Document NERamwRLMme5b4qo5LgKkVdb

^-'(S $ * t V$- -,t ' -H - C'%y` ' tn * -v. 1 VCM PROCESS ANALYSIS Process' Safety , - 1 4-^ , There'are'three major hazards in the VCM area: - ,`v a. <' ' * *W* . - a* JK * i 4j-< - Cr.J1'* \' ',*i \ e,`?w^rv,CJ^Jr -- > - < 4 < \ N. * . ;, t i'.-.^AcetVlene'l'-" design,and operation''of the acetylene handling : \ - ! *'.rVV i !j 'v' ..r-V"^ * 1 - "r'" : facilities'-'in*'the .VCM area are' conservative" to assure minimum. , . . v V; ''ll-' ' detonation hazard.-^Research. plans to Investigate the deflagration 1 X . - - ' characteristics of the mixed HCl-acetylene stream. It is cer tainly safer than pure acetylene, hut just how much more is un known. Present operation is conservative. : 7- * *i / Chlorine facilities - no good way apparently exists to combat a major chlorine spill. - Engineering has suggested a number of ways' to"minimize this hazard (L. B. Bullock to Operating Committee, Study of Hazards of'Chlorine Handling Facilities - Interim Report, 6/5/61).' Research'Intends to investigate better ways to fight a spill than the present best method (soda lime).' J* ) Mercury hazard - Technical Service and Research have as a continuing problem the job of preventing toxic pollution due to the use of mercuric chloride catalyst. Process Weaknesses Raw Materials ijJ-H Acetylene and ethylene are both upgraded raw materials. We are _ basio -in np-etylene--ami ivlll~he~Dasic in ethylene when~the' - Chocolate.J3aybu project is completed. We have good Sales con tracts. on--chlorine..---Thls--makes- us competitive--with uLlier major producers but-doesn't give us any unique position in raw CBY 1023428 RSV0031355 .tive chlbrinaition of a full^^ized reactor -"teerchiiTitopgl-cal ,,f3^xlblalty should es-twoTKydro carbon^' change e. g. If the lene JrroBL Chocc^Latj Bayou should become brtee~tc~Monsanto/ than, the' use pf incrSmental acetyepartfflgfirTg^ 2. Catalyst Usage /" Catalyst life has never been satisfactory. Pilot Plant work 'r"A indicated a catalyst yield of about^475' lbs. VCM/lb. catalyst. . -r j -- Plant yield wag about 240 lbs. VCM/lb* catalyst before the use > . - v- W- of series reactors and about 550 lbs. yCT^lb. catalyst after. 'V: The'primary reason for this low life is thought to be the impurities present in' our Sachsse acetylene. Sleediaon reports '' a-catalyst yield, of 715 lbs. VCJ^/lb. catalyst using carbide-based acetylene. We feel 1,000 lbs. Vd^/lb. catalyst is attainable using pure acetylene with our superior cerous chloride-containing catalyst. Technical Service has a continuing program to improve catalyst yield through testing in( the plant and in their smal^L test reac- , - ^ ^ ^ ,____ -H tors. Research has oa-^%heir agenda" a'^i'eview-o'f-tJa^L&a-talygt /!,, 0- :-S_//-A f, prpi~l pm in--nrripr---tf>--def-tne rooeanch-_work needed. CBY 1023429 RSV0031356 V Product Quality -5- The reactivity of Monsanto VCM, as measured by dilatometer polyrate, is the highest in the industry. There has been a great improvement in our VCM quality since the last area analysis was made in 1959. Main factors leading to this improvement were* Use of series reactor which allowed longer catalyst life while maintaining acetylene impurities in the reactor effluent at low levels. The new VCM fractionator, 22D14, which has resulted in virtual elimination of heavy-ends from our VCM. Chlorination of crude reaction VCM which has allowed reduction of butadiene and butene content to less than the 1 ppm level. All competitors are marketing extremely pure VCM. Our VCM compares well except for unusually "large" amounts of the saturated C4 hydro carbons. n-Butane normally is running at 20-50 ppm and isobutane at 10-50 ppm. Springfield feels that the butanes are chain transfer agents and desire a reduction. Additionally, VCM purchasers are extremely critical on quality. We feel that sensitive chromatography will become a sales tool, and on a chromatogram our butane peaks stick out like sore thumbs. Escambia has already questioned us about trace impurities in our VCM. Technical Service is now trying to locate the source of the butanes in our process in order to determine the cost of removing them. CBY 1023430 RSV0031357 ^We are.presently fighting an acidity problem which does not allow ^operation of-vthe plant as in the' expansion (''Split System !* *`r S ` "'k. _ - ** 'r "r {'"* ^ _______J_ >1 \ J_<_ 1' ^*u-i_____J_ j_______________x*__________j 1 J-J______. * j ____________________x. j _ ^ n _ -i l_ j_____ solution predicted for'-Julyror August `V` ' In summary, our VCM. is/as'far as we can tell, over 99*99# pure, -;'i y I I f ' with further improvement necessary before we can make the claim "as good or better than any VCM available'*. - V -C ompet-ition` jqi competition use the same processes for VCM that we use. Dow .. :* i .* .V '> /'t'C5'* lias oxidative chlorination know-how but we- do not know whether they 1 -* * * <_/. * are using it for EDO manufacture. A listing of VCM producers is given below: 'r Producer Allied Chemical Moundsvllle, V. Va. American Chemical Watson, Calif* Cumberland Chemical Calvert City, Ky. Diamond Alkali Houston, Tex. Dow Chemical__ Freeport, Tex r*" PI a c quemin e, La Capacity (MM lb.) .. . Raw Material 100 - Acetylene J 25 Ethylene 50 Acetylene 50 Acetylene 4_ uu - l6o A CBY 1023431 RSV0031358 Ethyl Corporation Baton Rouge, La. Houston, Tex. General Tire Ashtabula, Ohio B. F. Goodrich Calvert City, Ky. Louisville, Ky. Niagara Falls, N. Y. Goodyear Tire Niagara Falls, N. Y. Monsanto Chemical Texas City, Tex. Union Carbide Texas City, Tex. S. Charleston, W. Va. U. S. Rubber Painesvilie, Ohio 150 Ethylene 50 tt 200 30 Acetylene 100 Combined 100 Acetylene 4o Acetylene 50 Acetylene 150 Combined 100 Combined 150 Combined 250 60 Acetylene 1365 Dow's capacity at Placquemine Is expected to be 100 MM lbs./year in 1962. Plans for three other large plants have been announced. Monochem (U. S. Rubber - Borden) Is scheduled for 150 MM lbs. per year at Geismar, La. by 1962; U. S. Rubber's plant at Painesville, Ohio would presumably be shut down. Tenneco (Tennessee Gas) has recently announced plans for a 200 MM lbs. per year VCM plant in Houston. Diamond plans to have a 90 MM lbs. per year expansion on stream in Houston in January 1962. The impact of the drastic 19601961 VCM price drop^on these projects is unknown. CBY 1023*32 RSV0031359 1 6- - Monsanto,'Diamond, and Carbide (Texas City) now use hydrocarbon acetylene with, its associated impurity problems. Diamond, Tenneco, and Monochem all plan integrated plants using acetylene produced by" partial combustion.of methane. Alternate Processes A/" Monsanto has technology ml making VCM by cracking of EDC^by reac tion of acetylene and HC1 and by oxidative chlorination of ethylene (to EDC). Exploratory work has been done by Research on^oxidative chlorination and high temperature chlorination of ethane. The former gives ethyl chloride as product. .The high,temperature chlorination (so-called sudden chlorination) of ethane can be modi fied to give a wide variety ofproducts preferentially, including vinyl chloride, vinylidene chloride' and 1,1-dichloroethane. Sudden chlorination is new technology using a raw material which has not been upgraded; the technique suffers in that large quantities of HC1 (3 mols HCl/mol VCM) are made as by-product. Economics'are attractive only if HC1 can be moved at a chlorine value. '' - Areas for Improvement of Present Process CBY 1023433 l 1. Increased catalyst life and decreased catalyst cost. Purified acetylene Is the major improvement foreseeable here. - /, r, r / X 7 - t-u 1 t-M/a/. / z. .2 Elimination of equipment or process steps. Examples are elimination of the caustic washing and azeotropic drying step in EDC manufacture, or decreased number of crackers in opera ction If 3" cracker tubes are satisfactory. VLovO r Ai I/ t- L C f ,V ~C' -Jc 7 RSV0031360 "t v;' UA '1 1y ' -7- 3 Better plant control By instrumentation. Installation of . > ''* - 1 v. - . r'r f Jv igt ` *' "V, 7^AsW?.- ; /it: * chromatographs on the cracker absorber (22D5) overhead, on reactor effluent and on product column (22Dl4)`overhead are .^ examples' of.`such installations accomplished or planned. Wish' . . ** \ A* '"'fe i,_ . v i' Jfy Preparation of a mathematical model of the VCM plant for s optimizing yield and utility costs. This Includes work required to develop information to prepare such a model. Reduction of losses is a part of yield improvement. C. **4 Ch. SptJli PDM/jS 7/13/61 CBY 1023434 RSV0031361