Document Lp8Lnk0Odr7rLqKVM2rpZnb35

Still growing fast... 0 Chlorinated Hydrocarbons Ally] chloride, new high polymers, and vinyl chlo ride point to increasing de idee 7M0 mand for these versatile petrochemicals. New tech nology and production TOTAL PRODUCTION methods indicate most new plants will be based on pe troleum derived methane, ethylene, and acetylene R. K. Tralchlar, Th* Dow Chemical Company Freeport, Texas MB MO VINYL CHLQRIOC . ETHYL CHLORIDE- J_____ 1 TRICHLOROETHYLENE CARBON TETRACHLORIDE Ii PERCHIOROCTHYLENC A BRIGHT FUTURE U pre dicted for the chlorinated hydrocar bon industry. Certainly some of the products wilt eventually fall by the wayside; others will have their pro duction rates level off. Products which still have tremendous growth prospects are: (!) ally! chloride (expanding because of epoxy resin demand and the emphaii.s being placed on glycerine based polyure thane, and polyester resins; (2) the high polymer* of fluorocarbons which are baaed on chlorinated hydro carbons and (3) vinyl chloride which is just catching on in this country for structural and building materials. A 1970 production of approxi mately 4.5 billion pounds per year of chlorinated hydrocarbons, or an increase of 1.3 billion pounds per year over the production in I960, can be anticipated (Figure 1). At least 600 million pounds of this in creased capacity will come from Gulf Coast installations. PRODUCTION METHODS When studying chlorinated hydro carbon production methods and the 71 ------------- //II------ Ml 11 tnmiii urn nu ILiilLIiL lUUiUl ILLULUi ! II111111. .1111,11.111, was 1940 *43 1990 1939 1900 FIGURE 1 Here's bow the various compounds 6t into the overall picture. Notice that oaly ethyl chloride shows a definite down tread. March 19<}1--PmoLStnt Refiner --' 155 i AP00034165 Chlorinated Hydrocarbon! ... i rl r r. new and cheaper raw materials available, one point should be kept m mind; commercial ethylene from nat ural gas was not available in any quantity until the late 1930s and early 1940s add cheap acetylene from natural gas is still in the development stages. The data reported here include the various chlorinated hydrocarbons from coke, the sugar industry, calcium carbide, as well as the chlorinated hydrocarbons from the petrochemical sources. The ethylene and propylene glycol families have not been considered here, though the chlorohydrin process is still a major source of glycol production. Carbon tetrachloride, when introduced in the early 1900s, was made by reacting carbon bisulfide with chlo rine, Today the majority of the*United States' produc tion is made by chlorination of methane, or as a co-product with perchloroethylene in a thermal chlori nation process with hydrocarbon feed. Chloroform, first produced by the reaction of bleach ing powder and acetone or by the reduction of carbon tetrachloride with hydrogen and iron, is made today either by the chlorination of methane or the chlorina tion of methyl chloride, previously derived from meth anol. Methyl and methylene chloride are still produced today from methanol, but the major production is by methane chlorination. MAJOR PRODUCTS tlhyi Chloride. The original production (Figure 2) was based on ethyl alcohol. When ethylene from the natural gas became available, new facilities were con structed to use this new raw material. Notice alcohtf'^-k use continues today but only where justified by lockh^ conditions. Production data in this article it from U.S. Tariff Commission reports. Porchloroethylene (Figure 3) originally was produced by the chlorination of acetylene-derived trichloroethane to pcnta chlorethane and subsequent dehydrochlorina tion with lime to perchloroethylene. Now it is produced primarily fay the thermal chlorination of hydrocarbon . feeds such as methane, ethylene dichtoride, propylene, etc. Vinyl Chloride, based on ethylene raw material was introduced in the late 1940s (Figure 4), but in contrast with the two previous products, the production from both raw materials is still growing. Trichloroethylene, is the only commercial chlorinatedhydrocarbon which remains tied to acetylene for the major part of its production. Acetylene is the same basic product and raw material from which it was produced originally. Figure 3 points out the impact of imports on this product, not a change in manufacturing techniques. Notice that during the last several years imports have had a drastic effect on the growth of production in the United States. PLANT LOCATIONS Production centers for these products have changed"*' with the advances in process knowledge and new raw materials. Figure 6 shows what has happened since 1940. r. i i i r \ f r il l I 1 i 156 Petroleum Refiner--Pol. 40, bfo, 3 | AP00034166 Chlorinated Hydrocarbon!... i a > FIGURE 6--Here ere the locations el (Ueriuted hydrocarbon plants io the United States. In 1940. these plants were hi operation! 1.Ansual--Marinette, Wise. , 2. Brown--Berlin, N. H. 3. Diamond Alkali--Paincsville. Ohio 4. Dow Chemical--Midland, Mich. 5. Dow Chemical--Pittsburg, Calif. 6. Du Pont--Deep Water, N. J. 7. Du Pont--Niagara Falls, N.Y. 8. Du Pont--Wyandotte, Midi. 9. Ethyl Corporation--Baton Rouge, La. 10. Food Machinery--South Charleston, W. Va. 11. General Electric--Waterford, N*. Y. 12. Goodrich--Calvert City, Ky. 13. Goodrich--Niagara Falls, N. Y. 14. Hercules Powder--Hopewell, Va. v 15. Hooker--Niagara Falls, N. Y. 16. Stauffer--Niagara Falls, N. Y. . 17. Union Carbide--South Charleston, W. Va. 18. Wyandotte--Wyandotte, Mich. . In 1950 the following plants had come into operation! O 19. Dow Chemical--Freeport, Texas 20. Dow Coming--Midland, Mich. 21. Goodrich--Louisville, Ky. 22. Hooker*wTacoma, Wash. 23. Jefferson Chemical--Port NechesrTexas---r-:"TT7T 24. Monsanto--Texas City, Texas 25. Shell Chemical--Houston, Texas 26. US. Rubber--Painesville, Ohio 27. Union Carbide--Texas City, Texas In 1960 these plants were added to the list: A 28. Allied Chemical--Moundsville, W. Va. 29. American Chemical--Watson, Calif. 30. Columbia Southern--Barberton, Ohio 31. Diamond Alkali--Bell, W. Va. 32. Diamond Alkali--Deer Park, Texas 33. Dow Chemical--Plaquemine, La. 34. Dctrex--Aitabula, Ohio 35. Ethyl Corporation--Houston, Texas 36. Frontier Chemical--Wichita, Kan. 37. General Tire and Rubber--Astabula, Ohio 38. Kolker Chemical--Newark, N. J. 39. National Petrochemical--Tuscola, III. 40. Stauffer--Louisville, Ky. By 1961, these plants were planned or soon to become operational t 41. Columbia Southern--Lake Charles, La. 42. Monochem--Geismar, La. 43. Olin Mathieson--Doe Run, Ky. 44. Diamond Alkali--Houston, Texas (* IV ii t o ir. it r (-! 158 Petroleum Refiner--Vol. 40, No. 3 fi ( AP00034167 M FIGURE 4--Notice the competition' between acteyleae and FIGURE 3--TrichfcroethrSene remain! tied to acetylene for ethylene for vinyl chloride production with both growing the major put of its prooaetkm. However, notice me effect rapidly. of imports on U3. production. By 1940 the total United States capacity for the pro. duction of chlorinated hydrocarbons was made up of 18 major plant sites in 13 cities. Of these only the Ethyl Corporation in Baton Rouge was located on the Gulf Coast. One production location, Pittsburg, Calif., was the only plant then producing chlorinated hydrocarbons from natural gas based raw material. All other produc tion was based on alcohols, calcium carbide based acety lene, carbon disulfide, and the' like. By 1950 the total number of plant sites increased to 27 in 19 cities, with the major growth on the Gulf Coast. Of the new plants, Dow at -Freeport, Jefferson Chem ical at Port Neches, Monsanto at Texas City, and Shell Chemical in Houston were using natural gas base* for these new products. Also Elhyl Corporation's Baton Rouge plant and Dow at Midland were *witching part of their production to natural gas base. The Gulf Coast attracted these new plants because of abundant fuel, plentiful LPG feedstock, numerous salt domes, and the availability of water transportation. By i960 the number of plant sites increased to 40 in 29 cities. This growth resulted for three major reasons, 1. The use of methane as raw materials in the Ohio River area. 2. The expansion of vinyl chloride capacity in the Ohio River area by installing thermal cracking facilities to dehydrochlorinate ethylene dichloride to vinyl chlo ride and anhydrous hydrochloric acid. This will balance the hydrochloric acid needs on existing acetylene facil ities for the production of vinyl chloride. 3. The installation of acetylene-HCl facilities for the production of vinyl chloride in localities where existing plants were modernizing their facilities for the produc tion of trichloroethylene, making anhydrous hydrochloric add a by-product rather than essentially throwing the hydrochloric acid away by cracking the tetr&chloroethanes with lime. Notable examples of this are General Tire and Rub ber Company's Ashtabula, Ohio plant, which gets its anhydrous hydrochloric acid from Detrex's trichloro ethylene facilities in Ashtabula, Ohio; and Goodrich's Louisville (Kentucky) plant, which installed thennal cracking facilities to balance the older acetylene-HCl facilities for the production of vinyl chloride. Today there are some 44 major plant locations in the United States in 31 dries, producing chlorinated hydro carbons. In 1960 these installations produced approxi mately 3,250,000,000 pounds of chlorinated hydrocar bons. PRODUCTION CAPACITY Figure 7 shows United States production capacity. The top line shows the summation of the published caparities for the productionof chlorinatedhydrocarbons and includes some plantcapacityin stand-by condition only. It includes other plants that probably never will be run at design capacity again, because cheaper raw materials are available to produce the product more economically. The second curve in Figure 7 shows actual production of chlorinated hydrocarbons over the same period as the top curve. The lower two curves show the pro- March 1961--Petroleum Refiner > ` ; { *- t'' ; *' AP00034168 -4 (<C/t(or(naMd /lydrocarfeorw should continue to grow despite annual predictions that production of individual products will drop off due to market saturation because new uses continue to appear which Q more than compensate for losses due to outdated uses" 4! -* .4 duction capacity of the Gulf Coast vs. time and the production capacity of the United States less the Gulf Coast production vs. time. The 1970 point of all these curves are dotted show ing1 what could happen in the way of annual plant . capacity in 1970 and showing what has already been announced in the way of increased capacities "for 1970. The lower dotted lines indude Columbia. Southern's 100 million-pound-per-year ethylene dichloride plant in the Lake Charles, Louisiana area; it includes Monochem's, a company jointly owned by U.S. Rubber and Borden, announced plans for a 150 million-pound-peryear vinyl chloride installation to be located in the Gulf Coast area; it includes Olin Mathieson's new glycerine plant at Doe Run, Ky. Another expansion announced last summer is Diamond Alkali's multi-million-dollar ex pansion in Deer Park, Texas, to manufacture the acety lene requirements from natural gas and increase their vinyl chloride from 50 to 75 million pounds per year. Figure 1 shows total chlorinated hydrocarbon produc tion and individual compounds. The uses for these in dividual products have varied over the yean by a very |wide range. Some products, such as carbon tetrachloride and chloroform, whose major uses today are raw ma terials for the production of fluorinated compounds, were introduced originally as cleaning fluids, dry clean er*, pharmaceuticals, etc. Other products, such as ethyl chloride, have a questionable future, became of the ad vent of tetramethyllead as antiknock fluid in gasolines and because technology has introduced a new method '* using organic-aluminums as a 'new route to the much- used lead compound. In this process chlorinated hydro carbons are used, but only as intermediates, and only small fractions are required as compared to the old method of using the ethyl chloride as the ethyl radical in tetraethyllead. Despite annual predictions that production of these individual products will drop off, because of market saturation, and so forth, notice that ethyl chloride is the only one of these products through 1939 which ' .shows a definite downtrend. It is very evident that the curve for the older products has a flatter slope than the curve of those products introduced in the 1930s and 1940s. To date, however, new uses for each of these chlorinated hydrocarbon products appear requiring a higher production rate than the lots in production rate ef euuM \m. Ailtrauft Wwitf War ti ee> curred during the period shown in Figure 1, and alio the Korean conflict when special tax concessions were FIGURE 7--Shows a summation of production capacities for chlorinated hydrocarbons including some plants in standby condition and others sot operating at design capacity. This Is reflected by the actual production curve. Notice also the rapid growth of Gulf Coast production. Dotted lines show prodlcnoa of growth trends. R. K. Treichler is section superintendent in the Texas Division of The Dow Chem ical Company, Freeport, Texas. He began with Dow as a research and development engineer in the Or ganic Research Department in 1946 after his release from the U.S. hi * Navy. In 1948 Mr. Treichler trims- ft ferred into a chlorinated hydro- f^Y. carbon production unit and was later promoted to operating super intendent. Mr. Treichler received a B. in chemieal engineering from Rice University In 1944. Treichler issued for the manufacture of these products, neither of these events is obvious in the production patterns of chlorinated hydrocarbon*. Originally presented before the AIChE, New Orleans, February, 1961. ## March 1961--Petroleum Refiner 159 1, AP00034169