WO2015035954A1 - 一种含钛可溶阳极熔盐电解提取金属钛的方法 - Google Patents

一种含钛可溶阳极熔盐电解提取金属钛的方法 Download PDF

Info

Publication number
WO2015035954A1
WO2015035954A1 PCT/CN2014/086581 CN2014086581W WO2015035954A1 WO 2015035954 A1 WO2015035954 A1 WO 2015035954A1 CN 2014086581 W CN2014086581 W CN 2014086581W WO 2015035954 A1 WO2015035954 A1 WO 2015035954A1
Authority
WO
WIPO (PCT)
Prior art keywords
titanium
metal
anode
cathode
nitrogen
Prior art date
Application number
PCT/CN2014/086581
Other languages
English (en)
French (fr)
Inventor
朱鸿民
汪秋雨
焦树强
Original Assignee
北京科技大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 北京科技大学 filed Critical 北京科技大学
Priority to US15/022,324 priority Critical patent/US10081874B2/en
Publication of WO2015035954A1 publication Critical patent/WO2015035954A1/zh

Links

Images

Classifications

    • 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 invention belongs to the technical field of non-ferrous metallurgy, in particular to a method for preparing titanium metal by electrolysis of titanium-containing soluble anode molten salt.
  • Metal titanium has the advantages of low density, high specific strength, corrosion resistance, high temperature resistance, non-magnetic and non-toxicity; titanium alloy has memory function, superconducting function and hydrogen storage function. At present, titanium metal has been widely used in aerospace, military and other military fields and in the civil, chemical, marine, automotive, sports equipment, medical equipment, construction and other civilian fields, known as "future metal", "third metal.”
  • the mainstream production process of titanium metal is the Kroll method, that is, the metal magnesium thermal reduction method of titanium tetrachloride.
  • the core process is to put magnesium metal into the reactor and protect it with argon gas, heat it to 800 ° C ⁇ 900 ° C, and then add titanium tetrachloride and molten metal magnesium at a certain speed to prepare titanium sponge, titanium metal.
  • the purity is about 99.7%.
  • the metallurgical production process is complicated and cumbersome, energy consumption is high, and the cost is high, so that its price cannot be reduced. It is because of these reasons that the price of titanium metal is expensive, which greatly limits the application of titanium metal.
  • Japanese researcher Y. Hashimoto mixes excess carbon and TiO 2 as raw materials, and uses oxygen high temperature (>1700 ° C) to make oxygen-doped titanium carbide (Oxygen doped TiC), which is used as the anode in melting. Electrolysis in salt, cathode deposition to obtain pure titanium. However, the preparation process of the anode still relies on the very high temperature (>1700 ° C) reduction conditions, and does not essentially achieve the purpose of low-cost titanium extraction, and its electrolysis experiments are mainly low-oxygen titanium carbide, anode carbon Too high a level results in a large amount of anode slime, which makes continuous electrolysis impossible.
  • MER Corporation of the United States has developed a new electrolytic reduction process (WO2005/019501).
  • the process is a mixture of TiO 2 and C in a stoichiometric ratio, and is thermally reduced at 1100 ° C to 1300 ° C to obtain a mixture of titanium oxide and carbon, and then the composite anode is electrolyzed in an alkali metal molten salt system.
  • titanium The composite anode of the process is a mixture of low-oxide and carbon of titanium, and there is anode mud and residual carbon in the process of electrochemical dissolution. As the amount of residual carbon increases, the problem of short circuit of the electrode is caused and the product is contaminated.
  • Sichuan Pangang Group Co., Ltd. applied for a method for preparing titanium metal by titanium cyclic molten salt electrolysis (CN 101519789A) in 2009.
  • the method uses titanium tetrachloride as raw material to reduce titanium chloride to low-valent titanium.
  • Metal titanium is then obtained by molten salt electrolysis.
  • This method has the following problems: the use of titanium tetrachloride and titanium metal as raw materials is expensive, and the reaction rate of titanium tetrachloride reduced to low-priced titanium is low, which also causes production cost of titanium.
  • a method for preparing titanium metal (CN 101914788) was applied. When titanium concentrate was smelted, titanium oxide was directly mixed with excess carbon.
  • Titanium nitride or titanium carbonitride was prepared by nitrogen gas, and titanium was obtained by electrolysis. method. The process is formulated with excess carbon to produce titanium carbide or titanium carbonitride.
  • the method has the following problems: (1) Since the carbon to be added is excessive, the preparation of titanium carbide or titanium carbonitride has a carbon residue; (2) the process of long-time electrolysis of titanium carbide or titanium carbonitride as an anode. Among them, carbon will precipitate as elemental carbon and become residual carbon; the residual carbon produced by the above two conditions will pollute the quality of the cathode product, and it is easy to cause short circuit between electrodes, low current efficiency and high carbon content of products. .
  • the object of the present invention is to overcome the shortcomings of the prior art method for preparing metal titanium, such as long process flow, high energy consumption, low product quality of high purity titanium, or inability to achieve industrialization. Accordingly, the present invention provides a process which is simple in process, low in energy consumption, and capable of industrially producing high purity titanium metal.
  • the improvement of the present invention against the prior art is as follows: (1) low-cost synthesis of titanium compounds having metal conductivity (TiC x O y N z , TiO x N y , TiN x ); (2) and titanium The compound (TiC x O y N z , TiO x N y , TiN x ) is used as an anode material to extract pure titanium by molten salt electrolysis; (3) Titanium-containing compound (TiC x O y N z , TiO during electrolysis) Titanium in x N y , TiN x ) is dissolved in the electrolyte in the form of titanium ions, wherein the carbon-oxygen nitrogen is precipitated in the form of CO, CO 2 and N 2 , and there is no problem of carbon remaining in the anode.
  • titanium-containing material comprises rutile-type titanium white, anatase titanium white, metatitanic acid, ilmenite, vanadium-titanium magnetite, blast furnace type One or more of high titanium slag, high titanium slag and titanium suboxide;
  • the carbonaceous reducing agent comprises one of carbon, activated carbon, graphite powder, charcoal, petroleum coke, asphalt, coal coke One or more;
  • the titanium-containing compound prepared is one or more of TiC x O y N z , TiO x N y , TiN x , and the mole of carbon oxynitride of the Ti
  • the metal titanium is extracted by electrolysis in an alkali metal or alkaline earth metal halide molten salt, and the anode is formed of the obtained titanium-containing compound.
  • Metal titanium is obtained on the cathode; the cathode is formed by one or more of metal titanium, stainless steel, carbon steel, metal molybdenum, metallic nickel; the pole pitch of the anode and cathode is controlled between 1 cm and 50 cm; and the electrolyte is composed of alkali metal or Alkaline earth metal halide composition; cell voltage is controlled at 0.5V to 10.0V, anode current density ranges from 0.05A/cm 2 to 1.50A/cm 2 , and cathode current density ranges from 0.05A/cm 2 to 1.50A/ Cm 2 , the electrolysis temperature ranges from 300 ° C to 1000 ° C.
  • the nitrogen-containing atmosphere includes one or more of air, nitrogen, ammonia, nitrogen-hydrogen, nitrogen-argon, and other nitrogen-containing gas mixture.
  • the low-valent oxide of titanium is one or more of Ti 2 O 3 , Ti 3 O 5 , TiO, Ti 3 O.
  • the electrically conductive titanium-containing compound is prepared in a closed system or a semi-open system or an open system of a nitrogen-containing atmosphere.
  • the closed system is a system containing a partial pressure or atmospheric pressure (one standard atmospheric pressure) or a partial nitrogen atmosphere.
  • the electrolyte is one or more of CsCl 2 , CaCl 2 , LiCl, NaCl, KCl, MgCl 2 , AlCl 3 , CaF, NaF, KF, LiF and TiCl 3 , TiCl 2 , K 2 TiF 6.
  • the molar ratio of the titanium-containing material to the carbon-containing reducing agent is from 5:1 to 1:10.
  • the electrolysis temperature ranges from 400 ° C to 900 ° C.
  • the pole pitch of the anode and cathode is controlled between 3 cm and 40 cm; and the cell voltage is controlled between 1.5 V and 6.0 V.
  • the anode current density ranges from 0.05 A/cm 2 to 1.00 A/cm 2 ; and the cathode current density ranges from 0.05 A/cm 2 to 1.00 A/cm 2 .
  • the electrolyte holding container is one of stainless steel crucible, carbon steel crucible, titanium crucible, titanium alloy crucible, graphite crucible, molybdenum crucible or nickel crucible.
  • 1a is a schematic view showing an SEM of an anode block after heat treatment according to an embodiment of the present invention
  • 1b is an X-ray diffraction diagram of an anode block after heat treatment according to an embodiment of the present invention
  • Example 2 is an X-ray diffraction diagram of a reaction product obtained after heat treatment in Example 2 of the present invention
  • Example 3 is an X-ray diffraction chart of a reaction product obtained after heat treatment at 1500 ° C according to Example 3 of the present invention
  • FIG. 4 is a schematic view showing an SEM of an anode block after heat treatment according to Embodiment 5 of the present invention.
  • Figure 5 is an X-ray diffraction diagram of a cathode product of Example 7 of the present invention.
  • FIG. 6 is a graph showing a change curve of an anode gas in an electrolysis process in an electrolysis process according to an embodiment of the present invention.
  • Figure 7 is a schematic illustration of the SEM of a twelve cathode product in accordance with an embodiment of the present invention.
  • the carbonaceous reducing agent in the present invention refers to a reducing agent containing carbon as a main component, such as carbon, activated carbon, graphite powder, charcoal, petroleum coke, pitch, coal coke, and the like.
  • titanium-containing material comprises rutile-type titanium white, anatase titanium white, metatitanic acid, ilmenite, vanadium-titanium magnetite, blast furnace type One or more of high titanium slag, high titanium slag and titanium suboxide;
  • the carbonaceous reducing agent comprises one of carbon, activated carbon, graphite powder, charcoal, petroleum coke, asphalt, coal coke One or more;
  • the titanium-containing compound prepared is one or more of TiC x O y N z , TiO x N y , TiN x , and the mole of carbon oxynitride of the Ti
  • the metal titanium is extracted by electrolysis in an alkali metal or alkaline earth metal halide molten salt, and the anode is formed of the obtained titanium-containing compound.
  • Metal titanium is obtained on the cathode; the cathode is formed by one or more of metal titanium, stainless steel, carbon steel, metal molybdenum, metallic nickel; the pole pitch of the anode and cathode is controlled between 1 cm and 50 cm; and the electrolyte is composed of alkali metal or Alkaline earth metal halide composition; cell voltage is controlled at 0.5V to 10.0V, anode current density ranges from 0.05A/cm 2 to 1.50A/cm 2 , and cathode current density ranges from 0.05A/cm 2 to 1.50A/ Cm 2 , the electrolysis temperature ranges from 300 ° C to 1000 ° C.
  • the titanium-containing material includes rutile titanium white, sharp Titanium-alloy titanium white, metatitanic acid, ilmenite, vanadium-titanium magnetite, blast furnace type high titanium slag, high titanium slag and titanium low-oxide (Ti 2 O 3 , Ti 3 O 5 , TiO, Ti 3 O); carbon-containing reducing agents include carbon, activated carbon, graphite powder, charcoal, petroleum coke, asphalt, coal coke and other carbon-based substances; titanium-containing materials and carbonaceous reducing agents The ratio can be set to 5:1 to 1:20; the molar ratio is less than 5:1, the product contains a large amount of titanium suboxide, and the molar ratio is higher than 1:20, there will be a large amount
  • the tank voltage can be set to 0.5V ⁇ 10.0V, if the anode tank voltage is lower than 0.5V, the anode electrolysis rate is slow, resulting in low daily output, if the positive tank voltage is higher than 10.0V, it will cause overpotential High, the anode is prone to mechanical crushing, resulting in increased energy consumption and low anode current efficiency.
  • the tank voltage is preferably set to 1.5V to 6.0V; the anode current density can be set in the range of 0.05A/cm 2 to 1.50A/cm 2 , preferably 0.05A/cm 2 to 1.00A/cm 2 ; the cathode current density can be set in the range of 0.05 A/cm 2 to 1.50 A/cm 2 , preferably 0.05 A/cm 2 to 1.00 A/cm 2 ; Stainless steel crucible, carbon steel crucible, titanium crucible, titanium crucible, graphite crucible, molybdenum crucible or nickel crucible is selected.
  • the product size is also seen to be about 10 ⁇ m from the SEM image.
  • the electrical conductivity of the pressed block was sharply reduced from the initial 15-25 ohm cm to 0.005 ohm cm.
  • the graphite crucible was used to hold a NaCl-KCl-TiCl 2 salt in which the mass concentration of Ti ions was 5%, and an electrolysis experiment was carried out at 700 °C.
  • the prepared titanium compound (TiC x O y N z ) was used as the anode, the anode current density was 0.1 A/cm 2 , and a highly sensitive on-line gas collection system and mass spectrometer were used for on-line monitoring of the anode gas composition, and the anode discharge was analyzed.
  • the gas is N 2 , CO 2 and CO.
  • the cathode is made of carbon steel electrode.
  • the current density of the cathode is 0.1 A/cm 2 .
  • the constant current electrolysis is performed to control the anode-anode pole spacing of 3 cm. After 5 hours, the anode and cathode are taken out respectively.
  • the product was analyzed by XRD structural composition.
  • the product was a single phase of titanium metal, and the carbon, oxygen and nitrogen content range of the product was 30 ppm. , 150 ppm and 120 ppm.
  • the mixed phase of the graphite powder is converted into a mixed phase of the titanium compound TiN x and C, and the electrical conductivity of the pressed block is sharply reduced from the initial 15 to 25 ohm cm to 0.003 ohm cm.
  • the NaCl-KCl-TiCl 3 salt was placed in a metal molybdenum crucible, wherein the mass concentration of the Ti ion was 3.0%, and an electrolysis experiment was carried out at 750 °C.
  • the prepared titanium compound (TiN x ) and C were used as anodes, the anode current density was 0.15 A/cm 2 , and a highly sensitive on-line gas collection system and mass spectrometer were used for on-line monitoring of the anode gas composition, and the gas evolved from the anode was analyzed. Is N 2 .
  • the cathode is made of stainless steel electrode, the current density of the cathode is 0.15A/cm 2 , constant current electrolysis is performed, and the anode-anode pole spacing is controlled by 5 cm. After 5 hours, the anode and the cathode are taken out, and the electrolyte on the surface of the electrode is cleaned with 1 wt% of dilute hydrochloric acid, respectively.
  • the chloride ion was washed by deionized water, dried, and the current efficiencies of the anode and the cathode were respectively calculated to be 87.4% and 76.5%, respectively.
  • the XRD structural component analysis was performed on the product, and the product was a single phase of titanium metal, and the product was carbon and The oxygen content analysis was 250 ppm and 245 ppm, respectively.
  • TiO 2 99.5wt% 6.0g of graphite powder (C content 99.9%), mixed uniformly in a star ball mill, press-molded under 50MP pressure, and put the block into the semi-open heating furnace.
  • the NaCl-KCl-TiCl 2 -TiCl 3 salt was contained in a metal nickel crucible in which the mass concentration of Ti ions was 8%, and an electrolysis experiment was conducted at 800 °C.
  • the mixed phase of the prepared titanium compound (TiO x N y ) and Ti 3 O 5 was used as the anode, the anode current density was 0.25 A/cm 2 , the metal molybdenum was used as the cathode, and the cathode current density was 0.25 A/cm 2 constant current.
  • Electrolysis controlling the anode-anode pole spacing of 8 cm, after 5 hours, the anode and the cathode were taken out, and the electrolyte on the surface of the electrode was washed with 1 wt% of dilute hydrochloric acid, and then the chloride ion was washed with deionized water, dried, and the above experiment was repeated 5 times.
  • the current efficiency ranges of the anode and cathode were calculated to be 74.2 and 63.4%, respectively, and the product was subjected to XRD analysis.
  • the product was a single phase of titanium metal, and the oxygen and nitrogen contents of the product were analyzed to be 228 ppm and 285 ppm, respectively.
  • Example 2 80.2 g of titanium dioxide (TiO 2 99.5 wt%) and 28.0 g of petroleum coke (C content 89.0%) were weighed, and the raw materials were mixed as described in Example 1, and press-molded.
  • the block was placed under a micro-negative pressure in a closed hot furnace, and the temperature was maintained at 1500 ° C for 120 minutes under a N 2 atmosphere.
  • the calculated reaction rate was 97.6% by calculation of the weight loss rate, and the structural components of the product were analyzed by XRD.
  • the initial mixed phase of metatitanic acid and graphite powder is transformed into a single titanium compound (TiC x O y N z ) phase, and the electrical conductivity of the pressed block is sharply reduced from the initial 75-85 ohm-cm to 0.015 ohm. cm.
  • the NaF-KF-K 2 TiF 6 salt was placed in a metal titanium niobium with a Ti ion mass percentage concentration of 5%, and an electrolysis experiment was conducted at 800 °C.
  • the prepared titanium compound (TiC x O y N z ) was used as the anode, the anode current density was 0.3 A/cm 2 , and a highly sensitive on-line gas collection system and mass spectrometer were used for on-line monitoring of the anode gas composition, and the anode discharge was analyzed.
  • the gas is N 2 , CO 2 and CO, the cathode is metallic nickel, the cathode has a current density of 0.3 A/cm 2 , and the constant current electrolysis is performed to control the anode-anode pole spacing of 3 cm. After 5 hours, the anode and the cathode are taken out, respectively, with 1 wt%.
  • the current efficiency of the anode and cathode were calculated to be 95.3% and 93.5%, respectively.
  • the product was analyzed by XRD structural composition. The product was a single phase of titanium metal, and the carbon, oxygen and nitrogen content range of the product was 50 ppm. , 175ppm and 135ppm.
  • the electrical conductivity of the pressed block was sharply reduced from the initial 95-105 ohm-cm to 0.018 ohm-cm.
  • LiCl-KCl-TiCl 2 salt was placed in a metal nickel crucible in which the mass concentration of Ti ions was 8%, and an electrolysis experiment was carried out at 450 °C.
  • the prepared titanium compound (TiC x O y N z ) was used as the anode, the anode current density was 0.45 A/cm 2 , and a highly sensitive on-line gas collection system and mass spectrometer were used for on-line monitoring of the anode gas composition, and the anode discharge was analyzed.
  • the gas is N 2 , CO 2 and CO.
  • the cathode is made of titanium metal.
  • the current density of the cathode is 0.45 A/cm 2 .
  • the anode and cathode are separated by 8 cm. After 5 hours, the anode and cathode are taken out and 1 wt% respectively. Dilute hydrochloric acid to clean the electrolyte on the surface of the electrode, then wash the chloride ions with deionized water, dry, and repeat the above experiment 5 times.
  • the current efficiency ranges of the anode and cathode were calculated to be 94.7% and 93.9%, respectively.
  • the product was subjected to XRD analysis. The product was a single phase of titanium metal, and the carbon, oxygen and nitrogen contents of the product were analyzed to be 45 ppm and 228 ppm, respectively. 185ppm.
  • the mixed phase of acid and carbon is transformed into a single titanium compound (TiC x O y N z ) phase, and the electrical conductivity of the pressed block is sharply reduced from the initial 45-55 ohm-cm to 0.001 ohm-cm.
  • LiCl-KCl-TiCl 3 salt was placed in a metal titanium alloy, wherein the mass concentration of Ti ions was 7%, and electrolysis experiments were carried out at 450 °C.
  • the prepared titanium compound (TiC x O y N z ) was used as the anode, the anode current density was 0.5 A/cm 2 , and a highly sensitive on-line gas collection system and mass spectrometer were used for on-line monitoring of the anode gas composition, and the anode discharge was analyzed.
  • the gases are N 2 , CO 2 and CO, using stainless steel as the cathode, the current density of the cathode is 0.5 A/cm 2 constant current electrolysis, controlling the anode-anode pole spacing 10 cm, and taking the anode and cathode respectively after 5 hours with 1 wt% of thinning
  • the electrolyte on the surface of the electrode was washed with hydrochloric acid, and the chloride ion was washed with deionized water, dried, and the above experiment was repeated 5 times.
  • the current efficiency ranges of the anode and the cathode were calculated to be 96.9% and 95.5%, respectively.
  • the product was subjected to XRD analysis.
  • the product was a single phase of titanium metal, and the carbon, oxygen and nitrogen contents of the product were analyzed to be 30 ppm and 180 ppm, respectively. 185ppm.
  • the mixed phase of the acid and graphite powder is transformed into a single titanium compound (TiC x O y N z ) phase, and the electrical conductivity of the pressed block is sharply reduced from the initial 85-105 ohm-cm to 0.015 ohm-cm.
  • the CaCl 2 -KCl-TiCl 2 salt was placed in a metal titanium alloy, wherein the mass concentration of the Ti ion was 6%, and the electrolysis experiment was carried out at 750 °C.
  • the prepared titanium compound (TiC x O y N z ) was used as the anode, the anode current density was 0.65 A/cm 2 constant current electrolysis, and the highly sensitive on-line gas collection system and mass spectrometer were used for on-line monitoring and analysis of the anode gas composition.
  • the gases emitted from the anode are N 2 , CO 2 and CO, carbon steel is used as the cathode, the current density of the cathode is 0.65/cm 2 , the anode-to-anode pole spacing is 9 cm, and the anode and cathode are taken out after 1 hour of constant current electrolysis.
  • the electrolyte on the surface of the electrode was cleaned with dilute hydrochloric acid, and the chloride ion was washed with deionized water, and dried, and the above experiment was repeated 5 times.
  • the current efficiency ranges of the anode and cathode were calculated to be 95.1% and 92.6%, respectively.
  • the product was XRD analyzed. As can be seen from Figure 5 of the specification, the product is a single metal titanium phase, and the product is carbon, oxygen and The nitrogen content was analyzed to be 65 ppm, 355 ppm, and 200 ppm, respectively.
  • the structural composition of the product was analyzed by XRD, starting from the metatitanic acid and The mixed phase of charcoal is converted into a mixed phase of titanium compounds (TiO x N y and TiC x O y N z ), and the electrical conductivity of the pressed block is sharply reduced from the initial 110 to 125 ohm cm to 0.015 ohm cm.
  • a metal titanium alloy crucible was used to hold a CsCl 2 -NaCl-TiCl 2 salt in which the mass concentration of Ti ions was 4%, and an electrolysis experiment was carried out at 750 °C.
  • the prepared titanium compound (TiC x O y N z ) was used as the anode, the anode current density was 0.75 A/cm 2 constant current electrolysis, and the highly sensitive on-line gas collection system and mass spectrometer were used for on-line monitoring and analysis of the anode gas composition.
  • the gas evolved from the anode was N 2 , CO 2 and CO, and the titanium alloy was used as the cathode, and the current density of the cathode was 0.75 / cm 2 .
  • the anode-anode pole spacing was controlled to 12 cm.
  • the current efficiency ranges of the anode and the cathode were calculated to be 95.6% and 93.5%, respectively.
  • the product was subjected to XRD analysis. The product was a single phase of titanium, and the carbon, oxygen and nitrogen contents of the product were analyzed to be 50 ppm, 330 ppm and 170 ppm, respectively. .
  • the CaCl 2 -KCl-NaCl-TiCl 2 salt was placed in a metal titanium alloy, wherein the mass concentration of the Ti ion was 3%, and the electrolysis experiment was carried out at 750 °C.
  • the titanium compound (TiN X ) is used as an anode, the anode current density is 0.85 A/cm 2 constant current electrolysis, and a highly sensitive on-line gas collection system and mass spectrometer are used for on-line monitoring of the anode gas composition, as can be seen from Figure 6 of the specification.
  • the gas emitted from the anode is only N 2 and there is no precipitation of NO and NO 2 .
  • the metal nickel is used as the cathode.
  • the current density of the cathode is 0.85/cm 2
  • the anode-to-anode pole spacing is 15 cm
  • the anode is taken after constant current electrolysis for 2 hours.
  • the electrolyte on the surface of the electrode was cleaned with 1 wt% of dilute hydrochloric acid, and then washed with deionized water, dried, and the current efficiencies of the anode and cathode were calculated to be 101.5% and 96.5%.
  • the product was subjected to XRD analysis.
  • the single phase of titanium was analyzed for both oxygen and nitrogen contents of 275 ppm and 165 ppm, respectively.
  • the CaF 2 -KF-NaF-Na 2 TiF 6 salt was placed in a metal titanium alloy, wherein the Ti ion mass percentage was 6%, and an electrolysis experiment was carried out at 850 °C.
  • the prepared titanium compound TiC x O y N z
  • the anode current density was 0.90 A/cm 2 constant current electrolysis
  • the on-line monitoring of the anode gas composition was carried out by a highly sensitive on-line gas collection system and mass spectrometer.
  • the gases emitted from the anode are N 2 , CO 2 and CO.
  • the metal nickel is used as the cathode.
  • the current density of the cathode is 0.90/cm 2
  • the anode-to-anode pole spacing is 20 cm
  • the anode and cathode are taken out after 2 hours of constant current electrolysis.
  • 1wt% of dilute hydrochloric acid was used to clean the electrolyte on the surface of the electrode, then the chloride ion was washed with deionized water, dried, and the current efficiency of the anode and cathode was calculated to be 94.5% and 93.7%.
  • the product was subjected to XRD analysis, and the product was a single titanium.
  • the phase, while analyzing the carbon, oxygen and nitrogen contents of the product were 83 ppm, 375 ppm and 265 ppm, respectively.
  • a metal titanium alloy crucible was used to hold a CsCl 2 -LiCl-TiCl 2 -TiCl 3 salt in which the mass concentration of Ti ions was 1%, and an electrolysis experiment was carried out at 750 °C.
  • the prepared titanium compound (TiO x N y ) was used as the anode, the anode current density was 1.00 A/cm 2 constant current electrolysis, the metal molybdenum was used as the cathode, the cathode current density was 1.00/cm 2 , and the anode-anode pole pitch was controlled to be 6 cm.
  • the anode and the cathode were taken out, and the electrolyte on the surface of the electrode was washed with 1 wt% of dilute hydrochloric acid, then the chloride ion was washed with deionized water, and dried, and the current efficiency of the anode and the cathode was calculated to be 94.5% and 93.7%.
  • the product was subjected to XRD analysis, which was a single phase of titanium, and the product was analyzed for oxygen and nitrogen contents of 475 ppm and 249 ppm, respectively.
  • the titanium compound (TiC x O y N z ) prepared in the first embodiment was used as an anode, and the anode current density was 0.50 A/cm 2 , and constant current electrolysis was carried out in a 700 ° C NaCl-KCl-TiCl 2 molten salt system, wherein Ti The ion mass percentage concentration is 8%, the metal stainless steel is used as the cathode, the current density of the cathode is 0.50 A/cm 2 , the anode-anode pole spacing is controlled to 3 cm, and the anode and cathode are replaced every 2 hours to continue electrolysis, and the electrolysis is continuously performed for 20 hours. .
  • a total of 20.8 g of titanium metal was electrolyzed, and the total amount of titanium ions in the electrolyte was 5 g.
  • the electrolyte concentration did not change after continuous electrolysis for a long time, indicating that 20.8 g of titanium metal obtained by electrolysis was obtained from an electrolytic titanium compound (TiC x O y N z ). of.
  • the electrolyte on the surface of the electrode was washed with 1 wt% of dilute hydrochloric acid, and the chloride ion was washed with deionized water.
  • the product was subjected to XRD analysis on the product.
  • the product was a single phase of titanium, as can be seen from Figure 7 of the specification.
  • the current efficiency of the cathode was calculated to be 95.5%, and the carbon, oxygen and nitrogen contents of the product were analyzed to be 55 ppm, 227 ppm and 125 ppm, respectively.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

本发明提出一种含钛可溶阳极熔盐电解提取金属钛的方法，涉及有色金属冶金技术领域。该方法以含钛物料和含碳还原剂混合为原料混合均匀后压制成型，在含氮气氛下保持温度范围为1000℃～2000℃，反应30～600分钟；制备出导电性良好含钛化合物；然后以这种含钛化合物作为阳极在碱金属或碱土金属的卤化物熔盐中电解提取金属钛。本发明所述含钛可溶阳极熔盐电解提取金属钛的方法是一种工艺简单、能耗低并且能够实现工业化制取高纯金属钛的方法。

Description

一种含钛可溶阳极熔盐电解提取金属钛的方法 技术领域
本发明属于有色金属冶金技术领域，特别涉及一种含钛可溶阳极熔盐电解制取金属钛的方法。
背景技术
金属钛具有密度小、比强度高、耐腐蚀、耐高温、无磁无毒等优点；钛合金具有记忆功能、超导功能、储氢功能等。目前金属钛已经被广泛地应用于航空航天、军工等军事领域和化工、船舶、汽车、体育器材、医疗器械、建筑等民用领域，被誉为“未来金属”、“第三金属”。
目前金属钛的主流生产工艺为Kroll法，即四氯化钛的金属镁热还原法。其核心工艺是将金属镁放入到反应器中并充入氩气保护，加热到800℃～900℃，然后以一定的速度加入四氯化钛与熔融的金属镁反应制备海绵钛，金属钛的纯度为99.7％左右。其冶金生产工艺流程复杂繁琐、能耗大、成本高，使其价格无法降低，正是由于这些原因造成了金属钛的价格昂贵，大大的限制了金属钛的应用。
2000年英国剑桥大学D.J.Fray教授提出了一种以TiO2为原料在熔融CaCl2中阴极脱氧生产海绵钛的工艺(WO09963638)。其工艺具备如下特点：(1)电解脱氧效率低；(2)脱氧的过程复杂；(3)对氧化钛原料纯度要求较高。所以FFC工艺的工业化过程还需要一较长时期去设法解决上述的问题，在短期内尚难以期待通过该方法来替代Kroll法生产金属钛。
麻省理工学院的Sadoway教授的研究小组在1700℃下电解含TiO2氧化物熔体制得了液态金属钛。该工艺简单，可连续生产，同时阳极得到O2，对环境无污染。但由于该工艺操作温度为1700℃，其阳极需使用贵金属材料，成本高。另外，以熔体二氧化钛电解所制得的液体钛沉在电解槽底部与含有氧离子的高温熔融盐层直接接触，普遍存在产品含氧量高的问题，目前为止此类方法获得的金属钛含氧量均高于2％，距离可利用金属钛的质量要求还有很大的差距。因此，目前仍然无法期望以这种方法直接电解生态金属钛。
日本京都大学的冈部(Okabe)和小野(Ono)研究在CaCl2熔盐中，将TiO2用电解得到的活性钙还原二氧化钛为钛金属。与剑桥大学的FFC工艺的区别之处在于，金属钛不是通过二氧化钛阴极脱氧直接得到，而是通过电解出的金属钙然后还原TiO2得到的金属钛。该工艺同样存在类似剑桥大学的FFC工艺问题，电流效率低、产品质量含氧量高、原料二氧化钛纯度要求高等问题。
上世纪50年代，E.Wainer以TiC和TiO为原料混合后，在2100℃的高温下热处理形成固溶体(TiC-TiO)，以之为阳极在氯化物熔融盐中电解，研究发现阳极上有CO气体放出并且阳极区没有剩余产物(阳极泥)，经过长时间电解后可在阴极沉积获得纯钛。但是Wainer所提的方案需要以TiC和TiO为原料，其中TiO不容易制备和控制，并且TiC和TiO的固溶体是在采用电弧熔炼高温(＞2100℃)条件下制得的，显然在实际应用意义上还是存在问题。
日本研究工作者桥本(Y.Hashimoto)以过量的碳和TiO2为原料混合，采用电弧高温(＞1700℃)制成氧掺杂碳化钛(Oxygen doped TiC)，并以之为阳极在熔融盐中电解，阴极沉积得到纯钛。但是其阳极的制备过程仍然依赖于非常高温(＞1700℃)的还原条件，并没有在本质上达到低成本提取钛的目的，并且其电解实验都是以低氧的碳化钛为主，阳极碳含量太高导致产生大量阳极泥，使得连续电解无法正常进行。
美国MER公司开发出了一种全新的电解还原工艺(WO2005/019501)。该工艺是以TiO2和C按化学计量比混合，在1100℃～1300℃热还原得到钛的低价氧化物和碳的混合物，再以此为复合阳极在碱金属熔盐体系中电解得到金属钛。该工艺复合阳极为钛的低价氧化物和碳的混合材料，在电化学溶解的过程会有阳极泥和剩碳，随着剩碳的量的增加会在造成电极短路的问题而且污染产品。
2005年北京科技大学朱鸿民教授提出一种的新型清洁钛提取冶炼新工艺(ZL200510011684.6)，以二氧化钛和石墨为原料在1500℃下真空碳热还原制备出导电性良好的Ti2CO，并以此为可溶阳极材料在700℃的NaCl-KCl熔盐体系中电解提取高纯金属钛，阴极上得到的含碳含氧量均低于300ppm的高纯钛。该工艺已经深入研究了科学及机理问题，并且进行小规模的中式实验，验证了其可行性。
四川攀钢集团有限公司2009年申请了一种钛循环熔盐电解制取金属钛的方法(CN 101519789A)，该方法以四氯化钛为原料，用金属钛还原到低价钛的氯化物，然后通过熔盐电解获得金属钛。该方法存在以下问题：原料使用四氯化钛和金属钛价格昂贵，四氯化钛被还原的成低价钛的反应率低，同样造成钛的生产成本。2010年申请了一种制备金属钛的方法(CN 101914788)，以钛精矿熔炼钛渣时直接配入过量的碳在通入氮气制备氮化钛或碳氮化钛，经过电解获得金属钛的方法。该方法配入过量的碳来制备碳化钛或碳氮化钛。该方法存在以下问题：(1)由于配入的碳是过量的，所以制备碳化钛或碳氮化钛会有碳的剩余；(2)碳化钛或碳氮化钛作为阳极时长时间电解的过程中，其中的碳会以单质碳的形式析出，成为剩碳；以上两种情况产生的剩碳将会污染阴极产物的质量，而且容易造成电极间短路、电流效率低和产品含碳量高等问题。
发明内容
本发明的目的在于克服现有技术中制取金属钛方法流程长、能耗高、产品质量达不到高纯钛的标准或者无法实现工业化的缺点。因此，本发明提供一种工艺简单、能耗低并且能够实现工业化制取高纯金属钛的方法。
针对现有技术本发明的改进内容体现在：(1)低成本合成制备出具有金属导电性的钛化合物(TiCxOyNz、TiOxNy、TiNx)；(2)并以钛化合物(TiCxOyNz、TiOxNy、TiNx)作为阳极材料通过熔盐电解提取纯金属钛；(3)电解的过程中，含钛的化合物(TiCxOyNz、TiOxNy、TiNx)中的钛以钛离子的形式溶入电解质中，其中的碳氧氮以CO、CO2和N2形式析出，不存在阳极剩碳的问题(4)原料和产品分别在阳极和阴极上，保证产品不受原料中杂质影响；同时熔盐电解本身具有精炼的过程，该工艺将提取钛和精炼钛合二为一，直接在阴极上获得高纯金属钛。(5)原料和产品分别在阳极和阴极，可以通过连续更换电极实现连续化生产。综合以上改进内容，较现有技术具有工艺流程短、碳热还原效率高、中间产物少、直接获得高纯金属钛，阳极原料的纯度要求低、能耗低、清洁环保无污染等优点。
发明的目的在于提供一种以钛可溶阳极熔盐电解提取钛的方法，包括以下步骤：
(1)以含钛物料和含碳还原剂以摩尔比为5∶1～1∶20的比例混合为原料混合均匀后压制成型，在含氮气氛下保持温度范围为1000℃～2000℃，反应30～600分钟；制备出导电性良好含钛化合物；其中，所述含钛物料包括金红石型钛白、锐钛矿型钛白、偏钛酸、钛铁矿、钒钛磁铁矿、高炉型高钛渣、高钛渣和钛的低价氧化物中的一种或几种；所述含碳还原剂包括碳、活性碳、石墨粉、木炭、石油焦、沥青、煤焦粒中的一种或几种；制备出的所述含钛化合物为TiCxOyNz、TiOxNy、TiNx中的一种或几种，所述TiCxOyNz的碳氧氮的摩尔量比符合如下原则：0＜X≤Y＜1，0＜Z＜1，X+Y+Z＝1；所述TiOxNy的氧氮的摩尔量比符合如下原则：0＜X≤Y，X+Y＝1；所述TiNx的氮的摩尔量比符合如下原则：0＜X≤1；
(2)以步骤(1)得到的含钛化合物为原料制备成电极在碱金属或碱土金属的卤化物熔盐中通过电解的方法提取金属钛，其阳极由制得的含钛化合物形成，在阴极上获得金属钛；所述阴极由金属钛、不锈钢、碳钢、金属钼、金属镍中的一种或多种形成；阴阳极的极间距控制在1cm～50cm之间；电解质由碱金属或碱土金属卤化物组成；槽电压控制在0.5V～10.0V，阳极电流密度范围为：0.05A/cm2～1.50A/cm2，阴极电流密度范围分别为：0.05A/cm2～1.50A/cm2，电解温度范围在300℃～1000℃。
进一步的，所述含氮的气氛包括空气、氮气、氨气、氮气-氢气、氮气-氩气和其它含氮气体的混合气中的一种或几种。
进一步的，所述钛的低价氧化物为Ti2O3、Ti3O5、TiO、Ti3O中的一种或几种。
优选的，在含氮的气氛的密闭体系或半开放系统或开放体系下制备具有导电性的含钛化合物，。
优选的，所述密闭体系为部分正压或常压(一个标准大气压)或部分真空下的含氮气气氛的体系。
进一步的，所述电解质由CsCl2、CaCl2、LiCl、NaCl、KCl、MgCl2、AlCl3、CaF、NaF、KF、LiF中的一种或一种以上和TiCl3、TiCl2、K2TiF6、Na2TiF6中的一种或一种以上的混合盐作为熔盐电解质体系，其中熔盐电解质体系中Ti离子质量百分比浓度为1％-10％。
进一步的，所述含钛物料和含碳还原剂的摩尔比为5∶1～1∶10。
优选的，所述电解温度范围在400℃～900℃。
优选的，所述阴阳极的极间距控制在3cm～40cm之间；槽电压控制在1.5V～6.0V。阳极电流密度范围为：0.05A/cm2～1.00A/cm2；阴极电流密度范围为：0.05A/cm2～1.00A/cm2。
进一步的，所述电解质的盛放容器为：不锈钢坩埚、碳钢坩埚、钛坩埚、钛合金坩埚、石墨坩埚、钼坩埚或镍坩埚中的一种。
附图说明
图1a为本发明实施例一热处理后阳极块体SEM示意图；
图1b为本发明实施例一热处理后阳极块体的X射线衍射图；
图2为本发明实施例二热处理后得到反应产物的X射线衍射图；
图3为本发明实施例三1500℃热处理后得到反应产物的X射线衍射图；
图4为本发明实施例五热处理后阳极块体SEM示意图；
图5为本发明实施例七阴极产物的X射线衍射图；
图6为本发明实施例九电解过程中阳极气体随电解过程中的变化曲线；
图7为本发明实施例十二阴极产物的SEM示意图。
具体实施方式
下面结合示例性实施例对本发明的具体实施方式做进一步描述，并不因此将本发明的限制在所描述的示例性实施例范围内。本发明中的碳质还原剂指以碳为主要成分的还原剂，例如碳、活性碳、石墨粉、木炭、石油焦、沥青、煤焦粒等。
根据示例性实施例的一种钛化合物可溶阳极熔盐电解提取钛的方法包括以下步骤：
(1)以含钛物料和含碳还原剂以摩尔比为5∶1～1∶20的比例混合为原料混合均匀后压制成型，在含氮气氛下保持温度范围为1000℃～2000℃，反应30～600分钟；制备出导电性良好含钛化合物；其中，所述含钛物料包括金红石型钛白、锐钛矿型钛白、偏钛酸、钛铁矿、钒钛磁铁矿、高炉型高钛渣、高钛渣和钛的低价氧化物中的一种或几种；所述含碳还原剂包括碳、活性碳、石墨粉、木炭、石油焦、沥青、煤焦粒中的一种或几种；制备出的所述含钛化合物为TiCxOyNz、TiOxNy、TiNx中的一种或几种，所述TiCxOyNz的碳氧氮的摩尔量比符合如下原则：0＜X≤Y＜1，0＜Z＜1，X+Y+Z＝1；所述TiOxNy的氧氮的摩尔量比符合如下原则：0＜X≤Y，X+Y＝1；所述TiNx的氮的摩尔量比符合如下原则：0＜X≤1；
(2)以步骤(1)得到的含钛化合物为原料制备成电极在碱金属或碱土金属的卤化物熔盐中通过电解的方法提取金属钛，其阳极由制得的含钛化合物形成，在阴极上获得金属钛；所述阴极由金属钛、不锈钢、碳钢、金属钼、金属镍中的一种或多种形成；阴阳极的极间距控制在1cm～50cm之间；电解质由碱金属或碱土金属卤化物组成；槽电压控制在0.5V～10.0V，阳极电流密度范围为：0.05A/cm2～1.50A/cm2，阴极电流密度范围分别为：0.05A/cm2～1.50A/cm2，电解温度范围在300℃～1000℃。
根据示例性实施例的一种含钛化合物(TiCxOyNz、TiOxNy、TiNx)可溶阳极熔盐电解提取钛的方法中，含钛的物料包括金红石型钛白、锐钛矿型钛白、偏钛酸、钛铁矿、钒钛磁铁矿、高炉型高钛渣、高钛渣和钛的低价氧化物(Ti2O3、Ti3O5、TiO、Ti3O)；含碳还原剂包括碳、活性碳、石墨粉、木炭、石油焦、沥青、煤焦粒等含碳为主的物质；含钛的物料和碳质还原剂的按摩尔量计量配比可以设定为5∶1～1∶20；摩尔量的比值低于5∶1，则产物含有大量的钛低价氧化物，摩尔量的比值高于1∶20，则会有大量的剩碳，优选的范围为5∶1～1∶10；在含氮的气氛下制备钛化合物(TiCxOyNz、TiOxNy、TiNx)；制备钛化合物(TiCxOyNz、TiOxNy、TiNx)的温度范围为1000℃～2000℃；阴阳极的极间距控制在1cm～50cm，这里极间距低于1cm容易造成电极之间短路，这里极间距高于50cm，槽压过高，较优的范围为3cm～40cm；电解质由碱金属或碱土金属卤化物，或者由碱金属或碱土金属氧化物，或者由碱金属或碱土金属卤化物和氧化物形成；槽电压可设定为0.5V～10.0V，如果阳极的槽电压低于0.5V，阳极电解速率慢，造成日产量低，如果阳槽电压高于10.0V，则会造成过电位过高，阳极容易出现机械破碎，造成能耗增大阳极电流效率低，槽电压优选设定为1.5V～6.0V；阳极电流密度可设定范围0.05A/cm2～1.50A/cm2，优选0.05A/cm2～1.00A/cm2；阴极电流密度可设定范围0.05A/cm2～1.50A/cm2，优选0.05A/cm2～1.00A/cm2；盛放电解质的坩埚可选不锈钢坩 埚、碳钢坩埚、钛坩埚、钛合金坩埚、石墨坩埚、钼坩埚或镍坩埚。
以下，将给出一种含钛可溶阳极熔盐电解提取钛的方法的具体实施例，但实施例仅是示例性的，本发明不限于此。
实施例一
称取钛白粉(TiO299.5wt％)80.2g，石墨粉(C含量99.9％)21.0g，在星型球磨机中混合均匀，在10MP压力下压制成型，将块体放入密闭常压的加热炉中，在N2-H2的混合气氛下加热到1500℃保温120分钟，通过计算失重率计算发现反应率为98.3％，通过XRD分析产物的结构成分，如说明书附图1a和1b所示，由开始的二氧化钛和石墨粉的混合相转变成了单一的钛化合物(TiCxOyNz)相，从SEM图中也看出产物尺寸在10μm左右。压制块体的导电率由开始的15～25欧姆●厘米急剧的降为0.005欧姆●厘米。用石墨坩埚盛放NaCl-KCl-TiCl2盐，其中Ti离子质量百分比浓度为5％，在700℃下进行电解实验。以制备的钛化合物(TiCxOyNz)作为阳极，阳极电流密度为0.1A/cm2，并进行高灵敏的在线采气系统和质谱仪进行阳极气体成分的在线监测，分析出阳极放出的气体为N2，CO2和CO，阴极选用碳钢电极，阴极的电流密度为0.1A/cm2，进行恒电流电解，控制阴阳极极间距3cm，5小时以后取出阳极和阴极分别用1wt％的稀盐酸清洗电极表面的电解质，再用去离子水洗净氯离子，烘干，重复以上实验5次。分别计算阳极和阴极的电流效率分范围别为97.8％和94.8％，对产物进行XRD结构成分分析，该产物为金属钛的单一相，同时对产物进行碳、氧及氮含量范围分析分别为30ppm、150ppm和120ppm。
实施例二
称取钛白粉(TiO299.5wt％)80.2g，石墨粉(C含量99.9％)120.0g，在星型球磨机中混合均匀，在30MP压力下压制成型，将块体放入密闭常压的加热炉中，N2的气氛下加热到1400℃保温60分钟，通过计算失重率计算发现反应率为99.2％，通过XRD分析产物的结构成分，如说明书附图2中所示，由开始的二氧化钛和石墨粉的混合相转变成了钛化合物TiNx和C的混合相，压制块体的导电率由开始的15～25欧姆●厘米急剧的降为0.003欧姆●厘米。用金属钼坩埚盛放NaCl-KCl-TiCl3盐，其中Ti离子质量百分比浓度为3.0％，在750℃下进行电解实验。以制备的钛化合物(TiNx)和C作为阳极，阳极电流密度为0.15A/cm2，并进行高灵敏的在线采气系统和质谱仪进行阳极气体成分的在线监测，分析出阳极放出的气体为N2。阴极选用不锈钢电极，阴极的电流密度为0.15A/cm2，进行恒电流电解，控制阴阳极极间距5cm，5小时以后取出阳极和阴极分别用1wt％的稀盐酸清洗电极表面的电解质，再用去离子水洗净氯离子，烘干，分别计算阳极和阴极的电流效率分别为87.4％和76.5％，对产物进行XRD结构成分分析，该产物为金属钛的单一相，同时对产物进行碳和氧含量分析分别为250ppm和245ppm。
实施例三
称取钛白粉(TiO299.5wt％)80.2g，石墨粉(C含量99.9％)6.0g，在星型球磨机中混合均匀，在50MP压力下压制成型，将块体放入半开放加热炉中，在空气中1600℃保温90分钟，通过计算失重率计算，发现反应率为98.5％，通过XRD分析产物的结构成分，如说明书附图3所示，由开始的二氧化钛和石墨粉的混合相转变成了钛化合物(TiOxNy)和Ti3O5的混合相，压制块体的导电率由开始的165～175欧姆●厘米急剧的降为0.18欧姆●厘米。用金属镍坩埚盛放NaCl-KCl-TiCl2-TiCl3盐，其中Ti离子质量百分比浓度为8％，在800℃下进行 电解实验。以制备的钛化合物(TiOxNy)和Ti3O5的混合相作为阳极，阳极电流密度为0.25A/cm2，以金属钼作为阴极，阴极的电流密度为0.25A/cm2恒电流电解，控制阴阳极极间距8cm，5小时以后取出阳极和阴极分别用1wt％的稀盐酸清洗电极表面的电解质，再用去离子水洗净氯离子，烘干，重复以上实验5次。分别计算阳极和阴极的电流效率范围分别为74.2和63.4％，对产物进行XRD分析，该产物为金属钛的单一相，同时对产物进行氧和氮含量分析为分别为228ppm和285ppm。
实施例四
称取钛白粉(TiO299.5wt％)80.2g，石油焦(C含量89.0％)28.0g，按实施例一所述混合原料，压制成型。将块体放入密闭的热炉中微负压状体下，N2的气氛下1500℃保温120分钟小时，通过计算失重率计算发现反应率为97.6％，通过XRD分析产物的结构成分，由开始的偏钛酸和石墨粉的混合相转变成了单一的钛化合物(TiCxOyNz)相，压制块体的导电率由开始的75～85欧姆●厘米急剧的降为0.015欧姆●厘米。用金属钛坩埚盛放NaF-KF-K2TiF6盐，其中Ti离子质量百分比浓度为5％，在800℃下进行电解实验。以制备的钛化合物(TiCxOyNz)作为阳极，阳极电流密度为0.3A/cm2，并进行高灵敏的在线采气系统和质谱仪进行阳极气体成分的在线监测，分析出阳极放出的气体为N2，CO2和CO，阴极为金属镍，阴极的电流密度为0.3A/cm2，进行恒电流电解，控制阴阳极极间距3cm，5小时以后取出阳极和阴极分别用1wt％的稀盐酸清洗电极表面的电解质，再用去离子水洗净氯离子，烘干，重复以上实验5次。分别计算阳极和阴极的电流效率分范围别为95.3％和93.5％，对产物进行XRD结构成分分析，该产物为金属钛的单一相，同时对产物进行碳、氧及氮含量范围分析分别为50ppm、175ppm和135ppm。
实施例五
称取钛白粉(TiO299.5wt％)80.2g，木炭(C含量75.0％)35.0g，按实施例一所述混合原料，压制成型。将块体放入密闭常压加热炉中N2的气氛下1300℃保温300分钟，通过计算失重量计算发现反应率为97.8％，热处理后通过XRD分析材料的结构，由开始的二氧化钛和碳的混合相转变成了单一的钛化合物(TiCxOyNz)相，从说明书附图4中可以看出，获得了产物的尺寸在10μm左右。压制块体的导电率由开始的95～105欧姆●厘米急剧的降为0.018欧姆●厘米。用金属镍坩埚盛放LiCl-KCl-TiCl2盐，其中Ti离子质量百分比浓度为8％，在450℃下进行电解实验。以制备的钛化合物(TiCxOyNz)作为阳极，阳极电流密度为0.45A/cm2，并进行高灵敏的在线采气系统和质谱仪进行阳极气体成分的在线监测，分析出阳极放出的气体为N2，CO2和CO，用金属钛做阴极，阴极的电流密度为0.45A/cm2恒电流电解，控制阴阳极极间距8cm，5小时以后取出阳极和阴极分别用1wt％的稀盐酸清洗电极表面的电解质，再用去离子水洗净氯离子，烘干，重复以上实验5次。分别计算阳极和阴极的电流效率范围分别为94.7％和93.9％，对产物进行XRD分析，该产物为金属钛的单一相，同时对产物进行碳、氧及氮含量分析为分别为45ppm、228ppm和185ppm。
实施例六
称取偏钛酸(TiO(OH)298.0wt％)99.8g，石墨粉(C含量99.9％)24.0g，按实施例一所述混合原料，压制成型。将块体放入密闭微正压加热炉中，NH3的气氛下1450℃保温480分钟，通过计算失重量计算发现反应率为99.2％，热处理后通过XRD分析材料的结构，由开始的偏钛酸和碳的混合相转变成了单一的钛化合物(TiCxOyNz)相，压制块体的导电率 由开始的45～55欧姆●厘米急剧的降为0.001欧姆●厘米。用金属钛合金坩埚盛放LiCl-KCl-TiCl3盐，其中Ti离子质量百分比浓度为7％，在450℃下进行电解实验。以制备的钛化合物(TiCxOyNz)作为阳极，阳极电流密度为0.5A/cm2，并进行高灵敏的在线采气系统和质谱仪进行阳极气体成分的在线监测，分析出阳极放出的气体为N2，CO2和CO，用不锈钢作为阴极，阴极的电流密度为0.5A/cm2恒电流电解，控制阴阳极极间距10cm，5小时以后取出阳极和阴极分别用1wt％的稀盐酸清洗电极表面的电解质，再用去离子水洗净氯离子，烘干，重复以上实验5次。分别计算阳极和阴极的电流效率范围分别为96.9％和95.5％，对产物进行XRD分析，该产物为金属钛的单一相，同时对产物进行碳、氧及氮含量分析为分别为30ppm、180ppm和185ppm。
实施例七
称取偏钛酸(TiO(OH)298.0wt％)99.8g，石油焦(C含量89.0％)30.0g，按实施例一所述混合原料，压制成型。将块体放入半开放的加热炉中，NH3-N2的气氛1500℃保温240分钟，通过计算失重率计算发现反应率为97.7％，通过XRD分析产物的结构成分，由开始的偏钛酸和石墨粉的混合相转变成了单一的钛化合物(TiCxOyNz)相，压制块体的导电率由开始的85～105欧姆●厘米急剧的降为0.015欧姆●厘米。用金属钛合金坩埚盛放CaCl2-KCl-TiCl2盐，其中Ti离子质量百分比浓度为6％，在750℃下进行电解实验。以制备的钛化合物(TiCxOyNz)作为阳极，阳极电流密度为0.65A/cm2恒电流电解，并进行高灵敏的在线采气系统和质谱仪进行阳极气体成分的在线监测，分析出阳极放出的气体为N2，CO2和CO，用碳钢作为阴极，阴极的电流密度为0.65/cm2，控制阴阳极极间距9cm，恒电流电解5小时以后取出阳极和阴极分别用1wt％的稀盐酸清洗电极表面的电解质，再用去离子水洗净氯离子，洪干，重复以上实验5次。分别计算阳极和阴极的电流效率范围分别为95.1％和92.6％，对产物进行XRD分析，从说明书附图5中可看出，该产物为单一的金属钛相，同时对产物进行碳、氧及氮含量分析为分别为65ppm、355ppm和200ppm。
实施例八
称取偏钛酸(TiO(OH)298.0wt％)99.8g，木炭(C含量75.0％)15.0g，按实施例一所述混合原料，压制成型。将块体密闭常压放入热炉中NH3-Ar气氛下1100℃保温600分钟，通过计算失重率计算发现反应率为95.6％，通过XRD分析产物的结构成分，由开始的偏钛酸和木炭的混合相转变成了的钛化合物(TiOxNy和TiCxOyNz)混合相，压制块体的导电率由开始的110～125欧姆●厘米急剧的降为0.015欧姆●厘米。用金属钛合金坩埚盛放CsCl2-NaCl-TiCl2盐，其中Ti离子质量百分比浓度为4％，在750℃下进行电解实验。以制备的钛化合物(TiCxOyNz)作为阳极，阳极电流密度为0.75A/cm2恒电流电解，并进行高灵敏的在线采气系统和质谱仪进行阳极气体成分的在线监测，分析出阳极放出的气体为N2，CO2和CO，以钛合金为阴极，阴极的电流密度为0.75/cm2。控制阴阳极极间距12cm，恒电流电解5小时以后取出阳极和阴极分别用1wt％的稀盐酸清洗电极表面的电解质，再用去离子水洗净氯离子，洪干，重复以上实验5次。分别计算阳极和阴极的电流效率范围分别为95.6％和93.5％，对产物进行XRD分析，该产物为钛的单一相，同时对产物进行碳、氧及氮含量分析为分别为50ppm、330ppm和170ppm。
实施例九
称取高钛渣(TiO2含量89.0％)80.2g，石墨粉(C含量99.9％)48.0g，在星型球磨机中混 合均匀，在50MP压力下压制成型，将块体放入密闭常压加热炉中NH3-H2的气氛1700℃保温120分钟，通过计算失重率计算发现反应率为99.6％，通过XRD分析产物的结构成分，其中的二氧化钛和石墨粉转变成了钛化合物(TiNx)相，压制块体的导电率由开始的15～25欧姆●厘米急剧的降为0.01欧姆●厘米。用金属钛合金坩埚盛放CaCl2-KCl-NaCl-TiCl2盐，其中Ti离子质量百分比浓度为3％，在750℃下进行电解实验。钛化合物(TiNX)作为阳极，阳极电流密度为0.85A/cm2恒电流电解，并进行高灵敏的在线采气系统和质谱仪进行阳极气体成分的在线监测，从说明书附图6中可以看出，阳极放出的气体只有N2而没有NO和NO2的析出，用金属镍做阴极，阴极的电流密度为电解0.85/cm2，控制阴阳极极间距15cm，恒电流电解2小时以后取出阳极和阴极分别用1wt％的稀盐酸清洗电极表面的电解质，再用去离子水洗净氯离子，烘干，计算阳极和阴极的电流效率为101.5％和96.5％，对产物进行XRD分析，该产物为钛的单一相，同时对产物进行氧和氮含量分析为分别为275ppm和165ppm。
实施例十
称取钛铁矿(TiO2含量49.0％)80.2g，石油焦(C含量89.0％)20.0g，在星型球磨机中混合均匀，在30MP压力下压制成型，将块体放入密闭常压加热炉中NH3的气氛下加热到1200℃保温240分钟，通过计算失重率计算发现反应率为97.6％，通过XRD分析产物的结构成分，其中的二氧化钛和碳转变成了钛化合物(TiCxOyNz)相，压制块体的导电率由开始的60～70欧姆●厘米急剧的降为0.005欧姆●厘米。用金属钛合金坩埚盛放CaF2-KF-NaF-Na2TiF6盐，其中Ti离子质量百分比浓度为6％，在850℃下进行电解实验。以制备的钛化合物(TiCxOyNz)作为阳极，阳极电流密度为0.90A/cm2恒电流电解，并进行高灵敏的在线采气系统和质谱仪进行阳极气体成分的在线监测，分析出阳极放出的气体为N2，CO2和CO，用金属镍作阴极，阴极的电流密度为电解0.90/cm2，控制阴阳极极间距20cm，恒电流电解2小时以后取出阳极和阴极分别用1wt％的稀盐酸清洗电极表面的电解质，再用去离子水洗净氯离子，烘干，计算阳极和阴极的电流效率为94.5％和93.7％，对产物进行XRD分析，该产物为钛的单一相，同时对产物进行碳、氧及氮含量分析为分别为83ppm、375ppm和265ppm。
实施例十一
称取钛铁精矿(TiO2含量69.0％)，石墨粉(C含量99.9％)20.0g，在星型球磨机中混合均匀，在40MP压力下压制成型，将块体放入密闭常压加热炉中N2的气氛下1600℃保温360分钟，通过计算失重率计算发现反应率为99.6％，通过XRD分析产物的结构成分，由开始的二氧化钛和石墨粉的混合相转变成了单一的钛化合物(TiOxNy)相，压制块体的导电率由开始的135～145欧姆●厘米急剧的降为0.02欧姆●厘米。用金属钛合金坩埚盛放CsCl2-LiCl-TiCl2-TiCl3盐，其中Ti离子质量百分比浓度为1％，在750℃下进行电解实验。以制备的钛化合物(TiOxNy)作为阳极，阳极电流密度为1.00A/cm2恒电流电解，用金属钼作阴极，阴极的电流密度为1.00/cm2，控制阴阳极极间距6cm，恒电流电解2小时以后取出阳极和阴极分别用1wt％的稀盐酸清洗电极表面的电解质，再用去离子水洗净氯离子，烘干，计算阳极和阴极的电流效率为94.5％和93.7％，对产物进行XRD分析，该产物为钛的单一相，同时对产物进行氧及氮含量分析为分别为475ppm和249ppm。
实施例十二
以实施例一制备的钛化合物(TiCxOyNz)作为阳极，阳极电流密度为0.50A/cm2，在700℃ 的NaCl-KCl-TiCl2熔盐体系中进行恒电流电解，其中Ti离子质量百分比浓度为8％，用金属不锈钢作阴极，阴极的电流密度为电解0.50A/cm2，控制阴阳极极间距3cm，每隔2小时后更换阳极和阴极继续电解，连续化电解20小时。一共电解出20.8g金属钛，电解质中钛离子的总量为5g，连续长时间电解后电解质浓度没有变化，说明电解得到的20.8g金属钛是由电解钛化合物(TiCxOyNz)获得的。用1wt％的稀盐酸清洗电极表面的电解质，再用去离子水洗净氯离子，洪干对产物进行XRD分析，该产物为钛的单一相，从说明书附图7中可以看出，获得了尺寸在2μm左右的金属钛颗粒，计算阴极的电流效率为95.5％，同时对产物进行碳，氧及氮含量分析为分别为55ppm，227ppm和125ppm。

Claims (10)

  1. 一种含钛可溶阳极熔盐电解提取金属钛的方法：其特征在于，包括以下步骤：
    (1)以含钛物料和含碳还原剂以摩尔比为5∶1～1∶20的比例混合为原料混合均匀后压制成型，在含氮的气氛下保持温度范围为1000℃～2000℃，反应30-600分钟；制备出导电性良好含钛化合物；其中，所述含钛物料包括金红石型钛白、锐钛矿型钛白、偏钛酸、钛铁矿、钒钛磁铁矿、高炉型高钛渣、高钛渣和钛的低价氧化物中的一种或几种；所述含碳还原剂包括碳、活性碳、石墨粉、木炭、石油焦、沥青、煤焦粒中的一种或几种；制备出的所述含钛化合物为TiCxOyNz、TiOxNy、TiNx中的一种或几种，所述TiCxOyNz的碳氧氮的摩尔量比符合如下原则：0＜X≤Y＜1，0＜Z＜1，X+Y+Z＝1；所述TiOxNy的氧氮的摩尔量比符合如下原则：0＜X≤Y，X+Y＝1；所述TiNx的氮的摩尔量比符合如下原则：0＜X≤1；
    (2)以步骤(1)得到的含钛化合物为原料制备成电极在碱金属或碱土金属的卤化物熔盐中通过电解的方法提取金属钛，其阳极由制得的含钛化合物形成，在阴极上获得金属钛；所述阴极由金属钛、不锈钢、碳钢、金属钼、金属镍中的一种或多种形成；阴阳极的极间距控制在1cm～50cm之间；电解质由碱金属或碱土金属卤化物组成；槽电压控制在0.5V～10.0V，阳极电流密度范围为：0.05A/cm2～1.50A/cm2，阴极电流密度范围分别为：0.05A/cm2～1.50A/cm2，电解温度范围在300℃～1000℃。
  2. 根据权利要求1所述的含钛可溶阳极熔盐电解提取金属钛的方法，其特征在于含氮的气氛包括氮气、空气、氨气、氮气-氢气、氮气-氩气和其它含氮气体的混合气中的一种或几种。
  3. 根据权利要求1所述的含钛可溶阳极熔盐电解提取金属钛的方法，其特征在于，所述钛的低价氧化物为Ti2O3、Ti3O5、TiO、Ti3O中的一种或几种。
  4. 根据权利要求1或2所述的含钛可溶阳极熔盐电解提取金属钛的方法，其特征在于，在含氮气气氛的密闭体系或半开放系统或开放体系下制备具有导电性的含钛化合物。
  5. 根据权利要求4所述的含钛可溶阳极熔盐电解提取金属钛的方法，其特征在于密闭体系为部分正压或常压或部分真空下的含氮的气氛的体系。
  6. 根据权利要求1所述的含钛可溶阳极熔盐电解提取金属钛的方法，其特征在于，所述电解质由CsCl2、CaCl2、LiCl、NaCl、KCl、MgCl2、AlCl3、CaF、NaF、KF、LiF中的一种或一种以上和TiCl3、TiCl2、K2TiF6、Na2TiF6中的一种或一种以上的混合盐作为熔盐电解质体系，其中熔盐电解质体系中Ti离子质量百分比浓度为1％-10％。
  7. 根据权利要求1所述的含钛可溶阳极熔盐电解提取金属钛的方法，其特征在于，所述含钛物料和含碳还原剂的摩尔比为5∶1～1∶10。
  8. 根据权利要求1所述的含钛可溶阳极熔盐电解提取金属钛的方法，其特征在于电解温度范围在400℃～900℃。
  9. 根据权利要求1所述的含钛可溶阳极熔盐电解提取金属钛的方法，其特征在于：所述阴阳极的极间距控制在3cm～40cm之间；槽电压控制在1.5V～6.0V；阳极电流密度范围为：0.05A/cm2～1.00A/cm2；阴极电流密度范围为：0.05A/cm2～1.00A/cm2。
  10. 根据权利要求1所述的含钛可溶阳极熔盐电解提取金属钛的方法，其特征在于，所述电解质的盛放容器为：不锈钢坩埚、碳钢坩埚、钛坩埚、钛合金坩埚、石墨坩埚、钼坩埚或镍坩埚中的一种。
PCT/CN2014/086581 2013-09-16 2014-09-15 一种含钛可溶阳极熔盐电解提取金属钛的方法 WO2015035954A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/022,324 US10081874B2 (en) 2013-09-16 2014-09-15 Method for electrowinning titanium from titanium-containing soluble anode molten salt

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201310421132.7A CN103451682B (zh) 2013-09-16 2013-09-16 一种含钛可溶阳极熔盐电解提取金属钛的方法
CN201310421132.7 2013-09-16

Publications (1)

Publication Number Publication Date
WO2015035954A1 true WO2015035954A1 (zh) 2015-03-19

Family

ID=49734502

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/086581 WO2015035954A1 (zh) 2013-09-16 2014-09-15 一种含钛可溶阳极熔盐电解提取金属钛的方法

Country Status (3)

Country Link
US (1) US10081874B2 (zh)
CN (1) CN103451682B (zh)
WO (1) WO2015035954A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113104889A (zh) * 2021-05-08 2021-07-13 重庆大学 工业级偏钛酸一步法制备克级以上高纯相亚氧化钛纳米材料

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103451682B (zh) * 2013-09-16 2017-06-06 北京科技大学 一种含钛可溶阳极熔盐电解提取金属钛的方法
CN104451781A (zh) * 2014-12-08 2015-03-25 中国铝业股份有限公司 一种电解生产金属钛的阳极制备方法
CN104498982B (zh) * 2015-01-07 2017-04-26 攀钢集团攀枝花钢铁研究院有限公司 制备氮化钛的方法
CN105220180B (zh) * 2015-11-12 2017-10-24 攀钢集团攀枝花钢铁研究院有限公司 电解提取金属钛时复合阳极的制备方法
CN105838892B (zh) * 2016-04-06 2017-10-24 北京科技大学 一种提取钢铁厂钒渣中钛、铁、锰、钒和铬的方法
JP7096235B2 (ja) * 2016-09-14 2022-07-05 ユニバーサル アケメタル タイタニウム リミテッド ライアビリティ カンパニー チタン－アルミニウム－バナジウム合金の製造方法
CN108251866B (zh) * 2018-02-28 2019-12-03 昆明理工大学 一种金属钛粉的制备方法
CN110184626B (zh) * 2018-07-10 2021-06-22 东北大学 潮湿气氛的高温熔盐电解的电化学方法
WO2020044841A1 (ja) 2018-08-31 2020-03-05 東邦チタニウム株式会社 金属チタンの製造方法
CN109280941B (zh) 2018-11-16 2020-02-28 北京科技大学 一种钛铁复合矿·碳硫化—电解制备金属钛的方法
WO2020103366A1 (zh) 2018-11-23 2020-05-28 北京科技大学 一种电解-氯化-电解制备纯钛的装置及方法
CN109267100B (zh) * 2018-11-23 2021-01-15 北京科技大学 一种电解-氯化-电解制备纯钛的装置及方法
CN109650893A (zh) * 2019-01-14 2019-04-19 浙江海虹控股集团有限公司 一种低温制备含钛复合阳极的方法
CN109763148B (zh) * 2019-01-14 2020-11-03 浙江海虹控股集团有限公司 一种连续电解制备高纯金属钛粉的装置和方法
CN109811370B (zh) * 2019-03-15 2020-10-13 北京科技大学 一种电解-钛碳硫阳极-制备金属钛的方法
CN109825854A (zh) * 2019-03-26 2019-05-31 北京科技大学 一种熔盐电解-高温蒸馏制备高纯钛金属的装置及方法
CN110079837B (zh) * 2019-04-24 2020-10-13 北京科技大学 水溶性氟盐体系熔盐电解可溶性钛酸盐制备金属钛的方法
CN110042433A (zh) * 2019-05-08 2019-07-23 北京科技大学 一种含钛可溶性固溶体阳极的工业化生产方法
CN110304653B (zh) * 2019-07-12 2021-02-02 北京科技大学 一种碳化钛颗粒的表面改性方法
CN112301379B (zh) * 2020-10-14 2021-12-10 郑州大学 二氧化锆为原料制备金属锆的方法
CN112281191A (zh) * 2020-10-28 2021-01-29 攀钢集团攀枝花钢铁研究院有限公司 一种从钛矿制备钛铝合金的方法
CN112725817A (zh) * 2020-12-30 2021-04-30 重庆大学 一种熔盐电解制备碳化物陶瓷涂层的方法
CA3220641A1 (en) * 2021-06-30 2023-01-05 Yuta NAKAJO Method for producing titanium-containing electrodeposit and metal titanium electrodeposit
CN113699560B (zh) * 2021-07-17 2023-12-29 广西大学 一种氟氯混合熔盐体系可溶阳极电解制备金属钛的方法
CN113463135B (zh) * 2021-07-30 2022-09-30 昆明理工大学 一种氟化物熔盐中二氧化钛溶解-电解制备金属钛的方法
CN114481230B (zh) * 2022-02-25 2023-05-09 北京科技大学 一种高致密铪碳氧固溶体及其制备方法和一种电解制备金属铪的方法
CN114672850B (zh) * 2022-05-07 2023-08-29 华北理工大学 一种利用熔盐电解脱氧分离钛铝合金制取金属钛的方法
CN114941079B (zh) * 2022-05-24 2023-07-21 国瑞科创稀土功能材料(赣州)有限公司 一种镝铁合金中氧化物夹杂的脱除方法
CN115992373B (zh) * 2022-09-08 2024-02-02 湖南湘投轻材科技股份有限公司 一种钛铁合金材料的制备方法
CN115418679A (zh) * 2022-09-30 2022-12-02 昆明理工大学 一种氟化物熔盐-电活性氧化物体系中二氧化钛电解制备金属钛的方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB795386A (en) * 1955-06-24 1958-05-21 Ici Ltd Improvements in or relating to the electrolytic production of titanium
GB795416A (en) * 1955-12-16 1958-05-21 Horizons Titanium Corp Production of titanium by electrolysis of titanium nitride
WO1999063638A1 (en) 1998-06-05 1999-12-09 General Electric Company Terminal block for a protective relay
WO2005019501A2 (en) 2003-08-20 2005-03-03 Materials & Electrochemical Research Corp. Thermal and electrochemical process for metal production
CN101519789A (zh) 2009-03-30 2009-09-02 攀钢集团研究院有限公司 一种钛循环熔盐电解制取金属钛的方法
CN101914788A (zh) 2010-07-26 2010-12-15 攀钢集团有限公司 一种制备金属钛的方法
CN103451682A (zh) * 2013-09-16 2013-12-18 北京科技大学 一种含钛可溶阳极熔盐电解提取金属钛的方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4812301A (en) * 1986-04-24 1989-03-14 The United States Of America As Represented By The Secretary Of The Interior Production of titanium nitride, carbide, and carbonitride powders
US5227195A (en) * 1989-04-04 1993-07-13 Sri International Low temperature method of forming materials using one or more metal reactants and a halogen-containing reactant to form one or more reactive intermediates
US5942097A (en) * 1997-12-05 1999-08-24 The Ohio State University Method and apparatus featuring a non-consumable anode for the electrowinning of aluminum
JP2005510630A (ja) * 2001-11-22 2005-04-21 キューアイティー−フェル エ チタン インク． 液体状態の化合物を含む酸化チタンからチタン金属又は合金を電解採取する方法
CN100415940C (zh) 2005-05-08 2008-09-03 北京科技大学 一氧化钛/碳化钛可溶性固溶体阳极电解生产纯钛的方法
CN105393312B (zh) * 2013-07-23 2018-01-02 旭化成株式会社 铜和/或铜氧化物分散体、以及使用该分散体形成的导电膜

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB795386A (en) * 1955-06-24 1958-05-21 Ici Ltd Improvements in or relating to the electrolytic production of titanium
GB795416A (en) * 1955-12-16 1958-05-21 Horizons Titanium Corp Production of titanium by electrolysis of titanium nitride
WO1999063638A1 (en) 1998-06-05 1999-12-09 General Electric Company Terminal block for a protective relay
WO2005019501A2 (en) 2003-08-20 2005-03-03 Materials & Electrochemical Research Corp. Thermal and electrochemical process for metal production
CN101519789A (zh) 2009-03-30 2009-09-02 攀钢集团研究院有限公司 一种钛循环熔盐电解制取金属钛的方法
CN101914788A (zh) 2010-07-26 2010-12-15 攀钢集团有限公司 一种制备金属钛的方法
CN103451682A (zh) * 2013-09-16 2013-12-18 北京科技大学 一种含钛可溶阳极熔盐电解提取金属钛的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LI, ZHENGPING ET AL.: "Carbon-Thermal Reduction Nitridation of Blast Furnace Slag Bearing Titanium", JOURNAL OF IRON AND STEEL RESEARCH, vol. 17, no. 3, 30 June 2005 (2005-06-30), pages 15 - 17, PAGE 29 *
WANG, QIUYU ET AL.: "Producing metallic titanium through electro-refining of titanium nitride anode", ELECTROCHEMISTRY COMMUNICATIONS, 14 August 2013 (2013-08-14), pages 135 - 138 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113104889A (zh) * 2021-05-08 2021-07-13 重庆大学 工业级偏钛酸一步法制备克级以上高纯相亚氧化钛纳米材料
CN113104889B (zh) * 2021-05-08 2023-11-17 重庆大学 工业级偏钛酸一步法制备克级以上高纯相亚氧化钛纳米材料

Also Published As

Publication number Publication date
CN103451682B (zh) 2017-06-06
CN103451682A (zh) 2013-12-18
US20160222533A1 (en) 2016-08-04
US10081874B2 (en) 2018-09-25

Similar Documents

Publication Publication Date Title
WO2015035954A1 (zh) 一种含钛可溶阳极熔盐电解提取金属钛的方法
KR101370007B1 (ko) 금속 제조를 위한 열적 및 전기화학적 방법
CN108251866B (zh) 一种金属钛粉的制备方法
Yuan et al. A critical review on extraction and refining of vanadium metal
CN101949038B (zh) 一种电解法制备碳氧钛复合阳极的方法
WO2020098176A1 (zh) 一种碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法
CN106947874B (zh) 一种两步法制备高纯钛的方法
JP2013079446A (ja) 金属チタンの製造方法およびこの方法を用いて得られた金属チタン
CN104947152A (zh) 熔盐电解精炼法制备高纯钛的方法
Zhou et al. Electrolytic synthesis of ferrotitanium powders from ilmenite in CaCl2-NaCl melts at a lower temperature of 700° C
CN109811370B (zh) 一种电解-钛碳硫阳极-制备金属钛的方法
CN113106496A (zh) 一种钒碳氧固溶体阳极熔盐电解高纯金属钒方法
CN100532653C (zh) 一种熔盐电解提取钛的方法
Li et al. Preparation of Zirconium Metal by Electrolysis
Jiao et al. Editorial for special issue on high-temperature molten salt chemistry and technology
CN113699560A (zh) 一种氟氯混合熔盐体系可溶阳极电解制备金属钛的方法
CN113463135B (zh) 一种氟化物熔盐中二氧化钛溶解-电解制备金属钛的方法
CN113860362B (zh) 一种电化学制备除钒试剂及其四氯化钛除钒方法
CN113860363B (zh) 一种除去四氯化钛中钒杂质的方法
JP4198434B2 (ja) 金属チタンの製錬方法
CN113279022B (zh) 一种还原性熔盐介质及其制备方法
CN114853016A (zh) 由含铌矿物制备碳化铌钛的方法
Feng et al. Optimal V2O3 extraction by sustainable vanadate electrolysis in molten salts
Hu et al. Advanced extractive electrometallurgy
CN110408960A (zh) 氧化物熔融电解-真空精馏连续制备高纯钛的方法和设备

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14844217

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 15022324

Country of ref document: US

REEP Request for entry into the european phase

Ref document number: 2014844217

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2014844217

Country of ref document: EP