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WO2009139667A1 - Procédé et dispositif de production dans un autoclave de métaux chimiquement actifs - Google Patents

Procédé et dispositif de production dans un autoclave de métaux chimiquement actifs Download PDF

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Publication number
WO2009139667A1
WO2009139667A1 PCT/RU2009/000223 RU2009000223W WO2009139667A1 WO 2009139667 A1 WO2009139667 A1 WO 2009139667A1 RU 2009000223 W RU2009000223 W RU 2009000223W WO 2009139667 A1 WO2009139667 A1 WO 2009139667A1
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WIPO (PCT)
Prior art keywords
autoclave
reaction
cooling
heating
time
Prior art date
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Ceased
Application number
PCT/RU2009/000223
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English (en)
Russian (ru)
Inventor
Анатолий Евгеньевич ВОЛКОВ
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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
    • 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
    • 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
    • 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
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium

Definitions

  • the present invention relates to the field of the production of chemically active metals from ore raw materials and other compounds and can be used for the production of metals, including chemically active and refractory metals, which can be melted due to the occurrence of metallothermic reactions.
  • the method of metal reduction, the production of ceramics and other compounds, and the reactor device (autoclave) in which the metal reduction process is performed are selected as an analog.
  • This method involves mixing reagents (oxidizing agent and reducing agent), heating the charge, followed by loading the charge into the reactor, which is then transferred to the mine. After loading the charge, the reactor is closed and, depending on the target, vacuum or fill with inert or reaction gases, initiate the reaction.
  • CBC self-propagating high-temperature synthesis
  • This method proceeds in an enclosed space at ordinary pressures created by the reaction products. ⁇
  • the course of the CBC process is controlled by the change in gas pressure in the reactor and the temperature of the cooling water.
  • the CBC method has found great application in the production of nitrided ferroalloys for steelmaking. This is the most effective way to introduce nitrogen into steel.
  • the autoclave for implementing this method is made in the form of a thick-walled vessel, hermetically sealed on top with a lid, which is internally lined with refractory insulating ceramics, on the outside of which there is a water-cooling shirt.
  • the vessel is equipped with gates.
  • Reactors differ in the volume of the reaction zone: from 1 to 30 liters.
  • the internal structure of the reactor meets specific requirements, depending on the type of synthesized products.
  • the inner surface of the reactor is lined with graphite.
  • the reactor is equipped with a special device that allows filtering the reacting gases into the reaction zone.
  • the snap-in eliminates the evaporation of charge components and condensation on the inner surface of the reactor.
  • termite additives are used, which leads to an increased consumption of the reducing agent per ton of the alloy obtained, and, consequently, to the high cost of the metal;
  • the closest technical solution is a metallothermic method for the reduction of molybdenum from its oxides and a sealed cylindrical steel reactor (autoclave) lined with refractory (CaO, Al 2 O 3 ) (A.N. Zelikman - Metallurgy of refractory rare metals, - Moscow: Publishing House “Metallurgy”, 1986, p. 185).
  • This method involves mixing reagents (oxidizing agent and reducing agent), heating the mixture, followed by loading the mixture into a reactor (autoclave), which is then transferred to the mine. After loading the charge, the reactor is closed and, depending on the target, vacuum or fill with inert or reaction gases, and initiate the reaction using arson. Local initiation of the process of self-propagating high-temperature synthesis (CBC) is carried out from the control panel by supplying a short-term electrical impulse to a tungsten spiral relating to the initial charge. The reaction results in the separation of metal and slag. After which spontaneous cooling occurs, the subsequent unloading of the reaction products and their mechanical separation.
  • a reactor autoclave
  • This method proceeds in an enclosed space at ordinary pressures created by the reaction products.
  • CaO is introduced as a flux to reduce the melting temperature of the slag (Al 2 O 3 ) and its viscosity in the mixture.
  • Slag containing 20-30% CaO has a melting point of 1700-1800 0 C.
  • the reactor (autoclave) for implementing this method is made in the form of a cylindrical container lined from the inside, equipped with a bottom and a lid.
  • the reactor is made of seamless pipes of small diameter (300-400 mm) with a height of 1100-1200 mm, to which the bottom and cover are hermetically connected.
  • the specified method and device have the following disadvantages: - the inability to heat the prepared mixture directly in the autoclave, because the body of the autoclave (reactor) is lined with refractory insulating ceramics, which does not allow to conduct a recovery reaction preliminary heating of the powder mixture, in addition, when falling into the autoclave, the safety of the process is impaired, since the heated powder is prone to spontaneous combustion;
  • the technical problem of the proposed invention is to develop a method and device for its implementation, which allows to ensure the safety of the production of chemically active metals, reducing energy, economic and capital costs, as well as reducing costs and increasing the volume of metal produced.
  • the task is achieved in that in the autoclave production of chemically active metals, based on the inclusion of metal-thermal reduction of the reaction mixture in the autoclave under a certain (required) pressure, the autoclave is installed in a vertical hermetically sealed shaft, which functions as a direct-flow cooling pipe and ensures the safety of the process.
  • the autoclave body transfers the required heat for the reaction mixture in the first stage (before starting the charge ignition), and in the second stage it performs mold functions.
  • the heating time of the reaction mixture through the autoclave body and the cooling time of the body are calculated with particular accuracy, including the heating time of the autoclave, its transportation, cooling, electric ignition of the reaction mixture, so that the mechanical strength of the wall of the autoclave body due to cooling is restored simultaneously with an increase in gas pressure.
  • oscillations of such a frequency can be superimposed on the autoclave at which maximum recovery of the reduced metal is achieved.
  • a device for the autoclave production of chemically active metals contains a metal sealed container, an adjustment valve, an ignition system.
  • the device is characterized in that the tank, designed for installation in a shaft with running water, in the lower part is made in the form of a cone with a lid to facilitate removal of reaction products.
  • the tank can be equipped with a vibration device to create mechanical vibrations at the time of the reaction.
  • Figure l shows a device that implements the proposed method.
  • the proposed method is implemented using the device shown in Fig.l.
  • the device in the form of an autoclave is a metal sealed container with a melting chamber 1, the upper part of which is made in the form of a pipe, and the lower part is made in the form of a cone with a pallet 2, in which the reaction mixture melts due to metallothermy, which decomposes after melting into a metal ingot 3, formed on the cooled tray 2, and slag 4.
  • the autoclave is installed in a vertical shaft 5.
  • a pipe 6 is installed for supplying a jet of water to the cooled tray 2 and cooling the autoclave body. Subsequently, the water is discharged through line 7.
  • the top of the autoclave is closed by a lid 11, through which the electric valve 8 passes, and also the line 9 with an adjustable valve 10.
  • the bottom of the autoclave is mounted on vibration devices 13, which during the course of the reaction condense the reaction mixture, removing as much as possible into the ingot possible mass of metal.
  • the shaft 5 is hermetically closed by a cover 14 due to the locking mechanisms 15.
  • the process temperature Since the temperature of the process is proportional to its specific heat, the rate of aluminothermic melting also increases with the growth of the latter. In an out-of-furnace aluminothermal process, the rate of charge blending, determined by the temperature of the process, in turn, can affect the temperature level of smelting. With a decrease in the speed of the process, the fraction of heat losses proportional to the melting time increases, and, consequently, the temperature of the process decreases, and with an increase in the speed of the process, its temperature increases.
  • Another equally important point in the metallothermic reaction is the pressure at which the reaction proceeds.
  • the dependence of the rate of the metallothermal reaction on the magnitude of the external pressure is interesting not only from the point of view of practical smelting, but also to elucidate the mechanism of the out-of-furnace metallothermal process.
  • This mechanism can be disclosed by the example of an aluminothermic reaction. Due to the fact that gaseous substances are not included in the stoichiometric equation of the aluminothermic reduction reaction, and also due to the high boiling points of the starting materials and reaction products, it can be assumed that the main reactions the minothermal process occur between the condensed phases. In this case, the external pressure does not significantly affect the reaction rate.
  • the reaction rate is largely determined by the magnitude of the external pressure.
  • the rate of gas reactions will increase due to an increase in gas density and the number of collisions of gas molecules or due to an increase in the number of impacts of gas molecules on the surface of the condensed phase at the phase boundary.
  • the dependence of the propagation velocity of the reaction front of a number of aluminothermic mixtures (CG 2 O 3 + Al, Fe 2 Cb + Al, MnO 2 + Al) on external pressure was studied by A. F. Belyaev and L. D. Komkova.
  • an increase in pressure does not affect the reaction rate.
  • Pressure reduction to 50-100 mm RT. Art. also does not lead to a noticeable change in the reaction rate. This suggests that the aluminothermic reduction of chromium oxide at temperatures of 1900-2100 ° K occurs without the participation of the gas phase.
  • reaction rate increases with increasing pressure.
  • the greatest increase in speed is observed at pressures up to 20-40 atm. (20-40 bar).
  • the increase in velocity slows down, and with a decrease in pressure to 50-100 mm Hg. Art. the reaction rate decreases to 0.7-0.8 cm / sec.
  • termite additives are used.
  • a significant drawback of the use of termite additives is an increase in the consumption of a reducing agent per ton of the resulting alloy, which significantly increases the cost of metal and is not always economically justified.
  • Another disadvantage of using termite additives is an increase in the amount of slag and a decrease in the concentration of the main reducible oxide in the melt, which worsens the conditions of both the reduction of oxides and the deposition of droplets of the reduced metal. Therefore, in metallothermal processes, it is necessary to strive for a minimum consumption of termite additives.
  • preheating of charge materials is more effective, at which there are no costs for an expensive reducing agent.
  • the method of the proposed autoclave melting is designed to fulfill all the necessary conditions that contribute to the maximum recovery of the recoverable metal with minimal use of the metal reducing agent, and, therefore, is designed to minimize the cost of production. Increased efficiency in metal yield is ensured due to the fact that the normal release of a substance that occurs in open containers is prevented. So, for example, autoclave melting can provide a flow stocks under pressure, while many recovery reactions will proceed more fully with a higher metal yield efficiency. The gases formed during the course of the reaction in the autoclave, without leaving its inner space, thereby do not cool the reaction products and do not inhibit the recovery process, while these same gases create the necessary pressure, contributing to a more complete course of the recovery process. Therefore, due to this, capital costs are reduced. In order for the reaction products to be cleaner from gas inclusions, the autoclave can be evacuated before reduction and inert gases can be pumped into the interior.
  • the body of the autoclave is metal without an inner lining. This feature allows you to heat the prepared mixture directly in the autoclave before starting the recovery reaction. This allows you to very accurately control the heating temperature, to conduct heating in a vacuum or inert gas environment. If you pre-heat the powder mixture and then pour it into the autoclave, then the safety rules will be violated, since the heated powder is more prone to spontaneous combustion.
  • the heating time should be optimal so as not to expend unnecessary energy. Given the fact that it takes a certain time to warm up the reaction mixture in an autoclave, it is also necessary to take into account the time to transfer the autoclave from the heating furnace to the shaft, as well as the time to close and fill it with water. Most of the heat will be absorbed by the body of the autoclave and then due to radiation, convection of gases and thermal conductivity will be gradually transferred to the inside of the autoclave. When heating the reaction mixture, it is necessary to calculate the heating of the autoclave body in such a way as to take into account the thermal energy that will enter the charge during the transportation of the autoclave from the heating furnace to the shaft and the time before ignition of the reaction mixture.
  • the autoclave body will transfer part of the missing thermal energy to the reaction mixture to a theoretically calculated temperature.
  • the autoclave body In order for the autoclave body to regain its mechanical strength, since it will decrease due to its heating, it will need to be cooled with water before the moment of ignition. It should be noted that if the autoclave body is cooled for a long time, the reaction mixture inside the autoclave will be cooled. From an energy point of view, this will cause significant losses to the metal reduction process. Therefore, the technological process when implementing the proposed method for the autoclave production of chemically active metals takes into account the time required to cool the body of the autoclave, which must withstand the pressure created by the reaction products.
  • the autoclave body plays a large technological role in carrying out the reduction reaction, both at the preparation stage and at the subsequent stage of recovery. That is, through the autoclave body at the preparation stage, the reaction mixture is warming up. At the time of increasing gas pressure, the body cools and restores mechanical strength, holding gas pressure. When a metal ingot is formed, the body of the autoclave, and in particular its cooled copper tray, removes thermal energy from the ingot, thereby increasing the volume of metal produced, since the reduction reaction will shift to the right.
  • the autoclave is mounted on vibration devices 13, which operate due to pneumatics, electric motors, electromagnets, etc. drives.
  • vibration will reduce the viscosity of the melt and make heavier the droplets of the reduced metal, which will allow them to stand out from the slag in a larger volume and form into an ingot.
  • vibration will reduce the viscosity of the melt and make heavier the droplets of the reduced metal, which will allow them to stand out from the slag in a larger volume and form into an ingot.
  • Due to vibration mixing of the reaction mixture will increase, which will increase the fluidity and the reaction rate. Due to this, the reaction temperature will increase, the reduction time of the metal will decrease, which will reduce the metal consumption of the reducing agent, reduce the initial heating temperature of the charge (therefore, reduce the energy consumption of the process) and increase the yield.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

L’invention concerne la production de métaux chimiquement actifs à partir de minerai et peut s’utiliser pour produire des métaux chimiquement actifs pouvant être produits par fusion grâce à des réactions métallothermiques. Le procédé comprend la réduction métallothermique d’une charge de réaction dans un autoclave sous pression. L’autoclave est monté dans une cheminée étanche dans laquelle circule l’eau de refroidissement. Le boîtier de l’autoclave communique la chaleur nécessaire à la charge de réaction dans un premier stade et fonctionne comme un cristalliseur dans un deuxième stade. Le temps de réchauffement de la charge de réaction à travers le boîtier et le temps de refroidissement du boîtier sont calculés en tenant compte du temps de chauffage de l’autoclave, de transport, de refroidissement et d’allumage électrique du mélange de réaction de manière à ce que la résistance mécanique de la paroi de l’autoclave se rétablit grâce au refroidissement simultanément à l’augmentation de la pression des gaz. Le dispositif pour mettre en oeuvre ce procédé comprend un autoclave se présentant comme un récipient métallique étanche comportant un bac et un couvercle, une soupape de réglage, un système d’allumage et une cheminée. Le récipient est monté dans une cheminée refermable étanche à eau circulante, et sa partie inférieure se présente comme un cône et est dotée de vibreurs. Le dispositif assure la sécurité du processus et permet de réduire les frais et d’augmenter le volume de production de métal.
PCT/RU2009/000223 2008-05-12 2009-05-08 Procédé et dispositif de production dans un autoclave de métaux chimiquement actifs Ceased WO2009139667A1 (fr)

Applications Claiming Priority (2)

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RU2008118752 2008-05-12
RU2008118752/02A RU2405045C2 (ru) 2008-05-12 2008-05-12 Способ и устройство автоклавного производства химически активных металлов

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0170372B1 (fr) * 1984-07-03 1988-08-17 General Motors Corporation Réduction métallothermique d'oxydes de terres rares par du calcium métallique
RU2003128051A (ru) * 2003-09-18 2005-04-10 Открытое акционерное общество "Чепецкий механический завод" (ОАО ЧМЗ) (RU) Магниетермический способ получения губчатого циркония и устройство для его осуществления
RU2311469C2 (ru) * 2005-06-30 2007-11-27 Общество с ограниченной ответственностью Фирма "ДАТА-ЦЕНТР" (ООО Фирма "ДАТА-ЦЕНТР") Способ производства титаносодержащей продукции и устройство для осуществления способа

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100443603C (zh) * 2005-10-26 2008-12-17 武汉科技大学 利用含钛炉渣制备钛及钛合金的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0170372B1 (fr) * 1984-07-03 1988-08-17 General Motors Corporation Réduction métallothermique d'oxydes de terres rares par du calcium métallique
RU2003128051A (ru) * 2003-09-18 2005-04-10 Открытое акционерное общество "Чепецкий механический завод" (ОАО ЧМЗ) (RU) Магниетермический способ получения губчатого циркония и устройство для его осуществления
RU2311469C2 (ru) * 2005-06-30 2007-11-27 Общество с ограниченной ответственностью Фирма "ДАТА-ЦЕНТР" (ООО Фирма "ДАТА-ЦЕНТР") Способ производства титаносодержащей продукции и устройство для осуществления способа

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZELIKMAN A.N.: "Metallurgiya tugoplavkikh redkikh metallov", METALLURGIYA!, 1986, MOSCOW, pages 184 - 186 *

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RU2008118752A (ru) 2009-11-20
RU2405045C2 (ru) 2010-11-27

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