CN103031577B - Method for preparing titanium and titanium obtained by the method - Google Patents

Method for preparing titanium and titanium obtained by the method Download PDF

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Publication number
CN103031577B
CN103031577B CN201110293657.8A CN201110293657A CN103031577B CN 103031577 B CN103031577 B CN 103031577B CN 201110293657 A CN201110293657 A CN 201110293657A CN 103031577 B CN103031577 B CN 103031577B
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titanium
weight
metal
content
molten state
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CN103031577A (en
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周玉昌
穆天柱
闫蓓蕾
赵三超
杨仰军
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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Priority to CN201110293657.8A priority Critical patent/CN103031577B/en
Priority to DE102012108564.1A priority patent/DE102012108564B4/en
Priority to US13/618,945 priority patent/US20130084206A1/en
Priority to JP2012212196A priority patent/JP5526207B2/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C22B34/1281—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction using carbon containing agents, e.g. C, CO, carbides
    • 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

Abstract

The present invention discloses a method for preparing titanium, wherein the method comprises the following steps: (1) contacting a titanium-containing raw material of molten state and a carbonaceous reducing agent so that titanium dioxide in the titanium-containing raw material is reduced to low-valent titanium and the reduction product titanium slag of the molten state containing low-valent titanium is obtained; (2) cooling and molding the reduction product titanium slag of the molten state containing low-valent titanium from the step (1)to obtain a titanium-containing material with a porous structure, wherein the average hole diameter of the titanium-containing material with the porous structure is 1-10 mm and the porosity is 20-60%; and (3) electrolyzing by taking the titanium-containing material from the step (2) as an anode, the metal as a cathode, and the molten salt as electrolyte under the condition of electrolysis to get metallic elemental titanium. The method provided by the invention is simple in process, low in anode resistivity, difficult to polarization, easy to electrolyze, and high in purity of the final cathode product of titanium metal.

Description

A kind of preparation method of metal titanium and the metal titanium obtained by the method
Technical field
The preparation method that the present invention relates to a kind of metal titanium and the metal titanium obtained by the method.
Background technology
Titanium or titanium alloy has that density is little, specific tenacity is high, heat-resisting resistance to low temperature is good, solidity to corrosion is good and the series of advantages such as bio-compatibility is excellent, therefore, has the laudatory title of " following metal ", " space metal " and " marine metal ".
Titanium belongs to rare metal, but in fact the abundance of titanium elements in the earth's crust accounts for the 7th (0.45 % by weight), far away higher than many common metals.But because the character of titanium is active, require high to smelting technology, make people cannot obtain a large amount of titaniums, thus it is classified as the metal of " rare ".At present, the industrial process of unique current metal titanium is Kroll method in the world, and the method comprises makes the master operations such as titanium chloride, magnesium reduction-vacuum distilling, product aftertreatment and magnesium eletrolysis by containing titanium dioxide; Its advantage is the recycle that can realize chlorine, magnesium, but Kroll method exists long flow path, reduction ratio is low, reductive agent price is higher and the defect such as intermittent type operation, thus causes metal titanium production cost to remain high.That applies to civilian industry from aerospace, military project along with titanium metal constantly widens, and research and development titanium smelts new technology to reduce the study hotspot that titanium metal production cost has become titanium metallurgy industry.
Up to now, fused salt electrolysis process production titanium is considered to the production method being hopeful alternative Kroll technique most.Fused salt electrolysis process generally includes TiO 2fused salt electrolysis, TiCl 4the TiO of fused salt electrolysis and titanium 2carbothermic reduction product fused salt electrolysis etc.
TiO 2fused salt electrolysis typical process is FFC Cambridge technique, that is, with solid TiO 2as negative electrode, graphite as anode, CaCl 2as ionogen, when the decomposition voltage of impressed voltage lower than fused salt, the oxygen on negative electrode enters ionogen in the form of an ion, is diffused into anode place, is combined generates CO with carbon 2or CO gas, release at anode, metal titanium is then left on negative electrode.Different from traditional fused salt electrolysis process, FFC technique is a kind of completely new approach directly metal titanium and oxygen separating being obtained titanium, has environmental friendliness, technical process short and can realize the advantage of serialization; But up to the present, FFC technique only obtains successfully in laboratory, and also unrealized industrialization, traces it to its cause and be that FFC technique exists following problem: TiO 2cathode resistor rate is large, is difficult to realize stable electrolysis; Negative electrode (TiO 2) in impurity will all remain in titanium, obtain qualified metal titanium product requirement high-purity Ti O 2as raw material, the cost producing titanium is caused greatly to increase.
TiCl 4fused salt electrolysis typical process is Ginatta electrolysis process, the U.S., Japan, USSR (Union of Soviet Socialist Republics), Italy, France, China etc. have all carried out long-term and deep research to it, also Ji Jia midget plant was once established, but afterwards owing to there is problem in actual production, as diaphragm breakup, dendrite etc., fail to reach the technico-economical comparison of expectation, closedown of being forced to stop production.
TiO 2the typical process of carbothermic reduction product fused salt electrolysis is MER technique, that is, by TiO 2carry out after ball milling mixes with carbonaceous reducing agent, compression moulding also sinters; Or, by TiO 2to mix with carbonaceous reducing agent and after sintering, then mix with carbonaceous reducing agent and binding agent, compression moulding sintering.This complex process, and in the process preparing anode, if described anode suppresses to obtain undertighten, then it is easily scattered, and can not meet the demand of use; If anode is suppressed too tight, then may cause the problem bringing anodic polarization serious in electrolytic process.Adopt above-mentioned compression moulding and the method for sintering obtains anode material, its space and porosity lower, thus must cause the diffusion limited of the gases such as the CO produced in electrolytic process, electrolysis effectiveness is not good.
Summary of the invention
When the present invention adopts existing method to prepare metal titanium to overcome, there is complex process, gas diffusion limited, the defect easily bringing anodic polarization, be difficult to realize stable electrolysis, and provide that a kind of technique is simple, gas can spread relatively easily, not easily polarize, the preparation method of metal titanium that electrolysis is stable and the metal titanium that prepared by the method.
The invention provides a kind of preparation method of metal titanium, wherein, the method comprises the following steps:
(1) contacted with carbonaceous reducing agent by the titaniferous materials of molten state, the condition of contact makes the titanium dioxide in described titaniferous materials become Low-valent Titanium, and obtains the reduzate titanium slag containing Low-valent Titanium of molten state;
(2) the reduzate titanium slag cooling forming containing Low-valent Titanium of molten state step (1) obtained, obtains the titanium-containing materials with vesicular structure; The described average pore diameter with the titanium-containing materials of vesicular structure is 1mm-10mm, and porosity is 20%-60%;
(3) titanium-containing materials obtained with step (2) is for anode, and metal is negative electrode, and fused salt is ionogen, carries out electrolysis under electrolysis conditions, obtains metal titanium simple substance.
In addition, present invention also offers the metal titanium simple substance prepared by aforesaid method.
The titaniferous materials of molten state contacts with carbonaceous reducing agent by the present invention, makes the reduzate after contacting be molten state by controlling contact conditions, and by the reduzate cooling forming of described molten state.On the one hand, the reduzate of the molten state of gained directly can form anode by cooling forming, and do not need to sinter being pressed into anode after titaniferous materials and carbonaceous reducing agent mixing and ball milling again, also sinter after not needing that the mixture of the solid state reduction product obtained and binding agent is pressed into anode, technique is simple again; What is more important, the present inventor is surprised to find that, the direct cooling forming of reduzate titanium slag of the molten state obtained after contact under temperature and pressure of the present invention, it is 1mm-10mm that the titanium-containing materials formed has average pore diameter, porosity is the vesicular structure of 20%-60%, not only ensure that its demand as anode, also can ensure CO, CO that electrolysis produces 2can be spread well Deng gas; In addition, the reduzate that titaniferous materials contacts gained with carbonaceous reducing agent may contain TiO, Ti 2o 3, Ti 3o 5and Ti 4o 7in one or more, the reduzate obtained after making contact by control condition is molten state, and by direct for the reduzate of molten state cooling forming, can ensure that above-mentioned reduzate is solid-solubilized in together well, the anodic composition obtained is even, electrolytic process is steady.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The preparation method of metal titanium provided by the invention comprises the following steps:
(1) contacted with carbonaceous reducing agent by the titaniferous materials of molten state, the condition of contact makes the titanium dioxide in described titaniferous materials become Low-valent Titanium, and obtains the reduzate titanium slag containing Low-valent Titanium of molten state;
(2) the reduzate titanium slag cooling forming containing Low-valent Titanium of molten state step (1) obtained, obtains the titanium-containing materials with vesicular structure; The described average pore diameter with the titanium-containing materials of vesicular structure is 1mm-10mm, is preferably 3mm-7mm; Porosity is 20%-60%, is preferably 40%-60%;
(3) titanium-containing materials obtained with step (2) is for anode, and metal is negative electrode, and fused salt is ionogen, carries out electrolysis under electrolysis conditions, obtains metal titanium simple substance.
The present inventor is surprised to find that, the titaniferous materials of molten state is contacted with carbonaceous reducing agent, the titanic in titaniferous materials can not only be made to be reduced into Low-valent Titanium (as trivalent, divalence etc.) by controlling contact conditions, can also ensure that the product of gained is molten state, the interphase interaction of the Low-valent Titanium of different valence state is able to solid solution well.What is more important, after shaping for the reduzate titanium slag naturally cooling containing Low-valent Titanium of described molten state, the titanium-containing materials obtained has vesicular structure, CO, CO of producing when effectively can ensure electrolysis 2can be spread well Deng gas, electrolysis effectiveness is very good.
As a rule, titanium dioxide has very little or does not almost have solvability in molten salt electrolyte, and therefore, using it directly as anode, electrolysis effectiveness is not good.But after high price titanium is reduced into Low-valent Titanium, the reduzate of lower valency can show certain solvability in fused salt, and namely titanium ion is from anode electrolysis stripping, and becomes metal titanium simple substance in cathodic reduction.
According to the present invention, be in order to the high-valence state in titaniferous materials is reduced into Low-valent Titanium by the object that titaniferous materials contacts with carbonaceous reducing agent, in described Low-valent Titanium, there is hole, make its character between conductor and semi-conductor, can conductive capability be improved, be dissolved in molten salt electrolyte.The condition of described contact comprises the temperature of contact, the pressure of contact and the time contacted, wherein, the titanium dioxide in described titaniferous materials is made to become Low-valent Titanium and the reduzate titanium slag containing Low-valent Titanium obtaining molten state as long as the condition of described contact can meet.Under preferable case, the temperature of described contact can be 1650-2000 DEG C, and the pressure of contact can be-100Pa to 100Pa (absolute pressure), and the time of contact can be 2-10 hour; More preferably, the temperature of described contact is 1650-1750 DEG C, and the pressure of contact is-50Pa to 50Pa (absolute pressure), and the time of contact is 3-5 hour.
According to the present invention; titanic in described titaniferous materials can change with the ratio of the consumption of the carbon in carbonaceous reducing agent in a big way; but such as, owing to usually also containing other reducing substanceses, iron ion etc. in titaniferous materials, therefore; in order to improve reduction effect further; carbonaceous reducing agent often needs excessive a little, under preferable case, in titanium dioxide; the mol ratio of the titanic in described titaniferous materials and the carbon in carbonaceous reducing agent is 1: 1-3, more preferably 1: 1.5-2.5.
According to the present invention, described titaniferous materials can be selected from existing various titaniferous materials, and such as, described titaniferous materials can be ilmenite concentrate and/or Ti-containing slag.Selecting and purchasing is out from ilmenite or titanomagnetite for described ilmenite concentrate, its main component is titanium dioxide (content is 42-65 % by weight), ferric oxide (content is 5-40 % by weight), ferric oxide (content is 5-40 % by weight), and other contain the compound (content sum is 2-10 % by weight) of a small amount of phosphorus, sulphur, magnesium, calcium constituent.Described Ti-containing slag refers to titaniferous ore and smelts the residue after extracting other valuable metals, and its main component is titanium dioxide (content is 15-30 % by weight), calcium oxide (content is 10-25 % by weight), aluminum oxide (content is 10-20% % by weight) and silicon-dioxide (content is 10-28 % by weight).
According to the present invention, described carbonaceous reducing agent can be existing various carbonaceous reducing agent, as long as the high price titanium in titaniferous materials can be reduced into Low-valent Titanium, such as, described carbonaceous reducing agent can be selected from one or more in hard coal, bituminous coal, charcoal, coke and refinery coke.Described hard coal is the darkest coal of degree of coalification, and carbon content is higher, can reach more than 80 % by weight; Volatile matter is lower, below 10 % by weight.The carbon content of described bituminous coal is 75-90 % by weight.The carbon content of described charcoal is 65-95 % by weight.Described coke refers to by bituminous coal under the condition of isolated air, and be heated to 950-1050 DEG C, make through operations such as super-dry, pyrolysis, melting, bonding, solidification, contractions, its carbon content is 75-85 % by weight.Described refinery coke refers to crude oil through distillation by after separating of oil for weight matter, mink cell focus is again through product that hot tearing is transformed, from the appearance, coke is out-of-shape, black bulk (or particle) not of uniform size, has metalluster, the particle tool multi-pore structure of coke, carbon content can reach more than 90 % by weight, and all the other are hydrogen, oxygen, nitrogen, sulphur and metallic element.
The kind of the present invention to the metal as negative electrode is not particularly limited, if can with anode of the present invention with the use of, electrolysis obtains metal titanium simple substance.But in order to the purity also improving the metal titanium simple substance obtained work-ing life improving described anode, under preferable case, the metal as negative electrode can be selected from carbon steel, molybdenum, copper and mickel one or more.
As a rule, ionogen refers in water-soluble solution or in the molten state and just can conduct electricity the compound of (electricity is dissociated into positively charged ion and negatively charged ion).In the present invention, in order to improve the concentration of gained metal titanium simple substance, reduce the introducing of impurity, using fused salt as ionogen.Under preferable case, the fused salt that described fused salt is formed for alkali metal chloride and/or alkaline earth metal chloride melting.
According to the present invention, although the purity of the condition of electrolysis on the metal titanium simple substance obtained can not produce significant impact, in order to take into account efficiency and output, under preferable case, it is 0.05-2A/cm that described electrolytic condition comprises anodic current density 2, cathode current density is 0.05-2A/cm 2; More preferably, described anodic current density is 0.1-1A/cm 2, cathode current density is 0.1-1A/cm 2.
According to the present invention, the temperature of described fused salt, namely the temperature of electrolysis can in very large range change, as long as the gasification temperature Sum decomposition temperature of the satisfied fusing point of salt and the salt lower than formation fused salt higher than forming fused salt, such as, the temperature of described electrolysis can be 600-900 DEG C, is preferably 600-800 DEG C.The time of electrolysis can carry out choose reasonable according to the condition of the amount of the Low-valent Titanium of wanted electrolysis and electrolysis, makes the Low-valent Titanium of at least 90% change metal titanium simple substance into and is as the criterion.
According to the present invention, the oxygen of the metal titanium that electrolysis generates at the temperature of above-mentioned electrolysis easily and in air reacts, and therefore, in order to improve the purity of the metal titanium obtained, under preferable case, described electrolysis is carried out in rare gas element.Described rare gas element can be selected from one or more in nitrogen and periodic table of elements zero group gas, is preferably argon gas.
In addition, present invention also offers the metal titanium prepared by aforesaid method.
The present invention is not limited to the detail in above-mentioned embodiment, and within the scope of technical conceive of the present invention, can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Below will be described in more detail the present invention by embodiment.
Scanning electronic microscope (purchased from Hitachi company, model is S-4700) is adopted to record the average pore diameter of described titanium-containing materials in embodiment and comparative example; And adopt nitrogen adsorption method to record corresponding porosity.
Embodiment 1
This embodiment is for illustration of the preparation of metal titanium simple substance provided by the invention.
By Flos Bombacis Malabarici ilmenite concentrate (wherein, the TiO of 100g molten state 2content be 47.5 % by weight, Fe 2o 3content be 5.74 % by weight, the content of FeO is 34.48 % by weight, the content of CaO is 1.42 % by weight, the content of MgO is 6.22 % by weight) with the hard coal of 14g (wherein, the content of carbon is 78.5 % by weight) add in electric furnace, temperature be 1750 DEG C, pressure be the condition of-50Pa (absolute pressure) under smelt 5 hours, obtain melting titanium slag.Above-mentioned melting titanium slag is injected the steel casting die of Φ 400 × 600, cooling forming, obtains the titanium-containing materials with vesicular structure, and wherein, the average pore diameter of described titanium-containing materials is 5.75mm, and porosity is 45%.Using this titanium-containing materials as anode, the carbon steel rod of Φ 80 × 600 is as negative electrode, and NaCl-KCl is as molten salt electrolyte, and in 820 DEG C of electrolysis 300min under the condition of argon shield, wherein, anodic current density is 0.2A/cm 2, cathode current density is 0.2A/cm 2.After electrolysis completes, by negative electrode take out, naturally cold, and use successively 0.5 % by weight dilute hydrochloric acid and deionized water wash, oven dry, obtain the product 22.5g of containing metal titanium simple substance, the product of the metal titanium simple substance obtained with the measurement of xrf analysis method elementary composition as follows: the content of Ti is 98.5 % by weight, the content of Fe is 0.95 % by weight, the content of O is 0.37 % by weight, the content of H is 0.18 % by weight.
Embodiment 2
This embodiment is for illustration of the preparation of metal titanium simple substance provided by the invention.
By Flos Bombacis Malabarici ilmenite concentrate (wherein, the TiO of 60g molten state 2content be 47.5 % by weight, Fe 2o 3content be 5.74 % by weight, the content of FeO is 34.48 % by weight, the content of CaO is 1.42 % by weight, the content of MgO is 6.22 % by weight), Yunnan ilmenite concentrate (wherein, the TiO of 40g 2content be 49.85 % by weight, Fe 2o 3content be 9.68 % by weight, the content of FeO is 36.50 % by weight, the content of CaO is 0.24 % by weight, the content of MgO is 1.99 % by weight) with the hard coal of 20g (wherein, the content of carbon is 78.5 % by weight) add in electric furnace, temperature be 1650 DEG C, pressure be the condition of 50Pa (absolute pressure) under smelt 3 hours, obtain melting titanium slag.Above-mentioned titanium slag is injected the steel casting die of Φ 300 × 600, cooling forming, obtains the titanium-containing materials with vesicular structure, and wherein, the average pore diameter of described titanium-containing materials is 6.5mm, and porosity is 55.3%.Using this titanium-containing materials as anode, the carbon steel rod of Φ 60 × 600 is as negative electrode, and NaCl-KCl is as molten salt electrolyte, and under an inert atmosphere in 900 DEG C of electrolysis 300min, wherein, anodic current density is 2A/cm 2, cathode current density is 1A/cm 2.After electrolysis completes, by negative electrode take out, naturally cold, and use successively 0.5 % by weight dilute hydrochloric acid and deionized water wash, oven dry, obtain the product 23g of containing metal titanium simple substance, the product of the metal titanium simple substance obtained with the measurement of xrf analysis method elementary composition as follows: the content of Ti is 97.78 % by weight, the content of Fe is 0.85 % by weight, the content of O is 1.25 % by weight, the content of H is 0.12 % by weight.
Embodiment 3
This embodiment is for illustration of the preparation of metal titanium simple substance provided by the invention.
By Yunnan ilmenite concentrate (wherein, the TiO of 100g molten state 2content be 49.85 % by weight, Fe 2o 3content be 9.68 % by weight, the content of FeO is 36.50 % by weight, the content of CaO is 0.24 % by weight, the content of MgO is 1.99 % by weight) with the coke of 22g (wherein, the content of carbon is 85.5 % by weight) add in electric furnace, temperature be 1700 DEG C, pressure be the condition of 5Pa (absolute pressure) under smelt 4 hours, obtain melting titanium slag.Above-mentioned titanium slag is injected the steel casting die of Φ 200 × 400, cooling forming, obtains the titanium-containing materials with vesicular structure, and wherein, the average pore diameter of described titanium-containing materials is 3.5mm, and porosity is 60%.Using this titanium-containing materials as anode, the carbon steel rod of Φ 50 × 400 is as negative electrode, and NaCl-KCl is as molten salt electrolyte, and under an inert atmosphere in 850 DEG C of electrolysis 210min, wherein, anodic current density is 1A/cm 2, cathode current density is 1.5A/cm 2.After electrolysis completes, by negative electrode take out, naturally cold, and use successively 0.5 % by weight dilute hydrochloric acid and deionized water wash, oven dry, obtain the product 23.5g of containing metal titanium simple substance, the product of the metal titanium simple substance adopting the measurement of xrf analysis method to obtain elementary composition as follows: the content of Ti is 98.28 % by weight, the content of Fe is 0.55 % by weight, the content of O is 1.05 % by weight, the content of H is 0.12 % by weight.
Embodiment 4
This embodiment is for illustration of the preparation of metal titanium simple substance provided by the invention.
Metal titanium simple substance is prepared according to the method for embodiment 2, unlike, the temperature that the Flos Bombacis Malabarici ilmenite concentrate of described molten state contacts with hard coal is 1600.After electrolysis completes, by negative electrode take out, naturally cold, and use successively 0.5 % by weight dilute hydrochloric acid and deionized water wash, oven dry, obtain the product 20g of containing metal titanium simple substance, the product of the metal titanium simple substance obtained with semi-quantitative analysis measurement elementary composition as follows: the content of Ti is 97.5 % by weight, the content of Fe is 1.55 % by weight, the content of O is 1.25 % by weight, the content of H is 0.12 % by weight.
Comparative example 1
This comparative example is for illustration of the preparation of reference metal titanium simple substance.
Method according to embodiment 1 prepares metal titanium, unlike, the anode preparing metal titanium used prepares by the following method:
By 100g Flos Bombacis Malabarici ilmenite concentrate (wherein, TiO 2content be 47.5 % by weight, Fe 2o 3content be 5.74 % by weight, the content of FeO is 34.48 % by weight, the content of CaO is 1.42 % by weight, the content of MgO is 6.22 % by weight) with the hard coal of 14g (wherein, the content of carbon is 78.5 % by weight) add in electric furnace, temperature be 1750 DEG C, pressure be the condition of-50Pa (absolute pressure) under smelt 5 hours, obtain melting titanium slag.Be encased in the steel casting die of Φ 400 × 600 after the titanium slag of the molten state obtained is cooled, and make type at 50,000psi pressure, obtain into titanium-containing materials.Wherein, the average pore diameter of described titanium-containing materials is 200nm, and porosity is 10%.After electrolysis completes, by negative electrode take out, naturally cold, and use successively 0.5 % by weight dilute hydrochloric acid and deionized water wash, oven dry, obtain the product 11.9g of containing metal titanium simple substance, the product of the metal titanium simple substance obtained with the measurement of xrf analysis method elementary composition as follows: the content of Ti is 97 % by weight, the content of Fe is 1.95 % by weight, the content of O is 0.57 % by weight, the content of H is 0.48 % by weight.
Comparative example 2
This comparative example is for illustration of the preparation of reference metal titanium simple substance.
Method according to embodiment 1 prepares metal titanium, unlike, the anode preparing metal titanium used prepares by the following method:
By 100g Flos Bombacis Malabarici ilmenite concentrate (wherein, TiO 2content be 47.5 % by weight, Fe 2o 3content be 5.74 % by weight, the content of FeO is 34.48 % by weight, the content of CaO is 1.42 % by weight, the content of MgO is 6.22 % by weight) with the hard coal of 14g (wherein, the content of carbon is 78.5 % by weight) in ball grinder after ball milling 60min, inject the steel casting die of Φ 200 × 400,50, after 000psi pressure makes type, 1750 DEG C, pressure be the condition of-50Pa (absolute pressure) under sintering within 5 hours, obtain titanium-containing materials.Wherein, the average pore diameter of described titanium-containing materials is 300nm, and porosity is 15%.After electrolysis completes, by negative electrode take out, naturally cold, and use successively 0.5 % by weight dilute hydrochloric acid and deionized water wash, oven dry, obtain the product 12.1g of containing metal titanium simple substance, the product of the metal titanium simple substance obtained with the measurement of xrf analysis method elementary composition as follows: the content of Ti is 97.08 % by weight, the content of Fe is 1.45 % by weight, the content of O is 0.57 % by weight, the content of H is 0.48 % by weight.

Claims (9)

1. a preparation method for metal titanium, is characterized in that, the method comprises the following steps:
(1) contacted with carbonaceous reducing agent by the titaniferous materials of molten state, the condition of contact makes the titanium dioxide in described titaniferous materials become Low-valent Titanium, and obtains the reduzate titanium slag containing Low-valent Titanium of molten state;
(2) the reduzate titanium slag cooling forming containing Low-valent Titanium of molten state step (1) obtained, obtains the titanium-containing materials with vesicular structure; The described average pore diameter with the titanium-containing materials of vesicular structure is 1mm-10mm, and porosity is 20%-60%;
(3) titanium-containing materials obtained with step (2) is for anode, and metal is negative electrode, and fused salt is ionogen, carries out electrolysis under electrolysis conditions, obtains metal titanium.
2. method according to claim 1, wherein, in step (1), the condition of described contact comprises: the temperature of contact is 1650-2000 DEG C; The absolute pressure of contact is that-100Pa is to 100Pa; The time of contact is 2-10 hour.
3. method according to claim 1, wherein, in step (1), in titanium dioxide, the mol ratio of the titanic in described titaniferous materials and the carbon in carbonaceous reducing agent is 1:1-3.
4. the method according to claim 1 or 3, wherein, in step (1), described titaniferous materials is ilmenite concentrate and/or Ti-containing slag.
5. the method according to claim 1 or 3, wherein, in step (1), described carbonaceous reducing agent be selected from hard coal, bituminous coal, charcoal, coke and refinery coke one or more.
6. method according to claim 1, wherein, in step (2), described in there is the titanium-containing materials of vesicular structure average pore diameter be 3mm-7mm, porosity is 40%-60%.
7. method according to claim 1, wherein, in step (3), the metal as negative electrode be selected from carbon steel, molybdenum, copper and mickel one or more.
8. method according to claim 1, wherein, in step (3), described fused salt is alkali metal chloride and/or the alkaline earth metal chloride of molten state.
9. method according to claim 1, wherein, in step (3), it is 0.05-2A/cm that described electrolytic condition comprises anodic current density 2; Cathode current density is 0.05-2A/cm 2; Electrolysis temperature is 600-900 DEG C.
CN201110293657.8A 2011-09-30 2011-09-30 Method for preparing titanium and titanium obtained by the method Active CN103031577B (en)

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