ffllMffll IÎIIUMIIYI T
he craft of making steel is deceptively simple. Iron oxide is reduced to iron in a blast furnace; a carbon burnoff converts iron to steel. Major changes in these operations evolved over very long periods. The blast furnace, for example, hasn't altered in essentials since Columbus discovered the New World. Sometime in the late 1950's, however, the industry began to look at iron- and steelmaking as unit operations in which a better knowledge of the kinetics of competing reactions was needed. It was a change in thinking that invited new approaches to old problems. Since then, adoption of advanced technology has become the way of the steel industry. Chemists and chemical engineers have provided the necessary knowledge for this metamorphosis in steelmaking. The two major technological advances of the past 15 years are the basic oxygen furnace ( B O F ) , which produces more steel per reactor per year than the open hearth furnace, and continuous casting, which produces savings of about $9.00 per ton of steel over conventional ingot techniques. Both were developed in Europe. To take full advantage of these processes, steel companies in the U.S. began hiring more chemists and chemical engineers. At the same time, instrumentation for analyzing and computer systems for controlling processes were constantly being improved, and the new breed of steelman was adopting these advanced control concepts to his mills. The upshot of these and other important developments is that the steel industry now stands on the threshold of developing a continuous steelmaking process.
The Association of Iron and Steel Engineers is holding its annual convention in Cleveland this week, Sept. 14 through 17 at the Cleveland convention center. The iron and steel exposition is being held concurrently in the convention center exhibit hall. 48 C&EN SEPT. 21, 1970
steel presented by plastics with serious concern and has integrated forward into plastics from its raw material bases further than any other steel company. In addition to distilling coal tars, U.S. Steel purchased the industrial and protective coatings divisions of Pittsburgh Chemical Co. in 1964. In 1965, U.S. Steel acquired the remaining 50% of OXO Chemicals, Haverhill, Ohio. In 1968, it purchased the domestic business of Armour Agricultural Chemical Co. and the plastics operations of GATX. The firm has also expanded into phthalic and maleic anhydrides, phenol, acetone, and polystyrene. A U.S. Steel subsidiary produces vinylcoated steel for the construction industry. U.S. Steel's total chemical sales reached about $280 million last year.
Continuous steelmaking would link the batch operations found in today's mills into a steady flow system that would start with iron ore and produce finished billets at its end. A continuous steelmaking process is still years away, but as the industry continues to upgrade its technology toward continuous operations in both steelmaking and coking, patterns of chemical production and consumption will change markedly. In this report, C&EN takes a look at where the steel industry presently stands, the directions in which new technologies are likely to carry it, and what these developments bode for the chemical industry. Chemical
interests
The value of chemicals produced by the steel industry, including U.S. Steel Corp.'s total coal chemicals and other interests, is about $425 million. The steel industry, in turn, buys about $600 million worth of materials from the chemical industry. Aside from their output of coal chemicals and limestone, steel companies aren't heavily committed to chemical operations. U.S. Steel has viewed the challenge to
Next 10 years The steel industry is confronted by three enormous problems as the decade of the 1970's begins. In the first place, it must attract the necessary capital to permit far-ranging change in its productive plant. The steel industry must also earmark large sums of money for pollution control as public
This year BOF production will exceed open hearth U.S. steel production, millions of tons 150
~ji- ~J
120
^^^^
Total raw steel
90
^ ^ ^ ^ ^ ^ ^ ^ ^
60
Basic oxygen furnace \ ***** Electric furnace \ *****
30 0
Open hearth furnace
pe*«i*fi«»r* , " 1960
1965
a C&EN estimates. Source: American Iron & Steel Institute
Z^^*^"N |
1970 a
Although the goal is in sight a continuous steelmaking process is still a few years away
A €&EH Special
H. Clifford Neely, News Bureau Head, New York City
demand for reduced discharges from heavy industry to the atmosphere and streams continues to mount. Secondly, any energy crisis in this country would strike hard at the steel industry, and there are warning signs that such an energy crunch is in the making. Finally, steel management must work closely and more efficiently with one of the most powerful unions in the country. Since steel strikes halt all steel production, all of our industrial output can be crippled by a steel strike. The U.S. steel industry, the pride of the world 20 years ago, is falling rapidly behind in its ability to compete in world markets. Foreign producers not only enjoy lower wage rates but the productivities of their plants, owing to the adoption of the latest technologies and large units, are also higher in many instances. Last year, U.S. steel production was 141 million tons or 22.5% of the world total of 625 million tons. To maintain this share of the world market during the present decade, the U.S. industry will have to double its present capital spending level of $2.1 billion a year between now and 1980. Finding this money isn't going to be easy since the steel industry's financial performance has been lackluster in recent years. In 1969, according to the American Iron and Steel Institute (AISI), the steel industry earned $900 million on total revenues of $19.6 billion for a 4.69c profit margin. In terms of stockholders' equity, the return was 6.5%—not exactly the kind of performance guaranteed to make financing easy. Energy considerations may override the issue of the availability of capital in determining the technologies to be adopted by big steel. There is already a shortage of high-grade metallurgical coal for coking. Evidence of an energy crunch continues to mount. Natural gas supplies are inadequate, some electrical power plants in the Northeast are operating with a three-day inventory of coal, and brownouts have occurred in the New York City area. The consumption of large amounts of energy is inherent in the manufacture of steel. The industry's average
Molten pig iron constitutes about half the charge to this open hearth furnace SEPT. 21, 1970 C&EN 49
en iron from a blast furnace is chargedd into this 250-ton-capacity BOF
A 270-ton-capacity ladle pours steel into ingot molds at Bethlehem's BOF shop
energy consumption is 13 to 15 million kcal per ton of steel. Although some hope has been expressed of reducing this by as much as 15% during this decade, many experts are skeptical of attaining energy reductions of this magnitude. During 1969, the consumption of electric power by the iron and steel industry totaled 48.4 billion kWhr. A new record for electric power consumption was set in each year of the 1960's, according to AISI. Labor contracts in the steel industry expire next July and it could be a bad 50 C&EN SEPT. 21, 1970
year on the labor front. A domestic steel industry that has suffered a $5 billion gap in imports over exports in the past five years may find that labor peace is as important to its future as capital and technology. Industrial might Over the years the blast furnace has been the workhorse for the production of pig iron. (Pig iron contains 3 to 4% carbon. Steel is iron with 0.04 to 2.5% carbon; it may or may not con-
tain other alloying elements.) The blast furnace is a vertical reactor made up of three sections—the hearth, where molten metal and slag collects; the bosh, which is the combustion zone; and the stack, where the charge is preheated. Once loaded, the blast furnace contains alternate layers of limestone, coke, and ore. A blast of preheated air is admitted through tuyères or inlet ports located at the top of the hearth. Coke burns in the bosh or hottest section of the furnace. As the coke is consumed, the charge in the furnace falls and raw materials are admitted through a double-bell air lock in the top of the stack. Hot gases from the bosh pass upward in the furnace heating the burden as it falls. The atmosphere in the furnace is reducing. Molten iron collects in the hearth along with floating slag containing limestone flux, ash from the coke, and impurities refined from the ore. Iron and slag are tapped periodically. The gases leaving the blast furnace contain appreciable amounts of carbon monoxide, which can be burned to supply energy for the blowers or to preheat the air for the blast. A blast furnace today can cost more than $25 million so the steel industry has shown renewed interest in ways of bypassing the blast furnace in steelmaking. One way to do this is to use iron-rich feeds produced by direct reduction that can be charged directly to a steelmaking furnace. In direct reduction, beneficiated iron ore is reacted with a reducing gas, usually hydrogen or hydrogen and carbon monoxide, to produce an 85 to 95% pure iron charge for steel furnaces. Direct reduction, besides bypassing the blast furnace, requires no coke. There are thousands of grades of steel, but steels are classified into three categories for simplicity's sake—carbon steels, alloy steels, and stainless steels. The carbon steels are made primarily of iron and carbon; stainless steels are low-carbon with more than 12% chromium; alloy steels contain large amounts of alloying elements to produce specialty steels for uses such as bearings and tool steels. Carbon steels accounted for 88.4% of the 141 million tons of steel poured last year, alloy steels accounted for 14.8 million tons or 10.5% of the total, and stainless and heat-resistant steels accounted for 1.1% of the nation's total output of raw steel. There are three basic types of steelmaking furnaces. A fourth type, the Bessemer converter, is no longer used for large-tonnage steel production. During the 1960's production of steel in open hearth furnaces declined as production in both BOF and electric furnaces climbed steeply upward. The open hearth furnace (Siemans-
Martin furnace) is a rectangular covered furnace with burners and regenerative heat exchangers placed at each end. Scrap, pig iron, limestone, and some iron ore are charged to the furnace; a typical charge runs about 200 tons, and it can take several hours to load it. The charge is then heated for about eight hours. The atmosphere in the open hearth is oxidative because of an excess of air. BOFs In BOF's, a typical charge might be 45 tons of scrap, 110 tons of molten pig iron, and 10 tons of limestone. Oxygen is then admitted to the furnace through a lance inserted through the mouth. The supersonic stream of oxygen creates a carbon boil in the molten iron producing steel in 20 minutes in some cases. Supplemental fuels are not added to the BOF. The reaction of oxygen and carbon in the hot metal is exothermic, supplying enough heat to melt scrap equal to about 309c of the charge. This is a lower scrap loading than the open hearth, which usually operates on up to 50r/r scrap. In 1969, 60.2 million tons of steel were poured from BOF's in the U.S. This compares with 60.9 million tons from open hearths and 20.1 million tons from electric furnaces. In the later months of 1969, BOF output overtook open hearth for the first time. Despite the scrap limitation, it didn't take steel management long to realize that the economics of the BOF were all to the good. Besides, excess scrap could be melted and refined in electric furnaces. The acceptance of BOF steel also meant a large market for limestone. BOF's account for about 80% of limestone consumption in the steel industry, and lime consumption jumped from 4.6 million net tons in 1968 to 5.7 million tons in 1969, according to AISI.
Continuous casting After steel has been made, traditional practice is to pour the molten metal into ingot molds, transfer the molds to a stripping area where the ingots are removed from the molds, and then heat the ingots in soaking pits prior to rolling them into slabs, billets, or blooms for subsequent finishing. The second major steelmaking development of the 1960's was the growth of continuous casting in the U.S. The first continuous casting machine went into operation in the U.S. in 1962. By the end of this year, there will be about 19 million tons of continuous casting capacity in this country, or about 12% of the nation's total steelmaking capacity. The aim of continuous casting is to pull a taffylike ribbon of steel from an incandescent pool of molten metal. In the process, a ladle of molten steel is poured into a refactory-lined vessel called a tundish. The tundish maintains a constant pressure head of hot metal over the nozzles. From the nozzles at the base of the tundish, the steel passes through a water-cooled copper mold into a water spray area. Sufficient heat is removed in the mold to cause the skin of the metal to solidify, and the sprays cause a progressive freezing of steel inward. From the spray chamber, the steel passes, in some designs, through pinch rolls that divert it from a vertical fall to a horizontal run. On the horizontal run, the ribbon is cut into billets or slabs by mechanical cutters or by torch. Initially, small sections in single strands were cast. Today, an installation such as that built by Koppers for ENSIDEAS at Aviles, Spain, has three six-strand machines with an annual capacity of 1.1 million tons. Such ma-
chines can cast billets (cross section 8"X8" or smaller), blooms ( 8 " x 8 " or larger), or slabs (rectangular cross sections) as finished intermediates. Ladle size has grown from 10 to 20 tons in pilot plants in the early 1960's to up to 300 tons in today's shops. Coal chemicals The organic chemical industry in this country and Europe sprang from the fountainhead of aromatic raw materials given off in the coking of coal. Today, coal chemicals are far less important to the chemical industry than are petroleum- and natural gas-derived feedstocks. Coal tars and light oils are condensed from coke oven gases as byproducts of the manufacture of metallurgical coke for blast furnaces. In the early 1950's it became clear that the steel industry was going to be successful in reducing the amount of coke to produce a ton of hot metal in the blast furnace. The pounds of coke per ton of hot metal, or coke rate as it is called, fell from 1900 in 1949 to about 1260 last year. The decreasing coke rate led many observers to predict that the production of coal chemicals would drop rapidly. Accounts of the demise of coal chemicals have been highly exaggerated, however. In fact, 1965 and 1966 were record years for the production of coal tars in this country. Although the outlook for coal chemicals in the mid-1950's was bleak indeed the advent of BOF's gave these chemicals a new lease on life. Since BOF's are limited to a scrap charge of about 30% the difference is made up with hot metal from a blast furnace; the hot metal from a blast furnace requires coke in its manufacture.
U.S. steel imports are more than double exports Electric furnaces In an electric steel furnace, electricity is used to supply heat either by induction or an electric arc. Output from all electric furnaces last year accounted for 14% of the nation's total steel output. Although long identified with stainless and alloy steelmaking, electric furnaces are increasingly used to make carbon steels. Last year, 66 # of the steel made in electrics was carbon steel. Production of carbon steels was made economically possible by the development of larger reactors. Current furnaces operate at more than 80,000 kVA-more than double the usual kVA of as little as Rve years ago.
Steel trade, millions of dollars 2500
Imports
Exports
1965
1966
1967
1968
1969
Source: American Iron & Steel Institute
SEPT. 21, 1970 C&EN
51
After a 16-hour bake coke is pushed from the oven by a ram
In the 1960 decade the amount of steel produced in BOF's increased from 3.3 million tons to 60.2 million tons while the total output of steel climbed from 99 to 141 million tons. This growth in the use of BOF's but tressed the output of coal chemicals at a time when the industry was success fully reducing the amount of coke re quired to produce a ton of hot metal. The upshot is that the growth in hot metal production from blast furnaces from 66.5 million tons in 1960 to 95 million tons last year more than off set the decline in the coke rate, and about 700 million gallons of coal tar was produced last year. In the horizontal by-product coke oven, the mainstay of the steel in dustry, light oils and coal tars from coke ovens were valued at about $125 million in 1969. Coal tar is used as a roofing com pound and as a road-building material. It is also burned as fuel by steel com panies where its low sulfur and highly luminous flame that gives excellent ra diation to the bath make it an ideal fuel for open hearth furnaces. Of 751 million gallons of tar produced in 1968, 105 million gallons were burned as fuel and 644 million gallons were distilled. Miscellaneous uses ac 52 C&EN SEPT. 21, 1970
counted for 2 million gallons. The use of tar and pitch as fuel for blast fur naces is also increasing, according to AISI. The consumption of tar and pitch burned in blast furnaces nearly doubled during 1969 as compared to 1968, going from less than 23 million gallons to more than 43 million gallons because of increased injection at the base to increase temperatures and speed reactions. In distilling coal tars, about half the product produced is pitch. The major market for coal tar pitch is in the pro duction of electrodes for the aluminum industry. The next largest constituent of the tars is creosote. Creosote is still widely used to preserve wooden rail road ties and telephone poles. Naphthalene is the next most im portant product of distillation. Naph thalene's major use is as a starting ma terial for the production of phthalic anhydride. Other uses for naphtha lene are in the production of β-naphthol, an intermediate in the produc tion of rubber chemicals and dyes. The solvent naphtha cut from coal tars also provides the raw material for coumarone-indene resins. These resins now probably account for no more than 10% of the total hydrocarbon resin production of 349 million pounds in 1968. The bulk of hydrocarbon resin production is accounted for by raw materials obtained from the bot toms of ethylene crackers. Rounding out the chemicals derived from coal tars are the tar acids and tar bases, which occur as about 1% of coal tar. o-Cresol from cresylic acid is used as a starting material for methylchlorophenoxyacetic acid (MCPA) herbicide in Europe and in enamel for insulating electrical wiring and can linings in this country. In fact, the tar acids business is developing so rapidly that coal tar production can't meet demand. Two firms, Koppers and Pitt-Consol, have commercialized synthetic routes to o-cresol to supply this growing market. Tar bases are obtained in even smaller quantities than the tar acids. Major uses for these materials are as cyclic interme diates in the production of dyes and pharmaceuticals. There is little doubt that the coke rate will continue to decline in the fu ture. The decline won't be as rapid as in the past, however. A U.S. Steel ex perimental unit has operated at coke rates of 530. Such rates don't appear to be attainable in commercial units since, as one expert puts it, "there seems to be an irreducible minimum of coke needed in the blast furnace to provide a porous matrix for the molten metal." By 1980 the coke rate may stand at 1100 with some new blast fur naces attaining a rate of 900 or a little lower.
Again, the outlook for coal chemi cals in the 1970's isn't all that gloomy. The nation's output of steel will con tinue to grow so that the output of coke during the coming decade will probably increase slightly every year. For 1970, the output of metallurgical coke will likely reach 58 million tons; by 1980 it will rise to 60 million tons. Not a dramatic growth but one that ensures those industries dependent on coal chemicals and tars of generally constant supplies. Last year foundry uses accounted for 3.5 million tons of coke and industrial uses accounted for 2.8 million tons, for a total of 6.3 mil lion tons. Energy
shortage
The greatest threat to future sup plies of coal chemicals would be an energy shortage so severe that steel mills would burn their tars rather than sell them to outside users. This day may be much closer at hand than many in the industry now realize. On 11 different occasions this summer prior to Labor Day voltages in the New York metropolitan area were reduced by 5% to conserve power. Power shortages and voltage reductions trigger overheating in electric motors with possible damage to expensive steel rolling equipment. To conserve electric power for rolling operations steel mill operators might resort to shutting down their electric furnaces and burning more coal tars in open hearth furnaces for fuel. Another dark cloud on coal chemi cals' horizon is the worldwide shortage of coal for metallurgical coking pur poses. Shortages are developing and the price of both coal and coke has risen. Metallurgical coals produce cokes of high strength, low ash, and low sulfur content. There are two other developments that threaten the coal chemicals in dustry. They are: • Direct reduction processes that by pass the blast furnace completely. • Oxygen injection into the blast furnace, which would tend to lower the coke rate. In moving toward direct reduction, the steel industry has already taken a number of major steps to improve the iron content of ore fed to blast fur naces. Nearly 110 million tons of ag glomerated products such as sinter, pellets, briquettes, and nodules went into blast furnaces last year, according to AISI. This was 7.5 million tons more than in 1968. Prereduced pellets were used in the U.S. for the first time last year. These pellets are usually reduced using reformed natural gas until their iron content reaches 9 5 % . Pellets can be charged directly to BOF's or electric furnaces.
Experts say there is little or no danger that direct reduction will supplant blast furnaces in the near future. Despite their age, blast furnaces remain very efficient. An energy shortage is also likely to curb any significant shift away from blast furnaces to direct reduction processes. Direct reduction processes have been based, to date, on natural gas. Construction engineers in the steel industry say that the shortage of natural gas in this country would mean that any large commercial direct reduction units would have to be based on coal. The widespread acceptance of oxygen injection to blast furnaces by the steel industry would open a market for industrial gas makers equal to that created by B O F s . Today, BOF's are the largest single outlet for oxygen. Oxygen injection in blast furnaces permits use of lower-grade fuels and a reduction in coke burden. To date, steel companies have taken the position that oxygen injection in blast furnaces is economically about a standoff with other alternatives such as preheating the blast. New
technologies
At the 10th Latin American Iron & Steel Congress in Caracas, Venezuela, Edwin H. Gott, chairman of U.S. Steel, attempted to predict some of the directions technology would carry the world steel industry in the future. He spoke of a world steel production of 900 million tons by 1980 and a total cumulative capital requirement in this decade that would reach $200 billion to open new coal and ore mines, provide transportation equipment, and install additional production facilities. Mr. Gott says much work remains to be done in the development and perfection of direct reduction processes and subsequent steps that might set the stage for continuous steelmaking but adds, "I am confident that we shall see some form of continuous steelmaking being used during the next 10 years." Other developments Mr. Gott presages: • In coking the preheating of coal, continuous quenching, and a continuous process for the production of metallurgical coke. • Blast furnaces will be improved by better linings, increased top pressures, injection of supplementary fuels, use of higher blowing rates and hot blast temperatures, and enrichment of the blast with oxygen. • Continued growth in the use of BOF's and continuous casting steelmaking. • Increased use of degassing systems, which yield higher-quality steels by using a vacuum to lower the hy-
A coke-oven gas plant—products include tar, naphthalene, and light oil
Production of coal tar continues to decline Tar produced from coal, millions of gallons
900 800 700
1965
1966
1967
1968
1969*
a C&EN estimate. SEPT. 21, 1970 C&EN 53
tect because of its tendency to oxidize at the temperatures and low carbon concentrations present in an electric furnace near the end point of production. In its process, Carbide employs argon and oxygen addition to the reac-
tor to shift the solubility-temperature relationship of carbon and chromium with the result that low-carbon stainless can be produced with a 95% chromium recovery, which is well above the industry average. Airco's product can be called hyperclean steel. The cleanliness, which eliminates differences in longitudinal and transverse properties found in conventional steels, imparts toughness and corrosion resistance. The picture at the lower left shows one of the hearths in Airco's furnace. The process uses a combination of hard vacuum and electron beam heating to achieve vacuum refining, continuous casting, and the elimination of refractory contamination. Straight chrome steels comparable to chrome-nickel stainless steels can be produced, according to the firm. There are four stages to the process: • A standard vacuum induction melting furnace. • An induction-heated holding furnace. • A hard vacuum chamber (0.1 to 1 X 10~3 mmHg) in which metal heated by electron beams flows along a water-cooled copper hearth. • A continuous casting system. In the hard vacuum chamber, molten metal cascades down as many as five water-cooled copper hearths. The hearths provide mixing and a large surface area for volatilization of impurities. Heat to keep the metal on the hearth molten is supplied by electron beams from guns located beneath the hearth away from volatile impurities. Volatile impurities are evaporated from the metal and collected on condensate shields. Nonvolatile impurities are collected behind a slag barrier. From the last hearth, metal flows to a continuous casting station. Airco has started up a 30,000 ton-peryear electron beam hearth process at Berkeley, Calif.
sulfate is presently in oversupply owing to its production as a by-product of caprolactam manufacture. In some locations the glut is so severe that ammonium sulfate is a disposal problem. Energy for coking is supplied by the gases given off by coal. Roughly half the gases (primarily hydrogen with methane the second largest constituent) are required to supply heat to the coke unit. The remaining gas, of about 550 b.t.u. per cu. ft. heating value, is consumed by steel mills. Last year, 916 billion cu. ft. of coke oven off-gas was consumed by the steel industry, according to AISI. At its Keystone Project at Clairton,
Pa., U.S. Steel has attempted to use the coke oven off-gas to produce anhydrous ammonia. The firm uses a German Linde low-temperature separation process to recover hydrogen for ammonia synthesis. The plant has had its share of startup problems but success would mean that other valuable gases such as ethylene and propylene that are now burned could be recovered and upgraded to chemical products. Inert gas quenching of the finished coke product would also mean another large-scale use for nitrogen for blanketing. At the present time coke ovens are opened to the air at the end of the coking cycle, and the glowing hot
Specialty steels spawn two new technologies Union Carbide and Air Reduction Co. have harnessed advanced technologies to produce specialty steels. Union Carbide believes its argon-oxygen reactor (AOR) process offers stainless steel producers substantial savings in their raw material costs by virtually eliminating the amounts of chromium lost to oxidation in an electric furnace. Airco's electron beam process produces super-refined high strength nonnickel steels comparable to conventional stainless steels that do contain nickel. Carbide's process has been licensed by nine companies in the U.S. and five overseas. Joslyn Steel's 17-ton reactor is shown above. Raw material costs in stainless steel can run as high as $400 per ton compared to $40 to $50 a ton for straight carbon steel scrap for electric furnaces. Of the alloying elements added to stainless steels, chromium is the hardest to pro-
drogen and oxygen content of liquid steel. Coke ovens There has been no significant change in the design or operation of coke ovens in years; one reason for this is that coking is a highly efficient process. After roasting for 16 hours the coal carbonizes and tars, light oils, and oven gases are recovered. Coke oven gases contain ammonia, which is neutralized with sulfuric acid. The resulting ammonium sulfate, an excellent fertilizer for tobacco, is sold to the fertilizer industry. This is a $30 million a year business, but ammonium 54 C&EN SEPT. 21, 1970
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coke is pushed from the oven into gondola cars. The practice causes pollution and although inert gas quenching may not be economical despite the fact that heat from the gas can be recovered in a waste heat boiler, pollution considerations alone may cause steel companies to adopt inert gas quenching. Continuous
\
that's one difference
process
The concept of a continuous steel mill intrigues steelmen throughout the world. Such a mill might use direct reduction to prepare a charge suitable for a BOF. Molten metal from the BOF would then move directly to a continuous casting unit. Other variations are also possible. The BOF might be replaced with electric furnaces. Ultimately, direct steelmaking would combine the functions of a blast furnace and a steel furnace into one reactor. At present this appears to be an almost impossible chemical engineering problem since the first step involves a reduction and the steelmaking step an oxidation. The engineering is further complicated by a host of side reactions between impurities and slag. The BOF and continuous casting marry well. A BOF operates on low scrap loadings, and one of the major advantages of continuous casting is the reduction of internal scrap generated in the mill. Internal scrap is produced in ingot and slab trimming and from rolling operations. In conventional steelmaking, up to 30% of the steel poured is lost in ingot trimming and mill scale; continuous casting cuts these losses % to 10% or less. Major advantages for continuous casting are low capital and space requirements compared with the conventional process of turning steel into ingots. In addition, proponents of continuous casting say operating and maintenance costs are lower, process control is simpler, and yields are higher than in conventional ingot making. There are disadvantages to continuous casting, though. The largest market for steel in the U.S. is the automotive market—an 18.3 million ton market for steel last year. Auto body sheet is rimming steel, a low-carbon steel noted for its deep draw properties. Another large market for steel is food and beverage cans. Both auto and can steels owe part of their special properties to the aging process in ingots. The exact properties of these steels are impossible to duplicate in continuous casting. Steel companies have been able, however, to develop steels that can be continuously cast and offer comparable properties to present auto body and can steels.
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s SEPT. 21, 1970 C&EN 55
What we do with -CN will take your breath away. CNCH 2 COOH cyanoacetic acid CNCH2CONH2 cyanoacetamide CH3OOCCH2CN methyl cyanoacetate C2H5OOCCH2CN ethyl cyanoacetate CH 3 (CH 2 )900CCH 2 CN rc-decyl cyanoacetate (-CH 2 CH 2 OOCCH 2 CN) 2 butylène dicyanoacetate (-CH 2 OOCCH 2 CN) 2 ethylene dicyanoacetate T h e list above covers just a few of the cyano derivatives we produce. Their reactivity indicates their use in the synthesis of many new specialty chemical products. As you might imagine, there's no small trick to developing a line of HCN-derived products. As a result, we're pretty much alone in being able to offer you a major line of cyano chemicals. Plus, we're in a unique position to produce other cyano chemicals for you in full commercial quantities. Let us tell you more about our cyano compounds and about Kay-Fries. For information on a n d / o r evaluation samples, write, on your company letterhead, please, to: Kay-Fries Chemicals, Inc., 360 Lexington Avenue, New York, New York 10017.
m A
A
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CHEMICALS. INC.
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56 C&EN SEPT. 21. 1970
V
The steel business has been likened to an apothecary. There are thousands of shapes and kinds of steels. Casting lends itself to the continuous production of large quantities of one or two grades and billet sizes, not the myriad grades required today. Other disadvantages are that the mold can't be changed very easily once the pour has begun. Too, refractories don't last long. The tundish has to be relined and the molds and nozzles replaced after every 200-ton heat in some cases. Scrap and mini-mills The wildfire growth of BOF steelmaking during the 1960's shifted the scrap balance within the steel industry at the same time it bolstered the growth of coal chemicals. The increased use of BOF's meant that less scrap and more hot metal per ton of steel was being used. Excluding electric furnace steel production, the ratio of hot metal to steel made in the U.S. increased from 0.73 to 0.79 in the decade of the 1960's. It was soon apparent that scrap was in oversupply. Consequently, scrap prices tumbled, and electric furnace production became attractive. In response to the stimulus of lowcost scrap, mini-mills or small regional steel mills based on electric furnaces that could turn out anywhere from 50,000 to 500,000 tons of steel a year sprang u p across the country. Many of these firms had been scrap collectors until the advent of the BOF prodded them into expanding into steelmaking. There are about 40 such small mills, and AISI estimates these companies turned out about 2.3 million tons of raw steel last year. The staple of the regional producers' product line is reinforcing rods for concrete. The small mills offer customers speedy service and can compete in price with the majors within a radius of about 300 miles from their plants. By 1980, electric furnace output could reach 40 million tons if electric power is available. Industrial gases This year, in iron ore mining, coal production, and primary iron and steel operations, the steel industry will buy about $600 million worth of chemicals. Even staid markets such as pickling acid have changed in the past decade. In 1962, the pickling of steel to remove rust and mill scale prior to tinplating was a 1.2 million ton-a-year market for sulfuric acid. Today, hydrochloric acid dominates steel pickling with some 700,000 tons of 22 ° Baume acid likely to be used in pickling.
P A R R Stirred Reactors
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In the industrial gases sector, the steel industry used 220 million cu. ft. of oxygen. Oxygen injection to BOF's accounted for 52% of this total. Oxygen injection to open hearth furnaces is also increasing and accounted for 27% of the industry's oxygen use last year. Oxygen is also used in blast furnace injection, conditioning, and scrap cutting. Other promising new uses for industrial gases in steelmaking will be in the use of argon for blanketing in the continuous casting process. At present, argon is used to blanket ingots from oxygen and nitrogen contamination in pouring. Argon may also be used in protecting hot metal from reaction with atmospheric gases in continuous casting and for injection in BOF's to provide mixing during reboils. Inert-gas quenching of coke is an inviting new market for nitrogen. The use of large-scale direct reduction processes means increased hydrogen production. Should this hydrogen demand be met by partial oxidation of natural gas or naphthas, a sizable market for oxygen would be created. Coatings, both metallic and organic, are big business for chemical companies selling to the steel industry. The steel industry used more than 31,000 tons of tin in 1969 alone. Aluminum- and vinyl-coated steel are being used in increasing amounts and nontin lacquer coatings for cans offer a promising market for organic coatings of many types. The steel industry is also one of the nation's largest consumers of chemicals used to prepare surfaces prior to galvanizing and tinplating.
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pick your reaction rate= use
TYZOR* catalysts One of the beauties of TYZOR organic titanates as polymerization and resin cata lysts is that you can practically pick the reaction rate that suits you best. Here's why. At one end of the TYZOR family we have the simpler alkyl titanates. They react quickly and at room temperature, and rapidly undergo alcoholysis with hydroxyl-containing materials. If that's too fast for you, then try our chelates. We've bred a family of titanium chelates, each with its own hydrolysis rate. Some are slower than others. You can pick the right reaction rate by picking the right chelate. Some are so slow, in fact, that you can trigger the reaction whenever you want: just change the pH or add heat. TYZOR catalysts are time-keepers in many processes: esterification, resin polymeriza tion, polyester catalysis, aldol condensa tions, and hydroxy crosslinking. They've been used to make more and better epoxies, alkyds, silicones, olefins, phenol formalde hydes, polycarbonates, urethanes, and polylactones. If you'd like to pick your own reaction times, send us the coupon, and we'll send you our technical bulletin on TYZOR organic titanates. Du Pont Company Room 8773 Wilmington, Delaware 19898 Please send me your technical bulletin on TYZOR organic titanate catalysts. Name
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organic t i t a n a t e s S E P T . 2 1 , 1970 C & E N
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CHEMICAL MARKETING: THE CHALLENGES OF THE SEVENTIES ADVANCES IN CHEMISTRY SERIES No. 83 Twenty-one papers from a symposium sponsored by the ACS Division of Chemical Marketing & Economics, chaired by Robert L. Bateman. Surveys the challenges of the next decade in: • Agricultural chemicals, inorganic and heavy chemicals, organic chemicals, plastics • Market development • The marketing organization in large and medium sized chemical com panies • Selling, domestic and international • Advertising measurement • Technical service and application research • The computer for distribution con trol and forecasting demand and prices 199 pages with index cloth (1968) $9.50 cents in PUAS and foreign. Postpaid in U.S. and Canada; plus 30 Set of L.C. cards free with library orders.
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