Recycling

THE SECOND INTERNATIONAL CONGRESS NON-FERROUS METALS 2010, SEPTEMBER 24, 2010, KRASNOYARSK, RUSSIA
PART IX
RECOVERABLE RESOURCES OF METALLURGIC AND ELECTROCHEMICAL INDUSTRY: TECHNOLOGICAL, ENVIRONMENTAL AND ECONOMIC ASPECTS
The Second International Congress Non-Ferrous Metals 2010, September 24, Krasnoyarsk, Russia Contents
PART IX. RECOVERABLE RESOURCES OF METALLURGIC AND ELECTROCHEMICAL INDUSTRY: TECHNOLOGICAL, ENVIRONMENTAL AND ECONOMIC ASPECTS
The Approaches To The Increase of Iron-Containing Wastes Share . . . . . . . . . . . . . . . . . . . . . . . . . 480 in The Raw Material Balance N.I. Novikov Comprehensive Anthropogenic Wastes Utilization of Southern Kuzbas Mining . . . . . . . . . . . . . . . 483 and Smelting Complex, Problems and Perspectives. Exploring Situation F.I. Ivanov , E.V. Isakova , A.S. Golovko , V.A. Poluboyarov Technological Studies of Slag Samples From Karsakpaysk Copper Smelter for Metal . . . . . . . . . . 488 Re-Extraction Feasibility Study S.G. Gritsay, G.I. Krivopustova, A.O. Teut, N.I. Utrobina Sorption Recovery of PLatinum (II, IV) and Rhodium (III) From Chloride Solutions. . . . . . . . . . . 494 of Spent Catalysts D.. ashirin, .. elnikov, .N. nonova Prospects of Use of The Nonferrous and Rare Metals Containing in Coals and Coal Ashes . . . . . . 503 of Kuzbas for The Iron and Steel Industry of Siberian Region V.A. Salikhov, E.S. Ljubushkina Rhenium Extraction From Nickel-Based Complex Heat-Resistant Alloys . . . . . . . . . . . . . . . . . . . . 510 A.G. Kasikov, A.M. Petrova, V.T. Kalinnikov EPOS-Process New Technology of Effective Ore-Smelting and Industrial . . . . . . . . . . . . . . . 515 Wastes Processing in Plasma Ore-Smelting Shaft Furnace I.A. Bezrukov, S.N. Malyshev, O.B. Moiseyev, V.V. Pavlov, I.S. Parhomuk, .P. Kuznetsov Treatment of Radioactive Metallic Wastes by Melting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 520 I.E. Abroskin, U.N. Makaseev, A.C. Buynovsky, A.I. Abroskin, A.A. Chernoshchuk Processing of Fluorine-Containing Waste Sand Middling Products of Aluminum Production . . ..525 in Cement Industry B.P. Kulikov,V.D. Nikolaev,S.A.Ditrich, L.M. Larionov Effective Strength Resource Saving Technology in Steel Industry Revisited . . . . . . . . . . . . . . . . . . 533 N.I. Novikov
The Second International Congress Non-Ferrous Metals 2010, Krasnoyarsk Part IX Recoverable Resources of Metallurgic and Electrochemical ...
THE APPROACHES TO THE INCREASE OF IRON-CONTAINING WASTES SHARE IN THE RAW MATERIAL BALANCE
N.I. Novikov Novokuznetsk branch of the institute state educational highest vocational institution, Kemerovo State University, Novokuznetsk, Russia
In ferrous metal industry annually millions of iron-containing wastes appear, such as oxide scale, sullage, dust. About 4550 % of iron, which wastes contain, go back to production mainly through agglomerating and converter production, the rest 5055 % are whether accumulated in waste dumps and storage ponds, or lost outside the plants. Bringing back to the production the iron, which wastes contain, is an important economic aim. In metallurgical production iron-containing wastes formation take place at all stages of production process, starting from preparing iron ore raw materials to production of finished steel. The sources of iron-containing wastes formation and their volume are specified by the example of convert production of Western Siberian Steelworks and are shown in the table 1. Table 1 The sources and volume of iron-containing wastes at Western Siberian Steelworks
The volume of iron-containing wastes, thousands Converter production with productivity 7.5 million tones of steel, 86.7 Including 20.4 oxide scale of continuous-casting machine gas-cutting machine tailing of continuous-casting machine 22.5 gas-cleaning tailing 12.5 gas-cleaning dust 31.25 Blast-furnace department, including 539.6 tailing of aeration devices in the stockhouse 7.7 gas-cleaning tailing 56.9 flue dust 475.0 Agglomerative and preparation plant (minus sieve of sinter 312.5 less than 5 mm) Oxide scale of mill products 203.75 Total 1142.55 The sources of iron-containing wastes formation
The characteristic of iron-containing wastes on some parameters is shown in table 2. Table 1 The characteristic of iron-containing wastes
Item of materials Iron content, % Fraction, mm Oxide scale of continuous-casting machine 72.0 0.55.0 Tailing of gas-cutting machines 60.0 0.13.0 Continuous-casting machine Flue dust 48.5 0.12.0 Tailing of converter department gas-cleaning 59.7 0.12.0 Tailing of blast-furnace department gas-cleaning 58.5 0.12.0 Oxide scale of rolling-mill department 69.0 0.55.0 Minus sieve of sinter 55.4 up to 5.0 Humidity, % 1012 68 612 3040 1220 1612 up to 6.0
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According to the experts estimation, a tone of iron, produced from industrial wastes is 57 times cheaper than a tone of iron, produced from original raw material (iron ore). Iron ore mining costs rise every year because of geological conditions deteriorating, remoteness from steelworks and other factors. In this respect, manufactures of iron have started to tackle more actively the problems of using iron-containing wastes in production process. This works in the most active way at Magnitigorsk steelworks (open joint-stock company MMK), open joint-stock company Ural Steel, open joint-stock company Western Siberian steelworks (open joint-stock company ZSMK) and a number of other enterprises. Iron-containing wastes share in the raw material balance is from 7 % to 13 % and it is not the maximum. According to the experts estimation, the iron share in the raw material balance from the volume of accumulated iron-containing wastes in enterprises dumps is quite possible to increase 2 or 2.5 times for salvage of iron-containing wastes. For efficient usage of these wastes in steel industry it is necessary to prepare them beforehand. The preparation includes tailing dehydration and homogenization. This requires the building of a special department. There are a lot of various ways of tailing utilization well-known worldwide. The easiest and at the same time appropriate for steel industry option is the sequence of the following procedures: pulp thickening, drying on disk vacuum filters, then on drier drums to 6 % humidity. Tailing drying is made through gas fuel burning, or with hot air from the hot-blast stove behind the waste-heat boiler of the oxygen converter. So, using the pre-prepared tailings in converter procedure is technologically possible and economically reasonable, which is proved by local and foreign practice, including at ZSMK. At the same time, conveying a large number of finely dispersed materials with the particles size 0.25.0 mm through the solids pipe will lead to significant increase in dust formation in the convey areas and especially in the block of conveying the materials directly to the converter. On this basis conveying iron-containing and carbon-bearing materials to the converter needs to be made through the containers, similar to those used for loading of scrap metal to the converter. The load is advised to be made in the department of iron-containing materials preparing. Currently, the solution to the problem of more comprehensive utilization of iron-containing wastes is held by the lack of reliable and efficient technologies of recycling considerable amounts of oxidized secondary raw materials which are poor-graded for agglomerating. Actually, only oxide scale is comprehensively utilized. For example, at open joint-stock company MMK annually about 650,000 of oxide scale is formed and used in blast-furnace practice. On the other hand, there is an option of more efficient using of oily oxide scale in converters, and it has a number of technological, ecological and economical benefits. Decrease in oxide scale, especially oily oxide scale (about 150,000 tones) from the agglomerated charging material will contribute to saving fuel for the technological needs (6070 kg/t of agglomerate), increase in the equipment operating reliability and decrease in harmful wastes in the atmosphere, as the oils in agglomeration process mainly sublime, but dont burn. Then, during agglogases cooling, oil vapor condensate on the equipment surface as solid particles, and partly go to the atmosphere as oily fog and afterwards fall down and pollute the soil. Exclusion of oily oxide scale through agglomeration from charging material will improve the operating of stoves, as the permeability will increase and the moisture content of charging material will stabilize. Oil content in oxide scale is not a big drawback when it is used with converter technology, as oil is technological fuel and deoxidant and intensifies deoxidant processes in the oxide scale. Certainly, one will have to deal with preparing oxide scale for melting in converters, but the effect of bringing to production 150,000 tones of raw material annually, which is obvious in the iron ore raw material balance, will cover the costs. There are no difficulties with using non-oily oxide scale and welding slag, which is proved by the practice of their efficient using in 20002005 at the Novokuznetsk steelworks. During the period at open joint stock company ZSMK a version of converter process was applied with using a large amount of oxide scale (up to 1520 % of hot metal weight), which is two or three times a s big as its regular share in converter melting charging material. Heat, which is necessary for the process for heating and deoxidation of oxide scale, is produced as a result of cast iron residual element oxidation and decrease in solid carbon-bearing materials, mainly small-sized coke. Technological process takes place in converter, equipped with blow-off device for both joint and separated conveying of oxygen and azote. Cast iron is put into the converter, oxide
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scale is loaded, also coal-bearing and slag-forming materials with simultaneous stirring the bath through conveying blow-off mixture of oxygen and azote. The ratio of the blow-off mixture ingredients depends on the cast iron content and temperature, and also the oxide scale. As a result of mixing and interaction of all the materials, loaded to the converter, iron oxide deoxidation takes place and also transit of deoxidated iron into iron-carbon melt. The change of conveying the blow-off mixture of oxygen and azote into the converter (deoxidating blowoff) to oxygen blow-off for oxidating refining and heating of the metal, is made after recovery of iron-containing, carbon-bearing and slag-forming materials and getting the optimal sharing of recovered oxide scale iron between metal and slag. Achieving the optimal sharing allows the process of metal oxidation refinement and heating to work smoothly and without wastes to the given parameters on the temperature, constitution and liquid metal output. Lately, at ZSMK the oxide scale share in the iron-containing raw material balance has decreased. In our point of view, this is due to several reasons. The first one is lack of complex economic record of all the interconnected factors of oxide scale using in agglomerative, blast furnace and converter industries. Some negative sides of oxide scale using in agglomerative and blast furnace industries are mentioned above, but it is quite difficult to estimate them in terms of economics. The second one is that scrap metal replacement by oxide scale is connected to increase in cast iron share in the metal charging material that leads to metal products costs rise. This should be eliminated in the proper scrap metal pricing. In Russia in the last few years, there has been a firm tendency of fall in scrap metal price level compared to conversion pig iron. For example, in 1991 the cost of 1 tone of scrap metal in proportion to 1 tone of conversion pig iron was 0.5, in 20000.23, in 20070.21. In the world market scrap metal cost in proportion to conversion pig iron remains stable on the level of 0.8 to the conversion pig iron cost. If we estimate the metal cost in the Russian market objectively, using oxide scale and other iron-containing wastes will become profitable for metallurgical plants, as their retail price is much lower, then scrap metal price. This will allow to increase greatly their share in the iron-containing raw material balance at a steelworks. The manufactures are encouraged to increase the iron-containing wastes share in the raw material balance at metallurgical plants by a significant decrease in scrap metal preparing and recycling (by 1525 %), which makes manufactures whether increase the cast iron expenditure for steel smelting, or look for effective and appropriate ways of increasing the iron-containing wastes share in the raw material balance. To sum up, solutions to the problems with comprehensive utilization of steelworks wastes and increasing the iron-containing wastes share in the raw material balance is not possible without complex economical analysis and estimation of all energy, material and economic aspects of various versions of their using.
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COMPREHENSIVE ANTHROPOGENIC WASTES UTILIZATION OF SOUTHERN KUZBAS MINING AND SMELTING COMPLEX, PROBLEMS AND PERSPECTIVES. EXPLORING SITUATION
F.I. Ivanov 1, E.V. Isakova 1, A.S. Golovko 1, V.A. Poluboyarov 2
1
Novokuznetsk branch of the institute state educational highest vocational institution , Kemerovo State University, Novokuznetsk, Russia 2 Chemistry of Solids and Mechanochemistry Institute of SB RAS, Novosibirsk, Russia
The south of Kuzbas is a top-ranked mining and smelting region of country and it has one of the greatest differences between industrial economic potential, source of raw materials and level of fundamental scientific researches of region issues. The priority research area does relate to conservancy a secondary raw materials of mining and smelting wastes utilization, i. e. a scientific foundations of theirs recycling creation. This region is a coal mining leader in Russian Federation (especially, its high-quality sorts) as well as metallurgy and heavy engineering industry center, but the basic scientific researches in recycling carry out by certain small laboratories, ingressed the chemistry of solids and mechanochemistry institute of SB RAS (in Novosibirsk) and Kuzbas universities such as NBI KemSU, SibSU and KuzSTU. The history of Kemerovo regions industrial centers development related to tasks, that the country had in 3040 years of 20th century. At that time, the fastest achievement countrys and regions industry development on the strength of historical necessity (the industrial complex creation, 2nd World War e. t.c) was requested, that in turn it imposed certain constraints on conservancy and its ecological concepts adherence (on fact, the inobservance of theirs). The big industrial enterprises distribution performed under the principles of profitability, such as proximity the enterprises to resource origins and haulways. The infrastructure was created according to the same principles. Violent maintenance of natural resources, first of all coal and iron ore, led the region in short order to self-repair impossibility of environment and natural resources. The number of wastes, accumulated on the Kuznetsk Basins territory, numbered a hundreds of millions tonnes at the end of 20th century. For example, during the 2001 year if was appeared 855812.319 thousands tonnes of nontoxic industrial wastes, which included: dead-rocks 836410.260 thousands tonnes, ash-andslad wastes 2114.298 thousands tonnes, waste coal 13620.780 thousands tonnes. Solid domestic wastes are amount to 2 million tonnes. Waste piles, slurry ponds, tailing and rubbish dumps occupy mare than 40 thousands hectares of land, excepted from usage [1]. Especial unsightly situation has formed at the south of Kuzbas at region of towns Novokuznetsk and Prokopyevsk, where the major industrial enterprises of coal mining, ferrous and nonferrous metals and power industry are located. On the territory of these towns the solid wastes are presented by large-tonnage wastes from metallurgical, heat-and-power engineering and coalprocessing industry alongside with colliery wastes that include all components that wasnt ingress of saleable coal, such as top covers, interburden layer, impregnations, coal slack and low-quality carbons. The information about these wastes of Novokuznetsk is presented in table 1 [2]. Table 1 Large-tonnage wastes in Novokuznetsk at 1999
Item Slag Ash-and-slad wastes from heat stations and boiler rooms Coal mining and coal-cleaning wastes Wet magnetic separation wastes Solid domestic wastes Amount, tonnes 3029224 598000 2148176 1089201 315000 Reused, tonnes 3310550 33538 725491 Located in storages, tonnes 217096 564462 1421685 1089201 315000
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1. Slag The main amount of slag is generated by metallurgical giants as public corporation WSMW and NKMW. Research group successfully examined a scientific bases development of slags technological redistribution under the direction of doctor of technics, professor S.I. Pavlenko at Siberian State Industrial University. Results, related to open-hearth slag processing practice development, as dump likewise discharged wastes, were implemented on NKMW like perspective alternative source of raw materials. It was started the special crushing and screening plant to slag recycling. Non-magnetic fraction overworks into building materials; there are also carry out the creating of cement-free bindings and concretes efforts [35]. Researches of chemical and mineralogical composition that have executed under the direction of professor S.I. Pavlenko are represented in table 2 and displaying the possibility of goal attainment. Table 2 Results of open-hearth slag analysis (oxides, %)
Materials Discharged open-hearth slag Dump waste open hearth slag [SiO2] 15.16 8.05 [Al2O3] 10.65 11.04 [Fe2O3] 17.82 16.19 [MnO] 5.08 4.47 [CaO] 27.2 21.7 [MgO] 14.99 14.7 [SO3] 0.67 0.15 [TiO2] 1.06 1.06
Losses by ignition for discharged slag amount 0.16 %, by [CaO] free 0.47 %, by [FeO] 8.02 %. Losses by ignition for dump waste slag amount 1.18 %, by [CaO] free 0.21 %, by [FeO] 7.29 %. 2. Ash-and-slad wastes At present ash-and-slad wastes, which arise on public corporations Kuznetsk heat station, KMW heat station and West-Siberian heat station, locate on their own sludge storages and havent a wide application, however in research works by S.I. Arbuzov, V.A. Salihov an others [68] economic-geological suitability of recycling theirs is validated. It based on content analysis a variety of nonferrous and rare metals contained in carbons and ashes. Ash-and-slad wastes of heat stations accumulate in amount of 2.6 million tonnes annually and produce the applied interest to metals extraction. Table 3 summarizes the content of nonferrous and rare metals in carbons. Table 3 The content of nonferrous and rare metals in Kuzbas coal
Metal Content in coal, g/tonne 100500 100500 to 15 to 25 10300 200 to 50 to 3 to 1 13 13 to 1 Concentration, recommended to evaluation, g/tonne 500 500 100 50 100 1000 100 100 100 100 20 10 Maximum content in ash, g/tonne 5600 3000 3700 4800 16000 5800 5000 1500 430 3000 3000 2700 Conditions for ores, % 1015 3 0.5 2 1 1 1 0.51 0.3 0.1 0.04 0.1
Titanium Zirconium Copper Plumbum Zinc Barium Vanadium Tungsten Beryllium Niobium Gallium Germanium
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3. Waste coal recycling According State Standard 307722001 [9] waste coal is to be classified like anthropogenic mineral raw materials and accumulation of theirs like anthropogenic conglomerations of carbonic row [10]. Usmanova T. V. and Rihvanov L. N. classify these conglomerations to the 3rd, the 8th and the 10th types of anthropogenic coalfields [11]. Wastes of coal industry use to the best advantage on concentrating mill Abashevskaya, where coal rocks of class 1100 mm utilize partially in brick production, the rest of the amount utilizes in road embankment, weirs filling and others objects. Idea, developed in [1] and called overadiabatic combustion of carbon-bearing raw materials and synthesis gas production didnt meet with support in Kuzbas in spite of it obvious efficiency and ecological compatibility. 4. Solid domestic wastes Collecting and storage problem of solid domestic wastes has been solved in Novokuznetsk. It has been created highly mechanized high end factory that provides the accepting, preliminary recycling and storage of solid domestic wastes. 5. Refractory wastes (that arise from blockwork repair of metallurgical furnaces and heat stations boilers) represent the particular interest for authors of this research paper We propose to reuse all components of refractory wastes to remake refractory materials applying nanostructured binding agent in compliance with basic idea of recycling. The subject of inquiry is unshrinkable constructional refractory material and ceramics from refractory wastes technology development for usage it in extreme conditions [12, 13]. This technology uses attainments of mechanochemistry of solids in physical-chemical foundations development to involve in refractory wastes processing the main metallurgical enterprises of Kemerovo region. Objectives: 1. Binding agent development on basis of mechanochemical technology, including nanoparticles gaining, sized less than 100 nm (with specific surface more than 10 m 2/g). 2. Usage this binding agent for development the technology of gaining an unshrinkable material patterns on basis of refractory wastes recycling and test operation in extreme conditions. In the capacity of secondary raw materials there were used refractory wastes of WSMW (Novokuznetsk): dinas, chamotte, electrocorundum (figure 1). The trial designs prepare made on press -242 with pressure parameters fine-tuning in different press molds of 380125 mm and 150120 mm size. It also made by vibrocompressive method. The checkout of trial designs ran at West-Siberian test center (accreditation certificate RU.0001.21 07) and at WSMW for full-scale testing in soaking pits during the one year. The full-scale testing certificate is purely affirmative (table 4). Table 4 Physical-mechanical results of fire brick, gained from refractory wastes by vibrocompressive method
Trial design Chamotte brick Dinas brick Combined brick Characteristics Refractoriness Permanent linear shrinkage Refractoriness Permanent linear shrinkage Refractoriness Permanent linear shrinkage Unit of measure o % o % o % Checkout method 406969 540281 406969 540281 406969 540281 Checkout results 1540 0.75 1640 0.27 1550 0.60 State Standard requirements 1580 0.5 1580 0.5 1580 0.5
Physical-mechanical checkout results of chamotte brick (figure 2), made from secondary raw materials, conform to the State Standart specification 39096 Chamotte products. Checkout results of dinas brick, made from the same (secondary raw) materials, practically conform to the State Standart specification 415779 Dinas products by refractoriness, though overtop it to a considerable extent by strength characteristics.
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Fig. 1.Mountains of refractory wastes in area of pitch-magnesite workshop of WSMW
Fig. 2.Chamotte brick
The first stage, related to refractory wastes recycling possibility research and industrial refractories gaining using nanostructured binding agent, has finished successfully with support of Start programme and Small-scale enterprises in scientific and engineering business field development promotion fund. According to Start programme, to be entered into the 2nd stage of budgetary financing, its necessary equivalent cofinancing of investor at the rate of 1.5 million rubles. Sponsors that willing to affiliate with programme dont satisfy the conditions of I. M. Bortnik fund. This research has financed according to state contract 02.513.11.3188 since April the 23 rd of 2007 in the network of Researches and developments on priority ways of growth of scientific-technical complex of Russia at 20072012 years on topic called Foundations of higheffective methods of nanostructured nonshrinking corundum ceramics development and others refractories that work in extreme exploitation conditions gaining based on binding material from ultra- and nanodispersed powders gained by mechanochemical method. Lot was won by programme of nanotechnology and it was one, scientists of Kuzbas universities took the part in that. The creation possibility of high-concentrated and, that is most importantly, cheap silica sols demonstrated in patents: [1. Method of alkali silicate gaining. Patent RF 2187457 from 04 mar 2002. 2. Method of nonfired building materials making. Patent RF 2168481 from 31 jan 2001. 3. Method of refracting masses gaining. Patent RF 22143379 from 04 jun 2002. 4. Method of silicate bond gaining. Patent RF 2144552 from 20 jan 2000 and others patents]. Authors of this research paper have explored the market of Kemerovo region by demand for refractory materials. The basic providers of refractories to metallurgical enterprises of the region are the close corporation Magnesit of Sverdlovsk region and some providers from abroad, particularly from China. Preliminary technical and economical assessments that have been traced with a glance of nature-conservative and social significance of project are indicate of a considerable economical advantages of refractory ceramic products gained from a secondary raw materials. The basic consumers in Kemerovo region are: WSMW, NKMW, housing and communal services of Kuzbas towns, Kuzbassenergo and others. REFERENCES 1. /. . , . . , . . , . . , . . // : . . ., 911 2003 ., . . . 4851. 2. . [ ]/ : http://www.admnkz.ru/actionDocument.do?id=51922
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3. /. . , . . .// : . ., 911 2003 ., . . . 1923. 4. . ., /. . , . . // : . II .-. . . , 46 2006 ., . . . 68. 5. . ., /. . , . . . .: , 2005. 139 . 6. /. . , . . , . . , . . . , 2000. 248 . 7. . ., - /. . // : . III .-. . . 69 2009 ., . . . 136141. 8. . ., /. . // : . III .-. . . 69 2009 ., . . . 129136. 9. 307722001 . . . . 28 2001 . .: - , 2002. 15 . 10. . ., /. . , . . // . . 6. . .: , 2004. . 519540. 11. . ., /. . , . . // . . . . 2006. 4. . 2931. 12. , /. . , . . , . . , . . , . . //. . . 2007. 12. . 4952. 13. Poluboyarov V. A., Korotaeva Z. A., Bebko A. N., Ivanov F. I. Influence of the Nanostructure of Corundum Binder on the Strength of Nonshrinking Corundum Parts//Steel in Translation. 2009., Vol.39, 2. P.118121.
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TECHNOLOGICAL STUDIES OF SLAG SAMPLES FROM KARSAKPAYSK COPPER SMELTER FOR METAL RE-EXTRACTION FEASIBILITY STUDY
S.G. Gritsay, G.I. Krivopustova, A.O. Teut, N.I. Utrobina State Affiliate The Eastern Mining and Metallurgical Research Institute for Non-ferrous Metals Republic State Affiliate National Enterprise of Complex Processing for Mineral and Raw Material of the Republic of Kazakhstan (SA VNIItsvetmet RSA NE CPMRM RK), Ust-Kamenogorsk, Republic of Kazakhstan
Due to depletion of non-ferrous metal ore natural resources, enforcement of the requirements to storage conditions of wastes from metallurgical plants and rapid development of industrial technologies, industrial mineral deposits arouse interest. Economic motivations for increased interest to industrial wastes are as follows: lower costs of mining, because it is not necessary to build mine; concentration of minerals is similar to concentration in natural deposits; decreasing of charges for environmental damages after retreatment of wastes due to decreasing of their hazardous influence on the environment; after decreasing of concentration of components in the wastes down to safe, they can be used for production of construction materials, and areas, used as wastes pits, may be restored. The results of calculations of slag amount on the basis of geological-exploration studies of waste pits from Karasakpayskiy copper plant are shown in table 1. Table 1 Slag Amount and Concentration of Metals in Slag, Kept in Waste Pits of the Plant
Amount of waste slag (thousand tons) 2 885.7 Metal concentration in slag u, g/t kg 0.22 634 g, g/t t 10.25 29.6 u, % b, % Zn, % thousand tons thousand tons thousand tons 0.91 26.3 0.29 8.3 0.36 10.5
It is known [1], that the way of cooling of melting products from non-ferrous metallurgy, including copper matte and slag, has considerable influence on the level of the following metal recovery by dressing methods. Thus, low decreasing of slag temperature facilitates separation of metals, contained in slag (formation of secondary monominerals) and creates conditions for growing of larger crystal grains. Magnetic and flotation separation of copper from the slag, which has been cooled slowly, is more effective. And on the contrary, the process of quick cooling of copper slag, which is similar to the examined one, is accompanied by formation of fine-grained, cryptocrystalline structure, which is typical for hard melts. Separation of components in such a material causes difficulties. Laboratory technological researches Material composition and physical characteristics of copper slag from waste pits of Karasakpaysiy copper plant have been studied for many years. Mineral composition has been studied using ore microscope with high resolution. Several slag samples with different concentration of copper (from 0.2 % up to 5.3 %) and other element have been received for examination, which demonstrates that composition of the wastes differs greatly. Sample materials consist mostly from vitreous slag particles, containing different inclusions from metallurgical plant. Almost all vitreous slag contains particles of mono-magnetite (of different size, saturation and structure), having size from 220 up to 150 m and its aggregates, including latticed-dendritic-skeletal aggregates of metacrystalline magnetite. 85 % of
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all the vitreous slag particles together with magnetite contain different products from metallurgical plants mostly with copper-zinc composition (having low concentration of galena and gold) in the form of pearlitic ball particles (having diameter from 2 up to 150 m, sometimes 300420 m and bigger), presented as mixtures with different components, which are the following (in accordance with their prevalence rate): solid chalcocite-bornite solution, bornite, chalcocite, sphalerite, chalcopyrite and sometimes eutectic mixture of galena and chalcocite and also particles and discontinuous streaks of metallic copper and gold and silver (more rarely) particles. In a circumferential direction from these pearlites and bigger inclusions, there may be often seen thin discontinuous pectinal crusts, formed by thin metacrystalls of magnetite. Sphalerite may be seen not only in inclusions of mixtures of different composition and with solid chalcocite-bronite solution, but also in many particles of vitreous slag with magnetite in the form of thin (1.56 m in diameter) pearlitic inclusions of grey semi-transparent and hardly determinable spalerite. Around these particles of sphalerite, there may be seen discontinuous cover, represented by all copper-bearing components. About 15 % from total amount of vitreous slag particles, containing copper-zinc components (having size 10200 m), may be considered as free (from magnetite) slag particles. Together with plated-latticed layers or sections consisting of pure slag, the main body of the material consists from vitreous slag, impregnated by thin (16 m) copper-zinc perlites and ultra-thin (not more than 0.10.5 m) and almost invisible through the microscope inclusions of all the mentioned above copper-zinc components, which are absolutely inseparable from slag. Large amount of magnetite, contained in major part of the material, may be explained by very low effectiveness of magnetic separation during efforts of preliminary slag enriching. There has been measured specific weight of slag, which is 2.8 g/cm 3 and bulk weight is 1.61.8 g/cm 3. High concentration of iron (from 9 % up to 36 %), which hardness is 6.06.5 according to Mohs scale, and silicon (from 26 % up to 48 %) in copper slag is the main reason for difficult crushing of the material. Detailed chemical composition of one from the slag samples, analyzed in the laboratory, is shown in nable 2. Table 2 Analysis Results of Chemical Composition of Slag Laboratory Sample
Components Zinc Lead Copper Gold, g/t Silver, g/t Iron Pyrites sulfur Aluminum trioxide Iron trioxide Concentration, % 4.71 0.82 1.25 0.2 9.2 36.0 1.85 4.24 46.19 Components Calcium oxide Magnesium Oxide Silicon dioxide Barium oxide Indium Cadmium Bismuth Antimony Thallium Concentration, % 4.33 1.14 26.86 1.67 0.0021 0.005 >0.05 0.003 0.0013
The examination of ionic composition of liquid phase of slag slurry (table 3) shows that the dissolution level of calcium and magnesium sulfates is very high. Table 3 Ionic Composition of Liquid Phase of Slurry from Laboratory Sample of Copper Slag
Component Original copper slag 8.25 usol. 0.05 Zn 0.11 C 58 F 0.057 Mg 9.4 SO4 62.9 b <0.01
The results of analysis for states of the presented zinc, copper and lead compounds in slag are shown in table 4. It has been specified that 60.87 % of copper in slag is represented by sulfate forms, and 41.74 % from this amount is secondary copper minerals.
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Table 4 Analysis Results of Balance Composition of Laboratory Slag Sample

Mineral forms ZnCO3 ZnSiO2 ZnS Zntotal Concen- Distribu- Mineral Concen- Distributration % tion % forms tration % tion % 0.11 2.34 Cufree 0.22 17.39 1.69 35.88 Cufixed 0.27 21.74 2.91 61.78 Cusecon 0.52 41.74 CuS 0.24 19.13 4.71 100 Cutotal 1.25 100 Mineral forms PbCO3 PbS Pbjaros. Pbtotal Concentration % 0.08 0.19 0.55 0.82 Distribution % 9.76 23.17 67.07 100
Table 5 shows distribution of elements according to the grain-size category of laboratory slag sample. According to this table 91.6 % of copper concentrates in category of +0.074 mm, however, taking into account characteristics and size of mineral copper-bearing formations for flotation method of enriching there shall be used extra fine slag. Table 5 Grain Composition and Distribution of Components According to Grain-size Category of the Analyzed Slag Sample
Grain-size category, mm 2 +0.63 0.63+0.315 0.315+0.074 0.074+0.044 0.044+0.020 0.020 Total Output, % 43.93 39.55 7.33 3.45 2.15 3.59 100 Concentration, % Cu 1.18 1.23 1.40 1.44 1.66 1.57 1.25 SiO2 46.84 46.57 46.18 53.66 50.98 20.14 46.05 Fe 9.37 9.01 10.36 15.70 13.42 7.05 9.52 Cu 41.51 38.93 8.22 3.97 2.86 4.51 100 Distribution, % SiO2 44.68 40.00 7.35 4.02 2.38 1.57 100 Fe 43.22 37.42 7.98 5.69 3.03 2.66 100
Grinding coefficient of copper slag (in reference to copper-zinc ore) was 0.27. During open laboratory experiment campaign, which included slag grinding, basic copper floatation activities, control copper flotation, re-cleaning and re-grinding of tailings from re-cleaning and concentrate from control flotation, there were selected the level of grinding, reagents consumption and flotation time [2]. The experiments determined the following: grinding of slag shall be accomplished until 93 % of slag is in grain-size category of 74 m; of media shall be kept at the level of 1011; total consumption of reagents was the following: butyl xanthogenate 500 g/t, OFMB 40 g/t; total flotation time is 13 min.; it is necessary to foresee regrinding of 98 % middlings up to grain-size category 74 m. Table 6 shows the results of closed test, using selected parameters, according to the diagram, shown in Figure 1. Table 6 Technological Parameters of Laboratory Closed Test
Product Copper concentrate Tailings Initial copper slag Output, % 4.39 95.61 100.00 Concentration, % Cu Fe 20.21 10.34 0.38 9.48 1.25 9.52 Removal, % Cu Fe 70.95 4.76 29.05 95.24 100.00 100.00
490
Copper slag with grain size of -2+0 mm

Kx-200 g/t
Grinding up to 93% -0,074 mm category

t=70 min. Kx 100+100 g/t CMAC 300 g/t OFMB 20+10 g/t
Basic copper flotation t=5 min.

Kx 50+50 g/t OFMB 10 g/t
Copper recleaning t=2 min.
Control flotation t=6 min.
Copper concentrate
Tailings
Fig. 1. Diagram of Closed Test for Slag Processing with Reagent Mode Semi-industrial technology tests For development of practical basis for industrial processing of copper slag, tests of laboratory-developed technology has been accomplished in the enriching plant. For semi-industrial tests, there has been received more than 570 tons of slag from Karsakpayskiy copper plant, having moisture content of 2.7 %. The results of testing during receiving of raw material (table 7) shows considerable unhomogenuity of copper slags chemical composition, and high concentration of silicon dioxide in wastes from copper smelting plants caused problem for its crushing and grinding. During the tests, optimal variant of process flow-sheet for copper slag processing has been determined (fig. 2), reagent mode of copper flotation has been specified and recycling water influence on technological parameters of the process has been studied. The results of tests are shown in table 8. Table 7 Chemical Composition of Industrial Slag Sample
Sample No. 1 2 3 4 5 6 7 8 9 Portion sample Cu 5.33 1.25 1.72 1.61 0.74 0.67 0.24 2.50 0.22 1.52 Fe 12.47 9.52 11.57 12.64 11.12 12.52 7.17 9.41 7.51 10.37 Zn 1.88 0.40 0.70 0.76 0.23 0.35 0.09 0.56 0.15 0.54 Concentration, % As Sb Pb Ca 0.74 0.24 8.32 10.50 0.03 0.03 0.62 14.00 0.03 0.015 0.44 14.50 0.03 0.0027 0.84 14.00 0.03 0.0069 0.16 12.50 0.03 0.002 0.32 10.50 0.03 0.03 0.03 0.10 0.002 0.002 0.002 0.03 0.14 0.60 0.13 1.18 SiO2 35.50 46.05 46.20 46.53 48.69 47.74 S 1.76 0.10 0.56 0.34 0.12 0.10 0.10 2.11 0.10 0.01 Au, g/t 3.60 0.40 0.40 0.30 0.40 0.30 0.30 0.30 0.30 0.59 Ag, g/t 214.0 25.8 25.4 32.9 10.1 10.0 10.0 10.0 10.0 33.5
18.70 47.98 13.0 46.44 19.40 47.38 14.22 46.01
Table 8 Process Balance of Semi-industrial Processing of Slag

Products Initial slag Copper concentrate Tailings Output, % 100.0 4.94 95.06 Concentration, %, g/t Cu Zn Fe Au Ag 1.52 0.54 10.37 0.59 33.5 20.03 2.09 12.05 3.70 353.0 0.56 0.46 10.3 0.43 16.9 Cu 100 65.1 34.9 Removal, % Zn Fe Au 100 100 100 19.1 5.7 31.0 80.9 94.3 69.0 Ag 100 52.0 48.0
491
High concentration of iron in copper concentrate can be explained by its close association with copper in secondary sulfide minerals, i. e. in bornite (Cu5FeS4), predominating in slag composition.
Initial slag with grain size -16+0 mm
BX 200 g/t
1 stage of grinding
Classification in classifying screen drain sands Classification in hydrocyclone drain

2 stage of grinding
sands
BX 200 g/t OFMB 30 g/t
Basic copper flotation

BX 100 g/t OFMB 10 g/t
Recleaning
Control flotation
Copper concentrate
Classification in hydrocyclone sands regrinding drain
Tailings
Fig. 2. Process Flow-sheet of Semi-industrial Tests Process of copper slag enriching is accomplished using water closed circulation. Ionic composition of recycling water, which has been sampled during different stages of tests, is shown in table 9. Table 9 Ionic Composition of Recycling Water
Determined Ingredient Ionic Composition, mg/l, mg-eq/l Beginning of tests 7.8 0.7884 0.7252 0.3716 <0.5 5.0 9.73 84.17 2.4 433.31 1700 1088 Middle of tests 7.95 0.007 0.0277 0.013 30.5 5.1 17.02 74.15 48 690.5 1176 1596 End of tests 7.45 0.0065 0.1098 0.198 <0.5 2.4 36.07 36.07 32 456.77 508 1182
Cu+2 Zn+2 Pb+2 Total hardness Mg+2 Ca+2 Oxidation SO4 Suspended elements Dry residue
Taking into account high hardness of slag due to its silicate basis, which considerably complicated crushing and grinding, in laboratory tests for its desiliconization using clinkering by ammonium fluoride have been accomplished [3]. It has been determined that slag clinkering by this reagent during 2 hours under the temperature of 350 oC allows to reach the level of silicon dioxide removal of more than 99 % [4], which is positive for mechanical characteristics of slag.
492
Summary 1. Stale slag of Karsakpayskiy copper plant has unhomogeneous composition and is difficult industrial raw material for production of commercial copper concentrate (20 % Cu, 2 % Zn, 12 % Fe, 3.7 g/t Au, 353.0 g/t Ag). 2. The suggested process flow-sheet of slag enriching showed that copper recovery into concentrate under industrial conditions may be higher than 65 %, having commercial product output of about 5 %. Herewith, copper and zinc concentration in flotation tailings is about 0.5 % (of each one) and iron recovery into tailing is more than 94 %, zinc 80 %. 3. During Process tests, possibility of application of complete water circulation without negative influence on concentrate quality and on copper recovery level from slag into copper concentrate has been determined. 4.The results of experiments in slag desiliconization during its clinkering with ammonium fluoride show that it is possible to remove almost all silicon dioxide, which may considerably facilitate its following enriching. REFERENCES 1. Abdeyev M. A. Complex matte and converting. Alma-Ata: AGMNII AN KazSSR. 1962. p. 228 2. Gritsay S. G., Teut A. O. Development of process flow-sheet for copper recovery from stale waste slag of Karsakpayskiy copper smelting plant by enriching methods//Equipment and Technologies for enrichment of ore and non-ore materials. Materials from 6-th International Scientific-Practical Conference. Novosybirsk: Sybprint. 2008. p. 4046 3. Diachenko A. N. Halogenammonia technology for processing of metallurgical slag//Nonferrous Metals. 2005. No. 56. p. 7174 4. Study of physical and chemical principles of industrial raw-materials desiliconization during clinkering process with halides.//SAR Report (intermediate): 3.3.1142-FI/VNIItsvetmet; leader: Teut A. O., Ushakov N. N. Ust-Kamenogorsk, 2009. p. 32.
493
SORPTION RECOVERY OF PLATINUM (II, IV) AND RHODIUM (III) FROM CHLORIDE SOLUTIONS OF SPENT CATALYSTS
D.. ashirin, .. elnikov, .N. nonova Siberian Federal University, Krasnoyarsk, Russia
The present work is focused on sorption of platinum (II, IV) and rhodium (III) from chloride solutions on anion exchangers with different physical and chemical structure. The sorption was carried out from solutions with HCl concentration 0.014.0 mol/L. Platinum and rhodium concentrations in contacting solutions were 0.250.50 mmol/L. Sorption and kinetic properties of the chosen anion exchangers were investigated, and the basic parameters (exchange capacity, recovery degree, distribution coefficients, process rate, diffusion coefficients and half-exchange times) were calculated. The highest selectivity to noble metals was demonstrated by complexing anion exchanger Purolite S 985, strong base resin Purolite A 500 as well as weak base anion exchanger AM-2B produced in Russia. Introduction The production of platinum group metals is steadily growing as their industrial application becomes broader. However, since natural deposits of precious metals are being depleted, the technologies for noble metals recovery from different secondary raw materials (e. g. spent catalysts from organic synthesis or motor-car catalysts, electronic scrap etc.) are becoming more important [1, 2]. Low platinum and rhodium concentrations in these materials cause the application of sorption methods for the recovery of noble metals. These methods are characterized by high efficiency and ecological safety. The sorption recovery of platinum group metals is usually carried out from solutions obtained by decomposition of noble metals-containing materials. The breakdown of these samples is carried out by different methods, such as dissolution in acids, chlorination, smelting and other methods [36]. As a result, these solutions contain complexes of platinum group metals with different stability and chemical inertness. Moreover, the platinum group metals are affected by aquation and hydrolysis [2, 79]. The metal sorption from such solutions can be complicated, and some valuable compounds can be lost. In view of that, the high selectivity of sorbents is very important. Usually, the nitrogen-containing anion exchangers with functional groups of pyridine or amines are used for platinum group metals recovery from different solutions [2, 10]. As a rule, these resins recover platinum and rhodium by means of ion exchange between complex anions of Pt and Rh and mobile ions of the sorbent as well as by complexation between nitrogen atoms of sorbents functional groups and atoms of noble metals [10]. To make the ion exchangers applicable in industrial scale, it is important to know not only their sorption properties but kinetic characteristics as well, since the process rate is essential for industrial applicability of developed method. The present work is devoted to sorption recovery of platinum and rhodium at their simultaneous presence in chloride solutions on anion exchangers with different physical and chemical structure. Experimental We have chosen for investigation some anion exchangers, which physical-chemical properties are summarized in table 1. Before sorption all the anion exchangers were prepared according to the standard procedures and then converted to chloride form. The initial platinum stock solution was prepared by dissolution of 1.0 g of metallic platinum in aqua regia (mass ratio of l and NO3 was 3:1) with subsequent evaporation in water bath in the presence of hydrochloric acid and distilled water, aiming to decompose the salt of nitrosyl cations (NO)2 [PtCl6] and to withdraw the excess of nitric acid [7, 9]. The dry residue
494
Table 1 Physical-chemical properties of ion exchangers investigated

Trade name Purolite S 985 Purolite A 500 -2B Resin type Complex-forming anion exchanger Strong base anion exchanger Weak base anion exchanger Functional groups Polyamine groups Quaternary ammonia base Secondary and tertiary amines Physical structure MP MP MP EC to Cl , mmol/g 10.0 1.2 2.3 Swelling grade, % 42.0 37.1 21.1
EC exchange capacity; MP macroporous of H2 [PtCl6] was dissolved in hydrochloric acid. The content of platinum in this solution was determined by gravimetric method with ammonium chloride [9]. The initial stock solution of rhodium was prepared by sintering of 0.5 g of metallic rhodium with five-fold mass amount of BaO2 [9]. The content of rhodium in solution obtained was determined by gravimetric method with thiourea [9]. In this work we have investigated the freshly prepared chloride solutions simultaneously containing platinum and rhodium. Pt and Rh concentrations in these solutions were 0.250.50 mmol/L, and l concentration was varied from 0.01 to 4.0 mol/L. The platinum and rhodium concentrations in solutions were determined by spectrophotometrical method with SnCl2 [7, 9]. The concentrations and acidity of platinum and rhodium solutions were taken with an intention to make the experiment closer to real industrial conditions [2, 3]. The sorption concentration of Pt (II, IV) and Rh (III) was studied as follows: sorbent mass 0.1 g, volume of contacting solution 10.0 mL, stirring at (201) o. The equilibrium time was about 24 h. The efficiency of sorption recovery of platinum and rhodium on the chosen anion exchangers was estimated by means of exchange capacity (EC, mmol/L), distribution coefficients (D, mL/g), recovery degree (R, %) and separation factor (S). These values were calculated as follows:
OE =
( C0 C p ) V
q
(1)
where 0 and are the initial and equilibrium molar concentrations of platinum or rhodium in solution, respectively; V is the volume of contacting solution (mL) and q is the resin quantity (g).
OE ; Cp (C C p ) 100% R% = 0 ; C0 D S = Pt , D Rh D=
(2) (3) (4)
where DPt and DRh are the distribution coefficients of platinum in the presence of rhodium and of rhodium in the presence of platinum, respectively. The kinetic behavior of platinum and rhodium sorption was investigated by limited bath method with the corresponding criteria [11, 12]. The kinetic experiments were carried out under the intensive stirring of solution (800 rev/min). The contact times of resins and solutions were 0.5; 1; 2; 3; 5; 15;30 and 45 min; 1; 3; 6 and 24 h. The radius of the resin grains was (0.51.0) mm. After a certain time period, the resins and solutions were quickly separated and the liquid and solid phases were subjected to analysis. Then the concentrations of platinum and rhodium were determined by spectrophotometrical method. Using the Boyd-Adams model, the interpretation of results on kinetics was carried out [1113]. The exchange degree (F) was calculated from:
F=
Qt , Q
(5)
where Qt and Q are the amounts (mmol) of platinum or rhodium to the time t (s) and to the equilibrium time.
495
Then the kinetic curves were plotted on the coordinates F=(t) and the half-exchange time of the kinetic process (t1/2) was determined at F=0.5. After that, to confirm the applicability of the above model to the ion exchange kinetics in the systems investigated, the dependences Bt=(t) were plotted. According to the Boyds model [11, 12], the kinetic coefficient (B) was calculated from: (1,08)2 F 2 B= . (6) t If the process is controlled by gel diffusion, the function Bt=(t) should be linear. The diffusion coefficients were calculated according to the equation: r2 , (7) Ds = 4 2 t 12 where is the diffusion coefficient in ion exchanger grain (cm 2/s); r is the radius of the resin grain (cm); t1/2 is the half-exchange time (s) [11, 12]. All the results were subjected to statistical processing according to conventional procedures. The average experimental error for three to four parallel runs was no higher than 6 %. Results and discussion The ionic states of platinum (II, IV) and rhodium (III) in chloride solutions are studied in detail [2, 8, 9, 14, 15]. It is known that they depend on medium acidity and temperature. The system Rh (III) HCl H2Ois characterized by various transformations of complexes as well as by their aquation, hydrolysis, polymerization and isomerization. The hexachloroplatinate (IV) complex PtCl6] 2 predominates in strong acidic media (HCl>3 mol/L).With the dilution of these solutions (increase in pH value), the complexes of platinum (II) are formed, which co-exist in different ratios with chloride complexes of platinum (IV). Moreover, with the decrease in solutions acidity, the hydration and hydrolysis take place. These effects lead to formation of various aquachloro and aquahydroxo- complexes of platinum (II) and platinum (IV): [Pt (H2O)nCl4-n]n 2, [Pt (H2O)k (OH)mCl4m-k]k2, [Pt (OH)nCl4-n] 2, [Pt (H2O)nCl6-n]n 2, [Pt (H2O)k (OH)mCl6m-k]k2, [Pt (OH)mCl6-m] 2 (where n = 1, 2, k = 1, 2, m changes from 1 to 6). Besides that, binuclear complexes [Pt2 (H2O)2(OH)7Cl] can be also present in these systems [9, 1517]. The hexachlororhodiate (III) complex [RhCl6]3 prevails in solutions with hydrochloric acid concentration 6 mol/L or higher. With the decrease in acidity, the formation of aquachlorocomplexes[RhCln (H2O)6-n] 3 n (0<n<6) as well as of cis- and trans-isomerides [RhCl6]3 and [Rh (H2O)Cl5] 2is observed. The polymerization causes the formation of binuclear complexes [Rh2Cl9] 3 [2, 17]. Therefore, the dominant forms of rhodium (III) in the investigated systems are complexes[RhCl6]3 and [Rh (H2O)Cl5] 2 in 2 HCl solutions, whereas in solutions with pH=3, the complexes[Rh (H2O)2Cl4] and [Rh (H2O)3Cl3] 0 as well as cationic complexes[Rh + 2+ (H2O)4Cl2] and [Rh (H2O)5Cl] are also formed in these systems [2, 9, 16, 17]. Figure 1 contains the absorption spectrum of the initial platinum and rhodium solution at their simultaneous presence in 0.01 M HCl. It should be noted that absorption spectra of individual solutions of noble metals, which we have registered previously [18, 19], are in agreement with the data [2, 9, 16, 17]. It can be seen from Figure 1 that the absorption spectrum of freshly prepared chloride solution of platinum (II, IV) and rhodium (III) at their simultaneous presence reveals two absorption maxima at 218 and 251 nm. This is in accordance with works [2, 7]. The maximum at 218 nm indi cates a prevailing presence of complex [PtCl4] 2 and cis- and trans-complexes of rhodium (III) [Rh (H2)4Cl2]+ and [Rh (H2O)2Cl4] in Fig. 1. Absorption spectrum of chloride freshly solution of platinum (II). The second absorpprepared solution of platinum (II, IV) and rhotion maximum located at 251 nm corresponds dium (III) at their simultaneous presence in with hexachloro-complexes of platinum (II), 0.01 M HCl platinum (IV) and rhodium (III) [2].
496
We have studied in our previous works [18, 19] the sorption concentration of Pt and Rh from individual chloride solutions (table 2). In contrast to platinum, rhodium is recovered to a rather low extent by chosen anion exchangers. This is related to higher kinetic lability of platinum chloride complexes in comparison with rhodium complexes. The sorption recovery of both metals at their simultaneous presence in dependence on solutions acidity is presented in tables 3 and 4. It can be seen from these data that simultaneous recovery of Pt and Rh on the same anion exchangers is higher as compared to their individual sorption. It can be seen from the data that all the resins investigated recover more than 85 % of platinum from chloride solutions. However, rhodium is recovered significantly poorer that platinum, with the exception of anion exchanger Purolite S 985. With the decrease in solution acidity, the recovery degrees of Pt and Rh are growing. This phenomenon is caused by the structure of sorbents functional groups. Table 2 Sorption concentration of Pt and Rh from individual chloride solutions (0 (Pt)=0 (Rh)=0.25 mmol/L; (HCl) = 2.0 mol/L)
Purolite 500 85 20 R, % Purolite S 985 95 82 -2B 94 45
Pt Rh
Table 3 Sorption concentration of Pt in the presence of Rh from chloride solutions (0 (Pt)=0 (Rh)=0.25 mmol/L)
Trade name Purolite S 985 Purolite A 500 - B Parameter D, mL/g R, % D, mL/g R, % D, mL/g R, % 4.0 632 86.3 583 85.4 696 87.4 2.0 835 89.3 802 88.9 818 89.1 (HCl), mol/L 1.0 0.5 844 1471 89.4 93.4 900 1918 90.0 95.1 952 1342 90.5 93.2 0.1 1735 94.6 2093 95.4 2302 95.8 0.01 3151 96.9 5486 98.2 7071 98.6
Table 4 Sorption concentration of Rh in the presence of Pt from chloride solutions (0 (Pt)=0 (Rh)=0.25 mmol/L)
Trade name Purolite S 985 Purolite A 500 -2B Parameter D, mL/g R, % D, mL/g R, % D, mL/g R, % 4.0 1143 91.9 119 54.4 99 50.7 2.0 1554 93.9 120 54.5 146 59.4 (HCl), mol/L 1.0 0.5 1584 1594 94.0 94.1 125 169 55.5 62.8 226 235 69.3 70.2 0.1 1635 94.2 181 64.4 303 75.2 0.01 3024 96.8 223 69.1 355 78.0
It is known [10], that the ability of complexing ion exchangers (AM-2B and Purolite S 985) to formation of resin complexes can be estimated by degree of protonation of their functional groups. With the increase in pH of contacting solution, the deprotonation of nitrogen atoms of aminogroups is growing, i. e. their ability to complexation increases. Therefore, in strong acidic media (CHCl = 4 mol/L) the functional groups are completely protonated, and the weak base anion exchangers recover chloride complexes of platinum (II, IV) and rhodium (III) only through the ion exchange mechanism. With the decrease in solution acidity, when deprotonation of functional groups takes place, the additional complexation occurs beside the anion exchange between platinum or rhodium and nitrogen atoms of functional groups. The strong base anion
497
exchangers with quaternary ammonia base groups, unlike the weak base resins, do not possess the complexation ability. The recovery of platinum group metals on these sorbents practically does not depend on pH of contacting solution. In strong acidic media, the competing effect between complex anions of platinum or rhodium and chloride ions can take place during their sorption on strong base resins. Accordingly, the lesser the concentration of chloride ions is in solution, the weaker is their competing effect. This causes the higher recovery degree of Pt and Rh on anion exchanger Purolite A 500. Moreover, the lower recovery of rhodium (III) in comparison with platinum (II, IV) can be explained by greater kinetic inertness of its chloride complexes, especially in weak acidic media, owing to presence of neutral and charged aquacomplexes[Rh (H2O)3Cl3] 0, [Rh (H2O)2Cl4] , 2 [Rh (H2O)Cl5] [2]. To determine the mechanism of sorption concentration of Pt and Rh on chosen anion exchangers, we have registered the Raman spectra of these sorbents in initial chloride form and after saturation by solutions of noble metals. Figure 2 contains the Raman spectra for anion exchanger Purolite S 985. The comparison of resin spectra in initial form and after saturation with platinum in 0.01 M HCl (fig. 2 a) shows that two bands appear at 311 and 342 m1. They correspond to vibrations of NPtt bond, which is characteristic for complexation in the resin phase [20]. Moreover, these bands characterize vibrations of anions [PtCl4] 2 and [PtCl6] 2 in the anion exchanger phase, sorbed during the ion exchange [10, 20]. Comparing the Raman spectra of platinum in 1.0 M HCl and in 0.01 M HCl between themselves, the notable smoothing of band intensity is observed at 311 and 342 m-1 in case of strong acidic solution. These changes can be attributed to protonation of nitrogen atoms of functional groups in anion exchanger Purolite S 985.
Fig. 2. Raman spectra of anion exchanger Purolite S 985 saturated with platinum (a) and rhodium (b) The Raman spectrum of this sorbent saturated with rhodium solution contains two evident bands at 343 and 315 m1, which correspond to vibrations of NRh bond in the resin [10, 20]. In addition, the band at 343 m1 characterizes vibrations of complex anion[RhCl6]3sorbed through ion exchange mechanism (fig. 2 b). Therefore, the presented data show the mixed sorption mechanism of platinum (II, IV) and rhodium (III) chloride complexes on anion exchanger Purolite S 985. The sorption proceeds according to ion exchange (eq. 9) and to complexation mechanism (eq. 10). The strong base anion exchanger Purolite A 500 recovers Pt and Rh in conformity with anion exchange (eq. 9). The weak base anion exchanger AM-2B recovers rhodium through complexation (eq. 10), whereas platinum is sorbed by mixed mechanism (eq. 9 and 10). , ,
(9) (10)
where =Pt (Rh), L=Cl , n=4, 6 (for Pt) and 6 (for Rh), m=2 (for Pt) 3 (for Rh). The isotherms of platinum (II, IV) and rhodium (III) sorption were plotted for the anion exchangers investigated. These curves for the resin Purolite S 985 are presented in Figure 3. It is known [10, 11, 13] that their shape is an evidence of sorption selectivity.
498
It can be seen from figure 3 that isotherms are convex curves, indicating the selectivity of resins during ion exchange. Such isotherms are classified to Langmuir isotherms described as follows: K C eq EC = EC + , (11) 1 + K C eq where EC and EC are the equilibrium exchange capacity and the maximal exchange capacity of the resin to Pt or Rh, respectively, mmol/g; eq is the equilibrium Pt or Rh concentration, mmol/L; is the apparent constant of ion exchange equilibrium, L/mmol.
Fig. 3. Sorption isotherms of Pt in the presence of Rh (a) and Rh in the presence of Pt (b) on anion exchanger Purolite S 985 from chloride solutions (C (Pt)=C (Rh)=0.5 mmol/L) By transforming the equation (11) to the linear form:
1 1 1 1 = + EC EC EC K Ceq,
(12)
we calculated ion exchange equilibrium constants as well as values of maximal equilibrium exchange capacity and determination coefficients (R 2), which are summarized in tables 4 and 5. Table 4 Linear correlation of obtained sorption isotherms of platinum in the presence of rhodium from chloride solutions and parameters of Langmuir equation
Trade name Purolite -500 Purolite S-985 -2B 0.33 0.45 0.67 C (HCl)=2.0 mol/L 2.05 1.71 1.36 R2 0.962 0.992 0.970 0.41 0.36 0.38 C (HCl)=0.01 mol/L 6.25 6.33 8.12 R2 0.991 0.983 0.993
Table 5 Linear correlation of obtained sorption isotherms of rhodium in the presence of platinum from chloride solutions and parameters of Langmuir equation
Trade name Purolite -500 Purolite S-985 -2B 0.09 0.49 0.17 C (HCl)=2.0 mol/L 1.24 2.33 1.12 R 0.945 0.997 0.964
2
C (HCl)=0.01 mol/L 0.11 0.32 0.16 1.43 5.35 1.40 R2 0.947 0.999 0.986
It can be seen from tables 4 and 5 that the apparent constants of ion exchange equilibrium on anion exchangers investigated correlate with the selectivity of sorbents. Table 6 contains the separation factors of platinum and rhodium on the resins investigated. These values are more than 1, i. e. the separation of noble metals can be carried out during their recovery from freshly prepared chloride solutions.
499
Table 6 Separation factors of platinum and rhodium (HCl) Purolite -500 Purolite S-985
S 2.0 0.01 5.51 6.46 1.20 1.90 -2B 4.17 5.25
Therefore, all the anion exchangers investigated reveal a high affinity to platinum (II, IV) and rhodium (III) at their simultaneous presence, especially complexing resin Purolite S 985, which possesses the best sorption properties. Further we have studied kinetics of Pt and Rh sorption at their simultaneous presence from chloride solutions. The dependences of concentration process rate on time are represented in figure 4 for anion exchanger Purolite S 985.
Fig. 4. Kinetic curves of concentration process rate for Pt in the presence of Rh (a) and Rh in the presence of Pt (b) on anion exchanger Purolite S 985 in dependence on HCl concentration ( (Pt)= (Rh)=0.25 mmol/L) It can be seen from the figure 4 that the resin Purolite S 985 possesses good kinetic properties, since the process rate is high. Over a period of 20 min, the resins investigated are saturated with platinum to 5081 % and with rhodium to 3680 % of their total exchange capacity. The rate of sorption concentration is higher in weak acidic solutions. This fact is in accordance with the supposed process mechanism. It should be noted that the sorption rate of platinum and rhodium from strong acidic solutions is also high. Further we have determined the kinetics type during sorption of platinum and rhodium using the Boyd Adams model with the corresponding criteria [13]. Figure 5 contains the dependences Bt=f(t), which are consistent with the above-mentioned model for gel kinetics of ion exchange. It can be seen that these dependences are linear for all the resins investigated. It means that the whole sorption process is controlled by interdiffusion of the ions exchanged in a resin grain.
Fig. 5. Kinetic dependences of Bt function on time t for anion exchanger Purolite S 985 according to the Boyd Adams model for gel kinetics and effect of HCl concentration: (a) sorption of Pt in the presence of Rh; (b) sorption of Rh in the presence of Pt ( (Pt)= (Rh)=0.25 mmol/L)
500
Table 6 Kinetic parameters of sorption concentration of Pt (II, IV) and Rh (III) at their simultaneous presence from chloride solutions
Trade name Purolite 500 Pt C (HCl) 2.0 0.1 0.01 2.0 0.1 0.01 2.0 0.1 0.01 2.0 0.1 0.01 2.0 0.1 0.01 2.0 0.1 0.01 t1/2, s 427 356 306 1363 905 658 308 206 174 363 258 182 531 338 307 1501 517 488 D10 8, m 2/s 3.71 4.45 5.18 1.16 1.75 2.41 5.15 7.69 9.11 4.37 6.14 8.71 7.64 12.00 13.21 2.70 7.85 8.31
10 5, mmol/gs
1.60 2.57 2.80 0.79 0.90 1.23 3.45 4.08 6.41 2.61 3.56 3.76 1.84 2.04 2.98 0.83 1.62 2.02
Rh
Purolite S 985
Pt
Rh
-2B
Pt
Rh
It can be seen from table 6 that average diffusion coefficients are on the level of 108 cm 2/s and the sorption rate is on the level of 105 mmol/gs. With the increase in acid concentration in contacting solution, the half-exchange time is shorter, whereas the values of diffusion coefficients become greater for all the sorbents investigated. In case of rhodium recovery, the diffusion coefficients values are bigger and the half-exchange times are shorter than for platinum sorption. Therefore, the kinetic parameters comply with our perception of the resins selectivity. Based on the results obtained, the investigated anion exchangers can be recommended for recovery of chloride complexes of platinum (II, IV) and rhodium (III). REFERENCES 1. Buslaeva T. M. Platinum group metals and their role in contemporary society.//Sorosovskiy Obrazovetelny Zhurnal. 1999. V.11. P. 4549. 2. Zolotov Y. A., Varshal G. M., Ivanov V. M. Analytical chemistry of platinum group metals. Moscow: Editorial URSS, 2003. 592 p. 3. Spektor, O. V.; Ryumin, A. I.; Pochekutova, M. G. Methods for recovery of platinum group metals from spent catalysts.//Tsvetnye Metally. 1998. V.7. P. 3139. 4. Fontas C., Hidalgo M., Salvado V. Adsorption and preconcentration of Pd (II), Pt (IV) and Rh (III) using anion-exchange solid-phase extraction cartridges (SPE)//Solvent Extraction and Ion Exchange. 2009. V. 27. P. 8396. 5. Pechenyuk S. I. Sorption-Hydrolytic Precipitation of Platinum Group Metals. Leningrad: Nauka, 1991. 248 p. 6. Chugaev L. V. Metallurgy of noble metals. Moscow: Metallurgiya, 1987. 433 p. 7. Beamish, F. E. Analytical Chemistry of the Noble Metals. Oxford: Pergamon Press, 1968, 702 p. 8. Livingstone S. E. The Chemistry of Ruthenium, Rhodium, Palladium, Osmium, Iridium and Platinum. Oxford: Pergamon Press, 1967. pp. 155180. 9. Ginzburg S. I., Yezerskaya N. A., Prokofieva I. V. Analytical chemistry of platinum group metals. Moscow: Nauka, 1972. 617 p. 10. Saldadze K. M., Kopylova-Valova V. D. Complex-forming ion exchangers. Moscow: Khimiya, 1980. 356 p.
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11. Helfferich F. Ion Exchange. New York: McGraw Hill, 1962. 350 p. 12. Helfferich F. Ion exchange kinetics. In: Marinsky J. A. (Ed.) Ion exchange. A Series of Advances. Buffalo, New York: McGraw Hill, 1967, pp. 281331. 13. Kokotov Y. A., Pasechnik V. A. Equilibrium and kinetics of ion exchange. Leningrad: Khimiya, 1970. 243 p. 14. Cotton F. A., Wilkinson G. Advanced Inorganic Chemistry. A Comprehensive Text. New York: Wiley and Sons, 1969. 410 pp. 15. Kukushkin Y. N. Chemistry of coordination compounds. Moscow: Vysshaya shkola, 1985.455 p. 16. Sinitsyn N. M., Buslaeva T. M. Chemistry of halide complexes of platinum group metals. Moscow: Rosvuznauka, 1992. 79 p. 17. Buslaeva T. M., Umreyko D. S., Novitskiy G. G. Chemistry and spectroscopy of halides of platinum group metals. Minsk: Izdatelstvo Universitetskoe, 1990. 241 p. 18. Kononova O. N., Leyman . ., Melnikov A. M., Kashirin D. M., Tselukovskaya M. M. Ion exchange recovery of platinum from chloride solutions//Hydrometallurgy. 2010. V. 100. P. 161167. 19. Kononova O. N., Goncharova E. L., Melnikov A. M., Kashirin D. M., Kholmogorov A. G., Konontsev S. G. Ion Exchange Recovery of Rhodium (III) from Chloride Solutions by Selective Anion Exchangers//Solvent Extraction and Ion Exchange. 2010. V. 28 (3). P. 388402. 20. Nakamoto K. IR-spectra and Raman spectra of inorganic and coordination compounds. Moscow: Mir, 1991. 536 p.
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PROSPECTS OF USE OF THE NONFERROUS AND RARE METALS CONTAINING IN COALS AND COAL ASHES OF KUZBAS FOR THE IRON AND STEEL INDUSTRY OF SIBERIAN REGION
V.A. Salikhov, E.S. Ljubushkina Novokuznetsk branch of the institute state educational highest vocational institution Kemerovo State University, Novokuznetsk, Russia
Development of scientific and technical progress, introduction of scientific achievements in various areas of the industry (aviation, space etc.) have led to increase in the requirement for many nonferrous and rare metals, but they are mostly claimed in an iron and steel industry where it is made about 70 various metals, and also in a machine-building complex. Within last decade world extraction has increased on: nioby 35 %, tantalum 15 %, titan 32 %, copper and antimony 30 %, molybdenum 24 %, tin and bauxites on 10 % [1, 2, 3]. Placing of manufactures on extraction of metals and the extraction is defined by a number of factors: geological (metalloheric territory specialisation), economic (demand for mineral raw materials, conditions of working out of deposits), historical (formation of an infrastructure of mining and mountain-metallurgical areas), political (basically, an export-import policy) and social (preservation and creation of workplaces by means of government support, i. e. special state social programs). Prominent aspect for development of a mineral-raw-material base (MRB) of metal minerals are factors of placing of metallurgical manufacture: raw (location of manufactures near to sources of mineral raw materials), fuel and energy (affinity of manufacture to cheap sources of the electric power) etc. Now the great value gets the consumer factor (capacity of commodity markets), and also the transport factor. The important tendency of placement of the metallurgical enterprises is gravitation to the centers of consumption of the metals, having the corresponding infrastructure, the prepared qualified manpower etc. Besides, the establishment of close connections of the metallurgical enterprises with their clients, coordination in manufacture and sale planning is observed. For the nonferrous metallurgy enterprises it is now noticed worldwide strengthening tendency of the power orientation in the enterprises placing that can be explained by the development of metallurgy of light nonferrous metals and rare metals. Besides, it is observed a shift of metallurgical manufacture into developing countries which have more mineral raw materials. As a whole, as a result of the theoretical analysis of MRB rare and nonferrous metals, it is possible to draw following conclusions: Metal minerals, including nonferrous and rare metals, are claimed in many industries of the world; Consumption of nonferrous and rare metals grows all over the world, thus in developing countries the bottom stages of a production cycle prevail, and in economically developed countries high stages (including manufacture of rare metals); Economically developed countries pursue a policy of preservation of own stocks of mineral raw materials, increase import; (for example, Belgium produces metals, without having its own MRB). The considerable volume in manufacture of nonferrous and rare metals occupies secondary raw materials, thus secondary raw materials and metal semiproducts export not only developing countries, but also the economically developed ones (export of semiproducts of aluminium and titan to the developed countries is connected with high power consumption of their manufacture); Formal security by mineral raw materials of the majority of nonferrous and rare metals is high (tens and hundreds years), and real security, taking into account growth of extraction and consumption of metals and deterioration of mountain-geological and economic-geographical service conditions of ore deposits, is much less. All factors set forth above and tendencies of development of mountain-metallurgical manufacture are of great influence on development of MRB valuable rare and nonferrous metals both in the world and in the Russian Federation.
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Analysis MRB of nonferrous and rare metals in the Russian Federation shows that the Russian Federation, despite the crisis phenomena of a transition period, on the former takes leading places on stocks, extraction and consumption of the majority of nonferrous metals. At the same time it is necessary to notice that almost all deposits of nonferrous metals of Russia differ from geografo-economic conditions of working out that reduces profitability of their development. As consequence, the share of active stocks decreases, because of the high prices for the electric power and transport transportations, more than half of reconnoitered deposits of nonferrous and rare metals are unprofitable. Thus in connection with gradual lifting of the domestic industry by 2020 in the country growth of consumption of nonferrous metals (approximately in 1.52 times) [1] is predicted. Analysis MRB of rare metals in the Russian Federation shows that consumption of rare metals all over the world actively grows, and it will be obligatory to grow in Russia; Russian MRB possesses large stocks of almost all rare metals, but in a qualitative sense requires improvement; developments MRB of strategic rare metals demand interests of national safety. To the list of strategic kinds of the mineral raw materials, confirmed by the Order of the Government of the Russian Federation 50 from 1/16/1996, from among rare metals are mentioned Li, Be, Nb, Ta, TRY, Zr, Ge, Re, Sc [3]. Thus, carried out analysis MRB of nonferrous and rare metals in the world and in the Russian Federation confirms an urgency of use of the valuable nonferrous and rare metals containing in a waste of mineral raw materials. In the Kemerovo region considerable volumes of a waste of the mineral production which great part is made by ashes-slag waste of coals are saved up. They correspond to definition of technogenic deposits, as large-tonnage congestions of a waste of extraction and processing of mineral raw materials which can be used with economic effect. Thus it is possible to form such deposits by kinds of passing useful components taking into account their structure and concentration. The complex geologo-economic estimation of deposits based on the account of the basic and passing useful components, essentially raises economic potential of the reconnoitered stocks, allows to conduct their rational working out, and also promotes introduction in operation of remunerative deposits. Now technologies of extraction from mineral raw materials and a waste of many valuable metals, the last laboratory and semiindustrial tests are developed. A number of metals is taken in small amounts in the industrial way (Ge, V, Ti, Zr). For example, the brazilite for zirconium production is taken in small volumes from Hibin apatite deposits nepheline, grothite for getting titanic products. As a whole, complex working out is spent insufficiently, and an accumulated waste of extraction and processing of mineral raw materials, i. e. technogenic deposits are also used in small volumes. It can be explained by insufficient financing of research and development, the high cost price of experimental technologies, ecological danger of developed methods on extraction of metals. At the same time, decrease in profitable stocks of ore minerals assumes necessity of extraction of metals from complex ores, and also their extraction from technogenic deposits. Efficiency of working out of technogenic deposits, according to the author, is possible to estimate by means of the differential rent I (in comparison with ore deposits) and II (in comparison of methods of extraction of metals from a waste of mineral raw materials), and also by means of the dynamic rent (the additional income during the late periods of time). Thus the main methodological principles at an economic estimation of technogenic deposits are principles of systematic and integrated approach. The principle of systematic allows to consider not only geological, but also technological, and also social and economic and ecological aspects of realisation of projects on extraction of metals, for example from a waste of coal production. The integrated approach principle allows to carry out researches on the basis of mountain-geological and social and economic methods. The great value has a dynamic principle, and also a principle of priority development. The dynamic principle provides regular tracing of a situation, especially external social and economic and ecological factors, for acceptance of adequate decisions. The principle of priority development allows to predict situations in the markets of mineral raw materials for 1020 years. One of perspective directions of providing of an iron and steel industry with valuable and extremely scarce metals is use of coals and a coal waste which are estimated as a potential rawmaterial base of an iron and steel industry. For example, ashes-slag waste of the USA could provide not less than half of annual requirement of the country in such elements, as As, Be, Co, Ga, Ge, Hf, Nb, Se, Sr, , Tl, Y, and also in rare-earth elements. From this waste even at modern technologies such metals, as Al, Cd, Ga, Ge, Fe, Mo, Ti, V and Zn can be taken out. Separate coals with raised (more than 5 gr/ton) the content of germanium are considered as ore. [4].
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The Kuznetsk basin is one of the largest coal fields of the world with the reconnoitered stocks of coals about 60 billion ton, including 30 billion ton coked coals and about 20 billion ton coals of especially valuable marks; annual extraction makes more than 100 million ton. The estimation of the maintenance of valuable nonferrous and rare metals in coal deposits on geologoeconomic region of Kuzbas, made on the basis of the received by the author data, and also on the basis of the theoretical analysis of works of other researchers, has shown the following: 1) On deposits of Kuzbass there are some anomalies of several valuable rare and nonferrous metals (such as: Ti, Zr, V, W, Y, Co, Ga, Ge, Nb, Be) which are more often connected with tectonic breaks of layers, especially if layers are located near intrusive files. 2) Basically, the raised concentration of these metals are observed in southern and southeast geologo-economic region (Bajdaevsky, Bachatsky, Mrassky, Tom-Usinsk, Uskatsky, Osinovsky). 3) Practical interest, from the point of view of concentration of the metals, recommended to an estimation, can represent the titan and zirconium, and also a number of nonferrous and rare metals (Sr, Zn, Pb, Cu, V). Under a condition of complex extraction some interest also represent Ga, Ge, Be, Nb, W. 4) Actually nonferrous metals form, as a rule, insignificant anomalies in zones of tectonic broken layers, which more often connected with located hypsometric lower ore bodies of polymetallic deposits. The raised concentration on layers are formed only by aluminium (to 10 % and more). 5) Average maintenance in coals of rare and rare-earth metals are close to clarke maintenances or below it; practical interest (at selective working off and complex extraction) is represented by the anomalies of metals dated for zones of tectonic breaks. 6) a number of nonferrous metals (copper, zinc, lead), forming on separate coal deposits on layers of anomaly of hydrothermal genesis can be taken together with rare metals, and aluminium (in the presence of requirements and technologies) separately. 7) Special practical interest is represented by ashes-slag waste of processing of coals in which the maintenance of valuable nonferrous and rare metals can increase to 10 times and more. 8) In Kuznetsk coals steady concentration of precious metals (gold, platinum and silver) which would represent practical interest are not revealed. 9) The maintenance of radioactive elements (uranium and thorium) in Kuznetsk coals is much lower, than in other coal basins, but it is necessary to reveal their abnormal concentration representing ecological danger. 10) The maintenance of some toxic metals (mercury, chrome, arsenic, etc.) in Kuznetsk coals does not exceed 23 g/t, as a rule, and more often it is much lower; their extraction can be made together with valuable nonferrous and rare metals, regarding ecological reasons. Thus, the greatest interest for practical use represent titan and zirconium, and taking into account complex extraction zinc, barium and vanadium, occasionally manganese and yttrium, and in perspective strontium, niobium, gallium and germanium. Toxic and potentially toxic elements (arsenic, beryllium, manganese, nickel, lead, chrome, etc.) are revealed, but their maintenance is much less than maximum concentration limit, therefore their passing extraction is expedient. Practical interest to complex use of mineral raw materials is supported recently with perfection and creation of new technological schemes of enrichment and extraction of metals. For example, there is variety of the technological methods allowing to utilize effectively some kinds of ashes-slag waste for the purpose of extraction of some useful components from them. Thus, in the middle of the XX-th century they extracted aluminium and iron. The aluminium maintenance in coals exceeds 10 % that makes possible its industrial extraction. The magnetic fraction contains from 30 to 60 % of iron, and also in small amounts cobalt, nickel, titan and other valuable nonferrous and rare metals [4]. In the Kemerovo region the large metallurgical enterprises of black and nonferrous metallurgy (ZSMK, NKMK, Novokuznetsk aluminium and Kuznetsk ferroalloys factories) are located. Considering poor quality and great labour expenses while enriching local aluminium ores (bauxites and nepheline syenite), aluminium can be considered perspective additional mineral raw material. Low security of Siberian region with profitable iron-ore makes extraction of iron and other ferrous metals from ashes-slag waste deposits perspective. [5]. Directly from coals in the course of coking or from harms of ablation at power-generating coal burning they receive germanium. The basic source of its obtaining in the USSR was coal. Germanium is made basically on chemical-recovery factories from Donetsk coals or from germanium-rich power-generating coal. The technology of complex extraction germanium, gallium and other rare elements from cindery ablations is well fulfilled. Extraction of scandium from
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coals, very expensive metal with small volumes of extraction is perspective both in Russia and in the world, however the process of preliminary enrichment of ashes is extremely complicated: primary opening and metal transfer in a solution with an exit 6080 % is possible only in an autoclave that makes the process considerably more expensive. One of effective ways of decision of this problem is sorption leaching of ashes-slag waste. Similarly, i. e. with the help of leaching (for example, thermochlorination), it is possible to take gold, lithium, vanadium, tungsten, yttrium, rare-earth and other elements. So, from ashes-slag waste of power-generating brown coals it is taken to 4067 % of the titan, 4577 % of a beryllium, 7087 % of copper, 5081 % of manganese, 7484 % of arsenic, 4860 % of vanadium and 6283 % of gallium [4]. Predesigns show that on one pilot production on extraction of metals from ashes by a method of thermochlorination it is possible to process 2 thousand ton ashes within a year and to receive nearby 10 ton of titan, 10 ton zirconium, 1 ton vanadium and 100 kg of gallium. Thus the net profit will make about 30 million rbl. Shop on processing of ashes-slag waste can be a part of a mine, and the project can work on the basis of cooperation of tehnologo-economic relations between the coal-mining, processing, fuel and energy and metallurgical enterprises, i. e. to include consumers of coal and suppliers of ashes [5]. Calculation of stability of the project shows, that even capital and operational expenses increase to 100 % ( 1015 % a year) and profit reduces also to 2 times, the project pays off within 5 years. In 2006 the rise in prices for nonferrous and rare metals has considerably outstripped increase in cost of capital and operational expenses (table 1). Table 1 Change of the prices for metals (20002006)
Mineral raw materials and repartition products Tungsten Vanadium Aluminium metal Strontium metal Copper refined Nickel Tin Lead Zinc Molybdenum titan spongy Zirconium spongy Nioby Gallium Germanium Unit 2000 kg kg kg kg kg kg kg kg kg kg kg kg kg kg kg 10 10 1.5 60 22.5 58 5.57 0.60.9 11.3 510 10 25 6075 380400 8251300 Price, US dollar 2006 45 40 2.53 120 711 3035 1015 1.52 3.54 80 20 30 230240 1200 2500
The prices (in 2006 in comparison with 2000) on aluminium, lead, tin, cobalt have increased 2 times, on zinc, nickel, gallium in 3 times, on vanadium and tungsten 4 times, and on copper 5 times. By December, 2008 there was a sharp reduction of prices on nonferrous metals (1.52 times), the prices for the majority of rare metals till August, 2009 remained steady and had tendencies to grow, but then the prices have decreased (> 50 %). By the end of 2009 the price for rare metals have returned on level of August, 2009; the price on nonferrous metals in 2009, basically, had tendencies to decrease, the insignificant rise in prices is noted by the end of the year. This data confirms unstable character of the market of valuable nonferrous and rare metals. At the same time dynamics of the prices is in the limits providing stability of the project of valuable metals extraction.
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Operation of technogenic deposits allows to save considerable financial means (hundred million rbl. and more) on carrying out geological surveyance and building of the mining enterprises (indirect effect), and also improves an ecological situation. Ashes deposit areas of fuel-power stations in Kuzbas occupies several thousand hectare, and their volume is about 40 million ton. Taking into account high cost of farmland of 1 hectare (> 1 million rbl.) and expenses for storage of sailings 20 rbl./t a year, ecological effect is considerable and reaches the sum of hundreds million rbl. Thus, realisation of the project of valuable metals extraction from ashes-slag coal waste, leads to considerable total economic effect for the region. Besides, low expenses of processing ash disposal area to get concentrate (according to the available data about 1000 rbl./t), preferential taxes on subsoil use, on profit, VAT decrease, the high prices for metals and value factor of metals extraction from a concentrate ( 1), allow to lower size of the minimum maintenance, i. e. take f larger spectrum of valuable nonferrous and rare metals. In Kuzbas annually collects to 15 million ton of ashes-slag waste (including metallurgical and other enterprises one), where out of 2.6 million ton of an annual exit of ashes and slag of fuel-power stations, 2.4 million ton by the way of hydroremoval goes to sailings in the form of ashes-slag mixes, (now it is accumulated 40 million ton of them and it is possible to use not less than 20 million ton in concrete and solutions.). With the account of low maintenances of the majority of nonferrous and rare metals in coals (basically these are epigenetic and, less often, syngenetic anomalies), extraction of valuable nonferrous and rare metals from ashes-slag waste of fuel-power stations represents practical interest, where their stocks can make thousands ton, ten thousands ton and more (table 2). Valuable metals can be taken also from ashes of ablation, where their maintenance 23 times more than in ash disposal area. Table 2 Maintenances of some nonferrous and rare metals in Kuzbass coals
Metal Maintenance in coals, g/t 100500 100500 up to 15 up to 25 10300 200 up to 50 up to 3 100500 13 13 up to 1 Concentration recommended to an estimation, g/t 500 500 100 50 100 1000 100 100 1000 100 20 10 Maximum maintenance in ashes, g/t 5600 3000 3700 4800 16000 5800 5000 1500 2300 3000 3000 2700 Standards for ores, % 1015 3 0.5 2 1 1 1 0.51 5 0.1 0.04 0.1
Titan Zirconium Copper Lead Zinc Barium Vanadium Tungsten Strontium Nioby Gallium Germanium
Considering high demand of the industry of the Russian Federation for titan and Zirconium (accordingly: 600700 and 100 thousand ton a year) and low level of extraction (5 and 3 thousand ton a year), carried out on Lovozersky and Kovdorsky ore-dressing and processing enterprise (Murmansk area) and, hence, a high share of import it is necessary to consider expediency of passing extraction of these scarce metals on the basis of available skilled technologies of their extraction from ash-slag waste (for example, leaching, thermochlorination, etc.), which are less power-hungry in comparison with traditional ones (processing titan and zirconium rich silicates). Besides, considering requirement of nuclear technics, electronics in Sr, Y, Ga and Ge the careful estimation of these and other rare elements in ashes dump of fuel-power stations, with prospect to use these metals in the future, considering technological possibilities of their extraction. Also complex extraction together with rare metals and polymetals, such as Cu, Pb and Zn. is regarded perspective.
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The further development of the industry of Kuzbas, especially metallurgy and machinebuilding complex, the increase of local MRB demand some black, nonferrous and rare metals. Competitiveness of the mountain-metallurgical companies is defined by having their own MRB, production assortment, consolidation of separate manufactures. Technogenic deposits can be potential MRB of many valuable nonferrous and rare metals. In the Kemerovo region branches of manufacture of a mountain-metallurgical complex of the industry are traditionally developed. The metallurgical enterprises the Western-Siberian and Novokuznetsk metallurgical industrial complexes (WSMK and NKMK), Novokuznetsk aluminium factory, Open Society Kuznetsk ferroalloys bring the considerable contribution to national economy and areas. Black and nonferrous metallurgy provide about 40 % of industrial output of Kuzbas; 20 % of tax revenues in the regional budget and more than 40 % of currency receipts. In nonferrous metallurgy Novokuznetsk aluminium factory, the fifth enterprise by size in the country, provides more than 90 % of all production in area. The coal-mining companies, the mining enterprises for extraction and processing of ores black, nonferrous and precious metals work actively. Today the Kemerovo region provides more than 50 % of a national coal mining (including 79 % coked marks); more than 50 % of export of coals (basically, coked marks). At the same time it is necessary to note instability of development of Kuzbas economy. The basic sources of the Kemerovo region budget financing the tax to incomes of physical persons (approximately 25 %), payments for using natural resources (more than 10 %), the profit tax (more than 10 %) and the tax to property (about 10 %). To lower the budget deficiency it is necessary to increase incomes by one and a half time. Now manufacture growth occurs, basically, in so-called corporate sectors of economy which include the large mountain-metallurgical companies (Evrazholding, SibCEK, Russian aluminium and others). At the same time slump in production in mechanical engineering and in other not corporate sectors of economy (light, food-processing industry, agriculture etc.) is observed. In area economy the share of small enterprises (especially high technological ones) is insignificant, volume of investments into this sector of economy is insignificant too. The Kemerovo region lags behind the next Novosibirsk and Tomsk areas in sphere of innovative activity of economy. Expenses for technological innovations in Kuzbas three ten times less than in other industrial region analogues. One of variants of development of the high technological small enterprises is creation of compact manufactures on processing of technogenic waste and extraction from them valuable metals. These manufactures can be created as a part of the mountain companies on the basis of cooperation of tehnologo-economic relations between the power and coal-mining enterprises. Thus, small enterprises will get financial support for innovative transformations, i. e. for introduction of methods of extraction of valuable metals from technogenic deposits on the basis of scientific-technical progress. The manufacture diversification will provide additional profit to the coal-mining enterprises, i. e. will raise their financial stability in the conditions of stable work in difficult mountain-geological conditions. Out of ashes dump of fuel-power station accumulated within a year at the power enterprises of Kuzbas area it is possible to take not less than 100 ton Ti, Zr, Sr,> 10 ton V and Ga,> 1 ton Nb, Ge and of some other rare metals. Considering that fact that for extraction of valuable metals can be used not less than 20 million ton accumulated in the Kemerovo region of ashes dump of fuel-power station, it is possible to assume that volumes of extracted metals from them will be 10 times more. Comparing predicted volumes of extraction of valuable metals from ashes-slag waste of the coals accumulated on Kuzbas area territories, with requirements of the industry of the Russian Federation (table 2), it is possible to assume that these metals can be claimed, first of all, in the industry of the Kemerovo region and Siberian region. For example, according to the experts, predicted stocks of rare metals in complex apatite-magnetitovyh and rare metal ores and their waste in Murmansk area (a leading potential source of strategic raw materials of Russia) make billions ton (ores Ti), millions ton (ores Zr), considerable stocks of Ta, Nb and other rare metals. Their annual extraction can make from tens (Ta, Nb) and thousands ton (Li) to tens (Zr) and hundreds thousand ton (Ti). Thus, look-ahead indicators of stocks and extraction of rare metals here are several times above, than in ashes dump of fuel-power station of the Kemerovo region. The metals received from ashes-slag waste of coals of Kuzbas, can be claimed in electrotechnical mechanical engineering of the Kemerovo region, and also on machine-building, ferroalloy and other enterprises of Sibirian Federal Units (Novosibirsk and Irkutsk areas, Krasnoyarsk region). A number of valuable, scarce metals (such as Ti, Zr, Ga, Ge) can be claimed in
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other Russian markets and, probably, on foreign markets. Profit from metal realisation it is possible to define, taking into account conditions of sales spot and future, under the formula: P = (1 Pr 1 + 2 Pr 2 + n Pr n) E, (1)
Where: P profit on realisation of metals, rbl.; 1 n annual manufacture of grades of metals, ton or kg; Pr 1 Prn the high-quality prices per unit of output, rbl.; E expenses for manufacture and realisation of metals, rbl.; Volumes of annual manufacture of metals are defined on the basis of marketing researches of internal and foreign metals markets. Thus, it is possible to consider the ashes-slag waste of the coals which have been accumulated in Kuzbas, as potentially perspective mineralno-raw-material base for an iron and steel industry. It is especially important at increase of demand for metals on a foreign market, and in the near future on internal one. REFERENCES 1. Kozlovskij E. A., Malyutin JU. S.mineralno in economy of Russia//Markshejderija and minerals deposit development. 2002. 2. With. 828, 2002. 3. p. 618. 2. Novikov A. A., Blagutin J. L., Pinchuk A. V.problem of strengthening and expansions of a mineralno-raw-material base of nonferrous metallurgy in Russia//Mountain magazine. 2003. 10. p. 5862. 3. The Mineralno-raw-material base of rare metals in Russia: condition and ways of development/M. F. Komin, T. J. Usova, T. I. Zueva, D. S. Kljucharev, etc.//Investigation and protection of subsoil. 2004. 11. p. 3237. 4. Rare elements in coals of Kuznetsk basin/Arbuzov S. I., V. V. A. A., Rihvanov L. P. Kemerovo, 1999. 248 p. 5. Salikhov V. A. Scientific bases and perfection of a geologo-economic estimation of passing useful components of coal deposits (on an example of Kuzbas)/V. A. Salikhov; SibSIU. 2 edit.,. Kemerovo: Kuzbasvuzizdat, 2008. 249 p.
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RHENIUM EXTRACTION FROM NICKEL-BASED COMPLEX HEAT-RESISTANT ALLOYS

A.G. Kasikov, A.M. Petrova, V.T. Kalinnikov I.V. Tananaev Institute of chemistry and technology of rare elements and mineral raw materials of Kola science centre of RAS, Apatity, Russia
Rhenium recycling has recently become a burning issue. This is due to many factors, the principal one being runaway prices resulting from disbalance of supply-demand at the rhenium market. Peaking at 2008 (USD 10560\kg) [1], the Re prices remain fairly stable (6600 $/) [1], notwithstanding the ongoing economic crisis. In Russia, there is a special interest in rhenium owing to its loss as the result of the USSR disintegration. Nowadays, both the mineral sources and production capacities are in Kazakhstan, Uzbekistan and Armenia, and the Russian machine building totally depends on imported rhenium, needing it for the strategic aircraft- and spacecraft industries. Lacking commercially developed raw material resources, we are turning to Re-enriched (up to 79 %) [2] wastes of complex heat-resistant nickel alloys (HRNA). According to VIAM [3], the HRNA annually dumped in Russia amount to 2535 t. Even with an averaged rhenium content of 2.5 %, this may yield about 700 kg rhenium. Moreover, there are other valuable and expensive, rare and nonferrous metals (W, Mo, Nb, Ta, Ni, Co, Cr, etc) contained in multicomponent alloys, that may also be regenerated to achieve a really in-depth processing of the starting materials. As of today, we can enumerate several technologies of rhenium recycling from alloys [4]. However, according to A. Lipmann, an authority in the minor-metal issues [5], the industrial application of the methods for HNRA processing is limited due to their high cost (1 kg of secondary rhenium costs ~3000 USD\kg) and low effectiveness (the yield is ~70 %). Hence is the necessity to develop effectual technologies of rhenium recovery from HRNA. This work deals with rhenium recycling from the following products: From grinding wastes of HRNA parts of the ZhS-32 type (fig. 1), representing a finegrained powder (<0.16 mm, >95 mass/ %); From HRNA lump debris (up to 5 kg) of the ZhS-32 alloy (fig. 2).
Fig. 1. Rhenium-containing grinding wastes of HRNA The grinding of HRNA lump debris
Fig. 2. HRNA lump debris (ZhS-32 alloy)
As multicomponent products, HRNA are separated using pyrometallurgical methods [4]. The problem in this case consists in grinding the high-strength lumps (for instance, blades and other elements of turbine engines weighing several kg). Proceeding from own experience of hard nickel alloys processing [4], we proposed high-temperature alloying of the lumps with granulated aluminium. Melting at 15001700 o in an induction furnace for 0.5 h yielded a homogeneous alloy of a 4-kg charge with a mass ratio of m (alloy) : m (Al)=5:1. The nickel base of HRNA was converted to Ni3Al aluminide characterized by brittleness at low-temperatures, which permitted to grind the alloy after cooling in standard equipment (jaw crusher, disc attritor). Both the grainsize composition of the resulting alloy and the chemical composition of starting and dispersed rhenium-containing alloy wastes are presented, respectively, in tables 1 and 2.
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Leaching of HRNA wastes Analysis of technological solutions proposed for the processing of rhenium-containing alloy wastes (for details, see [4]) has revealed that irrespective of the decomposition method, rhenium can be extracted by two ways: by directly passing rhenium from wastes to solution (using, for instance, oxidizing distillation of Re2O7 and trapping the sublimate to solution; by oxidizing-thermal decomposition followed by leaching of the cake with water; by electrochemical oxidizing or acid leaching in oxidizing media); leaching of the alloy base metals and concentrating rhenium in the residue, wherefrom it is extracted (using electrochemical and acid methods to dissolve the base) We have tested acid leaching of rhenium-containing alloy wastes both in oxidizing environment and in the absence of an oxidizer. The leaching of fine-grained products in laboratory conditions was performed in 2-litre, mechanically agitated constant-temperature open glass reactors on the basis of IKA Werke elements. Table 1 Grain size of the ground product obtained after melting of lump wastes with aluminium
Fraction, mcm Content, mass % 250300 13.06 200250 9.54 160200 10.45 125160 13.80 71125 15.00 4071 16.25 -40 21.90
Table 2 Starting product composition

Product ZhS-32 alloy Grinding wastes Ground alloy with Al Ni 61.0 61.0 48.0 Co 9.0 6.8 6.3 Cr 4.9 3.4 3.1 Content of elements, mass % Mo W Re 1.0 8.5 2.6 0.9 4.3 2.3 0.9 6.5 1.5 Al 5.9 18.2 32.0 Ta 2.1 1.6 1.1 Nb 1.6 1.1 0.7
The leaching of rhenium-containing wastes in oxidizing conditions was performed by 1.5 6 mole/l H2SO4 solutions at S:L=1:1020 and a temperature of 7085 o. Since earlier it has been established that adding a peroxide oxidizer at the initial stage is undesirable due to a highly intensive interaction between the active fine-grained materials and H2SO4 with H2 evolution and self-heating of the reaction mixture to 7090 o, the first 23 hours the process was carried out without an oxidizer. After the reaction of the metal components with H2SO4 was largely over, the reaction mixture was gradually supplied with an oxidizer (for 1.52 h). At different times, the oxidizers were H2O2, Na2S2O8, (NH4)2S2O8, K2S2O8 solutions. Satisfactory results were obtained only with the first two reagents. In the latter two cases, the components extraction to solution was insufficient either due to the formation of nickel-ammonia alums or low solubility of potassium perrhenate. The concentrated oxidizing solution was fed to the reactor either in discrete portions every 10 minutes, proceeding from Voxid.:Vleach sol.=1:5, or continuously, drop-wise, at a rate maintaining the assigned redox potential value (RDP). The continuous feeding was performed using a Masterflex C/L microdosing peristaltic pump. The RDP was controlled by measuring it in the reaction mixture relatively the chlorine-silver-saturated electrode at a Tsch-300 digital voltammeter. The acids tested for the leaching of the alloy base were hydrochloric and sulphuric ones. The process occurred similarly to that described above, until the reaction between the metallic components and mineral acid (for 23 h) was over. In view of the vigorous H2 evolution in the case of fine-grained alloy and HCl interaction, the material was fed in batches. For non-ferrous metals, the resulting solutions were analyzed by the AAS method at a Shimadzu ICPE-9000 atom-emission spectrometer. Rhenium and refractory metals were analyzed by the AAS IPC method at a Plasma-400 atomic-emission spectrometer with induction-bound plasma. It was established that in the case of an oxidizer-free acid leaching, the nickel base dissolves, without much rhenium passing to the solution (table 3). The solid phase diminishes by 82 mass %, which makes it possible to concentrate rhenium in undissolved residue, where its content may increase to 9.3 mass %. It should be noted that hydrochloric acid is preferable for base leaching, because there arise no problems with subsequent separation of non-ferrous metals in chloride media. From a solid concentrate containing Re, Nb, Ta, and W, rhenium can be extracted in the form of Re2O7 by either hydrometallurgical methods or by high-temperature distillation.
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Table 3 The level of some elements recovery to solution in an oxidizer-free leached ground alloy with Al. S:L=1:15, =80 o, =3 h
Acid, mole/l 1.5 2.5 3.0 4.0 5.0 3.0 6.0 Acid H2SO4 H2SO4 H2SO4 H2SO4 H2SO4 HCl HCl Ni 89.8 94.2 95.4 92.5 96.2 55.2 83.2 Element recovery, % Mo 11.5 13.0 20.0 30.1 20.2 Re 1.5 2.0 2.1 5.6 8.0 0.3 0.8
An oxidizer, added to acidic leaching, noticeably promotes the rhenium recovery. Since Re is better isolated in sulphuric acid, the leaching of alloy wastes was performed by H2SO4. table 4 presents the results of rhenium, and some other metals, extraction from grinding wastes using different oxidizers in concentrated solutions. Evidently, the most convenient of them is hydrogen peroxide, effectively converting rhenium to solution without introducing impurities. Concentrated H2SO4(10N) solutions are necessary to dissolve the non-ferrous metal base to obtain leaching solutions with high enough acid contents, from which rhenium is extracted by the method described in [6]. able 4 The level of element recovery to solution during the oxidizing sulphuric-acid leaching of grinding wastes of the ZhS-32 type
Oxidizer, Vxid: Vsol=1:5 HNO3 H2O2 Na2S2O8 Ni 99.9 99.8 98.8 Element recovery, % Co Cr Re 99.9 99.8 98.3 98.2 98.6 99.8 70.0 Mo 77.2 80.0 66.9
Special experiments on optimizing of the oxidizer consumption have revealed that a practically total rhenium extraction can be achieved by adding hydrogen peroxide in amounts necessary to maintain ROP at 0.550.75 V for 23 hours, which noticeably reduced the H2O2 consumption compared with similar experiments. Rhenium solvent extraction from waste leaching solutions For selective solvent extraction of rhenium from HRNA waste leaching we tested, on both laboratory and larger, scales the extraction with secondary octyl alcohol [6]. This extractant is selective vis- -vis rhenium in a sulphuric acid medium in the presence of molybdenum and other non-ferrous metals [7]. Having a high capacity in terms of rhenium (~100 g/l), it can isolate this element from fairly concentrated solutions. In laboratory experiments, extraction from leaching solutions was carried out in glass separating funnels with a volume of 0.250.5 l at a room temperature (202 o) and under mechanical agitation. The extractant was domestic, pure brand 2-octanol, available and inexpensive. To prevent additional extraction of the acid from leaching solution, the extractant was preliminarily saturated with H2SO4. The time of contact between the phases was 5 min, the O:W ratio varied between 15:1, depending on operation. According to laboratory data, extracting from a solution after polishing wastes leaching containing, g/l: Ni 36.0; 5.7; r 3.6; 0.7; W 0.01; Re 2.4 and 4.2 mole/l H2SO4 in one stage at :W=1:1 yielded 97.9 % rhenium at a 22.8 % co-extraction of . After washing with water at :W=2:1, the bulk of Mo, not more than 20 % Re and practically the entire of co-extracted H2SO4 passed to the scrubbing water. After re-extracting with a 3 mole/l NH4OH solution at :W=1:1, we obtained a solution containing 1.9 g/l Re and 0.04 g/l , which means a 79.0 % level of rhenium extraction.
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Similar results were obtained in the course of an experiment with leaching solutions of ground alloy with added Al. The leaching solution had a concentration of, g/l: Ni 21.8; Co 3.0; Al 15; Cr 1.4; Mo 0.36; W 0.25; Re 0.75 and 3.7 mole/l H2SO4. In one stage at :W=1:1, the extraction to the organic phase was 97.3 % Re and only 19.4 % Mo, with 61.9 % of the latter and the bulk of H2SO4 recovered in a one-step scrubbing at : W =5:1, at an insignificant removing of rhenium. So, re-extracting with 3 mole/l NH4OH resulted in a purified rhenium-containing solution with rhenium and molybdenum concentrations of 0.5 g/l and 0.03 g/l, respectively. The Re extraction to ammonia re-extract was ~80 %. Apparently rhenium losses with scrubbing water can be eliminated by returning it to the process, for instance, to the extraction stage or to the leaching solutions preparation. The extraction process was organized in a laboratory cascade of mixer-settler extractors produced at ICTREMRM RAS in counter-flow regime, with returning of scrubbing water to extraction. This allowed to improve rhenium extraction from Re-containing alloy leaching solution. As a starting solution in 2-octanol-based, large-scale laboratory experiments, we uses the averaged solution from grinding waste leaching, which contained, g/l: Ni 30.2; Co 4.2; Cr 3.1; Mo 0.6; W 0.01; Re 2.0 and 4.5 mole/l H2SO4. Extraction was carried out at 3 cascade steps at a :W=1:2, whereupon the extract was transferred to scrubbing with an weak acidified aqueous solution (one cascade step) at :W=5:1. Re-extraction occurred at a 3 mole/l NH4OH at :W=3:1 (2 cascade steps). The amount of solution tested was 3.2 L. The obtained ammonia re-extract contained 12 g/l rhenium, from which distilling yielded ammonium perrhenate purified from main impurities. The results of spectral analysis of the salt produced are demonstrated in table 5. able 5 Spectral analysis data for ammonium perrenate obtained by solvent extraction from HRNA grinding wastes
Impurity Content, w/o Ni 0.001 Co <0.003 Al 0.01 Cr <0.003 Fe 0.01 Mo <0.003 W <0.01 a <0.03 Nb <0.01
It can be stated that rhenium can be selectively isolated from a solution of complex salt composition by using liquid extraction yielding purified ammonium perrhenate. Based on the new findings and experience gained from liquid extraction of molybdenum and H2SO4 from complex-salt solutions [810], we have proposed a basic flowsheet for in-depth processing of rhenium-containing alloy wastes (fig. 4), whereby pure rhenium and molybdenum salts, rare and non-ferrous metal concentrates, saving a part of H2SO4, returned to the stage of waste leaching.
Fig. 4. Basic flowsheet of in-depth processing of rhenium-containing wastes
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The work has been performed with the support of the RAS Presidium Support for Innovations and Developments programme. REFERENCES 1. Metal Price History Charts. Rhenium/ : [http://www.catalysts.basf.com 20.05.2010] 2. Kablov . N., Petrushin N. V., Bronfin M. B., Alekseev A. A. Peculiarities of monocrystalline heat-resistant nickel rhenium-doped alloys.//Metally. 2006. 5. P. 4757. 3. Paretsky V. M., Besser A. D., Gedgagov E. I. Ways of increasing rhenium extraction from ore and technogenic materials/Tsvetnye Metally. 2008. 10. P. 1721. 4. Kasikov A. G., Petrova A. M. Rhenium recycling from heat-resistant and special alloy wastes//Tekhnologiya Metallov. 2010. 2. P.212. 5. Lipmann A. Rhenium 2009 and beyond. 2009. Feb./A. Lipmann, M. Husakiewicz. : [http://www.lipmann.co.uk 20.05.2010] 6. RF Patent 2330900, MPK S22V 61/00, S22V 3/26. A method for rhenium (VII) extraction from an acid solution/A. G. Kasikov, A. M. Petrova (RF). 2006142845/02; Appl. 04.12.06; Publ. 10.08.08. Bull. 22. 7. Travkin V. F., Glubokov Yu. M. Molybdenum (VI) and rhenium (VII) extraction by aliphatic spirits//Tsvetnaya metallurgiya. 2008. 7. P. 2125. 8, RF patent 2159293 RF, MPK7 S22V 3/20, S01V 17/90. A method for the processing of solutions containing sulphuric acid and non-ferrous metals/G. P. Miroevsky, K. A. Demidov et al. 2000103985/02; Appl. 21.02.00; Publ. 20.11.00. Bull. 32. 9. A. G. Kasikov, A. M. Petrova. Sulphuric and hydrochloric acid extraction by high-molecular aliphatic spirits of different structures//ZhPrKh 2008. V. 81. 12. P. 19661970. 10. Reznichenko V. A., Palant A. A., Solovyov V. I. Comprehensive utilization of raw materials in refractory metal technologies. M.: Nauka, 1988. 240 p.
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EPOS-PROCESS NEW TECHNOLOGY OF EFFECTIVE ORE-SMELTING AND INDUSTRIAL WASTES PROCESSING IN PLASMA ORE-SMELTING SHAFT FURNACE
I.A. Bezrukov, S.N. Malyshev, O.B. Moiseyev, V.V. Pavlov, I.S. Parhomuk, .P. Kuznetsov EPOS, NSTU, Novosibirsk, Russia
On operating plasma ore-smelting shaft furnace advantages of use of technology EPOSprocess are proved. Achievement of high economy at processing of some ores and industrial wastes as alternative ore-smelting furnace which work under the traditional scheme is proved. In recent years we have developed and technically tested on several new production units [1 7] technology EPOS-process deoxidizing metals from ores and industrial wastes using a new generation of electric ore-smelting shaft furnace, heaters with plasma-burner of special construction. Based on proposals of a number of large Russian enterprises for treatment of ores and industrial wastes, for 20092010, were carried out numerical and experimental work on developing the technology of extracting metals from ore deposits the CHEK-SU, industrial waste of a number of mines and enterprises of Kuzbass, the Urals, as well as ore deposits in Georgia and Ukraine. Completed work has shown that EPOS-process perfectly suitable for processing a wide range of ore minerals, industrial wastes, metallurgical and extractive industries enterprises. Depending on the composition of the original product, techno commercial characteristics EPOS-process to reach tens of percent up to 2.5 or more times, and the organization of plant costs half the price. A general view of the electric RSHPP-1,5 I1 (power 1,5 MW capacity 1,0 ton silicomanganese or 4.5 tons of melt per hour. Furnace built by us in the of Novokuznetsk city. The first ore was melted in April 2009). Picture of the arc flame (heating area) and plasmatron are shown in Figure 13. Through a series of research works in recent years, the design of plasma ore-smelting shaft furnace has undergone significant improvements, while remaining nevertheless a fundamentally new and the base for development, Results of scientific, experimental and technical works was presented at scientific conferences [2, 46]. These technologies were discussed with leading experts Russia (including with the Director General of the Ural Institute of Metals, tsp.-corr. Academy of Sciences, prof. Smirnov, LA in 2010, heads of leading schools in the area of manganese ferroalloys). Estimates of many reputable independent experts can confidently assert that such a construction scheme of the furnace and smelting technology silicomanganese applied for the first time, has clear advantages and has no analogues.
Fig. 1. General view of plasma shaft furnace for technology EPOS-process
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Fig. 2. The plasmatron and form a working arc torch provided by the system of the plasma arc A comparative study and calculation options furnace of different furnace construction, we are concluded that there exist substantial preference of shaft type furnace, as prototypes for future high-power electrical thermal units for the deoxidizing processes taking place to replace the existing generation of furnaces, and developed a special perpetual plasmatron for realize the process. Many experts still not appreciated the advantages of the EPOS-process. Have in mind the pre-existing scheme construction of plasmatron and furnaces, their low resources, their shortcomings (including low efficiency), limiting their scope they insist on unpromising plasma-furnaces, on the development of domestic ferroalloy industry in the traditional, outmoded ways. This in the future, predestination its backwardness and noncompetitive. Therefore, we once again stop at the description of the technical solutions. For the first time realized the scheme of the process and furnace design of the plasma torch, operating under a layer of charge and in touch with her. Arc burns from the surface of the coaxial electrode charge, without the hearth electrode. For the first time realized the scheme of controlled recirculation of hot dusty raw gas entering the plasma torch. Graphite Electrode Capacity-part without stopping the process. The plasma torch has an unlimited resource. The geometry of the plasma torch is controlled during the melting process. Chemical and thermal energy reductant fully used in the furnace in the smelting process. Emissions of gas and dust in the gas cleaning system are small (diagram in fig. 4).
Fig. 3. Photo appearance RSHPP-1, 5I1 for the technology of EPOS-process
Fig. 4. General view and arrangement of equipment in the shop shaft furnaces
The ability to create conditions for the proper of deoxidation processes in the solid phase is an advantage by shaft-type furnace. You may receive additional savings of energy through heat transfer from flue gases to downloadable raw, due to saving of material by reducing the amount of dust, by making full use of the chemical energy of gases through the mine to work properly with feedstock. Experimentally confirmed that plasma properly structured and controlled will be operate exactly in the selected area of the furnace, will increase the percentage of minerals extracted from ore to 9095 % of the original, which makes plasma mine rehabilitation process, with its correct understanding and managing one of the most promising in the field of ore processing and disposal of industrial wastes.
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Fig. 5. Symbolic circuit Automated Control System management screen and remote control RSHPP-1,5 Briefly recall the features of EPOS-process: Essence of technology EPOS-process: The plasma torches are used, allowing to work under a layer of the loaded material (batch), with changeable geometry of a plasma torch. Plasmatrons work on the hot crude gases submitted at once from the furnace without temperature restrictions. The internal geometry (form) of the furnace is specially designed under EPOS-process technology. As the basic deoxidizers the controllable and operated environment is applied: hydrogen and carbon monoxide. EPOS-process takes place in the absence of an additional superfluous oxidizer, on an exit from the furnace gas 2 and steams 2. The high furnace shaft is used. Drying, preliminary heating and deoxidizing of solid phase (without fusion) processes are occur in the shaft. Conditions for correct courses of deoxidation processes in a solid phase are created. It is applied gas cycling: gas is got from a shaft, from furnace roof and it goes back to the furnace through plasmatron and through other pipelines. It provides full use of deoxidation abilities and reserved thermal energy gases from furnace atmosphere. The self-sufficient briquette is used, that is briquette contains an ore material, a carbonaceous deoxidizer and other necessary blending ratio, sufficient for a complete deoxidized of components of ore. As we pointed out earlier, and this is confirmed by long unsuccessful attempts by our competitors to repeat our results in the 200910 year, the technology is not have insignificant details and dimensions, in particular, the problem of plasma furnaces may be in the wrong scheme, inadequate resources, technical complexity and relatively low efficiency of steel-torches previous constructions. Traditionally used plasmtrons, used in the usual way, give the opposite effect and discredit the technology of plasma ore-smelting shaft furnace. This issue, we paid special attention, and today there are simple and reliable plasmatrons, including Coaxial, with controlled shape of the plasma torch with graphite electrodes, working with efficiencies over 97 %. Plasmatron has no limited on resource work. Plasmatron does not contaminate the liquid melt copper and other materials that are not contained in the furnace feed. Plasmatron allow the furnace to work relentlessly throughout the campaign, to routine maintenance and repairs to the furnace [712]. To improve efficiency we have organized a special way the geometry of the arc flame zone (heating area) and descent of the furnace feed to protect noncooled lining was carried out by it. It is believed that the use of plasma torches furnace roof, furnace shaft, plasmatrons to be water-cooled, water-cooled as are the basic elements of powerful arc furnace. This misconception comes from the misunderstanding of physical and chemical processes in the shaft and in the working chamber technology deoxidizing and melting going in plasma shaft furnace. Water-cooled in all parts of the furnace, without regeneration, making the technology a competitive disadvantage not only with the shaft-scheme, but even with a normal arc furnace. Quality of the work of the unit also provides the correct briquette, as we wrote in detail previously [2, 3, 6]. The use of EPOS-process reduces the dozens of times carryover material from the furnace, reduces Dust and Gas Cleaning system requirements, the annual dust emissions may be about 910 tonnes for the program output to 45000 tons silicomanganese per year (at the 5 furnaces specified capacity). The correct mode allows reduced power consumption by
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Table 1 Comparative evaluation of traditional technology ore-smelting furnace and technologies EPOS process for ore processing CHEK-SU ferromanganese and silicomanganese production
1 Parameter Number of furnaces CHEK-SU EPOS-process 427.6 7 463 199 112.7 362.4 140.875 1623987 919322.6 7.04 9.57 63.54 727 135.32 100.91 3 14.26 304.45 301.84 144.26 102.89 0.48 0.33 1.62 86.35 67.35 0.36 0.42 6.47 23.82 5.13 0.26 85.09 28.31 18.09 4.14 5.15 25.02 727 81.86 0 9.5 205.62 159.28 142.36 110.68 0.064 0.045 1.7 79.63 67.74 0.026 0.032 1.68 61.65 12.4 1.06 92.87 81.28 91.23 Effect Effect, times
2 Total power, MW 3 Installed capacity MVA 4 Electricity consumption, MWh Energy consumption, MWh 5 ton alloy 6 per ton of manganese 7 per ton of silicon Consumption charge, tons 8 Concentrates 9 Coke 10 Quartzite 11 Scale 12 Electrode mass 13 Furnace gas (dry), million Nm3 14 Slag, thousand tons Output thousand tons 15 Silicomanganese Mn P , % C, % 16 Ferromanganese/silicomanganese Mn P , % C, % 17 Associated alloy thousand tons Mn Ratio. retrieval, max., % 18 Mn 19 Si
-86.3 221.525 -704664 -2.9 -4.42 -38.52
1.77 2.57
1.7 1.86 2.54
-53.46 -100.91 6.5 -98.83 -142.56
1.65 0.32 1.48 1.9
7.79 -0.416 7.33
0.39 -0.334 13.13
1.09 2.87
the furnace more than half, reducing the specific power consumption and overall energy costs-up to 22.5 times. All these solutions have been fully incorporated in the draft electric RSHPP-1,5I1. A major new ambitious project ferroalloy production from ore is the project of processing ores CHECK-SU: Kuzbass, Krasnoyarsk, Usinskoe field. Reserves ores in Usinskoe (more than 98.5 million tons, total Russian reserves about 148.2 million tons) and its complexity (the presence of more than 92 million tons of carbonate and 5.7 million tons of oxidized ores), with collective processing of concentrate per year 727.14 thousand tons, with the amount of manganese 205.41 thousand tons (mass fraction of manganese in the collective concentrate 28.25 %) makes it relevant to new and modern approaches. If use of traditional open arc furnaces in this project will require about 360 MVA installed capacity furnaces. Thus, the question of cost optimization comes to the fore. A special feature of manganese Usinskoye raw materials is the high content of phosphorus, constituting 0.23 per cent in the oxidized and 0.15 per cent in the carbonate ore. Today there is a project ferroalloy production in the traditional manner, which provides the product with
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phosphorus 0.33 and 0.42 %. According to the experience of ferro-alloys, based on the mature market needs, we believe that the product with phosphorus 0.33 and 0.42 % will be in demand. The project may be already be very costly only on energy (not to mention the other features) and may be unprofitable in the future. We have done preliminary development of a modified process EPOS-process, under the above mentioned materials, which provides, in contrast to the framework of the project phosphorus concentration in the ferroalloy 0.33 and 0.42 %, phosphorus content 0.060.02 % or less. Estimates show that the process of technology EPOS-process is realized at nearly three times less than the installed capacity of equipment, and wasting power almost twice less than the traditional scheme of processing (table 1). This could fundamentally change the technology the better. The experimental data are processed briquettes for the project CHEK-SU showed positive results of the implementation process EPOS-process in the project, compared to conventional ovens. By authors also performed calculations of the technology EPOS-process for the processing of alloys without manganese ferrosilicon, ferrochromium, ferrovanadium, ferrotitanium and other ferroalloys. Each of these processes have significant individual characteristics that must be taken into account in the concept of plasma shaft furnace. Common to all processes is the possibility of significant savings in energy costs in the production of ferro alloys, increase in utilization deoxidizer up to two times, a drastic reduction of the material of the project, infrastructure costs, as well as multiple decrease dust and gas emissions. Currently implemented practical work on developing the technology for industrial ferrosilicon, preparation works on ferrotitanium. Scheme and design of shaft plasma furnace to implement EPOS-process in 2009. received a positive conclusion of examination of industrial safety. REFERENCES 1. . ., . . . , 2008. 7. . 46. 2. . ., . ., . ., . ., . . - . . , . . 69 2009 . 3. . . , . . , . . , . . . . . //2010, 1. . 1317. 4. . ., . ., . ., . . . . . // 7- . : - , 2008. 3212 . 5. . . , . . , . . , . . . . - , , , 1215 2009 . : - , 2009. 6. . . , . . , . . , . . , . . , . . . . - , , , 1215 2009 . : - , 2009. 7. . ., . . . . //2004, 4. . 1014. 8. . 13361. 05.11.2001. . . . 9. 13844. 05.11.2001. . . . 10. 13726. 05.11.2001. . . . 11. 14141. 01.10.2001. . . . ., . . 12. . . . . 2361375. 26.11.2007 .
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TREATMENT OF RADIOACTIVE METALLIC WASTES BY MELTING

I.E. Abroskin1, U.N. Makaseev2, A.C. Buynovsky2, A.I. Abroskin 2, A.A. Chernoshchuk 2
2 Seversk
SibUniversal Ltd., Novosibirsk, Russia Technical Institute of National Research Federal Nuclear University, Russia
An attempt to associate experimental experience of treatment radioactive metallic wastes by melting, which was accumulated on two largest factories, was made in this article. Availably machinery of substance responsible for radioactive pollution transition to slag was analyzed. For more than seventy years of nuclear industry history, collected the fair quantity of radioactive wastes (RAW), and the problem of their utilization became very important. The complication of solving this problem is that the radioactive wastes are different in composition and properties. Perhaps, the biggest problem of RAW treatment is extreme complexity, and because of this the high prices of offering technological decision. Thats why the land disposal is one of the most cheap problem decisions. Radioactive metallic wastes (RAMW) are one of the radioactive wastes. Like the typical RAW the metallic ones are generated on all stages of nuclear-fuel cycle. They are worked out components of equipment, underground leaching pipes, constructive components of fuel assembly. May be, total quantity of such wastes type in Russia is more than hundred thousand tones. [35] This problem is still not solved abroad, in particular on Kazaatomprom manufactures. Such wastes types are basically washed off up to indexes which are more than allowed radiation level, and this metal is not allowed even for limited reuse. Such RAMW are stored at closed industrial platforms. Processes of the open or deep waste burial though are relatively cheap methods do not lead to the problem solution, considering overall dimensions of RAW, and as consequence to the necessity of using considerable areas for burial grounds. The cases of RAMW plundering are known, when the polluted scrap metal simply was taken to points of reception of metal [1, 2]. Solving this problem at the expense of protection of ranges of a burial place is expensive because of their considerable extent [5]. There are also other methods of processing RAMW. On the majority of the enterprises of Rosatom, the surfaces wash method is used. The process essence is that the polluted detail is processed by various active agents, such as acids, alkalis, surfactant [19]. Additionally activation of a surface at the expense of mechanical influence by abrasive adaptation is used. The other variant is washing by use pulsating apparatus where process interaction of the polluted surface with a solution is intensified for the account pulsating contact of a washed surface and a washing solution [8]. The other method of improving the washing process is overlapping of ultrasonic fluctuations. Ativation of a surface at the expense of electrochemical influence is also interesting. [6, 7]. For this moment considerable experience in carrying out of this process is stored at the Rosatom enterprises, however there is a number of unsolved problems: The process is very complex in the presence of RAMW having big overall dimensions, or various forms of scrap metal. The process is unproductive, and shows low enough factors of clearing. In case of achievement of low indicators on the activity, allowing to use the received metal in a national economy without restrictions [21, 22], additional remelt stage is necessary. Significant amounts of a liquid radioactive waste (LRW) are formed. The offered way of processing RAMW by melting, not only free from above described methods disadvantages, but also allows to increase considerably technical and economic indicators of process of the recycling by reusing over 90 % of cleared scrap metal.
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The description of technological process The main objective of offered clearing was removal of the substances responsible for radioactive pollution, from surface and volume of metal components. The various forms of metal breakage are fragmenting preliminary, and then loaded into the induction furnace, where they are remelting. The induction furnace is an electrothermal installation for fusion of materials with use of induction heating. In the industry are applied basically induction crucible furnaces and induction channel furnaces. The crucible induction furnace (CIF) consists of inductor, which is the solenoid executed from a copper water cooled tube, and crucible which produced from ceramic materials, depending on properties of melt, or from graphite and steel in special cases. Lacks of such furnaces are: Rather low temperature of the slags, being at a mirror of melt for the purpose of its technological processing, slag in CIF is warmed up from metal, therefore its temperature is always low; Rather low fettling firmness at high melt temperature. Heat change presence (sharp fluctuations of furring temperature at full metal plum) [12]. Processed metal was formed during works on reception of ceramic uranium fuel (UO2 tablets), and as cycle of manufacturing of fuel assembly. The share of uranium activity is about 60 %, thus it is main radionuclide responsible for radioactive pollution, the others of 40 % are brought by products of radioactive decay of uranium. Activity of a breakage is: on activity to 100 particles/sm 2, on activity to 20000 particles/sm 2. Uranium is presumably presented on a surface in a kind of oxide substance. From the diagramme of uranium condition, one can see that uranium does not form intermetallic substance in so small concentration thats why all present metallic uranium in the course of heating will be easily oxidized by free oxygen to octaoxide threeuranium U3O8. Uranium on a surface can be also present in the form of sulphatic, nitrate, and other substance if the processed material was formed as a result of work of sorption or extraction processes or during reception of uranium oxide through sedimentation of ammonium deuranium, so-called the SOAD process. However all substances are oxidized and decayed during heating, giving oxides [13, 14]. The essence of technological process consists in redistribution of the substances responsible for radioactive pollution, and their transition from volume to a surface of the melt metal. Thus, radioactive components emerge in the top zone. The given process can be caused by two reasons: As it was specified earlier, uranium on a surface is in a kind of oxide substance. The minimum oxide density is characteristic for -UO3 and is 7.15 g/sm3, the given phase is steady to temperature 600 oC, further passes into form U3O8. Density of other U-O systems are presented in table 1. Table 1 Density of U-O systems
Systems UO UO2 U O9 U3O9 UO3 Density / 3 13.63 10.96 11.16 8.39 8.34
Density of uranium particles is more than that of stainless steel, consequently, the particles should go down in the fused metal however the carried out researches have shown that substance responsible for radioactive pollution, move upwards in volume of the fused metal. The reason of such behaviour can be the fact that proceeding from the diagramme of conditions and experimental data, all uranium oxides at temperature above 1200 oC are passed into according to the reaction UxOy XUO2 + (y 2x)/2O2 (1)
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Free oxygen promotes carrying the uranium deoxide particles from the melt volume onto the surface. The other reason is that the above described effect of displacement, can be the mechanical mixing. As it is known, in the course of CIF work, metal mixes up intensively that can lead to carrying out of particles onto the melt surface. In both cases, keeping of uranium deoxide particles on a melt surface, presumably, occurs thanks to forces of a superficial tension. However in case of keeping the fused bath for a long time, gradual subsidence of uranium deoxide particles is possible. Partial interaction of uranium substances with free O2, C and N2, being in melt, can be the other reason of carrying particles in the top area. Such process is characteristic at metallothermic uranium restoration. As a result of interaction substances of variable structure uranium oxicarbonitrides are formed. The given substances are characterized by low density, so they are capable to emerge in metal volume. [10, 13]. Such behavior of uranium substances in melt has allowed to organized the process of remelting in the induction furnace with prompting pseudo slag [20]. However deviations of the received ingots from demanded norms have repeatedly been found out, during the treatment. Partial subsidence of uranium oxide particles and their fastening in melt vollume could be a reason of such deviation. For an exception of such deviation of the processed metal from demanded norms, the decision to introduce a complex of the substances promoting fastening of materials, responsible for radioactive pollution, on the melt surface was accepted. The process with gumboils application cared out in the arc steel-smelting furnace (ASF), because of the complexity of the process organization with slag application in ASF. ASF is the electric furnace in which the thermal effect of an electric arch for fusion of metals and other materials is used. Steel fusion is conducted in the working space limited by the domeshaped arch from above, spherical pallet from below and walls from the sides. Pod and wall fireresistant masonry concluded into a metal casing from outside. Through symmetrically located three apertures in the arch current-carrying electrodes are introduced into working space. The scrap metal was loaded above with the charging tub help. The one third part of scrap metal party was loaded manually, to save the fettling. Release of ready steel and slag was carried out through steel-tapping hole and trench by an inclination of working space. Slag serves like an environment where metal containing inclusions removed leave as a result of chemical reaction or dissolution and per se it is a system where necessary regulation of the impurity maintenance is carried out. Also slag carries out a number of auxiliary functions, for example, protects the fused metal from direct atmospheric oxidation, prevents formation of a pipe defect and internal shrinkage. All it means that, varying slag structure, it is possible to influence on the ingot chemical compound and structure [12]. Among all variants of the slag systems, the mix of calcium fluoride (CaF2) and calcium oxide (CaO) in the 3:2 ratio has appeared to be the most suitable. The entered gumboil weight is about 5 % from the weight of loaded metal. It is necessary to notice that the gumboil was introduced during the process into already fused metal. After slag building up and 3060 minutes equalizing, slag was downloaded, carrying away with itself the substances responsible for radioactive pollution. Now the basic question there is a mechanism of retention of radioactive substances in slag. On one of the theories, slag mechanically keeps uranium oxides particles or oxicarbonitrides and promotes better separation of the substances responsible for radioactive pollution. On another, the uranium is kept by slag because of the intermediate substances formation. However it is an absolutely authentic fact that the radioactive substances pass into a slag structure and are well separate from metal. After slag separation the fused metal was poured into forms and cooled. The weight of the metal downloaded with slag, makes about 810 % of weights. Micro photos of the slag surface, made on an electronic microscope, are presented in figures 1 and 2. Such process realisation at Ulbinsky metallurgical combine has allowed to treat about 800 tons of the polluted metal scrap. The important thing is that the all received ingots had following indicators: on volume: alpha activity less than 1 particle/sm2, beta activity is less than 20 particles/sm2. Volume activity did not exceed 300 Bk/kg. Appearance of ready ingots is presented in figure 3.
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Fig. 1. Micro photo of slag surface, lower part
Fig. 2. Micro photo of slag surface, head part
Fig. 3. Appearance of the received ingots
After the slag research, following indicators of activity have been received: surface activity from1500 to 2000 particles/sm 2min, volume one from 35 to 60 kBk/kg. There were no deviations from indicators, during the installation operating time. All received ingots corresponded to demanded norms so, the received metal is suitable for application in a national economy without restrictions [21, 22]. REFERENCES 1. http://forum-msk.org/material/lenty/332827.html. 2. http://www.school12-murmansk51.narod.ru/radia.htm. 3. http://vybory.org/articles/1234.html. 4. http://eco.rian.ru/business/20100203/207554308.html. 5. http://www.nuclearpolicy.ru/publications/rezonans/rez7.shtml. 6. . ., . ., . ., . ., .,. . . 2328050. . 2 2008 2006100787). . 27.06.2008. . 18. 7. . 5776500 G 21 F 9/28. . 10.10.80 151411.
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8. . GB 1142776. 9. . . . .: , 1962. 10. . . . , . . . . . 2. ., , 1968, 484 . 11. . . ., . . - , 1970 . 240. 12. . . ., . . ., ., , 1973, 192 . 13. . . . . . 1964 . 398 . 14. . . . , , . 1978. 15. . . . . ., , 1985, 440 . 16. . . ., . . ., , 1973, 320 . 17. . . : .- .: . -, 1982.- 304., . ( ). 18. . .: . .,/. . . . . ., , 1985, 408 . 19. . . : .: , 2007448 .: . 20. . : 2268515 21. 2.6.1.79999 . 22. 99. .
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PROCESSING OF FLUORINE-CONTAINING WASTES AND MIDDLING PRODUCTS OF ALUMINUM PRODUCTION IN CEMENT INDUSTRY
B.P. Kulikov 1, V.D. Nikolaev 1, S.A. Ditrich 2, L.M. Larionov 1
1
Limited Liability Company Trading House Baikalsky Aluminii, Irkutsk, Russia 2 OJSC RUSAL Bratsk, Bratsk, Russia
Production of aluminum by electrolysis of cryolite-alumina melts involves a complex of interrelated, series-parallel processes, each of them is specified by a certain technological level of development. Permanent progressive advance of improving methods and means of process conduct notwithstanding, numerous engineering problems have yet to be solved. These problems are due to lack of theoretically and economically substantiated engineering solutions and a powerful leverage to improve production efficiency. Evolution of aluminum industry at the present stage involves development and implementation of resource-saving and environmentally friendly technologies to process secondary resources and technogenic wastes. Engineering solutions implemented to reduce material and labor expenditures in operating production, unmarketable wastes and middling product efficiently involved into processing shall increase competitiveness, economic attractiveness and environmental safety of aluminum business. Formation and accumulation of fine fluorocarbon-containing wastes is a serious problem for aluminum smelters. Annually 4 Siberian smelters (IrkAZ, BrAZ, KrAZ, NkAZ) store in settling ponds more than 70 thousand tons of wastes, mirabilite formation not included. The settling ponds of the smelters are on the verge of being filled. Remaining period of their service life is at OJSC RUSAL-Bratsk 68 years, at OJSC IrkAZ-SUAL 12 years. To build new settling ponds is conjectural for two reasons: first, it is the problems with land allocation because there are no free areas in the immediate vicinity of the smelters; second, it is considerable financial expenditures amounting to hundreds of million rubles. These reasons make the issues of managing aluminum production wastes processing top priority. Changes in electrolytic processes of aluminum production made most developments related to recycling of valuable components (Na, Al, F) to electrolysis process lose their applicability. Bath acidification in aluminum cells changed the balance of structural consumption of fluorine and sodium compounds. Apparent now is the disproportion between increased yield of alkaline regeneration cryolite (due to increasing HF concentration in electrolysis gases from acid bath) and its limited use in electrolysis of aluminum. Today economically viable and environmentally sound is to process in large scale fluorocarbon-containing wastes by outside consumers. This can be use of wastes in ferrous metallurgy, to make building materials, in cement industry or to process into alumina as part of sintering aggregate. The part of wastes and middling products to be processed to be recycled into aluminum process is small. This conclusion is based on two circumstances: ) Mammoth stock of accumulated wastes, and their annual increase by tens of thousands tons make their processing into aluminum fluoride or acid fluorides, i. e. into products in demand by aluminum smelters technically difficult and economically inadvisable. Technical difficulties are related to the necessity to process wastes by multiconversion processes (employing hydrofluoric or sulfuric acids). ) Utilization of wastes in related sectors can make the balance between the generation stock and waste processing negative and radically improve the environmental situation. Waste utilization scale in ferrous metallurgy, cement industry, in alumina production can amount to tens of thousands annually because annual production of cast iron, steel, cement, alumina is measured in millions of tons. Expenses to prepare wastes for related sectors are minimal and all too often are limited just to drying. Limited Liability Company Trading House Baikalsky Aluminii initiated a project to process fine fluorocarbon wastes of aluminum production in cement industry. The project is based
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on a process employing fluorine-containing wastes of aluminum production as mineralizer for production of Portland cement clinker [1, 2]. The essence of the process is to replace conventionally used calcium-fluoride-based mineralizers for wastes and middling products of aluminum production. This solves two problems at the same time: considerable volume of fluorocarbon-containing wastes is utilized, and cement industry receives adequate replacement of natural mineralizer based on fluorite ore or concentrate. In addition the aluminum-smelter-wastes-based mineralizer can be efficiently used in cement plants, which earlier did not use mineralizers. In this case its use will reduce the primary cost of products due to reduced fuel consumption and/or increased output of clinker sintering furnaces. Currently most cement plants in Russia do not use mineralizers. The reasons is remoteness of calcium fluoride sources from potential consumers, because major deposits of fluorite ore are in Siberian and Far Easter regions and in Mongolia. In the European part fluorite is not produced in industrial scale, because of inconsiderable reserve and low content of base material CaF2 in the ore. High cost of fluorite raw plus cost of transportation to the nearest manufacturers in Transbaikal krai to the central and western part of Russia make use of calcium fluoride in European cement plant unprofitable. Owing to low cost of electrode scrap and reduced transport expenses technogenic aluminum-smelter-wastes-based mineralizers minimize expenses of cement producers. The transportation costs are low because the electrode scrap is supplied to Siberian cement plants from Bratsk Aluminum Smelter, for the European cement plants from Volgograd Aluminum Smelter. Certification of fluorocarbon-containing wastes Certification of fluorocarbon-containing wastes of aluminum production transferred them into secondary raw category Electrode scrap for cement industry. Specifications 1789001533642742009 were developed for the electrode scrap and included into the State Register of Standards: registration 003667, code 191483. Protocol of Sanitaryand Healthcare Inspection of Rospotrebnadzor was issued for Specifications 1789001 533642742009. Rospotrebnadzor also issued a positive conclusion of toxicological examination of electrode scrap. Electrode scrap for cement industry shall meet norms and regulations presented in table 1. Table 1 Requirement specifications for electrode scrap
Index Weight fraction of fluorine, %, not less than Weight fraction of carbon, %, not more than Weight ratio of sodium to fluorine, %, not more than Weight fraction of absorbed moisture, %, not more than Norm 15.0 50.0 0.8 20.0
Subject to these requirement specifications are not only wastes, but also some fluorinecontaining middling products of aluminum production, viz.: carbon dust, crushed bath material, recovered cryolite, etc. Mineralizing properties of electrode scrap Studies were carried out by thermogravimetry, high-temperature radiography, X-ray phase and chemical analyses. Thermogravimetric analysis was carried out with STA 449 Jupiter synchronous thermal analysis instrument. Samples were heated to the temperature from 25 oC to 1480 oC at the rate of 8 degrees /min with deficient oxidizer (5 % oxygen) to model the atmosphere in commercial clinker sintering furnace. Sample 1 is the mixture of raw slurry with water at the ratio of 1:0.2; sample 2 is the mixture of raw slurry with fluorocarbon-containing wastes of aluminum production (electrode scrap) and water at the ratio of 1:0.0054:0.4. With this addition of mineralizer fluorine content in the raw slurry (sample 2) was 0.1 % weight. The weight of first sample was 118.4 mg, weight of the second sample was 170.2 mg. Studies were performed in alumina crucibles. Qualitative and quantitative composition of gas products of thermolysis during the experiments were monitored with quadrupole mass-spectrometer Aelos with electron impact energy 70 eV.
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Initial slurry components used as to produce cement clinker were raw materials of OJSC Volskcement with the following composition: limestone 79.5 %, clay 15.7 %, butts 3.5 %, highaluminate clay 1.3 %. Chemical composition and module characteristics of raw material are given in table 2. Phase composition of the raw slurry is represented by calcium carbonate CaCO3, quartz SiO2, hematite Fe2O3, heulandite Na2Ca(Al2Si6)165H2O and mica KMg3 (AlSi3O10)(OH)2. Table 2 Characteristics of raw slurry of OJSCVolskcement
SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O 13.77 3.23 Cl
TiO2 P2O5 Mn2O3
3.32 42.84 1.15 0.51 0.29 0.60 0.009 0.15 0.21 0.020 0.94 2.10 0.97 42.4
Notes: 1) Sc saturation coefficient is an indicator specifying incomplete saturation of silica with calcium oxide in clinker formation process: CaO (1.65Al2O3 + 0.35Fe2O3) Sc = ; 2.8SiO2 ; 2) n is the silica modulus: % SiO2/( % Al2O3 + % Fe2O3); 3) p is the alumina (aluminate) module: % Al2O3/ % Fe2O3; 4) W is the water content in the slurry, % weight. Thermogams of sintering of individual raw slurry and slurry with electrode scrap are given in fig. 1, 1 and 2, 2 .
Fig. 1. Thermogams of sintering of individual raw slurry
Fig. 2. Thermogams of sintering of raw slurry with electrode scrap
Fig. 1
Fig. 2
CaCO3 decarbonization with carbon dioxide liberation (mass number 44) To study effect of sodium fluoroaluminate (cryolite and chiolite) on sintering of raw slurry additional studies were carried out. With this aim the raw slurry was added in 10-fold quantity of fluorine-containing mineralizer, which maintained fluorine content in the slurry ~1.0 %. Mineralizer dose was increased because when fluorine content in the samples is about ~0.1 % low intensity of analytical lines denies identification of fluorine-containing compounds. The slurry with in-
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creased dose of mineralizer was sintered at 1000 C, 1100 C, after that the cooled sinters were analyzed with automatic X-ray diffractometer D 8 ADVANCE with copper anode (fig. 3, 4). Thermal radiography was carried out with Shimatzu XRD 700, Bragg-Brentano focusing with monochromator with diffracted beam in Cu-emission with sample heating rate 10 degrees /min in air within range 5001200oC. The composition of examined samples was analogous to samples 1, 2 of thermogravimetric analysis (without addition of water). The X-ray spectrum was recorded upon achievement of preset temperature with subsequent heating of the same sample to higher temperature under the following conditions: voltage 40 kV, current 50.0 mA, scan space 1060 degrees, scanning pitch 0.1 degrees, scanning speed 1.5 degrees/min. Diffraction patterns were recorded at constant temperature. Diffraction patterns were recorded at temperatures 25, 500, 600, 700, 800, 900, 1000, 1100, and 1200 C. Variation of intensity of most characteristic analytical lines of components of raw slurry and sintering products is given in fig. 5, 6 and in table 3.
Fig. 3. X-ray radiograph of products of raw slurry sintered with electrode scrap, 1 % F, t=1000 oC
Fig. 4. X-ray radiograph of products of raw slurry sintered with electrode scrap, 1 % F, t=1100 oC Table 3
Temperature dependence of analytical lines intensity, pulse/s

t,oC 25 500 600 700 800 900 1000 1100 1200 25 500 600 700 800 900 1000 1100 1200 3 3.03 14616 11260 9704 6262 Individual raw slurry -SiO2 Fe2O3 C3S -2S 3 3.34 2.53 1.764 2.40 2.70 1525 292 642 228 670 232 1462 636 202 338 5668 582 174 106 104 406 4660 466 138 160 170 3540 230 124 198 194 270 3146 144 88 186 208 242 2316 92 98 236 218 410 Raw material slurry with added electrode scrap (0.1 % F) 14834 906 268 12254 866 242 9944 738 244 9316 776 246 396 5158 618 214 426 4790 434 180 188 188 266 4046 204 136 242 222 292 3060 94 114 256 240 332 2.405 2096 94 290 278 464 4F 2.64
136 186 266 292
190 254 224 274 294 336
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J pulse/
1600 1400 1200 1000 800 600 400 200 0 25 500 600 700 800 900 1000 1100 1200
CaO with scrap CaO raw Fe2O3 with scrap Fe2O3 raw CaCO3 with scrap CaCO3 raw -SiO2 with scrap -SiO2 raw
J pulse/s
500 450 400 350 300 250 200 150 100 50 0 600
t,oC
700
800
900
1000
1100
1200
C3A with scrap C3A raw C3S with scrap C3S raw
C4AF with scrap C4AF raw -C2S with scrap -C2S raw
t,oC
Fig. 5. Temperature dependence of intensity of Fig. 6. Temperature dependence of intensity analytical lines of initial components of indi- of analytical lines of sintering products of individual raw slurry and slurry with addition of vidual raw slurry and slurry with addition of electrode scrap (0.1 % in terms of fluorine) electrode scrap (0.1 % in terms of fluorine) Discussion of experimental results Thermogravimetry In sintering thermogram of individual raw slurry (fig. 1) endothermic effect in range 35165 oC, accompanied by loss of sample weight by 20.8 %, is due to water evaporation. In range 600900 oC endothermic effect with sample weight loss by 27.0 % (32.0 mg) is due to decarbonization CaCO3 with liberation of CO2, which is proved by the signal from the massspectrometer (mass number 44) (fig. 1 ). In range 9001450 oC one endothermic effect observed at 1310 oC is caused by melting of the reaction mixture. Slight endothermic deviation is related to overlapping endothermic and exothermic effects, the latter dominate and are caused by synthesis of base clinker minerals. Sintering of raw slurry with fluorine-containing mineralizer in range 260890 oC is attended by loss of sample weight by 20.5 % (34.9 mg) and several thermal effects (fig. 2). The first thermal effect in temperature range 600 oC is exothermic and is caused by carbon burning from the fluorocarbon-containing mineralizer. The following endothermic effect is related to decomposition of calcium carbonate. The endoeffect of thermal dissociation of calcium carbonate is partly overlapped by exoeffects caused by burning of carbon and resins, and formation of tricalcium aluminate 3 and tetracalcium alumoferrite 4F. Both effects are accompanied by liberation of 2 into the gas phase which is proved by the signal of the mass-spectrometer (mass number 44) (fig. 2 ). It should be noted that oxidation of carbon which is part of the mineralizer releases 0.95 mg of 2, while the total amount of released 2 is 32.85 mg. In range 8901450 oC the 2.1 % (3.6 mg) loss of weight by the sample is accompanied by several thermal effects (fig. 2). Basic endothermic processes in this temperature range are connected with formation of the liquid phase, polymorphic transformations of silicon dioxide and belit 2S. Exothermic effects are caused by synthesis of base clinker compounds: C4AF, 3, C2S, C3S. Comparison of thermograms of raw slurry sintering with fluorine-containing mineralizer (fig. 2) and without it (fig. 1) shows that addition of fluorine in the amount of 0.1 % weight intensifies thermal dissociation of calcium carbonate. Decarbonization of CaCO3 in the presence of mineralizer starts at 500550 oC, while without it dissociation starts at 680 C. Intensity of 2 liberation with mineralizer is maximum at 720 oC, without mineralizer at 850 oC. 2 liberation from the slurry with mineralizer is stepwise, with different intensity at different temperatures. So, addition of electrode scrap to the raw slurry shifts the beginning of CaCO3 decarbonization two the lower temperature range with positive effect on the subsequent synthesis of clinker compounds. High-temperature radiogaphy From figures 5 and 6 and table 3, presenting temperature dependencies of intensity of analytical lines of initial components and sintering products of individual raw slurry and slurry with addition of electrode scrap, it is apparent that samples have no visible changes up to 600 oC, the composition of samples is identical to the initial one. Decreasing intensity of basic line of CaCO3 is indicative of the start of limestone decomposition process.
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At 700 oC it is obvious that concentrations of elementary oxides of silicon, calcium, iron tend to decrease, while the tricalcium aluminate 3 and alumoferrite 4F tend to increase. To evaluate content of calcium carbonate and calcium, silicon and iron content we used the strongest lines free from overlapping, therefore dependence of their intensities on temperature is obvious. At 700 oC both samples start solid-phase reactions between calcium oxide and dehydration products of clay minerals to produce calcium silicates which is proved by emergence on thermograms of lines 2.89, 2.78 and 2.75 . The content of clinker phases is not sufficient to accurately identify them, as the said lines belong both to alit and belit, while the weaker lines specific for these compounds did not emerge yet. The thermogram of individual slurry exhibits clear lines of calcium oxide 2.403 and 1.699 . In the sample with addition of electrode scrap no calcium oxide lines are observed, which is probably related to interaction of with aluminum oxide. Thermograms of both samples produced at temperature 800 oC have no 3 lines, and the analytical line of free calcium oxide reaches its maximum. The sample of individual slurry at this temperature exhibits clear lines of alit 3S, tricalcium aluminate C3 A and belit -2 S. Besides the said phases the sample with electrode scrap addition has ferrite phase C4 AF. Further increase of temperature reduces intensity of analytical lines of initial components of raw slurry aCO3, Al2O3, SiO2, Fe2O3 (fig. 5) and increases the quantity of clinker compounds in sintering products (fig. 6). Intensity of lines C3, 3S, -2S, 4F in slurry sintered with electrode scrap is 1325 % higher than in sintering of individual raw slurry, which proves the intensifying properties of the mineralizer. So, experiments proved that the solid-phase sintering processes in the samples under study start as early as 700800 oC, and interaction of clay materials with calcium oxide with electrode scrap addition is higher than in mineralizer-free slurry. Interaction of electrode scrap with raw slurry Behavior of basic compounds of fluorine-containing mineralizer during sintering of clinker aggregate produced by thermogravimetric and X-ray phase analysis is presented by the following basic equations (table4). Table 4 Interaction of electrode scrap components with raw slurry components Interaction Reaction Temperature range, oC 725 1 3Na5Al3F14 = 5Na3AlF6 + 4AlF3 Na3AlF6 = 3NaF + AlF3 850950 2 C + O2 = CO2 + Q 450950 3 2AlF3 + 3CaO = 3CaF2 + Al2O3 7501000 4 2NaF + 2O + 2CaF2 = 2CaF3 + Na2O 10001200 5 10001150 6 11CaO+7Al2O3+CaF2 = CaO 11Al2O3 7CaF2 10001250 7 AlO3 + 3CaO = 3CaO Al2O3 2CaF2 + SiO2 = 2CaO + SiF4 12001300 8 At 725 oC chiolite incongruently melts to produce cryolite and a melt containing cryolite and aluminum fluoride [3]. Cryolite is thermally more stable as compared to chiolite, its melting temperature is 1008 C [4]. However, in range 850950 oC cryolite thermally dissociates to form sodium fluoride and aluminum fluoride (reaction 2). Dissociation of cryolite is intensified by interaction of highly active calcium oxide formed by decomposition of limestone and aluminum fluoride in reaction 4. At 1000 oC all aluminum fluoride transforms into calcium fluoride and aluminum oxide. Sodium fluoride formed by thermal dissociation of cryolite starts interacting with 2O and CaF2 at temperatures above 1000 oC (reaction 5). Prior to this interaction sodium fluoride acts as mineralizer more efficiently, at that, than CaF2 [5]. In temperature range 10001200 oC sodium fluoride is replaced by potassium fluoride which interacts with CaF2 to form aF3 (reaction 5, fig. 3, 4). In addition, complex compound CaO11Al2O37CaF2 forms in the same temperature range. Highly active aluminum oxide forming from aluminum fluoride is bound into tricalcium aluminate 3 (reaction 7). Carbon which is part of aluminum production wastes burns in temperature range 450950 oC to form carbon dioxide (reaction 3). During sintering of raw slurry a part of calcium fluoride interacts with silicon oxide to form highly active CaO and gaseous silicon tetrafluoride (reaction 8).
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Industrial tests Tests conducted formed theoretical basis to industrially approve the developed technology to use aluminum-production-wastes-based fluorine-containing mineralizers to produce Portland cement clinker. Electrode scrap was tested in 6 plants: Angarsky, Timlyuysky, Altaisky, Notroitsky, Volsky, Iskitimsky cement plants. Initially the technology was industrially elaborated in OJSCAngarskcement. To produce cement OJSCAngarskcement uses unconventional raw materials crystalline limestone and fuel ash, contrary to conventional limestone and clay. This has negative impact on clinker formation processes and the quality of clinker produced. Production of Portland cement clinker from unconventional raw material necessitates use of mineralizer, for this OJSCAngarskcement used natural calcium fluoride. Pilot tests to replace calcium fluoride by electrode scrap helped elaborate basic process variables of raw slurry sintering to produce clinker with high physical-mechanical characteristics. In other cement plants electrode scrap was tested to replace expensive calcium fluoride and to intensify clinker sintering in the plants which did not use mineralizers. In the latter case the electrode scrap acted as an additional component of raw slurry. After successful tests of electrode scrap in OJSCIskitimsky cement, the management of the cement plant made a decision to expand the test scale; for this purpose Bratsk Aluminum Smelter supplied 1000 tons of mineralizer. After industrial tests Volsky and Novotroitsky cement plants also made decisions to enlarge the test scale. Industrial tests found that: 1. Optimum addition of electrode scrap into raw slurry is 0.100.25 % in terms of fluorine. 2. Electrode scrap improves spreadability of raw slurry by 515 %, depending on its rheological properties. This makes possible to reduce by several percent moisture content in the raw slurry and reduce fuel consumption to sinter the clinker. 3. Carbon which is part of the electrode scrap acts as a burning addition intensifying processes in the medium-temperature zone of the sintering furnace. 4. Addition of electrode scrap to raw slurry with its invariable moisture content reduces specific fuel consumption by 46 kg/1 t of clinker and increases output of sintering furnaces by 24 %. 5. Clinker produced with addition of electrode scrap exhibits food structure of basic clinker minerals and grindability (fig. 7). 6. In some instances addition of electrode scrap was found to strengthen protective coating on the refractory lining of the tubular rotary kiln. 7. Electrode scrap does not affect buildingengineering properties and physical-mechanical characteristics of the cement produced. 8. Among negative aspects of electrode scrap application is addition of sodium to raw slurry which is objectionable. Addition of electrode scrap to the raw slurry in the amount of Fig. 7. Portland cement clinker 0.100.15 % weight in terms of fluorine inmicrostructure creases sodium content 0.060.10 % weight which is admissible for most cement plants. Mastering industrial production of Portland cement clinker with electrode scrap Pilot tests of new mineralizer demonstrated that application of electrode scrap does not change cement production process in OJSC Angarskcement and does not reduce qualitative characteristics of the clinker produced. This makes possible to recommend this addition to be used as a mineralizer to sinter Portland cement clinker. In 2005 OJSC Angarskcement continued testing electrode scrap. In one year 7.7 thousand tons of slurry were processed to produce 457.7 thousand tons of cement clinker. The quality of clinker was satisfactory: its activity varied from 45 MPa to 48 MPa which is consistent to the activity of clinker with addition of electrode scrap. Annual economic benefit was 2.31 million rubles. In 2007 slurry was supplied to OJSC Angarskcement by Irkutsky Aluminum Smelter. In the course of one year more than 14 thousand tons of electrode scrap were supplied to be processed in 20072008.
531
In 2009 a work package was realized to enlarge the scale of electrode scrap application from Bratsk Aluminum Smelter to OJSC Angarskcement: Extraction of Electrode scrap from reclaimed Settling Pond 2 at OJSC Bratsk-RUSAL project has been developed; long-term (10 years) contract to extract electrode scrap in the amount up to 400 thousand tons from OJSC Bratsk-RUSAL and supply to OJSC Angarskcement, to clean settling pond 2 of OJSC Bratsk-RUSAL to restore the newly produced aluminum production wastes; amount of electrode scrap delivery to OJSC Angarskcement in 2009 was 11400 t. In 2009 conditioned electrode scrap was first delivered to Altaisky cement plant. After successful pilot tests in 2010 the plant completely turned to electrode scrap instead of earlier use fluorite ore. REFERENCES 1. Patent 2383506 , 04 7/42. Method of Protland Cement Production./Kulikov B. P., Nikolaev M. D., Kuznetsov A. A., Pigarev M. N. Priority of 30.09.2008. Publ. 10.03.2010. Bul. 7. 2. Kulikov B. P., Barinov V. V., Nikolaev M. D. et al. Development and Implementation of Clinker Sintering Technology Employing Technogenic Mineralizer on the Basis Of Secondary Fluorine-Containing Resource of Aluminum Production.//Abstract of presentation at PetroCem conference 2010. S. Petersburg. . 8081. 3. Toritsky I. A., Zheleznov V. A. Metallurgy of Aluminum. Reference Guide. Chapter XIV./.: Metallurgiya. 1977. 392 p. 4. Non-ferrous metallurgists reference book. Production of Aluminum./.: Metallurgiya, 1971. 560 p. 5. Volkonsky B. V., Konovalov N. F., Makashev S.D Mineralizers in Cement Industry./., Stroiizdat, 1964. 200 p.
532
EFFECTIVE STRENGTH RESOURCE SAVING TECHNOLOGY IN STEEL INDUSTRY REVISITED

N.I. Novikov Novokuznetsk branch of the institute state educational highest vocational institution Kemerovo State University, Novokuznetsk, Russia
Material and energy consumption in metal products manufacture within Russian companies is 2025 % and 8090 % respectively higher in comparison with developed western countries [1]. The most important tendency for reduction of energy and material consumption is resource saving technology. Under present-day economic conditions due to commercializing it is necessary to find effective source of materials, process fuel and all kinds of energy, widely introduce modern resource saving technologies. In ferrous metal industry it is especially important for steelmaking process stage, where the best converter process technology alternative with wide processing mixture ratio of metal stock and process fuel is to be tried out. At Zapsibmetkombinat (JSC ZSMK) the number of resource saving technologies were developed, passed industrial tests and were accepted into production in partnership with the author. For example, at JSC ZSMK for the first time in native ferrous metal industry there was developed and passed industrial test steelmaking practice by 100 % smelting burdening using metal scrap in a converter with a capacity of 130 t (KKZ-1). The main purpose of this technology introduction is material resources economizing and foremost economizing of highpriced steel-making iron. In 2006 at JSC ZSMK conditions the cost of 1 t of metal scrap was a bit more then 60 % from the cost of 1 t of liquid steel-making iron. With such price ratio for the basic kinds of materials for smelting burdening there is no need to give any other reasons. Although it is necessary to define such aspect as process fuel expenses. Surely process fuel expenses for 1 t of melted steel by 100 % smelting burdening using metal scrap are higher then by traditional burdening hot metal and metal scrap. In order to minimize the expenses for melted steel production using this processing technology to get the necessary temperature in a bath furnace where melting takes place not only normal oxygen lancing through the form is used but metal scrap preheating is used, coal (steaming coal, is chipper) is added, about 4060 kg per tone of melting charge and small coke after the coking, with worsen furnace burden grain fineness for blast furnace smelting and has a negative impact on blast-furnace run (reduces blast furnace technical-and-economic indexes by iron smelting). According to this steelmaking technology to provide melting charge melt in a converter and normal slag adjustment metal scrap is filled into the converter in portions in definite periods of time it provides the desired temperature. Based on the calculation process fuel unit costs for 1 t of melted steel by converter burdening with metal scrap in comparison with traditional converter burdening smelting using hot metal and metal scrap is 6268 % higher. However production calculations for 1 t of melted steel by 100 % metal scrap charging and traditional converter burdening show that production cost for 1 t of steel by 100 % usage of metal scrap is 1113 % lower. Based on this fact one comes to a conclusion that the 100 % usage of metal scrap in converter melting charge is a working resource saving technology in steel industry. We consider that to become widely used in economics the viewed technology needs to be worked out in more details as far as the technological aspects is concerned and is to get an integrated economic appraisal for all energy-material-economic aspects in different alternatives. Process fuel costs reduce for melted steel production is up-to-date not only by 100 % burdening using metal scrap. Heat-transfer efficiency in converter smelting is defined mostly by the way of heat-transfer entering into the converter, the entering time depending on the smelting period and quality of materials used as a heat-transfer.
533
At JSC ZSMK the technology of heat-transfer entering through a blowout pipe and through a conveying pipe is worked out. In the first case heat-transfers were loaded along the bath lancing. In the second case before the beginning of bath lancing (metal scrap preheating) and using combined process [2]. Under present-day conditions the best practice is metal scrap preheating in converter. As heat-transfers within this technology own-produced coke and different coal ranks from Kuzbass coal companies are used. Yearly time history for coke and coal consumption rate is shown on figure 1.
Coke consumption rate, kg/t Coal consumption rate, kg/t 25 20
19,2 18,9 19,6 17,5 17 17,5 21,4
12 10 8 6 4 2 0 2001 2002 2003 2004 2005 2006 2007 Years b)

8,26 7,3 6,26 9,74 7,5 6,75 8
15 10 5 0
2001 2002 2003 2004 2005 2006 2007 Years )
Fig. 1. Changes for coke and coal consumption rate, years 20012007: a) in an oxygen-converter plant (OCP) 1; b) in OCP 2 The measures pointed above led to reduction of high-priced cast iron consumption rate and to achievement of the necessary sensible heat in converter bath (according to the steelmaking practice). Changes in cast iron consumption rate per tone of melted steel is given on drawing 2.
Cast iron consumption rate, kg/t Cast iron consumption rate, kg/t 860 850 840 830 820 810 800 790 780 770 840
834,4
853,2
830 820 810 800 790 780

800 807,8
829,5
815,4 808 811,6 805,4
810,1 800,2 801,8
810,4 808,5 806,6
807
1999 2000 2001 2002 2003 2004 2005 2006 Years )
1999 2000 2001 2002 2003 2004 2005 2006 Years b)
Fig. 2. Changes in cast iron consumption rate, years 19992006: a) in OCP 1; b) in OCP 2 Operation by reduced cast iron flow using heat-transfers did not lead not only to oxidation enrichment of metal and dross more then it is regulated in a process message (drawing 3) but to reducing of good steel make.
FeO containing in dross, %
19,3 18,9 19,1 18,1
FeO containing in dross, %
19,5 19 18,5 18 17,5 17 16,5 16
17,9
17,7 17,4 17,2
1999 2000 2001 2002 2003 2004 2005 2006
22 21,5 21 20,5 20 19,5 19 18,5 18
21,4
21,5 20,9
20,7
20,4
19,8 19,4
19,3
1999 2000 2001 2002 2003 2004 2005 2006
) b) Fig. 3. Changes in FeO containing in dross, years 19992006: a)in OCP 1; b) in OCP 2
Years
Years
534
The other perspective and significant resource saving technology for company economics is the steel continuous casting. Although this technology is not new in the world iron-andsteel industry, but nevertheless it is relevant for Russian companies and especially for WestSiberian region. For example on one of the leading companies in iron-and-steel industry in Russia JSC West Siberian Metallurgic Plant (JSC ZSMK) which is within Evrazgruop Holding and has a 45 year history the continuous casting is used only for about 56 years. Nowadays at the plant using a continuous-casting machine (CCM) about 3238 % of melted steel is ladled out (CCM production capacity lets to ladle out about 5055 %) and it is the fact to think about. The company conversion to 100 % continuous casting using the CCM is now stopped and this problem solving within the plant is postponed for some indefinite time (long term prospects). Meanwhile both world practice and technical-economic performance on JSC ZSMK in the last 5 years show the undeniable advantage of using the CCM for steel ladle out. The information given in table 1 proves this fact. Table 1 Production cost per 1 t for steel products of different types, made of rolled billet and continuous cast steel billet from dead-melted steel (DMS) and low alloy steel (LAS), RUB
List of items produced Rod DMS Rod LAS Angle bar DMS Angle bar LAS Channel bar DMS Channel bar LAS Beam DMS Beam LAS Average production cost, RUB. Rolled billet 7459.02 8090.93 7417.17 8001.25 7435.33 8021.10 7507.36 8092.06 7753.03 Continuous cast steel billet 7142.73 7635.61 7100.88 7587.94 7062.11 7547.60 7203.32 7692.40 7371.56 Difference 316.26 455.32 316.29 413.31 373.22 474.61 304.04 399.66 381.47
Additionally after putting the CCM into operation the plant got the opportunity to widen greatly the output products grade composition and therefore to move from production of common steel types (unkilled steel, semikilled steel) to production of higher quality steel types (deadmelted steel and low alloy steel). Steel products made of high quality steel are of high demand on market and the economic effect for the company is higher. Changes in grade composition of steel produced at ZSMK in 20052009 in % are given in table 2. Table 2 Changes in grade composition of melted steel produced on OAO ZSMK in 20052009, %
Steel type Unkilled Semikilled Dead-melted Low alloy and alloy 2005 16.5 76.9 1.1 5.5 2006 9.9 53.2 30.5 6.4 2007 8.3 49.0 34.8 7.9 2008 5.8 41.0 40.6 12.6 2009 2.0 15.2 64.5 18.3
Strong rising of high quality steel types production volume in the last years was caused by slab caster setting in operation, which in short time has been brought to the designed capacity (2.5 MIO t slab continuous casting per year). Based on successful operation of billet and slab CCM one can consider the complete changeover of the OCP-1 for continuous casting in the future without building the third CCM, but it will take to modernization of the working CCMs, which is much (4045 %) cheaper then to build the third CCM. According to plant specialists estimates increase in active CCMs productivity for about 25 30 % can be provided by using practically tested innovations and by increase of process organization level. So, in a billet CCM in 2008 running downtime due to the lack of melted steel was 25 days or 8.5 % from time rating. Significant reserve for productivity increase is in casting sequence increasing, which nowadays on ZSMK is only 89 melting operations and on foreign companies (Japan, France, India, Korea) it is more then 100 melting operations per production run.
535
Continuous casting application in steel industry leads to expenses economy due to technological conversion elimination. By an ordinary ladle out (ingots technology) the technological conversion has the following structure converter ladle to mold casting stripper soaking pit station blooming-billet mill and the structure by continuous casting is the following: converter ladle furnace CCM rolling mill. Expenses (labor cost, process fuel, electrical energy, production labor hours, upkeep expenses etc.) per each technological conversion grow, accordingly the more technological conversions we have the more the production cost of metal products is. In addition to this, continuous casting application provides metal yield increase due to discards minimization and to process fuel cost saving, which is spent for ingot heating before rolling; one gets labor hour savings that gives the opportunity to raise production; it provides quality improvement for metal products and finally it leads to diminution in working hours and to labor conditions improvement (labor becomes more automated). To make a conclusion we can say that the change from ordinary steel ladle out to continuous casting provides substantial improvements both for economic and ecological indexes not only in steel melting production but also for the steel company in general that leads to its cost effectiveness and turn out products competitiveness increase. One of the effective resource saving technologies in steelmaking is the application of used tyres as a process fuel within an oxygen-converter process. As a fuel, rubber component has evident advantages in comparison with the best coal types; low ash content 23 %, almost zero humidity and extremely high combustion value 33.5 37.7 J/kg. Converter configuration and the present converter smelting technology let to load the whole ties into the converter providing their quick and complete burning in bulk oxygen atmosphere (99.5 %) by high temperature (13001500 oC). Availability of strong gas-cleaning units with water recycling closed cycle almost entirely removes any environmental pollution probability. The developed technology supposes loading of 610 tyres for smelting or 3.35.5 kg/t steel in 160 t converter (OCP-1) together with metal scrap and burning them additionally to coal rank TOM which has the following characteristics: grain-size 1315 mm; humidity not more then 8 %; ash content not more then 13 %; volatile not more then 17 %; combustion value 25.128.1 MJ/kg. Technical analyses results of tyres after metal cord removal are given in table 3. The lowest combustion value calculated to working mass is 33.535.6 MJ/kg. Tyres organic part on an average consists of working/organic mass elements %: carbon 85.5/88.0; hydrogen 8.00/8.20; oxygen 2.30/2.40; nitrogen 0.40/0.40. Table 3 Technical analyses results for tyre casting, %
Tyres type Humidity, % 0.46 0.55 0.61 0.53 0.40 1.00 0.401.00 Ash content, % Volatile content, % Containing, % sulphur unvarying carbon 1.32 1.40 1.42 1.63 1.70 1.62 1.321.70 27.76 28.47 28.83 29.23 28.28 28.23 27.7629.23
260508 280508 260508 320508 Small-sized tires 84015 205/7014 Limit value
Medium-sized tires 3.15 71.2 2.63 70.6 3.30 70.0 2.38 69.9 2.10 3.33 2.103.30 71.0 70.5 69.971.2
During industry research there were estimated technological indexes for converter smelting and dust-gas burst into the atmosphere, including dust level, sulfur oxide and carbon content. The obtained results showed that by tyres application there is no negative influence on smelting characteristics production date and on quality of the steel made (table 4). Steel sulphur content was not stated. The used tyres application admitted to increase heat arrival at a converter at the expense of fuel burning heat increase and improvement of heat transmission conditions owing to increase of flame brightness under soot burning that provided fuel consumption decrease in the period of iron bar preheating.
536
Table 4 Averaged technical economic work rates of 160 t converters with used tires application
Rates Number of meltings Charges, kg/t of fluid steel Cast iron Iron bar Limestone Used tires Coal Job duration, minutes: preheating blowing Oxygen total makeup, m 3/melting Cast iron composition, %: Si n S Cast iron temperature, o Metal composition at the first turndown, %: n S Metal temperature at the first turndown, o Slag composition at the first turndown, %: Fgeneral MgO Slag basic capacity Melted steel yield, % Technology Worked-out common 100 100 773.3 313.6 53.7 2.8 14.2 5.19 21.5 9703 0.35 0.43 0.016 0.17 1326 0.13 0.16 0.021 0.015 1620 22.8 3.5 3.7 92.0 775.1 312.0 54.0 18.5 6.0 21.6 9695 0.38 0.42 0.016 0.16 1330 0.10 0.15 0.020 0.016 1610 24.1 3.5 3.6 92.0
It is established that tyres input into a converter has not influenced dust content in released into the atmosphere gases. High temperature and oxygen excess in a converter bath promoted full tyres burning and their thermal decomposition products that excluded atmosphere pollution with incomplete fuel burning products (soot, carbon oxide, hydrocarbons). S2 concentration in gases released into the atmosphere was not higher than in a common coal using technology. Thus tyres are valuable heat energy source for high temperature metallurgical processes. The worked out technology of steel smelting in oxygen converters with used tires application is low cost-based, ecologically permissible and is the recycling mass method that helps to solve wastes utilization problems in developed metallurgical industrial regions. The recourse-saving steel industry technologies considered in this article provide an enterprise with essential improvements of technical economic rates that increase its financial stability and competetiveness both in foreign and home market. REFERENCES 1. Nikolaev A. L. and others. Iron-containing waste materials raw materials for steel industry/ A. L. Nikolaev, A. A. Nikolaev, V. N. Jurchenko, N. I. Novikov, A. G. Zaraeva//Regional conference transactions, Novokuznetsk, 911 october 2003/Under the editorship of F. I. Ivanov and V. K. Butorin: NFI KemGU. Novokuznetsk, 2003. P. 1214 Works 2. JSC West Siberian Metallurgical Plant. Access mode: www.zsmk.ru. 27.01.2010.
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THE SECOND INTERNATIONAL CONGRESS NON-FERROUS METALS 2010, SEPTEMBER 24, 2010, KRASNOYARSK, RUSSIA

Fig. 1.Mountains of refractory wastes in area of pitch-magnesite workshop of WSMW

Fig. 2.Chamotte brick

Table 4 Analysis Results of Balance Composition of Laboratory Slag Sample

Copper slag with grain size of -2+0 mm

Grinding up to 93% -0,074 mm category

Basic copper flotation t=5 min.

Copper recleaning t=2 min.

Control flotation t=6 min.

18.70 47.98 13.0 46.44 19.40 47.38 14.22 46.01

Table 8 Process Balance of Semi-industrial Processing of Slag

Classification in classifying screen drain sands Classification in hydrocyclone drain

BX 200 g/t OFMB 30 g/t

Basic copper flotation

Classification in hydrocyclone sands regrinding drain

Table 1 Physical-chemical properties of ion exchangers investigated

(2) (3) (4)

RHENIUM EXTRACTION FROM NICKEL-BASED COMPLEX HEAT-RESISTANT ALLOYS

Fig. 2. HRNA lump debris (ZhS-32 alloy)

Table 2 Starting product composition

Fig. 4. Basic flowsheet of in-depth processing of rhenium-containing wastes

Fig. 1. General view of plasma shaft furnace for technology EPOS-process

Fig. 3. Photo appearance RSHPP-1, 5I1 for the technology of EPOS-process

-86.3 221.525 -704664 -2.9 -4.42 -38.52

1.7 1.86 2.54

-53.46 -100.91 6.5 -98.83 -142.56

1.65 0.32 1.48 1.9

7.79 -0.416 7.33

0.39 -0.334 13.13

TREATMENT OF RADIOACTIVE METALLIC WASTES BY MELTING

Fig. 1. Micro photo of slag surface, lower part

Fig. 2. Micro photo of slag surface, head part

Fig. 3. Appearance of the received ingots

TiO2 P2O5 Mn2O3

Fig. 1. Thermogams of sintering of individual raw slurry

Fig. 2. Thermogams of sintering of raw slurry with electrode scrap

Temperature dependence of analytical lines intensity, pulse/s

136 186 266 292

190 254 224 274 294 336

EFFECTIVE STRENGTH RESOURCE SAVING TECHNOLOGY IN STEEL INDUSTRY REVISITED

12 10 8 6 4 2 0 2001 2002 2003 2004 2005 2006 2007 Years b)

2001 2002 2003 2004 2005 2006 2007 Years )

830 820 810 800 790 780

815,4 808 811,6 805,4

810,1 800,2 801,8

810,4 808,5 806,6

1999 2000 2001 2002 2003 2004 2005 2006 Years )

1999 2000 2001 2002 2003 2004 2005 2006 Years b)

FeO containing in dross, %

19,5 19 18,5 18 17,5 17 16,5 16

17,7 17,4 17,2

1999 2000 2001 2002 2003 2004 2005 2006

22 21,5 21 20,5 20 19,5 19 18,5 18

1999 2000 2001 2002 2003 2004 2005 2006

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