C&N
special report
TRIETHYLENE GLYCOL
ETHYL CHLORIDE
ETHYLENE DIBROMIDE
The flow chart from ethylene to end products follows devious paths. First-line derivatives—as polyethylene or ethyl alcohol, for example—can be put to use directly. Or the first-line derivatives can be converted to second-line derivatives, as shown here for ethylene oxide; and these, in turn, can be converted to subsequent derivatives. The possibilities in end products become seemingly endless 148
C&EN
SEPT.
10,
196 2
E
THYLENE
A Five-Year Forecast CAPACITY BY 1964 about 9 billion pounds annually DEMAND BY 1967 about 8 billion pounds annually RESULT a comfortable relationship between capacity and demand WALTER S. FEDOR, Senior Associate Editor Ethylene is booming again. The industry is off in another capacity race which should raise the nation's supply potential to more than 9 billion pounds a year by the end of 1964. Capacity this year should total 7.4 billion pounds, but an expected demand of about 6.1 billion pounds will pose problems of overcapacity. By 1967, however, demand should approach 8 billion pounds, providing a comfortable relationship between capacity and demand. In the tradition of ethylene production, most expansions are taking place along the Gulf Coast; and based on present plans, that area will have 74% of our total ethylene capacity. Another 23% will be located in the central United States. The latest round of expansions features several large plants: • Monsanto's 550 million-pound-a-year plant at Chocolate Bayou, Tex., should start production later this year. • Gulf plans a 400 million-pound plant at Cedar Bayou, Tex., which it hopes will be the center of several satellite operations. • Amoco plans a similar development at Morris, 111., with a plant that should have a capacity of about 250 million pounds. • Allied's ethylene unit at a proposed complex in Geismar, La., should have a capacity of 300 million pounds.
• B. F. Goodrich Chemical plans to build a 250 millionpound plant at Calvert City, Ky. This plant will produce ethylene both for sale and for captive use. Besides these ambitious undertakings, several smaller expansions are either under way or planned by El Paso Natural Gas/Rexall Chemical, Sun Olin, and Texas Eastman. Further, Dewey Oil & Refining is believed to be interested in the ethylene business, and the trade expects Collier Carbon to build a plant. Significantly, about 80% of the new production is destined for captive use, so that added pressure will be put on merchant ethylene producers. These currently include Gulf, Humble, Petroleum Chemicals, Phillips, Mobil, Union Carbide Olefins, and Sun Olin, and naturally other ethylene producers sell the olefin when demand is large. Ethylene sales reached 3.36 billion pounds last year, according to the Tariff Commission. However, these include intercorporate sales, such as between Union Carbide Olefins and Union Carbide Chemicals. Excluding such movement, ethylene sales were likely nearer 1.5 billion pounds in 1961. Production grew from 3.05 billion in 1955 to 5.66 billion pounds in 1961, an 11%? average annual rate of increase. Looking to the future, production should hit 6.1 billion pounds this year, and it should rise to near 8 billion pounds in 1967. Practically all of the ethylene produced is transported by pipeline, with Gulf owning the largest line stretching some 175 miles from Port Arthur to Beaumont, Houston, SEPT. 10, 196 2 C & E N
149
ETHYLENE PRODUCTION Millions of Pounds 8000 r
6000
4000
2000
n» '50
I I I I I I I I I I 1 I I I i I1 '52
'54
'56
'58
'60
Source: U.S. Tariff Commission
'62* *C&EN
'67* estimates
and Orange, Tex. The product moving through most of these lines now is 99.9% ethylene. But only a few years ago it was chiefly 98% or less, and firms had to upgrade the material when higher purity was desired. About 35% of the ethylene produced today comes from refinery gases and 60% comes from liquefied petroleum gas with the balance coming from miscellaneous raw materials. The cost of producing it is probably 3.5 to 4.0 cents a pound, including raw materials, labor, fuel, taxes, and various fixed charges. It currently sells on contract for 5.0 cents a pound f.o.b. along the Gulf Coast, a price at which it has held for some time. East Coast material sells for 3 / 4 cent higher, and any midwest movements would likely add a half cent to a cent. There are frequent reports of sales at 4.5 cents, but the trade consensus is that the 5-cent price is pretty firm. This is not to say, however, that there isn't some price shaving at times. Contracts often run five to 10 years, with some going for three to five years. But, whatever their period, most contracts have escalator provisions to cover the rising costs of raw materials, labor^ and the like. Ethylene s future depends, of course, upon the well established traditional outlets. Polyethylene, ethylene oxide, halogen derivatives, ethyl alcohol, and styrene monomer should take about 7.4 billion pounds five years hence, compared to more than 6.0 billion pounds this year. But adding to future prospects are the ethylene-propylene elastomers, which are about to break into the rubber market. EPR (ethylene-propylene rubber) can contain between 20 and 80% ethylene, with 50% being an average. The material will move into nontire markets first and into tire markets later (C&EN, March 12, page 88). Output should run near 9 million pounds this year, rising to 184 million pounds in 1967. Straight-chain alcohols such as those made by Continental Oil should consume about 60 million pounds of ethylene by 1967. And the ripening alpha-olefin field is drawing intense interest from Continental, Enjay, Gulf, California Chemical, and others. Developments in biodegradation of detergents will strongly influence the future of the .alphaolefins. Other possibilities in ethylene's future lie in acetaldehyde production directly from ethylene via the Wacker process. Celanese uses such a route now, and Union Carbide has a license. All told, miscellaneous ethylene uses that are rather small today can add up to 300 million pounds of the olefin annually by 1967. Polyethylene—Top
POLYETHYLENE PLANT. Dow Chemical's polyethylene plant atFreeport, Tex., has a 100 million-pound-a-year capacity. Polyethylene took 33% of all ethylene consumed last year
150
C&EN
SEPT.
10, 196 2
Ethylene
User
The polyethylenes constitute a fantastic success story for the chemical industry. This year's production will approach, or perhaps even pass, 2 billion pounds-nearly 30% of the total plastics and resins output. About 1.6 billion pounds will be high-pressure produced (low density), and 400 million pounds will be low-pressure produced (high density). Last year 1.32 billion pounds of high pressure polyethylene and 286 million pounds of low pressure polyethylene were produced, to bring a total of 1.6 billion pounds. In contrast, only 55 million pounds of polyethylene were produced in 1950, all by Carbide and Du Pont. Since that year, the average annual production growth rate has been 40%, and last year 15 producers were making the material. Naturally, this growth rate has lessened, averaging 25%
a year since 1955; but the rate is still expected to be about 15% annually over the next five years. This would bring polyethylene production to nearly 3 billion pounds in 1967, with a consequent demand for nearly 3.15 billion pounds of ethylene. As a part of the market, polyethylene accounted for 3 3 % of ethylene's consumption last year, and in five more years it should take 40%. Current polyethylene capacity totals about 2.6 billion pounds, of which about 75% is for conventional material. Despite the present capacity level's implication of excess, more expansions are expected. Actually, the picture of excess capacity is misleading, since it applies only to high density material. Conventional polyethylene is running at nearly 85% of capacity, and film grade resins are in tight supply. High density producers, on the other hand, are operating at about 65% of capacity, but even here the rate is improving. As would be expected, lower prices have helped polyethylene sales. In addition, grade pricing by Carbide, Eastman, and others has discouraged the below-list selling that became part and parcel of the ethylene business, although such selling is still a problem with injection molding grades. Under grade pricing, substandard conventional molding resins sell for 22 cents a pound, and belowspecification film grade resins go for 2 3 V 2 cents. Top grade conventional polyethylene still goes for 27V 2 cents a pound, while the high density type sells for 32 cents. Copolymers, such as those made with acrylates, acetates, and butenes, constitute a separate aspect of the polyethylene business. Made primarily in linear facilities, most copolymers have specific uses-for blow-molded detergent bottles, for example-and they bring prices above those for regular grade material. Blow molding, incidentally, should be a 185 million-pound market in 1962. This, together with a market for film at 525 million pounds and for injection molding resins at 210 million pounds, should bring total consumption (sales) to nearly 1.9 billion pounds. Hence, polyethylene is well ahead of earlier forecasts which originally had been considered optimistic. The supposed weakness in polyethylene's future lies in the export market. Export declines have been forecast repeatedly, and they may well appear now that European tariffs have been raised; but the fact remains that, thus far, such declines have not appeared. This year's exports are going at a rate which could bring the total to 400 million pounds, about 30% more than in 1961.
Slow Growth for Ethylene
MAJOR ETHYLENE CONSUMPTION Millions of Pounds \ Outlet 1960 1962 1967 Ethyl alcohol 1120 1190 1150 Ethylene oxide 1580 1550 1650 Ethyl chloride 250 230 185 Ethylene dibromide 32 32 35 Ethylene dichloride 400 430 480 Polyethylene 1405 2100 3150 Styrene monomer 555 575 800 Miscellaneous 50 70 300 Totals 5392 6137 7790 Source: C&EN estimates
Oxide
Polyethylene displaced ethylene oxide last year in the latter's historic role as top user of ethylene, but the oxide will still consume 26% of the olefin's output. Last year, ethylene oxide production was 1.29 billion p o u n d s some 12% less than in 1960-and this year's rate is below 1960's; but a prewinter spurt should bring production to about 1.3 billion pounds. Ethylene oxide has a myriad of uses, the most important being for ethylene glycol and to a lesser extent for di-, tri-, and polyethylene glycol, glycol ethers, ethanolamines, acrylonitrile, and nonionic surface-active agents. These end uses should post gains over the next five years. Production of ethylene oxide through 1967, however, should increase only 2 % a year, as opposed to 5.5% since 1955, because of the leveling of needs for ethylene glycol. This would mean production of about 1.55 billion pounds in
CLEAR VIEW. This year's market for polyethylene film should be 525 million pounds, much for wrapping everything from apparel to zucchini, from loaves of bread to locomotives
SEPT.
10, 1962 C&EN
151
1967, with a consequent need for 1.65 billion pounds of ethylene. In this connection we should remember that, on the average, it takes 1.0 to 1.1 pounds of ethylene to make a pound of oxide via direct oxidation processes, compared to 0.8 pound by the chlorohydrin route. Ethylene oxide capacity is about 1.7 billion pounds now, not including 130 million pounds of capacity owned by Carbide in Puerto Rico. The most significant change in oxide production in recent years has been the nearly complete switch to direct oxidation, using either the Shell or Scientific Design routes. Dow still uses the chlorohydrin methods, as does Jefferson Chemical; but by and large, chlorohydrin facilities have been converted to produce propylene oxide. Monsanto included ethylene oxide in the original plans for its Chocolate Bayou complex, but deferred such plans this year; and it is doubtful that others would plan to produce oxide until demand gets much closer to supply. Direct oxidation processes have helped to push the oxide's price down. It was 19V4 cents a pound in 1951, and it plunged to 1 3 1 / 2 cents in 1954 before rising to the present 15 1 / 2 -cent level. The tendency should be for ethylene oxide's price to rise in the future, but competitive pressures so far have deferred prospective hikes. Aside from intermediates, ethylene oxide is also used in food sterilization and fumigants; but these are negligible outlets.
COLD MARKET. Antifreeze is the big market for ethylene glycol. But the market won't change much, climbing but little in coming years; so glycol use won't change much either
E T H Y L E N E GLYCOL CAPACITIES
Company Allied Chemical Atlas* Calcasieu Chemical D o w Chemical D u Pont** General Aniline & Film H o u s t o n Chemical Jefferson Chemical Olin M a t h i e s o n Union Carbide Chemical W y a n d o t t e Chemicals
Ethylene Glycol Market
Capacity Millions of Pounds 35 10 75 350 150 35 100 180 100 750 90 T o t a l 1875
* Based on fermentation ** Based on formaldehyde Source: C&EN estimates
1 GLYCOL E T H E R S CAPACITIES Capacity Millions of 1 Company Pounds 1 D o w Chemical 1 Midland, Mich.) 40 (combined) I Freeport, Tex. \ 1 Olin M a t h i e s o n 1 Brandenburg, Ky.
C&EN
SEPT.
10, 196 2
1 1
20
1 Union Carbide Chemicals* 1 I n s t i t u t e , W.Va. } S o u t h Charleston, W.Va. ( 150 (combined) T e x a s City, Tex. ( Seadrift, Tex. J T o t a l 210 1 * Union Carbide is expanding possibly by at least 50% I Source: C&EN estimates 152
|
1
1 \
Mature
As antifreeze goes, so goes ethylene glycol. It follows that, since the antifreeze market is essentially static, glycol's future isn't encouraging. It's a question of incremental gains. Last year, glycol production was 1.14 billion pounds, down 12% from 1960; and about 1.15 billion pounds are expected this year, with a mild rise to 1.2 billion pounds projected for 1967. Present capacity is roughly 1.9 billion pounds a year. Permanent type antifreeze takes about 85 to 90% of the ethylene glycol produced; and last year, glycol antifreeze demand was about 115 million gallons, a bit higher than in the previous year. About the same is expected in 1962, and it shouldn't be much different five years from now. Glycol types claim 95% of the antifreeze market now and could take 97 to 98% in five years. That's just about the limit. Future hopes for glycol growth are keyed to vehicle registrations, and this picture becomes muddied by the advent of the compact car, whose 10- to 11-quart cooling systems compare to 18 or 19 quarts for conventional size automobiles. On top of this, impending development of gas turbine cars poses a continuing threat, and some models of these should be available to the public by 1967. More promotion of automobile air conditioning could provide a lift for the glycol market. Promotion of long-life antifreeze by Dow, Du Pont, and Union Carbide did not succeed very well. Buyers weren't enthusiastic about higher prices; and, frankly, many motorists never drain their glycol anyway. They simply add more inhibitor each year—and some don't even do that. Hence, future growth for ethylene glycol must rely on nonantifreeze outlets. There is more trouble here. The death knell for ethylene glycol's use in cellophane was sounded by fears of toxicity, which resulted in a transfer to the use of propylene glycol as a humectant-plasticizer. Expanded use of
explosives such as glycol dinitrate was clipped by ammonium nitrate's growth, and the industry could hardly become excited over prospects for alkyd resins. These three outlets consumed 55 to 60 million pounds of ethylene glycol in 1961 and should take only 50 million pounds five years from now. Exports ran 64 million pounds last year, down some 50 million pounds from I960, and the trade estimates that exports will be somewhat less in five years. The only significant growth in ethylene glycol end uses lies in polyester fibers and films, which are generally formed on the basis of the reaction between ethylene glycol and dimethyl terephthalate. Output of polyester fibers should reach 135 million pounds this year, rising to 230 million pounds in 1967. Polyester films should reach 30 million pounds this year and move up to 70 million pounds in Rve years. Miscellaneous uses for ethylene glycol include hydraulic fluids and brake fluids, and such outlets are up-and-down markets. Nothing really large looms here to promise a push in glycol demand.
1 1 1 1 1 1 1 1 1
ETHYLENE OXIDE CONSUMPTION (Major Derivatives) Millions of Pounds \ 1960 1962 1967 Outlet 860 925 830 Ethylene glycol 96 98 113 Diethylene glycol 37 40 45 Triethylene glycol 36 33 44 Polyethylene glycol 85 115 145 Glycol ethers 112 120 150 Ethanolamines 50 42 40 Acrylonitrile 170 180 265 Surface-active agents 1458 1672 Totals 1501 Source: C&EN estimates
Other Glycols The various higher glycols cannot contribute much to any over-all increase in ethylene oxide consumption. But such chemicals, including di-, tri-, and polyethylene glycol and the glycol ethers, do have some promise in themselves. The di- and tri- materials are produced as coproducts in ethylene glycol manufacture in the ratio: 100 parts ethylene glycol, 10 parts diethylene glycol, one part triethylene glycol. Diethylene production was about 102 million pounds in 1961, and a similar amount is expected this year. That production is used mainly to make triethylene glycol, an outlet which should take 22 to 25 million pounds this year. Exports provided a large market, accounting for some 20 million pounds in I960, but that amount will probably be halved this year and should go even lower by 1967. Declines in the market for diethylene glycol are also expected in gas purification uses, which now consume about 10 million pounds. One well known use for the material is in solvent extraction (Udex) of benzene, toluene, and xylene, but this market is giving way to triethylene glycol. Polyester resins provide a growth area, particularly where the polyesters are based on isophthalic acid. This use should take nearly 13 million pounds in 1962 and rise to about 20 million pounds in five years, tracing fairly closely the growth rate of isophthalic acid. Other markets include brake fluids, textile specialties, and urethane foams and elastomers. All told, diethylene glycol production should reach 120 million pounds in 1965. Meanwhile, triethylene glycol output should approach 52 million pounds, compared to 40 million pounds this year. Like diethylene glycol, it has a myriad of uses, but about 30% is used in gas dehydration. Solvent extraction, as mentioned earlier, is the best prospect for future growth and should take about 5 million pounds in five years, compared to about a million pounds this year. Other outlets include emulsifiers, lubricants, polyesters, and alkyd resins. Production of polyethylene glycols should run to 30 million pounds in 1962, compared to 28 million pounds in 1961, but the future of polyethylene glycols seems to lie beyond 1967. Union Carbide Chemicals began to produce these glycols in 1947. Other producers now are Dow, Olin Mathieson, Wyandotte, Jefferson, Allied, and more recently,
ETHYLENE OXIDE PRODUCTION Millions of Pounds 1600 1500 1400 1300 1200 1100 1000
'50
'52
I I I I I I I I I I M '54 '56 '58 '60 '62*
Source: U.S. Tariff Commission
I
4
'67*
C&EN estimates
S E P T . 10, 1962 C&EN
153
ETHANOLAMINES CAPACITIES Capacity Millions of Pounds 1 Allied Chemical Orange, Tex. Dow Chemical Midland, Mich. Freeport, Tex. Jefferson Chemical Port Neches, Tex. Olin Mathieson Brandenburg, Ky. Union Carbide Chemicals Seadrift, Tex. South Charleston, W.Va.
10 30 10 40 10
Total
60 60 220
Ethanolamines Make Steady Progress
Source: C&EN estimates
ETHANOLAMINES PRODUCTION Mono Ethanol Amine
H i l l D i E t h a n o l Amine T r i E t h a n o l Amine
Millions of Pounds 175
'54 '55 '56 '57 '58 '59 '60 '61 '62* '67* Source: U.S. Tariff Commission * C&EN estimates
154
C&EN
SEPT.
10, 196 2
\ 1
General Aniline & Film. They are made by reacting ethylene oxide with ethylene glycol or water, and a variety of molecular weights is obtainable. They have many uses, including plasticizers, lubricants, and emulsifiers. By 1967, about 35 to 40 million pounds should be made annually. Glycol ethers, the reaction products of ethylene oxide witfi various alcohols, have leaped into prominence. Demand should approach 205 million pounds this year and rise to about 240 million pounds in 1967, which means a need for about 120 million pounds of ethylene oxide. Present capacity for producing the ethers is estimated at 210 million pounds, with Carbide having 150 million pounds, and Olin and Dow dividing the balance. Carbide, incidentally, is expanding its operations along this line. Typical compounds in this group of products are ethylene glycol monoethyl ether and diethylene glycol monoethyl ether. One reason for anticipating growth in this market lies in jet fuel additive specifications that were issued on April 1. These call for a mixture of 87% glycol ether (methyl cellosolve) and 13% glycerine for de-icing purposes. This alone could amount to a 30 to 35 million-pound market. Other uses for the materials include solvents for acrylic lacquers, brake fluids, and detergents.
Ethanolamines are in an unusual situation in the presentday chemical industry, in that list prices haven't declined despite much overcapacity. Monoethanolamine lists for 25 cents a pound (tanks, freight allowed), diethanolamine is posted at 2 4 1 / 2 cents, and triethanolamine at 22 cents. These prices have existed since the mid-1950's and, furthermore, there are no reports of below-list selling. Capacity hasn't changed in several years. The ethanolamines are made by five companies with a total capacity of 220 million pounds annually and with Union Carbide Chemicals owning 55% of the supply potential. Actually, since the process seems so simple, it is surprising that other firms haven't entered the market. Reaction of ethylene oxide with ammonia provides the product, usually in a ratio of 1.2 pounds per pound of oxide; and the yields of mono-, di-, and tri- product can be varied by reaction conditions. Ethanolamines production has increased 8% annually since 1955, and a future growth of an estimated 6% annually should bring output to 170 million pounds in 1967. Last year, 127.2 million pounds were made, of which 34% was monoethanolamine, 39% was diethanolamine, and 27% was triethanolamine. This production was just a shade over 1960's level, but the distribution in that year was difrerent-35, 43, and 22% for the MEA, DEA, and TEA, respectively. This shift was due to the use of triethanolamine as a plasticizer in certain cellophanes, an outlet which developed partly because of the shift to propylene glycol in cellophane coating. The ethanolamines are characterized by an extremely diverse end use pattern, which includes detergents, textile chemicals, gas scrubbing, pharmaceuticals, emulsion polishes, and corrosion inhibitors. Thus the outlook must involve steady growth. Consumption should approach 153 million pounds in 1.965, compared to about 118 million pounds in 1962. Detergents are the largest outlet for the product, accounting for 3 1 % of consumption, and the situation shouldn't
change as this application takes 50 million pounds in 1967. DEA will probably account for 30 to 35 million pounds, MEA about 10 million pounds, and TEA about 8 million pounds. The materials are used mostly in liquid detergents, as opposed to solid detergents, and hopes for wide use in the latter did not materialize. Also, the trend to lowsudsing detergents has crimped the ethanolamines in this field. Gas scrubbing to remove acid gases claims about 2 5 % of all the ethanolamine produced. Growth here should be modest because of competition from hot potassium carbonate solution and other agents. MEA is preferred in gas scrubbing because hydrocarbons are more soluble in it than in DEA or TEA. This market should take 40 million pounds of ethanolamines in 1967, of which 30 million should be MEA. Other significant outlets for the materials include textile specialties, which should use 23 million pounds in 1967, compared to about 20 million pounds this year. DEA has about half of that business; but TEA has the bulk of the cosmetics market, which should rise to about 16 million pounds in five years. This market should run to about 11 million pounds this year. The balance of the ethanolamines will find many uses, such as in herbicides, plasticizers, waterproofing agents, corrosion inhibitors, and morpholine. As a group, the miscellaneous markets will grow modestly to about 24 million pounds of ethanolamines in 1967.
ETHANOLAMINES DOMESTIC CONSUMPTION
|
1 Outlet
Millions of Pounds 1960 1962 1967
Detergents 1 Gas scrubbing 1 Textile chemicals Cosmetics Miscellaneous Totals
35 27 18 10 20 110
Source:
37 29 20 11 21 118
\
50 40 23 16 24 153
C&EN estimates
ETHYLENE DERIVATIVES PRODUCTION Millions of Pounds 3000
Nonionic Surfactants Show Promise 2500 With an average production increase of 16% annually since 1955, nonionic surface-active agents are the fastest growing class of surfactants. Output reached 446 million pounds last year, roughly 5% higher than in 1960. This year's production should be about 460 million pounds, and the outlook for 1967 indicates about 625 million pounds. Most nonionics are liquids. Although more than 50% are used in industrial applications such as commercial laundries and the textile industry, a key reason for the nonionic spurt is a trend to low-sudsing detergents for household use. Oddly, this was considered a detrimental characteristic a decade ago. During the past decade, liquid detergents have had a startling growth. Sales soared to 711 million pounds in 1961, compared to 38 million pounds in 1951—a 34% average annual growth rate. Liquids will continue to grow, but at a less spectacular rate in the years ahead. The liquid detergent business falls into three major categories—heavyduty, light-duty, and all-purpose cleaners—with light-duty materials taking about 70% of the market and heavy-duty types taking about 15%. There are several major classes of nonionic detergents. The various alkanolamides make up the largest single class, with the most important ones being products made from lauric acid and diethanolamine. About 75 to 80% of the alkanolamides are used in household detergents, with the balance winding up in industrial applications. But some 70 to 7 5 % of the various alkylphenol-ethylene oxide derivatives are used for industrial applications such as in textile specialties and metal cleaners. Nonionics are also made from tall oil and ethylene oxide, fatty alcohols and ethylene oxide, and various polyols such as sorbitol and mannitol; and the many types use varying amounts of ethylene oxide. For example, it takes 0.64
Polyethylene,
2000 Styrene monomer
1500
Ethyl alcohol (synthetic)
1000
500 Ethyl chloride
I I I I I I I I I I I I I I I I '50
'52
'54
'56
'58
Source: U.S. Tariff Commission
SEPT.
'60
'62*
'67
*C&EN estimates
10, 1 9 6 2 C & E N
155
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GENERAL ANILINE & FILM
Refinery gas Chlorohydrin
60
Ethylene
Baton Rouge, La. (17) Beaumont, Tex. (20)
Process or Probable Major Raw Material
E t h y l chloride
Odessa, Tex. (31)
Houston, Tex. (23) FOSTER G R A N T
Probable Present Expansion Product ( Capacity by 1964 (millions of pounds) — Ethylene 190 Ethylene oxide 60 Ethylene 125 dichloride Conventional 50 polyethylene — 530 Ethylene 240 Ethylene oxide E t h y l chloride 200 Ethylene dichloride 125 Conventional 100 polyethylene Styrene 500
LPG Ethylene Ethylene
180
Conventional polyethylene
10
Ethylene oxide
60
Ethylene Ethylene dichloride
—
Direct oxidation 250
LPG
100
Port Neches, Tex. (20)
Linear polyethylene
13
Baton Rouge, La. (17)
Linear polyethylene
75
W. R. GRACE (Cosden Petroleum)
Big Springs, Tex. (30)
Styrene
70
G U L F OIL
Port Arthur, Tex. (21) Cedar Bayou, Tex. (22)
Ethylene
425
—
Refinery gas
Ethylene
—
400
LPG
W. R. G R A C E
HERCULES POWDER
Parlin, N.J. (1) Hopewell, Va. (7)
HOUSTON CHEMICAL
Beaumont, Tex. (20)
H U M B L E OIL & R E F I N I N G (Enjay Chemical)
Bay way, N.J. Baton Rouge, La. (17)
Baytown, Tex. (23)
a)
Linear polyethylene E t h y l chloride
80 25
Ethylene
Ethylene oxide
80
Direct oxidation
Ethylene Ethylene
175 590
Synthetic ethyl alcohol Ethylene
(55 million gallons) 80 SEPT.
_
Refinery gas Refinery gas, LPG, and crude oil
—
Refinery gas
10,
196 2 C & E N
157
Location and Key Number on Map
Company JEFFERSON CHEMICAL
P o r t Neches, T e x . (20)
Product Ethylene E t h y l e n e oxide Ethylene dichloride
KOPPERS
P o r t Reading, N . J . (1) K o b u t a , P a . (6) Port Arthur, Tex. (21)
Linear polyethylene Ethylene Styrene Conventional polyethylene
Probable Expansion Present by 1964 Capacity (millions of pounds)
Refinery gas Chlorohydrin D i r e c t oxidation
250 120 90 15 30 25 174
—
E t h y l ether
—
L P G and refinery gas
60
MOBIL CHEMICAL
Beaumont, Tex. (20)
Ethylene
380
MONSANTO CHEMICAL
T e x a s City, T e x . (24)
Ethylene Ethylene dichloride Conventional polyethylene Styrene Ethylene
175
Chocolate B a y o u , T e x . (25)
Process or Probable Major Raw Material
LPG
100 130 560 550
MONTROSE CHEMICAL
Henderson, N e v . (33)
E t h y l chloride
10
ODESSA STYRENE
Odessa, T e x . (31)
Styrene
70
OLIN MATHIESON
Brandenburg, K y . (15)
Ethylene E t h y l e n e oxide Ethylene dichloride
100 70
Ethanol
LPG D i r e c t oxidation
45 —
/ Refinery gas
P E T R O L E U M CHEMICAL
L a k e Charles, L a . (19)
Ethylene
300
P H I L L I P S CHEMICAL
Sweeny, T e x . (25) Pasadena, T e x . (23)
Ethylene Linear polyethylene
530 120
PITTSBURGH PLATE GLASS
L a k e Charles, L a . (19)
Ethylene dichloride
100
REXALL CHEMICAL
Odessa, T e x . (31)
Conventional polyethylene
120
Deer Park, Tex. (23)
Ethylene
150
—
Refinery gas
Houston, Tex. (23)
Synthetic ethyl alcohol E t h y l chloride Ethylene
(26 million gallons) 80 45
—
Ethylene LPG
Styrene
215 70
SHELL CHEMICAL
Torrance, Calif. (32) Los Angeles, Calif. (32) SINCLAIR-KOPPERS
Houston, Tex. (23)
Styrene
SPENCER CHEMICAL
Orange, T e x . (20)
Conventional polyethylene
135
SUN-OLIN
Marcus Hook, P a . (3) Claymont, D e l . (3)
E t h y l e n e oxide
60
SUNTIDE
Corpus Christi, T e x . (28)
Styrene
60
TENNECO
Houston, T e x . (23)
Styrene
60
158
C&EN
SEPT.
10, 196 2
Ethylene
105
Refinery gas, LPG
D i r e c t oxidation 120
Location and Key Number on Map
Company
Product
TEXAS EASTMAN
Longview, T e x . (29)
Ethylene Synthetic ethyl alcohol Conventional polyethylene
UNION CARBIDE CHEMICALS
Institute, W.Va. (8)
E t h y l e n e oxide Synthetic ethyl alcohol Styrene E t h y l e n e oxide Ethylene dichloride Synthetic ethyl alcohol E t h y l e n e oxide Synthetic ethyl alcohol E t h y l e n e oxide Ethylene dichloride Synthetic ethyl alcohol E t h y l e n e oxide
S o u t h Charleston, W.Va. (8)
Whiting, I n d . (12) T e x a s City, Tex. (24)
Seadrift, T e x . (26) Torrance, Calif. (32) UNION CARBIDE OLEFINS
UNION CARBIDE
PLASTICS
CHEMICALS
50
LPG
120 D i r e c t oxidation
150 (10 million gallons) 120 40
D i r e c t oxidation
175 (45 million gallons) 100 (15 million gallons) 150
Direct oxidation
125 (65 million gallons) 225
Direct oxidation
Direct oxidation
Direct oxidation
50
Ethylene
325
—
LPG
Ethylene
350
—
Ethane
Ethylene
225
—
Refinery gas
Ethylene
550
—
Refinery gas
Ethylene
700
—
LPG
Ethylene
150
—
Refinery gas
Institute, W.Va. (8) S o u t h Charleston, W.Va. (8) Whiting, I n d . (12) T e x a s City, T e x . (24) Seadrift, T e x . (26)
Linear polyethylene Conventional polyethylene Conventional polyethylene Conventional polyethylene Conventional polyethylene Linear polyethylene Conventional polyethylene
—
LPG
Tuscola, IU. (14)
Houston, T e x . (23)
WYANDOTTE
175 (20 million gallons)
Process or Probable Major Raw Material
Institute, W . V a . (8) S o u t h Charleston, W . V a . (8) Whiting, I n d . (12) T e x a s City, T e x . (24) Seadrift, Tex. (26) Torrance, Calif. (32)
Torrance, Calif. (32) U.S. I N D U S T R I A L CHEMICAL
E t h y l e n e oxide
Probable Present Expansion Capacity by 1964 (millions of pounds)
Wyandotte, Mich. (11) Geismar, L a . (18)
Ethylene Synthetic ethyl alcohol E t h y l chloride Conventional polyethylene Conventional polyethylene Linear polyethylene Ethylene E t h y l e n e oxide Ethylene dichloride E t h y l e n e oxide
30 90 80 200 140 25 80 330 (46 million gallons) 50
Ethylene
120 180 60 —
30 10 7 60
C r u d e oil Chlorohydrin Direct oxidation
SEPT.
10, 196 2 C&EN
159
MMMMMMMUn
E T H Y L ALCOHOL C O N S U M P T I O N * 1 Mill ions of Gallons 1962** 1967** 1 1960
Outlet Acetaldehyde Miscellaneous syntheses (acetic acid, ethyl acetate, ethyl chloride, others) Solvents Miscellaneous Totals 1
Source:
156
150
130
56 65 2 279
58 67 2 277
70 80 2 282
1
Stanford Research Institute
* Fiscal year ending June 30 ** C&EN estimates
The ethyl alcohol market seems due ALCOHOL PLANT. for a decline, one reason being new routes to acetaldehyde. Shell's Houston plant has capacity of 26 million gallons
160
C&EN
SEPT. 10, 1962
pound of ethylene oxide per pound of polyethylene glycol ether, but it takes 0.73 pound of oxide per pound of polyethoxyethyl tridecyl ether. Most generally, though, it takes 0.5 pound of ethylene oxide per pound of nonionic. It is expected that nonionic surface-active agents will consume 265 million pounds of ethylene oxide in 1967, compared to 180 million pounds this year. Another outlet for ethylene oxide is acrylonitrile. Present capacity is about 515 million pounds, but only 70 million pounds of this capacity, owned by Union Carbide, use the ethylene oxide route. The rest is made either from acetylene or from propylene and ammonia. Acrylonitrile production was 250 million pounds last year, but the need for ethylene oxide in this production was only 40 million pounds. Future use of ethylene oxide here depends on Union Carbide, which should manage a proportionate share of acrylonitrile growth.
Ethyl Alcohol Market Is Mature, Too The situation regarding future demand for synthetic ethyl alcohol is not too promising, since new technology offers other routes to acetaldehyde, the largest outlet for this substance. For example, Celanese is now using the Wacker process to manufacture acetaldehyde directly from ethylene (C&EN, Aug. 6, page 2 9 ) . Also, 2-ethylhexanol, a major use for acetaldehyde, is being made by the oxo process-about 40% was made by this method in 1961 and the proportion will go higher in the years ahead. Last year, about 150 million gallons of ethyl alcohol were used to make acetaldehyde, but this use will likely decline to about 130 million gallons in 1967. It could go even lower. Consequently, industrial ethyl alcohol output and consumption will grow only 1 to 2% annually in the foreseeable future. Last year, 295 million gallons of industrial ethyl alcohol were made. About 90% came from synthetic sources, and the balance was produced by fermentation. The synthetic variety is made either directly from ethylene or through the ethyl sulfate process, in which ethylene reacts with sulfuric acid and the product is hydrolyzed to the alcohol. Synthetic capacity is about 282 million gallons annually, divided among five producers. Carbide has 135 million gallons of that capacity. In addition, Publicker can make between 100 and 150 million gallons of ethyl alcohol through its fermentation operations. Production should reach only 305 million gallons in 1967 and, hence, capacity seems quite adequate for future needs. Roughly, 4.3 to 4.4 pounds of ethylene are used for each gallon of alcohol; this means that about 1.19 billion pounds of ethylene will be needed in five years. Hence, the alcohol will still be a major outlet for ethylene. Aside from acetaldehyde, ethyl alcohol is used to make many other derivatives, including acetic acid, vinegar, ethyl acetate, and ethyl chloride. Such miscellaneous outlets consumed about 60 million gallons of ethyl alcohol in 1961, and this should rise to 70 million gallons in 1967. Other uses for the alcohol are as solvents for resins, lacquers, pharmaceuticals, cleaning compounds, and proprietary uses. These accounted for 70 million gallons in 1961 and should follow the traditional 3 % annual solvent growth. All told, ethyl alcohol consumption should run about 282 million gallons in 1967. Another problem area in ethylene's future lies among
the halogen derivatives—ethyl chloride, ethylene dichloride, and ethylene dibromide. The chloride and dibromide are pegged directly to tetraethyllead(TEL), while the dichloride, although also used in TEL, is consumed mostly in making vinyl chloride monomer. TEL's growth prospects aren't encouraging for several well known reasons:
SURFACE ACTIVE AGENTS PRODUCTION Millions of Pounds 5000|
• Automotive gasoline demands should increase only 2.5% annually through 1967. • Aviation gasoline demand has dropped sharply, and it should retreat even more in the future. • Tetramethyllead(TML) is now moving into the antiknock market, and it could take anywhere from 20 to 50% of today's T E L business. Further, the halogen picture is complicated by new processes for making TEL, for example, by methods based on Ziegler chemistry. The conventional way to T E L is via the sodium-lead-ethyl chloride route, and roughly, 90% of all ethyl chloride production is consumed in T E L manufacture. T E L sales were about 485 million pounds last year, including exports of some 42 million pounds. Total sales of antiknock fluid in five years may not exceed 565 million pounds, with possibly 15 to 2 5 % of this being TML. Reported ethyl chloride production was 496.9 million pounds in 1961, but it may actually be somewhat h i g h e r there is some suspicion in the trade that some chloride was used in a major, but unreported, application. Excluding speculation over unidentified markets, ethyl chloride output seems destined to decline to about 425 million pounds by 1967, based on present trends for TEL. Ethyl chloride capacity is rated at about 810 million pounds now—considerably above reported production— with Ethyl Corp. and Dow being the largest producers. Almost all of this capacity is from routes based on ethylene or ethane, with the balance coming from ethyl alcohol. Meanwhile, ethylene dichloride capacity totals 1.42 billion pounds now, and Goodrich is expected to enter the field. Besides, about 100 million pounds can be made as a by-product of chlorohydrin ethylene oxide. Production was 1.35 billion pounds this year, about 6% more than in 1961. About 90% is produced by addition of chlorine to ethylene, and the balance comes as a by-product of chlorohydrin ethylene oxide operations. Production is projected to reach 1.5 billion pounds in 1967, mainly because of a growing polyvinyl chloride market. About 8 5 % of ethylene dichloride production is used to make vinyl chloride monomer. The monomer is made in two ways, either from acetylene and hydrochloric acid or by pyrolysis of the dichloride. In the latter, hydrochloric acid is a by-product, so some companies react this with acetylene for more vinyl chloride monomer. Vinyl chloride production was 1.04 billion pounds last year, with essentially all of it going into polyvinyl chloride resins. Vinyl extrusions, flooring, and sheet are pacing the field to new heights, and PVC demand should reach 1.12 billion pounds in 1962, with an increase to 1.45 billion pounds in five years. Aside from making vinyl chloride monomer, about 15% of the ethylene dichloride output is used as a scavenger in antiknock fluids. This market will not be affected by the growth of TML, since it will be used as a scavenger there also. Ethylene dichloride demand for antiknock use should run about 160 to 165 million pounds in 1967, following the trend of antiknock fluid. It makes up 18.8% of the anti-
1000 Liquid detergents 500 Nonionic surfactants I I I I I I I I I I I I I I I I '50 '52 '54 '56 '58 '60 '62* '67* Source: Soap & Glycerine Producers *C&EN estimates
VINYL CHLORIDE PRODUCTION Millions of Pounds 1600
1400
1200 Vinyl chloride monomer 1000
Polyvinyl chloride & copolymers
200
ol '52
1 I 1 1 1 1I 1 1 I 1 1 11 '54
'56
'68
'60
Source: U.S. Tariff Commission SEPT.
'62*
'67*
* C&EN estimates 10, 1962 C&EN
161
1 I I 1 1 1 1 1
1 1
STYRENE MONOMER CONSUMPTION | Millions of Pounds I Outlet 1960 1962 1967 \ Polystyrene and impact styrene resins 1150 820 750 Styrene-butadiene rubber 500 550 555 Protective coatings 130 95 90 Polyesters 63 105 57 Exports 60 130 158 Miscellaneous 350 140 145 Totals 1750 1803 2295 Source: C&EN estimates
POLYSTYRENE FOAM. The material is being used here as insulation and a vapor barrier in curing concrete. This year's monomer output should be 1.8 billion pounds
REPRINTS . . . . . . of this commodity survey on ethylene are available at the following prices: One to nine copies—$1.00 each 10 to 49 copies—15% discount 50 to 99 copies—20% discount Prices for larger quantities on request Address orders to Reprint Department, ACS Applied Publications, 1155 16th St., N.W., Washington 6, D.C.
162
C&EN
SEPT. 10, 196 2
knock fluid's content and is not used in aviation gasolines. The remaining halogen compound, ethylene dibromide, has only one significant use—antiknock fluid. It makes up 17.9% of the auto mix and 35.7% of the aviation mix. Dibromide's production was about 190 million pounds last year, and output shouldn't increase much over the next few years; in fact it could decline, depending upon the way aviation gasoline goes. But ethylene dibromide will be used with both TEL and TML. Styrene Growth Outlook Still Good Styrene monomer's progress over the past few years has been most surprising, and its future is still promising, despite a slowdown since 1960. Actually, styrene monomer is more properly a benzene derivative, but it takes 0.32 pound of ethylene to make a pound of styrene via the ethyl benzene process, the prime route to the monomer. Last year, styrene monomer production reached 1.76 billion pounds, only 1% more than in the previous year. This year, output should approach 1.8 billion pounds, but output at midyear was lagging a bit behind 1961's pace. Over-all, styrene growth rate averaged 12% annually since 1950 and about 9% annually since 1955. For the next five years, a rate nearer 7% is expected, and this should bring production to about 2.4 billion pounds. Present capacity for making the monomer is, about 2.4 billion pounds, with about 9 5 % coming from the reaction between ethylene and benzene and the balance coming from direct extraction from aromatic streams. Styrene is one of several major organics that have been battered by price attrition since 1955, having sold for 18 cents a pound then and being down to 1 0 l / 2 cents now. Styrene's boom is due to plastics and elastomers, with the former being the most important outlet now. Production of the various styrene resins reached 1.15 billion pounds in 1961, and it is expected to be somewhere between 1.25 and 1.3 billion in 1962. This year, production of impact grade and general purpose polystyrene should approach 850 million pounds and at midyear it was adhering to the rate toward that quantity. About 90% of these resins is used in molding and extrusion operations, with the rest going into films and foams. The latter are quite promising areas for styrene resinsvarious expanding and extruded foams were a 50 millionpound business in 1961, and the market should at least double in the next Hve years. Extruded foam beads have particularly good prospects in the specialty paper field, and films are just getting under way and should be a 50 million-pound market by 1967. Hope is held, too, for the various polystyrene copolymers, such as those based on acrylonitrile-butadienestyrene (ABS). These are classed as engineering plastics, and they are competitive with die-cast metals in many applications. About 60 million pounds were made in 1961 and about 200 million pounds are expected to be produced in 1967. The remaining major outlet for styrene is for styrenebutadiene rubber (SBR). This market has reached its peak and should decline mildly over the next five years because of competition and use with other elastomers such as polybutadiene (C&EN, March 12, page 88). Last year, 1,104,000 long tons of SBR were produced, and only 1,000,000 long tons are expected in 1967. By then various styrene demands should consume 800 million pounds of ethylene, compared to 575 million pounds this year.
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