Document 6bLyrr1dmD6OapVb3eBZJjYx9

TENNECOINTER-OFFICE MEMO CHEMICALS, INC. ipct To W. C. Champion at Flemington From P, M. Reed at Pasadena Subject Analytical Capability @ Shin-Etsu's Kichima Plant for Detecting VCM in Air date November 7, 1974 Copy TO Mr. D. R. Keck Summary t The G. C. equipment employed at Kishima is equivalent to that used at Pasadena. The operator, Mr. Hashimoto, used a syringe for injection with excellent reproducibility. The attenuator was checked and found to be very linear. However, the electrometer is slightly non-linear in the range used for 1 ppm. The deviation will cause the results to be high by up to 16% of the amount reported. This can be negated by the use of standards in the appropriate range. Shin-Etsu also employs a color change tube for the detection of VCM in low ppm range. This is a "Gastech" tube similar to the MSA tubes. It is distributed in the U.S. by the Environmental Control Division of the Bendix Co. The system employs two tubes. The first catalytically de composes the VCM releasing HC1 while the second detects the HC1. ShinEtsu reports the data as generated, however, lab tests indicate the "Gastech" value is 40-65% of the true value. The tubes must be kept refrigerated until used and then warmed up. The temperature of the tube may affect the catalytic efficiency. Shin-Etsu is limited to a single standard gas containing 46.2 ppm VCM in pure air. Based on this standard the following relationship exists between our Pasadena lab and their Kishima lab: Cylinder Pasadena Kishima #1 1.7 ppm 1.2 ppm #5 5,0 ppm 4.7 ppm This agreement is good between laboratories and will be better if Kishima can obtain low standards. There is only one supplier of standard gases in Japan according to Mr. Ogowa and they claim low range VCM standards are unstable. I explained how the cylinder must be pre-treated for this service but he did not feel he could get his supplier to pre-treat the cylinder. The "content" test for LE was discussed. Shin-Etsu does not run the test and the supplier admitted it is difficult to get reproducible results. He supplied a few ideas which will be pursued. The Century Analyzer OVA employed at Kishima has the same limitations as those used in the U.S. Since the Shin-Etsu plant is on the up-wind side of the complex the background is very low. Agreement between this unit and the GC will be summarized elsewhere but looks very reasonable. COLOR!TE 013246 Mr. Ogowa reported he had purchased a gas sampling value for the VCM in afr G.C. I discussed our method of equalizing the pressure in the loop to insure reproducibility. The Kishima laboratory is capable of determining VCM in air at low levels with the same precision as our laboratories. PMR/az Attachment COLORITE 013247 i; i h3 H: U) M 00 pEL sflQ t A_ i C*, VJ l/*oD il wos CjZOu/#. Tb^*t 89 D5eTy*eCfi4- A ... . s Dfc -4-tO *4 q6! OWjCirFrttii~ 00 3 / 0 Z4 a -zo) (* /-- 01 ct. teUP M. f--1------------------------ ------------------------- (/O ------w 1........... ............... -kv- | BEIOJitff \____/ t ri ^5TC &ysTew\ A -- * -' l CEOTfiA'- ] tOHTZOL tLoCkW -- O - N -------------------- CPlTATm'-*t*_!> Worth PVC P-8 Layout of Kashima lant Ke^to Monitoring, Points PLfl-nt) TABLE I PROGRAM FOR EVALUATING VCM LEVELS IN THE AIR AT THE KASHIMA PVC PLANT \ I. GAS CHROMATOGRAPHIC TESTING A. Average VCM Levels - 8-Hour Charcoal Tube Locate tubes and pumps in following areas: 1. bagging area (spot sample with plastic bag also) 2. screening building (spot sample with plastic bag also) 3. control room (spot sample with plastic bag also) " 4. yard area downwind from dryer stacks 5. recovery area B. Spot Samples for GC with Glass Bulbs All points 1 to 26, three samples each. C. Personnel Monitoring - 10-Minute Charcoal Tube 1. Operators: a, upper floor operator - when opening the reactor b. lower floor operator - when transferring wet screening and sampling slurry 2. Recovery and Utility: a. sample during solution make-up b. sample when draining water condensate c. sample - water wash column draining column bottoms draining 3. Dryer Operator: a. during dryer clean-out b. during dryer sampling 4. Bagger * 5. Fork Lift Operator COLORITE 013249 TABLE I Page 2 D. Schedule 1. Wednesday Morning: October 30th: a. Mr. Reed to work with GC and establish chromatographs with 1 ppm and 5 ppm test gas. b. Mr. Poarch to work with OVA monitoring taking glass bulb samples. 2. Wednesday Morning: a. Mr. Poarch to make second OVA tour and collect more glass bulb samples. b. Start 10-minute charcoal tube personnel monitoring: (1) reactor deck operator (a) opening reactor (b) washing reactor (2) dryer operator (3) recovery operator (4) bagger (we carry pump) (5) fork lift operator 3. Full monitoring Thursday and Friday day and evening shifts: Begin 8-hour charcoal tube tests n. OVERALL OBJECTIVE A. Two sets of five 8-hour charcoal tubes (100 tubes) (duplicate sets - two sets Shin-Etsu, two sets Tenneco) B. Three sets 26-glass bulb samples. C. Five sets each Job type (5 x 12) - duplicates for Shin-Etsu and Tenneco. PROGRAM WHILE IN KASHIMA LABORATORY 1. Determine 95% confidence level of GC method used at 1 ppm and 5 ppm (minimum of 10 analyses). If deviation is greater than 25%, do ten more analyses. If still greater, determine reason. 2. Determine relationship of Shin-Etsu standards to Tenneco standards. 3. Repeat 1. above for Gastec method. J.W. Poarch/P.M. Reed 10/29/74 COLORXTE 013250 io-tsli Mo^JitoTOu^^ta >Mi I t-\ ULt, fOo~r^ ' /?u. 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(, 0 as AJC S C* u 0 . 26 . 27 KJo 3 '>&'/*AJO * >/r^- A. _o 0 28 OSM'iM* {k}AT& PS<lJtrW &. C. 0 2? Sl<-0 </tAT &. L. 0 0 -* 1.0 1-4 0 0 0 a.r 0 0 4.3 0/S o,c4 0 0 -- 0 fT* 3 2 2.3 0 O, S' ~|4 o,4 O- / o,Z /~2 ST 0,S 0 O -0 c.s o./s 0 o;2 0.2- O.z 0 0.<S 0 / O 0 /,S O f0 10 10 o.z 0 0.1 f.o 0.4 0. & <7.3 o.s 3o $n,o CL^ortfVZ. A- L. 0 0 0 0 31 Silo uJ^st ._. - S.L , 0 6 0 0 32 Siuo tOf k*r, Ni / O Sr* 33 Si L.O ItAST To 8 3/! Si <- o C#jnft. Tbi^ 35" 5itO (Ufir* Tot> 3G 6D DiSOl^aK 7?W*i 37 hJo 2 Sf C 0,^6 I-* TW &.L. &. - , zb Mo IO^ilOi SoeJT-M &, i. 37 uJ&e.enooi.tj iOw 4a r*jSiOtf luOjO/ec Jov|><5; ? 6.A4.T- /irp; 4i_ t*j PKcc-ie'^ kIexm, uJtvr 47 tu PAte>-. ^Of3Mj asr 43 Sctecuf^ Icct*. AT P.2 -- -- -- -- -- & 0 0 0 0 0 0 0 0 0,3 o.s 0.3 0,3 -- 0 0 0, s 0 O.S" 0 .S' r<e_ o.ofe 0 o.s* .:2 D.Ot 0 0 a b- 0 - 0 ___ o.s _ 0 ft .. 0 2S ?-}& O 0 O .02 /.s O.fa <3.3 0 0 0 0 o.s 0 44 4S _4S 47 45 Stittcwfi jL Rccm, Z^F.2 ittfrf R*\ 3e0FV. CoOk.UU I/JAtT^L Cc, ij^31 uJfijOf'r*:'* rffe^s iMe*roF C./r) u/or*`ac,c*jfrCjP >._* 0 o.L 0.4 -- . -- - -_ 0 0 O.Ofe e> 0 O0 0 0 00 0 0 0 0.0 2 0 0 0.7 ____ 0 O.s- 0.02 0. i rc 0*2 1c2o G C_ 0.07 o.)4 2.3 0 'GoP it /'s/74 TABLE IV SHIN-ETSU MONITORING DATA VCM CONCENTRATION IN AIR DURING VARIOUS DRAINING-OUT OPERATIONS (MEASUREMENTS WITH CENTURY OVA, CORRECTED FOR BACKGROUND) COLORITE 013253 Operation Time R-03 drain tank under VCM gas cooler immediately after 2 minutes after 4 minutes after 6 minutes after R-07 gas holder immediately after start immediately after stop 1 minute after stop 5 minute after stop R-05 VCM recovery blower (roots) immediately after start 1 minute after stop 2 minutes after stop R-02 to R-OS drain pipe between water scrubber and VCM recovery blower immediately after start 1 minute after stop Air Over Sewer, ppm VCM Air in Surroundings, ppm VCM Operation Frequency 1% or more 50 to 100 7 to 10 ND 100 to 200 20 to 40 2 0 1 time per day 1% or more 30 to 50 8 5 100 to 1000 5 to 7 3 to 4 0 to 1 1 time per day 100 to 1000 1 time per day - 1 to 2 -0 mm t 10 to 20 2 to 3 1 time per day TABiii, V SHIN-ETSU MONITORING DATA VCM CONCENTRATION IN AIR DURING STRAINER EXCHANGE OPERATIONS Strainer Exchange Operations Time R-039-1 strainer exchange start - 0 minutes after 4 minutes * after 7 minutes after 11 minutes after 12 minutes R-039-2 strainer exchange * after 0 minutes after 5 minutes after 9 minutes after 13 minutes after 15 minutes Operation 3M Downwind Close to Strainer 1.5M Height Operation Frequency a VCM purge b opening top head c just after opening top head d during filter ex- change e set the top head f gas replacement g end of all oper- tion 10 to 15 200 to 500 15 to 25 8 to 10 2 to 3 500 to 1000 70 to 100 100 to 200 1 time per 2 days 10 to 20 10 to 15 0.5 to 0.8% 3 to 15 a VCM purge b opening top head c just after opening top head d during filter exchange e set the top head f gas replacement g end of all operation 1000 15 2 to 3 400 20 to 30 (max 400) 100 to 200 20 to 30 (max 500) 7 to 8 1000 2 to 3 1 time per 2 days COLORITE 013255 TABLE V Page 2 Strainer Exchange Operations Time Operation 3M Downwind Close to Strainer 1.5M Height Operation Frequency P-008 after VCM charge pump ' after 0 minutes a VCM purge after 7 minutes after 11 minutes * after 17-18 minutes b opening top head c just after open ing top head d during filter ex change e set the top head f gas replacement after 20 minutes g end of all oper ation 15 to 30 (max 500) 20 to 40 (max 300) 3 to 7 100 to 1000 1 time 3 days 100 to 300 17 to 35 30 to 60 40 to 60 " 3 to 15 (max 50) 3 to 15 (max 100) (@ 10M, 50 to 70) 1 to 2 P-002 before VCM transfer pump 0 3 7 10 12 a VCM purge b opening top head c just after opening top head d during filter ex change e set the top head f gas replacement g end of all oper ation 10 to 20 (max 400) 1000 200 to 300 7 to 10 100 to 200 20 (max 200) 10 to 15 5 to 10 (max 100) - 1 to 2 5 100 to 500 0 to 2 1 time 2 days COLORITE 0 1 3 2 5 6 ,TA3L,, VI SHIN-ETSU MONITORING DATA VCM CONCENTRATION IN AIR SURROUNDING ROTATING EQUIPMENT COLORITE 013257 Equipment Number Equipment Description R-OOS R-014-1 R-014-2 R-022 R-026 R-031 P-003 P-006-1 P-006-2 D-006 VCM recovery blower #1 compressor #2 compressor recovery VCM pump crude VCM pump reflux pump VCM transfer pump #1 VCM charge pump #2 VCM charge pump slurry pump #1 " #2 '* ,f #3 rt tf 4 Operating Condition Close to Seal Surrounding Area 1 to 2 0 1% or more 10 to 15 -- 500 to 1000 10 to 15 0,5 to 1% 15 to 20 1% or more 70 to 100 1% or more 100 to 300 ISO to 200 12 to 22 1% or more 100 to 200 0.5 to 3 0,5 to 3 0 to 1 0.5 to 1 0.5 to 1 0 ** ppm VCM Shutdown Close to Seal Surrounding Air 0,5 to 1, 5 0 -- 0.5 to 1% 5 1.5 to 3.5 0 -- 0.5 to 2.5 0 -- 70 to 150 3 to 5 --- NOTE: Measurements of surrounding ,air taken at same height of machine approximately 1M downwind. TABLE v SHIN-ETSU MONITORING DATA VCM CONCENTRATION IN AIR NEAR THE TOP MANHOLE OR REACTOR TAKEN 1 TO 2M DOWNWIND Q HEIGHT ABOVE MANHOLE AS NOTED (MEASURED WITH CENTURY OVA, CORRECTED' FOR BACKGROUND) Date & Reactor Number Operation Monitoring Height -> 10/5 ' 0.1M No. 3 1.5M 10/7 0.1M No. 1 1.5M 10/12 0.1M No. 5 1.5M 10/12 No. 3 0.1M . 1.5M immediately after opening manhole flexhose in manway after 3f minute ft tt " " 3 minutes tt TT " " 5 minutes tr ft ,f " 10 minutes IT tt " ,f 15 minutes ft tt " "20 minutes 1% 20-30 5 5 7 - open bottom manhole, ppm elapsed time after slurry discharge 3 minutes after bottom manhole open start washing @ bottom manhole 1 minute after above elapsed time after bottom manhole open 30-50 14 min. 3-13 ppm 0-1 5 min. 1000 70 3 3 7-8 - 1000 80-100 15 . 4 2 2 1 1000 100 35 4 3 3 2 IX 20-30 6-10 1 2 - 1000 20-30 7-12 1 2-10 - 1% IX 1000-3000 L0OO-3OOO 25-45 35-55 2-3 1.5 1-2 1-2 -- -- 50-70 14 min. 50-100 0-1 5 min. 1000 40 min. 100-200 2-3 5 min. 1000 40 min. 100-200 1-2 5 min. 50-100 14 min. 7-11 O.5-1.5 5 min. 100-1000 14 min. 12 0.5-1,5 5 min. 100-1000 13 min. 26-65 4-14 6 min. 100-1000 13 min. 12-25 9-25 6 min. COLORITE 013258 COLORITE 013259 TABLE SHIN-ETSU MONITORING DATA VCM CONCENTRATION IN AIR DURING SLURRY DISCHARGE 1 TO 2M DOWNWIND FROM WET SIEVE (MEASURED WITH CENTURY OVA, CORRECTED FOR BACKGROUND) Date -------- ^ 10/4 Operation Reactor Number__ ^ 2 after start of discharge 3 minutes after start of discharge 5 minutes after start of discharge 10 minutes after start of discharge at finish of discharge 3 minutes after finish of discharge 5 minutes after finish of discharge 10 minutes after finish of discharge * 15 minutes after finish of discharge 1800-2000 500-1000 300-700 10-150 2-3 0 1 0 0 ^Connected handhole of wet sieve to exhaust blower with flexible hose. 10/5 3 500-1000 250-350 100-200 100-200 1-2 0.2 0 0 0 10/7* 1 10-100 1-2 0.5-1 3-10 0.5 0.5 1.5 1.5 1 10/12* 5 100-300 100-200 25-45 . 3-8 1 0-1 - - 10/12* 3 100-500 3 0-70 3 1 3 0-1 - - - TABLE IX SHIN-ETSU LONG-TERM (6-7 HOUR) MONITORING COLORITE 013260 Date Time On/Off Sample Point Screen Room, 3rd Floor Central Control Room Yard - Downwind Recovery Area Polymerization Building - 4th Floor - #5 (E. Wall) t Polymerization Building - 4th Floor - #1, #2 (E. Wall) Polymerization Building - Ground Floor --Between #1 and.Slurry Tank 10/30/74 1430/2030 1.1 1.3 0.3 0.7 - - 10/31/74 1030/1630 0.9 0.9 0.1 0.5 - - 11/1/74 1030/1750 0.5 - 1.0 4.6 0.3 W. C. Champion 11/20/74 TABLE X OPERATOR TIME BREAKDOWN - KASHIMA OPERATING PERSONNEL Location Foreman CD Central Control Room 4' 10" (2) Job Sitev 3' 00" * Cafeteria 50" Ass't. Foreman 3' 50" 3' 20" 50" Board Man 6' 40" 30" 50" Time/Shift Polymerization Operators 4th Fir. 2nd Fir. Discharge 2' 40" 2' 40" 2' 40" 4' 30" 4' 30" 4' 30" 50" 50" 50" Dryer Operator Recovery & Utility 3' 00"^ *2' 10" 4' 10" 5' 00" 50" 50" C O L O R IT E (1) includes time in break room. (2) for Foreman and Assistant Foreman - roving, 5 times/shift. O (3) Includes time analyzing resin samples. H W M TABLE XI TIME-WEIGHTED VCM EXPOSURE AVERAGES KASHIMA OPERATING PERSONNEL Job Classification Foreman Assistant Foreman Board Man 4th Floor Polymerization Operator 2nd Floor Polymerization Operator Discharge Operator t Dryer Operator Recovery and Utility Operator 8-Hour Time-Weighted VCM Exposure, ppm Without Respirators With Respirators With CCR at 0.1 ppm VCM 7.2 2.5 0.8 7.2 2.5 0.8 3.0 3.0 0.2 20.0 2.6 1.5 12.2 1.5 0.4 12.2 1.5 0.4 1.4 1.4 0.2 71.9 2.0 1.0 COLORITE 013262 W.C. Champion H /2 0/74