CN104141156A

CN104141156A - Method for using TiO2 (as raw materials) for performing molten salt electrolysis to produce titanium powder or sponge titanium

Info

Publication number: CN104141156A
Application number: CN201310162568.9A
Authority: CN
Inventors: 乔卫林
Original assignee: Individual
Current assignee: Individual
Priority date: 2013-05-06
Filing date: 2013-05-06
Publication date: 2014-11-12

Abstract

The invention discloses a method for using TiO2 (as raw materials) for performing molten salt electrolysis to produce titanium powder or sponge titanium, and belongs to the technical field of metallurgy of rare metal. The aims that a traditional method adopting residual titanium and the sponge titanium as the raw materials for producing the titanium powder is replaced with the method adopting the TiO2 as the main production raw materials for performing direct molten salt electrolysis to produce the titanium powder, and in addition, a traditional metallic sodium or magnesium metal reduction method adopting titanium tetrachloride as the raw materials is replaced with the method using the TiO2 as the raw materials for performing molten salt electrolysis to produce the sponge titanium are achieved. Therefore, the production cost is reduced, and the whole production equipment investment cost is reduced. According to the technical scheme, electrolytes which enable the powdery TiO2 to continuously, stably and efficiently generate electrolytic reaction in the electrolytes and enable the metallic titanium to be obtained in the negative electrode are researched, and due to the suitable electrolytes, smooth performing of the electrolysis method can be ensured, and the method of taking the TiO2 as the raw materials for performing molten salt electrolysis to produce the titanium powder or sponge titanium can be completed. According to the main purpose of the new technology, the new technology is mainly used for industrial production of the titanium powder and the metal sponge titanium.

Description

Use TiO 2titanium valve or sponge titanium are produced in (being raw material) fused salt electrolysis

One, technical field

This new technology belongs to rare metal field of smelting, and segmentation belongs to that metallic titanium powder is produced and sponge titanium suitability for industrialized production part.

Two, technical background

1, producing titanium valve both at home and abroad is at present mainly with the residual titanium of metal, metal titanium pin, sponge titanium are raw material, at high temperature with hydrogen reaction generation titanium hydride, then by titanium hydride crushing grinding to certain fineness, then make titanium hydride be converted into metallic titanium powder titanium hydride powder dehydrogenation under high-temperature vacuum condition.The numerous and diverse long flow path of this explained hereafter metallic titanium powder production technique, efficiency are low, and production cost is high.

2, at present both at home and abroad the method for suitability for industrialized production sponge titanium be with rutile (be TiO ₂) at high temperature add charcoal add chlorine carry out chlorination generate titanium tetrachloride, titanium tetrachloride stays purification through essence again, titanium tetrachloride after purification reacts by sodium Metal 99.5 or MAGNESIUM METAL the mixture that generates metal titanium and sodium-chlor or magnesium chloride again under high-temperature vacuum condition, after having reacted, carry out again the mask work of metal titanium and sodium-chlor or magnesium chloride, after separation completes, produce the electrolysis production system that sponge titanium and magnesium chloride enter electrolysis production sodium Metal 99.5 or production MAGNESIUM METAL again and carry out electrolysis production sodium Metal 99.5 or MAGNESIUM METAL, producing a large amount of chlorine will reclaim simultaneously, the chlorine reclaiming is used further to produce titanium tetrachloride.The production method production technology difficulty of traditional sponge titanium is large in a word, complex manufacturing, Production Flow Chart is long, production process need be with a large amount of chlorine production titanium tetrachlorides, in the time producing sodium Metal 99.5 or MAGNESIUM METAL by electrolytic process, can produce again a large amount of chlorine simultaneously, chlorine is poisonous and severe corrosive gas, once chlorine leakage will cause very large prestige evil to environment, so the material requirements of traditional sponge titanium production method required equipment is very high, integral device cost is also very high, cause the production cost of current suitability for industrialized production sponge titanium higher, the production cost of sponge titanium per ton is roughly equal to 50,000 yuan of left and right of Renminbi.

Three, summary of the invention

1, pass through a large amount of research experiments for many years, adopt a kind of new low-temperature molten salt to make ionogen, Direct Electrolysis TiO ₂production metallic titanium powder or production (metal) sponge titanium, in the process of this new technology electrolysis production metal titanium, produce metal titanium at negative electrode, what produce at anode is oxygen, produces in process of production without any toxic and harmful, also produces without any waste liquid, waste residue.

2, this production metallic titanium powder or the relative traditional method of sponge titanium new technological process flow process are simple, and integral production is low for cost, and it is mainly that it uses TiO ₂(being titanium dioxide) directly carries out electrochemical reaction in electrolyzer, and a step produces metal titanium, in process of production TiO ₂be with the Powdered electrolyzer that adds, do not need that TiO2 is added to some other material compacting sinterings and become electrode.Because this new technological process is simple, equipment manufacturing cost is low, so the titanium valve of producing or sponge per ton cost are also lower, and approximately 3.5 ten thousand yuan of left and right per ton.

3, this new technology production titanium valve equipment used and industrialization electrolytic aluminum equipment are basic identical; only electrolyzer sealing applying argon gas need be done to protection gas confused; so just can ensure that on negative electrode, metallic titanium powder is not oxidized in the time coming out of the stove; wash separation titanium valve and ionogen Deng the cooling rear taking-up in argon gas of the metallic titanium powder on negative electrode; it is dry that titanium valve is washed clean final vacuum, cooling packing.Washing electrolyte solution evaporation concentration dehydrates rear backspace electrolyzer recycling.Use TiO ₂do raw material electrolytic process and produce titanium valve, anode adopts graphite material, pure titanium plate for negative electrode.600～700 DEG C of electric tank working temperature.2.0～4.0 volts of electric tank working voltages.

4, this new technology production sponge titanium electrolyzer used and industrialization electrolytic aluminum equipment are basic identical, only need to increase in addition a set of zinc distillation equipment for purifying, anode electrolytic cell is graphite, negative electrode is that zinc content is greater than 99.99% pure metal zinc, in electrolysis production process, in electrolyzer, add TiO at regular time and quantity ₂along with constantly carrying out of electrolysis, titanium is enrichment in cathode zinc liquid constantly, in the time that the content of titanium in cathode zinc liquid reaches 20% left and right, can extraction unit divide negative electrode titanium zinc alloy liquid to send into and in zinc distillation equipment for purifying, carry out vacuum zinc distillation, thereby reach separating of titanium and zinc, can obtain pure metal shape sponge titanium, distilling in addition the pure zinc that condensation obtains can recycle by backspace electrolyzer.Electrolysis sponge titanium electrolytic cell working temperature is 650～950 DEG C, 2.0～4.0 volts of bath voltages.

5, adopt the current efficiency of this new technology electrolytic metal titanium valve and sponge titanium to be greater than 96%.

6, this new technology production titanium valve main production raw material is TiO ₂(being Cornstarch).Ionogen, producing sponge titanium main raw material is TiO ₂, ionogen, metallic zinc.

7, this new technology composition of electrolyte is: sodium-chlor, calcium chloride, Calcium Fluoride (Fluorspan), Sodium Fluoride, lithium fluoride composite fused salt ionogen.Its chemical constitution is: NaC1% (0～49)-CaCl ₂% (16～61)-LiF% (0～6)-NaF% (0～19).

8, this new technology electrolysis production metal titanium current efficiency is high, and production stability is good, and production cost is low, and production efficiency is high, and quality product is high, is suitable for commercial scale production titanium valve and sponge titanium.

Four, embodiment

1, produce titanium valve by this new technology, only need after ionogen prepares, add in electrolyzer, starting electrolyzer reaches after 600～700 DEG C electric tank working temperature, (is TiO at regular time and quantity toward adding Cornstarch in electrolyzer ₂), can constantly carry out producing titanium valve on negative electrode along with electrolysis, when titanium valve on negative electrode reaches after some amount, at protectiveness argon gas, gas divides middle taking-up cooling, waits after cooling and washes separate electrolyte, after vacuum-drying, can obtain finished product titanium valve.

2, produce sponge titanium by this new technology, add in electrolyzer after ionogen prepares, starting electrolyzer makes electrolyzer in predetermined work temperature (700～900 DEG C), (is TiO at regular time and quantity toward adding Cornstarch in solution groove ₂), can be along with electrolysis constantly carries out can constantly producing metal titanium (forming titanium zinc alloy liquid) in cathode zinc liquid, when cathode zinc liquid titanium concentration reaches 20% left and right, can extract cathode zinc titanium alloy liquid out, this zinc titanium alloy liquid is sent into and in zinc distillation equipment for purifying, carried out vacuum and steam and stay separation of Zinc, can obtain pure sponge titanium finished product, can obtain pure metal zinc, metallic zinc is returned to electrolyzer again and is recycled simultaneously.

Claims

1. technical characterictic: use TiO ₂the technical characterstic of (being raw material) fused salt electrolysis production titanium valve or sponge titanium is as follows:

1, adopt pulverous TiO ₂for directly adding, raw material in electrolyzer, carries out electrolysis production titanium valve or sponge titanium;

2, lower by the working temperature of electrolysis production titanium valve or sponge titanium electrolytic cell, temperature range is 600～950 DEG C;

3, in electrolysis production, bath voltage is lower 2.0～4.0 volts, and current efficiency is greater than 96%, and economize on electricity property is good;

4, production technique is simple, and production cost is low, and facility investment is few;

5, when this new technology is produced sponge titanium, utilize metallic zinc to do negative electrode, make metal titanium and metallic zinc that electrolysis generates form liquid alloy, after in zinc titanium alloy liquid, titanium reaches finite concentration, extract out, carrying out the vacuum distilling of titanium zinc separates, obtain sponge titanium, thereby complete the suitability for industrialized production of electrolytic process production sponge titanium.

2. new technology electrolyte ingredient used and content

The ionogen that this electrolysis is made up of sodium-chlor, calcium chloride, Calcium Fluoride (Fluorspan), Sodium Fluoride, lithium fluoride composite fused salt, its chemical constitution is: NaC1% (0～49)-CaCl2% (16～61)-LiF% (0～6)-NaF% (0～19).