CN115305516A - Method for preparing metal titanium by reducing titanium dioxide through molten salt electrolysis - Google Patents
Method for preparing metal titanium by reducing titanium dioxide through molten salt electrolysis 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 125
- 239000010936 titanium Substances 0.000 title claims abstract description 110
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 108
- 150000003839 salts Chemical class 0.000 title claims abstract description 105
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 71
- 239000002184 metal Substances 0.000 title claims abstract description 71
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 61
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 48
- 239000003792 electrolyte Substances 0.000 claims abstract description 81
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 44
- 239000000956 alloy Substances 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 17
- 229910002804 graphite Inorganic materials 0.000 claims description 17
- 229910001220 stainless steel Inorganic materials 0.000 claims description 17
- 239000010935 stainless steel Substances 0.000 claims description 17
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 16
- -1 titanium ions Chemical class 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 229910001338 liquidmetal Inorganic materials 0.000 description 20
- 230000008569 process Effects 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052593 corundum Inorganic materials 0.000 description 10
- 239000010431 corundum Substances 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000001502 supplementing effect Effects 0.000 description 6
- 239000000155 melt Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 229910014459 Ca-Ni Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910014473 Ca—Ni Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- 239000004484 Briquette Substances 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- BLOIXGFLXPCOGW-UHFFFAOYSA-N [Ti].[Sn] Chemical compound [Ti].[Sn] BLOIXGFLXPCOGW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000009870 titanium metallurgy Methods 0.000 description 1
- 229910001773 titanium mineral Inorganic materials 0.000 description 1
Images
Classifications
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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
-
- 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
- C25C7/06—Operating or servicing
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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
The invention relates to a method for preparing metal titanium by reducing titanium dioxide through molten salt electrolysis, which comprises the steps of firstly constructing an electrochemical system which is formed by filling an anode molten salt electrolyte in an anode chamber and inserting an anode, filling a cathode molten salt electrolyte in a cathode chamber and inserting a cathode, wherein the anode molten salt electrolyte and the cathode molten salt electrolyte are not in contact with each other and are connected through a liquid alloy at the bottom in an electrolytic cell, adding titanium dioxide into the anode chamber, and electrifying and electrolyzing to obtain the metal titanium at the cathode. The method has the advantages of low requirement on titanium dioxide raw materials, simple flow, low energy consumption, environmental friendliness and capability of directly obtaining the metal titanium with higher purity.
Description
Technical Field
The invention belongs to the field of titanium metallurgy, and particularly relates to a method for preparing metal titanium by reducing titanium dioxide through molten salt electrolysis.
Background
The metal titanium has high specific strength and corrosion resistance, and is widely applied to the fields of aerospace, chemical engineering, energy, medical treatment and the like.
The titanium mineral is mainly rutile (TiO) 2 ) And ilmenite (FeTiO) 3 ). Because of the strong affinity of titanium to elements such as oxygen and carbon, extraction is very difficult. Ilmenite needs to be treated to obtain high titanium slag (the main component is titanium dioxide TiO) 2 ). The rutile or high titanium slag is converted into titanium tetrachloride TiCl through carbon adding and chlorination 4 Then rectifying to remove impurities to obtain pure TiCl 4 . Then carrying out metallothermic reduction to obtain the titanium sponge. At present, the thermal reduction method mainly includes two methods, i.e., kroll method (magnesium reduction) and Hunter method (sodium reduction). Industrially, the Kroll process is mainly used.
The Kroll method has the disadvantages of long process flow, multiple working procedures, discontinuous production and long period, and causes high cost. Thus, kroll itself has also recognized that the magnesiothermic reduction process will soon be replaced by electrolysis.
In fact, researchers are always investing a lot of manpower to research the electrolytic method. However, regardless of the electrolysis of TiO 2 、K 2 TiF 4 Or TiCl 4 Difficulties are encountered which are difficult to overcome. Or because the product has high impurity content, or because the current efficiency is low, or because the corrosion is serious, or because the equipment structure is complicated, or because the dendrite titanium is deposited and is difficult to separate from the molten salt, or because the environmental cost is high, etc., the industrial application has not been realized so far.
In 2000, the FFC method was introduced by Cambridge university. Different from the idea of the traditional electrolytic method, the medium adopted by the FFC method is calcium chloride fused salt instead of fluoride fused salt, so that the FFC method is more environment-friendly. The FFC process does not pursue the dissolution of the titanium compound in the molten salt, but rather uses the titanium dioxide compact as a cathode. The FFC method is different from the traditional electrolysis method in the working principle, titanium is not deposited from molten salt, but utilizes the characteristics of valve metal oxide (unidirectional conductivity: the titanium can not conduct electricity when being used as an anode and can conduct electricity when being used as a cathode), and the cathode is polarized, so that titanium ions in the cathode are reduced into metallic titanium in situ. During reduction, oxygen anions are separated from a cathode, enter a melt, migrate to an anode under the action of coulomb force and are oxidized into oxygen to be separated out (when a carbon anode is adopted, oxygen and carbon further react to generate CO and CO 2 ). However, the cathode titanium dioxide briquette is gradually reduced from outside to inside, and oxygen diffusion and separation are more and more difficult, so that the cathode current density is low and the overvoltage is high. To obtain titanium with low oxygen content, severe over-electrolysis is required and the current efficiency is low. And impurities such as iron, carbon and the like are easy to enter the product.
The OS process of kyoto university, japan, also employs calcium chloride electrolyte, where calcium ions are reduced to calcium on a cathode titanium mesh. The titanium dioxide is not compacted but is continuously added in the form of powder, and is reduced to titanium powder by calcium near the cathode. Compared with the FFC method, the dispersed granular cathode titanium dioxide is more favorable for the diffusion and migration of oxygen ions than the solid block. But metal calcium dissolvesDecomposed in CaCl 2 In (2), the electron conductivity of the melt is increased, resulting in a decrease in current efficiency. Furthermore, the formed metal and molten salt are mixed and difficult to separate. And the amount of molten salt used is large. Impurities such as iron and carbon are also easy to enter the product.
EMR/MSE method proposed in Japan, tiO 2 The reduction of (2) is carried out in stages. Firstly, the Ca-Ni alloy is prepared by fused salt electrolysis, and then the Ca-Ni alloy is used as a reducing agent to reduce TiO 2 Metallic titanium is generated. TiO is added in consideration of easy formation of alloy of titanium and nickel to be contaminated 2 Is arranged in a hanging basket and immersed in the fused salt to avoid direct contact with Ca-Ni alloy. The method can work in a semi-continuous way, but the metal titanium, the Ca-Ni alloy and the molten salt coexist, so that the product is difficult to separate, and the equipment and the process are complicated.
Also, a liquid metal such as bismuth, zinc, etc. is used as a cathode, and titanium dioxide is electrolyzed by molten salt to produce a Bi-Ti or Zn-Ti alloy. However, it has been reported that the obtained bismuth alloy contains only 0.6 to 2.2at% of titanium, but 17.9 to 34.9at% of calcium. When liquid zinc is used, the cathode titanium content is said to be about 20%. However, the obtained alloy needs to be treated by electrolysis or distillation to obtain titanium.
It can thus be seen that the existing processes for the electrolytic production of titanium from titanium dioxide involve various problems to a different extent which need to be overcome, so that the Kroll process has hitherto been the major industrial process. Moreover, the above processes all have very stringent purity requirements for the titanium dioxide raw material used in order to obtain acceptable metallic titanium.
Disclosure of Invention
The invention aims to provide a method for preparing metal titanium by taking titanium dioxide as a raw material and adopting a molten salt electrolysis method, which has the advantages of low requirement on the titanium dioxide raw material, simple process, low energy consumption, environmental friendliness and capability of directly obtaining the metal titanium with higher purity.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing metallic titanium by reducing titanium dioxide through molten salt electrolysis is implemented by utilizing an electrolytic cell, wherein the electrolytic cell comprises an anode chamber and a cathode chamber, an anode molten salt electrolyte is contained in the anode chamber, an anode is inserted in the anode chamber, a cathode molten salt electrolyte is contained in the cathode chamber, a cathode is inserted in the cathode chamber, and a liquid alloy is also contained at the bottom in the electrolytic cell; the anode molten salt electrolyte and the cathode molten salt electrolyte are not contacted with each other and are connected through liquid alloy;
adding titanium dioxide into the anode chamber, electrifying the electrolytic cell to operate, reducing the titanium dioxide in the anode chamber into titanium atoms at the interface of the anode molten salt electrolyte and the liquid alloy and dissolving the titanium atoms into the liquid alloy, meanwhile, oxidizing the titanium atoms in the liquid alloy into titanium ions at the interface of the liquid alloy and the cathode molten salt electrolyte, allowing the titanium ions to enter the cathode molten salt electrolyte and reducing the titanium atoms on the surface of the cathode to form a metal titanium product.
According to the method for preparing the metallic titanium by reducing the titanium dioxide through molten salt electrolysis, the anode molten salt electrolyte and the cathode molten salt electrolyte are both halide molten salts. Preferably, the anode molten salt electrolyte consists of CaCl 2 、BaCl 2 And one or more of LiCl, naCl, KCl, csCl, liF, naF and KF. The cathode molten salt electrolyte consists of LiCl, naCl, KCl and CaCl 2 、MgCl 2 With TiCl 2 And/or TiCl 3 And (4) forming. The electrolytes of the cathode chamber and the anode chamber are all halides, the components of the electrolytes are common halides, and the electrolytes have certain solubility to low-valence titanium; the cathode chamber is selected to be chloride only in consideration of the influence on the titanium impurity deposited on the cathode.
According to the method for preparing the metallic titanium by reducing the titanium dioxide through molten salt electrolysis, the anode is graphite, and the cathode is stainless steel, tungsten or molybdenum. The anode is graphite and reacts with oxygen ions in the anode molten salt electrolyte to generate CO or CO 2 (ii) a The cathode is a high-temperature-resistant conductor.
According to the method for preparing the metallic titanium by reducing the titanium dioxide through molten salt electrolysis, the liquid alloy is formed by the solute metal Ti and the melt metal. The metal activity of the melt metal is lower than that of titanium, and the melt metal and the titanium form a low-melting-point alloy, the melting point of the alloy is lower than 1000 ℃, and specifically, the alloy can be an alloy consisting of one or more of Cu, sn, sb, zn, pb, bi and Ni.
When in work, solid titanium dioxide is added into the anode chamber, the area of the cathode electrode is 1 to 20 times of that of the anode electrode, and the solid titanium dioxide is continuously added under the condition of continuous operation at 0.05 to 2.0A/cm 2 The anode current density of (2) is controlled at a temperature of 400 to 1000 ℃. CO and CO are separated out at the anode 2 Gas, cathode deposition metallic titanium product. Furthermore, in order to improve the flatness of the cathode deposited titanium, in the electrolysis process, the reverse current accounting for 1-5% of the total electrolysis time is increased, so that the dense titanium deposited by the cathode is homogenized.
During electrolysis, the titanium dioxide in the anode chamber is reduced to titanium atoms at the interface of the anode molten salt electrolyte and the liquid alloy, and the titanium atoms are contacted with the liquid metal to be dissolved. Meanwhile, oxygen ions originally combined with titanium move to the anode under the drive of an electric field, and then lose electrons and are oxidized into zero-valent oxygen, and then the oxygen ions react with the anode to generate CO and CO 2 And (4) escaping. Meanwhile, titanium atoms in the liquid alloy on one side of the cathode chamber are oxidized into titanium ions at the interface of the liquid alloy and the cathode molten salt electrolyte, the titanium ions enter the cathode molten salt electrolyte and then move to the cathode under the driving of an electric field, and the obtained electrons are reduced into titanium atoms to form a metal titanium product. In the process of reducing the titanium in the anode chamber, metal which is more active than metal titanium is difficult to enter liquid alloy; in the titanium oxidation process of the cathode chamber, metal which is more inert than metal titanium is difficult to enter a cathode molten salt electrolyte, and finally a metal titanium product with higher purity is obtained by the cathode.
The invention has the beneficial effects that:
(1) The operability is strong. Titanium dioxide is added into the anode chamber, the current density in the electrolytic process is controlled, and titanium in liquid metal is supplemented in real time, so that titanium can be deposited at the cathode.
(2) The quality requirement of the raw materials is relaxed. The titanium dioxide raw material with certain impurity content can be adopted to produce the metallic titanium by electrolysis, which solves the problems of raw material purchase and production cost caused by the requirement of high-purity titanium dioxide raw material in the traditional electrolysis method.
(3) The purity of the product is ensured. Impurity ions with different electrochemical behaviors can be effectively controlled in the anode molten salt electrolyte or the liquid alloy, so that the purity of the prepared metallic titanium is high.
Drawings
FIG. 1 is a schematic cross-sectional view of an electrolytic cell according to an embodiment of the present invention;
wherein, 1-anode; 2-anodic molten salt electrolyte; 3-liquid alloy; 4-titanium dioxide inlet; 5-a cathode; 6-cathode molten salt electrolyte.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It should be apparent that the described embodiments are only some of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The method for preparing metallic titanium by reducing titanium dioxide through molten salt electrolysis is implemented by using an electrolytic cell shown in fig. 1, wherein a liquid alloy 3 is contained at the bottom in the electrolytic cell, the internal area of the electrolytic cell above the liquid alloy 3 is divided into an anode chamber and a cathode chamber by a partition plate, an anode molten salt electrolyte 2 is contained in the anode chamber and an anode 1 is inserted in the anode chamber, a cathode molten salt electrolyte 6 is contained in the cathode chamber and a cathode 5 is inserted in the cathode chamber, and the anode molten salt electrolyte 2 and the cathode molten salt electrolyte 6 are not in contact with each other and are connected through the liquid alloy 3.
Example 1
Anode molten salt electrolyte: caCl 2 Weighing 200g; cathode molten salt electrolyte: naCl and KCl were mixed in a mass ratio of 1:1 to 200g and 7.8wt% of titanium subchloride (TiCl) 2 :TiCl 3 4:1); preparing 400g of metal Cu, sn and Ti according to the mass ratio of 73;
the metal is put in an electrolytic bath and heated to 950 ℃ to be melted, and then the anode molten salt electrolyte and the cathode molten salt electrolyte are respectively added into a crucible to be melted. Graphite electrode is used as anode and stainless steel as cathode. Yang (Yang)When titanium dioxide is added into the electrode chamber at a constant speed, the current density of the anode is controlled to be 50mA/cm 2 (the area of the cathode electrode is 1 time of that of the anode electrode), and the electrolysis time is 24 hours;
supplementing 27g of metal titanium into the liquid metal, continuously maintaining the original current density for electrolysis, and continuously adding titanium dioxide into the anode chamber at a constant speed for 24 hours;
replenishing 27g of metal titanium into the liquid metal again, and continuously maintaining the concentration at 50mA/cm 2 Continuously adding titanium dioxide at a constant speed according to the current density, wherein the electrolysis time is 24 hours;
the cathode was taken out, and the mass of the cathode was weighed to obtain 138.3g of metallic titanium.
Example 2
Anode molten salt electrolyte: caCl 2 NaCl is prepared into 2kg according to the mass ratio of 54; cathode molten salt electrolyte: naCl and KCl were mixed in a mass ratio of 1:1 to 2kg and 8.7wt% of titanium subchloride (TiCl) 2 :TiCl 3 5:1); preparing 4kg of metal Sn and Ti according to a mass ratio of 90;
the metal is put in an electrolytic bath and heated to 900 ℃ to be melted, and then the anode molten salt electrolyte and the cathode molten salt electrolyte are respectively added into a crucible to be melted. Graphite electrode is used as anode and stainless steel as cathode. While adding industrial titanium dioxide into the anode chamber at constant speed, controlling the current density of the anode at 100mA/cm 2 (the area of the cathode electrode is 1 time of that of the anode electrode), and the electrolysis time is 12h;
supplementing 270g of metal titanium into the liquid metal, continuously maintaining the original current density for electrolysis, and continuously adding industrial titanium dioxide into the anode chamber at a constant speed for 12 hours;
supplementing 270g of metal titanium into the liquid metal again, and continuously maintaining the concentration at 100mA/cm 2 Continuously adding the industrial titanium dioxide into the anode chamber at constant speed according to the current density, wherein the electrolysis time is 12 hours;
the cathode was taken out and the mass of the cathode was weighed to obtain 1276.5g of metallic titanium.
Example 3
Anode molten salt electrolyte: caCl 2 KCl is prepared into 200g according to the mass ratio of 54; cathode molten salt electrolyte: naCl, KCl according to 11 preparing 200g of titanium subchloride (TiCl) and adding 11.3wt percent of titanium subchloride 2 ) (ii) a Preparing 4000g of metal Cu, sn and Ti according to the mass ratio of 23.5;
the metal is put in an electrolytic bath and heated to 700 ℃ for melting, and then the anode molten salt electrolyte and the cathode molten salt electrolyte are respectively added into a crucible for melting. Graphite electrode is used as anode and stainless steel as cathode. While adding industrial titanium dioxide into the anode chamber at constant speed, controlling the current density of the anode at 50mA/cm 2 (the area of the cathode electrode is 1 time of that of the anode electrode), and the electrolysis time is 24 hours;
supplementing 27g of metal titanium into the liquid metal, continuously maintaining the original current density for electrolysis, and continuously adding industrial titanium dioxide into the anode chamber at a constant speed for 24 hours;
27g of metallic titanium was added again to the liquid metal, and the mixture was kept at 50mA/cm 2 Continuously adding the industrial titanium dioxide into the anode chamber at a constant speed, wherein the electrolysis time is 24 hours;
the cathode was taken out and the mass of the cathode was weighed to obtain 145.39g of metallic titanium.
Example 4
Anode molten salt electrolyte: caCl 2 Weighing 200g; cathode molten salt electrolyte: naCl and KCl are mixed according to the proportion of 1:1 in a mass ratio of 200g and 10.6wt% of titanium subchloride (TiCl) 3 ) (ii) a Preparing 400g of metal Cu, sn and Ti according to the mass ratio of 73;
the metal is put in an electrolytic bath and heated to 950 ℃ to be melted, and then the anode molten salt electrolyte and the cathode molten salt electrolyte are respectively added into a crucible to be melted. Graphite electrode is used as anode and stainless steel as cathode. While titanium dioxide is added into the anode chamber at a constant speed, the current density of the anode is controlled to be 50mA/cm 2 (the area of the cathode electrode is 1 time of that of the anode electrode), and the electrolysis is stopped after the electrolysis time is 24 hours;
the cathode stainless steel plate was taken out. Connecting the corundum tube wrapped with the metal W rod with the liquid metal, contacting tungsten at the head of the corundum tube with the liquid metal, connecting tungsten at the tail of the corundum tube with a power supply, connecting an anode chamber electrode with a power supply anode, connecting the W rod with a cathode, and controlling the current density to be 50mA/cm 2 In the anode chamber, the mixture is uniformly addedAdding titanium dioxide, and stopping electrolysis after the electrolysis time is 24h.
Taking a graphite electrode as an anode and a stainless steel plate as a cathode, applying an electric field while adding titanium dioxide into the anode chamber at a constant speed, and controlling the current density to be 50mA/cm 2 And stopping electrolysis after 24 hours of electrolysis.
The cathode electrode was taken out, and the cathode deposit was weighed to obtain 84.4g of metallic titanium.
Example 5
Anode molten salt electrolyte: caCl 2 、BaCl 2 Preparing 200g according to the mass ratio of 35; cathode molten salt electrolyte: naCl200g was added and 9.3wt% of titanium subchlorides (TiCl) were added 2 、TiCl 3 1:1); preparing 400g of metal Cu, sn and Ti according to the mass ratio of 73;
the metal is put in an electrolytic bath and heated to 1000 ℃ for melting, and then the anode molten salt electrolyte and the cathode molten salt electrolyte are respectively added into a crucible for melting. Graphite electrode is used as anode and stainless steel as cathode. While titanium dioxide is added into the anode chamber at a constant speed, the current density of the anode is controlled to be 2000mA/cm 2 (the area of the cathode electrode is 1 time of that of the anode electrode), and the electrolysis is stopped after the electrolysis time is 1 h;
the cathode stainless steel plate was taken out. Connecting the corundum tube wrapped with the metal W rod with the liquid metal, wherein the tungsten at the head of the corundum tube is in contact with the liquid metal, the tungsten at the tail of the corundum tube is connected with a power supply, an anode chamber electrode is connected with a power supply anode, the W rod is connected with a cathode, and the current density is controlled to be 2000mA/cm 2 Adding titanium dioxide into the anode chamber at a constant speed, and stopping electrolysis after the electrolysis time is 1 h;
graphite electrode is used as anode, stainless steel plate is used as cathode, titanium dioxide is slowly added into the anode chamber, electric field is applied at the same time, and current density is controlled to be 2000mA/cm 2 Stopping electrolysis after 1 hour of electrolysis;
the cathode electrode was taken out, and the cathode deposition was weighed to obtain 60.3g of metallic titanium.
Example 6
Anode molten salt electrolyte: caCl 2 Preparing 200g of LiCl and NaCl according to the mass ratio of 8; cathode molten salt electrolyte: naCl and KCl are mixed according to the proportion of 1:1 in a mass ratio of 200g and 8.5wt% of titanium subchloride (TiCl) 2 、TiCl 3 3:1); preparing 400g of metal Cu and Ti according to the mass ratio of 3:1;
the metal is put in an electrolytic bath and heated to 950 ℃ to be melted, and then the anode molten salt electrolyte and the cathode molten salt electrolyte are respectively added into a crucible to be melted. Graphite electrode is used as anode and stainless steel as cathode. While titanium dioxide is added into the anode chamber at a constant speed, the current density of the anode is controlled to be 1000mA/cm 2 (the area of the cathode electrode is 10 times that of the anode electrode), and the electrolysis time is 2h;
supplementing 22g of metal titanium into the liquid metal, continuously maintaining the original current density for electrolysis, and continuously adding titanium dioxide into the anode chamber at a constant speed for 2 hours;
22g of metallic titanium is added into the liquid metal again, and the liquid metal is kept at 1000mA/cm 2 Continuously adding titanium dioxide into the anode chamber at constant speed with the current density of (2) for electrolysis;
the cathode was taken out, and the mass of the cathode was weighed to obtain 133.4g of metallic titanium.
Example 7
Anode molten salt electrolyte: caCl 2 Preparing 200g of LiCl and NaCl according to the mass ratio of 8; cathode molten salt electrolyte: naCl and KCl are prepared into 200g of the raw materials according to the mass ratio of 1:1, and 8 weight percent of low-valent titanium chloride (TiCl) is added 2 ) (ii) a Preparing 1000g of metal Sb and Ti according to a mass ratio of 96;
the metal is placed in an electrolytic bath, heated to 900 ℃ and melted, and then the anode molten salt electrolyte and the cathode molten salt electrolyte are respectively added into a crucible for melting. Graphite electrode is used as anode and stainless steel is used as cathode. Adding high titanium slag powder (TiO) into the anode chamber at constant speed 2 >94%) while controlling the anode current density to 50mA/cm 2 (the area of the cathode electrode is 20 times of that of the anode electrode), the electrolysis time is 24 hours, and the reverse current is increased for 1min every 29min in the electrolysis process;
supplementing 27g of metal titanium into the liquid metal, continuously maintaining the original current density for electrolysis, and continuously adding high titanium slag powder into the anode chamber at a constant speed for 24 hours;
27g of metallic titanium was added again to the liquid metal, and the mixture was kept at 50mA/cm 2 Continuously adding high titanium slag powder into the anode chamber at a constant speed according to the current density, wherein the electrolysis time is 24 hours;
the cathode was taken out, and the mass of the cathode was weighed to obtain 142.9g of metallic titanium.
Example 8
Anode molten salt electrolyte: caCl 2 Preparing 200g of LiCl according to the mass ratio of 54; cathode molten salt electrolyte: naCl and KCl were mixed in a mass ratio of 1:1 to 200g and 11.3wt% of titanium subchloride (TiCl) 2 ) (ii) a Preparing 4000g of metal Cu, sn and Ti according to the mass ratio of 23.5;
putting metal into an electrolytic cell, heating to 700 ℃ for melting, and respectively adding an anode molten salt electrolyte and a cathode molten salt electrolyte into a crucible for melting; graphite electrode is used as anode and stainless steel as cathode. While adding industrial titanium dioxide into the anode chamber at constant speed, controlling the current density of the anode at 50mA/cm 2 (the area of the cathode electrode is 1 time of that of the anode electrode), and the electrolysis time is 24 hours;
the circuit is disconnected, the corundum rod wrapping the metal wire is inserted into the liquid alloy, and the metal end is contacted with the liquid alloy; taking a graphite electrode of the anode chamber as an anode, connecting a metal lead to a cathode, and electrifying for 24 hours to enable the content of the metal titanium in the liquid alloy to reach the initial content; then taking out a corundum rod (internal metal wire) cathode, taking cathode chamber stainless steel as a cathode, maintaining the original current density for electrolysis, and continuously adding industrial titanium dioxide into the anode chamber at a constant speed for 24 hours;
27g of metallic titanium was added again to the liquid metal, and the mixture was kept at 50mA/cm 2 Continuously adding the industrial titanium dioxide into the anode chamber at a constant speed, wherein the electrolysis time is 24 hours;
the cathode was taken out and the mass of the cathode was weighed to obtain 145.39g of metallic titanium.
Example 9
Anode molten salt electrolyte: preparing 200g of LiCl and KCl according to the mass ratio of 45; cathode molten salt electrolyte: liCl and KCl were mixed in an amount of 200g and 2.3wt% of titanium subchloride (TiCl) in a mass ratio of 45 2 ) (ii) a The metal Sn and Ti are in accordance with 99.70.3 to prepare 4000g;
putting metal into an electrolytic bath, heating to 400 ℃ for melting, and respectively adding an anode molten salt electrolyte and a cathode molten salt electrolyte into a crucible for melting; graphite electrode is used as anode and tungsten is used as cathode. While adding industrial titanium dioxide into the anode chamber at constant speed, the current density of the anode is 0.05A/cm 2 (the cathode electrode area is 20 times the anode electrode area); and electrolyzing for 24 hours.
The circuit is disconnected, the corundum rod wrapping the metal wire is inserted into the liquid alloy, and the metal end is contacted with the liquid alloy; taking a graphite electrode of the anode chamber as an anode, connecting a metal lead to a cathode, and electrifying for 24 hours to enable the content of the metal titanium in the liquid alloy to reach the initial content; then taking out the cathode of the corundum rod (internal metal wire), taking stainless steel of the cathode chamber as the cathode, maintaining the original current density for electrolysis, and continuously adding industrial titanium dioxide into the anode chamber at a constant speed for 24 hours;
27g of metallic titanium was added again to the liquid metal, and the mixture was kept at 50mA/cm 2 Continuously adding the industrial titanium dioxide into the anode chamber at a constant speed, wherein the electrolysis time is 24 hours;
and taking out the cathode, and weighing the mass of the cathode to obtain the metal titanium.
Comparative example
Anode molten salt electrolyte: caCl 2 Weighing 200g; cathode molten salt electrolyte: naCl, KCl, tiCl 2 、TiCl 3 200g of titanium subchloride (TiCl) are prepared according to the mass ratio of 1:1 and 7.8wt percent of titanium subchloride is added 2 :TiCl 3 4:1); metals Cu and Sn were as follows 3:1, preparing 400g by mass;
the metal is put in an electrolytic bath and heated to 950 ℃ to be melted, and then the anode molten salt electrolyte and the cathode molten salt electrolyte are respectively added into a crucible to be melted. Graphite electrode is used as anode and stainless steel is used as cathode. When titanium dioxide is added into the anode chamber at a constant speed, the electrolysis time is 24 hours under the control of the current density (the area of a cathode electrode is 1 time of that of an anode electrode) which is the same as that of the embodiment;
the cathode metal titanium tin content is higher.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (7)
1. A method for preparing metallic titanium by reducing titanium dioxide through molten salt electrolysis is characterized in that,
the method is implemented by using an electrolytic cell, wherein the electrolytic cell comprises an anode chamber and a cathode chamber, an anode is inserted in the anode chamber, a cathode is inserted in the cathode chamber, a cathode molten salt electrolyte is inserted in the cathode chamber, and liquid alloy is also contained at the bottom in the electrolytic cell; the anode molten salt electrolyte and the cathode molten salt electrolyte are not contacted with each other and are connected through liquid alloy;
adding titanium dioxide into the anode chamber, electrifying the electrolytic cell to operate, reducing the titanium dioxide in the anode chamber into titanium atoms at the interface of the anode molten salt electrolyte and the liquid alloy and dissolving the titanium atoms into the liquid alloy, meanwhile, oxidizing the titanium atoms in the liquid alloy into titanium ions at the interface of the liquid alloy and the cathode molten salt electrolyte, allowing the titanium ions to enter the cathode molten salt electrolyte and reducing the titanium atoms on the surface of the cathode to form a metal titanium product.
2. The method of claim 1, wherein the anode molten salt electrolyte and the cathode molten salt electrolyte are both halide molten salts.
3. The method of claim 2, wherein the anode molten salt electrolyte is comprised of CaCl 2 、BaCl 2 And one or more of LiCl, naCl, KCl, csCl, liF, naF and KF.
4. The method of producing metallic titanium by reduction of titanium dioxide by molten salt electrolysis according to claim 2, wherein the method is characterized in thatThe cathode molten salt electrolyte consists of LiCl, naCl, KCl and CaCl 2 、MgCl 2 With TiCl 2 And/or TiCl 3 And (4) forming.
5. The method for producing metallic titanium by reduction of titania by molten salt electrolysis according to claim 1, wherein the anode is graphite and the cathode is a stainless steel, tungsten or molybdenum cathode.
6. The method for preparing metallic titanium by reducing titanium dioxide through molten salt electrolysis according to claim 1, wherein the liquid alloy is an alloy formed by solute metal Ti and molten metal, the metal activity of the molten metal is lower than that of titanium, the molten metal and the titanium form a low-melting-point alloy, the melting point of the alloy is lower than 1000 ℃, and the alloy is preferably an alloy formed by one or more of Cu, sn, sb, zn, pb, bi and Ni.
7. The method for preparing metallic titanium by reducing titanium dioxide through molten salt electrolysis according to claim 1, wherein the area of the cathode electrode is 1-20 times that of the anode electrode, and the current density of the anode is 0.05-2.0A/cm when the electrolysis cell is in normal operation 2 The temperature is 400-1000 ℃.
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Citations (4)
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|---|---|---|---|---|
| US2861030A (en) * | 1956-10-19 | 1958-11-18 | Timax Corp | Electrolytic production of multivalent metals from refractory oxides |
| GB855665A (en) * | 1956-05-18 | 1960-12-07 | Timax Corp | Improvements in or relating to processes for the electrolytic production of titaniummetal |
| CN104947152A (en) * | 2014-03-31 | 2015-09-30 | 湖南创元铝业有限公司 | Method for preparing high-purity titanium by fused-salt electrolytic refining |
| CN107475751A (en) * | 2017-09-22 | 2017-12-15 | 湖南金纯新材料有限公司 | A kind of device and method that pure titanium is prepared by the use of liquid alloy as electrode |
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2021
- 2021-05-08 CN CN202110499876.5A patent/CN115305516A/en active Pending
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| GB855665A (en) * | 1956-05-18 | 1960-12-07 | Timax Corp | Improvements in or relating to processes for the electrolytic production of titaniummetal |
| US2861030A (en) * | 1956-10-19 | 1958-11-18 | Timax Corp | Electrolytic production of multivalent metals from refractory oxides |
| CN104947152A (en) * | 2014-03-31 | 2015-09-30 | 湖南创元铝业有限公司 | Method for preparing high-purity titanium by fused-salt electrolytic refining |
| CN107475751A (en) * | 2017-09-22 | 2017-12-15 | 湖南金纯新材料有限公司 | A kind of device and method that pure titanium is prepared by the use of liquid alloy as electrode |
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| 莫畏等: "《钛冶金》", vol. 2, 30 June 1998, 冶金工业出版社, pages: 46 * |
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