CN108585034B - Method for preparing high-strength artificial rutile from ilmenite - Google Patents
Method for preparing high-strength artificial rutile from ilmenite Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 82
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000002386 leaching Methods 0.000 claims abstract description 73
- 239000002245 particle Substances 0.000 claims abstract description 32
- 238000010405 reoxidation reaction Methods 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 27
- 239000007790 solid phase Substances 0.000 claims description 24
- 230000001590 oxidative effect Effects 0.000 claims description 23
- 230000003647 oxidation Effects 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 11
- 150000007522 mineralic acids Chemical class 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 150000007529 inorganic bases Chemical class 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 abstract description 17
- 239000012535 impurity Substances 0.000 abstract description 11
- 239000010936 titanium Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052719 titanium Inorganic materials 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 238000010298 pulverizing process Methods 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 17
- 238000009835 boiling Methods 0.000 description 8
- 238000005660 chlorination reaction Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000000571 coke Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000012795 verification Methods 0.000 description 4
- 238000007664 blowing Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NSYYPXSKPGPMBW-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].Cl Chemical compound [O-2].[O-2].[Ti+4].Cl NSYYPXSKPGPMBW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/0475—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for preparing high-strength artificial rutile from ilmenite, and belongs to the technical field of metallurgy. The invention aims to solve the problem of the prior artificial rutileThe method for preparing the high-strength artificial rutile from the ilmenite has the problems of low strength and easy pulverization. The method changes the microcosmic composition and the shape of the ilmenite by performing high-temperature oxidation-weak reduction-high-temperature reoxidation pretreatment on the ilmenite, so that the ilmenite has good reaction activity and mechanical force resistance in the subsequent acid leaching-alkali leaching impurity removal process, the titanium recovery rate is more than 98 percent, the product quality is high, and TiO is2Higher content, better particle size retention and lower fine powder proportion.
Description
Technical Field
The invention belongs to the technical field of metallurgy, and particularly relates to a method for preparing high-strength artificial rutile from ilmenite.
Background
The boiling titanium dioxide chloride is the development trend of the titanium dioxide industry in the world at present. Compared with the titanium white produced by the sulfuric acid process, the titanium white is more advanced, but has more strict requirements on raw materials. Ilmenite is the most abundant titanium resource in the world, and most of ilmenite has high contents of impurities such as iron, calcium, magnesium, silicon and the like, so that ilmenite cannot be directly used as a boiling chlorination raw material, and all ilmenite generally needs upgrading treatment. Therefore, the production of synthetic rutile raw materials for boiling chlorination from ilmenite has been a major development in the titanium industry.
Among the various proposed methods for preparing artificial rutile by taking ilmenite as a raw material, the hydrochloric acid leaching method has the most development prospect due to the advantages of high impurity removal efficiency, acid recycling and the like. The pre-weakening reduction-hydrochloric acid pressure leaching process proposed by the U.S. benalite company in patent US3967954 is a hydrochloric acid process that was widely used in the early days; but it must use high-grade ilmenite placer as raw material, otherwise, the efficiency of impurity removal is not high. On the basis of BCA, researchers also put forward strong oxidation-weak reduction-hydrochloric acid leaching process technologies, such as patents US4097574, US5885324, CN201010276812 and the like, which have stronger adaptability to raw materials and higher impurity removal efficiency and can simultaneously treat various ilmenites with different weathering degrees and different grades; however, the processes also have the problems that the product is pulverized and the particle size does not meet the use requirement of subsequent boiling chlorination. Researchers have noticed this problem, and it is proposed in patent CN201310534032 that after ilmenite is pretreated by strong oxidation-weak reduction, a fluidized bed leaching method is adopted to reduce agitation during acid leaching, which method indeed greatly reduces pulverization during acid leaching, and most of the product maintains original particle size; however, the oxidation-reduction pretreatment and acid leaching processes are not changed essentially, so that the method does not change the low strength of the synthetic rutile product, once the product is applied to the subsequent boiling chlorination process belonging to a dense-phase gas-solid fluidized bed, strong particle collision can cause the re-pulverization of the synthetic rutile raw material, thereby causing the problems of greatly reduced titanium yield in the chlorination process, increased pressure of a dust removal system and the like.
Disclosure of Invention
The invention aims to solve the technical problems that the artificial rutile produced by the prior art is low in strength and easy to pulverize.
The technical scheme adopted by the invention for solving the technical problems is to provide a method for preparing high-strength artificial rutile from ilmenite, which comprises the following steps:
A. oxidizing and roasting ilmenite to obtain oxidized ore with the oxidation rate of more than or equal to 80%;
B. reducing and roasting the oxidized ore obtained in the step A in a reducing atmosphere to obtain reduced ore with the reduction rate of more than or equal to 80%;
C. b, oxidizing and roasting the reduced ore obtained in the step B to obtain reoxidized ore with the oxidation rate of more than or equal to 50%;
D. c, leaching the reoxidized ore with inorganic acid, and performing liquid-solid separation to obtain a leached solid phase;
E. d, leaching the leached solid phase obtained in the step D with an inorganic alkali solution, carrying out liquid-solid separation and washing to obtain a primary artificial rutile product, and calcining the primary artificial rutile product to obtain the high-strength artificial rutile.
In the method for preparing high-strength artificial rutile from ilmenite, step A contains 40-60 wt% of TiO2And 1 to 8% by weight of SiO2。
In the method for preparing the high-strength artificial rutile from the ilmenite, in the step A, the particle size distribution of the ilmenite is 60-200 meshes.
In the method for preparing the high-strength artificial rutile from the ilmenite, in the step A, the oxidizing roasting temperature is 850-1050 ℃.
In the method for preparing the high-strength artificial rutile from the ilmenite, in the step A, the oxidizing roasting time is 0.5-2 hours.
In the method for preparing the high-strength artificial rutile from the ilmenite, in the step B, the temperature of reduction roasting is 700-800 ℃.
In the method for preparing the high-strength artificial rutile from the ilmenite, in the step B, the reduction roasting time is 0.5-4 hours.
In the method for preparing the high-strength artificial rutile from the ilmenite, in the step C, the oxidizing roasting temperature is 850-1050 ℃.
In the method for preparing the high-strength artificial rutile from the ilmenite, in the step C, the oxidizing roasting time is 0.2-0.5 h.
In the method for preparing the high-strength artificial rutile from the ilmenite, in the step D, the inorganic acid is hydrochloric acid or sulfuric acid.
In the method for preparing the high-strength artificial rutile from the ilmenite, in the step D, the concentration of the inorganic acid is 15-25 wt%.
In the method for preparing high-strength artificial rutile from ilmenite, in the step D, the volume-mass ratio of hydrochloric acid to reoxidized ore is 3-4: 1.
in the method for preparing the high-strength artificial rutile from the ilmenite, in the step D, the stirring speed is controlled to be 200-500 r/min during the inorganic acid leaching.
In the method for preparing the high-strength artificial rutile from the ilmenite, in the step D, the leaching temperature is 80-105 ℃.
In the method for preparing the high-strength artificial rutile from the ilmenite, in the step D, the leaching time is 2-6 hours.
In the method for preparing high-strength artificial rutile from ilmenite, in the step E, the inorganic base is NaOH or KOH.
In the method for preparing the high-strength artificial rutile from the ilmenite, in the step E, the concentration of the inorganic alkali solution is 5-15 wt%.
In the method for preparing high-strength artificial rutile from ilmenite, in the step E, the volume-mass ratio of the inorganic alkali solution to the leached solid phase is 1-3: 1.
in the method for preparing the high-strength artificial rutile from the ilmenite, in the step E, the leaching temperature is 30-80 ℃.
In the method for preparing the high-strength artificial rutile from the ilmenite, in the step E, the leaching time is 0.5-1 h.
In the method for preparing the high-strength artificial rutile from the ilmenite, in the step E, the calcining temperature is 300-700 ℃.
In the method for preparing the high-strength artificial rutile from the ilmenite, in the step E, the calcining time is 0.2-1 h.
In the method of the present invention, the oxidation rate represents (trivalent Fe content/total Fe content) × 100%, and the reduction rate represents (1-trivalent Fe content/total Fe content) × 100%.
The volume-mass ratio in the invention is that liquid is measured by volume, solid is measured by mass, the two are units with the same order of magnitude, for example, when the volume unit is L, the mass unit is kg.
The invention has the beneficial effects that:
the method changes the microcosmic composition and morphology of the ilmenite by performing high-temperature oxidation-weak reduction-high-temperature reoxidation pretreatment on the ilmenite, so that the ilmenite has good reaction activity and mechanical resistance in the subsequent acid leaching-alkali leaching impurity removal process, the titanium recovery rate reaches more than 98 percent, and the obtained artificial rutile has high strength and TiO2The content is higher, the granularity is better maintained, the fine powder proportion is lower, and the loss is small when the catalyst is used for subsequent boiling chlorination.
The method has strong adaptability to ilmenite raw materials, the high-temperature reoxidation process is an autothermal reaction, the energy consumption is low, the time consumption is short, the requirement on equipment is lower, and the existing equipment can be directly utilized; simple process, high efficiency, low cost and large-scale continuous production.
Drawings
FIG. 1 is a schematic process flow diagram of the process for preparing high-strength synthetic rutile from ilmenite.
Detailed Description
On the basis of fully researching the reaction process and change rule of ilmenite in the processes of oxidation-reduction pretreatment and acid leaching, the invention provides a production process for preparing high-strength artificial rutile by treating ilmenite through high-temperature oxidation-weak reduction-high-temperature reoxidation-acid leaching-alkali leaching, which comprises the following steps:
A. oxidizing and roasting ilmenite to obtain oxidized ore with the oxidation rate of more than or equal to 80%;
B. reducing and roasting the oxidized ore obtained in the step A in a reducing atmosphere to obtain reduced ore with the reduction rate of more than or equal to 80%;
C. b, oxidizing and roasting the reduced ore obtained in the step B to obtain reoxidized ore with the oxidation rate of more than or equal to 50%;
D. c, leaching the reoxidation ore obtained in the step C by hydrochloric acid, and carrying out liquid-solid separation to obtain a leached solid phase;
E. and D, leaching the leached solid phase obtained in the step D by using a NaOH solution, carrying out liquid-solid separation and washing to obtain an artificial rutile primary product, and calcining the primary product to obtain the high-strength artificial rutile.
In the step A of the method, the adopted ilmenite contains 40-60 wt% of TiO2And 1 to 8% by weight of SiO2The other main components comprise 25-40 wt% of FeO and Fe2O30 to 10 wt%, MgO0 to 8 wt%, CaO0 to 1.5 wt%, and Al2O30 to 1.5 wt%; and because the subsequent boiling chlorination process requires that the particle size of the artificial rutile is distributed between 60 and 200 meshes, the particle size distribution of the ilmenite is controlled to be 60 to 200 meshes, more than 98 percent of the finally prepared artificial rutile is distributed between 60 and 200 meshes, the particle size of the product is well maintained, and the proportion of fine powder is low.
In the step A of the method, oxidizing roasting is generally carried out in air or oxygen atmosphere in a fluidized bed or a rotary kiln, the temperature is 850-1050 ℃, and the time is 0.5-2 h, so that the oxidation rate of the obtained oxidized ore is controlled to be more than or equal to 80%; the higher the oxidation rate of the oxidized ore is, the higher the subsequent reduction roasting activity is, and the product quality is favorably controlled.
In step B of the process of the present invention, the reduction roasting is generally carried out in a fluidized bed or rotary kiln in H2The reduction is carried out in a reducing atmosphere (such as coal gas or hydrogen) with the volume content of more than 20 percent or CO with the volume content of more than 30 percent, the temperature is 700-800 ℃, the time is 0.5-4 h, and thus the reduction rate of the obtained reduced ore is controlled to be more than or equal to 80 percent; the higher the reduction rate of the reduced ore, the more the holes in the ilmenite particles are, which is beneficial to the subsequent reoxidation and acid leaching.
In the step C of the method, oxidizing roasting is generally carried out in air or oxygen atmosphere in a fluidized bed or a rotary kiln, the temperature is 850-1050 ℃, and the time is 0.2-0.5 h, so that the oxidation rate of the obtained oxidized ore is controlled to be more than or equal to 50%; reoxidation results in the formation of mainly TiO within the mineral particles2High oxidation rate is beneficial to TiO2The generation is beneficial to keeping high strength in the acid leaching process of mineral particles; and the high-temperature reoxidation procedure in the step C is self-heating reaction, so that the energy consumption is low and the time consumption is short.
In the steps A to C of the method, in order to save energy, in the working procedures of high-temperature oxidation, weak reduction and high-temperature reoxidation, the materials filled in a thermal state are generally adopted for roasting.
The method changes the microcosmic composition and the shape of the ilmenite by carrying out high-temperature oxidation-weak reduction-high-temperature reoxidation pretreatment on the ilmenite, so that the ilmenite has good reaction activity and mechanical force resistance in the subsequent hydrochloric acid leaching-alkali leaching impurity removal process.
In the step D of the method, inorganic acid with the concentration of 15-25 wt% and reoxidized ore are preferably adopted according to the volume mass ratio of 3-4: 1, acid leaching; wherein the leaching temperature is 80-105 ℃, and the leaching time is 2-6 h; after acid leaching is finished, carrying out solid-liquid separation to obtain a leaching solid phase and a leaching solution; the leaching equipment for acid leaching needs to adopt a leaching ball or a fluidized bed with stirring, the stirring speed during hydrochloric acid leaching is controlled to reach 200-500 r/min, the stirring is favorable for solid-liquid diffusion, and the leaching reaction rate is increased. Wherein, the inorganic acid can be hydrochloric acid or sulfuric acid; when hydrochloric acid is adopted, the hydrochloric acid can be sprayed, recovered and processed into regenerated acid, and the regenerated acid is recycled for the leaching process, so that acid recycling is realized, but if sulfuric acid is adopted, the recycling difficulty is high.
In the step E of the method, an inorganic alkali solution with the concentration of 5-15 wt% and a leaching solid phase are preferably adopted according to the volume mass ratio of 1-3: 1, leaching and alkaline leaching to remove impurities; wherein the leaching temperature is 30-80 ℃, and the leaching time is 0.5-1 h; the alkaline leaching process is mainly used for removing Ca and Si impurities in silicic acid impurities which cannot be taken out by acid leaching, so that the artificial rutile has better quality; wherein the inorganic base is NaOH or KOH; in the alkaline leaching step, the reaction conditions are relatively mild, and the reaction amount is small, so the alkaline leaching has no strict requirements on equipment and stirring speed.
After the alkaline leaching is finished, carrying out solid-liquid separation, and washing the obtained solid phase to obtain an artificial rutile primary product; during washing, in order to save cost, the leachate obtained in the step D can be washed firstly, and then the leachate is washed by water to remove impurity ions and the like adsorbed on the solid; and E, calcining the artificial rutile primary product in a rotary kiln at the temperature of 300-700 ℃ for 0.2-1 hour to obtain a high-strength artificial rutile product.
Preferably, the method for preparing the high-strength synthetic rutile by the ilmenite comprises the following steps:
A. mixing ilmenite (TiO)240 to 60% by weight of SiO21-8 wt%) in a fluidized bed or a rotary kiln, and oxidizing and roasting for 0.5-2 h at 850-1050 ℃ in air or oxygen atmosphere to obtain oxidized ore with the oxidation rate of more than or equal to 80%;
B. charging the hot oxidized ore into the next fluidized bed or rotary kiln in H2Reducing and roasting at 700-800 ℃ for 0.5-4 h in a reducing atmosphere of (volume content is more than 20%) or CO (volume content is more than 30%) to obtain reduced ore with reduction rate of more than or equal to 80%;
C. the hot reduction ore is then put into the next fluidized bed or rotary kiln, and is oxidized and roasted for 0.2 to 0.5h at 850 to 1050 ℃ in the air or oxygen atmosphere, so as to obtain reoxidation ore with the oxidation rate of more than or equal to 50 percent;
D. carrying out secondary oxidation on the ore with 15-25 wt% of inorganic base (hydrochloric acid or sulfuric acid) in a liquid-solid volume-mass ratio of (3-4): 1(L/kg), controlling the stirring speed to be 200-500 r/min, leaching at 80-105 ℃ for 2-6 h under normal pressure, and separating liquid from solid to obtain a leaching solid phase and a leaching solution;
E. using 5-15 wt% of inorganic base (NaOH or KOH) solution to leach out solid phase, wherein the volume mass ratio of liquid to solid is 1-3: and (3) leaching at 30-80 ℃ for 0.5-1 h under 1(L/kg), separating liquid from solid, washing a solid phase with the leachate obtained in the step (D), washing with water to obtain an artificial rutile primary product, and calcining the primary product in a rotary kiln at 300-700 ℃ for 0.2-1 h to obtain a high-strength artificial rutile product.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
The present example selects the main components of ilmenite: TiO 22：46.76％、FeO：35.59％、Fe2O3：5.12％、MgO：6.62％、CaO：1.03％、SiO2：4.56％、Al2O3: 1.26 percent; the particle size distribution is 60-200 meshes, and the average particle size is 185 mu m; the preparation method comprises the following specific steps:
A. oxidizing and roasting ilmenite for 1h at 1000 ℃ in an air atmosphere in a fluidized bed to obtain oxidized ore with the oxidation rate of 95%;
B. reducing and roasting the oxidized ore for 1h at 750 ℃ in coke oven gas in a fluidized bed to obtain reduced ore with the reduction rate of 92%;
C. oxidizing and roasting the reduced ore for 0.2h at 1000 ℃ in an air atmosphere in a fluidized bed to obtain reoxidized ore with the oxidation rate of 87%;
D. putting 20 wt% hydrochloric acid for reoxidation ore in a reactor with strong stirring (the rotating speed is 500r/min), wherein the liquid-solid ratio is 4: 1(L/kg), leaching for 4h at the temperature of 105 ℃, and carrying out solid-liquid separation to obtain a leached solid phase and a leaching solution, wherein more than 98.5 percent of the solid phase has the granularity distribution of 60-200 meshes, and the average granularity is 183 mu m;
E. leaching solid phase is treated by 8 weight percent NaOH in a liquid-solid ratio of 2: 1(L/kg) and leaching for 0.5h at the temperature of 50 ℃, after solid-liquid separation, washing the leachate obtained in the step D for 1 time, then washing the leachate for 2 times by using water to obtain an artificial rutile primary product, and calcining the artificial rutile primary product in a rotary kiln at the temperature of 500 ℃ for 1h to obtain a high-strength artificial rutile product.
The high-strength artificial rutile product obtained in the embodiment has more than 98% of particle size distribution between 60 meshes and 200 meshes, has an average particle size of 183 mu m, and mainly comprises the following components: TiO 22：94.14％、FeO：2.15％、MgO：0.61％、CaO：0.11％、SiO2：2.13％，Al2O3: 0.68 percent, and the recovery rate of Ti in the whole process is 98.5 percent; the verification test shows that the product uses N in a cold gas-solid fluidized bed2Fluidizing at 0.5m/s for 2 hr, maintaining the granularity unchanged basically and blowing quality loss less than 0.5%.
Example 2
The present example selects the main components of ilmenite: TiO 22：47.8％、FeO：37.81％、Fe2O3：3.66％、MgO：6.28％、CaO：0.83％、SiO2：2.32％、Al2O3: 1.23 percent; the particle size distribution is 60-200 meshes, and the average particle size is 194 mu m; the preparation method comprises the following specific steps:
A. oxidizing and roasting ilmenite for 1.5h at 950 ℃ in an air atmosphere in a fluidized bed to obtain oxidized ore with the oxidation rate of 93%;
B. reducing and roasting the oxidized ore for 0.5h at 800 ℃ in coke oven gas in a fluidized bed to obtain reduced ore with the reduction rate of 91%;
C. oxidizing and roasting the reduced ore for 0.3h at 950 ℃ in an air atmosphere in a fluidized bed to obtain reoxidized ore with the oxidation rate of 82%;
D. in a flask with strong stirring (500 r/min) 20 wt% hydrochloric acid for reoxidation ore, the liquid-solid ratio is 4: 1(L/kg), leaching for 4 hours at the temperature of 105 ℃, and carrying out solid-liquid separation to obtain a leached solid phase and a leaching solution, wherein more than 98% of the solid phase has the granularity distribution of 60-200 meshes, and the average granularity is 191 mu m;
E. leaching solid phase is treated by 8 weight percent NaOH in a liquid-solid ratio of 2: 1(L/kg) and leaching for 0.5h at the temperature of 50 ℃, after solid-liquid separation, washing the leachate obtained in the step D for 1 time, then washing the leachate for 2 times by using water to obtain an artificial rutile primary product, and calcining the artificial rutile primary product in a rotary kiln at the temperature of 500 ℃ for 1h to obtain a high-strength artificial rutile product.
The high-strength artificial rutile product obtained in the embodiment has more than 98% of particle size distribution between 60 meshes and 200 meshes, the average particle size of 191 microns, and the main components of: TiO 22：96.23％、FeO：1.67％、MgO：0.58％、CaO：0.09％、SiO2：0.94％，Al2O3: 0.40 percent, the recovery rate of Ti in the whole process is 98.3 percent, and the verification test shows that the product uses N in a cold gas-solid fluidized bed2Fluidizing at 0.5m/s for 2 hr, maintaining the granularity unchanged basically and blowing quality loss less than 0.5%.
Comparative example 1 (no reoxidation process)
The comparative example selects ilmenite of example 1, and the specific preparation steps are as follows:
A. oxidizing and roasting ilmenite for 1h at 1000 ℃ in an air atmosphere in a fluidized bed to obtain oxidized ore with the oxidation rate of 95%;
B. reducing and roasting the oxidized ore for 1h at 750 ℃ in coke oven gas in a fluidized bed to obtain reduced ore with the reduction rate of 91%;
C. 20 percent by weight of hydrochloric acid for reducing ore is put in a reactor with strong stirring (the rotating speed is 500r/min), and the liquid-solid ratio is 4: 1(L/kg), leaching for 4h at the temperature of 105 ℃, and carrying out solid-liquid separation to obtain a leached solid phase and a leaching solution, wherein the average particle size of solid particles is only 26 mu m, and is less than 10% between 60 and 200 meshes;
D. leaching solid phase is treated by 8 weight percent NaOH in a liquid-solid ratio of 2: 1(L/kg) at the temperature of 50 ℃ for 0.5h, after solid-liquid separation, washing the leachate obtained in the step C for 1 time, then washing the leachate with water for 2 times to obtain an artificial rutile primary product, and calcining the artificial rutile primary product in a rotary kiln at the temperature of 500 ℃ for 1h to obtain an artificial rutile product.
The synthetic rutile product obtained by the comparative example has the particle size distribution with the original particle size of less than 10% between 60 and 200 meshes, the average particle size of 22 mu m and the main components: TiO 22：93.87％、FeO：2.19％、MgO：0.65％、CaO：0.10％、SiO2：2.12％，Al2O3：0.63 percent, the recovery rate of Ti in the whole process is 90 percent, and because the granularity is too small, the Ti does not meet the boiling chlorination requirement completely, and a fluidization verification test is not carried out.
Comparative example 2 (no reoxidation process, hydrochloric acid leach without agitation)
The comparative example selects ilmenite of example 1, and the specific preparation steps are as follows:
A. oxidizing and roasting ilmenite for 1h at 1000 ℃ in an air atmosphere in a fluidized bed to obtain oxidized ore with the oxidation rate of 95%;
B. reducing and roasting the oxidized ore for 1h at 750 ℃ in coke oven gas in a fluidized bed to obtain reduced ore with the reduction rate of 91%;
C. reducing ore is treated with 20 wt% hydrochloric acid in a reactor without stirring, and the liquid-solid ratio is 4: 1(L/kg), leaching for 4h at the temperature of 105 ℃, and carrying out solid-liquid separation to obtain a leaching solid phase and a leaching solution, wherein the average particle size of solid particles is 97 mu m, and the particle size of the solid particles is only 48% between 60 and 200 meshes;
D. leaching solid phase is treated by 8 weight percent NaOH in a liquid-solid ratio of 2: 1(L/kg) and leaching for 0.5h at the temperature of 50 ℃, after solid-liquid separation, washing the leaching waste liquid obtained in the step C for 1 time, then washing the leaching waste liquid with water for 2 times to obtain an artificial rutile primary product, and calcining the artificial rutile primary product in a rotary kiln at the temperature of 500 ℃ for 1h to obtain an artificial rutile product.
The synthetic rutile product obtained by the comparative example has the particle size distribution of 47% of original particle size between 60 and 200 meshes and 94 μm of average particle size, and comprises the following main components: TiO 22：93.87％、FeO：2.19％、MgO：0.65％、CaO：0.10％、SiO2：2.12％，Al2O3: 0.63 percent, the recovery rate of Ti in the whole process is 92 percent, and the verification test shows that the product uses N in a cold gas-solid fluidized bed2Fluidizing at 0.5m/s for 2 hr to reduce the average grain size to 71 micron and to reach blowing quality loss of 31%.
Claims (9)
1. The method for preparing the high-strength artificial rutile by the ilmenite is characterized by comprising the following steps: the method comprises the following steps:
A. oxidizing and roasting ilmenite to obtain oxidized ore with the oxidation rate of more than or equal to 80%;
B. reducing and roasting the oxidized ore obtained in the step A in a reducing atmosphere to obtain reduced ore with the reduction rate of more than or equal to 80%;
C. b, oxidizing and roasting the reduced ore obtained in the step B to obtain reoxidized ore with the oxidation rate of more than or equal to 50%;
D. c, leaching the reoxidized ore with inorganic acid, and performing liquid-solid separation to obtain a leached solid phase;
E. d, leaching the leached solid phase obtained in the step D with an inorganic alkali solution, carrying out liquid-solid separation and washing to obtain an artificial rutile primary product, and calcining the primary product to obtain high-strength artificial rutile;
in the step A, 40-60 wt% of TiO is contained in the ilmenite21 to 8% by weight of SiO225 to 40 wt% of FeO and 0 to 10 wt% of Fe2O30 to 8 wt% of MgO, 0 to 1.5 wt% of CaO and 0 to 1.5 wt% of Al2O3。
2. The process for producing high strength synthetic rutile of claim 1 wherein the ilmenite is selected from the group consisting of: in the step A, the particle size distribution of the ilmenite is 60-200 meshes.
3. The process for producing high strength synthetic rutile of claim 1 wherein the ilmenite is selected from the group consisting of: in the step A, the oxidizing roasting temperature is 850-1050 ℃; the time of oxidizing roasting is 0.5-2 h.
4. The process for producing high strength synthetic rutile of claim 1 wherein the ilmenite is selected from the group consisting of: in the step B, the temperature of the reduction roasting is 700-800 ℃; the time of the reduction roasting is 0.5-4 h.
5. The process for producing high strength synthetic rutile of claim 1 wherein the ilmenite is selected from the group consisting of: in the step C, the temperature of oxidizing roasting is 850-1050 ℃; the time of oxidizing roasting is 0.2-0.5 h.
6. The process for producing high strength synthetic rutile of claim 1 wherein the ilmenite is selected from the group consisting of: in step D, at least one of the following is satisfied:
the inorganic acid is hydrochloric acid or sulfuric acid;
the concentration of the inorganic acid is 15-25 wt%;
the volume-mass ratio of the inorganic acid to the reoxidation ore is 3-4: 1.
7. the process for producing high strength synthetic rutile of claim 1 wherein the ilmenite is selected from the group consisting of: in step D, at least one of the following is satisfied:
when the inorganic acid is leached, the stirring speed is controlled to be 200-500 r/min;
the leaching temperature is 80-105 ℃;
the leaching time is 2-6 h.
8. The process for producing high strength synthetic rutile of claim 1 wherein the ilmenite is selected from the group consisting of: in step E, at least one of the following is satisfied:
the inorganic base is NaOH or KOH;
the concentration of the inorganic alkali solution is 5-15 wt%;
the volume mass ratio of the inorganic alkali solution to the leached solid phase is 1-3: 1.
9. the process for producing high strength synthetic rutile of claim 1 wherein the ilmenite is selected from the group consisting of: in step E, at least one of the following is satisfied:
the leaching temperature is 30-80 ℃;
the leaching time is 0.5-1 h;
the calcining temperature is 300-700 ℃;
the calcining time is 0.2-1 h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885324A (en) * | 1996-07-26 | 1999-03-23 | Tiomin Resources, Inc. | Method for the production of synthetic rutile |
| CN101851004A (en) * | 2010-06-25 | 2010-10-06 | 长沙矿冶研究院 | Method for producing artificial rutile by using residual slope accumulated ilmenite |
| CN102786082A (en) * | 2012-04-09 | 2012-11-21 | 中国科学院过程工程研究所 | Method for preparing artificial rutile |
| CN107285378A (en) * | 2017-08-18 | 2017-10-24 | 攀钢集团研究院有限公司 | The method that ilmenite concentrate prepares macroporous titanium dioxide material |
-
2018
- 2018-07-17 CN CN201810785059.4A patent/CN108585034B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885324A (en) * | 1996-07-26 | 1999-03-23 | Tiomin Resources, Inc. | Method for the production of synthetic rutile |
| CN101851004A (en) * | 2010-06-25 | 2010-10-06 | 长沙矿冶研究院 | Method for producing artificial rutile by using residual slope accumulated ilmenite |
| CN102786082A (en) * | 2012-04-09 | 2012-11-21 | 中国科学院过程工程研究所 | Method for preparing artificial rutile |
| CN107285378A (en) * | 2017-08-18 | 2017-10-24 | 攀钢集团研究院有限公司 | The method that ilmenite concentrate prepares macroporous titanium dioxide material |
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