Document zz9m6KkwD79e5q51ryoaBVdGg

r jrikcA j ISSaaiJiaUifilejiV i Monsanto's Taxes city vinyl plant Is plonaarlng commercial applications of oxychlorination. OXYCHLORINATION Donald P. Burke and Ryle MUler What this country needs is i good 5*-'lb. vinyl chloride ntonomcr, And that is exactly what it can get from nxyohlorioatioD declare some ardent boosters oi the process. Others say axychlO' nn&tion is simply tool that gives more flexi bitity to some operations. Wherever the trutl lies--and it's probably somewhere between tb< two extremes--oxychlorination is generatinj more interest among chemical processors than anything since the development of stereopolymerizatfcm. The reason for ihe interest in cheaper vinyl chloride is straightforward. Ii costs 3c- lb. to coavert the monomer into polyvinyl chloride. With the monomer selling for 5^/lb.. it means the polymer could sell for 8</lb. And at that price, it would he able to compete handily with a number of conventional structural materials on a straight cost-strength basis. If it should prove capable of competing with metals, brick, glass, or wood, it could capture a significant share of the building market. And il would quickly zoom ioto the No. 1 spot among plastics. Oxychtorinatinn is anything hut a new August 22. 1954 CHEMICAL WEEK 93 AP000341 TECHNOLOGY idea, of course. In concept, in fact, it'a simply a variation on the ancient Deacon, theme of making chlorine by the oxidation of hydrogen chloride. Actually, some of the current interest in making vinyl chloride centers on use of Deacon process improvements to generate chlorine in' a separate unit. The term, oxychlorinatioo, bow* ever, more properly describes an in stiu Deacon process. In single re actor, hydrogen chloride is oxidized to chlorine, which reacts with an or* game compound to form a chlorinat ed derivative. Even that is not new; it's Ibe basis for the classic Raschig phenol process. What is new is its application to ali- phatics, and particularly to ethylene. The immediate focus is on making eihyleoe dichloride (EDO) for vinyl chloride production. But the longrange ramifications extend into the whole field of chlorinated solvents. Take trichloroethylene, (or instance; 90% of U.S. capacity is acetylene* based. Successful oxychlorination processes could mean that future ca pacity would be based on ethylenederived EDC. Who's Doing It: Four firms io this country now are using oxychlorisation commercially (for products other than phenol). Three of them are oxychlorinating ethylene to make EDC, while the fourth--Du Pont--is oxychlorinating methane at Orange, Tex., to make chlorinated hydrocarbons. Dow is employing oxychlorination to make EDC at Freeport, Tex., and Pltqucmiae, La.; Monsanto, at Texas City; and Goodrich Chemicals at its new plant at Calvert City, Ky. Far and away the biggest oxychlorination project yet revealed is the French Solvay 3 30-million-lbs./year vinyl chloride venture (CW Technology Newsletter, June 13). Using know how purchased from Ethyl Corp., this company will put up Ibe worid'a larg est vinyl chloride plant It will em ploy oxychlorination for its entire production of intermediate EDC. Indications are, moreover, that the project may turn out to be even bigger. The 330 million lba./year, it is felt, may represent only French Solvay's share of a plant In which others are participating. Total capacity might hit 500 millions lb*./year. A number of other oxychlorination ventures are close to commercializa tion or in advanced stages of develop- 'ment. (1) Pittsburgh Plate Glass has done a lot of work on oxychlorination. It is not saying much right now and, despite widely circulated reports to the contrary, it's a safe assumption that the company is not yet oxychlorinating on a commercial scale. This is prohably only moments away, however. (2) Frontier Chemical also has done n^ueh solid development work on oxychlorination, and has been talking to contractors about know how arrangements. Any manufactur ing project, however, would probably take the form of a joint venture. (3) Hooker has carried a process through the pilot plant. Oxychlorina tion is bound to be a serious con tender for its new chlorinated hydro carbon veniure in Louisiana. (4) Stauffer is believed to have an oxychlorination process in an ad vanced stage but will not discuss the subject. (5) Allied, which makes vinyl chlor ide from its own HCI and purchased acetylene (from Carbide), may have an oxychlorination trick up its sleeve for Geismar, La. Like Stauffer, it will not talk. Engineering firms are active in the field. Lumraus is offering modified Deacon as well as oxychlorination processes. Scientific Design can be expected to have an announcement soon. Pullman, in its annual report said that subsidiary M. W. Kellogg in conjunction with a major (un named) oil company is investigating improved vinyl processing. It's a safe bet that this means oxychlorination. (Continental Oil, when asked if it were Kellogg's partner, had no com ment.) Technical Enterprises, which has rights to Air Reduction's modified Deacon process (CIK, July 6, '57, p. 74) is offering that method as well as oxychlorination. It says, however, that while it is prepared to offer a complete Deacon package, a firm in terested In oxychlorination would have to do tome development work of its own. Fluor Corp. has talked to at least one firm with know-how for sale. Chemical consultants, too, are hip deep in oxychlorination projects. If you toss a stone at a group of con sultants, the odds are good that you'll hit a man involved in an oxychlorina- tion study. Market Impact: At the Chemical Market Research Assn, meeting in New York last spring, Dow investi gators gave a paper on uses of HO. A little-more-thaa-iacidental mention of oxychlorination generated a lot of heat aod a fair amount of light. In the question-and-answer session following the paper. Dow's J. M. Henske estimated that HCI now is being substituted for 455 tons day of chlorine. Most of this is being done by Monsanto, Dow and Goodrich, all of whom use the HCI to make EDC. It means that upward of 360 million lbs. of EDC are being made by oxychlorination. Monsanto's oxychlorina tion capacity is 30 million Ibs./year. Dow probably accounts for the larger share of the remainder--it's one way the company has quietly raised its EDC capacity to a whopping 800 mil lion lbs./ycar {table, p. 102). Substi tution of HQ for chlorine, incident ally. means that the market is being spared 500 lotu/day of caustic. Fourth Round In Japan: Through out the rest of the industrialized world, interest in oxychlorination is running high. Id Japan, for instance, oxy chlorination is getting serious consid eration as a key process in the coun try's next round of vinyl chloride expansion. The third round, just about completed, is expected to raise ca pacity to 615,000 tons/year. At the moment, however, production is run ning behind demand; the shortage for fiscal '64 is expected to be 77,000 tons. Industry is pressuring MITI (Minis try of International Trade and Indus try) to start considering a fourth round. MITI, however, will probably not reach a decision for another year at least. Meanwhile, Toyo Soda, which will complete a 61,000-tons/year vinyl plant this September, would like to pul in a 33,000-tons/year plant using its own oxychlorination process. Asahi Glass ig tied up with Pittsburgh Plate Glass in id oxychlorination venture. An Asahi spokesman, however, says it has not submitted a proposal to 94 CHEMICAL WEEK August 22, 1964 AP00034137 Estimated production cost* lor vinyl chloride /ib .) Vinyl costs: balanced oxychlorination vs. acetylene Aufutt 22, 1964 CHEMICAL WEEK 9S AP00034138 TECHNOLOGY * MITl for a plant. Similarly, Mitsu The ethylene-bated process, on the bishi Chemical is experimenting with other hand, calls for a higher capital oxychlorination but has no firm plans investment. It is a two-step process. 10 use it in'its Mizushima project now And O.SH lb. of HCl i< produced under construction. Toyo Koatsu has for each pound of vinyl. What the been researching oxyiihlorinatioti in ethylene process has that the acetylene tensively for some time. It plans a process lacks is low-cost starting ma petrochemical center in Sakai, near terials. Osaka, in cooperation with Mitsui In the past, several big vinyl chlor But chances of government approval ide producers operated "balanced" in the immediate future are not bright. vinyl plants. That is, both ethylene By the lime the project is approved, and acetylene are used in two opera oxychlorination is bound to play an tions. By-product HCl from the important role in production of vinyl cracking of EDC is fed to the second chloride monomer. Nissan Chemical plant, where it reacts with acetylene also has hopes for making vinyl chlo to make more vinyl. The percentage ride via oxychlorination. It would im of total vinyl chloride made from eth port technology from Continental Oil. ylene and acetylene differs from year COSTS ARE THE ATTRACTION to year but it has not varied much from 50-50. Some of the newer pro Oxychlorination's popularity hinges ducers (Monochem, Tenneco) favor on attractions of cheap ethylene, tcetylcpe.yBrnJJow has stuck to eth which would replace acetylene, as a ylene. `Monjamo and Carbide employ starting material. The availability of balanced production. And Goodrich, cheap by-product HC1 is another the No. 1 produoer, which has his important consideration and one that torically favored acetylene for its could bring more producers into the U.S. production, started buying EDC fold. Here's why: several years ago in a move toward The big oil and chemical com a balanced operation. (Last year, it panies that are getting into produc tion of linear alkylates for the new probably bought 55 million lbs. of EDC from Pittsburgh Plate Glass soft detergents appear to have settled for vinyl production.) In its new Cal on processes that will generate large quantities of HCL One approach is to vert City operations, Goodrich is em ploying oxychlorination in a new type chlorinate a paraffin, then dehydroebiorinate to form an olefin and two of balanced plant based entirely on ethylene. And Monsanto na~T>eeiP moles of HCL The other involves re using oxychlorination to supplement action of the chlorinated paraffin directly with benzene. In this case, its acctylcne-HCl production. Setting the Parameters] An exami the HCl is taken off in the alyklation nation of raw-ntaicrial requirements step. In either case, % lb. of HCl is reveals the reasons for the trend formed for each pound of linear away from acetylene as a vinyl chlor alkylate. Proposed capacity of 600 mil ide raw material. It takes 0.45 lb. lion lbs. of linear alkylate means a of acetylene and o.fei in. of HCl to potential_2Li^-ffi31ion ibs. oFflQl. make a pound of vinyl. If acetylene file cofttliuatkiu "of available HCi^- is charged in at 94/lb. (a low figure), cheap ethylene and oxychlorination know-how could well be enough to encourage new vinyl capacity. and HCl at 24 lb., it means that rawimaterial costs are 5,24/lb. To that Imust be added 0.9-14/lb. for other -- Till New--ffnlnnrr; charges* to give a manufacturing cost vinyl chloride has been made mainly in two ways: (1) Ethylene and chlo- of 6.24/lb. And that still does not include any administrative or selling rioe react to form EDC, which is cracked to vinyl chloride and HCl. charges, research and development costs or profits. Vinyl chloride is of* Or (2) acetylene. and HCl react to form vinyl chloridp directly. The sec ond process bas much to commend it. flcially quoted at 84/lb., freight equalized, out ns moving ter ss little -aa-6M Ulb. iCW Market Newsletter, It's a straightforward high-yield reac July 18). tion with no by-product problems. . *Tft s 100'million IhtYretr riant. TbeM.epsu Capital investment for a plant is mod urouid include charge* (or a<il`(>ei| depreciation, ieiarsncn. tie., that, when addt<i 10 raw-TBilcrial est and operating costs are smalt. Mt*. would prorice* * "faclory ' or "tM" coal fer makiflt yitiyr-ehtorid*. M CHEMICAL WEEK August 2Z 1964 On the other hand, an operation using ethylene to make vinyl chloride and employing" oxychlorination lo make more EDC would have a net requirement of 0.5 lb. of ethylene and 0.67 lb. of chlorine per pound of vinyi. uther costs would be slightly higher than in the ethylene process --1.3-1.44/lb.--but the difference be tween ethylene and acetylene could easily compensate for them. The subject 1s not one that lends itself to simple generalities. A study based on official quotes can easily go astray because of special cases, where products move below lists. Sometimes, the special cases far outnumber the normal. Here, however, are the price parameters for the four key mate rials: acetylene, ethylene, chlorine, and HCl: Acetylene: Companies buying acet ylene to make vinyl chloride are probably paying 9.5-L2.54/lb. In the past, the rock-bottom for acetylene prices bas been considered to be 8- 104/lb. However, captive producers, oper ating partial-oxidation plants, can probably charge acetylene into a process at a shade under 74/lb., pos sibly 6.84/lb. As a survival matter, merchants of carbide-hased acetylene could probably set a lower price on the output of amortized plants; 74/- lb, is conceivable. Ethylene: The current price of merchant cthvTCTT'n"~'^'~?*i'lf I'nttT is 4.754/Ib. with downward escala tion depending on volume. The aver age price to large users is probably / 4.25-4.504/lb. charge nM** Captive producer places on his ethyl-' ene depends on a number of factors: size and efficiency of-the plant, and importantly, the return he is talcing on the. ethylene unit. Some large us ers are undoubtedly charging ethylene n less Utah 44/ lb. In sumffrf the big new punts now contemplated or completed, ethylene could he charged ,at less than 3^/lb.ray 2.94/tb. This could, of course, exert a pressure on merebam prices, bringing (hern- well under 44/lb. Chlorine: OnoleA price for chlorine (gas) is $65/ ton. But a large user should have no trouble getting over- thc-fence fhlrr"* ,f Tf. possible thst, under favorable condi-\ tions,, this could fall to $48/ton,y hr AP00034139 As ,1 vinyl chloride raw material acetylene teems to show oft to best advantage when it is the product of a plant making ethylene and acetylene (as in (he Wuiff process). In this scheme, naphtha or other liQht hydrocarbons would be fed to the Wuiff furnace; vinyl would be produced In a balanced operation. Compare this with a vinyl plant based entirely on ethylene. Here, by-product HCI from the cracking of ethylene dichloride (EDO intermediate would be oxidired to chlorine and relumed to'help form more EDC. The figures (balow) for this comparison were prepared forCW in association with The Lummus Co., which offers the Wuiff process, various oxyehlorinallon processev-and Deacon modifications, A choice between ] oxychlonnation and a modified Deacon depends upon a num ber of variables. Alec ftedniss of Technical Enterprises (New York) thinks the Deacon Is slightly more expensive but gives more flexibility. On the other hand. Shell has come up with some techniques (e.g.. feeding a dilute HCI stream to the chlorination step) that are potential cost cutters. In any case, there does not seem to be a significant difference between the yields of oxychtorination and Deacon processes. And their utility requirements are not much different. The ranges (per pound of vinyl chloride): steam, l.B-3.3 lbs/, cooling water. 27-51 gal.; process water. 0-0.61 gal.; power, 0.19-0.21 kwh. fuel requirement* are 1,500 Btu./lb. for either approach. 5':Kh^econom rflfaw Material*-.4'''' j> :* i 1-. ' Naphtha ) . Eihvwne " | Chlo<nf! 1 } ' CetAiyJts end * ! . chemicals i ( Caustic sod-i * ! ' Phenm ''bs. lbs bv -l1illJ-. I1 ,, h.. ..*+y l . J i.o 4b 30 ' _ ibs. 3.3 lbs. 10 0 Utilities 5feam Cooling water Process water ' J -P0WM Fuel j Labor lbs. O Oft qal. ooo? gal. 0.015 kwh. 06 l.QOO Stu 0 01b 1 ^ men shift J32.000 year Mhre< shifts) fixed Charges Deyi-rriAt..-..; -tC-r t;.. --.di.Mftnaiv 'O ir i Wolff fc. ` .. -*" Ethylene Complex Complex (modified Deacon) Units Needed Cost per pound of vinyl . Units Needed Cost per pound of vinyl ! 1 1.05 1 . ' 0.625 ^r "1.05* 1.S8 * 0.6 . 0.67 ' 2.25*2.oo i 11 \ ; ; 1 0.001 0.0005 0.14 0.003 0.005 0.0036 0.001 0.07 0:258 0.01 ; . 5.25 . 26.1 0.325 0.324 -4,350* , 7 i li 0.315 0.092 0.005 0.195 --0.065* 0.15 1.175 j 3.29 47.52 0.18 l 0.191,500 6 l* 0.197 0.095 0.003 r 0.114 0.023 . 0.128 . ' , | ,] 0.588 u j 4.905* 5.504* 1 Basis; 150 million Ibs.ryear of vinyl chloride. / 'V Capita): S4-A 9 million ior etnyiene complex using modified Deacon/S8 million for complex making-vinyl.bv a balanced operation using ethylene and acetylene from a Wultt process plant. anOIncludmg the cost of the-Wuiff plant,'.Credit. The Wuiff project for vinyl chloride comes off very well under the conditions chosen. For an incremental investment of $4 million, the differential cost of production <0,599*/lb.) yields an additional $900,000 In pretax profits. Taking additional depreciation of $40Q.000/yeer, it means the $4 million gen erates $1.3 million/year cash flow. It should be remembered, however, that different conditions could change results dras tically. if ethylene were charged in at 3.2*/lb., for example, the differential would be wiped out. $y the same token, it would probably ba fairar to compare 3.24. lb. ethylene with ethane (rather than with naphtha) as the Wuiff feed, and in this case the differential might reappear. In short, these figures are useful mainly as a general formula into which variables can be inserted to give an answer for a given set of circumstances. It should be remembered, too, that the capital costs are for a contractor's battery-limits plant. The operating company would have to count on a higher investment for such things as working capital and land; off-site facilities could add 30%. August 22. 1964 CHEMICAL WEEK 97 TECHNOLOGY i 2.4^/lb. HowY:ap7iv< timers charge and over-ihc-fencc chlorine. One buy their material is complicated by the fact that t.l lbs. of caustic is gener ated per pound of chlorine. So the ing acetylene at the upper end of the range would not he able to meet the 6.2^/lb. vinyl price, even with free value of chlorine depends on the mar , fiCl and with no allowance for ad ket for the rest of the "package.** A ministrative or selling costa. At the company like Dow, the world's big gest producer--and user--of chlorine an probably charge chlorine into a process at slightly less than $30/ton. 1.5</Ib. However, that figure, is prob ably a safe minimum for normal op eration--and only under favorable caustic market conditions. HCl: The price of HC1 is probably postulated low prices for both ethylene and <acetylenc, the difference is less dramatic. It should be remembered, * though, that small differences take on more significance at the lower cost. Reads to Vinyl: There are now five processes and combinations of processes for vinyl chloride manufacture: (I) ethylene and chlorine; (2) S35-40/ton. Monochem, for in stance, is thought to be paying close to $38/ton for HC1 (from Morion Salt). The price, moreover, is for HC1 in solution, so that Monochem must add costs of (distillation. Under more acetylene and HCI; (3) balanced op eration using acetylene and ethylene; \{4) straight oxychlorination of ethyl ene; (5) a balanced operation using oxychlorinalion. The straight ethylene process form favorable conditions, HCI might be ing EDC and HCI has a number of purchased for $25/ton. In the case attractions. Capital requirements are of a producer charging his own by .only slightly higher than those of a product HCI to a process, the range comparable acetylene-HCI plant. And is wide open. If it presents a disposal problem, the HCI could carry a nega manufacturing costs are attractive if adequate credit for HCI is made. tive charge. -0.11 /lb. Cases of Companies like Dow and American negative, or even no raw-material charges in chemical processing, how ever, almost always prove illusory. Dow has made an economic evalu ation on the subject of HCI. It con Chemical can probably show good costs for vinyl chloride. Dow has a variety of uses for HCI and oxychlo* rination skills too. American Chem ical's HCI is used to react with more cludes that it should be worth no more than 70% of the value of chlorine. That would mean, for example, that the top price should be S3S 'ton, if chlorine is valued at $50/ton- The , ethylene to make tetraethyl lead. Ethyl Corp.. is in a particularly enviable spot. It has large HCI re quirements for its tetraethyl lead pro duction {i,c.. in the reaction of ethylene bottom price, it feels, is S!2/tort. This , and HCI to make ethyl chloride). At is set by sulfuric acid and is equivalent one time, irt fact. Ethyl operated a --on an acidity basis--to the cheapest sulfuric that can be purchased. Most companies seem to be trans ferring HG at prices In the middle of that range. Pittsburgh Plate Glass, for example, is thought to be charging S25/ton for C1 into an oxychlorination unit. One engineering company is basing its estimates on S30/ton. Stating the Ciuet By placing rawmaterial requirements against a back drop of price ranges for key mate rials, it is possible to compare the costs ,of vinyl chloride made from acetyl, ene and from ethylene using oxychlormation to balance the production (chart, p. 95). It can be seeD that a firm buying HCI and acetylene (even at the longer end of the cost range) would have difficult time compet ing with one using purchased ethylene Mannheim furnace to make HG (with salt cake by-product). By going into vinyl chloride, it fotind a highly at tractive alternate. The firm also built a plant to make ethyl chloride by the direct chlorina tion of ethane. This. too. yields HCI as a by-product. And with two new sources of HCI. it was able to close down its Mannheim furnaces. ("Morton nicely filled the void with a Har greaves operation producing both salt eake and HCI). Ethyl does not always operate its direct chlorination process; it's used to regulate needs for HG and ethyl chloride. What Ethyl charges for its vinyl chloride, then, depends in good meas ure on what costs it places on the HG used in making ethyl chloride. By tnking a hefty credit for it. it could show vinyl costs that would he diffi cult to match. Lending weight to the industry belief that Ethyl costs its vinyl at between 4-54/lb. (and probably closer to the lower figure) is the prob ability that the company will use vinyl chloride as a starting material for making its chlorinated solvents (vinyiidene chloride, methyl chloroform, trichloroethylene). Regarding HG, few companies are as well situated as Ethyl. But even Ethyl has done a lot of work on oxychtorination processing, as evidenced by its sale of know-how to French Soivay. Long-term planning could be behind Ethyl's interest in oxychlorinalion. Vinyl chloride and chlorinated hydrocarbons in general are growing faster1 than tetraethyl lead is. NEW HOPE FOR ACETYLENE .. In the early '30s, it was popular to talk of the cemiog battle between acetylene and ethylene as materials for petrochemical manufacture. As technology settled down, however, each found its riiche. But in the past few years, ethylene has been quietly picking away at acetylene's markets; today many observers see nothing but a grim future for acetylene. Principal reasons: acetylene is inherently more expensive than ethylene and improved technology has found ways of utiliz ing ethylene for more processes. Car bide-based acetylene is proved technology but power costs bulk large in this scheme and impose geographic restrictions. Hydrocarbon acetylene has also been "proved" to the extent that plants have been built and oper ated. But running These plants has nor always been easy and unexpected maintenance difficulties have added as much as 14/lb- to operating costs. The soot problem has been a particu larly knotty one. A plant manager of ooe of the pio neering complexes using the BASF hydrocarbon acetyleoe process was re cently asked his opinioo of the even tual answer. "There is no one solution." he says. ``You do everything you can and then you learn to get along with it.* More recently, Diamond has installed Montecatim's acetylene process, and Ten- neco has .put In the SBA (Social Beige de L'Azote) process. But thus far at least, neither has proved a smash- 9* CHEMICAL WEEK August 22. 1964 AP00034141 How oxychlorination saves steps in vinyl synthesis THREE-STEP PROCESS TWO-STEP PROCESS ONE-STEP PROCESS 1. Modified Deacon yields chlorine :HCI+*iOs->Ch + HsO A chiorine-fronvhydrogen chloride plant is being de signed by Shell. HCl-oxidation patents: U.S. 85.370; 141,333; 165,802 (Deacon). U.S. 2,204,172; 2.204.733:2.312,952; 2.271,056; 2,447,834 (Air Reduction). U.S. 2,577,808: 2,547,928 (Dow). U.S. 2,746,844 and South Africa 63/1650 (Shell). U ' __ 1 ' ' 2 ,,. which is used to make CDC Ch+CiHt--* CiHaCH The direct addition of chlorine to ethylene is well established in large com mercial vinyl plante. The key patents: U.S. 2,099,231; 2.284,479 (Shell). British 553,959 (Distillers Ltd.). U.S. 2,601,322 (Jefferson Chemical). U.S. 2,929.852 (Union Car bide). British 781,414 (Celsnese). i Oxychlorination combines 1 and 2 2HCl+HOi+ C/s+2Cjtf- JCzHiCh+HiO This process appears to be nearing widespread utilization. By feeding on a mixture of chlorine and hydrogen chloride It ab sorbs the hydrogen chlo ride from the pyrolysis of ethylene dichloride; thus it offers a balanced route for vinyl production. Patents on this approach are numerous. Some of the more recent end more -- significant: U.S. 2,636,864; 2,762,401; 2,752,402; 2,866,830 (Dow). U.$. 2,644,846; French 1,352,657; Belgian 630,738; British 907,435 (Shell). French 1,304,711; 1,323,939; 1,341,* ) 711 (Pittsburgh Plate Glass). Belgian 636,856; British 932,130; French 1,321,708 (Distillers Ltd.). French 1,304,911; Belgian 608,676 (Dynamtt Nobel AG.). French 1,359,016; Belgian 632,' 044 (imperial Chemical Industries). Belgian 643,262:643.263 (Vulcan). 3. Pyrolysis of EDC yields vinyl chloride CiH<Clr+CiH*Cl-HC\ Most of today's vinyl chloride production involves pyrolysis of ethylene dichloride, and the newer oxychtorlnation-based proc esses also depend on this reaction. Important patents: U.S. 2,474,206; 2,569,923 (Shell). British 569,291 (Distillers). And U.S. 2,412,308 (Mathtesen) on by-produced HCI. 7 Oxychlorination and pyrolysis * JCaffaCf+ffeO This general routs is on_ the frontier of oxychlorinalion technology. Some of . these processes start with ethane, insteed of ethylf cne* In those cases it ap pears that the ethane is cracked to ethylene, which , > is oxychlorinated to ethyl ene dichloride; the latter I is simultaneously cracked' to -vinyl chloride.* Such processes are'outgrowths of chlorinated solvent pro duction, and they u'sually direct the reaction by re cycling undesired chlorine compounds. Critics of these processes ques tion the availability of . ethane for large-scale production. Other proc esses introduce new tech nology. Case in point: a limited-direct chlorination over a Deacon-type cats- lyst supplemented with paliadtous chloride- and11 ... directive agents (e.g., esters and ethers). Dis tillers Ltd. has a pat ent (see below) on this method. Key patents isi sued thus far: French 1,360,896; 1,355,870; 1,355,886; 1,341,711. Brit ish 916,137; 913,040; 934,329.1 Belgian 631,155; 631,725 (all Pitts burgh Plate Glass). British ' 918.062 (Distillers Ltd.). Belgian 637,537 (Toyo Koatsu). Belgian 614,467 (Imperial Chemical Indus tries). Belgian 636,443 (Vulcan Materials). Auiutt 22. 1964 CHEMICAL WEEK 99 t AP00034142 TECHNOLOGY t Processes employed by U.S* vinyl producers Capadtyr Proas* T*- . Goodrich Chemical1*' - * Niagara Felts, N.Y. ^ Louisville, Ky. t Calvert (Jity. [ Onion Carbide vV'-J . . So. Cherlestonrw. Va.lL 5 _ TeiasCity. Terf.w* "fA-T I Ethyl Corp. r. * Baton Rouge,-la. Houston , ` acetylene 335 catylene(total) ethylene e '-v 'L'/' 280 . !-.bl(sc*rats (total) r.v 180 B0 a.:n i Oow Chemical. 7 vj&YS&flj Freeport, Tex.-, ** C *200 - . Plaqusmine, La,/' (total) ' TenhecoChemical' Houston vr.'.*'7 . 170 iacetyteno-Jg^ Allied Chemical Moiindaville, W.-Va.,-yjjg L Monochem** ''tip ` j Geismar.-La-.." 150 Saeatyjwe^iid 150 * <i .. `A m TMi M: Monsanto- 1 TtxasCfty. ,, 150 | Air Reduction t (Cumberland ClYemi&ftj t Salve* City, Ky^.7 '*vjj 60 Diamond Alkali' leer Park,Tex,^/yHfl . . 90 Sbafanced W pfeetylene and^f pxych]0r!ntior| f^jjg ^alancedT^^I Goodyear- ^ -N iagara-Fails, N.y;\o^ 45 General Tire " , Ashtabula, O. . `V x 30 ..acetylene ~ ^ American Chemical -Tjfj long Beach, Calif. 40 Total 1,960 ^ethylene " -.rj-vri It has never been publicized, hut Union Carbide has been operating * Wulff plant at Institute. W. Va., since '62. This unit can make tip to 12 million tbs./year of acetylene. Carbide says it started up in '62, met perform ance guarantees in the same year. And l.ummus. which offer* the Wulff proc ess. reports a lot of interest, primarily overseas, in the Wulff process. (Fluor also offers a Wulff process plant.) In Japan, Kureha ha* developed a process for making vinyl; chloride from a gaseous mixture of!acetylene and ethylene and this, too, is getting a dose look. Kureha built the process into a Sl0.5-million plant to make 66 million Ibs./year of vinyl at Nishiki. The process, it says, cut construction costs by 20%. Figuring on naphtha at 18/lb.. chlorine, at 38/lh.. and oxv'gen at I 4 8/1h.. Kureha say* the proc ess can cut selling price of viny) chloride to 6f/lb. This it expects to achieve when production reaches 110 million lbs./year "in the near fu ture." In Japan, at least, one com pany which has made an oxychlorination arrangement with > U.S. com pany, is having serious second -ihdughts. ft is now thought to be leaning coward the Kureha process The idea of using the dilute gas (ethylene and-'acetylene) from the pyrolysis of hydrocarbon* ha* been advocated by SBA {CW, April II, p. 7?). In fact, SBA says that it obtained the first patent* on the process in '39. It feels the patents are basic, em phasizes (hat it intends to do its ut most to see that they are enforced. OXYCHLORINATION KEYS tCsttmated in million pounds^yeer. Goodrich'* fcig switch to a balanced'operation with oiyChlorination at Calvart City me^es it difficult to pm down it* pretenl operation*. Lest year it made probably 280 million lbs. gt vinyl at il* three plant*. Historically. it h been based on acetylene. But it started to purchase EDC several year* age. It* ne> opera tions at Calvert City will probably set the patiern for the linn's future production. "Borden ortd U S. Rubbor. Jfci*. None of the companies now work ing on oxvchlorination or employing ifcommercially is saytng, much about its process. Dow probably has had more commercial experience than 1 rtnv other firm, both from the stand point of time and quantity of mate ! ing success: both Diamond and Ten- ers believe, i' .i plant making both rial processed. It regards oxychlori* neco have started suits because of acetylene and ethylene. This might nation as.a "flywheel" operation, to i what they .regard as unsatisfactory prove particularly attractive for vinyl balance its requirements for EDC and < operations. chloride manufacture. In any event, vinyl chloride against the supply of Du Post has developed a modified- processes such as the perentally prom chlorine aod.HCI. arc process it is proud of. But even ising Wulff, are getting a lot of seri-' Dow's work is an outgrowth of Du Pont is working both sides of ous study. It's possible to show at-" studies on modified Deacon process the-street, using an acrylonitrile proc tractive costs for making vinyl chlor ing and is covered by three patents ess based on propylene as well as one ide io a balanced operation using eth (U.S. 2,636,864; 2,752.402; 2,866.- based on acetylene. The'best bet, some acetylene boost- ylene and acetylene' from a Wulff furnace (chan, p O'). ' 830), Dow's oxyqbiorination process is not looked on as a primary method 100 CHEMICAL V/EEK August 22. 1964 4 r. * AP00034143 What's news in mixing? SOLID-LIQUID DISPERSIONS SPEEDED Ever-Increasing demands for faster, more complete'solid-liquid dispersions typify today's CPI requirements. Efficient deagglomeration and creation of scientific turbu lence and hydraulic shear for tho rough wetting of particles are essential. Ability of Cowles Dissolvers to speed ultimate dispersion is attrib utable to the unique HI-SHEAR* impeller and efficient power delivery L "D" writs-Mater m4 HI -SHEAR* imptlltr umblltt <' tiitt tank, batch or conlimieui optrttieis. 10 HA up. R, ---- 1 1 A 1VHV" ttmt - Custom mot*ls with MPD* vtnbit spate trantMis. tlons, hydraulic lilts, full iitilrumtntstien, ite. S-SO H P. "VH" isrlis-Similtr ta atwva. with standard Cowlts transminign. M50 HA. i 1 halp solve preMams slmilsr to "D" tarns, Wid* H.P. rant*. or two-IMtd ___ maters lor crtaltr Hail- . ... _ .-- -...bHIty, systems. Each Cowles is built to highest quality standards, expertly engineered to amply meet or exceed design specifications. Each is com pact. operates economically. Impel ler cannot dog--is easy to dean. Applications include processing of liquid-Iiquidand gas-liquid materials and a wide variety of products such as adhesives, textile colors, chem icals, foods, coatings, plastics, plastjsols, organisols, metallic disperaionsr and hundreds of similar ones. > FREE cost cutting demonstration-^ in your plant Let our Application Service De partment show you how the right model "COWLES DISSOLVER." properly applied, can improve qual ity, cut coats.-Write us today on your business letterhead. w___ M0REH0USE-C0WLE?, INC. 1180 Sin Fernando Read Im tagiIts (5, California Product XqriMPWiwi in Principal Citict nhdiiMlWCiiilaDIwilwr Q>.. I--. TECHNOLOGY for making liDC. Although it rep resents an achievement of no small stature, the process probably is not one `that many others would find overwhelmingly attractive. Monsanto also has been operating an oxychlorination unit at Texas City. The unit was shut down during '61 and *62 because acrylonitrile demand was down and the firm had excess acetylene. As the acrylonitrile market improved, the oxychlorination unit was reactivated and has been operating for 18 months. The plant is a fluidizedbed unit employing oxygen, rather than air. The oxygen poses no problems for Monsanto; it has a plant at the site for its acetylene production. Oxygen requirements, are modest: stoichiometricaiiy, 0.13 lb. is needed per pound of vinyl and prices of tonnage oxygen are less than Vi4;\to. PPG's approach is also thought to call for oxygen, rather than air. Fron tier, on the other hand, uses air in a fixed-bed process. It apparently does nof attain complete conversion of HCl. About 5% of the total HC1 fed to the' unit appears as 20% acid in a by-product stream. This, of course, can be credited to the process or cleaned up for recycle. Frontier Chem ical has a number of patents on oxychlorination. Its key ones, however, are just starting to appear (Belgian patents 643,262; 643.263. The Fron tier patents are appearing in tandem. One relates to oxychlorination of aliphailcs: the other, aroptatics). Shell's oxychlorination wrinkle is a three-step method in which chlorine is produced from HC1 in a separate unit. One of Shell's contributions: feed ing a dilute chlorine aaa into an adjoining unit for chlorination. KesuT ..reduccd-pyrtocation costv'The Shell "group is piarTnmjf'a""" 30.000-Ion/year, plant employing the chlorinefrom-HCl process in the Netherlands, -auiiLShell has been seeking customers' for toe pfdtrwr-Iuutiliaes efhrtdized bed and features a catalyst consisting of a mixture of copper and other chlorides. The reaction temperature is 630-800 F. considerably below the 850-1220 F typical of tbe Deacon. The lower temperature, as Shell points out, favors conversion of HCl into chlorine, also reduces corrosion prob lems. Tbe process employs either oxygen or air; Shell suggests oxygen only if it is available at an attractive Ethylene dlchlorJde maker* C1 Momitpinanny CftBACttV* American Chemjeel Watson, Calif. Diamond Alkali Deer-Park, Tex. 40 110 Dow Freeport, Tex. Plaquemine, La. 500 300 Ethyl Corp. Baton Rouge, La. Houston, Tax. 300 140 Monsanto Texas City, Tex. 210 Olln MethJeaon ,,, Brandenburg. Ky. 100 Pittsburgh Plata Qlaas Lake Charles. La.. . 12D Union Carbide South Charleston, W. Va. 200 Texas City, Tex. 240 Total 2.260 'Estimated in million seundi/vor price. The content of the effluent dc- , pends upon the feed HCl. But one set V of conditions, produces a 48% chlorine Y stream that can be used, says Shell, y "in various industrialprocesses." Deacon's Descendant Air Reduc tion's process, being offered *by Tech nical Enterprises, can trace its lineage to the Deacon process, as in fact can all-the straight oxychlorination proc esses now aL*vurtr ui-~umjer develop ment. In th^ Deacon process^fiydrogen chloride KOXiUind wlllTair over a hot copper catalyst to produce chlo rine and water. Tbe reactions proceed in two steps--hydrogen chloride oxi dation at about 1000 F, followed by catalyst regeneration at about 550 F t--but all modern processes conduct tese reactions in one step. Furthertore, all oi the patent innovations ''deal either with improving the selec tivity of the complex reaction, or with catalyst volatilization, a problem in herent in the Deacon process. Catalyst volatilization can be partly suppressed by adding alkali metal chlorides (U.S. 2,206;399). Copper chloride, however,, will sublime and concentrate in places in a motionless bed Of catalyst. Result: hot spots, which are -the main drawback of fixed-bed reactors. These hot spitsmake it difficult to remove the beat < of the mildly exothermic Deacon rcac- 102 CHEMICAL WEEK August 22. 1964 AP00034144 -**.. --------f--"T * = - - -r - f i III " DIRECT MANUFACTURE c) Quitenwy Ammonium Compounds < Propisnatet )EW1 Pirabans 3(esters of p-hydrox* beiuoic acid) E*" Aqua Ammonia * EZ Ammonium Aeitite i*1* Calcium Aeotatt Sodium Diacotito Otter Acetate Saits 3 * 3 * Sattvel Otter Organic Acids Sodium Hyprochlorite E m" ) AND OTHER PRODUCTS ON A CUSTOM BASIS In addition to prompt and dependable delivery of these high quality materials of our own manufacture we provide a complete custom manufacturing and development eervice for items that do not fit your current processing Sched ules. We have glass lined, stainless steel, high temperature and low pres sure equipment. Inquirt today aipul both our products ana cervices. WASHINE CHEMICAI CORPORATION uwu TECHNOLOGY ions, thus complicate temperature Du Pont, Esso, Frontier, Imperial ontrol. Chemical Industries, Pechiney, Pitts Hot spots can be overcome by burgh Plate Class. Shell, Toyo Ko- witching to fluidi2ed-hed reactors, atsu. yith the particle-buoying reaction The patents indicate that catalysts :ases passing ypward instead of down- are a key subject for research and yard, through (he catalyst bed. How- development. Distillers, which is not ver, these fluidized-bed reactors pre- now offering an oxychlorination proc ent three additional problems: (1) the ess, has a series of patents that could alkali metal salts, which suppress cop he significant <Belgi&n patents 630,- per chloride volatility by forming a 963 and 636,856; British patent 932,- low-melting eutectic, cause the catalyst 130 and French patent, 1,321,708). particles to become sticky and ag Yields of ethylene chloride, based on glomerate in the fluidized bed; (2) the ethylene, are pegged as high as 96.5% catalyst particles are gradually pulver in these patents. Only some 1.4% of ized in the fluid bed, so that dust col the ethylene feed is oxidized to car lectors must be installed in the highly bon dioxide. And yields over 90%. corrosive gases leaving the reactor; based on hydrogen chloride, are re and (3) the combined reactions and ported. uniform temperatures of the fluidized The Distillers Catalyst makes some bed are less favorable to the produc radical departures from conventional tion of chlorine. oxychlorination catalysts. It uses a Chlorine Acceptors: Oxychlorina- support (for the copper chloride! of (ion is a big step forward in improv activated alumina--rather than dia- ing the equilibrium' limitations of the tcmaceous earth, silica gel. pumice, Deacon process. The hydrocarbon present serves as a "chlorine acceptor" broken fire brick'* etc.."which are the conventional supports. Also, the Dis and in effect moves the equilibrium in tillers catalyst includes 0,2-10.0% rare the desired direction. This, of course, is the foundation of the Rasehig proc earth metals, such as cerium, lantha num, and neodymium, which have ess. atomic numbers between 57 and 71. In oxychlorination.`however, HQ is ( - Only one other oxychlorination cat buroed in the presence of a hydro- 'j alyst appears lo use-rare earths. And carbon, and the trick is to keep the ` (his catalyst, patented by Shell (Brit hydrocarbon from burning. In the : ish 907,435) states that conversion of Rasehig process the hydrocarbon is ; ethylene info dichloroethane is prac benzene, which is stable because of its tically quantitative, while the exam resonating* structure. Paraffins and' ples cited in the patent state that more hranched-chain compounds present a than 90% of the hydrogen chloride is differeot set of problems, Branched- converted. Otherwise, this Shell cat chain hydrocarbons, in particular, alyst uses a silica-gel support having prove difficult subjects for oxyehlo- an unusually large surface area (200 rination. Ethylene is in the interme sq. meters/gram). diate class; it's tougher to process than To suppress volatilization of the benzene, easier than ethane. copper chloride, both the Distillers Even in the case of ethylene, howj catalyst and the Shell catalyst employ ever, some oxygenated products are about one part alkali metal salt tKCI) bound to form, and their presence to one part copper chloride. Both could conceivably raise havoc. There's catalysts are made by impregnating a belief that trace quantities can cause the baked or calcined support mate difficulties when the monomer is polymerized. Monsanto, however, rial with a solution of copper chloride and then evaporating to dryness. says that it has experienced no such In this impregnation technique, the problems with its process, rare earth catalysts appear to differ Catalytic Keys: Although most of from other oxychlorination catalyst the companies involved will not give preparations. The support for the rare details of their processes, the patent earth catalysts is soaked in copper literature Is enlightening. Over a dozen chloride solution and then dried, innovations in oxychlorination tech nology have sholvn up in patents. whereas some other processes empha size spraying or dropping a copper Among the contributors: Distillers, chloride solution onto a hot catalyst -HiebtHkUn*. which l*o rr-oniil*, caa W nhkiijgiied. Mctbylnaphthalana and immm tea* to dtirade under OKrcblorinatign coerfldoni. support, so that the solution is vapor ized before it has a chance to sink 106 CHEMICAL WEEK August 22. 1964 I i ------- AP00034145 TECHNOLOGY AUGUST 17,1964 these items were added to the famous list of in. In fact, an early Dow chlorine from-hydrogen chloride process (U.S. 2,547,928) features a technique for recovering volatilized copper chlor Eastman Organic Chemicals: 9280 9167 6648 8916 Aselanyl Chloride BP 147-I48V7 mm. . ClCOtCH-HCOCI..,MW tu.it (Ethylencdinltrilo)tetraacetie Acid Cerium Monosodium Salt . * ....................... t-CHjNICHjCOO) j]jCJ4'H;0 .. .`JIW 194.44 4-Hydroxy-3.-mthoixybanzaic Aeid MP 213-214* ........................... HOCnH.iOCKxCDOH... HW 1M.1l 2-Iodothiophene BP fl5-flfl*/10 mm. . . . 8CBjCHCKiC!...UW I1Q.04 f 25 ir. S 4..10 mo g. 14.50 3.90 25 c. 15.60 10 p. 26 c. 25 c100 c- 5.00 12.60 0.76 24.35 ide by continuously absorbing the vapors in condensed hydrochloric acid and returning this solution to the re actor, where it is sprayed over the hot fluidized bed of catalyst. A recent British patent (941,353) to Du Pont stresses the measled, or , spotted, appearance of the desired catalyst, which has the copper chlor ides irregularly distributed over the surface of the catalyst support ma terial (calcined diatomaceous earth). f { r 9036 Palnfeic Aeid Sodium Salt CHj(CHj) hCOOMa ,.. MW S18.41 811 Pentyl Ether BP 183-166* [CKa(CKih]:9r...NW||AS.I> ! 26 c100 c, 2.35 7.90 2.70 H.25 However, the Du Pont patent points out that copper chloride salts remain on the surface of the support mate rial, even though the support material Men su6|t to fungi witntut nttict Is immersed in the copper .chloride solution. 3 and in larger-than-laboratory quantities Another feature cited for the Shell compounds may be available even if they aren't on the list. If' there fa anything you need, n*k- catalyst is an unusually low reaction temperature: 4,85 F for oxychlormai- DiitiiUalion Products Induetrice, Rochester, S. K. ing ethylene to EDC- This low tem i perature is purported .to virtually Distillation Preducts Industries is a division of Eastman Kodak Company eliminate corrosion and copper chlo ride volatilization. Thus, this catalyst appears to .have ticket},, the problems of the fixed-bed oxychlorination reac tor and if it doesn't agglomerate or pulverize in a fluid bed, it may .have licked the problems of the fluid-bed (in multiwall Q7and plastic bags) reactor, as well. ( Selectivity by Control! The import ance of close operating control for 7 f I ...... . ~ir H J.t? KfJ! ."'ri&iM v -Ai--'v hr v * l ..<2 high yields is pointed up in a volumin ous group of recent patents* to Pitts burgh Plate Glass. These, plus some issued to Vulcan Materials Co. (Fron tier Chemical), illustrate the pivotal position of EDC in the production of a wide range of chlorinated hydro r t i I. carbons, including vinyl chloride, vi- niiidene chloride, ethyl chloride, perchloroethylene, trichloroethylene, etc l Besides serving as feed for the con ventional pyrolysis vinyl chloride proc What goes on the bag is sometimes as important as what goes in it. ess, EDC can he further chlorinated in oxychlorination reactions. The usual copper chloride catalyst stabilized Thai's why we have our own commercial art department. Our artists are specialists in multiwall and plastic bag surface design, How good arc Ihcy? Ask the 0*1 customer whose bag look a Merit Achievement Award in the 1963 National Flexible Packaging Association competition. Graphic know>how is just pari of Right Bag Service. Your 0-1 representative can make it`pay off for you. with potassium chloride is employed. EDC may also be used as a diluent to direct further chlorination reactions, as shown in Belgian patent 636,443 to Frontier. In the PPG process the EDC con version is carried out in two steps IOB CHEMICAL WEEK August 22. 1964 Frtoek: j,M1,2i,173,n02r4.i.is1G.3r0o4,.911i..iss>,,s3m2J.a3n9d. 1,317,433. British! 416,hr. Ml.au And 9J4.J39. Bw5nr 607,673, 611.135. 631,411 ind 431.72S. !. i AP00034I46 W-C 1 TECHNOLOGY "Wont the secret, young fella? Life really begins when you discover 'Spencer Service is Wonderful!'" Heed Nylon? Call Spencer! Sptnew Chamieal Division Quit Oil Corporation SPINCE* PRODUCTS. S|i<e*ltut*l Chtnlcdi IndDMrial CMalnll RlMiiCl Fluikl* Pi'lifmi Wasd XOimIvm Highest purity at lowest cost This is another SCHULTZ Steam-Methane Hydrogen Plant delivered in die past year. Hie designs give flexibility of operation for remote control. Start-up can be accomplished in 3 to 4 hours, production varied or shutdown in minutes. For full information applicable to your hydrogen problem, write, wire or phone 35 Yens Experience building Hydrogen Plants (British 913,040): (1) chlorination, in which hydrogen chloride is a hy-product; arid (2), oxychlorinaiion. in which by-product hydrogen chloride is used as the chlorinating agenl. Yields of chlorinated hydrocarbons appear to be about 80%. while chlorine utilization is said lo he as high as 82%. PPG is said to he using a version of this process to make chlorinated com pounds in pilot quantities. However, a more striking variation of oxychlorinatiohis described in sev eral PPG patents that cite ethane us the starting material. Tn a combined cracking and oxj'cfiioiTnatjon reaction (French 1.341,7] 1), approximately 30% of the eVhane is converted into vinyl chloride and 50% cracked to ethylene, while some 20% of toe ethane is burned. And in French patent 1,355,870, the vinyl chloride alone is recovered by distillation, while the ethylene and chlorinated hydrocar bons are recycled to be Converted into vinyl chloride. PPG is currently offer ing vinyl chloride fror*n a proposed plant that is believed'Ho incorporate these techniques. Selectivity by Separation: PPCi's patents also bring out fhe critical rrtfe of EDC fn the newer oxychlorinafion routes to vinyl chloridei'Thi question, here, is when to crack. Three answers are proposed: (!) crack EDCas a pure component, (2) crack it in a recycle stream with selected other Chlorinated components, or (3) crack'it in situ. The first approach is the one now used commercially in the U.S. The second, where EDC is recycled with Other chlorinated hydrocarbons after the vinyl is removed, is described m the PPG patents and a Belgian patent (637.537) to Toyo Koulsti. And the third is described in Belgian patent 614,467 to iCl, as well as in British patent 956.657 to S. Tsutsumi, a pro fessor of Osaka University (Japan). The critical operating variable in these different approaches is tempera ture. Ethylene can he oxychlorinatcd to EDC over conventional catalysis at about 57D F. whereas EDC is not cracked until the temperature reaches 850-950 F. - The proponents of the two-step route sny that, while an extra step is required' to crack EDC separately, this extra step is justified by the increased yields resulting from the lower operating temperatures. Osaka University's Tsutsumf ap pears to get around this problem by 112 CHEMICAL WEEK August 22, 1964 TECHNOLOGY r /< Stability is child's play for VEEGUM'T Fromthlxotropie paints to paper eoat-. logs, from pastel crayons to ceramic glazes, whatever the product... stabil ity is child's play for Vcequm T. Veequm T Is our technical-grade of magnesium aluminum silicate. A hydro philic colloid, it disperses in water read* lly without soaking, it is supplied in the form of odorless, tasteless, non-toxic, small white flakes. Added to your formula, VeeeuM T will retard the settling of pigments, stabilize emulsions, impart body and serve as a non-migrating binder. If you require e more highly refined product with these seme properties, we suggest you try our regular grade of Veeouu. suitable for cosmetic and phar maceutical uses. For more Information and sample of the Vcccum grade best suited for your products, fill out end send us ths cou pon below, attached to your letterhead. R. T. VANDERBILT COMPANY. INC. DP- ISO Pi* A**.. N.V. 17. N T, pim tend Infermitlen wi VEEGUM T ttr uis l th* lllawtn| iftdiulrlal prerineUi Hire btrarmtliM 911 Ui rtcular inN of VEEGUM for n In tlit foilwriftf eemtle proAxtn PtMM MM umslt * veequm t rr*T niMtlM UNpll r vceetrM j, ' _____ Ttwr ____________________ employing vacuum (460 millimeters of mercury or less) and ultraviolet light. Temperatures are thus reduced. His patent says that vinyl chloride yields of 85-90% based on ethylene are ob tained when the pressure is- 360 milli meters--over 95% when the pressure is under 260 millimeters. \ Otherwise some of the recent oxycblorination patents show that re searchers are still looking for new solutions of the old problems of cop per chloride volatility, hot spots in fixed beds, etc, Belgian patent 632.044 to ICl defcHbes a process for pass ing the feed' to the oxycblorination reactor through ft bath of molten cop per, chloride; so that the feed vapors will contain enough copper chloride vapors to suppress its volatilization from the catalyst. This process appears to permit the use of fixed-bed reactors, si'nce it eliminates hot spots. And Peehtney appears to have de veloped b dual-reactor process (French * patents 1)286,839 and 1,304,072) com bining benefits of both the fixed and fluid beds, while avoiding the dif ficulties of both- According to these patents, the lirgest part of the heal of (reaction is liberated during the earlp paru of the oxycblorination re action, >and the products of this early reaction can subsequently act as diluents1 to hold down the temper ature. - So Pochiney has proposed a fluidized-bed reactor to be immediately followed by a fixed-bed reactor. Heat exchange, residence time and feed materials to the fluid-bed reactor are controlled'to limit the temperature and keep conversion below 80%. The fluidbed effluent passes immediately over and down through a fixed-bed reactor, which collects any fines that result from catalyst attrition. Hot spots are said to be eliminated. And yields of EDC from ethylene are said to be well over 95%. Weighing Up: Such high yields ap pear to be the rule rather than the exception in oxychlorination proces ses. The importance of yield should not be underestimated. However, judg/ ifif from the work that has been done, it does not seem likely that significant differences can be expected on this score. Other factors are significant in weighing the merits of the various processes: whether oxygen or air is 114 CHEMICAL WEEK August 22. 19*4 AP00034I48 r, TECHNOLOGY used, (he life of the catalyst, and $ the materials used against corrosion. Whether a fluid-bed or fixed-bed process represents the best approach is a matter of some dispute. Some fed that & fluid-bed process is in herently more expensive but that it is justifiable on the basis of superior per formance. A company considering licensing might find the overbearing considera tion to be the amount of develop ment work that has been done on the process and the size of the royalty payments. Acetylene's Future: Regardless of tbe meriU of the individual oxychlor- inaiion processes, it seems certain that the new technology will have a heavy impact on the future of acetylene. And acetylene can hardly afford to lose many more markets. Some time ago, it lost out in this country as a raw material for acetaldehyde. And Shawinigan Chemicals, which has been looked on as an operation to "upgrade hydropower'1 through acetylene chem icals, switched to ethylene for its acetaldehyde expansion (CW, July 6, 63, p. 28). Acetylene captured the acrylonitrile market from ethylene oxide (except in the case of Union Carbide, which has an unusually favorable posi tion in oxide); but it is now losing out there to propylene. ICl aod Celaoese are switching to ethylene for their one-step vinyl acetate processes (CW Technology Newsletter, June 6). And some think it is only a matter of time before Du Pool does the same. ISTEEL SHIPPING Oxychlorination has already cut into acetylene's vinyl chloride outlets. Future inroads could reflect the suc cess of such operations as Kureha's, | CONTAINERS the Wulff process and other new hy drocarbon processes. And oxychlo rination could help elbow acetylene ! C PAINTED right out of tbe manufacture of chtorinated solvents, trichloroethylene, in I ODECORATED particular. It could leave chloroprene as the only important chemical de LINED rived exclusively from acetyleoe. The companies that would be most immediately affected would be the big carbide-based acetylene merchants --Union Carbide and Air Reduction. If oxycbtorioatlon processes are suc cessful, acetylene prices would have to drop drastically for acetylene to remain competitive. And at the very WARREN, OHIO beat that would be felt in acetylene profits. lit CHEMICAL WEEK August 22. 1964 AP00034149 .VIEWS PLUS INTERPRETATION New route t Oxyehlorination offers a new solution to old problem; vinyl chloride from ethyl* ene can be produced without finding a high-value outlet for by-product HCI Edwin F. Edwards and Theodore Weaver The Fluor Corp., Ltd. Los Angeles Vinyl chloride is made today on a commercial scale from eith er of two raw materials, acetyl ene or ethylene. With acetylene feed, the synthesis is accom plished by the simple addition of hydrochloric acid: CaHj 4. HCI CaH,Cl (1) With ethylene feed a two-step synthesis is involved. First, chlorine is added to ethylene to produce 1,2-dichloroethane (commonly called ethylene di chloride or EDC). Then, the dichloroethane is dehydrochlorinated, usually by thermal treat ment, to produce the vinyl chlor ide product and by-product hy drochloric acid: C9H4 + Cla C#H4CU (2) C*H4C1* C-HjCl + HCI (3) For both of these routes, the fixed charges against capital per pound of product are low. Thus, the final economic choice be tween these two alternate hy drocarbon feed materials de pends very heavily on their rela tive costs, and on the value of the by-product hydrochloric acid. Ethylene is usually cheaper than acetylene; therefore, one tends to be attracted to the eth ylene route. However, the con ventional ethylene-based synthe sis as described above degrades one pound of chlorine to HCI for every pound of chlorine that ap pears in the vinyl chloride pro duced. In a really large plant it is often very difficult to find a high value use for such a large quantity of HCI. Several producers have sought a solution to this by combining the ethylene and acetylene routes into a single facility, producing essentially equal amounts of vinyl chloride from each hydro carbon raw material, and using the waste HCI from the ethyl ene operation as the chlorine source for the acetylene-based section of the plant. But, this too, has its drawbacks. First, the average cost of hydrocarbon raw material is increased by the higher price paid for acetylene. Second, one is forced to employ two smaller units in lieu of a single, larger one, -with the at tendant increase .in unit capital cost and operating labor. Today, a new, potentially attractive so lution to this problem is avail able through the use of an oxy- chlorination reaction. Oxyehlorination is a general term referring to reaction in which a mixture of oxygen and HCI is employed to bring about a chlorination reaction. As ap plied in the present instance, oxyehlorination means a combi nation of by-product HCI from reaction (3) with oxygen (usu ally in the form of air) to bring about the chlorination of ethyl ene to produce 1,2-dichloro- ethane; C2H4 4- V09 4- 2 HCI *C2H4C1j 4* H=0 (4) The dichloroethane thus pro duced is then dehydrochlorinated conventionally to make vinyl chloride. Oxyehlorination thus pro vides the possibility of making vinyl chloride from ethylene CHEMICAL ENOINEESING PROSRESS, [Vot. 41, No. I) January 1965 21 AP00034150 VIEWS PLUS INTERPRETATION without significant degradation of chlorine. The requirement for fresh chlorine for the ethylene based route is thus cut in half, and essentially all of the chlor ine feed appears in the final product vinyl chloride. This now makes the choice between the acetylene- and ethylene-based processes essentially a question of the relative cost of the two hydrocarbons. What's been happening A review of the literature shows that oxychlorination of hydrocarbons was conceived as early as 1922. In the intervening years there has been sporadic interest, building more recently to a high level of activity. The technical literature on oxychlorination processes is con fined largely to the information contained- in issued patents; however, a review of these brings out a number of interest ing and important features: 1. The reactions are general ly catalyzed by metallic chlorides, the one most commonly mentioned being __cupric chloride. 2. For.any given chlorination reaction there is an opti mum temperature, and temperature control is crit ical. If the temperature drops too far below the op timum, the reaction is diffi cult to initiate. On the other hand, too high a temperature level will cause the formation of compounds with a higher chlorine content than de sired. 3. Catalytic reactors employ ed in oxychlorination tend to form hot spots, which in turn cause poor tempera ture control, and may cause the catalyst to vapor ize and migrate through the bed. A number of interesting solu tions have been proposed to overcome the temperature con trol and hot spot problems. One Figure 1. Vinyl chloride from ethylene with oxychlorination. solution is to conduct the reac tion in a fluidized bed of cata lyst, another is to use inert filler materials such as silicon car bide, in a fixed bed of catalyst. Today, several different proc esses have been successfully demonstrated on a pilot plant and commercial scale. Specific process details are treated as proprietary and confidential. Thus, only the over-all results may be described. How the process works The oxychlorination process discussed in this article h&B been commercialized by a substantial chemical' company whose pri mary business is the production of chlorinated organic chemi cals. The process has been fully tested in a pilot plant, and a commercial plant jp uder construction. In the oxychlorination proc ess, ethylene and hydrogen chloride are reacted over a cu pric chloride catalyst at a mod erate pressure and temperature. The cupric chloride catalyst is supported on a fixed bed of inert material: 2 CuCl2 +C*H* ^ CsH4C12 + CusClj CusCls -{- Os ^ CuOCuCla CuOCuCla + 2 HC1 * 2 CuClj + HfiO The exothermic heat of reaction is removed by generating steam (at about 150 Ib./sq. in. gage) and special provisions are made for maintaining uniform tem perature throughout the reactor. The reactor effluent is cooled with cooling water and refrig erant to separate dichloroethane and water from nitrogen and unreacted oxygen. A small amount of unreacted HC1 leaves the system with the water as a 20% aqueous solution. Vinyl chloride monomer Figure 1 illustrates how the oxychlorination process can be used in a complete vinyl chloride plant. In this plant two reactors are used to produce the dichloro- SO C$\ ethane (DCE) which is dehydrochlorinated to yield vinyl chloride. One employs the oxy chlorination process described above and the other a conven tional process for making DCE. About half of the DCE inter mediate is produced in the oxy chlorination reactor from ethyl ene and the HC1 resulting from the thermal dehydrochlorination of DCE. The rest of the DCE is produced in the conventional .1 January 1965 - chemical ensineerin6 progress. (Voi. ti. No. i) AP00034151 SCOPE reactor from chlorine and ethyl quirements for the two ethylene catalyst, usually mercuric chlor ene. Thus, in such a plant chlor- based processes and the classical ide supported on carbon, in a inejeouirements are about one acetylene process are given in tubular reactor. The reaction is half those for a conventionar Table 1. carried out at about atmospheric vinyl chloride plant based on In the classical acetylene, pressure and around 200C. ethylene, and there is no co based process vinyl chloride is Heat of reaction 1b removed by product HCI. The oxychlorina- produced by reacting HCI and a coolant which circulates tion section of the plant has al acetylene in the presence of a through the reactor. Reactor ready been described. In the conventional reactor section of the plant the chlorine and ethylene are reacted in a circulating stream of DCE. A small amount of an inexpensive catalyst is added to the BCE to Ethyfeftrroute Acetylene insure completion of the reac tion. Noncondensables are sepa rated from the reactor effluent and the effluent is washed free of impurities. DCE from the conventional and oxychlorination sections of the plant are combined, dried, Raw materials Ethylene 99%, tons Chlorine 99%, tons HCI produced, tons Acetylene 99.8%, tons Oxychlor. fr 0.484 1 ^ 0.674 4 --, Conv. 0.476 1.205 0.590 -- route ---- 0.424 and purified in the DCE purifi HCI 99.8%, tons 1 -- 0.596 cation section. Drying is carried out by azeotropic distillation Utilities, catalysts A dram. and the remaining purification steps by ordinary distillation. Power, kwh The latter yield a highly purified Steam 214 154 156 DCE, plus light and heavy ends 150 Ib./sq. in. gage, tons cuts. Purified DCE is dehydro- Steam chlorinated in a pyrolysis fur 50 Ib./sq. in. gage, tons 0.46 1.07 1.05 1.07 0.51 -- nace in the vinyl chloride mono mer section. The furnace outlet is cooled and fed to a distillation train. In the distillation train Cooling water 80*F, tons Fuel gas, mmBtu Catalysts, chem. & supplies, $ 257 3.5 1.25 236 3.5 1.10 80 -- 0.91 anhydrous HCI, unreacted im pure DCE, and vinyl chloride Operating labor are separated from each other. Supervisor HCI is fed to the oxychlorina Operators tion reactor and unreacted DCE 1/day 5/shift 1/day 4/shift 1/day 3/shift recycled to the DCE purification section. Inhibitor is added to the vinyl chloride monomer (VCM) and the monomer is sent to product storage. The conventional process for manufacturing vinyl chloride Ethylene route Oxychlor. Conv. Acetylene route from ethylene and chlorine em Battery limits plant ploys all the process steps de scribed above except the oxv- Off-sites $4,700.000~/$3,700,000 53,400,000 1,200,000 1,200,000 800,000 chlorlnation step. K tnus ftas ifCl US a co-preauct which must Working capital 300.000 380,000 240,000 be disposed of. Plans for any Startup expenses 200.000 180,000 150,000 new venture using the conven tional ethylene route must ~bf Land, negligible necessity inclu5e the marfetinpr or captive use of about 0.6 ton Royalty--not included HCI/ton VCM. Operating ~ re Total $6,400,000 $5,460,000 $4,590,000 CHEMICAL ENSINEERINS RROORBS, (Vol. 4|, No. 0 January 1965 23 AP00034152 VIEWS PLUS INTERPRETATION effluent gras is cooled and the vinyl chloride recovered and purified by distillation. What does It cost? To illustrate the economics of oxychlorination in vinyl chloride manufacture, we have developed costs for producing: 200,000,000 lbs,/year of vinyl chloride by the three process routes described above--ethylene with oxychlor ination, conventional ethylene, and acetylene. Comparative manufacturing costs for the various routes are presented in the form of calculated minimum profitable selling prices for vinyl chloride. Since raw material prices and the value of by-prod uct HC1 vary from situation to situation, profitable selling prices are presented as a func tion of these important vari ables. Likewise, since fixed charges, royalty, and profit will vary from company to company, these elements of manufacturing costs are presented In such a manner that the reader may ad just them to fit his own particu lar situation. However, reason able changes in the allowance made for fixed charges, royalty, and profit do not alter the rela tive economics of the various routes. Capital cost estimates which are shown in Table 2, include all equipment, materials, construc tion labor, engineering and con struction fees for erection of the plants in ready-to-operate con dition in a Gulf Coast location. The estimates are predicated on building the plants at sites where the necessary utilities would be supplied from central utility producers. Utility costs used in the economic analysis al low for all direct and indirect charges and profit associated with producing the utilities; thus no capital need be added for the utility producers. Although offsite capital costs will vary from site to site, it is our experience that the estimates made for Table 2 are reasonably good averages for the type sites envisioned. They include the cost of product storage and load ing facilities and storage for heavy chlorinated organics and other minor products. In the case of the ethylene route plants, the offsite estimates include chloride unloading and storage. The gaseous raw materials-- ethylene, acetylene, and HCI-- are assumed to be delivered from adjacent plants by pipe line. To illustrate the differences in the three process routes and to show the magnitude of the vari ous components of manufactur ing costs, typical manufacturing cost and profitability calcula tions are shown in Table 3, for two typical Gulf Coast situa tions: Case 1. Ethylene is available from a large ethylene plant by pipeline at 4.64/lb. There is an "across the fence mar- Raw materials Ethylene at4Vfc#/lb. Chlorine at $50/ton By-product HCI at $25/ton Acetylene at 8^/lb. HCI at $50/ton Total raw materials Direct conversion costs Labor and supervision Chemicals, catalysts & supplies Utilities Maintenance Plant general expense Total conversion cost Estimated selling and corporate administrative costs Estimated to be required for depreciation, taxes, insurance, royalty, and profit Minimum profitable selling price $/ton */lb. Ooliars/short ton Case 1 Case 2 Ethylene route Oxychior. Conv. Acetylene route 43.56 33.70 -- 77.26 42.84 _60.25 (14.75) 88.34 67.84 29.80 97.64. 1.79 1.25 4.35 2.35 2.47 12.21 1.46 1.10 4.04 1.85 1.97 10.42 1.12 0.91 1.63 1.70 1.62 6.98 1.50 1.50 1.50 26.00 116.97 SJL 22.00 122.26 6.1 18.00 124.12 6.2 24 January 1965 JJ ? CHEMICAL ENGINEERING NOSUBS. (Vel. 11, No. I) AF00034I53 SCOPE VALUE OF BY PRODUCT HCI AT PLANT BATTERY LIMITS /TON Figure 2. Effect of HCI value on the cost of making vinyl chloride from ethylene end chlorine. Figure 3. Comparison of ethylene and acetylene processes for making vinyl chloride. ket" for 118,000,000 lb./ year of by-product HCI at a value of $25/ton at the vinyl chloride plant battery limits. Case 2. Acetylene is available from a large acetylene plant by pipeline at 80/lb. HCI is purchased "across the fence" from a chlorine plant manufacturing the HCI by reacting chlorine and hydrogen. Cost of the HCI is assumed to be the same as that for purchased liquid chlorine, as the cost of "burning" hydrogen and chlorine is small, and chlor ine cell gas would be used rather than liquid chlorine. The unit costs and indirect charges used in the calculations are given in Table 4. How the routes compare The importance of the oxychlorination process depends on the fact that markets for by product HCI are limited in many cases. In the United States there are many areas of local surplus of HCI, and in many cases HCI 1. Labor 2. Direct supervision 3. Chemicals, catalysts and supplies 4. Utilities Electric power Steam 150 Ib./sq. in. gage 50 Ib./sq. in. gage Coaling water Fuel gas 5. Maintenance 6. Plant general 7. Selling & corporate administrative cost 8. Depreciation, taxes, insurance, royalty, and profit $3.20/hr. plus 20% for vacation, holiday, sick leavp and other benefits. $ll,500/yr. At prices prevailing on U. S. Gulf Coast 0.6*/kw.h. 450/1000 lb. 400/1000 lb. 20/1000 gal. circulated 250/mmbtu 5% of Battery limits capital cost /year 80% of maintenance and operat ing labor to cover local plant ad ministration, accounting, person nel, purchasing, and analytical laboratory labor. Allowance of $150,000/year. Assumed at 40% total capital shown in Table 2/year. CHEMICAL ENGINEERING PROGRESS, (Yd. *1. No. I) January 1965 25 AP00034154 VIEWS PLUS INTERPRETATION. is being: neutralized and disposed of as a waste. In such areas the conventional ethylene route suf fers a severe competitive disad vantage because of the need to dispose of sizeable quantities of HCI. By employing the oxychlor- ination process it is possible to produce vinyl chloride from ethylene and chlorine without also producing HCI. The market ing of anhydrous HCI from a conventional plant is compli cated by the fact that the HCI by-product from the pyrolysis of DCE is not a normal item of commerce. It can be disposed of by pipeline to an adjoining fa cility, absorbed in water and shipped as aqueous HCI, or shipped in special pressurized tank cylinders. The first method is often the only economic way of disposing of the large quan tity of HCI produced in a con ventional ethylene-based vinyl chloride plant. In the second method, the value of the HCI is reduced and shipping costs are increased due to the need for transporting water. In the third, shipping costs can be prohibi tive due to the need to ship the anhydrous gas in expensive, high-pressure, tank cylinders. Thus, the value of by-product HCI may vary considerably, de pending upon the availability of the market and its proximity to the vinyl chloride plant. Using the same basis as for Case 1, Table 3, the minimum profitable selling price has been determined for vinyl chloride manufactured by the conven tional ethylene route at several different values for the by-prod uct HCI produced by this proc ess. These are plotted in Figure 2. The corresponding minimum profitable selling price for the oxychlorination route is also plotted in Figure 2 to show the advantage of the oxychlorina tion route at various values for by-product HCI. Note that the value shown for HCI is the value of this material as a gas at the plant battery limits after taking account of expenses associated with collecting, delivering, and selling it to the ultimate cus tomer. Figure 2 illustrates that in plants of the size studied in this paper, the additional capital cost and operating requirements of the oxychlorination route are usually justified when the spread between the value of chlorine and the value of by-product HCI is more than about $16 per ton, A word of caution is in order. This "break-even spread" varies with plant size. For smaller plants a distinctly larger value may be found. Ethylene vs. acetylene Most vinyl chloride producers in this country are operating plants using the conventional ethylene route or a combination of tiie conventional ethylene and acetylene routes. However, some producers have found the classi cal acetylene route more econom ical and have selected it for their plants. Since their choice was made before the commer cialization of the oxychlorina tion process, it is now appropri ate to make a new comparison of the ethylene and acetylene synthesis routes. To permit the rapid evalua tion of the relative merits of the ethylene and acetylene routes for other particular situations, we have developed a picture of the minimum profitable vinyl chloride selling prices as a func tion of these raw material costs. This picture is presented in Fig ure 3. The minimum profitable selling prices shown were calcu lated using the same conversion and indirect costs as in the earlier analysis given in Table 3. Again, it was assumed that HCI would be produced in a chlorine plant, as explained in a the description of Case 2. Thus the chlorine cost is the same for both the synthesis routes shown. Figure 8 illustrates that for new large plants in most, if not all, U. S. locations the ethylene route with oxychlorination is more economic than the acetyl ene route. On the Gulf Coast, for Instance, where one may pic ture large quantities of ethylene selling on long-term contracts for 4 to 4Hf/lb. and acetyl ene for 7H to 9^/lb.F tile ethylene route with oxychlorina tion is the clear-cut choice. This does not automatically foredose the future of acetylene as a raw material for vinyl chloride, in other circumstances. For example, yhere existing process units are now on hand, the economic comparison be tween the alternate raw mate rials may change. Even more important may be changes in the relative cost of ethylene and acetylene that will occur in for eign situations, particularly where ethylene must be made on a small scale from a naphtha feedstock. In some of those cases the acetylene route may indeed be the better choice. The oxychlorination process permits economic manufacture of ethylene-based vinyl chloride in areas where low cost ethylene is available and there is a poor market for anhydrous HQ1. When the spread between the values of chlorine and by-prod uct HCI is more than about $15 /ton (taking HCI as a gas at the plant battery limits) vinyl chloride can be produced at a lower cost in a large plant using the oxychlorination process than in a similar size plant using the conventional ethylene-based process. In the U. S., except for un usual acetylene and ethylene cost relationships, the ethylene route should prove more econom ic than the acetylene route for new vinyl chloride plants. Edwards Weaver 26 January 1965 CHEMICAL ENeiNEHINe NtOCAESS, {Vot. LI, No. II AP00034155 I TJ: O o W 4* (si fj.-;.-h i- \ JVryiorio To devolopo a pi-or^cs <-v oxj;:hlyr.lii:;!-i an of nothnno to produce chlorinate^1 nathanes. Opera'- rr.nr ' I .'>n :-(i devoX'';- 'ccuva.t'? on-' lyni.n in ordor to ottatn gooi wnbevial `balunr-*- Procedure The opet'obion of tlie muripl.ant ic Oenciihcd i\\ * he e'ccea'pEinyinp: Clou s-licct. Ttv^ re/>o< lof ^ rcre cylinder methane. nil* mX Jiyrircritlcrlf. no5 x. Data Ttftil'.e ruun of tour-hour duration were mrO.c. The rcnnlln of JO Tuns vote inccnsi.r.tnnt necessitating minor ohangos in tlio product 'Tcoveiy system and nnaJ ya is:. Hjrdrochlori c acid (HC1), carbon dlcrJds (CO^) and cH dolin'? ICL^) are* rv'Dnuret] by TolumeiTJc titrati on3. The remaining components except uater nre measured by pas chrcrant''prnphic mabhedo. n-,0 \o ron~i'T`-"d by ncight- cll.i[`errm-.c. The data obtained for the lost i.;ro runs fWo- ?6 and 17) in listed bel.ou. V\< Reactant Flcwr (Molcn/Ittv'r) . au_ a* Run Ho. 16 Run Ho. 17 0.370 0.3T0 0-5H 0.577 Temperature 7vv`.n1:n r<". .. f 2. 168 2. 3.68 HCl , l.oM l.?lM Run ITo. 16 n.m Tk>. Vf 7 h _5_. _7_ J}_ 3`J? ;?' -a? 5 ;2T 3?6 via y;:= ~ * t ; -o b rrf due t.i (t'r'X*u*; Ic1 v : wv cti [iv; r.'-r :ri CTOl.^ CO1 a jy ,,cr Run Ho. 16 Run Ho. 3.7 0.<50 c. rB75 O.0J/J5 o. o-vfk O.OJMO O-C'bl a.o!i95 o. 0373 0.02lf o.cpt6 0. Ciil6 0. C870 t Ox.ychlorina.tion ethane ( continued) - 2- Interpretation of Data A ccoplote carbon analysis was obtained on runs 16 and IT; however, the numbers for methyl chloride are estimated. Sosas of this material vaporised when the collection traps were allowed, to vara to room tes^erature. A separate procedure will be used to measure tneth:/! chloride yields. AP00034I57 Reactor (nickel) - Packed witli LyV Celite 22 pellets "burdened :ri.th % Cu" gc CuCla'^HaO yf> ITa* as llaCl \\t rt AP00034158