WO2020098176A1 - 一种碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法 - Google Patents

一种碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法 Download PDF

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WO2020098176A1
WO2020098176A1 PCT/CN2019/076500 CN2019076500W WO2020098176A1 WO 2020098176 A1 WO2020098176 A1 WO 2020098176A1 CN 2019076500 W CN2019076500 W CN 2019076500W WO 2020098176 A1 WO2020098176 A1 WO 2020098176A1
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titanium
carbon
anode
sulfide
ilmenite
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French (fr)
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焦树强
田栋华
焦汉东
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北京科技大学
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • 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
    • C25C7/02—Electrodes; Connections thereof
    • C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the invention relates to the technical field of nonferrous metal extraction, in particular to a carbon / sulfurized ilmenite composite ore anode-electrolytic method for preparing titanium metal.
  • titanium metal Due to its excellent physical and chemical properties, titanium metal is widely used in aviation, aerospace, petroleum, chemical, automotive, medical equipment, civil construction and other fields, and is known as “future metal” and "strategic metal”.
  • titanium metal is mainly based on the Kroll method, which is the reduction of titanium tetrachloride by magnesium metal.
  • the core process is to first put metal magnesium into the reactor and heat it to 800 ⁇ 900 °C, then add TiCl 4 at a certain speed to react with the molten metal Mg to prepare Ti. Its purity is about 99.7%. But its metallurgical production process is complicated, energy consumption is high, cost is high, and high-purity titanium tetrachloride is required. As a result, the production price of titanium metal is expensive, which greatly limits the wide application of titanium metal in the civilian market.
  • Sichuan Pangang Group Co., Ltd. applied for a method of preparing titanium metal by electrolysis of titanium circulating molten salt in 2009 (CN101519789A).
  • This method uses TiCl 4 as a raw material to reduce low-valent titanium chloride with titanium metal, and then melts Salt electrolysis to obtain metallic titanium.
  • This method has the following problems: the cost of raw materials is high, both titanium tetrachloride and metallic titanium are used, and the reduction reaction rate of titanium tetrachloride is low.
  • the company applied for a method of preparing titanium metal (CN101914788) in 2010. After smelting titanium slag with titanium concentrate, an excessive amount of C is directly added to prepare titanium carbide or titanium carbonitride under the introduction of N 2 .
  • the method has the following problems: excessive carbon is blended, carbon residue will still exist in the electrolysis process, and the carbon content in the product exceeds the standard.
  • metal titanium in molten salt they are all based on titanium oxides. Because of their strong affinity with oxygen, and Ti-O is easy to form a solid solution, resulting in a high content of titanium oxide, if you can avoid the use of oxidation It will be beneficial to prepare low-oxygen titanium. However, the solubility of sulfur in titanium is very low (approximately 0.02 at.%) And does not form a solid solution, making it easier to separate.
  • Research by Japanese R.O. Suzuki scholars has shown that carbon disulfide gas can effectively reduce the raw materials of titanium-containing ores and prepare titanium disulfide. However, titanium sulfide is applied at the cathode for reduction or deoxidation.
  • the process for preparing titanium metal in the prior art has the disadvantages of long process flow, high energy consumption, product quality not reaching the standard of high-purity titanium, or inability to realize industrial production applications.
  • the present invention proposes direct carbon disulfide treatment of ilmenite, sintering the obtained titanium sulfide and titanium carbide to prepare a titanium carbon sulfur anode, and using the anode for electrochemical metallurgy Refining titanium, carbon disulfide and S 2 gas produced by the anode can effectively recycle the titanium-containing raw materials, and achieve efficient recycling of energy and resources.
  • the present invention provides a carbon / sulfurized ilmenite composite ore anode-electrolytic method for preparing titanium metal, directly treating ilmenite with carbon disulfide, and sintering the obtained titanium sulfide and titanium carbide to prepare titanium carbon sulfur
  • the anode is used for electrochemical metallurgical extraction of titanium.
  • the carbon disulfide and S 2 gas produced by the anode can effectively circulate titanium-containing raw materials to achieve efficient recycling of energy and resources and continuous production of high-purity titanium.
  • the present invention provides a carbon / sulfurized ilmenite composite ore anode-electrolytic method for preparing metallic titanium, characterized in that the preparation steps include:
  • an implementation manner is further provided, and the mixture is specifically: the titanium-containing material, the carbon-containing reducing agent, and the sulfur reducing agent in a molar ratio of 1: The ratio of 2.0: 2.0 to 1: 2.5: 3.0 is evenly mixed.
  • the sulfidation reaction conditions of the S1 are: a burning reaction is carried out under the protection of an inert atmosphere, and the holding temperature range during the reaction is 700 ° C to 1600 ° C , The reaction time range is 30min ⁇ 900min.
  • an implementation manner is further provided, wherein the titanium sulfide and the titanium carbide are vacuum-sintered in S2 to prepare the titanium carbon sulfur.
  • an implementation manner is further provided.
  • the electrolysis temperature range is 70 ° C. to 1600 ° C.
  • the distance between the cathode and the anode is 1 cm. ⁇ 50cm
  • electrolysis cell voltage range is 0.5V ⁇ 10.0V
  • anode current density range is 0.05A / cm 2 ⁇ 1.50A / cm 2
  • cathode current density range is 0.05A / cm 2 ⁇ 1.50A / cm 2 respectively .
  • the electrolyte during electrolysis in S3 is: CsCl 2 , CaCl 2 , LiCl, NaCl, KCl, MgCl 2 , AlCl 3 , CaF, A mixed salt composed of one or more of NaF, KF, and LiF and one or more of TiCl 3 , TiCl 2 , K 2 TiF 6 , and Na 2 TiF 6 .
  • an implementation manner is further provided, and the mass percentage of titanium ions in the electrolyte is 1% -10%.
  • the titanium-containing material is rutile titanium dioxide, anatase titanium dioxide, titanium concentrate, titanium nitride, titanium carbide, titanium One or more of carbon oxide, titanium carbon oxynitride, metatitanic acid, ilmenite, vanadium titanium magnetite, blast furnace type high titanium slag, high titanium slag and titanium low-cost oxide.
  • the carbon-containing reducing agent is one of carbon, activated carbon, graphite powder, charcoal, petroleum coke, pitch, and coal coke particles or Several.
  • the cathode is one or more of titanium metal, stainless steel, carbon steel, metal molybdenum, and metal nickel.
  • the present invention can obtain the following technical effects: Compared with the existing soluble anode, the titanium carbon sulfur anode electrolysis is used to directly deposit metal titanium on the cathode, and the CS 2 gas / S 2 produced by the anode Achieving efficient use of energy circulation and continuous electrolysis without generating anode slime during the entire electrolysis process will greatly reduce the cost of titanium metal extraction and efficient resource utilization of titanium-containing ores.
  • FIG. 1 is a flow chart of a method for preparing metal titanium by electrolysis of carbon / sulfide ilmenite composite ore provided by an embodiment of the present invention
  • 2a and 2b are X-ray diffraction patterns of a titanium carbon sulfur anode prepared by synthesis provided by an embodiment of the present invention
  • FIG. 3 is a voltage-gas curve diagram in the electrolysis process provided by an embodiment of the present invention.
  • FIG. 4 is a schematic diagram of XRD of a cathode titanium product provided by an embodiment of the present invention.
  • FIG. 5 is a SEM schematic diagram of the cathode product titanium provided by an embodiment of the present invention.
  • FIG. 1 is a flow chart of a method for preparing metal titanium by electrolysis of carbon / sulfide ilmenite composite ore provided by an embodiment of the present invention.
  • a carbon / sulfurized ilmenite composite ore-electrolytic method for preparing titanium metal includes steps as follows:
  • Step (1) preparation of titanium sulfide
  • the titanium-containing material, carbon and sulfur reducing agent are uniformly mixed in a molar ratio of 1: 2.0: 2.0 to 1: 2.5: 3.0, and the mixture is used as a raw material to carry out the burning reaction in a closed pressure-resistant and high-temperature container, so that It is completely and completely vulcanized to prepare a titanium sulfide product with good conductivity.
  • the titanium-containing material includes rutile titanium dioxide, anatase titanium dioxide, metatitanic acid, ilmenite, vanadium-titanium magnetite, blast furnace type high titanium slag, high titanium slag and titanium low-cost oxide
  • the carbon-containing reducing agent includes one or more of carbon, activated carbon, graphite powder, charcoal, petroleum coke, pitch, coal coke particles
  • the sulfur is industrially used Sulphur powder.
  • the prepared titanium sulfide is titanium disulfide and trace other sulfides.
  • titanium sulfide is sintered at a high temperature or smelted into an electric arc furnace to form a solid solution, and the solid solution is used as an anode, so as to perform electrochemical electrolysis to prepare metallic titanium.
  • the related reaction mechanism involved is:
  • titanium carbon sulfur anode (Ti 2 C x S 1-x , x ⁇ 0.5); the present titanium carbon sulfur anode contains titanium sulfide and titanium Carbon and sulfur are collectively referred to as titanium carbon-sulfur composite compounds.
  • titanium carbon-sulfur composite compounds using titanium sulfide and titanium carbide or titanium sulfide and carbon as raw materials to prepare metal titanium carbon sulfur anodes according to the following reaction stoichiometric ratio:
  • TiS 2 + 3Ti + 2C 2Ti 2 CS + 2CO;
  • TiS + TiC Ti 2 CS
  • the metal titanium is extracted by electrochemical electrolysis technology.
  • the cathode product is metal titanium with a single phase; the anode generates CS 2 and S 2 gases, and the gas is recovered to achieve recycling; the relevant reaction mechanism involved in this electrochemical electrolysis is:
  • the titanium carbon-sulfur electrode obtained in step (1) and step (2) is used to extract titanium metal by electrochemical smelting in a molten salt electrolyte system.
  • the anode generates CS 2 and S 2 gases, and the cathode metal is obtained;
  • the cathode is formed of one or more of titanium metal, stainless steel, carbon steel, metal molybdenum, and metal nickel. S 2 and CS 2 gases will be used in the preparation of titanium sulfide to achieve efficient recycling of energy.
  • the electrolyte is composed of molten salt electrolyte system (halide, halide-fluoride, fluoride, etc.); specifically, the composition of the molten salt electrolyte system is CsCl 2 , CaCl 2 , LiCl, NaCl, KCl, MgCl 2 , AlCl 3 , A mixed salt of one or more of CaF, NaF, KF, and LiF and one or more of TiCl 3 , TiCl 2 , K 2 TiF 6 , and Na 2 TiF 6 , where the Ti in the molten salt electrolyte system
  • the ion mass percentage concentration is 1% to 10%.
  • the electrolyte storage container is: one of stainless steel crucible, carbon steel crucible, titanium crucible, titanium alloy crucible, graphite crucible, iron-manganese crucible, molybdenum crucible or nickel crucible.
  • the cell voltage is controlled at 0.5V to 10.0V
  • the anode current density range is: 0.05A / cm 2 to 1.50A / cm 2
  • the cathode current density range is respectively: 0.05A / cm 2 to 1.50A / cm 2
  • the electrolysis temperature range At 70 °C ⁇ 1600 °C, the anode and cathode electrode spacing is controlled between 1cm ⁇ 50cm.
  • the cell voltage is controlled at 1.5V to 6.0V;
  • the anode current density range is: 0.05A / cm 2 to 1.0A / cm 2 ;
  • the cathode current density range is: 0.05A / cm 2 to 1.0A / cm 2 ; electrolysis
  • the temperature range is 400 °C ⁇ 900 °C;
  • the anode and cathode pole spacing is 3cm ⁇ 40cm.
  • Titanium sulfide is prepared by processing the CS 2 gas recovered in step (3) by electrolysis to prepare titanium sulfide;
  • the titanium-containing ore materials include rutile titanium dioxide, anatase titanium dioxide, titanium concentrate, titanium nitride, titanium oxycarbide, titanium oxynitride, metatitanic acid, ilmenite, vanadium titanium magnetite , One or more of blast furnace type high titanium slag, titanium carbide, titanium dioxide, high titanium slag and titanium low-cost oxide;
  • Titanium dioxide (TiO 2 , 99.5% by weight), graphite powder (99.95), and sulfur powder (99%) are prepared in a molar ratio of 1: 2: 2.1, for a total of 100 g.
  • the titanium disulfide and titanium carbide were used for SPS sintering at 1450 ° C to finally synthesize Ti 2 CS ceramic material.
  • the XRD diffraction patterns of the synthetic materials are shown in Figures 2 (a) and 2 (b).
  • a corundum crucible containing 150g of NaCl-KCl eutectic molten salt was used to conduct related electrolysis experiments at 750 °C.
  • the cathode adopts a nickel rod with a diameter of 2 mm
  • the reference electrode is an AgCl / Ag electrode of NaCl-KCl-AgCl (0.04 wt%)
  • the prepared Ti 2 CS is an anode.
  • FIG. 3 is a voltage-gas curve in the electrolysis process of the present invention
  • FIG. 4 is an XRD diffraction pattern of the product
  • FIG. 5 is an SEM electron microscope pattern of the cathode titanium.
  • titanium concentrate FeTiO 3 was carbonized and vulcanized at 1200 ° C.
  • the treated product was a mixed powder of FeS and Ti 2 CS.
  • the mixed powder was immersed in 1 mol / L dilute hydrochloric acid, vacuum filtered, and then oven dried at 80 ° C. to obtain titanium carbon sulfur ceramic material powder (Ti 2 CS).
  • the anode was vacuum sintered and pressed to form a Ti 2 CS anode.
  • a corundum crucible containing 150 g of NaCl-KCl-TiCl 2 eutectic molten salt was used for the relevant electrolysis at 750 ° C.
  • the cathode uses a nickel rod with a diameter of 2 mm, and the reference electrode is an AgCl / Ag electrode with NaCl-KCl-AgCl (0.04 wt%).
  • a constant current electrolysis with a current density of 0.1 A / cm 2 was performed for 4 hours, and the gas generated from the anode was passed into a high-temperature reactor containing TiO 2 for reduction to prepare TiS 2 or TiS. Then, the cathode product is subjected to ultrasonic cleaning with distilled water and 1 wt% HCl hydrochloric acid, and the final product is subjected to XRD detection to obtain a metal titanium powder with a single phase.
  • TiS and TiC were prepared according to the molar ratio of 1: 1, mixed and ground in a star ball mill for 12h, and vacuum sintered to prepare Ti 2 CS anode.
  • a corundum crucible containing 150g of CaF 2 -KF-NaF-Na 2 TiF 6 eutectic molten salt was used to conduct related electrolysis experiments at 850 °C.
  • Ti 2 CS as the anode was fired to perform constant current electrolysis at an anode current density of 0.5 A / cm 2 , and the anode and cathode spacing was 5 cm. After 4 hours of electrolysis, the titanium powder product was obtained on the cathode nickel rod.
  • TiS titanium sulfide
  • Example 3 The titanium sulfide (TiS) prepared by gas reduction in Example 3 and the freshly prepared TiC were mixed and ground in a star ball mill for 24h, and 5g was weighed and pressed into a small piece with a diameter of 10mm * 10mm under a pressure of 10Mpa and placed in In a pressure-resistant and temperature-resistant container, it is placed in a muffle furnace under the protection of argon atmosphere for vacuum sintering into a cylinder with a diameter of 10 mm * 20 mm.
  • the sintered Ti 2 CS was used as the anode, and the cathode current density was 0.05 A / cm 2 for constant current electrolysis. The cathode and anode spacing was 10 cm. After 4 hours of electrolysis, the titanium powder product was obtained on the cathode nickel rod. TiS 2 is recovered in Ti 2 C 0.25 O 0.25 N 0.5 ore material for reduction treatment. The cathode product is cleaned and dried by soaking in distilled water and 1wt% dilute hydrochloric acid. The final product is titanium powder with uniform phase.
  • Titanium dioxide (TiO 2 ) is obtained by drying in the lower oven. Titanium dioxide (TiO 2 , 99.5% by weight), charcoal (C content 75%), and sulfur powder (99%) were prepared in a molar ratio of 1: 2.5: 2.3, a total of 10 g.
  • TiS fired was used as the anode, and the cathode current density was 0.05A / cm 2 for constant current electrolysis.
  • the cathode and anode spacing was 10cm.
  • the titanium powder product was obtained on the cathode nickel rod.
  • the cathode product is cleaned and dried by soaking in distilled water and 1wt% dilute hydrochloric acid.
  • the final product is titanium powder with uniform phase.
  • titanium dioxide titanium dioxide (TiO 2 ). Titanium dioxide (TiO 2 , 99.5% by weight), petroleum coke (C content 89%), and sulfur powder (99%) were prepared according to a molar ratio of 1: 2.3: 2.2, a total of 10 g.
  • a corundum crucible containing 150 g of CaF 2 -KF-NaF-Na 2 TiF 6 eutectic molten salt was used to conduct related electrolysis experiments at 850 ° C. TiS fired was used as the anode, and the anode current density was 0.5A / cm 2 for constant current electrolysis. The anode and cathode spacing was 5cm. After 4 hours of electrolysis, the titanium powder product was obtained on the cathode nickel rod. The cathode product is cleaned and dried by soaking in distilled water and 1wt% dilute hydrochloric acid. The final product is titanium powder with uniform phase.
  • titanium sulfide and titanium carbon sulfur materials for soluble anodes has the following distinctive features:
  • Titanium sulfide used in the preparation of titanium carbon-sulfur anodes can be obtained by treating titanium-containing concentrates with CS 2 gas generated during the electrolysis process, effectively solving vanadium-titanium magnetite, titanium dioxide, titanium carbide, titanium nitride, and titanium Disposal of titanium, carbon, oxygen and other titanium-containing raw materials;
  • Titanium carbon sulfur and titanium sulfide are used as soluble anodes.
  • titanium is dissolved in the electrolyte in the form of ions, and CS 2 is discharged from the anode for recycling, effectively achieving efficient and comprehensive utilization of resources and energy;
  • Direct electrolysis in the electrolyte can deposit titanium metal with lower oxygen content at the cathode to achieve efficient recovery of anode gas.
  • the titanium carbon-sulfur anode has high electrolysis efficiency, less intermediate products, directly obtains high-purity metal titanium, continuous production without anode slime, and can realize the treatment of energy minerals Use characteristics.

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Abstract

一种碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法，涉及有色金属冶金矿物处理及熔盐电化学提取钛冶金技术领域，该方法以含钛矿原料、碳(C)和硫(S)为原料经烧结反应，制备出导电性良好的钛碳硫或硫化钛阳极材料。采用该钛碳硫或硫化钛阳极在熔盐电解质体系中成功制备金属钛。采用所述钛碳硫复合可溶性阳极，在熔盐电解过程中将在阴极沉积金属钛，阳极产生CS 2和S 2气体，且该气体有效的应用于矿石的处理制备硫化钛原料，是一种工艺简单、能耗低、连续化生产且实现能源资源的高效循环利用。本发明提供的技术方案适用于碳硫化-电解制备金属钛的过程中。

Description

一种碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法 【技术领域】
本发明涉及有色金属提取技术领域，尤其涉及一种碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法。
【背景技术】
金属钛因其优异的物理化学性能，而被广泛应用于航空、航天、石油、化工、汽车、医疗器械、民用建筑等领域，而且素有“未来金属”、“战略金属”等美誉。
到如今，金属钛工业化生产工艺主要以Kroll法为主，即金属镁还原四氯化钛法。其核心工艺是先将金属镁放入到反应器中，并加热到800～900℃，然后以一定的速度加入TiCl 4与熔融的金属Mg进行反应而制备Ti，其纯度约为99.7％。但是其冶金生产过程复杂、能耗大、成本高，并且需要高纯四氯化钛。从而造成金属钛的生产价格昂贵，大大限制了金属钛在民用市场的广泛应用。
为了寻找一种能够有效代替Kroll法的工艺，广大科研工作对TiO 2在熔体中的性能进行相关研究。2000年英国剑桥大学D.F.Fray教授课题组提出以压制烧结后的TiO 2为阴极，石墨棒为阳极，在CaCl 2电解质中进行电脱氧工艺,该工艺被称为FFC剑桥法(WO09963638)。目前，该工艺尚未工业化应用生产，主要是由于以下因素的影响：(1)电流效率较低；(2)阴极脱氧过程较为复杂；(3)TiO 2的纯度需要较高。相比于FFC工艺，2002年日本京都大学的Okabe和Ono研究组在氯化钙熔盐中，将TiO 2用电解得到的活性Ca还原TiO 2为钛金属。该工艺是通过阴极电解分解出的金属钙进一步还原TiO 2而得到。目前该工艺 也没有工业化应用，其主要原因是存在电流效率低、产品含氧量较高以及对二氧化钛原料的要求较高等问题。该两项工艺都是针对电解槽体系中的阴极进行研究。
麻省理工学院的Sadoway教授课题在1700℃下电解含TiO 2氧化物的溶体，成功得到了液态金属钛。虽然该工艺简单，可连续生产，同时在阳极得到O 2；但是该工艺的电解温度巨高，对使用的坩埚和阳极材料需要极大的挑战，造成高昂的生产成本。并且阴极得到的钛在熔盐渣的底部，造成较高的氧含量，难于氧化物渣进行分离。因此，目前仍然无法工业化生产电解金属钛。
对于可溶性阳极的研究大约从上个世纪50年代开始，但都是针对碳化钛系列阳极进行。约1950年，E.Wainer教授以TiC和TiO为原料混合后，在2100℃下采用电弧炉熔炼形成TiC-TiO固溶体，并以该材料为阳极在氯化物溶体中进行电解，研究发现在阳极区域有CO气体生成，并且熔盐中没有阳极泥的产生，经长时间电解后，在阴极电极上沉积有金属钛。
日本学者Y.Hashimoto在TiO 2和C过量的混合物中，采用电弧熔炼制备氧掺杂碳化钛，并以其为阳极在熔盐中长时间电解，在阴极制备出了金属钛。但是其阳极制备过程中仍然依赖于高温(1700℃)的还原条件下，并且如果C含量过高，长时间电解将会造成阴阳极间的短路以及阳极泥的产生。
美国MER公司开发了一种全新的电解还原工艺(WO2005/019501)。该工艺是以TiO 2和C按化学计量比混合，在1100℃～1300℃热还原的钛低价氧化物和碳的混合物，再以此为复合阳极在氯化物熔盐电解质中电解成功获取金属钛。该工艺复合阳极为碳和低价氧化物的混合材料，在电化学溶解的过程中会有阳极泥和残余的碳产生，长时间电解同样存 在电极短路等问题。
2005年北京科技大学电化学冶金团队提出一种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Ti 2CO可溶性阳极，并采用该材料在700℃下的氯化物熔盐电解体系，在阴极上成功得到氧含量低于300ppm的高纯钛。在后期的工艺完善和研究进程中相继提出以TiC xO yN z(O<X≤Y＜1,0＜Z＜1，x+y+z＝1)为可溶性阳极的电极材料，都将在阴极成功获得金属钛(CN201310421132.7)。该工艺成功研究了科学和机理问题，并且进行了相应的中式实验研究，将有待进一步工业化应用推广。
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(CN101519789A)，该方法是以TiCl 4为原料，用金属钛还原低价钛的氯化物，然后通过熔盐电解获得金属钛。该方法存在以下问题：原材料的成本较高，均采用四氯化钛和金属钛，并且四氯化钛的还原反应速率较低。并且该公司2010年申请了一种制备金属钛的方法(CN101914788)，以钛精矿熔炼钛渣后直接配入过量的C，在通入N 2下制备碳化钛或碳氮化钛。该方法存在以下问题：配入的碳过量，电解过程中仍然会存在碳的残余以及产物中碳含量的超标。
2011年剑桥大学D.F.Fray教授课题组提出的Chinuka冶炼工艺(US 9181604B2)，具体是采用Ti-C-O系阳极，电解过程中将在阳极释放一氧化碳气体，阴极回收金属钛。该工艺可使用于处理一下低品味的含钛矿。
在熔盐中电解制备金属钛工艺中，均基于钛的氧化物，由于太与氧较强的亲和力，且Ti-O很容易形成固溶体，造成生产的钛氧含量偏高，如果能避免使用氧化物，将有益于制备低氧量的钛。然而，硫在钛中的 溶解度很低(约为0.02at.％)，且不会形成固溶体，更容易分离。日本R.O.Suzuki学者研究表明二硫化碳气体可以有效的还原含钛矿石原料，制备二硫化钛。但是硫化钛均是在阴极进行还原或者脱氧的应用研究。
综上所述，现有技术中制取金属钛的工艺存在流程长、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生产应用的缺点。
针对钛矿的高效利用和钛冶炼工艺现存的诸多问题，本发明提出对钛铁矿的直接二硫化碳处理，将得到的硫化钛和碳化钛进行烧结制备钛碳硫阳极，采用该阳极进行电化学冶金提炼钛，阳极产生的二硫化碳和S 2气体可以有效的循环处理含钛原料，实现能源和资源的高效循环利用。
【发明内容】
有鉴于此，本发明提供了一种碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法，对钛铁矿直接进行二硫化碳处理，将得到的硫化钛和碳化钛进行烧结制备钛碳硫阳极，采用该阳极进行电化学冶金提炼钛，阳极产生的二硫化碳和S 2气体可以有效的循环处理含钛原料，实现能源和资源的高效循环利用和高纯钛的连续化生产。
一方面，本发明提供一种碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法，其特征在于，制备步骤包括：
S1、对包括含钛物料、含碳还原剂和硫还原剂的混合料进行硫化，制备出硫化钛；
S2、以所述硫化钛和碳化钛为原料，制备出钛碳硫；
S3、以所述硫化钛或所述钛碳硫为阳极，采用电化学电解技术在阴极提取金属钛；
S4、收集电解时阳极产生的CS 2和S 2气体，用于对所述含钛物料进行硫化。
如上所述的方面和任一可能的实现方式，进一步提供一种实现方式，所述混合料具体为：所述含钛物料、所述含碳还原剂和所述硫还原剂以摩尔比1:2.0:2.0～1:2.5:3.0的比例均匀混合。
如上所述的方面和任一可能的实现方式，进一步提供一种实现方式，所述S1的硫化反应条件为：惰性气氛保护下进行灼烧反应，反应时的保温温度范围为700℃～1600℃，反应时间范围为30min～900min。
如上所述的方面和任一可能的实现方式，进一步提供一种实现方式，所述S2中对所述硫化钛和所述碳化钛进行真空烧结制备所述钛碳硫。
如上所述的方面和任一可能的实现方式，进一步提供一种实现方式，所述S3中电解时，电解温度范围为70℃～1600℃，所述阴极和所述阳极的极间距范围为1cm～50cm，电解的槽电压范围为0.5V～10.0V，阳极电流密度范围为0.05A/cm 2～1.50A/cm 2，阴极电流密度范围分别为0.05A/cm 2～1.50A/cm 2。
如上所述的方面和任一可能的实现方式，进一步提供一种实现方式，所述S3中电解时的电解质为：CsCl 2、CaCl 2、LiCl、NaCl、KCl、MgCl 2、AlCl 3、CaF、NaF、KF、LiF中的一种或多种和TiCl 3、TiCl 2、K 2TiF 6、Na 2TiF 6中的一种或多种组成的混合盐。
如上所述的方面和任一可能的实现方式，进一步提供一种实现方式，所述电解质中钛离子质量百分比为1％～10％。
如上所述的方面和任一可能的实现方式，进一步提供一种实现方式，所述含钛物料为金红石型钛白、锐钛矿型钛白、钛精矿、氮化钛、碳化钛、钛碳氧、钛碳氮氧、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者几种。
如上所述的方面和任一可能的实现方式，进一步提供一种实现方式，所述含碳还原剂为碳、活性碳、石墨粉、木炭、石油焦、沥青、煤焦粒中 的一种或者几种。
如上所述的方面和任一可能的实现方式，进一步提供一种实现方式，所述阴极为金属钛、不锈钢、碳钢、金属钼和金属镍中的一种或多种。
与现有技术相比，本发明可以获得包括以下技术效果：与现有的可溶性阳极相比，采用该钛碳硫阳极电解在阴极上直接沉积得到金属钛，阳极产生的CS 2气体/S 2实现能源循环高效利用，且整个电解过程中不产生阳极泥而可实现连续化电解，将大幅降低钛的金属提取成本和含钛矿石的高效资源化利用。
当然，实施本发明的任一产品并不一定需要同时达到以上所述的所有技术效果。
【附图说明】
为了更清楚地说明本发明实施例的技术方案，下面将对实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其它的附图。
图1是本发明一个实施例提供的碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法流程图；
图2a和图2b是本发明一个实施例提供的合成制备的钛碳硫阳极X射线衍射图；
图3是本发明一个实施例提供的电解过程中的电压-气体曲线图；
图4是本发明一个实施例提供的阴极钛产物的XRD示意图；
图5是本发明一个实施例提供的阴极产物钛的SEM示意图。
【具体实施方式】
为了更好的理解本发明的技术方案，下面结合附图对本发明实施例 进行详细描述。
应当明确，所描述的实施例仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。
在本发明实施例中使用的术语是仅仅出于描述特定实施例的目的，而非旨在限制本发明。在本发明实施例和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式，除非上下文清楚地表示其他含义。
图1是本发明一个实施例提供的碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法流程图。如图1所示，一种碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法，其步骤包括：
步骤(1)、硫化钛的制备
将含钛物料、碳和硫还原剂以摩尔比为1:2.0:2.0～1:2.5:3.0比例均匀混合，以该混合料为原料，在密闭耐压耐高温容器中进行灼烧反应，使其彻底完全硫化，制备出导电性良好的硫化钛产物。高温高压灼烧反应时使用惰性气氛保护其反应。保温700℃～1600℃，反应30～900min；优化温度为1000℃～1300℃，时间为60～300min；成功制备出导电性良好的TiS 2、TiS、Ti 2S、Ti 3S、Ti 6S和Ti 4S 5等硫化物。
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者几种；所述的含碳还原剂包括碳、活性碳、石墨粉、木炭、石油焦、沥青、煤焦粒中的一种或者几种；所述的硫为工业使用的硫粉。制备出的硫化钛为二硫化钛及微量其它硫化物。并对该硫化钛进行高温烧结或电弧炉熔炼成固溶体，将该固溶体作为为阳极，以便进行电化学电解制备金属钛。涉及到的相关反应机理为：
FeTiO 3+S→FeS+TiO 2+O 2，△G＝-43.459kJ/mol(1100℃)(矿石的硫化)；
TiO 2+C+S→TiS 2+CO，△G＝-35.891kJ/mol(800℃)(钛白粉的硫化)；
TiO 2+C+S→TiS 2+CO 2，△G＝-18.365kJ/mol(800℃)(钛白粉的硫化)；
TiS 2+Ti＝TiS；
TiO 2+2C+S→TiS+2CO△G＝-17.949kJ/mol(1100℃)；
TiO 2+C+S→TiS+CO 2△G＝-24.451kJ/mol(1600℃)。
步骤(2)、钛碳硫阳极的制备
以步骤(1)所述制备的硫化钛和碳化钛为原料，进行真空烧结制备钛碳硫阳极(Ti 2C xS 1-x,x≤0.5)；本钛碳硫阳极包含硫化钛和钛碳硫，统称为钛碳硫复合化合物。其中，以硫化钛和碳化钛或者硫化钛和碳为原料分别按照以下反应的化学计量比制备金属钛碳硫阳极：
TiS 2+3Ti+2C＝2Ti 2CS+2CO；
TiS+TiC＝Ti 2CS；
2TiO 2+5C+S＝Ti 2CS+4CO。
步骤(3)、电化学电解制备金属钛
以步骤(1)制备的硫化钛或步骤(2)制备的钛碳硫为阳极，采用电化学电解技术提取金属钛。反应时，阴极产物为物相单一的金属钛；阳极产生CS 2和S 2气体，对气体进行回收实现循环利用；该电化学电解涉及到的相关反应机理为：
2S→S 2(g)，T>885K；
C+S 2(g)→CS 2(g)；
总反应为TiS→Ti+S 2(g)；
Ti 2CS→Ti+CS 2(g)。
以步骤(1)和步骤(2)得到的钛碳硫电极在熔盐电解质体系中通过电化学冶炼方法提取金属钛，电解过程中阳极产生CS 2和S 2气体，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。S 2和CS 2气体将用于硫化钛的制备，实现能源循环高效利用。
电解质由熔盐电解质体系(卤化物，卤化物-氟化物，氟化物等)组成；具体的，熔盐电解质体系的组成为CsCl 2、CaCl 2、LiCl、NaCl、KCl、MgCl 2、AlCl 3、CaF、NaF、KF、LiF中的一种或一种以上和TiCl 3、TiCl 2、K 2TiF 6、Na 2TiF 6中的一种或一种以上的混合盐，其中熔盐电解质体系中Ti离子质量百分比浓度为1％～10％。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、铁锰坩埚、钼坩埚或镍坩埚中的一种。
槽电压控制在0.5V～10.0V，阳极电流密度范围为：0.05A/cm 2～1.50A/cm 2，阴极电流密度范围分别为：0.05A/cm 2～1.50A/cm 2，电解温度范围在70℃～1600℃，阴阳极的极间距控制在1cm～50cm之间。优选的，槽电压控制在1.5V～6.0V；阳极电流密度范围为：0.05A/cm 2～1.0A/cm 2；阴极电流密度范围为：0.05A/cm 2～1.0A/cm 2；电解温度范围在400℃～900℃；阴阳极的极间距为3cm～40cm。
步骤(4)、气体的回收利用
对步骤(3)电解回收的CS 2气体进行含钛矿料处理制备硫化钛；
所述的含钛矿料包括金红石型钛白、锐钛矿型钛白、钛精矿、氮化钛、钛碳氧、钛碳氮氧、偏钛酸、钛铁矿、钒钛磁铁矿、高炉型高钛渣、碳化钛、二氧化钛、高钛渣和钛的低价氧化物中的一种或者几种；
TiO 2+CS 2(g)→TiS 2+CO/CO 2(g)；
TiC+CS 2(g)→TiS 2+C；
TiC+CS 2(g)→TiS+C；
TiN+CS 2(g)→TiS 2+N2+C；
TiO+CS 2(g)→TiS+CO+S 2(g)。
具体实施例1：
钛白粉(TiO 2，99.5wt％)，石墨粉(99.95),硫粉(99％)按照摩尔比为1:2:2.1进行配制，共100g。在球形球磨机中混合研磨12h，并称取5g在10Mpa压力下压制成型为直径5mm*5mm的小片，并置于一端密闭的玻璃管中，采用耐高温有机胶对其进行密封处理，保证玻璃管在高温下不漏气。然后将该玻璃管置于马弗炉中，在1000℃下灼烧反应10h然后温度降至室温，切开玻璃管取出TiS 2材料。采用该二硫化钛和碳化钛进行1450℃SPS烧结，最终合成Ti 2CS陶瓷材料。合成材料的XRD衍射图见图2(a)和2(b)所示。用刚玉坩埚盛有150g的NaCl-KCl共晶熔盐在750℃下进行相关电解实验。其中阴极采用直径2mm的镍杆，参比电极为NaCl-KCl-AgCl(0.04wt％)的AgCl/Ag电极，制备好的Ti 2CS为阳极。施加0.4V(vs.Ag/AgCl)的恒电位电解4h，阳极气氛通入到置有TiC粉末的管式炉中进行气氛还原制备TiS 2。电解后对阴极镍杆上的产物进行蒸馏水浸泡超声波清洗和1wt％HCl盐酸清洗，最终得到金属钛粉末。其中，图3是本发明电解过程中的电压-气体曲线图，图4为产品的XRD衍射图谱，图5为阴极钛的SEM电镜图谱。
具体实施例2：
首先对500g的钛精矿FeTiO 3在1200℃下进行碳和硫化处理，处理后的产品为FeS和Ti 2CS混合粉末。然后对该混合粉末在1mol/L的稀盐酸中进行浸泡处理，并进行真空过滤，然后在80℃下烘箱烘干得到 钛碳硫陶瓷材料粉末(Ti 2CS)。对该阳极进行真空烧结压制成Ti 2CS阳极。用刚玉坩埚盛有150g的NaCl-KCl-TiCl 2共晶熔盐在750℃下进行相关电解。其中阴极采用直径2mm的镍杆，参比电极为NaCl-KCl-AgCl(0.04wt％)的AgCl/Ag电极。进行电流密度为0.1A/cm 2的恒电流电解4h，阳极产生的气体将通入到盛放有TiO 2的高温反应器中进行还原制备TiS 2或者TiS。然后对阴极产物进行蒸馏水超声波清洗和1wt％HCl盐酸清洗，最终产物经XRD检测得到物相单一的金属钛粉末。
具体实施例3：
以TiS和TiC按照摩尔比为1：1配制，在星型球磨机中混合研磨12h，并进行真空烧结制备Ti 2CS阳极。采用刚玉坩埚盛有150g的CaF 2-KF-NaF-Na 2TiF 6共晶熔盐在850℃下进行相关电解实验。以烧制成型的Ti 2CS为阳极，阳极电流密度为0.5A/cm 2下进行恒电流电解，阴阳极间距为5cm，电解4小时后在阴极镍棒上得到钛粉产物。阳极产生的气体通入置有Ti 2CO的的管式炉(1500℃)中，电解过程中产生的气体将还原处理Ti 2CO，得到TiS产品。阴极产物采用蒸馏水浸泡和1wt％的稀盐酸进行清洗、烘干。最终产物为物相均匀的钛粉。
具体实施例4：
首先对500g攀西地区的钒钛磁铁矿在1300℃下进行碳化处理，处理后的产品在1mol/L的稀盐酸中进行浸泡处理，并进行磁选和真空抽滤，最终产物在80℃下烘箱烘干得到碳化钛(TiC)。采用实施例3中气体还原制备的硫化钛(TiS)和刚制好的TiC在星型球磨机中混合研磨24h，并称取5g在10Mpa压力下压制成型为直径10mm*10mm的小片，并置于耐压耐高温容器中，在氩气气氛保护条件下置于马弗炉中进行压制真空烧结为直径10mm*20mm的圆柱体。用刚玉坩埚盛有 150g的CaF 2-KF-NaF-Na 2TiF 6共晶熔盐在850℃下进行相关电解实验。以烧制成型的Ti 2CS为阳极，阴极电流密度为0.05A/cm 2下进行恒电流电解，阴阳极间距为10cm，电解4小时后在阴极镍棒上得到钛粉产物，并且阳极气体通入Ti 2C 0.25O 0.25N 0.5矿料中进行还原处理回收TiS 2。阴极产物采用蒸馏水浸泡和1wt％的稀盐酸进行清洗、烘干。最终产物为物相均匀的钛粉。
具体实施例5：
首先对500g攀西地区的钒钛磁铁矿在1300℃下进行硫化处理，处理后的产品在1mol/L的稀盐酸中进行浸泡处理，并进行磁选和真空抽滤，最终产物在80℃下烘箱烘干得到钛白粉(TiO 2)。对钛白粉(TiO 2，99.5wt％)，木炭(C含量75％),硫粉(99％)按照摩尔比为1:2.5:2.3进行配制，共10g。在星型球磨机中混合研磨24h，并称取5g在10Mpa压力下压制成型为直径10mm*10mm的小片，并置于耐压耐高温容器中，在氩气气氛保护条件下置于马弗炉中，在1200℃下灼烧反应10h然后温度降至室温获得物相以TiS为主和微量的碳。该TiS进行压制真空烧结为直径10mm*3mm的圆柱体。用刚玉坩埚盛有150g的CaF 2-KF-NaF-Na 2TiF 6共晶熔盐在850℃下进行相关电解实验。以烧制成型的TiS为阳极，阴极电流密度为0.05A/cm 2下进行恒电流电解，阴阳极间距为10cm，电解4小时后在阴极镍棒上得到钛粉产物。阴极产物采用蒸馏水浸泡和1wt％的稀盐酸进行清洗、烘干。最终产物为物相均匀的钛粉。
具体实施例6：
首先对500g的高钛渣在1200℃下进行硫化处理，处理后的产品为FeS和TiO 2混合粉末。然后对该混合粉末在1mol/L的稀盐酸中进行浸泡处理，并进行真空过滤，然后在80℃下烘箱烘干得到钛白粉(TiO 2)。 对钛白粉(TiO 2，99.5wt％)，石油焦(C含量89％),硫粉(99％)按照摩尔比为1:2.3:2.2进行配制，共10g。在星型球磨机中混合研磨12h，并称取2g在10Mpa压力下压制成型为直径5mm*5mm的小片，并置于一端密闭的玻璃管中，采用耐高温有机胶对其进行密封处理，保证玻璃管处于密封状态在高温下不漏气。然后将该玻璃管置于马弗炉中，在1000℃下灼烧反应10h然后温度降至室温，切开玻璃管取出TiS材料。该TiS进行压制真空烧结为直径10mm*3mm的圆柱体。用刚玉坩埚盛有150g的CaF 2-KF-NaF-Na 2TiF 6共晶熔盐在850℃下进行相关电解实验。以烧制成型的TiS为阳极，阳极电流密度为0.5A/cm 2下进行恒电流电解，阴阳极间距为5cm，电解4小时后在阴极镍棒上得到钛粉产物。阴极产物采用蒸馏水浸泡和1wt％的稀盐酸进行清洗、烘干。最终产物为物相均匀的钛粉。
采用硫化钛和钛碳硫材料为可溶性阳极具有以下鲜明特点：
(1)能够低成本的制备合成具有金属导电性的钛碳硫阳极(TiS、TiS 2、Ti 2CS，Ti 2C xS 1-x等)；
(2)制备钛碳硫阳极使用的硫化钛可通过电解过程中产生的CS 2气体处理含钛精矿制得，有效解决了钒钛磁铁矿、钛白粉、碳化钛、氮化钛、钛碳氧、钛碳氮氧等含钛原料的堆弃问题；
(3)钛碳硫和硫化钛作为可溶性阳极，在电解过程中钛以离子形式溶解在电解质中，而CS 2从阳极排出循环利用，有效实现资源能源的高效综合利用；
(4)由于碳和硫的亲和力较强，在电解温度下能够较形成CS 2气体循环利用；
(5)在电解质中直接电解，能够在阴极沉积氧含量较低的金属钛，实现阳极气体的回收高效利用。
(6)有效解决了单纯使用碳化钛阳极电解过程中碳在电解质中的游离问题；
综上所述，较现有的可溶性阳极相比，该钛碳硫阳极具有电解效率高、中间产物少、直接获得高纯金属钛，连续化生产且不产生阳极泥，可实现能源矿物的处理利用等特点。
以上对本申请实施例所提供的一种碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法，进行了详细介绍。以上实施例的说明只是用于帮助理解本申请的方法及其核心思想；同时，对于本领域的一般技术人员，依据本申请的思想，在具体实施方式及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本申请的限制。
如在说明书及权利要求书当中使用了某些词汇来指称特定组件。本领域技术人员应可理解，硬件制造商可能会用不同名词来称呼同一个组件。本说明书及权利要求书并不以名称的差异来作为区分组件的方式，而是以组件在功能上的差异来作为区分的准则。如在通篇说明书及权利要求书当中所提及的“包含”、“包括”为一开放式用语，故应解释成“包含/包括但不限定于”。“大致”是指在可接收的误差范围内，本领域技术人员能够在一定误差范围内解决所述技术问题，基本达到所述技术效果。说明书后续描述为实施本申请的较佳实施方式，然所述描述乃以说明本申请的一般原则为目的，并非用以限定本申请的范围。本申请的保护范围当视所附权利要求书所界定者为准。
还需要说明的是，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的商品或者系统不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种商品或者系统所固有的要素。在没有更多限制的情况下，由语句“包括一个……”限定的要素，并不排除在包括所述要素的商品或者系统中 还存在另外的相同要素。
应当理解，本文中使用的术语“和/或”仅仅是一种描述关联对象的关联关系，表示可以存在三种关系，例如，A和/或B，可以表示：单独存在A，同时存在A和B，单独存在B这三种情况。另外，本文中字符“/”，一般表示前后关联对象是一种“或”的关系。
上述说明示出并描述了本申请的若干优选实施例，但如前所述，应当理解本申请并非局限于本文所披露的形式，不应看作是对其他实施例的排除，而可用于各种其他组合、修改和环境，并能够在本文所述申请构想范围内，通过上述教导或相关领域的技术或知识进行改动。而本领域人员所进行的改动和变化不脱离本申请的精神和范围，则都应在本申请所附权利要求书的保护范围内。

Claims (10)

  1. 一种碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法，其特征在于，制备步骤包括：
    S1、对包括含钛物料、含碳还原剂和硫还原剂的混合料进行硫化，制备出硫化钛；
    S2、以所述硫化钛和碳化钛为原料，制备出钛碳硫；
    S3、以所述硫化钛或所述钛碳硫为阳极，采用电化学电解技术在阴极提取金属钛；
    S4、收集电解时阳极产生的CS 2和S 2气体，用于对所述含钛物料进行硫化。
  2. 根据权利要求1所述的碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法，其特征在于，所述混合料具体为：所述含钛物料、所述含碳还原剂和所述硫还原剂以摩尔比1:2.0:2.0～1:2.5:3.0的比例均匀混合。
  3. 根据权利要求1所述的碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法，其特征在于，所述S1的硫化反应条件为：惰性气氛保护下进行灼烧反应，反应时的保温温度范围为700℃～1600℃，反应时间范围为30min～900min。
  4. 根据权利要求1所述的碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法，其特征在于，所述S2中对所述硫化钛和所述碳化钛进行真空烧结制备所述钛碳硫。
  5. 根据权利要求1所述的碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法，其特征在于，所述S3中电解时，电解温度范围为70℃～1600℃，所述阴极和所述阳极的极间距范围为1cm～50cm，电解的槽电压范围为0.5V～10.0V，阳极电流密度范围为0.05A/cm 2～1.50A/cm 2，阴极电流密度范围分别为0.05A/cm 2～1.50A/cm 2。
  6. 根据权利要求1-5任一所述的碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法，其特征在于，所述S3中电解时的电解质为：CsCl 2、CaCl 2、LiCl、NaCl、KCl、MgCl 2、AlCl 3、CaF、NaF、KF、LiF中的一种或多种和TiCl 3、TiCl 2、K 2TiF 6、Na 2TiF 6中的一种或多种所组成的混合盐。
  7. 根据权利要求6所述的碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法，其特征在于，所述电解质中钛离子质量百分比为1％～10％。
  8. 根据权利要求1-5任一所述的碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法，其特征在于，所述含钛物料为金红石型钛白、锐钛矿型钛白、钛精矿、氮化钛、碳化钛、钛碳氧、钛碳氮氧、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者几种。
  9. 根据权利要求1-5任一所述的碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法，其特征在于，所述含碳还原剂为碳、活性碳、石墨粉、木炭、石油焦、沥青、煤焦粒中的一种或者几种。
  10. 根据权利要求1-5任一所述的碳/硫化的钛铁复合矿阳极-电解制备金属钛的方法，其特征在于，所述阴极为金属钛、不锈钢、碳钢、金属钼和金属镍中的一种或多种。
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