CN109055781A - A method of titanium products are prepared using ferrotianium grandidierite as raw material - Google Patents
A method of titanium products are prepared using ferrotianium grandidierite as raw material Download PDFInfo
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- CN109055781A CN109055781A CN201810757820.3A CN201810757820A CN109055781A CN 109055781 A CN109055781 A CN 109055781A CN 201810757820 A CN201810757820 A CN 201810757820A CN 109055781 A CN109055781 A CN 109055781A
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- titanium
- raw material
- ferrotianium
- grandidierite
- iron
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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
- C22B34/1218—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 dry processes
- C22B34/1222—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 dry processes using a halogen containing agent
Abstract
The present invention relates to a kind of methods for preparing titanium products as raw material using ferrotianium grandidierite, belong to chemical field.Preparation method includes: that ferrotianium grandidierite raw material is incorporated carbon raw material after evenly mixing by certain stoichiometric ratio, it heats up and restores under certain atmosphere, iron component is set to be reduced into metallic iron, titanium component is converted into oxidation of coal titanium, carbon titanium oxynitrides, and other components (aluminium, magnesium, calcium, silicon) are maintained at oxidation state.After the separation of iron component, slag phase is handled through cryogenic selective chlorination, can directly obtain the titanium tetrachloride that grade is higher than 99%.The present invention can effectively reduce the method cost that existing iron and titanium extract, and it effectively solves the problems, such as other oxides during existing chlorination while being chlorinated, significantly increase the selectivity of chloride process in titanic chloride production process, improve the chlorination efficiency of titanium, highly purified titanium products can be directly obtained, it is purified without subsequent purification, greatlies simplify the method flow that ferrotianium grandidierite extracts iron and titanium elements.
Description
Technical field
The present invention principally falls into chemical technology field, is related to a kind of side that titanium products are prepared using ferrotianium grandidierite as raw material
Method, and in particular to the method that titanium tetrachloride is prepared as raw material using ferrotianium grandidierite and prepares titanium dioxide.This method is by accurate
High temperature carbon thermal reduction is controlled, makes the iron constitutional changes metallic iron in ferrotianium grandidierite, titanium component is changed into oxidation of coal titanium, carbon nitrogen
Titanium oxide and other oxides constitute mixture as chlorizated raw material, can directly obtain four highly purified chlorinations through chlorination processing
Titanium；Highly purified titanium dioxide can be obtained after titanium tetrachloride is oxidation-treated.
Background technique
Ferrotianium grandidierite, it is widely distributed, reserves are rich such as China's Panxi Diqu, the vanadium titano-magnetite in Chengde area
Richness, resource are huge, and wherein titanium resource accounts for 91% or more of national titanium resource, have high comprehensive utilization value.No matter
Be at present industrial ferrotianium grandidierite smelt use " blast furnace-converter " technique or Recent study person to propose " turn bottom
Molten point-fine grinding magnetic separation-pickling of furnace direct-reduction-electric furnace " technique, basic technology route are by the iron in mineral, vanadium oxidation
Object is reduced into vanadium-bearing hot metal, and titanium component is then mainly entered in slag in the form of low oxide.Due to furnace charge and smelting technique water
Flat difference, than relatively high, a large amount of titanium slag is difficult to be effectively treated slag iron, is largely processed to grain slag, slag rubble, swollen
The lower building materials materials of the economic values such as swollen slag and slag pearl, titanium component therein are unable to get effective use, this is to China
Titanium resource abundant causes huge waste.
For the part Ti-containing slag, " high temperature cabonization-low temperature chlorination " technique in the prior art passes through high temperature cabonization mistake
Titanium component in Ti-containing slag is reduced into titanium carbide by journey, utilizes titanium carbide (TiC) and gangue content (Al2O3、MgO、CaO、SiO2)
Chlorination selectivity, to carbonization clinker carry out low temperature chlorination processing prepare titanium tetrachloride, to realize in ferrotianium grandidierite
The recycling and utilization of titanium component.However, due to the technique by carbonizing reduction terminal point control at titanium carbide (TiC), in chlorination reaction
The carbon generated in the process will promote gangue content (Al in a manner of reduction2O3、MgO、CaO、SiO2) chlorination, significantly reduce
The selectivity of chlorination process, and then cause to contain a certain amount of chlorinated impurities (AlCl in the titanium tetrachloride prepared3、MgCl2、
CaCl2、SiCl4), it is necessary to mating subsequent refining step and recovery process carry out secondary treatment, could obtain the tetrachloro of higher degree
Change titanium.This just brings the unnecessary waste of raw and auxiliary material, while reducing the chlorination efficiency of titanium, causes process flow elongated,
Increase technology difficulty, process economics cost.Obviously, the work of titanium tetrachloride is prepared using ferrotianium grandidierite in the prior art
Skill is urgently further improved.
Meanwhile the richness comprising carbon (nitrogen) titanium oxide generated after iron is being prepared using other ferrotianium raw materials in the prior art
It is found during the progress titanium products production of titanium phase substance, due to process conditions difference, the specific ingredient of carbon (nitrogen) titanium oxide is deposited
More gangue content is caused to be chlorinated under a variety of possibilities, partial picture, so that the purity of obtained titanium products is different, if
It industrially applies, still needs to carry out certain post-processing to the titanium products for not meeting purity requirement, because without from root
The quality stability of production titanium products is solved the problems, such as in sheet.
Summary of the invention
In view of the above technical problems, the present invention provides a kind of method for preparing titanium products as raw material using ferrotianium grandidierite, energy
It is enough effectively to solve to utilize part gangue content (Al in ferrotianium grandidierite production titanium tetrachloride technical process2O3、MgO、CaO、SiO2)
It is chlorinated the problem for causing product impurity more simultaneously, substantially alleviates the pressure of subsequent refining and edulcoration process, effectively promotes titanium group
The chlorination efficiency divided reduces resource consumption and process costs, significantly improves the utilization rate of titanium resource in ferrotianium grandidierite.
The present invention is achieved by the following technical solutions:
A method of titanium products being prepared using ferrotianium grandidierite as raw material, the described method comprises the following steps:
(1) ferrotianium grandidierite raw material is subjected to broken pretreatment；
(2) it is incorporated carbon containing reducer in being crushed pretreated raw material, obtains mixture；
(3) heat up under certain atmosphere to the mixture and carry out reduction reaction, obtain include richness titanium phase substance, iron and
The reduzate of slag phase component；
(4) separation is discharged in the iron in the reduzate, obtains the first point of production comprising rich titanium phase substance and slag phase component
Object；
(5) just product is divided to be placed in chlorination appratus as chlorizated raw material for described, carries out selectivity at a certain temperature
Chlorination, during the selective chlorination, slag phase component is maintained at the solid state of oxide, the richness titanium phase substance chlorination
Titanium tetrachloride vapors are generated, is collected after condensation and obtains the titanium tetrachloride product that purity is higher than 99%.
Further, the rich titanium phase substance includes oxidation of coal titanium TiCmOnWith carbon titanium oxynitrides TiCxNyOzIn at least one
Kind；
The oxidation of coal titanium TiCmOnIn, m+n=1 and 0.5≤m/n≤1；
The carbon titanium oxynitrides TiCxNyOzIn, x+y+z=1,0 y≤1 < and 0.5≤x/z≤1.
Further, the amount for the carbon containing reducer being incorporated in step (2) can will be in the ferrotianium grandidierite raw material
Ferriferous oxide be all reduced into metallic iron, and the titanium oxide in the ferrotianium grandidierite raw material can all can be restored
At the mixture of oxidation of coal titanium or carbon titanium oxynitrides or both.
Further, the process of heating described in step (3) keeps the temperature a period of time after reaching set temperature.
Further, described heat preservation a period of time refers to heat preservation 2~10 hours.
Further, in step (3), 1100~2200 DEG C of progress reduction reactions are warming up to.
Further, in step (3), 1100~1400 DEG C of progress reduction reactions are warming up to.
Further, atmosphere described in step (3) includes argon gas, nitrogen or air atmosphere.
Further, after step (2) and before step (3), further include by the mixture ball milling, be uniformly mixed simultaneously
The step of compression moulding.
Further, in step (4), it includes: in reduction reaction that isolated method, which is discharged, in the iron in the reduzate
The molten iron of reduction is expelled directly out under high temperature after progress；Or it is removed in reduzate by the way of the gravity treatment, magnetic separation of solid iron
Iron.
It further, further include to described before discharge separates iron when by the way of the gravity treatment of solid iron, magnetic separation
Reduzate carries out pretreated step, to the reduzate carry out pretreated step include be crushed, ultrasound, ball milling divide
Dissipate processing.
When further, by the way of the magnetic separation using solid iron, after pre-processing to the reduzate, magnetic is obtained
Raw material is selected, the magnetic separation raw material is placed in magnetic plant and carries out magnetic separation.
Further, in step (5), the temperature of selective chlorination is carried out are as follows: 200~600 DEG C.
Further, the ferrotianium grandidierite includes ilmenite, vanadium titano-magnetite, ilmenite concentrate, iron ore concentrate, high titanium slag and gold
Any one in red stone or any two or more combination.
Further, the carbon containing reducer includes active carbon, graphite powder, charcoal, petroleum coke, pitch, coke powder and coal dust
In any one or any two or more combination.
A method of titanium dioxide being prepared, four chlorinations prepared with any one of claim 1-15 the method
Titanium is raw material, oxidation-treated to prepare titanium dioxide.
Different from being gone back in turn due to generating carbon after chlorination in the prior art using titanium carbide (TiC) as main chlorination object
The former other oxide (Al of chlorination2O3, MgO, CaO and SiO2) technique that causes product impure.Method provided by the present invention is by titanium
The carbothermic reduction process of iron grandidierite is accurately controlled in specific carry out degree, i.e. ferriferous oxide in raw material is completely reduced into
Metallic iron, titanium oxide are completely reduced into oxidation of coal titanium TiCmOnAnd/or carbon titanium oxynitrides TiCxNyOz；And accurately control carbon oxygen
Than (the oxidation of coal titanium TiCmOnIn, m+n=1 and 0.5≤m/n≤1；The carbon titanium oxynitrides TiCxNyOzIn, x+y+z=1,0
Y≤1 < and 0.5≤x/z≤1) so that all carbons with oxidation of coal titanium TiCmOnAnd/or carbon titanium oxynitrides TiCxNyOzIn
Oxygen element form carbon oxide gas discharge, do not generate and any promote other oxide (Al2O3, MgO, CaO and SiO2) chlorination
The carbon occurred is reacted, so as to avoid oxide (Al other during subsequent chloride process2O3, MgO, CaO and SiO2) chlorination
The generation of reaction improves the selectivity of chloride process.
Therefore, method provided by the present invention not only significantly reduces the burden of subsequent purification dedoping step, avoids existing
The unnecessary consumption of raw and auxiliary material, improves the chlorination efficiency of titanium in row titanium tetrachloride production technology, reduce process economics at
This, while also an easier, effective approach is provided for low grade titan raw material production titanium tetrachloride and titanium white chloride: it is specific
Ground, in the discharge for accurate the control reduction and ferrous components for completing iron in ferrotianium grandidierite, titanium component by equipment such as blast furnace, electric furnaces
Afterwards, to contain oxidation of coal titanium TiCmOnAnd/or carbon titanium oxynitrides TiCxNyOz；(the oxidation of coal titanium TiCmOnIn, m+n=1 and
0.5≤m/n≤1；The carbon titanium oxynitrides TiCxNyOzIn, x+y+z=1,0 y≤1 < and 0.5≤x/z≤1) clinker carry out
Cryogenic selective chlorination can directly obtain the titanium tetrachloride product that grade is up to 99%, need not move through secondary refining and purification step
Suddenly, implementing process is clearly distinguishable from scheme in the prior art, and the preparation process for solving various titanium products direct cannot obtain
The problem of to high-purity titanium product, technical effect is substantially better than the prior art；Using the titanium tetrachloride product as raw material, at oxidation
Highly purified titanium dioxide can be prepared after reason, greatly simplify the preparation process of titanium products and make the titanium products provided that there is height
Purity, high-quality and high competitiveness.
In addition, proposition of the invention is so that the preparation process for producing iron and titanium products from ferrotianium mineral intergrowth is simplified, high
Effect, smoothness, eliminate the redundant and complicated in previous preparation process, and only bias toward the extraction and application of ferro element and cause titanium first
Element enters clinker or heap is abandoned or handled with complicated and inefficiency technology mode, so that potential value is not fully exerted
The case where, be conducive to making full use of for mineral resources and social resources.
Advantageous effects of the invention:
1) ferrotianium grandidierite raw material is incorporated carbon raw material after evenly mixing by certain stoichiometric ratio by the method for the invention,
It heating up and restores under certain atmosphere, iron component is made to be reduced into metallic iron, titanium component is converted into oxidation of coal titanium, carbon titanium oxynitrides,
And other components (aluminium, magnesium, calcium, silicon) are maintained at oxidation state；By the accurate control to ferrotianium grandidierite production method, obtain
Rich titanium phase substance in being different from the prior art, with special component is greatly mentioned using the richness titanium phase substance as chlorizated raw material
The selectivity for having risen chloride process in the prior art improves the chlorination efficiency of titanium, has obtained having stabilizing quality and height pure
The titanium products of change, simplify process flow, reduce resource consumption；
2) the method for the invention provides a variety of ferrous components separate modes, enhances the flexibility and economy of technique；
3) the method for the invention in raw material iron and titanium ingredient made full use of, process is simple and compact, technique
Parameter stability, production cost be low, environmental-friendly, energy conservation and environmental protection；
4) the method for the invention adaptability to raw materials is strong, is widely portable to the ferrotianium grandidierite of various grades.
5) the method for the invention can be effectively reduced the process costs that existing iron and titanium extract, and effectively solve existing chlorine
The problem of other oxides are chlorinated simultaneously during chemical industry skill, significantly increases the choosing of chloride process in titanic chloride production process
Selecting property improves the chlorination efficiency of titanium, can directly obtain highly purified titanium products, purifies, greatlies simplify without subsequent purification
The process flow of ferrotianium grandidierite extraction iron and titanium elements.
Detailed description of the invention
Fig. 1 is the method flow diagram that titanium tetrachloride is prepared by raw material of ferrotianium grandidierite；
Fig. 2 is the X ray diffracting spectrum of reduzate lower part under 1 argon atmosphere of the embodiment of the present invention；
Fig. 3 is the X ray diffracting spectrum on reduzate top under 1 argon atmosphere of the embodiment of the present invention；
Fig. 4 is the X ray diffracting spectrum of 1 low temperature chlorination residue of the embodiment of the present invention；
Fig. 5 is the X ray diffracting spectrum of 1 oxidation product of the embodiment of the present invention；
Fig. 6 is the X ray diffracting spectrum on reduzate top under 1 argon atmosphere of comparative example of the present invention；
Fig. 7 is the X ray diffracting spectrum of 1 low temperature chlorination residue of comparative example of the present invention；
Fig. 8 is the X ray diffracting spectrum on reduzate top under 2 argon atmosphere of comparative example of the present invention；
Fig. 9 is the X ray diffracting spectrum of 2 low temperature chlorination residue of comparative example of the present invention.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is explained in further detail.It should be appreciated that specific embodiment described herein is used only for explaining the present invention, and
It is not used in the restriction present invention.
On the contrary, the present invention covers any substitution done on the essence and scope of the present invention being defined by the claims, repairs
Change, equivalent method and scheme.Further, in order to make the public have a better understanding the present invention, below to of the invention thin
It is detailed to describe some specific detail sections in section description.Part without these details for a person skilled in the art
The present invention can also be understood completely in description.
The so-called ferrotianium grandidierite of the present invention is the general designation of a kind of ore, is contained such as China's Panxi Diqu, Chengde area
The various ores rich in titanium and iron such as vanadium titano-magnetite, specifically include ilmenite, vanadium titano-magnetite, ilmenite concentrate, iron ore concentrate, height
At least one of ores such as titanium slag, rutile.
Broken equal pretreatment can be carried out to ferrotianium grandidierite when method starts, to increase the surface area of ore, be conducive to
Reducing agent contact guarantees that sufficiently reaction, the process can carry out in the equipment such as raymond mill.
After being incorporated carbon containing reducer in miberal powder, ball milling mixing is uniformly and by powder pressing forming；
Carbon containing reducer specifically include active carbon, graphite powder, charcoal, petroleum coke, pitch, coke powder to few in, coal dust etc.
It is a kind of；
The amount of carbon containing reducer supplying is calculated according to chemical reaction metering ratio, and carbothermic reduction process control is being closed
Suitable carry out degree, so that the ferriferous oxide in raw material is completely reduced into metallic iron, titanium oxide is completely reduced into carbon oxygen
Change the mixture of titanium, carbon titanium oxynitrides or both；
It heats up under certain atmosphere to the mixture in the equipment such as blast furnace or electric furnace and carries out high temperature reduction reaction, gas
It is any that atmosphere can be argon gas, nitrogen, air or its mixture；Wherein, temperature-rise period are as follows: be slowly warming up to about 1100~2200
DEG C, more preferably 1100~1400 DEG C；A period of time is kept the temperature after reaching set temperature, according to circumstances soaking time is 1~15
Hour is differed, and more preferably 2~10 hours；
It is reacted by high temperature reduction, the ferriferous oxide in ferrotianium grandidierite raw material is completely reduced into metallic iron, titanyl
Object is completely reduced into the mixture of oxidation of coal titanium, carbon titanium oxynitrides or both；
By the iron removal in obtained reduzate, using processes such as such as cooling, broken, crushing, wet-milling, refinements to reduction
After product pretreatment, humidifying powder can be placed in progress magnetic separation separation in magnetic plant, sufficiently to remove iron phase component therein,
Wherein annular energy processing cycle flow stock can be used in magnetic plant；Or after reduction reaction progress under high temperature by the iron of reduction
Water is expelled directly out.Two ways is finally obtained comprising rich titanium phase substance and slag phase component (Al2O3, MgO, CaO and SiO2) just
Divide product；
Just product will be divided to be placed in chlorination appratus as chlorizated raw material, selective chlorination is carried out at 200~600 DEG C, it is rich
Titanium phase substance chlorination is collected at titanium tetrachloride vapors, after condensation obtains the titanium tetrachloride product that purity is higher than 99%, slag phase component
Then it is maintained at the solid state of oxide；
Titanium dioxide can be obtained after the titanium tetrachloride product of acquisition is oxidation-treated, can also be used as the raw material of Titanium production
It uses.
Examples and Comparative Examples are the special efficacies in order to preferably show present invention disclosed above technology in detailed below
Or feature, according to agreement well known to crowd, the invention patent core content range to be protected is not restricted to following implementation
Technical data and condition provided by example.
Embodiment 1
Weigh ilmenite (FeO:42.7%, TiO that 200.0g is broken into fine particle through vibromill2: 47.5%), and supplying
42.9g graphite powder (carbon content 99.9%) is placed in planetary ball mill and is uniformly mixed, powder pressing forming juxtaposition after ball milling
For argon atmosphere and 2000 DEG C are to slowly warm up in high temperature furnace, in control furnace, and heat preservation is cooled to room temperature after 3 hours, is divided
For the reduzate of upper and lower two parts, lower part is through its structure of X-ray diffraction analysis, as shown in Figure of description 2, also to originate in
Object iron；Top is through its structure of X-ray diffraction analysis, is oxidation of coal titanium (TiC as shown in Figure of description 30.5O0.5, x/z=1)
With the mixture of other oxide components not being reduced.It can be seen that after the reduction of carbon heat selective, in ferrotianium grandidierite
Ferriferous oxide is reduced into metallic iron and is deposited on lower part, and titanium oxide is reduced into oxidation of coal titanium (TiC0.5O0.5) and other oxidations
Object component (Al2O3-MgO-CaO-SiO2) it is in top.Reduzate upper block after broken and be ground to 200 mesh or less,
Chlorination processing is carried out at 200 DEG C, X-ray diffraction analysis is carried out to residue after complete reaction, as a result such as Figure of description 4
It is shown, it is other oxide component (Al2O3-MgO-CaO-SiO2)；After the further oxidation processes of chlorizate, aoxidized
Product is through X-ray diffraction analysis, is titanium dioxide (TiO as a result as shown in Figure of description 52), constituent analysis shows its purity
It is 99.4%, this shows for the titanium component in ferrotianium grandidierite to be reduced into carbon (nitrogen) titanium oxide (TiCx(Ny)Oz) after carry out chlorine again
Change processing, may be implemented the selective chlorination between titanium component and other oxide components, may finally obtain highly purified
Titanium tetrachloride and titanium dioxide.
Embodiment 2:
Weigh the high titanium slag (Fe that 200.0g is broken into fine particle through vibromill2O3: 10.5%, TiO2: 77.7%), match
Enter 48.1g graphite powder (carbon content 99.9%) and be placed in planetary ball mill to be uniformly mixed, powder pressing forming is simultaneously after ball milling
It is placed in high temperature furnace, for nitrogen atmosphere and is to slowly warm up to 1300 DEG C in control furnace, heat preservation is cooled to room temperature after 7 hours, is obtained
It is divided into the reduzate of upper and lower two parts, reduzate deposition of iron is through its structure of X-ray diffraction analysis on lower part, top
Carbon titanium oxynitrides (TiCxNyOz, x/z=0.75) be not reduced the mixture of component.Reduzate upper block is through being crushed simultaneously
After being ground to 200 mesh or less, chlorination processing is carried out at 400 DEG C, and X-ray diffraction point is carried out to residue after complete reaction
Analysis is other oxide component (Al2O3-MgO-CaO-SiO2), after the further oxidation processes of chlorizate, obtains oxidation and produce
Object is titanium dioxide (TiO through X-ray diffraction analysis2), constituent analysis shows that its purity is 99.1%.
Embodiment 3:
Weigh the iron ore concentrate (Fe that 200.0g is broken into fine particle through vibromill2O3: 47.3%, FeO:29.2%, TiO2:
12.4%), supplying 38.6g graphite powder (carbon content 99.9%) is placed in planetary ball mill and is uniformly mixed, powder after ball milling
Compression moulding is placed in high temperature furnace, and 1700 DEG C are to slowly warm up in semi Open System, and heat preservation is cooled to room temperature after 5 hours,
X-ray diffraction analysis to reduzate is the results show that ferriferous oxide quilt after the reduction of carbon heat selective, in ferrotianium grandidierite
It is reduced into metallic iron, titanium oxide is reduced into carbon titanium oxynitrides (TiCxNyOz, x/z=0.5), other components are not gone back then
It is former.Reduzate upper block carries out chlorination processing, to fully reacting after broken and be ground to 200 mesh or less at 400 DEG C
X-ray diffraction analysis is carried out to residue afterwards, is as the result is shown other oxide component (Al2O3-MgO-CaO-SiO2), to chlorine
After changing the further oxidation processes of product, obtaining oxidation product through X-ray diffraction analysis is titanium dioxide (TiO2), constituent analysis is aobvious
Show that its purity is 99.6%.
Comparative example 1 (is only restored to Ti2O3):
Weigh ilmenite (FeO:42.7%, TiO that 200.0g is broken into fine particle through vibromill2: 47.5%), and supplying
21.4g graphite powder (carbon content 99.9%) is placed in planetary ball mill and is uniformly mixed, powder pressing forming postposition after ball milling
For argon atmosphere and 2000 DEG C are to slowly warm up in high temperature furnace, in control furnace, and heat preservation is cooled to room temperature after 3 hours, is divided
For the reduzate of upper and lower two parts, reduzate deposition of iron is such as said on lower part, top through its structure of X-ray diffraction analysis
It is titanium sesquioxide (Ti shown in bright book attached drawing 62O3) be not reduced the mixture of component.Reduzate upper block is through broken
And after being ground to 200 mesh or less, chlorination processing is carried out at 400 DEG C, and X-ray diffraction point is carried out to residue after complete reaction
Analysis, as a result as shown in Figure of description 7, it can be seen that the titanium sesquioxide (Ti of part2O3) it is oxidized to titanium dioxide (TiO2),
This shows if the titanium component in ferrotianium grandidierite is not reduced into carbon (nitrogen) titanium oxide (TiCx(Ny)Oz), it will lead to chlorination
Reaction can not be normally carried out.
Comparative example 2 (is restored to C/O=0.33):
Weigh ilmenite (FeO:42.7%, TiO that 200.0g is broken into fine particle through vibromill2: 47.5%), and supplying
35.7g graphite powder (carbon content 99.9%) is placed in planetary ball mill and is uniformly mixed, powder pressing forming postposition after ball milling
For argon atmosphere and 2000 DEG C are to slowly warm up in high temperature furnace, in control furnace, and heat preservation is cooled to room temperature after 3 hours, is divided
For the reduzate of upper and lower two parts, reduzate deposition of iron is such as said on lower part, top through its structure of X-ray diffraction analysis
It is oxidation of coal titanium (TiC shown in bright book attached drawing 80.25O0.75) be not reduced the mixture of component.Reduzate upper block warp
After being crushed and being ground to 200 mesh or less, chlorination processing is carried out at 400 DEG C, and X-ray is carried out to residue after complete reaction and is spread out
Analysis is penetrated, as a result as shown in Figure of description 9, still chlorination reaction does not occur for remaining titanium monoxide (TiO), this shows to work as
Carbon (nitrogen) titanium oxide (TiC in reduzatex(Ny)Oz) carbon-to-oxygen ratio less than 0.5 when, it will cause chlorination reaction that can not carry out thorough
Bottom.
Comparative example 3 (is restored to C/O=1.5):
Weigh ilmenite (FeO:42.7%, TiO that 200.0g is broken into fine particle through vibromill2: 47.5%), and supplying
45.7g graphite powder (carbon content 99.9%) is subsequently placed in planetary ball mill and is uniformly mixed, after ball milling after powder pressing forming
It is placed in high temperature furnace, for nitrogen atmosphere and is to slowly warm up to 2000 DEG C in control furnace, heat preservation is cooled to room temperature after 3 hours, is obtained
It is divided into the reduzate of upper and lower two parts, reduzate deposition of iron is carbon through its structure of X-ray diffraction analysis on lower part, top
Titanium oxide (TiC0.6O0.4) be not reduced the mixture of component.Reduzate upper block through it is broken and be ground to 200 mesh with
After lower, chlorination processing is carried out at 400 DEG C, and X-ray diffraction analysis is carried out to residue after complete reaction, is as the result is shown it
Its oxide component (Al2O3-MgO-CaO-SiO2), after the further oxidation processes of chlorizate, obtains oxidation product and penetrated through X
Line diffraction analysis is titanium dioxide (TiO2), constituent analysis shows that its purity is 94.2%, this shows when reduzate carbon (nitrogen)
Titanium oxide (TiCx(Ny)Oz) carbon-to-oxygen ratio be greater than 1 when, it will lead to other oxides while chlorination reaction occur, so influence
The purity of titanium tetrachloride product.
Comparative example 4: it is restored to TiC
Weigh ilmenite (FeO:42.7%, TiO that 200.0g is broken into fine particle through vibromill2: 47.5%), and supplying
57.1g graphite powder (carbon content 99.9%) is subsequently placed in planetary ball mill and is uniformly mixed, after ball milling after powder pressing forming
It is placed in high temperature furnace, for argon atmosphere and is to slowly warm up to 2000 DEG C in control furnace, heat preservation is cooled to room temperature after 3 hours, to also
The X-ray diffraction analysis of object is originated in the results show that the ferriferous oxide in ferrotianium grandidierite is reduced after the reduction of carbon heat selective
At metallic iron, titanium oxide is reduced into titanium carbide (TiC), and other components are not reduced then.Reduzate upper block warp
After being crushed and being ground to 200 mesh or less, chlorination processing is carried out at 400 DEG C, and X-ray is carried out to residue after complete reaction and is spread out
Analysis is penetrated, is as the result is shown other oxide component (Al2O3-MgO-CaO-SiO2), to the further oxidation processes of chlorizate
Afterwards, obtaining oxidation product through X-ray diffraction analysis is titanium dioxide (TiO2), constituent analysis shows that its purity is 91.1%, this
Show if the titanium component in ferrotianium grandidierite is reduced into titanium carbide (TiC), it will lead to other oxides while chlorine occurs
Change reaction, and then influences the purity of titanium tetrachloride product.
Claims (16)
1. a kind of method for preparing titanium products as raw material using ferrotianium grandidierite, which is characterized in that the described method comprises the following steps:
(1) ferrotianium grandidierite raw material is subjected to broken pretreatment；
(2) it is incorporated carbon containing reducer in being crushed pretreated raw material, obtains mixture；
(3) it heats up under certain atmosphere to the mixture and carries out reduction reaction, obtain including rich titanium phase substance, iron and slag phase
The reduzate of component；
(4) separation is discharged in the iron in the reduzate, obtains dividing product comprising rich titanium phase substance and the first of slag phase component；
(5) just product is divided to be placed in chlorination appratus as chlorizated raw material for described, carries out selective chlorination at a certain temperature,
During the selective chlorination, slag phase component is maintained at the solid state of oxide, and the richness titanium phase substance chlorination generates
Titanium tetrachloride vapors collect after condensation and obtain the titanium tetrachloride product that purity is higher than 99%.
2. a kind of method for preparing titanium products as raw material using ferrotianium grandidierite according to claim 1, which is characterized in that described
Rich titanium phase substance includes oxidation of coal titanium TiCmOnWith carbon titanium oxynitrides TiCxNyOzAt least one of:
The oxidation of coal titanium TiCmOnIn, m+n=1 and 0.5≤m/n≤1；
The carbon titanium oxynitrides TiCxNyOzIn, x+y+z=1,0 y≤1 < and 0.5≤x/z≤1.
3. a kind of method for preparing titanium products as raw material using ferrotianium grandidierite according to claim 1 or claim 2, which is characterized in that
The amount for the carbon containing reducer being incorporated in step (2) can all restore the ferriferous oxide in the ferrotianium grandidierite raw material
At metallic iron, and the titanium oxide in the ferrotianium grandidierite raw material can be all reduced into oxidation of coal titanium, carbon nitrogen oxygen
Change the mixture of titanium or both.
4. a kind of method for preparing titanium products as raw material using ferrotianium grandidierite according to claim 1, which is characterized in that step
(3) in temperature-rise period described in, a period of time is kept the temperature after reaching set temperature.
5. a kind of method for preparing titanium products as raw material using ferrotianium grandidierite according to claim 4, which is characterized in that described
Heat preservation a period of time refers to heat preservation 2~10 hours.
6. a kind of method for preparing titanium products as raw material using ferrotianium grandidierite according to claim 4, which is characterized in that described
Set temperature is 1100~2200 DEG C.
7. a kind of method for preparing titanium products as raw material using ferrotianium grandidierite according to claim 4, which is characterized in that described
Set temperature is 1100~1400 DEG C.
8. a kind of method for preparing titanium products as raw material using ferrotianium grandidierite according to claim 1, which is characterized in that step
(3) atmosphere described in includes argon gas, nitrogen or air atmosphere.
9. a kind of method for preparing titanium products as raw material using ferrotianium grandidierite according to claim 1, which is characterized in that in step
Suddenly after (2) and before step (3), further include the steps that the mixture ball milling, be uniformly mixed simultaneously compression moulding.
10. a kind of method for preparing titanium products as raw material using ferrotianium grandidierite according to claim 1, which is characterized in that step
Suddenly in (4), by the iron in the reduzate be discharged isolated method include: after reduction reaction carries out under high temperature by reduction
Molten iron is expelled directly out；Or iron in reduzate is removed by the way of the gravity treatment, magnetic separation of solid iron.
11. a kind of method for preparing titanium products as raw material using ferrotianium grandidierite according to claim 10, which is characterized in that when
It further include being pre-processed to the reduzate before discharge separates iron when by the way of the gravity treatment, magnetic separation of solid iron
The step of, to the reduzate carry out pretreated step include be crushed, ultrasound, ball milling decentralized processing.
12. a kind of method for preparing titanium products as raw material using ferrotianium grandidierite according to claim 10, which is characterized in that when
When by the way of the magnetic separation of solid iron, after pre-processing to the reduzate, magnetic separation raw material is obtained, the magnetic separation is former
Material, which is placed in magnetic plant, carries out magnetic separation.
13. a kind of method for preparing titanium products as raw material using ferrotianium grandidierite according to claim 10, which is characterized in that
In step (5), the temperature of selective chlorination is carried out are as follows: 200~600 DEG C.
14. a kind of any one of according to claim 1-2,4-13 method that titanium products are prepared as raw material using ferrotianium grandidierite,
It is characterized in that, the ferrotianium grandidierite includes in ilmenite, vanadium titano-magnetite, ilmenite concentrate, iron ore concentrate, high titanium slag and rutile
Any one or any two or more combination.
15. a kind of any one of according to claim 1-2,4-13 method that titanium products are prepared as raw material using ferrotianium grandidierite,
It is characterized in that, the carbon containing reducer includes appointing in active carbon, graphite powder, charcoal, petroleum coke, pitch, coke powder and coal dust
It anticipates one or any two or more combination.
16. a kind of method for preparing titanium dioxide, which is characterized in that obtained with the preparation of any one of claim 1-15 the method
The titanium tetrachloride obtained is raw material, oxidation-treated to prepare titanium dioxide.
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