Document dQE2B3ZmO3ndwnOLVoR23mkG9

(conoco) Interoffice Communication To J. A. DeBernardi, VCM Plant, Lake Charles */ / From G. J. Husen, Chemicals Research, Ponca City Data May 5, 1977 sublet "Summary of Chemical Research Division Service Work for the Lake Charles VCM Plant," M. A. Newman The attached report summarizes Chemical Research Division VCM Plant related research since 1970. Over one hundred seventy (170) reports and many other communications are summarized. This report should be helpful for acquainting new personnel with prior work. The reports and letters are available in Engineering Research Section files or the R&D Library. Please contact us if we can assist in obtaining any additional infor mation. Research Group Supervisor Engineering Research Section lag/jw CC + Enc FK:WRS:DVP:WRBe:OCK:AJLu:RCL:MAN CMS:ROC:DHS:GOF:RELe:RWM:RDG WBC:BDR:GF: OF .'Library CUH 00000052 Technical Service Report No. TSR - CEN - 77 - 1 To: J. A. DeBernardi Title: Summary of Chemicals Research Divisions Service Work for the Lake Charles1 VCM Plant Date: Objective: " April 15, 1977 To present a summary of all the work Chemicals Research has done for the Lake Charlesh VCM plant from 1970 through February, 1977. Introduction This report was compiled in order to organize the variety of work Chemicals Research and Development has done for the VCM plant since 1970, The major topics are arranged as follows: ,, 1. General 2. EDC 3. EDC Cracking 4.. EDC Purification 5. Environment Aspects 6. HC1 Purification 7. Oxychlorination 8. New Technology 9. VCM 10. VCM Incinerator 11. VCM Plant Liquid By-products 12. VCM Purification 1 3 4 5 7 10 12 17 19 20 21 23 The general category includes such things as meetings where a wide variety of topics were covered, and subjects that were not easily categorized. The types of communications included are: Interoffice Conwunications, Plant Progress Reports, Information Searches, Research Reports and VCM-related literature articles. None of R & D's Monthly Progress Reports are included in this summary, but they are available for further information. Most of the reports and communications are available in the Engineering Re search Section files; however, reports not in the file are designated through out the report as IN LIBRARY. OOOOOB-5J 23 CUH J. A. DeBernardi Page 2 April 15, 1977 Also available from R & D is the report from the Stauffer Symposium held in 1976. The plant should have the notes from the first (1971) and second (1973) Stauffer Symposiums. ri. n. Assistnat Research Chemical Engineer Engineering Research Section lag/ck Enc CDH 000008524 VCM SERVICE WORK SUMMARY 1970 - FEBRUARY, 1977 GENERAL TOPICS STAUFFER VCM SYMPOSIUM; 839-0, 1971 This is a confidential report of the discussion of companies attending the Stauffer Symposium. PROJECT REVIEW--VCM RELATED TOPICS, DECEMBER 8; 1971, 839-0, 1971 Subjects discussed were 1) plant studies on caustic washing of EDC to remove methyl chloride precursors, 2) laboratory investigation on the effect of conversion level and EDC contaminants on by-product formation in pyrolysis of EDC, 3) water washing of acid treated VCM, 4) reduction in tar production by separate chlorination of the EDC recycle from the VCM tower, and 5) the Stauffer experimental oxychlorination catalyst. CONOCO VCM PRODUCT QUALITY MEETING, LAKE CHARLES, LOUISIANA; 839-0, 1971 Subjects discussed were 1) analytical methods for VCM, 2) the butadiene impurity problem, 3) light ends column plugging, 4) reactor modeling studies, 5) catalyst improvement, 6) diluent, 7) effluent treatment, and 8) process changes. PROJECTS REVIEW MEETING, LAKE CHARLES VCM PLANT; 839-0, 1972 Projects discussed were 1) the EDC cracking studies, 2) butadiene re moval from VCM, and 3) removal of copper from hydroblast water via cen trifugation. REVIEW OF VCM PLANT OPERATING AND QUALITY PROBLEMS, APRIL 7, 1972; 839-0 1972_________________ ___ Subjects discussed were 1) reduction of butadiene concentration in prod uct VCM, 2) methyl chloride in the product VCM, 3) oxygenates in EDC tars, and 4) laboratory studies of EDC cracking. WATER DISPLACEMENT OF VCM VAPOR AT ATMOSPHERIC PRESSURE-TEST OF WATER SAMPLING PROCEDURE; 839-0, 1975 Tests were conducted at PVC pilot plant on displacement of VCM vapor with heated water. Based on these tests, it did not appear that this method would be generally applicable for all vessels in VCM service. DISTRIBUTION OF VCM PLANT CAUSTIC USAGE; 839-0. August-December, 1976 CWH 000008 ACTION STEPS FROM JOINT MEETING OF VCM PLANT, CRD, PED, AND PRODUCT MANAGEMENT--VCM PLANT, SEPTEMBER 29, 1976; 839-0, Auqu$t-Decent>er, 1976 Too numerous to list here. ACTION STEPS FROM JOINT MEETING OF VCM PLANT, CRD, AND PED--FEBRUARY 1, 1977; 839-0, 1977_______________________ Too numerous to list here. VALUE OF PLANT L0SSES--1970; 839-0, 1970 NOTES ON MEETING WITH DON BUTTER AND OTHERS; 839-0, 1970 Many research projects were discussed. REACTIONS OF CHLORINE AND ETHYLENE Information Search 70-47. IN CONOCO LIBRARY - 2- CWH 000008527 REACTIONS OF 1,2-DICHlOR.OETHANE; 839-0, 1971 An information search. EDC DRYING; 839-0, 1968 Methods of drying EDC. -3- CWH 000008528 EDC CRACKING PRELIMINARY DATA ON LABORATORY CRACKING EXPERIMENTS; 839-0, 1971 The report lists conclusions and data leading to those conclusions. The conclusions are: 1. Impurities in EDC contribute to methyl chloride formation and cracking inhibition. 2. EDC cracking rate increases dramatically by increased surface/vol ume ratio in reactor. 3. A number of low-level by-products are formed in cracking reaction which generally inhibit the reaction. A STUDY OF THE FORMATION OF BY-PRODUCTS DURING THE PYROLYSIS OF EDC-A RESEARCH PROPOSAL; 839-0, 1971 PYROLYSIS OF 1,2-DICHLQRQETHANE; 839-0, 1972 As conversion increased, it appears that by-product formation increases. A study of YCM and impurity production as a function of residence time was reconmended. EXPERIMENTAL STUDIES OF EDC PYROLYSIS; 839-0-1-72; Research Report Experiments on pyrolysis of 1,2-dichloroethane to vinyl chloride are re ported. The object of this work was to ascertain the side reactions which lead to the formation of by-products, particularly methyl chloride and butadiene. The level of all by-products formed, relative to vinyl chloride formed, increased exponentially with increases in 1,2-dichloroethane conversion level. Formation of methyl chloride is enhanced when 2-chloroethanol is present in the feed but does not go to zero when the 2-chloroethanol is removed. Formation of butadiene is enchanced when ethyl chloride is present in the feed. The effect of a number of pos sible contaminants on both by-product formation and 1,2-dichloroethane conversion level was examined. Increasing the surface area in the reac tor was found to increase the pyrolysis rate and decrease by-product formation. IN CONOCO LIBRARY. - 4- CUH 0000085 EDC PURIFICATION ADDITION OF PHOSPHITE OR PHOSPHORATE ESTERS TO EDC DISTILLATION COLUMN; 839-0, 1971 A copy of a patent was enclosed as a possible means of solving an EDC column reboiler fouling problem. PLUGGING OF THE LIGHT ENDS COLUMN AT THE VCM PLANT; 839-0, 1972 There were two opinions on why the column was plugging: 1) arrmonia working itself down the column causing a solids buildup and 2) an emul sion containing polymeric material upstream plugging the holes. PURIFICATION OF 1,2-DICHL0R0ETHANE; 839-0, 1972 Amine treating might be a probable method for abbreviated EDC purifica tion. PROGRESS REPORT, NOVEMBER, 1971; 839-0. 1971 Work was continued on caustic treatment of EDC for removal of methyl chloride precursors and the VCM cloud problem. PROGRESS REPORT; 839-0, 1971 Analysis of Competitor's EDC--Samples of EDC producers were compared with Conoco's furnace feed and sales grade EDC. PROGRESS REPORT, DECEMBER, 1971; 839-0, 1972 1. Methyl Chloride Problem Caustic strength in caustic wash vessel T-102 would have to be kept high for additional mixing between P-102 and T-102 to be effective in removing 2-chloroethanol. 2. Emulsion Problem in T-101 No conclusions reached on why emulsions are forming in the caustic wash vessel. cum oooooa -5 PROGRESS REPORT, OCTOBER, 1971; 839-0, 1971 1. Methyl Chloride Problem Caustic washing of 2-chloroethanol was carried out in stages. The washing was to simulate a proposed reactor scheme REMOVAL OF 2-CHLOROETHANOL (METHYL CHLORIDE PRECURSOR) FROM EDC VIA BAUXITE ADSORPTION; 839-0, 1971 The life of the bauxite was too short to be economically attractive to remove all of the 2-chloroethanol. REDUCTION OF METHYL CHLORIDE IN LAKE CHARLES PRODUCT VCM VIA REMOVAL OF PRECURSOR 2-CHLOROETHANOL; 839-0, 1971____________________________ A linear relationship between concentration of 2-chloroethanol and methyl chloride was found. The intercept value of 44 ppm was not even close to the 10 ppm objective. REMOVING 2-CHLOROETHANOL FROM DICHLOROETHANE; 834-0, 1971 This is a literature search. PROGRESS REPORT, JULY, 1971; 839-0, 1971 1. Methyl Chloride Problem Checks were made of different plant streams for 2-chloroethanol, a major methyl chloride precursor. Some experiments were also con ducted for 2-chloroethanol removal. 2. Methyl Chloride-2-Chloroethanol Correlations; 839-0, 1971 A correlation of amount of methyl chloride from amount of 2-chloro ethanol was given# -6- CUH 000008531 ENVIRONMENTAL ASPFCTS AIR POLLUTION AFTERBURNER PROJECT FOR VCM PLANT, 839-0, 1972 VCM plant considering installing an afterburner on C-500 vent stack to meet environmental requirements on ethylene. CATALYTIC OXIDATION--VCM PLANT, 839-0, 1975 A list of questions that need to be answered by piloting a catalytic oxidation unit and review of proaress on both catalytic oxidation and incineration. REMOVAL OF VCM FROM VCM PLANT VENT STREAMS DESIGN AND RESEARCH PLAN? AND OBJECTIVES, 839-0, 1975 DESIGN BASIS FOR DISPOSAL OF VCM PLANT VENT GAS ANO LIQUIDS--ADDITIONAL DATA, 839-0, 1975____________________ DESIGN BASIS FOR DISPOSAL OF VCM PLANT VENT GAS AND LIQUIDS, 839-0, 1975 PROJECT 839-0--REMOVAL OF VCM FROM VCM PLANT VENT STREAMS VIA CATALYTIC OXIDATION, 839-0, 1975 MINUTES--NOVEMBER 5, 1975, MEETING ON VCM EMISSION CONTROL PROJECT, 839-0, 1975 The purpose of the meeting was to review the overall status of the project and to examine the technical feasibility of developing and designina a catalytic oxidation unit within the anticipated EPA time limits. PROGRESS REPORT--VCM EMISSION CONTROL PROJECT, 839-0, 1975 The two areas discussed were 1) Incineration and Ouenching and 2) Scrubbing, Neutralization, and Offsites. ORIGIN OF ACETALDEHYDE AND ETHYLENE OXIDE IN RECENT VCM PLANT STREAMS AND RESEARCH ON THEIR REMOVAL BY SOLID REAGENTS, 839-0, JAN.-MAY, 1976 VCM EMISSION CONTROL SERVICE--DEFINITION OF VENT STREAMS, 839-0, JAN.MAY, 1976 -7- 0000085 CUH R&D PROJECT--CATALYTIC OXIDATION OF VCM CONTAINING STRFAMS, 839-0, JAN.MAY, 1976 Catalytic Oxidation will not be feasible in time to meet EPA requirements. PROJECT STATUS--CATALYTIC OXIDATION OF VCM CONTAINING STREAMS, 839-0, JAN.-MAY, 1976_______________________________________________________________________ Catalytic Oxidation will not be feasible in time to meet EPA requirements. ENGINEERING AND COST STUDY OF AIR POLLUTION CONTROL FOR THE PETROCHEMICAL INDUSTRY--VOLUME 3--ETHYLENE DICHLORIDE MANUFACTURE BY OXYCHLORINATION, 839-0, JAN.-MAY, 1976 PROJECT 839-0--REMOVAL OF VCM FROM VCM PLANT VENT STREAMS VIA CATALYTIC OXIDATION--MEETING OF DEC. 17, 1975; 839-0, JAN.-MAY, 1976 Proposal and discussion of further work. FREE CHLORINE EMISSION FROM VCM DESTRUCTION SYSTEM, 839-Q, JAN.-MAY, 1976 General information concerninq free chlorine formation and emission-EPA`s requirements and impact on the system. OXY BY-PASS TEST RUN, 839-0, AUG.-DEC., 1976 Analyses for. different components in different streams. Other studies' data are also included. VCM PLANT WASTE TREATMENT SYSTEM IMPROVEMENTS: ACTION PLAN, 839-0, AUG.- DEC,, 1976 ________________ ___ Factors determining action plan were: 1. EDC and 2-chloroethanol levels in biotreatment pond. 2. Soluble BOD removal across the treatment system, and 3. Suspended solids removal in final clarifier. DETECTING AND MONITORING VINYL CHLORIDE IN AIR Information Search 76-23. IN CONOCO LIBPARY -8- ooooooe5533 I PROGRESS REPORT, OCTOBER, 1971; 839-0, 1971 1. Plant Vent Problems Work on identifying the source of an objectionable odor from C-500 vent gas stack was done. VCM ADSORPTION ON ACTIVATED CARBON PROCESS--ADSORPTION AND STEAM REGENER ATION; 820-27-1-75, Research Report Carbon adsorption was found to be a feasible method of reducing the VCM concentration in air or nitrogen streams to below 10 ppmv. The effect of temperature, VCM concentration, feed humidity, and residual water in the bed on loading was determined. Carbon activity was unchanged over 30 cycles, but a carbon attrition rate of 0.326 percent/cycle occurred. The adsorption was found to take place in a narrow zone in the bed. The effect of residual water, flow rate, and feed VCM concentration on the outlet VCM concentration preceding this zone was determined. A recom mended regeneration time of 30 minutes and a steam rate of .0133 lb steam/lb carbon minute were determined. IN CONOCO LIBRARY THE BIOTREATABILITY OF VCM PLANT WASTE WATER; 839-1-1-73, Research Report With the exception of ethylene dichloride, which can be removed from VCM plant waste water by air stripping, the waste can be efficiently reduced by about 50 mg/1 B0Ds (a 95 percent reduction) and 350-450 mg/1 COD (an 80 percent reduction) residuals by activated sludge biotreatment. The nature of the residual COD was not determined. The present oxidation basins are oversized by fourfold for most efficient operation, although this overexposure does allow EDC stripping to occur. The plant can be operated under the excessive residence conditions if a way can be found to settle the clarifier suspended solids with additives. To achieve adequate biotreatment, the raw waste must be supplemented with phos phate. COD and BOD loading must be carefully controlled within a rather narrow range for efficient COD and BOD removal. IN CONOCO LIBRARY -9- 00** 00 HCl PURIFICATION RESEARCH REPORT NO* 842-1-1-70--REMOVAL OF ORGANIC CONTAMINANTS FROM HYDROGEN CHLORIDE PRODUCED IN THE VINYL CHLORIDE MONOMER PLANT, 842-1, 1970 _____ _____ _____ ______ This report covers the building and operation of a pilot plant to evaluate removal of organic components from HC1. HC1 PURIFICATION, 842-1, 1970 HC1 Purification of organics was dropped because the plant could buy its supply of HCl, If needed, the plant would blend the unpurified HCl directly. TRIP REPORT-REVIEW OF PILOT PLANT PURIFICATION OF HCl FOR THE ANCON METHYLCHLORIDE PLANT, 842-1 , 1969 HCl FOR ANCON, 842-1, 1969 A check of the ability of oxychlorination catalyst to convert residual acetylene in HCl to heavier chlorinated compounds. This was in consider ation as a backup approach. HCl CLEANUP PROJECT, 842-1, 1969 Liquid HCl must be free of chlorine before being returned to oxychlorination catalyst. PLANS FOR OPERATION OF HCl PURIFICATION PLANT, 842-1, 1969 Temperature, space velocity, and chlorine addition were to be studied. If these were optimal, a catalyst life study would begin. CHANGES IN DESIGN--HCl PURIFICATION PILOT PLANT FOR LAKE CHARLES VCM PLANT, 842-1 , 1969 ECONOMICS OF HCl PURIFICATION--VCM PLANT, 842-1 , 1969 PROJECT SCHEDULE--HCl FOR ANCON W.O. M-2288 LAKE CHARLES PETROCHEMICAL PLANT, 842-1, 1969 Tentative project schedule for mechanical design, procurement, and construction of the HCl purification system. - 10 - CUH 00000853 PHOT PLANT RESEARCH-HOI FOR ANCON, 842-1, 1969 Priorities of information to procure in pilot plant. CHLORINATION PROCESS PILOT PLANT DESIGN--HC1 FOR ANCON, 842-1, 1969 Actual design specs are given. HC1 FOR ANCON, MEETING APRIL 25, 1969, 842-1, 1969 Several routes for removing acetylene from HC1 were discussed. HC1 CLEANUP VIA CHLORINATION/CONDENSATION, 842-1, 1969 Chlorination followed by condensation seems to be best method for removinq contaminants. A pilot study is necessary to answer more thoroughly some questions. TRIP REPORT--WORK BY AUTHOR AT VCM PLANT ON HC1 CLEAN-UP MARCH 16, 1969 TO APRIL 4, 1969, 842-1 , 1969_________ __________ .___________ PRELIMINARY DESIGN AND ECONOMICS FOR HCl PURIFICATION-CHLORINATION PLUS DISTILLATION, 842-1, 1969 HC1 CLEAN-UP PROJECT, 842-1, 1969 A critique of the HC1 Clean-up desiqn. MEETING--OCTOBER 28, 1969, ANALYTICAL PROBLEMS OF THE HC1 CLEAN-UP PILOT UNIT, 842-1 , 1969 HCl CLEAN-UP PROCESS, 842-1, 1969 A presentation of plant scale design. COMPLETE ANALYSIS OF HYDROGEN CHLORIDE GAS, 842-1, 1969 Provided by Hooker Chemical. A NEW METHOD FOR ON-STREAM ANALYSIS OF HYDROCARBON CONTENT IN GAS-PHASE HCl, RESEARCH REPORT NO. 585-4-3-69, DECEMBER, 1969; 842-1, 1969 -n - i009*3 OXYCHLORINATION STEAM DILUENT ADDITION TO OXYCHLORINATION REACTORS; 839-0, 1971 Injection of steam into primary oxychlorination reactors reduces formation of ethyl chloride by-product. OXYCHLORINATION REACTION IMPURITY FORMATION VERSUS PROCESS INPUT AIR DEW POINT VARIATIONS: A PLANT DATA TEST OF THE STARKS-HACKETT PROCESS; 839-0, 1971 The idea that ethyl chloride and other impurities mipht be a function of moisture is borne out, especially as catalyst ages. FIXED-BED OXYCHLORINATION YIELDS 1,2-DICHLOROETHANE; 839-0, 1972 REMOVAL OF COPPER FROM HYDROBLAST WATER USED TO CLEAN THE VCM PLANT OXYCHLORINATION REACTORS; 839-0, 1972________________________________________________ A pilot centrifugation study was done to reduce the copper content in the reactor wash water at turnaround, when catalyst washed out. DISCUSSION OF GOODRICH OXYCHLORINATION SYSTEM AT VCM PLANT ON MARCH 3, 1973; 839-0, 1974___________________________________________________ Subjects discussed were: 1. Goodrich Royalties and Liabilities 2. Process Capital Costs 3. Catalyst 4. Process 5. Materials of Construction 6. Past Process Improvements and Problems HIGH PRESSURE DROP IN OXYCHLORINATION REACTOR R-303; 839-0, Jan.-May, 1976 This report gives an explanation why the unusually high pressure drop. Research Report 839-0-2-71, "A Study of Ethylenic Carbon Formation versus Catalyst Activity in a CuCl2-KC1-AT2O3 Oxychlorination Catalyst" is enclosed. PROGRAM TO DETERMINE IF HC1 FROM OLIN'S TDI PROCESS IS ACCEPTABLE AS FEED TO CONOCO*S OXYCHLORINATION PROCESS; 839-0, Aug.-Dec., 1976. - 12 - OOOOOSS^7 CUH HC1 SPLITTING IN THE OXYCHLQRINATIQN UNIT; 839-0, Aug.-Dec., 1976 Action steps to determine safety (due to flammability) were decided. EXPLOSION LIMITS OF THE SYSTEMS C2H4/O2/N2 UP TO 26 ATM AND 20nC; 839-0, Aug.-Dec., 1976____________________________________________ FLAMMABILITY IN OXYCHLORINATION WITH HC1 SPLITTING; 839-0, Aug.-Dec., 1976 HC1 splitting does not cause a flammability problem. FLAMMABILITY AND EXPLOSIBILITY OF ETHYLENE AND 1,2-DICHLOROETHANE; 839-0, Aug.-Dec. , 1976_________________________________ ________________________________________ Literature search. CONTINENTAL FLAMMABILITY STUDY--SOUTHWEST RESEARCH INSTITUTE MEETING, AUGUST 19, 1976; 839-0, Aug.-Dec., 1976 _______________________ A meeting was held to examine facilities and talk with Southwest about studying flammability region of ethylene 1,2-Dichloroethane. ETHYLENE/EDC/HC1 FLAMMABILITY STUDY; 839-0, Aug.-Dec., 1976 A review of what would be expected from the flammability study. EXPERIMENTAL STUDIES OF IRON-ALUMINA CATALYST BEHAVIORS IN R305, VCM PLANT, WESTLAKE , LOUISIANA; 839-0, Aug.-Dec., 1976_____________________ REMOVAL OF CHLORINE AND ETHYLENE FROM OXYCHLORINATION VENT GAS; 839-0, Aug.-Dec., 1976 OLIN HC1 USAGE-OXYCHLORINATION UNIT; 839-0, Aug.-Dec., 1976 This IOC discusses problems of using 01 in HC1 in oxychlorination unit. REDUCTION OF ETHYLENE AND HC1 LOSSES FROM THE OXYCHLORINATION SYSTEM; 839-0, 1970 KINETICS OF THE OXYCHLORINATION OF ETHYLENE; 839-0, 1970 - 13 CUM 000008538 OXY VENT RECYCLE TO R-101 FOR C?Hd RFCOVERY--VCM; 839-0, 1970 Economic benefits of recycling unreacted ethylene from oxychlorination to direct chlorination. REDUCTION OF ETHYLENE AND HC1 LOSSES FROM THE OXYCHLORINATION SYSTEM; 839-0, 1970 Ideas were suggested for investigations in order to make best recommenda tions on how to reduce ethylene and HC1 losses significantly. METHODS FOR INCREASED CONVERSION IN R-304 CLEAN-UP REACTOR; 839-0, 1970 THE PARAMETERS AFFECTING OPERATION OF THE STAUFFER OXYCHLORINATION REACTION SYSTEM; 839-Q, Report dated September 22, 1969_______________________ R-302 TUBE FAILURES; 839-0, 1968 The tubes appear to Have failed due to burning of carbon deposited in the catalyst. I REPORT OF WESTLAKE OXYCHLORINATION REACTOR MEETING, AUGUST 25, 1969; 842-1, 1969 PRELIMINARY EVALUATION OF STAUFFER'S SPHERICAL PARTICLE OXYCHLORINATION CATALYST; 839-0, 1971___________________________________ The preliminary evaluation revealed 1) the alumina support for the spherical catalyst did not evolve from Conoco materials and 2) relative to the present oxychlorination catalyst the spherical particles possess: a. approximately equal surface area and catalytic activity. b. lower cumulative pore volume c. greater crush strength A STUDY OF CATALYST AND REACTOR BEHAVIORS IN THE VAPOR-PHASE OXYCHLORINATION OF ETHYLENE; 839-0-2-69, Research Report This report pertains to the theory and practice of the vapor-phase oxy chlorination of ethylene. It is of specific relevance to the large-scale operation of the Stauffer-designed Westlake, La., VCM plant ox.y unit, especially to the catalyst degradation phenomena therein. IN CONOCO LIBRARY - 14 - A FURTHER STUDY OF CATALYST AND REACTOR BEHAVIORS IN THE VAPOR-PHASE QXYCHLQRINATION OF ETHYLENE; 839-0-2-70, Research Report This report describes our latest views and data on the vapor-phase oxychlorination of ethylene, especially to large-scale VCM plant operations. It concerns catalyst degradation, reactor changes and instrumentation. Several new methods of catalyst evaluation, certification and analysis are also given herein. IN CONOCO LIBRARY AN OPERATIONAL STUDY OF R-303 0XYCHL0RINAT10N REACTOR DECOKING; 839-0-7-70, Research Report_____________________________________________ __________________ _ A restricted variables study was made of the in-plant, on-stream feasibility of the catalyst decoking of the R-303 Cu2Cl2~KCl-AI2O3 catalyst. While no decoking was observed, there did appear to be an improved reactor per formance after this decoking test. The process conditions necessary for catalyst decoking are given in the report. A brief correlation of reactor behavior with impurity formations through the oxychlorination test interval is included. IN CONOCO LIBRARY SINGLE-PELLET MICROREACTOR STUDIES OF GAS DILUENCY EFFECTS IN THE VAPORPHASE OXYCHLORINATION OF ETHYLENE; 839-0-1-71, Research Report A reactor using a single oxychlorination catalyst pellet was used to study the effect on the pellet temperature of various gas-phase diluents to the feed gases of the reactor. It was found that gas dilution with compatible and feasible gases was an effective way of reducing individual pellet temperatures caused by the oxychlorination reaction. By using a means of reducing the individual pellet temperature during reaction, the catalyst degradation can be reduced and the life of the catalyst extended. IN CONOCO LIBRARY A STUDY OF ETHYLENIC CARBON FORMATION VERSUS CATALYST ACTIVITY IN A CuCl?KCl-Al^O? OXYCHLORINATION CATALYST; 839-0-2-71, Research Report This experimental report explores the kinetics of carbon formation from ethylene pyrolysis within a Harshaw CuCl2-KC1-A12O3 oxychlorination catalyst. Since the oxychlorination activity is related to carbon formation, catalyst activity measurements were made upon these variously carbonized catalyst pellets, this via a C2H4-HCI-O2 oxychlorination catalyst activity measure ment. The time-temperature-catalyst activity as related to carbon formation are presented. These specific data pertain to oxychlorination catalyst design, reactor design, and process design. IN CONOCO LIBRARY. - 15 r.a'.t'jAO OQOO^ CAiV' MICROREACTOR (SCANA) ANALYSES OF OXYCHLORINATION CATALYST PERFORMANCE FROM THE NOVEMBER 1970 VCM PLANT SHUTDOWN; 839-0-4-71, Research Report A study was made of the oxychlorination catalyst activity of samples of the Harshaw oxychlorination catalysts removed in November, 1970, from three ethylene oxychlorination reactors at our VCM plant at Westlake, Louisiana. The study was made using the sinale-pellet microreactor (SCANA) developed for catalyst activity determinations. It was found that the catalyst activity varied widely because of the extremes in operating environment and because of catalyst dusting and the resulting caking within a reactor tube. IN CONOCO LIBRARY - 16 - oooo<08Sa1 NEW TECHNOLOGY NEW ROUTE TO VINYL CHLORIDE--VINYL CHLORIDE PROCESS HAS WIDE RANGE OF BY-PRODUCTS; 839-0, 1971_______________________________________ An adiabatic reactor produces monomer from chlorine gas, ethylene, and recycle dichloroethylene. Process conditions control the ratios of chlori nated by-products. ADVANCEO MITSUI TOATSU VINYLCHLORIDE PROCESS; 839-0, 1972 A description of the Mitsui Toatsu Vinylchloride Process. HYDROGENATION OF HYDROGEN CHLORIDE FROM AN EDC CRACKING UNIT Information Search 76-25. IN CONOCO LIBRARY ENGINEERS TELL HOW TO CUT COSTS; 839-0, 1972 A process for turning HC1 wastes into chlorine was revealed. CHLORINE MADE IN THE MODERN STYLE WITHOUT CAUSTIC; 839-0, 1972 A discussion of the Kel-chlor Process for converting waste HC1 into chlorine. HYDROGEN CHLORIDE TO CHLORINE VIA THE KEL-CHLOR PROCESS; 839-0, 1973 LUMMUS "TRANSCAT" VCM PROCESS--VCM FRACTIONATION STUDY; 839-0, 1973 An evaluation of the fractionation section of the Lummus "Transcat" VCM process design was made as part of the overall "Transcat" process technical feasibility study. TRANSCAT REVIEW WITH LUMMUS; 839-0, 1973 Subjects discussed were 1) the features of "Transcat," and 2) various production cases Conoco would need to analyze usefulness of the process. TRANSCAT PROCESS; 839-0, 1973 A list of questions about the process to ask Lummus. 17 - 00^A'2' 00 CALL REPORT--LUMMUS/CONOCO MEETING, DECEMBER 19, 1973 -- "TRANSCAT" VCM TECHNOLOGY; 839-0, 1974 Doubts about "Transcat" were discussed, especially the scarcity of ethane feedstocks. SPECULATIVE ECONOMICS OF CHLORINATION AND OXYCHLORINATION OF ETHANE AND ETHYLENE--PART I: EDC PRODUCTION; 819-4-1-71, Research Report Speculative economic calculations were made for seven alternate routes for producing ethylene dichloride (EDC) from ethane or ethylene by chlori nation and/or oxychlorination. The seven routes and required netback prices for 18 percent DCF return are summarized as follows: PROCESS RNP, j/Lb Chlorination of high purity ethylene 3.2 Chlorination of dilute ethylene 4.0 Dehydrohalogenation of ethyl chloride 3.6 Oxychlorination of ethyl chloride 3.8 Chlorination of ethane with HC1 electrolysis 5.4 Oxychlorination of ethane to ethylene 4.0 Oxychlorination of ethane (hypothetical case) 3.3 IN CONOCO LIBRARY SPECULATIVE ECONOMICS OF CHLORINATION AND OXYCHLORINATION OF ETHANE AND ETHYLENE, PART II: VCM PRODUCTION; 819-4-2-77, Research Report Speculative economic calculations were made for ten alternate processes for producing VCM from ethylene, ethane, and naphtha. Results indicated that two processes have a significant economic advantage over the conven tional high purity ethylene process. These are: 1. Lummus process for oxychlorination of ethane to VCM. 2. "One-Step" process for oxychlorination of ethane to VCM. Two other processes have a marginal economic advantage over the conventional process, but the advantage was in the same range as the accuracy of the calculations. It was recommended that study be continued on the Lummus process and the "one-step" process. IN CONOCO LIBRARY - 18 - .qOOOB cutf VCM EXPLOSIVE AND FLAMMABILITY CHARACTERISTICS OF VCM Information Search 75-10. IN CONOCO LIBRARY 19 - 544 VCM INCINERATOR / INCINERATION RECYCLE DUE VCM BY-PRODUCTS; 839-0, 1972 Incineration of chlorinated hydrocarbons replacing dumping at Akzo's plant in 1974. I 7DISPOSAL or CHLORINATED BY-PRODUCTS; 839-0, 1972 An article from Chem. Eng, on using incinerators for organic wastes. VCM INCINERATOR DESIGN; 839-0/1975 A listing of the information needed to produce a "Class A" design for VCM pi ant. DESIGN BASICS--VCM VENT GAS INCINERATOR; 839-0, Jan.-May, 1976 ./ TRIPS TO JOHN ZINK COMPANY AND TRANE THERMAL COMPANY TO DISCUSS CHLORINATED HYDROCARBON INCINERATION DESIGN; 839-0, Jan.-May, 1976 ^ PLANT TRIP TO SHELL CHEMICAL COMPANY'S VCM INCINERATION SYSTEM AT NORCO, LOUISIANA; 839.-0, Jan.-May, 1976 VCM INCINERATION-ENVIRONMENTAL IMPACT STUDY REFERENCES; 839-0, Jan.-May, 1976 RESEARCH PROPOSAL-CORROSION STUDY FOR EVALUATION OF INCONEL 600 AND CARBON STEEL USE IN INCINERATION WASTE HEAT BOILER; 839-0, Aug.-Dec., 1976 CORROSION TESTING--COMPARATIVE CORROSION RATES ON CARBON STEEL AMD INCONEL 600 IN C12 AND HC1 ATMOSPHERES; 839-0, 1977 This study was done in order to determine the expected corrosion rates on the waste heat boiler tubes in the VCM incinerator. OPERATION OF CORROSION STUDY FOR EVALUATION OF INCONEL 600 AND CARBON STEFL USE IN INCINERATOR WASTE HEAT BOILER; 839-0, 1977 INCINERATION OF VCM CONTAINING GAS STREAMS Information Search 76-5. IN CONOCO LIBRARY 20 - VCM PLANT LIQUID BY-PRODUCTS VCM PLANT RY-PRODUCTS; 839-0, 1975 The different and most feasible methods of handling the by-products. VCM PLANT BY-PRODUCT?; 839-0, Jan.-May, 1976 To find new uses for by-product chemicals seems fruitless. Incineration with HC1 and energy recovery was suggested. DEHYPROCHLORINATION OF CHLORINATED HYDROCARBONS Information Search 76-25. CHLORQLYSIS OF ALIPHATIC AND AROMATIC COMPOUNDS TO CCU; 839-0, 1972 This paper is a method on converting VCM tars to CCI4. FINDING PROFITS IN CHLORINATED HYDROCARBON WASTES; 839-0, 1972 Discussion of different firms' methods of handling chlorinated hydro carbons. STATUS REPORT--OXYGENATES IN EDO TARS; 839-0, 1972 The plant had to reduce the oxygenate levels in their tars to sell them. Three aspects of this problem were investigated: 1) removal of oxygenates from the tars, 2) identification of the oxygenate source streams, and 3) removal or prevention of oxyqenate in the source streams. DISPOSAL OF VCM TARS; 839-0, 1973 This IOC explains a scheme for converting VCM tars into ethane and muriatic acid by direct hydrogenation over molten zinc chloride catalyst. CHLORINATED TAR DISPOSAL; 839-0, 1973 A summary of three approaches to the VCM tar problem: 1. Decomposition of tars to HC1 and carbon. 2. Burning tars to produce HC1 feed for a new oxvchlorination reactor. 3. Burn tars, feed effluent directly to existing ox.y reactors. - 21 0000085 curt DECOMPOSITION OF CHLORINATED TARS IN A NICKEL REACTOR; 839-0, 1973 PYROLYTIC DECOMPOSITION OF VCM PLANT CHLORINATED TARS; 5505-1-1-73, Research Report Chlorinated tars from the VCM plant were decomposed in a nickel reactor in the absence of air at 1,100F and 260 psig to yield carbon, hydrogen chloride, methane, ethane, vinyl chloride and traces of incomplete decom position products. No water is formed, allowinq the HC1 to be recovered for VCM production and the methane and ethane to be consumed as fuel. The carbon can be handled as a solid waste or burned. IN CONOCO LIBRARY 22 - oo**A/ 00 VCM PURIFICATION SELECTIVE HYDROGENATION OF VINYL CHLORIDE; 839-0, 1971, Information Search This report sought to find literature to describe a process that selectively and catalytically removes hydrogenated olefinic compounds present as impurities in VCM. No specific process was found, but the report contains some general information. LAKE CHARLES VCM PLANT BY-PRODUCT PROBLEMS The topics discussed were 1) butadiene removal via oleum treatment of the VCM, 2) methyl chloride removal from VCM, and 3) laboratory pyrolysis of EDC. RESEARCH REPORT NO. 839-0-6-71 "REMOVAL OF MFTHYL CHLORIDE FROM VCM" BY DR. RONNIE D. GORDON; 839-0,1971____________ Two relatively expensive methods were found for reducing methyl chloride content in VCM from approximately 50-100 ppm to less than 15 ppm. RESULTS OF TEST TO REMOVE RESIDUAL ACID FROM OLEUM-TRFATED VCM; 839-0, 1971 Data were given on several test runs and it was concluded that probably some sort of water wash would be the best means of removing residual acid. OLEUM TREATING SYSTEM FOR REMOVAL OF BUTADIENE FROM VINYL CHLORIDE MONOMER; 839-0, 1971________________ This is a rough draft of a Conoco paper to be presented at the annual Stauffer Symposium relating to butadiene removal technology. SUMMARY OF WORK ON THE PROBLEM OF ACID CARRY-OVER ON THE BO TRFATMENT PROCESS; 839-0, 1Q71___________ After oleum treatment of VCM, the residual acid was neutralized in the caustic wash, but was causing numerous problems. Pilot or plant water washing system was suggested. PROPOSAL FOR BRIEF PILOT STUDY OF RESIDUAL ACID IN OLEUM TREATED VCM; 839-0, 1971 A study would show whether the treatment system should be a coalescer or of the adsorption type. CLIH 000008548 - 23 - REACTION CONTROL FOR POSSIBLE BY-PRODUCTS FORMATION REDUCTION IN R-3D4; 839-0 > 1971 If methyl chloride problem solely is R-304, maybe the hot spot value could be lowered. VCM IMPURITIES PROGRAM; 839-0, 1971 Work was being done on analytical problem of analyzing butadiene in VCM samples that had been in contact with HC1 in metal sample cylinders. MARCH 11 MEETING WITH STAUFFFR CHEMICAL COMPANY, OLEUM TREATING SYSTEM; 839-0, 1971 Planned submittal of oleum treating system paper was enclosed. REMOVAL OF 1,3 BUTADIENE FROM VCM VIA ION EXCHANGE RESINS; 839-0, 1972 Sulfonic Acid ion exchange resin preferentially removes small quantities of 1,3 butadiene, but also undesirable levels of carbonyls are produced. A REPORT ON WORK DONE TO REMOVE RESIDUAL ACID AND OTHER IMPURITIES FROM OLEUM TREATED VCM; 839-0, 1972 Conclusions from this study are 1. Water washing the VCM prior to caustic washing will remove the residual acid and colored bodies. 2. In some cases the addition of the water wash lowered the aldehyde level; in other cases it did not. 3. Ion exchange would be more expensive than water washing for removal of the residual acid. 4. A plant test run should be conducted to investigate water washinn using your present oleum treatment facilities and small laboratory equipment. REMOVAL OF BUTADIENE FROM VINYL CHLORIDE MONOMER; 839-0, 1970 Research Report No. 859-0-5-70 REMOVAL OF 1,3 BUTADIENE FROM VINYL CHLORIDF MONOMER USING OLEUM AND CONCENTRATED SULFURIC ACID; 839-0, 1970 __ Research Report No. 839-0-6-70 24 - CUH 00000354? REMOVAL OF CONTAMINANTS FROM VCM IN A SIDEDRAW TOWER--VCM PLANT-LAKE CHARLES, LOUISIANA; 839-0, 1970 TRIP REPORT AND RESULTS OF TEST RUNS FOR THE RFMOVAl OF BUTADIENE FROM VCM WITH OLEUM CONDUCTED AT THE VCM PLANT; 839-0, 1970 TRIP REPORT ON VCM PLANT TEST RUN TO REMOVE BUTADIENE; 839-0, 1970 The oleum treatment may be permanently used in the plant but will need some minor adjustments. OPERATION OF BUTADIENE REMOVAL SYSTEM; 839-0, 1970 EXAMINATION OF VCM SAMPLES GRJ 2856-42-F THROUGH -&2-S; 839-0, 1970 BD REMOVAL SYSTEM OLEUM TRFATING PROCESS; 839-0, 1970 Flow diagram with some dimensions given. REMOVAL OF BUTADIENE FROM VCM; 839-0, 1970 A general synopsis of the problem and the solution. BUTADIENE IN VCM; 839-0, 1970 A program to reduce butadiene in VCM was outlined. MATERIALS.OF CONSTRUCTION FOR VCM OLEUM SEPARATOR; 839-0, 1970 A discussion of the pros and cons of different construction materials. PRELIMINARY DATA FOR BUTADIENE REMOVAL FROM VCM USING PLEUM; 839-0, 1970 The pilot plant is explained and data given. PILOT TESTING OF SULFURIC ACID TRFATING OF VCM; 839-0, 1970 This is a preliminary survey of the requirements of a pilot plant. BUTADIENE REMOVAL FROM VCM; 839-0, 1970 A discussion of two methods to remove butadiene from VCM: 1) contacting with concentrated sulfuric acid, and 2) use of oxy catalyst. 25 - CWH 000008 VISIT TO VCM PLANT; 839-0, 1970 The bench scale sulfuric acid removal scheme was explained and the possi bility of removing other impurities by the same process. TRIP REPORT--MEETING ON VCM QUALITY AT LAKE CHARLES, JUNE 10, WO; 83-0, 1970 Problems discussed were: 1) Cloudy Monomer, 2) Butadiene Problem, and 3) VCM specifications. RESEARCH REPORT NO. 839-0-1-70 "CLOUD FORMATION IN VCM" BY DRS. C. M. STARKS AND R. 0. GORDON; 839-0, 1970 PROGRESS REPORT, NOVEMBER, 1971 Work was continued on the VCM cloud problem and on the caustic treatment of EDC for removal of methyl chloride. PROGRESS REPORT; 839-0, 1971 Methyl Chloride Problem-2-chloroethanol may be precursor of methyl chloride. PROGRESS REPORT, OCTOBER, 1971; 839-0, 1971 1. Cloudy Monomer Problem The oxygen content of some plant streams was measured since oxygen could cause clouding. ECONOMICS OF MeCl REMOVAL FROM VCM USING MFA; 839-0, 1971 COST FOR PILOTING THE MeCl REMOVAL FROM VCM; 839-0, 1971 REMOVAL OF METHYL CHLORIDE FROM VCM; 839-0, 1971 The economics of a pilot size operation were given. METHYL CHLORIDE REMOVAL FROM VCM; 839-0, 1970 A catalyst developed for methyl chloride removal deactivated much too soon to be economical. - 26 - CWH 000008551 MEETING WITH VCM PLANT PERSONNEL CONCERNING METHYL CHLORIDE REMOVAL FROM VCM; 839-0, 1971 REMOVAL OF METHYL CHLORIDE FROM VCM; 839-0, 1970 Research work and a proposed pilot study were discussed. METHYL CHLORIDE-2-CHLOROETHANOL CORRELATION; 839-0, 1971 A correlation of amount of methyl chloride from amount of 2-chloroethanol was niven. REMOVAL OF METHYL CHLORIDE FROM VCM; 839-0-6-71, Research Report Methyl chloride (MeCl) has been removed from vinyl chloride monomer (VCM) usinq two different methods. Treatment of VCM vapor with metal oxides on alumina at ca_ 150C or treatment of liquid VCM with 10 w/o monoethanol amine (MEA) at 60-70C successfully removes MeCl from VCM. IN CONOCO LIBRARY 27 - 000009 i r^ f^' y : ' vf .800000 HflC l1 ii 1-T.j.. f*.-*- *l - -i - *VAT**S- "V : , , B^saws- <^->7 cVr^s* WUC/ ^ / ilfpll^I>fe . ^-C^tSs'/:; ^.-**- :--_- * -'%-'s t"-,'*-.';Vwv^>;*.'>^:/. . > xif . :;v-:^-.: ~?i/-^J* " --- (??s7 t&*FD -- ^aoy \yppj --- ---- '--* -- --- -- PP -- / Zbl OO-ts JTS'&'Z. oss? pjfr __2. -Sv -------: Gf2sS VQQ2. LP ~Q o2p ^ff 275r5_ ~ 'fFP> GDXT^ZJ frzr ----- -------/ ->TTT ^TPjFT ;,, ^/sr ... (?V/: NVfi GQtP~~ PPZ& __________ = Crnt&j _ --------- >_* S-0-W~) Js* yy -^*9^10^, ' James O. Gibson (conoco) To Date EefTof fowBifsT/o/J SfffltZ TA /% ' 3/^J u n / f/UD rfi/uf / - i?oS - _> icvcp- M - 7-3 __ /c vcP- m - 7-y /OffUS 7L-E. 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