CN1069072A - Method for recovering titanium from composite matrix containing titanium nitride - Google Patents

Method for recovering titanium from composite matrix containing titanium nitride Download PDF

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CN1069072A
CN1069072A CN 91105786 CN91105786A CN1069072A CN 1069072 A CN1069072 A CN 1069072A CN 91105786 CN91105786 CN 91105786 CN 91105786 A CN91105786 A CN 91105786A CN 1069072 A CN1069072 A CN 1069072A
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titanium
matrix
carbon
nitrogenize
starting material
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CN1037982C (en
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G·J·莫斯特
B·R·罗尔曼
R·J·韦德莱克
R·C·巴克斯特
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Anglo American Corp of South Africa Pty Ltd
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Crucible SA
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    • C22B34/124—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 titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
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Abstract

本发明提供一种由含有氮化钛的复合基体中回 收钛的方法。该方法包括氯化基体中的氮化钛而得 到含有氯化钛的反应产物，并由反应产物中分离氯化 钛。本发明还提供生产所述的含氮化钛的复合基体 的方法，通过氮化含钛的复合原材料，如复合的冶金 钛铁渣和钛铁矿、钙钛矿、镁钛铁矿以及深绿辉石中 的钛而生产的。The invention provides a compound matrix containing titanium nitride The method of collecting titanium. The method involves chlorination of titanium nitride in a matrix to obtain to the reaction product containing titanium chloride, and to separate the chloride from the reaction product titanium. The present invention also provides the production of the composite matrix containing titanium nitride method, by nitriding titanium-containing composite raw materials, such as composite metallurgical In ferro-ilmenite slag and ilmenite, perovskite, mafia-ilmenite and dark omphacite produced from titanium.

Description

By the method that reclaims titanium in the complex matrix that contains titanium nitride
The present invention relates to reclaim the method for titanium with the form of titanium chloride or titanium oxide by containing with in the complex matrix of titanium nitride as its component.More particularly, the present invention relates to a kind of being applicable to by the method that reclaims titanium in the described matrix with the titanium chloride form, and described matrix is by Nitriding Compound mineral or metallurgical raw material, as ilmenite or contain the ferrotianium slag of titanium oxide and other metal oxides, particularly contain 30-80%(weight) or lower low-grade ferrotianium slag, wherein titanium is with TiO 2The ilmenite of expression and blended metal oxide or titanate makes.
According to the present invention,, may further comprise the steps by containing titanium nitride as the method that reclaims titanium in the complex matrix of its component:
Titanium nitride in the chlorination matrix, and obtain containing the reaction product of titanium chloride;
From reaction product, separate titanium chloride.
To explain below, the chlorination of titanium nitride is to obtain as TiCl by chloridating gas is contacted under 200-500 ℃ temperature with matrix 4Titanium chloride, and as mentioned above, this method is applicable to by reclaiming titanium in the matrix that obtains by Nitriding Compound mineral or metallurgical raw material.Therefore, present method can comprise, makes the step of nitrogen titanium matrix by the titanium in the nitrogenize titaniferous composite materials.
Though present method for as contain 80%(weight) above high titanium value is (with TiO 2Expression) mineral or metallurgical raw material have actual value, but present method is useful as ilmenite or slag particularly for metallurgical raw material, and they more or less are compound, and have be lower than 80%(weight) or be lower than 30% or even lower low titanium value (with TiO 2Expression).Therefore, starting material can be a kind of 80%(weight that contains at the most) the compound metallurgical ferrotianium slag of titanium value, perhaps, starting material also can be selected from rutile, ilmenite, uhligite, picrocrichtonite, pyrgom with and composition thereof mineral.
Because nitriding step is at high temperature, with nitrogen by or cross granular starting material and implement easily, method can comprise a kind of raw-material step of nitrogenize, this raw-material largest particle particle diameter is as best one can little by the mode that can implement or suit, 10-2000 μ m for example, its median size is at most 600 μ m, and preferably, the scope of largest particle particle diameter and average grain diameter is at 50-100 μ m.Therefore present method can comprise, reduced raw material particle size to largest particle particle diameter 2000 μ m at the most before the titanium nitrogenize, and the average grain particle diameter is at most the step of 600 μ m.The reduction of particle diameter, general with crushing and grinding, and the distribution of final grain diameter and grain diameter is decided by the consideration of economic aspect usually.Be easy to high speed and fully carry out nitrogenizing reaction owing to surface-area increases, the cost of grinding can be disregarded.
As mentioned above, nitrogenize generally is under any pressure condition of high temperature, normal pressure or highly compressed, with nitrogen by or cross the particulate state starting material and carry out, and in reducing environment, be effective with excessive nitrogen, and reducing environment can be, for example, by in starting material, provide by suitable proportion composite grain shape carbon.In other words, the nitrogenize of titanium is can be by under high temperature and reducing environment, and the nitrogen that stoichiometry is excessive contacts with starting material and carries out.The good news is, use the excessive nitrogen of stoichiometry, can from reaction zone, remove carbonic acid gas, and can suppress the generation of undesirable titanium carbide.Be used for the preferred gas of nitrogenize, though comprise 25%(volume at least) nitrogen, certainly, nitrogen content high more (up to 100%) then can be obtained better nitriding result.Nitriding step can be at suitable metallurgical reaction, and as rotary kiln or cupola furnace, fluid bed reactor in the perhaps similar reactor, carries out with solid raw material.Starting material can certainly use liquid, and nitrogenize is in bucket or electric furnace, are undertaken by using suitable jet apparatus injection nitrogen.
Preferably, starting material are with the carbon uniform mixing after mixture of raw material is provided, and are best under 1200-1350 ℃ of temperature preferably at 1100-1600 ℃ 1000 ° of-1800 ℃ of temperature, with nitrogen defeated through or failed starting material.The required time of nitrogenize becomes inverse relationship with temperature, and in addition, employed accurate temperature will be considered economy, uses the advantage of lesser temps to disappear because of the long nitridation time of need.Therefore, particularly, nitrogen can be under 1000-1800 ℃ temperature with raw-material the contact, under the situation that the carbon that the reducing environment of providing is arranged exists, carry out, exist at the carbon that capacity is being arranged, consuming existing all oxygen in the environment, and provide in the starting material reduction titanium value (as TiO 2) be the excessive carbon of the needed stoichiometry of titanium.
Certainly, nitrogen is input to the speed of mixture of raw material, should be enough to reach in the allowed time satisfaction of nitrogenize.Average retention time can be 1/2-5 hour, and was perhaps shorter, as 1-3 hour.In addition, at at a high speed defeated nitrogen, the cost of defeated nitrogen and thermal losses and and between the unreacted nitrogen by raw mix, should consider from economic aspect is compromise: and it should be noted that the gas excellent contact, for example, in fluidized-bed or rotary kiln, then enough with the starting material that segment as 1-2 hour shorter residence time.
Nitrogenizing reaction is a strong endothermic reaction.Therefore must provide heat to keep temperature of reaction to reaction zone.This can pass through reactor, for example, heats by using electrical heater or plasma arc, and/or implements by the heating of giving of nitrogen.When nitrogen is pure basically, and during by suitable heat exchanger indirect heating, then wherein any heating can be by the device of burner, and common combusting carbonaceous fuel is as producer gas, coal-tar fuel, heavy oil or meticulous coal, all use air, to obtain required temperature, therefore, with the mixture of nitrogen and carbon monoxide and water vapor, under the condition of anaerobic basically, be passed in the raw mix as nitrogen.In other words, carbonaceous fuel can burn in air and provides combustion gases, this gas to contact with starting material so that described high temperature to be provided, and provides reductive condition required carbon amount with the form of carbon monoxide.Therefore, method can comprise that the carbonaceous material with the finely divided particulate shape mixes with starting material so that the step of reducing environment to be provided.
According to other method, except other heat supply method, can make input contain aerobic, air in the raw-material nitrogen material gas, and contain the external carbon of capacity in the starting material, with by burning by removing deoxidation in the air, this is feasible to replace heat supply.This just helps to keep the heat supply of nitrogenizing reaction.
The essentially no oxygen of nitrogen when input mixes the carbon amount ratio that forms raw mix with starting material, can be the 100-300% of stoichiometric number, is generally the 150-200% of stoichiometric number, and " stoichiometric number " is meant and reduces titanium (with TiO in starting material 2Expression) required carbon amount when being TiN, this depends on existing reaction conditions.As mentioned above, when input air, the external carbon of capacity then will be provided, to guarantee from air, removing deoxidation, for example, for this reason, except essential oxide compound being reduced in the nitride process of titanium in the nitrogenize starting material, with institute's bonded oxygen in the starting material react necessary excessive beyond, the excessive carbon amount of stoichiometry slightly also will be arranged.As mentioned below, if chlorination is to carry out in than the reducing environment a little less than the nitrogenize environment, then this method need be removed some excessive carbon at least certainly after nitrogenize.
With starting material blended carbon, mainly be coal, hard coal, coke, industrial carbon, charcoal, graphite or analogue, have been found that, decolorizing carbon, as dim or jet-black, all can obtain satisfied result, same, preferred carbon, should be form and starting material uniform mixing, and the particle diameter of carbon be similar to raw-material particle diameter, for example with segmentation, 50-100 μ m, or littler.These small-particle particle diameters are easy to separate carbon in the nitrogenize material after the nitrogenize from fluidized-bed, take or wash out carbon granule out of by the high speed fluidisation.
Preferred chlorinating step is to carry out in the reducing environment more weak than nitrogenize environment.
Promote than carrying out chlorination in the reducing environment more weak when the nitrogenize, mainly can comprise, carbon is mixed the reducing environment of carrying out nitrogenize to provide with starting material, after its add-on and/or speed should make nitriding step, the ratio of the carbon in the nitrogenize matrix will be lower than when nitrogenize begins and the ratio of raw material blended carbon, and preferably, as far as possible or feasible low as best one can, in nitridation process, making whole carbon all be oxidized to carbonic acid gas basically, is irreducibility with the environment that causes chlorination to be carried out basically.
If require to have quite high carbon ratio example in the starting material, with promote titanium rapidly and/or nitrogenize fully, then when nitrogenize is complete, can not guarantee carbon-free basically.In this case, method can comprise, behind nitriding step, before the chlorinating step, separates the step of carbon from the matrix that contains titanium nitride.This can implement by physical separation step, for example, with gas fluidized when containing the titanium nitride matrix, then can blow away separation carbon, and when containing the titanium nitride matrix with the liquid fluidisation, but flotation separation carbon then, the carbon of flocculated suspension in liquid and contain the titanium nitride matrix, then by as flotation or similar method by wherein separating throw out.In other words, method preferably includes, and after nitrogenize and before the chlorination, separates the step of carbon from matrix.Can in the used fluidized-bed of nitrogenize, separate carbon, to reduce the reductibility of environment by blowing.
Beyond thoughtly be, before chlorinating step, the reductibility of described reduction environment can suppress or be more preferably other metal oxide formation muriate in the elimination starting material in the chlorinating step process, reduce the consumption of chlorine thus, and reduce undesirable muriate product.The applicant thinks that this characteristics of present method help limiting those titaniums, the muriatic formation in the gaseous metal of iron and vanadium, and the formation of the solid chloride of restriction manganese, magnesium and calcium.In the titanium chloride product, the metal chloride except that titanium all is undesirable impurity, and, by fusion, may aggravate reactor, as the obstruction of fluidized-bed in described temperature.
Because in starting material, generally there is (＜1%(weight) in manganese with admissible a small amount of ratio), and its muriatic fusing point and boiling point be respectively 650 ℃ and 1290 ℃, because it is easy to from TiCl 4The middle separation be not so be considered as TiCl to it 4Undesirable especially impurity in the product.Similarly consideration also is applicable to calcium and magnesium, and their amount is higher, but has high melt point and boiling point.In addition, because the chlorination of magnesium and calcium, the chlorination than titanium on kinetics is slow, thereby gaseous state TiCl 4Can proceed to much bigger degree, and cause the formation of solid chloride of magnesium and calcium quite few, owing to the muriate that consumes magnesium and calcium helps TiCl 4Production, thereby these impurity are being no more than to allow ratio and exist to be necessary.
For example, the chlorination of the titanium nitride that obtains from the nitrogenize starting material can be adopted a kind of chloridating gas, as, HCl, CCl 4, SCl 2Or preferred Cl 2, in suitable temperature (to Cl 2For 200-500 ℃, be 350-450 ℃ preferably) stimulate the menstrual flow or undertaken by the nitrogenize matrix.Change sentence and say that perhaps the chlorination of titanium nitride can be by being selected from Cl 2, HCl, CCl 4, SCl 2With and composition thereof chloridating gas, under 350-450 ℃ temperature, contact with matrix and obtain as TiCl 4Titanium chloride.Relevant this respect, the applicant is surprised to find that, selects suitable nitriding temperature (as 1200-1350 ℃), can guarantee that after its nitrogenize, starting material still keep being suitable for the graininess of chlorination grain diameter.There is no need further to reduce again raw-material particle diameter, and only need cool off and move into suitable reaction vessel, as fixed bed, reverse swirler or simply, fluidized-bed.After described cooling, by magnetic separate and/or weight fraction from, any metal that can remove in the nitridation process simply to be produced.Thus, can further reduce or be more preferably the generation of removing undesirable metal chloride.
Above-mentioned chlorination temperature will be selected like this, makes that the TiN in the nitrogenize matrix is converted to TiCl 4, and under these temperature, the applicant thinks that other the main volatilizable chlorizate that can give birth to by any thing volume production is a transition metal chloride, as iron(ic) chloride (FeCl 3), vanadium chloride (VCl 4), vanadium oxydichloride (VOCl 3) and silicon chlorides (SiCl 4).Any FeCl 3Or vanadium chloride and/or vanadium oxydichloride and TiCl 4Condensation in the gas that is easy to together produce by photochlorination vessel.Any FeCl that produces 3, can be at normal atmosphere, basically than TiCl 4Or VOCl 3Condensation under the higher temperature, and can be easy to therefrom remove, for example in swirler or similar containers, by isolating solid FeCl at 290 ℃ 3And TiCl 4Gas.It should be noted that FeCl in this respect 3306 ℃ of fusions, and be decomposed into FeCl at 315 ℃ 2And Cl 2, FeCl 2Fusing point be higher than 315 ℃, and Cl 3Be gas; TiCl 4136 ℃ of vaporizations; VOCl 3126 ℃ of vaporizations; SiCl 458 ℃ of vaporizations, and VCl 4148 ℃ of vaporizations.Therefore, TiCl thereafter 4With any VOCl 3Or VCl 4Condensation together is (as by any SiCl 4Or separate in the analogue), separate after this pure basically TiCl then by known distillating method 4Can be easy to be oxidized to TiO by currently known methods 2, a kind of valuable pigment.
It should be noted that calcium, magnesium and manganese are all arranged at most of oxygen containing composite mineralss.Thereby they also are present in the used most of starting material of present method, particularly in the metallurgical slag.Present method is distinctive to be to adopt the low temperature chlorination temperature with surprising advantages, and this causes reducing the chlorination of these metals.In addition, the more important thing is that these metal chlorides are solid in the time of 200-500 ℃.Compare with the sort of chlorating that under temperature higher and that be enough to these metal chlorides of fusion, carries out that this is that substantial advantage is arranged, because fusion can cause reactor, as the obstruction of rotary kiln or fluidized-bed.
About chlorination, it should be noted that this is a kind of thermopositive reaction.For example, fluidized-bed reactor is used for chlorination, then the heat of Chan Shenging can be removed by fluidizing gas, and majority of gas is an inert carrier gas, and if needed, heat also can reclaim from these gases with currently known methods.
Chloridating gas can as use a kind of rare gas element by the form of dilution, fails the matrix of via nitride as argon gas or nitrogen dilution, when chloridating gas is Cl 2The time, can be by 10%Cl at least 2The mixed nitrogen of (volume), for example, the 20-80%(volume) Cl 2, and can under normal pressure or high pressure, import.Therefore, in a concrete scheme, chloridating gas can be the Cl with nitrogen dilution 2, form and contain the 20-80%(volume) and Cl 2Mixed gas.As what considered economically, chloridating gas can be failed the via nitride matrix, and its average retention time is 10-120 minute, and being enough to does not need the chlorination in the permission time of the TiN in the nitride material with excessive chloridating gas to satisfied completeness.As mentioned above, compare, reduce the reductibility of environment in the chlorinating step, can reduce except TiCl with nitriding step 4The muriatic ratio that is generated in addition, and reaction conditions that can the selective chlorination step is to reduce this other muriatic generation, the existing description above the kinetics that these muriates generate.
At TiCl 4With any VOCl 3After the condensation, wherein residual chloridating gas and nitrogen can be recycled in the photochlorination vessel, as chloridating gas input or additional the adding.
As hereinafter discussing in more detail, the applicant finds that the ferrotianium slag that Witbank obtains, and rutile and ilmenite can carry out nitrogenize according to method of the present invention by Highveld Steel and Vanadium corporation Limited.The nitrogenize matrix that this slag of nitrogenize is produced when X-ray diffraction analysis, provides clear and definite TiN crystalline phase, even have, also is other clear and definite crystalline phase of few any remarkable thing.Do not find to have titanium carbide or titanium carbonitride to form, also carbide or the carbonitride without any other metal forms.Therefore can think that the remaining component in nitriding step in the starting material slag forms vitreous non-crystalline state matrix phase, and the overwhelming majority (90%) (weight) or more in the titanium) can change nitride into.In next step chlorination, concerning any material, the muriate of generation has only TiCl 4, FeCl 3And VOCl 3, and these muriates all are to be easy to condensation and isolating as mentioned above.
Between nitriding step and chlorinating step, or beginning, present method can comprise the step by magnetic resolution iron in the material to be processed, and, for improving effect, can be with starting material at first with carbon and suitable fusing assistant, as CaCo 3, for example under 800-1200 ℃, handle, so that iron oxide reduction Cheng Tie.This step can reduce the FeCl that is finally produced 2The amount of waste product (consult: as people such as MacMillan, *Proposed Process for Treatment of Low-Grade Titaniferous Ores ' (method that low-grade ilmenite is handled) US Department of the Interior, Bureau of Mines Report of Investigations 4638, January 1950).
When containing the titanium oxide composite materials and be a kind of blended metal oxide or titanate, for example, as ilmenite (FeOTiO 2), uhligite (CaOTiO 2), pyrgom (Ca(Ti.Mg.Al) (Si.Al) 2O 6) or have picrocrichtonite (MgO.2 TiO 2) and so on ore, nitriding step can cause in nitrogenize is carried out by the metal that produces one or more metallic states in the non-titanium metal that exists in described blended metal oxide or the titanate.
These metals can be used physical method before chlorinating step, as weight or magnetic resolution method, perhaps usefulness for example adopts leaching and so on the chemical process of hydrochloric acid, separates from this matrix.Therefore, usually, when the matrix that contains titanium nitride, when also containing the metal except that titanium, present method can comprise, before chlorination by the step of separating metal in the described matrix.
Before chlorination, no matter be the reductibility that reduces environment, perhaps before chlorination, separate any metal that is produced, perhaps both's usefulness as mentioned above, all depend on the used raw-material performance of compound ferrotianium widely, and this can measure by routine test.In addition, as require in principle before chlorination, to eliminate fully reductibility environment and generation as described in any metal, but from considering that economically these steps are not proceed to completely.
The present invention also provides a kind of and makes a kind of titanium nitride that contains as its composition from the titaniferous composite materials, and is applicable to the matrix method that above-mentioned titanium reclaims.
Therefore, according to a further aspect in the invention, provide a kind of production nitrogen titanium as its composition and be applicable to the method for the matrix that above-mentioned titanium value reclaims, this method comprises, be selected from compound metallurgical ferrotianium slag, ilmenite, uhligite, geikielite with and composition thereof the titaniferous composite materials in titanium carry out nitrogenize.
The present invention also relates to the titanium that reclaims at any time by above-mentioned recovery method, and the invention still further relates to by what aforementioned production method was produced and contain the matrix that titanium nitride is made its composition.
Referring now to accompanying drawing and example, the present invention is described by embodiment.
In the accompanying drawing:
Fig. 1 shows by the resulting ferrotianium slag of Highveld iron and steel and vanadium company limited (Steel and Vanadium Corporation Limited), uses Cuk aThe X-ray diffraction style that ray records, its ° 2 θ scopes are 10-110 °;
Fig. 2 represents that to the slag of style shown in Figure 1, after following embodiment 1 nitrogenize, its ° 2 θ are the similar diffraction pattern of 32-80 ° of scope;
Fig. 3 represents, is used for being undertaken by the slag of embodiment 1 nitrogenize the schematic section of chlorating equipment;
Fig. 4 represents, according to the schematic section of the used equipment of embodiment 2 nitrogenize.
Embodiment 1
To contain the 30%(weight of having an appointment) the titanium value (presses TiO 2) the ferrotianium slag of Highveld Steel and Vanadium Corporation Limited grind and be crushed to the particle of particle diameter less than 1000 μ.With median size is the carbon of the dim shape of 0.5 μ, in 20%(weight) ratio compare mixing with slag.
The sample of slag and dim mixture is packed in the Alpha-alumina crucible, and be placed in the electrically heated tube furnace.This stove is repeated to vacuumize (4 times) until 20 torrs (Torr), and with high purity nitrogen (99.9998%(volume)) flushing.Defeated in stove with the flow velocity of the 40ml/min nitrogen gas stream that this is stable then.
Heat stove then lentamente, in 5 hours,, be heated to 1550 ℃, and 1550 ℃ of insulations 10 hours, so that the nitrogenization raw material mixture, and obtain the matrix of nitrogenize from room temperature with 5 ℃/minute basicly stable heating rate.Then stove is naturally cooled to room temperature, the nitrogenize matrix is carried out the X-ray diffraction analysis with the sample of raw mix (not nitrogenize).
The X-ray diffraction of raw mix be illustrated in Fig. 1 and the nitrogenize matrix be shown in Fig. 2.Fig. 1 represents that raw mix has quite high crystallization degree, and Fig. 2 shows, points out at the peak by many TiN clearly among Fig. 2, and except the basic ratio of TiN, the nitrogenize matrix is comparatively unbodied.
Before the nitrogenize, raw mix is a black, and after the nitrogenize in matrix, macroscopic spot to many light color.
Relate to Fig. 3 now, the nitrogenize matrix generally is chlorination in the equipment of several 10 expressions with reference.Equipment 10 comprises a tube electric heater 12, wherein settles one to be furnished with a glass inlet port pipe 16 and a tubular type glass reactor 14 that leads to the glass outlet pipe 18 of glass receiving flask 20.Bottle 20 has a glass gas outlet tube 22, and container 14 is equipped with thermopair 24 and a porous agglomerating glass disc 26.
During use equipment 10, the garden that 10 gram nitrogenize matrixes are placed in the container 14 is coiled, and will be with Cl 2The chloridating gas that exists is failed through managing 16 with the speed of 60 ml/min, and the temperature of chlorinator by well heater 12, with every grade of about speed of 50 ℃, is heated to 350 ℃ temperature step by step by room temperature simultaneously, in this case, and Cl 2Beginning and matrix reaction.When 1.5 hours afterreactions have tended to fully, with regard to stopped reaction.
In product receiving flask 20, obtain about 6 reaction product that restrain by managing 18, be yellowish brown liquid, also have a small amount of red solid thing.Decanting liq, the row element analysis of going forward side by side, analytical results is shown in table 1:
Table 1
Element %(weight)
Cl 75,8
Ti 20,9±0,3
V 0,93±0,03
Si 0,18±0,06
Al 0.01
Fe 0,01
Mg 0,005
Cr Do not detect
Cu Do not detect
Find out that from the analytical results that is shown in table 1 Al of detected minute quantity, Fe, Mg, Cr and Cu can disregard, and think and contain TiCl in the liquid 4, VCl 4And/or VOCl 3And SiCl 4Mixture and wherein be dissolved with number of C l 2, analytical results is shown in following table 2:
Table 2
Compound %(weight)
TiCl 4 82,7
VCl 4And/or VOCl 3 3,5
SiCl 4 1,1
Cl 2 12,7 (surpluses)
For test reduces the feasibility of the reductibility carry out the chlorination environment, having in the presence of the carbon, according to reaction:
In pipe 18, carry out pure V 2O 5Chlorination.
Chlorination is carried out at 350 ℃, and reaction continues more than 1 hour under each situation.Under first kind of situation, generate jonquilleous VOCl 3Product, and under second kind of situation, generate the VCl of avy blue 3Product.
Under the situation that does not have carbon to exist, revision test is not seen reaction, afterwards with 50 ℃ of elevated temperatures of each increase, and keeps 30 minutes under every rising temperature once, until 450 ℃ of top temperatures.Do not see any reaction takes place, this shows owing to the reducing environment that does not have carbon to provide, at least with regard to V 2O 5, suppressed to cause generating VoCl 5And VCl 3Pay reaction.
Embodiment 2
With titaniferous composite materials, slag among the embodiment 1 and ilmenite and the carbonaceous reducing agent that exists with coal and charcoal form, separated pulverizing is ground to the particle that maximum particle diameter is no more than 53 μ m.Then with starting material and carbonaceous reducing agent in required ratio uniform mixing, with the mixture of supplying raw materials.
The sample of different material mixture is respectively charged into electrically heated, and in two graphite boats in the horizontal pipe stove of sealing, this boat contains 5 kinds of samples of each 40 gram altogether.
With 255 ℃/hour speed heating stove, till the working temperature of placing the sample place is 1300 ℃, carry out keeping working temperature, then the naturally cooling stove in 3 hours processes of nitrogenize at sample.In the Total Test process, with stable nitrogen gas stream (purity＞99%(volume)) import the stove of flowing through.
Under each situation, all prepared two kinds of raw mixs, a kind of is to contain raw-material titanium value (with TiO 2) be reduced to the carbon of the required stoichiometric ratio of titanium, another kind of then contain 100% excessive carbon.
Every part is that 40 four kinds of raw mix samples that restrain are placed in the boat, and by above-mentioned, using flow velocity is the nitrogen material gas of 620 ml/min, these samples of nitrogenize simultaneously.
The matrix reaction product of gained, qualitative with the X-ray diffraction method, and carry out quantitative chemical analysis to measure the TiN amount that is generated.Titanium content is by fusion, then uses atomic absorption spectrophotometer, and the nitrogen that exists is to measure with chemical analysis.
The used slag and the chemical ingredients of ilmenite are incorporated in the following table 3; And the conversion percentage of the TiN of gained is summarized in following table 4.
Used the same reference number of same section among Fig. 3 among Fig. 4.Reactor 14 is pipes of a kind of aluminosilicate, and manage 16,18 and bottle 20 all be stainless.Graphite boat is with 28 expressions, and heating unit is with 30 expressions.Porous aluminosilicate garden dish filter set is with 26 expressions, and it separates the entrance and exit of reactor 14, and well heater 12 is done as a whole, uses wrapped with insulation.
Table 3
Form Starting material
Ferrotianium slag (weight %) Ilmenite (weight %)
TiO 2 30,5 a 48,8
SiO 2 20,75 1,3
MgO 14,10 1,0
CaO 16,8 0,04
Al 2O 3 13,65 0,7
Cr 2O 3 0,19 ＜0,01
FeO 5,15 47,9
V 2O 3 1,05 0,12
MnO 0,69 0,82
aPrincipal mode: pyrgom (Ca(TiMg.Al) (Si, Al) 2O 6);
Uhligite (caTiO 3)
A small amount of form: pseudobrookite (Fe 2O 3TiO 2) ulvite (Fe 2TiO 4)
Table 4
Starting material Carbonaceous reducing agent Reductive agent add-on (% of stoichiometry C ratio) Be converted into the %(weight of TiN)
Slag Charcoal 100 73.6
Slag Charcoal 200 92.9
Slag Coal 100 73.8
Slag Coal 200 92.7
Ilmenite Charcoal 100 72.9
Ilmenite Charcoal 200 94.9
Ilmenite Coal 100 75.8
Ilmenite Coal 200 91.6
Embodiment 1 has confirmed method of the present invention, is feasible to the ferrotianium slag that is used for being obtained by Highveld Steel and Vanadium Corporation Limited.Particularly, Fig. 2 shows, adopts 1550 ℃ of following nitrogenize, can be satisfactorily the titanium in the nitrogenize slag in high proportion, and high selectivity is arranged.Table 2 further shows, can only be contained VCl 4And/or VOCl 3, SiCl 4And Cl 2TiCl as impurity 4Chlorizate, and these impurity by the distillation can be from TiCl 4In be easy to separate, and obtain highly purified TiCl 4
If desired, this TiCl 4Be converted into TiO easily 2
Embodiment 2 shows, above-mentioned slag of nitrogenize and ilmenite are feasible at 1300 ℃, and use the excessive carbon of 100% stoichiometry, can obtain being higher than 90%(weight) high TiN transformation efficiency.Can expect, best temperature, reductive agent ratio, the reaction times etc. will cause better conversion.
The advantage that the present invention gives prominence to is to provide a kind of method, can be used in the slag among the embodiment at least, the ferrotianium slag is converted into value product, i.e. TiCl 4/ TiO 2This slag produces as waste material in the production of the steel of Highveld iron and steel and vanadium company limited and vanadium, and single its volume is a potential environment difficult problem at least.Present method has reduced the refuse amount that will throw away, and all is to allow on the ecology by any refuse that the inventive method produced, and to some industry, has the potential purposes as Cement industry.In addition, for example, contain the ilmenite of quite low ratio titanium value, can be advantageously used for starting material in the method.

Claims (17)

1, a kind of method that reclaims titanium is characterized in that, reclaims titanium by containing in the complex matrix of titanium nitride as its composition, the steps include:
Titanium nitride in the chlorination matrix, and obtain containing the reaction product of titanium chloride;
From reaction product, separate titanium chloride.
2, the method for claim 1 is characterized in that, the chlorination of titanium nitride is by with chloridating gas, contacts with matrix under 200-500 ℃ temperature, and obtains as TiCl 4Titanium chloride.
3, claim 1 or 2 method is characterized in that, it comprises by the titanium of nitrogenize in the titaniferous composite materials and makes the step that contains the titanium nitride matrix.
4, the method for claim 3 is characterized in that, starting material are to contain 80%(weight at the most) the compound metallurgical ferrotianium slag of titanium value.
5, the method for claim 3 is characterized in that, starting material are to be selected from complete red stone, ilmenite, uhligite, picrocrichtonite, pyrgom and composition thereof.
6, the method for each claim among the claim 3-5 is characterized in that, this method comprises, before titanium nitride, reduce raw-material grain diameter to largest particle particle diameter and be at most 2000 μ m, and the average grain particle diameter is at most the step of 600 μ m.
7, the method for each claim among the claim 3-6 is characterized in that, the nitrogenize of titanium is by in high temperature and reducing environment, contacts with starting material with the excessive nitrogen of stoichiometry and carries out.
8, the method for claim 7, it is characterized in that, nitrogen is under 1000-1800 ℃ temperature with raw-material the contact, and under the situation that the carbon that reducing environment is provided exists, carry out, there is the carbon of capacity to exist, with all oxygen that exists in the consumption environment, and to reducing titanium in the starting material (with TiO 2Expression) provide stoichiometry excessive carbon to the necessary carbon of titanium.
9, the method for claim 8 is characterized in that, combusting carbonaceous fuel makes combustible gas contact with starting material so that combustible gas to be provided in air, so that described high temperature to be provided, and provides reducing environment necessary carbon amount with the carbon monoxide form.
10, the method for claim 8 is characterized in that, this method comprises that the granular carbon material with segmentation mixes with starting material so that the step of reducing environment to be provided.
11, the method for claim 10 is characterized in that, this method is included in after the nitrogenize and before the chlorination, separates the step of carbon from matrix.
12, the method for above-mentioned each claim is characterized in that, the chlorination of titanium nitride is by being selected from Cl 2, HCl, CCl 4, SOl 2With and composition thereof chloridating gas, under 350-450 ℃ temperature, contact, and obtain as TiCl with titanium nitride 4Titanium chloride.
13, the method for claim 12 is characterized in that, chloridating gas is Cl 2, it forms with nitrogen dilution and contains the 20-80%(volume) and Cl 2Mixed gas.
14, the method for above-mentioned each claim is characterized in that, contains the titanium nitride matrix and also contains metal except that titanium, and this method is included in before the chlorination step by separating metal in the described matrix.
15, titanium is characterized in that they are that method by aforesaid each claim reclaims.
16, a kind of production contains titanium nitride as its composition and be applicable to the method for the complex matrix of claim 1 method, it is characterized in that, this method comprises the titanium in the titaniferous composite materials of nitrogenize, described starting material be selected from the metallurgical ferrotianium slag of compound, titanium titanium ore, uhligite, picrocrichtonite, pyrgom with and composition thereof.
17, a kind of complex matrix that contains titanium nitride, it is to produce by the method for claim 16.
CN91105786A 1990-07-25 1991-08-01 Process for recovery of titanium values from complex matrix comprising titanium nitride Expired - Lifetime CN1037982C (en)

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CN100402678C (en) * 2006-11-14 2008-07-16 隋智通 Process for separation and production of titanium-rich materials from titanium-containing blast furnace slag
CN102428195A (en) * 2009-05-29 2012-04-25 日立金属株式会社 Method for producing titanium metal
CN103261456A (en) * 2010-12-13 2013-08-21 Csir公司 Upgrading Titanium-Containing Materials
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Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB795386A (en) * 1955-06-24 1958-05-21 Ici Ltd Improvements in or relating to the electrolytic production of titanium
US3060002A (en) * 1959-09-25 1962-10-23 Dow Chemical Co Pressure leaching of titaniferous material
DE2103255C3 (en) * 1971-01-25 1974-05-30 Parlee Anderson Corp., Burlingame, Calif. (V.St.A.) Carbothermal process for reducing an oxide from a reactive metal
SE431231B (en) * 1982-05-28 1984-01-23 Skf Steel Eng Ab WAY TO Separate and Extract Iron and Its Alloys from Fine-grained Oxide Raw Materials
CN1005629B (en) * 1987-10-27 1989-11-01 冶金工业部攀枝花钢铁公司钢铁研究院 Method for preparing titanium tetrachloride from titanium-containing blast furnace slag

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CN100402678C (en) * 2006-11-14 2008-07-16 隋智通 Process for separation and production of titanium-rich materials from titanium-containing blast furnace slag
CN102428195A (en) * 2009-05-29 2012-04-25 日立金属株式会社 Method for producing titanium metal
CN102428195B (en) * 2009-05-29 2014-12-10 日立金属株式会社 Method for producing titanium metal
CN103261456A (en) * 2010-12-13 2013-08-21 Csir公司 Upgrading Titanium-Containing Materials
CN103261456B (en) * 2010-12-13 2015-03-18 Csir公司 Upgrading Titanium-Containing Materials
CN116393247A (en) * 2023-04-17 2023-07-07 攀钢集团攀枝花钢铁研究院有限公司 Method for recovering carbon and titanium from blast furnace slag low temperature chlorination titanium tailings and dust collection slag

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