POLLUTIO
SSION TEST
O
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Waste Management
Office of Air Quality Planning and Standards
Emission Measurement Branch
Research Triangle Park. North Carolina
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SOURCE TEST TRICHLOROETHYLENE DEGREASER ADSORBER
at
The Vic Manufacturing Plant
Minneapolis, Minnesota
by
George W. Scheil
Midwest Research Institute
EPA Project Report No. 76-DEG-l
FINAL REPORT
EPA Contract No. 68-02-1403, Task No. 16
MRI Project No. 3927-C(16)
For
Environmental Protection Agency
Research Triangle Park
North Carolina 27711
Attn: Mr. William Grimley
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PREFACE
This work reported herein was conducted by Midwest Research In-
stitute (MRI) under the Environmental Protection Agency (EPA) Contract
No. 68-02-1403, Task No. 16.
The project was under the technical supervision of Mr. Paul C.
Constant, Jr., Head, Environmental Measurements Section of the Physical
Sciences Division of MRI. Dr. George W. Scheil served as project leader
and was assisted by Messrs. R. G. Cobb and Bruce DaRos. Messrs. William
Grimley and John Bellinger of EPA assisted with the field activities. Mr.
Grimley, EPA Project Officer, coordinated activities and Mr. Bellinger,
EPA Project Engineer, collected process data.
MIDWEST RESEARCH INSTITUTE
Paul C. Constant, Jr.
Program Manager
Approved:
L. J. VSjhannon, Assistant Director
Physical Sciences Division
February 11, 1976
11
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TABLE OF CONTENTS
I. Introduction i
II. Summary and Discussion of Results ]_
III. Process Description and Operation 11
IV. Sampling Locations 15
V. Sampling and Analytical Procedures 15
Appendix A - Gas Chromatograms 21
Appendix B - Mass Spectra Data 55
Appendix C - Pitot Calculations 64
Appendix D - Method 106 - Determination of Vinyl Chloride From
Stationary Sources 70
iii
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LIST OF FIGURES
No. Title Page
1 Sample Chromatogratn from an Inlet Sample 4
2 Graph of Inlet and Outlet THC Concentrations during
Testing 6
3 Graph of Carbon Adsorption Bed Efficiency . 7
4 Diagram of Degreaser, Carbon Adsorber, Ductwork, and Sample
Points 12
5 Diagram of THC Valve Porting 19
6 Section of THC Recorder Chart 20
C-l Approximate Velocity Profiles in Inlet Duct 66
LIST OF TABLES
No. Title Page
I Gas Chromatography Analysis Data 3
II Half-Hour Averages of THC Analyzer Data 5
III Summary of Analytical Results 9
IV Pitot Data and Calculated Stack Flow Rates at Inlet .... 10
V Workload Data 14
VI Calibration Gas Data 18
B-I Major Peaks - Trichloroethylene Peak Versus Table of Major
Peaks Data 57
B-II Eight Major Peaks of Trichloroethane and Tetrachloroethane. 58
C-I "V Ap Estimates from Figure C-l 67
IV
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I. INTRODUCTION
This report discusses testing of a carbon adsorption unit used
to control vapor emissions from an open top vapor degreaser.* The purpose
of this test was to measure the adsorber bed efficiency, defined as the
percentage of solvent that is adsorbed from the inlet gas stream. The
unit tested was a Model 572, automatic, double-bed, carbon adsorption
system made by Vic Manufacturing Company of Minneapolis, Minnesota. The
adsorber is installed at the Vic Manufacturing plant and has been used
to control trichloroethylene emissions from a Baron-Blakeslee Model D95P
Degreaser for the past 8 years. Vapor emissions from the degreaser pit
are collected by pulling air through lip vents around the top edge of
the pit, filtering out particulates in a dust bag and then adsorbing the
trichloroethylene vapors on activated charcoal beds. The solvent is then
periodically steam-stripped from the beds and reused.
Tests were performed by Midwest Research Institute from September
9 to 11, 1975. The tests included one full cycle of the system from re-
generation until breakthrough occurred on September 10. A shorter cycle
was then tested on September 11. Semicontinuous measurements for total
hydrocarbons were made with a flame ionization detector (FID) on the inlet
and outlet ducts of the carbon adsorber. Several integrated gas-bag sam-
ples were also obtained at both the inlet and outlet ducts. These samples
were analyzed for trichloroethylene by a gas chromatograph equipped with
an FID. The identity of the trichloroethylene peak was confirmed by mass
spectral analysis and a tentative identification made of two minor com-
ponents in the gas stream.
II. SUMMARY AND DISCUSSION OF RESULTS
The inlet concentration of trichloroethylene to the carbon bed
varied over two orders of magnitude during the test. The outlet concen-
tration showed a very smooth gradual increase which appears to be related
only to the total amount of trichloroethylene adsorbed on the bed. Bed
saturation occurred at approximately 15 hr operating time--roughly twice
the usual interval between regenerations at this plant. During the first
8 hr of operation after regeneration, the average bed efficiency met the
design limit of 95% removal of trichloroethylene.
These data are intended to be used for the development of a standard
of performance for new solvent degreaser operations.
-------
Equipment setup was completed on September 8, 1975. Approxi-
mately 1 hr before the end of the shift, both adsorption beds were back
on line after being recycled. At 0820 on September 9, 1 hr after degreaser
startup, and two running hours after bed desorption, the total hydrocarbon
(THC) flame ionization analyzer was brought on-line; therefore, the first
data points occur at 2 hr from the start of the cycle. By 0914, the ve-
locity traverse was completed and the first set of integrated gas sampling
on both inlet and outlet was started. On the first day the calibration
gases were not made until the afternoon so the THC analyzer was calibrated
only at the end of the day. On the following days the THC analyzer was
calibrated in the morning and in the afternoon. The gas chromatograph
calibration was always made immediately before or in the middle of the
sample analyses.
Table I shows the data from the gas chromatography analyses.
Areas were measured by multiplying the height times the peak width at
one-half the height. Due to the instability of the gas chromatograph un-
der field conditions, only the area measurements were used in calculating
•concentrations although the peak heights are also reported. Figure 1 shows
a sample chromatogram. The peak at retention time (Tr) =3.7 rain is the
trichloroethylene peak. Copies of the chromatograms are in Appendix A,
and the results of a mass spectra (MS) analysis of an inlet sample, which
was brought back to MRI after testing, appears in Appendix B. The identi-
fication of the trichloroethylene peak was confirmed with MS with no de-
tectable interferences. The peak at Tr = 3.0 min was identified as 1,1,1
trichloroethane and the peak at Tr = 6.4 min was 1,1,2,2 tetrachloroethane.
The peak at Tr = 1.3 min is the air peak and most of the response probably
comes from methane, although no confirmation of this was possible. The
other peaks were too small to identify.
The peak areas were corrected back to a common sample loop tem-
perature of 50 C, since the gas chromatograph responds to the mass of the
sample and not the concentration. Sample concentrations were obtained
from a linear least square fit of each day's calibration runs.
Table II shows the results of the THC analysis and Figure 2 shows
the THC results in graph form. Figure 3 shows the THC data reported as bed
efficiency. Due to the large quantity of data generated by the THC analyzer
only the 1/2-hr averages are reported here. The morning and evening cali-
brations showed about a 10% drift over 7 to 8 hr. All calibration points
for each day were used to generate a linear least square fit, and the re-
sults of this calculation were used to determine the concentrations at
the inlet and outlet. The sharp decrease at 15 hr corresponds to the re-
generation of the carbon beds from 1300 to 1500 on September 10.
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TABLE I
GAS CHROMATOG8APHY ANALYSIS DATA
Date
9/9
9/10
9/11
Sample
Standard
46 ppm
46 ppm
46 ppm
46 ppm
9.0 ppm
9.0 ppm
9.0 ppm
9.0 ppm
4.6 ppm
4.6 ppm
4.6 ppm
4.6 ppm
Inlet 2
Inlet 2
Outlet 3
Outlet 3
Inlet 1
Inlet 1
Outlet 3
Outlet 3
Inlet 4
Inlet 4
Outlet 5
Outlet 5
4.6 ppm
4.6 ppm
4.6 ppm
8.9 ppm
8.9 ppm
43 ppm
43 ppm
Outlet 6
Outlet 6
Outlet 6
Outlet 9
Outlet 9
Outlet 8
Outlet 8
Inlet 7
Inlet 7
Inlet 7
4.8 ppra
4.8 ppm
45 ppra
45 ppm
9.4 ppm
9.4 ppm
9.4 ppra
Inlet 10
Inlet 10
Inlet 10
Outlet 11
Outlet 11
Outlet 11
Outlet 12
Outlet 12
Outlet 12
Sample Loop
Temperature
(°C)
62
58
55
53
54
54
52
51
51
51
51
51
51
51
51
51
51
51
50
50
51
51
51
51
51
51
51
51
51
50
50
51
51
51
53
53
53
53
51
51
50
46
46
46
46
46
46
46
48
48
48
48
48
48
48
48
48
Peak
Height
800
863
902
968
196
210
202
195
121
124
134
125
1,660
1,710
19
18
1,820
1,880
14.5
15.0
1,700
1,760
148
152
125
110
112
234
228
1,070
1,060
294
313
312
678
677
670
675
2,380
2,400
2,435
120
124
1,380
1,370
286
270
278
1,640
1,570
1,650
81
81
81
80
78
91
Peak Heights/
(Corrected)
830
880
920
980
198
212
203
195
121
124
134
125
1,660
1,710
19
18
1,820
1,880
14.5
15.0
1,700
1,760
148
152
125
110
112
234
228
1,070
1,060
294
313
312 .
685
684
677
683
2,380
2,400
2,435
119
123
1,370
1,360
282
266
274
1,630
1,560
1,640
80
80
80
79
77
90
Peak
Area
3,440
3,800
4,060
4,260
920
880
910
940
545
570
535
525
7,450
7,360
78
77
8,010
8,460
55
52
7,140
7,200
620
610
475
440
448
980
1,010
4,800
4,750
1,260
1,410
1,340
2,850
2,840
3,015
3,040
10,900
11,000
9,980
600
620
5,790
5,750
1,170
1,160
1,140
6,560
6,420
6,590
331
332
34 i
344
329
365
Peak AreaS/
(Corrected)
3,570
3,890
4,120
4,300
930
890
915
940
545
570
535
525
7,450
7,360
78
77
8,010
8,460
55
52
7,140
7,200
620
610
475
440
448
980
1,010
4,800
4,750
1,260
1,410
1,340
2,880
2,870
3,040
3,070
10,900
11,000
9,980
590
610
5,720
5,680
1,160
1,150
1,130
6,520
6,380
6,550
329
330
339
342
327
363
Trlchloroethylene
Measured (ppm)
_
-
-
-
-
-
-
-
-
-
-
-
90
89
0.7
0.7
97
102
0.8
0.8
64
65
5.9
5.8
-
-
-
-
-
-
-
11.6
12.9
12.3
26.1
26.0
27.5
27.7
98
99
89
.
•
-
-
-
-
-
51
50
52
2.9
2.9
2.9
3.0
2.8
3.1
ji/ Peak height/area corrected to sample loop temperature of 50 C.
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\ i
Figure 1 - Sample Chromatogram From an Inlet Sample
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TABLE II
HALF-HOUR AVERAGES OF tHC ANALYZER DATA
Total Hydrocarbons
as Trichloroethylene
(ppm)
Time
9/10
9/11
0820-
0900-
0930-
1000-
1030-
1100-
1130-
1200-
1230-
1300-
1330-
1400-
1430-
1500-
0739-
0839-
0900-
0930-
1000-
1030-
1100-
1130-
1200-
1230-
1300-
1330-
1400.
1430-
1500-
0732-
0820-
0900-
0930-
1000-
1030-
1100-
1130-
1200-
1230-
0900
-0930
-1000
-1030
-1100
-1130
-1200
-1230
-1300
-1330
-1400
-1430
-1500
-1528
-0815
-0900
-0930
-1000
-1030
-1100
-1130
-1200
-1230
•1300
•1330
•1400
• 1430
• 1500
•1527
•0800
0900
•0930
1000
1030
1100
1130
1200
1230
1310
Inlet
83
192
89
144
140
106
99
70
40
133
55
58
115
100
37
117
120
88
111
54
95
134
109
124
127
156
128
110
212
56
136
78
46
54
39
62
40
46
51
Outlet
4.5
4.6
3.9
4.0
4.1
3.6
3.0
2.8
2.9
4.4
4.2
5.7
6.2
8.0
6.7
11.6
14.2
17.8
22.2
27.6
34
41
49
55
86
123
63
6.9
12.2
7.0
7.9
7.8
7.6
7.5
7.3
7.5
7.6
7.3
7.8
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First bed returned to adsorption,
begin desorption of second bed.
First bed desorption begins,
trichloroethylene load to
second bed doubles.
T.ME (H») Desorption
Figure 2 - Graph of Inlet and Outlet THC Concentrations During Testing
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100
a.
~> 80
JJ
x
"«
2
o
IE 60
u
in
O
U
^40
u
z
UJ
u
20
UJ
CQ
8! 10 12 14
TIME (Mrs)
16:
18
20
22
24,
Figure 3 - Graph of Carbon Adsorption Bed Efficiency
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Table III summarizes the integrated gas sample results and com-
pares the approximate THC response found on the integrated samples to the
average level measured by the THC analyzer. The THC response of the chro-
matograms was determined by measuring the total area of the chromatogram,
multiplying it by the trichloroethylene concentration, and then dividing
the result by the area of the trichloroethylene peak. The agreement of
the two methods is excellent considering instrument drift and the approxi-
mation for the THC of the integrated samples.
The data from the daily pitot traverses are given in Table IV.
Although the pitot readings were not made at the proper points prescribed
in EPA Method 2,!/ the sample point was more than 20 diameters from the
nearest flow disturbance, which allows a reasonably accurate velocity
determination since the velocity profile was nearly ideal in the duct.
Details of the calculations are given in Appendix C.
Assuming an average flow of 5,100 scfm, time to breakthrough
of 15 hr, and a density of 5.85 g/liter for trichloroethylene vapor, a
total of 80 kg or 176 Ib of solvent vapor went into the absorber. At the
end of the first cycle, 267 Ib were recovered from the holding tank. An
explanation of this discrepancy is given in Section III.
A value for the bed efficiency of this unit is nearly impossible
to determine due to the large inlet level variations which depend very
strongly on the amount of degreasing being done, the speed of raising work
out of the pit and other variables involved in the degreasing operation.
Since the average inlet level for the first cycle was 104 ppm, an average
bed efficiency of 95 to 97% was observed for the first 8 hr of operation.
For the second cycle, the efficiency was lower, probably due to incomplete
stripping after the bed reached saturation.
From the behavior of the bed during these tests, the outlet con-
centration is independent of the inlet concentration, but instead is a
function of the quantity of solvent present in the bed. The outlet level
rises on a smooth curve independent of changes in the inlet levels. Once
the entire bed reaches saturation, the outlet level increases very rapidly.
During the first 50% of the time to breakthrough, the outlet level is at
a low level and nearly constant.
While trichloroethylene may represent 80% of the inlet THC re-
sponse, it was sometimes only 20% on the outlet. Thus, the use of a THC
analyzer may give inflated readings if used to measure trichloroethylene
in such a unit.
I/ Federal Register, Vol. 36, No. 247, December 23, 1971,
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TABLE III
SUMMARY OF ANALYTICAL RESULTS
Approximate THC Content Time Average of THC
\o
Sample
No.
Inlet 1
Inlet 2
Outlet 3
Inlet 4
Outlet 5
Outlet 6
Inlet 7
Outlet 8
Outlet 9^
Inlet 10
Outlet 11
Outlet 12
Date/Time
9-9/0914-1214
9-9/0914-1214 '
9-9/0914-1214
9-10/0800-1000
9-10/0800-1000
9-10/0949-1049
9-10/1100-1300
9-10/1100-1300
9-10/1100-1300
9-11/0825-1125
9-11/0825-1125
9-11/0825-1125
Trichloroethylene
Found (ppm)
100
90
0.7
64
5.8
12
98
28
26
51
2.9
3.0
of Integrated Bag
Sample (ppm)
125
110
3.5
80
10
20
. 120
45
45
65
6.0
6.0
Analyzer During Bag
Sample Period (ppm)
120
120
3.7
90
12.5
22
115
45
45
70
7.6
7.6
_a/ Leak in the outer container on this sample—very little actual flow until 1215.
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TABLE IV
PITOT DATA AND CALCULATED STACK FLOW'RATES AT INLET
Pitot Traverse and Static Pressure in Inches of Water
Flow Rate
Barometric Stack Standard
Test Inches from Port Static Pressure Temperature Percent 1^0 Velocity Flow Rate Conditions
Date No. ~~~3 ~6 IJJ?jjZ Ts~ Pressure (mm He) (°C) (Assumed) (£t/min) (ft3/min) (ft3/min)
9/9 1 1.00 0.80 0.83 0.81 0.82 6.9 746 21 1 3,180 5,520 5,370
9/10 2 0.70 0.69 0.81 |0.78 0.76 6.5 740 21 1 2,900 5,120 4,860
i—•
o
9/11 3 0.65 0.70 0.82 0.84 0.79 6.6 742 21 1 2,880 5,090 4,840
_a/ Sampling location.
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The major problem encountered during testing was serious leaks
in the outer rigid container on the integrated gas trains. After function-
ing properly on the first day, two of the four containers developed leaks
on the second day. Three partial sets of bag samples were collected on
the second day while repairs were being made. On the third day, no sampling
problems were encountered. Since the rotameter measures only the air going
out of the container, it cannot show if air is being pulled into the outer
case instead of sample gas going into the
III. PROCESS DESCRIPTION AND OPERATION
Figure 4 is a diagram of the degreaser and the carbon adsorp-
tion unit at the plant. The trichloroethylene solvent is boiled at the
bottom of the pit. The vapors then condense on the metal components be-
ing cleaned. Large objects are lowered into the pit by hoist. Smaller
objects are loaded onto a pallet or metal cage which is then lowered into
the pit. The work being cleaned should be left in the pit until condensa-
tion ceases to be formed on the work. Most of the solvent vapor that es-
capes beyond the cooling coils is then pulled into the lip vents around
the top of the pit. The gases go underground to a dust bag behind the
degreaser and through an overhead duct to the carbon adsorption unit.
After passing through the carbon beds, the airstream is vented to the
roof.
The plant normally operates on a 0730-1630 weekday schedule.
When the degreaser is not in use, the adsorption unit and draft fan are
shut down and a lid is put on the degreaser pit. The adsorption unit op-
erates with a nominal flow of 5,000 cfm and both beds in parallel. In .
normal operation for this plant, the beds are recycled once per 8-hr day.—
The first bed is usually steam-stripped for about 1 hr, then the second
bed is similarly regenerated. With one bed on recycle, the air flow is
cut to 3,000 cfm. The recovered trichloroethylene is condensed out, sep-
arated from the water condensate, and then stored in a holding tank for
later return to the degreaser. The unit design adsorption rate is 225
Ib/hr of trichloroethylene.
However, to develop breakthrough data, the beds were not desorbed until
14 operating hours had elapsed.
11
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18" Round Duct
ROOF
VENT
10-1/2'
1/2" Outlet
Port
Figure 4 - Diagram of Degreaser, Carbon Adsorber, Ductwork, and Sample Points
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The equipment specifications for the carbon bed and degreaser
are summarized below:
Equipment Specifications
For Carbon Adsorption System
Beds: Two
Depth: 20-21 in. carbon
1,500 Ib carbon per bed
Diameter - 72 in.
Type activated carbon: Union Carbide JXC4 by 10
Age carbon: installed 1968—about 7 years old
Model: No. 572 Vic
Fan: 20 h.p.
Duct diameter: 18 in.
Steam pressure: 2-4 psig
Scheduling: Regenerated each bed once per 8-hr day usually 12:30
to 1:30 and 1:45 to 2:45 p.m.
Fan: 7:15 a.m. to 3:30 p.m.
For Degreaser
Type: Open top vapor degreaser
Model: Baron Blakeslee Model No. D95P
Opening: 5 ft by 12 ft 6 in. - freeboard
4 ft by 12 ft - vapor chamber
Freeboard height: 34 in. when at equilibrium (i.e., solvent vapor
line to lip)
Heating: steam at about 12 psig
Cooling coils: seven levels; condensing on second to bottom coil;
uses tap water
Solvent: Trichloroethylene
Table V lists the workload of the degreaser during the test as
recorded by the EPA project engineer.
Solvent Recovery Data
The data of the solvent recovered from the carbon adsorber are
too inaccurate to use. A malfunction of the carbon adsorber condenser and
water separator caused the inaccuracy. The purpose of the data was to pro-
vide a check for the concentration measurements.
13
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TABLE V
WORKLOAD DATA
12/9/75
Tuesday
morning
Tuesday
afternoon
Wednesday
. a/
morning—
Obiect Cleaned
Large rack load
Smaller rack load
Square tank
Rack load
Rack load
Cylinder wrap
Heads
Long cylinder
Unit Weight
(lb)
1,025
965
250
965
965
900
1,500
1,000
Times
Cleaned
4
5
2
2
3
1
2
1
Total
Total Weight
(lb)
4,100
4,825
500
1,930
7,720
900
3,000
1,000
23,975
« 12 tons
_a/ Workload data was recorded until desorption began. That is time
200 to 1400.
14
-------
The solvent recovered was measured as 267 Ib or 24 gal., but
this is based upon the incorrect assumption that the solvent in the wa-
ter separator was all boiled away* One to 3 days before the test began
a malfunction occurred when the cooling water from the condenser cut off.
Consequently, the steam passed directly into the water separator and
boiled off most of the solvent. Vic personnel made no mention of this up-
set until John Bellinger inquired as to why the recovery system failed
to produce solvent after the September 10 desorption. Although the con-
denser cooling system had been corrected, most of the solvent had been
boiled out of the water separator, thus upsetting the measurements. The
water separator normally contains a constant volume of solvent, so that
the runoff after each desorption equals the solvent recovered. An unde-
termined volume in the separator was boiled off during the malfunction,
so that the amount of desorbed solvent could not be quantified. An ap-
proximation of the solvent desorbed comes to 176 Ib as derived from av-
erage flow and concentration data. The value of 267 is unreasonably high
in comparison, and thus the assumption that the water separator was empty
before the measured desorption is probably incorrect.
IV. SAMPLING LOCATIONS
The sampling points are shown in Figure 4. Since the adsorption
unit is sealed (no flow can be added or lost between inlet and outlet),
pitot traverses were run only on the inlet duct. After the traverse was
run each morning, the pitot was fixed at the center of the duct and both
inlet and outlet integrated samples were drawn proportional to this pitot
reading. At both the inlet and the outlet a 1/4-in. O.D. stainless steel
probe was mounted with the end of the tube at the center of the duct. A
glass wool plug in the end of the probe kept out particulates. The 1/4-in.
O.D* stainless steel sample lines were wrapped with heating tape and heated
slightly above ambient temperature to prevent condensation. The inlet and
outlet lines were brought to the THC analyzer which was located on a table
between the sample points. At the analyzer, each sample stream was then
split with lines going into the analyzer and to the integrated gas bags.
V. SAMPLING AND ANALYTICAL PROCEDURES
Integrated gas sampling and analysis was done according to the
July 18, 1975 draft procedure for Method 106 - Determination of Vinyl
Chloride from Stationary Sources. A copy of the procedure is given in
Appendix D. For this test the following changes and modifications were
made in the procedure:
15
-------
1. The Teflon tubing used to connect the Tedlar bags to the
various other parts of the apparatus was not changed for each sample due
to the low reactivity of trichloroethylene.
2. Since an automatic sample valve was not available, a man-
ually operated valve with a 5-ml stainless steel loop was used. The sam-
ple loop temperature was approximately 50 C.
3. The column used was a 3 m x 1/8 in. O.D. stainless steel
column packed with 20% SP-2100/0.1% Carbowax 1500 on 100/120 mesh Supel-
coport. The column was operated at a flow rate of 20 ml/min and 120° C.
4. The calibration procedure was modified since trichloro-
ethylene boils above room temperature. A septum vial containing a small
amount of liquid trichloroethylene was immersed in a water bath at room
temperature. A gas tight syringe was then flushed twice from the vial
headspace and then filled to maximum. After briefly flaming the needle
to expel any trace of liquid, the plunger was set to the proper volume
and gas was injected into the Tedlar bag in the normal manner.
The primary danger in using this method is that traces of liq-
uid might be injected into the bag with the saturated vapor. If care is
taken to ensure that the needle does not contact the liquid phase, the
only source of liquid is the thin film of liquid on the inside surface
of the septum. By briefly heating the needle before setting the plunger
to the proper index mark, any liquid within the needle or on its outer
surface will be boiled off. (Since the syringe is already filled with va-
por, the vapor from the boiling trichloroethylene will be expelled out
the end of the needle.)
The temperature of the water bath was measured with an accur-
ate thermometer and the barometric pressure was also measured. With this
information the vapor pressure of trichloroethylene can be calculated :i/
log 10 PT = 7.02808 -
The final trichloroethylene concentration (C) is then:
*T • Vi
„
C =
P . V . 1,000
j./ Lange, Handbook of Chemistry, 10th Edition, p. 1438 (1961),
16
-------
P is the barometric pressure in mm Hg, Vi is the volume in
milliliters of gas injected, and V is the volume in liters of nitrogen
in the bag. The calibration data for this test are given in Table VI.
5. The flow rate into the Tedlar bags was not always 0.5 liters/
min, but varied according to the sampling duration of each run. On the 9th
the flow rate was initially 0.25 liters/min, on the 10th it was 0.5 liters/
min, and on the llth the flow rate was 0.4 liters/min. During all runs
the pitot reading did not change enough to require a change in the sampling
rate initially established.
6. When analyzing the calibration gases the bag was connected
directly to the sample valve and compressed gently for 10 sec to purge
the valve. Then the valve was actuated immediately, and a shut-off valve
located on the sample inlet was closed until the next sample.
Total hydrocarbons were measured with a modified Beckman Model
6800 THG Analyzer. The instrument was modified so that the two sample
streams could be alternately injected directly into the flame ionization
detector. A 10-port pneumatic sample valve inside the instrument was con-
nected as shown in Figure 5. The sample loops had 1-ml volumes. The carrier
gas used was air. The vent connections went to a small vacuum pump via
flow restrictors so that each sample line was being pulled through the
valve by the pump. At a flow rate of *" 100 ml/min the sample loops re-
main at ambient pressure. The instrument was calibrated each day using
the same gas mixtures used to calibrate the gas chromatograph. The inter-
nal valve control timing was set to activate the valve to sample the first
gas stream, then, 30 sec later, the valve deactivated to sample the sec-
ond stream. At 60 sec the master timer is reset and begins a new cycle.
Thus the recorder trace shows peaks every 30 sec with every other peak
being on the same sample line. A sample of the chart is shown in Figure
6. The series of peaks which slowly increase from right to left repre-
sent the outlet concentration. The highly variable peaks in between are
for the inlet. The analyzer also contains provisions for differing scale
factors for the two peaks. In the example the inlet is operating at a
xlO attenuation factor and the outlet at xl. The sudden increases in the
inlet readings are caused by work being lowered or raised into the de-
greaser pit, which disturbs the air flow temporarily. Also, if the work
is raised rapidly, some solvent evaporates after passing the cooling zone
and the vapor is then drawn into the lip vent.
17
-------
TABLE VI
CALIBRATION GAS DATA
00
Nominal
Concentration
Date (ppm)
9/9
9/10
9/11
5
10
50
5
10
50
5
10
50
Rotameter
Reading
(mm)
141
141
141
140
140
140
139
139
139
Flow Rate Time
(liter/min) (min)
.806 12.0
.806
.806
.800
.800
.800
.794
.794
.794
10.0
10.0
12.0
10.0
10.33
12.25
10.0
10.5
Volume
Injected
(ml)
.5
.8
4.0
.5
.8
4.0 -
.5
.8
4.0
PT
(mm Hg)
66
68
69
66
66
66
69
69
69
P
(mm Hg)
746
746
746
740
740
740
742
742
742
N£ Volume
(liter)
9.672
8.06
8.06
9.60
8.00
8.26
9.73
7.94
8.34
Concentration
(ppm)
4.6
9.0
46
4.6
8.9
43
4.8
9.4
45
-------
Sample In
Carrier Gas
#2 Loop
Sample In
Vent
Vent
Loop
#2Loop
Figure 5 - Diagram of THC Valve Porting
19
-------
I
I
*
-9
-s—-I-
%t
u
-I
-1 -
• t
1
irio — -•
Figure 6 - Section of THC Recorder Chart
(chart reads from right to left)
20
-------
APPENDIX A
GAS CHROMATOGRAMS
21
-------
NO. 497000 ItlDS !'• NO»IH»UP CO.. PHItA.
-------
JSL L_ •' i jL _..
-------
-------
NO. 491000
-------
IKlDS 11 NO«IM»UP CO.. PHUA.
I
80
70
60
50
40-
i • i y ..
26
-------
NO. 492000 IflOS & NORTHRUP CO.,
-------
NO. 492OQO IffDS & NOtTHttJP CO.. *HUA.
28
-------
-------
NO. <97000 IFf&S e. Mrn'-'iKUP CO, PHUA.
--t™
90
SO
70
60
40-
30
20
-------
HO. 1920OO ICO', & NOR!HDU(> Co
1.
-------
??000
-------
NO, 477000 inn-, & uOBTMRUP CO. FMII ».
33
-------
NO. 477OOO IEFOS 4 NOftTHRUP CO.. FHHA.
-------
NO. 497000 ICFOS & HORIHB'jp en, PHIU.
-------
NO. 4'
-75
90
80
70-
60
50
40
36
-------
37
-------
-------
39
-------
40
-------
NO. 497000 IFiy, r. NOR'HRVP C
-------
& NO
AUl. I.'J I.I ', /
-------
'0' 1 NOHNtUP CO. TMII4.
43
-------
-------
AM IN IJ, \ A
45
-------
46
-------
NO. 49200O urnr, t. un'.THtur co. pint*:
47
-------
NO. 49IOOO UID5 (V NOPnixup CO.. rmi*.
-------
49
-------
NO. t.'.'OTO
-------
NO. 4?tOOO IKDS i NC'?'t<9'jr CO. PHIIA.
51
-------
52
-------
53
-------
54
-------
APPENDIX B
MASS SPECTRA DATA
55
-------
A mass spectra scan using conditions identical to those during
the field test shows only three identifiable peaks. The air peak obscures
the peaks with retention times of 1.3 and 2.1 rain. The peak with reten-
tion time of 3.7 min is the trichloroethylene peak. Table B-I shows the
major mass peaks and their intensities. All eight characteristic peaks
are present in the scan (labeled 7416 by the mass spectrometer) and the
correlation is excellent for this peak. No evidence of a co-eluting in-
terference could be found in the MS data.
The scan labeled 7413 corresponds to the peak of retention time
3.0 min and the scan labeled 7427 corresponds to the peak of retention
time 6.4 min. The mass spectral scans for these are of low intensity.
Table B-II shows the eight major peaks of the probable compounds in order
and indicates only the presence (+) or absence (-) in the scan. A (B) in-
dicates the peak also appeared in the background scan. The probable major
components of these peaks are 1,1,1 trichloroethane for 7413 and 1,1,2,2
tetrachloroethane for 7427. Copies of the computer scan for the three
peaks and the background scan together with the ion-current response of
the chromatogram follow Table B-II.
56
-------
TABLE B-I
MAJOR PEAKS - TRICHLOROETHYLENE PEAK VERSUS TABLE OF MAJOR PEAKS DATA
Trichloroethylene
Maior Peaks
Mass Relative Intensity
130
132
95
97
134
60
99
62
100
97
87
57
32
27
9
9
Mass
130
132
9 5 a/
97
60
134
62
99
Scan No. 7416
Relative Intensity
100
80
69
60
32
28
9
6
j*/ Also in background.
57
-------
TABLE B-II
EIGHT MAJOR PEAKS OF TRICHLOROETHANE AND TETRACHLOROETHANE
00
1,1,1 Trichloroethane
Mass Scan 7413
97 +
99 +
61 +
26 B
27 B
63 +
117 B
119 +
1,1,2 Trichloroethane
Mass Scan 7413
83
97 +
61 +
85 B
99 +
26 B
27 B
63 +
1,1,2,2 Tetrachloroethane
Mass Scan 7427
83 B
85 B
168 +
87
95 B
166 +
131 +
133 B
1,1,1,2 Tetrachloroethane
Mass Scan 7427
131 +
133 B
117 B
119
135
95 B
121
97
-------
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29
30
32
36
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63
-------
APPENDIX C
PITOT CALCULATIONS
64
-------
Since the pitot readings were not made at the centroids of equal
areas, some method of estimating the proper readings must be made. By plot-
ting the square roots of the pitot readings versus distance from the port
(shown in Figure C-l) and reading the profiles at the normal equal area
centroids, an average value of the stack velocity can still be calculated
using Eq. 2-2 of EPA Method 2.1/ The readings from this method of approxi-
mation are given in Table C-I. The readings from the second axis are as-
sumed to be equivalent. Due to the nearly flat velocity profile, the re-
sulting average flow velocity error is < 5%, even though the wrong points
were measured. Copies of the original data sheets are at the end of this
section. After making the approximation for ~V Apave. > all calculations
were made using EPA Method 2.
II Federal Register. Vol. 36, No. 247, December 23, 1971,
65
-------
1.1
%
*
1.0
\
0.9
0.8
0.7
0.6
I
I
I
0
6 9 12
INCHES FROM PORT
15
18
Figure C-1 - Approximate Velocity Profiles in Inlet Duct
66
-------
TABLE C-I
Ap ESTIMATES FROM FIGURE C-l
Ap from Figure C-l
Point No.
1
2
3
4
y
(1.2 in.)
(4.5 in.)
(13.5 in.)
(16.8 in.)
Ap
1
0
0
0
0
9-9
.06
.92
.91
.87
.94
9-10
0
0
0
0
0
.85
.83
.87
.87
.855
9-11
0
0
0
0
0
.79
.83
.91
.87
.85
ave
67
-------
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68
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Project No.
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69
-------
APPENDIX D
METHOD 106 - DETERMINATION OF VINYL
CHLORIDE FROM STATIONARY SOURCES
70
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METHOD 106—DETERMINATION OF VINYL CHLORIDE
FROM STATIONARY SOURCES
INTRODUCTION
Performance of this method should not be attempted
by persons unfamiliar with the operation of a gas
chromatograph, nor by those who are unfamiliar with
source sampling, as there are many details that are
beyond the scope of this presentation. Care must be
exercised to prevent exposure of sampling personnel
to vinyl chloride, a carcinogen.
1. Principle and Applicability.
1.1 An Integrated bag sample of stack gas containing vinyl
chloride (chloroethene) is subjected to chromatographic analysis,
using ,a flame ionization detector.
-'1.2 The method is applicable to the measurement of vinyl chloride
in stack gases from both vinyl chloride and polyvinyl chloride manu-
facturing processes, except where the vinyl chloride is contained in
particulate matter.
2. Range and Sensitivity.
^
The lower limit of detection will vary according to the
chromatograph used. Values reported include 1 x 10 mg and
4 x 10"7 mg. .
3. Interferences.
In the course of a study to identify the interference potential
of several hydrocarbons associated with vinyl chloride, none were
found to prevent resolution of the vinyl chloride peak with the
Chromosorb 102 column. However, if resolution of the vinyl
Mention of trade names on specific products does not constitute
endorsement by the Environmental Protection Agency.
71
-------
chloride peak is not satisfactory for a particular sample, then
chromatograph parameters may be altered with prior approval of
the Administrator.
4. Apparatus.
4.1 Sampling (Figure 1).
4.1.1 Probe—Stainless steel, Pyrex glass, or Teflon .tubing
according to stack temperature, each equipped with a glass wool
plug to remove particulate matter.
4.1.2 Sample line—Teflon, 6.4 mm outside diameter, of
sufficient length to connect probe to bag. A new unused piece is
employed for each series of bag samples that constitutes an emission
test.
4.1.3 Male (2) and female (2) stainless steel quick-connects,
with ball checks (one pair without) located as shown in Figure 1.
4.1.4 Tedlar bags, 100 liter capacity—To contain sample.
*
4.1.5 Rigid leakproof containers for 4.1.4, with covering to
protect contents from sunlight.
4.1.6 Needle valve—To adjust sample flow rate.
4.1.7 Pump—Leak-free. Minimum capacity 2 liters per minute.
4.1.8 Charcoal tube—To prevent admission of vinyl chloride to
atmosphere in vicinity of samplers.
4.1.9 Flow meter—For observing sample flow rate; capable of
measuring a flow range from 0.10 to 1.00 liters per minute.
4.1.10 Connecting tubing—Teflon, 6.4 mm outside diameter, to
assemble sample train (Figure 1).
72
-------
4.1.11 Pi tot tube—Type S (or equivalent), attached to the
probe so that the sampling flow rate can be regulated proportional
to the stack gas velocity.
4.2 Sample recovery.
4.2.1 Tubing—Teflon, 6.4 mm outside diameter, to connect bag
to gas chromatograph sample loop. A new unused piece is employed
for each series of bag samples that constitutes an emission test,
and is to be discarded upon conclusion of analysis of those bags.
4.3 Analysis.
4r.3.1 Gas chromatograph--With flame ionization detector,
potentiometric strip chart recorder and 1.0 to 5.0 ml heated
sampling loop in automatic sample valve.
4.3.2 Chromatographic column—Stainless steel, 2.5 m x 6.4 mm,
containing 80/100 mesh Chromosorb 102.
4.3.3 Flow meters (2)—Rotameter type, 0 to 100 ml/min capacity.
4.3.4 Gas regulators—For required gas cylinders.
4.3.5 Thermometer—Accurate to one degree centigrade, to
measure temperature of heated sample loop at time of sample injection.
4.3.6 Barometei—Accurate to 5 mm Hg, to measure atmospheric
pressure around gas chromatograph during sample analysis.
4.4 Calibration.
4.4.1 Tubing—Teflon, 6.4 mm outside diameter, separate pieces
marked for each calibration concentration.
4.4.2 Tedlar bags—Sixteen-inch square size, separate bag
marked for each calibration concentration.
4.4.3 Synnge~-0.5 ml, gas tight.
73
-------
4.4.4 Syringe--50 pi, gas tight.
4.4.5 Flow meter—Rotameter type, 0 to 1000 ml/min range
accurate to ± IX, to meter nitrogen 1n preparation of standard
gas mixtures.
4.4.6 Stop watch—Of known accuracy, to time gas flow In
preparation of standard gas mixtures.
5. Reagents. It 1s necessary that all reagents be of chromatographic
grade.
5.1 Analysis.
5.1.1 Helium gas or nitrogen gas—Zero grade, for chromato-
graphic carrier gas.
5.1.2 Hydrogen gas--Zero grade.
5.1.3 Oxygen gas—Zero grade.
5.2 Calibration.
5.2.1 Vinyl chloride, 99.9+3S~For preparation of standard gas
mixtures.
5.2.2 Calibration cylindecs (3), optional—One each of 50, 10
and 5 ppm vinyl chloride in nitrogen with certified analysis.
5.2.3 Nitrogen gas—Zero grade, for preparation of standard
gas mixtures.
6. Procedure.
6.1 Sampling. Assemble the sample train as in Figure 106-1.
Perform a bag leak check according to Section 7.4. Observe that all
connections between the bag and the probe are tight. Place the end
of the probe at the centroid of the stack and start the pump with
74
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the needle valve adjusted to yield a flow of 0.5 1pm. After a
period of time sufficient to purge the line several times has
elapsed, connect the vacuum line to the bag and evacuate the bag
until the rotameter indicates no flow. Then reposition the sample
and vacuum lines and begin the actual sampling, keeping the rate
proportional to the stack velocity. Direct the gas exiting the
rotameter away from sampling personnel. At the end of the sample
period, shut off the pump, disconnect the sample line from the bag,
and disconnect the vacuum line from the bag container. Protect the
bag container from sunlight.
r
6.2 Sample Storage. Sample bags must be kept out of direct sun-
light. When at all possible, analysis is to be performed within 24
hours of sample collection.
6.3 Sample recovery. With a new piece of Teflon tubing
Identified for that bag, connect a bag inlet valve to the gas chro-
matograph sample valve. Swjtch the valve to withdraw gas from the
bag through the sample loop.
6.4 Analysis. Set the column temperature to 155°C, the detector
temperature to 225°C, and the sample loop temperature to 70°C. When
optimum hydrogen and oxygen flow rates have been determined, verify
and maintain these flow rates during all chromatograph operations.
Using zero helium or nitrogen as the carrier gas, establish a flow
rate in the range consistent with the manufacturer's requirements for
satisfactory detector operation. A flow rate of 40 ml/min has been
shown to produce adequate separations. Observe the base line
periodically and determine that the noise level has stabilized and
that base line drift has ceased.. Purge the sample loop for thirty -
75
-------
seconds at the rate of 10.0. ml/min, then activate the sample valve.
Record the injection time (the position of the pen on the chart
at the time of sample injection), the sample number, the sample
loop temperature, the column temperature, carrier gas flow rate,
chart speed and the attenuator setting. Record the laboratory
pressure. From the chart, select the peak having the retention
time corresponding to vinyl chloride, as determined in Section 7.2.
Measure the peak area, Am, by use of the automatic integrator.
Record A and the retention time. Repeat the injection at least
two times or until two consecutive vinyl chloride peaks do not vary
1n area more than 5%. The average value for these two areas will be
used "to compute the bag concentration.
7. Calibration and Standards.
7.1 Preparation of vinyl chloride standard gas mixtures. Evacuate
a sixteen-inch square Tedlar bag that has passed a leak check (described
1n Section 7.4) and meter in 5.0 liters of nitrogen. While the bag is
*
filling, use the 0.5 ml syringe to inject 250 yl of 99.9+% vinyl
chloride through the wall of the bag. Upon withdrawing the syringe
needle, immediately cover the resulting hole with a piece of ad-
hesive tape. This gives a concentration of 50 ppm of vinyl chloride.
In a like manner use the other syringe to prepare dilutions having
10 and 5 ppm vinyl chloride concentrations. Place each bag on a
smooth surface and alternately depress opposite sides of the bag
50 times to further mix the gases.
7.2 Determination of vinyl chloride retention time. This
section can be performed simultaneously with Section 7.3, Establish
76
-------
chromatograph conditions identical with those in Section 6.3,
above. Sst attenuator to X 1 position. Flush the sampling loop
with zero helium or nitrogen and activate the sample valve. Record
the injection time, the sample loop temperature, the column tempera-
ture, the carrier gas flow rate, the chart speed and the attenuator
setting. Record peaks and detector responses that occur in the
absence of vinyl chloride. Maintain conditions. Flush the sample
loop for 30 seconds at the rate of 100 ml/min with one of the vinyl
chloride calibration mixtures and activate the sample valve. Record
the injection time. Select the peak that corresponds to vinyl chloride.
r
Measure the distance on the chart from the injection time to the time
at which the peak maximum occurs. This quantity, divided by the
chart speed, is defined as the retention time. Record.
7.3 Preparation of chromatograph calibration curve. Make a
gas chromatographic measurement of each standard gas mixture (described
1n Section 7.1) using conditions identical with those listed in
Section 6.3 above. Flush the sampling loop for 30 seconds at the
rate of 100 ml/min with each standard gas mixture and activate the
sample valve. Record C , the concentrations of vinyl chloride
\*
injected, the attenuator setting, chart speed, peak area, sample
loop temperature, column temperature, carrier gas flow rate, and
retention time. Record the laboratory pressure. Calculate A , the
C
peak area multiplied by the attenuator setting. Repeat until two
Injection areas are within 5%, then plot those points vs Cr. When
v«
the other concentrations have been plotted, draw a smooth curve
77
-------
through the points. Perform calibration daily, or before and
after each set of bag samples, whichever is more frequent.
7 .'4 Tedlar bag leak checks. Before each use, make sure a
bag is leak-free by checking it for leaks. To leak check, connect
a water manometer and pressurize the bag to 5-10 cm H20 (2-4 in. 1^0
Allow to stand for 10 minutes. Any displacement in the water
manometer indicates a leak. (Note: An alternative leak check
method is to pressurize the bag to 5-10 on H20 or 2-4 in. H20 and
allow to stand overnight. A deflated bag indicates a leak.)
8. Calculations.
r
8.1 Determine the sample peak area as follows:
A,. = /LA* Equation 106-1
c m f _ ^
where:
AC = The sample peak area.
= The measured peak area.
A, = The attenuation 'factor.
8.2 Vinyl chloride concentrations. From the calibration curve
described in Section 7.3, above, select the value of C that corresponds
to A_, the sample peak area. Calculate C. as follows:
CRT.
Cb s p T 1 Equation 106-2
i r
where:
C. = The concentration of vinyl chloride in the bag sample
1n ppm.
Qc = The concentration of vinyl chloride indicated by the gas
chromatograph, in ppm
»•»
78 '
-------
V, iv
/v\
Liter(Glass Wool)
Probe
t
Reverse("S") Type
Pitot Tube
Stack Wall
X
w
Pitot Manometer
Teflon^
Sample Line
Vacuum Line
Ball -j.
Checks u
Male
Quick
IT No
U Checks
Flow Meter
Needle Valve
Pump
Rigid Leak Proof
Container
?.-;;//<• i:'-'-.fi •'•••" -A.
^^iv^v^r
A
Charcoal Tube
Figure 106-1. Integrated bag sampling train.
(1)
Mention of trade names on specific products does not constitute
endorsement by the Environmental Protection Agency.
-------
P ° The reference pressure, the laboratory pressure recorded
during calibration, mm Hg.
T, « The sample loop temperature on the absolute scale at the
time of analysis, °K.
P.. = The laboratory pressure at time of analysis, mm Hg.
T = The reference temperature, the sample loop temperature
recorded during calibration, °K.
9. References.
1. Brown, D. W., Loy, E. W. and Stephenson, M. H. "Vinyl
Chloride Monitoring Near the B. F, Goodrich Chemical Company in
Louisville, Kentucky." Region IV, U. S. Environmental Protection
Agency, Surveillance and Analysis Division, Athens, Georgia,
June 24, 1974.
2. "Evaluation of A Collection and Analytical Procedure for
Vinyl Chloride in Air," by G. D. Clayton and Associates, December 13,.
1974. EPA Contract No. 68-02-1408, Task Order No. 2, EPA Report
No. 75-VCL-l.
80 '
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