CN105220180A - The preparation method of composite anode during electrowinning metal titanium - Google Patents
The preparation method of composite anode during electrowinning metal titanium Download PDFInfo
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- CN105220180A CN105220180A CN201510770409.6A CN201510770409A CN105220180A CN 105220180 A CN105220180 A CN 105220180A CN 201510770409 A CN201510770409 A CN 201510770409A CN 105220180 A CN105220180 A CN 105220180A
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Abstract
The present invention relates to the method for fused salt electrolysis metallurgical production metal, particularly the method for electroextraction by molten salt electrolysis titanium, be specifically related to the preparation method of composite anode during a kind of electrowinning metal titanium.The inventive method, comprises the following steps: a, raw material prepare: measure the titanium content M in the titanium liquid obtained in Production By Sulfuric Acid Process titanium white process; B, composite anode materials mix: obtain adding reductive agent and binding agent, rinsing in titanium liquid to a step, obtain the mixture mixed; Prepared by c, composite anode: mixture is made type at 0.5 ~ 1.5MPa pressure, dry, and calcining, obtains titaniferous composite anode; Producing of d, metal titanium: with titaniferous composite anode for galvanic anode, is negative electrode with carbon steel, according to fused salt electrolysis process, cell cathode obtains metal titanium.The method that the present invention prepares anode material is simple, and energy consumption is low, and anode material speed of reaction is fast.
Description
Technical field
The present invention relates to the method for fused salt electrolysis metallurgical production metal, particularly the method for electroextraction by molten salt electrolysis titanium, be specifically related to the preparation method of composite anode during a kind of electrowinning metal titanium.
Background technology
Titanium and titanium alloys because its fusing point is high, large, the corrosion-resistant feature such as by force of light specific gravity, intensity, be widely used in modern Aviation, rocket-powered missile industry, spationautics, firearms naval vessels, bio-medical material and chemical industry equipment etc.
At present, unique is in the world Kroll method, namely magnesium reduction for industrial titanium method processed, produces the consumable electrode remelting of titanium sponge vacuum available or electron beam melting purification that obtain.The whole production process of Kroll method comprises the electrolysis of magnesium chloride, titaniferous materials chlorination, magnesiothermic reduction and vacuum distilling and deviates from magnesium chloride and excess metal magnesium four major portions.Due to its long flow path, the factor such as operation is many, energy consumption is high, cost of sponge Titanium is remained high, and its price is far above the price of iron and steel, and unit weight price is also more than 3 times of metallic aluminium, limits the application of titanium in every profession and trade.
Have a variety of to the research preparing metal titanium method, more representative propose as: univ cambridge uk FFC method, OS method that Kyoto Univ Japan proposes, Japan the PRP technique, fluotitanate reduction etc. that propose such as Okabe.These methods all also exist still unvanquishable technical problem at present, so all do not realize industrialization.
Publication number is " CN1712571A ", disclose a kind of titanium method processed that titanium dioxide does main raw material, the method prepares a kind of sosoloid TiCTiO of electroconductibility with carbon or titanium carbide reduction titanium dioxide, then soluble anode is done with this sosoloid, carry out fused salt electrolysis, finally can obtain metal titanium on negative electrode.The method has the advantages such as technique is simple, electrolytic process carries out continuously, but the method needs under the condition of high-temperature vacuum, prepare sosoloid TiCTiO, makes the method energy consumption high.
Publication number is the United States Patent (USP) of " US7410562B2 ", discloses one TiO
2-C composite anode prepares the method for metal titanium, the method is the method that thermal and electrochemical process combines, its main points are heat-treated with carbon and titanyl compound, form TiCxOy composite anode, then carry out fused salt electrolysis with this TiCxOy composite anode as soluble anode, obtain metal titanium at negative electrode.The method has similar relative merits with above-mentioned Chinese invention patent, and equally, need under high-temperature vacuum, carry out thermal reduction and prepare composite anode, therefore the energy consumption of the method is still higher.
Above-mentioned two patents are in thermal reduction step, and the C in titaniferous material overflows with the form of CO, and this causes reductive agent consumption for very large.
Summary of the invention
For the deficiencies in the prior art, it is low that technical problem to be solved by this invention is to provide a kind of energy consumption, and the method for metal titanium is prepared in the fused salt electrolysis that reaction efficiency is high.
Electrowinning metal titanium of the present invention time composite anode preparation method, comprise the following steps:
A, raw material prepare: measure the titanium content M in the titanium liquid obtained in Production By Sulfuric Acid Process titanium white process;
B, composite anode materials mix: the reductive agent adding 12%M ~ 20%M in the titanium liquid that a step obtains, then add the binding agent of 1%M ~ 5%M, mix, obtain mixture; Wherein, reductive agent+binding agent=13%M ~ 23%M;
Prepared by c, composite anode: mixture b step obtained makes type at 0.5 ~ 1.5MPa pressure, dry 3 ~ 5h at 100 ~ 120 DEG C, at 300 ~ 350 DEG C of calcining 2 ~ 4h, obtains titaniferous composite anode;
Producing of d, metal titanium: the titaniferous composite anode obtained with step c is galvanic anode, is negative electrode with carbon steel, according to fused salt electrolysis process, cell cathode obtains metal titanium.
Further, as preferred technical scheme, electrowinning metal titanium described above time composite anode preparation method, in titanium liquid, wherein preferably add the reductive agent of 17%M in b step, more preferably add the binding agent of 3%M.
Electrowinning metal titanium described above time composite anode preparation method, wherein reductive agent is carbon dust.
Electrowinning metal titanium described above time composite anode preparation method, wherein binding agent is pitch.
Further, as preferred technical scheme, electrowinning metal titanium described above time composite anode preparation method, wherein in step c, mixture makes type at 1MPa pressure, at 100 DEG C after dry 4h, at 300 DEG C, calcine 4h, obtain titaniferous composite anode.
Electrowinning metal titanium of the present invention time composite anode preparation method, in the preparation process of composite anode, do not have visible reduction reaction to occur, but when fused salt electrolysis, the CO of generation
2amount is 1/3 ~ 1/2 of CO, so just can reduce the consumption of reductive agent, reduces production cost, by carrying out XRD detection to the anode material of preparation, shows still only have TiO
2exist mutually with C two kinds of things, but reaction efficiency when electrolysis is more taller than prior art, therefore can draw: in calcination process, inventive mixture there occurs slight reaction, and its effect has the effect of catalysis, and when making electrolysis, anodic reaction is accelerated.
Embodiment
Electrowinning metal titanium of the present invention time composite anode preparation method, comprise the following steps:
A, raw material prepare: measure the titanium content M in the titanium liquid obtained in Production By Sulfuric Acid Process titanium white process;
B, composite anode materials mix: the reductive agent adding 12%M ~ 20%M in the titanium liquid that a step obtains, then add the binding agent of 1%M ~ 5%M, mix, obtain mixture; Wherein, reductive agent+binding agent=13%M ~ 23%M;
Prepared by c, composite anode: mixture b step obtained makes type at 0.5 ~ 1.5MPa pressure, dry 3 ~ 5h at 100 ~ 120 DEG C, after material block to be formed deviates from free-water, at 300 ~ 350 DEG C of calcining 2 ~ 4h, be that material at high temperature removes crystal water, obtain titaniferous composite anode;
Producing of d, metal titanium: the titaniferous composite anode obtained with step c is galvanic anode, is negative electrode with carbon steel, according to fused salt electrolysis process, cell cathode obtains metal titanium.
Carry out drying and calcining after the bright mixture compression moulding of this law, wherein drying is to deviate from free-water (or planar water), generally carrying out at low temperatures, material block of the present invention is in air at room temperature atmosphere, as long as the time is long, also can deviate from free-water, raised temperature can shorten time of drying; But when starting, can't direct high temperature drying, otherwise expect that block can ftracture and dissipate; Calcining is to deviate from crystal water, therefore needs certain temperature, and the present invention in theory calcining temperature does not have the upper limit, but in order to reduce energy consumption, therefore determination calcining temperature of the present invention 300 ~ 350 DEG C.
Further, as preferred technical scheme, electrowinning metal titanium described above time composite anode preparation method, in titanium liquid, wherein preferably add the reductive agent of 17%M in b step, more preferably add the binding agent of 3%M.
Electrowinning metal titanium described above time composite anode preparation method, wherein reductive agent is carbon dust.
Electrowinning metal titanium described above time composite anode preparation method, wherein binding agent is pitch.
Further, as preferred technical scheme, electrowinning metal titanium described above time composite anode preparation method, wherein in step c, mixture makes type at 1MPa pressure, at 100 DEG C after dry 4h, at 300 DEG C, calcine 4h, obtain titaniferous composite anode.
This step of metatitanic acid is produced at the titanium hydrolysis of sulfate process titanium dioxide production process, metatitanic acid amount is obtained according to the percent hydrolysis of titanium liquid, with addition of the carbonaceous reducing agent of calculated amount, and add pitch as binding agent, together mix rinsing (sulfuric acid method titanium pigment production technique has rinsing process), like this through pulling an oar several times, rinsing, titaniferous materials (metatitanic acid) and carbonaceous reducing agent and binding agent can be made to be mixed to get completely evenly, and when being conducive to electrolysis, anodic reaction is carried out thoroughly.Pitch belongs to hydrophobic material, and it is waterproof, also water-soluble hardly, and the present invention utilizes the water-fast characteristic of pitch, thus makes it play its adhesiveproperties at calcination process.
Meanwhile, carbonaceous reducing agent add the strainability improving metatitanic acid, this mixture shortened greatly than the solid-liquid separation time of simple metatitanic acid; Which also eliminates the batch mixing step of prior art, and by the present invention's operation, two kinds of mixing of materials more even, is conducive to the carrying out of reduction reaction.
After rinsing, filter block, through overmolding, drying, calcining (sulfuric acid method titanium pigment original process), is met the composite anode of electrolysis requirement.
Test finds the material block intensity difference after firing not adding pitch, can not use as composite anode during electrolysis; And when add pitch add as binding agent a certain amount of after, material block intensity after firing meets requirement during electrolysis completely.
Thermal reduction step of the prior art generates the soluble solids of TiO/TiC, and when thus making fused salt electrolysis, the resistance of anode material is low, and anodic reaction is good, efficiency is high; But anode material prepared by the present invention carries out XRD detection, shows still only have TiO
2exist mutually with C two kinds of things, but reaction efficiency when electrolysis is higher than prior art.This shows: in calcination process, and this mixture there occurs slight reaction, and its effect has the effect of catalysis, and when making electrolysis, anodic reaction is accelerated, and improves production efficiency.
The present invention utilizes titanium hydrolysis to produce metatitanic acid (hydrated titanium dioxide) to decomposite fresh TiO when calcining
2molecule with addition of reductive agent C react, produce micro-nascent state material, then seize TiO when electrolysis
2in O, play the effect of catalysis.But note, once TiO
2after depositing, (after generating, storage period is long) reacts with C just needs very high temperature.
Below in conjunction with embodiment, the specific embodiment of the present invention is further described, does not therefore limit the present invention among described scope of embodiments.
Embodiment 1
Step one, prepared by anode
Raw material: titanium liquid, carbon dust, pitch;
By the titanium liquid of a constant volume, according to the percent hydrolysis determined, calculate measuring containing Ti after hydrolysis, add the carbon dust of 17% and the pitch of 3% in mass ratio, mix.Carry out rinsing according to the existing step of sulfate process titanium dioxide, obtain titaniferous mixture.According to 10kg/cm
2pressure forming, then dry 3 ~ 5h at 100 ~ 120 DEG C, after material block to be formed deviates from free-water, at 300 ~ 350 DEG C of calcining 2 ~ 4h, be that material at high temperature removes crystal water, obtain the composite anode of titaniferous material, the sample block obtained highly freely falls at 1 meter, sample block keeps complete, can meet the requirement of next step electrolysis.Carry out X-ray diffraction means analysis to this material to show, remain C and TiO
2mixture.
Step 2, fused salt electrolysis
The block material obtained with step one is anode, and carbon steel is negative electrode, conveniently molten salt electrolysis method electrolysis composite anode, and with gas analyzer detected gas composition in electrolytic process, the shielding gas used is argon gas;
Meanwhile, be that the anode material block in the patent of " CN1712571A " is anode with publication number, carbon steel is negative electrode, under identical electrolysis system and identical electrolytic parameter, carry out electrolysis, and what obtain the results are shown in shown in following table 1:
Anodic reaction speed ratio comparatively before table 1 electrolysis and after electrolysis
Compare discovery by data in table 1, before non-electrolysis, to produce gas volume identical for patent " CN1712571A " and anode material of the present invention, and electrolysis is after 20 minutes, under same case, and CO, CO that the present invention produces
2amount all wants many than the gas produced in patent " CN1712571A ", and this shows: under same case, during electrolysis, reaction efficiency of the present invention is but high than the speed of reaction of patent " CN1712571A "; In addition when fused salt electrolysis, the CO of generation
2amount is 1/3 ~ 1/2 of CO, so just can reduce the consumption of reductive agent, reduces production cost.
Comparative example 1
Step one, prepared by anode
Raw material: titanium liquid;
By the titanium liquid of a constant volume, according to the percent hydrolysis determined, calculate measuring containing Ti after hydrolysis, add the carbon dust of 20% in mass ratio, mix.Carry out rinsing according to the existing step of sulfate process titanium dioxide, obtain titaniferous mixture.According to 10kg/cm
2pressure forming, the then dry composite anode obtaining titaniferous material for 4 hours under 300 DEG C of normal pressures, the sample block obtained highly freely falls at 1 meter, and sample block is pulverized completely, can not meet the requirement of next step electrolysis.
Claims (5)
1. electrowinning metal titanium time composite anode preparation method, it is characterized in that: comprise the following steps:
A, raw material prepare: measure the titanium content M in the titanium liquid obtained in Production By Sulfuric Acid Process titanium white process;
B, composite anode materials mix: the reductive agent adding 12%M ~ 20%M in the titanium liquid that a step obtains, then add the binding agent of 1%M ~ 5%M, mix, obtain mixture; Wherein, reductive agent+binding agent=13%M ~ 23%M;
Prepared by c, composite anode: mixture b step obtained makes type at 0.5 ~ 1.5MPa pressure, dry 3 ~ 5h at 100 ~ 120 DEG C, at 300 ~ 350 DEG C of calcining 2 ~ 4h, obtains titaniferous composite anode;
Producing of d, metal titanium: the titaniferous composite anode obtained with step c is galvanic anode, is negative electrode with carbon steel, according to fused salt electrolysis process, cell cathode obtains metal titanium.
2. according to claim 1 electrowinning metal titanium time composite anode preparation method, it is characterized in that: the reductive agent adding 17%M in b step in titanium liquid, then add the binding agent of 3%M.
3. according to claim 1 or 2 electrowinning metal titanium time composite anode preparation method, it is characterized in that: reductive agent is carbon dust.
4. according to claim 1 or 2 electrowinning metal titanium time composite anode preparation method, it is characterized in that: binding agent is pitch.
5. according to claim 1 electrowinning metal titanium time composite anode preparation method, it is characterized in that: in step c, mixture makes type at 1MPa pressure, at 100 DEG C after dry 4h, at 300 DEG C, calcine 4h, obtain titaniferous composite anode.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101949038A (en) * | 2010-09-21 | 2011-01-19 | 攀钢集团钢铁钒钛股份有限公司 | Method for preparing TiCxOy composite anode with electrolysis method |
| CN101947652A (en) * | 2010-09-21 | 2011-01-19 | 攀钢集团有限公司 | Method for preparing C-O-T (carbon-oxygen-titanium) composite anode by microwave heating |
| CN103451682A (en) * | 2013-09-16 | 2013-12-18 | 北京科技大学 | Method for extracting metal titanium through molten salt electrolysis of titanium-containing soluble anode |
| CN104451781A (en) * | 2014-12-08 | 2015-03-25 | 中国铝业股份有限公司 | Preparation method of anode for producing metallic titanium by electrolysis |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101949038A (en) * | 2010-09-21 | 2011-01-19 | 攀钢集团钢铁钒钛股份有限公司 | Method for preparing TiCxOy composite anode with electrolysis method |
| CN101947652A (en) * | 2010-09-21 | 2011-01-19 | 攀钢集团有限公司 | Method for preparing C-O-T (carbon-oxygen-titanium) composite anode by microwave heating |
| CN103451682A (en) * | 2013-09-16 | 2013-12-18 | 北京科技大学 | Method for extracting metal titanium through molten salt electrolysis of titanium-containing soluble anode |
| CN104451781A (en) * | 2014-12-08 | 2015-03-25 | 中国铝业股份有限公司 | Preparation method of anode for producing metallic titanium by electrolysis |
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