international
Petroleum coke finds growing use in Europe But economics of refining methods, composition of crude oil work against large-scale European production of the coke Western Europe's demand for petroleum coke will likely rise to 3.8 million metric tons by 1975, 50% more than was used there in 1970. And unless local capacity is sizably increased (which is unlikely anytime soon) most of it will continue to come from the U.S. A number of technical and economic reasons lie at back of the growing European requirement for the coke and the lack of local supply, notes Albert Hahn of the Bureau d'Etudes Industrielles de l'Institut Français du Pétrole (BEICIP), near Paris. He has drawn up a detailed study of the petroleum coke situation in Europe that becomes available this month. On the one hand, shifting economic patterns are making the coke more attractive as an energy source. And on the other, process industries are turning to it as an alternate source of carbon for a widening variety of nonenergy uses. However, the economics of European oil refining practices, and the average composition of Europe's crude oil supply itself, don't favor wide-scale production of the coke there. Petroleum coke is the hard, cindery material that results from slowly heating the heavy, viscous bottoms from oil refining operations. The highly olefinic volatiles emerging from the cokers are normally blended into petroleum fractions after hydrogénation. The solid coke is removed using high-pressure water jets when the cokers have cooled. There are two stages in petroleum coke production. One results in "green" coke, which contains a certain amount of entrained volatile material. Additional heating of green coke produces calcined coke. Currently, annual consumption of green coke in Europe is about double that of calcined coke—1.6 million metric tons in 1970 out of a total of 2.5 million metric tons. By 1975, the use pattern will shift slightly in favor of calcined coke, according to the BEICIP survey. By that time, Mr. Hahn predicts, total demand of 3.8 million metric tons will likely include 2.2 million metric tons (58%) of the green variety
and 1.6 million metric tons of the calcined. The reason for the shift is the continuing improvement in the calcined product through research by producers and users. The major use of green coke is as an energy source. At 13,700 B.t.u. per pound, it is ahead of coal coke, which averages 11,800 B.t.u. Another factor in its favor is the recent doubling in price of coal coke in Europe, which moved up from about $27 per metric ton in 1969 to $54 last year. For these reasons, European steel producers are using green petroleum coke in increasing amounts in their blast furnaces, although because of its friability, it is limited to about a 10% blend with mineral coal to avoid the danger of clogging the flues. Green coke is also being used to heat power plant boilers and cement kilns. Calcined coke, on the other hand, is used primarily in operations involving reduction technology. Although the technology itself isn't particularly new, coke from petroleum is now competing more effectively with coke from other sources such as coal and pitch. Reduction of alumina to aluminum is by far the biggest single use for calcined petroleum coke in Europe. For instance, in 1970, some 700,000 metric tons of the coke (75% of the total calcined coke used) went toward aluminum production. However, Mr. Hahn predicts that this share will slip in the years ahead, perhaps to 60%, or about 960,000 metric tons, of 1975's total calcined coke demand. A number of other uses for calcined coke likely will emerge as properties of the product are improved. For example, production of graphite electrodes for steel furnaces likely will take more petroleum coke. Indeed, in 1970, 165,000 metric tons of it (more than 18% of the total calcined) were converted to such electrodes. There is a steadily growing demand, too, for calcined coke as a source of graphite for electric motor components, clutch plates, and corrosion-resistant processing equipment. Mr. Hahn also foresees a number of chemical uses for calcined petroleum coke. One could be in producing titanium dioxide from rutile by the chlorine route. Others might be in the manufacture of elemental phosphorus and calcium carbide. Europe continues to look to the U.S. as the principal source of its petroleum coke needs. One reason is the nature of the oil refining operation itself, which is geared to the generally greater demand
in Europe for light and heavy grades of fuel oil. This, in turn, reduces the availability of fractions that would otherwise go to the cokers. In contrast, U.S. refining conditions, generally more severe, are aimed at squeezing the last drop of gasoline from a barrel of crude. There are currently four main producers of petroleum coke in western Europe. Marathon Oil is producing some 140,000 metric tons annually at Burghausen, West Germany, as is Deurag Nerag—a 50-50 venture between Shell and Standard Oil Co. (N.J.) —at Hanover, West Germany. Continental Oil has capacity for 200,000 metric tons per year at Immingham, U.K. Last year, Gelsenberg brought on stream a 150,000 metric-ton-per-year coker near Dusseldorf, West Germany. Norway's Norsk Hydro is the only major company at the moment with definite plans for building a petroleum coker with a projected capacity of up to 160,000 metric tons per year. Meanwhile, Shell is pondering the possibility of building a coker in conjunction with its 450,000-metric-ton (ethylene) cracker at Moerdijk, the Netherlands, which is due for startup next year. The material remaining after the cracking operation could be suitable for coking.
Hahn: number of chemical uses possible July 17, 1972 C&EN
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CIRCLE 7 ON READER SERVICE CARD C&EN July 17, 1972
Problems hit Japan fertilizer industry Japan has become a major factor in the world fertilizer picture. One of the largest producers of nitrogen fertilizers, it ranks first in worldwide exports of the product. Large-scale ammonia plants in Japan presently have a total capacity of more than 4.6 million tons as NH3. Most of their output is exported to the People's Republic of China and Southeast Asian countries. However, the Japanese fertilizer industry currently is in "serious structural depression" faced with such problems as worldwide overcapacity in nitrogen and declining domestic demand, Denichiro Goto, counselor for chemical fertilizer to Japan's Ministry of International Trade and Industry, told the Fertilizer Institute's annual marketing conference, held in White Sulphur Springs, W.Va., last month. And clouding the future is the growing self-sufficiency in fertilizers of many Asian countries, including China. Prior to World War II, the products of the Japanese fertilizer industry were limited to ammonium sulfate and superphosphate, and Japan's total fertilizer capacity was only sufficient to meet domestic demand. Today Japan ranks third in nitrogen fertilizer output (the U.S. is first, followed by the U.S.S.R. As the world's largest exporter of nitrogen fertilizer, Japan ships abroad more than 60% of its nitrogen fertilizer production. In 1970-71, for instance, it consumed 866,000 tons (as N) or 38% of output domestically, exported 1.41 million tons (as N) or 62%. Japan's ratio of domestic consumption to exports of all fertilizers is about 59 to 41. Japan's fertilizer industry, besides being plagued with the excess world nitrogen supply, has two big problems of its own, Mr. Goto told the meeting. One problem is that demand in Japan for fertilizer has begun to decline, primarily because of restrictions on the production of rice. The second problem is that revaluation of the Japanese yen last December has hit exports hard. The current operating level for fertilizer plants is less than 80%. To try to improve the demand picture, several steps are being taken. These include emphasizing greater use of fertilizer on products other than rice (such as vegetables and fruits), promoting forest fertilization, and setting up an orderly export system. In sharp contrast to ammonia, the phosphate industry in Japan is largely behind the times. Average output of a phosphoric acid plant, for instance, is only 100 tons per day, Mr. Goto says. But with assistance from the government, large-scale plants are being built. Two plants capable of producing 400 tons of ammonium phosphate, 200 tons of phosphoric acid, and 1000 tons of sulfuric acid per day are now in operation; one is under construction.
The big problem, however, is the cost of the main raw materials—phosphoric acid and sulfuric acid. Japan is totally dependent on imports for phosphate rock and must build larger and deeper ports to permit the use of large ships for more economical movement of phosphate rock, Mr. Goto says. As for sulfuric acid, older plants must be modernized. But "even after these requirements are satisfied, it is still difficult to know whether the phosphate industry of Japan can compete with the U.S." in international markets, with its abundant supply of phosphate rock and low-cost sulfuric acid, says Mr. Goto. Moreover, an increase in the price of Florida phosphate rock would "definitely strike a serious blow" to Japan's phosphate industry, because more than half of Japan's supply of the rock comes from the Florida fields. In 1970-71, Japan imported 3.1 million tons of phosphate rock—1.8 million tons from the U.S. Japan is also dependent on imports for potash. Major exporters of potash to Japan, in order of decreasing amounts, are Canada, U.S., Soviet Union, Israel, France, and North Africa. The import price of potash, which had been gradually falling, is now rising steadily because of Canada's controlled production program. In 1970-71, Japan imported 701,000 tons of potash as K 2 0 . Of this total, 289,000 tons (about 41%) came from Canada. Fertilizer supply and demand in the Far East will generally be in balance by 1974 or 1975—although the balance may last only a short time, Mr. Goto says. There is already "a sign of improvement" in the demand-supply relationship of urea. The major importer of fertilizer in the Far East is the People's Republic of China, followed by India, Indonesia, the Philippines, Vietnam, Pakistan, Bangladesh, and Sri Lanka (formerly Ceylon). China has been Japan's biggest fertilizer customer. "Until recently, the fertilizer demand of China was thought to be indefinitely large like a Rubber stomach,' " Mr. Goto says. But "the result of last year's trade negotiation with China, including the amount of [the] contract and the price, revealed that China is no more a rubber stomach." Still, China has been importing an increasing percentage of its nitrogen fertilizer needs from Japan—from 62% in 1969 to 72% last year. At the same time, China has been drastically cutting its imports of nitrogen fertilizer from Nitrex, ANIC of Italy, and the U.K.'s Imperial Chemical Industries. Meanwhile, Middle East and East European countries have been trying to expand their share of nitrogen exports to China. Meanwhile, China is actively building medium- or small-scale fertilizer plants in an effort to increase its self-sufficiency. Premier Chou En-lai has stated that China produced 14 million tons of fertilizer in 1970 and expects to produce 30 to 35 million tons annually by
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CIRCLE 74 ON READER SERVICE CARD July 17, 1972 C&EN
17
Some uncommon analyses from uncommon instruments· Characterize materials for f l a m m a b i l i t y a n d smoke production w i t h a n e w technique. Couple a Du Pont Thermogravimetric Analyzer (TGA) with a Du Pont 410 Photometer and you've got a reliable way to characterize materials as to their flam mability and smoke pro l PHOTOMETER duction properties. A n d you can do it with sample sizes of only 1 mg. to 1 gm. 0 lOO 2 0 0 3 0 0 4 0 0 5 0 0 6OO 7 0 0 Definitions of "flameTEMPERATURE °C retardant" materials are TGA /", SAMPLE 2 changing. Government Η . V / Η , agencies concerned with Η " PHOTOMETER ·*\ U l \ \' ,' q public safety and welfare \ i t'*'' v \j now view extent and rate 1 ! '' 1 1 : > of smoke p r o d u c t i o n as 1 h ~ ^ J 1 —ι i m p o r t a n t in e v a l u a t i n g ι — 1 — L_ 2: l O O 2 0 0 3 0 0 4 0 0 5 0 0 6OO TEMPERATURE.°C flame-retardant materials. The Du Pont TGA system measures the loss of weight as the sample is heated. In this procedure, the vapors evolved at various temperatures are directed to a photo meter which measures optical density. Above are analyses of two flame-retardant urethane foams. Sample 2 is a better flame-retardant because residual weight is greater at any given temperature; however, it produces more smoke at lower temperatures, which could make it unsatisfactory for some uses. For more information on this application or instru ment, circle 19 on Reader Service Card. Quickly find 6 0 0 leaks that w o u l d n ' t fill a thimble in a hundred years. Do it in an hour, every hour on a semiconductor production line. That's what Du Pont's 24-140 Leak Detector is for, a high-speed check of the hermetic leak tightness of small components. If there are any leaks, the detector finds them . . . and more important, if there are no leaks, it proves that too. Parts with helium sealed inside are tested in the in strument's vacuum cup. Any helium that leaks out is de tected and the part rejected. For larger pressure and vacuum systems, Du Pont's 24-1 20B finds leaks just as small. It tests for leaks of Apollo capsules; also protects the " l i f e " of TV picture tubes, fire extinguishers and refrigerators. For more information on this application or instru ment, circle 2 0 on Reader Service Card. Du Pont markets a wide variety of analytical and process instruments. Each one has behind it Du Pont's many years of experience. Customers see this experience reflected in our instruments' uncommon capabilities and in the breadth of available application data. Du Pont Co., Wilmington, DE 19898.
1975, Mr. Goto points out. As a result China's imports of fertilizers will gradually decrease over the next few years and "eventually become practi cally zero by the end of 1975 or 1980 at the latest," Mr. Goto warns. From this viewpoint, the fertilizer industry in any major nation should correct its way of approaching the Asian market, he says.
No shakeup foreseen from Japan's Tanaka
I I I
MPDHP Instruments 18
C&EN July 17, 1972
At 54, Kakuei Tanaka is Japan's young est postwar prime minister. He breaks tradition in that he rose to power through the Diet, to which he was first elected in 1947, rather than through the usual channel of graduation from an elite university and years of grooming in the ministerial bureaucracies. In a Japanese version of the log-cabin story, Mr. Tanaka became wealthy through a construction firm he founded soon after World War II, following an unpromising start on a farm in remote Niigata prefecture and little formal schooling. His administration ex perience began with appointment as minister of posts and telecommunica tions in 1957. He was twice minister of finance and has also served as secretarygeneral of the ruling Liberal-Democratic Party (LDP). Since last year he has headed the Ministry of International Trade and Industry. Despite Mr. Tanaka's reputation for decisive action, no sudden change in economic or trade policy is likely as a result of the new look in Tokyo. The LDP holds a comfortable majority in the Diet, but Japanese cabinets are in fact coalitions put together by the LDP's not-always-congenial factions. Mr. Tanaka's election to the party presi dency this month (which in turn handed him the prime ministry) required the aid of several factions, all of which have been accommodated by cabinet posi tions. In practice, a "unified view" among ministries concerned must be realized before any significant change can occur in Japanese policy. This tends to damp any new waves an incoming prime minister might make.
