CN103422122B - A kind of method of titanium dioxide direct Preparation of Titanium - Google Patents
A kind of method of titanium dioxide direct Preparation of Titanium Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 62
- 239000010936 titanium Substances 0.000 title claims abstract description 61
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 61
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 21
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 24
- 239000002608 ionic liquid Substances 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 11
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 6
- 239000010439 graphite Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 30
- 239000003792 electrolyte Substances 0.000 claims description 9
- -1 1-butyl-3-methyl imidazolium tetrafluoroborate Chemical compound 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 239000000428 dust Substances 0.000 claims 2
- 238000005453 pelletization Methods 0.000 claims 2
- PLWSZOQYWKLNIL-UHFFFAOYSA-N 1-butyl-2-chloro-3-methyl-2h-imidazole Chemical compound CCCCN1C=CN(C)C1Cl PLWSZOQYWKLNIL-UHFFFAOYSA-N 0.000 claims 1
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 40
- 239000002184 metal Substances 0.000 abstract description 40
- 230000009467 reduction Effects 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000009856 non-ferrous metallurgy Methods 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract 2
- 239000008188 pellet Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011829 room temperature ionic liquid solvent Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
本发明涉及一种二氧化钛直接制备金属钛的方法，属于有色金属冶金技术领域。首先通过二氧化钛粉、碳粉和粘结剂混合均匀后制备预还原二氧化钛电极，其中粘结剂为水或PVA，然后将预还原二氧化钛电极为阴极，石墨或其它惰性材料为阳极，在电解液为离子液体、电解电压为2.8～3.2V、电解温度为25～120℃的条件下进行电解还原12～48h，然后取出阴极，冲洗和干燥即得到阴极产物金属钛。本发明缩短了工艺流程、极大地降低了能耗，实现清洁生产。The invention relates to a method for directly preparing metallic titanium from titanium dioxide, belonging to the technical field of nonferrous metallurgy. Firstly, the pre-reduced titanium dioxide electrode is prepared by mixing titanium dioxide powder, carbon powder and binder evenly, wherein the binder is water or PVA, and then the pre-reduced titanium dioxide electrode is used as the cathode, and graphite or other inert materials are used as the anode. Under the conditions of ionic liquid, electrolysis voltage of 2.8-3.2V and electrolysis temperature of 25-120°C, electrolytic reduction is carried out for 12-48 hours, and then the cathode is taken out, washed and dried to obtain metal titanium as the cathode product. The invention shortens the technological process, greatly reduces energy consumption, and realizes clean production.
Description
技术领域 technical field
本发明涉及一种二氧化钛直接制备金属钛的方法，属于有色金属冶金技术领域。 The invention relates to a method for directly preparing metallic titanium from titanium dioxide, belonging to the technical field of nonferrous metallurgy.
背景技术 Background technique
钛具有比强度大、密度小、耐高温、抗腐蚀、无磁等优异的性能而广泛应用于航天、石油、能源、交通、化工、生物医学等领域，而且其应用领域正在不断的扩展。 Titanium has excellent properties such as high specific strength, low density, high temperature resistance, corrosion resistance, and non-magnetic properties, so it is widely used in aerospace, petroleum, energy, transportation, chemical, biomedical and other fields, and its application fields are constantly expanding.
目前钛的生产方法主要有两种：镁热还原法(Kroll法)和钠热还原法(Hunter法)。因为Hunter法比Kroll法生产成本高，所以钛生产普遍使用的是Kroll法。Kroll法是以镁还原—真空蒸馏法为代表的海绵钛生产工艺。它将钛矿富集—氯化—精制制取TiCl4，接着在氩气或氦气气氛中用镁将TiCl4还原为海绵钛，然后进行真空蒸馏分离除去镁和MgCl2，最后经过产品处理得到成品海绵钛。此工艺流程中有两个重要的循环，即镁循环和氯循环，而镁的外循环和氯循环是通过高温融盐电解氯化镁得到的。因此该工艺流程长，操作复杂，生产成本高，环境污染严重。经过几十年的发展，Kroll法也进行了一系列的改进，但多年来的研究工作证明，一些局部的技术改良无法改变高成本这一现状。因此，有必要研究流程短、成本低及对环境友好的制备方法，使金属钛能在更多的领域得到应用。为寻求新的低成本的钛制备工艺，国内外均做了大量的研究工作。研究的新工艺有熔盐电解法（FFC法）。该方法首先将TiO2烧制成阴极，然后采用CaCl2高温熔盐体系作为电解质，在800～1000℃下直接将其电解还原为金属钛。由于该法直接从TiO2电解得到金属钛，极大地简化了工艺流程及设备，因此能明显降低能耗和生产成本（据估计，该法的生产成本仅为Kroll法的三分之一）。但是，该方法到目前为止只是在实验室获得成功，要实现大规模生产，首先要解决TiO2阴极制备及导电性不好的问题，其次要实现电解槽的密闭和气氛保护，然后还必须克服电解过程中钛离子价态变化对电流效率的影响。而要同时解决以上问题，在实践中还有很大的难度。而且熔盐电解要在800℃的温度下进行，需要消耗一定的能量并腐蚀设备。因此，迫切需要发展一种工艺简单、节能、低成本的钛制备新技术，而离子液体的出现无疑为此提供了新的可能。 At present, there are two main production methods of titanium: magnesium thermal reduction method (Kroll method) and sodium thermal reduction method (Hunter method). Because the Hunter method is more expensive than the Kroll method, the Kroll method is commonly used in titanium production. The Kroll method is a sponge titanium production process represented by the magnesium reduction-vacuum distillation method. It concentrates titanium ore - chlorination - refining to produce TiCl4, then reduces TiCl4 to sponge titanium with magnesium in an argon or helium atmosphere, then conducts vacuum distillation to separate and remove magnesium and MgCl2, and finally obtains finished sponge after product treatment titanium. There are two important cycles in this process flow, namely the magnesium cycle and the chlorine cycle, and the external cycle of magnesium and the chlorine cycle are obtained by electrolysis of magnesium chloride with high-temperature molten salt. Therefore, the technological process is long, the operation is complicated, the production cost is high, and the environmental pollution is serious. After decades of development, the Kroll method has also undergone a series of improvements, but years of research have proved that some local technical improvements cannot change the high cost. Therefore, it is necessary to study preparation methods with short process, low cost and environmental friendliness, so that titanium metal can be applied in more fields. In order to find a new low-cost titanium preparation process, a lot of research work has been done at home and abroad. The new process of research is molten salt electrolysis (FFC method). In the method, TiO2 is first fired into a cathode, and then a CaCl2 high-temperature molten salt system is used as an electrolyte to directly electrolytically reduce it to metallic titanium at 800-1000°C. Because this method directly obtains metal titanium from TiO2 electrolysis, the process and equipment are greatly simplified, so energy consumption and production costs can be significantly reduced (it is estimated that the production cost of this method is only one-third of that of the Kroll method). However, this method has only been successful in the laboratory so far. To achieve large-scale production, firstly, the problems of TiO2 cathode preparation and poor conductivity must be solved, and secondly, the airtightness and atmosphere protection of the electrolytic cell must be realized, and then the electrolysis must be overcome. The influence of the valence state change of titanium ions on the current efficiency during the process. However, it is very difficult to solve the above problems at the same time in practice. Moreover, molten salt electrolysis needs to be carried out at a temperature of 800°C, which consumes a certain amount of energy and corrodes equipment. Therefore, there is an urgent need to develop a new technology for titanium preparation with simple process, energy saving and low cost, and the emergence of ionic liquids undoubtedly provides new possibilities for this.
离子液体是室温离子液体的简称，是一种由阴、阳离子组成，在室温或室温附近呈液态的有机盐。它具有电化学窗口宽、导电性好、液态范围宽、无蒸汽压、稳定性好等优异性能，是一种绿色溶剂。在电沉积方面，离子液体融合了高温熔盐和水溶液的优点：具有较宽的电化学窗口和良好的导电性，在室温下即可得到在高温熔盐中才能电沉积出的金属和合金，但没有高温熔盐那样的强腐蚀性；同时在离子液体中还可电沉积得到大多数能在水溶液中得到的金属，且无副反应，因而得到的金属质量更好，电流效率更高，特别是对铝、钛、硅和锗等很难在水溶液中电沉积得到的金属及其合金更是如此。离子液体的上述特性及其良好的电导率使之成为电沉积研究的崭新液体，在电沉积金属方面得到越来越多的应用。 Ionic liquid is the abbreviation of room temperature ionic liquid, which is an organic salt composed of anion and cation, which is liquid at room temperature or near room temperature. It has excellent properties such as wide electrochemical window, good conductivity, wide liquid range, no vapor pressure, and good stability. It is a green solvent. In terms of electrodeposition, ionic liquids combine the advantages of high-temperature molten salts and aqueous solutions: they have a wide electrochemical window and good electrical conductivity, and metals and alloys that can be electrodeposited in high-temperature molten salts can be obtained at room temperature. But it is not as corrosive as high-temperature molten salt; at the same time, most of the metals that can be obtained in aqueous solution can be obtained by electrodeposition in ionic liquids, and there is no side reaction, so the obtained metals have better quality and higher current efficiency, especially This is especially true for metals such as aluminum, titanium, silicon and germanium that are difficult to electrodeposit in aqueous solution and their alloys. The above characteristics of ionic liquids and their good electrical conductivity make them a brand-new liquid for electrodeposition research, and they are increasingly used in electrodeposition of metals.
发明内容 Contents of the invention
针对上述现有技术存在的问题及不足，本发明提供一种二氧化钛直接制备金属钛的方法。与现有的金属钛制备方法相比，本发明缩短了工艺流程、极大地降低了能耗，实现清洁生产，本发明通过以下技术方案实现。 Aiming at the problems and deficiencies in the above-mentioned prior art, the present invention provides a method for directly preparing titanium metal from titanium dioxide. Compared with the existing method for preparing metal titanium, the present invention shortens the process flow, greatly reduces energy consumption, and realizes clean production. The present invention is realized through the following technical solutions.
一种二氧化钛直接制备金属钛的方法，其具体步骤如下： A method for directly preparing metal titanium from titanium dioxide, the specific steps are as follows:
（1）制备预还原二氧化钛电极：首先将二氧化钛粉、碳粉和PVA按照质量百分比100：（12～16）：（1～2）混合均匀并压制成块状混合物，然后在还原气氛中将块状混合物在温度为1200～1300℃的条件下煅烧1～4h得到预还原二氧化钛电极；或首先将二氧化钛粉、水和碳粉按照质量百分比100：（6～10）：（12～16）混合均匀并压制成直径为1～10mm的球团状混合物，然后在还原气氛中将球团状混合物在温度为1200～1300℃的条件下煅烧1～2h得到预还原二氧化钛球团，最后将球团装入钛篮内即得到预还原二氧化钛电极； (1) Preparation of pre-reduced titanium dioxide electrode: first, mix titanium dioxide powder, carbon powder and PVA according to the mass percentage of 100: (12-16): (1-2) and press them into a block mixture, and then put the block in a reducing atmosphere The mixture is calcined at a temperature of 1200-1300°C for 1-4 hours to obtain a pre-reduced titanium dioxide electrode; or first mix titanium dioxide powder, water and carbon powder according to the mass percentage of 100: (6-10): (12-16) And press it into a pellet-like mixture with a diameter of 1-10mm, then calcinate the pellet-like mixture at a temperature of 1200-1300°C for 1-2 hours in a reducing atmosphere to obtain pre-reduced titanium dioxide pellets, and finally pack the pellets Put it into the titanium basket to get the pre-reduced titanium dioxide electrode;
（2）制备金属钛：以步骤（1）得到的预还原二氧化钛电极为阴极，石墨或其它惰性材料为阳极，在电解液为离子液体、电解电压为2.8～3.2V、电解温度为25～120℃的条件下进行电解还原12～48h，然后取出阴极，冲洗和干燥即得到阴极产物金属钛。 (2) Preparation of titanium metal: the pre-reduced titanium dioxide electrode obtained in step (1) is used as the cathode, graphite or other inert materials are used as the anode, the electrolyte is an ionic liquid, the electrolysis voltage is 2.8-3.2V, and the electrolysis temperature is 25-120 Under the condition of ℃, perform electrolytic reduction for 12-48 hours, then take out the cathode, rinse and dry to obtain the cathode product metal titanium.
所述钛篮的网孔目数为100～200目。 The mesh number of the titanium basket is 100-200 mesh.
所述离子液体为碱性氯代1-丁基-3-甲基咪唑-三氯化铝（BmimCl-AlCl3）、碱性氯代1-乙基-3-甲基咪唑-三氯化铝（EmimCl-AlCl3）、1-丁基-3-甲基咪唑四氟硼酸盐（[Bmim]BF4）、1-乙基-3-甲基咪唑四氟硼酸盐（[Emim]BF4）或1-丁基-3-甲基咪唑六氟磷酸盐（[Bmim]PF6）。 The ionic liquid is basic chlorinated 1-butyl-3-methylimidazole-aluminum trichloride (BmimCl-AlCl 3 ), basic chlorinated 1-ethyl-3-methylimidazole-aluminum trichloride (EmimCl-AlCl 3 ), 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF 4 ), 1-ethyl-3-methylimidazolium tetrafluoroborate ([Emim]BF 4 ) or 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim]PF 6 ).
上述离子液体皆为市购分析纯。 The above-mentioned ionic liquids were all analytically pure commercially available.
本发明的有益效果是：（1）本发明直接将二氧化钛转化为金属钛，产物金属钛含氧量较低，且与传统的金属钛生产方法相比，本发明缩短了工艺流程、极大地降低了能耗；（2）与现行研究的FCC法相比，本发明电解还原温度低，采用离子液体电解还原温度在130℃以下，高温熔盐电解温度在800℃以上，降低了670℃，在很大程度上节约成本、降低了能耗和减缓了对设备的腐蚀；（3）由于二氧化钛导电性差，本发明将二氧化钛在碳还原气氛下煅烧，使二氧化钛分子部分脱氧变为半导体，改善阴极的导电性，提高电解过程中的电化学脱氧效率，且将阴极二氧化钛采用球团状，可进一步加快反应速率，提高电化学脱氧效率。 The beneficial effects of the present invention are: (1) The present invention directly converts titanium dioxide into metal titanium, and the product metal titanium has a lower oxygen content, and compared with the traditional production method of metal titanium, the present invention shortens the process flow and greatly reduces (2) Compared with the currently researched FCC method, the electrolytic reduction temperature of the present invention is low. The electrolytic reduction temperature of the ionic liquid is below 130°C, and the high-temperature molten salt electrolysis temperature is above 800°C, which is 670°C lower. To a large extent, it saves cost, reduces energy consumption and slows down the corrosion of equipment; (3) Due to the poor conductivity of titanium dioxide, the present invention calcines titanium dioxide in a carbon-reducing atmosphere to partially deoxidize titanium dioxide molecules and turn them into semiconductors, improving the conductivity of the cathode It can improve the electrochemical deoxidation efficiency in the electrolysis process, and the cathode titanium dioxide is made of pellets, which can further speed up the reaction rate and improve the electrochemical deoxidation efficiency.
具体实施方式 detailed description
下面结合具体实施方式，对本发明作进一步说明。 The present invention will be further described below in combination with specific embodiments.
实施例1 Example 1
该二氧化钛直接制备金属钛的方法，其具体步骤如下： This titanium dioxide directly prepares the method for metal titanium, and its specific steps are as follows:
（1）制备预还原二氧化钛电极：首先将二氧化钛粉、碳粉和PVA按照质量百分比100：16：2混合均匀并压制成块状混合物，然后在还原气氛中将块状混合物在温度为1200℃的条件下煅烧1h得到预还原二氧化钛电极； (1) Preparation of pre-reduced titanium dioxide electrode: first, mix titanium dioxide powder, carbon powder and PVA according to the mass percentage of 100:16:2 and press it into a block mixture, and then put the block mixture in a reducing atmosphere at a temperature of 1200 ° C Calcined for 1 h under the same conditions to obtain a pre-reduced titanium dioxide electrode;
（2）制备金属钛：以步骤（1）得到的预还原二氧化钛电极为阴极，石墨为阳极，在电解液为离子液体、电解电压为2.8V、电解温度为25℃的条件下进行电解还原12h，然后取出阴极，冲洗和干燥即得到阴极产物金属钛。其中离子液体为[Bmim]Cl-AlCl3，金属钛的氧含量小于1%。 (2) Preparation of titanium metal: use the pre-reduced titanium dioxide electrode obtained in step (1) as the cathode, graphite as the anode, and perform electrolytic reduction for 12 hours under the conditions of ionic liquid electrolyte, electrolysis voltage of 2.8V, and electrolysis temperature of 25°C , and then take out the cathode, rinse and dry to obtain the cathode product metal titanium. The ionic liquid is [Bmim]Cl-AlCl 3 , and the oxygen content of the metal titanium is less than 1%.
实施例2 Example 2
该二氧化钛直接制备金属钛的方法，其具体步骤如下： This titanium dioxide directly prepares the method for metal titanium, and its specific steps are as follows:
（1）制备预还原二氧化钛电极：首先将二氧化钛粉、碳粉和PVA按照质量百分比100：12：1混合均匀并压制成块状混合物，然后在还原气氛中将块状混合物在温度为1300℃的条件下煅烧4h得到预还原二氧化钛电极； (1) Preparation of pre-reduced titanium dioxide electrode: first, mix titanium dioxide powder, carbon powder and PVA according to the mass percentage of 100:12:1 and press it into a block mixture, and then put the block mixture in a reducing atmosphere at a temperature of 1300 ° C Calcined for 4 hours under the same conditions to obtain a pre-reduced titanium dioxide electrode;
（2）制备金属钛：以步骤（1）得到的预还原二氧化钛电极为阴极，铂电极为阳极，在电解液为离子液体、电解电压为3.2V、电解温度为120℃的条件下进行电解还原48h，然后取出阴极，冲洗和干燥即得到阴极产物金属钛。其中离子液体为[Bmim]BF4，金属钛的氧含量小于1%。 (2) Preparation of titanium metal: the pre-reduced titanium dioxide electrode obtained in step (1) is used as the cathode, and the platinum electrode is used as the anode, and the electrolytic reduction is carried out under the conditions that the electrolyte is an ionic liquid, the electrolysis voltage is 3.2V, and the electrolysis temperature is 120°C After 48 hours, the cathode was taken out, rinsed and dried to obtain the cathode product metal titanium. The ionic liquid is [Bmim]BF 4 , and the oxygen content of the metal titanium is less than 1%.
实施例3 Example 3
该二氧化钛直接制备金属钛的方法，其具体步骤如下： This titanium dioxide directly prepares the method for metal titanium, and its specific steps are as follows:
（1）制备预还原二氧化钛电极：首先将二氧化钛粉、碳粉和PVA按照质量百分比100：14：1混合均匀并压制成块状混合物，然后在还原气氛中将块状混合物在温度为1250℃的条件下煅烧2h得到预还原二氧化钛电极； (1) Preparation of pre-reduced titanium dioxide electrode: first, mix titanium dioxide powder, carbon powder and PVA according to the mass percentage of 100:14:1 and press it into a block mixture, and then put the block mixture in a reducing atmosphere at a temperature of 1250 ° C Calcined for 2 hours under the same conditions to obtain a pre-reduced titanium dioxide electrode;
（2）制备金属钛：以步骤（1）得到的预还原二氧化钛电极为阴极，石墨为阳极，在电解液为离子液体、电解电压为3.0V、电解温度为100℃的条件下进行电解还原24h，然后取出阴极，冲洗和干燥即得到阴极产物金属钛。其中离子液体为EmimCl-AlCl3，金属钛的氧含量小于1%。 (2) Preparation of titanium metal: use the pre-reduced titanium dioxide electrode obtained in step (1) as the cathode, graphite as the anode, and perform electrolytic reduction for 24 hours under the conditions that the electrolyte is an ionic liquid, the electrolysis voltage is 3.0V, and the electrolysis temperature is 100°C. , and then take out the cathode, rinse and dry to obtain the cathode product metal titanium. The ionic liquid is EmimCl-AlCl 3 , and the oxygen content of the metal titanium is less than 1%.
实施例4 Example 4
该二氧化钛直接制备金属钛的方法，其具体步骤如下： This titanium dioxide directly prepares the method for metal titanium, and its specific steps are as follows:
（1）制备预还原二氧化钛电极：首先将二氧化钛粉、水和碳粉按照质量百分比100：10：16混合均匀并压制成直径为1mm的球团状混合物，然后在还原气氛中将球团状混合物在温度为1200℃的条件下煅烧1h得到预还原的二氧化钛球团，最后将球团装入具有导电性的网孔100目的钛篮内即得到预还原二氧化钛电极； (1) Preparation of pre-reduced titanium dioxide electrode: first, mix titanium dioxide powder, water and carbon powder according to the mass percentage of 100:10:16 and press them into a pellet-like mixture with a diameter of 1mm, and then pelletize the mixture in a reducing atmosphere Calcined at 1200°C for 1 hour to obtain pre-reduced titanium dioxide pellets, and finally put the pellets into a conductive 100-mesh titanium basket to obtain a pre-reduced titanium dioxide electrode;
（2）制备金属钛：以步骤（1）得到的预还原二氧化钛电极为阴极，铂电极为阳极，在电解液为离子液体、电解电压为2.8V、电解温度为25℃的条件下进行电解还原12h，然后取出阴极，冲洗和干燥即得到阴极产物金属钛。其中离子液体为BmimCl-AlCl3，金属钛的氧含量小于1%。 (2) Preparation of titanium metal: the pre-reduced titanium dioxide electrode obtained in step (1) is used as the cathode, and the platinum electrode is used as the anode, and the electrolytic reduction is carried out under the conditions that the electrolyte is an ionic liquid, the electrolysis voltage is 2.8V, and the electrolysis temperature is 25°C 12h, then take out the cathode, rinse and dry to obtain the cathode product metal titanium. The ionic liquid is BmimCl-AlCl 3 , and the oxygen content of the metal titanium is less than 1%.
实施例5 Example 5
该二氧化钛直接制备金属钛的方法，其具体步骤如下： This titanium dioxide directly prepares the method for metal titanium, and its specific steps are as follows:
（1）制备预还原二氧化钛电极：首先将二氧化钛粉、水和碳粉按照质量百分比100： 6：12混合均匀并压制成直径为10mm的球团状混合物，然后在还原气氛中将球团状混合物在温度为1300℃的条件下煅烧2h得到预还原的二氧化钛球团，最后将球团装入具有导电性的网孔200目的钛篮内即得到预还原二氧化钛电极； (1) Preparation of pre-reduced titanium dioxide electrode: first, mix titanium dioxide powder, water and carbon powder according to the mass percentage of 100:6:12 and press them into a pellet-shaped mixture with a diameter of 10mm, and then pellet the mixture in a reducing atmosphere Calcined at a temperature of 1300°C for 2 hours to obtain pre-reduced titanium dioxide pellets, and finally put the pellets into a conductive titanium basket with 200 meshes to obtain a pre-reduced titanium dioxide electrode;
（2）制备金属钛：以步骤（1）得到的预还原二氧化钛电极为阴极，石墨为阳极，在电解液为离子液体、电解电压为3.2V、电解温度为120℃的条件下进行电解还原48h，然后取出阴极，冲洗和干燥即得到阴极产物金属钛。其中离子液体为[Emim]BF4，金属钛的氧含量小于1%。 (2) Preparation of titanium metal: use the pre-reduced titanium dioxide electrode obtained in step (1) as the cathode, graphite as the anode, and perform electrolytic reduction for 48 hours under the conditions of ionic liquid electrolyte, electrolysis voltage of 3.2V, and electrolysis temperature of 120°C , and then take out the cathode, rinse and dry to obtain the cathode product metal titanium. Among them, the ionic liquid is [Emim]BF 4 , and the oxygen content of metal titanium is less than 1%.
实施例6 Example 6
该二氧化钛直接制备金属钛的方法，其具体步骤如下： This titanium dioxide directly prepares the method for metal titanium, and its specific steps are as follows:
（1）制备预还原二氧化钛电极：首先将二氧化钛粉、水和碳粉按照质量百分比100： 8：14混合均匀并压制成直径为5mm的球团状混合物，然后在还原气氛中将球团状混合物在温度为1250℃的条件下煅烧1.5h得到预还原的二氧化钛球团，最后将球团装入具有导电性的网孔120目的钛篮内即得到预还原二氧化钛电极； (1) Preparation of pre-reduced titanium dioxide electrode: first mix titanium dioxide powder, water and carbon powder according to the mass percentage of 100:8:14 and press it into a pellet-like mixture with a diameter of 5mm, and then pellet the mixture in a reducing atmosphere Calcined at a temperature of 1250°C for 1.5 hours to obtain pre-reduced titanium dioxide pellets, and finally put the pellets into a conductive titanium basket with a mesh size of 120 mesh to obtain a pre-reduced titanium dioxide electrode;
（2）制备金属钛：以步骤（1）得到的预还原二氧化钛电极为阴极，铂电极为阳极，在电解液为离子液体、电解电压为3.0V、电解温度为100℃的条件下进行电解还原24h，然后取出阴极，冲洗和干燥即得到阴极产物金属钛。其中离子液体为[Bmim]PF6，金属钛的氧含量小于1%。 (2) Preparation of titanium metal: the pre-reduced titanium dioxide electrode obtained in step (1) is used as the cathode, and the platinum electrode is used as the anode, and the electrolytic reduction is carried out under the conditions that the electrolyte is an ionic liquid, the electrolysis voltage is 3.0V, and the electrolysis temperature is 100°C After 24 hours, the cathode was taken out, rinsed and dried to obtain the cathode product metal titanium. Among them, the ionic liquid is [Bmim]PF 6 , and the oxygen content of metal titanium is less than 1%.
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