Document gEQXJLNkMeOEpYm5QVO498KaN

I CD Interoffice Communication to R. D. Ganblin F'om J. E. Cearley oate January 2, 1976 -o o F C- o 3- % e d5 Status of Chemical Exposure Abatement Program r3 W3 0 V _o V O A. CU STATUS The initial comprehensive monitoring of the first group of chemicals considered as "high risks11 has been completed, and we now know which of these chemicals have the greatest potential for employee exposure to unacceptable levels. Additional chemicals have been added to the monitoring list as the sampling program progressed. The permissible exposure levels of the chemicals that have been monitored thus far are presented in Table 1, and the monitoring results (Juns-Novomber, 1975) are shown in Table 2. The sampling techniques and analytical methods being used for the various chemicals are depicted in Table 3. The results of the sampling and analyses for the chemicals monitored thus far indicate time-weighted employee exposures are below the action level. The primary exposure problems encountered have been the short term high level exposures that exceed the ceiling and/or maximum peak concentrations, i.e., methyl chloride, hydrogen chloride, benzene, and ammonia. Corrective measures to reduce these short-term high level exposures to acceptable concentrations are either in the planning stages or are being carried out (Table 4). B. CHEMICALS WITH EXPOSURE-REDUCT ICMI REQUIREMENTS 1. Ammonia The areas of the plant having the greatest potential for employee exposure to anr.onia are around the ammonium hydroxide storage tank located in Section 500 of the Alcohol Unit and the ammonium hydroxide storage and day tank located at the Holding Pond. In Section 500, high ammonia exposures occur only when the ammonium hydroxide storage tank is being filled by tank truck. The storage tank vents to grade (open sewer); and while being filled, there is considerable cuantities of a."*onia vapors emitted to the atmosphere. Previous area monitoring showed levels in excess of the ceiling limitation of 50 ppm for 5 minutes. In order to reduce the exposure levels, the storage tank vent will be rerouted to the acid holding pit, with the discharge being located below the surface of the water; this will scrub out a significant portion of the emissions. In adaition, a nc-od with a vent to the atmosphere will be installed over the acid holding pit, which will reduce employee exposure to emissions from the pit. MCD 000009339 R. D. Gamblin Page 2 January 2, 1976 At the holding pond, ammonia is added to the waste water as a nutrient for the biological organisms in the Aerated Lagoons. Personal monitoring indicated expsoure levels were below the action level, which was because employees filling the day tank position themselves upwind so as to avoid the ammonia emissions. However, area monitoring showed levels in excess of the action level. In order to reduce the ammonia emissions, the vent and discharge lines from the ammonium hydroxide storage and day tanks were extended so that the outlets w'ere located below the water level. Vie have not been adding ammonium hydroxide for several months, so we have not been able to monitor these operations since the corrections were made. As soon as we begin nutrient additions, monitoring will be conducted. 2. Phosgene The potential for phosgene exposure exists in the Methyl Chloride Unit; phosgene is present in the hydrogen chloride feed from 01in when there is an upset in their system. Vie recently had two laboratory personnel exposed to high phosgene levels while working on the mobile GC monitor located at the Methyl Chloride Unit; this occurred when the unit was being started up. In order to prevent additional employee exposure, a phosgene analyzer has been installed on the HC1 stream at the Methyl Chloride Unit. The instrument has performed very well so far. In addition, Olin will install an identical analytical instrument at their location to monitor the HC1 line to the Chemical Plant. With these two instruments in operation, we should not have any more "surprise" high level exposures. An additional safeguard is the fact that we currently analyze methyl chloride 4 to 5 times daily. Our calculations indicate that a phosgene level of 200 ppm would be necessary for the potential to exist for employee exposure to levels in excess of the ceiling limi tation. In addition, an employee would have to be exposed to approxi mately 5000 ppm of methyl chloride with a phosgene level of 10 ppm in order to be exposed to the ceiling limitation. With the product sampling program and the HC1 feed monitoring, we should be able to prevent employee exposure to unacceptable phosgene levels. 3. Hydrogen Chloride The prirary exposure problem with HC1 is when personnel collect samples at the Methyl Chloride Unit for routine analysis. The sample bombs are vented directly to the atmosohere in the immediate area of tha employee. A design for a sampling system that will reduce exposure to an acceptable level lias been completed and issued. MOD 000009340 R. D. Gamblin Page 3 January 2, 1976 4. Benzene Personal ronitoring of Ethylene Unit employees indicated the tireweighted average levels vsre below the action level of 5 ppn. However, fixed pcir.t ronitoring ^as indicated levels in excess of the ceiling 1 imitation for the `u 5 -* cb hater Settler and a sewer vent located at the base of the lie't arcetics distillate tower. Of these two sources of emission, the Quench Water Settler is by far the r.ajor source of benzene exposure. In addition to these emission source points, preliminary sailing has indicated potential exposure problems with the 2C1 first stage knockout drum drain to the sewer. Another potential source of benzene exposure is the API separator located at the Holding Pend; this separator receives discharges from the Alcohol and Ethyl en-e Units oily water sewers. The Ethylene discharge includes discharges from the Quench Water Settler, thereby creating the potential fer benzene emissions. The mobile GC analyzer has been relocated at the API separator, and'monitoring will be con ducted to determine benzene levels. The initial intensive ronitoring program for benzene will be com pleted by January 1, 1575. As soon as all the data is evaluated, recommendations will be made as to the corrective actions needed to reduce benzene exposures to an acceptable level. 5. Ethyl erg Oxide Personnel exposures to ethylene oxide have been well below the action level. One potential exposure problem picked up by area monitoring was a vent off the ETO reactor that discharges to an open ditch. This vent is used to blowdown and purge the reactor at the end of each run. A steam-traced knockout pot with a vent 10 feet above the ETO Building will be installed (cost estimate of SI,250). Since the emissions are intermittent and of a short duration, this system will be adequate. The OVA instrument will be used to periodically monitor the EO system in order to detect any leaks; this is important since ethylene oxide cannot be detected by s"ell until concentrations are up around 7C0 ppm. 6. f`etuy1 Chloride Methyl cMoride is the cu2~ical that has presented the greatest problem as far as eroloyes exposure is concerned. Although personal monitoring has indicated exposure 1evels teiew tre action level, grab samples and mobile GC analyses indicated occasional high levels that exceed the ceiling limitation. T're major problem areas where exposures to MCD OOOOOQ34i R. D. Gamblin Page 4 January 2, 1976 concentrations in excess of the 300 ppm maximum peak limitation are possible are: 1. Bleeding the D-7 compressor suction knockout drum. 2. 'Bleeding D-8 oil wash knockout drum. 3. Additions of caustic to T 11-20. 4. Collection of sample bombs for laboratory analysis - venting to the atmosphere occurs. 5. Loading of tank cars - venting to the atmosphere. 6. Location of vents on low and high side of compressor piston rod seal. 7. Numerous atmospheric emergency vents throughout the unit. 8. Vents and bleeders into open sewer. 9. Relief valves in the unit. 10. Location of chiller vent stack. A design for reducing emissions when collecting samples for lab analysis has been completed and is being reviewed. The remaining items have been assigned to Process Engineering, and as soon as the designs are complete (February, 1976), cost estimates will be made. The OVA instrument was used recently to go through the unit and locate leaking valves, seals, etc. During the last turnaround, the major leaks 'were repaired, thereby reducing fugative emissions. We recently submitted an AFE for the purchase of an OVA instrument for the Methyl Chloride Unit so that operations can routinely check for leaks. C. PROPOSED SCHEDULE FOR 1976-1977 PERSONNEL "(TUTORING PROGRAM The proposed schedule for monitoring of chemicals in the plant for the next two years (1976-1977) is present^in Table 5. We will attempt to adhere to this schedule, although proposed and finalized standards for various chemicals by OSHA ray change the priority of cur sampling schedule. Our existing manpower prevents us from moving ahead any faster than what is proposed; therefore, it will take us a minimum of two years to look at all of the more obvious chemical exposures. MCD 0000093^2 R. D. Gamblin Page 5 January 2, 1976 The general format that will be followed in our sampling program is as fol lov.'s: 1. In all monitoring, sarples reDresentative of each job classification for all shifts will be collected. !.'e will attempt to monitor at least 50:- of the employees in each operation or process. In addition to operations ogrscnr.el, maintenance employees will be monitored, particularly during turnaround and major repair work where the potential for high level exposures is greatest. 2. Monitoring of an ooeration or process will be repeated at least monthly when the concentration has been found to exceed the action level. 3. If the concentrations exceed the recommended TLV standards, monitoring will be conducted at biweekly intervals until two consecutive surveys indicate the adequacy of the control measures taken. 4. Samples will be .collected semi-annually for those chemicals below the action level and considered as "high risk," i.e., methyl chloride, hydrogen chloride, ethylene oxide, and benzene. Other chemicals below the action level will be monitored every 12 to 18 months, de pending on the chemical's toxicity and the potential that exists for employee exposure. 5. For those chemicals that have relatively high established TLV values, and we are assured exposures do not approach the action levels, written determinations will be made and placed in our files. Some of the chemicals currently believed to fit this category are butadiene, pentane, LPA solvent, propane-propylene, and various raw materials and supplies, such as various lialco products. We currently are considering placing phosgene in this category, since a phosgene analyzer has been installed on the HC1 feed line and Olin Chemical is in the process of installing an analyzer at their facility. In addition, we analyze the methyl chloride product four to five times daily, and we know how much ohosgene must be present in the product for the potential of exposure to unacceptable levels to exist. 6. As time permits, training programs will be develooed for the various chemicals, V.q realize the importance of training programs, but our manpower is such that we are unable to develop this area as rapidly as we would like. 7. Routire plant inspections (ore to two tires per month) will be made to evaluate housekeeping activities and work habits in the various units. 000009343 MCD R. D. Gamblin Page 6 January 2, 1976 8. Where feasible, engineering design changes will be made to reduce erployee exposures to acceptable levels. Where engineering controls are not feasible, personal protective equipment will be utilized. The Chemical Plant will adhere to this format as much as possible, al though proposed and finalized OSHA regulations for various chemicals may require changes in our current schedule. In addition, there are no established sampling and analytical procedures for some of the chemicals to be nonitored, and we may run into difficulties here. D. COSTS OF CORRECTIVE MEASURES REQUIRED FOR EXPOSURE REDUCTIQflS At the present time, we do not have a good feel for the cost of corrective measures that will be required to reduce employee exposures to acceptable levels. It appears that the major expenditure will be for the Methyl Chloride Unit. The design work for reducing emissions in the "ethyl Chloride Unit is scheduled to be completed by February 1, 1976; once the design has been reviewed and approved, cost estimates will be made. E. MOf-ilTCRIriG EQUIPMENT In order to adequately carry out the monitoring program, we will need some additional monitoring equipment (Table 6). A tentative estimate of the costs of sampling equipment that will definitely be needed in 1976 is approximately $4,000. Additional analytical equipment that may be required has been included in Table 6 as 1977 Capital Budget items. J. E. Cearley mbr Enclosures cc + encs: RAC RHG DDZ OOP MCD 000009344 TABLE 1 Chenical Methyl Chloride Methanol Hydrogen Chloride Phosgene Ethylene Oxide Benzene Sulfuric Acid Butanol Hexanol Ethanol Acetic Acid Ammonia Carbon Monoxide Vinyl Chloride Chlorine Calcium Hydroxide ^Asbestos 8-Hour Time Weighted Average Action Level Acceotable Cei 1 i r.g Concentration Acceptable Maximum Peak Above the Acceptable Ceiling Concentration for an 8-Hour Shift 100 ppm 50 ppm 200 ppm - 50 ppm 10 ppm 100 ppm 2.5 ppm 0.025 ppm 25 ppm 5 ppm 1 mg/m3 0.5 mg/n3 50 ppm 25 ppm Mo Establi shed TLV 200 pern (5 minutes in every 3 hrs.) - 5 ppm 0.05 ppm - 25 ppm (10 minutes) - - 300 ppm - - - 50 ppm - 1000 ppm 10 ppm - 50 ppm 500 ppm 5 ppm 25 ppm 25 ppm - - 50 ppm (5 minutes) - - - 1 ppm 0.5 ppm 5 ppm (15 minutes) - 1 ppm 2 ng/m3 0.5 ppm 1 ng/r3 - - Two Fibers ( 5 rricrem ;ters)/cc of air **Monitoring handled by Safety ttCD 0000934S TABLE 1 (CONT'D.) 3TE: 1. Acceptable Ceiling Concentration (C) - Those chemicals preceded by a "C" snail at no tine exceed_one ceifing value given for that material in the table, unless a maximum peak value is designated. 2. 8-Hour Ti~e '..'eichted Average - An employee's exposure to a designated chemical snail net exceed tne 3-hour time weighted average in any 8hour work shift of a 40-hour work week. 3. Action-level - The action level is one-half the TLV; if exposures are below this level, then no further action is required, other than monitoring every 6 months. Hcv.-ever, if exposures are greater than the action level, then more frequent monitoring is required (generally montniy), medical surveillance must be implemented, control measures must be improved, and various other requirements are necessary. 4. Maximum Peak Above Acceptable Ceiling Concentration - The ceiling standard may-be exceeded for short periocs (generally 5 to 30 minutes) up to a concentration defined as "acceptable maximum peak above the acceptable ceiling concentration for an 8-hour shift." MOD 000009346 Method u .< u Ck H ot* 4* - >co: fe". Ci c p. c -* : W uwaV nu o> VvO\o rw-t ttf--\0 o o O C--T *"> 0k*k*4 0 9>0 04 O O 3 o o o p\Q o o m ^ A c tio n L e v e lK Max P erm issible Level J>Mox P orm lsslbla Level Averfizu P o in t Environm ental CO C r^ b Grub Caipl<:3- - E raser D raper Tubca xCActton OOH oo O O VO ft O C"> O IT* Oft o CO ft f o oo oo r>fHt on o ow*\ --* o"-<i H8 vO Cvrfti Oh m*- ftO r-< eo 4OT o Ju2 X roe-4 V "*CoDwu3 ou4 oc W3 *v34 U< w*yyy1 wucOcyy aC<C"*l>%cvHO fC--M ft 0-vOnS'\ ft O ft CuMi O?* CM -J- rH-k *Cv 0r4 o /x*-c0>>4: U To3 0 x C k. p.oC0-4 ooc X Xuoeu0I ^4 ocaKy o*-4 ec x*4; U o **5 & ISU 3 5 0c Jx --S > koW*. e ?e.. o WHN* weg3 0 tOtcC5J eu aCew ouy ot* coc. Oi <a hcd 000093^7 ' - Ti"o C h c n ic o l (L) MCD 0 0 0 0 0 9 3 4 8 LASrOJS MATERIAL Methyl Chloride Ethylene Oxide Methanol Hydrochloric Acid Sulfuric Acid !*ioi*'ne Benienc Vinyl Chloride Ethanol, Butanol, Kexanol Aaaonla SAy?LE CCl-TJCTIOll AWSOTRPNT TABLE 3 dpsorbewp KEFTRElfCE DFTECTTOR KEVAPK8 X. Slpln SP*J 2, Huttl-Conpla Point Environsente! GC 3. CVA Century 5 Portable CC Carboslevc-B Prl-60/100 scab bOO mg Sec-bJ/6o nesh 100 mg 1. Multi-sample Point Environr.cuial (JC 1. Slpln SP-3 Silica Gel (30/60 aeah) b00 mg - primary 100 ag - backup 2. Multl-Sanpla Point Envlronentcl GC V Dre?er Tubes 1. Midget Iisplnger* .OUf 3odium Hydroxide 2. Draper Tubes 1. Hldeet Implngera 1* godlua Hydroxide 1. Dra.'-r Tubes l. Slpln SP-3 Cslgon TCP 12x30 Cher^oai, 300 Big 2. KUltl-Saapla Point Environ mental GC 3. Draper Tubea k, OVA Century 90 portable GC 1. Slpln SP-3 Calgoa PC? 12x30 Charcoal, 500 ag 1. Slpln SP-3 Calgon POP 12x30 Charcoal, 300 ag Prl Sec-100 ag 2. Multi-Staple point Environ mental GC 3. OVA Century 96 portable GC 1. Midget Inplnger 0.1 tf Sulfuric Acid 2. Droger Tubes , r. Bend lx Flasher 300C LCCP FID, 6', 1/8" Poropak q-3 (100/120 eeah) 100C Result# hsapared by Mgb biatdlty (rain), flash tube prior to uaa. FID, 10*. 1/6" Cnrbovex l?M {1S> on W) 80C Area monitoring Veter rm FID, 10*, 1/0" Carbowax 1500 (lOj on W) 60C LCCP-KIOSK 859*1 FID, 0', 1/0" Propek QS (100/120 aeah) U5C FID, 0', 1/8" carbowex 1500 <10* on V) 0OC Leak Detection and Peak Concent rat Ion St udias Area monitoring, Motet Poor reaulta by Slpln pump# sad air beg# 0`,'J Recovery, plan to uaa fliebar after preliminary itudy Area aonltorlog AIHA Colorlmetrlc-thlocyanata Poor aenatttvltr Minimum detection la .9 ppa la 15 alnute aaaple. Plan to Imvaatlgste Hlran J for peak ADtA . Carbon Dlaulflda Colorlnetrlo-Barlua Sulfata FID, 20', 1/0" DECS tl2i orv P)(60/CO !>} 65 for 6 alnutcs to lbQ" at 6 per minute. FID, 8*, 1/0" SE-30 90 <6* on 100/120 aesb varoport 30) Minimum detection la .2 mg/m^ Poor aenaltlvltv Area aooltorlng Carbon Dlaulflda Carbon Dlaulflda containing 1% 2-Butanol and .2* Dodccanol LCCP-HICQH 356-14566-1 FID FID, 20*, 1/8", DE09 (12* on P, 60/80 aeah) 65 for 6 almitea to IbO at 8 per alnute FID, 10*, 1/8" FFAP (10* on 60/80 aeah W) Leak detection nod peak coaeentrb11 on atudlea Run by VCM - Paul fataar 6 alcohol* can alio be datcmlaed Recovery - Ethanol - 55-&0* Butanol 72*88* BICflB PID, 8*. 1/0", 6E-30 <6* on 100/120 maah varoport 30) 90 pm Area Monitoring Leak Detection ColorImatrlo-Reaslar Reagent, Mlainua detection .3 ppm la f alnute sample 1 *i 1! 6 ^ 0 6 0 0 0 0 0 crow TAu.^ 4 CORRECTIVE MEASURES FOR REDUCING CHEMICAL EXPOSURES CHEMICAL Ammonia MCI Ethylene Oxide UNIT Waste Mater Holding Pond (Nutrient Addition) Alcohol Methyl Chloride Ethnxylation MAJOR SOURCE(S) OF EXPOSURE Filling of Ammonium Hydroxide Storage and Day Tank; Discharge for Day Tank Filling of Ammonium Hydroxide Storage Tank - Vents to Atmosphere Sampling HC1 Feedstock Vent used to Blowdown ETO Reactor at Grade Level CORRECTIVE ACTION Discharge and vent lines extended to below the water level of the influent waste water Vent line rerouted to Acid Hold ing Pit and extended to below the water level Redesign sampling system enclosed loop Install knockout pot and vent to atmosphere COMPLETION DATE 2-1-76 4-1-76 2-1-76 Methyl Chloride Methyl Chloride Benzene Ethylene Ethylene Offsites Loading of Tank Cars - Venting to Atmosphere Bleeding of Knockout Drums Sample Bomb Collections Additions of Caustic to T 1120 Various Vents, Pel ief Valves, and Bleeders Quench Hater Settler Vent off of Light Aromatics Distillate Tower AIM Separator at Haste Water Holding Pond Manholes along Ethylene Oily Hater Sewer Line Designs currently underway to provide engineering changes for reduction of emissions Monitoring for benzene has recently been completed and the data is being evaluated. Recommendation as to corrective measures needed are being pre pared Design to be complete by February 1, 1976 Recommenda tions by 1-31-76 STATUS Complete Work rescheduled due to priority Design issued 12-30-75 Original cost ost Mii.itc was high; project redesigned work rescheduled Assigned to Process Engineering for dcsign work Recomrendations as to corrective action needed being pre pared TABLE 5 CHEMICAL Methyl Chloride Methanol Hydrogen Chloride Sulfuric Acid Ethylene Oxide Benzene Vinyl Chloride Ammonia Hydrogen Sulfide Butanol Ethanol Hexanol Carbon Monoxide Chlorine Calcium Hydroxide Acetic Acid Chromate Mercury Hexane Phosphoric Acid Caustic Sulfur Dioxide Methyl Chloride Hydrogen Chloride Ethylene Oxide Benzene Sulfur Dioxide TBC TPT Nalco Products Methyl Chloride Methanol Ethylene Oxide Benzene Vinyl Chloride UNIT January 1 - February 15, 1976 Methyl Chloride Methyl Chloride, Ethylene Methyl Chloride Methyl Chloride, Alcohol, Cooling Towers Ethoxylation February 15 - May 1, 1976 Ethylene, Ethylene Offsites Ethylene Alcohol, Ethylene Offsites Normal Paraffin Alcohol Alcohol Alcohol May 1 - June 1, 1976 Alcohol Ethylene and Alcohol Cooling Towers Steam Plant Ethoxylation Alcohol Cooling Tower East and West Shops June 1 - August 1, 1976 Alcohol Ethylene Offsites, Ethoxylation Ethylene, Methyl Chloride Steam Plant Methyl Chloride Methyl Chloride Ethoxylation Ethylene, Ethylene Offsites August 1 - October 31, 1976 Normal Paraffin, Methyl Chloride Ethylene Alcohol Ethylene, Ethylene Offsites, Normal Paraffin Methyl Chloride Methyl Chloride Ethoxylation Ethylene, Ethylene Offsites Ethylene MCD 000009350 TABLE 5 (COMT'D.) CHEMICAL Butanol Cthanol Hexanol Total Hydrocarbons Merox Methyl Chloride Methanol Hydrogen Chloride Sulfuric Acid Ethylene Oxide Benzene Vinyl Chloride Sulfur Dioxide Ammonia Hydrogen Sulfide Butanol Ethanol Hexanol Sulfur Dioxide Carbon Monoxide A1 umina Methyl Chloride Ethylene Oxide Benzene Vinyl Chloride Chlorine Caustic Phosphoric Acid Hexane Sulfur Dioxide Calcium Hydroxide Acetic Acid UNIT November 1 - December 31, 1976 AT cohol A1 cohol A1 cohol ATE Quench, Waste Water Holding Pond Ethylene, Ethylene Offsites January 1 - March 31, 1977 Methyl Chloride Methyl Chloride Methyl Chloride Methyl Chloride, Cooling Towers Ethoxylation Ethylene, Ethylene Offsites Ethylene Ethylene April 1 - June 30, 1977 Alcohol, Ethylene Offsites Normal Paraffin Alcohol Alcohol Alcohol Alcohol Alcohol Alcohol July 1 - September 30, 1977 Methyl Chloride Ethoxylation Ethylene, Ethylene Offsites Ethylene Ethylene and Alcohol Cooling Towers October 1 - December 31, 1977 Methyl Chloride, Ethylene, Ethylene Offsites Ethoxylation, Ethylene Offsites Alcohol Normal Paraffin, Methyl Chloride Stean Plant Ethoxylation MCD 000009351 METHOD 1, 2 1, 2 1, 2 2 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1' 1 1 1 1 1 1 1 1 TABLE 5 (CONT'D.) NOTE: Monitoring for asbestos will be conducted whenever employees come in contact with the material, which is only when old insulation is removed. Monitoring is handled by Safety. 1. Personal Dosimetry 2. Mobile Multi-Point GC MCD 000009352 TABLE 6 MONITORING EQUIPMENT EQUIPMENT Oil HAND Sipin S-P3 Pump Bendix C-115 Pump *Century Organic Vapor Analyzer (OVA) MSA Pump Bendix Flasher (For use with Lab. G.C.) NUMBER COST 4 $1 ,600.00 2 On Loan From VCM Plant 1 $4,000.00 1- 1 $ 700.00 *One additional OVA on order for Methyl Chloride Unit EQUIPMENT MEEDS DURING FIRST QUARTER 1976 Sipin S-P3 Pump Sipin S-Sl Pump Bendix C-115 Pump NUMBER COST 4 $1,600.00 2 $ 800.00 2 $1,200.00 1977 CAPITAL BUDGET ITEMS Laboratory G.C. Analyzer Miran-II Infrared Portable Analyzer MDA Personal Monitoring System a) Pumps b) Analyz3r Miscellaneous MOD 000009353 NUMBER COST 1 $8,500.00 1 $6,500.00 4 $3,000.00 1 $2,500.00 $5,000.00