U.K. and Italy Queue U p Second and Third Behind First-Place W e s t Germany in Olefin Capacity in Europe
Part 2
UNITED
iaisra»T#rai
68
C&EN
AUG.
31,
1964
Olefins Until several years ago the United Kingdom led western Europe in ethylene and propylene capacity. Then West Germany forged ahead with a just-completed round of new plants and expansions, leaving the U.K. in second place with annual capacities of 576,000 metric tons of ethylene and 371,400 metric tons of propylene. Not that U.K. producers are idle. Their current plans call for hiking annual ethylene capacity about 60% to 933,000 metric tons, and propylene capacity about 70% to 625,000 by 1967. This new capacity includes what will be two of the world's largest naphtha crackers: Imperial Chemical Industries' (ICI) cracker at Wilton (204,000 metric tons a year ethylene capacity) and Shell's cracker at Carrington (153,000 metric-ton-a-year ethylene capacity). Meanwhile, West German producers are building new capacity of their own and so should maintain their lead; but the gap will have narrowed. The British chemical industry was probably the first in Europe to turn to petroleum as a source of olefins. British Celanese, now a subsidiaiy of Courtaulds, began to make ethylene and propylene by cracking naphtha as early as 1941. But not until 1949 in the U.K. was propylene made on a large scale from petroleum fractions. That was the
year Shell started separating propylene from refinery streams at Stanlow for use in its solvents production. At about the same time, The Distillers Co., Ltd., and British Petroleum formed British Hydrocarbon Chemicals (BHC) to make petrochemicals. In 1951, BHC built a naphtha cracker at Grangemouth (Scotland). Soon, Esso Petroleum, ICI, and Shell Chemical also built naphtha crackers. These developments marked a big change in the British chemical industry, which, until the end of World War II, had derived most of its organic chemicals from fermentation alcohol and coal. Now about 70% of British organic chemicals are petroleum-based. All l/.K.'s Ethylene Is Naphtha-Based All the ethylene and most of the propylene used in the U.K. as chemical feedstock is made by cracking light naphtha. Getting the naphtha is no problem. Britain's oil refining capacity last year hit 57 million metric tons versus only 2.6 million in 1947. Britain imports petroleum mainly from the Middle East, North Africa, and the Far East. The big oil hunt in the North Sea may yield petroleum deposits—oil or gas or both—on Britain's doorstep. Britain's main olefin producing and
in Europe processing complexes are located at Wilton and Billingham (on England's northeast coast), at Grangemouth, (near Edinburgh), at Fawley (near Southampton), at Carrington (near Manchester), and at Baglan Bay (in south Wales ). Britain's ethylene goes into a typical spectrum of chemicals—polyethylene, ethylene oxide, ethanol, styrene, and ethylene dichloride. Operating at full capacity, units for making these five products would consume slightly less than 500,000 metric tons a year of ethylene—almost 90% of current ethylene capacity. There are no official data on actual ethylene production. These five chemicals will continue to be the big levers under future ethylene growth in the U.K. But they will get significant help from polyvinyl acetate. Vinyl acetate, formerly acetylene's private preserve, now will be made from ethylene by ICI and, possibly, also by a joint plant project of Distillers Co. and Courtaulds. Ethylene-propylene rubber may eventually be made in the U.K., too. Polyethylene
Flourishes in the O.K.
Sometimes, products invented at home have to be exported before they flourish. Not so with polyethylene (or polythene as it's more commonly called in Britain), Britain's most important
plastic. Invented in 1933 by ICI's Gibson and Fawcett, and first commercially produced in 1937, polyethylene will this year clear 200,000 metric tons. This is Europe's largest output. Polyethylene took over from polyvinyl chloride as Britain's largest-volume plastic in 1959. Production last year was about 190,000 metric tons (allowing for polypropylene production which is included but not broken out in the official government statistics), 13% more than in 1962. Average annual growth for the 10-year period 1954 through 1963 was almost 30%. Polyethylene still looks vigorous in its home territory and production should grow at a 15 to 20% a year rate for the next five years. At 20% a year, production should be approaching 500,000 metric tons by the end of 1968. Last year's production accounted for 203,000
This is the second of a three-part series on olefins in Europe. Tart I, which appeared on Aug. 3, discussed the West German and French olefin situations. Fart 3, which will appear on Sept. 28, will cover Spain, Benelux, and Scandinavia.
metric tons of ethylene, about 35% of total ethylene capacity. British producers export a go,od deal of their production. Last year, for example, exports were 77,500 metric tons, about 4 1 % of production. That's almost the same amount exported by West German firms. About 90% of last year's exports were low-density polyethylene, the rest high-density. Meanwhile, imports, though sizable (almost 20,000 metric tons last year) were only 10.5% of production plus imports. Total annual capacity of Britain's five producers—Bakélite Xylonite, BHC, ICI, Monsanto Chemical, and Shell Chemical-now stands at 225,000 metric tons. However, this figure can vary, since Shell's high-density polyethylene unit can also make polypropylene. With plants currently approaching full capacity, producers are raising capacities to a total of 256,000 metric tons a year by the end of this year. By 1967, further expansions will raise the total to 389,000 metric tons a year. Of the current capacity, 189,000 metric tons (84%) is low-density material, and 24,000 metric tons (16%) high-density material. These figures too, vary somewhat, depending on polypropylene production. ICI, home of low-density polyethylene, is Britain's largest producer, with AUG. 31, 1964 C & E N
69
All Ethylene in the U.K. Is Made by Cracking Light Naphtha an annual capacity of 112,000 metric tons. Shell also makes low-density polymer in a 15,300 metric-ton-a-year plant using the Badische Anilin- & Soda-Fabrik process. Government production statistics don't list the two types separately. According to one producer, however, probably 85% of production last year was the low-density polymer, 15% high-density. Apparent consumption (production plus imports less exports ) of both types was 132,000 metric tons last year, 33% above the previous year's figure. About 60% of the low-density polyethylene consumed in Britain last year went into film and injection moldings. Blow-molded products and cable insulation each took about 12% of the low-density total. A rapidly growing outlet in the U.K. for low-density polyethylene film is fertilizer bags, where more and more heavy gage material is being used. The fertilizer industry will probably use about 40 million polyethylene bags this year (more than 7000 metric tons of polymer). By 1967, the number of fertilizer bags used could hit 100 million, requiring more than 18,000 metric tons of polyethylene film. Biggest uses for high-density polyethylene are in blow-molded and injection-molded products. These outlets together accounted for almost 70% of the high-density material consumed last year in Britain. And use of blow-molded containers —especially for household cleaning agents and toiletries—is increasing. More petroleum products are being marketed in such containers, too. Ethylene Oxide Has Slow, Steady Rise Although polyethylene has left it far behind as a user of ethylene, ethylene oxide still takes a goodly share of the market. Since government statistics don't list the compound, it's impossible to quote consumption precisely. On the basis of capacity, though, ethylene oxide could use as much as 97,000 metric tons a year of ethylene (17% of total ethylene capacity). Britain's three ethylene oxide pro70
C&EN
AUG.
3 1 , 1964
ducers—Shell (41,000 metric tons a year capacity), ICI (36,000 metric tons a year capacity), and Union Carbide (20,000 metric tons a year capacity)—all use a direct oxidation process. Shell is currently expanding its ethylene oxide capacity to 66,000 metric tons annually. Most of Britain's ethylene oxide is converted into ethylene glycol. The glycol, in turn, is used to make antifreeze and both saturated and unsaturated polyestrs. Some glycol is used as a softening agent for cellophane. For antifreeze, the fast-growth days are probably over. For one thing, the rate of car population growth is tapering off. For another, the number of British car owners who use antifreeze has probably stabilized at about 90%. (Apparently, the rest continue the old practice of British car owners of draining the water from their cars each night.) The rising popularity of smaller cars like British Motor Corp.'s Mini Minor, the Austin Seven, and Human Imp isn't helping matters either. The other big outlet for ethylene glycol—polyesters—holds more promise for growth. Britain's annual capacity
Ethylene-Use Capacity List Headed by Polyethylene Capacity in metric tons; ethylene equivalent in metric tons in parentheses Major ethylene outlets Polyethylene Styrene Ethanol (synthetic) Ethylene dichloride
1964 256,200 (270,000) 137,700 (44,000)
1967 388,800 (408,000) 137,700 (44,000)
61,300 (42,800)
61,300 (42,800)
131,000 (41,300) 80,000 (15,000)
Ethylene oxide
96,900 (96,900)
131,000 (41,300) 80,000 (15,000) 61,000 (20,300) 122,500 (122,500)
Total ethylene requirements
(510,000)
(693,900)
Tetraethyllead
—
Vinyl acetate
Source: C&EN estimates
of 40,500 metric tons of fiber and film made from saturated polyesters of the polyethylene terephthalate type now represents a potential outlet for 14,000 metric tons of ethylene glycol. This is equivalent to some 10,000 metric tons a year of ethylene oxide. ICI is the only producer of these polyesters in Britain. The company's two Terylene fiber plants have a combined annual capacity of 36,400 metric tons. The company is boosting its fiber-production capacity by 2 5 % , bringing it to 45,500 metric tons by the end of next year. Its Melinex polyester film plant has a capacity of 4100 metric tons a year, twice that of two years ago. Last year production of unsaturated polyesters was 14,000 metric tons, 2200 metric tons more than 1962. This production probably consumed 700 metric tons of ethylene glycol. This use, though small, gives some indication of the growing use of these chemicals in such products as glass-reinforced plastics, translucent sheeting, and polyester-based surface castings. Britain's only producer, BHC, of technical-grade ethanol uses the direct synthesis route from ethylene and steam. No government data are available, but BHC's Grangemouth plant is probably operating close to capacity (61,300 metric tons a year). The firm's naphtha cracker supplies the ethylene. At full capacity this unit would consume some 43,000 metric tons a year of ethylene. Distillers Co., which owns 50% of BHC, takes all the alcohol made at Grangemouth for its own use or for external sales. Styrene Outlets Grow 15% Yearly Since British production data for ethylbenzene and styrene aren't available, it's hard to pinpoint the amount of ethylene consumed by this outlet. But styrene consumption is probably rising at 12 to 15% a year, according to at least one market research man. Britain's ethylbenzene capacity is between 185,000 and 200,000 metric tons a year. This capacity provides a potential ethylene requirement of 59,000 to 64,000 metric tons a year.
Production of Britain's two ethylbenzene producers is captive and most of it goes into the firms' styrene manufacture. Forth Chemicals (one third Monsanto, two thirds BHC) has two styrene units (annual capacity of each is 51,000 metric tons). Shell Chemical has a styrene unit whose capacity will soon be stepped up to 36,000 metric tons a year. In addition to the ethylbenzene Shell uses in its styrene plant in Britain, the company ships about 20,000 metric tons a year of the material to Pernis (Holland) where Shell Nederland Chemie dehydrogenates it to styrene. Shell uses its Dutch-made styrene to turn out styrene-butadiene latex in Holland in a 60,000 metric-ton-a-year plant. Styrene's two big outlets in the U.K. are p.olystyrene and styrene-butadiene rubber. Output of polystyrene reached 78,000 metric tons last year, 13% over the 1962 figure. The generalpurpose plastic has had good solid growth over the past nine years, too, racking up an average annual production increase of 14% since 1954. This steady growth helped polystyrene ease into third place among British plastics, passing alkyd resins in 1962. Almost 34% (25,800 metric tons) of Britain's polystyrene production was exported last year, 20% more than exported in 1962. Imports also rose by 20% to 5000 metric tons last year. Apparent consumption was thus 55,600 metric tons last year, 10% more than the year before. Britain's total annual capacity for polystyrene in 1963 was 92,000 metric tons, providing a potential outlet for about 100,000 metric tons of styrene. With demand for polystyrene growing both at home and overseas, two of Britain's larger producers, Shell and Monsanto, are raising their capacities. Furthermore, Mobil Chemicals, a Socony Mobil subsidiary, will begin polystyrene production this year in a 7100 metric-ton-a-year plant at Stroud (Gloucestershire). The firm may later raise this to 20,000 metric tons. By the end of this year, total polystyrene capacity in the U.K. will be 124,000 metric tons a year. Styrene's other big outlet, styrenebutadiene rubber, is made by only one producer—International Synthetic Rubber Co. Its plant, located at Fawley near Esso's big refinery, started up in 1959, and several expansions have raised capacity to 122,000 metric tons a year. This capacity represents a
ICI is the U.K.'s only producer of saturated polyesters, a big outlet for ethylene glycol. Annual capacity for the company's polyester fibers is 36,400 metric tons
Production of Olefins in the U.K. Is Off and Running
1954 1955 1956 1957 1958 1959 1960 1961 1962 1963 1964 est. 1965 est. 1966 est. 1967 est. 1968 est. 1969 est. 1970 est.
Polyolefins 18,700 29,200 42,000 51,400 70,200 100,700 125,700 129,000 174,700 201,100 231,500 266,100 305,800 351,600 404,400 464,800 534,400
(metric tons) Polyvinyl Polyvinyl Chloride Acetate 6,300 42,700 49,000 10,600 47,300 10,400 69,100 10,600 74,200 12,400 88,600 13,300 107,800 15,200 108,600 16,800 116,800 18,500 153,900 21,000 172,200 22,100 192,800 23,200 215,900 24,400 241,800 25,600 270,800 26,800 302,800 28,100 339,000 29,600
Polyesters Polystyrene {unsaturated) 23,400 500 22,800 1,000 25,200 2,200 33,100 3,500 35,900 4,800 40,700 6,700 49,600 8,900 52,500 10,000 68,800 11,700 77,600 13,900 86,900 15,300 97,200 16,900 108,800 18,500 121,900 20,300 136,700 22,400 153,100 24,600 171,400 27,000
Sources: U.K. Board of Trade Statistics; C&EN estimates
AUG.
31, 1964
C&EN
71
potential styrene requirement of about 30,000 metric tons a year. Although polystyrene and styrenebutadiene rubber are styrene's breadand-butter outlets, new copolymers based on styrene and acrylonitrile are beginning to move into the picture. So far these products have been made in only relatively small quantities. Output of acrylonitrile-butadiene-styrene and acrylonitrile-styrene resins last year was probably no more than 2500 metric tons. But production this year may double and generate a styrene demand of about 2000 metric tons. Demand for the new engineering resins could grow at a rate of 15 to 20% a year in Britain as new uses develop. Marbon (a Borg-Warner subsidiary), for example, recently introduced a technique for chromium plating parts made from acrylonitrile-butadiene-styrene resin. This development
could open up new applications ranging from car door handles to bathroom faucets. Ethylene Dichloride Crowds Acetylene as a Route to Polyvinyl Chloride Ethylene dichloride, just starting as a route to vinyl chloride in West Germany and France, is already well established in Britain. British Geon (55% owned by Distillers, 4 5 % by B. F. Goodrich) has been using the combined ethylene dichloride-acetylene process for some time. (In this process, ethylene dichloride is cracked to give vinyl chloride and hydrochloric acid; then the acid is used to hydrochlorinate acetylene to give more vinyl chloride. ) BHC supplies the ethylene dichloride to British Geon; Distillers supplies the calcium carbide for making acetylene. BHC is Britain's only large-scale
ethylene dichloride producer. Its capacity now totals 131,000 metric tons a year, which means a potential outlet for some 40,000 metric tons a year of ethylene. British Geon is switching to naphtha as a source of acetylene. The cracker size hasn't been disclosed, but it may have a designed output of 25,000 to 30,000 metric tons a year of acetylene. The company hasn't yet made a final decision whether to build a cracker based on the Badische Anilin- & SodaFabrik cracking process .or on the Wulff process. The new acetylene unit is part of British Geon's $11 million expansion program now under way. Vinyl chloride capacity by 1966 will be raised to 133,000 metric tons a year from the current 77,500 metric-ton-a-year level. PVC capacity is being increased from 71,500 metric tons a year now and should reach 92,000 metric tons an-
By 1967 Ethylene Capacity in the United Kingdom Should Increase by 60% Ethylene Company
Plant
Location
Current Capacity (Metric
Cavacity Aftei Expansion To>ns per Year)
B R I T I S H C E L A N E S E , LTD.
Spondon
25^00
25,500
BRITISH HYDROCARBON C H E M I C A L S , LTD.
B a g l a n Bay Grangemouth
56,100 137,700
56,100 137,700
ESSO P E T R O L E U M CO., LTD.
Fawley
112,100
112,100
IMPERIAL CHEMICAL INDUSTRIES, LTD. SHELL C H E M I C A L CO., LTD. TOTALS
Wilton
112,800
347,000
Carrington
102,000 576,200
255,000 933,400
Remarks Naphtha owned Naphtha Naphtha owned Naphtha owned Naphtha
s t e a m c r a c k e r ; t h e c o m p a n y is a w h o l l y s u b s i d i a r y of Courtaulds s t e a m cracker s t e a m c r a c k e r ; t h e c o m p a n y is j o i n t l y by B r i t i s h P e t r o l e u m a n d D i s t i l l e r s s t e a m c r a c k e r ; t h e c o m p a n y is a w h o l l y s u b s i d i a r y o f S t a n d a r d Oil Co. ( N . J . ) steam cracker
Naphtha steam cracker
Polyethylene BAKELITE XYLONITE, LTD.
Grangemouth
35,700
61,300
BRITISH HYDROCARBON C H E M I C A L S , LTD. IMPERIAL CHEMICAL INDUSTRIES, LTD.
Grangemouth
2Î~4ÔÔ
2ÎT4ÔÔ
143,000
2047000
M O N S A N T O C H E M I C A L S , LTD. S H E L L C H E M I C A L CO., L T D .
Fawley Carrington
25,500 15,300 15,300
2X5ÔÔ 61,300 15,300
225,200
38818ÔÔ
Wilton
TOTALS
L o w - d e n s i t y p o l y e t h y l e n e ; U n i o n C a r b i d e proce s s ; t h e c o m p a n y is j o i n t l y o w n e d by D i s t i l l e r s and Union Carbide High-density polyethylene; Phillips process Low-density polyethylene; Imperial Chemical I n d u s t r i e s p r o c e s s ; c u r r e n t l y u n d e r g o i n g exp a n s i o n t o 143,000 m e t r i c - t o n - a - y e a r c a p a c i t y , w h i c h will be c o m p l e t e b e f o r e t h e e n d o f t h e year; other e x p a n s i o n s are also p l a n n e d Low-density; BASF process Low-density p o l y e t h y l e n e ; BASF process T h e c o m p a n y h a s c a p a c i t y f o r 15,300 m e t r i c t o n s a y e a r of e i t h e r h i g h - d e n s i t y p o l y e t h y l e n e ( Z i e g l e r p r o c e s s ) or o f p o l y p r o p y l e n e
Ethylene Oxide IMPERIAL CHEMICAL INDUSTRIES, LTD.
Severnside
35T7ÔÔ
35JÔÔ
S H E L L C H E M I C A L CO., L T D . U N I O N C A R B I D E , LTD. TOTALS
Carrington FawJey
4^800 20,400 96,900
66,400 20,400 122,500
72
C&EN
AUG.
31,
1964
D i r e c t o x i d a t i o n o f e t h y l e n e ; a 70-mile p i p e l i n e c o n n e c t s Fawley w i t h Severnside for s u p p l y i n g e t h y l e n e t o ICI Direct o x i d a t i o n of e t h y l e n e Direct o x i d a t i o n of e t h y l e n e
Ethylene Glycol Location
Current Capacity (Metric
Capacity After Expansion To\as per Year)
Company
Plant
IMPERIAL CHEMICAL INDUSTRIES, LTD. S H E L L C H E M I C A L CO., L T D . U N I O N CARBIDE, LTD.
Severnside
n.a.
rua~!
Carrington Fawley
n.a. n.a.
n.a. n.a.
Grangemouth
61,300
Hull
n.a.
Remarks
Ethanol BRITISH HYDROCARBON CHEMICALS, LTD. D I S T I L L E R S CO., LTD.
61,300 n.a.
Synthesis Fermentation
Styrene FORTH C H E M I C A L S , LTD.
Baglan Bay
51,000
51,000
S H E L L C H E M I C A L CO., L T D .
Grangemouth Carrington
51,000 25,500
51,000 35,700
127,500
137,700
16,300 20,300
16,300 20,300
3,000
TOTALS
U s e s c a p t i v e e t h y l b e n z e n e ; t h e c o m p a n y is jointly o w n e d by British H y d r o c a r b o n Chemicals ( t w o t h i r d s ) a n d M o n s a n t o Co. ( o n e t h i r d ) Uses captive ethyl benzene Uses captive ethyl benzene; expansion from 25,500 m e t r i c - t o n - a - y e a r c a p a c i t y will b e c o m plete by t h e e n d of t h e year
Polystyrene B.X. P L A S T I C S , L T D . D I S T R E N E , LTD.
Manningtree Barry
KAYLIS C H E M I C A L S , LTD. M O B I L C H E M I C A L S , LTD. M O N S A N T O C H E M I C A L S , LTD.
Bolton Stroud Newport
—
19,000
3,000 7,100 31,600
SHELL C H E M I C A L CO., L T D .
Carrington
23,400
35,800
STERLING MOLDING MATERIALS, LTD. TOTALS
Stalybridge
10,200
10,200
92,200
124,300
122,000
122,000
J o i n t l y o w n e d by D i s t i l l e r s a n d U n i o n C a r b i d e J o i n t l y o w n e d by D i s t i l l e r s a n d D o w C h e m i c a l International Plant due for start-up before t h e e n d of t h e year E x p a n s i o n f r o m 19,000-metric-ton a n n u a l c a p a c i t y t o be c o m p l e t e by t h e e n d o f t h e y e a r E x p a n s i o n f r o m 23,400-metric-ton a n n u a l c a p a c i t y t o b e c o m p l e t e by t h e e n d o f t h e y e a r
Styrene-Butadiene Rubber INTERNATIONAL SYNTHETIC R U B B E R CO., L T D .
Fawley
Acrylonitrile-Butadiene-Styrene and Acrylonitrile-Styrene Resins D I S T I L L E R S CO., LTD
Barry
1,000
n.a.
MARBON CHEMICAL (DIVISION OF B O R G - W A R N E R C O R P . )
Grangemouth
5,100
n.a.
M O N S A N T O C H E M I C A L S , LTD
Newport
2,000
4,000
STO-CHEM, LTD.
Bromsgrove
7,700
7,700
15,000
n.a.
TOTALS
Acrylonitrile-butadiene-styrene; plant capable of considerable expansion Acrylonitrile-butadiene-styrene; plant now undergoing e x p a n s i o n ; capacity after expansion hasn't been revealed Acrylonitrile-butadiene-styrene a n d acrylonitrilestyrene Acrylonitrile-butadiene-styrene; the company m a k e s N a u g a t u c k C h e m i c a l ' s Kralastic copolymers
Polyvinyl Chloride BAKELITE, LTD.
Aycliffe
B R I T I S H G E O N , LTD.
Barry
IMPERIAL CHEMICAL INDUSTRIES, LTD.
Hillhouse
10,200
10,200
71,500
A t>out 92,000
117,200
148,000
Uses m o n o m e r m a d e by British G e o n ; the c o m p a n y is p a r t o f B a k é l i t e X y l o n i t e Uses captive vinyl chloride m a d e from a c o m bination process that uses acetylene a n d e t h y l e n e a s t h e u l t i m a t e raw m a t e r i a l s ; t h e c o m p a n y is j o i n t l y o w n e d b y D i s t i l l e r s (55%) a n d B. F. G o o d r i c h (45%); e x p a n s i o n t o 92,000-metrict o n - a n n u a l c a p a c i t y t o be c o m p l e t e d by e a r l y 1965; f u t h e r e x p a n s i o n s a r e p l a n n e d Uses captive vinyl chloride m a d e from acetylene; expansion from 117,200-metric-ton annual capacity t o be c o m p l e t e by t h e e n d of t h e year
198,900 ^ b o u t 2 5 0 , 2 0 0 ~
TOTALS
Vinyl Acetate BRITISH CÉLANESE, LTD. COURTAULDS, LTD., A N D DISTILLERS C O . , LTD.
Spondon (Hull)
30,600 8,200
~~HuTi
H E D O N C H E M I C A L S , LTD. IMPERIAL CHEMICAL INDUSTRIES, LTD. TOTALS n.a.:
Not available
Source:
3M5ÔÔ
Wilton
Shut down ~~ T h e p l a n t will use e t h y l e n e , b u t it has not b e e n a n n o u n c e d w h e t h e r a c e t i c a c i d w i l l also be u s e d ; t h e c o m p a n i e s will b u i l d a plant, b u t the n a m e of the operating c o m p a n y has not b e e n a n n o u n c e d ; H u l l is t h e l i k e l y l o c a t i o n f o r the plant S h u t d o w n ; t h e c o m p a n y is j o i n t l y o w n e d by Distillers a n d S h a w i n i g a n ( C a n a d a ) The c o m p a n y will use e t h y l e n e , but has not a n n o u n c e d w h e t h e r i t will a l s o u s e a c e t i c a c i d
61,200
Cà-EN es timates
ÏÔ72ÔÔ AUG.
31,
1964
C&EN
73
In the U.K., as in Most of "Western Europe, Propylene Is Ethylene's S h a d o w nually by early next year. The company will probably expand polymer capacity further by 1966. Meanwhile, ICI, Britain's other vinyl chloride producer, uses the acetylene route. The firm is building an oilbased acetylene plant (BASF process) having an annual capacity of 51,000 metric tons. The fact that ICI is building a new acetylene plant doesn't necessarily mean that the firm won't also begin using the combined process, although ICI hasn't revealed such plans. ICI doesn't say what its vinyl chloride monomer capacity is. However, its PVC capacity by year's end will be increased to 122,500 metric tons annually from the current level of 117,200 metric tons. Additional expansions should raise ICI's PVC capacity to 148,000 metric tons by 1966 or 1967. Polyvinyl chloride, while it hasn't surged ahead in the U.K. as much as it has on the Continent, still can boast a very respectable showing. Last year, production climbed to 154,000 metric tons, 32% above the previous year. Since 1954, its average annual growth has been almost 16%. PVC exports jumped to 30,500 metric tons last year, almost 62% more than the year before that. Imports rose 29 7c to 38,800 metric tons. Thus Britain is a net importer of PVC, despite the fact that the country's total annual capacity will be 225,000 metric tons by the end of the year. Approximately 50 % of the PVC consumed in the U.K. last year went into sheet, wire coating, and floor tile. A battle is now shaping up between PVC and polyethylene over the market for disposable containers and extruded pipe. Although PVC is rapidly proving to be an attractive outlet for ethylene dichloride, the dichloride's second major consumer, tetraethyllead, is probably in for declining fortunes. Use of alkyl antiknock compounds has been growing in Britain, to be sure—some market research experts say 6 to 10% a year. But gasoline producers seem to be turning more to tetramethyllead. Associated Octel, sole manufacturer of antiknock compounds in the U.K., 74
C&EN
AUG.
3 1,
1964
Capacity in metric tons; propylene equivalent in metric tons in parentheses
Britain has been rising at a healthy pace. Last year's production was 21,100 metric tons, 14% above the year before, and equal to the average annual growth in production of the material since 1954.
Major propylene outlets Isopropyl alcohol
Propylene—Overcapacity
Propylene Capacity in U.K. Will Increase Slightly
Propylene oxide Cumene Polypropylene Propylene tetramer Acrylonitrile Total propylene requirements Source:
1964 132,700 (119,200) 45,400 (50,400) 117,000 (52,000) 37,700 (39,600) 20,400 (21,500)
1967 132,700 (119,200) 45,400 (50,400) 117,000 (52,000) 37,700 (39,600)
—
40,800 (35,000)
(282,700)
(296,200)
—
C&EN estimates
has two plants—a total annual capacity of 80,000 metric tons. The firm makes its own ethylene dichloride, using about 15,000 metric tons a year of ethylene piped from Shell Chemical's Carrington cracker. Polyvintjl Acetate Opens Up a New and Growing Outlet for Ethylene Polyvinyl acetate, one of acetylene's last unsullied strongholds, is yielding to ethylene in Britain. Both ICI and a joint firm—formed by Distillers and Courtaulds and revealed earlier this year, but as yet unnamed—plan to build ethylene-based vinyl acetate plants having a total annual capacity close to 61,000 metric tons. Neither ICI nor Distillers has disclosed process details. Thus, it's not yet clear whether the reaction will be run straight through from ethylene, or whether acetic acid will also be used. Since both firms make acetic acid, it may be that they plan to use ethylene to make only the "vinyl" portion of the vinyl acetate molecule. For this type of reaction, about 20,000 metric tons of ethylene a year would be needed to feed the two new plants when they are operating at capacity. Polyvinyl acetate production in
Mounts
In Britain, as in most of western Europe, propylene is ethylene's shadow. Each time ethylene capacity rises, so does that of propylene. This is so because all of Great Britain's ethylene is produced in naphtha steam crackers which turn out close to 0.7 pound of propylene by-product per pound of ethylene. Unfortunately, U.K. requirements for propylene don't shadow those of ethylene. As a result, British producers, long on propylene now, face even greater excess supply in the coming years. Although British government statistics don't list propylene derivatives, a look at capacities pretty well tells the story. Annual propylene capacity in Britain now totals 371,400 metric tons. But total propylene requirement for all of Britain's propylene derivatives, based on full-capacity operation, is only 283,000 metric tons a year—about 76% of propylene capacity. By 1967, however, the situation will be worse. Ethylene's sharp 62% leap in capacity will drag propylene capacity up 68% to 624,500 metric tons a year. Requirements for propylene, however, will crawl forward only 5% to 296,000 metric tons a year, according to presently known company plans. That's barely 47% of the expanded capacity. And these figures are based on full-capacity operation of all plants making propylene derivatives, which is unlikely. Not that Britain's propylene suffers from any lack of outlets. They're there, but they just aren't big enough. Isopropyl alcohol, propylene oxide, phenol and acetone (from propylenederived cumene), propylene tetramer, oxo products, and polypropylene, to name the main ones, all consume the olefin. In addition, acrylonitrile is
looming as a new and promising propylene use. None of these outlets, except for isopropyl alcohol, is really big yet, however. Polypropylene may eventually soak up much of the excess capacity, but this will be an uphill climb in a market dominated by polyethylene. Isopropyl Alcohol Is Britain s Leading Propylene Outlet Isopropyl alcohol is well ahead of its closest rivals, cumene and propylene oxide, as a propylene outlet. Pro-
duction of the alcohol reached 123,000 metric tons last year and was 9 3 % of capacity. About 110,000 metric tons of propylene were consumed in this production. Nevertheless, none of the four producers (Courtaulds, BHC, ICI, and Shell) has disclosed any expansion plans. This may be because cumenederived acetone is cutting into isopropyl alcohol's acetone market. Practically all of Britain's isopropyl alcohol is dehydrogenated to acetone. Total U.K. acetone capacity is 142,000 metric tons a vear.
Shell, one of the U.K.'s large isopropyl alcohol and acetone makers, uses its acetone captively to make a wide range of solvents like methyl ethyl ketone and methyl isobutyl ketone. Shell also uses acetone in its epoxy resin production. This outlet is small, probably no more than several hundred metric tons a year. Cumene is ranging itself against isopropyl alcohol as a source of acetone. BHC, the U.K.'s only cumene maker, has capacity for 34,700 metric tons a year of the chemical at Grangemouth. The company has recently decided to
Acetone
Phenol
Polyolefsns
Polyvinyl chloride
Polystyrene
Styrène
(Thousands of Metric Tons)
EXPORTS IMPORTS n. a.: Not available Source: U.K. Customs and Excite
AUG.
3 1 , 1964
C&EN
75
Propylene Overcapacity Problems in the United Kingdom Will Be Worse by 1967 Capacitif After Expansion per Year)
(Jompany
Plant
Location
Current Capacity (Metric
BRITISH CELANESE, LTD. BRITISH HYDROCARBON CHEMICALS, LTD. IMPERIAL CHEMICAL INDUSTRIES, LTD. SHELL CHEMICAL CO., LTD. SHELL REFINING CO., LTD. TOTALS
Spondon Baglan Bay Grangemouth Wilton ~
18,400 38,800 112,100 97,000
18,400 38,800 112,100 243;000
Naphtha Naphtha Naphtha Naphtha
Carrington Stan low
71,400 33,700 371.400_
178,500 33,700 624,500
Naphtha steam cracker From refinery streams
Propylene
Tons
Remarks steam steam steam steam
cracker cracker cracker cracker
Polypropylene IMPERIAL CHEMICAL INDUSTRIES, LTD.
Wilton
11,200
22,400
SHELL CHEMICAL CO., LTD.
Carrington
15,300
15,300
26,500
37,700
TOTALS
The company has a Montecatini license; currervtly undergoing expansion from 11,200 metric-ton-ayear capacity; expansion will be complete by the end of the year The company has capacity for 15,300 metric tomTa year of either polypropylene or high-density polyethylene under a license from Montecatini
Isopropyl Alcohol BRITISH HYDROCARBON CHEMICALS, LTD. COURTAULDS, LTD. IMPERIAL CHEMICAL INDUSTRIES, LTD. SHELL CHEMICAL CO., LTD. TOTALS
Grangemouth Spondon Wilton Stanlow
3Ô76ÔÔ
30,600 Ï5730Ô 46,000
-
T573ÔÔ 46,000 4Ô78ÔÔ 132,700
40,800 132,700
Phenol (from cumene) BRITISH HYDROCARBON CHEMICALS, LTD. IMPERIAL CHEMICAL INDUSTRIES, LTD.
Grangemouth
2Ô74ÔCT
Billingham
TOTALS
2ÔT4ÔÔ
Process developed by Distillers
35T7ÔÔ
The company will use the UNISIR process developed by Societa Italiana Résine (Milan); plant will be operating by the end of the year
56,100
20,400
Acetone BRITISH HYDROCARBON CHEMICALS, LTD. COURTAULDS, LTD. DISTILLERS CO., LTD.
Grangemouth
IMPERIAL CHEMICAL INDUSTRIES, LTD. SHELL CHEMICAL CO., LTD. TOTALS
Biiiingham
Spondon Hull
Carrington
Î2T4ÔÔ-
12,400
Phenol/cumene
-
Ï47300 37,800
From isopropyl alcohol From isopropyl alcohol made by British Hydroca?bon Chemicals From isopropyl alcohol Phenol/cumene by-product From isopropyl alcohol
Ï4730Ô 37.800 30,600 21,800 25,500 142,400
3076ÔÔ 21,800 25,500 142,400
143,000
175,000
by-product
Oxo Alcohols IMPERIAL CHEMICAL INDUSTRIES, LTD.
t h e company makes a wide range of oxo alcohols; butyl alcohol and isobutyl alcohol only are based on propylene
Propylene Oxide nÛPERIALr^ÉMICÀL^ÎNbUSTRIES, LTD. PFIZER, INC. SHELL CHEMICAL CO., LTD.
Wilton Baglan Bay Carrington
TOTALS
18,400
18,400 ΓδΤΟΟΟ About 12,000 About 45,400
-
15,000 About 12,000 About 45,400
Converted to polyethers for polyurethanes Converted to polyethers Converted to polyethers
Propylene Tetramer Grangemouth
BRITISH HYDROCARBON CHEMICALS, LTD.
Sells tetramer to Grange Chemicals, Ltd., for making synthetic detergents; unit is being converted to cumene production and tetramer will no longer be made; Grange Chemicals is jointly owned by British Hydrocarbon Chemicals (two thirds) and California Chemical Co. (one third)
20,400
Acrylonitrile Grangemouth
BORDER C H E M I C A L S , L T D .
n.a.:
Not available
76
C&EN
Source:
AUG.
31,
C 6 \ E N estimates
1964
4ÔT8ÔÔ
Process developed by Distillers; one-step reaction between propylene and ammonia; British Petroleum, Distillers, and Imperial Chemical Industries each have a one-third interest in Border Chemicals
switch its propylene tetramer plant entirely to cumene production, bringing its annual cumene capacity to 117,000 metric tons by the early part of next year and raising potential propylene requirement for cumene to close to 52,000 metric tons a year. BHC hasn't said anything so far about raising its phenol capacity beyond the present 20,400 metric-ton-ayear level. However, it does say that ICI will take "a large proportion" of the additional cumene output for the 35,700 metric-ton-a-year phenol plant that ICI is now building at Billingham. The ICI phenol unit, due to start up by the end of the year, will use the UNISIR process developed by Societa Italiana Résine (Milan). The increasing quantities of acetone available from the cumene-phenol production could cause a drop-off in isopropyl alcohol production and a consequent decline in propylene requirement for making the alcohol. However, the additional propylene needed for the expanded cumene output should more than offset this decline. Polyurethane Foams Boost Over-All Propylene Oxide Needs Growing demands for flexible and semirigid polyurethane foam in Britain are helping make propylene oxide a major propylene outlet. Other uses for propylene oxide such as propylene glycol and surfactants are helping, too. Current propylene oxide capacity in the U.K. totals 30,000 metric tons a year. Britain's two producers, ICI and Shell, will be joined by Pfizer later in the year when it starts up its plant at Baglan Bay (Wales). Total U.K. capacity will then be about 45,000 metric tons a year (50,000 metric tons a year propylene equivalent). Last year, U.K. producers made about 15,000 metric tons of polyurethane foams, 29% more than in 1962. Automobile seat padding took about 40% of the flexible and semirigid urethane foams used last year. Furniture padding took another 37%. A promising development is Shell's and British Motors' joint research program aimed at working out a single operation for molding polyurethane foam seats for cars. This would avoid wasteful and time-consuming cutting of slabs to size. Britain's four polyalcohol producers (ICI, Lankro Chemicals, Pfizer,
Fertilizer packaging is one of the many growing uses for polypropylene in the U.K.
and Union Carbide) have a total annual capacity of 27,000 metric tons. Shell plans to start up a unit later this year that will raise the total to nearly 37,000 metric tons a year. Oxo Alcohols Provide a Steadily Growing Outlet for Propylene Since 1951, ICI has been making a wide range of alcohols by reacting olefins with carbon monoxide and hydrogen. The technique, known as the oxo process, yields alcohols with one carbon atom more than the starting olefin. Propylene gives rise to η-butyl alcohol and isobutyl alcohol. I d ' s production of higher alcohols— isooctyl alcohol, nonyl alcohol, and isodecyl alcohol, for example—is based on purchased heptenes, di-isobutylene, and nonene. ICI—the only maker of oxo alcohols in the U.K.—is expanding annual ca pacity for the alcohols from the pres ent 143,000-metric-ton level to 173,000 metric tons in 1965. Output can be varied depending on demand, but
the company doesn't give a breakdown of the amounts of each type of alcohol that it makes» ICI sells η-butyl alcohol and iso butyl alcohol for use as paint solvents. Its acetic acid esters go into oilbased paints; the phthalic acid esters go into synthetic latex and water emulsion paints. The future of these two alcohols, therefore, is tied to the paint industry which, in the U.K., has been steadily growing although not at a very spectacular rate. U.K. emulsion paint sales, for example, rose from 11.4 million gallons in 1954 to 14.7 million gallons in 1962. One ICI market forecaster predicted a 5% growth rate for the C 4 alcohols. This growth will reflect exports which, ac cording to ICI, have been climbing at a sprightly clip. The higher oxo alcohols go into plasticizers, hydraulic fluids, lubricat ing oil additives, and surface-active agents. Esters of isodecyl alcohol are used for making selective weed killers such as 2,4-D. The plasticizers have their main outAUG.
31, 1964
C&EN
77
let in polyvinyl chloride plastics. U.K. polyvinyl chloride output is continuing its upward swing. Last year's production probably came close to 154,000 metric tons compared with the 43,000 metric tons made in Britain in 1954. Proptjlene Tetramer's Star Dims Propylene tetramer is in trouble in Britain as elsewhere in Europe. Tabbed as the nondegradable culprit in tetrapropylene benzene sulfonate detergents, the tetramer is fast losing its main outlet. No law such as West Germany's that blocks use of biologically hard detergents is likely to get on the books soon in Britain. But voluntary regulation spurred by a standing watchdog committee set up in 1957 to keep an eye on foam and pollution is accomplishing much the same thing as a law. Meanwhile, British detergent makers are switching to other active ingredients, such as Shell's Dobane JN, which is based on cracked wax olefins. BHC is Britain's only producer of propylene tetramer. The company has now decided to convert its 20,000 metric-ton-a-year polymerization unit to cumene production.
Acrylonitrile's Star Rises Acrylonitrile is a bright spot in an otherwise uninspiring line-up of propylene uses. Britain's demand for acrylonitrile is fast increasing and may top 40,000 metric tons a year by 1966, because of mounting interest in acrylic fibers and acrylonitrile-butadiene-styrene and acrylonitrile-styrene resins. There's no acrylonitrile made yet in Britain. Thus, all the material now used in the U.K. is imported, mainly from the U.S. This situation will change in 1966, when Border Chemicals (owned jointly by British Petroleum, Distillers, and ICI) starts up its 41,000 metric-ton-a-year plant at Grangemouth. Border Chemicals' plant will need about 35,000 metric tons a year of propylene when it is operating at capacity. The firm will use Distillers' one-step vapor-phase process based on propylene, ammonia, and air. Government statistics don't list U.K. output of acrylic fiber or acrylonitrilecontaining copolymers. However, if size of plant expansions now under way is a measure, need for acrylonitrile in the U.K. is rapidly increasing. The bulk of acrylonitrile used in the 78
C&EN
AUG. 31, 1964
U.K. goes into acrylic fiber. By 1966, Courtaulds could use 24,000 metric tons of acrylonitrile for its expanded Courtelle fiber production. Chemstrand will need about 11,000 metric tons of the chemical for its Acrilan fiber production. Therefore, acrylic fiber could mean potential demand for some 35,000 metric tons of acrylonitrile by the time Border Chemicals' plant comes on stream. Potential demand for acrylonitrile for making acrylonitrile-type copolymers could reach some 4000 metric tons a year by 1966. Thus, it looks as though all of Border Chemicals' acrylonitrile output may be committed by the time its plant comes on stream. One and possibly more acrylonitrile plants may well be in the cards for Britain in the next three years.
Polypropylene Isn't Big in Britain as Yet; But Dont Count It Out Last year, apparent consumption of polypropylene in Britain was 8200 metric tons. Although this was double the 1962 level, it was still well below the 26,300-metric-ton U.K. annual capacity. The two producers, ICI and Shell, optimistically look for demand for the plastic to increase by about 50% a year during each of the next few years. To encourage greater use, both firms trimmed prices by as much as 6 1 / 2 cents per pound (for colored resin) earlier this year. This followed a similar price cut in 1963. British polypropylene can't count on much of an export market since licensing agreements bar exports to many areas. The two big outlets for U.K. polypropylene are packaging film and rigid containers. This year, some 200 metric tons may go into film use. ShorkoMetal Box and ICI are the two polypropylene film makers in Britain. ICI has two plants for making the polypropylene monofilament yarn trade-named Ulstron. These plants have a combined capacity of 4500 metric tons. ICI was the first to make polypropylene in Britain starting production there in 1960. Shell followed soon after. ICI is doubling its annual capacity to 22,000 metric tons by the end of the year. Shell's 15,300 metricton-a-year unit can also turn out highdensity polyethylene, but the company doesn't indicate the current production split.
ITALY Behind much of the recent growth of Italy's chemical industry, the fourth largest in western Europe, are petrochemicals. In the past 12 years, petrochemical complexes, some of them among the largest in Europe, have sprouted—at first mainly in the North but more recently in the underdeveloped South, Sicily, and Sardinia. Italy's own plentiful supplies of natural gas together with imported crude oil feed these plants. Italy's chemical producers have been so eager to build petrochemical plants that they now find themselves with excess capacity for a number of products. Ethylene is a key case in point. Italian ethylene production last year totaled 201,000 metric tons, 2 1 % above 1962's 166,000 metric tons, according to data of Aschimici (Italy's chemical producers' association). Ethylene production in 1961 was 124,000 metric tons. Prior data are incomplete. Annual ethylene capacity, however, is now 362,000 metric tons—second largest in the European Economic Community and third largest in western Europe. Another 141,000 metric tons a year is due to come on stream by 1965 or 1966, making the total then 503,000 metric tons a year.
By 1965, ethylene requirements might be about 300,000 metric tons, still well below capacity. But by the end of 1968, requirements could be up around 560,000 metric tons a year, exceeding presently planned total capacity. Thus, based on an optimistic view of presently available information, there will be a balance between capacity and demand during 1968 with a need for more capacity by the end of that year. However, much hinges on the export market, because Italian producers ship a large share of their polyethylene, polystyrene, polyvinyl chloride, and styrene-butadiene rubber to foreign markets. In addition, home consumption is picking up, and some chemical executives expect substantial increases in this sector in the next five years. A big factor is the rising standard of living of Italians, especially in the North. Except for a small amount (6500 metric tons a year) obtained as a byproduct in acetylene manufacture from natural gas at ANIC's Ravenna plant, all Italian ethylene comes from naphtha steam crackers. Of the two new units coming on stream at the end of this year, one is a steam cracker, the other a thermal crude cracker. Virtually all Italian ethylene production is captive. As elsewhere in Europe, the big demand is for fuel oil rather than gasoline; so naphtha is plentiful. Some Italian producers claim that Italian ethylene is cheaper than that produced elsewhere in Europe because Italy gets cheaper crude oil. The crude oil is cheaper, they say, because Italy is closer to sources in North Africa and the Middle East. Italy also uses large quantities of cheap Russian crude oil. Ethylene plants are located in the North, deep in the South, and on the islands of Sicily and Sardinia. The Italian government helps out in various ways—loans, subsidies, tax exemptions, and reductions in rail transport charges, among others—when plants are built in the underdeveloped South or on the two offshore islands.
though it may become one in the next few years. For 1963, almost all (197,000 metric tons) of the total 201,000 metric tons of ethylene consumed in Italy can be accounted for, using government or Aschimici data. The ethylene consumption pattern was as follows: polyethylene ( 5 2 % ) , ethylene dichloride (24% ), ethylene oxide ( 13% ), styrene ( 9 % ) , and miscellaneous ( 2 % ) . By 1968, based on a total requirement of 557,000 metric tons, the picture may look something like this: polyethylene ( 4 7 % ) , ethylene dichloride ( 2 6 % ) , styrene ( 1 4 % ) , ethylene oxide ( 6 % ) , acetaldehyde ( 5 % ) , and miscellaneous ( 2 % ) . Polyethylene
Forges Ahead
Italy's polyethylene production has been increasing by leaps and bounds. In 1963, the figure was 100,000 metric tons, 27% higher than the year before. From 1954 through 1958, the average rate of growth was 27.5% a year. In 1959, the production curve took a sharp upswing, and from that year through 1963, the average annual rate of growth was 67%. A good bit of this production is exported. For example, in 1962 exports were 31,500 metric tons, just under 40% of production. Almost 1 1 % of these exports went to Spain and the Belgo-Luxembourg Economic Union and 7% to the U.K. Polyethylene capacity in Italy cur-
rently stands at about 179,000 metric tons a year. About 8 3 % (149,000 metric tons) is made by high-pressure process and 17% (30,000 metric tons) by low-pressure process. Currently, there are five producers of polyethylene in Italy: Monteshell Petrochimica, which makes both low- and highpressure-process resins; Celene (owned jointly by Union Carbide and Edison) ; ANIC, chemical arm of state-owned ENI (Ente Nazionale Idrocarburi); ABCD (Asfalti, Bitumi, Cementi, e Derivati), owned by Bombrini ParodiDelfino; and Solvay. About 56% of Italy's polyethylene capacity was used last year. But at the end of this year or by early next year, polyethylene capacity will increase when Societa Italiana Résine (SIR) starts up its high-pressure-process polyethylene plant (at Porto Torres, Sardinia) with a capacity of 20,000 metric tons a year. About the same time Rumianca will bring its polyethylene plant (at Cagliari, Sardinia) on stream with a high-pressure-process polyethylene capacity of 18,000 metric tons and a low-pressure-process polyethylene capacity of 10,000 metric tons. SIR is also considering building a second 20,000-metric-ton plant that might use the Amoco low-pressure process. If Italian polyethylene production increases 20% this year over last, it will reach 120,000 metric tons. And if it continues at this rate, it would be Text continues on page 82
Polyethylene and Ethylene Dichloride Are Italy's Pace Setters Among Ethylene Outlets Production of ethylene in metric tons (Ethylene equivalent in metric tons in parentheses) Major ethylene outlets Polyethylene Ethylene oxide Styrene Ethylene dichloride
1962
1963
79,000° (83,000) 19,250 (19,250) 52,000 (16,600) 135,000 (43,000)
100,000 (105,000) 25,000 (25,000) 57,000 (18,200) 153,000 (49,000)
1964 (est.) 120,000 (126,000) 26,000 (26,000) 68,000 (22,000) 175,000 (56,000)
nil
nil
Where It Goes
Acetaldehyde
nil
Polyethylene, ethylene dichloride, and styrene will be the big levers under ethylene growth, with some aid from ethylene oxide, though historically the oxide has not been an important product in Italy. Ethylene-based acetaldehyde is not yet a factor,
Miscellaneous
n.a. (3,807) n.a. (165,657)
Totals
n.a. (3,800) n.a. (201,000)
n.a. (4,000) n.a. (234,000)
1968 (est.) 249,000 (262,000) 32,000 (32,000) 250,000 (80,000) 450,000 (145,000) 40,000 (28,000) n.a. (10,000) n.a. (557,000)
a Figure includes a small amount of polyisobutylene. Sources: Istituto Centrale di Statistical Associazione Nazionale dell'lndustria Chimica; C&EN estimates
AUG.
31f 1964
C&EN
79
Italian Ethylene Capacity Is the Third Largest in Western Europe Ethylene Company
Plant
ASFALTI, B I T U M I , CEMENTI, Ε D E R I V A T I , S.p.A. A N I C , S.p.A.
Gela ( S i c i l y )
C E L E N E , S.p.A.
Ravenna Priolo ( S i c i l y )
MONTESHELL PETROCHIMICA (50/50 J O I N T V E N T U R E OF M O N T E CATINI A N D SHELL) R U M I A N C A , S.p.A. S Ï ^ Ë b T S Ô N , S.p.A. SOCÎÊTÀ Ï N D U S T RIALE C A T A N E S E SOCIETA I T A L I A N A
RESINE
SOLVAY & CO., S.A.S. TOTALS
Location
Ragusa (Sicily)
Brindisi Ferrara Cagliari (Sardinia) Mantua Priolo (Sicily) Porto Torres (Sardinia) Rosignano
Current Capacity (Metric
Capacity After Expan sion Ton s per Year)
Remarks
"25TÔ0Ô
n.a.
N a p h t h a s t e a m cracker
75,000
n.a.
N a p h t h a s t e a m c r a c k e r ; t h e c o m p a n y is o w n e d by E n t e N a z i o n a l e I d r o c a r b u r i From natural gas J o i n t l y o w n e d by U n i o n C a r b i d e a n d S o c i e t a Edison Naphtha steam cracker Naphtha steam cracker
6,500 n.a. 8ÔTÔÔÔ 50,000
n.a. 40, 000 n.a. n.a.
5Ï71500 5Ô7ÔÔÔ 75,000
n.a. n.a. 5ÔTiÔÔÔ
n.a. 36ÎT5ÔÔ
n.a. 502,!5ÔÔ
D u e o n s t r e a m b y t h e e n d o f 1964; t h e r m a l c r a c k i n g of i m p o r t e d crude w i t h a L u m m u s u n i t Naphtha s t e a m cracker Na~phtha s t e a m c r a c k e r ; t h e c o m p a n y is o w n e d by S o c i e t a E d i s o n N a p h t h a s t e a m c r a c k e r d u e o n s t e a m by l a t e 1964 or e a r l y 1965 E x p a n s i o n s l a t e d f o r 1965 or 1966; S o l v a y c a p a c i t y not included
Polyethylene ASFALTI, B Ï T U M I , C E M E N T I , Ε D E R I V A T I , S.p.A. A N I C , S.p.A. C E L E N E , S.p.A.
Ragusa (Sicily) Gela ( S i c i l y ) Priolo ( S i c i l y )
MONTESHELL
Brindisi Ferrara Ferrara Capliari (Sardinia) Capliari (Sardinia)
PETROCHIMICA
R U M I A N C A , S.p.A. STARLENE SOCIETA I T A L I A N A
RESINE
Porto T o r r e s (Sardinia)
2576ÔÔ
n.a,
High-pressure-process (BASF) polyethylene
35TÔÔÔ 35,000
n.a. n.a.
"3Ô7ÔÔÔ 24,000 14,000 n.a.
n.a. n.a. n.a. Î 8 J 300
n.a.
ÎÔ7ÔÔÔ
High-pressure-process (ICI) polyethylene High-pressure-process (Union Carbide) polyethylene High-pressure-process polyethylene High-pressure-process polyethylene Low-pressure-process polyethylene High-pressure-process (Rexall) polyethylene; d u e o n s t r e a m by t h e e n d o f 1964 L o w - p r e s s u r e - p r o c e s s ( S t a n d a r d Oil Co. o f I n d . , ) d u e o n s t r e a m by 1965; t h e c o m p a n y is o w n e d by R u m i a n c a High-pressure-process polyethylene; due on s t r e a m by e n d o f 1964 Low-pressure-process polyethylene planned; may use A m o c o process Low-pressure-process (Phillips) polyethylene
n.a.
207 20,1000
SOLVAY & CO. TOTALS
Rosignano
~16,000 179,000 149,000 30,000
n.a. 2477'ÔÔÔ 187, 000 60, 000
High-pressure-process polyethylene totals Low-pressure-process polyethylene totals
Ethylene Oxide A N I C , S.p.A. C E L E N E , S.p.A. MONTESHELL PETROCHIMICA
"Gela ( S i c i l y ) Priolo ( S i c i l y ) Brindisi Ferrara Porto Torres (Sardinia)
2ÏÏJÎHX) 15,000 25,000
n.a. n.a. n.a.
60,000
n.a.
Gela ( S i c i l y )
20,000
n.a.
C E L E N E , S.p.A.
Priolo ( S i c i l y )
ÏÔTÔÔCJ
n.a.
MONTESHELL
Brindisi Ferrara
20,000
n.a.
50,000
n.a.
67ÔÔÔ 2,000 1,500 9,500
n.a. n.a. n.a. n.a.
n.a.
n.a.
(10,000)
n.a.
SOCIETA I T A L I A N A
RESINE
TOTALS
Direct oxidation process Direct oxidation process Direct oxidation process Under study
Ethylene Glycol A N I C , S.p.A.
PETROCHIMICA
TOTALS
Also m a k e s di-, tri-, a n d polyethylene glycol a n d glycol ethers Also m a k e s di-, tri-, a n d polyethylene glycol a n d glycol ethers
Ethanolamines A N I C , S.p.A. C E L E N E , S.p.A. MONTESHELL PETROCHIMICA TOTALS
Geja (SjcHyJ PrFoloJSicily) Ferrara
Ethanol (synthetic) A N I C , S.p.A.
Ravenna
SOCIETA ITALIANA
80
C&EN
Porto Torres (Sardinia)
RESINE
AUG.
31,
1964
Captive use for m a k i n g b u t a d i e n e for styrenebutadiene rubber production Plans d e p e n d on m a r k e t
Styrène Plant
Location
Current Capacity (Metric
Capacity After Expansion Tonis per Year)
Remarks
Company Ravenna Ferrara Mantua
MN OIN SHELL PETROCHIMICA A CT, ES.p.A. S I C E D I S O N , S.p.A. SOCIETA ITALIANA
RESINE
Porto Torres (Sardinia)
2Ô7ÔÔÔ 16,000 80,000
n.a. n.a. n.a.
15,000
n.a.
131,000
n.a.
Livorno Ferrara Mantua Macherio
16,000 20,000 50,000 20,000 106,000
n.a. n.a. n.a. n.a. n.a.
A N I C , S.p.A.
Ravenna
90,000
n.a.
W. R. G R A C E & CO. TOTALS
Near Naples
1,000 91,000
n.a. n.a.
5,000 5,000 1,000
n.a. n.a. n.a.
11,000
n.a.
TOTALS
U s e s 50,000 m e t r i c t o n s t o m a k e sells rest Buys imported ethyl benzene
polystyrene,
Polystyrene DOW C H E M I C A I T A L I A N A , S.p.A. MONTESHELL PETROCHIMICA S I C E D I S O N , S.p.A. SOCIETA I T A L I A N A R E S I N E TOTALS
Styrene s u p p l i e d f r o m Porto Torres (Sardinia)
Styrene-Butadiene Rubber Also m a k e s ton plant
c/>polybutadiene in
10,000-metric-
Acrylonitrile-Butadiene-Styrene Resins A N I C , S.p.A. MONTECATINI SOCIETA ITALIANA
Ravenna Rho
Milan
RESINE
TOTALS
Buys acrylonitrile Buys acrylonitrile S e m i c o m m e r c i a l u n i t ; buys acrylonitrile a n d has no plans at p r e s e n t to m a k e it
Ethylene Dichloride R U M I A N C A , S.p.A.
Cagliari
S I C E D I S O N , S.p.A.
Mantua
100,000
n.a.
SOCIETA I N D U S T R I A L E CATANESE MONTESHELL PETROCHIMICA TOTALS
Priolo ( S i c i l y )
100,000
n.a.
Brindisi
130,000 330,000
n.a. n.a.
For v i n y l c h l o r i d e a n d PVC p r o d u c t i o n
40,000
From acetylene m a d e f r o m natural gas
n.a.
C o m b i n e d process—50/50 a c e t y l e n e a n d e t h y l e n e dichloride
50,000
E x p a n s i o n p l a n n e d f o r 1964 or 1965 f o r v i n y l c h l o r i d e a n d PVC p r o d u c t i o n , w i l l h a v e U.S. R u b b e r ' s N a u g a t u c k Chemical Division license S h i p p e d to Porto Marghera p l a n t for vinyl chloride a n d PVC p r o d u c t i o n For p e r c h l o r o e t h y l e n e p r o d u c t i o n
Polyvinyl Chloride MANIFATTURA CERAMICA POZZI, S.p.A. MONTECATINI
Terni Brindisi Cagliari (Sardinia) Porto Marghera Ravenna
R U M I A N C A , S.p.A. S I C E D I S O N , S.p.A. SOCIETA C H I M I C A
Ferra n d i n a
RAVENNA
Ferrara Pieva V e r g o n t e
S O L V I C , S.p.A. U.S. R U B B E R - R U M I A N C A TOTALS
n.a. 80,000 160,000
—
n.a. 30,000
120,000
n.a.
35,000
n.a.
n.a. 10,000 400,000
n.a. n.a. 470,000
O n s t r e a m 1964 or 1965; c r a c k i n g e t h y l e n e d i chloride C o m b i n e d process—50/50 a c e t y l e n e a n d e t h y l e n e dichloride All f r o m a c e t y l e n e ; t o t a l m o n o m e r c a p a c i t y is 40,000 t o 50,000 m e t r i c t o n s a n d t h e d i f f e r e n c e goes to Wacker a n d for copolymers; the comp a n y i s j o i n t l y o w n e d b y A N I C (51%) a n d W a c k e r C h e m i e (49%) From acetylene Solvic n o t i n c l u d e d
Ethyl Chloride SOCIETA I N D U S T R I A L E CATANESE MONTESHELL PETROCHIMICA TOTALS
Priolo (Sicily)
25,000
n.a.
Ferrara
12,000 37,000
n.a. n.a.
Ethyl chloride a n d perchloroethylene
Acetaldehyde A N I C , S.p.A.
Ravenna
75,000
n.a.
SOCIETA E D I S O N ( S E T T O R E CHIMICA)
Porto Marghera
12,000
n.a.
87,000
n.a.
TOTALS n.a.:
Not available
Source:
C&EN
All a c e t y l e n e - b a s e d ; partially used to m a k e butadiene with ethanol A c e t y l e n e - b a s e d : Edison has license for HoechstWacker direct oxidation route a n d m a y event u a l l y b u i l d a 60,000 m e t r i c - t o n - a - y e a r p l a n t
estir nates
AUG.
31,
1964
C&EN
81
Italian Polyethylene Production May Reach Full Capacity by 1968 right at capacity (247,000 metric tons, including SIR's second plant) by 1968. CONFINDUSTRIA, the Italian manu facturers' association, predicts produc tion of polyethylene and polypropylene (the estimate groups the two polymers together) of 120,000 metric tons in 1964 and of 180,000 metric tons in 1966, an average annual gain of 22%. Judging by past performance, poly ethylene has a reasonable chance of growing at a 207c-per-year clip. Opti mists feel that an awakening market in Italy's South coupled with growing export markets in Africa, for example, could provide the necessary spring. Not all Italians are optimists, of course. An official of one of Italy's largest chemical firms complains that the chemical business in Italy is not just bad, but very bad. "You can't make people eat plastics," he says. Furthermore, he says his firm's sales men constantly complain about lowpriced imports from the U.S. and Japan. When reminded that this is the usual complaint against Italian producers, he replied with the ques tion: "Who's pushing whom?" Be that as it may, more Italians do indeed seem to be "eating" plastics, particularly polyethylene, and in a variety of ways. Sheet and film and injection-molded products together take some 807c of all polyolefins (mainly polyethylene) consumed in
Italy. This total share has been split almost equally in the past several years with a small edge in favor of injectionmolded articles. Now, the pattern is gradually shift ing in favor of sheet and film as de mand for packaging film rises. This year, sheet and film will probably take 4 3 % of polyolefins consumed, while injection-molded products should ac count for 37%. Blow-molded products are also growing relatively more im portant in the Italian market. Ethylene Oxide Growth May Level Off It's only been in the past five years that ethylene oxide in Italy has aroused interest. Until 1959, ethylene oxide production rocked along at minimal rates, hitting about 2500 metric tons annually between 1956 and 1959. It was made by the chlorohydrin route, using ethylene separated from cokeoven gas. Then, as more petroleumbased ethylene became available and as the ethylene glycol market grew, spurred by increasing prosperity in Italy's North, producers turned to direct oxidation and raised capacities. Production doubled every year (on the average) from 1959 through 1962, when it reached 19,250 metric tons. Last year, production moved ahead 30% to 25,000 metric tons. With this initial climb behind it, and lots of
ethylene glycol around, ethylene oxide looks like a five percenter for the next several years. At that rate, production would reach 32,000 metric tons a year in 1968, requiring 32,000 to 35,000 metric tons of ethylene. CONFIN DUSTRIA, however, is more opti mistic and foresees an average annual growth from 1963 through 1966 of 26% a year with a production of 50,000 metric tons of the oxide in 1966. Total ethylene oxide capacity is about 60,000 metric tons a year split about evenly among Monteshell Petrochimica, Celene, and ANIC. Thus, it looks like overcapacity for at least three years anyway, even if CON FINDUSTRIA proves right. Imports Hold Back Styrene Styrene brings up the rear as a major user of ethylene in Italy. Pro duction last year reached 57,000 metric tons, topping 1962's value by 10% and accounting for about 18,000 metric tons of ethylene. Imports of both styrene and ethylbenzene, however, have been high; so production alone doesn't give a full measure of styrene's potential as a consumer of ethylene. Take 1962, for example. Styrene production was 52,000 metric tons, representing 16,600 metric tons of ethylene equiva-
Italian Production of Ethyl ene and Its Derivatives Continues to Rise
Ethylene Polyethylene" Ethylene oxide Polystyrene Polyvinyl chloride Styrene-butadiene rubber Styrene Ethylene dichloride Ethanolamines Monoethylene glycol
(metric tons) 1957 1958
1954
1955
1956
n.a. 3,055 n.a. 6,430 n.a.
n.a. 4,704 n.a. 7,249 n.a.
n.a. 5,944 2,560 9,571 46,000
n.a. 7,055 2,870 12,404 52,000
n.a. n.a. n.a. n.a. n.a.
n.a. n.a. n.a. n.a. n.a.
n.a. n.a. n.a. n.a. n.a.
n.a. n.a. n.a. n.a. n.a.
1959
1950
1961
1962
1963
n.a. 8,082 2,570 15,693 67,000
n.a. 13,000 2,350 21,815 79,000
n.a. 34,246 6,700 33,743 106,000
123,992 53,617 16,500 44,667 151,000
165,657 79,562 19,250 65,000 195,000
201,000 100,000 25,000 n.a. 220,000
n.a. n.a. n.a. n.a. n.a.
47,000 n.a. n.a. n.a. n.a.
71,000 n.a. n.a. 76 2,386
88,000 38,000 118,000 32 4,782
91,000 52,000 135,000 2,048 10,224
n.a. 57,000 153,000 n.a. n.a.
α Figures include a small amount of polyisobutylene. n.a.: Not available Sources: Istituto Centrale di Statistica; Associazone Nazionale dell'lndustria Chimica;; Organization for Economic Cooperation a nd Development; C&EN estimates
82
C&EN
AUG.
3 1 , 196 4
lent. But imported styrene totaled 20,600 metric tons and imported ethylbenzene (presumably to feed SIR's styrene plant at Porto Torres ) reached 14,400 metric tons. About 1100 metric tons of styrene were exported. Computing apparent consumption (production plus imports minus exports) from these figures gives a value of about 86,000 metric t o n s equivalent to about 27,000 metric tons of ethylene. ( In this calculation, ethylbenzene is considered equivalent to styrene.) This consumption represents 6 3 % more ethylene than was actually used by Italian producers in making styrene. Italian producers, whose total annual styrene capacity is now 131,000 metric tons, can more than handle domestic requirements as indicated by apparent consumption. If they are successful in replacing imports with their own material, styrene should have no trouble in the next five years passing ethylene oxide as an ethylene consumer. Styrene's main outlet, polystyrene, has been doing very well since 1954. From 1954 through 1958, average growth rate was 25% a year. In the period 1958 through 1962, the rate was 4 3 % a year. Production was about 65,000 metric tons in 1962. Total capacity is about 106,000 metric tons a year. So production should snug up to current capacity this year or next. Exports have been substantial, amounting to 24,500 metric tons in 1962 (38% of production), and 26,142 metric tons last year. Biggest buyer has been West Germany, which took 4900 metric tons (in 1962). Imports in 1962 amounted to 7600 metric tons, about half of which came from the U.S. Styrene-butadiene rubber, the monomer's other big outlet, has moved along briskly, too. According to estimates of Chemische Werke Huels, Italian production has increased at about 2 5 % a year from 1959 through 1962. Exports of styrene-butadiene rubber have also been heavy, accounting for 40,000 metric tons (44%) of estimated 1962 production of 91,000 metric tons. Of this total, 12,800 metric tons (32%) went to the Soviet Union and 10,300 metric tons (26%) to France. Figures for 1963 show Italian exports of 47,900 metric tons, with large amounts again going to the Soviet Union and France. Styrene-butadiene rubber imports, which had not been very high, rose sharply
Sheet, Film, and Injection-Molded Products Continue to Take at Least 80% of Italy's Polyolefins Sheet and film Injection molding Blow molding Cables and electrical insulation Pipes Miscellaneous Total: Source:
1961
1962
1963
41% 45 8 3 1 2 100%
42% 40 10 4 1 3 100%
43% 37 11 4 1 4 100%
C&EN estimates
Sheet and film is the largest single outlet for polyolefins in Italy. Typical of the far-reaching applications of sheet and film is this agricultural use of polyethylene
last year to almost 14,000 metric tons. If styrene outlets can hold their export markets and if the new acrylonitrile-styrene copolymers take hold, the monomer should be able to advance at 20% a year in the next five years. Based on consumption, this rate of increase could generate a 250,000 metric-ton-a-year styrene requirement by the end of 1968, about twice present capacity. This would mean an ethylene requirement of about 80,000 metric tons a year. But if styrene imports continue to be troublesome, they
could drop the amount of styrene delivered by domestic producers to about 200,000 metric tons. Ethylene Dichloride—Up
and Coming
Until three or four years ago, ethylene dichloride in Italy wasn't a particularly large-tonnage product. By 1963, though, production had climbed to 153,000 metric tons, 13% above the 1962 figure, and accounted for about 49,000 metric tons of ethylene. This was enough to maintain ethylene AUG.
3 1 , 1964
C&EN
83
dichloride as the second largest Italian ethylene consumer, a position it has held for several years. Polyvinyl chloride is behind ethylene dichloride's swift rise in importance as an ethylene consumer, for Italian producers were early in using the combined ethylene dichlorideacetylene route in Europe. Half of Sicedison's capacity for vinyl chloride at Porto Marghera (120,000 metric tons a year) is based on the combined process. This means a full-capacity
requirement for ethylene dichloride of about 100,000 metric tons a year. Polymer, a Montecatini subsidiary, uses the same setup at Terni and Brindisi, where total annual capacity is another 240,000 metric tons of vinyl chloride. Half of this vinyl chloride capacity is based on ethylene dichloride, and thus at full capacity would require about 200,000 metric tons a year of the dichloride. Finally, by late this year or early next, Rumianca plans to start up a
30,000 metric-ton-a-year polyvinyl chloride plant at Cagliari (Sardinia) based on ethylene dichloride cracking. This plant will need still another 50,000 metric tons a year of the dichloride. In addition, Sincat has a capacity of 100,000 metric tons a year of ethylene dichloride at its Priolo (Sicily) plant for perchloroethylene production. Operating at full capacity, these plants would consume about 450,000 metric tons a year of ethylene dichlo-
Polyethylene
Styrene
Ethylene dichloride
Polystyrene
Propyl alcohols
Phenol (synthetic)
Over-All, Exports of Italian Ethyleneand PropyleneBased Products Top Imports (Thousands of Metric Tons)
EXPORTS IMPORTS n.a.: Not available SourcM*. IttHuto Central· di Statistic·; Ataociazon· National· dtll'lnduttri· Chimie· 84
C&EN
AUG.
31,
1964
ride and use close to 145,000 metric tons a year of ethylene. Thus, polyvinyl chloride will continue to account for most of ethylene dichloride's growth. Polyvinyl chloride itself has an outstanding growth curve. From 1954 through 1963, production climbed an average 3 1 % a year. Last year, production hit 220,000 metric tons. In 1962, a mammoth 83,200 metric tons (38% of production) were exported, large amounts going to West Germany,
Holland, the U.K., France, and the U.S.S.R. CONFINDUSTRIA estimates that polyvinyl chloride production will rise at a rate close to 1 3 % a year through 1966, similar to the rate it maintained from 1961 to 1963. At this rate, polyvinyl chloride production would hit between 400,000 and 450,000 metric tons a year in 1968. Total capacity by 1965 will be about 475,000 metric tons a year (not counting Solvic's). This capacity could be fully used by 1968.
Other Italian polyvinyl chloride producers haven't disclosed their plans regarding switching to ethylene dichloride. Some likely will. But even if none do, the requirement for ethylene dichloride by Sicedison, Montecatini, and Rumianca should generate a need for about 145,000 metric tons a year of ethylene by 1968. About 40% of polyvinyl chloride consumed in Italy is of the rigid type, much of it in pipe, valves, and the like. Italy is ahead of other European coun-
Ethyl benzene
Ethanolamines (ail)
Ethylene glycols
P o l y v i n y l chloride
Styrene-butadiene rubber
Propylene glycols
Acetone (100%)
Dodecylbenzene
Polypropylene
AUG. 31, 1964 C & E N
85
In Italy There Is Too Much Propylene, Not Enough Big Outlets Propylene
Capacity After Expansion Tom? per Year)
Remarks
Plant
ASFALTI, B I T U M I , CEMENTI, Ε D E R I V A T I , S.p.A. A N I C , S.p.A. C E L E N E , S.p.A. MONTESHËLL PETROCHIMICA
Ragusa
ÎOÔÔ
n.a.
By-product of e t h y l e n e p l a n t
Gela ( S i c i l y ) Priolo ( S i c i l y ) Brindisi Ferrara Cagliari
30,000
n.a. 25,000 n.a. n.a. 37TÔÔ0
Mantua Priolo ( S i c i l y )
3ÔTÔÔ0 50,000
n.a. n.a.
By-product of e t h y l e n e plant By-product of ethylene plant By-product of ethylene plant By-product of e t h y l e n e plant D u e o n s t r e a m by t h e e n d o f 1964; b y - p r o d u c t o f ethylene plant By-product of e t h y l e n e plant By-product of e t h y l e n e plant
30,000
By-product of e t h y l e n e plant
R U M I A N C A , S.p.A. S I C E D I S O N , S.p.A. SOCIETA I N D U S T R I A L E CATANESE SOCIETA I T A L I A N A R E S I N E
Location
Current Capacity (Metric
Company
Porto T o r r e s (Sardinia)
TOTALS
60,000 40,000
— 222,000
314,000
Isopropyl Alcohol MONTESHELL
PETROCHIMICA
8,000
n.a.
2,000 12,500
n.a. n.a.
14,500
n.a.
Mantua Porto T o r r e s (Sardinia)
30,000
n.a. (14,000)
Brindisi Ferrara
15,000 20,000 35,000
Priolo ( S i c i l y )
50,000
Ferrara
Propylene Oxide MONTECATINI C E L E N E , S.p.A.
Ferrara Priolo ( S i c i l y )
TOTALS
Experimental Societa Industriale Catanese supplies propyle n e ; C e l e n e also m a k e s p r o p y l e n e g l y c o l
Dodecene S I C E D I S O N , S.p.A. SOCIETA I T A L I A N A
RESINE
—
Also i n t e r m i t t e n t n o n e n e p r o d u c t i o n Plans shelved; the c o m p a n y feels t h a t dodecene is c h e a p e r t o b u y
Polypropylene MONTESHELL
PETROCHIMICA
TOTALS
n.a. n.a. n.a.
Cumene SOCIETA I N D U S T R I A L E CATANESE SOCIETA I T A L I A N A R E S I N E
Porto Torres (Sardinia) Solbiate
TOTALS
n.a. 60,000
30,000 80,000
Merchant cumene D u e t o c o m e o n s t r e a m b y t h e f a l l o f 1964
n.a. n.a.
Captive; o u t p u t to phenol plant
M a d e by a l k a l i n e f u s i o n r o u t e ; t h e c o m p a n y is o w n e d by M o n t e c a t i n i From c u m e n e ; p h e n o l s h i p p e d to Porto Marghera p l a n t for c a p r o l a c t a m p r o d u c t i o n From c u m e n e From m e r c h a n t c u m e n e
Phenol (synthetic) A Z I E N D E COLORI N A Z I O N A L E A F F I N I , S.p.A. S I C E D I S O N , S.p.A.
Savona
8,000
n.a.
Mantua
30,000
n.a.
SOCIETA I T A L I A N A R E S I N E SOCIETA I T A L I A N A R E S I N E G U L F
Solbiate Porto T o r r e s (Sardinia) Porto M a r g h e r a
20,000 40,000
n.a. n.a.
3,000 101,000
n.a. n.a.
20,000 25,000
n.a. n.a.
45,000
n.a.
V E T R O C O K E , S.p.A. TOTALS
M a d e by a l k a l i n e f u s i o n r o u t e
Acetone (from cumene) S I C E D I S O N , S.p.A. SOCIETA I T A L I A N A R E S I N E G U L F
Mantua Porto Torres (Sardinia)
TOTALS
Glycerol Gela ( S i c i l y )
A N I C , S.p.A.
86
C&EN
AUG.
31,
1964
—
48,000
Planned
Acrylonitrile Company
Plant Location
ANIC, S.p.A. RUMIANCA, S.p.A.
Gela (Sicily) Cagliari (Sardinia) Porto Marghera
SICEDISON, S.p.A.
Capacity After Current Expansion Capacity (Metric Tons? per Year)
— —
—
15,000
15,000
n.a.
Ferrara
10,000
n.a.
Ferrara Priolo (Sicily)
25,000 38,000
n.a. n.a.
63,000
n.a.
Remarks Under study On stream by mid-1965; Sohio process using propylene From acetylene
Ethylene-Propylene-Rubber MONTESHELL PETROCHIMICA
Oxo Products MONTESHELL*PETROCHIMICA CELENE, S.p.A. TOTALS
2-Ethylhexanol, butanol, isobutanol; late 1963
on stream
Perchloroethylene SOCIETA INDUSTRIALE CATANESE RUMIANCA, S.p.A.
Priolo (Sicily)
20,000
n.a.
Cagliari (Sardinia)
10,000
n.a.
30,000
n.a.
30,000 50,000
n.a. n.a.
80,000
n.a.
TOTALS
Joint venture with Pittsburgh Plate Glass; also makes trichloroethylene
Dodecylbenzene SICEDISON, S.p.A. SOCIETA ITALIANA RESINE
Mantua
TOTALS n.a.:
Not available
Source:
Buys dodecene in U.S.
Cù-EN estimates
tries in use of rigid polyvinyl chloride, except for Holland. Thus far, no acetaldehyde is ethylene-based in Italy. Edison has a license for the Hoechst-Wacker process, though, and may be considering putting up a 40,000-metric-ton unit in the next year or two. It's not unlikely that an Edison plant will be on stream and running at full capacity by the end of 1966. If so, it would need about 28,000 metric tons a year of ethylene. Besides the big ethylene users, there are several others that deserve mention. Sincat makes ethyl chloride at Priolo (Sicily). The plant's annual capacity is 25,000 metric tons, which means that it would consume about 9000 metric tons a year of ethylene (at full capacity). Rumianca, in a joint venture with Pittsburgh Plate Glass, plans to make chlorinated solvents in a 10,000 metric-ton-a-year plant at Cagliari ( Sardinia ). Ethylene consumption there would be about 3500 metric tons a year. Propylene Has the Same Problems in Italy as Elsewhere Propylene in Italy presents the usual problem: too much propylene, not
enough big outlets. Most Italian propylene is a by-product of ethylene production, but so far is without uses matching ethylene's growing outlets. Producers turned out about 150,000 metric tons in 1963 versus 133,000 metric tons in 1961, for a gain of 1 3 % . Annual capacity, however, is now 222,000 metric tons and will rise to 314,000 metric tons by 1966. Italian producers turn out all the major propylene-derived products—isopropyl alcohol, propylene oxide, nonene, dodecene, cumene, polypropylene, oxo products, and ethylene-propylene rubber. In addition, acrylonitrile, now made only from acetylene in Italy, will be made from propylene by next year. Isopropyl alcohol has so far not sparked much interest in Italy. Montecatini, the only major producer in Italy, has an annual capacity of 8000 metric tons. Production figures aren't available, but data on acetone are. Since about 10% of the acetone produced in 1962 came from isopropyl alcohol (90% from cumene), some idea of isopropyl alcohol production can be had by calculating back from acetone. This calculation, of course, doesn't allow for other isopropyl alcohol outlets.
At any rate, of the 45,000 metric tons of acetone produced in 1962, about 4500 metric tons probably came from isopropyl alcohol. About 5500 metric tons of isopropyl alcohol would have been needed to make this amount. Other isopropyl alcohol outlets, such as solvents, drugs and pharmaceuticals, and exports, may have pushed total production to 8000 metric tons—an amount that would consume about 7000 metric tons of propylene. This is only a ballpark estimate, however. Propylene oxide is just getting started in Italy, although Montecatini has had an experimental 2000-metricton plant for several years. Last December, Celene started up a new 12,500-metric-ton plant at Priolo. Nearby Sincat supplies the propylene for this operation. Part of the oxide production goes into propylene glycols. Propylene glycol imports amounted to 3000 metric tons in 1962, 3500 metric tons in 1961, and 2400 metric tons in 1960. Exports have been negligible, naturally. With Celene's plant, imports will likely drop, exports climb. Nonene is produced intermittently by Sicedison at Mantua, according to an Edison executive. Sicedison also AUG.
31, 1964
C&EN
87
Production of Propylene and Related Products in Italy Moves Up Yearly Propylene Polypropylene Phenol (synthetic) Acetone
1954
1955
1956
1957
1958
1959
1960
1961
1962
1963
n.a. n.a. 6,209 2,423
n.a. n.a. 6,758 2,910
n.a. n.a. 7,049 4,445
n.a. n.a. 7,736 4,198
n.a. n.a. 10,129 3,803
n.a. n.a. 11,981 4,920
n.a. n.a. 16,032 12,793
108,483 n.a. 31,756 16,715
133,103 15,000 45,000 23,000
150,000 n.a. 70,000 n.a.
n.a.: Not available Sources: Istituto Centrale di Statistical Associazone Nazionale dell'lndijstria Chimica ; Organization for Economic Cooperation and Development; C&EN estimates
makes dodecene at Mantua in a 30,000 metric-ton-a-year plant for use as raw material for dodecylbenzene. Italy's biggest dodecylbenzene maker is SIR, whose plant capacity is 50,000 metric tons a year. SIR, however, buys its dodecene on the open market. The question of biodegradability of detergents hasn't been seriously discussed in Italy—yet. For Italy, the problem isn't acute because of the short distance from any point to two seas, and because of deep water wells. Nevertheless, industrial areas like Milan may one day be afflicted. The general feeling is that some sort of law will eventually come into being, enacted either by Italy on her own or by the E E C . Meanwhile, dodecylbenzene producers will continue making the product. The law in West Germany and the threat of similar action in the U.S. are having an effect on Italian producers, however. For example, SIR had planned to build its own dodecene plant, but now finds it can buy cheaper material from the U.S. Eventually, no matter what happens in Italy, Italy will be affected by detergent laws in the countries to which she exports. And Italian dodecylbenzene exports have been sizable. In 1962, exports amounted to 31,000 metric tons, with the Belgo-Luxembourg Economic Union taking 27%, Holland 18%, Spain 12%, and France 10%. As a hedge against changing markets, SIR, for one, plans to build a straight-chain dodecylbenzene plant, buying normal paraffins on the market. So the long-range prospect for dodecene, probably Italy's biggest propylene outlet, is continued growth for a while but eventual extinction as detergent laws become widespread. Italy's total annual capacity of 80,000 metric tons of cumene—with more to come—makes cumene a significant factor in Italy's propylene picture. Sincat and SIR are Italy's two 88
C&EN
AUG.
3 1 , 196 4
cumene producers. Sincat has a capacity of 50,000 metric tons a year at its Priolo plant, and uses most of its production captively to make phenol and acetone at Sicedison's Mantua plant. Capacity is 30,000 metric tons a year of phenol and 20,000 metric tons a year of acetone. Sicedison's phenol production goes to make cyclohexanone, which is then shipped to the firm's Porto Marghera caprolactam plant. SIR has been making cumene for five years at its Solbiate plant, which has an annual capacity of 30,000 metric tons. The plant's output feeds the firm's phenol plant close by. SIR-Gulf also makes phenol and acetone by the cumene route at Porto Torres (Sardinia). Annual plant capacity is about 40,000 metric tons of phenol and about 25,000 metric tons of acetone. Gulf now supplies the cumene, but SIR says it will start up its own cumene plant this fall. Synthetic phenol production has been rising steadily since 1954, reaching 45,000 metric tons in 1962. Average growth in that time was 28% a year. Of Italy's total phenol capacity of 101,000 metric tons a year, about 89% is from cumene. Phenol exports amounted to 7500 metric tons in 1962. Imports have fallen off rapidly as Italian firms have added production capacity. Imports in 1962 were 1600 metric tons compared to 7500 in 1960. Polypropylene Is Not Doing Spectacularly Well Even though Italy is the home of polypropylene, the polymer's success there hasn't been earth-shaking. According to Montecatini's Dr. Giulio Ballabio, 1962 total production was 15,000 metric tons. With the Brindisi plant now on stream, total annual capacity is about 60,000 metric tons. According to one of Montecatini's top research men, the firm is quite satisfied with polypropylene's prog-
ress in Italy and elsewhere. He feels the future looks promising, pointing to the availability of propylene, which many agree makes polypropylene basically attractive. Polypropylene surpasses linear polyethylene in certain properties such as stiffness and hardness, and some high-temperature properties (melting point is 176° C. versus 130° C. for linear polyethylene), he says. Polypropylene is also superior, he says, in that it's not subject to environmental stress cracking, has a lower specific gravity and higher gloss, and is more easily molded. And he points to the excellent film possible with polypropylene. At the same time, he admits that the polymer's low-temperature resilience has been poor, but says that this can be improved. Problems of dyeability are now being solved, he says. Montecatini can now produce a dyeable fiber, although it is awaiting final test results before marketing the material. Acrylonitrile
Is Coming Along
Acrylonitrile is beginning to arouse interest in Italy. Thus far, though, none of the chemical is produced via propylene. Sicedison has a 15,000 metric-ton-a-year plant at Porto Marghera that uses acetylene. Montecatini makes acrylates, methacrylates, and acrylonitrile-butadiene-styrene resins, but buys its acrylonitrile. Rumianca plans to make 15,000 metric tons a year of the chemical at Cagliari using the Sohio process, which it has licensed. It may thus be the first to use the propylene route in Italy. ANIC is considering making acrylonitrile at Gela, using the propyleneammonia route. The firm is currently building an acrylic fiber plant at Pisticci in the South, but will buy the raw material for the present. SIR, too, is moving into acrylonitrile-butadiene-styrene resins and is starting up a 1000-metric-ton semi-
Memo to: EQUIPMENT and INSTRUMENT MANUFACTURERS
From: Re:
THE LUMMUS COMPANY
Dr. Utah Tsac
How Industrial & Engineering Chemistry helps you sell
At Lummus, we select and place millions of dollars worth of equipment and instru ments into the plants and processes we de sign, engineer and construct. With more than 3,000 permanent specialists and over 50 years of experience, we have accounted for nearly 1,000 major projects throughout the world for industry and Government. As Coordinator of Chemical Plants at Lummus, I can tell you that a large part of our
success has resulted from the creative use of your products. This is why Industrial & Engineering Chemistry is so important to us and, consequently, to you. We rely on its editorial contents for the latest in chemical technology and we read your ads in Industrial & Engineering Chemistry to stay abreast of the equipment and instruments we need for our processes.
INDUSTRIAL & ENGINEERING CHEMISTRY Advertising
Management:
REINHOLD PUBLISHING CORP.
430 Park Ave., N. Y. C. 10022
C & Ε Ν 89
EASTMAN Organic
Chemicals
may be available in
larger-than-laboratory quantities even if they aren't in our catalog. IF THERE IS ANYTHING YOU NEED, ASK Distillation Products Industries, Rochester, N.Y. 14603.
These compounds 9306 8866
were added to the list on
Aug.31,1964:
N-Amidinobenzamide MP 158-160°
25 g.
7.30
Cyclohexyl Isocyanate BP 166-168°
25 g.
4.10
100 g.
13.75
5 g.
2.70
C H 2 ( C H 2 ) . , C H N C O . . . M W 125.17
8903 9048
l,3-Diallyl-2-thiourea MP 48-50° CH 2 :CHCH 1 »NHCSNHCH 2 CH:CH2...MW 156.25
25 g.
9.60
Dimethyl Glutarate BP 102-104°/14 mm
25 g.
3.85
100 g.
12.85
CH.iOCO(CH 1 ») ;j COOCH fj ...MW 160.17
9020
p-Nitrophenyl Acetate MP 78-79° C H . J C O O C H H ^ N O J . . . MW 181.15
9049
10 g. $ 3.50
C e H r , C O N H C ( : N H ) N H 2 . . . M W 163.18
Ν,Ν,Ν',Ν'-Tetramethyl-o-phenylenediamine BP 96-97V14 mm (CH;})oNC (i H. l N(CH: J )._»...MW 164.25
25 g.
5.50
100 g.
19.30
5 g.
3.85
25 g.
15.35
Prices subject to change without notice.
aPi Distillation Products Industries is a division of Eastman Kodak Company
No surface glaze or coating
commercial plant. It has no imme diate plans to make acrylonitrile, al though it has considered making it from propylene. A possibility is a joint venture with Rumianca. Thus, there seems to be considerable interest in acrylonitrile and its main outlets. Celene brought its new oxo plant on stream at Priolo at the end of last year. The new plant turns out 2ethyl hexanol, butanol, and isobutanol and has a total annual capacity of 38,000 metric tons. Monteshell Petrochimica also makes oxo prod ucts at Ferrara. In ethylene-propylene rubber, Mon teshell Petrochimica has things pretty well sewed up at the moment in Italy. It has production facilities at Ferrara but no information on the amount made at the plant is available.
You Can Purchase Single or Combined Reprints of This C&EN Special Report Reprints of this special three-part report on olefins in Europe can be purchased singly or combined. Part 1, which appeared Aug. 3, covered West Germany and France. Part 2, in this issue, reports on Italy and the United Kingdom. Part 3, which will be pub lished on Sept. 28, will include Spain, Benelux, and Scandinavia. The re prints will be available at the following prices: Single reprints (Parts 1, 2, or 3) 1 to 49 copies $0.50 each Combined reprints (Parts 1, 2, and 3) 1 to 49 copies $1.00 each 50 to 100 copies of either the single or combined reprints may be had at a 20% discount Prices for larger quantities available on request TO:
REPRINT DEPARTMENT ACS Applied Publications 1155 Sixteenth Street, N.W. Washington, D.C. 20036
FROM: Name
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for 75 years the only perma nently satisfactory material for chemical laboratory table tops, shelving, sinks, splash backs, drain boards and fume hoods. Prompt delivery. ALBERENE S T O N E - A DIVISION OF THE GEORGIA M A R B L E COMPANY. For FREE literature and technical assistance address: THE ALBERMAR COMPANY, 386 PARK AVE. SOUTH, NEW YORK 16, N. Y., DEPT. Ν
90
C&EN
AUG.
31,
1964
Number
Zip code of
copies
P a r t i I Part 2 I Part 3 I Combined Amount enclosed $
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α,β,β-Trifluorostyrene Introductory 1 0 - g r a m sample for $ 2 5 . M O L E C U L O N RESEARCH C O R P O R A T I O N 139 Main Street, Cambridge, Mass. 02142
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All Brand New in original factory cartons. Oxygen cylinders. Type 304, 400 P.S.I. V*" pipe thread openings at each end except A-4 and A-6. J-1, 24 X 48", 80 gal., 10 gauge, 18,000 cu. in. Wt. 150 $11(J 00 lbs., ship wt. 250 lbs., F.O.B. Baton Rouge, La., $300 value. ' , υ · G-1,12 X 24"; 2100 cu. in. 16 gauge, wt. 35 lbs., F.O.B. % 0() 50 Chicago, Brand New '"* G-1, perfect, like new ' 18.°
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