• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The plant for the electrolytic production of a metal in a molten salt bath by deposition at the cathode in the solid state includes an outer casing (2), means (16a, 20a) for maintaining an atmosphere inert to the metal to be produced in the casing, a container (6) within the casing and arranged to contain the molten salt bath and having a movable cover (48), a plurality of electrodes (52) suspended in the molten salt bath each bearing on means (54a, 54b) for supporting it and connecting it electrically, the means comprising for each of the electrodes a pair of electrically conductive elements (56) facing each other and supported respectively by two opposite walls of the container and handling means (8) associated with the outer casing for removing any one of the electrodes from the container after raising of the movable cover.
    公开号:SU1540657A3
    申请号:SU864027846
    申请日:1986-07-21
    公开日:1990-01-30
    发明作者:Винченцо Джинатта Марко；Орселло Джанмикеле
    申请人:Электрокимика Марко Джинатта С.П.А. (Фирма)；
    IPC主号:
    专利说明:

    This invention relates to the electrolytic production of metals in molten salt baths, in particular for metals such as titanium, zirconium and hafnium.
    The aim of the invention is to increase productivity and reduce its cost.
    Figure 1-3 shows the longitudinal sections of the respective adjacent parts of the installation; FIG. 4 shows the connection of the parts shown in FIGS. 1-3 with each other; figure 5 is a section aa in figure 1; figure 6 - section bb in fig.Z; Fig. 7 is a part of the installation illustrating the elements in isometry; on Fig - part of the installation of figure 5, on an enlarged scale; figure 9 - part of the installation, a partial section; figure 10 - elements shown in figure 9, a partial section; figure 11 - the electrode used in the installation; on Fig - section bb In figure 11.
    The installation shown in the drawings contains an outer metal casing 1 forming the main chamber 2, which is practically isolated from the environment and in which there is a container 3 for a bath of molten salts, in which electrolysis is carried out, and also contains a control device 4
    The casing 1 has 1 front chamber 5 in which materials are exchanged between the environment and the main chamber 2. The front chamber 5 is equipped with gas-tight doors 6 and 7, which connect it with the chamber 2 and the external environment, respectively.
    Outside the casing 1, vacuum pumps 8 and 9 are located, having corresponding pipes 10 and suction, which are connected respectively to chambers 2 and 5, maintaining in them a controlled atmosphere, in particular, an atmosphere that is inert relative to the metal being produced. At position 12, the electrode is shown, and at positions 13, 14, the capacity of the compressed
    five
    0
    5 5
    0
    five
    inert gas, usually argon, from where the inert gas enters the casing 1 through pipes 15 and 16, respectively.
    The tank 3 for a bath of molten salts is a parallelepiped with heat insulating lining.
    17, adjacent to the casing 1, as well as with refractory inner lining
    18.In the inner lining there is a metal shell 19, which also has the shape of a parallelepiped and is a crucible for a bath of molten salts. The metal sheath 19 rests on the base of the refractory inner lining 18. Preferably, there is a gap between the current walls of the sheath 19 and the refractory inner lining 18
    20. Heating elements 21 (FIG. 3) are installed in that part of the side walls of the refractory inner lining 18, which faces the side walls of the shell 19, heating the bath of molten salts in the crucible to the melting point and maintaining this temperature. Heating means in the form of heating elements 21 are also located at the base of the refractory inner lining 18. The bath of molten salts can be heated by electrodes immersed in an electrolyte, which are powered by alternating voltage transformers (or use heating elements 21).
    The container 3 is equipped with a sealing means 22, which prevents the passage of corrosive gases from the crucible through the gap 20 and eliminates the corrosion of the heating elements.
    21. The sealing means consists of a container 23 that runs along the entire upper edge of the refractory inner lining 18 and in which the molten metal 24 is located.
    The plate 25 is immersed vertically in the molten metal in the vessel 23 and welded to the flange 26 attached to the upper edge of the shell 19.
    The choice of metal in the vessel depends on the temperature level of the lining material. This metal should have a melting point below the operating temperature of the lining material.
    The pipe 27 passes through the wall of the container 3 and connects with the gap 20, as well as with the vacuum pump 8 parallel to the pipe 10, maintaining the pressure in the gap 20 substantially equal to the pressure in the chamber 2.
    The outer casing 1 holds the frame 28, which overlaps the upper edge of the inner lining 18 and acts as a support for several lifting movable covers 29, which, resting on the frame 28, cover the container 3 and exclude the release of gaseous substances arising during the electrolysis process from tank 3 to chamber 2.
    Each cover 29 has a hydraulic line 30 connected to it, connected to the wall of the outer casing 1 and intended to lift the cover to the vertical position, allowing the control device 4 to be located inside the tank 3.
    The electrodes 31 inside the vessel 3 are held by the elements 32 and 33, with an electrical connection between them (Fig. 9).
    Each of the supporting and electrically conductive elements 32 and 33 comprises an electrically conductive rod 34, which is a hollow steel rod enclosed by a tightly mounted electrical insulating flame resistant sleeve 35, which is inserted into a tubular metal element 36. Each tubular element 36 passes through a frame 28 filled with refractory material , in the direction perpendicular to the corresponding wall of the container 3. The end 37 of each rod 34, which is outside the container 3, is connected to a power supply 38, which supplies a constant current, and the other end 39 passes inside the tank 3 and has a seal 40.
    A pair of rods 34 facing each other, is located in the opposite walls of the tank 3, holding the electrodes 31.
    Inside each rod 34 there is a heat exchange device consisting of two concentric tubes 41 and 42 through which a cooling fluid circulates, the inlet of which is indicated
    0
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    five
    five
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    position 43, and the output - position 44. Circulating coolant during the production of metal provides a high electrical conductivity of the rod, increasing the electrical efficiency of the installation.
    Fig. 10 shows in detail a device for mounting each rod 34 in the case 1 with the exception of the passage of air into the container 3 or the exit of gaseous substances from it during the operation of the installation, while providing electrical insulation for each rod.
    Each rod 34 is welded to an annular flange 45 clamped by bolts 46 between two annular flanges 47 and 48. The annular flange 48 is welded to the outer casing 1 and presses the annular clamping gasket to the flange 45. Between the annular flange 48 and the outer surface of the rod 34 there are bushings 49, 50 made of an electrically insulating material, such as asbestos or fluoroplastic. The annular sealing sleeves 51, 52 are located between the flanges 45 and 47. Inside the flange 47 there is a sleeve 53 covering a metal sleeve welded to the rod 34. In the flange 48 and the sleeve 53, channels 54 and 55 are provided for circulating coolant.
    Fig. 11 shows an electrode 31, in particular a cathode, which is used in an apparatus according to the invention. The electrode includes a housing 56 that holds a hollow metal cylinder 57 on which the resulting metal is deposited. Two arms 58 and 59 extend from the body, at their distant ends there are recesses 60, corresponding to the shape of seal 40 at ends 39 of rods 34.
    The surfaces of the recesses extend at an angle of 110-130 to each other, preferably at an angle of 120e ().
    The electrical contact between the electrode and the support rod is provided by the weight of the electrode itself, as well as by the inclination of the surfaces of the seals 40 to each rod 34, which provides a significant reduction in powder deposition in electrical contact areas between the electrode and the corresponding stop rod.
    The invention is not limited to the specific device of the electrodes 31 or their specific arrangement inside the crucible, they can vary within wide limits, although the principle of formation of a support for each electrode as well as the electrical connection described above remains the same.
    The installation device and, in particular, the electrode device of the invention allows independent electrical control for each electrode, which makes it easy to replace the electrodes without stopping the process for disassembling the electrolyzer. This provides advantages when using graphite anodes, which can be accidentally broken.
    In the event of a power interruption, the electrodes can be quickly removed from the electrolyte bath, thereby eliminating the electrocution that can be caused by a decrease in the volume
    bath when it is cooled.
    The installation allows it to introduce a composition containing the produced metal in a solid or gaseous state. The installation can only be used to clean the base metal. If the supply is carried out in a gaseous state, the supply nozzles (not shown) can pass through the walls of the container 3. If the supply is made in the solid state, then the solid metal composition or the metallic raw material can be supplied using the control unit 4. For this, the anodes can have T-shaped supports, shown in Fig. 11, with baskets attached to the lower ends, in which a solid composition containing the metal to be produced, or metallic raw materials are placed.
    In the vessel 3 there are thermocouples for controlling the temperature inside it, as well as samplers and sensors for measuring parameters that change during operation. In addition, the tank 3 is equipped with a vacuum pump, a pipe from which passes into the inside of the crucible to remove the gases formed during the electrolysis process. Exhaust gases can be cleaned outside the plant or removed.
    The control device 4 comprises a guide 61 located in the casing 1 and installed in parallel
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    0 5 0
    5 0 5
    the longitudinal edge of the container 3. The manipulator 62 is mounted on the guide 61 with the possibility of movement by a driving device and has a forked lever 63 with a grip 64 at the end, which interacts with the arms 58 and 59 that are on each electrode. Manipulator 62 has a predominantly oil drive located outside the casing, and fluid supply pipes pass through seals in the walls of the outer casing.
    To remove the electrodes or at least to move them, it is enough to lift one or more covers 29 by hydraulic actuators 30, providing access to the manipulator 62 inside the vessel 3 and removing the specified electrode. This operation does not require interrupting the electrolysis process. After the sealing gas-tight door 6 is opened, the electrode is removed from the container 3 and is placed in the front chamber 5 with the aid of the manipulator 62 in the cooling chamber, followed by the removal of the metal product. A new electrode, e.g., a -the latch 65, stored in the main chamber 2 on the guide 66, can be immediately taken by the manipulator and placed in an electric bath without interrupting the operation of the installation.
    The manipulator can be controlled automatically or with the help of an operator who sees the inside of the container directly through the holes 67, provided with covers and made in the walls of the outer casing.
    Additional devices of the installation of the invention, such as furnace 68 and metal removal means in the form of a scraper device 69, can be placed in chamber 5. Furnace 68 has removable roof 70 and support device 71 for hanging cathode 72 in the furnace after it is removed from the molten salt bath.
    A scraper device 69 for removing a metal product comprises a housing 73 with a bottom 74, as well as a scraper 75 that removes the deposited metal from the surface of the cathode.
    In the process of metal production, the cathode, on the active surface of which a metal product is deposited, is removed from the bath of molten salts and placed with the manipulator 62 in the furnace 68, in which the melting point of the molten salts is maintained. The cathode is kept in the furnace for a period of time sufficient for the electrolyte to be completely removed from the surface. The electrolyte is saturated with the derivative metal dissolved in it and in the ionized state, and since the material is valuable, it is collected in a crucible 76 in the furnace. As soon as the electrolyte is removed, the metal product is removed from the cathode surface by inserting the cathode into the scraper device 69 using the manipulator 62. The metal product that is collected on the open hearth 74 is removed from the casing 1 by the carriage 77
    i
    The casing also forms the chamber 78
    to remove the manipulator, which is located near / with the front chamber 5 and is connected to it by a sliding valve 79. Atmospheric control is maintained in the chamber 78 by supplying inert gas to it. The main purpose of the chamber 78 is to remove the manipulator, which is transferred for repair and deoxidation into the chamber 2, in which it flows around the gases leaving the electrolyzer. For this, the chamber 78 has a guide 80 that coincides in direction with the guide 61, as well as rollers 81. The manipulator can move along the guide 82, along which the rollers 81 roll.
    A pair of hydraulic cylinders 83, driven outside the casing 1, moves the guide 80 along the guides 82, positioning it near the guide 61 after opening the slide valve 79 and thus continuing the last guide and moving the manipulator to the chamber 78 extract.
    Adjacent to the chamber 2 is an additional chamber 84, in which electrodes 85 are stored, which lie on rails that move from the hydraulic drive to move the electrodes through the connecting gate 86 to the chamber 2.
    Each electrode 85 has a flexible pipe 87 attached to the body of the electrode, through which the material to be processed is loaded into a bath in
    d) about 15, 20
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    in the form of particles or liquid in inert gas. Each flexible tube is screwed onto a coil 88, its outer end is connected to reservoir 89 for the feed material. The electrode, which is introduced into chamber 2 through connection valve 86, can be positioned in the electrolysis cell by means of a manipulator that supports a flexible pipe through which raw materials are charged, usually TiCl or TiO, if titanium is produced. If the feed material blocks the supply pipe, which can occur when loading a solid material, the electrode can be removed from the bath and sent to chamber 84, the flexible pipe being wound and replaced or cleaned, and the process can be continued because the raw material loading is interrupted for a long time. small period of time. This is another distinctive feature of the invention in comparison with analogs, since in conventional installations it is impossible to replace the pipe through which the raw material is loaded without stopping the operation of the entire electrolyzer.
    Next to an additional chamber 84, a chamber 90 is located, having a movable arch 91 and connected to the surrounding space through an additional damper 92. Chamber 90 is used to store several pipes for sampling electrolyte. The electrolyte analysis is carried out by raising the movable roof 91, moving the probe with the manipulator into the bath of molten salts, and then transferring the pipe to chamber 90. An additional valve 92 allows the sample to be withdrawn from the housing, while restricting the release of inert gas from the housing 1.
    A plant in accordance with the invention can be used to carry out refining and extraction processes. It can, for example, include a crucible with an extraction chamber to produce a metal (for example, titanium) from an electrolyte with a size (in diameter) of 1.5x1.5 and a length of 3 seconds. Three flat cathodes with an active surface of 2 mg each with a total capacity of 200 kg of metal / day can be placed in this chamber. The crucible may contain a chamber for the solution11
    ny metal in the electrolyte (for example, titanium from TiCl) of size (in diameter) 1.5 x 1.5 and 2 m long, as well as two cathodes for the cathode dissolution of the compound.
    The proposed installation works in such a way that each of the electrodes to be extracted is removed after 24 hours of operation. After the end of the operating time at the cathode, the cover 29 is opened, the electrode 31 is lifted by means of the -control device 4 and placed in the furnace 68 to regenerate the electrolyte. After that, the resulting metal is scraped off with the help of the device 69. Immediately after placing the developed cathode into the furnace, the transporting means places the new cathode in the baths with molten salt. The time required for this operation does not exceed several minutes, so that the installation can operate almost continuously.
    权利要求:
    Claims (1)
    [1]
     Invention Formula
    An installation for the electrolytic production of a reactive metal, mainly titanium, zirconium
    1540657
    12
    0
    five
    and holding each electrode located opposite each other in two opposite walls of the container near its opening, each of the conductive elements is installed using a hollow rod protruding at one end inside and the other outside the vessel to connect to a source of electrical power, the end of the rod inside the tank is made with compaction and heat exchange means in the form of concentric tubes with circulating fluid located in the cavity of the rod, each of the electrodes is made with a T-shaped support, having the two shoulders extending from the base and the supporting recess on the outer end, in a form corresponding to the shape of the seal of each conductive element in the form of a dihedral angle with planes at an angle of 110-130 ° relative to each other, the movable cover of the container lifting elements located close to each other and supported by the upper edge of the container, and actuators for interacting with the corresponding element of the lid for raising it,
    or hafni containing outer casing, 30 installation equipped with a main chamber
    Means for introducing an inert gas into the outer casing, a container located inside the bath casing of molten salt, having a top opening with a movable lid, 1 heating means, suspended electrodes, control means for removing electrodes from the bath and means for removing the resulting metal from the surface of the electrode, characterized in that, in order to increase productivity and reduce its cost, it is equipped with a pair of electrically conductive elements for connecting
    0
    for positioning the control means and the anterior chamber, which is connected to the main chamber and to the external environment through gas-tight doors, the furnace, the anterior chamber to accommodate at least one electrode for the extraction of metals after its removal from the bath, the additional chamber for storing the electrodes communicating with the main chamber through the flap, and flexible pipes for supplying raw materials associated with the electrodes.
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    同族专利:
    公开号 | 公开日
    DK339486A|1987-01-23|
    AT46369T|1989-09-15|
    IN167797B|1990-12-22|
    YU130086A|1987-12-31|
    NO862906D0|1986-07-18|
    IT1199898B|1989-01-05|
    FI862999A0|1986-07-21|
    FI81839B|1990-08-31|
    PT83029A|1986-08-01|
    CA1291442C|1991-10-29|
    US4670121A|1987-06-02|
    YU43954B|1989-12-31|
    NO862906L|1987-01-23|
    EP0210961B1|1989-09-13|
    EP0210961A1|1987-02-04|
    DK339486D0|1986-07-16|
    AU6013686A|1987-01-29|
    IL79443A|1989-10-31|
    JPS6270590A|1987-04-01|
    FI81839C|1990-12-10|
    AU569976B2|1988-02-25|
    IL79443D0|1986-10-31|
    MX163400B|1992-05-11|
    ES2000707A6|1988-03-16|
    BR8603451A|1987-03-04|
    FI862999A|1987-01-23|
    DE3665612D1|1989-10-19|
    PT83029B|1992-08-31|
    IT8567669D0|1985-07-22|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3562134A|1966-06-08|1971-02-09|Nat Lead Co|Continuous process for producing magnesium metal from magnesium chloride|
    NO124039B|1968-06-07|1972-02-21|Montedison Spa|
    US3580835A|1969-02-24|1971-05-25|Kaiser Aluminium Chem Corp|Electrolytic reduction cell|
    US4089770A|1977-07-11|1978-05-16|E. I. Du Pont De Nemours And Company|Electrolytic cell|
    US4133728A|1978-01-26|1979-01-09|E. I. Du Pont De Nemours And Company|Electrolytic cell with switching means|
    DE3102021C2|1981-01-22|1984-02-23|Siemens AG, 1000 Berlin und 8000 München|Device for the galvanic deposition of aluminum|GB8805447D0|1988-03-08|1988-04-07|British Petroleum Co Plc|Chemical process|
    US4923577A|1988-09-12|1990-05-08|Westinghouse Electric Corp.|Electrochemical-metallothermic reduction of zirconium in molten salt solutions|
    US4923579A|1988-09-12|1990-05-08|Westinghouse Electric Corp.|Electrochemical process for zirconium alloy recycling|
    US4874475A|1988-09-12|1989-10-17|Westinghouse Electric Corp.|Molten salt extractive distillation process for zirconium-hafnium separation|
    US4865695A|1988-09-12|1989-09-12|Westinghouse Electric Corp.|Preparation of complexes of zirconium and hafnium tetrachlorides with phosphorus oxychloride|
    US4865694A|1988-09-12|1989-09-12|Westinghouse Electric Corp.|Electrochemical decomposition of complexes of zirconium or hafnium|
    JPH06240499A|1993-02-12|1994-08-30|Yamaha Corp|Plating method and apparatus|
    ITTO970080A1|1997-02-04|1998-08-04|Marco Vincenzo Ginatta|PROCEDURE FOR THE ELECTROLYTIC PRODUCTION OF METALS|
    US6063254A|1997-04-30|2000-05-16|The Alta Group, Inc.|Method for producing titanium crystal and titanium|
    US6309595B1|1997-04-30|2001-10-30|The Altalgroup, Inc|Titanium crystal and titanium|
    US6024847A|1997-04-30|2000-02-15|The Alta Group, Inc.|Apparatus for producing titanium crystal and titanium|
    US7504017B2|2001-11-22|2009-03-17|Qit-Fer Et Titane Inc.|Method for electrowinning of titanium metal or alloy from titanium oxide containing compound in the liquid state|
    JP2011058015A|2009-09-07|2011-03-24|Toyo Tanso Kk|Electrolytic device|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    IT67669/85A|IT1199898B|1985-07-22|1985-07-22|PLANT FOR ELECTROLYTIC PRODUCTION IN THE BATH OF MELTED SALTS OF REACTIVE METALS|
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