CN104451783A - Method for preparing metal through direct electrolysis of refractory metal oxysalt - Google Patents

Method for preparing metal through direct electrolysis of refractory metal oxysalt Download PDF

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Publication number
CN104451783A
CN104451783A CN201410724949.6A CN201410724949A CN104451783A CN 104451783 A CN104451783 A CN 104451783A CN 201410724949 A CN201410724949 A CN 201410724949A CN 104451783 A CN104451783 A CN 104451783A
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refractory metal
oxysalt
metal
electrolysis
fused salt
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CN201410724949.6A
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王明涌
翁威
王东
王志
公旭中
郭占成
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Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
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Abstract

The invention discloses a method for preparing metal through direct electrolysis of a refractory metal oxysalt. The method comprises the following steps: with the refractory metal oxysalt as a raw material, CaCl2 or a mixture of CaCl2 and alkali chloride as a fused salt, mixing the refractory metal oxysalt with the chloride fused salt evenly; heating to 300 DEG C under an inert atmosphere protection to remove moisture out of the fused salt; heating to electrolyzing temperature, electrolyzing, and cooling to room temperature after electrolyzing is ended; and washing a cathode deposition product and a product at the bottom of the fused salt and baking, so as to obtain refractory metal powder. The refractory metal oxysalt disclosed by the invention is the closest to raw ore in an existing ore processing procedure, and the refractory metal is prepared from the refractory metal oxysalt as the raw material by direct electrolysis, so that the technological process is greatly shortened; and the method is friendly to the environment.

Description

A kind of refractory metal oxysalt Direct Electrolysis prepares the method for metal
Technical field
The present invention relates to chemical industry metallurgical field, be specifically related to a kind of preparation method of refractory metal.
Background technology
Refractory metal refers to titanium, zirconium, the hafnium of the IVth subgroup in the periodic table of elements, the vanadium of V subgroup, niobium, tantalum, chromium, tungsten, the molybdenum of the VIth subgroup, the metallic elements such as the rhenium of the VIIth subgroup.Refractory metal is as the group of a class fusing point higher than 1650 DEG C, and can play an important role in national economy with its outstanding physics, chemistry, machinery and nuclearity, particularly in stratosphere, status is more important.
Current industrial mainly with the oxide compound of refractory metal or muriate for raw material, adopt hot reducing method to produce refractory metal.As adopted V 2o 5for raw material, calcium metal is that vanadium metal (calciothermy) produced by reductive agent; Adopt TiCl 4for raw material, Mg is that metal titanium (Kroll technique) produced by reductive agent.With refractory metal oxide or muriate for raw material produces metal by thermal reduction mode, the production of raw material exists complex process, long flow path, pollution are large, high in cost of production shortcoming; The selection of method exists processing unit require height, produce discontinuous, product purity is low and pollute the problems such as large.The raw material Vanadium Pentoxide in FLAKES producing vanadium metal as calciothermy need obtain by the complicated technology such as heavy and calcining through ammonium, this process a large amount of high salt ammonia nitrogen waste water of release and waste gas, and Kroll technique Raw TiCl 4production need through superchlorination, distillation obtains smart TiCl 4raw material, then obtain titanium sponge through the step such as magnesium reduction and vacuum separation, this raw materials technology Mg and TiCl 4production process is complicated, and cost is high, the TiCl produced in the large and chlorination process of facility investment 4and Cl 2there is severe corrosive and contaminative.Therefore, develop new production method and adopt new raw material significant to prepare refractory metal.
Fused salt electrolysis process produces refractory metal becomes the study hotspot replacing hot reducing method.
2000, univ cambridge uk Fray proposed a kind of with TiO 2for raw material is at melting CaCl 2the technique (W009963638) of titanium sponge is produced in middle negative electrode deoxidation.This technique is applicable to other refractory metal oxides equally and prepares metal.This technique possesses following features: electrolytic efficiency is low, and deoxidation speed is slow and high to the purity requirement of raw material titanium dioxide raw material.
Okabe and Ono (Metall.Mater.Trans.B, 2003, vol.34B, pp.287-295) of Jingdone district university of Japan proposes at CaCl 2in-CaO fused salt, electrolysis obtains active metal Ca, then reduces TiO 2prepare the method for metal Ti.The method current efficiency is low, to raw material TiO 2purity requirement is high.
Sadoway professor (US Patent No.5185068, J.Mater.Res., Vol.10, No.3, Mar 1995) of Massachusetts Polytechnics contains TiO by electrolysis 2oxide melt electrolysis at 1700 DEG C obtain liquid metal titanium.The method service temperature is high, and product titanium is of poor quality, and cost is high.
2005, University of Science & Technology, Beijing professor Zhu Hongmin propose a kind of with titanium dioxide and graphite for raw material prepares the good soluble anode Ti of electroconductibility at 1500 DEG C 2cO, and with the electrolysis in molten chloride of this soluble anode, the method (ZL200510011684.6) of metal titanium is proposed.The preparation temperature of the method soluble anode is high, and preparation process is complicated.
Sichuan Pangang Group Co., Ltd. has applied for a kind of method (CN101519789A) of preparing metallic titanium by electrolyzing titanium-circulated molten salt for 2009.The method raw material adopt titanium tetrachloride be raw material, expensive raw material price and preparation difficulty.
Chinese patent CN 102978664A adopts vanadium tetrachloride to be raw material, and in molten chloride, electrolysis obtains vanadium metal.The method take vanadium tetrachloride as raw material, expensive raw material price and preparation difficulty.
The method producing refractory metal above by fused salt electrolysis be all still with refractory metal oxide or muriate for raw material, do not solve oxide compound or muriate stock preparation process long flow path, pollute the problems such as large.At present, refractory metal oxide or muriatic production are with metal oxyacid salts intermediate for raw material mostly, are produced by techniques such as decomposition, calcinings.The present invention propose directly with refractory metal oxysalt for raw material, the novel method of Retrospect of Fused Salt Electrolysis Process for Producing Refractory Metals, avoids the techniques such as decomposition, calcining, significantly shortens Production Flow Chart, and avoid problem of environmental pollution.
Summary of the invention
The object of the invention is to provide that a kind of it does not need additional reducing agent with the method for refractory metal oxysalt for the direct Retrospect of Fused Salt Electrolysis Process for Producing Refractory Metals of raw material, and technique is simple, and flow process is short, operational safety, without gaseous detonation hidden danger, and non-environmental-pollution.
The object of the invention is to be achieved through the following technical solutions: a kind of refractory metal oxysalt Direct Electrolysis prepares the method for metal, comprises the following steps: adopt refractory metal oxysalt as raw material, with CaCl 2or CaCl 2be fused salt with alkali metal chloride mixture, refractory metal oxysalt mixes with alkali metal chloride fused salt, and the mass percent of refractory metal oxysalt in alkali metal chloride fused salt is 1 ~ 10%; Under inert atmosphere protection, be warming up to the moisture in 300 DEG C of removing alkali metal chloride fused salts, be warming up to electrolysis temperature, carry out electrolysis, after electrolysis terminates, be cooled to room temperature, cathodic deposition product and fused salt bottoms obtain refractory metal powder through washing, oven dry.
The negatively charged ion of described refractory metal oxysalt is CrO 4 -, Cr 2o 7 2-, VO 4 3-, VO 3 -, NbO 3 -, TaO 3 -, TiO 3 2-, ZrO 3 2-.The corresponding salt fusing point of above-mentioned oxysalt negatively charged ion is low, is easy to dissociate, and is beneficial to reduce service temperature and the treated most direct product of refractory metal raw ore is above-mentioned oxygen acid root, selects above-mentioned oxysalt negatively charged ion to be beneficial to and shortens metal metallurgy smelting flow process, reduce energy consumption.
The positively charged ion of described refractory metal oxysalt is Li +, Na +, K +, Ca 2+, Ba 2+.The oxysalt that above-mentioned positively charged ion is corresponding is cheap and easy to get, is beneficial to and reduces costs.
Described alkali metal chloride is one or more in LiCl, NaCl and KCl.Above-mentioned muriate is cheap and easy to get, and and CaCl 2easy formation eutectoid point, is beneficial to and reduces costs and service temperature.
The temperature of described electrolysis is the minimum eutectic temperature higher than selected alkali metal chloride fused salt, and lower than the decomposition temperature of selected refractory metal oxysalt.Fused salt good conductivity, and refractory metal oxysalt is stablized.
The minimum eutectic temperature of described alkali metal chloride fused salt is 550 ~ 900 DEG C.Electrolysis temperature is low, is beneficial to reduction energy consumption.
Described cathode material is graphite, Cu, Mo, Ni, Cr, Al and alloy thereof or the refractory metal corresponding to oxysalt and alloy thereof.Cathode material good conductivity, low price, is beneficial to and reduces costs.
Described electrolysis voltage is 2.5 ~ 4.0V, and electrolysis time is 4h ~ 12h.Separate out without chlorine, be beneficial to and improve operating environment, reduce equipment corrosion rate, and metallic product purity is high, can ensure that the electrolysis of refractory metal raw material is complete, improve recovery rate.
Compared with prior art, the advantage that the method for the invention has is: the present invention adopts refractory metal oxysalt to be that metal is prepared in the direct fused salt electrolysis of raw material, and raw material is easy to get, environmental friendliness, and facility investment is little.Adopt the present invention, existing refractory metal preparation flow will significantly shorten (as Fig. 1), and production cost is expected to significantly reduce.For different refractory metal oxysalts, metal purity that once electrolytic obtains is up to 95 ~ 99%, and current efficiency is up to 50 ~ 70%, and once electrolytic recovery rate is up to 85 ~ 95%.
Accompanying drawing explanation
Fig. 1 conventional refractory preparation of metals flow process and preparation flow comparison diagram of the present invention.
The product chromium pictorial diagram of Fig. 2 obtained by potassiumchromate;
The product chromium XRD figure of Fig. 3 obtained by potassiumchromate;
The product chromium SEM-EDS of Fig. 4 obtained by potassiumchromate schemes;
The product chromium XRD figure of Fig. 5 obtained by Sodium chromate;
The product vanadium XRD figure of Fig. 6 obtained by vanadic acid sodium;
The product titanium XRD figure of Fig. 7 obtained by sodium titanate.
Embodiment
With reference to embodiment, the present invention is specifically introduced, but embodiment should not be considered as concrete restriction of the present invention.
Embodiment 1
Take 17.5g potassiumchromate; 133.5g Repone K and 199g calcium chloride mix; be placed in corundum crucible; the corundum crucible being loaded with Repone K, calcium chloride and potassiumchromate mixture is placed in airtight steel reactor, under argon shield, is heated to 300 DEG C of insulation 12h, then under argon shield, is warming up to 900 DEG C; anode is graphite rod; negative electrode is NiCr alloy, applies 3.2V voltage and carry out electrolysis between anode and cathode, and electrolysis time is 4 hours.After electrolysis terminates, be cooled to room temperature, cathode deposit and fused salt bottoms are through the dilute hydrochloric acid of PH=3 and deionized water wash, namely the metal powder (as shown in Figure 2) of grey black is obtained after drying, microtexture is spongy (as shown in Figure 4), XRD and EDS confirms that product is mainly chromium metal (shown in Fig. 3 and Fig. 4), purity 96%, current efficiency 68.43%, recovery rate 93.9%.
Embodiment 2
Take 10.3g Sodium chromate, 114.8g sodium-chlor and 217.7g calcium chloride to mix; be placed in corundum crucible; the corundum crucible being loaded with sodium-chlor, calcium chloride and Sodium chromate mixture is placed in airtight steel reactor; 300 DEG C of insulation 12h are heated under argon shield; then under argon shield, 850 DEG C are warming up to; cathode and anode is graphite rod, applies 2.5V voltage and carry out electrolysis between anode and cathode, and electrolysis time is 8 hours.After electrolysis terminates, be cooled to room temperature, cathode deposit and fused salt bottoms are through the dilute hydrochloric acid of PH=3 and deionized water wash, namely hafnium metal powfer is obtained after drying, XRD result confirms that product only exists the diffraction peak (as shown in Figure 5) of chromium metal, purity 94%, current efficiency 63%, recovery rate 95%.
Embodiment 3
Take 17.5g sodium metavanadate; 114.8g sodium-chlor and 217.7g calcium chloride mix; be placed in corundum crucible; the corundum crucible being loaded with sodium-chlor, calcium chloride and sodium metavanadate mixture is placed in airtight steel reactor; under argon shield, be heated to 300 DEG C of insulation 12h, then under argon shield, be warming up to 800 DEG C, cathode and anode is graphite rod; between anode and cathode, apply 4.0V voltage carry out electrolysis, electrolysis time is 12 hours.After electrolysis terminates, be cooled to room temperature, cathode deposit and fused salt bottoms are through the dilute hydrochloric acid of PH=3 and deionized water wash, namely metal vanadium powder is obtained after drying, XRD result confirms that product only exists the diffraction peak (as shown in Figure 6) of vanadium metal, purity 96.93%, current efficiency 50%, recovery rate 89%.
Embodiment 4
Take 17.5g calcium titanate; 114.8g sodium-chlor and 217.7g calcium chloride mix; be placed in corundum crucible; the corundum crucible being loaded with sodium-chlor, calcium chloride and calcium titanate mixture is placed in airtight steel reactor; under argon shield, be heated to 300 DEG C of insulation 12h, then under argon shield, be warming up to 900 DEG C, cathode and anode is graphite rod; between anode and cathode, apply 4.0V voltage carry out electrolysis, electrolysis time is 12 hours.After electrolysis terminates, be cooled to room temperature, cathode deposit and fused salt bottoms are through the dilute hydrochloric acid of PH=3 and deionized water wash, namely metallic titanium powder is obtained after drying, XRD result confirms that product only exists the diffraction peak (as shown in Figure 7) of metal titanium, purity 99%, current efficiency 61%, recovery rate 87.6%.
Embodiment 5
Take 10.3g Sodium chromate, 114.8g sodium-chlor and 217.7g calcium chloride to mix; be placed in corundum crucible; the corundum crucible being loaded with sodium-chlor, calcium chloride and Sodium chromate mixture is placed in airtight steel reactor; 300 DEG C of insulation 12h are heated under argon shield; then under argon shield, 600 DEG C are warming up to; cathode and anode is graphite rod, applies 3.5V voltage and carry out electrolysis between anode and cathode, and electrolysis time is 8 hours.After electrolysis terminates, be cooled to room temperature, cathode deposit and fused salt bottoms, through the dilute hydrochloric acid of PH=3 and deionized water wash, namely obtain hafnium metal powfer after drying, purity 95%, current efficiency 60%, recovery rate 91%.
Embodiment 6
Take 17.5g potassium bichromate; 133.5g Repone K and 199g calcium chloride mix; be placed in corundum crucible; the corundum crucible being loaded with Repone K, calcium chloride and potassiumchromate mixture is placed in airtight steel reactor, under argon shield, is heated to 300 DEG C of insulation 12h, then under argon shield, is warming up to 850 DEG C; anode is graphite rod; negative electrode is NiCr alloy, applies 3.2V voltage and carry out electrolysis between anode and cathode, and electrolysis time is 4 hours.After electrolysis terminates, be cooled to room temperature, cathode deposit and fused salt bottoms, through the dilute hydrochloric acid of PH=3 and deionized water wash, namely obtain hafnium metal powfer after drying, purity 95%, current efficiency 66.3%, recovery rate 91.9%.
Embodiment 7
Take 17.5g vanadic acid sodium; 114.8g sodium-chlor and 217.7g calcium chloride mix; be placed in corundum crucible; the corundum crucible being loaded with sodium-chlor, calcium chloride and sodium metavanadate mixture is placed in airtight steel reactor; under argon shield, be heated to 300 DEG C of insulation 12h, then under argon shield, be warming up to 800 DEG C, cathode and anode is graphite rod; between anode and cathode, apply 4.0V voltage carry out electrolysis, electrolysis time is 12 hours.After electrolysis terminates, be cooled to room temperature, cathode deposit and fused salt bottoms, through the dilute hydrochloric acid of PH=3 and deionized water wash, namely obtain metal vanadium powder after drying, purity 95.13%, current efficiency 51%, recovery rate 90%.
The present invention directly with refractory metal oxysalt for raw material, produce metal by fused salt electrolysis.Shorten technical process, avoid the discharge of waste water and gas, overcome problem of environmental pollution; Significantly reduce production cost; Do not need to use reducing gas, drastically increase the security of production, improve Working environment.
It should be noted that, according to the various embodiments described above of the present invention, those skilled in the art are the four corners that can realize independent claim of the present invention and appurtenance completely, implementation procedure and the same the various embodiments described above of method; And non-elaborated part of the present invention belongs to techniques well known.
The above; be only part embodiment of the present invention, but protection scope of the present invention is not limited thereto, any those skilled in the art are in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.

Claims (8)

1. refractory metal oxysalt Direct Electrolysis prepares a method for metal, it is characterized in that comprising the following steps: adopt refractory metal oxysalt as raw material, with CaCl 2or CaCl 2be fused salt with alkali metal chloride mixture, refractory metal oxysalt mixes with alkali metal chloride fused salt, and the mass percent of refractory metal oxysalt in alkali metal chloride fused salt is 1 ~ 10%; Under inert atmosphere protection, be warming up to the moisture in 300 DEG C of removing alkali metal chloride fused salts, be warming up to electrolysis temperature, carry out electrolysis, after electrolysis terminates, be cooled to room temperature, cathodic deposition product and fused salt bottoms obtain refractory metal powder through washing, oven dry.
2. a kind of refractory metal oxysalt Direct Electrolysis according to claim 1 prepares the method for metal, it is characterized in that: the negatively charged ion of described refractory metal oxysalt is CrO 4 -, Cr 2o 7 2-, VO 4 3-, VO 3 -, NbO 3 -, TaO 3 -, TiO 3 2-, ZrO 3 2-.
3. a kind of refractory metal oxysalt Direct Electrolysis according to claim 1 prepares the method for metal, it is characterized in that: the positively charged ion of described refractory metal oxysalt is Li +, Na +, K +, Ca 2+, Ba 2+.
4. a kind of refractory metal oxysalt Direct Electrolysis according to claim 1 prepares the method for metal, it is characterized in that: described alkali metal chloride is one or more in LiCl, NaCl and KCl.
5. a kind of refractory metal oxysalt Direct Electrolysis according to claim 1 prepares the method for metal, it is characterized in that: the temperature of described electrolysis is the minimum eutectic temperature higher than selected alkali metal chloride fused salt, and lower than the decomposition temperature of selected refractory metal oxysalt.
6. a kind of refractory metal oxysalt Direct Electrolysis according to claim 5 prepares the method for metal, it is characterized in that: the minimum eutectic temperature of described alkali metal chloride fused salt is 550 ~ 900 DEG C.
7. a kind of refractory metal oxysalt Direct Electrolysis according to claim 1 prepares the method for metal, it is characterized in that: described cathode material is graphite, Cu, Mo, Ni, Cr, Al and alloy thereof or the refractory metal corresponding to oxysalt and alloy thereof.
8. a kind of refractory metal oxysalt Direct Electrolysis according to claim 1 prepares the method for metal, and it is characterized in that: described electrolysis voltage is 2.5 ~ 4.0V, electrolysis time is 4h ~ 12h.
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Cited By (7)

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CN104911635A (en) * 2015-05-05 2015-09-16 中国科学院过程工程研究所 Method for alkali recovery and molten salt circulation in electrolytic process of refractory metal oxacid salt
CN105225721A (en) * 2015-08-26 2016-01-06 贵州理工学院 A kind of high connductivity composition metal oxidation powder body material and preparation method thereof
CN109338116A (en) * 2018-11-22 2019-02-15 王娜 A kind of method that short route processing titanium slag extraction prepares titanium and its alloy nanoparticle
CN110079837A (en) * 2019-04-24 2019-08-02 北京科技大学 The method that water-soluble fluorine salt system molten-salt electrolysis soluble titanium hydrochlorate prepares Titanium
CN112941567A (en) * 2018-07-10 2021-06-11 东北大学 Electrochemical method and apparatus for high temperature molten salt electrolysis in humid atmosphere
CN112981467A (en) * 2021-02-04 2021-06-18 重庆大学 Method for reducing carbon pollution in molten salt electrolysis process
CN115142096A (en) * 2021-03-30 2022-10-04 中国科学院过程工程研究所 Method for improving electrolysis efficiency of refractory metal prepared by molten salt electrolysis and purifying molten salt

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104911635A (en) * 2015-05-05 2015-09-16 中国科学院过程工程研究所 Method for alkali recovery and molten salt circulation in electrolytic process of refractory metal oxacid salt
CN105225721A (en) * 2015-08-26 2016-01-06 贵州理工学院 A kind of high connductivity composition metal oxidation powder body material and preparation method thereof
CN105225721B (en) * 2015-08-26 2017-04-19 贵州理工学院 Highly-conductive composite metal oxidation powder material and preparation method thereof
CN112941567A (en) * 2018-07-10 2021-06-11 东北大学 Electrochemical method and apparatus for high temperature molten salt electrolysis in humid atmosphere
CN112941567B (en) * 2018-07-10 2024-02-23 东北大学 Electrochemical method and device for high-temperature molten salt electrolysis in humid atmosphere
CN109338116A (en) * 2018-11-22 2019-02-15 王娜 A kind of method that short route processing titanium slag extraction prepares titanium and its alloy nanoparticle
CN110079837A (en) * 2019-04-24 2019-08-02 北京科技大学 The method that water-soluble fluorine salt system molten-salt electrolysis soluble titanium hydrochlorate prepares Titanium
CN110079837B (en) * 2019-04-24 2020-10-13 北京科技大学 Method for preparing metal titanium by electrolyzing soluble titanate by using water-soluble fluoride salt system molten salt
CN112981467A (en) * 2021-02-04 2021-06-18 重庆大学 Method for reducing carbon pollution in molten salt electrolysis process
CN112981467B (en) * 2021-02-04 2024-01-26 重庆大学 Method for reducing carbon pollution in molten salt electrolysis process
CN115142096A (en) * 2021-03-30 2022-10-04 中国科学院过程工程研究所 Method for improving electrolysis efficiency of refractory metal prepared by molten salt electrolysis and purifying molten salt

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