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Historical Overview of Refractory Technology in the Steel Industry K NIPPON STEEL TECHNICAL REPORT No. 98 JULY 2008 UDC 666 . 7 Technical Report Historical Overview of Refractory Technology in the Steel Industry Kiyoshi SUGITA* Abstract The historical transitions and progress since the ancient times in refractory tech- nology for iron and steelmaking is briefly reviewed. In addition to describing the core historical facts for each era and their features, some discussions on the history from specified viewpoints such as raw material resources, energy, ecological as- pects, refractory-manufacturing, and R&D methodology are attempted. Modern re- fractory technology is not simply based on materials technology any more. It has grown into an integrated system technology including heat engineering, monitoring techniques, furnace design, lining installation, and furnace operation. The history proves that the most contributory factor to the development of refractory technology is the technlogical innovations of iron and steelmaking processes. limit of the decomposition temperature for clay minerals (ca. 800℃); 1. Introduction that was some time in the early Bronze Age (BC 4000 - 3000). It is One of the oldest technical texts in the history of mining and reasonable to presume that the pits for firing earthenware were dug metallurgy, De Re Metallica (by Agricola, G., 1556), lists ore, fuel into some kind of soil resistant to fire. The desired function of the and refractory materials including heat insulators, as the three sub- soil was to retain the heat (thermal insulation) and not to deform stances essential for metal refining. All through the Iron Age from under the heat (fire resistance, or refractoriness). ancient times up to now, refractory has been closely engaged in iron Upon the advent of the Iron Age (ca. BC 2000 and thereafter), and steelmaking, contributing to human civilization. iron was produced by reducing iron ore using charcoal in a furnace. The study of refractory technology along its historical develop- Higher temperatures were required inside iron-producing furnaces, ment is not only useful for better understanding of its background and the inner lining of such furnaces had to withstand not only the and essence, but also for taking lessons from the past for the further heat but also the mechanical and chemical corrosion inflicted by the advancement of technology. In this sense, the author would like to materials charged into them (wear resistance). Therefore, it would overview herein the history of refractory technology for iron and be appropriate to presume that refractory in its present definition, steel production from several viewpoints. characterized by thermal insulation, refractoriness, wear resistance For further details of individual historical events in refractory and adequacy for furnace inner linings, was born in tandem with technology, more specific data and details of technical literature, the iron producing technology. readers are requested to refer to the publications listed as 1) to 12). The refractories for the ironmaking furnaces in ancient times can be described as follows: 2. Characteristics of Different Historical Periods (1) Mostly devoid of definite shapes, while blocks cut from natural 2.1 Ancient times, middle ages and era of renaissance stones and fireclay bricks were only partially used. Mankind probably first became aware of refractory as a material (2) The main component materials were silica rock (SiO2 system) or “resistant to fire” at the time that the temperature of primitive pit fireclay (Al2O3-SiO2 system) containing numerous impurities. kilns dug into the ground for firing earthenware reached the upper (3) Refractory materials of carbon-metal oxide systems (mixture of * D. Eng., Ex-Fellow of Nippon Steel Corporation, Honorary Member of the Technical Association of Refractories, Japan, Member of the Engineering Academy of Japan - 8 - NIPPON STEEL TECHNICAL REPORT No. 98 JULY 2008 Fig. 1 Typical lining design of charcoal-fired blast furnace (16th-17th century) fine charcoal and clay) were developed and widely used not only in Europe but also in Japan (the tatara furnaces blown by foot- activated bellows) and in China. It is interesting to know that the history of refractories for iron and steel production began with mixtures without definite shape (un- shaped refractories) and carbon-added composite materials, which account for most of the refractories presently used for the steel in- dustry. The first ironmaking furnaces capable of producing molten iron (charcoal blast furnaces) in Europe appeared sometime around the 14th century (see Fig. 1), but the advance of refractory technology Fig. 2 Furnace make-up of typical integrated steelwoks in the latter was slow. In China, where charcoal blast furnaces had been built far Industrial Revolution Era earlier than in Europe, more advanced refractories were used, but their component systems were very similar to the European quali- Table 1 Chronological table for steelworks refractories (I) ties. (the Industrial Revolution Era) 2.2 Era of the industrial revolution Modern refractory technology is considered to have begun dur- 14-15th century Charcoal-fed blast furnace ing the era of the Industrial Revolution (the 18th to 19th centuries). 1709 Coke-fed blast furnace After originating in the UK on three main pillars, namely, steam en- 1735 Crucible steelmaking gines, coal and steel, the Industrial Revolution expanded to other 1784 Paddle furnace European countries. As a result, many new industries using furnaces 1806 Magnesia crucible as their principal production facilities, popularly called “the smoke- 1810 Beehive coke oven stack industries”, appeared, and a wide variety of industrial furnaces 1820 Silica brick (invented) were invented and applied, spurring the advance of refractory tech- 1834 Graphite crucible nology. 1850 Saga paddle furnace The main drive in this advance was, no doubt, the steel industry; 1853 Water-cooled blast furnace the basic concepts of the furnaces that form the production system structure of integrated steelworks (illustrated in Fig. 2) were estab- 1856 Bessemer converter Silica brick (produced) lished in the second half of this period. New types of iron and steel- 1857 Cowper hot stove making furnaces from coke-fed blast furnaces to electric arc furnaces Kamaishi blast furnace were built and new types of refractory were developed for different 1858 Siemens open hearth furnace applications (see Table 1). 1863 Carbon block Typical iron and steelmaking furnaces developed during this pe- 1864 Martin open hearth furnace riod and their main characteristics are listed below. 1868 Silica brick for OH furnace (i) Coke-fed blast furnace, using coke as the reducing agent and 1879 Thomas converter Tar dolomite brick heat source in place of charcoal. 1880 Magnesia bottom (OHF) (ii) Hot stove, employing regenerative heat exchangers of refrac- 1881 Magnesia brick tory to supply high-temperature air to a blast furnace. 1885 Chrome brick (iii) Coke oven, to carbonize coal into coke. (iv) Open hearth furnace, a reverberatory furnace for steel produc- 1899 Héroult electric arc furnace tion employing regenerative heat exchangers to utilize its own OH: open hearth, OHF: open hearth furnace - 9 - NIPPON STEEL TECHNICAL REPORT No. 98 JULY 2008 waste heat (see Fig. 3). ing of kilns and vessels, new applications were introduced to exert (v) Converter, a steelmaking furnace to burn impurities in molten new functions: these included regenerators, gas-blowing tuyeres, pig iron with air blown in from the bottom to use them as the and stoppers and nozzles to control the flow of molten metal. heat source (see Fig. 4). (3) The development of the tar-dolomite brick made the Thomas (ba- Whereas fireclay brick, or chamotte brick (Al2O3-SiO2 system) sic) converter viable, and silica brick made the Bessemer (acidic) which evolved presumably from ancient earthenware brick, accounted converter and open-hearth furnace commercially operable. for most of the refractories before the Industrial Revolution, various (4) Various new techniques were developed in the fields of furnace new materials were developed during this period. However, the de- construction, cooling of refractory lining, and heat insulation, and velopment of new refractory materials could not fully meet the in- they were incorporated as the core constituents of refractory tech- creasingly demanding requirements of diverse functions of the new nology. types of furnaces developed one after another. (5) Diatomaceous brick was developed (UK patent in 1893) as the The state of refractory technology at that time can be summa- first lining material specially designed for heat insulation. rized as follows. 2.3 Opening of Japan to international society (1) The quality of fireclay brick was improved, and in addition, silica, The Industrial Revolution in Japan, which began more than half tar-dolomite, and magnesia bricks appeared as new and high-per- a century later than in Europe when the country opened its doors to formance types of bricks. international society, showed rapid development during the decades (2) Besides the traditional application of refractories to the inner lin- from the end of the Shogunate Period to the beginning of the Meiji Era (1850s to 70s). The year 1851, when the first reverberatory fur- nace (a paddle furnace) in Japan was commissioned in the present Saga Prefecture, can be called Year One of Japan’s modern refrac- tory technology. Thereafter, the country quickly absorbed various refractory tech- nologies from abroad and incorporated
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