WO2006103944A1 - PROCESS FOR PRODUCING Ti OR Ti ALLOY, AND PULL-UP ELECTROLYSIS METHOD APPLICABLE TO SAID PROCESS - Google Patents
PROCESS FOR PRODUCING Ti OR Ti ALLOY, AND PULL-UP ELECTROLYSIS METHOD APPLICABLE TO SAID PROCESS Download PDFInfo
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- WO2006103944A1 WO2006103944A1 PCT/JP2006/305227 JP2006305227W WO2006103944A1 WO 2006103944 A1 WO2006103944 A1 WO 2006103944A1 JP 2006305227 W JP2006305227 W JP 2006305227W WO 2006103944 A1 WO2006103944 A1 WO 2006103944A1
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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
- C25C3/26—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
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- 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
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- 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
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- 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
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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
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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
- C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts
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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
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
Definitions
- the present invention provides a method for producing ⁇ or Ti alloy at a low cost in an efficient manner, and obtaining Ca that can be used for reduction of Ti and other non-reducible metals as solid Ca and bath salt. It is related with the pulling-up electrolysis method which can do.
- Metals such as Ti, Zr, Ta, Hf, and V are useful metals each having excellent characteristics.
- metal Ti and Ti alloys are excellent in corrosion resistance, design, etc., and are lightweight and excellent in mechanical properties.
- its use has been expanding, including the use of non-toxic metals for medical devices as a metal.
- TiCl tetrasalt titanium
- molten Mg is filled in a reaction vessel, and a TiCl liquid is supplied to the liquid surface from above, Melting M
- the reaction takes place only near the molten Mg surface, the TiCl supply rate is limited.
- the generated Ti powder is agglomerated due to the adhesiveness between molten Mg and Ti, and sinters and grows by the heat of the melt, so it is difficult to take out the generated Ti out of the reaction vessel. Therefore, it is difficult to continuously manufacture products, and there is a limit to improving productivity, resulting in increased manufacturing costs and extremely high product prices.
- Ca can be used in addition to g.
- Ca has a stronger affinity for C1 than Mg, and is in principle suitable as a reducing agent for TiCl.
- TiCl is reduced by Ca
- Ca has a stronger affinity for C1 than Mg. In principle, it is suitable as a reducing agent for TiCl.
- metal Ca is mainly produced by volatile reduction using carbonate as a raw material!
- German technical literature (“HANDBUCH DER TECHNISCHEN ELEKTROCHE MIE” DRITTER BAND (1934) p. 128-p. 164 "Calcium, Strontium, Barium.” Von Dr. V. Makow)
- the molten CaCl was electrolyzed and remelted to separate the adhering salt.
- Manufactures Ca It is described.
- the voltage during electrolysis is very high. Therefore, it can be predicted that a large amount of electric energy with a large required power (current X voltage) will be consumed and the manufacturing cost will increase.
- the present invention has been made in view of such circumstances, and provides a method for producing T or Ti alloy by Ca reduction, and in particular, a method for producing Ti or Ti alloy efficiently and inexpensively.
- This is the first purpose.
- Ca which can be used for the reduction of Ti, can be applied to the manufacturing method of the above-mentioned T and Ti alloys, with low cell voltage and high current efficiency.
- the second objective is to provide a pull-up electrolysis method that can be obtained at the same time.
- the molten salt is reacted with a metal chloride containing TiCl to Ca in the molten salt.
- T and Ti alloys are continuously produced.
- Establishing a method hereinafter referred to as “Method for producing T or Ti alloy by Ca reduction” including various embodiments
- An electrolysis method was proposed. The development process and knowledge gained for each method will be explained separately in “Method of producing Ti or Ti alloy by Ca reduction” and “Pulling electrolysis method”.
- TiC is produced by extracting CaC 1 produced as a by-product to the outside of the reaction vessel and electrolyzing it.
- the reaction field (the region where the reaction between Ca and TiCl occurs) becomes too hot and the reaction vessel wears down drastically.
- the Ca is solidified together with the molten CaCl solution.
- rod-like Ca is formed by electrolysis of molten CaCl.
- Fig. 1 shows the production of Ca by electrolysis of molten CaCl disclosed in the German technical literature.
- the solidified salt adheres to the surface of this calcium rod, it is remelted and separated in calcium chloride. It is described that the current density of the force sword during electrolysis is 125 AZcm 2 , the voltage is 35 to 40 V, and the purity of the re-dissolved metal Ca is 98 to 99%.
- the present inventors developed a pulling electrolysis method capable of obtaining Ca that can be used for the reduction of refractory metals, particularly Ti.
- the resulting Ca can be extracted and electrolyzed, and the generated Ca can be used in the reaction of the formation of metals such as Ti in the reaction vessel.
- metals such as Ti in the reaction vessel.
- reaction field is limited to the vicinity of the Mg liquid surface
- heat generation area is widened and cooling is facilitated, so the TiCl supply rate can be greatly increased and productivity is significantly improved.
- the present inventors further reduced the energy loss due to repeated heat generation and heat removal, and further reduced the difficulty in controlling the temperature of the reaction field.
- the molten CaCl solution was extracted from the reaction vessel and electrolyzed
- the produced Ca is recovered together with the molten CaCl solution as a solid, and this solid is reduced.
- solid Ca and bath salt are supplied as a Ca source in the molten salt containing CaCl in the reaction vessel when producing T or Ti alloy by Ca reduction, for example, solid Ca
- the metal Ca is supplied as the Ca source, it can be dissolved quickly and uniformly, and the reaction between the metal salt containing TiCl and Ca can proceed uniformly over a wide range in the reaction vessel.
- the present invention is based on the above-mentioned results of the study on the production method of T or Ti alloy by Ca reduction, and further in the context of such production technology of Ti or Ti alloy by Ca reduction. (A) to (d) based on the knowledge of the following (1) to (3) Ti or Ti alloy production method and the following (4) and (5) pulling electrolysis method It is a summary.
- Electrolysis of the reduction process that produces Ti alloy and the bath salt extracted from the reduction process This is a method for producing a T alloy or Ti alloy that includes an electrolysis step for generating Ca, and collects solids containing Ca and bath salts in the electrolysis step and transfers the solids to the reduction step. This is a method for producing cocoons or Ti alloys.
- Solid state as defined in the present invention means that Ca and bath salts are solid on the surface of the cathode when the cathode is pulled up (however, the surface is wet during solidification) It is included). Specifically, when the entire solid body is solid (that is, when the solidification is completed), it is solid in appearance but actually partly solid, This means that any solid bath salt or the like that is incompletely solidified and contains a molten bath salt or the like is included.
- the bath salt extracted from the reduction process is electrolyzed, and Ca and bath salt are recovered as solids and transferred to the reduction process.
- the production and thermal efficiency can be greatly improved, and the reaction temperature can be easily controlled, making it possible to manufacture Ti or Ti alloys at a low cost.
- the pulling electrolysis method of the above (4) and (5) is a method of recovering Ca by regulating the bath temperature, cathode current density, voltage, and cathode pulling rate within a predetermined range. With low current and high current efficiency, Ca can be obtained as solid Ca and bath salts with relatively low power consumption.
- Figure 1 shows the production of Ca by electrolysis of molten CaCl as disclosed in the German technical literature.
- FIG. 2 is a diagram for explaining the pulling electrolysis method of the present invention.
- FIG. 3 is a diagram illustrating the relationship between the cathode pulling rate and the current efficiency when the electrolysis method of the present invention is performed.
- FIG. 4 is a graph showing the relationship between bath temperature and cathode pulling rate in pulling electrolysis.
- FIG. 5 is a diagram showing a configuration example of a metal Ti production apparatus by Ca reduction.
- the method for producing a T alloy or Ti alloy of the present invention is a metal containing TiCl in Ca in a Ca-containing bath salt.
- a more specific configuration is "Ca in the Ca-containing bath salt contains TiCl.”
- It includes a reduction step in which metal chloride is reacted to form Ti or Ti alloy in the bath salt, and an electrolysis step in which the bath salt extracted from the reduction step is electrolyzed to produce Ca.
- it is a method for producing a Ti alloy, in which a solid containing Ca and a bath salt is recovered in the electrolysis step, and the solid is transferred to the reduction step.
- the solid material containing Ca and bath salt is recovered in the electrolysis process, and the solid material is transferred to the reduction process. It is an invention.
- a molten salt is used as the bath salt. It is usually preferable to use a molten salt containing CaCl.
- the reduction reaction with Ca proceeds, so it can be used as a bath salt.
- the method of collecting the solid is not limited at all! ⁇ .
- the Ca generated in the electrolysis process is taken out as a solid substance containing a bath salt, and the salt strength of the electrolysis bath is taken out and transferred to the reduction process (that is, the reduction process proceeds, for example, charged into the reaction vessel). .
- the transfer of Ca produced in the electrolysis process to the reduction process may be carried out using the entire amount as the above-mentioned solid matter, or a part thereof as the above-mentioned solid matter, and others may increase the Ca concentration, for example.
- the production efficiency can be increased and the heat efficiency can be greatly improved by reducing the heat loss.
- the cooling capacity of the entire reaction system can be improved, the reaction temperature can be easily controlled, the raw material charging speed can be increased, and the production of Ti or Ti alloy by Ca reduction can be performed more efficiently and cheaply. . It is also possible to make the device compact.
- the recovered Ca and the Ca concentration in the solid containing the bath salt are obtained.
- the Ca concentration in the solid can be 20% by mass
- the electrolysis temperature can be set to 800 ° C
- the Ca concentration can be set to 30% by mass.
- the electrolysis temperature it is possible to control the Ca concentration in the solid containing Ca and the bath salt. For this reason, for example, when the temperature of the reaction field where the reduction reaction occurs is lowered, the electrolysis temperature is lowered to lower the Ca concentration in the solid, and conversely, the reaction rate in the reduction process is to be increased. In some cases, it is possible to use and separate Ca and bath salt-containing solids according to the operating conditions, such as raising the electrolysis temperature to increase the Ca concentration in the solids.
- the bath salt is electrolyzed at a bath temperature of 680 to 900 ° C., a cathode current density of 0.1 to 200 AZcm 2 and a voltage of 10 V or less, and is fixed on the cathode surface.
- the bath salt and Ca are recovered in solid form by pulling up the cathode at a pulling speed of 0.05 cmZmin or more while adhering and solidifying the shape.
- FIG. 2 is a view for explaining the pulling electrolysis method of the present invention.
- a bath salt 2 is held in an electrolytic cell 1 and an anode 3 and a cathode 4 are attached.
- chlorine (C1) is generated at the anode 3
- Ca is deposited at the cathode 4.
- Such precipitation of Ca and the adhesion and solidification force of the bath salt in the vicinity of the precipitated Ca repeatedly occur as the cathode 4 is pulled up, and are immersed in the bath salt 2 when the cathode 4 starts electrolysis.
- the solid Ca and bath salt 5 contained in a mixed state of Ca and bath salt are formed downward.
- this solid Ca and bath salt contain CaCl in the reaction vessel when used as a Ca source in the production of Ti or Ti alloy by Ca reduction.
- Any material that dissolves quickly and uniformly when supplied as a Ca source in a molten salt containing 2 may be used.
- any salt can be used as the bath salt as long as the temperature can be adjusted within the above temperature range and Ca is generated by electrolysis.
- a mixture of Ca halide salt for example, binary mixed salt such as calcium fluoride and salt calcium, salt calcium and salt potassium, or salt calcium, calcium fluoride
- Use ternary mixed salts such as salt and potassium. Since the melting point of the bath salt can be changed by using such a mixed salt, it is possible to select the bath salt according to the set bath temperature.
- the bath temperature is 680 to 900 ° C.
- the reaction temperature is too low to cause the formation of Ca electrolysis, while when the bath temperature exceeds 900 ° C, the dissolved amount of the produced Ca in the bath salt is small. This is because increasing the current efficiency makes it difficult to obtain high current efficiency (ie, Ca recovery efficiency).
- the cathode current density is 0.1 to 200 AZcm 2 .
- the lower limit of the current density depends on the rate at which Ca generated by electrolysis is re-dissolved in the bath, and if the current density is less than 0.1 lAZcm 2 , Ca cannot be recovered because the dissolution rate of Ca in the bath salt is faster than the rate of Ca formation.
- the upper limit of the current density is 200 AZcm 2, and if the current density exceeds this value, the voltage cannot be lowered even if the distance between the electrodes is adjusted, and the power consumption increases. That's it.
- the cathode current density is 0.1 to 70 AZcm 2 , the voltage can be reduced to 5 V or less, and the power consumption can be greatly reduced, which is desirable. Furthermore, if the cathode current density is 10 to 50 AZcm 2 , in addition to a significant reduction in power consumption, it is possible to obtain a high current efficiency of 90% or more.
- this range is the optimum range for the cathode current density.
- the reason for setting the voltage during electrolysis to 10 V or less is to suppress the increase in power consumption as much as possible.
- the electrolysis under high voltage (35-40V) described in the German technical literature is considered to be a force considered to cause electrolytic deposition of metal Ca.
- Ca, Ca and bath salt are used. Since it collects as a solid substance in which is mixed, a high voltage is not necessary.
- the lower limit of the voltage is not particularly defined, it must be at least higher than the decomposition voltage of molten CaCl (approximately 3.2 V) in order for Ca to proceed and precipitation of Ca.
- the cathode pulling speed is 0.05 cmZmin or more. If the pulling rate is slower than this, it will be difficult to attach the produced Ca to the cathode surface. This is thought to be due to the fact that the produced Ca dissolves and spreads widely in the bath.
- the upper limit of the pulling speed is not particularly defined. This is because, as specified by the electrolysis method of the present invention, if the operation of pulling up the cathode while solidifying and solidifying the cathode surface is carried out, the upper limit of the pulling rate is naturally determined. That is, if the pulling speed is too fast, the cross-sectional area of the solid that is pulled up becomes too small (that is, it becomes thin), and the solid that is pulled up is cut in the middle, making it impossible to pull it up continuously. Considering such restrictions on the pulling operation, it is desirable that the pulling speed is less than lOcmZmin.
- FIG. 3 is a diagram illustrating the relationship between the cathode pulling rate and the current efficiency when the electrolysis method of the present invention is performed. This is an example of electrolysis at a voltage of 10 V or less and a distance between electrodes of 7 cm or less.
- the age and solid lines indicate the bath temperature during electrolysis at 720 ° C (720 ° C electrolysis), and the dashed line indicates the bath temperature at 800 ° C (800 ° C electrolysis).
- the mark indicates the case of using a cylindrical cathode with a diameter of 8 mm
- the mark indicates the case of using a cylindrical cathode with a diameter of 5 mm
- the mark ⁇ indicates the case of using a cylindrical cathode with a diameter of 15 mm.
- the current efficiency is determined by the amount of deposited Ca, which is also determined based on Faraday's law.
- the Ca in the solid matter on the cathode surface does not include Ca which has been deposited on the cathode surface and then dissolved or exfoliated, so the current efficiency here is synonymous with the Ca recovery efficiency.
- the current efficiency of the 800 ° C electrolysis is lower than that of the 720 ° C electrolysis over the entire range of the pulling rate. This is because the higher the bath temperature, the greater the amount of Ca dissolved in CaCl, the lower the amount of Ca recovered.
- the Ca concentration is 20% by mass.
- the Ca concentration is 30% by mass. The details of this phenomenon are unknown, but when the bath temperature is high, the bath salt attached to the cathode surface (deposited Ca surface) at the time of pulling is easy to flow off before solidifying and separate from Ca, and in the collected solids This is thought to be due to the concentration of Ca.
- the bath temperature the recovered solid Ca and the Ca concentration in the bath salt
- the degree of Ca can be controlled, and when using this solid Ca and bath salt as a Ca source, the Ca concentration can be grasped and the concentration can be arbitrarily determined.
- FIG. 4 is a diagram showing the relationship between bath temperature and cathode pulling rate in pulling electrolysis.
- the hatched portion in the figure is a region where the pulling speed is 0.05 cmZmin or more and good current efficiency (ie, Ca recovery efficiency) expressed by the above equation (1) is obtained.
- Ca and bath salt are recovered in solid form.
- solid means a solid state in appearance.
- the term “solid” means a solid state in appearance.
- the bath temperature at which the bath temperature is high and the melting point of the bath salt is large, the solid state on the cathode surface.
- Ca While the bath salt adhering to the pulled cathode surface is difficult to solidify, Ca generally has a higher melting point than the bath salt, so it precipitates as a solid from the beginning or immediately becomes a solid even in a molten state. This is because unsolidified bath salt is taken into the solid.
- Ca is obtained as solid Ca and bath salt with low voltage and high current efficiency (and with relatively low power consumption). be able to.
- This solid Ca and bath salt are particularly effective when used as a Ca source in the production of Ti or Ti alloy by Ca reduction.
- This manufacturing process includes the manufacturing method of Ti or Ti alloy by Ca reduction of the present invention, that is, That is, by reacting Ca in the Ca-containing bath salt with a metal chloride containing TiCl, Ti is added to the bath salt.
- the present invention includes a reduction step for producing a Ti alloy and an electrolysis step for electrolyzing a bath salt extracted from the reduction step to produce Ca.
- FIG. 5 is a diagram showing an example of the configuration of a metal Ti production apparatus using Ca reduction.
- TiCl is used as a raw material
- Ca-containing bath salt containing CaCl is used as a Ca-containing bath salt.
- a salting process for producing TiCl is added.
- a reducing agent supply pipe 7 for supplying Ca as a reducing agent is provided at the ceiling of the reaction vessel 6.
- the bottom of the reaction vessel 6 has a taper shape that is gradually reduced in diameter in order to promote the discharge of the generated Ti particles, and the generated Ti particles are discharged at the center of the lower end.
- Ti discharge pipe 8 is provided.
- a cylindrical separation wall 9 is disposed inside the reaction vessel 6 with a predetermined gap between the inner surface of the straight body portion. At the top of the reaction vessel 6, the CaCl in the vessel is moved to the side.
- Discharged molten salt discharge pipe 10 is provided, and TiCl which is Ti raw material is supplied at the bottom
- a raw material supply pipe 11 is provided through the separation wall 9 so as to reach the center of the container.
- the surface is set at a level higher than the molten salt discharge pipe 10 and lower than the upper end of the separation wall 9.
- the TiCl gas is added to the molten CaCl liquid inside the separation wall 9 by the raw material supply pipe 11.
- the Ti particles are compressed to squeeze the molten CaCl solution.
- the electrolysis step 13 the molten CaCl solution 13b introduced into the electrolytic cell 13a from the reaction vessel 6 and the separation step 12 is separated into Ca and C1 gas by electrolysis.
- the Ca generated on the cathode 13d side is recovered as solid Ca and bath salt 13e mixed with Ca and bath salt by pulling up the cathode 13d, returned to the reaction vessel 6, and replenished with Ca. .
- Ca may be replenished (supplied) using the above-mentioned solid Ca and bath salt as a whole, or a part thereof may be used as the above-mentioned solid Ca and bath salt.
- CaCl solution may be used.
- solid Ca and bath salt 13e generate heat generated by the reaction between TiCl and Ca.
- TiO is chlorinated in the presence of carbon powder (C) to produce TiCl. Also C powder
- the reducing agents Ca and C1 gas are cycled.
- the replenishment of gold is substantially only by supplementing TiO and C.
- the genus Ti can be produced continuously, but at this time, solid Ca and bath salt recovered by the electrolysis method of the present invention can be suitably used as a Ca source.
- the bath salt extracted from the reduction process is electrolyzed, and Ca and the bath salt are recovered as solids.
- the method of transferring to the reduction step can use the latent heat of fusion that the solid material has to suppress heat generation in the reduction process, greatly improve production efficiency and thermal efficiency, and control the reaction temperature. This makes it easy to increase the raw material charging speed and produce Ti or Ti alloy efficiently and inexpensively.
- the pulling electrolysis method of the present invention is a method of recovering Ca by regulating the bath temperature, cathode current density, voltage, and cathode pulling rate within a predetermined range, and with low voltage and high current efficiency. Thus, it is possible to obtain solid Ca and bath salt with relatively little power consumption.
- this solid Ca and bath salt dissolve quickly and uniformly in the reaction vessel. This is because the metal chloride containing Ca and TiCl melts during the reduction reaction.
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/887,511 US20090101517A1 (en) | 2005-03-29 | 2006-03-16 | Method for Producing Ti or Ti Alloy, and Pulling Electrolysis Method Applicable Thereto |
EP06729224A EP1876248A1 (en) | 2005-03-29 | 2006-03-16 | PROCESS FOR PRODUCING Ti OR Ti ALLOY, AND PULL-UP ELECTROLYSIS METHOD APPLICABLE TO SAID PROCESS |
EA200702096A EA200702096A1 (en) | 2005-03-29 | 2006-03-16 | METHOD OF MANUFACTURING Ti OR ALLOY Ti AND THE APPLICABLE METHOD FOR ELECTROLYSIS WITH EXTRACTION |
CA002602801A CA2602801A1 (en) | 2005-03-29 | 2006-03-16 | Process for producing ti or ti alloy, and pull-up electrolysis method applicable to said process |
AU2006229128A AU2006229128A1 (en) | 2005-03-29 | 2006-03-16 | Process for producing Ti or Ti alloy, and pull-up electrolysis method applicable to said process |
NO20075092A NO20075092L (en) | 2005-03-29 | 2007-10-09 | Process for producing Ti or Ti alloys, and process for winding electrolysis application for the process |
Applications Claiming Priority (4)
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JP2005-094205 | 2005-03-29 | ||
JP2005094205A JP2006274340A (en) | 2005-03-29 | 2005-03-29 | METHOD FOR PRODUCING Ti OR Ti ALLOY |
JP2005096690A JP4227113B2 (en) | 2005-03-30 | 2005-03-30 | Pull-up electrolysis method |
JP2005-096690 | 2005-03-30 |
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WO2006103944A1 true WO2006103944A1 (en) | 2006-10-05 |
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US (1) | US20090101517A1 (en) |
EP (1) | EP1876248A1 (en) |
AU (1) | AU2006229128A1 (en) |
CA (1) | CA2602801A1 (en) |
EA (1) | EA200702096A1 (en) |
NO (1) | NO20075092L (en) |
WO (1) | WO2006103944A1 (en) |
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AR076863A1 (en) | 2009-05-12 | 2011-07-13 | Metalysis Ltd | APPARATUS AND METHOD FOR REDUCTION OF SOLID RAW MATERIAL. |
MY180279A (en) | 2010-11-18 | 2020-11-26 | Metalysis Ltd | Electrolysis apparatus |
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JP2006057143A (en) * | 2004-08-20 | 2006-03-02 | Toho Titanium Co Ltd | Method and device for producing metal by molten salt electrolysis |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2205854A (en) * | 1937-07-10 | 1940-06-25 | Kroll Wilhelm | Method for manufacturing titanium and alloys thereof |
US2845386A (en) * | 1954-03-16 | 1958-07-29 | Du Pont | Production of metals |
-
2006
- 2006-03-16 WO PCT/JP2006/305227 patent/WO2006103944A1/en active Application Filing
- 2006-03-16 EP EP06729224A patent/EP1876248A1/en not_active Withdrawn
- 2006-03-16 AU AU2006229128A patent/AU2006229128A1/en not_active Abandoned
- 2006-03-16 EA EA200702096A patent/EA200702096A1/en unknown
- 2006-03-16 US US11/887,511 patent/US20090101517A1/en not_active Abandoned
- 2006-03-16 CA CA002602801A patent/CA2602801A1/en not_active Abandoned
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2007
- 2007-10-09 NO NO20075092A patent/NO20075092L/en not_active Application Discontinuation
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2111531A (en) * | 1981-07-11 | 1983-07-06 | Toho Titanium Co Ltd | Method for manufacturing titanium metal |
JPS6447823A (en) * | 1987-08-17 | 1989-02-22 | Toho Titanium Co Ltd | Production of metallic titanium |
JP2002129250A (en) * | 2000-10-30 | 2002-05-09 | Katsutoshi Ono | Method for producing metallic titanium |
JP2004131784A (en) * | 2002-10-09 | 2004-04-30 | Katsutoshi Ono | Method for smelting metallic titanium |
JP2005068540A (en) * | 2003-08-28 | 2005-03-17 | Sumitomo Titanium Corp | METHOD AND APPARATUS FOR PRODUCING METAL THROUGH REDUCTION BY Ca |
JP2005068539A (en) * | 2003-08-28 | 2005-03-17 | Sumitomo Titanium Corp | Method and apparatus for producing metal |
JP2006057143A (en) * | 2004-08-20 | 2006-03-02 | Toho Titanium Co Ltd | Method and device for producing metal by molten salt electrolysis |
Also Published As
Publication number | Publication date |
---|---|
NO20075092L (en) | 2007-12-19 |
EP1876248A1 (en) | 2008-01-09 |
AU2006229128A1 (en) | 2006-10-05 |
US20090101517A1 (en) | 2009-04-23 |
CA2602801A1 (en) | 2006-10-05 |
EA200702096A1 (en) | 2008-04-28 |
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