CN101412536A - Preparation of synthetic rutile - Google Patents
Preparation of synthetic rutile Download PDFInfo
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- CN101412536A CN101412536A CNA2008101775204A CN200810177520A CN101412536A CN 101412536 A CN101412536 A CN 101412536A CN A2008101775204 A CNA2008101775204 A CN A2008101775204A CN 200810177520 A CN200810177520 A CN 200810177520A CN 101412536 A CN101412536 A CN 101412536A
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Abstract
The invention provides a method for preparing artificial rutile. The method comprises the following steps: titanium concentrate is subjected to oxidizing roasting and reducing roasting for removing impurities in oxidizing roasting products; and the products of which the impurities are removed are calcined, wherein the oxidizing roasting is performed in the presence of oxidizing gas, the reducing roasting is performed in the presence of reducing gas, and the oxidizing roasting and the reducing roasting are performed in a fluidized bed reactor. By adoption of the method, the high-grade artificial rutile can be prepared by adopting coarse fraction titanium concentrate as a raw material and can also be prepared by adopting micron-sized fraction titanium concentrate as the raw material.
Description
Technical field
The present invention relates to the preparation method of artificial rutile.
Background technology
Vanadium titano-magnetite is a kind of mineral intergrowth of multielement, and its composition is with the different difference that exist in the place of production.Iron content in the vanadium titano-magnetite (oxide form with iron in the ore deposit exists) amount is 30-34 weight %, and is main as the raw material that extracts iron, vanadium, titanium.The mine tailing that vanadium titano-magnetite (raw ore) is chosen behind the iron ore concentrate can be used to reclaim ilmenite concentrate, this ilmenite concentrate can be used to produce artificial rutile, yet handling ilmenite concentrate, existing employing electrosmelting or reduction bubble method can not effectively remove the assorted element of matter such as calcium in the ilmenite concentrate, magnesium, and the grade of the artificial rutile that obtains (being the content of titanium dioxide in the artificial rutile) is all lower, all is not suitable as the raw material that fluidizing chlorination is produced titanium tetrachloride.In order to obtain the artificial rutile than higher-grade, CN 101244841A discloses a kind of production method of artificial artificial rutile, comprises the steps: a, ilmenite concentrate in 800-1100 ℃ of oxidizing roasting, then in 600-900 ℃ of reducing roasting; The hydrochloric acid normal pressure of b, concentration 18-24% contacts the ilmenite concentrate after the reducing roasting down; C, washing, filtration; D, the calcining of collection filter cake are promptly.
Summary of the invention
The object of the present invention is to provide a kind of new method for preparing artificial rutile, adopt this method, can make more high-grade artificial rutile when not only being raw material, and also can make artificial rutile when being raw material than higher-grade with the micro-size fraction ilmenite concentrate with the coarse fraction ilmenite concentrate.
The invention provides a kind of preparation method of artificial rutile, this method comprises: ilmenite concentrate is carried out oxidizing roasting and reducing roasting, remove the impurity in the product of reducing roasting, with the product calcining of removing behind the impurity, described oxidizing roasting is carried out under oxidizing gas, and described reducing roasting is carried out under reducing gas; Wherein, described oxidizing roasting and reducing roasting are carried out in fluidized-bed reactor.
In rotary kiln, can carry out the oxidizing roasting and the reducing roasting of coarse fraction ilmenite concentrate, but when being that raw material is when preparing artificial rutile with the micro-size fraction ilmenite concentrate, if also carry out the oxidizing roasting and the reducing roasting of ilmenite concentrate with rotary kiln, then can be owing to bonding between the micro-size fraction ilmenite concentrate influence the normal operation of equipment, thus cause the grade of the artificial rutile that makes lower.
And the method for artificial rutile for preparing provided by the invention is by carrying out oxidizing roasting and reducing roasting in fluidized-bed reactor, agglutinating problem between the micro-size fraction ilmenite concentrate then can not appear, when in fluidization oxidized still (fluidized-bed reactor when carrying out oxidation is called " fluidization oxidized still "), carrying out oxidizing roasting, can make TiO contained in the ilmenite concentrate by oxidizing roasting
2Crystal formation be converted into rutile-type more fully, when in fluidized reduction furnace (fluidized-bed reactor when reducing is called " fluidized reduction furnace "), carrying out reducing roasting, can make the ferric oxide in the product after the oxidizing roasting be reduced to iron protoxide more fully by reducing roasting, thereby in follow-up removal of impurities operation, can more effectively remove the oxide impurity of de-iron, therefore, by making described oxidizing roasting and reducing roasting in fluidized-bed reactor, carry out to improve the grade of the artificial rutile that makes.
In addition, in fluidized-bed reactor, carry out oxidizing roasting and reducing roasting, can also enhancing mass and heat transfer, enhance productivity greatly; Bed is in the state of motion, can keep temperature even, avoids local superheating, and is easy to control; In addition, because when using fluidized-bed reactor, the high-temperature gas that comes out from the fluidization oxidized still can enter preheater and can carry out preheating to ilmenite concentrate, and the high-temperature gas that comes out from fluidized reduction furnace can heat the fluidization oxidized still, thereby improve the utilization ratio of heat, cut down the consumption of energy.
Embodiment
The invention provides a kind of preparation method of artificial rutile, this method comprises: ilmenite concentrate is carried out oxidizing roasting and reducing roasting, remove the impurity in the product of reducing roasting, with the product calcining of removing behind the impurity, described oxidizing roasting is carried out under oxidizing gas, and described reducing roasting is carried out under reducing gas; Wherein, described oxidizing roasting and reducing roasting are carried out in fluidized-bed reactor.
The ilmenite concentrate that reclaims the mine tailing after the vanadium titano-magnetite (raw ore) of Panxi Diqu is chosen iron ore concentrate mainly contains metatitanic acid iron (FeOTiO
2) crystal, also contain the oxide impurity sosoloid of magnesium, manganese, aluminium, vanadium, silicon etc.The method that reclaims ilmenite concentrate from above-mentioned mine tailing generally has two kinds of methods, i.e. gravity treatment and gravity treatment add the method for flotation, the TiO in the ilmenite concentrate that obtains by the above-mentioned mine tailing of gravity treatment
2Grade generally more than 47 weight %, and particle diameter is bigger, general particle diameter be the 35-200 order promptly greater than 74 microns to smaller or equal to 450 microns account for more than the 85 weight %, generally this ilmenite concentrate that obtains by the above-mentioned mine tailing of gravity treatment is called " gravity treatment ilmenite concentrate " or " coarse fraction ilmenite concentrate ", be available commercially, particle diameter is that the above ilmenite concentrate of 200 orders then is difficult to elect by gravity treatment, in order to improve the rate of recovery of ilmenite concentrate in the above-mentioned mine tailing, people improve ore-dressing technique, to carrying out flotation again through the above-mentioned mine tailing of gravity treatment, the TiO in the ilmenite concentrate that obtains by flotation
2Grade be generally 44-47 weight %, and particle diameter is less, general particle diameter for-200 orders promptly smaller or equal to 74 microns account for 60-80 weight %, generally this ilmenite concentrate that obtains by flotation is called " flotation ilmenite concentrate " or " micro-size fraction ilmenite concentrate ", be available commercially.
Can be to reclaim the mine tailing after vanadium titano-magnetite is chosen iron ore concentrate and the ilmenite concentrate that obtains as the ilmenite concentrate of raw material among the present invention, can be gravity treatment ilmenite concentrate and/or flotation ilmenite concentrate, in the described gravity treatment ilmenite concentrate particle diameter for greater than 74 microns to smaller or equal to 450 microns account for more than the 85 weight %, in the described flotation ilmenite concentrate particle diameter smaller or equal to 74 microns account for 60-80 weight %.
Among the present invention, the purpose of described oxidizing roasting is in order to make the TiO in the ilmenite concentrate
2Crystal conversion be rutile-type.Mainly exist through contained iron protoxide impurity in the ilmenite concentrate of oxidizing roasting with the form of ferric oxide, if directly it is carried out pickling impurity removal, the clearance of ferro element very low (being about 40%-60%) then, therefore the purpose of described reducing roasting is that ferric oxide is reduced to iron protoxide, the clearance (up to more than 90%) of ferro element can be improved thus, and then the grade of the artificial rutile that makes can be improved.
Fluidized-bed reactor generally comprises segregation section, settling section and the conversion zone that interconnects from top to bottom; Described oxidizing roasting comprises: with the conversion zone of ilmenite concentrate and oxidizing gas importing fluidized-bed reactor, make ilmenite concentrate and oxidizing gas contact reacts, will with the product of oxidizing roasting after oxidizing gas contacts with derive from settling section and segregation section respectively with the oxidizing gas after ilmenite concentrate contacts; Described reducing roasting comprises: with the product of oxidizing roasting and the conversion zone of reducing gas importing fluidized-bed reactor, make the product and the reducing gas contact reacts of oxidizing roasting, will with the product of reducing roasting after reducing gas contacts with derive from settling section and segregation section respectively with the reducing gas after the product of oxidizing roasting contacts.
Wherein, ilmenite concentrate and oxidizing gas can import fluidized-bed reactor (promptly by oxidizing gas ilmenite concentrate being blown into fluidized-bed reactor) from same inlet, also can import fluidized-bed reactor (being that ilmenite concentrate and oxidizing gas import fluidized-bed reactor from feed-pipe and reaction gas inlet respectively) from different inlets, but because the wearing and tearing of the described feeding manner fluid bedreactors that ilmenite concentrate is blown into fluidized-bed reactor by oxidizing gas are more serious, therefore, preferred ilmenite concentrate imports fluidized-bed reactor with oxidizing gas from different inlets, and promptly ilmenite concentrate and oxidizing gas import fluidized-bed reactor from feed-pipe and reaction gas inlet respectively.In like manner, the product of preferred oxidizing roasting also imports fluidized-bed reactor from different inlets with reducing gas, i.e. the product of oxidizing roasting and reducing gas import fluidized-bed reactor from feed-pipe and reaction gas inlet respectively.
The catalytic condition of ilmenite concentrate and oxidizing gas comprises: the flow velocity of ilmenite concentrate is the 0.3-20 kilograms per cubic meter with the ratio of the flow velocity of oxidizing gas, the temperature of oxidizing roasting is 600-1500 ℃, the pressure of oxidizing roasting is 5-100 kPa, the time of oxidizing roasting is 30-100 minute, and the linear velocity of oxidizing gas in fluidized-bed reactor is the 0.05-1 meter per second.Under the preferable case, the flow velocity of ilmenite concentrate is the 0.6-20 kilograms per cubic meter with the ratio of the flow velocity of oxidizing gas, the temperature of oxidizing roasting is 800-1100 ℃, the pressure of oxidizing roasting is 8-50 kPa, the time of oxidizing roasting is 40-90 minute, and the linear velocity of oxidizing gas in fluidized-bed reactor is the 0.1-0.65 meter per second.
Described oxidizing gas can contain the gas of oxygen, for example can be oxygen and/or air.The product of oxidizing roasting is measured with X-ray diffractometer, obtained XRD spectrum figure, analyze this collection of illustrative plates, can determine TiO contained in the product of oxidizing roasting
2Crystal formation be rutile-type.
In addition, the catalytic condition of the product of oxidizing roasting and reducing gas comprises: the flow velocity of the product of oxidizing roasting is the 0.3-20 kilograms per cubic meter with the ratio of the flow velocity of reducing gas, the temperature of reducing roasting is 400-1000 ℃, the pressure of reducing roasting is 5-100 kPa, the time of reducing roasting is 25-100 minute, and the linear velocity of reducing gas in fluidized-bed reactor is the 0.05-1 meter per second.Under the preferable case, the flow velocity of the product of oxidizing roasting is the 0.6-20 kilograms per cubic meter with the ratio of the flow velocity of reducing gas, the temperature of reducing roasting is 500-800 ℃, the pressure of reducing roasting is 8-50 kPa, the time of reducing roasting is 30-80 minute, and the linear velocity of reducing gas in fluidized-bed reactor is the 0.1-0.65 meter per second.
Described reducing gas is specifically as follows in hydrogen, the carbon monoxide one or more for ferric oxide being reduced to the gas of iron protoxide.
Among the present invention, described oxidizing roasting is carried out in different fluidized-bed reactors with reducing roasting.
Under the preferable case, can carry out preheating to the ilmenite concentrate that preadmission is gone in the fluidization oxidized still, the temperature of preheating can be 600-700 ℃, ilmenite concentrate through this preheating can carry out oxidizing reaction quickly in the fluidization oxidized still thus, when using fluidized-bed reactor, the high-temperature gas that comes out from the fluidization oxidized still can enter preheater and can carry out preheating to ilmenite concentrate, and can heat the fluidization oxidized still from the high-temperature gas that fluidized reduction furnace comes out, thereby can improve the utilization ratio of heat, cut down the consumption of energy.
Among the present invention, the method for removing the impurity in the product of reducing roasting comprises: the product of reducing roasting is contacted with acidic solution, wash and isolate and solid product after acidic solution contacts.
The purpose of described contact be in the product of removing reducing roasting can with the impurity of acidic solution reaction, for example, ferric oxide, iron protoxide, magnesium oxide, calcium oxide etc., described acidic solution can be hydrochloric acid, in aqueous nitric acid and the aqueous sulfuric acid one or more, but consider to be preferably hydrochloric acid from the angle of environmental protection and save energy, because with the mother liquor process spray roasting after the hydrochloric acid contact, can make the iron in the mother liquor, magnesium, the muriate of calcium etc. is converted into hydrogenchloride and corresponding metal oxide, hydrogenchloride promptly obtains hydrochloric acid through washing, hydrochloric acid can be recycled and reused for contact, therefore is preferably aqueous hydrochloric acid.
The number of times of described contact is The more the better, the number of times of contact is many more, then total duration of contact is short more, dust removal rate is high more, but from dust removal rate be convenient to operating aspect and take all factors into consideration, described frequency of exposure can be for 1-5 time, be preferably 3-5 time, can be 2-6 hour total duration of contact, be preferably 1.5-4 hour, in addition, when once contacting before the hydrionic concentration ratio in the used acidic solution when once contacting after preferred in the used acidic solution hydrionic concentration low, more preferably be concentration gradient between the hydrionic concentration in the used acidic solution during each time contact, and during adjacent contact for twice in the used acidic solution hydrionic concentration difference big more, dust removal rate is high more, for example, hydrionic concentration difference can the 1.5-3 mol in the adjacent twice when contact used acidic solution, according to this preferred implementation, impurities removing efficiency can be further improved, thereby the grade of the artificial rutile that makes can be further improved.
Hydrionic concentration can be the 4-10 mol in the described acidic solution, the liquid-solid ratio of the product of described acidic solution and reducing roasting can be 2-5:1 milliliter/gram during each the contact, described contact temperature can be 80-120 ℃, and be 1-6 hour total duration of contact.
Among the present invention, described separation method can be conventional method such as filtration under diminished pressure or centrifugation.Described is in order to remove the acidic solution of the solid product surface attachment in the contact after product to the purpose of washing with product after acidic solution contacts.Washing used solvent is water, and washing is not till have acid ion to be detected, and described acid ion is one or more in chlorion, nitrate ion and the sulfate ion.
In addition, remove the time of the product behind the impurity in order to shorten calcining, save energy, preferably the solid product that obtains after filtration under diminished pressure or the centrifugation is dried, the temperature of described oven dry can be 80-120 ℃, and the time of oven dry can be 3-10 hour, in the industrial production, can directly dry with the gas that from fluidized reduction furnace, comes out, can further cut down the consumption of energy like this it.
Described incinerating temperature can be 400-600 ℃, and the incinerating time can be 30-100 minute, and under the situation of having carried out above-mentioned preferred oven dry, the described incinerating time is preferably 30-80 minute and gets final product.
Among the present invention, in order further to improve the grade of prepared artificial rutile, preferably the product after the calcining is carried out the back magnetic separation, the magneticstrength of back magnetic separation can be 6000-9000 Gauss, purpose is the magnetic impurity of removing in the product, can obtain the higher artificial rutile of grade.
In addition, in order further to improve the grade of prepared artificial rutile, can also be after reducing roasting with before acidic solution contacts, product to reducing roasting carries out preceding magnetic separation, the magneticstrength of preceding magnetic separation can be 1000-3000 Gauss, purpose is the part non-magnetic impurity of removing in the product of reducing roasting, this non-magnetic impurity mainly is impurity such as silicon, because iron contained in the product of reducing roasting this moment is more, the impurity such as silicon that a part is coated with iron can be removed by preceding magnetic separation, the higher artificial rutile of grade can be obtained thus.
Below by embodiment the preparation method of artificial rutile of the present invention is made more specific description.
Embodiment 1
A, oxidizing roasting: get 20 kilograms of micro-size fraction ilmenite concentrates and (purchase in climbing steel group micro-size fraction ilmenite concentrate (20# ore deposit), chemical composition analysis sees Table 1, particle size analysis sees Table 2), carry out in 650 ℃ preheater earlier that preheating is laggard goes into the fluidization oxidized still (fluidized-bed reactor when promptly carrying out oxidation, comprise the segregation section that interconnects from top to bottom, settling section and conversion zone) in carry out oxidizing roasting, wherein, ilmenite concentrate enters conversion zone from the feed-pipe of the bottom that is positioned at fluidized-bed reactor, air enters conversion zone from the reaction gas inlet of the bottom that is positioned at the fluidization oxidized still, the product of oxidizing roasting is from the discharge nozzle output of the settling section that is positioned at the fluidization oxidized still, oxidizing gas is from the reaction gas outlet output of the segregation section that is positioned at fluidized-bed reactor, the flow velocity of regulating air is 8 cubic metres/hour, the input speed of ilmenite concentrate is 5 kilograms/hour, make that the ratio of flow velocity and the flow velocity of air of ilmenite concentrate is 0.625 kilograms per cubic meter, the linear velocity of air in the fluidization oxidized still is 0.1 meter per second, the temperature of oxidizing roasting is 1000 ℃, the pressure of oxidizing roasting is 10 kPas, and the oxidizing roasting time is 55 minutes;
Reducing roasting: the product of the oxidizing roasting of coming out from the fluidization oxidized still again fluidized reduction furnace (when promptly reducing fluidized-bed reactor, comprise the segregation section that interconnects from top to bottom, settling section and conversion zone) in carry out reducing roasting, wherein, the product of oxidizing roasting enters conversion zone from the feed-pipe of the bottom that is positioned at fluidized reduction furnace, regulating coke-oven gas (being made up of carbon monoxide and hydrogen) enters the mouth from the reaction gas of the bottom that is positioned at fluidized reduction furnace and enters conversion zone, the product of reducing roasting is from the discharge nozzle output of the settling section that is positioned at fluidized reduction furnace, coke-oven gas is from the reaction gas outlet output of the segregation section that is positioned at fluidized-bed reactor, the flow velocity of regulating coke-oven gas is 8 cubic metres/hour, the input speed of the product of oxidizing roasting is 5 kilograms/hour, make that the ratio of flow velocity and the flow velocity of coke-oven gas of product of oxidizing roasting is 0.625 kilograms per cubic meter, the linear velocity of coke-oven gas in fluidized reduction furnace is 0.1 meter per second, the temperature of reducing roasting is 800 ℃, the pressure of reducing roasting is 10 kPas, the reducing roasting time is 30 minutes, obtains the product-modification ilmenite concentrate of reducing roasting; Wherein the high-temperature gas that comes out from the fluidization oxidized still enters preheater ilmenite concentrate is carried out preheating, and the high-temperature gas that comes out from fluidized reduction furnace heats the fluidization oxidized still.
Then the modification ilmenite concentrate that obtains is carried out preceding magnetic separation (magneticstrength is 1600 Gausses), select non magnetic mine tailing 4.3 weight %, the magnetic concentrate accounts for 95.7 weight %.The content of titanium dioxide is 19.02 weight % in the non magnetic mine tailing, and the content of silicon-dioxide is 27.9 weight %; The content of titanium dioxide is 48.47 weight % in the magnetic concentrate, and the content of silicon-dioxide is 3.04 weight %.
B, get before 2 kilograms of processes the magnetic concentrate after the magnetic separation and carry out three times with aqueous hydrochloric acid and contact, contact aqueous hydrochloric acid for the first time with 10 mol, for the first time contacting the used time is 1 hour, contact aqueous hydrochloric acid for the second time with 7 mol, for the second time contacting the used time is 1 hour, contact aqueous hydrochloric acid for the third time with 4 mol, contacting the used time for the third time is 1 hour, the liquid-solid ratio of aqueous hydrochloric acid and magnetic concentrate is 3.2:1 (milliliter/gram) during each the contact, the temperature of contact is 102 ℃, and contact pressure is a normal pressure.
C, water after to cooling-sedimentation with reduce pressure washing and filtering of product after aqueous hydrochloric acid contacts, washing till do not have chlorion to be detected, then with filter cake 100 ℃ of oven dry 5 hours down.
D, the product after will drying were calcined under 500 ℃ 60 minutes, obtained artificial rutile.
Then the artificial rutile that obtains is carried out back magnetic separation (magneticstrength is 6000 Gausses), select that the magnetic mine tailing accounts for 3.5 weight %, non magnetic artificial rutile accounts for 96.5 weight %.The content of titanium dioxide is 16.70 weight % in the magnetic mine tailing, and the content of silicon-dioxide is 30.4 weight %; The chemical constitution of the non magnetic artificial rutile product after raw material and the back magnetic separation sees Table 1, and the content of different-grain diameter sees Table 2, and as can be seen from Table 2, the particle diameter of the particle diameter of the artificial rutile that obtains and raw material micro-size fraction ilmenite concentrate is suitable.
Table 1
Table 2
| Title | 150 microns (weight %) | 74 microns to≤150 microns (weight %) | 44 microns to≤74 microns (weight %) | ≤ 44 microns (weight %) |
| The micro-size fraction ilmenite concentrate | 0.4 | 25.5 | 39.25 | 34.85 |
| Artificial rutile | 0.4 | 23.8 | 40.23 | 35.57 |
Embodiment 2
Prepare artificial rutile according to embodiment 1 described method, different is,
In a, the oxidizing roasting, the flow velocity of regulating air is that 1 cubic metre/hour, the input speed of ilmenite concentrate are 20 kilograms/hour, make that the ratio of flow velocity and the flow velocity of air of ilmenite concentrate is 20 kilograms per cubic meter, the linear velocity of air in the fluidization oxidized still is 0.65 meter per second, the temperature of oxidizing roasting is 850 ℃, the pressure of oxidizing roasting is 20 kPas, and the oxidizing roasting time is 90 minutes;
In the reducing roasting, the flow velocity of regulating coke-oven gas is that 1 cubic metre/hour, the input speed of the product of oxidizing roasting are 20 kilograms/hour, make that the ratio of flow velocity and the flow velocity of coke-oven gas of product of oxidizing roasting is 20 kilograms per cubic meter, the linear velocity of coke-oven gas in fluidized reduction furnace is 0.65 meter per second, the temperature of reducing roasting is 550 ℃, the pressure of reducing roasting is 20 kPas, and the reducing roasting time is 70 minutes.
B, getting before 2 kilograms of processes the magnetic concentrate after the magnetic separation carries out four times with aqueous hydrochloric acid and contacts, contact aqueous hydrochloric acid for the first time with 10 mol, for the first time contacting the used time is 0.5 hour, contact aqueous hydrochloric acid for the second time with 8 mol, for the second time contacting the used time is 0.5 hour, contact aqueous hydrochloric acid for the third time with 6 mol, contacting the used time for the third time is 0.5 hour, the aqueous hydrochloric acid that contacts with 4 mol for the 4th time, the 4th used time of contact is 0.5 hour, the liquid-solid ratio of aqueous hydrochloric acid and magnetic concentrate is 2.5:1 (milliliter/gram) during each the contact, the temperature of contact is 115 ℃, and contact pressure is a normal pressure.
C, bake out temperature are 80 ℃, and drying time is 10 hours.
D, maturing temperature are 400 ℃, and roasting time is 80 minutes.
The content of the titanium dioxide in the non magnetic artificial rutile product after the back magnetic separation that the result obtains is 91.62 weight %.
Embodiment 3
Prepare artificial rutile according to embodiment 1 described method, different is,
In a, the oxidizing roasting, the flow velocity of regulating air is that 2 cubic metres/hour, the input speed of ilmenite concentrate are 16 kilograms/hour, make that the ratio of flow velocity and the flow velocity of air of ilmenite concentrate is 8 kilograms per cubic meter, the linear velocity of air in the fluidization oxidized still is 0.3 meter per second, the temperature of oxidizing roasting is 900 ℃, the pressure of oxidizing roasting is 45 kPas, and the oxidizing roasting time is 60 minutes;
In the reducing roasting, the flow velocity of regulating coke-oven gas is that 2 cubic metres/hour, the input speed of the product of oxidizing roasting are 16 kilograms/hour, make that the ratio of flow velocity and the flow velocity of coke-oven gas of product of oxidizing roasting is 8 kilograms per cubic meter, the linear velocity of coke-oven gas in fluidized reduction furnace is 0.3 meter per second, the temperature of reducing roasting is 700 ℃, the pressure of reducing roasting is 45 kPas, and the reducing roasting time is 50 minutes.
B, getting before 2 kilograms of processes the magnetic concentrate after the magnetic separation carries out five times with aqueous hydrochloric acid and contacts, contact aqueous hydrochloric acid for the first time with 10 mol, for the first time contacting the used time is 0.3 hour, contact aqueous hydrochloric acid for the second time with 8.5 mol, for the second time contacting the used time is 0.3 hour, contact aqueous hydrochloric acid for the third time with 7 mol, contacting the used time for the third time is 0.3 hour, the aqueous hydrochloric acid that contacts with 5.5 mol for the 4th time, the 4th used time of contact is 0.3 hour, the aqueous hydrochloric acid that contacts with 4 mol for the 5th time, the 5th used time of contact is 0.3 hour, the liquid-solid ratio of aqueous hydrochloric acid and magnetic concentrate is 4.2:1 (milliliter/gram) during each the contact, and the temperature of contact is 90 ℃, and contact pressure is a normal pressure.
C, bake out temperature are 120 ℃, and drying time is 3 hours.
D, maturing temperature are 600 ℃, and roasting time is 40 minutes.
The content of the titanium dioxide in the non magnetic artificial rutile product after the back magnetic separation that the result obtains is 92.83 weight %.
Comparative Examples 1
Prepare artificial rutile according to embodiment 1 described method, different is that oxidizing roasting and reducing roasting are all carried out in rotary kiln in a step.
The content of the titanium dioxide in the non magnetic artificial rutile product after the back magnetic separation that the result obtains is 80.01 weight %.
Embodiment 4
Prepare artificial rutile according to embodiment 1 described method, different is, the coarse fraction ilmenite concentrate that adopts 20 kilograms in a step is as raw material (purchasing in climbing steel group coarse fraction ilmenite concentrate (10# ore deposit)), the chemical composition analysis of the non magnetic artificial rutile product after the back magnetic separation that raw material and result obtain sees Table 3, particle size analysis sees Table 4, the particle diameter of the particle diameter of the artificial rutile that obtains as can be seen from Table 4, and raw material coarse fraction ilmenite concentrate is suitable.
Table 3
Table 4
| Title | 450 microns (weight %) | 145 microns to≤450 microns (weight %) | 88 microns to≤145 microns (weight %) | 74 microns to≤88 microns (weight %) | ≤ 74 microns (%) |
| The coarse fraction ilmenite concentrate | 0.43 | 48.55 | 30.92 | 11.29 | 8.81 |
| Artificial rutile | 0.34 | 33.99 | 46.75 | 9.9 | 9.02 |
Comparative Examples 2
Prepare artificial rutile according to embodiment 4 described methods, different is that oxidizing roasting and reducing roasting are all carried out in rotary kiln.
The content of the titanium dioxide in the non magnetic artificial rutile product after the back magnetic separation that the result obtains is 92.06 weight %.
Embodiment 5
Prepare artificial rutile according to embodiment 1 described method, different is that in the b step, the aqueous hydrochloric acid of 7 mol is all used in three contacts.
The content of the titanium dioxide in the non magnetic artificial rutile product after the back magnetic separation that the result obtains is 90.51 weight %.
Embodiment 6
Prepare artificial rutile according to embodiment 1 described method, different is, adopts once contact in the b step, and concrete grammar is as follows:
Get that the magnetic concentrate after the magnetic separation once contacts with aqueous hydrochloric acid before 2 kilograms of processes, contact aqueous hydrochloric acid with 7 mol, contacting the used time is 5 hours, the liquid-solid ratio of aqueous hydrochloric acid and magnetic concentrate is 3:1 (a milliliter/gram) during contact, the temperature of contact is 102 ℃, and contact pressure is a normal pressure.
The content of the titanium dioxide in the non magnetic artificial rutile product after the back magnetic separation that the result obtains is 90.25 weight %.
Claims (12)
1, a kind of preparation method of artificial rutile, this method comprises: ilmenite concentrate is carried out oxidizing roasting and reducing roasting, remove the impurity in the product of reducing roasting, with the product calcining of removing behind the impurity, described oxidizing roasting is carried out under oxidizing gas, and described reducing roasting is carried out under reducing gas; It is characterized in that described oxidizing roasting and reducing roasting are carried out in fluidized-bed reactor.
2, the preparation method of artificial rutile according to claim 1, wherein, fluidized-bed reactor comprises segregation section, settling section and the conversion zone that interconnects from top to bottom,
Described oxidizing roasting comprises: with the conversion zone of ilmenite concentrate and oxidizing gas importing fluidized-bed reactor, make ilmenite concentrate and oxidizing gas contact reacts, will with the product of oxidizing roasting after oxidizing gas contacts with derive from settling section and segregation section respectively with the oxidizing gas after ilmenite concentrate contacts;
Described reducing roasting comprises: with the product of oxidizing roasting and the conversion zone of reducing gas importing fluidized-bed reactor, make the product and the reducing gas contact reacts of oxidizing roasting, will with the product of reducing roasting after reducing gas contacts with derive from settling section and segregation section respectively with the reducing gas after the product of oxidizing roasting contacts.
3, the preparation method of artificial rutile according to claim 1 and 2, wherein, the catalytic condition of ilmenite concentrate and oxidizing gas comprises: the flow velocity of ilmenite concentrate is the 0.3-20 kilograms per cubic meter with the ratio of the flow velocity of oxidizing gas, the temperature of oxidizing roasting is 600-1500 ℃, the pressure of oxidizing roasting is 5-100 kPa, the time of oxidizing roasting is 30-100 minute, and the linear velocity of oxidizing gas in fluidized-bed reactor is the 0.05-1 meter per second.
4, the preparation method of artificial rutile according to claim 3, wherein, the flow velocity of ilmenite concentrate is the 0.6-20 kilograms per cubic meter with the ratio of the flow velocity of oxidizing gas, the temperature of oxidizing roasting is 800-1100 ℃, the pressure of oxidizing roasting is 8-50 kPa, the time of oxidizing roasting is 40-90 minute, and the linear velocity of oxidizing gas in fluidized-bed reactor is the 0.1-0.65 meter per second.
5, the preparation method of artificial rutile according to claim 1 and 2, wherein, the catalytic condition of the product of oxidizing roasting and reducing gas comprises: the flow velocity of the product of oxidizing roasting is the 0.3-20 kilograms per cubic meter with the ratio of the flow velocity of reducing gas, the temperature of reducing roasting is 400-1000 ℃, the pressure of reducing roasting is 5-100 kPa, the time of reducing roasting is 25-100 minute, and the linear velocity of reducing gas in fluidized-bed reactor is the 0.05-1 meter per second.
6, the preparation method of artificial rutile according to claim 5, wherein, the flow velocity of the product of oxidizing roasting is the 0.6-20 kilograms per cubic meter with the ratio of the flow velocity of reducing gas, the temperature of reducing roasting is 500-800 ℃, the pressure of reducing roasting is 8-50 kPa, the time of reducing roasting is 30-80 minute, and the linear velocity of reducing gas in fluidized-bed reactor is the 0.1-0.65 meter per second.
7, the preparation method of artificial rutile according to claim 1 and 2, wherein, described ilmenite concentrate is gravity treatment ilmenite concentrate and/or flotation ilmenite concentrate.
8, the preparation method of artificial rutile according to claim 1, wherein, the method of removing the impurity in the product of reducing roasting comprises: the product of reducing roasting is contacted with acidic solution, wash and isolate with product after acidic solution contacts in solid product.
9, the preparation method of artificial rutile according to claim 8, wherein, the number of times of described contact is 1-5 time, hydrionic concentration is the 4-10 mol in the described acidic solution, the liquid-solid ratio of the product of described acidic solution and reducing roasting is 2-5:1 milliliter/gram during each the contact, described contact temperature is 80-120 ℃, and be 1-6 hour total duration of contact, and described acidic solution is one or more in hydrochloric acid, aqueous nitric acid and the aqueous sulfuric acid.
10, the preparation method of artificial rutile according to claim 9, wherein, the number of times of described contact is 3-5 time, and be 1.5-4 hour total duration of contact, after when once contacting before the concentration ratio of used acidic solution when once contacting the concentration of used acidic solution low.
11, the preparation method of artificial rutile according to claim 8, wherein, described isolating method is filtration under diminished pressure or centrifugation; Washing used solvent is water, and washing is not till have acid ion to be detected, and described acid ion is one or more in chlorion, nitrate ion and the sulfate ion.
12, the preparation method of artificial rutile according to claim 1, wherein, described incinerating temperature is 400-600 ℃, the incinerating time is 30-100 minute.
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| CN101935065A (en) * | 2010-09-09 | 2011-01-05 | 中南大学 | Method for preparing artificial rutile from rock ore type titanium concentrate with high calcium and manganese content serving as raw material |
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| CN106430297A (en) * | 2016-08-31 | 2017-02-22 | 于京辉 | Method of continuously preparing artificial rutile and dedicated device thereof |
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| CN103266221B (en) * | 2013-06-04 | 2014-09-17 | 彭武星 | Method for roasting ores or slag |
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| CN108726575A (en) * | 2018-05-21 | 2018-11-02 | 上海交通大学 | The method for preparing nanometer di-iron trioxide iron oxide red as raw material using rutile mether liquor |
| CN108910942A (en) * | 2018-10-09 | 2018-11-30 | 龙蟒佰利联集团股份有限公司 | A method of synthetic rutile is prepared by high calcium magnesium titanium slag |
| CN109179494A (en) * | 2018-10-09 | 2019-01-11 | 龙蟒佰利联集团股份有限公司 | A method of synthetic rutile is prepared by ilmenite concentrate |
| CN109399706A (en) * | 2018-10-09 | 2019-03-01 | 龙蟒佰利联集团股份有限公司 | A method of UGS slag is upgraded with high calcium magnesium titanium slag |
| CN110627118A (en) * | 2019-10-31 | 2019-12-31 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for solving refining of artificial rutile |
| CN112410539A (en) * | 2020-10-30 | 2021-02-26 | 河南佰利联新材料有限公司 | Method for sorting titanium middlings containing weak magnetic gangue minerals |
| CN114045404A (en) * | 2021-11-16 | 2022-02-15 | 攀钢集团攀枝花钢铁研究院有限公司 | Titanium concentrate hydrogen reduction method |
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