W . C. UHL and E. E. JUTERBOCK Technical Information Division, Esso Research and Engineering Co., Linden, N . J .
l/EC
ANNUAL
REVIEWS
Petroleum 1957 Petroleum was still a dynamic industry in 1957: Product d e m a n d increased, but a t a reduced rate Plant expansion continued Octane
race
slackened
Jet fuel d e m a n d tion gasoline
but
surpassed
N e w processes i m p r o v e d quality '
little avia-
product
Effort to develop shale oil w a s i n tensified Expansion in petrochemicals continued
G
ROWTH IN over-all domestic d e -
m a n d for petroleum products in 1957, about 2 . 5 % , was mostly in gasoline, distillates, a n d so-called other products. Gasoline was supported by t h e 6,000,000 passenger automobiles produced in 1957, which raised the car population by 5 % . However, the strongest growth, nearly 5 % , was in " o t h e r " products where t h e m a i n factors were continued expansion of military jet fuels, good markets for liquefied petroleum gas, a n d continued growth in petrochemicals. Although the rate of increase in d e m a n d for 1957 fell short of the 3 . 5 % for 1956, refiners were willing
to invest in plant expansion. A n nouncements indicate t h a t about 444,000 barrels per day of new capacity will be added during the next 12 to 18 months, boosting total capacity about 5 % . Motor Fuels
T h e rise in antiknock quality of gasoline tapered off only slightly. Average octane numbers a r e now going u p about one unit p e r year. Ethyl C o r p . surveys show weighted national-average Research octane numbers of p r e m i u m fuels for the m o n t h of J a n u a r y in 1955 through 1957 as 94.3, 96.2, a n d 97.4, respectively, a n d for October 1957 as 98.1.
Domestic Demand for Petroleum Products 6
40001
Est. 1957 D e m a n d % Change o v e r 1956 3000
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Aircraft Fuels: Jets Surge Ahead
(Domestic Demand)
250 Gasoline 200
D B
150
1 Jet Fuel 100
50
with concomitant high rate of heat transfer to the combustor liner of the engine a n d resultant deterioration. T h e solution m a y be to limit the content of condensed-ring aromatics. Rocket fuels consume only a n insignificant quantity of petroleum. Hydrocarbons, however, are still the major liquid rocket fuel. T h e principal alternatives to hydrocarbons are alcohol, aniline, or hydrazine. T h e oxidizing agent required with the fuel can be liquid oxygen, nitric acid, or hydrogen peroxide. T h e new high-energy boron fuels received a great deal of attention during the year; they are most advantageous for air-breathing missiles and m a n n e d aircraft, but they have application to rockets, also. Engine Trends
0 1953
1954
Correspondingly, the average engine compression ratios for new cars continued their steady c l i m b — from 8.5 in 1956 to 9.0 in 1957, a n d a n estimated 9.4 in 1958. A b o u t 9 0 % of the 1957 model cars require gasoline of at least 98 Research octane n u m b e r a n d 9 0 % of the 1958 models will require 99. O c t a n e numbers above 100 are determined by matching the fuel in a laboratory test engine against isooctane plus the required a m o u n t of tetraethyllead. T h e r e has been some confusion as to the scale on which the results are expressed, b u t the industry now seems ready to standardize on a scale recommended by the Coordinating Research Council. A gasoline matching iso-octane plus 1 ml. of tetraethyllead per gallon for example, is said to have 108.6 octane number. A manganese derivative of methylcyclopentadiene was suggested as a new antiknock additive. Although not yet available for commercial application, it is regarded as the most promising c o m p o u n d yet discovered in the search for materials to compete with tetraethyllead. If accepted, it will probably supplement rather than replace tetraethyllead. Major oil companies are still split on the three-grade marketing system introduced last year. According to
1955
1956
1957 (EST.)
this system, service stations offer regular, premium, and superp r e m i u m gasoline. However, some majors are still sticking to two grades, a n d one c o m p a n y is offering in a limited sales area five grades blended at the service station p u m p . Aircraft Fuels
I n 1957, jet fuel surpassed aviation gasoline. As of mid-September, world-wide estimated orders for commercial aircraft were 507 piston-type planes, 599 turboprops, a n d 429 j e t types. Furthermore, an estimated 235 turboprops are already in service throughout the world. T h e most important jet fuel from the standpoint of volume is the JP-4 grade, a wide-cut product, containing both kerosine a n d gasoline, with a boiling range extending from 140° to 550° F. Because of its availability in large volume, it has been specified for military use, both in this country and by N A T O forces. A kerosine-type fuel is anticipated, however, to become the backbone product for use in commercial j e t airliners. It is safer t h a n JP-4 because of its high flash point, b u t presents a rather interesting technical problem—luminosity of the flame,
O n e automotive engineering development that came into public notice in 1957, use of a fuel injection system in place of a carburetor, could affect gasoline quality. Proponents claim it permits savings in gasoline consumption when properly installed and tuned u p . Engine octane requirements are said to be reduced. However, car manufacturers m a y use such a cushion to increase compression ratios. Another advantage claimed is increased tolerance for low- and high-boiling fractions in the fuel. Fuel injection is not far into the future like gas turbines or free-piston engines in passenger cars. Several systems are already available as optional equipment in several makes of cars. However, they cost between $400 a n d $500 extra and no great swing to these devices is anticipated in 1958. N o major developments in gas turbines occurred during the year, although some motor manufacturers expect eventual use of this type of power plant for heavy trucks in the higher horsepower ranges. I n 1957, the first free-piston engine for marine use appeared in this country, although French m e r c h a n t ships have been using this type of propulsion to a certain extent for several years. Also the first experimental tractor powered by a freepiston engine appeared. Interest in use of residual fuels for diesel engines was strong. M a r i n e diesels are the primary consumers, but some railroads have also begun to use residuals in locomotives. VOL. 50, NO. 1
·
JANUARY 1958
45 A
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Processing Developments Major processes are showing a n interesting growth-rate pattern as shifts in product volume a n d quality requirements are reflected. For years, the greatest improve m e n t in octane rating was obtained as a by-product of catalytic cracking. Today, sufficient catalytic cracking capacity is installed to handle sub stantially all available feedstocks. Attention of refiners has turned toward processes designed specifi cally to improve octane number, such as catalytic reforming, alkylation, and isomerization. T h e growth of catalytic reforming has h a d two significant effects on processing techniques: It has pro vided a ready source of aromatic hydrocarbons for petrochemical uses, which refiners have begun to utilize. Also, by making large quantities of hydrogen available, it has fostered the development of hydrogen treat ing. Often the first candidate for
hydrogen treating is the feed to the reformer itself, because desulfurization to avoid catalyst poisoning a n d corrosion is becoming more wide spread. Hydrogen is also used to treat gasoline and middle distillates, a n d it offers m a n y advantages over old-line processes, such as acid treating and doctor sweetening. Alkylation, a key process for avia tion gasoline manufacture during World W a r I I , has returned to the limelight because of its ability to make the 1 0 0 + octanes needed by today's motor cars. Installed ca pacity had hovered at about 200,000 barrels per day, until 1955 when the current upsurge began. Isomerization is another process being revived. O n l y a few units are now either in operation or u n d e r construction, but at least four processes are being licensed for the catalytic isomerization of pentanes and hexanes. T h e appeal of isomerization for octane improvement is seen in the
Other Oil Sources
Growth Rates of Major Domestic Processes 5*00 4000
Catalytic Cracking
3000 2000 1000 2000 1600
Catalytic Reforming
1700 800
1
WO
1 2000
1600
Hydrogen Processes
1700 M0
400
Ï75 MO
Alkylation
725 150 75
March 3 1 , 1957
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INDUSTRIAL AND ENGINEERING CHEMISTRY
July 1, 19S8 (Proincted)
following figures: Research octane n u m b e r for rc-pentane is 88.7 with 3 ml. of tetraethyllead, but 108.7 for ζ'ίο-pentane ; for rc-hexane it is 65.3, b u t 96.6 to 105.2 for the isomers. Add to this the fact that the process is applicable to the low-boiling frac tions which are not m u c h improved by catalytic reforming, and the reasons for interest become evident. Without isomerization, the fractions boiling below 200° F. are the lowestoctane portion of the total gasoline. O t h e r methods proposed for im proving the octane of light fractions were catalytic dehydrogenation of isopentane to isopentene, a n d dehydrogenative reforming of Ce-Cs streams over chromia-alumina cat alyst to give a mixture of aromatics and olefins. Refiners now have yields of re sidual fuel oil under better control and obtain this flexibility by using vacuum distillation of residua a n d coking. Because fuel oil is the least valuable liquid product from crude oil, there has been a n in centive to convert it to lighter hydrocarbons.
J u l y 1, 1959 (Projected)
Increasing costs of finding oil have furnished an incentive for changing methods of crude oil production. Secondary recovery from depleted fields has become more economical, and deeper wells are being drilled in areas already worked over. R e newed interest in shale oil m a y be another manifestation of this trend. A major oil c o m p a n y has p u t a prototype shale-oil retort into oper ation, a n d it has been proposed that the U. S. N a v y reactivate the Bureau of Mines demonstration oil-shale plant at Rifle, Colo. Most petroleum technologists feel that oil from shale is still m a n y years in the future because of the high cost of mining shale and the formidable refining problems known to exist. Still, the huge reserves of oil shale in the Colorado Rockies are the best insurance against run ning out of oil. Counting only deposits which assay 15 or more gallons per ton of rock, over a trillion barrels of oil are contained. Possi bly 60 billion barrels—twice the proven domestic crude petroleum reserves—are accessible by present mining methods. T h e Athabaska oil sands of C a n a d a , another potential source
of oil, are believed to contain about 300 billion barrels, but only a small fraction of this is readily accessible by conventional strip-mining techniques. Bitumen separated from the sand is similar to some of the heavy California c r u d e oils, a n d c a n b e refined by known methods. O n e C a n a d i a n oil c o m p a n y has announced plans for a $50,000,000 project in the oil sands fields, a n d another American firm is reportedly active. T h e r e are also known deposits of oil sands in the region near Vernal, U t a h , west of the Rifle, Colo., oil shale regions. N a t u r a l asphalt as a source for petroleum hydrocarbons became a commercial reality in 1957 when the 700-ton-per-day plant of American Gilsonite Co. went onstream in August at G r a n d Junction, Colo. T h e company's own holdings in gilsonite deposits are estimated equal to 100,000,000 barrels of oil. Petrochemicals T h e oil industry continues to have the utmost faith in the long-term future of petrochemicals. Published figures [Petroleum Processing (1957)] state that 1957 domestic production of aliphatic, aromatic, a n d inorganic petrochemicals will reach 38.3 billion pounds—a 6 % increase over last year, and about 2 5 % of the total chemicals o u t p u t of this country. I n 10 years, petrochemicals' share of total domestic chemical o u t p u t is expected to reach 5 0 % . Aliphatics—normal and branched chain hydrocarbons a n d their derivatives—represent 23.5 billion pounds of the 1957 total or about 6 1 % . Aromatics a n d their derivatives represent some 4 billion pounds or about 1 1 % . Inorganics (ammonia a n d sulfur) take u p the balance of 10.7 billion pounds, or 2 8 % , a n d have lately shown the fastest rate of growth. I n terms of n u m b e r of companies a n d plants, the petrochemical industry in the U n i t e d States a n d C a n a d a has expanded 3 0 0 % in the past 6 years. Estimated total capital investment is between $4 and $5 billion, with another $1 billion or more pegged for spending in the next year or two on new construction or expansion projects. T o d a y , there are 206 companies a n d 409 plants in operation, u n d e r construction, or planned in the U n i t e d States a n d C a n a d a . T h e r e
are 74 entirely new plants u n d e r construction or planned, a n d 55 expansion projects at existing facilities. Of the 206 companies, 66 are outright petroleum firms or their subsidiaries, 76 are new petrochemical enterprises, 56 are chemical firms, a n d 8 are joint ventures of oil a n d chemical companies.
Outlook for Some Major Products Synthetic a m m o n i a still has a very bright future in spite of a current temporary slump because of oversupply. T h e prime source of nitrogen chemicals for both agricultural and industrial use, it accounts for about 8 3 % of the domestic nitrogen supply. T h e r e are an estim a t e d 52 plants with a nitrogen capacity of some 3,900,000 tons per year, in this country. By comparison, other nitrogen sources such as coke-oven gases, natural organics, a n d imports r u n a b o u t 500,000 tons per year. I n aromatics, today's petroleum industry accounts for about 3 5 % of the benzene, 8 0 % of the toluene, and 9 0 % of the xylene produced in the United States. Principal chemical outlets for aromatics are about like this: for benzene, 4 1 % goes into styrene manufacture, 22% into phenol, 9 to 1 0 % into adipic acid for nylon, a n d 7 to 8 % into detergent intermediates. Toluene goes into explosives, solvents, and, in rapidly growing quantities, into the polyurethanes. Xylenes are largely tied to their oxidation products, dibasic acids a n d anhydrides, and from these to some synthetic textiles. T h e cresylics from petroleum now are providing a larger share of the total supply. T e n years ago, 1 7 % of available domestic cresylics came from petroleum. I n 1957, the available supply almost trebled, and 3 1 % came from oil. Butadiene capacity rose 4 2 % , to a level of over 1,000,000 tons per year. Growth is associated largely with expanding requirements for synthetic rubber, although fungicides, fibers, a n d drying oils now c o m m a n d a share of the market. A temporary oversupply of butadiene in recent months has intensified the search for new uses. Ethylene is still the leading petrochemical, mainly because of polyethylene, ethylene oxide (for ethylene glycol manufacture), and ethyl
alcohol. Together, these three uses account for 6 9 % of the 4 billion pounds of ethylene consumed a n n u ally. Although acetylene has been talked about as a better building block t h a n ethylene for m a n y new products, oil companies have not yet laid their money on the line. N o n e of the domestic acetylene producing plants is operated by a petroleum company. Propylene is regarded by some authorities as having an even larger market potential in the polymer field t h a n ethylene. According to its proponents, polypropylene has for some uses more attractive properties t h a n polyethylene. Little polypropylene activity has been reported, although a n u m b e r of companies are known to be carrying out extensive research programs. In Europe the polymer is in commercial production.
Atomic Energy T h e r e is little prospect of competition between petroleum and the atom as sources of energy for some years to come, especially as far as gasoline and home heating fuel are concerned. A market vulnerable to competition from atomic energy might be heavy fuel oil used to power electric generation stations. This represented about 2 . 3 % of total petroleum d e m a n d in the United States for 1956. Another vulnerable market is fuel for ship propulsion which comprises about 5 . 7 % of total domestic d e m a n d (including both civilian a n d military). During 1957, however, estimated costs of generating electric power by atomic energy have gone u p m a r k edly. Investment in this country is now estimated to be twice that for a coal-fired plant. Use of atomic energy to drive large numbers of m e r c h a n t vessels does not seem imminent. However, it is interesting that oil tankers are regarded as better suited to " a t o m i z a t i o n " t h a n other types of ships. I n the use of the atom as a tool by the petroleum industry, no significant technological break-throughs; reached public notice in 1957, a l though a large p a r t of the oil a n d petrochemical industry is actively engaged in research. VOL. 50, NO. 1
·
JANUARY 1958
47 A
