CN117512708A - Method for green manufacturing of titanium alloy by molten salt continuous electrolysis - Google Patents
Method for green manufacturing of titanium alloy by molten salt continuous electrolysis Download PDFInfo
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- CN117512708A CN117512708A CN202311481415.0A CN202311481415A CN117512708A CN 117512708 A CN117512708 A CN 117512708A CN 202311481415 A CN202311481415 A CN 202311481415A CN 117512708 A CN117512708 A CN 117512708A
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- electrolysis
- titanium alloy
- argon environment
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- molten salt
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- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 127
- 238000000034 method Methods 0.000 title claims abstract description 75
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 65
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 150000003839 salts Chemical class 0.000 title claims abstract description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 126
- 229910052786 argon Inorganic materials 0.000 claims abstract description 60
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001816 cooling Methods 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000004321 preservation Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 230000008859 change Effects 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005275 alloying Methods 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001132 Ar alloy Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000010936 titanium Substances 0.000 description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 13
- 229910052719 titanium Inorganic materials 0.000 description 13
- 239000000956 alloy Substances 0.000 description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 7
- 238000003723 Smelting Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000004876 x-ray fluorescence Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009417 prefabrication Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001285 shape-memory alloy Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/36—Alloys obtained by cathodic reduction of all their ions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/005—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells for the electrolysis of melts
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
Landscapes
- 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 present application provides a method of manufacturing a titanium alloy comprising: mixing titanium dioxide, titanium alloy element to be manufactured and water, and sintering to obtain a preform; b, using the prefabricated body as a cathode body, and carrying out electrolysis with an anode body in a molten salt electrolysis tank under the protection of argon to obtain titanium alloy; c, taking out the titanium alloy, storing in an argon environment, and putting a cathode body to be used, which is pre-stored in the argon environment, into an electrolytic tank for next round of electrolysis; d, taking out the titanium alloy to be taken out from the argon environment for treatment after cooling, and putting a new cathode body into the argon environment for preservation for later use; e, taking out and storing in an argon environment when the anode body is consumed to the rest 20-30%, and putting the anode body to be used, which is stored in the argon environment in advance, into an electrolytic tank for the next round of electrolysis; repeating b-e. The method can realize batch electrolysis of each furnace to form closed-loop circulation continuous electrolysis without stopping furnace and reducing temperature, and part of raw materials can be recycled, thereby realizing continuous manufacturing of the prepared titanium alloy.
Description
Technical Field
The invention belongs to the technical field of electrolytic titanium, and particularly relates to a method for continuously electrolyzing molten salt to manufacture titanium alloy in a green way.
Background
The titanium alloy has the physical and chemical properties of special high temperature/low temperature resistance, corrosion resistance, high specific strength and the like, belongs to strategically advanced materials, is widely applied to the fields of aerospace, petrochemical industry, ships, medical treatment, construction and life, can be used as functional materials such as hydrogen storage materials, shape memory alloy materials and the like, and cannot be replaced in the important position of the high-end manufacturing field. According to the application scene and the technical route, the novel materials used in the military industry chain are mainly divided into three categories of high-temperature alloy, titanium alloy and carbon fiber. The prior art for manufacturing titanium alloy is to prepare pure titanium firstly, then put together pure titanium and intermediate alloy elements for remelting, and the process flow is long, complex, high in energy consumption and batch. The price of the titanium alloy is far higher than that of most structural metal materials and alloy materials due to the complex process flow, and the application amount and market range of the titanium alloy are greatly limited. Therefore, a new process technology for preparing the green titanium alloy by a short-process one-step in-place method with high efficiency and low energy consumption is urgently needed to be developed.
Disclosure of Invention
In view of the above, the invention aims to provide a green method for manufacturing titanium alloy by molten salt continuous electrolysis.
In the traditional titanium alloy smelting process, metallic titanium is required to be smelted firstly, and then intermediate alloy elements are added for secondary smelting, so that the problems of complex working procedure, long process flow, higher energy consumption, lower efficiency and the like are solved. The invention provides a technological method for manufacturing titanium alloy in one step, which has the advantages of short technological process, simple operation and high efficiency, is a novel process for directly preparing the titanium alloy by solid electrolysis after mixing titanium dioxide with intermediate alloy of the prepared titanium alloy or oxide mixture thereof and other raw materials based on a molten salt solid deoxidation method, and has better balance in the aspects of compact technological process, improved electrolysis efficiency, capability adjustment flexibility and the like; the whole process avoids the links of chlorine reduction and the like in the titanium manufacturing process, and greatly reduces pollution.
The application provides a method for green manufacturing of titanium alloy by molten salt continuous electrolysis, which comprises the following steps:
step a), mixing titanium dioxide, titanium alloy elements to be manufactured and water, and sintering to obtain a preform;
step b), the prefabricated body is taken as a cathode body, electrolysis is carried out on the prefabricated body and an anode body in a molten salt electrolysis tank under the protection of argon, and titanium alloy is obtained by dynamically adjusting electrolysis voltage;
step c), taking out the titanium alloy, storing in an argon environment, and putting a standby cathode body which is pre-stored in the argon environment into an electrolytic tank for the next round of electrolysis;
step d), taking out the titanium alloy to be taken out from the argon environment for treatment after cooling, and putting a new cathode body into the argon environment for preservation for later use;
step e), taking out and storing in an argon environment when the anode body is consumed to the rest 20-30%, and putting the anode body to be used, which is stored in the argon environment in advance, into an electrolytic tank for the next round of electrolysis;
repeating steps b) to e).
In some specific implementations, the alloying element is selected from one or more of iron, manganese, tungsten, aluminum, vanadium, nickel, nitrogen, tin, zinc, niobium, molybdenum, chromium, copper, silicon, zirconium, palladium, and the like.
In some specific implementations, in step a), the sintering atmosphere is vacuum or argon; the sintering temperature is 300-900 ℃; the sintering time is 0.5-3.0 hours.
In some specific implementations, the anode body is graphite.
In some specific implementations, the molten salt in the molten salt electrolysis cell is chloride molten salt.
In some specific embodiments, the chloride is selected from CaCl 2 、LiCl、BaCl 2 One or more of NaCl and KCl.
In some specific implementations, in the step b), the voltage of the electrolysis is 3 to 9V; the temperature of the electrolysis is 800-1100 ℃; the electrolysis time is 9-36 hours.
In some specific implementations, the method of dynamically adjusting the electrolysis voltage includes:
in the electrolysis process, electrolysis current is observed every 10-60 minutes, and the electrolysis voltage is adjusted according to the change degree of the electrolysis current.
In some specific implementations, the method of cooling is selected from manual cooling and/or natural cooling; and the temperature is reduced to be close to the room temperature.
In some specific implementations, in step d), the treatment is specifically a washing treatment with dilute acid.
The method provided by the invention adopts an argon environment, the cathode body and the anode body for the next round of electrolysis are stored in the argon environment, and the cathode body for the next round of electrolysis is directly transferred into an electrolytic tank for continuous electrolysis after the previous round of electrolysis is finished, so that the furnace does not need to be stopped; and the titanium alloy after the previous round of electrolysis is preserved in an argon environment, is taken out after being cooled to room temperature, is continuously put into a new cathode body for standby in the argon environment, is taken out and preserved in the argon environment when the anode body is consumed to the rest of 20-30%, and is put into an electrolytic tank for the next round of electrolysis. By repeating the steps, each furnace batch is electrolyzed without stopping the furnace, thus forming closed-cycle continuous electrolysis, and molten salt can be recycled, thus realizing continuous electrolysis green manufacture of directly obtaining titanium alloy by electrolyzing titanium dioxide and titanium alloy elements in one step, further greatly improving the production efficiency and reducing the production cost of the titanium alloy.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a method for continuously electrolyzing molten salt to manufacture titanium alloy in green mode, which comprises the following steps:
step a), mixing titanium dioxide, titanium alloy elements to be manufactured and water, and sintering to obtain a preform;
step b), the prefabricated body is taken as a cathode body, electrolysis is carried out on the prefabricated body and an anode body in a molten salt electrolysis tank under the protection of argon, and titanium alloy is obtained by dynamically adjusting electrolysis voltage;
step c), taking out the titanium alloy, storing in an argon environment, and putting a standby cathode body which is pre-stored in the argon environment into an electrolytic tank for the next round of electrolysis;
step d), taking out the titanium alloy to be taken out from the argon environment for treatment after cooling, and putting the titanium alloy into a cathode body in the argon environment for preservation for later use;
step e), taking out and storing in an argon environment when the anode body is consumed to the rest 20-30%, and putting the anode body to be used, which is stored in the argon environment in advance, into an electrolytic tank for the next round of electrolysis;
repeating steps b) to e).
The technical scheme of the invention is characterized in that the steps b) to e) are connected together to form a closed cycle, the continuous electrolysis is performed without stopping the furnace, the molten salt is not required to be cooled, the molten salt is recycled, the energy is saved, the efficiency is improved, the process that pure titanium is required to be manufactured first for manufacturing the titanium alloy is omitted, and the green manufacturing of the titanium alloy by one-step in-place continuous electrolysis of the cycle of all furnace batch electrolysis except prefabrication and cleaning is realized.
Firstly, mixing titanium dioxide, prepared titanium alloy elements and water, and then sintering to obtain a preform. In some specific implementations, the water is preferably deionized water; the titanium dioxide is preferably titanium dioxide.
In some specific implementations, the alloying elements include, but are not limited to, iron, manganese, tungsten, aluminum, vanadium, nickel, nitrogen, tin, zinc, niobium, molybdenum, chromium, copper, silicon, zirconium, palladium, and the like, and may be one or more thereof. In some specific implementations, the alloying element material may be elemental alloying element and/or an oxide of alloying element, such as Al 2 O 3 、V 2 O 3 、Al、V、V 2 O 5 Etc.
In the invention, the proportion of the titanium dioxide to the alloy element material is proportioned according to the content proportion of the alloy element of the prepared titanium alloy and the specification or standard.
In the present invention, the ratio of the total mass of the titanium dioxide to the alloy element material to the mass of water is preferably 1 (1-10), more preferably 1 (1-8), still more preferably 1 (1-6), and most preferably 1 (1-3).
In the present invention, the mixing preferably further comprises: modeling; the shaping is preferably carried out by extrusion or casting; the shape after the modeling is preferably a cylinder, a sphere or a plate.
In the invention, the sintering environment is vacuum or argon, and the sintering temperature is preferably 300-900 ℃, preferably 400-800 ℃, more preferably 500-700 ℃; the sintering time is preferably 0.5 to 3.0 hours.
In the present invention, the preform is preferably columnar, the diameter of the columnar is preferably 2 to 10mm, and the length is preferably 30 to 100mm; the preform is preferably plate-shaped; the thickness of the plate is preferably 2-12 mm, the width is preferably 10-100 mm, and the length is preferably 30-300 mm; the preform is preferably spherical; the diameter of the sphere is preferably 2 to 12mm.
And after the prefabricated body is obtained, the prefabricated body is taken as a cathode body, and is electrolyzed with an anode body in a molten salt electrolyzer under the protection of argon, and the titanium alloy is obtained by dynamically adjusting the electrolysis voltage. In some specific implementations, the molten salt is preferably selected from chloride molten salts, more preferably selected from CaCl 2 、LiCl、BaCl 2 One or more of NaCl and KCl, preferably CaCl 2 One or more of KCl and NaCl.
In the present invention, the cathode body preferably further includes an iron plate; preferably, the prefabricated body and the iron plate are fixed together by iron wires or iron nets to be used as a cathode body; the length of the iron plate is preferably 30-1000 mm, more preferably 100-800 mm, and most preferably 300-500 mm; the width is preferably 20 to 1000mm, more preferably 100 to 900mm, most preferably 500 to 800mm; the thickness is preferably 2 to 12mm, more preferably 5 to 10mm, most preferably 5 to 8mm.
In the present invention, the anode body is preferably a graphite rod or a graphite plate; the length of the graphite plate is preferably 300-1500 mm, more preferably 300-1200 mm, and most preferably 500-800 mm; the width is preferably 20 to 500mm, more preferably 50 to 500mm, most preferably 200 to 400mm; the thickness is preferably 10 to 70mm, more preferably 20 to 70mm, most preferably 30 to 50mm.
In the present invention, the cathode body and the anode body are preferably placed in an electrolytic cell containing molten salt for electrolysis, preferably under the protection of argon; the electrolysis is performed under the protection of argon.
In the present invention, the temperature of the electrolysis is preferably 800 to 1100 ℃, more preferably 900 to 950 ℃; the electrolysis voltage is preferably 3-9V, and the electrolysis voltage is preferably dynamically adjusted in the electrolysis process; the electrolysis time is preferably 9 to 36 hours, more preferably 15 to 30 hours, and most preferably 16 to 24 hours.
In the present invention, the method of dynamically adjusting voltage preferably includes:
in the electrolysis process, electrolysis current is observed every 10-60 minutes, and the electrolysis voltage is adjusted according to the change degree of the electrolysis current.
In the present invention, the electrolysis current is preferably observed every 20 to 40 minutes, more preferably every 30 minutes.
In the invention, the dynamic voltage is preferably adjusted in time in the electrolysis process according to the intensity of the dynamic change of the current, so that the current is in a state of slowly changing rather than severely jumping to exceed the previous value by 30%.
In the present invention, the method of dynamically adjusting the electrolytic voltage more preferably includes:
observing the electrolysis current every 10-60 minutes in the electrolysis process, and adjusting the electrolysis voltage according to the increase of 0.1-0.5V when the variation amplitude of the electrolysis current does not exceed 30% of the original current (the last electrolysis current); when the change in the electrolysis current exceeds 30% of the original current (last electrolysis current), the electrolysis voltage is adjusted to the last electrolysis voltage.
In the present invention, the electrolytic voltage increase is preferably adjusted to 0.1 to 0.3V, more preferably to 0.3V.
In the present invention, the electrolytic current and voltage during the electrolysis can be observed through the meter display.
In the present invention, it is preferable to transfer the titanium alloy cathode body into an argon atmosphere; and the cathode body and the anode body are placed in the argon environment in advance, and the cathode body placed in advance is placed in an electrolytic tank for the next round of electrolysis.
In the present invention, the argon ambient cooling method is preferably selected from artificial cooling and/or natural cooling; the cooling is preferably near room temperature; the time of the cooling is preferably determined based on the meter display temperature.
In the invention, after the cooling is finished, the titanium alloy is taken out of the argon environment, and a group of new cathode bodies are put into the argon environment for standby, and the cycle is carried out once per electrolysis cycle.
In the invention, when the anode body is consumed to the rest of 20-30%, the anode body is taken out and stored in an argon environment, and the anode body to be used, which is stored in the argon environment in advance, is put into an electrolytic tank for the next round of electrolysis.
In the invention, the titanium alloy is preferably cleaned after being taken out, so as to obtain clean titanium alloy; the cleaning is preferably performed by adopting dilute acid and clear water; the dilute acid is preferably selected from dilute sulfuric acid, dilute hydrochloric acid or dilute acetic acid.
The method provided by the invention can effectively improve the efficiency and avoid secondary energy consumption caused by the processes of firstly manufacturing pure titanium, mixing the pure titanium with titanium alloy elements, then secondarily smelting, and cooling and reheating in the process of preparing titanium alloy in batches by using the electrolytic cell. Meanwhile, the adoption of the real-time dynamic electrolytic voltage adjustment process can realize flexible adjustment of productivity under the condition that main production equipment and basic process parameters are not changed greatly. The method provided by the invention has better balance in the aspects of compact process flow, pollutant generation control, electrolysis efficiency improvement, capacity dynamic adjustment capability and the like, and fills up the short plates in the aspects of complex process, long flow, low efficiency, higher cost and the like in the titanium alloy manufacturing field.
The method for green production of titanium alloy by continuous electrolysis of molten salt provided in the present application will be described in detail with reference to examples.
Example 1
30g of titanium dioxide are taken and 2.3g of Al are added 2 O 3 And 1.15gV 2 O 3 And 35g deionized water are uniformly stirred and extruded into a diameter<Drying strips with the diameter of 10mm, putting the strips into a vacuum sintering furnace for sintering at 700 ℃ for 1.5 hours, naturally cooling, taking out the strips, putting the strips into an alumina crucible, and connecting the strips with an iron rod to serve as electrodes; simultaneously, a carbon rod with the diameter of 15mm and the length of 300mm is put into the carbon rod as an electrode, 2kg of anhydrous calcium chloride is added, then the carbon rod is put into an electrolytic electric furnace with the protection of argon environment for sealing, the temperature is raised to 900 ℃ for electrolysis, the adjustment range of the electrolytic voltage is 3.1-4.4V, the voltage is dynamically adjusted in the electrolysis process, the electrolytic current is observed every 30 minutes in the electrolysis process, and when the change amplitude of the electrolytic current does not exceed 30% of the original current (the last electrolytic current), the electrolytic voltage is adjusted according to the increase of 0.1V; when the change of the electrolysis current exceeds 30% of the original current (last electrolysis current), adjusting the electrolysis voltage to the last electrolysis voltage; after electrolysis for 24 hours, taking out the cathode after electrolysis, putting the cathode into an argon environment, and transferring the cathode pre-stored in the argon environment into an alumina crucible for continuous electrolysis; taking out the cathode after the last electrolysis when the argon environment is naturally cooled to be close to the room temperature, putting a group of new cathodes for standby, and cleaning the taken-out cathode by dilute hydrochloric acid to obtain clean titanium alloy; and taking out the anode body and storing the anode body in an argon environment when the anode body is consumed to the rest 20-30%, and putting the anode body to be used, which is stored in the argon environment in advance, into an electrolytic tank for the next round of electrolysis.
The titanium alloy TC4 (Ti 6Al 4V) prepared in example 1 of the invention is gray, shows metallic luster after polishing, and is sampled and subjected to X-ray fluorescence spectrum detection analysis, wherein the oxygen content is 1150ppm, the titanium content is 90.23wt%, the Al content is 6.08wt% and the vanadium content is 3.69wt%.
Example 2
16g of titanium dioxide is taken and 1.17g of Al is added 2 O 3 And 0.6gV 2 O 3 And 20g of deionized water are uniformly stirred and extruded into a diameter<10mm strips, dried and placed in argonSintering in a gas sintering furnace at 600 ℃ for 2 hours, naturally cooling, taking out, putting the gas sintering furnace into a graphite crucible, connecting the graphite crucible with an iron rod to serve as an electrode, putting a carbon rod with the diameter of 10mm and the length of 300mm as a counter electrode, adding 1.5kg of anhydrous calcium chloride and 450g of anhydrous potassium chloride, putting the carbon rod into an electrolytic furnace in an argon protection environment to be sealed, heating to 810 ℃ to start electrolysis, adjusting the electrolytic voltage to 3.2-4.7V, dynamically adjusting the voltage in the electrolytic process, observing the electrolytic current every 20 minutes in the electrolytic process, and adjusting the electrolytic voltage according to 0.2V when the change amplitude of the electrolytic current does not exceed 30% of the original current (the last electrolytic current); when the change of the electrolysis current exceeds 30% of the original current (last electrolysis current), adjusting the electrolysis voltage to the last electrolysis voltage; after electrolysis for 16 hours, taking out the cathode after electrolysis, storing the cathode in an argon environment, and transferring the cathode stored in the argon environment into a graphite crucible for continuous electrolysis; taking out the cathode after the last electrolysis when the argon environment is naturally cooled to be close to the room temperature, putting a group of new cathodes and anodes for standby, and cleaning the taken-out cathodes by dilute hydrochloric acid to obtain clean titanium alloy; and taking out the anode body and storing the anode body in an argon environment when the anode body is consumed to the rest 20-30%, and putting the anode body to be used, which is stored in the argon environment in advance, into an electrolytic tank for the next round of electrolysis.
The titanium alloy prepared in the embodiment 2 of the invention is spongy, is silver gray metal luster after polishing, is sampled and subjected to X-ray fluorescence spectrum detection analysis, and has the main indexes of 1701ppm of oxygen, 88.95wt% of titanium, 5.85wt% of Al and 5.20wt% of V.
Example 3
100g of titanium dioxide is taken and 7.6g of Al is added 2 O 3 And 4.17gV 2 O 5 And 150g of deionized water are uniformly stirred and extruded into a thickness<Drying a plate with the length of 5mm and the width of 100mm and with the width of 50mm, putting the plate into a vacuum sintering furnace for sintering at 900 ℃ for 2 hours, naturally cooling, taking out, putting the plate into a carbon steel crucible, connecting the plate with an iron plate to be used as an electrode, simultaneously putting a carbon plate with the thickness of 10mm and the length of 200mm and the width of 30mm into the plate to be used as a counter electrode, adding 5kg of anhydrous calcium chloride and 0.3 kg of anhydrous sodium chloride, and putting the plate into the vacuum sintering furnace togetherIn an electrolytic electric furnace protected by argon environment, heating to 930 ℃ to start electrolysis, wherein the adjustment range of the electrolysis voltage is 3.3-5.1V, dynamically adjusting the voltage in the electrolysis process, observing the electrolysis current every 10 minutes in the electrolysis process, and adjusting the electrolysis voltage according to the increase of 0.1V when the change amplitude of the electrolysis current does not exceed 30% of the original current (the last electrolysis current); when the change of the electrolysis current exceeds 30% of the original current (last electrolysis current), adjusting the electrolysis voltage to the last electrolysis voltage; after 27 hours of electrolysis, taking out the cathode body after electrolysis, transferring the cathode body into an argon environment, and transferring the cathode stored in the argon environment into a crucible for continuous electrolysis; and taking out the cathode after the last electrolysis when the argon environment is manually cooled to be close to the room temperature, putting a group of new anode bodies and cathode bodies for standby, taking out the anode bodies stored in the argon environment when the electrolysis is circulated until the anode is consumed to the rest of 20-30%, putting the standby anode bodies stored in the argon environment into an electrolytic tank, and then carrying out the next round of electrolysis.
The titanium alloy plate prepared in example 3 of the invention is gray black, metallic luster appears by polishing and extrusion, the main indexes of the titanium alloy plate are sampled and subjected to X-ray fluorescence spectrum detection analysis, the oxygen content is 1531ppm, the titanium content is 89.44wt%, the Al content is 6.25wt% and the V content is 4.31wt%.
The method adopts real-time dynamic voltage adjustment in the process of preparing the titanium alloy, has higher efficiency compared with constant voltage, obtains higher purity of the titanium alloy, has shorter time for preparing the titanium alloy, can improve the production efficiency, reduce the energy consumption, can effectively control the generation of pollutants to further reduce the pollution, and realizes flexible adjustment of the productivity under the condition that main production equipment and basic process parameters are not changed greatly; the process of manufacturing pure titanium and then mixing the pure titanium with titanium alloy elements for secondary smelting in the traditional technology is omitted, and the process flow is greatly reduced; the secondary energy consumption and batch raw material loss caused by the cooling and reheating processes in the batch titanium alloy manufacturing process of the electrolytic tank are avoided; effectively controls and greatly reduces the production of pollutants and realizes green manufacture. Is especially suitable for industrial mass production and manufacture. The method provided by the invention has better balance in the aspects of compact process flow, reduced energy consumption, improved electrolysis efficiency, dynamic capacity adjustment capability, pollution control and the like, and the method provided by the invention has better balance in the aspects of compact process flow, green manufacture, namely pollutant generation control, improved electrolysis efficiency, dynamic capacity adjustment capability, cyclic use of raw materials, greatly reduced production cost, reduced frequent heating, energy conservation, consumption reduction and the like. The short plates in the aspects of complex process flow, heavy secondary smelting burden, discontinuous batch production in a furnace, incapability of recycling raw materials and the like in the field of titanium alloy smelting are filled.
While the invention has been described and illustrated with reference to specific embodiments thereof, the description and illustration is not intended to limit the invention. It will be apparent to those skilled in the art that various changes may be made in this particular situation, material, composition of matter, substance, method or process without departing from the true spirit and scope of the invention as defined by the following claims, so as to adapt the objective, spirit and scope of the present application. All such modifications are intended to be within the scope of this appended claims. Although the methods disclosed herein have been described with reference to particular operations being performed in a particular order, it should be understood that these operations may be combined, sub-divided, or reordered to form an equivalent method without departing from the teachings of the present disclosure. Thus, unless specifically indicated herein, the order and grouping of operations is not a limitation of the present application.
Claims (10)
1. A method for green manufacturing of titanium alloy by molten salt continuous electrolysis, comprising the following steps:
step a), mixing titanium dioxide, titanium alloy elements to be manufactured and water, and sintering to obtain a preform;
step b), the prefabricated body is taken as a cathode body, electrolysis is carried out on the prefabricated body and an anode body in a molten salt electrolysis tank under the protection of argon, and titanium alloy is obtained by dynamically adjusting electrolysis voltage;
step c), taking out the titanium alloy, storing in an argon environment, and putting a standby cathode body which is pre-stored in the argon environment into an electrolytic tank for the next round of electrolysis;
step d), taking out the titanium alloy to be taken out from the argon environment for treatment after cooling, and putting a new cathode body into the argon environment for preservation for later use;
step e), taking out and storing in an argon environment when the anode body is consumed to the rest 20-30%, and putting the anode body to be used, which is stored in the argon environment in advance, into an electrolytic tank for the next round of electrolysis;
repeating steps b) to e).
2. The method according to claim 1, wherein the alloying element is selected from one or more of iron, manganese, tungsten, aluminum, vanadium, nickel, nitrogen, tin, zinc, niobium, molybdenum, chromium, copper, silicon, zirconium, palladium.
3. The method according to claim 1, wherein in step a), the sintering atmosphere is vacuum or argon; the sintering temperature is 300-900 ℃; the sintering time is 0.5-3.0 hours.
4. The method of claim 1, wherein the anode body is graphite.
5. The method of claim 1, wherein the molten salt in the molten salt electrolysis cell is a chloride molten salt.
6. The method of claim 5, wherein the chloride is selected from the group consisting of CaCl 2 、LiCl、BaCl 2 One or more of NaCl and KCl.
7. The method according to claim 1, wherein in step b), the voltage of the electrolysis is 3 to 9V; the temperature of the electrolysis is 800-1100 ℃; the electrolysis time is 9-36 hours.
8. The method of claim 1, wherein the method of dynamically adjusting the electrolytic voltage comprises:
in the electrolysis process, electrolysis current is observed every 10-60 minutes, and the electrolysis voltage is adjusted according to the change degree of the electrolysis current.
9. The method according to claim 1, wherein the method of cooling is selected from manual cooling and/or natural cooling; and the temperature is reduced to be close to the room temperature.
10. The method according to claim 1, characterized in that in step d) the treatment is performed, in particular a washing treatment with dilute acid.
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