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WO2020103366A1 - 一种电解-氯化-电解制备纯钛的装置及方法 - Google Patents

一种电解-氯化-电解制备纯钛的装置及方法

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Publication number
WO2020103366A1
WO2020103366A1 PCT/CN2019/079833 CN2019079833W WO2020103366A1 WO 2020103366 A1 WO2020103366 A1 WO 2020103366A1 CN 2019079833 W CN2019079833 W CN 2019079833W WO 2020103366 A1 WO2020103366 A1 WO 2020103366A1
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Prior art keywords
electrolytic cell
electrolysis
cathode
anode
titanium
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PCT/CN2019/079833
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English (en)
French (fr)
Inventor
焦树强
王哲
焦汉东
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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Priority claimed from CN201821942940.2U external-priority patent/CN209024654U/zh
Priority claimed from CN201811408695.1A external-priority patent/CN109267100B/zh
Application filed by University of Science and Technology Beijing USTB filed Critical University of Science and Technology Beijing USTB
Priority to US16/612,739 priority Critical patent/US11180863B2/en
Publication of WO2020103366A1 publication Critical patent/WO2020103366A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • 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
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
    • 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
    • C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
    • C25C3/08—Cell construction, e.g. bottoms, walls, cathodes
    • C25C3/12—Anodes
    • 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
    • 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
    • C25C3/36—Alloys obtained by cathodic reduction of all their ions
    • 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
    • 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

Definitions

  • the invention relates to a device and a method for preparing pure titanium by electrolysis-chlorination-electrolysis, belonging to the field of metal titanium production by electrolysis.
  • Titanium metal has many excellent physical and chemical properties, its low density (4.5g / cm 3 ), high melting point (1660 °C), corrosion resistance, oxidation resistance, non-toxic and harmless, with good biocompatibility, known as "Future Metal”. It has a wide range of applications in aerospace, chemical and chemical industry, ships and ships, biomedical, civil building materials and sports equipment. On this basis, people call titanium metal with a titanium content higher than 99.95% or 99.99% (ie 3N5 or 4N) as high-purity titanium metal. High-purity titanium metal not only has the excellent properties of ordinary titanium metal, but also its excellent elongation (50-60%), section shrinkage (70-80%) and ultra-low content of harmful impurity elements are ordinary titanium Matchable. Therefore, high-purity titanium is favored in high-end fields such as high-end microelectronics, cutting-edge aerospace technology, precision ultra-large-scale integrated circuits and display screens.
  • the anode sponge titanium is dissolved and the cathode titanium ions are deposited to obtain high-purity titanium metal.
  • the method is short and can effectively control the oxygen content in the product to obtain low-oxygen high-purity titanium metal.
  • the preparation of sponge titanium is ultimately inseparable from the Kroll method, so its upstream process is complicated and inefficient, which ultimately results in a higher cost of molten salt electrolytic refining with sponge titanium as the anode.
  • the present invention provides an apparatus and method for preparing pure titanium by electrolysis-chlorination-electrolysis.
  • TiC x O y or TiC x O y N z obtained by mixing, briquetting and carbothermal reduction of titanium dioxide and carbonaceous material powder at a certain ratio is used as raw materials.
  • TiCl 4 gas is chlorinated; this gas passes through the conduit to the cathode of the second electrolysis cell, and the solubility of TiCl 4 in the second electrolysis cell is utilized to further electrolyze high-purity titanium metal; at the same time, the Cl produced by the anode 2 It is recycled to the chlorination reactor of the first electrolytic cell to continue to participate in the chlorination of TiC x O y or TiC x O y N z .
  • the device and method for preparing pure titanium by electrolysis-chlorination-electrolysis avoid the lengthy and complicated batch production characteristics of the Kroll method from the source, simplifying the entire process flow And reduce the production cost of high-purity titanium prepared by Kroll method or conventional molten salt electrolysis method.
  • the selection of the molten salt component of the first electrolytic cell can be determined according to changes in the market or the requirements of the alkali metal, alkaline earth metal, aluminum metal or alloy required by the customer, thereby increasing the effective value of the by-products.
  • the invention provides a device and method for preparing pure titanium by electrolysis-chlorination-electrolysis. Compared with the Kroll method or molten salt electrolysis using sponge titanium as a raw material to prepare high-purity titanium metal, the method has the characteristics of simple process, low cost, and high-value by-product preparation.
  • Fig. 1 is a schematic diagram of a device for preparing pure titanium by electrolysis-chlorination-electrolysis according to the present invention.
  • the device is composed of a first electrolysis cell, a second electrolysis cell, a chlorination reactor and a gas guide tube.
  • the first electrolytic cell and the second electrolytic cell are arranged horizontally, and a heating and temperature control system is provided at the bottom and surroundings of the first electrolytic cell and the second electrolytic cell for controlling the temperature of the electrolyte in the electrolytic cell.
  • the chlorination reactor is located at the upper position of the anode of the first electrolyzer, with a porous ceramic separator at the bottom; the material of the chlorination reactor shell is steel material, lined with ceramic materials; and there is independent heating and temperature outside the chlorination reactor
  • the control system is used to control the material temperature inside the chlorination reactor.
  • the first gas pipe is located at the anode position in the first electrolysis cell and connected to the bottom of the chlorination reactor; one end of the second gas pipe is connected to the top of the chlorination reactor and the other end is located at the cathode position in the second electrolysis cell; One end of the three gas guide tubes is located at the anode position in the second electrolytic cell, and the other end is connected to the first gas guide tube in the first electrolytic cell; the material of the gas guide tube is steel, lined with ceramic or polytetrafluoroethylene material.
  • the method for preparing pure titanium by electrolysis-chlorination-electrolysis using the device of the present invention includes the following steps:
  • the first electrolytic cell uses molten alkali metal chloride, alkaline earth metal chloride, aluminum chloride or their mixture as the supporting electrolyte, the anode is carbon material, the cathode is metal material, the temperature of the electrolytic cell is controlled at 150-1000 ° C, chlorine The temperature of the chemical reactor is controlled at 200 ⁇ 600 °C; after the start of electrolysis, Cl ⁇ migrates to the anode, and the reaction generates Cl 2 ; the anode product Cl 2 enters the chlorination reactor through the porous separator through the first gas guide tube, and TiC x O y or TiC x O y N z in the chlorination reactor reacts to generate TiCl 4 gas; this gas enters the cathode area of the second electrolysis cell through the second gas guide tube;
  • molten alkali metal chloride, alkaline earth metal chloride, or a mixture thereof is used as the supporting electrolyte, the anode is carbon material, and the cathode is metal material, and the temperature of the electrolytic cell is controlled at 500-1000 ° C; after the start of electrolysis, The TiCl 4 gas delivered by the second gas pipe enters the molten salt at the cathode of the second electrolyzer. Ti 4+ reacts at the cathode to produce low-valent titanium ions. The low-valent titanium ions continue to react and deposit pure titanium at the cathode. The reaction is as follows :
  • Cl - migrates to the anode, produces Cl 2 at the anode, transports it to the first gas pipe through the third gas pipe, mixes with Cl 2 produced at the anode of the first electrolytic cell, enters the chlorination reactor and participates in TiC x O y Or chlorination of TiC x O y N z ;
  • step 4) the cathode is recharged into two electrolytic cells, and the new TiC x O y or TiC x O y N z raw materials are loaded into the chlorination reactor, and a new round of The operation of electrolytically producing high-purity titanium.
  • the carbonaceous material powder is one or a combination of graphite, petroleum coke, carbon black, coal, and charcoal.
  • the number ratio of oxygen atoms in titanium dioxide to carbon atoms in the carbonaceous material powder is 1.2: 1 to 0.5: 1, preferably 1: 1 to 0.667: 1.
  • the cathode metal material in the first electrolytic cell and the second electrolytic cell is titanium, carbon steel or nickel.
  • the current density during electrolysis in the first electrolytic cell and the second electrolytic cell are respectively: anode, 0.01A / cm 2 ⁇ 2.00A / cm 2 ; cathode, 0.01A / cm 2 ⁇ 2.00A / cm 2 .
  • the by-products obtained from the first electrolyzer can be precisely customized to improve the utilization value of the by-products.
  • FIG. 1 is a schematic diagram of an apparatus for preparing pure titanium by electrolysis-chlorination-electrolysis of the present invention
  • Icon number 1. The first electrolytic cell, 2. The second electrolytic cell, 3. The chlorination reactor, 4. The porous ceramic separator, 5. The first gas pipe, 6. The second gas pipe, 7. The third gas pipe trachea.
  • the first electrolytic cell uses NaCl-AlCl 3 eutectic salt as electrolyte
  • the second electrolytic cell uses NaCl-KCl eutectic salt as electrolyte
  • both electrolytic cells are protected by inert gas.
  • the temperature of the first electrolyzer is controlled at 150 °C, and the cathode and anode both use graphite as the electrode, and the current density is 0.5 and 1A / cm 2 respectively ;
  • the temperature of the second electrolyzer is controlled at 750 °C, the anode uses graphite and the cathode uses For nickel metal plates, the current densities of the cathode and anode are 1 and 2A / cm 2, respectively .
  • the high-purity titanium metal is collected from the cathode nickel plate of the second electrolysis cell, and the high-purity titanium powder or crystal is obtained by acid washing, water washing, drying, packaging, etc., from the cathode of the first electrolysis cell Collect metal aluminum.
  • the first electrolytic cell uses NaCl-MgCl 2 -AlCl 3 eutectic salt as electrolyte
  • the second electrolytic cell uses NaCl-LiCl-KCl eutectic salt as electrolyte, and both electrolytic cells are protected by inert gas.
  • the temperature of the first electrolyzer is controlled at 550 °C, and the cathode and anode both use graphite as the electrode, and the current density is 0.5 and 1.5A / cm 2 respectively ;
  • the temperature of the second electrolyzer is controlled at 600 °C, the anode uses graphite and the cathode Using metal titanium plates, the current densities of the cathode and anode are 0.5 and 1A / cm 2, respectively .
  • the high-purity titanium metal is collected from the cathode nickel plate of the second electrolysis cell, and the high-purity titanium powder or crystal is obtained by acid washing, water washing, drying, packaging, etc., and collected from the cathode of the first electrolysis cell Magnesium-aluminum alloy.
  • the first electrolytic cell uses LiCl-KCl eutectic salt as electrolyte
  • the second electrolytic cell uses NaCl-CaCl eutectic salt as electrolyte
  • both electrolytic cells are protected by inert gas.
  • the temperature of the first electrolytic cell is controlled at 750 ° C, the cathode and anode both use graphite as the electrode, and the current density is 0.2 and 1.5A / cm 2 respectively ;
  • the temperature of the second electrolytic cell is controlled at 800 ° C, the anode uses graphite and the cathode Using metallic nickel plates, the current densities of the cathode and anode are 0.5 and 1.5 A / cm 2, respectively .
  • the high-purity titanium metal is collected from the cathode nickel plate of the second electrolysis cell, and the high-purity titanium powder or crystal is obtained by acid washing, water washing, drying, packaging, etc., and collected from the cathode of the first electrolysis cell Potassium metal.

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  • 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)

Abstract

一种电解-氯化-电解制备纯钛的装置及方法，属于电解法生产金属钛领域。第一电解槽（1）以熔融碱金属氯化物、碱土金属氯化物、氯化铝或它们的混合物为电解质，第二电解槽（2）以熔融碱金属氯化物、碱土金属氯化物或它们的混合物为电解质；第一电解槽（1）阳极处产生的Cl 2通过第一导气管（5）进入储有TiC xO y或TiC xO yN z原料的氯化反应器（3）中，在200℃～600℃温度下氯化出TiCl 4气体；该气体经过第二导气管（6）通入第二电解槽（2）中阴极处，利用TiCl 4在第二电解槽（2）中的溶解性，进而电解出高纯钛金属；同时阳极产生的Cl 2又循环至氯化反应器（3）中继续参与TiC xO y或TiC xO yN z的氯化。该方法工艺简单，清洁高效；同时可根据需求，精确定制第一电解槽所得副产物，进一步提升经济效益。

Description

一种电解-氯化-电解制备纯钛的装置及方法 技术领域
本发明涉及一种电解-氯化-电解制备纯钛的装置及方法，属于电解法生产金属钛领域。
背景技术
钛金属具有诸多优异的物理化学性能，其密度低(4.5g/cm 3)、熔点高(1660℃)、抗腐蚀、耐氧化、无毒无害，具有良好的生物相容性，被称为“未来金属”。其在航空航天、化学化工、船舶舰艇、生物医疗、民用建材和体育器材等领域具有广泛的应用。在此基础上，人们将钛含量高于99.95％或99.99％(即3N5或4N)的钛金属称为高纯钛金属。高纯钛金属不仅拥有普通钛金属所具有的优良性能，同时，其优异的延伸率(50-60％)、断面收缩率(70-80％)以及超低含量的有害杂质元素是普通钛无法企及的。因此，高纯钛在高端微电子、尖端航天技术、精密超大规模集成电路及显示屏等高端领域备受青睐。
目前，高纯钛的工业化生产主要有两种方法，一种是Kroll法，另一种是熔盐电解法。前者以TiO 2经过配碳、氯化得到TiCl 4，TiCl 4再经过镁热还原得到钛金属，而副产物MgCl 2则需要采用熔盐电解法进行分解，从而实现循环利用。整个流程繁杂冗长、产率有限。此外，为了得到高纯钛金属，所用原料(TiCl 4及镁金属)往往需要更高的纯度，这就增加了高纯钛的制备成本。后者以海绵钛为阳极，以含钛卤化物熔盐为电解质，电解过程中阳极海绵钛溶解，阴极钛离子沉积，得到高纯钛金属。该方法相对于Kroll法流程简短，且可有效控制产物中的氧含量，得到低氧高纯钛金属。然而，海绵钛的制备终究离不开Kroll法，因此其上游流程复杂、低效，最终造成以海绵钛为阳极的熔盐电解精炼成本较高。
针对上述问题，本发明提出了一种电解-氯化-电解制备纯钛的装置及方法。以二氧化钛和碳质材料粉按一定的比例混合、压块、碳热还原所得TiC xO y或TiC xO yN z为原料。在第一电解槽中电解熔融碱金属氯化物、碱土金属氯化物、氯化铝或它们的混合物，阳极所得氯气通入储有TiC xO y或TiC xO yN z原料的氯化反应器中，进而氯化出TiCl 4气体；该气体经过导管通入第二电解槽中阴极处，利用TiCl 4在第二电解槽中的溶解性，进而电解出高纯钛金属；同时阳极产生的Cl 2又循环至第一电解槽氯化反应器中继续参与TiC xO y或TiC xO yN z的氯化。相对于Kroll法或常规熔盐电解法制备高 纯钛金属，该电解-氯化-电解制备纯钛的装置及方法从源头上避免了Kroll法冗长复杂的批次生产特点，简化了整个工艺流程，且降低了Kroll法或常规熔盐电解法制备高纯钛的生产成本。此外，第一电解槽熔盐组分的选择可以根据市场变化或客户需求的碱金属、碱土金属、铝金属或合金的要求而定，从而提高副产品的有效价值。
发明内容
本发明提供一种电解-氯化-电解制备纯钛的装置及方法。相对于Kroll法或以海绵钛为原料的熔盐电解制备高纯钛金属，该方法具有流程简洁、成本低廉，且可制备高价值副产物的特点。
附图1为本发明的电解-氯化-电解制备纯钛的装置示意图，装置由第一电解槽、第二电解槽、氯化反应器和导气管组成，其装置设备特点为：
所述第一电解槽与第二电解槽水平设置，第一电解槽与第二电解槽底部和四周有加热与温控系统，用于控制电解槽中电解质的温度。
所述氯化反应器位于第一电解槽阳极的上部位置，底部设置多孔陶瓷隔板；氯化反应器壳体材质为钢材，内衬有陶瓷材料；氯化反应器外部有独立的加热与温控系统，用于控制氯化反应器内部物料温度。
所述第一导气管位于第一电解槽内的阳极位置，并与氯化反应器底部连接；第二导气管一端连接氯化反应器顶部，另一端位于第二电解槽内的阴极位置；第三导气管一端位于第二电解槽内的阳极位置，另一端与第一电解槽内的第一导气管连接；导气管材质为钢材，内衬有陶瓷或聚四氟乙烯材料。
采用本发明装置电解-氯化-电解制备纯钛的方法包括如下步骤：
1)按照化学反应计量比将二氧化钛和碳质材料粉混料均匀后，压制成型，在900～1600℃温度范围内在真空条件中制得TiC xO y或在氮气气氛下制得TiC xO yN z，装入氯化反应器中；
2)第一电解槽以熔融碱金属氯化物、碱土金属氯化物、氯化铝或它们的混合物为支持电解质，阳极为碳材料，阴极为金属材料，电解槽温度控制在150～1000℃，氯化反应器温度控制在200～600℃；电解开始后，Cl -迁移到阳极，发生反应产生Cl 2；阳极产物Cl 2经由第一导气管穿过多孔隔板进入氯化反应器中，并与氯化反应器中的TiC xO y或TiC xO yN z发生反应产生TiCl 4气体；该气体经由第二导气管进入第二电解槽阴极区域；
3)第二电解槽中以熔融碱金属氯化物、碱土金属氯化物或它们的混合物为支持 电解质，阳极为碳材料，阴极为金属材料，电解槽温度控制在500～1000℃；电解开始后，由第二导气管输送的TiCl 4气体在第二电解槽阴极处进入熔盐，Ti 4+在阴极处发生反应产生低价钛离子，低价钛离子继续反应在阴极沉积得到纯钛，反应如下：
Ti 4++e＝Ti 3+
Ti 3++e＝Ti 2+
Ti 2++2e＝Ti
Cl -迁移到阳极，在阳极处产生Cl 2，经由第三导气管输送至第一导气管中，与第一电解槽阳极处产生的Cl 2混合，进入氯化反应器中参与TiC xO y或TiC xO yN z的氯化；
4)一个电解周期结束后，将两个电解槽中阴极产物取下，并经过酸洗、水洗、烘干等处理步骤，从第二电解槽的阴极上收集产品高纯钛金属，从第一电解槽的阴极上收集副产品碱金属、碱土金属、铝金属或合金。
5)在步骤4)完成后，将阴极再装入两个电解槽中，并将新的TiC xO y或TiC xO yN z原料装入氯化反应器中，再进行新一轮的电解生产高纯钛的操作。
所述步骤1)中，碳质材料粉为石墨、石油焦、炭黑、煤炭、木炭中的一种或几种的组合。
所述步骤1)中，二氧化钛中氧原子与碳质材料粉中碳原子的个数比为1.2:1～0.5:1，优选1:1～0.667:1。
所述步骤2)和3)中，第一电解槽和第二电解槽中阴极金属材料为钛、碳钢或镍。
所述步骤2)和3)中，第一电解槽和第二电解槽中电解时的电流密度分别为：阳极，0.01A/cm 2～2.00A/cm 2；阴极，0.01A/cm 2～2.00A/cm 2。
相对于现有技术，本发明的优点在于：
1)、将氯气制备、碳氧化钛或碳氮氧化钛低温氯化及四氯化钛电解三个部分于同一装置完成，该工艺简洁、清洁、高效；
2)、避免了Kroll法生产过程所涉及的镁热还原及MgCl 2的电解分解等过程，从而大大的缩短了高纯钛的制备流程；
3)、双电解槽的应用，将碳氧化钛或碳氮氧化钛低温氯化与TiCl 4电解还原分开，既有利于高纯钛的制备，保证钛的纯度，又将两个阳极产生的Cl 2实现循环利用，进一步降低了污染和能耗；
4)、可根据市场变化或客户需求，精确定制第一电解槽所得副产物，从而提高副产物利用价值。
附图说明
图1为本发明的电解-氯化-电解制备纯钛的装置示意图；
图标号：1.第一电解槽，2.第二电解槽，3.氯化反应器，4.多孔陶瓷隔板，5.第一导气管，6.第二导气管，7.第三导气管。
实施例1
将二氧化钛和石墨粉按照质量比40:12混料均匀后，压制成型，在1400℃真空烧结3小时制得TiC 0.5O 0.5并装入氯化反应器中。第一电解槽以NaCl-AlCl 3共晶盐为电解质，第二电解槽选用NaCl-KCl共晶盐为电解质，两个电解槽均采用惰性气体保护。电解时，第一电解槽的温度控制在150℃，阴、阳极均采用石墨作为电极，电流密度分别为0.5和1A/cm 2；第二电解槽温度控制在750℃，阳极采用石墨，阴极采用金属镍板,阴、阳极电流密度分别为1和2A/cm 2。一个电解周期结束后，从第二电解槽的阴极镍板上收集高纯钛金属，并经过酸洗、水洗、烘干、封装等得到高纯钛粉末或晶体，从第一电解槽的阴极上收集金属铝。
实施例2
将二氧化钛和石墨粉按照质量比40:15混料均匀后，压制成型，在1600℃真空烧结2小时制得TiC 0.25O 0.75并装入氯化反应器中。第一电解槽以NaCl-MgCl 2-AlCl 3共晶盐为电解质，第二电解槽选用NaCl-LiCl-KCl共晶盐为电解质，，两个电解槽均采用惰性气体保护。电解时，第一电解槽的温度控制在550℃，阴、阳极均采用石墨作为电极，电流密度分别为0.5和1.5A/cm 2；第二电解槽温度控制在600℃，阳极采用石墨，阴极采用金属钛板,阴、阳极电流密度分别为0.5和1A/cm 2。一个电解周期结束后，从第二电解槽的阴极镍板上收集高纯钛金属，并经过酸洗、水洗、烘干、封装等得到高纯钛粉末或晶体，从第一电解槽的阴极收集镁-铝合金。
实施例3
将二氧化钛和石墨粉按照质量比40:12混料均匀后，压制成型，在1300℃氮气气氛下烧结3小时制得TiC 0.2O 0.2N 0.6并装入氯化反应器中。第一电解槽以LiCl-KCl共晶盐为电解质，第二电解槽选用NaCl-CaCl共晶盐为电解质，两个电解槽均采用惰性气体保护。电解时，第一电解槽的温度控制在750℃，阴、阳极均采用石墨作为电 极，电流密度分别为0.2和1.5A/cm 2；第二电解槽温度控制在800℃，阳极采用石墨，阴极采用金属镍板,阴、阳极电流密度分别为0.5和1.5A/cm 2。一个电解周期结束后，从第二电解槽的阴极镍板上收集高纯钛金属，并经过酸洗、水洗、烘干、封装等得到高纯钛粉末或晶体，从第一电解槽的阴极收集金属钾。
当然，本发明还可以有多种实施例，在不背离本发明技术实质的情况下，熟悉本领域的技术人员可根据本发明的公开做出各种相应的改变和变型，但这些相应的改变和变形都应属于本发明所附的权利要求的保护范围。

Claims (7)

  1. 一种电解-氯化-电解制备纯钛的装置，其特征在于，包括第一电解槽、第二电解槽、氯化反应器和导气管；
    其中，第一电解槽(1)与第二电解槽(2)水平设置，第一电解槽(1)与第二电解槽(2)底部和四周有加热与温控系统，用于控制电解槽中电解质的温度；氯化反应器(3)位于第一电解槽(1)阳极的上部位置，底部设置多孔陶瓷隔板(4)；
    氯化反应器(3)壳体材质为钢材，内衬有陶瓷材料；氯化反应器(3)外部有独立的加热与温控系统，用于控制氯化反应器(3)内部物料温度；
    第一导气管(5)位于第一电解槽(1)内的阳极位置，并与氯化反应器(3)底部连接；第二导气管(6)一端连接氯化反应器(3)顶部，另一端位于第二电解槽(2)内的阴极位置；第三导气管(7)一端位于第二电解槽(2)内的阳极位置，另一端与第一电解槽(1)内的第一导气管(5)连接；导气管材质为钢材，内衬有陶瓷或聚四氟乙烯材料。
  2. 一种采用如权利要求1所述的装置制备纯钛的方法，其特征在于，主要包括以下步骤：
    1)按照化学反应计量比将二氧化钛和碳质材料粉混料均匀后，压制成型，在900～1600℃温度范围内在真空条件中制得TiC xO y或在氮气气氛下制得TiC xO yN z，装入氯化反应器中；
    2)第一电解槽以熔融碱金属氯化物、碱土金属氯化物、氯化铝或它们的混合物为支持电解质，阳极为碳材料，阴极为金属材料，电解槽温度控制在150～1000℃，氯化反应器温度控制在200～600℃；电解开始后，Cl -迁移到阳极，发生反应产生Cl 2；阳极产物Cl 2经由第一导气管穿过多孔隔板进入氯化反应器中，并与氯化反应器中的TiC xO y或TiC xO yN z发生反应产生TiCl 4气体；该气体经由第二导气管进入第二电解槽阴极区域；
    3)第二电解槽中以熔融碱金属氯化物、碱土金属氯化物或它们的混合物为支持电解质，阳极为碳材料，阴极为金属材料，电解槽温度控制在500～1000℃；电解开始后，由第二导气管输送的TiCl 4气体在第二电解槽阴极处进入熔盐，Ti 4+在阴极处发生反应产生低价钛离子，低价钛离子继续反应在阴极沉积得到纯钛，反应如下：
    Ti 4++e＝Ti 3+
    Ti 3++e＝Ti 2+
    Ti 2++2e＝Ti
    Cl -迁移到阳极，在阳极处产生Cl 2，经由第三导气管输送至第一导气管中，与第 一电解槽阳极处产生的Cl 2混合，进入氯化反应器中参与TiC xO y或TiC xO yN z的氯化；
    4)一个电解周期结束后，将两个电解槽中阴极产物取下，并经过酸洗、水洗、烘干处理步骤，从第二电解槽的阴极上收集产品高纯钛金属，从第一电解槽的阴极上收集副产品碱金属、碱土金属、铝金属或合金；
    5)在步骤4)完成后，将阴极再装入两个电解槽中，并将新的TiC xO y或TiC xO yN z原料装入氯化反应器中，再进行新一轮的电解生产高纯钛的操作。
  3. 根据权利要求2所述制备纯钛的方法，其特征在于，所述碳质材料粉为石墨、石油焦、炭黑、煤炭、木炭中的一种或几种的组合。
  4. 根据权利要求2所述制备纯钛的方法，其特征在于，所述二氧化钛中氧原子与碳质材料粉中碳原子的个数比为1.2:1～0.5:1。
  5. 根据权利要求2或4所述制备纯钛的方法，其特征在于，所述二氧化钛中氧原子与碳质材料粉中碳原子的个数比为1:1～0.667:1。
  6. 根据权利要求2所述制备纯钛的方法，其特征在于，所述第一电解槽和第二电解槽中，阴极金属材料为钛、碳钢或镍。
  7. 根据权利要求2所述制备纯钛的方法，其特征在于，所述第一电解槽和第二电解槽中电解时的电流密度分别为：阳极，0.01A/cm 2～2.00A/cm 2；阴极，0.01A/cm 2～2.00A/cm 2。
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