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WO2009139666A1 - Procédé et dispositif de production de métaux chimiquement actifs par résistance électrique de tiges - Google Patents

Procédé et dispositif de production de métaux chimiquement actifs par résistance électrique de tiges Download PDF

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Publication number
WO2009139666A1
WO2009139666A1 PCT/RU2009/000222 RU2009000222W WO2009139666A1 WO 2009139666 A1 WO2009139666 A1 WO 2009139666A1 RU 2009000222 W RU2009000222 W RU 2009000222W WO 2009139666 A1 WO2009139666 A1 WO 2009139666A1
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WO
WIPO (PCT)
Prior art keywords
metal
contacts
cathode
slag
reaction
Prior art date
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Ceased
Application number
PCT/RU2009/000222
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English (en)
Russian (ru)
Inventor
Анатолий Евгеньевич ВОЛКОВ
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Individual
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Individual
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Application filed by Individual filed Critical Individual
Publication of WO2009139666A1 publication Critical patent/WO2009139666A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C22B4/08—Apparatus
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C22B34/1268—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/14—Obtaining zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C22B4/06—Alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon

Definitions

  • the present invention relates to the production of chemically active metals and can be used to produce titanium, zirconium, vanadium, tungsten, niobium, etc. metals.
  • the minimum temperature required to start a spontaneous metallothermic reaction should exceed the melting point of the reduced oxides by 1.5-2 times.
  • the process temperature should be chosen so that the temperature of the melt at the end of the precipitation period of the droplets of the reduced metal, continuing during the industrial smelting, is higher than the crystallization temperature of the slag, since the slag must have sufficient fluid mobility throughout the formation of the metal ingot.
  • the process temperature should be as low as possible, since an increase in the temperature of the after-furnace process is associated with additional costs and can lead to a decrease in the reducibility of the reaction mixture and increased evaporation of elements during melting.
  • the closest technical solution selected as a prototype is a method for the recovery of titanium and zirconium with calcium. (A.N. Zelikman - Metallurgy of refractory rare metals, - Moscow: Izd-vo "Metallurgy", 1986, pp. 414-419).
  • This method is carried out in sealed apparatus, where the briquetted mixture is loaded.
  • the apparatus is filled with argon, heated to a temperature of 1000-1100 0 C, maintained at this temperature for one hour.
  • the reduction product is crushed, treated with a large volume of water, then diluted with hydrochloric acid, washed with water and dried in vacuum.
  • the reduction of titanium and zirconia with calcium is used to obtain fine-grained powders of titanium and zirconium, which can be used to obtain products by powder metallurgy, as well as in the form of powders (mainly zirconium) in pyrotechnics and as getters in electronic devices.
  • MeO 2 + 2Ca Me + 2CaO; (1) where Me is Ti or Zr.
  • Calcium reduction is carried out in sealed apparatus made of heat-resistant steel, where a briquetted mixture of TiO 2 or ZrO 2 with s calcium (in the form of chips). Distilled calcium must be used.
  • the apparatus is pumped out, filled with argon, heated to 1000–1100 ° C and maintained at this temperature for about 1 hour.
  • the reduction product is crushed, treated with a large volume of water [to remove part of CaO in the form of Ca (OH) 2 ], then diluted with HCl, washed with water and dried in vacuum at 40-50 0 C.
  • the closest analogue to the claimed device is a device for producing titanium (A.N. Zelikman - Metallurgy of refractory rare metals, - Moscow: Izd. "Metallurgy", 1986, p. 423), containing a casing with refractory lining, placed in it anodes, cathode basket with cathode rods, terminals for connecting current. On top of the cell is closed by a lid with a pipe for supplying raw materials.
  • the disadvantage of this device is the insignificant yield due to the low speed of the process, because the electrolyte cannot be heated to high temperatures, the high cost of assembly, high energy costs.
  • the technical task of the proposed invention is to develop a method and device for its implementation, which allows to reduce energy costs, increase productivity, yield by increasing the speed of the process, the uniformity of heating.
  • the method for the production of reactive metals by the method of rod electrical resistance involves heating the reaction mixture by providing electrical resistance, in the presence of a reducing agent, with reduction at the metal cathode and oxygen anode, at V this charge is not formed into an electrode, but preliminarily laid in the reaction zone, holding the inner cavity of a special insulated body, and the metal recovery process is carried out according to the following chain: power heating of the recoverable charge inside the case due to the creation of electrical resistance when voltage is applied to the contacts, metallothermal reduction of the metal inside the case, separation of the reaction charge into metal.
  • the metal under the action of force gravity moves to the cathode, due to electrolysis, being cleaned of non-metallic inclusions, and slag is forced out to the anode, on which oxidizing agents are released.
  • the necessary thermal energy for the separation of metal and slag comes from electrical resistance, after the start of the reaction, with constant compression of the contacts to the reaction mixture with a certain force.
  • the process of heating the charge begins when it reaches its optimal resistance under the influence of compression pressure, and during melting a strictly defined amount of heat is supplied from the outside, which contributes to the maximum recovery of the recovered metal.
  • the specified technical result is achieved by the fact that in the device for the production of chemically active metals by the method of rod electrical resistance, containing a vertically arranged housing with an insulating layer, an anode and a cathode, according to the invention, the function of the anode and cathode is performed by the contacts, the latter being located at the bottom of the housing and is simultaneously a pallet Moreover, each contact is equipped with a compression punch and is cooled.
  • the optimal charge resistance is selected due to the specific packing of the charge components inside the container, while the metal reducing agents can be used in the form of a rod, spiral, mesh, etc.
  • Figure l shows a device that implements the proposed method for the production of chemically active metals by the method of rod electrical resistance. The best embodiment of the invention
  • the proposed method implements using the device shown in Fig.l, which shows a vertical section.
  • the device comprises a tubular body 1 with an insulating layer 2, where the reaction mixture is placed. Above and below are placed copper cooled contacts 3, which are connected to opposite poles, the top to the positive, and the bottom to the negative pole. The contacts are pressed by two punches 4 to the reaction mixture, which during the reaction is divided into slag 5 and metal being reduced 6. The reaction mixture is closed in the insulating layer 2 and held by the tubular body 1. The reaction mixture is heated by creating electrical resistance, which is widely used in industry for heating metal lengthy workpieces.
  • the electrical contact heating method is based on the ability to connect a heated body to an electrical circuit. At the same time, heat is released in it according to the Joule-Lenz law:
  • An important condition for rational heating of the reaction mixture is the ability to accurately and quickly measure the temperature and reliably regulate it. With contact heating, various temperature control methods can be applied. Since the amount of heat generated is proportional to the duration of heating in accordance with formula (2), the temperature can be adjusted by turning off the current in time.
  • the work of the proposed method and device can be disclosed by the example of reduction of iron and titanium from ilmenite.
  • the electrical conductivity of ilmenite concentrate is approximately 2.0 ... 2.5 Ohm ⁇ -cm "1 , that is, the impurities present in it increase the resistance.
  • ilmenite has such conductivity even in the solid state at a temperature of about 1000 0 C, which practically does not change during the transition from a solid to a liquid state.
  • the ilmenite melt is characterized by a weak temperature dependence of electrical conductivity.
  • the electrical conductivity of ilmenite decreases. This indicates that titanium-containing slags differ not in ionic but in electronic conductivity.
  • Ilmenite concentrate is the main raw material for producing ferrotitanium. Due to the proposed method, it is possible to produce from ilmenite 25 ... 35% of ferrotitanium in an aluminothermic method. In this case, the initial energy necessary for slag formation and achievement of the required temperature, when the reduction of titanium oxides actively begins to take place, is released due to the heat of reactions of the interaction of aluminum with oxidizing agents introduced into the charge.
  • fluxing components are also introduced into the charge. This contributes, in addition to necessary for the reduction of titanium and iron oxides, the additional use of aluminum.
  • the process is enhanced by the occurrence of electrolytic reactions.
  • the principal features of the method are that the required amount of heat at different stages of the metallothermal reactions can be precisely controlled based on the Joule-Lenz formula (2). Unlike conventional resistance heating lengthy metal billets, the process of metallothermal reduction of metals is complicated by the fact that due to the flow of chemical, electrolytic, etc. processes, the resistance of the reaction mixture will change all the time.
  • the reduction of the metal is enhanced by the electrolytic reaction, since the lower contact 3, where the reduced metal 6 is collected, serves as the cathode, and non-metallic reaction products are oxidized on the anode 3. Yu In contrast to the heating of metal lengthy workpieces, heating the reaction mixture can be, on the other hand, easier, since the reaction mixture can have a resistance much greater than that of metal, therefore, the tubular body 1 can have a shorter length but a larger diameter, which allows produce a correspondingly greater volume of recoverable metal.
  • the reaction mixture can change its resistance at the stage of its preparation, before the reaction. That is, at a certain pressure by the punches 4, through the cooled contacts 3, when the charge particles are compressed, its electrical resistance will change. Therefore, the technology of the metallothermal process takes into account these features. That is, the operator, when compressing the reaction mixture, passes a current and voltage of a certain magnitude through it in order to determine the changing resistance, while the magnitude of the current and voltage are selected so as not to cause sufficient heating of the mixture and spontaneous recovery reaction. Upon reaching the calculated resistance due to the external compression pressure, the operator passes such a current and voltage through the reaction charge that triggers a spontaneous metal reduction reaction.
  • the operator As the reaction proceeds, as mentioned above, the operator, according to a given program, introduces from the outside exactly as much energy as to recover as much metal as possible.
  • the voltage inside the reaction mixture is set so that due to the flow of electrolytic processes, as much as possible to restore the metal.
  • the resistance of the reaction mixture will depend on the amount of fluxing additives in this mixture, which can serve as CaF 2 , CaO, Al 2 O 3 , etc. Therefore, it is possible to regulate it by selecting the amount and type of fluxing additives.
  • the total resistance of the reaction mixture can be selected by the arrangement of its components inside the container. So, for example, if the overall resistance of the mixture is too high, if it is uniformly mixed, it will be impossible to supply a sufficiently large current and voltage to it for initial heating. In this case, to reduce the resistance of the charge should be specialized laying of its components.
  • metal reducing agents having low resistance can be stacked inside the container in the form of separate rods, spirals, etc., connecting the upper and lower contacts with each other, thereby passing current through them these places will heat up the entire volume of the reaction mixture, by itself, giving an impetus to the development of a spontaneous reaction.
  • Reducing metals can also be used in the form of a rod, wire, pipe, wire mesh, etc., laid inside the container, around which the remaining reaction mixture is poured.
  • the lower cooled copper contact 3 in this device serves as a simultaneously cooled tray on which the reduced metal crystallizes, thereby mixing the reaction to the right and increasing the yield of metal.
  • the diameter of the workpiece due to the increase in heating time should not be more than 150 mm or it is necessary to use installations of excessively high power;
  • the ratio of the length of the workpiece to the diameter should be at least 30: 1;

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L’invention concerne la production de métaux chimiquement actifs. Elle permet de réduire la consommation d’énergie électrique et d’augmenter la productivité. Le procédé consiste à placer une charge de réaction, constitué d’oxyde du métal à réduire et de métal de réduction, dans une zone de réaction, à réchauffer la charge et à obtenir le métal et le laitier. On effectue la réduction et la séparation en utilisant les contacts ayant la fonction d’anode et de cathode. Le réchauffement est assuré par la résistance électrique de la charge lors de la circulation de courant électrique et l’alimentation des contacts en tension lors du mouvement du métal réduit vers la cathode et lors du mouvement du laitier vers l’anode. L’énergie thermique nécessaire à la séparation du métal et du laitier est assurée par la compression continue des contacts contre la charge, qui s’effectue avec une force déterminée, lesdits contacts servant à communiquer des vibrations basse ou haute fréquence. Le dispositif comprend un boîtier monté vertical comportant une couche isolante destiné à accueillir la charge de réaction et des contacts assurant la fonction d’anode et de cathode pour créer une résistance électrique de la charge lorsqu’une tension électrique alimente les contacts. La cathode est disposée dans le bas du boîtier est sert simultanément de bac. Chaque contact est doté d’un poinçon de compression et est refroidi.
PCT/RU2009/000222 2008-05-12 2009-05-08 Procédé et dispositif de production de métaux chimiquement actifs par résistance électrique de tiges Ceased WO2009139666A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2008118761/02A RU2008118761A (ru) 2008-05-12 2008-05-12 Способ и устройство производства химически активных металлов методом стержневого электросопротивления
RU2008118761 2008-05-12

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WO2009139666A1 true WO2009139666A1 (fr) 2009-11-19

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB800311A (en) * 1956-06-22 1958-08-27 Nat Lead Co Method and apparatus for producing refractory metal compacts
US5242481A (en) * 1989-06-26 1993-09-07 Cabot Corporation Method of making powders and products of tantalum and niobium
RU2063598C1 (ru) * 1993-05-12 1996-07-10 Акционерное общество закрытого типа "Белый соболь" Электропечь сопротивления

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB800311A (en) * 1956-06-22 1958-08-27 Nat Lead Co Method and apparatus for producing refractory metal compacts
US5242481A (en) * 1989-06-26 1993-09-07 Cabot Corporation Method of making powders and products of tantalum and niobium
RU2063598C1 (ru) * 1993-05-12 1996-07-10 Акционерное общество закрытого типа "Белый соболь" Электропечь сопротивления

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZELIKMAN A.N.: "Metallurgiya tugoplavkikh redkikh metallov", METALLURGIYA, 1986, MOSCOW, pages 414 - 419 *

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Publication number Publication date
RU2008118761A (ru) 2009-11-20

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