Document dQzbNRbOp3RkJ1mBEaZQ03gr9
50933
CONFIDENTIAL
DOW CHEMICAL U.S.A.
TEXAS DIVISION FREEPORT. TEXAS 7754 J
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CO
FOR THE USE OF DOW EMPLOYEES ONLY ENVIRONMENTAL HEALTH REPORT
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CHEMICAL EXPOSURE EVALUATION
TRICHLOROETHYLENE PRODUCTION PLANT
B-1J00
,,
file Nn B15-2206 natf March 18. 1982 author __L-__Regier
L' --V '
VLUer" Oiv.nct Qt
Summary
As part of the Industrial Hygiene Program in the Trichloroethylene
I[production plant, B-1500, 8-hour time-weighted average and short term
potential exposures were evaluated in September and October, 1981. Monitoring was done to evaluate potential exposures to ethylene dichloride trichloroethylene, 1,1,2-trichloroethane, 1,1-dichloroethane, perchloroethylene, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, and vinyl chloride.
All exposures were within acceptable exposure limits on both a short term and an 8-hour time-weighted average basis. Additionally, the additive exoosure to more than one chlorinated hydrocarbon was within the acceptabl limit.
The monitoring work did indicate that analysis of samples in the control room was the major source of exposure in the plant. Consideration should be given to the installation of a ventilation hood in the control.room. The process sampling procedure could also be improved with some minor revisions.
v/obs
Disf-ibution P. i. Reis B-1510 D. R. Jones B-1510 D. L. Simeroth B-1510 "K. H. Oelfke A-1107
X. W. Rampy 1803 Midland
R. R. Langner 2030 Midland
Marlene Swank 1303 Midland * F. D. Axe - Pittsburg *' R. L. Dostal 1803 Midland * S. A. Goode - OCD * C. E. Halphe n - Plaquemin * Gary Meier - Strongsville * R. D. Olson - Sarnia
* Greg Dickson - 322 Bldg.-Michigan
* A. W. Schaffer - Tulsa
File B15-2206
2 March 18, 1982
INTRODUCTION
As part of the Industrial Hygiene Program in the Trichloroethylene Production Plant, B-1500, 8-hour time-weighted average and short-term personnel monitoring was done during September and October, 1981. Monitoring was done to evaluate potential exposure to ethylene dichloride, trichloroethylene, 1,1,2-trichloroethane, 1,1-dichloroethane, perchloroethylene, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane,and vinyl chloride.
METHODOLOGY
Both 8-hour and short term sampling was done by collection of air contaminants on one gram charcoal tubes using Sipin air sampling pumps. For 8-hour sampling the Sipin pumps were calibrated and adjusted to give a flow rate of about 100 ml/minute. The pumps used for short term monitoring were calibrated and adjusted to give a flow rate of about 200 ml/minute. A charcoal tube, with both sealed ends opened, was placed in the plastic tube holder. During 8-hour sampling the tube holders were clipped in the general breathing zone of the employee. Short term air sampling was done by holding the tube holder in the general breathing zone of the employee by hand.
The charcoal tubes were analyzed by desorption in 10 ml chilled carbon disulfide and injection of the CS solution into a gas chromatograph. A six foot by one-eighth inch, four percent oronite column was used to analyze for ethylene dichloride, trichloroethane, perchloroethylene, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloro ethane and vinyl chloride. The chromatograph oven was operated isothermally at 105C. For the analysis of 1,1-dichloroethane, a
nine foot by one-eighth inch , a 10 percent IGEPAL CO-880 column was used with the oven operating isothermally at 80 C. A flow rate of 30 cc/minute nitrogen carrier gas was used with both columns. All analytical work was done by Leroy Jones of Analytical Services.
The validity of the analytical method was checked by spiking three charcoal tubes directly with 40 pi of a carbon dislufide solution containing 394 ug 1,1-dichloroethane, 509 ug ethylene dichloride, 423 pg 1,,,1,2-trichloroethane, 524 pg trichloroethylene, 612 pg of 1,1,1,2-tetrachloroethane, and 686 pg 1,1,2,2-tetrachloroethane. After spiking, air was drawn through the tubes at about 100 cc/minut< for about 145 minutes. Desorption efficiencies found by this method were 93% 1,1-dichloroethane, 93% 1,2-dichloroethane, 92% 1,1,2-tri chloroethane, 96% 1,1,1,2-tetrachloroethane, 90% 1,1,2,2-tetrachloro ethane and 90% trichloroethylene. Desorption efficiencies.of 90% for perchloroethylene and 93% for vinyl chloride were used in the calculations and were based on work previously done.
PROCESS AND JOB DESCRIPTIONS
?, ..........
.-rcJucfldPLTsuant
, - - r i - C ' 0'? -j
Process and job descriptions for the Trichloroethylene production
plant are given in Appendix A.
r,
R&S 039687
File B15-2206
3 March 18, 1982
EVALUATION CRITERIA
Personnel monitoring was performed to determine potential exposure on both a daily time-weighted average and a short term exposure basis. The results of the monitoring are compared with recommended exposure guidelines (Industrial Hygiene Guide, IHG) given in Table V, Appendix B.
Also listed in the table is the source of the recommended standard. These values are based on reliable toxicology data and industrial experience and represent levels to which it is believed that nearly all workers may be exposed without adverse effects. The Industrial Hygiene Guides given represent both the acceptable time-weighted average for a normal eight-hour work day and the acceptable short term excursion limits.
As a group, the chlorinated hydrocarbons exhibit similar consequences of overexposure. Among these are systemic effects to the liver and kidney from chronic overexposure, and central nervous system depression from acute overexposure. Due to this similarity and the likelihood that potential exposures will occur to more than one of the chlorinated hydrocarbons during the work day, it is necessary to give consideration to the combined, rather than individual, effect of the compounds when evaluating the monitoring results.
The addit.ive effect of the different chlorinated hydrocarbons is
accounted for by calculating the sum of the ratios of the observed
exposure to the Industrial Hygiene Guide for each chlorinated hydro
carbon. If this sum exceeds 1.0, then the combined exposure is in
excess of the acceptable limits. An example calculation is given in
Table IV, Appendix B. Exposure levels (given in Tables III & IV)
reported as "less than" indicate the material was not detected in the
sample. For the purposes of averaging (Table I) and calculating^'Pursuant
potential additive exposure (Table II), these values are considered
zero.
- ':]-
RESULTS AND CONCLUSIONS
IV 'X `.-i jj: vt , ,, Eight-hour time-weighted average (TWA) exposures "tb "the ,ue'ight chemicals were within acceptable limits for all job classifications (Table I). Additionally, as noted in the evaluation criteria, the potential additive effect of exposure to more than one compound has to be considered. The results of this evaluation are given in Table II. In no case did the calculated E value exceed unity which means that the potential additive effects of all the chemicals were also within acceptable limits.
Short term exposure monitoring was set up such that exposures above the Short Term Excursion Limit (STEL) could be detected. None of thf five short term samples showed exposures in excess of the STEL for any of the eight chemicals. However, it should be pointed out that this does not mean there were no excessive peak exposures.
R&S 039688
File B15-2206
4 March 18, 1982
RESULTS AND CONCLUSIONS (Contd.)
--^
Of the eight chemicals, trichloroethylene exposures were the highest for all job classifications monitored. Control A Operators, who spent less than five percent of the shift in the process area during the monitoring period, had a higher average exposure to trichloroethylene than the Control C Operators who spent about 33 percent of the shift in the process area (Table I). This can be accounted for by the fact that Control A Operators analyze process samples in the control room on a lab bench with no ventilation hood. The average time in the control room for the Control A Operators was 460 minutes during the monitoring period, and the average for the Control C Operators was 310 minutes in the control room. The average TWA exposure to trichloro ethylene for the Control A Operators was 4.0 ppm. If this 4.0 ppm value is multiplied by the 310/460 time ratio, 2.7 ppm is obtained which is in fair- agreement with the average 2.1 ppm exposure to trichloroethylene found for the Control C Operators. This suggests that the primary source of exposure to trichloroethylene is in the control room.
The Shift Foreman job classification showed the highest average 8-hour TWA exposure totrichloroethylene (Table I). However, this may be accounted for by the diversity of the Shift Foreman's activities. The 6.0 ppm trichloroethylene exposure value is the average of two samples, one of which was 11.2 ppm a.id the other 0.7 ppm. The 11.2 ppm 8-hour TWA value, in light of the lower exposures to Control A and Control C Operator's who spend the entire shift in the Trichloroethylene Plant, is not a typical value. It was the result of supervising activity in the process area which does not occur daily.
Some excursion monitoring (16-19 minutes) during process sampling did not show particularly high concentrations. However, the procedure of clearing sample lines by flushing material on the ground or into open buckets could easily result in excessive peak exposures. Peak exposure monitoring of these activities was not done during this survey but is planned for 1982.
One area sample was taken to determine if excessive levels of tetrachloroethanes exist in the B-2, C-2 area. This was done because the Class 2 Operator and Control C Operator make routine rounds in the area to check equipment. The results show that overexposures to tetrachloroethanes, on a short term basis, do not happen in this area under normal operating conditions (Table IV),
RECOMMENDATIONS
While the monitoring work revealed that all exposures were within acceptable levels, on the basis of good industrial hygiene practices (to minimize unnecessary sources of exposure) the following recommenda tions should be considered:
File B15-2206
5 March 18, 1982
RECOMMENDATIONS (contd.)
1. Install a small bench hood in the control room to control the vapors from process sample analysis.
2. Use recirculating lines for sample taps (possibly a syringe needle sampler)to reduce or eliminate the need to clear sample lines,
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12;:
R&S 039690
PLR/bbs
File B15-2206
5 March 18, 1982
COMMENDATIONS (contd.)
1. Install a small bench hood in the control room to control the vapors from process sample analysis.
2. Use recirculating lines for. sample taps (possibly a syringe needle sampler)to reduce or eliminate the need to clear sample lines.
Pursuant
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File B15-2206
TAULt, i
SUMMARY OF 8-HOUR TIME-WEIGHTED AVERAGE EXPOSURES (PPM) TRICHLOROETHYLENE PRODUCTION B-1500
R&S 039692
J03 CLASSIFICATION
Shift Foreman JOB I.D. NO.
66900-21000
NO. OF SAMPLES `
1
2 0.03
IHG*
10
J03 CLASSIFICATION Control A Operator
JOB I.D. NO. 66900-80100
NO. OF SAMPLES 3
1 <0.06
IHG*
10
J03 CLASSIFICATION
NO. OF SAMPLES
Control C Operator
3
1 <0.06
JOB I.D. NO. 66900-80300
. IHG*
10
! i
2 5.95
3 <0.1
100'
10
.4 <0.4
.5 <0.2
200 .100..
67 0.2 <0.2
.8 <0.3 v
inn JU__ :-- . _i .i--------
l--- --------------
1
|*m
s
3 0.07
4 <0.1
5 <0.07
6 ' 0.1
7 <0.07
48- - <0709- -
!
100 10
200 100
100 -JU_______U________
2 2.07
3 <0.04
4 <0.1
5
or*' o
6 0.07
7 <0.07
8 <0.09
100 10
200 100
100 O.l
1
Chemicals
1. Ethylene dichloride 2. Trichloroethylene 3. 1,1,2-trichloroethane 4. 1,1-dichloroethane 5. Perehloroethylene
. 6. 1,1,1,2-tetrachloroeuhane 7. 1,1,2,2-tetrachloroethane 8. Vinyl chloride
*IHG - ^fclustrial Hygiene Guide
File BlS-ZiiUb R&S 039693
)B CLASSIFICATION
NO. OF SAMPLES *'
i
Class II Operator
1
<0.06
JOB I.D. NO. V}
66900-80600 ^ T)
)3 CLASSIFICATION^ v
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IHG*
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10 1
2
0,6
100'
3
<0.03
10 .
Oo
-<N
4 .5 6
7
<0.06 <0.05
<0.05 . <0.05
100
100
0.1 -
8 <0.07
1
2345678
)3 CLASSIFICATION
- -:l, i
^
------------------------------------------------------------------ 1 234
5
6
Chenicals
1. Ethylene dichloride 2. Trichloroethylene 3. 1,1,2-trichloroethane 4. 1,1-dichloroethane
5. Perchloroethylene 6. 1,1,1,2-tetrachloroethane 7. 1,1,2,2-tetrachloroethane 8. Vinyl chloride
File B15-2206 TABLE II
SUMMARY OF CALCULATED Em VALUES TRICHLOROETHYLENE PRODUCTION B-1500
JOB CLASSIFICATION
Emm
Shift Foreman Control Operator A Control Operator C Class II Operator
0.06 0.04 0.02 0.01
R&s 039694
h:' --
w
DESCRIPTION OF ACTIVITY
. Control Room (429 min.) o"
. Taking routine samples - Y column overhead, Y column bottom, Z c.olumn bottom, M3 product, D-25 - (7 min.)
<0.06 ' 1.1 <0.04
R&S 039695
. Analyzed samples -{15 min.)
4-
<0.01
<0.07
<0.06 <Q. 07
<0.09
Exposure Time (Min.)
4'5l'
1. Ethylene dichloride 2. Trichloroethylene 3. 1,1,2-trichloroethane 4. 1,2-dichloroethane
5. Perchloroethyl'ene 6. 1,1,1,2-tetrachloroethane 7. 1,1,2,2-tetrachloroethane 8. vinyl chloride
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DO* INDUSTRIAL HYGIENE GUIDE:
10 ppm 100 ppm 10 ppm
200 ppn ' 100 ppm 100 ppm
0.1 ppn| 1 gpm
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DESCRIPTION OF ACTIVITY . i
1. Control rocm {439 nan.)
'j
2. Took routine samples - X column
overhead, Y column overhead & bottom, Z olumn overhead & bottom
(5 min.)
<0.05
4
3. Analyzed samples {15 min.)
4. Went to trichlor structure to operate inhibitor valve (3 min.)
2'
%
2.9
3
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R&S 039696
. <0.04
-*
<0.1
<0.07 .
--?---------
6'
8
i
<0.06
<0.06
<0.08
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EXPOSURE-TIME (MIN.) >462 - *
1. Ethylene dichloride 2. Trichloroethylene 3. 1,1,2-trichloroethane 4. 1,2-dichloroethane ..
5. Perchloroethylene 6. 1,1,1,2-tetrachloroethane 7. 1,1,2,2-tetrachloroethane ,8. vinyl chloride-
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DOVf INDUSTRIAL HYGIENE GUIDE:
10 ppm
100 ppm 10 ppm
l4ft:
TVA EXPO
r {C0NC. X EXPOSURE TIME)/TOTAL TIME
8 200 ppm 100 ppm 100 ppm 0.1 ppm 1 ppm
%
00
SS . s Z
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Ut-i'-nit'iXUW U ACTIV 1`1'X
1. Control rocm (440 min.)
*
2. Taking samples - X column overhead, Y column bottom, Z column product, D-25 overhead, M column product (8 min.)*
<0.05
3. Analyzed samples (10 min.)
0 4. Checked tetras unit (5 min.)
5. Checked tri,chlor still area
(5 min.)
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2 7;9
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-- - i-
R&S 039697
0.2
<0.01 <0.06 0.3
<0.06
<0.08
o* c
t r
x> o2
"' ' --" ' 1
I I IN ,
EXPOSURE TIME (MIN.) (468 ^ ..
1. Ethylene dichloride 2. Trichloroethylene 3. 1,1,2-trichloroethane 4. 1,2-dichloriethane .
5. Perchloroethylene. 6. 1,1,1,2-tetrachloroethane 7. 1,1,2,2-tetrachloroethane 8. vinyl chloride
9*2
fU C
IhemicalDOW -INDUSTRIAL HYGIENE CUIDE:
1 10 ppm
:2 100 ppm
3 10 ppm
41. 5 1,
200 ppm 100 ppm
6 78 100 ppm 0.1 ppm Aff
TVA EXPOS
---------------------
- Z (C0HC. X EXPOSURE TIME)/TOTAL TIME
'
------- .................. ...... " --
- .................. ................................................. .................................................... -- ...............................................
--
- --
..........................
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DESCRIPTION OF ACTIVITY
1
6:33 a.m. - Shift Foreman's office Acid tower area,r B-1506, B-1511.
8:00 a.m. - HC1 compressor area switchgear room
0.06 <*
2
l
0.7
3 <0.04
4 <0.1
-M.--... - ---------T--l n H &S 039698
1
' <0.06
<0.06
<0.06
*
8 <0.08
8:30 a.m. - trichlor control rocm & &-101 9:30 a.m. -B1506, B1511, B15i3
shop
10:30 a.m. - B1506, B1511, B1513 she P
10:55 a.m. trichlor control roan B1506, B1511,.B1513
* if .
1: p.m.-trichloro structure
supervising work on- out of service
line, S oolurin area, B1506, B1511
Br-1501
?-
rrl
i
EXPOSURE TIME (MU'!.) 452 * l .
1. Ethylene 'dichloride 2. Trichloroethylene 3. 1,1,2--trichloroethane 4. 1,2-dichloroethane*
` .7
5. Perchloroethylens 6. 1,1,1,2-trichloroethane 7. 1,1,2,2-tetrachloroethane 8. vinyl chloride
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DOV? INDUSTRIAL HYCIEXE GUIDE: | _iq ppn 1100 prm
10 con
TVA EXPOSE - Z (C0HC, X EXPOSURE TIME) /TOTAL TIKE
200 nan inn ran MOO prm
rt 1 ppnl T_ppn
p
DESCRIPTION OP ACTIVITY
1
:15 a.m. supervised cutting peration.in acid area, DEE area, Cl tank car load rack, HC1 cmpressor area
:15 a.m. - Id 'control roan
<0.02
)
- <1
2 11.2
3 <0.1.;
4 <0.4
5
1 ; <0.2
6 78
0.4
<0.2
<0.3
R&S 039699
: 30 a.m. - Trichlor control roan
.0:15 a.m. IE1 canpressor area
.0:35 a.m. - Trichlor control roan .2:25 p.m.-T60 area where new dping being installed, writing jerrrdts to recharge filter, checked
1500 block area with exception of warehouse. Noted an odor around '31B during clearing process (about 5 min) 1:00 Trichlor control roan
sv
:\ n
* *.
EXPOSURE TIME (MIN.) , 419- ..
1. Ethylene dichloride 2. Trichloroethylene . 3. 1,1,2-trichloroethane 4. 1,1,dichloroethane
y
5.`Perchloroethylene 6 1,1,1,2-tetrachloroethane 7. 1;1,2,2-tetrachloroethane 8. vinyl chloride
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DOW INDUSTRIAL HYGIENE GUIDE:
Effll 100 ppm 10 ppm
4 200 ppm
100 ppm
100 ppm 0.1 pgr
Tl'A EXPOSE - l (C0NC. X EXPOSURE TIME)/TOTAL TIME
r mm r f!*
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MUII3
00
o
ta m
HmM
I
25
2O5
DESCRIPTION OF ACTIVITY
Q--.LJjL-ILi ttU-JAjl JJ.
/ VVi.yv lyj-. J^Vi.
1/1y
6:30 a.m.-control room
7:14 a.m.-routine check of tetras
<0.06
unit,trichlor structure, acid structure,
<0.02
<0.04
<0.09
NH, compressor 7:28 a.m.-control room
R&s 039700
8:00 a.m-dew point on S column
8:10 a.m.-control roan
8:23 a.m.-tetras unit area
8:20 a.m.-control room
8:31 a.m.-hose down HCl compressor 4lab
8:40 a.m.-put J-21 in servicetacid
area)
8:43 a.m.-control room
9:05 a.m-blocked PCI lines
9:45 a.m.-control roan
10:03 a.m.-close valves in acid area
near 12B tank
10:13 a.m.-control rocm
11:15 a.m.-went to .Power 4 to put acid line in service.
EXPOSURE TIME (MIN.)-, 451
11:45 a.m.-control roan , 12:49 p.m.-took J-21 out of service 12:57 p.m.-control roan 1:20 p.m.-punped T-32 to warehouse area.1:25 p.m.-acid area to close vfelve
.
1. Ethylene dichloride 2. Trichloroethylene 3. 1,1,2-trichloJroethane 4. 1,2-dichloroethane
on P2B
1:30 p.nv-switchgear rocm
1:31 p.m.-control rocm
1:35 p.m.-truned on P-7 water purrp
2:00 p.m.-control rocm
2:10 p.m. stop
<0.07
<0.07
<0.07
<0.09
5. Perchloroethylene 6. 1,1,1,2-tetrachloroethane 7. 1,1,2,2-tetrachloroethane 8. vinyl chloride
r^WFTPAT.
DO*' INDUSTRIAL HYGIENE GUIDE:
10 ppm
2 100 ppm 10 ppm
200 ppm
100 ppm
100 ppm 0.1 ppm
TVA EXP!
Z (C0NC. X EXPOSURE TINE)/TOTAL TIME
yi r 3C o
cottoo\ 5:
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DESCRIPTION OF ACTIVITY
6:33 a.m.-control rocra
7:05 a.m. turned on P10A pump, made rounds checking equipment 7:13 a.m.-control room 7:45 a.m.-blocked leaking valve on sanple point on A-3 column 7:48 a.m.-worked in HCl compressor area 8:00 a.m. control room 8:04 a.m. blocked in F31B tetras filter, tank farm area to red tag nitrogen line, worked around HC1 compressors 8:20 a.m. went to blow F13B back to tank 8:36 a.m. control rocm 8:42 a.m.-switchgear roan,B31 compressors 9:20 a.m.-pumped T-32 trichlor for t/t loading, checked F31B filter 9:25 a.m. control rocm 9:45 a.m. checked to make sure F31B cleared 9:52 a.m. control rocm 10:12 a.m. H31 compressor area ' 10:17 a.m. control rocm 1:05 F.m. opened valve on J21 tcwer shut off P10A pump '. 1:12 p.m. check acid lines 1:52 p.m. control rocm 2:15 p.m. stop
<0.05 S 3.2
<0.04
<0.1
<0.07
0.2
R&S 039701
<0.07
EXPOSURE TIME . (MIN.}
.462.
1. Ethylene dichloride 2. Trichloroethylene 3. 1,1,2--trichloroethane 4. 1,2-dichloroethane
5.' Perchloroethylene 6. 1,1,1,2-tetrachlOroethane 7. 1*, 1,2,2-tetrachlorofethane 8. vinyl chloride
<0.09
CHEMICAL
DO* INDUSTRIAL HYGIENE GUIDE:
10 ppm
4''
100 ppn 10 ppn 200 ppm 100 ppm 100 ppm
8 0.1 ppm 1 ppm
TKA EXF^RE - E (CONC. X EXPOSURE TIME)/TOTAL TIME
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DESCRIPTION OF ACTIVITY h 1
2
<J 'A iWly X-i-fijU
3
:29 a.m. control room
<0.05
:55 a.m. took gauge readings & made
>utine check of trichlor, tetras, &
:id area
00 a.m. control room
45 a.m. T-60 HC1 area to trace
;s *
zto 1
`L.f C'
T t r :i
Lj XSJ
<0.04
:t *
' -I
56 a.m. control room
01 a.m. switchgear roan
09 a.m. control room
20 a.m. tetra structure-opened val re--
iecked S column -trying to purge jlumn with nitrogen
*
:30 a.m. closed valve on reboiler
aar S column
'V.;
37 a.m. control roan
53 a.m. traced' B31 lines
54 a.m. control room
3:27 a.m. worked on S column aboiler to get nitrogen purge working
EXPOSURE TIME (MIN.)
3:34 a.m. control rocm
L:32 a.m. shut off steam line at
column
1. Ethylene dichloride
L:35 control room
2. Trichloroethylene
:12 p.m. trichlor structure, B1503 3. 1,1,2-trichloroethane
arehouse, closed out of service line 4. 1,2-dichloroethane
:20 p.m. control roan
:08 p.m. stop
4 <0.1
5. <0.7
6 <0.06
7 <0.06
R&S 0 39702
459. !i___ 5 Perchloroethylene 6. 1,1,1,2-tetrachloroethane 7. 1,1,2/2-tetrachloroethane 8. Vinyl chloride
8 <0.09
1
9-
R
r+ '*
!H
n\ lc (U
to-1
;
01 * * P
T
00
EIEMICAL DO* INDUSTRIAL HYGIENE CHIDE:
10 ppm
.2 100 ppm 10 ppm
8 200 ppm 100 ppm 100 ppm 0.1 ppm* 1 ppm
Tw\ EXPOSURE - l {C0NC. X EXPOSURE TIME)/TOTAL TIME
DESCRIPTION OF ACTIVITY
7:02 a.m. control
<0.6
0.6
<0.03
<0.06 K0.05
<0.05
<0.05
7:23 a.m. took out trash 7:30 a.m. control''lab area
R&S 039703
8:02 a.m. made check for punp
leaks in tetras, trichlor & acid areas.
n
8:27 a.m. control room
8:40 a.m. made check of pumps for Ijsaks
in warehouse area
9:04 a.m. control room
9:05 a'.m. blocked H01 lines at
B-4400, Power 4
9:45 a.m.- control rocm
10:15 a.m. greased fans in tetras
unit
10:24 a. m. control room
10:25 a.m. warehouse area
10:35 a.m. control rocm & control
lab 1:30 p.m. acid structure check
EXPOSURE TIME (MIN) . 423.;
pumps 1:45 p.m. control lab.
1. Ethylene dichloride 2. Trichloroethylene
5. Perchloroethylen6 6. 1,1,1,2-tetrachloroethane
3. 1,1,2-trichloroetharie
7. 1,1,2,2-tetrachloroethane
4.1,1-dichioroethane `
8.'vinyl chloride
8 <0.07
t-* >
o >
S5 OJ I
03
CHEMICAL
D0VJ INDUS"rT,.L HYGIENE GUIDE:
IP-EBB.
2
100 orm 10 oom
xexpoWre t (conc. exposure time)/total time
4 *J 200 pan
lQQ.PPm ]QQ.gm. (1,1 nrrt.l-jarm
p
<->'ijVWi ri brjBSfirtVj
SHORT-TERM EXPOSURE MONITORING RESULTS
DESCRIPTION OP ACTIVITY
ontrol Operator A-Taking X column, ' column, Z column, D25, M column amples &.analyzing samples in ontrol room.
1 <0.7
/29/81 (19 minutes)
ontrol Operator A - Taking X 'column column, Z column, M-3, D25 samples analyzing sanples in control roan <0.9
0/13/81
(16 minutes)
lass 2 Operator checking pumps or leaks in tetras unit
<1.0
0/13/81
(8"minutes)
ontrol Operator A-Analyzing sanples n lab bench frcm X, Y, Z columns
<1.0
2 h
SHORT TERM EXPOSURE SUMMARY (PPM)
3 .4
5 6
<2.0 * <0.5
03g ?04
<0.8
<0.8
4.7
<0.8
_
<1.0
<1.0
*
<2.0
<1.0
1
--
,
<3.0
<0.7
*
<2.0
2v2
<1.2
<1.1
7' 8`
<0.8
<1.0
<1.0
<1.0
<2.0- <1.0
<1.2
<1.0
0/5/81 (11 minutes)'
urea sample_between C-2 & B-2
n tetras unit
t--c) .. rj
.0/5/81
(48;mihutes)^
: %
> 5*
<0.3 '
<1.0
<0.2
1
1. Ethylene dichloride 2. Trichloroethylene 3. 1,1,2-trichloroethane 4. 1,1-dichloroethane
<0.7
<0.4
<0.4
<0.4
5. Perchloroethylene 6. 1,1,1,2-tetrachloroethane 7. 1,1,2,2-tetrachloroethane 8. vinyl chloride
<0.5
,,
CHEMICAL
1
DOVi IXDUS^vL HYGIENE GUIDE:* 15
*Short Term Excursion Limit (opn)
.2 150
3
20
*
' 4. i ^ 25(T
5'
150
i
6
100
7 10 .
8 1
Wr
r
I
Ju--i*
r .
c 1i
ct ri
M5 to
r 7
o CTi
X
O c
c
67
2r
2 a r'
C
P C. |j
I*
u!p~oj r* o
s
Mr
3i
I Or 3* i 3' O> 8-i
Pr
rdt1 1v* I;
Kl *
j
1 1
*
* c > r
1
.
11 i
R&S 039705
APPENDIX A 1. Process Descriptions 2. Job Descriptions
* iX!.`
sue
R&s 039706
File B15-2206
TRICHLOROETHYLENE
PROCESS DESCRIPTION
Trichloroethylene is formed in one high temperature thermal chlorina tion reactor (400C) and one thermal cracking reactor (500C). Ethylene dichloride and chlorine are fed to the thermal chlorination reactor and the reaction is quenched in the A-3 column. Overheads from the A-3 quench column, consisting of HC1 and chlorinated hydro carbons, are condensed and the chlorinated hydrocarbons are sent to the X lights removal column. The HC1 goes to an absorber system where it is contacted with water, dissolved, and stored for distribu tion as 32% Hydrochloric Acid.
The X column overhead material which consists primarily of ethylene dichloride, dichloroethylenes, and vinylidene chloride is recycled back to the reactor. The bottom stream from X column goes to the Y heavies recycle column where perchloroethylene and tetrachloroethanes are removed as the bottom stream and are sent back to the reactor along with the X overheads to control the reactor temperature. The Y column overheads are sent to the Z finishing column where primarily carbon tetrachloride is taken off overhead. The Z column product stream goes to a mixer and decanter, through the M drying column, and finally through check tanks and storage tanks where the trichloro ethylene is collected for loading and distribution. The product is recirculated through refrigeration units during storage.
Tetrachloroethanes from Plant A are sent through the B-2 .feed column which removes heavy products as the bottoms stream which goes to a heavies storage tank along with the bottoms stream from the A-3 quench column. The heavies consist of perchloroethane, tetrachloro, pentachloro-, and hexachloroethanes along with chlorinated butenes and tubanes. The heavies are sent to A-1800 as B-recycle for further processing. The B-2 column overheads consist primarily of tetrachloro ethanes which go to the thermal cracking reactor. The reactor product goes through a quench nozzle to the C-2 recycle column which separates remaining tetrachloroethanes as the bottom stream which is recycled back to B-2. The C-2 column overheads go to the PS finishing column where carbon tetrachloride is removed and sent to the B-recycle tank. Trichloroethylene from the PS column bottom stream also goes through the M frying column along with trichloroethylene from the Z column.
mens-nj
bbs
3/19/82
' File B15-2206
TRICHLOROETHYLENE AND AQUEOUS HCL PLANT B-1500 BLOCK
JOB DESCRIPTIONS
Assistant Superintendent - Supervises the operations and personnel in the Trichloroethylene plant. Aqueous HCL plant, unit laboratories, and unit services. Coordinates and issues instructions in the operation of each unit. Spends approximately 20% of his time out doors .
Production Foreman - Coordinates production activities (rates, personnel, safety, and maintenance) with the unit supervisors, superintendents, and maintenance foreman. Supervises five shift foremen. Spends approximately 50% of time outdoors. Works in the Trichloroethylene plant. Diethylene Ether plant, and the HC1 plants.
Shift Foreman (5) - Supervisor on duty each shift along with the
plant shift operators. Supervises the operation of the Trichloro
ethylene plant, Diethylene Ether plant, HCL plants, and EDC/Alpha-
Di plants.
Spends approximately 50% of his time outdoors.
Lab Supervisor - Supervises lab work on environmental, process, and shipping analyses. Interfaces with production plants to solve plant problems with lab support. Some development work is done to improve analytical capabilities as well as solving plant problems. Exposure to chemicals minimal due to short period of time that chemicals are handled--less than 10%.
Lab Technicians (2)- Responsible for all nonroutine sample analyses. Works with plantsto do necessary analytical work to solve plant problems. Also responsible for daily water analyses for contamina tion. Chemical exposures small due to quantities of material handled.
Control A Operators (5) - The A control is responsible for the operation of the thermal chlorinator, tetras cracker, and the acid absorption columns. Duties include startup, shutdown, analysis, & adjustments to operating parameters for safe and profitable opera tion of the units. Outside activities include sampling, which takes 5 to 10% of each shift. (Under non-emergency situations, the Control A is basically an indoor job.)
Control C Operators (4) - The C control is the eyes and hands of the Control A. He handles all outside activities such as: clearing equipment for maintenance, switching pumps, opening/closing valves, touring area for problems, etc. The C control spends 80% of his shift in the field. Indoor activities include documentation of levels, transfers, broken down equipment, etc.
Class II Operator (1) The Class II operator is responsible for
lubrication/--airea- cleanup, and other various duties. The Class II
operator also takes. carel'of the acid distribution system on day
shift.
~ " ' '
LZ
R&S 039708
File B15-2206 TRICHLOROETHYLENE AND AQUEOUS HCL PLANT B-1500 BLOCK JOB DESCRIPTIONS (conti.)
Unit Supervisor - Directly responsible for safety, production, morale, maintenance, technology, projects, reports, etc., in the smooth operation of a production facility. Thirty percent of schedule is outdoor activities such as: vessel inspection, maintenance setup/ followup, area monitoring, project followup, etc.
\r)
r
Lit
,:a\
bbs
R&S 039709
Table V Table VI
APPENDIX B Industrial Hygiene Guidelines Example Em Calculation
R&S 039710
r
LZ''r'~ a P:
riv
: "i
File B15-2206
CHEMICAL
1
Ethylene dichloride Trichloroethylene 1,1,2-Trichlo roethane 1,1-Dichloroethane Perchloroethylene
TABLE V INDUSTRIAL HYGIENE GUIDELINES
TLV1(PPM) (8 HR. TWA)
10
STEL2 (PPM) 15
100 150
10 20
200 250
100 150
1,1,1,2-Tetrachloroethane 1,1,2,2-Tetrachloroethane Vinyl Chloride
(100) 0.1 1
(100) 10 1
SOURCE* ACGIH ACGIH ACGIH ACGIH ACGIH
(NE) DIHG OSHA
1. TLV *= Threshold Limit Value, TWA = Time Weighted Average t
2. STEL = Short Term Excursion Limit 3. ACGIH - American Conference of Governmental Industrial Hygienists
(NE) * Not established DIHG = Dow Industrial Hygiene Guideline OSHA = Occupational Safety and Health Act
R&S 039711
bbs
-rl
; if,
LlWvs
File B15-2206
TABLE VI EXAMPLE Em CALCULATION
Assume an individual has the following 8-hour time-weighted average exposures during a shift.
Exposure
TLV
Ethylene dichloride Trichloroethane 1,1,2-Trichloroethane Perchloroethylene 1,1,2,2-Tetrachloroethane Vinyl chloride
5 ppm 20 ppm
6 ppm 20 ppm 0.8 ppm 0.7 ppm
10 ppm 100 ppm
10 ppm 100 ppm 0.1 ppm
1 ppm
Calculate the sum of the ratios of the exposure concentrations to the Threshold Limit Value Concentrations:
c, c_ c,,
C
I,1
+
I_2
+ -1 +....... I,3
In
=
Em
Where C is the exposure concentration and I is the TLV concentration
_5 + 20_+6_+ 20 10 100 10 100
0^08 0.1
^= 1
The E value of 3.0 is greater than unity and therefore the additive effect of the chemicals is excessive.
R&S 039712
bbs
