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US20080053838A1 - Method for Production of Metal by Molten-Salt Electrolysis and Method for Production of Titanium Metal - Google Patents

Method for Production of Metal by Molten-Salt Electrolysis and Method for Production of Titanium Metal Download PDF

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Publication number
US20080053838A1
US20080053838A1 US11/576,891 US57689105A US2008053838A1 US 20080053838 A1 US20080053838 A1 US 20080053838A1 US 57689105 A US57689105 A US 57689105A US 2008053838 A1 US2008053838 A1 US 2008053838A1
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United States
Prior art keywords
metal
calcium
electrolysis
chloride
molten
Prior art date
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Abandoned
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US11/576,891
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English (en)
Inventor
Masanori Yamaguchi
Yuichi Ono
Susumu Kosemura
Eiji Nishimura
Tadashi Ogasawara
Makoto Yamaguchi
Masahiko Hori
Toru Uenishi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Osaka Titanium Technologies Co Ltd
Toho Titanium Co Ltd
Original Assignee
Toho Titanium Co Ltd
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Publication date
Application filed by Toho Titanium Co Ltd filed Critical Toho Titanium Co Ltd
Assigned to TOHO TITANIUM CO., LTD., SUMITOMO TITANIUM CORPORATION reassignment TOHO TITANIUM CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HORI, MASAHIKO, OGASAWARA, TADASHI, UENISHI, TORU, YAMAGUCHI, MAKOTO, KOSEMURA, SUSUMU, NISHIMURA, EIJI, ONO, YUICHI, YAMAGUCHI, MASANORI
Assigned to OSAKA TITANIUM TECHNOLOGIES CO., LTD. reassignment OSAKA TITANIUM TECHNOLOGIES CO., LTD. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: SUMITOMO TITANIUM CORPORATION
Publication of US20080053838A1 publication Critical patent/US20080053838A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth 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
    • C22B34/10—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
    • C22B34/129—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 by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium

Definitions

  • the present invention relates to the recovery of metal from a chloride thereof, and in particular, relates to a method for production of metal by molten-salt electrolysis. Furthermore, the present invention relates to a method for production of titanium metal using the metal produced by the method.
  • titanium metal which is a simple substance
  • Kroll method in which titanium tetrachloride is reduced by molten magnesium to obtain sponge titanium
  • various kinds of improvements have been made to reduce the cost of production.
  • the Kroll method is a batch process in which a set of operations is repeated noncontinuously, there is a limitation to its efficiency.
  • the present invention has been completed in view of the above circumstances, and an object of the present invention is to provide a method for production of metal by molten-salt electrolysis, in which metal used for reducing, such as an oxide or chloride of titanium metal, is efficiently recovered, and another object of the present invention is to provide a method for production of titanium metal in which the metal produced by the method is used.
  • the method for production of metal by molten-salt electrolysis of the present invention is a method for production of metal by molten-salt electrolysis which is performed by filling molten salt of a metal chloride in an electrolysis vessel having an anode and a cathode, and a molten salt which reduces solubility of the metal in the molten salt is used.
  • the metal produced in the above-mentioned method is used as a reducing agent of titanium tetrachloride.
  • FIG. 1 is a conceptual cross sectional diagram showing the electrolysis vessel used in the molten salt electrolysis of the present invention.
  • the metal is calcium metal
  • the metal chloride is calcium chloride
  • the chloride added to reduce the melting point of the electrolysis bath of the molten salt of the present invention is potassium chloride
  • FIG. 1 shows a desirable embodiment of the apparatus structure to perform the present invention.
  • reference numeral 1 indicates an electrolysis vessel, and an electrolysis bath 2 mainly containing calcium chloride is filled in the vessel.
  • the electrolysis bath 2 is heated to a temperature above the melting point of calcium chloride by a heater, which is not shown, so as to be maintained in a melted condition.
  • a bath of a mixture of calcium chloride and potassium chloride is used as the electrolysis bath 2 . Not only can the melting point of the electrolysis bath 2 be reduced by adding potassium chloride to calcium chloride, but the solubility of calcium metal in the electrolysis bath 2 can also be reduced.
  • Reference numeral 3 indicates an anode and reference numeral 4 indicates a cathode, and they are immersed in the electrolysis bath 2 .
  • a dividing wall 5 made of graphite is arranged between the anode 3 and the cathode 4 .
  • chloride ions in the electrolysis bath 2 are attracted to the anode 3 and donate electrons, forming chlorine gas 6 , which is expelled from the system.
  • Calcium ions are attracted to the cathode 4 and accept the electrons, forming calcium metal 7 , which is deposited on the surface of the cathode 4 .
  • the temperature of the electrolysis bath 2 be not less than 650° C. which is a eutectic temperature of calcium chloride and potassium chloride, and that it be not more than 1000° C.
  • the temperature of the electrolysis bath is maintained at not less than the eutectic temperature of calcium chloride and potassium chloride and at not more than the melting point of calcium metal (845° C.).
  • the temperature of the electrolysis bath 2 is maintained at not less than the melting point of calcium metal.
  • the temperature of the electrolysis bath is different depending on whether the target calcium metal is to be recovered in a solid state or a melted state, as explained above; however, the bases for improving recovery efficiency are the same.
  • the upper limit is set at 1000° C.; however, in the case in which the present invention is performed at a temperature not less than the melting point of calcium metal, recovery becomes difficult if solubility of calcium which dissolves in the molten salt is increased.
  • the vapor pressure of calcium metal increases above 1000° C., and it becomes difficult to recover the calcium metal that is generated. Therefore, in the present invention, the upper limit of the temperature of the electrolysis bath 2 is desirably not more than 1000° C.
  • the range of temperature of the electrolysis bath 2 is desirably from 650° C. to 850° C. If the temperature of the electrolysis bath 2 is less than 650° C., the electrolysis bath 2 will solidify, as mentioned above. If the temperature of the electrolysis bath 2 is 650° C. or more, it is possible for an electrolysis bath containing a sufficient calcium source to be prepared, and the rate of generation of calcium will be high. In addition, if the temperature is 850° C. or less, the rate of dissolution of calcium in the electrolysis bath 2 will be low, and deterioration of material used for the electrolysis vessel or the like will be low; this temperature range is therefore desirable for practicing the present invention.
  • the eutectic composition of the electrolysis bath 2 mentioned above is 25 mol % as a ratio of addition of potassium chloride to calcium chloride. Therefore, it is desirable that potassium chloride in the electrolysis bath 2 also be selected to be not more than 25%. It is desirable that the amount of potassium chloride in the electrolysis bath 2 be low; however, from the viewpoint of reducing the melting point of the electrolysis bath 2 , it is desirable that the amount be higher. Therefore, the ratio of the addition of potassium chloride to calcium chloride should be determined while considering the tradeoffs.
  • the present invention is performed at a temperature not less than the melting point of the electrolysis bath 2 and that not more than 845° C. (not more than the melting point of calcium metal), it is possible for the calcium metal to be deposited near the electrode and to be recovered in a solid state.
  • the metal is dispersed in the bath as metal particles, and since the specific gravity thereof is less than that of the bath, the particles float up to the surface of the bath around the cathode.
  • the metallic particles it is possible to recover them in a mixed condition with the electrolysis bath, and as an embodiment of the present invention, a mixture of the electrolysis bath and solid metal or the metal alone can be recovered.
  • the solubility of calcium metal in the electrolysis bath 2 can be reduced by controlling the concentration of chlorides added to the electrolysis bath 2 .
  • concentration of chlorides added to the electrolysis bath 2 As a result, calcium metal in a solid state is partially deposited at the surface of an electrode and is dispersed in the bath.
  • the specific gravity of calcium metal partially generated in a melted state is lower than that of the bath, it will ultimately float up near the cathode as a melted metal.
  • the present invention can be performed in the temperature range.
  • the recovery since it would take a long time to separate calcium metal dispersed in the bath and the electrolysis bath 2 , it is desirable that the melted calcium and the electrolysis bath 2 be recovered in a mixed state.
  • the molten salt and calcium it is possible for the molten salt and calcium to be entirely recovered in a solid state. In the case in which the recovery method is performed, it is possible to use the entire range of the temperature of the present invention.
  • Calcium metal deposited on the surface of the cathode 4 is partially dissolved in the electrolysis bath 2 , and calcium metal partially floats up to the surface of the electrolysis bath.
  • the calcium metal which floated up to the surface of the electrolysis bath may flow to near the anode and will be blocked by the dividing wall 5 to efficiently reduce the back reaction with chlorine gas generated at the anode 3 .
  • solubility of calcium in the electrolysis bath is more desirably not more than 1.5%, and by selecting the solubility, the recovery efficiency of calcium metal generated by electrolysis can be improved further.
  • a method for reducing the solubility of calcium metal in the electrolysis bath two methods may be considered. One is a method in which the content of calcium chloride is decreased and the content of potassium chloride, sodium chloride or calcium fluoride is increased to reduce the solubility of calcium metal, and the other is a method in which the temperature of the electrolysis bath 2 is reduced. By each of these methods, the solubility of the calcium metal in the electrolysis bath can be efficiently reduced. It should be noted that the solubility of calcium metal can be efficiently reduced if the temperature of the electrolysis bath is near the melting point of calcium chloride in the case of the bath of calcium chloride alone.
  • Calcium metal or the electrolysis bath 2 in which calcium metal is precipitated and recovered in this way, can be used in direct reduction of titanium oxide, for example.
  • solubility of calcium versus calcium chloride can be reduced to a level of 0.1 % to 0.3%, in a temperature range of 650° C. to 800° C. in the electrolysis bath 2 .
  • the melting point of the electrolysis bath can also be reduced. Since the melting point of calcium chloride is 780° C. and the melting point of calcium metal is 845° C., calcium metal in a solid state can be deposited on the cathode 4 in the case in which the temperature of the conventional electrolysis bath consisting of calcium chloride alone is set at 800° C. In this case, the difference between the temperature of the electrolysis bath and the melting point of the electrolysis bath (780° C.) is only 20° C., and since the electrolysis bath would solidify if the temperature were to go below the melting point, it is necessary that the temperature of the electrolysis bath be controlled precisely.
  • the melting point of the electrolysis bath 2 is reduced by mixing the above-mentioned chlorides in the electrolysis bath 2 , precise control of temperature is no longer required, and molten-salt electrolysis can be performed reliably.
  • the electrolysis bath 2 does not solidify even if the temperature of the electrolysis bath 2 is set at around 750° C., calcium metal can be deposited in a solid state on the cathode 4 .
  • electrolysis can be performed in the electrolysis bath having a temperature about 30 to 140° C. lower than in the case of the bath of calcium chloride alone.
  • the cathode 4 is pulled out of the electrolysis bath 2 , and the calcium metal is scraped off to be recovered.
  • the cathode is transported to a recovery vessel, which is prepared in advance and which is not shown, and calcium metal deposited on the cathode is melted and recovered by heating the recovery vessel to a temperature not less than the melting point of calcium metal.
  • the mixed salt in which sodium chloride or calcium fluoride is added instead of the potassium chloride mentioned above, can be used as the electrolysis bath 2 .
  • the eutectic temperature of the mixed bath in which sodium chloride is added to calcium chloride is 500° C.
  • the eutectic temperature of the mixed bath in which calcium fluoride is added to calcium chloride is 670° C.
  • the temperature of the electrolysis bath 2 can be effectively reduced compared to the case of the melting point of calcium chloride (780° C.) alone.
  • the temperature of the electrolysis can also be reduced, and as a result, dissolution loss of calcium metal generated in the electrolysis reaction of the electrolysis bath 2 can also be efficiently reduced.
  • the voltage of the electrolysis be selected so as not to cause deposition of potassium metal. Since the theoretical decomposition voltage of calcium chloride is 3.2 V and the theoretical decomposition voltage of potassium chloride is 3.4 V, a range of from 3.2 V to 3.4 V is desirable. However, if the electrolysis is performed at a decomposition voltage of not less than 3.4 V, potassium metal that is produced will react with calcium chloride to produce calcium metal. Therefore, it may not cause a substantial problem even if the decomposition voltage is high.
  • the amount of electricity supplied to the electrolysis vessel 1 and rate of deposition of metal can be increased.
  • both surfaces of the dividing wall 5 will be polarized.
  • Metal is deposited on the anode-side of the dividing wall 5 and chlorine gas is generated on the cathode-side of the dividing wall 5 when the voltage applied reaches twice the theoretical decomposition voltage.
  • the chlorine gas generated on the cathode-side of the dividing wall 5 could bring the back reaction with calcium metal generated at the cathode 4 , reducing the yield of calcium metal.
  • the voltage applied to the anode 3 and cathode 4 is desirably an electrolysis voltage which does not produce the polarization of the dividing wall 5 .
  • Such a range of voltages is not less than the theoretical decomposition voltage of calcium chloride and is less than twice thereof. Practically, it is from 3.2 V to 6.4 V.
  • the anode used in the present invention is required to be made from a material which is durable when exposed to chlorine gas at high temperature.
  • a material which is durable when exposed to chlorine gas at high temperature As such a material, graphite is desirable. Not only is graphite durable when exposed to chlorine gas at high temperature, but it is also durable in electrolysis baths at high temperature, and it has appropriate conductivity. It is desirable that the anode be arranged penetrating an upper lid of the electrolysis vessel 1 , which is not shown, while being immersed in the electrolysis bath 2 .
  • the surface of the anode 3 consisting of graphite and penetrating the upper lid can be coated with a ceramic material. Such a structure can minimize a corrosion of the graphite.
  • the cathode since chlorine gas is not generated from the cathode, the cathode, at least, can be made of a material durable to molten salt at high temperature, such as a conventional carbon steel.
  • a material durable to molten salt at high temperature such as a conventional carbon steel.
  • a steel material having a low concentration of carbon is desirable. This carbon steel is desirable since it is durable to molten salt and calcium metal at high temperatures. In addition, it is practical since it is inexpensive and durable.
  • the dividing wall of the present invention must be made from a material that is durable to calcium chloride and chlorine gas at high temperature, similar to the case of the anode. Practically, graphite is desirable.
  • the dividing wall itself can be constructed of graphite, or alternatively, an inner part may be constructed of a ceramic and the outer part may be constructed of graphite, and the strength thereof at high temperatures can be maintained for long periods.
  • the dividing wall is required to be dense as possible as can; however, some porosities in the wall, which do not allow penetration and migration of calcium metal generated in the cathode 4 to the anode side, do not pose problems in conducting the present invention. Furthermore, it is not necessary for the lower edge of the dividing wall to reach the bottom part of the electrolysis vessel, and it is sufficient for the dividing wall to have a sufficient length so as not to allow calcium metal generated at the cathode 4 or a calcium chloride layer having precipitated calcium metal to migrate to the anode.
  • Chlorine gas is recovered from the system, and for example, it can be used in a chlorination reaction of titanium ore.
  • calcium metal can be used in a reduction reaction of titanium oxide or titanium chloride using molten salt to produce titanium metal.
  • it can be used as the reducing agent of titanium tetrachloride disclosed in Japanese Unexamined Patent Application Publication No. 2005-068540, to produce ingots of titanium metal.
  • it can be used as the reducing agent of titanium metal in the FFC method in which titanium oxide is used as a raw material disclosed in Japanese Application Laid Open No. 2002-517613.
  • the melting point of the electrolysis bath can be reduced, which brings to the reduction of the electrolysis temperature, and as a result, the solubility of calcium metal in calcium chloride can be reduced. Furthermore, since the ratio of calcium chloride in the electrolysis bath is decreased by using the mixed salt, the amount of the calcium metal dissolved into the electrolysis bath can be reduced compared to the case in which calcium chloride alone is used as the electrolysis bath.
  • the electrolysis bath 2 having the above-mentioned eutectic composition, or a composition not more than that, is desirable.
  • the melting point of the electrolysis bath can be reduced, and the solubility of calcium metal in the electrolysis bath can be reduced.
  • the calcium metal generated according to the present invention can be efficiently recovered compared to the conventional methods.
  • the electrolysis of the molten salt of calcium chloride is started.
  • calcium metal is deposited on the cathode in a solid state. After depositing a predetermined amount of calcium metal on the cathode in a solid state, electric power supply to the positive and cathodes is stopped.
  • the cathode having deposited calcium metal on its surface, is transferred to a recovery vessel which is heated to a temperature not less than the melting point of calcium metal, and the calcium metal deposited on the surface of the cathode is melted so that it can be recovered.
  • the electrolysis of the molten salt of calcium chloride was started.
  • the electrolysis of the molten salt calcium metal in a solid state floated up to the bath surface around the cathode.
  • the electrolysis bath and calcium metal were drawn off and recovered from the bath surface around the cathode.
  • the recovered calcium content in the electrolysis bath was measured to be 50%.
  • the amount of calcium metal generated was measured from the recovered amount and the concentration, and a ratio was calculated with a theoretical generated amount calculated from the time of electric power supply. As a result, it was confirmed that not less than 75% of calcium metal was recovered. This operation was repeated, and the efficiency was improved.
  • the amount of calcium metal generated was measured from the recovered amount and the concentration, and a ratio with a theoretical generated amount calculated from the time of electric power supply was calculated. As a result, it was confirmed that not less than 60% of calcium metal was recovered. This operation was repeated, and the efficiency was improved. As an additional experiment, the electrolysis bath consisting of calcium chloride at 85% and potassium chloride at 15% was maintained at 950° C. and solubility of calcium in a saturated state was measured, and it was 2.8%.
  • a molten salt in which the added ratio of potassium chloride to calcium chloride was 25 mol % was prepared, and calcium metal corresponding to 10 wt % of the total of all the molten salts was added to the molten salt to perform heating and melting testing.
  • the heating temperature was set at several levels to determine the effects on the recovery ratio of calcium metal.
  • Table 1 there was a tendency for the recovery ratio of calcium metal to continuously decreased with increasing temperature in a range of heating temperature of 800° C. to 1000° C.
  • the heating temperature was above 1000° C., a strong tendency for the recovery ratio of calcium metal to decrease was observed.
  • An electrolysis bath consisting of calcium chloride alone was maintained at 900° C., a voltage of 4.5 V was applied to an anode made of carbon and a cathode made of carbon steel, so as to begin an electrolysis of a molten salt of calcium chloride. At this time, little melted calcium metal was observed at the surface of electrolysis bath. The electrolysis bath around the surface was drawn off to analyze the concentration of calcium metal, and the concentration of the calcium metal was 1%. In addition to the electrolysis examination, the solubility of calcium in a saturated state in calcium chloride at 900° C. was measured, and it was 3.2%.
  • metal used for reduction of oxides or chlorides of titanium can be efficiently recovered by the present invention.

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
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  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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US11/576,891 2004-10-12 2005-10-05 Method for Production of Metal by Molten-Salt Electrolysis and Method for Production of Titanium Metal Abandoned US20080053838A1 (en)

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JP2004-297873 2004-10-12
JP2004297873 2004-10-12
PCT/JP2005/018452 WO2006040979A1 (ja) 2004-10-12 2005-10-05 溶融塩電解による金属の製造方法および金属チタンの製造方法

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US (1) US20080053838A1 (ja)
EP (1) EP1808513A4 (ja)
JP (1) JP4602986B2 (ja)
CN (1) CN101040064A (ja)
AU (1) AU2005293039A1 (ja)
CA (1) CA2582039A1 (ja)
EA (1) EA011110B1 (ja)
NO (1) NO20072149L (ja)
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US20100282602A1 (en) * 2007-07-18 2010-11-11 Green Metals Limited Electrode materials
US20110083969A1 (en) * 2008-01-31 2011-04-14 University Of Leeds Process
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