CHEMICALS COMMODI
TY
E T H Y L E Ν Ε ΟX I D E R. M . J O S L I N a n d A . B . STEELE, Carbide
and C a r b o n Chemicals
Co.
W i t h 1955 ethylene o x i d e production running close to ca pacity, additional facilities in 1 9 5 6 m a y m e a n excess. G r o w t h market trends for antifreeze a n d ethylene o x i d e derivatives indicate this will b e t e m p o r a r y JITHYLENE OXIDE, 29 years after it was first produced commercially in the United States, reached an estimated rate of 650 million pounds in 1954. In those 29 years, production nearly doubled every five years. Next to ethanol, ethylene oxide is the most important derivative of ethylene, taking about 30% of the ethylene pro duction. Over the years, about 10O derivatives of ethylene oxide Have achieved commercial acceptance; about 25 of these derivatives are now sold at an annual volume of over 1 million pounds. Directly or indirectly, these derivatives have benefited every indus try. The automobile industry;, in par ticular, has been influenced—about onehalf of the ethylene oxide produced is converted to antifreeze bases,* solvents for finishes, brake fluid components, resins, and other products used by the automotive industry. At present six companies are producing ethylene ox ide in 11 plants with a new plant in California nearing completion. Ethylene oxide was first synthesized by Wurtz, who reported it and other oxides in 1859. More than 50 years passed before markets for ethylene ox
ide and its derivatives (notably ethyl ene glycol) seemed promising and be fore raw materials became available in sufficient quantity and at a low enough price to open the door to large scale commercial use of ethylene oxide. In 1914 3 George O. Curme, Jr., now a member of the board of directors, Union Carbide and Carbon Corp., started his research on the chemistry of ethylene a t Mellon Institute. In 1920, a chlorhydrin pilot plant was estab lished at Clendenin, W. Va., to capital ize on these investigations. After five years of pilot plant investigations at Clendenin, the project was moved to South Charleston, W. Va., near the present Blaine Island plant of Carbide and Carbon Chemicals Co., a division o£ Union Carbide and Carbon, The first large scale oxide unit began opera tion there in 1925. Ethylene glycol was t h e first ethylene oxide derivative marketed. I t was followed by the familiar glycol-ethers, Cellosolve and Carbitol solvents; and by the ethanolarrxines and Carbowax polyethylene gly cols, Patents for a process of making ethyl ene oxide by direct oxidation of ethyl
ene were taken out by T. E. Lefort in 1931 and assigned to the Société Française de Catalyse Généralisée. These patents were acquired by Carbide and Carbon and further elaborated into a commercial process. The first plant producing ethylene oxide by the direct oxidation of ethylene commenced operation in 1937. In the chlorhydrin synthesis of ethylene oxide H*0 + Cli —> HC1 -f- HOC1 CH2=CH2 -f HOC1 -* HOC2H4CI HOC2H4CI + VsCa-iOH)* - * Ο / \ 72CaCl2 -f H 2 0 + CH2—CH2 optimum conditions are reached when the yield of ethylene chlorhydrin is approximately 87 to 90% and ethylene dichloride is 6 to 9%. Small amounts of dichlorethyl ether are also formed. The crude chlorhydrin solution is fed into equipment where ethylene di chloride and dichlorethyl ether are re moved. The solution is then allowed to react with caustic soda or hydrated lime and the ethylene oxide removed as fast as it is formed. Maximum yields of ethylene oxide are about 9 5 % . DEC.
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19 55
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•1 .!
L
Ethyiene oxide and ethylene glycols are produced in this unit at Carbide and Carbon's Institute, W. Va., plant The direct oxidation reaction really amounts to " a controlled burning of ethylene. Reaction products are ethylene oxide, carbon dioxide, and water. 0 2 C H 2 = C H 2 • f- 0 2
2CH 2 =CH 2 -Ι Ο
6Ο2
/ \ • 2CH2—CHj 4C0 2 + 4H 2 0
/ \
-1- 50 2 -> 4C0 2 + 4H 2 0 Silver in its elemental form seems to be a specific catalyst. The most suc cessful catalyst supports are inert mate rial of irregular shape and large sur face area. T h e careful use of reaction inhibitors, such as the alkyl halides, helps to prevent undesirable side re actions. Until 1954, Carbide and Carbon was 2 C H.2—OH2
the only American company making ethylene oxide by direct oxidation of ethylene. As late as the early 1950's large facilities using the chlorhydrin synthesis were being constructed. In recent years, however, interest has focused on the direct oxidation method. Contributing to this shift in emphasis have been the rising price of chlorine (the chlorhydrin method needs about 2.1 pounds of chlorine per pound of oxide); the greater availability of high* purity, low-cost ethylene (the direct method requires about 1.2 pounds of ethylene for every pound of ethylene oxide, while the chlorhydrin method takes about 0.9 p o u n d s ) ; and the de velopment of commercially feasible direct oxidation techniques. Other fac tors influencing interest in the direct oxidation process have been the prob
New Text 5312
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1955
lems entailed in marketing co-products of the chlorhydrin synthesis and the high cost of constructing facilities resistant to hypochlorous acid and ethylene chlorhydrin. Still, for many firms—particularly those that have chlo rine available and those operating smaller capacity plants—the chlorhydrin process continues to be of interest. Applications A r e M a n y Ethylene oxide reacts exothermically with all compounds having a labile hydrogen atom (water, alcohols, amides, phenols, cellulose, ammonia, amines, organic acids.) This reaction permits the introduction of the hydroxyethyl group ( - C H 2 C H 2 O H ) into a variety of compounds and results in products with greater water-solubility and higher boiling points. Further re action with ethylene oxide yields poly ethylene oxide derivatives. For ex ample, ethylene oxide reacts with water to make ethylene glycol; further re action yields polyethylene glycols. Etuvlene oxide reacts with hydrophobic substances containing a labile hydrogen atom (fatty acids or alkylated phenols, for example) to make nonionic surface active agents. The water-solubility and surface-activity of the products are determined b y the number of moles of ethylene oxide reacted with the hydro phobic structure. T h e affinity of ethylene oxide for strong acids makes
CHEMICALS it valuable for removing t h e last traces of acid where the use of aqueous al kalies is undesirable. Ethylene Glycol. Ethylene oxide combines with water to make ethylene glycol. In this reaction about 10% diethylene glycol and 1% triethylene glycol are also formed.
New Text Automotive and Aircraft Plastics, Rubber, Film
Ο CH2—CHo 4- HOH -* HOC2H4OH Ο
/
Synthetic Detergents
\
HOCH4OH + CIi 2 —CH 2 - * HOC2H4OC2H4OH Ο / \ HOC*H 4 0H + a:(CH 2 -CH 2 ) -* HO(C 2 H 4 0)r 4-1 + OH Ethylene glycol production takes somewhat more than half the output of ethylene oxide. About three fourths of the ethylene glycol production goes into nonvolatile-type antifreeze. Hence, the antifreeze market has had a power ful influence on the growth of ethylene oxide. Other uses for ethylene glycol are growing rapidly and making a valuable contribution toward broaden ing the market for ethylene oxide. The second largest use for ethylene glycol is in the manufacture of ethylene glycol dinitrate for low-freezing dyna mite. At one time most accidents in volving dynamite resulted from its freezing. By lowering the freezing point of dynamite, ethylene glycol di nitrate has helped to make it safer to handle. Another big use for ethylene glycol is as a moistening agent for cellophane. Over 300 million pounds of cellophane were produced in 1954. Many grades contain 10 to 15% ethylene glycol be cause it is an effective humectantplasticizer that contributes flexibility over a wide temperature and humidity range. Ethylene glycol is a solvent and suspending medium for ammonium perborate, the conductor in practically all electrolytic capacitors. These capac itors are essential parts in radios, TV sets, automatic washers, and other electronic equipment. Combinations of ethylene glycol, glycerol, and pentaerythritol react with phthalic anhydride, and other dibasic and fatty or rosin acids, to make alkyd resins which are widely used in surface coatings. Ethylene glycol, diethylene glycol, 1,2,6,-hexanetriol, and other polyols are caused to react with dibasic acids
Textiles
Petroleum
Other
New Text Ethylene Glycol (anti-freeze)
Ethylene Glycol (industrial) Diethylene Glycol and Triethylene Glycol Ethanolamines Glyccl-Ethers Polyethylene Glycols Other Uses
(adipic is the most common) to make polyesters. These polyesters are crosslinked with diisocyanates to yield polyurethane elastomers that show promise in such applications as tires, shoe soles, and film. The cross-linked diisocyanates can also be fabricated as rigid or flexible foams that are oil-, chemical-, and fire-resistant. Ethylene glycol condenses with di methyl terephthalate to yield a poly ester resin that is spun into Dacron fiber or cast as Mylar film, Polyester-glass fiber laminates appear to have large future markets in the manufacture of building materials, auto bodies, furniture, railway cars, and other products. The resins in these laminates are generally made from
maleic anhydride or fumaric acid, an unsaturated monomer such as styrene, and a glycol. Propylene glycol fur nishes the major portion of glycol, b u t ethylene and diethylene glycols are also used. Diethylene Glycol. Sales of diethyl ene glycol last year exceeded 41 million pounds requiring about 34 million pounds of ethylene oxide. Probably the earliest tonnage use for diethylene glycol was as a plasticizer for the phe nolic resin used to bind cork granules in gaskets and tile. Diethylene glycol also finds important applications as a dyestuff solvent, hemp saturant in a gas-main anti-leak, a n d dehydrating agent for natural gas. One of the newer uses for diethylene glycol is in DEC.
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CHEMICALS the Udex process for selective absorp tion of aromatic hydrocarbons from various hydrocarbon mixtures. P o l y e t h y l e n e Glycols. Polyethylene glycols are characterized by good lu bricity, blandness, heat stability, and inertness to many chemical agents. They are humectants and water-soluble lubricants a n d find markets in such di versified applications as rubber mold lubricants and washable ointment bases. As intermediates for plasticizers and emulsifiers, they find applications in coatings, pharmaceuticals, cosmetics, and agricultural chemicals. They are marketed in a range of molecular weights. Carbowax polyethylene glycols, for example, are sold commer cially in average molecular weights of 200, 300, 400, 600, 1000, 1540, 4000, and 6000. Higher molecular weight polyglycols are offered in experimental quantities. Ethylene Chlorhydrin. Ethylene cWorhydrin is obtained b y t h e hypochlorination of ethylene. If t h e anhy drous product is desired, it is m a d e by reacting ethylene oxide with hydrogen chloride. Ethylene chlorhydrin with trimethyl amine yields choline chloride, a feed supplement for poultry. T h e reaction of ethylene chlorhydrin with formaldehyde yields dichlorethyl for mal. Dichlorethyl formal has long been the basis of the polysulfide rub bers, which a r e mainly used in making self-sealing fuel lines a n d fuel tanks for military aircraft. Acrylonitrile. Ethylene cyanohydrin, produced by combining ethyl ene oxide with hydrogen cyanide, is an intermediate in t h e traditional process for making acrylonitrile. About 63 million p o u n d s of acrylonitrile were m a d e last year, most of it by t h e oxide route. Ο CH 2 —CH 2 + HCN - * HOC2H4CN HOC2H4CN __ E>0 > CH2=CHCN Acrylonitrile-butadiene elastomers are oil-resistant a n d have excellent lowtemperature properties. Acrylic fibers a r e well known to the consumer as dynel, Acrilan, a n d Orion. Acrylo nitrile has also shown promise as a cyanoethylating agent for modifying cotton, as a copolymer for plastics, and as a chemical intermediate. Ethfittolomines» Ethylene oxide re acts with ammonia to form mono-, di-, 5314
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and trietiianolarnines. By controlling the ammonia-ethylene oxide ratio, t h e production of t h e different ethanolaniines c a n , within certain limits, b e controlled. HOC2H·.•·*
\ FOUNTAINS • · · offer a way to more adequately
protect
employees' eyesight and avoid costly insurance claims... by providing a safe method for workers to flush injurious chemicals and particles from their own eyes immediately — before greater damage can be donel And, wherever there is danger of workers' hands, face or clothing being contaminated by acids or caustic chemicalsinstall HAWS Emergency Drench Shower Equipment. Cost is negligible. Ask your plumbing contractor, or write today for complete information.
H A W S D R I N K I N G FAUCET C O . 14 3 9 F O U R T H S T R E E T · BERKELEY 1 0 , C A L I F O R N I A
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Published statistics on antifreeze con sumption, like most statistics, a r e in complete and require interpretation. Weather is difficult to predict and buy ing attitudes of car owners are h a r d t o forecast. Events of the past few years have emphasized these difficulties. Still, the preceding figures give a n idea of t h e growing market for ethylene glycol as an antifreeze. Points worth considering, too, are the trend toward larger engines that use more antifreeze, and the trend toward nonvolatile anti freeze. It is estimated that within a few years close t o 70% of the antifreeze market may go t o ethylene glycol. Other Growth Markets, Industrial applications for ethylene oxide have recently been growing at an annual rate of about twice that for antifreeze use. A few of the higher growth rate appli cations are surface active agents; polyglycols; ethanolamines; polyester fab rics, films, elastomers, and plastics. Nonionic surface active agents have been riding t h e synthetic detergent boom. Over 2 billion pounds of for mulated synthetic detergents were sold in 1954. The active ingredients used in formulating these products represent a market for about 61 million p o u n d s of oxide. T h e proportion of the market going to ethylene oxide is increasing due, in part, t o the growing m a r k e t for low-sudsing household detergents containing poly glycol esters and ethers and the increasing use of alkylolarnides as organic builders in high-sudsing detergents. In addition, industry i s every day finding new uses for ethylene oxide derived surfactants because of their excellent grease dispersing p r o p erties, chemical stability, and insensitivity to h a r d water. T o meet the growing demands and t o meet the needs of national policy, t h e productive capacity for ethylene oxide has expanded rapidly. Production for 1954 was a b o u t 650 million p o u n d s and was somewhat under capacity for that year, partly rejecting the effects of a mild winter. Production for 1955 is running close to capacity, which is currently estimated at about 850 mil lion pounds. With the completion of additional facilities next year, however, a condition of excess capacity may exist. In the meantime, the companies with years of experience, with established antifreeze outlets, and with a range of chemicals derived from ethylene oxide will be in the best position to benefit from the versatility of ethylene oxide, H
from a SPECIAL kernel of corn,
Photo courlesy of Corn Industries Research Foundation, Inc.
S T A R C H wrtifci Ixlglcily "toranoliecl molecules —that effectively resists r é t r o g r a d a t i o n o r "set b a c k " after c o o k i n g . This is A M I O C A , N a t i o n a l ' s highly b r a n c h e d , 1 0 0 % a m y l o p e c t i n s t a r c h * . It forms strong, clear, c o n t i n u o u s films a n d exhibits excellent resistance t o jelling. A few of A M I O C A ' S practical uses include: • Paper Sizing and Finishing—for calender stack and size press application to improve gloss ink printability, surface strength, w a x holdout and as a presize f o r protective coatings. • Frozen Food Thickening—also for pie fillings, soups, etc., where clarity and a minimum of rétrogradation are essential. • Textile Sizing, Printing and Finishing. • Adhesive o r Bonding Applications. • Extender f o r Synthetic Resins—where cold stability is desirable. • Replacement for Expensive Natural and Synthetic Thickeners. W h e r e c a n y o u use A M I O C A ? *AM/OCA (omylopectin) is one of the two molecular components of ordinary corn starch. The other comoonen/ known as amylose—which is linear, is obsenf in the AMIOCA starch. AMIOCA is produced from α υη/ς ,e hybrid corn grown especially /or National, and refined in our Indianapolis plant.
Afafien&C STARCH P R O D U C T S I N C . 270 Madison Avenue, New York 16
·
3641 So. Washtenaw Avenue, Chicago 32
·
735 Battery Street, San Francisco 11 DEC.
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