Document 5DgQKq3EdrJYQrVyR5YQxj885

CONFIDENTIAL PPG INDUSTRIES Subject to Prrzcoti^e 0 iJVTJTDTT IT-3 14th Judicial District ^ CENTRAL ENGINEERING - RES 613.0 746 LAKE CHARLES - RES <31 1 *- r.Order .._ pro'tBCti ; roUtt Di/prl Hoi " CONFIDENTIAL THE RELIABILITY STUDY OF THE PROPOSED VDCM VENT TO NUMBER THREE INCINERATOR AT LAKE CHARLES November 12, 1979 J. W. Barton and D. T. Rigler Distribution J.R. Farst (Abstract Only) T.G. Brown/O.L. Cromeans T.G. Taylor/R.P. Lynch J.E. Fike/j.B. Atleman/R.A. Jacobs R.E. Baker/j.H.Morgan/R.E. Sanders G.K. Jordan/M. Juves/A.W. Sharp L. C. Joiner C. R. West Authors Key Words Reliability Study Vinylidene Chloride Monochloroacetylene Incineration Methane SL 012005 ABSTRACT CONFIDENTIAL! fSybpett tn protective Order or I4tn Oacuc.x^i district Court Mo. 91-1x45 TABLE OF CONTENTS Page 1 INTRODUCTION 2 DISCUSSION 2 RESULTS 4 TABLE I 5 CONCLUSION 6 APPENDIX 8 FIGURE 1 9 FIGURE 2 10 FIGURE 3 11 CALCULATIONS 12 SL 012006 ABSTRACT CONFIDENTIAL: Protective Order Subject to ,i,,i gj-oi-pict Court orf 14th Jucn `r..i - ! 1 i- A significant souce of organic discharge info the atmosphere in Plant B is the vent from the DH still condenser unit at VDCM. One component of this vent Is MCA (monochloroacetylene). This MCA is unstable and can become explosive if con centrated in the vent stream. There are two methods of treating the vent from the DH unit; one is to destroy the MCA in a reactor and the other is to mix methane with the vent and burn the total vent in an incinerator. The proposal is to mix methane with the vent and burn the resulting stream instead of operating a plant which had at best a 70% conversion rate of MCA. It was recommended that a reliability study be conducted on the proposed system to detect potential hazards. The major hazard considered was an explosive mixture in the vent line from the DH still condenser to the incinerator. The problems of polymerization and peroxide formation were considered, but were not thought to contribute to a hazardous condition. The release of hydrocarbon from the vent line was also considered, but the normal releases to the vent stack have not been considered. A fault tree for an explosive mixtur e In the vent is shown in Figures 1, 2 and 3. The results indicate that with a recommended proof test interval of six months, the potential for an explosive mixture.in the vent to the incinerator would be 4.25 x 10"^ occ/yr. A hydrocarbon release from the vent line due to a hole in the line, flange leaks, and valve leaks wxild be 0.7535 occ/yr. It is recommended that the vent line be steam traced from the DH vent condenser to the anti-back flow valve installation. The flow of methane into the vent should not be less than 75 percent of the combined vent flow. The vent low flow alarm should be set at a minimum of 50 percent of the methane addition flow. A method and procedure should be established to extinguish any fire that could possibly occur at the vent stack. Overall,the design and instrumentation of the vent line from the DH condenser to the #3 Incinerator is good. SL 012007 INTRODUCTION CONFIDENTIAL! to Protective Order 04. ijjaicioj District Court In the manufacture of Vinylidene Chloride Monomer, VDCM, a small amount of Monochloroacetylene, MCA, Is made. This chemical is both toxic and explosive in sufficient concentrations. It is removed from the product stream in the over head vapors from the DH still and then vented with other non-condensibles from the DH still condenser. Presently, this condenser vent stream is hydrochlorlnated in a reactor to destroy the MCA and most of the accompanying VDC is recovered. The MCA unit has been plagued with problems and consequently a lot of organic vapors have been vented to the atmosphere. Because more capitol is needed to make this unit reliable enough to meet environmental standards, an alternate solution for disposing of the DH still vent stream has been proposed. The alternate plan is to dilue the vent gases with methane, pipe the mixture to ^3 Incinerator, and burn them. DISCUSSION A study has been made to determine if there is any significant hazard involved in the proposed plan for incinerating the gases from the DH still condenser vent. Several possible problem areas were investigated. These boiled down to two general areas of concern: (1) An increase in the amount of MCA in the condenser vent gas, and (2) A large reduction or total loss of methane gas as a diluent. The operation of the DH still condenser would remain almost as it is now. To improve this operation, a tempering water pumping loop has been proposal. In hot weather, cooling tower water at 80F or above Is used to condense the vapors. When the cooling tower water temperature is less than 80F, too much VDC and MCA will condense, increasing the amount of MCA retained in the system and eventually leading to an increased amount of MCA vapor in equilibrium. The tempering water system would utilize only enough cold water to maintain the recirculating water at approximately 90 F. Increased system pressure would also cause increased condensation and eventual build up of MCA in the vent stream. Pressure control valves are installed to relieve excess pressure. MCA in the condensate (reflux) is monitored by the operator twice per shift. Samples are collected and analyzed with a gas chromatograph. The criteria for safe operation is that the typical concentration of MCA in the reflux be 1.5% by weight with a maximum guideline value of 2.5%. Critical concentrations of MCA in the vapor phase are 50% by volume for an explosion to occur in the absence of air and a VDC to MCA ratio of 1.5 to 1 by volume for an explosive mixture with air. It would require a concentration of approximately 5% MCA in the liquid phas reflux SL 012008 0 CONFIDENTIAL: Subject to Protective Order of 14th dudioioj L'i timet Court U'c. Hi-114 5 to produce a 50% by volume concentration of MCA in the vapor. Therefore, monitoring the MCA concentration is very important to the safe operation of the still condenser. Methane gas would be added to the vent stream near the still condenser vent line before the combined stream is piped some 2,000 feet to the incinerator. The methane is added as a diluent to prevent a dangerous increase in MCA concentration as VDC condensers In the long pipeline during cold weather. Actually, the theoretical dew point of MCA would be lowered to approximately 0F by adding enough methane to obtain an 85% by volume concentration of non-condensibles, methane and nitrogen. To insure that methane is being added in sufficient quantity, backup instrumentation would be installed which would (1) measure flow rates of methane and the total vent stream, (2) give alarms in case of low flow, and (3) shut down the vent line to the incinerator in case of further reduction or loss of methane. Upon shutdown, the vent gases would go to an existing scrubber stack until either the plant is shutdown or the flow problem is corrected. An incinerator shutdown would also divert the vent gases to the stack. A flame arrestor would be installed near the incinerator to prevent flame propagation back through the vent header and a small stream of nitrogen would be added to purge flammable gases from the header whenever the system is shut down. This study was made to determine the-frequency of occurrence of increases in MCA coming from the DH still condenser from various causes and of a loss of methane flow and subsequent failure of the back-up instrumentation. Also considered in this study was the frequency of hydrocarbon releases from any point other than from the scrubber stack, where the vent will be diverted each time there is a shutdown. Not considered as potential hazards are polymerization of VDC and peroxide formation in the vent line. A small amount of condensation of VDC will be expected and some polymerization of this liquid. The proposed design of the vent line includes provisions for unflanging the 3" steel pipeline at maximum 100 foot intervals and at each elbow so that polymer can be removed more systematically when necessary. Because this is a pressurized and enclosed system, no peroxide formation is expected. Although polymerization of VDC was not considered a hazard, it was necessary to confirm the dew point of the proposed gas mixture to ascertain that sufficient methane was present to prevent large scale condensation of VDC, which could create a hazardous mixture of the MCA. A computer program, LOADLIB, was used to confirm dew points. Air temperatures for Lake Charles as reported by the National Oceanic and Atmospheric Administration were available for determining minimum temperatures. 3- - SL 012009 CONFIDENTIAL: Subject'to Protective Order Oj jndr'.c ... n4 strict Court * For the purposes of this study, we assumed that concentrations of MCA being supplied to the DH still were a constant value, i.e. we only studied hazards created within the still condenser and beyond. Basic information for this study included: memos from R. A. Jacobs dated August 3, 1979 entitled "Process Design for Incineration of VDC Plant Vent"; ORC Minutes by R. E. Sanders dated August 9, 1979 entitled "Details of VDC Plant Incineration Proposal"; memo from R. A. Jacobs dated September 5, 1979 entitled "Results of MCA Plant Vent Analysis"; memo from L. Burden dated October 1, 1979 entitled "Status of Efforts to Lower MCA Plant Emissions"; the Triethane and VDCM operating manuals; PPG/Dravo drawings 2786-2, CPD-2786-2-700-SK-1, SK-2 and SK-3; discussions with operating personnel; discussions with process engineers and with Larry Joiner from the Central Engineering staff; and a fable containing recent MCA analyses made by operators over a one month period of time. Failure rate data for equipment, instrumentation and human error were taken from ICI sources. Plant historical data were used for loss of methane flow and other events pertaining to this study. Fault trees were constructed to show the occurrence of high MCA concentration in the condenser vent gas; to show the potential failure rate for methane addition; and to show the failure of the total stream flow measurement and shutdown system. Calculations were made to show the effect of proof test intervals on the frequency of occurrence of the top events. Intervals of three months, six months, one year and for no testing were used. RESULTS Fault trees are shown on Figures 1, 2 and 3. Detailed calculations are given in the Appendix. Proof test intervals of three months, six months, one year and no proof test were used in the initial calculations. As shown on the fault trees, there are two main events which lead to a hazardous condition: (1) High MCA in the condenser vent, and (2) no or low methane flow in the vent line to the incinerator. These two events would occur independently of each other and would have to occur simultaneously to cause the potentially explosive hazard to exist. The hazard rate for the occurrence of two simultaneous events is calculated by the following equation: H = (^) (f2) (t1 + t2) Where fi and f2 are the hazard rates in occurrences per year for the two events and ti and t2 are the duration in years for those two events. SL 012010 4- - <:o* ..... sutoi* o ^ 1. to Dic'lJ-V J^lClqi-^145 t-io. yi Co^1" TABLE I HAZARD RATES FOR SIMULTANEOUS OCCURRENCES Proof Test Inverval 3 months 6 months 1 year No test Hazard Rate - No or Low Methane .0060 occ/yr .0225 occ/yr .0713 occ/yr .3419 occ/yr Hazard Rate High MCA .2052 occ/yr .2301 occ/yr .2301 occ/yr .2301 occ/yr Combined Hazar Years Per Occurrence .00001 o/y 100,500 .00004 o/y 23,500 .00013 o/y 7,416 .00065 o/y 1,546 5- - SL 012011 COSFID^TIRL: Fr?Cp^^ict Court ^ i-}1 ^-J.,^:rict We estimated that the incidence of high MCA in the condenser vent could last for 24 hours and that methane flow could be shut off or reduced for 48 hours if all backup instrumentation failed. Results of the calculations using this equation for all four proof test intervals are shown in Table i. A six month proof test interval was chosen as the recommended Interval, This would yield a methane loss every 44 years which was deemed as an acceptable value. Because there is only one backup instrument loop on the existing vent system, the proof test interval doesn't change the hazard rate for a high MCA level very much. The occurrence of a high MCA level in the condenser vent doesn't necessarily lead to a hazard at that point. However, if the diluent gas flow is reduced or lost and the air temperature is low, more VDC would condense and further concentrate the MCA in the line to the incinerator, producing the hazardajs condition. It is very important that the MCA concentration in the condenser system be monitored to prevent problems within the existing equipment even though the hazard is low for the incinerator line itself. Another potential hazard which was quantified is the incidence of hydrocarbon releases to the atmosphere from the proposed vent line. Normal releases at the scrubber stock were not considered because this is planned. The frequency of leaks from the vent line was estimated to be 0.75 per year or once every 16 months. This number represents all leaks, the majority of which would be very small, such as at valve stems and flanges. Because the vent line would operate at low pressures, usually under 10 psi, the release rate Is expected to be incon sequential . Dew points of the vent stream with diluent methane were checked using the computer program LOADLIB. For a stream containing 75% by volume non-condensibles, the dew point was 0F. For a stream containing 50% non-condensibles, the dew point was approximately 42F. The "normal11 average temperature for Lake Charles is a minimum in January at 52 F. The lowest single reading was 12 F with a low daily average of 27 F. Because low temperatures have a very short duration in Lake Charles, it is felt that condensation on these rare occurrences will be minimal. We therefore recommend an alarm point for the methane system when the flow reaches the level which would give a 50% by volume concentration of non condensibles. CONCLUSIONS The design and instrumentation for the DH still vent condenser line to the incinerator is good. The major hazard that could occur in this vent line is that it could possibly 6- - SL 012012 CO^IBB^TIAL: . active Order /-\ -f- lA^h JutdoicFiat5l,t^D^isrtircictt Court deflagrate due to a high concentration of MCA. To minimize the possibility of a high concentration of MCA, the vent is enriched with methane which is then routed to the ^3 Incinerator. With the present design and the controls, alarms and shutdown system being proof tested every s^x months, the probability of forming an explosive mixture of MCA is 4.26 x 10 occurrence/year. This converts to 23,474 years/occurrence. In the original design, there were to be knockout pots installed in the system. It was decided to eliminate the knockout pots but to leave a short stub that may be tied into later. It is our recommendation that the proposed stubs be eliminated also. The probability of VDCM polymerization and the formation of peroxides was considered and it was decided that these would be operational problems and not lead to a hazardous condition. The release of MCA, considered explosive and toxic, from the system was also considered. The type release considered was a release from the pipe itself, the pipe flanges or the valves in the system. The probability of this type release is 0.7535 occurrence/year or 1 .327 years/occurrence. The normal releases to the scrubber stack vent were not considered. A point to consider would be a procedure or technique to extinguish a fire that could possibly occur at the vent stack. To minimize any problem with condensate in the vent line from the DH Still vent condenser to the anti-backflow valve installation, the vent line should be insulated and steam traced. The flow of methane into the vent system should not be set lower than 75% of the combined flow of methane and vapors to the incinerator. The vent low flow alarm should be set at a minimum of 50% of the methane addition flow Into the system. AuthorDote: ))-/4-79 Author: v --'Date: -7 - SL 012013 CONFIDENTIAL? Subject to Protective Order ef 14th Judicial District Court No. 91-1145 Si. 12014 VDCM VENT T0 WttHeKATofi FIGURE 1 S,riCEJ I rf 3 CO o N> O cn ___ l i 2.0652 McA in Hfruit WUt/iser 0.2302 H t & i) fv.u S' OfTVA rflrf fitiK > l M c ON OFfj ? VBfJ 7 to oerFf i m&f/ .2302 /V> At/0 cower V- r*rF-1 *835 cf> wc J* O* (+1-1- 3* CD a C( (+ oo 0.2302 j..v HlG-H MCA A>---- IN CONDENSf/ft--| ^ lVErJrtl = 1/305 r r_ .0225 __ NO a H > (v ME1 DANE R0K/ - IN VFNI J-IWE t2 = 2/365 i `-j -5 ^fl yCl -< Fj !lj 4.26 x 10 POTFOTIAiL/ 0 C3 +J 1.3 H X f7 A; l KF ! (t > f ;-* tr1 MIKT-O/tE ; <3 * -- CD IT = ^2^1^ >+'). 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