Mar-11. 2009 N Reducing the Storage of Methyl Isocyanate at Rhdne-Poulenc’s Facility in Institute, West Virginia An Interim Technical Report to People Concemed Aboitt Methyl Isocyanate Prepared by Milton Lapkin, Ph.D. for The Good Neighbor Project for Sustainable Industries and The Environmental Careers Organization Preface by Sanford Lewis Director, The Good Neighbor Project for Sustainable Industries November 12, 1994 2756 iP 1Mar-11 2009 No-276 ACKNOWLEDGEMENTS The Good Neighbor Project is a project of the Tides Foundation. ‘We wish to acknowledge the generous support of the North Shore Unitarian Universalist Veatch Program, the Beldon Fund, the Bauman Foundation and the Public Welfare Foundation. We gratefully acknowledge the assistance of the following people in the preparation of this report: Diane Mailey, Erin Heskett, Jane Gallagher, Evelyne Chemouny, and the nationwide team of ECO Advisors. iPMar-11 2009 No-2765 =P. Redueing the Storage of Methyl Isocyanate at RhOne-Poulene’s Facility in Institute, West Virginia TABLE OF CONTENTS EXECUTIVE SUMMARY PREFACE 1. Introduction to the issue of MIC inventory seduction - improving inherent safety. 1 2. Industrywide production and consumption of methyl isocyanate ........ UN 3. Overview of methods of production of methyl isocyanate (MIC) at Rhéne- Ponlene! aad lebsevehere (LUNN MLN IIL A 3 4, Details regarding MIC and pesticide produétion operations at the Institute plan... . 3 5, Potential options for reducing storage of MIC at the Instinnte plant ....... Us 6. Conclusion and recommendations: the need for a more detailed MIC inventory reduction analysis 13 REFERENCES | NNUNI On 15 APPENDICES I. Background information regarding thé Good Neighbor Project, TI, Background information regarding the Environmental Careers Organization program of technical advisors for toxics use reduction Il. Resume of Technical Advisor Milton Lapkin, Ph.D. IV. Chomical formulas and structures of MiC-related products in Institute ‘V. Worldwide producers of MIC (Table 1) ‘VI. Worldwide consumers of MIC (Fable 11)Mar-11 2009 No-2765 =P. 4 EXECUTIVE SUMMARY OF TECHNICAL REPORT ,ON REDUCING THE INVENTORIES OF MIC AT THE RHONE-POULENC FACILITY IN INSTITUTE, WEST VIRGINIA The Good Neighbor Project for Sustainable Industries and The Environmental Careers Organization BACKGROUND After the Bhopal disaster, Union Carbide sold its agricultural division to the french chemical company RbGne-Poulenc (R-P). Among the facilities involved was a large pesticide plant in Institute, West Virginia. The production and storage of methyl isocyanate (MIC) has continued at that plant under R-P’s ownership, despite the fact that this was the poison that killed thousands in Bhopal. Many other companies that used MIC in the past have either eliminated the substance’s storage or eliminated its use entirely since the India disaster, rather than continuing to endanger workers and communities. A disaster waiting to happen? The Rhéne-Poulenc plant may be a disaster waiting to happen. There have been a number of accidents at the Institute plant, including a major explosion in the methomyl unit on August 18, 1993, which killed one worker and spewed toxic fumes into the community. The methomyl unit utilizes MIC; the explosion impact itself impinged on MIC-related equipment. An investigation of the 1993 accident by OSHA alleged numerous points of neglect by the company’s management, including a company-wide yield-enhancement program thet accelerated production outputs at the plant without ensuring adequate safety reviews. A 1994 analysis published by Rhéne-Poulenc found that 2 “worst case” MIC release at the plant could cause deaths for a nine mile radius, and injuries for up to twenty eight miles from the plant. Community alliance demands independent safety audit, In response to the looming hazard of the R-P plant, an informal alliance has formed among a local community group (People Concerned About Methyl Isocyanate, orMar-T1. 2009 2:29PM No.2765 P. §Mar-11 2009 2:2 No.2785 P. & PCMIC), unions which represent some of the workers inside the plant (the ‘Affiliated Construction Trades, or ACT) , and officials and professors at the nearby West Virginia State College. All members of the alliance have been demanding that the company fund a fully independent, comprehensive safety audit of the facility, with an auditor selected and supervised by the community and labor organizations. The proposal for this audit is modelled after a legelly binding agreement which was entered between a Rhéne-Poulenc facility and its neighbors in Manchester, Texas. The Texas Precedent, In June 1992, a serious accident occurred at an R-P chemical plant in Manchester, Texas ~ a release of a cloud of sulfur Gioxide. At least 27 people were sent to area hospitals. With the assistance of a statewide environmental organization, Texans United, the community won an agreement which gave the community specific rights never before recognized in Texas, R-P agreed to pay for an independent environmental audit by an export selected and supervised by a panel of community residents and Texans United. Among the features of the agreement are: + A broad audit, which includes review of regulatory compliance, safety training, accident prevention, emergency response, waste analysis and information systems, monitoring programs, and waste minimization practices. + Public disclosure of company documents, including hazard assessment and risk analysis, lists of accidents/upsets/near- misses/corrective actions, and waste minimization and reduction plans. + RP committed to "negotiate in good faith" on the audit recommendations. + Citizens are entitled to accompany the auditor and conduct other inspections by appointment, + The agreement is legally binding because it is integrated to the firm's operating permit under the hazardous waste law. A similar agreement is now being sought in Institute, West Virginia. For the Institute plant, such an assessment would include an overall appraisal of theMar-11 2009 No.2766 =P. 7 plant's safety, as well as an appraisal specifically of the potential for reducing the amount of storage of methyl isocyanate at the plant. However, it must be recognized that R-P was forced into the strong Texas agreement by a well- organized community pressure culminating in a challenge to the firm's proposed operating permit. R-P has not proven willing to voluntarily match their Texas agreement in the absence of such pressure tactics in West Virginia. Reducing inventories of MIC - A priority safety goal, While other safety measures may help to reduce the /ikelihood of disaster, nothing but climinating the massive inventories of MIC at the site can ensure that a Bhopal-like disaster involving an MIC release that kills off thousands of residents will not occur in Institute, ‘Therefore, any independent safety review should include a focus on appraisal of MIC inventory reduction options. Launching and conducting the study. In June, 1994, PCMIC decided that this issue could not wait; they secured the services of two national service organizations, the Good Neighbor Project for Sustainable Industries (GNP) and the Environmental Careers Organization (ECO), to commence an evaluation of MIC inventory reduction at the plant. GNP helps neighbors and workers to oversee pollution prevention, toxics use reduction and plant safety. ECO conducts training and other support for environmental jobs, and conducts a national program of technical assistance for toxics use reduction. Together the national organizations contracted with an experienced R&D chemist, Milton Lapkin Ph.D., to undertake the inventory reduction evaluation. PCMIC asked the company to cooperate with Lapkin in his assessment, but they have neither offered a site visit nor the in-depth information exchange needed to complete an appraisal. Despite the company’s lack of in-depth cooperation, Dr, Lapkin was able to conduct preliminary analysis using mostly publicly available data, A draft of the report was published in October 1994 and circulated to the company and other experts. \Sne-Poul e company acknow ventory reduction, R-P officials have explicitly stated that they will not allow a comprehensive community controlled safety audit consistent with the Manchester, Texas model. They have also acknowledged in a meeting with the Good Neighbor Project and the report author on November 4, 1994 that they have never conducted a complete assessment of iiMar-11 2009 No-2765 =P. the economic feasibility of eliminating MIC storage through a no-storage direct feed approach. R-P has reported spending a substantial sum — $30 million - on upgrading the Institute Plant in its Institute Modification Project. Many of these expenditures helped to improve the safety of the plant (e.g. reducing storage of phosgene). However, some of them may have been inconsistent with the long term goal of eliminating MIC inventories. There is a possibility that the company’s failure to plan for the eventual elimination of MIC inventories may have already led to purchases of some equipment ill-suited to an eventual shift to the no-storage approach to MIC production. SYNOPSIS OF REPORT FINDINGS. Rhéne-Poulenc’s Institute Plant Lags Behind Other Firms in MIC Reduction. Our initial research indicates that the Rhéne-Poulenc plant in Institute is one of the last chemical plants, world-wide, engaged in large scale storage of MIC. (The plant has a rated capacity to store up to 240,000 pounds of MIC, which is about three times the amount released in Bhopal.) No other plants in the U.S. continue to stockpile MIC. Many other companies who produce the same pesticides as R-P have found ways of doing so while eliminating bulk storage of MIC. These companies have dealt with the clear hazard of MIC by eliminating the product's usage or storage. For instance, at the time of the Bhopal disaster, the Du Pont company reportedly stored as much as 250,000 pounds of MIC at its LaPorte Texas plant. The company has since then spent an estimated $10 to 12 million to build a system that consumes MIC in final products immediately after it is produced. In such a "no storage continuous feed" system, there is no need to store any MIC on the site. As an ounce is produced, an ounce is consumed, rather than storing hundreds of tons of MIC on-site as R-P does. Other companies such as the Israeli pesticide firm Makhteshim-Agan have found ways of making the same products with different materials — avoiding the use of MIC entirely. In fact, even‘at the Institute plant, prior to 1973 the pesticide Sevin was made without the use of MICMar-11 2009 No-2765 =P. In contrast to these other companies, R-P officials acknowledged in a recent meeting with report’s author in Washington, D.C. that the company has never conducted a complete evaluation of the potential to eliminste the storage of MIC. While the R-P plant and other plants have installed various safety features, a lesson of Bhopal is that safety features are prone to failure. In the Bhopal accident, numerous safety devices failed to function as intended. Safety system failures have also occurred at the Institute plant and other plants in the Kanawha Valley, leading to numerous public safety crises and scares in the community. Various technologies deserve consideration at Rhéne-Poulene. This report identifies a number of technologies worthy of exploration for reducing the inventories of MIC at the Institute Plant. A hierarchy of options is identified, from strategies that could eliminate MIC storage, to some that could substantially reduce the inventories. Among the options discussed are: + Converting to a “no storage continuous feed" system to produce pesticide utilizing MIC fed directly ftom a continuous producing unit to pesticide production without any intervening storage: + Changing scheduling of pesticide production within the existing production configuration to minimize storage needs. * Shifting to in-line quality testing of MIC rather than testing temporarily stored batches of the chemical. + Changing pesticide production formulas, or changing the products that the company makes at the site. NEXT STEPS? R-P officials have stated that they intend to look at various measures for improving plant safety beginning in January 1995. The report recommends that the following measures be taken at that time: + The company should conduct an in-depth technical and economicMar-11 2009) 2:90 No-2765 =P. 10 analysis of inventory reduction options, beginning with the strongest options identified in this report. + The company should allow the author and representatives of the Good Neighbor Project and People Concerned About MIC to participate in the development and review of the MIC inventory reduction study, including on-site review, open sharing of relevant documents and information, and appropriately focused dialogue. + The company should implement the inventory reduction measures which prove feasible. For additional details on this assessment, obtain the full report: Lapkin, Milton, Report on Inventory Reduction Opportunities for Methyl Isocyanate at the Rhéne-Poulene Facility in Institute, WV, November 1994. The Good Neighbor Project ($5). The Good Neighbor Project for Sustainable Industries, P.O. Box 79225, Waverly, MA 02179 USA (617) 489-3686/ (617) 489-2482 fax/ email: sanlewis@ige.apc.org. viMar-11 2009 No-2766 =P. 11 Reducing the Storage of Methyl Isooyanate at RhOne-Poulenc’s Facility in Institute, West Virginia The Good Neighhor Project for Sustainable Industries and The Environmental Careers Organization for People Concerned About Methyl Isocyanate PREFACE, Sanford Lewis, Director The Good Neighbor Project for Sustainable Industries The attached report summarizes available information on the potential for reducing inventories of methyl isocyanate (MIC) at Rhone-Poulenc’s Institue, West Virginia plant. The report, prepared by chemist Milton Lapkin, PhD., on behalf of People Concerned About Methyl Isocyanaie, is based primarily on a literature search, correspondence and press reports regarding Rhéne-Poulenc. Context of Report ‘The production and storage of MIC at the Rhone-Poulenc facility represents a long-standing safety concern to the community, dating back to when the plant was owned by the Union Carbide Corporation, This concern was ‘triggered by the Bhopal, India disaster at 2 similar Union Carbide facility, in which more than 4,000 people were killed and lundreds of thousands were injured by a release of MIC. An analysis conducted by Rhéne-Poulenc in its Risk Management Plan for MIC published in 1994 indicates that @ worst case MIC release at the plant could cause deaths for a nine mile radius from the plant (with one hour of exposure to a cloud of MIC), and injuries for up to twenty eight miles. There have been s number of accidents at the Institute plant. Between 1980 and 1984 there were 28 leaks of MIC at the Institute plant according to Union Carbide’s records. Anoth. MIC accident occurred at the plant in 1990. As a result of this history, and especially after @ major explosion at the Institute plant in 1993, community and labor organizations in Institute have been asking the company to find a fully independent, comprehensive safety audit of the facility, with an auditor selected and supervised by the community and labor organizations. Such an audit could be modelled after a process at a RhGne-Poulenc facility in Manchester, Texas, in which a legally binding agreement set forth the terms of the auditMar-11 2009) 2:91PM No-2765 =P. 12 ‘An independent appraisal of MIC inventory reduction opportunities could be one aspect of such an independent review. However, due to large safety risks involved and the immediate availability of Dr. Lapkin, the community organization has sought to advance this aspect of the safety seview in advance of a total audit of safety and prevention options. ‘The objective of Dr. Lapkin’s review is to identify measures to reduce inventories of MIC in Institute while preserving jobs and the local economy. In June, 1994, People Concerned ‘About Methyl Isocyanate, having secured the services of Dr. Lapkin, asked Rhéne-Poulenc to cooperate with Dr. Lapkin in his assessment, A face-to-face mecting conducted with the company’s Vice President, Environmental Director and Plant Manager in November 11994 in response to a draft of this report proved a useful information interchange and resulted in some refinements of the report. However, they have so far declined to provide the depth of information exchange needed to complete Dr. Lapkin’s appraisal. By and lauge, this interim report reflects the extent of analysis that Doctor Lapiin ean complete regarding the facility without fimther cooperation from the company. Preliminary research indicates that Rhone-Poulenc in Institute is one of the last chemical, plants, world-wide that is engaged in large-scale storage of MIC. In ascertaining the opportunities for minimizing MIC at R-P, the Good Neighbor Project and its technical advisor have conducted research on the status of MIC production worldwide. While our research is only preliminary, it appears that the R-P Institute facility may be storing more MIC than is stored at any other chemical plant in the world. Other facilities which produce the same pesticides as R-P either do so in ways that avoid bulk storage of MIC. or have developed chemical pathways to avoid the use of MIC. Rhdne-Poulenc appears to be the only company in the U.S. that is continuing the practice of bulk storage of MIC. The other two producers, Sandoz and Du Pont, have switched to continuous "no storage, direct feed” processes, which consume the MIC to make pesticides as soon as it is produced. There are as many as 13 plants in the world that produce MIC. Out of these, few appear continue to store substantial quantities of MIC before it is consumed. For instance, the Bayer Corporation consumes all of the MIC produced in Western Europe. Bayer makes and consumes its MIC in Germany and Belgium. At least one source has indicated that Bayer stores only minimal amounts of MIC on-site. ‘A producer of one the same products as R-P (carbaryl, carbofuran and methomyl) in Israel Makhteshim-Agan has asserted that it docs not utilize MIC in production, but has developed altemative chemical pathways. Mitsubishi Kasei (Japan) has shifted to no storage, direct feed processes like the other U.S. companies.Mar-11 2009 2:9 No-2765 =P. 18 ‘Who has performed this study Dr. Milton Lapkin is an R&D chemist with 35 years experience in the chemical industry. He conducted his review on behalf of the local citizens group at the request of the Good ighbor Project and the Environmental Carcers Organization (ECO). The Good Neighbor Project is a three year old effort of the nonprofit Center for the Study of Public Policy. It provides communities, goverment, corporations and labor unions with support in promoting sustainable local industries through pollution prevention, toxics use reduction and plant sustainability. The Good Neighbor Project focuses on “greening"existing firms through stakeholder auditing, ic. involving neighbors and workers in assessing opportunities for progress on environmental, safety and economic concerns. The Environmental Carcers Organization is a twenty year old organization which provides training and jobs placement on environmentally-related jobs. ECO works for the Gevelopment of professionals, the promotion of careers, and the inspiration of individual action. This is accomplished through placement, career advice, career products, research and consulting. Founded in 1972, ECO has five regional offices across the country and 5,000 alumni. ECO has established a nationwide program to train and engage a network of career chemists and engineers to advise local citizens’ groups and companies on toxics use reduction opportunities. Dr. Lapkin’s services were provided by ECO and GNP under this special Technical Advisor for Toxics Use Reduction Program, as a service to the community and company. Solicit: of comments ‘The circulation of this report is being undertaken to further encourage Ridne-Poulenc to consider cooperating with this extemal review. The report is being circulated to the company end to other technical experts and persons knowledgeable about the methyl isocyanate or the R-P plant. We will be appealing worldwide for technical solutions that can be applied to the situation at the R-P plant. Further reports to the community are anticipated in the furure. ‘Comments should be mailed to the Good Neighbor Project. Sanford Lewis, Director ‘The Good Neighbor Project for Sustainable Industries PO Box 79225 Waverly MA 02179 USA 617 489-3686 phone! 617 489-2482 faxMar-11. 2009 No-2765 =P. 14 Reducing the Storage of ‘Methyl Isocyanate at RhOne-Poulenc’s Facility in Institute, West Virginia ABSTRACT Statistics on the use and storage of MIC. The report notes that most companies worldwide have eliminated bulk storage of MIC; RhGne-Poulenc appears to be the only company in the U.S. that is continuing the practice of bulk storage. The uses of MIC at RhOne-Poulenc. The report details current uses of MIC at Rhone- Poulene and the apparent chemistry of those processes. Potential technical options for inventory reduction of MIC at Rhéne-Poulenc. The report notes a hierarchy of potential paths for reducing inventories of MIC at Rhéne-Poulene. Among the options discussed are: + Converting to a direct feed system to produce pesticide utilizing MIC fed from a continuous producing unit without intermediate storage, thereby eliminating MIC stockpiling. + Changing scheduling of MIC production within the existing production configuration to minimize storage needs. + Shifting to in-line quality testing rather than testing stored batches of MIC. + Changing pesticide production formulas, or changing the products that the company makes at the site. The options set forth in the report are not intended to be exhaustive, but represent those identified based on available data. Refinement and expansion of the list would require additional cooperation from the management of Rhéne-Poulenc. The report concludes with recommendations for the company to conduct an in-depth study of the range of inventory reduction options, and to allow participation of the consultant and the interested organizations in this appraisal.2009 2:92 No-2765 =P. 16 Literature Review Report Regarding Inventory Reduction of Methyl Isocyanate at RhOne-Poulene’s Facility in Institute, West Virginia Milton Lapkin, Ph.D. Environmental Careers Organization and Good Neighbor Project Technical Advisor to People Concerned About Methyl Isocyanate 1. INTRODUCTION TO THE ISSUE OF MIC INVENTORY REDUCTION - IMPROVING INHERENT SAFE’ Rbéne-Poulene routinely stores up to 135,000 pounds of MIC on-site; their rated capacity allows storage of up to 240,000 pounds of MIC. [ref. 15]. These large amounts of MIC are. substantially in excess of the amount of MIC that caused the Bhopal disaster. The reduction of these stockpiles of MIC at RhOne-Poulenc is the only secure way to avoid a Bhopalstyle MIC accident in Institute While various safety measures can help to seduce the lételthood of en MIC disaster at the Institute plant, the most reliable means for preventing a chemical disaster would be the elimination of most of the MIC storage on the site. Safety systems are prone to failure, 25 numerous previous incidents at Union Carbide and R-P facilities have demonstrated. For example, in the course of the Bhopal disaster, there were numerous safety system failures: ‘The Union Carbide plant in Bhopal, India was equipped with secondary prevention end mitigation systems specifically designed to prevent a release of methy! isocyanate (MIC), @ deadly gas. However, inadequate design, component failures, and lagging maintenance activities resulted in every one of these systems being compromised. Specific elements in ‘the causal structure of the eventual release include: * the refrigeration unit, designed to maintain an appropriate temperature in the MIC unit and therefore prevent an exotherm, was not in operation, * the vent gas line, intended for carrying MIC to an emergency scrubber, leaked MIC to directly to the atmosphere, * the gas that did get to the scrubber was not neutralized because of a lack of alkali in the sorubber, * the vent gas scrubber was designed for @ capacity of 5 to 8 tonnes. The MIC tank's capacity was 70 tonnes, * che temperature indicator on the MIC tank was not functioning,Mar-11 2009 2 No-2765 =P. 16 % the flare tower for burning off the released MIC was not functioning, and * the water curtain (high pressure water sprayers) for neutralizing MIC could reach a height of only 10 meters whereas MIC leaked from the vent gas line at about 33 meters. (ref. 10] The plant which is currently operated by R-P in Institute has also been the site of safety system failures, Aficr Bhopal, there were safety system upgrades at the plant, including a hazardous gas detection system and a water-spray system designed to impede the migration of a release off-site, were installed. However, accidents have still occured: Despite these improvements, a noxious cloud of methylene chloride and aldicarb oxide escaped from the plant. The escape went undetected by plant personnel due to the following. factors: + a high temperature alarm was out of service, * a level indieator inthe tank was broken, * the newly installed gas detection system had not been programmed to test for aldicarb oxide, and * the water spray curtain intended to impede the migration of the gas offsite was inadequately designed for the given release. [ref. 10] ‘As a result of this sequence of mechanical failures at the Institute plant, 135 people in four Kanawha Valley communities were hospitalized. Had the release involved a substantial amount of ‘methyl isocyanate, the toll in injuries and deaths could have been far worse, One of the most far reaching solutions to preventing chemical accidents is eliminating the storage of chemicals that could cause an accident. Such a solution improves safety regardless of the potential failure of the system. Evaluating the potential for reducing inventorics of MIC at R-P is the purpose of this review. 2. INDUSTRYWIDE PRODUCTION AND CONSUMPTION OF METHYL JSOCYANATE Review of chemical industry literature reveals that Rhéne-Poulenc in Institute, W.V., is apparently the only remaining U.Sbased company which continues to stockpile substantial inventories of MIC. The two other US. producers of MIC, the Sandoz and Du Pont corporations, have reported converting to in-line production and consumption, in which MIC is consumed immediately as it is created. “The most recent available data, SRI's 1991 report {ref. 1], identified consumption of MIC and volume of pesticides produced from MIC for 1989 in the US at the levels shown in Table I. See ‘Table II in the Appendix for a preliminary summary of known data regarding international production of MIC and Table TI! in the Appendix for pesticide products made from MIC worldwide. wvMar-11 No-2765 =P. 17 2009) 2:99 In the United States the production of insecticides carbaryl, carbofuran, methomyl, and aldicarb, are the major consumers of MIC. Worldwide, pesticides are the principal ad probably the only commercial uses of MIC. Very stall volumes of MIC have at times been used to manufacture pharmaceuticals but itis not clear how widely this is done today. An example is, cimetidine (Zagamet), an antiulcer agent which originally utilized MIC in a manufacturing step. However the producer, SmithKline, now uses a different synthetic route. Eli Lilly originally used MIC in the U.S. as a reactant to produce tebuthiuron (Spike). However, they have moved their production operations to Brazil and simultaneously redesigned their process to eliminate the use of MIC. Of the users of MIC worldwide, most users either produce MIC continuously and convert it as it is formed (ie. for immediate use), rely upon other producers” facilities to produce pesticide products on their behalf at the site of MIC production (known as tolling arrangements), import finished pesticide products or intermediates made with MIC, or have eliminated the use of MIC in producing their finished products, OCYANA’ RHONE-POULENC AND ELSEWHERE a. Production at Rhéne-Poulenc ‘The traditional process for producing MIC, which is apparently the mode of production used by Rhéne-Poulenc at Institute,W.V., involves the reaction of monomethylamine and phosgene to yield carbamoyl chloride, which is subsequently decomposed to MIC and hydrochloric acid (HC!). To avoid a reverse reaction, generally, an acid acceptor is sometimes required to neutralize the HCI (ref. 3] ‘The Rhone-Poulenc facility at Institute, WV produces MIC continuously and stores the isocyanate for later use in manufacturing their pesticides, or delivers it to the adjacent FMC plant from a storage unit adjacent to the FMC facility. Rhone-Poulenc produces carbaryl (Sevin), aldicarb (Temik), and methomy! from MIC, and FMC produces carbofuran (Furadan). The Institute MIC plant is reported to have & capacity of 40 million metric pounds (Jan 1991) but modifications to the plant have changed its size. According to U.S. government figures for MIC reported for 1989, actual production values for MIC are probably less then 15 MM Ibs., based on the sales values of the pesticides derived from the isocyanate. [ref 1} If we assume that pesticides derived from MIC have not grown very rapidly the MIC production values for the Institute plant may be no more than 20-25 million pounds.Mar-11 2009 2:44 No-2765 =P. 18 TABLE 1 CONSUMPTION OF MIC IN THE UNITED STATES FOR 1989 Pesticide MIC,_Ibs. _ Production, Ibs. Producer Carbaryl 8.0 Million 25 Million Rhéne-Poulene (SEVIN) Carbofuran 2.9 Million 10 Miltion FMC (FURADAN) Aldicarb 2.5 Million Rhéne-Poulenc (TEMIK) Methazole 0.3 Million 0.1 Mi Sandoz - in tine process Methomyl 2.0 Million 5 Million ‘Du Pont in line Rhéne-Poulenc.** (imermediate for LARVIN) ‘TOTAL 15.7 Million tbs MIC 47.6 Million ths Pesticides * Du Pont purchased 2 million pounds of MIC in 1985, sufficient to manufacture 5 million pounds of methomyi, when total production by Rh@ne-Poulenc and Du Pont was 10 million pounds. The total use level fell to half this amount in 1989 and Du Pont now uses ano storage, direct feed process. Du Pont's production in 1994 is not known, but probably represents an amount somewhat greater than Rhdne-Poulene current production or conversion of methomyl. The Du Pont no storage, direct feed plant was reported to cost about 10-12 million dollars. [ref. 3] ** Rhdne-Poulenc manufactures methomyl but does not sell it domestically. It either sells the insecticide outside the United States or converts it captively in its Institute, West Virginia plant to the insecticide thiodicarb (Larvin). b. Other Routes To Synthesizing MIC 1, Dy Pont: Du Pont has commercialized at their La Porte, TX facility a closed- loop process using a reactor design that generates MIC and converts it to finished pesticide as itis made, The process involves the reaction of methyl amine and carbon monoxide which yields N- methylformamide. This can subsequently be oxidized to MIC in the presence of a silver estalyst. (refs. 2 and 3] As a result of production in this manner, at any given time the reactor contaias only a few pounds of MIC, which can be further reacted to the desired carbamate insecticide, Bulk. storage of MIC is avoided.Mar-11 No-2765 =P. 19 2. Baver: Beyer has also patented # nonphosgene route to MIC that reacts either N'N-dimethylurea or methylamine with diphenyl carbonate to produce the isocyanate, The coproduct phenol can be recycled to diphenyl carbonate by reaction with phosgene or carbon monoxide. 4 Bayer spokesman has also claimed to store only minimal quantities of MIC at production sites, [ref 3] 3. Degussa Degussa has patented a process for production of MIC from potassium cyanate and dimethyl sulfate. Some smaller pesticide producers in Southeast Asia apparently generate MIC for captive use by this route. The higher costs of raw materials make this route uneconomical except in unusual circumstances. [refi 1 and 9] 4. UCTION OPERATIONS AT THE INSTITUTE PLANT. a. MIC storage in Institute Figure | illustrates the MIC production facility at Rhéne-Poulenc in Institute. The Rhéne-Poulenc plant has three independent reactor units for manufacturing their pesticides, which are supplied from ‘two MIC storage tanks. In addition, the facility has 2 quality control "Make" tank to test the quality of the MIC before it is transferred to storage. The tanks consist of: -A 40,000 pound capacity quality control “Make’ tank; “A” in Fig. 1. ‘A 200,000 pound capacity underground storage unit; °B? in Fig. 1 ~A 40,000 pound capacity above ground storage unit supplied once a day from the underground storage unit: °C’ in Fig. 1. FMC’s facility adjacent to the Rhéne-Poulenc plant is supplied by pipeline from the above ground, 40,000 Ib. tank. frefs. 3 and 7] The amount of MIC stored in Institute is reported by the company never to excced 240,000 pounds [ref. 6}, although the capacity of the tanks would appear to accommodate as much as 280,000 pounds . Company representatives have stated that the plant seldom if ever stores MIC anywhere near the maximum capacity of the storage units, [ref. 15] Daily storage requirements are ds production requirements according to the company, and reportedly averaged less than 135,000 pounds in April and May, 1993. [ref. 4] b. Previous measures by RhGne-Poulene to reduce the storage of hazardous materials associated with MIC production. Pubtic policy repercussions from Union Carbide’s Bhopal, India accident have markedly changed the manufacturing procedures and handling of MIC. In the United States and Westem Europe, rail or truck shipments across state or country boundaries are banned. Producers of MIC-based products have been forced to locate directly adjacent to an MIC plant, or to develop low volume elosed-loop systems for immediate conversion to the final product.Mar-11 No-2765 =P. 20 Since the demand for shipment has ceased, so have the shipment-related inventories in Institute. Further inventory: reductions at the Institute plant resulted fiom downsizing the production units and ‘modifying the instruments and equipment to permit running at lower rates. In 1989 the company stored as much as 480,000 pounds of MIC on site. As part of the company’s Institute Modification Program, reported by the company to involve a total expenditure of $50 million, facilities have been modified and improved and the inventory of MIC required for operations reduced by more than half. [ref, 15] Among the measures associated with these expenditures are the following: Eliminating phosgene storage. The phosgene, which is an intermediate in the production of MIC, is another very toxic material. The phosgene reactant is prepared from carbon monoxide and chiorine. Rhéne-Poulenc built a new downsized phosgene unit in 1993, which allowed for the immediate conversion of phosgene to MIC as it is made, so that storage facilities for phosgene are reportedly no longer required.{ref. 5] If this information is accurate, the company succeeded in designing a system to eliminate phosgene storage; a similar methodology would be a preferred approach for MIC ~ to produce it for pesticide production without storage. However, it should be noted that in 1994 the company published a worst ease scenario for Phosgene indicating storage of up to 6500 pounds of Phosgene and a one-hour lethal impact zone (ERPG 3) of four miles from the Facility. [ref. 16]. Eliminating chlorine barging. Chlorine, used in the manufacture of phosgene, no longer is barged into the facility. The chlorine is now received in 90-ton railroad cats {tef. 5] and unloaded in an isolated totally enclosed building, Reducing Storage of MIC. Current storage of MIC at Rhéne-Poulenc’s Institute site is large enough to present a major public health hazard, as demonstrated by worst case accident appraisal calculations. However, the company has stated that their inventory of MIC currently is about 20 % of the inventory that normally was stored in the 1980's, when shipments throughout the country of MIC in tank cars and drums were commonplace, and tank cars were held on site, [ref. 7] Today the MIC inventory can range at peak levels at from one and 4 half to three times the amount released in Bhopal; thus a large potential hazard remains. ¢. Synthesis of Pesticides Rhéne-Poulenc manufactures three pesticide products at Institute: SEVIN (carbaryl); TEMIK {aldicarb); and LARVIN (thiccarb). FMC manufactures one pesticide product at Institute: FURADAN (carbofuran.) Figure 1 shows our best understanding of the layout of the MIC storage units and its distribution to the various pesticide reactors. When all reactors producing pesticides are opcrating at their maximum rates, the total usage of MIC is about 100,000-130,000 tbs per da The maximum operating rate for MIC manufacture is reported to be about 150,000 pounds per day. This is an important factor in establishing the minimum inventory of MIC required to meet the demands of the pesticide units when they are operating at capacity. All commercial carbamate insecticides marketed in the United States are monomethyl carbametes. ‘These may be produced by the reaction of methy! isocyanate with the hydroxyl group of an alcohol, phenol, oxime or other hydroxysubstituted hetercyctic compound. (An altemate route without an isocyanate intermediate is to react a compound containing the appropriateal iP Figure 1Mar-11 2009 2:98 hydroxy! functionality with phosgene to give a chloroformate, which is then reacted with methylamine). (ref 5] 1, Sevin (6325-2) This is probably manufactured in a continuous seactor unit from MIC and alpha-naphithol. ( See Reactor ’D’ in Fig. 2). The MIC is supplied from the underground storage tank "B’, probably by pipeline to the continuovs reactor "D'. The requirements for MIC for ‘this unit are not known, but probably do not exceed 46,000 Ibs. per day at maximum capacity. 2. Temik (116-06-3) This is manufactured in a batch reactor ( Reactor °E’) with a cycle time permitting twice a day production schedules. The final step is the reaction of the oxime with MIC. Based on the available information, the Temik batch reactor requires 7000 Ibs of MIC per rn, producing about 21,000 Ibs. of Temik pesticide during each cycle. Reactor cycles are believed to permit two runs per day. Therefore, the Temik reactor has a requirement of 14,000 tbs. of MIC per day when filly operational. It is not known to this author whether Rhéne-Poulenc manufactures the intermediates at this site, or the intermediates are supplied from another source. One commercial ‘process involves reacting, isobutene with nitrosyl chloride, by reacting the formed dimeric adduct with sodium methy! sulfide, and converting the resulting oxime into the carbamate pesticide with MIC, 3, Larvin (59669-26-0) The process probably involves a two step reaction in which MIC produces Methomyl, an intermediate pesticide from the oxime in a continuous process in Reactor "F’, Rhone-Poulene may be packaging the Methomyl for export, or using it as an intermediate for further reaction with sulfur dichloride to produce the final product in Reactor °G*. Again, it is not known whether the intermediate oxime is manufactured on site. The requirements for MIC for Reactor ’F’ probably approach 20,000 Ibs. per day. The MIC supplied to this reactor is fed from the above ground, 40,000 1b. second storage tank °C’. Tank °C’ is probably filled once a day from the underground storage tank *B’, 4. Furadan (1563-66-2) This pesticide is manufactured by FMC in a batch reactor, Reactor 7H, whose requirements for MIC are probably around 20,000 Ibs. per day. However, as much as 40,000 pounds may sometimes be required. The MIC is supplied from the above ground storage tank °C’, [fig 1] which is also the source of the MIC for Larvin manufacture (see above). The final step in the manufacture of this pesticide is the reaction of MIC with the phenol derivative. ‘The MIC is supplied by pipeline from the 40,000 Ib. above ground storage tank °C’ directly to the FMC batch reactor for conversion to product. According to R-P officials, FMC does not store MIC independently on their property. [ref. 15] d._ Summary of Factors which may affect Inventory Requirements for MIC at Rhéne- Poulenc in Institute, The requirements for the volume of MIC storage may relate to a number of different inter-related issues:2009) 2:96 No-2765 =P. 28 9) The system design is for asynchronous production and storage rather than continuous no storage, direct feed production as adopted in several other faciities; bythe cooling system for MIC storage requires 2 minimum level of MIC to operate efficiently; ©} Production units are not located next to one another and utilize separate storage systems; d) A storage unit for freshly made material is required to allow quality _—_testing: ¢) The maximum daily production usage of MIC is reported to be about 125,000 Ibs.. but ach process unit bas separate MIC demands and schedules of production which may require the availability of MIC feedstocks; ) The minimum throughput levels of MIC are not known and may constrain pacing. 5 POTENTIAL OPTIONS FOR REDUCING STORAGE OF MIC AT THE INSTITUTE, WEST VIRGINIA PLANT . Without further cooperation of the management of the Rhéne-Poulene plant and an on-site review, it js not possible to generate an exhaustive list of options for inventory reduction, nor to evaluate the feasibility of the various options. However, the following are some options which occur to me from extemal review of this facility, which may be worthy of further examination in a cooperative review of technical options. 1 have grouped these options in dectining order of potential inventory reduction inppact. It is likely that other options would become apparent in an on-site visit, and that some of these options might be readily ruled out on further inquiry. ‘The other producers and users of MIC in the US have eliminated bulk storage of MIC by shifting to continuous, no storage, direct feed processes in which the MIC is consumed immediately in the n of end products, Similar types of processes might be explored for the Rhéne-Poulenc plant. It should be noted, however, that RAOne-Poulenc is also the only U.S. consumer of MIC thet is utilizing the substance for multiple end-products. This may render the task of reducing inventories relatively more complex than its U.S. competitors. It appears, however, that at least one other worldwide producer, Mitsubishi Kasei of Japan, is engaged in no storage, direct feed production for multiple end products. [ref. 12] Various options for shifting to a wholly continuous approach similar to that employed by other firms, may be possible at the Institute plant. For instance, 2 properly sized continuous reactor utilizing MIC fed directly from its continuous reactor might produce each pesticide sequentially and entirely eliminate the need for MIC storage. In contrast, beginning with inclusion of a continuous no storage, direct feed feed system for just one of the production systems at the site (Sevin, which is already made by a continuous process reaction}, could result in a 55% reduction in total MIC storage volume.Mar-11 No.2755 =P ‘An evaluation of the potential for conversion to a continuous no storage, direct feed system for one or all of the pesticide production units at RhOne-Pouleuc would necessarily involve examination of many factors: capital and operating costs; safety issues involved in operating several reactors simultaneously from one MIC source; the modernization and growth plans of the company for the overall facility; location of individual reactor units relative to the source of MIC; the need for sufficient capacity of the MIC production unit to meet the demands of all reactors simultaneously and other capital expenditures needed at the site, It should be noted that the Institute plant is actually in a somewhat favorable position to consider ‘conversion to a pastial or complete change to the no storage, direct feed approach. The MIC is in fact produced in a continuous process it Which the reactants, phosgene and methylamine are fed ‘continuously. However, once the MIC is produced it is collected and stored, What would be needed to sharply reduce storage of MIC would be further modification of the operatious so that “MIC is not stored after production but fed directly to pesticide reactors. Since both Sevin (carbaryl) ‘and Methomyl are currently manufactured by continuous processes, the direct feed of MIC from the production unit to each of these reactors by proportional pumps could eliminate the need for substantial MIC. storage for these pesticides -- probably reducing needed MIC storage by more than 70%, Adapting the other two product lines, Temik and Furadan, to this direct feed approach, however, would entail conversion of batch processes to continuous processes, which would likely also entail more substantial costs. .. Changing scheduli tion within the existing production configuration. In contrast to a complete no storage, direct feed system which might require a substantial new capital investment, some inventory reductions could be accomplished by scheduling changes. From its public and private comments, the company is apparently studying some changes of this kind Various scheduling options might be worth exploring. For example: + Staggering production of pesticides to lower daily MIC output and storage requirements. By scheduling production more evenly over the whole year, the company might avoid increasing production when demand is high, drawing instead upon finished pesticide inventory. This approach might require greater stockpiling of finished pesticide inventories. + Manufacturing a larger quantity of intermediate (e.g. methomy!) or finished pesticides, so that MIC production can be run at a constant, but readily consumeable volume. A higher product inventory could allow the plant to accommodate varying requirements of four different consumer systems, and startups, shutdowns and increased/decreased demands, + Scheduling MIC produetion to be more closely synchronized with anticipated pesticide production demand. This “just-in-time” production approach could be accomplished through careful risk analysis of supply/demand levels, given various production scenarios. Scheduling changes such as these could keep inventories of MIC at ot significantly below the 100,000 pound fevel, rather than swelling storage to higher levels. A successful lowering of MIC inventory would depend on either, stockpiling of more pesticide product (which may depend on market risk issues), or on reliability of production systems (for the just-in-time approach). 102009 2 No-276 Figure 2 P. 2b Simplified schematics of Rhéne-Poulenc and altemative closed loop production systems -Y WT | MIC eel SUIT production unit At RhGne-Poulene, MIC is stored in multiple tanks after it is produced, while it awaits consumption in pesticide production. MIC > Pesticide | production unit production unit At several other companies, MIC is consumed in pesticide production immediately after it is created, Little or no MIC storage occurs.Mar-11 2009) 2:97PM No-276 | Hierarchy of MIC Inventory | Reduction Options at Rhéne-Poulenc’s Institute Plant i with rough approximations of resuiting inventor ‘Current operating conditions. | Maximum Inventory of MIC on-site: 240,000 Ibs. [Scheduling changes such as inventorying more final product or scheduling pesticide production more unifomly throughout the year. Maximum inventory of MIC on-site: 135,000 Ibs. A [Convering Sev reacor to det fed rom MIC production unit (no storage of MIC for production of Sevin). Maximum inventory of MIC on-site: 75,000 Ibs. |Converting existing continuous processes (Sevin and Methomyi) o direct MIC feed. Maximum inventory of MIC on-site: 35,000 Ibs. } CUTE Le All reactor units except Temik are converted to direct feed of MIC with no storage. | Na ex inventory of MIC on-site: 10,000 Ibs, Converting al processes to 100% direct feed of MIC with no storage of MIC. Maximum inventory of MIC on-site: i 10 to 100 ths. | ‘The inventory level specifications listed above are not intended to be exact with cur- rent facility status. They simply represent relative opportnities for MIC storage r- action to show potential areas of preference.Mar-11 2009) 2:97PM No-2765 =P. 27 The company has stated that they plan on again reviewing their overall operetions and inventory requirements following one year’s experience with the changes that have been introduced, At that time, Janvary 1995, they plan on again considering further changesfref 15] c. Shifting to in-line quality testing. ‘The quality control “make” wank can store as much as 40,000 pounds of MIC. This tank is reportedly used for testing for water content, A rapid incline test for water content could allow elimination of the need to move MIC through this storage system. Material could then flow continuously either to production systems, or to the main storage system. A rapid in-line quality control test for water content eaists and could be considered for its applicability. d, Production changes: changing production chemistry or product outputs. ‘A complete analysis of options for improving the inherent safety of an MIC-utilizing facility could 20 beyond examination of MIC inventory reduction measures. Other forms of safety enhancement ‘that could render the facility inherently safer may deserve examination, e.g. alternate methods of making the same pesticide products that might utilize different reaction conditions or materials that ‘would reduce the potential severity of a worst case accident. fref. 10] In fact, prior to 1973 the Institute plant did not utilize MIC when producing Sevin. (ref. 9]. Jk should also be noted that there is the potential for decline in markets for some of the company’s products due to environmental concems. in 1990, Rhone-Poulenc announced a voluntary halt on the sale of Temik (aldicarb) for use on potatoes, because of concems about groundwater contamination (ref. 11} and in 1991 on bananas. Aldicarb is registered in 70 countries for use on numerous crops, ©, cotton, potatoes, coffe, citrus, and sugar beets, Further company, public or governmental initiatives to restrict Temik sales might mean lower MIC demand and storage at the site, It is not possibie to appraise the potential for more dramatic changes, such as changes in product chemistry or product types, without further cooperation from Rhone-Poulenc. Further chemistry review might indicate ways of producing the same or similar products without consumption of MIC, Similarly, the direction of fume production and growth plans for the Institute plant may influence the degree to which MIC inventories will rise or fall in the furure 6. CONCLUSION AND RECOMMENDATIONS: THE NEED FOR A MORE DETAILED INVENTORY REDUCTION ANALYSIS ‘The analysis set forth in this paper represents only a very preliminary review of the Rhéne-Poulenc facility's options for inventory reduction. Company officials have acknowledged that they have never conducted a complete analysis of the most far reaching inventory reduction options for MIC, the scope of which could only be superficially sketched by the hierarchy of options identified in this report, due to the company’s refusal to cooperate in-depth. In developing this study, the author lacked the detailed information and analyses which would likely have been available if the company 13Mar-11 No.2755 =P viewed this endeavor cooperatively. This information would include: + A more detailed set of flow and process diagrams needed to identify process flow demands; + Identification of factors that might limit Rhdne-Poulenc’s ability to switch to a no storage direct feed approach to consuming MIC; + Considerations regarding storing additional inventory of product or intermediates, instead of storing as much MIC; + Long term production, growth and modemization plans at the Institute plant that may affect the potential for inventory reduction. While R-P has published a four page "Risk Management Plan" regarding the Institute facility's MIC storage, that publication provides none of this information needed to aid in the appraisal of inventory reduction options sought by the community organizations. Recommendations R-P officials have stated that they intend to look at various measures for improving plant safety beginning in January 1995. We recommend that the following measures be taken at that time: + ‘The company should conduct an in-depth technical and economic analysis of inventory reduction options, beginning with the strongest options identified in this report, + The company should allow the author and representatives of the Good Neighbor Project and People Concemed About MIC to participate in the development and review of the MIC inventory reduction study, including facility review, open sharing of relevent documents and information, and appropriately focused dialogue. + The company should implement the MIC inventory reduction options that prove feasible. i4Mar-11 No-2765 =P. 29 REFERENCES SRI, International Chemical Economtcs Handbook. Monoisoeyanates, April 1991 2) Chemical and Engineering News, Nov. 9, 1992, p.9 3) "Methyl Tsocyanate: The Chemistry of ¢ Hazard,” Chemical and Engineering News, Feb. 11, 1985, p27. 4) Memorandum from Rhone-Poulene plant manager Tom Dalesio to Ken Ward, June 17, 1994. 5) Ken Ward Jr, ‘Chlorine Unloading Safer’, Charleston Gazerte. 6) Ken Ward Reduction, West Virginia Building Construction Trades, ‘Rhone-Poulese Can’t Promise MIC 7) Rhone-Poulenc, News Release, “Rhone-Poulene Announces Institute Modification Project For 1993", March 2, 1993 i 8) Ulmann’s Encyclopedia of Industrial Chemistry, St Edition, VCH, Verlegsgellschaft, Weinheim, Germany, 1989, Vol AS, *Carbamates and Cazbamoyl Chloside," p51 9) "Bhopal Report,” Chemical and Engineering News, February 11, 1985, p . 32 10)Nicholas A. Ashford and others, The Encouragement of Technological Change for Preventing Chemical Accidents: Moving Firms from Secondary Prevention and Mitigation to Primary Prevention (Cambridge, Mass.: Massachusetts Institute of Technology, 1993) 11) Extension Toxicology Network, "Fact Sheet on Aldicarb,” Revised September 1993. 12) "Union Carbide Fights for its Life," Business Week, December 24, 1984, p.52 13) Neal Sandler, “Israel grapples with hazardous waste," Chemical Engineering, April 29, 1985, p. 12, 14) "Gas leak touches a nerve in Europe," New York Times, December 7, 1984. 15) Meeting of Milton Lapkin and Sanford Lewis with Rhéne-Poulene officials Jean-Pierre Martinet, Vice President, Phil Curry, Environmental Director and Van Long, Institute Plant Manager to receive feedback on draft of this report, November 4, 1994, Washington, D.C. 16) Rhone-Poulene, Risk Management Plan for Phosgene, 1994. 15