CN112408470A - Method for producing titanium dioxide by using waste denitration catalyst based on high-temperature calcination method - Google Patents
Method for producing titanium dioxide by using waste denitration catalyst based on high-temperature calcination method Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 239000002699 waste material Substances 0.000 title claims abstract description 72
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000003837 high-temperature calcination Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 39
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 239000003513 alkali Substances 0.000 claims description 37
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 31
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 239000012535 impurity Substances 0.000 claims description 20
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000007667 floating Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910020494 K2WO4 Inorganic materials 0.000 claims description 3
- 229910020264 Na2TiO3 Inorganic materials 0.000 claims description 3
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 3
- 229910019501 NaVO3 Inorganic materials 0.000 claims description 3
- 229910010252 TiO3 Inorganic materials 0.000 claims description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 12
- 238000011084 recovery Methods 0.000 abstract description 8
- 239000000284 extract Substances 0.000 abstract 1
- 238000012958 reprocessing Methods 0.000 abstract 1
- 235000010215 titanium dioxide Nutrition 0.000 description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 239000002956 ash Substances 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- 239000002920 hazardous waste Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 238000003912 environmental pollution Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 229910000805 Pig iron Inorganic materials 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910010298 TiOSO4 Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- NWJUARNXABNMDW-UHFFFAOYSA-N tungsten vanadium Chemical compound [W]=[V] NWJUARNXABNMDW-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
-
- 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
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
- C01P2006/82—Compositional purity water content
Abstract
The embodiment of the invention discloses a method for producing titanium dioxide by using a waste denitration catalyst based on a high-temperature calcination method. Compared with the prior art, the method extracts the titanium dioxide material by a high-temperature calcination method, reduces the calcination times and specifically explains the process of extracting the titanium dioxide material, simplifies the recovery process flow of the titanium dioxide, and reduces the reprocessing cost of the waste denitration catalyst.
Description
Technical Field
The embodiment of the invention relates to the field of denitration catalyst recovery, and particularly relates to a method for producing titanium dioxide by using a waste denitration catalyst based on a high-temperature calcination method.
Background
The Selective Catalytic Reduction (SCR) denitration technology is an efficient and stable flue gas denitration technology in the related technologies, wherein an SCR catalyst is a key material for efficiently and cheaply removing nitric oxide in flue gas, and is widely applied to a coal-fired flue gas denitration process of a thermal power plant, and the service life of the catalyst is only about 3-4 years due to the fact that flue gas is scoured and abraded and various impurities are continuously accumulated in the catalyst.
The main component of the SCR catalyst is titanium dioxide (containing TiO approximately)275-85%), tungsten oxide (containing about WO)34-8%) and vanadium pentoxide(containing about V)2O50.3-1.0%), and a large amount of retired catalysts belong to hazardous waste (HW50), which not only causes environmental pollution, but also causes resource waste.
Therefore, the waste denitration catalyst is used for recovering precious metals, waste materials can be changed into valuable materials, environmental pollution is reduced, recycling and reduction of dangerous waste are effectively realized, and the method has good economic benefit and social benefit. At present, related patents also exist in China for recovering precious metals by using waste denitration catalysts.
Chinese patent CN101921916A discloses a method for recovering metal oxide from waste flue gas denitration catalyst: roasting the waste denitration catalyst at the high temperature of 650 ℃, removing Hg, Ag and organic impurities adsorbed on the surface, and then adding Na2CO3Mixing, grinding, calcining at a high temperature of 650-700 ℃ to form a sinter cake, crushing the sinter cake, soaking in 80-90 hot water, precipitating and filtering to obtain a precipitated titanate crude product and a filtrate, and pickling, filtering, washing and roasting the titanate crude product to obtain TiO2The powder and the filtrate are respectively prepared into V through a series of treatments2O5、MoO3And WO3Producing a product; however, the Chinese patent CN101921916A uses two high-temperature roasting processes, and sodium carbonate is mixed and ground to be fine before the second roasting process<200 mu m, the operation is more complicated, and the sintered block after the second roasting is crushed, soaked in water and filtered to be subsequently made into TiO2The process of (A) is not specified, but is mainly directed to the preparation of V2O5、MoO3And WO3The product discussion is more detailed, and thus the Chinese patent CN101921916A mainly aims at recovering V2O5、MoO3And WO3These three products.
Chinese patent CN106337133B discloses a method for recovering titanium, vanadium and tungsten from waste denitration catalyst: mixing the waste SCR denitration catalyst, an iron raw material, a carbon-containing raw material, an adhesive and a calcium-containing raw material, granulating into a spherical material, and calcining at the high temperature of 1500-1650 ℃ to obtain vanadium-tungsten-containing pig iron and titanium slag; however, the method proposed in chinese patent CN106337133B mainly aims at preparing pig iron and titanium slag, the calcination temperature is as high as 1500-1650 ℃, and is not suitable for the preparation or production of titanium dioxide.
Chinese patent CN103526031A discloses a method for recovering SCR waste flue gas denitration catalyst: crushing the waste catalyst, roasting at a high temperature of 650-700 ℃ to obtain sintered blocks, crushing the sintered blocks to be less than or equal to 200 meshes to obtain uniform powder, putting the powder into hot water at a temperature of 80-90 ℃, stirring and soaking the powder at a liquid-solid weight ratio of 5-10: 1, then adding NaOH solution at a solid-liquid mass ratio of 4:1, and adding a cosolvent Na according to a solid-sodium carbonate mass ratio of 8:12CO3And then heating and stirring at the constant temperature of 75-100 ℃, and carrying out solid-liquid separation on the obtained solid-liquid mixture. Adding sodium sulfate powder and water into the obtained precipitate, mixing, adding concentrated sulfuric acid, heating and boiling until the precipitate is completely dissolved into TiOSO4Cooling, adding sulfuric acid to adjust pH>0.5. Adding water to dilute the titanium solution until all the solution generates white precipitate Ti (OH)4Placing the titanium white powder for complete drying, and calcining at the high temperature of 650-700 ℃ to obtain a titanium white powder finished product; however, the chinese patent CN103526031A also undergoes two high temperature bakings, and the operation process is too complicated, and the process flow is too long, which will result in high production cost, and is not suitable for the commercial production of titanium dioxide.
Therefore, in the related technology, the related process for recovering titanium dioxide from the waste denitration catalyst is not mature, namely, the existing method still has room for improvement in the aspects of cleaning, energy saving, recovery rate and purification of titanium and the like.
Disclosure of Invention
The embodiment of the invention provides a method for producing titanium dioxide by using a waste denitration catalyst based on a high-temperature calcination method, which mainly aims to solve the following technical problems in the related art: one of the technical problems is to improve the recovery rate of the titanium dioxide of the waste denitration catalyst; the second technical problem is to simplify the recovery process flow of titanium dioxide.
The invention discloses a method for producing titanium dioxide by using a waste denitration catalyst based on a high-temperature calcination method, which comprises the following specific steps:
(1) ash removal and impurity removal: the method comprises the following steps of (1) cleaning floating ash of the waste denitration catalyst by using a high-pressure air gun or a water washing mode, and removing impurities in pores of the waste denitration catalyst;
(2) crushing: crushing the waste denitration catalyst treated in the step (1) to 5-20 mm to obtain a flaky waste denitration catalyst;
(3) mixing alkali liquor: fully mixing the waste denitration catalyst treated in the step (2) with alkali liquor to obtain a mixture of the waste catalyst and alkali, wherein the mixing ratio is 3.5: 1-1.5: 1;
(4) and (3) calcining: calcining the mixture of the waste catalyst and the alkali in a rotary kiln to obtain spherical calcined substance with the diameter of 2-10mm, wherein the calcining temperature is 800-1000 ℃, and the calcining time is 3-6 hours;
(5) grinding: feeding the spherical calcined substance and dilute alkaline water with the concentration of 0.5-5.0% into a ball mill to be ground to 50-200 meshes, wherein the solid content of slurry is 20-35%, and the temperature of the slurry is 60-90 ℃;
(6) filtering and washing: pumping the ground slurry formed in the step (5) into a plate-and-frame filter press for filtering and washing until the pH value of the filtrate is less than 9.0;
(7) and (3) drying: conveying the material treated in the step (6) to a drying kiln, and drying by using hot air at 550-850 ℃ to obtain a dried material with the water content of 0.3-3.0;
(8) fine grinding: and (3) conveying the dried material into a refiner for fine grinding, wherein the average particle size of the finely ground material is 0.20-10 mu m, and thus obtaining a titanium dioxide finished product.
Optionally, the waste denitration catalyst in the step (2) is crushed, and impurities in the holes are further removed through a vibrating screen.
Optionally, the alkali in step (3) is Na2CO3、K2CO3、Na2CO3And one of a mixture with NaOH.
Optionally, the waste catalyst and alkali mixture in the step (3) is obtained by draining.
Optionally, the spent catalyst and the alkali mixture in the step (4) are calcined in a rotary kiln and simultaneously subjected to an alkali reaction.
Optionally, the reaction formula of the alkali reaction is:
TiO2+Na2CO3/K2CO3＝Na2TiO3/K2TiO3+CO2↑；
WO3+Na2CO3/K2CO3＝Na2WO4/K2WO4+CO2↑；
V2O5+Na2CO3/K2CO3＝NaVO3/K2VO3+CO2↑
optionally, the mixture of the waste catalyst and the alkali in the step (4) is calcined at a high temperature in a rotary kiln at a gradient temperature.
Optionally, the filtered and washed material in step (6) is air-blown to remove excess moisture.
Compared with the related art, the invention has the following beneficial effects:
according to the invention, the waste denitration catalyst is cleaned to remove impurities and mixed with alkali liquor, and then the waste catalyst after alkali reaction is calcined for one time to obtain the titanium dioxide material to be ground and washed, so that the materials after impurity removal can be obtained by roasting twice in the related technology, and the titanium dioxide material can be obtained by a plurality of processes; in addition, in the embodiment of the application, the calcined material is ground, filtered and washed to obtain the titanium dioxide material to be dried, so that the recovery process of the titanium dioxide material is further simplified, the hazardous wastes such as the waste denitration catalyst can be comprehensively utilized at a simpler and cheaper production cost, waste materials are changed into valuable materials, the reclamation and reduction of the hazardous wastes are realized, the environmental pollution is effectively reduced, and the economic and social benefits are better; and the whole recycling production process has no waste discharge, and the cleaning and the safety of the production process can be realized.
Drawings
FIG. 1 is a process flow diagram of the method for producing titanium dioxide from a waste denitration catalyst based on a high-temperature calcination method.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Reference herein to "a plurality" means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
The invention is further illustrated in the following examples in connection with fig. 1.
Example 1
(1) Ash removal and impurity removal: and (3) cleaning floating ash of the waste denitration catalyst by using a high-pressure air gun or a water washing mode, and removing impurities in the pores of the waste denitration catalyst.
(2) Crushing: and (2) crushing the waste denitration catalyst treated in the step (1) to 5-20 mm to obtain the flaky waste denitration catalyst.
(3) Mixing alkali liquor: and (3) fully mixing the waste denitration catalyst treated in the step (2) with alkali liquor to obtain a mixture of the waste catalyst and alkali, wherein the mixing ratio is 3.5: 1-1.5: 1.
(4) And (3) calcining: calcining the mixture of the waste catalyst and the alkali in a rotary kiln to obtain spherical calcined substance with the diameter of 2-10mm, wherein the calcining temperature is 800-1000 ℃, and the calcining time is 3-6 hours.
(5) Grinding: the spherical calcined substance and dilute alkaline water with the concentration of 0.5-5.0% are input into a ball mill together and ground to 50-200 meshes, the solid content of slurry is 20-35%, and the temperature of the slurry is 60-90 ℃.
(6) Filtering and washing: and (4) pumping the ground slurry obtained in the step (5) into a plate-and-frame filter press for filtering and washing until the pH value of the filtrate is less than 9.0.
(7) And (3) drying: and (4) conveying the material treated in the step (6) to a drying kiln, and drying by using hot air at 550-850 ℃ to obtain a dried material with the water content of 0.3-3.0.
(8) Fine grinding: and (3) conveying the dried material into a refiner for fine grinding, wherein the average particle size of the finely ground material is 0.20-10 mu m, and thus obtaining a titanium dioxide finished product.
In summary, in the embodiment of the present application, compared with a titanium dioxide recovery method in the related art, the method provided by the invention includes cleaning the waste denitration catalyst to remove impurities, mixing the waste denitration catalyst with the alkali solution, and then calcining the waste catalyst after the alkali reaction to obtain the titanium dioxide material to be ground and washed, and the method does not need to calcine the waste catalyst twice in the related art to obtain the material after removing the impurities, and needs to perform several processes to obtain the titanium dioxide material; in addition, in the embodiment of the application, the calcined material is ground, filtered and washed to obtain the titanium dioxide material to be dried, so that the recovery process of the titanium dioxide material is further simplified, the hazardous wastes such as the waste denitration catalyst can be comprehensively utilized at a simpler and cheaper production cost, waste materials are changed into valuable materials, the reclamation and reduction of the hazardous wastes are realized, the environmental pollution is effectively reduced, and the economic and social benefits are better; and the whole recycling production process has no waste discharge, and the cleaning and the safety of the production process can be realized.
Example 2
On the basis of the above embodiments, the embodiments of the present application further illustrate some steps.
(1) Ash removal and impurity removal: and (3) cleaning floating ash of the waste denitration catalyst by using a high-pressure air gun or a water washing mode, and removing impurities in the pores of the waste denitration catalyst.
Wherein, the impurities in the pores comprise plugs such as fly ash and the like and impurities.
(2) Crushing: and (2) crushing the waste denitration catalyst treated in the step (1) to 5-20 mm to obtain the flaky waste denitration catalyst.
And (2) coarsely crushing the waste denitration catalyst cleaned with impurities in the step (1) to form irregular sheet-shaped objects of 5-20 mm.
And (3) crushing the waste denitration catalyst in the step (2), and further removing impurities in the holes through a vibrating screen.
(3) Mixing alkali liquor: and (3) fully mixing the waste denitration catalyst treated in the step (2) with alkali liquor to obtain a mixture of the waste catalyst and alkali, wherein the mixing ratio is 3.5: 1-1.5: 1.
Wherein the alkali in step (3) is Na2CO3、K2CO3、Na2CO3And one of NaOH mixture; in addition, the waste catalyst and alkali mixture in the step (3) is obtained by leaching and drying.
Waste denitration (4) calcination: calcining the mixture of the waste catalyst and the alkali in a rotary kiln to obtain spherical calcined substance with the diameter of 2-10mm, wherein the calcining temperature is 800-1000 ℃, and the calcining time is 3-6 hours.
Wherein, the mixture of the waste catalyst and the alkali in the step (4) is calcined at high temperature under the gradient temperature of a rotary kiln. According to the temperature gradient in the rotary kiln, the material slowly rolls along with the rotation of the rotary kiln from low temperature to high temperature, so that all components in the waste catalyst fully react with alkali to form spherical calcined objects with the diameter of 2-10mm, namely, the waste catalyst and alkali mixture in the step (4) are calcined in the rotary kiln and simultaneously subjected to alkali reaction.
The reaction formula of the alkali reaction is as follows:
TiO2+Na2CO3/K2CO3＝Na2TiO3/K2TiO3+CO2↑；
WO3+Na2CO3/K2CO3＝Na2WO4/K2WO4+CO2↑；
V2O5+Na2CO3/K2CO3＝NaVO3/K2VO3+CO2↑。
(5) grinding: the spherical calcined substance and dilute alkaline water with the concentration of 0.5-5.0% are input into a ball mill together and ground to 50-200 meshes, the solid content of slurry is 20-35%, and the temperature of the slurry is 60-90 ℃.
(6) Filtering and washing: and (4) pumping the ground slurry obtained in the step (5) into a plate-and-frame filter press for filtering and washing until the pH value of the filtrate is less than 9.0.
Mixing the ground slurry obtained in the step (5) according to process conditions, pumping the mixture into a plate-and-frame filter press for filtering and washing, and washing with water until the pH value of the filtrate is less than 9.0; and (6) blowing the filtered and washed material with air to remove redundant moisture.
(7) And (3) drying: and (4) conveying the material treated in the step (6) to a drying kiln, and drying by using hot air at 550-850 ℃ to obtain a dried material with the water content of 0.3-3.0.
(8) Fine grinding: and (3) conveying the dried material into a refiner for fine grinding, wherein the average particle size of the finely ground material is 0.20-10 mu m, and thus obtaining a titanium dioxide finished product.
The invention is not to be considered as limited to the particular embodiments shown and described, but is to be understood that various modifications, equivalents, improvements and the like can be made without departing from the spirit and scope of the invention.
Claims (8)
1. A method for producing titanium dioxide by using a waste denitration catalyst based on a high-temperature calcination method is characterized by comprising the following steps:
(1) ash removal and impurity removal: the method comprises the following steps of (1) cleaning floating ash of the waste denitration catalyst by using a high-pressure air gun or a water washing mode, and removing impurities in pores of the waste denitration catalyst;
(2) crushing: crushing the waste denitration catalyst treated in the step (1) to 5-20 mm to obtain a flaky waste denitration catalyst;
(3) mixing alkali liquor: fully mixing the waste denitration catalyst treated in the step (2) with alkali liquor to obtain a mixture of the waste catalyst and alkali, wherein the mixing ratio is 3.5: 1-1.5: 1;
(4) and (3) calcining: calcining the mixture of the waste catalyst and the alkali in a rotary kiln to obtain spherical calcined substance with the diameter of 2-10mm, wherein the calcining temperature is 800-1000 ℃, and the calcining time is 3-6 hours;
(5) grinding: feeding the spherical calcined substance and dilute alkaline water with the concentration of 0.5-5.0% into a ball mill to be ground to 50-200 meshes, wherein the solid content of slurry is 20-35%, and the temperature of the slurry is 60-90 ℃;
(6) filtering and washing: pumping the ground slurry formed in the step (5) into a plate-and-frame filter press for filtering and washing until the pH value of the filtrate is less than 9.0;
(7) and (3) drying: conveying the material treated in the step (6) to a drying kiln, and drying by using hot air at 550-850 ℃ to obtain a dried material with the water content of 0.3-3.0;
(8) fine grinding: and (3) conveying the dried material into a refiner for fine grinding, wherein the average particle size of the finely ground material is 0.20-10 mu m, and thus obtaining a titanium dioxide finished product.
2. The method of claim 1, wherein the crushing of the spent denitration catalyst in the step (2) further removes impurities in the pores by using a vibrating screen.
3. The method according to claim 1, wherein the base in the step (3) is Na2CO3、K2CO3、Na2CO3And one of a mixture with NaOH.
4. The method according to claim 1, wherein the mixture of the spent catalyst and the alkali in the step (3) is obtained by draining.
5. The method as claimed in claim 1, wherein the spent catalyst and the alkali mixture in the step (4) are subjected to alkali reaction while being calcined in a rotary kiln.
6. The method of claim 5, wherein the base is reacted according to the formula:
TiO2+Na2CO3/K2CO3＝Na2TiO3/K2TiO3+CO2↑；
WO3+Na2CO3/K2CO3＝Na2WO4/K2WO4+CO2↑；
V2O5+Na2CO3/K2CO3＝NaVO3/K2VO3+CO2↑。
7. the method as claimed in claim 1, wherein the spent catalyst and alkali mixture in step (4) is subjected to high temperature calcination at a gradient temperature of a rotary kiln.
8. The method of claim 1, wherein the filtered and water-washed material in step (6) is air-blown to remove excess moisture.
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