CN113860362B - Electrochemical preparation vanadium removal reagent and titanium tetrachloride vanadium removal method thereof - Google Patents
Electrochemical preparation vanadium removal reagent and titanium tetrachloride vanadium removal method thereof Download PDFInfo
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- CN113860362B CN113860362B CN202111231361.3A CN202111231361A CN113860362B CN 113860362 B CN113860362 B CN 113860362B CN 202111231361 A CN202111231361 A CN 202111231361A CN 113860362 B CN113860362 B CN 113860362B
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 80
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 29
- VZVLQKOGWNLVAC-UHFFFAOYSA-J tetrachlorotitanium vanadium Chemical compound [V].Cl[Ti](Cl)(Cl)Cl VZVLQKOGWNLVAC-UHFFFAOYSA-J 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 106
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 73
- 239000003792 electrolyte Substances 0.000 claims abstract description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 15
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 7
- 238000005192 partition Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 6
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 claims description 6
- 239000010962 carbon steel Substances 0.000 claims description 6
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000007670 refining Methods 0.000 abstract description 4
- 239000007790 solid phase Substances 0.000 abstract description 4
- 238000004070 electrodeposition Methods 0.000 abstract description 2
- 239000013589 supplement Substances 0.000 abstract 1
- 238000009835 boiling Methods 0.000 description 16
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 16
- 238000005660 chlorination reaction Methods 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QLOKAVKWGPPUCM-UHFFFAOYSA-N oxovanadium;dihydrochloride Chemical compound Cl.Cl.[V]=O QLOKAVKWGPPUCM-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000009870 titanium metallurgy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/02—Halides of titanium
- C01G23/022—Titanium tetrachloride
- C01G23/024—Purification of tetrachloride
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/06—Electrolytic production, recovery or refining of metals by electrolysis of melts of aluminium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
A titanium tetrachloride vanadium removal method for electrochemically preparing a vanadium removal reagent comprises the following steps: step 1, electrolyzing graphite serving as an anode and conductive metal serving as a cathode in an electrolytic cell containing an electrolyte system with aluminum chloride to obtain metal aluminum; step 2, introducing vanadium-containing crude titanium tetrachloride into an electrolytic aluminum chloride-containing electrolyte system for vanadium removal; and 3, collecting the evaporated titanium tetrachloride to obtain the titanium tetrachloride after vanadium removal. The method can realize the supplement of the electrolyte aluminum chloride through the aluminum chloride impurities in the crude titanium tetrachloride, and simultaneously can remove the ferric chloride impurities in the crude titanium tetrachloride through electrochemical deposition, thereby being beneficial to realizing the clean production of refining the titanium tetrachloride and the recycling of solid phase substances.
Description
Technical Field
The invention relates to the field of titanium metallurgy, in particular to an electrochemical preparation vanadium removal reagent and a titanium tetrachloride vanadium removal method thereof.
Background
Titanium tetrachloride is an intermediate raw material for producing titanium dioxide and titanium sponge, the current industrial production methods of titanium tetrachloride can be divided into a boiling chlorination method and a molten salt chlorination method according to the furnace type, the boiling chlorination method is a method for preparing titanium tetrachloride by suspending titanium-containing materials and petroleum coke in a fluidized state through chlorine gas and performing chlorination reaction at high temperature, the enterprises in the United states, japan, china and the like all adopt a boiling chlorination technology at present, but the technology has high requirements on raw materials, and particularly has strict requirements on the content of calcium and magnesium impurities (MgO + CaO is less than or equal to 1.5 wt%); the molten salt chlorination is to directly add chlorine, titanium-containing materials and petroleum coke into a molten salt medium, realize chlorination of the titanium-containing materials under the action of strong stirring of the chlorine, has the advantages of strong raw material adaptability, good crude titanium quality and the like, is particularly suitable for treating low-grade titanium raw materials which cannot be treated by boiling chlorination, and is widely applied to enterprises such as an independent body, china and the like. However, no matter the crude titanium tetrachloride is produced by boiling chlorination or molten salt chlorination, the crude titanium tetrachloride contains certain impurities,can be divided into three types of impurities with high boiling point, low boiling point and similar boiling point according to the difference of boiling points, wherein the impurities with high boiling point are FeCl 3 、AlCl 3 Etc. can be removed by distillation, etc., and low boiling point substances such as SiCl 4 、CS 2 Etc. can be removed by distillation, while the boiling point is close to that of VOCl 3 And the like, need to be chemically removed.
At present, the vanadium and H removal mode of crude titanium tetrachloride in the industry mainly comprises the vanadium and H removal of copper wires 2 S vanadium removal, organic vanadium removal and aluminum powder vanadium removal 4 types, wherein the copper wire vanadium removal is quit from production due to factors such as large environmental pollution, difficult copper wire regeneration and the like. H 2 S vanadium removal is only mastered by Japan at present due to factors such as large equipment corrosion, high environmental protection requirement and the like, organic vanadium removal has the advantages of simple operation, low raw material cost and the like, and is adopted by most enterprises in Japan, america and China, but partial organic impurities can enter fine titanium tetrachloride to cause the carbon content in the product to exceed the standard; the aluminum powder is subjected to vanadium removal by high-temperature reaction of the aluminum powder and titanium tetrachloride to prepare low-valence titanium ore pulp, and then the low-valence titanium ore pulp is reacted with coarse titanium tetrachloride to obtain VOCl 3 Reduced to VOCl with high boiling point 2 The technology is adopted by the independent countries and some enterprises in China at present, and has the advantages of stable quality of titanium tetrachloride, low organic impurities and the like. But compared with the vanadium removal process of organic matters, the vanadium removal process of aluminum powder has the defects of high vanadium removal cost, complex working procedures and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a vanadium removal reagent prepared by electrochemistry and a titanium tetrachloride vanadium removal method thereof, which realize the clean production of titanium tetrachloride refining and the recycling of solid phase substances.
In order to achieve the purpose, the invention provides the technical scheme that:
a titanium tetrachloride vanadium removal method for electrochemically preparing a vanadium removal reagent comprises the following steps:
step 1, electrolyzing graphite serving as an anode and conductive metal serving as a cathode in an electrolytic cell containing an electrolyte system with aluminum chloride to obtain metal aluminum;
step 2, introducing vanadium-containing crude titanium tetrachloride into an electrolytic aluminum chloride-containing electrolyte system for vanadium removal;
and 3, collecting the evaporated titanium tetrachloride to obtain the titanium tetrachloride after vanadium removal.
Furthermore, the electrolytic cell is divided into an anode region and a cathode region by a partition wall, wherein graphite constitutes the anode region, and conductive metal constitutes the cathode region.
Further, the conductive metal is one of carbon steel, molybdenum and tungsten.
Further, the electrolyte system with aluminum chloride is a molten salt system composed of aluminum chloride and an alkali metal chloride or an alkaline earth metal chloride.
Further, the electrolysis reaction in the step 1 and the vanadium removal reaction in the step 2 are carried out in a protective atmosphere, wherein the protective atmosphere is one or more of argon, nitrogen and helium.
Further, in step 2, crude titanium tetrachloride containing vanadium is passed into the electrolyte system of the cathode region.
Further, in step 2, the feeding speed of the vanadium-containing crude titanium tetrachloride into the electrolytic system with aluminum chloride is carried out according to the molar ratio of vanadium oxychloride in the vanadium-containing crude titanium tetrachloride to metallic aluminum generated at the cathode being less than or equal to 3.
Further, in step 1, the electrolysis voltage for electrolysis is 2.5 to 4.0V.
Further, in step 1, the electrolysis temperature for the electrolysis is 140 to 440 ℃.
The electrochemically prepared vanadium removal reagent comprises aluminum chloride and alkali metal chloride or alkaline earth metal chloride.
The invention has the beneficial effects that:
the electrochemical preparation vanadium removal reagent provided by the invention overcomes the technical problems of large raw material loss, high cost and the like of the traditional vanadium removal reagent. The titanium tetrachloride vanadium-removing method for electrochemically preparing the vanadium-removing reagent of the invention adopts AlCl in crude titanium tetrachloride 3 The impurities can realize the AlCl electrolyte 3 In addition, at the same time, the material can also be removed by electrochemical depositionRemoval of FeCl from crude titanium tetrachloride 3 Impurities are beneficial to realizing the clean production of titanium tetrachloride refining and the recycling of solid phase substances, and the method has stronger popularization and application prospects.
Drawings
FIG. 1 shows a schematic flow diagram of a titanium tetrachloride vanadium removal process for electrochemically preparing a vanadium removal reagent according to the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
The titanium tetrachloride vanadium removal method for electrochemically preparing the vanadium removal reagent, disclosed by the invention, comprises the following steps as shown in figure 1:
step 1, electrolyzing graphite serving as an anode and conductive metal serving as a cathode in an electrolytic cell containing an electrolyte system with aluminum chloride to obtain metal aluminum;
step 2, introducing vanadium-containing crude titanium tetrachloride into an electrolytic aluminum chloride-containing electrolyte system for vanadium removal;
and 3, collecting the evaporated titanium tetrachloride to obtain the titanium tetrachloride after vanadium removal.
The invention relates to a titanium tetrachloride vanadium removal method for electrochemically preparing a vanadium removal reagent, wherein an electrolytic cell is divided into an anode area and a cathode area by a partition wall, wherein graphite forms the anode area, conductive metal forms the cathode area, the graphite is connected with a direct current power supply anode, and the conductive metal is connected with the direct current power supply cathode. The conductive metal can be carbon steel, molybdenum, tungsten and the like, and carbon steel is preferred. In one embodiment, the electrolytic cell is a retort.
Due to aluminum chloride (AlCl) 3 ) Can be mixed with lithium chloride (LiCl), sodium chloride (NaCl), potassium chloride (KCl), and magnesium chloride (MgCl) 2 ) Calcium chloride (CaCl) 2 ) The alkali metal chloride or alkaline earth metal chloride forms low boiling point substance, so that the electrolyte system with aluminum chloride is selected from molten salt system composed of aluminum chloride and alkali metal chloride or alkaline earth metal chlorideIs an electrolyte system. The proportion of the aluminum chloride and other molten salts is determined according to the lowest melting point value formed by various molten salt components. The selection of the corresponding electrolysis temperature also needs to be determined according to the melting point of the selected electrolyte system, and generally the lowest electrolysis temperature needs to be higher than the melting point of the electrolyte system by more than 20 ℃.
In a preferred embodiment, the electrolysis voltage is controlled to be 2.5-4.0V, and the cathode and the anode react during the electrolysis process as follows:
an anode region: 3Cl - +3e→1.5Cl 2 (g)
A cathode region: al (Al) 3+ -3e→Al
And (3) total reaction: alCl 3 →Al+1.5Cl 2 (g)
During electrolysis, metallic aluminum is obtained at the cathode and chlorine gas is obtained at the anode.
Electrolysis for a period of time, which may be 0.5 to 2.5 hours, preferably 2 hours, to produce a quantity of aluminum metal at the cathode to facilitate subsequent reaction with titanium tetrachloride, followed by feeding crude titanium tetrachloride containing vanadium to the electrolyte system in the cathode zone of the cell where the following reactions will occur:
3TiCl 4 +Al→3TiCl 3 +AlCl 3
VOCl 3 +TiCl 3 →VOCl 2 (s)+TiCl 4 (g)
3VOCl 3 +Al→3VOCl 2 (s)+AlCl 3
titanium tetrachloride (TiCl) in crude titanium tetrachloride containing vanadium 4 ) Reacting with metallic aluminum generated at the cathode to generate titanium trichloride (TiCl) 3 ) And aluminum chloride. Vanadium oxytrichloride (VOCl) in vanadium-containing crude titanium tetrachloride 3 ) Reacting with the generated titanium trichloride to generate titanium tetrachloride and precipitated vanadyl dichloride (VOCl) 2 ) And the vanadium oxychloride also reacts with the aluminum metal formed at the cathode to form aluminum chloride and precipitated vanadium oxychloride. The separation of vanadium oxychloride from titanium tetrachloride is achieved by the escape of titanium tetrachloride above the boiling point, so the reaction temperature for vanadium removal needs to be controlled above 140 ℃ (the boiling point of titanium tetrachloride is 136 ℃). Due to excessive temperatureThe titanium trichloride is gasified to influence the vanadium-removing reaction temperature, so the highest vanadium-removing reaction temperature needs to be lower than the disproportionation temperature of the titanium trichloride, namely lower than 440 ℃. Therefore, the electrolysis temperature should be controlled to 140 to 440 deg.C, and in a preferred embodiment, the electrolysis temperature is controlled to 140 to 300 deg.C.
In addition, in order to ensure the vanadium removal effect, the feeding speed of the vanadium-containing crude titanium tetrachloride needs to be less than or equal to the stoichiometric ratio (i.e. molar ratio 3. Therefore, the feeding speed of the vanadium-containing crude titanium tetrachloride into the electrolytic electrolyte system with aluminum chloride is carried out according to the molar ratio of the vanadium oxychloride in the vanadium-containing crude titanium tetrachloride to the metal aluminum generated by the cathode being less than or equal to 3.
The amount m of cathode aluminum metal produced during electrolysis can be calculated as follows:
m＝0.3356ηIt
wherein eta is current efficiency, I is current delivered within t time, A; t is time, s. The metallic aluminum generation amount can be calculated according to the formula, so that the feeding amount of the vanadium-containing crude titanium tetrachloride in the time t can be determined, and the feeding speed of the vanadium-containing crude titanium tetrachloride can be further determined.
In addition, the crude titanium tetrachloride containing vanadium also contains aluminum chloride and ferric chloride (FeCl) 3 ) And the like, wherein the aluminum chloride can be used for supplementing the aluminum chloride loss and the like in the electrolyte system with the aluminum chloride, and the aluminum chloride balance in the electrolyte system with the aluminum chloride is realized. The ferric chloride can generate metallic iron by discharging at the cathode preferentially, so that the recycling of the ferric chloride can be realized in the vanadium removing process of the invention, and the general equation of the reaction is as follows:
FeCl 3 →Fe+1.5Cl 2 (g)
in the titanium tetrachloride vanadium removal method for electrochemically preparing the vanadium removal reagent, in order to prevent the electrolyte and titanium tetrachloride from absorbing water and deteriorating, the electrolysis reaction and the vanadium removal reaction are required to be carried out in a protective atmosphere, and the protective atmosphere can be formed by one or more of argon, nitrogen and helium.
In one embodiment, a condenser tube is used to collect the vaporized titanium tetrachloride.
The invention provides a titanium tetrachloride vanadium removal method for electrochemically preparing a vanadium removal reagent, wherein the electrochemically prepared vanadium removal reagent comprises aluminum chloride and alkali metal chloride or alkaline earth metal chloride.
The specific embodiment of the titanium tetrachloride vanadium removal method for electrochemically preparing the vanadium removal reagent is described below.
Example 1
Weighing AlCl with equal molar ratio in an argon-protected glove box 3 Placing NaCl and NaCl in a distillation flask with an intermediate partition wall, heating to 180 ℃ to melt the electrolyte, connecting phi 10mm graphite with a direct current power supply anode to form an anode, connecting a phi 8mm carbon steel rod with a direct current power supply cathode to form a cathode, controlling the direct current voltage to be 2.8V to perform electrolysis (the electrolysis current is about 4A), and after 2 hours of electrolysis, introducing VOCl into an electrolyte system in the cathode region 3 The crude titanium tetrachloride containing vanadium with the content of 0.1854 percent (mass percent) is controlled at the feeding speed of 50ml/min, and a condensing tube is adopted to collect the evaporated titanium tetrachloride. VOCl in collected titanium tetrachloride 3 The content is 0.0003 percent, the removal rate reaches 99.84 percent, and FeCl is added 3 The content is reduced from 0.0235 percent to 0.0003 percent, and AlCl is added 3 The content is also reduced from 0.1187% to 0.0067%.
Example 2
Weighing a mixture in a molar ratio of 1: alCl of 2 3 And MgCl 2 Placing in a distillation flask with an intermediate partition wall, heating to 200 deg.C to melt electrolyte, connecting graphite of phi 20mm with anode of DC power supply as anode, connecting molybdenum rod of phi 10mm with cathode of DC power supply as cathode, controlling DC voltage to 3.2V to perform electrolysis (electrolytic current is about 6.5A), electrolyzing for 2 hr, and introducing VOCl into electrolyte system in cathode region 3 0.2503 percent (mass percentage) of crude titanium tetrachloride containing vanadium, the feeding speed is controlled to be 80ml/min, a condensing tube is adopted to collect the evaporated titanium tetrachloride, and VOCl in the collected titanium tetrachloride 3 The content is 0.0001%, the removal rate reaches 99.96%, and FeCl 3 The content is reduced from 0.1307 percent to 0.0001 percent, and AlCl is added 3 The content is also reduced from 0.1874% to 0.0053%.
Example 3
Weighing a mixture in a molar ratio of 1: alCl of 2 3 Putting LiCl-KCl (equal molar ratio) in a distillation flask with an intermediate partition wall, heating to 140 ℃ to melt the electrolyte, connecting graphite with 20mm of phi with a direct current power supply anode to form an anode, connecting a carbon steel rod with 8mm of phi with a direct current power supply cathode to form a cathode, controlling the direct current voltage to be 2.5V to perform electrolysis (the electrolysis current is about 3.6A), electrolyzing for 2 hours, and introducing VOCl into an electrolyte system in the cathode region 3 0.1753 percent (mass percentage) of crude titanium tetrachloride containing vanadium, the feeding speed is controlled to be 40ml/min, and a condensing tube is adopted to collect the evaporated titanium tetrachloride. VOCl in collected titanium tetrachloride 3 The content is 0.0002 percent, the removal rate reaches 99.89 percent, and FeCl is added 3 The content is reduced from 0.0835% to 0.0002%, and AlCl 3 The content is also reduced from 0.0915% to 0.0056%.
Example 4
Weighing AlCl with equal molar ratio in a helium-protected glove box 3 Putting LiCl and LiCl into a distillation flask with an intermediate partition wall, heating to 440 ℃ to melt the electrolyte, connecting graphite with phi 20mm to a direct current power supply anode to form an anode, connecting a tungsten rod with phi 10mm to a direct current power supply cathode to form a cathode, controlling the direct current voltage to be 4.0V to perform electrolysis (the electrolysis current is about 8.2A), electrolyzing for 2 hours, and introducing VOCl into an electrolyte system in the cathode region 3 0.2136 percent (mass percentage) of crude titanium tetrachloride containing vanadium, the feeding speed is controlled to be 100ml/min, and a condensing tube is adopted to collect the evaporated titanium tetrachloride. VOCl in collected titanium tetrachloride 3 The content is 0.0002%, the removal rate reaches 99.91%, and FeCl 3 The content is reduced from 0.1531% to 0.0005%, and AlCl is added 3 The content is also reduced from 0.1653% to 0.0072%.
In the implementation of the titanium tetrachloride vanadium removal method for electrochemically preparing the vanadium removal reagent, the electrolytic current value is related to the resistance value of an electrolyte system with aluminum chloride, and the resistance value of the electrolyte system with aluminum chloride is related to the polar moment of an electrode, the insertion depth and the conductivity of the electrolyte system with aluminum chloride, and the electrolytic current value can be adjusted by adjusting the parameters.
The electrochemical preparation vanadium removal reagent provided by the invention overcomes the technical problems of large raw material loss, high cost and the like of the traditional vanadium removal reagent. The titanium tetrachloride vanadium-removing method for electrochemically preparing the vanadium-removing reagent of the invention adopts AlCl in crude titanium tetrachloride 3 The impurities can realize the AlCl of the electrolyte 3 Supplementing and simultaneously removing FeCl in crude titanium tetrachloride by electrochemical deposition 3 Impurities, is beneficial to realizing the clean production of refining titanium tetrachloride and the recycling of solid phase substances, and has stronger popularization and application prospect
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (6)
1. A titanium tetrachloride vanadium removal method for electrochemically preparing a vanadium removal reagent is characterized by comprising the following steps:
step 1, electrolyzing graphite serving as an anode and conductive metal serving as a cathode in an electrolytic cell containing an electrolyte system with aluminum chloride to obtain metal aluminum at the cathode, wherein the electrolysis temperature of the electrolysis is 140-440 ℃;
step 2, introducing vanadium-containing crude titanium tetrachloride into the electrolytic system with the aluminum chloride for vanadium removal, wherein the electrolytic system with the aluminum chloride is a molten salt system consisting of aluminum chloride and alkali metal chloride or alkaline earth metal chloride, and the introduction speed of the vanadium-containing crude titanium tetrachloride into the electrolytic system with the aluminum chloride is carried out according to the molar ratio of vanadium oxychloride in the vanadium-containing crude titanium tetrachloride to metallic aluminum generated by a cathode and is less than or equal to 3;
step 3, collecting the evaporated titanium tetrachloride to obtain titanium tetrachloride after vanadium removal;
the electrolysis reaction in the step 1 and the vanadium removal reaction in the step 2 are both carried out in a protective atmosphere;
in the step 2, the vanadium-containing crude titanium tetrachloride is introduced into an electrolyte system in a cathode region;
the electrolysis time in the step 1 is 0.5 to 2.5 hours;
the vanadium-containing crude titanium tetrachloride also contains aluminum chloride and ferric chloride, wherein the aluminum chloride is used for supplementing the loss of the aluminum chloride in the electrolyte system with the aluminum chloride, and the ferric chloride is preferentially discharged at the cathode to generate metallic iron.
2. The titanium tetrachloride vanadium removal method for electrochemically preparing a vanadium removal reagent according to claim 1, wherein the electrolytic cell is divided into an anode region and a cathode region by a partition wall, wherein the graphite constitutes the anode region and the conductive metal constitutes the cathode region.
3. The method for removing vanadium from titanium tetrachloride for electrochemically preparing a vanadium removal reagent according to claim 2, wherein the conductive metal is one of carbon steel, molybdenum and tungsten.
4. The method for removing vanadium from titanium tetrachloride for electrochemically preparing a vanadium removal reagent according to claim 2, wherein the protective atmosphere is one or more of argon, nitrogen and helium.
5. The method for removing vanadium from titanium tetrachloride by electrochemically preparing a vanadium removal reagent according to claim 2, wherein the electrolysis voltage of the electrolysis in the step 1 is 2.5 to 4.0V.
6. An electrochemically prepared vanadium removal reagent for use in the titanium tetrachloride vanadium removal process for electrochemically preparing a vanadium removal reagent according to any one of claims 1 to 5, wherein the electrochemically prepared vanadium removal reagent comprises aluminum chloride and an alkali metal chloride or an alkaline earth metal chloride.
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