Document J315VV66Xoqo3oJjaogD65jbB

COMPANY CONFIDENTIAL PRELIMINARY INDUSTRIAL HYGIENE SURVEY OF THE TEXAS CITY PLANT Monsanto Company Department of Medicine & Environmental Health Industrial Hygiene Section St.Louis, Mo. Conducted November, 1975 Written by S.A. Roberts MAP 004927 LAM000753 Distribution 1. P.E. Brubaker Plant Manager, Texas City Plant 2. George Roush, Jr.,M.D. Medical Director Dept, of Medicine & Environmental Health 3. E. N. Brasfield Director, Manufacturing MPPC Petrochemicals Division 4. Harry M. Keating Manager - Environment and Energy Affairs MPPC St. Louis, Mo. 5. E.W. Jones Superintendent - Personnel Texas City Plant 6. J.E. Fox Industrial Hygienist Texas City Plant 7. R. L.Miller S&PP St. Louis, Mo. 8. File Copy MAP 004928 IAM000754 INTRODUCTION At periodic intervals an Industrial Hygiene Survey is conducted by the Medical Department to determine if possible occupational exposure problems exist in a given plant. The results of such a survey are con tained in this report. The survey includes an examination of the job classifi cations and materials a worker might handle or be exposed to in each classification along with a notation on pro tective equipment provided to prevent or lessen exposure. The survey also includes a walk-thru examination of each operating unit with recommendations to eliminate exposure problems observed. Thi6 report is based upon conditions and practices observed and information supplied by management personnel at the time of the visit. It does not purport to list all hazards nor to indicate that other hazards do not exist. If there is an error or omission, please send the correction to: Steven A. Roberts Monsanto Company Medical Department St. Louis, Missouri MAP 004929 3- LAM000755 INDEX Title Page..................................................................................................... 1 Distribution................................................................................................ 2 Introduction ...................................................................................... 3 Index...............................................................................................................4 Departments Ethylbenzene and Styrene .................................................. 5 Acetic Acid....................................................................................... 27 Methanol - Syn Gas...................................................................... 33 Lactic Acid......................................................................................... 39 Oxo-Alcohol......................................................................................... 46 Ethylene................................................................................................ 6l Polyethylene ............................................................................... 67 HDPE..................................................................................... 73 Phthalic Anhydride .................................... .... 8o HCN, TBA, and LN..............................................................................87 Appendix A - Substances With Assigned Exposure Standards . . . 102 Appendix B - General Observations and Distribution Department . . 104 MAP 004930 LAM000756 MONSANTO COMPANY INDUSTRIAL HYGIENE SURVEY POSSIBLE EXPOSURE INVENTORY COMPANY MPPC DIVISION Petrochem. PLANT Texas City DEPARTMENT: Ethylbenzene and styrene Products: Ethylbenzene Styrene 1 Ethylbenzene (to styrene) 1. Styrene monomer 2 Aluminum chloride (27# solution)2. Toluene__________ 3 Hydrogen chloride (17# solution)3. Styrene Tar 4 Flux oil 4. Benzene__________ 6 7 8 Employee: 1st Shift 2nd Shift 3rd Shift 4th Shift EB 5 4 4 6 Sty. "ET 7 7 Ethylbenzene Hourly Hourly Hourly Hourly EB IT Sty 7 Salaried Salaried Salaried Salaried Totals 19 22 Hourly Buildings Involved: 1 2 3 jj, ------------- Supervisor: J. P. Irwin (EB), S. E. Knipling (Sty.) 4 7 Salaried MAP 004931 LAM000757 MONSANTO COMPANY INDUSTRIAL HYGIENE SURVEY MATERIALS DATA SHEET Division MPPC Plant Texas City Department 13-1^ Ethylbenzene + CT7 Operation Supervisor j. p. Irvin Date Nov. 14, 1975 Building Raw Materials Intermediates Finished Products Benzene Ethylene Aluminum granules Anhydrous HC1 5056 NaOH solution Chlorine (CT7 only) MB-103 -Biocide (CT7 only) Ethyl Chloride (Used only occasionally as HC1 sub stitute) Calgon SL 500 Boiler Water Additive (Mixture of NTA and EDTA) Nitrilotrlacetic Acid (NTA) Benzene Polyethylbenzenes (pri marily diethylbenzene) Catalyst Complex (Aluminum chloride organic complex,--'75# AICI3 by weight) Offgas (mainly CH4 & C2H5 sent to Power Z for boiler feed) Ethylbenzene 21% AICI3 Solution (BP) 11% HC1 Solution (BP) Flux Oil (Heavy ends used in 15/16 or as boiler fue Mlbcfe.uAneous Materials; Various lab reagents used for (1) water hardness and pH analysis (2) boiler control - SL-500, Sulfite, Cond. measurements MAP 004932 LAM000758 MONSANTO COMPANY INDUSTRIAL HYGIENE SURVEY ^ 00493.3 MATERIALS DATA SHEET Division MP&P Plant Texas City Department Dept. 15 & l6 (Styrene) Supervisor s. E. Knipling Date 11/17-''75 Building i6d Raw Materials Intermediates - Finished Products Ethylbenzene Molten Sulfur 8556 Tertiary Butyl Catechol in Methanol Flake Caustic) NapSO^ ) Water NaNOo ) Treating 2-4 Dinitro Phenol (DNP or NSI) future Shell 105 Dehydrogenetior Catalyst 50# NaOH 17# Muriatic Acid Department 15 Off Gas DM-Mixture of EB, SM, Toluene, Ba, High Boilers 15# DNP in DM 25# DNP in DM 1056 Na Salt of DNP Waste water containing traces of DNP Styrene Monomer inhibite Tert.Butyl Catechol Ethylbenzene Toluene Benzene Styrene Tars MiBc6lj.aneous Materials: Analytical Chemicals Starch HCL (2556) 1/30 N HCL Potassium Iodide Solution (10#) Potassium Iodate Solution Neutral Barium Chloride (10#) Phenolphthalein Phosphate Reagent #2 (Colorimetr Phosphate Determination) Phosphate Reagent #3 (Colorimetr Phosphate Determination) Conductivity Reagent A (Conductc metric Solids Determination) LAM000759 MAP 004934 R e c y c le P o ly e th y lb e n z e n e (PEB) B lock Flow Diagram F igure 1 i LAM000760 * $ v, i \ 1 MAP 004935 fvK <o '*sv LAM000761 A Tobf-x LAM000763 PROCESS DESCRIPTION The four mejor steps In the process ere: 1. Menufacture of ethylbenzene by the alkylation of benzene with ethylene (Dept. 13) 2. Purification of ethylbenzene by distillation from the alkylated liquor (Dept. 14). 3. Dehydrogenation of ethylbenzene to styrene (Dept. 15). 4. Distillation of the dehydrogenated reaction mixture to recover the styrene product (Dept. l6). The Interconnection of these processing steps is shown in the block-flow diagram in Figure 1. Further process description is as follows: 1. Alkylation: The chemistry of the alkylation process is involved with the following reactions: Alkylation A1C1,.HC1 C6H6 + C2H4 --------------^ c6h5c2h5 CgHg + nC2H4~^-----------^ C6H5(C2H5)n polyethylbenzenes (PEB) Transalkylation AlCl., ,HC1 c6H5 <c25> n + c66 4---* ^^ C6H5C2H5 PEB BZ EB MAP 004939 LAM000765 PROCESS DESCRIPTION (continued) In the alkylation process, alkylation (and some transalkylation) is accomplished in the alkylator. Part of the fresh dry ben zene feed to the unit, benzene bottoms from the.benzene absorber (contains fresh make-up and recycle HC1), and aluminum chloride catalyst are fed to the highly back mixed reactor. Ethylene is introduced through a sparger. Heat of reaction is removed in an external pumped cooling loop. Off-gas from the reactor (ethane impurity in ethylene) is cooled to remove aromatics, combined Kith off-gas from the benzene ab sorber, scrubbed with PEB to recover aromatics and HC1, scrubbed with water to remove remaining HC1 and used as fuel gas. Alkylate (including unreacted benzene) from the alkylator is combined with recycle PEB (from distillation) and transalkylated in the transalkylator (plug flow hold tank)^ Both alkylation on transalkylation are conducted at 160-I80 C. Total liquid from the transalkylator is flashed to remove some of the unreacted benzene and recycle benzene. Flasked vapor is condensed in.a partial condenser and a benzene absorber column. Condensate from the partial condenser is rich in EB and is com bined with the liquid alkylate from the flash. Vapor from the partial condenser is scrubbed with benzene In the benzene absorber to condense recycle HC1 and aromatics. Fresh make-up HC1 (or ethylchloride) feed to the unit Is also fed to the benzene absorber. The small amount of unabsorbed gas from the top of the benzene absorber column (mostly ethane impurities in ethylene feed) is combined with reactor off gas for PEB and water scrubbing and use as fuel gas. Benzene feed to the benzene absorber is part of the fresh cold benzene feed to the unit. Benzene along with absorbed HC1 (recycle and fresh make-up) and aromatics from the bottom of the column is pumped to the alkylator. MAP 004940 LAM000766 PROCESS DESCRIPTION (continued) Liquid alkylate from the flash is cooled, combined with alky late and spent cstalyst complex from the old alkylation unit and washed (aqueous AlCl^j caustic, water). In the old alkylation dry benzene is mixed with ethylene, re cycle polyethylbenzenes (PEB) from the alkylated liquor (AL) distillation area and aluminum chloride catalyst complex (CC) promoted with HCL. The mixture is pumped through line orifice elkylators and a transalkylation vessel. The reaction is con ducted at 100-120 C. The resulting AL is cooled, degassed, separated from the CC, and combined with alkylate from the new alkylation unit for washing. MAP 004941 LAM000767 PROCESS DESCRIPTION (continued) 2. AL Distillation: The alkylated liquor (AL) from the Alkylation is fraction ated in five distillation steps. In the first step recycle benzene is recovered as the overhead product. This recycle benzene, combined with fresh make-up and recycle benzene from SM distillation, is dried in an azeotropic column and fed to Alkylation. The bottoms from the recycle benzene fractionation is fed to ethylbenzene columns where ethylbenzene is recovered as the overhead product. Ethylbenzene is fed to Dehydro genation. Bottoms from the ethylbenzene columns is further fractionated in two more columns in series. The combined overhead from these columns is the recycle polyethylbenzenes (PEB) which are recycled to Alkylation. By-product flux oil from the bottoms of this last column is fed to SM Distillation where it is used to dilute styrene tar. Excess beyond requirements for styrene tar dilution Is sold as a fuel blending 6tock. AL Distillation shares a circulating dilute caustic system with SM Distillation. If efficiency of the alkylate wash system decreases, caustic is sprayed into the overhead of the recycle benzene column to decrease corrosion. 3. Dehydrogenation: In the ethylbenzene dehydrogenation area the major chemical reaction is: Catalyst C6H5C2H5- C6H5C2H3 + H2 Ethylbenzene Styrene Hydrogen Side reactions produce benzene, toluene, CC^, and high boilers (principally alpha-methyl styrene). Fresh EB from the AL distillation area combined with recycle EB from SM distillation is vaporized, superheated, mixed with superheated steam and catalytically dehydrogenated in a series of two fixed-bed, radial flow reactors. Since the reaction is endothermic, the effluent from the first reactor stage is reheated with Incoming superheated steam in a heat exchanger before entering the second reactor stage. High steam dilutions are used because the steam supplies a "heat sink" in the reaction zone and reduces the partial pressure of the reaction products. Low pressure and high temperature are favorable to the reaction equilibrium, thus subatmospheric pressures are used in addition to the steam dilution. The reactor effluent 1b cooled by generating steam and then partially con densed. The noncondensible off-gas is compressed cooled, scrubbed with ethylbenzene and chilled to recover the aromatic hydrocarbons and utilized as a fuel. The condensed material is separated into an organic and an aqueous phase. The organic phase (DM) which contains styrene, EB and lesser amounts of benzene, toluene and high boilers is sent to the DM distillation area. The aqueous phase is pumped to condensate strippers where organics and dissolved CO^ are stripped with steam. The stripped condensate is filtered and returned to the boiler plant. LAM000768 MAP 004942 4. SM Distillation: Product styrene monomer is recovered from the dehydro genated mixture (DM) by fractionation. In the EB/SM splitters the DM is distilled to take overhead the EB and lighter components. DNP inhibitor is added to the column feed to inhibit polymerization of styrene. The styrene and heavier components (including DNP) leave the bottom of the first column and are then distilled to separate the styrene product as overhead. Tertiary butylcatechol (TBC) inhibitor is added in the overhead of this column in order to prevent polymerization of the product styrene monomer. Product styrene monomer is chilled and pumped to storage. The bottoms from the styrene product column are stripped in a separate column to maximize styrene recovery. Overheads from the stripping column are recycled to the styrene product column. Flux oil from the AL distillation area is added to the lower portion of the stripping column to keep the styrene tars fluid. The bottoms from the stripping tower may be sold or used as a fuel. The overheads from the EB/SM splitter are fractionated in a series of three columns. In the first of these three columns (EB Recovery Column) toluene and lighter components are taken overhead and most of the recycle EB is taken out the bottom. In the second and third column recycle benzene and by-product toluene are separated from the remaining EB. TBC inhibitor solution is prepared for use by batch mixing with styrene monomer DNP inhibitor will probably (details not yet firm) be recovered in a continuous unit that extracts the DNP from the styrene tar as the sodium salt with an aqueous cauBtic wash. Then the aqueous solution is acidified (HC1) and dissolved in a slip stream of the DM feed to the EB/SM Splitter. Make-up DNP will probably be added to the acidification step as the aqueous sodium salt solution. LA A/1000769 Process Facilities Description - NSI (Non-Sulfur Inhibitor) Acid ificatlon/Dlssolvlng System Acidification and dissolution of NSI in DM takes place in a continuous stirred pot. Feeds are NSI sodium salt solution, 20# Muriatic Acid, and DM. Overflow from the stirred pot flows to a continuous settling tank. Water phase from the settler is the aqueous waste from the unit. It flows to the area sump, organics are skimmed and returned to the process and the waste is pumped to the plant waste treatment plant. Organic phase from the settler (NSI/DM solution) is water washed in a circulating pump mixer/settler system. Unwashed NSI/DM solution and make-up utility water are introduced into the suction of the water circulating pump. Effluent from the pump is separated in the continuous separator tank. Most of the water phase is recirculated. A portion of the water phase is pumped as make-up water to the Recovery System. Washed NSI/DM Solution from the separator is pumped through a coalescer/settler (to remove entrained water phase) to storage from which it is pumped to the EB/SM Splitter feeds. NSI Recovery System SM tar from SM distillation is contacted with caustic solu tion in a continuous mixer/settler system. The caustic solution converts the NSI to the water soluble sodium salt. Mixing of SM tar, 50# caustic, and salt solution is in the salt solution circulating pump. The mixture is separated in hold tank. Most of the aqueous salt solution is recir culated to contact SM tar feed. A portion of the aqueous salt solution is recovered NSI feed to the Acidification/Dissolving system. The SM tar phase from the separator is pumped through a coalescer and separator to remove entrained caustic solution (required to meet ash specification) and then to storage for subsequent use as fuel. MAP 004944 LAM000770 Back-up Dissolving System This batch dissolving system provides a back-up feed of 15# NSI solution in DM from purchased 86# NSI cry stal when normal aqueous salt solution feed is not avail able or when the Acidification/Dissolving or normal feed systems are inoperable. Two dissolvers are provided -- a batch being prepared in one while the other is used for feed to distillation. The 15# solution is prepared by stirring crystals (dumped from drums) with DM at 80 C (steam on jacket) and pH less than 1.0 (20# Muriatic acid added). After settling, water phase is pumped to hold tank snd the batch is ready for feed to distillation. Organic phase separated in the hold tank is 8dded to the next batch and aqueous phase is pumped to waste treatment. Storage/Feed System This system provides inventory of NSI as 2.5# solution in DM and feed pumps to distillation. MAP 004945 LAM000771 LAM000772 LAM000773 LAM000774 INDUSTRIAL HYGIENE SURVEY WORKROOM DATA MAP 004949 OBSERVATIONS ETHYLBENZENE Department 13 is the alkylation unit/ Department l4 is the distillation unit - together known as the ethylbenzene unit. Aluminum dust is dropped into a hopper in which polyethylated benzene is added to flow the aluminum into the catalyst manu facturing system. A benzene sample is taken from the process about once a day. Organic process samples are tsken about 10-15 times a day. Samples are generally obtained by placing 8 jar under a faucettype unventilated top. (Sample overflow is directed into an open flushed sewer.) The SL (alkylated liquor) is composed of approximately 40# benzene, 40% ethylbenzene and 20# diethylbenzene. Note: During the walk-thru of this unit contract personnel under indirect Monsanto supervision were observed tearing out old piping by pulling the pipe lengthwise out of the pipe sup ports. This action stripped the old Insulation from the pipe. The insulation appeared to be asbestos. The insulation was scattered on the roadway and was evident as much as 100 feet from the actual stripping. Contract personnel were sweeping the material In its dry state. The dust level appeared very excessive. Prompt action by Monsanto employees resulted in the curtailment of this operation until the material could be wetted down and personal protective equipment obtained. STYRENE Department 15 Is the Dehydrogenation unit; Department l6 is the styrene monomer unit. During the time of the survey sulfur was still being used as the styrene monomer inhibitor. Sulfur-type odors were easily noticed. This department plans to use another inhibitor (NSInon-sulfur Inhibitor: 2,4 dinitrophenol) in the near future. The process description and block-flow diagram precede this page. Tert.-butyl Catechol is presently used to inhibit stored styrene monomer. Two maintenance foremen are normally assigned to the styrene unit. The odor of styrene was prevalent through out the unit. Each train is turned around every nine months for about two weeks. Some of the styrene tars are sewered. The bottoms pumps are sampled once dally. Odors were easily apparent around the 14D2 column. The odors were characteristic of sulfur MAP 004950 LAM000776 STYRENE (continued) compounds but I was told the odors were primarily toluene. The salt water pump system (SWPS) is a high noise area with exposure approximately one hour/shift. Filter-aid (J-M Hydroflo) is shoveled manually into the filter. Styrene tars are stored prior to disposal in a large tank located next to the condensate stripper. Personnel Indicated a new con densate stripper area was being planned because of the poor access and layout of the present stripper. A musty odor was noticeable in the control room. LAM000777 RECOMMENDATIONS - Ethylbenzene and Styrene It _i recommended personnel exposure to the following subaUances be determined: benzene ethylene hydrogen chloride chlorine ethyl chloride NTA sulfur compounds (H2S, SO2, etc.) ainitrophenol sodium hydroxide iodine barium toluene styrene silica, crystalline and amorphous LAM000778 MONSANTO COMPANY rNDlir.TKTAT. lfYOIKNK .".HKVKY POSSIBLE EXPOSURE INVENTORY COMPANY MP&P DIVISION Petrochemicals PLANT Texas City DEPARTMENT: Acetic Acid Products: 1 Glacial Acetic Acid 2 Propionic Acid 3 4 5 6 7 8 Employee: 1st Shift 2nd Shift 3rd Shift 4th Shift St, days--------------------------Totals Buildings Involved: 4 Hourly 4 Hourly 4 Hourly 4 Hourly 1 Hourly 17 Hourly 1 -13i 2 i^ .153. 154 Supervisor: B. L. Johnson Salaried Salaried Salaried Salaried l -1/2 MAP 004953 LAM000779 Division Plant Department MONSANTO COMPANY INDUSTRIAL HYGIENE SURVEY MATERIALS DATA SHEET Supervisor Date Building Raw Materials Intermediates Finished Products Carbon Monoxide Methanol Rhodium catalyst Iodine catalyst Condensate Methyl Iodide Hydrogen Iodide Acetic Acid Propionic Acid Mibbelianeous Materials Potassium Hydroxide ) Chelating agents for process Hypo phosphorous acid) MAP 004954 LAM000780 A ce/~ /c . / ii .* l5 I LAM000781 Observations - Acetic Acid Carbon monoxide is obtained from the methanol department. Rhodium is in powder form and iodine is in crystal form. The waste stream with the chelates are sold for its low grade propionic acid con tent. The potential for carbon monoxide exposure exists as indi cated by previous environmental sampling conducted by John Fox. A method is needed to determine iodine exposure. Blood tests are conducted on the one iodine handler every six months to check for iodine accumulation in the body. Iodine is added to the process about three times per year with about four hours exposure required. The employe is required to wear complete body protection. The iodine is dissolved in methanol to make methyl iodide. A carbon monoxide monitor is located outside of the control room with re mote sensors in the control room, analytical building and the catalyst building. The iodine is partially exhausted through a scrubber to the atmosphere. Rhodium is added to the process in a similar manner with local exhaust control. The main reactor is sampled from an open tap into a portable Jug. Off-spec product is reworked thru the process. Waste streams are usually trickled thru a limestone bed. MAP 004956 LAM000782 Recommendations Acetic Acid It is recommended personnel exposure to the following substances be determined: Carbon monoxide Methanol Rhodium catalyst Iodine catalyst Methyl iodide Acetic acid Potassium hydroxide MAP 004958 LA ft/1000784 MONSANTO COMPANY INDUSTRIAL HYGIENE SURVEY POSSIBLE EXPOSURE INVENTORY 7 COMPANY MP&P DIVISION Petrochemical PLANT Texas City DEPARTMENT: Methanol-Syn/GAS JU Products: 1 Methanol (ship & in-plant (95%) C.B., PP, Spfld, Eugene) 2 CO______ (all to Acetic Acid Dept.) 3 H9/CO (50/50 -* to Oxo ROH) 4 Hj______ (To Oxo ROH - HDPE) 5 6 7 8 Bnployee: 1st Shift 2nd Shift 3rd Shift 4th Shift *10 Hourly 6 Hourly 6 Hourly 6 Hourly 6 Salaried Salaried Salaried Salaried Totals Buildings Involved: 1 2 3 4 28 Hourly includes 4-5 trainees Supervisor: C. M. Hancock/ T. L. Nelson 6 Salaried LAM000785 m ap 004959 MONSANTO COMPANY INDUSTRIAL HYGIENE SURVEY MATERIALS DATA SHEET Diviaion Petrochemical Plant Texas City Department meoh - Syn/Gas Supervisor Date Building C. M. Hancock 11/76 Raw Materials Intermediates Finished Products Natural Gas Carbon Dioxide Steam Syn Gas - H2, CO, C02,CH Resid Gas - E2, co* C02 1 NiO Catalyst ZnO CuO/ZnO " (ICI 51-1) Hydrazine Sodium Nitrate Trichelok (NTA based chelator by Calgon) Chlorine Santobrite ' Hercules HF 502 Sodium Hydroxide Freon 22 Compressor Oil Methanol CO H2/CO Ho toifecfei-iAneous Materials: j^AP 004960 LAM000786 Tex# 5 Mejj-'J' o lJ_ Syn G^s Plant /fiocgs /TLow Q/ag*a^ LAM000787 X* * IX OBSE RVATICNS - Methanol The process consists of two basic sections: reformer and synthesis. In the reformer section two reactions are possible: ch4 + H20 CO + 3H2 co2 + h2 .------ ^ CO + h2o In the synthesis section these reactions occur: CO + 2H2 -------^ CH3OH C02 + H2---------CO + h2o The crude methanol therefore consists of about 20% water. Two flares consumes impure C0/H2 gas. The two major industrial hygiene concerns of the MeOH department are carbon monoxide and noise. At the time of the survey plant per sonnel did not feel they could meet the NIOSH proposed standard of 35 ppm time-weighted average over a 8 hour workday (200 ppm ceiling). Plant personnel indicated they were going to install CO monitors to sequentially sample 7-8 locations in the unit. Most CO samples recorded to date were said to have less than 100 ppm. The "Cold Box" operation requires special precautions: radio-contact between operators, hearing protection, and cryogenic insulation of process equipment. The NiO catalyst bed is replenished every 2-3 years and the ZnO catalyst is changed every 1-2 years (for sulfur removal). Another catalyst is used in the Converter Section. The catalyst is a ZnO/CuO with an all aluminum base (ICI No-51-1) There may be some dust exposure during loading and unloading of the catalyst pellets. The chelating agent used is Nitriloacetic acid (NTA) based. MAP 004962 LAM000788 --<c-t ^C0CrrH/33.--- ----af-t.)-Hoc * * ----------- !---- 11 I1, 1 e B9Q CL oifOn wsoca>1)1 2 4CLOXPtCCt 1 < It>>Ut ^< Ui uZj o< cs w i o jt K 5* > 2 toto* 00 z S \> -1 CJ\ oo**r <o oe * 4h/1 Q. 3 O z *aaH nza< H *0->) u3 ao L. a O v) CULS-i O O 3 S3 a> c O 4-> EW CmHO 4H>41 u CcOo Xa) Eh oH ea> o 0 4L->l C(1L) ao: 0oc(0 X X u y >1 i y0>> Uy0. o o oo cO *c < 4) o 4O> n* X *D u<>v (L0l N xa --TnOrrTz 0i*ldS3IC iNjMdino} 3AUD3iOBd S00LU3* A3* NOli OUN3A TVDINVH33H hx 3 ioon %* |o ft o ?? 5 X* >t- * <a z < 44 \44 4J *H C 4C 0 O CO CO H a o m-c 0 u CO K l Li <3 Z ao rO 4-> H 0) <N C1 M rH oz aLl < a _ - O 4-> IH 3 4-1 -H Uo tt) H w N U rH E O O Li rH 0 Ll 4-1 c 0o c H tfP o o rH Ll a O 44 4-i XJ -H Ll .C (0 W 0\ ffl CM Li 4J CD H +J G 10 3S U C Ll ID' H CD C rH Ll tt) -H 3 *EH *OQ A -p CO Ll >Ll CD O O rH 44 CL-H <#> E c iOn 1co0 OE aLl o Li . CD 4-1 E 'Ll Ll -H OX 44 CO tt) \ OS -1 M o s t p o t e n t i a l CO e x p o s u re S a m p le s MeOH, C o o lin g W ater Ll AC ' tat) O(D 4coELOH4i o<PcH3QmTXrXOH)) UOCUOU0 ri C0>O) CO 0H OH CQD) cr * 4WO4 *tNHj CttO) O(0 -Orl H 0 u0c0>t4-asH4; *ccoo 4J Ll -H O C CO 3 CO 0) C Ll H 0U tt) EO -Erl O 4-* CO Ll UO 44 O 4-> O 4-> 10 rl Ll <#> C CD ooa mX O Li a o N xa 0 04) CQ O *4-i iJ *H X> X rH C CO 0 >,\ UWH 4-> CO 4J H C XJ 3C CO c H 10 Ll AC 0) (DCS EH 44 404 4J tt) tr 44 tr> c O 10 -H LlrH op 0 0 O 4J O CQ O ro. H 4-> CO 10 CD rH 4-) rH -H 4-> 4-1 H CO *H 4J X CO 4H Ll CO h 44 a\ DOOH a1) Ll 0 <H pH X 44 tt) 44 C C *H *H C 44 s CO 0 C E CO H C Ll 2CO 10 O ErH tat) LAM000789 RECOMMENDATIONS It is recommended employee exposures to the following substances be determined: Carbon Monoxide Methyl Alcohol Nickel Compounds Copper/Zinc Compounds Hydrazine NTA Chlorine Sodium Hydioxide Noise MAP 004964 LAM000790 MONSANTO COMPANY INDUSTRIAL HYGIENE SURVEY POSSIBLE EXPOSURE INVENTORY COMPANY MICC DIVISION SCO/FFC PLANT Texas City DEPARTMENT Lactic Acid Products: 1 Lactic Acid - 88# USP 2 Lactic Acid - 50# Pood Grade 3 Lactic Acid - 88# Technical Grade 4 Lactic Acid - 50# Technical Grade 5 6 7 8 finployee: let Shift/vac + lday + 1 C. 0. 2 op Hourly 2nd Shift 1 2 Hourly 3rd Shift 1 2 Hourly 4th Shift 1 2 Hourly + 1 sup + 1 Fr Salaried Salaried Salaried Salaried Totals Buildings Involved: 1 2 3 4 Supervisor: 14 Hourly (non exempt) 1 Salaried (exempt foreman) Alden R. Wilson LAM000791 MAP 004965 MONSANTO COMPANY INDUSTRIAL HYGIENE SURVEY MATERIALS DATA SHEET Division MICC Plant Texas City Department Lactic Acid Supervisor Alden R. Wilson Date 11-19-75 Building ----- Raw Materials Lactonitrile Methanol Steam Condensate Anhydrous HC1 Ammonia Dow-Corning Antifoam FG-10 Sodium Hydroxide - 25# Muriatic Acid - 30# Anion Resin - Duolite A-4 Cation Resin - Duolite C-25 Activated Carbon Intermediates Methyl Lactate Ammonium Chloride Finished Products Lactic Acid 88# USP 50# Food Grade 88# Tech. Grade 50# Tech. Grade Ammonium Chlorine Miscellaneous Materials: Si02 (resin bed sand) MAP 004966 LAM000792 LAM00793 Lactic Acid OBSERVATIONS Lactic Acid is a colorless, odorless liquid used as a food acidulent, and in food emulsifiers, in pH adjustment for leather tanning and as an intermediate for making the acid's esters and salts. The process is 7 step Batch process: 1. Esterification 2. Centrifugation 3. Methanol distillation 4. Methyl Lactate distillation 5. Hydrolysis 6. Concentration 7. Resin Bed purification There is no routine vessel opening. The Resin Bed is regenerated about every 2 weeks. Resin is received via truck monthly. The area is considered a high hazard area because of the Cyanide exposure potential. Sand is present on the resin bed. MAP 004969 4* LAIVI000795 LAM000796 Lactic Acid Recommendations It is recommended that personnel exposure levels to the TolTowing chemicals be documented: - Methanol - Hydrogen chloride - Ammonia - Sodium Hydroxide - Carbon dust - Lactonitrile - Crystalline Silica o4971 LAM000797 MONSANTO COMPANY rNnur.THTAL HYOIKNK .'IIIKVKY POSSIBLE EXPOSURE INVENTORY COMPANY MICC DIVISION PLANT Texas City DEPARTMENT: Dept. 48/56 Ov~- f\ic c?''r<5:_ Products: 1 Oxo Alcohol 2 HOE (Heavy Oxo ends) 3 LEOB (Light Ends Oxo Bottoms) 4 LEOH (Light Ends OXo Heads) 5 S-711 6 S-790 7 DUP (Diundecyl Phthalate) 8 Employee: 1st Shift 2nd Shift 3rd Shift 4th Shift 10 Hourly 6 Hourly 6 Hourly 6 Hourly Totals Buildings Involved: 1 2 1= 28 Hourly Supervisor: L.J. Povse 6 Salaried -0- Salaried -0- Salaried -0- Salaried 6 Salaried MAP 004972 LAM000798 MONSANTO COMPANY INDUSTRIAL HYGIENE SURVEY MATERIALS DATA SHEET Division MICC Plant Texas City Department Oxo/Ester Supervisor l.J. Povse Date Nov. 1975 Building Raw Materials Solids Activated Carbon Bisphenol A Cobalt Catalyst Filter Aid Copper chromite catalyst* Oxalic Acid Nickel catalyst Stannous Oxalate Pumice Soda Ash Cobalt Oxide Intermediates Finished Products Liquids Aldehydes Sodium Cobalt Carbonylate Gases Cobalt Hydrocarbonyl Liquids Oxo Alcohol Plasticizers - S-711 - S-790 - DUP HOE LEOB LEOH Liquids Mixed Olefins Sulfuric Acid Phthaliac Anhydride Oxo Alcohol & Fractions Gases Carbon Monoxide Hydrogen Miscellaneous Materials: Micro Cel T-38 Now being tested for acidity control in ester unit. * Barium stabilized MAP 004973 LAM000799 0X0 PROCESS LAM000800 - - p rr. . &**} *K t. Map 004976 5o LAM000802 rv s. ESTER PROCESS - SIMPLIFIED BLOCK FLOW DIAGRAM LAM000803 f S IM P LIFIE D FLOW - ESTER PROCESS PROCESS AND FACILITIES DESCRIPTION There are four main process steps in the production of Oxo alcohol: 1. Qxo reaction 2. Catalyst recovery 3. flydrogeneration 4. Distillation 1. Oxo Reaction a. Catalyst Generation The function of this step is to replace normal cobalt losses by generating cobalt hydrocarbonyl from cobalt oxide and introducing it into the process. This allows the catalyst concentration in the olefin feed to the oxo reactors to be maintained at 0.2 wt. % cobalt. Catalyst is lost in three streams: 1) Extractor bottoms stream to the sewer, 50-100 ppm cobalt. 2) In the aldehyde stream to the hydrogenerators, 10 ppm cobalt. 3) As carryover to the residue gas header from the top of the vent on the olecat hold tank scrubber. Catalyst slurry is made by mixing cobalt oxide with heavy oxo ends to form a 10% slurry. The slurry is pumped to the catalyst generator where it is mixed with Byn gas (1.1 - 1.3 H2C0 ratio) at a temperature of 120-130C. and about 3300 pslg which converts cobalt oxide to cobalt hydrocarbonyl which is a gas. Effluent from the generator is injected into the third stage oxo reactor. Temperature'of the catalyst transfer line must be kept at 70C or above to prevent the catalyst from crystallizing. Co203 + 3H2 + 8C0--Co2(C0)g + 3^0 MAP 004979 Cobalt hydrocarbonyl is a gas at 2000 pslg and is a toxic material, b. Oxo-Reaction Carbon monoxide and hydrogen (syn gas) added to an ethylenic bond (olefin) compound in the presence of cobalt hydrocarbonyl forms the aldehyde. R-CH-Cl^ + H2 + Co HCo(CO)^ R-CH^CH^CHO The reaction takes place between 3000-3300 psig and 118-140C in oxo reactors called oxodromes. They operate on a density gradient principle similar to a thermo syphon reboiler and behave kinetically as back mixed reactors with materials entering at the bottom of one leg and disengaging at the top U bend. Heat of reaction is removed by heat exchangers in the downward leg of the oxodrome. LAM000805 PROCESS AND FACILITIES Si""PTION (cont.) Conversion Is 6'^ in the first stage by controlling temperature at ll8-125C. In the second stage conversion is increased to 90# by controlling temperature at 124-138C. In the third stage con version is increased to 97# by controlling temperature to 128-l4oC. Composition of the effluent stream from the final oxodrome is: Aldehydes Low Boilers Alcohol Formate Residue 75-81# 3-7# (paraffin and olefin) 3.5-5# 3-4# 5-12# (heavy ends and acetal) 2. Catalyst Recovery a. Decobaltatlon This step changes the catalyst to a water soluble form to allow for separation, recovery and recycle. This Is done by mixing a 2^# aqueous solution of sodium carbonate into the effluent stream from the oxodrome. The temperature is 120-130C and pressure 3100 psig. Residence time is 30 minutes. b. High/Low Pressure Separation The effluent stream is cooled to 4oC then flows to the high pressure separator where unreacted feed gas Is separated from the aldehyde and aqueous carbonylate solution. Liquid from the high pressure gas separator is let down to the low pressure separator. Gas flashes to the residue gas header and liquid flows down into the decanter where the organic (aldehyde) phase separate from the aqueous phase (carbonylate). c. Wash Column The wash column provides a means for washing the organic phase free of carbonylate. Carbonylate is reduced in the organic stream from 750 ppm to 50 ppm. 6oC condensate enters the upper part of the column while the aldehyde stream flows upwards through the column. Steam is sparged at the bottom for temperature control. MAP 004980 A LAM000806 PROCESS AND FACILITIES DESCRIPTIONS feont.) a. Cobalt Extraction The extractor regenerates the catalyst to the active form, cobalt hydrocarbonyl, from the sodium cobalt carbonylate and maintai ns a con stant concentration of 0.25# - 0.27# cobalt in olefin. Carbonylate is mixed at the top of an extractor column with 3# sulfuric acid which converts the carbonylate to cobalt hydrocarbonyl. Olefin is introduced into the bottom of the extractor column along with syn gas for mixing. Olecat, olefin and catalyst, overflows from the top of the column to the olecat feed tank. 3. Hydrogenation Hydrogenation of the aldehyde to alcohol is done in the liquid phase by passing the aldehyde over fixed bed catalysts. The aldehyde stream is filtered through a pumice filter fed to remove dissolved cobalt catalyst. Hydrogen is mixed with the aldehyde stream before the pumice filters. Primary reaction is carried out at 900-750 psig and 140-210C and the secondary reaction is carried out at 750-500 psig and l6o-210C. The primary reactors are filled with a barium-stabilized copper chromite catalyst, the secondary reactors with cobalt-on-refractory oxide. 4. Distillation Distillation removes light and heavy ends from the crude alcohol. Distillation consists of three sections, each with one distillation column. The first section column and auxiliaries removes light ends from the oxo alcohol. The second section column and auxiliaries enriches the light ends in heptanol such that it can be recycled within the process. The third section column and auxiliaries separate the heavy ends from the light ends - free alcohol. MAP 004981 LAM000807 OBSERVATIONS Oxo Operators rotate daily in the unit. Maintenance workforce usually consists of 2 each of pipefitters, machinists, and I. & E. Carbon monoxide is monitored in the work area by an "Ecolyzer" direct-reading instrument next to the synthesis gas compressors. The principal raw materials are olefin supplied by Ethyl Corp. and feed gas (H2 + CO) and hydrogen supplied from the Texas City methanol unit. The principal product from the unit is oxo-alcohol which is a mixture of CyC^C^i alcohols. It is pumped to bulk storage and then to Department 56, to tank cars (10-20K gallons), to tank trucks (6K gallons) or to ships for overseas shipment. Major by-products include: LEOB - The heavy ends of the alcohol recovery column which are DECANE with 3-10# HEPTANOL. LEOB is trucked to Chocolate Bayou and used as ethylene cracking feed. LEOH - The overhead vapors from the alcohol recovery columns which are light paraffins (mostly heptane and octane) and 1-5# heptanol. LEOH us used as ethylene cracking stock in either Texas City or Chocolate Bayou. HOE - The heavy ends of the alcohol product column which contain heavy ends and 3-7# C-j^ Alcohol. This product is sold under the name HOE. MAP 004982 LAM000808 OBSERVATICKS - S-711 There are four process steps in the production of S-711. 1. Raw material storage 2. Esterification 3. Finishing 4. Finished product storage. Phthalic anhydride (PA) and oxo-alcohol (OA) are supplied by pipeline from storage tanks. PA is charged through a weigh tank while OA is metered in to the reactor. A pre-weighted catalyst charge is manually dumpted into a charging vessel and washed into the reactor with alcohol. The reactants are agitated, heated, vacuum applied and reflux commences. The water-alcohol azeotrope is condensed and separated with the alcohol phase returning to the column as reflash and the aqueous phase passing to a storage tank. A sample is taken and titration made to determine if the reaction is complete. Oxalic acid is then added from pre weighed bags after the reactor is vented. The batch cycle is about 6 hours. The crude ester is pumped thru an interchanger for steam stripping to remove excess alcohol and Impurities, to pre cipitate remaining catalyst and to lower product acidity. The ester is fed to a rotary vacuum filter which has been precoated with filter-aid, a scraper blade continuously removes the outer layer of the cake. The finished product (after filtering) is pumped to storage tanks. The filtrate is landfilled. qq4983 LAM000809 Observations - Phthalic Anhydride Phthalic Anhydride is produced from o-xylene by vaporizing the xylene by injecting it into a hot air stream which passes thru a catalyst-filled fixed bed reactor. The resultant crude PA desublines in a condenser and any phthalic acid present is dehy drated in the treatment (predecomposer) vessels. The crude is finally purified in two distillations. Sulfur dioxide is used to activate the vanadium pentoxide catalyst. The catalyst is chargee every 6 years with about one week required for the pack ing of fresh catalyst. By-products such as maleic anhydride, benzoic acid, and phthalic acid sre flared or reconverted in the process. MAP 004984 LAM000810 o fre s h a ir system p ro v id e d . I- 1 XanId I Xt mask DUP, sam ples p e r sample schedule o xOixdo.e , soSd-a7 1a1 ,h s .S -c7o9b0 ,a llt I)IuXs tI 8 a* c o tn CO o\ J f *=! & o0 e IU o>c 3< 1U z tu < a 5s 8 in 00 o> 2O oc * o o H Q. 3 mo U. 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IP CQ 03 03 CO 0*"i . s a m p le s c h e d u DUP, s a m p le s Oxo, soda ah o x id e , S -7 H S ta n n o u s o x a la o x a l i c a c i d ,f i cl i m ic ro c e l, e s te rs as need O le fin , o le c a t c o b a lt carbony! sa m p le s tw ic e /i A ll m a te ria ls < c e p tio n b a s is D U S T R IA L H Y C IE N I WORKROOM DA None '! / p- 1 z 10 v Q, pz o OX 0 0 <r4 P3 c5 0 *5 a c OP w a p> H o o p* 0 X o o "3 TO H .-3 Eh s h. _o 1 W 0 e Ik d O ----------o--------- wg~s--------- Ox s OOP Xo x o* O P Jh 3 4143 P 0x . 03 P d 0>AP PE O OP o QP O Ox 9P Pp u in d 63 ONO O >RC PO 0) s o o E 03 O 3 dp d o 0>R. O >d in 3P P P P c <8 P o o P c d TO p P o ON p 03 P O O 03 pd cm pp xoe 3 3P O i--1 a pp 0P Od p ox p o occ EP P 0) m o Ox P 3 03 TO 0 TO 03 CU < z p pp > d C 03 cu 03 O 03 P P H OVx O 03 P TO PO P O 03 O P K Jh a 03 03 UP 03 <D 003 PP>R E d e Cup P ds d d o o aJ C -h 53 0 03 C 0 d p 0 0)00 WPP CO C CUP WPP O EH p z P^-L o 03 P r CUOx^ <^ a D -- 0 Cm 03 p J u 03\ O PPP ---------- o in 03 D P TO p P Cm 3 PP O 03 cu m o o\ XP O a '--' pp 0 Ox O PP CQ 03 CU o O O\ XP o o TO --P P 3 P Ox O 03 P CU P O TO 03 \ pp TO --' W . jCifea sq.Bq.0^ pd o 03 P cu pa pd POO) cos, ; 3 *H | ! EP C i P 03 o P Ox ( f * , P Ox O CO r [ 03 P>. ( 3 P do 0) O * + OSH : P o, < 3 PP E ( d 3 o ;. O O' O ( O 03 P J4 Eo 5 O Ox P TO l2EV.9dSOx 0u - P0 ^ 03 Ox -P Ox 03 _ x t-a CC 03 C 0 0P " PP TO CU P 03 TO a .>o to TO TO c E Pr+0*2 *2 9* ^ ^ 5s o W0 0TO XO ^O o p 0P O Ox mp P p TO 03 0) \ P CUP TO O ^ w P d Ox 0P Z -j= . P TO Ox 03\ P CUP 0 O^" w LAM000812 Cm H <h n. < aes ___la. 0) a. c o --r H KA c*~ cv o\ I--I > .> OJ T& 9 CO Q Ul > tc S *" 01 o pH n so>: oe *' 3 CO O t 09 oW !* 5^ 55 e c O *3 jet (oi $ rH o CO as K 09 Eh Zi* .iZ i vt k. O O T9 * CC C ft) <3 r? o S o- 22 IT (0 N (0 ____S. ----------crow-r~" TOT9 M0: VHI9S3M i N3 Mrf 1003 3AU33X0MM S00Hi3W n* M0I1TI1N3A lVSIMVHOSOf mkj noon io *o 2: av <o ae z < e o Or O < Z I O co Sh pH ft 43 +3 pCH 0C9 CH ea co a e r0H$ p3H 4 p*4H 09 O09* 4O-h +3 CO T9 aeS a5 t09< m X) pH CO cj r<H O09 fUt) U o 4-i 43 pH 43 c C 43 0) 09 e Sa 4o4 a.*p( pH 3\R. 3 txo c o) t- 0) CO CO ft) . >2 pH 43 T9 03 CH 09 dS pi 09 x: 09 as -H O U E 4h CO pH co Co pH 43 ft 0) ft) X w oc TOft.TJ C IT>H aJ CVJ ft) pH O 4-1 XO CD c C pH M O O pH 43 43 C c o d*4S 0f9t pH 0) CD co ft pH > O 0e) Sh U pH 09 09 43 f3t 4C3O 4h WOO T O r o*p~s 09 g CVJ o co pH CD aS > C o pH 43 ft 09 V X ft) C o 43 J* 4-1 0) a! 43 09 4 CO E C9 0) pH \43 4-i O T9 O X 4-. pH O O 09 C pH O C'CR'h. pH pH O co me pH C0 pH >C >4 O CD 43 09 CO 43 C ft U pH ft) 3 09 C ft CO ft 3 CO aco) c pH - 4h 6 Ich> OHc) m>R o 00 o O pH ? CO 43 *3 Si pH C pH a> a ft) 4-h ft 3 ft4-i aS CO o ft ft) \ 09 ft) E pH *h E O p<H JC +3 pH 43 OU co aS & .c o pH 43 ft a) C9 X 0) c o 09 C > pH ft) O C9 43 pH as e 4h t) 4-1 4h ft O O e ft) o o E 2~ 09 43 pH pH >4-1 O e O Sh 09 43 ft>R C 3 IA O CO ON C9 I a) 5-, O C 0$ pH aS O'--' En-p aS 43 co 09 ^ *h aS C9 T9 ft)---CO O CO >3 pH cJ t TJ 94 v_- 0) ft 3 CO LAM000813 RECOMMENDATIONS - Dept. 49/56 It is recommended employee exposure and environmental leveTs be determined to the following compounds: Crystalline Silica Amorphous Silica Cobalt compounds Copper compounds Oxalic Acid Nickel compounds Stannous Oxalate Sulfuric Acid Phthalic Anhydride Carbon Monoxide NlAP 004988 LAM000814 MONSANTO COMPANY r >) r POSSIHLIi EXPOSURE INVENTORY COMPANY MPPC DIVISION PLANT Texas City DEPARTMENT: Ethylene Products: 1 Ethylene (99-8#, 98.0 high rates) 2 Propylene (92#-C3H6, 7*-C3Hg, l Allene, 1% Methyl Acetylene) 3 Ethane 4 Offgas (67#-methane, 30#-H2, 1% Ethylene, 2#-C02) 5 Acetylene 6 Ch+ Oils 7 8 Employee 1st Shift 2nd Shift 3rd Shift 4th Shift Vacation Totals Buildings Involved 6 Hourly 6 Hourly 8 Hourly 6 Hourly 1 Hourly 2 5 Hourly Non-exempt 3 Salaried 0 Salaried 0 Salaried 0 Salaried 3 Salaried Exempt 1 2 Supervisor: D. D. Kos MAP 004989 LAM000815 MONSANTO COMPANY INDUSTRIAL HYGIENE SURVEY MATERIALS DATA SHEET Division MPPC Plant Texas City Department Ethylene Supervisor d. D. Kos Date Nov. i4, 1975 Building Raw Materials Snifo Condensate (Gas Oil) Intermediates Ethane LEOH (hexene, octane) * (Light ends overhead) Caustic (50#) **' r DMP (Dimethyl formamide Sodium Nitrite Ethylene Propylene Steam Finished Products Ethane-recycle, crack Ethylene-Dept. 13 Propylene - C. B. Offgas (CH^, Hg)-fuel Acetylene (HOPE, flar C4 + Oils (C.B. Quencl Col) MAP 004990 LAM000816 TEXAS CITY ETMVUCXIE fL A N T P LO W D IA G R A M Observations - Ethylene The ethylene unit uses Kellogg type furnaces. Special No. 1 fuel oil (SNIPO) is the primary raw material. There is a typical "sour gas" odor throughout much of the department. Operating personnel rarely spend over 2-3 hours out in the production unit as most of the shift time is spent in the control room. Process waste andQcondensates drain to a central condensate pit which is about 50 C and open to the atmosphere. Caustic pellets are added in a room adjacent to the Gravitometer shed. There are several high noise areas designated in the process area; most noticeable areas include the SNIFO preheater (1 hour/shift) and the cooling tower compressors (2 hrs./shift). The compressor area has 3 crack gas compressors and 6 refrigera tion compressors. The noise level appears quite high and of pre dominantly low frequency noise. Sampling is conducted at the caustic scrubber. Dimethyl formamide (DMF) is pumped from drums into the process. The odor of DMF was very pronounced on the windward side of the 10K2 water scrubber. The water scrubber removes the DMF from the process stream. Operat ing personnel indicate the amine odor is common in this area. Maintenance personnel normally assigned to Dept. 10 include one maintenance foreman, two pipefitters, two machinists, two boiler makers, two insulators and 1-2 I. & E. technicians. MAP 004992 LAM000818 MAP 004993 r.x C hief O perator |D lre ct8 a c tiv ity o f A ll m a te ria ls produced other operators. In J charge o f u n it o p e ra tlp n . | Recommendations - Ethylene It is recommended That area and personnel monitoring be conducted to deter mine the potential for dimethyl formamide exposure. That applicable recommendations contained in the NIOSH recommended sodium hydroxide standard be instituted. That workplace exposures be characterized, especially at condensate sumps. That noise dosimeters be utilized to determine the extent of noise exposure. MAP 004994 l/M\A000820 MONSANTO COMPANY INDUSTRLAL HYGIENE SURVEY POSSIBLE EXPOSURE INVENTORY - V'.rry.:-;^ |. ------ -- COMPANY MPPC DIVISION Polymers PLANT Texas City DEPARTMENT: PoJlyethy__le__n_e____P__o_lymerization (35P) Products: 1 Pnlypt-hylsnp Powder (blow molding) 2 Polyethylene Powder (injection molding). 3 4 Ammonia trans shipping 5 6 7 8 anployee: 1stShift 2 vac. 2 day 4 Hourly 2nd Shift 4 Hourly 3rd Shift 4 Hourly 4th Shift 4 Hourly Totals Buildings Involved: 1 I= 16 Hourly M^00499s Supervisor: R. W. Ceyanes 3 Salaried 0 Salaried 0 Salaried Salaried 3 Salaried LAM000821 MONSANTO COMPANY INDUSTRIAL HYGIENE SURVEY MATERIALS DATA SHEET Division MPPC Supervisor R. w. Ceyanes Plant Texas city Date Nov. 18, 1975 Department Polyethylene polymer izatiorP*1^^0^ Raw Materials Intermediates Hexane Methanol Catalyst Complex Ethylene HCL Titanium tetrachloride* di-Isobutanol Aluminum hydric e Acetylene Hydrogen Butene Isobutanol 20% Caustic Lime Steam Condensate Ammonia Finished Products Polyethylene Calcium Chloride Ammonia (pumping statio: Catalyst Mlbfcfelj.aneouB Materials: MAP 004996 LAM000822 Lxn.s 3 Section 9.2 pr c*C/ /r /Z^Tn. S ~ *>Tf94f*./*{* (? - cb Vppff- Tn Kf P$ M/\P 004997 LAW1000823 eHt x * .. i* *<f ' 1 ^WVW^V r^v Hex* jjr Section 14.11 Oept 35 P r# st --- 1 - * gm n W' AnA| Mturnt _!1 V^X *r^ #jO -<T) K m*: L /x> n% aN ** 11 i.l *i__s1 i, T i~ %? *; , i. r* -- ^5 *\ V* - MHi * tyf' ffl fl*A<--' i LAM000824 Jfcwir- *!.-MAP 004998 LAM000825 RECOMMENDATIONS - Polyethylene Polymerization It is recommended personnel exposure to the following substances be determined: Hexane Methanol Sodium Hydroxide Isobutanol Calcium oxide Ammonia Hydrogen chloride Nitf 00500 LAM000826 MONSANTO COMPANY INDI/.`'TNT AI. lfYCIKNK .'SURVEY POSSIBLE EXPOSURE INVENTORY COMPANY MPPC . DIVISION Polymers PLANT Texas City DEPARTMENT: HDPE Products: 1 H.D. Polyethylene Blow Molding 2 H.D. Polyethylene Inject. Molding 3 4 Note: H.D. = High Density 5 6 7 6 Employee: 1st Shift 2nd Shift 3rd Shift 4th Shift 8 Hourly 7 Hourly 7 Hourly 7 Hourly 4 Salaried 0 Salaried 0 Salaried 0 Salaried Totals Buildings Involved: 1 22L 2 85 Control Room l Penthouse -LagiSLPVtt Supervisor; 29 Hourly 4 Salaried MAP 005001 G-.W. Hanks LAM000827 MONSANTO COMPANY INDUSTRIAL HYGIENE SURVEY MATERIALS DATA SHEET Division Plant Texas City Department H.D. Polyethylene Supervisor G.W. Hanks Date Nov. '75 Building 35 Raw Materials Air 75 lb. steam 600 lb. steam Nitrogen Calcium Hydroxide, Lime Armostat 310 Carbowax Glycerol Monosterate Ional Chromate (water treatment) Methanol Hexane Ethylene Dilauryl thiodi propionate (DLTDP) Ziegler catalyst (tiCl^ w/dialkyl aluminum) Diisobutyl Aluminum hydride (Dialkyl aluminum) Intermediates Finished products Blow Molding Powder Blow Molding Pellets Injection Molding Powder Injection Molding Pel (High Density Poly ethylene) wiBceixaneous Materials: .1. Ziegler catalyst residues in powder - 2 Special additives as required anti-oxidants cu inhibitor per customer Irgonox 1010 005002 LAM000828 HxGrt Poi'-iCTn^LfcvAT J~Tc>c. Tyr^s C--' - KjoJ*, ____________ _ "TV r- C<^ O~ i_i "Cic Rp' fo:; Z 5(^0" L*~ 0 C(S.T( -St v.fs SA ` [ + ^Nj \ "V'W. Low) .t '. Cov'T\`\rw,'?v; So-^o HoT h,Ort ^C^T-, i -giuRfty Oi<;tsTHa c**. .m wrKi-^ CPT, ^tcootrt' Coao*'^`V<KT^_ M*Ns>e" * I>s, ^rotoufT ro Lcrv Tkk*s l--------------- Z*% &*r' *2 O7o fLOCV(C'--^ 3o*7o K- sfpp*.. p- r><* ? 5003 LAM000829 OBSERVATIONS - HDPE The most obvious health hazard potentials are noise, dust and Hexane exposure. Noise dosimetry has been obtained by John Fox (This writer has not seen the data). Noise levels are in the mid-90 dB(A) range. The particle size distribution of the HDPE dust was reported as follows: micrometer ----- 58--------- 75 62 8 under 44 % weight : 12.5 27 18 14 11 17.5 loo.o The housekeeping was not good even though the area was washed down daily. Calcium hydroxide is added from 50 pound bags. Operators wear respirators for this operation. MAP 005004 LAM000830 INDUSTRIAL HYGIENE SURVEY WORKROOM DATA LAM000831 (o0 spao>: *0)' 3u au 3 n oW ua-si oo 0) o P3 S3 a c OP SIt/i INDUSTRIAL HYGIENE SURVEY WORKROOM DATA Cm *-- n n < tEo t.Q- &1 Cm! C o C\J *s CM aa S> a> a T) *> cc <C pV v> O a rr ig N03 ___.. its oDr TX1O0]'Si IJiMOiwwidsa* iau iNjntf mo3 ov-j- S00M13H | A3* { HOUOI1N3A1 $u 1Y3IHVH03>iC Hxa iydoi c Ito & 1K *u*i Ofat U a< o<z Sh P < k CO p 4) P iH 4) a Sh 4) H >> p PO co rK0t) E-i > i i -O t.. : 9 Ua O O c o IL o < 7. oz ra43. UV o p0) bDP CP P (0 hWo> CU rt *3 Xi a rct w pc aa> rot oa Sh p PO<H 3P P Xo v rt x: Sh 4>\ art Oa'c--m rH p < 4) .E p a o 4> O c in p p 3 *3 V O Or! > E Sh cq 0) P P po P tc>oj oo O3 3 <Srl CD Vrt E ebQ co c co rt 0)0) p E C P bO E rSht Art jao Pc 4> O Sh P o, rt o> rt o a& vr sh > O rt P rt T3 X Sh in 4) Qa) cnC?I o rt >> E a. 4Sah) *ao> pw >P P3 Sh O 3 4) xO: E p 4) P CO P Po P> ao 4) P Sh p-tft. POO O rt CM C'-- rt >3 E rt 4) *3 Sh\ aOC--M pp C 4> rl C pc C ` rt E C O H _ CD rt 4)00 Sh S Soh ini 4a) cm a -- LAM000832 RECOMMENDATIONS - KDPE It is recommended exposure levels to the following compounds loe' cTetermined: Calcium Hydroxide Methanol Ethylene Hexane Polyethylene Glycol Dust Noise (Carhowax) It ijs recommended a more environmentally acceptable substitute Tor water treatment chromates be utilized. 005007 LAM000833 MONSANTO COMPANY TNPlir.TUTAI, 1IYGIKNK SURVEY POSSIBLE EXPOSURE INVENTORY COMPANY MICC DIVISION Plasticizer PLANT Texas City DEPARTMENT: Phthalic Anhydride Products: 1 Phthalic Anhydride 2 3 4 5 6 _____ 7 8 Employee: 1st Shift 5 Hourly 2nd Shift 4 Hourly 3rd Shift 4 Hourly 4th Shift 4 Hourly Swing Operator 1 i?xTry opera lot Totals (vat. "relief hourly . 19 Buildings Involved: 1 Dent. 2 2~ MAP 005008 Supervisor: T. S. Hellen 4 Salaried Salaried Salaried Salaried 4 Salaried LAIV/000834 MONSANTO COMPANY INDUSTRIAL HYGIENE SURVEY MATERIALS DATA SHEET Division MICC-Plasticizer Plant Texas City Department 53 Supervisor T. S. Hallen Date Nov. 17, 1975 Building - Raw Materials Intermediates Finished Products .1. Air 2 O-xylene (barge) 1. Crude Phthalic Anhy 1. Phthalic Anhydride dride 98% (99-5%+) 3. SO2 (Tank Truck-Liq.) 4. Vanadium Pentoxide # Benzoic acid Maleic Anhydride * (Cat.) Phthalic acid 6 - Toluic Acid o - Toluic Aldehyde 5. Sodium Sulfide (BFW) 6. Hydrazine (BFW) Phthalide 7. Sodium Hydroxide (BFW' 8. Sulfuric Acid (BFW) Mlfedfei-ianeous Materials'! Mot ;C-Fuj- "'So MAP 005009 LAM000835 S' < ,o o--o \/ O MAP 005010 LAM000836 > r_ (> e i*i J 3 J. * * i'll lo r j- 2 U' gi ^it-. Ji 8 ? i: 55 on** O tI u n1 o*1 !; on CD i`( ft * ]]1 ('E i5 fi 1 LAM000837 LAM000838 Recommendations - Phthalic Anhyd'-irie It is recommended employee exposure to the following substances be determined: o-xylene sulfur dioxide vanadium pentoxide (dust and fumes) phthalic anhydride maleic anhydride hydrazine sodium hydroxide sulfuric acid heat MAP 005013 LAM000839 MONSANTO COMPANY INDUSTRIAL HYGIENE SURVEY POSSIBLE EXPOSURE INVENTORY COMPANY MICC DIVISION Rubber Chem. & Food Products PLANT Texas City DEPARTMENT: HCN (19) TBA (25) , LN (27) Products: 1 Hydrogen Cyanide (99%+) 2 t-Butvlamine (97%+; 99%+) 2 Lactonitrile (85%+) 4 5 6 7 8 Qnployee: 1st Shift 2nd Shift 3rd Shift 4ttr-Shift- 7 Hourly 6 Hourly 6 Hourly Honfly- Totals Buildings Involved: 1 2 3 4 Supervisor: R. T. Hanunann 19 Hourly + 3 Trainees) WAP 0050W 5 Salaried 0 Salaried 0 Salaried Salaried* 5 Salaried LAM000840 Division Plant Department KCN-ANTO COMPANY INDUSTRIAL HYGIENE SURVEY MATERIALS DATA SHEET Supervisor Date Building Raw Materials 3CN Air Methane Ammonia Pt-Rh Catalyst h2so4 Water Monoammoni\un Phosphate Intermediates Finished Products Hydrogen Cyanide (.99%) TBA Hydrogen Cyanide Isobutylene Water Sulfuric Acid Sodium Hydroxide Steam LN Hydrogen Cyanide Acetaldehyde Sodium Hydroxide Phosphoric Acid Water t-Butyl Formamide Sulfat< ! t-Butyl Amine (>97%) Sodium Sulfate Sodium Formate Water t-Butyl Alcohol (>99%) (To Nitro for Santocure NS) Formic Acid Polyisobutylene (To C-G) Lactonitrile (>85%) (To LA) MAP 005015 LAM000841 DEPT. 19 * HCN BRIEF PROCESS DESCRIPTION At Texas City, HCN is produced continuously using the Andrussow process (DuPont) in a plant made up of three parallel catalytic reactors, an ammonia recovery system, and an HCN fraction system. For the past 5 years, HCN demand has averaged from 10-20*70 of capacity. As a result, the unit runs on one reactor for approximately 10 to 15 days/month, building HCN inventory, then is down the remainder of the month. Although this mode of operation does not change the basic process, it has created many special problems. The HCN reactor is fed a carefully ratioed mixture of air, natural gas, and ammonia vapor. Each gas must be temperature and pressure controlled for accurate meterings and be totally clean and dry to prevent damage to the catalyst (a thin platinum gauze). The feeds react while passing through the gauze forming a mixture of HCN vapor, unreacted NH3, residual N2, and combustion products. Oxidation supplies the heat necessary to convert NK3 and CH* to HCN and heats the gauze up to 1100 to 1200 deg. C. The hot gas is cooled in a waste heat boiler, generating 150 psig steam, and then a CTW exchanger. The cooled gase6 flow to the ammonia recovery system. The gas is scrubbed to remove unreacted ammonia. The absorbent (ammonium phosphate) is steam stripped to free the ammonia and regenerate the absorbent. The overhead fron the ammonia stripper (NH3 and HzO) is then fractionated to produce NH3 vapor for recycle to the HCN reactor and the column bottoms are pumped to chlorinat The gases leaving the ammonia absorber still containing traces of NH3, and the HCN product are scrubbed first with dilute 6ulfuric acid to destroy any re maining NH3 and then with chilled water to absorb the HCN. Gases from the HCN absorber go to Power 2 and are burned a6 a low Btu value fuel. The chilled water containing the HCN product is steam stripped, then fractionated and the HCN is pumped to storage. Water from the stripper bottoms is cooled by a process cooling tower, then chilled and returned to the absorber. Excess water is pumped to chlorination. MAP 005016 LAM000842 I i QO**7 LAM000843 /IfV P oseA / CyAa 'dci A aiJ o fa c tu # 4/ i 6+ \5 M !$ v> 't Ft; i *?> >* > Sj *V I I \ 5 LAW1000844 DEPT. 25 - TBA Brief Process Description Tertiary-butylamine (TBA) 16 produced in three process steps. The first two stepB, reaction and hydrolysis, occur in two parallel trains of automatically sequenced batch equipment. The third step, purification, iB continuous. The unit will produce in excess of 18M lbs/year, at over 84% yield, operating at a 90% OST. The reaction step produces TBFA by reacting IBY, HCN, HZS04 and water under temperature control. The HCN and IBY are measured by weight, premixed and fed as a liquid into the glass lined reactor, precharged with aqueous sulfuric acid. The feed rate is adjusted so that the external cooler can hold the reactor temperature at 75 throughout the IBY-HCN charge. In the hydrolysis step, the resulting tertiary- butyl formamide sulfate intermediate, by products and unreacted raw materials are transferred to a hydrolyzer precharged with H20 and caustic. The NaOH neutralizes the TBFA sulfate to TBFA, neutralizes unreacted H2SO4, and hydrolyzes TBFA forming TBA and sodium formate. The hydrolyzer is agitated to provide good mixing. The TBA is steam stripped from the hydro lysis mass to yield a crude TBA-water mixture. The hydrolyzer bottoms, containing HCN and various sodium salts is pumped to waste treatment. In the purification step, the crude TBA is continuously fractionated to produce specification grade TBA. \ MAP 005019 LAM000845 4 * <0I\ kC45 <0 \J Q 0 <o S ^N I <M + SJ n u > I Sj 1 Vv*,j A 'T' to f PII > ~z Sj Vj 0 1 ? o 5 `O Vu ! & i <3 I <3 1 _ rsj II > Sj 43 $ >~ ^y ca K 5j Q Sj I s<Sf >o N| K C9_:i $ 3 -j I s o ** 3 ** ~? s3 >v \U ^V 5e MAP 005021 Uu.j 0 i k I uAM000847 DEPT. 27 - LN Brief Process Description The lactonitrile (LN) plant has a demonstrated capacity of 18M lbs/year. Demand is captive to Lactic Acid. LN is produced from hydrogen cyanide (HCN) and acetaldehyde (AcH) in a single step continuous, pH controlled, externally cooled reactor. The reaction is exothermic and pH dependent. The overall reaction is: O OH II HCN + CH3 - C - H --^ CH3 - C - C = N I H In practice all reactor feeds are continuously introduced into a circulating mass of 85 to 90% LN (water is used alone for startup). AcH and HCN are fed at a one to one mole ratio, sufficient water is fed to diiute the product LN to ~ 88%. caustic is fed under pH control to maintain a 5.2 pH. The mass circulates from the reactor through the external cooler which removes sufficient heat to hold the reactor at 48 deg. C. The LN product is continuously drawn off by level control, stabilized with phosphoric acid, cooled, and sent to product storage via two rundown tanks. Standard process yields are over 95% of theory. No significant side products are formed. MAP 005022 LAM000848 LAM000849 L iq u id PfJASE CxdTHC^M/C 'VeACTlO*/ UVfjf>\ LAM000850 OBSERVATIONS HCN, TBA, LN The three departments operate in one general area. The area is considered a high hazard area. There are alarms at the safety showers. A "buddy" system is utilized for sampling. The cyanide is refrigerated so its vapor pressure is low. Sulfuric acid is received from tank cars while caustic is shipped in barges. TBA wastes go to Department 24 (waste treatment). HCN is sampled about twice daily into jugs from open taps. Gloves and goggles are required throughout the units. Ammonia is pumped via Durco type pumps. i MAP 005025 LAM000851 LAM000852 LAM000853 RECOMMENDATIONS - HCN, TBA, LN It is recommended environmental levels and personnel exposure to the following substances be determined: Ammonia Sulfuric Acid Platinum Rhodium Hydrogen Cyanide Sodium Hydroxide Acetaladehyde Phosphoric Acid MAP 005Q28 LAM000854 APPENDIX' A SUBSTANCES WITH ASSI GNED EXPOSURE STANDARDS SUBSTANCE Carbon dioxide Nickel Zinc oxide Hydrazine - skin NTA Chlorine Sodium hydroxide Methyl alcohol Carbon monoxide Methane Ammonia Platinum Rhodium ppm 5000 - 1 1 - 200 50 50 - Sulfuric acid - Hydrogen cyanide - skin 10 Acetaldehyde 200 Phosphoric acid - t-Butyl Alcohol Formic acid 100 c; Butylamine - skin. 5 Hexane 500 Ethylene CSIIA Mg/M3 OTHER ppm Mg/M3 9000 1 5 1.3 0.1 0.1 (D> 1 3 2 2(c)(b) 260 55 35 - simple asphyxiant 35 5o<Hp> 0.002 (salts) 0.1 dusts,fumes 0.001 salts 1 11 360 MAP 005029 1 300 P 15<C) 1800 5 100 i5(b) 360^ simple asphyxiants(B) LAM000855 SUBSTANCE OTHER Acetylene Hydrogen Isobutyl alcohol Calcium oxide Hydrogen chloride Xylene (skin) ppm 100 5 100 Mg/M3 ppmMg/M-' simple asphyxiants( 3oo '5 7 (C) simple asphyxiants() ,(D) 50 150 ,(E) 435 Sulfur dioxide Vanadium pentoxide dust fume Phthalic anhydride 5 2 13 0.5(C) 0.l(C) 12 0. 5 0.65 (c) 6<d) Maleic anhydride 0.25 1 Dimethyl formamide(skin) 10 30 Inert dust - total respirable Iodine 0.1 15 5 10 Methyl Iodide (skin) 5 28 Acetic acid Asbestos 10 25 2 fibers/cc (longer than 5 um)fe) Silica see 1975 TLV book NOTES - All values are 8-hour time weighted average (TWA) unless indicated with a (C). Footnote Designation A) - EMEH guideline B) - 1975 TLV I D) - 1975 TLV Ej - 1976 TLV Notice of Intended Change F) - NIOSH Recommended Standard MAP 005030 G) - Effective 7/1/76 LAM000856 ArPENDIX B General Observations - ?e:-:as City The plant is located within the city limits of Texas City, Texas bounded on the east by Galveston Bay, extensive industrial development on the south and west, and residential areas of Texas City to the north. The terrain is flat and subject to flooding during intense Gulf Coast rainstorms and hurricanes. The plant has been a manufacturing site since World War I, when a sugar refinery was built. The area is the location of a large refinery and petrochemical complex at the mouth of Galveston Bay. At the time of the survey (Nov., 1975), there were 1571 employees, 465 exempt, 199 non-exempt and 907 wage-roll. Distribution Department Distribution Department employees load and unload all major raw materials and products at about 18 different locations from barges cars, and trucks. There are 42 wage-roll pumper-gagers, 5 foremen, 1 clerk and 1 supervisor. Each shift (12/shift) has a chief operator. The chief assigns personnel who rotate job-toJob. There may be 4-5 months between job rotation. The pipefitte probably have the most potential chemical exposure during connect/ disconnect operations at barges, cars, and trucks. Respirators are not presently required in any area. Some compounds are sampled by dip cups. Operators also gage and take temperatures. See the attached sheet for materials generally found in the Distribution Department. Map0503i LAM000857 Distribution I--partment SAMPLES Condensate Snlfo Tech Grade 50# Lactic Acid Food Grade 50# Lactic Acid Tech. Grade 88# Lactic Acid U.S.P. Grade Lactic Acid Phthalic Anhydride Spec. #1 CyCg Alcohol Oxo Alcohol T13-2 LEOB 48D502 BTMS. LEOB 48D501 OH LEOB 48D502 OH HOE 48 HOE C]_i Alcohol Tertiary Butylamine 25D1 Prod. Diundecyl Phthalate DUP Dioctyl Phthalate Santicizer 711 Santicizer 790 Acetic Acid Acrylonitrile Caustic Soda Ethylchloride Ethylbenzene Isobutylene Methanol Styrene Sulfuric Acid Petroleum Naphtha (Toluene) Vinyl Acetate (Lactonitrile) Aluminum Chloride Flux Oil Propylene Styrene Tar HCN Acetaldehyde Benzene Acetone ACY Butaneol Hexane Naphthalene Phenol Muriatic (HC1) acid Olefins (mixed) 0-xylene Aluminum granules Polyethylene pellets MAP 005032 LAM000858