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RECEIVED
APR 14 1969 DEPT 5475
A Study of Vinyl Chloride Vapor Concentrations in Avon Lake Polymerizers
E.B. Katzenmeyer, -Jr. E.G. DeCapita R.S. Morgan
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Summary
The level of vinyl chloride in the atmosphere of a polymerizer after various suction times is quantified. It is concluded that if 500ppm is the allowable maximum when a man enters the poly, there is very little margin of safety in the current plant procedure. In fact, there probably are occasions when the concentration of vinyl chloride exceeds 500 ppm when a man enters a poly.
If the allowable maximum were reduced to the order of 100 ppm, some major changes will be needed. More efficient air changes of poly atmosphere and/or early removal of most of the polymer adhering to the poly surface will be needed.
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Introduction:'
During mid-1967, it was agreed between Mr. J.L. Nelson and Mr. W.E. McCormick that studies should be conducted in polymerizers of one or two of the PVC Plants to evaluate personnel exposures to vinyl chloride during poly cleaning operations. Some preliminary studies were subsequently carried out at both the Louisville and Avon Lake Plants, but an analysis of this data indicated a questionable reliability. Therefore, during the*last quarter of 1968, a more detailed group of studies was carried out to quantify the effect of some of the variables experienced during poly cleaning operation at the Avon Lake General Chemical Plant. The collection of the samples and the measurements of the poly ventilation rates were performed by Mr. Katzenmeyer. These samples were analyzed by gas chromatographic techniques by Mr. DeCapita and his group. The statistical analyses of the results were performed by Mr. Morgan. The results obtained and the conclusion accruing from them follow.
Results:
148 separate air samples were collected between the period of 9-18-68 to 11-19-68 in 32 different polys. Ten different resins were manufactured in these polys in the Avon Lake Plant. The air samples were collected by a technique developed between Mr. DeCapita and the Department of Industrial Hygiene and Toxicology, involving the use of a small evacuated glass vial placed at a specific location in the poly to extract an instantaneous air sample from the poly. Two sampling locations were chosen: at the level of the bottom agitator, and at 6 ft. above the floor of the polymerizer. Both locations were on the center vertical axis of the poly. The collected samples were transmitted on the same day to Mr. DeCapita for subsequent gas chromatographic analyses. When vinyl chloride concentration exceeds 100,000 ppm, the absolute value of the number becomes questionable, but is thought to be relatively reliable. In order to obtain a reliable estimate of the ambient vinyl chloride concentration in the poly workroom, an air sample was collected 1 ft. above the open manhole of the poly being sampled, during the period of ventilation of the poly.
The results of these studies are presented in Table I. They show that poly concentrations vary from 10 ppm to 300,000 ppm, depending upon; the time at which the sample was taken, the location at. which the sample was collected, the type of resin being manufactured, and the rate of ventilation of the poly. The vinyl chloride concentration was not effectively reduced by washing poly walls with water after opening.
The ventilation rate of each poly, in which atmospheric samples were taken, was measured. This was performed by using an Alinor Velometer to determine the inward air velocity through the manhole. The results of these measurements are also shown in Table I. The ventilation rate was found to vary from 23 to 551cfm with one hose in use. The rate of ventilation was purposely increased on many of the polys by the insertion of a second hose to determine what effect such increase would have on the atmospheric, concentration of vinyl chloride. These comparative results with- one versus two hoses ar^ shown in Table I.
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Discussion:
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Because of plant schedules and practices data was not obtained on
each type of resin in each size polymerizer. However, the following combinations were obtained:
Paste (L21 type) Pearl (101 type) Pearl (102 and 103 type) Copolymer (135 type) Latex (Geon 450X20)
1100 X X X X
3300
X X
4000 X
4300 X
Figure 1 indicates that the rate of vinyl chloride removal is lowest in small poly; and that the small poly will level out at a higher concentration. The real reason for this is thought to be because of one or all of the following facts;
1. Ratio of Surface area to volume is greatest in the 1100 gallon poly.
2. The ambient concentration of VC1 in Unit A, which houses the 4300 gallon polys, ranges from 8-30 ppm; while the areas housing the 3300 gallon polys and the 1100 gallon polys have ambient VC1 concentrations in the range of 18-90, and 20-140 ppm respectively.
3. The 1100 gallon polys are stainless steel and old, while the 3300 and 4300 gallon polys are glass lined. Perhaps less polymer buildup exists on the glass lined surfaces and hence less effect due to residual vinyl chloride monomer in polymer clinging to the walls.
It was thought that increased ventilation would decrease the vinyl chloride concentration in proportion to the increase in ventilation rate. The decrease in vinyl chloride concentration was less than expected with two hoses. It appears that the air movement within the poly does not sufficiently mix the vinyl chloride rich atmosphere with, the incoming air. If this is the case-, then the efficiency of ventilation could be improved by the installation of a means to distribute the air throughout the entire cross-sectional area of the poly.
Figures 7 and 8 are essentially the same as Figure 1 except they are drawn for the cfm rates that generally exists at the Avon Lake General Chemical
Plant. These two graphs indicate that the present evacuation system and
procedure is inadequate to arsur..
that vinyl chloride concentration in
the poly is less than 500 ppm.
Conclusions:
1. More efficient ventilation of a poly is obtained by having the ventilation hose 1 ft. off the bottom than at higher levels (See Figure 2).
2. It appears from the data (Figures 4, 5 and 6) that air samples collected within the poly will be strongly influenced by air currents, channeling of the ventilation corridor, etc.
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3. Atmospheric concentrations in polys, when ventilated and entered in accordance with the Plant's routine procedure (hose on the bottom, 30 minutes after opening), were found to vary from 25 ppm to 1539 ppm. This wide variation was observed even with closely controlling the location of the ventilation hose, and indicates further need for better control. It is known that the time of entrance is often less than 30 minutes after opening, and an observation of the Plant's routine procedures clearly demonstrates that the hose is frequently not on the bottom. It can therefore, be assumed that many times, personnel exposures are considerably higher than those obtained under these controlled conditions.
4. The data indicate (See Figure 3) that atmospheric concentrations in polys for low conversion pearl polymer can be expected to exceed 500 ppm after 20 minutes of ventilation.
5. It, of course, is impossible to reduce the atmospheric concentration inside the poly below that existing outside of the poly. There are occasions when this atmospheric concentration exceeds 100 ppm.
6. Serious consideration is being given to reducing to a minimum personnel exposures to vinyl chloride. The data of this study indicate that there are poly vapor concentrations that cannot be further reduced without major changes in manufacturing and operating procedures. These data show that a ventilation rate of 250 cfm, with an evacuation time of 30 minutes, can be expected to produce a poly concentration of 220 ppm for a 1100 gallon poly, 320 ppm for a 3300 gallon poly, and 400 ppm for a 4300 gallon poly (See Figure 1). To obtain lower levels will require considerably greater ventilation rates and/or evacuation times.
Distribution:
R.L. Bowles L.B. Crider C.H. Lufter W.E. McCormick (8) Technical Council C.T.F, File (2)
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Table 1 yinyl Chloride Concentration in Various Polymerizers
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Date
Poly No.
9-23-68 18
Bldg. 451
9-23-68
Bldg. 451
34
9-23-68 24
Bldg. 451
-'30-68 4
Bldg. 451
9-30-68 Bldg. 451
49
10-8-68 Bldg. 451
23
10-8-68 Bldg. 451
13
9-18-68 Bldg. 461
147
L.
Poly Size Gals. 1100
1100
Resin No.
135
Type Resin
CoPolyner
Paste
121F4 Paste
Exhaust
Hose
Location
Min.
1-Agitator
on
No. Exhaust
2-Eye
of Be fore
Level
Hoses Sample
1 2 10
Rate CFM
182
Sample Location
*
1 -Agitator
2-Eye Level
VC1 ppm In
Ambient Poly
1 21 2i 3
21 1
103
22
2
70
35 1
45
1 1 10 125 1 42 333
1100
135 CoPolymer
2
20 1 21 2 35 1 1 5 112 2
159 158 121 24 256
1100
110X 127
Paste
1
1100
Paste
2
1100
135 Paste
2
1100
135 Paste
1
3300
102EP FI
Low Conv. Pearl
1
___________
2
1
2
1
2
19 20 35
6 21
22 * 36
5
20 21 35
5
20 20 35
5
20 20 35 12
23 24 25 25 36
1 2 2 174 2 2
1 2 100 1
1 2 1 273 1
1 2 1 129 2
2 1 2 234 1
_______
1 2 1 2
1
116,242 256 195
59 482 145
142 114 72 322
1286 181 1224 28 152,590
1185 754 235
133 842
209 316 . 158 21 (J334 tn I-H41 40109 Ck 06 * <j^l2
74
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Date
.-12-68 Bldg. 461
Poly No.
148
Poly Size Gals.
3300
11-12-68 Bldg. 461
116
* 1100
washed
11-12-68 Bldg. 461
107
1100
11-12-68 Bldg. 461
143
3300 washed
11-19-68 Bldg. 461
116
1100
11-19-68 Bldg. 461
112
1100
11-13-68 Bldg. 464
201
4300 washed
-13-68 oldg. 46'-t
205
4300 washed
Resin Type No. Resin
103EP F76
Low
Conv. Pearl
101EP F21
High Conv. Pearl
101EP F21
High Conv. Pearl
102EP F5
Low Conv. Pearl
101EP F21
High Conv. Pearl
102EP F5
Low Conv. Pearl
103EP F5
Low Conv. Pearl
103EP Low F5
Hose Location 1-Agitator
2-Eye Level
Min. on.
No. Exhaus t. of Be fore
Hoses Sample
Rate CFM
1 1 1 85 -
31 32 61 90 122 1 1 5 23
38 39
65 95 125 1 1 1 126
30 31 60 90 121 1 2 2 279
31 32 62 91 120 1 2 2 233
11
12
11
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30 31 60 90 120
1 173
31 32 61 91 119
3 -
30 31 60 91 121
4
32 33 63 93 12 7
720 396
Sample Location 1-Agitator
2- Eye Level
VC1 ppm
Abient
In Pol-
1 18 309,01;
1 1*535 2 1,48c 2 941 1 23; 2 13', 1 62 266, 706
1 302 2 326 2 242 1 162 2 148 2 21 8, 036
1 322 2 82 1 166 2 95 1 87 1 63 187,312
1 12C 2 r97 2 6C 1 - 66 2 41 2 29 1,882
1 20C 2 161 1 58 2 98 1 135 2 73 15,69:
1 98
2 8<
1 6!
2 8<
1 10! 1 14 7, iv.
1 2`
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21
1 O) 1
2
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14
2 TT 6. 67
1 11 14 46 14 2C
Date
Poly No.
11-13-68 215
Bldg. 464
/
Poly Size Gals.
4300
Resin No.
104EP
Type Resin
Low Conv. Pearl
.
11-13-68 Bldg. 464
204
4300 washed
103EP F5
Low Conv. Pearl
' 19-68
,ig.
464
203
4300
103EP
F7l
Low Conv. Pearl
9-23-68 Bldg. 463
5 4400 450X3 Latex
Exhaust
Hose
Location
Min.
1-Agitator
on.
No. Exhaust
,2-Eye Level
of Before Hoses Sample
Rate CFM
o*~--
Sample Loca ticn 1-Agitator
2-Eye Level
VC1 Abient
PPm
In Poly
1
1
3
690
1
15 2,437
-
30 1
43
31 2
39
60 2
35
92 1
20
122 2
19
1
1
2 398
2
7 11,374
31 1
25
32
2 *
21
66 1
19
92 2
21
118 1
10
1
1
2 551
2
13 6,502
32 1
97
33 2
90
60 1
63
* 91
2
25
119 1
39
1
1
6 145
2
22 75,134
11 20 21 *
36
37
1 1 2 1 2
11,928 4,310 4,822 3,433 1, 994
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( B.F. Goodrich Chemical Company
Inter-Organization Correspondence
To E.B. Katzenmoyer Location Akron
Date September 3; 1968
From E.G. DeCapita EGD-55-68
Subject Analysis of Room and Poly Atmospheres From the ALGCP
Your samples of room and poly atmospheres taken at the Avon Lake General Chemical Plant have been analysed by gas chromatography. Quantitative results are tabulted below.
The amount of vinyl chloride in samples No. 1 and 2 taken 8/l/68 and sample No. 1 taken 8/8/68 is grossly out of the calibration range of the standard gas sample used for this analysis. My estimate of the amount of vinyl ciiloride in these samples is 18-20$ for sample No. 1 and 5-7$ for sample No. 2 of 8/1/68.' Sample No. 1 of 8/8/68 is in the 8-10$ range.
Date Sampled
8/1/68
8/8/68
Sample No.
1
2
3
4
5 6
7
8
1
2 3 4 5 6
Samole Location
ppm VC1
Poly opened
5 min. after vent bore
15 min. after vent bore
Man enters
10 min. after man enters
30 min. after man in
Atmospheric sample 10 min.
Atmospheric sample 30 min.
after after
man man
in in
70 40 27 24 13 10
Poly opened 5 min. after 2 vent bores 15 min. after 2 vent bores Man enters 10 min. after man in Atmospheric sample 10 min. after man in
122 58 29 18 10
cc: R.J. Wolf J.L. Nelson R.N. Rylands R.W. McKay W.E. McCormick W.T. Gunning D. Desrosiers L.B. Crider R'.M. Sandfry V.C. Fraser Technical Council
CTF File (2)
BFG38983
E.G. DeCapita Staff Technical Services
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