs were necessary.
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
47
-------
(1 mv reference) with integrator overload occurring at 2.3 mv and integrator
resolution of about 3 (Jv (1 count/3 sec) with normal accuracy of about 6 (Jv
overall including the conversion accuracy of the recorder.
Programming allows appropriate descriptions of each.chromatogram, selec-
table 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 selec-
table 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 then with an overall baseline factor. Both programs
have difficulty giving accurate results for small slowly rising peaks due
to the effect of counting noise. Concentrations are reported using a single
external calibration factor (99 ppm propane standard) using the average of
pre- and posttest standard runs (a minimum of six standard peaks total).
The program result printouts are in Appendix J (in ESED confidential data
files).
The propylene/propane peaks are not resolvable on the column used.
The single observed peak was artificially 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 interac-
tion 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 various samples showed propane as a variable
portion of the composite peak, with significant variations with sample run
or site.
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 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
a midget impinger train 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 ± 5%. The cause of the poor endpoint is still unknown. Analytical log
sheets for this procedures are in Appendix L (in ESED confidential data files).
The residual bag volume was measured and an estimate of the sample vol-
umes withdrawn was made to calculate the gas phase concentrations of the
organics found in the condensates. The condensates were injected directly
in 2 |Jl liquid portions using the conditions established for the gas sampling,
buth with injection through a septum onto the column. Concentrations were
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calculated by peak area using a 1,600 [Jg/g acetone/1,500 [Jg/g acetaldehyde
standard in water. The condensate analyses were performed by digital integra-
tion using an improved analysis program given in Appendix M. Output data
from this program is included in Appendix J.
Stack traverses for outlet flow rate were made using EPA Methods 1
through 4 (midget impingers) and NO was sampled at the outlet using EPA
Method 7. X
Total organic carbon was sampled at the outlet using the tentative EPA
procedure given in Appendix A. The VOC analytical procedure used by PCS
followed the EPA proposed Method 25 except in the calibration procedure and
catalyst checks:
1. Calibration of the analyzer for the analysis of the combusted trap
contents is performed at the following conditions:
a. Oxidation catalyst - on-line
b. Reduction catalyst - on-line
c. Column - 100°C
An attenuation is chosen based on estimated concentrations from the trap
burnout traces (NDIR output) and triplicate injections of two or three stan-
dard (C02 in air) are made. Triplicate injections of the intermediate collec-
tion tank are then made and concentrations calculated by comparing peak areas
to the best fit straight line of the standard data.
2. Calibration for the analysis of the tank portion of the sample is
done again using standards chosen to bracket the expected range of the samples
being analyzed. An attenuation is chosen on the FID to provide adequate
sensitivity and two or three calibration standards are injected in triplicate.
Peak areas are measured by an electronic integrator and the best fit straight
line is calculated for the resulting area versus concentration data. From
this, the sample concentrations are calculated for the nonmethane organics
backflush peak. This calibration procedure is done at a minimum before and
after analysis of a set of samples. Recalibration is of course done should
any of the samples require a sensitivity change.
3. The oxidation catalyst efficiency check is made at the following
conditions:
a. Reduction catalyst - bypassed
b. Oxidation catalyst - on-line at 860 ± 20°C
c. Column - either at 0°C or 100°C
Injections of a standard mixture of CH4 are made at maximum sensitivity and
any response noted. If oxidation is 100% no response will show up. If a
response is noted the concentration is measured and an efficiency of oxidation
49
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calculated. An average efficiency of 99.5% or greater for triplicate injec-
tions is judged acceptable.
4. The reduction catalyst check is performed as follows:
a. Reduction catalyst - on-line at approximately 400°C
b. Oxidation catalyst - bypassed
c. Column - 0°C to permit separation of C02 and CH4
Injections of a mixture of equal concentrations C02 and CH4 are made and
the resulting peak areas compared. Efficiencies typically are 99 to 100%,
which is considered adequate since the manufacturers analysis of the standard
mixture is accurate to only ± 2%.
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 analy-
sis .
Single GC chromatograms 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 N for a listing of
all compound retention indices measured on the analytical column.
Sample calculations for the various methods used are listed in Appendix 0.
A Beckman Model 402 continuous THC analyzer was used for monitoring
general outlet performance and by plant personnel to adjust incinerator per-
formance.
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