CN115305518A - Recycling method of low-valent titanium chloride - Google Patents

Recycling method of low-valent titanium chloride Download PDF

Info

Publication number
CN115305518A
CN115305518A CN202210853581.8A CN202210853581A CN115305518A CN 115305518 A CN115305518 A CN 115305518A CN 202210853581 A CN202210853581 A CN 202210853581A CN 115305518 A CN115305518 A CN 115305518A
Authority
CN
China
Prior art keywords
titanium
low
chloride
valence
recycling method
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210853581.8A
Other languages
Chinese (zh)
Inventor
毕福丽
刘峰
王丽艳
陈建立
李建军
祝永红
张美杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yunnan Guoti Metal Co ltd
Original Assignee
Yunnan Guoti Metal Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yunnan Guoti Metal Co ltd filed Critical Yunnan Guoti Metal Co ltd
Priority to CN202210853581.8A priority Critical patent/CN115305518A/en
Publication of CN115305518A publication Critical patent/CN115305518A/en
Pending legal-status Critical Current

Links

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
    • C25C3/26—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
    • C25C7/02—Electrodes; Connections thereof
    • C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts
    • 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

Abstract

The invention discloses a recycling method of low-valence titanium chloride, which comprises the following steps: obtaining low-valent titanium chloride, and performing impurity removal treatment and component analysis to obtain the low-valent titanium chloride to be utilized; obtaining and melting analytical soda metal chloride, and adding the to-be-utilized low-valence titanium chloride to obtain low-valence titanium-containing molten salt electrolyte; electrolyzing the low-valence titanium-containing molten salt electrolyte to obtain metal titanium; the low-valence titanium chloride is prepared into low-valence titanium-containing molten salt electrolyte which can be used as electrolyte for preparing simple substance titanium by a molten salt electrolysis method, thereby realizing the recycling of titanium resources.

Description

Recycling method of low-valent titanium chloride
Technical Field
The invention relates to the technical field of waste recycling in industrial production, in particular to a recycling method of low-valence titanium chloride.
Background
At present, the method for producing titanium sponge at home and abroad is mainly a magnesiothermic reduction method, and the reaction principle is that titanium tetrachloride is introduced into reduction containing molten magnesiumIn a reactor, carrying out reduction reaction on gaseous titanium tetrachloride and liquid magnesium under the protection of inert gas to produce titanium and magnesium chloride, wherein the reaction comprises the following steps: tiCl (titanium dioxide) 4 +2Mg＝Ti+2MgCl 2 . At the initial stage of the reduction reaction, the magnesium amount is sufficient, but the active substances are insufficient, so the reaction is slow, the middle stage of the reaction is a rapid reaction stage, the titanium lump is mainly generated at the stage, but at the later stage of the reaction, the magnesium amount is insufficient, the disproportionation reaction can be carried out at the moment to generate low-valent titanium chloride, and the generated low-valent titanium chloride not only pollutes the titanium lump and influences the product quality, but also blocks a tail gas pipeline and simultaneously influences the distillation effect.
The patent publication No. CN214496437A solves the problem that discharged low-valence titanium blocks a tail gas pipeline, and the patent publication No. CN112831675A solves the problem that the low-valence titanium affects the distillation effect, but the collected low-valence titanium does not have a definite purpose at present and is basically treated as waste, so that the waste of titanium resources is caused.
Disclosure of Invention
In order to solve the problems, the invention provides a method for recycling low-valence titanium chloride, which converts the low-valence titanium chloride into electrolyte containing low-valence titanium molten salt, and electrolyzes the electrolyte, thereby achieving the purpose of recycling titanium in low-valence titanium chloride.
The invention discloses a recycling method of low-valence titanium chloride, which comprises the following steps:
obtaining low-valent titanium chloride, and performing impurity removal treatment and component analysis to obtain the low-valent titanium chloride to be utilized;
obtaining analytically pure alkali metal chloride, adding the to-be-utilized low-valence titanium chloride after melting to obtain low-valence titanium-containing molten salt electrolyte;
and electrolyzing the low-valence titanium-containing molten salt electrolyte to obtain the metallic titanium.
Further defined, in the step of preparing the low-valent titanium chloride to be utilized, the impurity removal treatment comprises vacuum drying.
Further, the drying temperature in the vacuum drying is 120 ℃ to 170 ℃, preferably 135 ℃ to 150 ℃.
Further defined, the alkali metal chloride comprises sodium chloride and/or potassium chloride, preferably a mixture of sodium chloride and potassium chloride, preferably the potassium chloride is present in a molar ratio of 1:1.
Further defined, the temperature of the alkali chloride during the melting process is 700 ℃ to 720 ℃.
Further, the method also comprises the step of drying the alkali chloride before the alkali chloride is melted, and preferably, the drying temperature is 110-130 ℃, and preferably 118-123 ℃.
Further, in the step of preparing the metallic titanium, titanium sponge is used as an anode, and carbon steel is used as a cathode.
Further defined, the titanium sponge comprises equi-inner titanium and/or equi-outer titanium, and preferably equi-inner titanium.
Further defined, the preparing the titanium carbide or titanium metal is performed in an inert gas atmosphere.
The invention has the beneficial effects that:
1. the low-valence titanium chloride used in the invention has high purity and does not pollute electrolyte.
2. The low-valence titanium chloride washed by water is dried in vacuum, so that the water in the low-valence titanium can be removed, and the water and the divalent titanium are prevented from reacting, namely 2TiCl 2 +2H 2 O→2tTi(OH)Cl 2 +H 2 (g) (ii) a The measurement of the titanium content and the titanium valence distribution in the low-valence titanium is helpful for accurately controlling the simple substance titanium content and the contents of the divalent titanium and the trivalent titanium in the low-valence titanium electrolyte when preparing the low-valence titanium electrolyte.
3. According to the invention, the low-valence titanium chloride generated by the oxidation-reduction reaction is prepared into the low-valence titanium electrolyte for recycling, so that the content of the divalent titanium and the trivalent titanium can be accurately controlled, and the pollution of other impurities to the electrolyte is avoided.
4. The low-valence titanium electrolyte prepared by the method can be used as an electrolyte for preparing simple substance titanium by a molten salt electrolysis method, and can also be used for preparing an electrolyte for titanium carbide, so that the recycling of titanium resources is realized.
Detailed Description
In the process of producing the titanium sponge, the inventor of the invention finds that the disproportionation reaction is carried out to generate the low-valent titanium chloride in the later reaction period due to insufficient magnesium consumption, the low-valent titanium chloride not only can cause the blockage of a tail gas pipeline, but also can influence the distillation effect, and most importantly, a large amount of low-valent titanium chloride powder is remained on the cover of a reactor after the distillation is finished, and is directly treated as waste at present, so that the waste of titanium resources is caused.
The inventor of the invention finds that the low-valence titanium-containing molten salt electrolyte which meets the electrolytic performance is generated by adopting the alkali metal chloride and the low-valence titanium chloride to carry out redox reaction, and the low-valence titanium-containing molten salt electrolyte can be used for preparing simple substance titanium, so that the low-valence titanium chloride can be recycled by preparing the low-valence titanium-containing molten salt electrolyte.
The invention discloses a recycling method of low-valence titanium chloride, and as used herein, the low-valence titanium chloride refers to a mixture of divalent titanium chloride and trivalent titanium chloride; the recycling method comprises the following steps:
s1, obtaining low-valence titanium chloride, and performing impurity removal treatment and component analysis to obtain the low-valence titanium chloride to be utilized;
in the invention, the obtaining of the low-valence titanium chloride can be specifically as follows: a low-valent titanium chloride collecting tank from the reduction pressure relief process, and the collecting process is separated from impurities.
In the invention, the component analysis refers to the measurement of the valence of titanium ions in the low-valence titanium chloride, namely the valence distribution condition of titanium, which is helpful for accurately controlling the content of titanium in the low-valence titanium electrolyte and the content of divalent titanium and trivalent titanium, and avoids the problems of low recovery rate, uncontrollable valence and slow reaction speed in the preparation of the low-valence titanium electrolyte.
In the present invention, the following method can be used to measure the divalent and trivalent titanium ions in the low-valent titanium chloride: dissolving low-valent titanium chloride with sulfuric acid and ammonium sulfate, cooling, and titrating with ammonium ferric sulfate standard solution by using potassium thiocyanate as an indicator; the method for measuring di-and trivalent titanium ions in the low-valent titanium chloride can be as follows: dissolving the titanium dioxide by using sulfuric acid and ammonium sulfate, adding water and hydrochloric acid, heating for dissolving, cooling, and then titrating by using potassium thiocyanate as an indicator and ferric ammonium sulfate standard solution, wherein the measured value is the content of the secondary titanium and the trivalent titanium; ICP (inductively coupled plasma) can be used for detecting the total titanium content in the low-valence titanium chloride, namely 0.5g of the low-valence titanium chloride is added with 5ml of concentrated hydrochloric acid for dissolving, and the volume is determined to be 200ml after dissolving, so that the detection can be carried out.
In the invention, the impurity removal treatment comprises vacuum drying of the low-valence titanium chloride, and removal of free water and crystal water in the low-valence titanium chloride, so that the reaction of the low-valence titanium and water is avoided, and the introduction of moisture in electrolyte is avoided; suitably, the drying temperature in vacuum drying is 120 ℃ to 170 ℃, preferably 135 ℃ to 150 ℃, the drying time varies accordingly according to the drying temperature, generally 8 to 12 hours, the vacuum degree is less than 133Pa, preferably-1 Pa to 10Pa; the drying temperature is generally from 110 ℃ to 130 ℃, suitably from 118 ℃ to 123 ℃, and the drying time varies according to the drying temperature, generally from 8 to 12 hours.
S2, obtaining and melting the analytical soda metal chloride, and adding the to-be-utilized low-valence titanium chloride to obtain a low-valence titanium-containing molten salt electrolyte;
as used herein, the term "analytically pure" refers to a reagent used in analytical determinations wherein the level of impurities does not interfere with the analytical determination.
In the present invention, the alkali metal chloride may be sodium chloride and/or potassium chloride, and is preferably a mixture of sodium chloride and potassium chloride, and more preferably a mixture of sodium chloride and potassium chloride in an equimolar ratio.
In the present invention, the melting temperature may be 700 to 720 ℃, suitably 700 to 710 ℃; in the invention, before the alkali metal chloride is melted, the alkali metal chloride can be dried to avoid the reaction of water in the alkali metal chloride and the divalent titanium from influencing the content of the divalent titanium in the electrolyte.
In the invention, the adding amount of the titanium subchlorides to be utilized is determined according to the titanium content in the titanium subchlorides.
And S3, electrolyzing the electrolyte containing the low-valence titanium molten salt to obtain metal titanium.
In the invention, the metal titanium is used as a cathode, carbon steel is used as an anode and metal is used in electrolysisThe titanium can be selected from titanium powder, titanium sponge or titanium rod titanium sponge, and the titanium sponge can be selected from 0 in national standard A Grade-5 titanium sponge and extra-grade titanium or waste titanium, and the particle size is generally 3 mm-12.7 mm.
In the present invention, the electrolysis is carried out in an inert gas such as helium, neon, argon, etc., suitably argon.
The reactions occurring during electrolysis are:
cathode: ti 2+ +2e＝Ti
Ti 3+ +3e＝Ti
Anode: 2 Cl-2e = Cl 2
And (3) total reaction: tiCl (titanium dioxide) 2 ＝Ti+Cl 2
2TiCl 3 ＝2Ti+3Cl 2
Has the beneficial effects that:
1. the low-valence titanium electrolyte is prepared from the low-valence titanium chloride generated by the reduction reaction, so that the recycling of the low-valence titanium is realized;
2. according to the invention, the low-valence titanium chloride is recycled, so that the economic benefit is improved, and the pollution of the low-valence titanium chloride to the environment is avoided;
3. the low-valence titanium electrolyte prepared by the method can accurately control the contents of divalent titanium and trivalent titanium according to needs, and the problems of low recovery rate, uncontrollable valence state and low reaction speed of the prepared low-valence titanium electrolyte are solved.
The invention can prepare the metal titanium by using the low-valence titanium chloride, and the titanium sponge can be replaced by the waste titanium, so that the economic value of the waste titanium can be improved.
Examples
Example 1
The method for preparing molten salt electrolyte with titanium content of 3wt% by using low-valence titanium oxide and electrolyzing metal titanium comprises the following steps:
s1, drying the obtained low-valence titanium chloride powder in a vacuum drying oven at 120 ℃ for 8 hours, measuring that the total titanium content of the low-valence titanium chloride powder is 40.37wt%, the content of divalent titanium and trivalent titanium is 39.72wt%, weighing 38.7379g for later use, wherein the vacuum degree of the vacuum drying oven is-1 Pa;
s2, uniformly mixing 585g of sodium chloride and 745g of potassium chloride (the molar ratio is 1:1), drying in a drying oven at 700 ℃ for 4 hours, putting into a reactor, adding the low-valence titanium chloride powder prepared in the step S1, and uniformly mixing to obtain a low-valence titanium-containing molten salt electrolyte;
s3, assembling a cathode and an anode, taking carbon steel as the anode, taking titanium sponge as the cathode, then introducing argon, starting to heat up, heating to 250 ℃, carrying out vacuum dehydration for 6 hours, heating to 750 ℃ to melt the titanium, starting electrolysis after connecting the cathode and the anode until metal titanium is electrolyzed at the cathode, wherein the purity of simple substance titanium in the metal titanium is 99.7wt%.
From the embodiment 1, the low-valence titanium chloride-containing molten salt electrolyte is prepared by recycling the low-valence titanium chloride powder, and the purity of the simple titanium in the metallic titanium prepared by using the low-valence titanium-containing molten salt electrolyte as an electrolytic material is high, so that the recycling of the waste low-valence titanium chloride powder is realized, the environmental pollution is avoided, the waste utilization is realized, and the economic value of the waste is improved.
Finally, it should be noted that: the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A method for recycling low-valent titanium chloride, characterized by comprising:
obtaining low-valence titanium chloride, and performing impurity removal treatment and component analysis to obtain the low-valence titanium chloride to be utilized;
obtaining and melting analytical soda metal chloride, and adding the to-be-utilized low-valence titanium chloride to obtain low-valence titanium-containing molten salt electrolyte;
and electrolyzing the low-valence titanium-containing molten salt electrolyte to obtain the metallic titanium.
2. The recycling method according to claim 1, wherein in the step of preparing the titanium subchlorides to be used, the impurity removal treatment comprises vacuum drying.
3. The recycling method according to claim 2, wherein the drying temperature in the vacuum drying is 120 ℃ to 170 ℃, preferably 135 ℃ to 150 ℃.
4. The recycling method according to claim 1, wherein the alkali metal chloride comprises sodium chloride and/or potassium chloride, preferably a mixture of sodium chloride and potassium chloride, preferably the potassium chloride is present in a molar ratio of 1:1.
5. The recycling method according to claim 1, wherein the temperature of the alkali chloride during melting is 720 ℃ to 700 ℃.
6. The recycling method according to any one of claims 1 to 5, further comprising drying the alkali chloride before melting the alkali chloride, preferably at a temperature of 110 ℃ to 130 ℃, preferably 118 ℃ to 123 ℃.
7. The recycling method according to claim 1, wherein in the step of preparing the metallic titanium, titanium sponge is used as an anode, and carbon steel is used as a cathode.
8. The recycling method according to claim 1, wherein the titanium sponge comprises equi-inner titanium and/or equi-outer titanium, preferably equi-inner titanium.
9. The recycling method according to claim 1, wherein the preparation of the titanium carbide or the titanium metal is performed in an inert gas atmosphere.
10. A metallic titanium produced by the recycling method according to any one of claims 1 to 9.
CN202210853581.8A 2022-07-11 2022-07-11 Recycling method of low-valent titanium chloride Pending CN115305518A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210853581.8A CN115305518A (en) 2022-07-11 2022-07-11 Recycling method of low-valent titanium chloride

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210853581.8A CN115305518A (en) 2022-07-11 2022-07-11 Recycling method of low-valent titanium chloride

Publications (1)

Publication Number Publication Date
CN115305518A true CN115305518A (en) 2022-11-08

Family

ID=83856060

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210853581.8A Pending CN115305518A (en) 2022-07-11 2022-07-11 Recycling method of low-valent titanium chloride

Country Status (1)

Country Link
CN (1) CN115305518A (en)

Similar Documents

Publication Publication Date Title
CN103451682A (en) Method for extracting metal titanium through molten salt electrolysis of titanium-containing soluble anode
CN104818388B (en) A kind of indium tin oxide vacuum reduction separating indium and the method for stannum
CN107587167A (en) A kind of crystal formation of aluminium electrolyte containing lithium changes method
WO2011015845A2 (en) Treatment of titanium ores
CN104947152A (en) Method for preparing high-purity titanium by fused-salt electrolytic refining
CN103991882B (en) The fluorine in phosphoric acid by wet process liquid phase is utilized to prepare the method for Potassium monofluoride
Song et al. The influence of fluoride anion on the equilibrium between titanium ions and electrodeposition of titanium in molten fluoride–chloride salt
CN103882477A (en) Electrolyte and molten salt for preparing metal titanium, and metal titanium preparation method
CN103147096B (en) Method for preparing molten-salt electrolyte containing low-valent titanium chloride and method for extracting titanium
EP2631310B1 (en) Method for cyclically preparing titanium sponge and coproducing potassium cryolite using potassium fluotitanate as intermediate material
EP2631217B1 (en) Method for cyclically preparing boron and coproducing sodium cryolite using sodium fluoborate as intermediate material
Che et al. Recovery of metallic Bi from PbBi slag: An integrated process of chloride leaching and electrowinning
EP2631309B1 (en) Method for cyclically preparing titanium sponge and coproducing sodium cryolite using sodium fluotitanate as intermediate material
CN110453098A (en) Rare Earth Electrolysis fused salt waste residue synthetical recovery rare-earth process
CN104451205B (en) Indium extraction method capable of efficiently removing iron
CN115305518A (en) Recycling method of low-valent titanium chloride
Serwale et al. Purification of crude titanium powder produced by metallothermic reduction by acid leaching
Liu et al. Effect of fluoride ions on coordination structure of titanium in molten NaCl-KCl
CN113860362B (en) Electrochemical preparation vanadium removal reagent and titanium tetrachloride vanadium removal method thereof
CN115418679A (en) Method for preparing metallic titanium by electrolyzing titanium dioxide in fluoride molten salt-electroactive oxide system
CN113860363B (en) Method for removing vanadium impurities in titanium tetrachloride
CN113279022B (en) Reducing molten salt medium and preparation method thereof
CN110668409B (en) Method for preparing TiN by taking electrolyte for electrorefining titanium as raw material
EP2631216A1 (en) Method for cyclically preparing boron and coproducing potassium cryolite using potassium fluoborate as intermediate material
CN106191929B (en) The method that Titanium is separated from titanium electrolysis cathode product

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination