CN114682307A - Treatment method of waste denitration catalyst, titanium-tungsten powder, denitration catalyst and preparation method thereof - Google Patents
Treatment method of waste denitration catalyst, titanium-tungsten powder, denitration catalyst and preparation method thereof Download PDFInfo
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- CN114682307A CN114682307A CN202011625666.8A CN202011625666A CN114682307A CN 114682307 A CN114682307 A CN 114682307A CN 202011625666 A CN202011625666 A CN 202011625666A CN 114682307 A CN114682307 A CN 114682307A
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- denitration catalyst
- fluoride
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- tungsten powder
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 64
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000000843 powder Substances 0.000 title claims abstract description 51
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 59
- 239000002904 solvent Substances 0.000 claims abstract description 39
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 3
- 239000003049 inorganic solvent Substances 0.000 claims description 3
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000003495 polar organic solvent Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 13
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910052721 tungsten Inorganic materials 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- -1 and in addition Inorganic materials 0.000 description 3
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
- B01J38/66—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to the field of recycling of waste denitration catalysts, and discloses a treatment method of a waste denitration catalyst, titanium-tungsten powder, a denitration catalyst and a preparation method of the denitration catalyst. The treatment method of the waste denitration catalyst comprises the following steps: 1) crushing the waste denitration catalyst to obtain a crushed material; 2) the pulverized material is contacted with a fluoride in the presence of a solvent under a condition of pH of 4 or less. The treatment method is simple, convenient and efficient, has strong selectivity, and can remove various impurities simultaneously only by one-step reaction. The obtained titanium-tungsten powder has extremely low content of impurities except titanium-tungsten as a main component and excellent quality.
Description
Technical Field
The invention relates to the field of recycling of waste denitration catalysts, and particularly relates to a treatment method of a waste denitration catalyst, titanium-tungsten powder, a denitration catalyst and a preparation method of the denitration catalyst.
Background
The selective catalytic reduction method is the most widely applied flue gas denitration technology internationally at present, is basically applied to most power plants in many countries and regions in the world, and has wide commercial application due to the advantages of no generation of byproducts, no secondary pollution, simple device structure, safe and reliable operation, simple and convenient maintenance, low one-time investment, high denitration efficiency of over 90 percent and the like.
At present, the most widely used flue gas denitration catalyst(SCR catalyst) is V2O5-WO3/TiO2A honeycomb catalyst. The catalyst is made of TiO2As a carrier, V2O5And WO3As active ingredient in preparation V2O5-WO3/TiO2The glass fiber is added in the process of forming the honeycomb catalyst to improve the mechanical property of the catalyst, and the main components of the glass fiber are Si and Al. In addition to this, there is also V2O5/TiO2Denitration catalyst, V2O5-MoO3/TiO2Denitration catalyst, V2O5-MoO3-WO3/TiO2Various types of denitration catalysts, etc.
Because the denitration catalyst is in a severe environment operation condition for a long time in the use process, alkali metal elements (such as K, Na and the like) are attached and accumulated in the use process, and then the catalyst is poisoned, and in the operation process, the smoke dust can block the catalyst pore channels, so that the denitration catalyst can be disabled and scrapped after 2 to 4 years under the long-term action of the factors.
If the waste denitration catalyst cannot be treated correctly and effectively, not only is a huge waste caused to resources, but also secondary pollution is caused to the environment, and if toxic substances in the denitration catalyst are not treated properly, the denitration catalyst also can harm the human health. Therefore, there are many studies related to the recovery treatment of the spent denitration catalyst.
CN101921916A discloses a method for recovering metal oxide from waste flue gas denitration catalyst, in the method, after the waste flue gas denitration catalyst is crushed, high-temperature pre-roasting pretreatment is carried out, Na is added according to proportion2CO3Mixing, pulverizing, and high-temperature roasting. The sintered blocks are put into hot water after being crushed and stirred and leached. The obtained titanate crude product is subjected to acid washing, filtering, water washing and roasting to obtain TiO2. The process needs to be roasted at the high temperature of 650-700 ℃ in the reaction process, not only has high energy consumption, but also has high operation risk coefficient, and the method has complex treatment flow and is difficult to operate.
CN103526031A discloses denitration of waste flue gasThe method adopts a hydrometallurgy process, and comprises the steps of crushing the waste flue gas denitration catalyst, carrying out pre-roasting treatment, and then adding NaOH solution in proportion for dissolving. Dissolving, solid-liquid separating, adding sulfuric acid into the precipitate, leaching, settling, hydrolyzing, treating with salt, and roasting to obtain TiO2. The method also needs to be roasted at the high temperature of 650-700 ℃, and in addition, TiO product is obtained2The method also needs complex steps of pre-roasting treatment, alkali dissolution, solid-liquid separation, acid dissolution, sedimentation, roasting and the like, and has high requirements on equipment, large investment and high cost.
Therefore, how to realize an efficient and simple treatment method for the waste denitration catalyst is one of the problems to be solved in the field.
Disclosure of Invention
The invention aims to solve the problems of harsh treatment conditions, complex flow, high cost and the like of the waste denitration catalyst in the prior art, and provides a treatment method of the waste denitration catalyst, titanium tungsten powder, a preparation method of the titanium tungsten powder and the denitration catalyst using the titanium tungsten powder.
In order to achieve the above object, a first aspect of the present invention provides a method for treating a spent denitration catalyst, the method comprising the steps of:
1) crushing the waste denitration catalyst to obtain a crushed material;
2) the pulverized material is contacted with a fluoride in the presence of a solvent under a condition of pH of 4 or less.
Preferably, in the step 2), the crushed material, the fluoride and the acid are contacted with the solvent.
Preferably, the fluoride is one or more of ammonium fluoride, sodium fluoride and tetramethylammonium fluoride; more preferably, the fluoride is ammonium fluoride.
Preferably, the acid is one or more of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, acetic acid, oxalic acid, citric acid, formic acid, and trichloroacetic acid.
Preferably, the solvent is an inorganic solvent and/or other polar organic solvent; more preferably, the solvent is water and/or ethanol.
Preferably, in step 2), the pH is 1-4; more preferably, in step 2), the pH is 1.5 to 3.
Preferably, in step 2), the contacting conditions include: the contact temperature is 0-40 ℃, and the contact time is 0.5-5 h; more preferably, in step 2), the contacting conditions include: the contact temperature is 25-40 ℃, and the contact time is 0.5-2 h.
Preferably, in the step 1), the particle size of the crushed material is 10-200 meshes; more preferably, the particle size of the crushed material is 18-40 mesh.
Preferably, in the step 2), the weight ratio of the crushed material to the solvent is 1: 1-100; more preferably, the weight ratio of the crushed material to the solvent is 1: 20-40.
Preferably, the fluoride is used in an amount of 0.1 to 3mol in terms of fluorine element with respect to 1L of the solvent; more preferably, the fluoride is used in an amount of 0.2 to 1mol in terms of fluorine element with respect to 1L of the solvent.
Preferably, the method further comprises the steps of carrying out solid-liquid separation, washing and drying on the contacted materials.
In a second aspect of the present invention, there is provided a method for preparing titanium tungsten powder, which is carried out according to the method of the first aspect of the present invention, wherein the component of the spent denitration catalyst contains V2O5、TiO2And WO3。
In a third aspect, the present invention provides a titanium tungsten powder prepared by the method of the second aspect.
Preferably, in TiO2The content of titanium in the titanium tungsten powder is more than 90 wt%.
The fourth aspect of the present invention provides a method for preparing a denitration catalyst, wherein the titanium tungsten powder prepared by the method of the second aspect of the present invention or the titanium tungsten powder of the third aspect of the present invention is used as a raw material to prepare the denitration catalyst.
In a fifth aspect, the present invention provides a denitration catalyst, wherein the denitration catalyst is prepared by the method of the fourth aspect.
Through the technical scheme, the waste denitration catalyst is ground and reacts with fluoride under the condition that the pH value is below 4 in the presence of the solvent, so that various impurities in the waste denitration catalyst can be removed, the treatment process is simple, convenient and efficient, the selectivity is high, and various impurities can be removed simultaneously only through one-step reaction.
Secondly, the treatment method of the waste denitration catalyst provided by the invention is used for treating the waste denitration catalyst containing V2O5、TiO2And WO3The waste denitration catalyst can obtain high-purity titanium-tungsten powder, and other impurities are removed while main component titanium and effective component tungsten in the denitration catalyst are kept, so that the obtained titanium-tungsten powder has extremely low content of impurities except the main component titanium-tungsten and excellent quality.
In addition, the method can also effectively remove the degraded vanadium element in the waste denitration catalyst, and reduce the adverse effect of the degraded vanadium element on the catalyst prepared by the titanium-tungsten powder.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides a method for treating a spent denitration catalyst, wherein the method comprises the steps of:
1) crushing the waste denitration catalyst to obtain a crushed material;
2) the pulverized material is contacted with a fluoride in the presence of a solvent under a condition of pH of 4 or less.
According to the present invention, the spent denitration catalyst may be various spent denitration catalysts for denitration, which are conventional in the art, without particular limitation, and for example, the spent denitration catalyst may be V2O5-WO3/TiO2Catalyst for denitration system and V2O5/TiO2Catalyst for denitration system and V2O5-MoO3/TiO2Spent denitration catalyst and V2O5-MoO3-WO3/TiO2A denitration catalyst, and the like.
In a preferred embodiment of the present invention, the spent denitration catalyst is V2O5-WO3/TiO2Is a waste denitration catalyst containing 80-90 wt% of TiO21-5% by weight of WO31-5% by weight of SiO20.5-5% by weight of V2O50.5 to 2% by weight of Al2O30.01-2 wt% of Na2O, CaO 0.01-2 wt%, SO 0.01-2 wt%30.01 to 2 wt.% of K2O, 0.01-2 wt% Fe2O30.01 to 1 wt% of As2O30.1 to 5% by weight of MoO3And minor amounts of other impurities.
In the invention, in order to enlarge the contact area of the waste denitration catalyst with fluoride and a solvent and better perform subsequent treatment, the waste denitration catalyst is crushed to obtain crushed materials.
According to the present invention, the pulverization treatment may be performed by various methods for performing the pulverization treatment, which are conventional in the art, for example, one or more of ball mill grinding, rod mill grinding and impact mill grinding may be employed without particular limitation as long as the pulverization treatment can be performed on the spent denitration catalyst.
According to a preferred embodiment of the present invention, the waste denitration catalyst is pulverized by a ball mill grinding method.
According to the present invention, the particle size of the pulverized material may be 10 to 200 mesh, and preferably, the particle size of the pulverized material is 18 to 40 mesh. Although theoretically, the higher the material crushing degree is, the better the subsequent treatment effect is, the inventor of the present invention finds that the subsequent treatment effect can be ensured by controlling the particle size of the crushed material within the above range, and the particle size of the material is reduced by continuously crushing, the treatment effect cannot be further improved, and the problems of treatment cost increase and the like caused by the excessively fine crushed material can be avoided within the particle size range defined by the present invention.
In addition, the inventors of the present invention finally found, through a great deal of research in the actual production process: by contacting the pulverized material with a fluoride in the presence of a solvent under the condition that the pH is 4 or less, selective cleaning can be achieved by utilizing the difference in action properties between different components in the spent denitration catalyst and the fluoride under an acidic condition.
Specifically, in the spent denitration catalyst, K+、Na+Monovalent cations are easy to adsorb on the surface of the waste denitration catalyst, and under the pH condition defined by the invention, H ions can adsorb K on the surface of the waste denitration catalyst+、Na+And the cations are displaced, so that the elution separation is realized.
Further, elements such as Si and Al have extremely high coordination constants with fluorine ions, e.g. Al3+And F-The accumulative coordination constant logK value is as high as 89.2, and under the pH condition defined by the invention, the corrosion washing strength can be enhanced, so that elements such as Si, Al and the like can be removed with high selectivity.
Further, Ca2+Ion is easy to react with F-Stable bonds are formed, insoluble substances are formed, and the inventors of the present invention have unexpectedly found in experiments that the insoluble substances are not easily deposited on the surface of the crushed material (i.e., the waste catalyst particles) in the contact system of the present invention, but exist in the liquid, and can be easily removed by simple solid-liquid separation. The reason why the above phenomenon occurs is not clear at present, and the inventors speculate that calcium fluoride forms ultrafine particles suspended in the mixed solution, and the particles are not easily sedimented, and thus the cleaning and removal can be easily performed.
In addition, the first and second substrates are,although V2O5Is also an active component of the denitration catalyst, but the inventors of the present invention have found that it is deteriorated in a long-term catalyst reaction to seriously lower the catalytic activity of the denitration catalyst, and thus, in the treatment method provided by the present invention, V can be added2O5Together with other impurities.
In addition, W element is not easy to react with F-Complex formation and thus substantially free from attack by fluoride ions, while Ti, W oxides are difficult to wash away by the treatment process of the present invention under the pH conditions defined herein, and thus retained.
In addition, the Mo element cannot be easily washed away by the treatment method provided by the invention, and the retention can be realized.
Thereby, impurities and undesired V can be selectively removed simply and efficiently2O5Component (b), and the desired components of titanium, tungsten, molybdenum, and the like are retained.
According to the present invention, the pH is not particularly limited as long as the pH is 4 or less to achieve the object of the present invention, and for example, the pH may be 0.5, 1, 1.5, 2, 2.5, 3, 3.5, or the like. Preferably, the pH is 1 to 4, more preferably, the pH is 1.5 to 3; further preferably, the pH is 1.5-2.5. If the pH is less than the above preferred range, although good treatment effect can be obtained, the risk during the operation is greatly increased and the safety of the operation is seriously lowered. When the pH is higher than the above range, the treatment effect of the present invention cannot be achieved.
According to a preferred embodiment of the present invention, the pulverized material, fluoride, acid and solvent are brought into contact with each other, thereby achieving the present invention at a pH of 4 or less.
In the present invention, the solvent may be conventionally selected in the art, and is not particularly limited. For example, the solvent may be an inorganic solvent and/or a polar organic solvent. Preferably, the solvent is water and/or ethanol; more preferably, the solvent is water.
In the present invention, the acid may be one used in the art to mentionSupply H+The conventional choice of ions, making acidic conditions, for example, can be various inorganic and organic acids commonly used in the art.
As the inorganic acid, for example, one or more of sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid may be mentioned.
As the organic acid, for example, one or more of acetic acid, oxalic acid, citric acid, formic acid, and trichloroacetic acid may be mentioned.
Preferably, the acid is an inorganic acid; more preferably, the acid is sulfuric acid.
In addition, according to the present invention, there is no particular limitation on the concentration of the acid as long as the pH can be adjusted to the conditions defined in the present invention by the addition of the acid.
In the present invention, the fluoride may be various organic and/or inorganic fluorides conventionally used in the art, as long as F can be provided in the solvent-The ion is not particularly limited. For example, the inorganic fluoride may be ammonium fluoride, sodium fluoride, or the like, and the organic fluoride may be tetramethylammonium fluoride or the like. Preferably, the fluoride is ammonium fluoride.
According to the present invention, the amount of the solvent may be determined according to the amount of the pulverized material, and the weight ratio of the pulverized material to the solvent may be 1: 0.3 to 100; preferably, the weight ratio of the crushed material to the solvent may be 1: 10-80 parts; more preferably, the weight ratio of the crushed material to the solvent may be 1: 20-40. The usage of the solvent is limited in the range, so that the crushed material can be fully and efficiently contacted with the fluoride, and the contact effect is improved.
According to the invention, the amount of said fluoride may vary within wide limits, for example, it may be 0.1 to 3mol, calculated as elemental fluorine, with respect to 1L of said solvent; preferably, the fluoride may be used in an amount of 0.2 to 1mol in terms of fluorine element with respect to 1L of the solvent. The use amount of the fluoride is limited in the range, so that the contact effect of the fluoride and the crushed material can be ensured, and the utilization rate of the fluoride is improved.
In the present invention, the contact may be carried out by various methods without particular limitation, and for example, the pulverized material and fluoride may be simultaneously added to a solvent in the above amounts, and the pH may be adjusted with an acid; or mixing fluoride and a solvent, adding the crushed material into the mixed solution of the fluoride and the solvent, and adjusting the pH value with acid; or mixing the pulverized material with a solvent first, then adding a fluoride, adjusting the pH with an acid, and the like. Preferably, the pulverized material and fluoride are added to a solvent and the pH is adjusted with an acid.
In the present invention, the contacting conditions may include: the contact temperature is 0-40 ℃, and the contact time is 0.5-5 h; preferably, the contacting conditions include: the contact temperature is 25-40 ℃, and the contact time is 1-2 h. Although increasing the contact temperature may improve the processing efficiency, hydrogen fluoride gas is generated when the temperature is too high, which creates a potential risk. By carrying out the contact under the above conditions, smooth reaction of the waste denitration catalyst with the fluoride can be ensured.
In addition, according to a preferred embodiment of the present invention, the contact is performed under stirring, thereby promoting the progress of the contact reaction and improving the treatment efficiency. The stirring may be performed by various methods commonly used in the art for stirring, and is not particularly limited, and for example, mechanical stirring, magnetic stirring, and the like may be used, and thus, the details thereof will not be repeated.
According to the present invention, after the completion of the contact, the contacted material may be subjected to solid-liquid separation by various means generally employed in the art, for example, filtration, centrifugation, membrane separation, and the like, to thereby obtain the contacted material.
In addition, in order to further remove impurities attached to the surface of the contacted material, the contacted material may be further washed, and the washing may be performed by various methods generally used in the art for washing, without particular limitation, for example, the contacted material may be washed with 3 to 10 times of deionized water.
Secondly, the materials obtained after the contact can be dried. The drying can also be carried out by adopting the drying conditions which are conventional in the field, for example, the drying temperature can be 60-200 ℃, and the drying time can be 1-24 h; preferably, the drying temperature can be 110-150 ℃, and the drying time is 2-10 h.
By adopting the treatment method provided by the first aspect of the invention, impurities in the waste denitration catalyst can be remarkably removed with high selectivity.
In a second aspect, the present invention provides a method for preparing titanium-tungsten powder, which comprises treating a powder containing V with the treatment method of the first aspect of the present invention2O5、TiO2And WO3The waste denitration catalyst is treated, so that the titanium-tungsten powder is prepared.
In the present invention, when preparing the titanium-tungsten powder, the preparation method may be the same as the treatment method described in the first aspect of the present invention, and details thereof are not repeated herein.
In a third aspect, the present invention provides a titanium tungsten powder prepared by the method of the second aspect.
According to the invention, with TiO2The content of titanium in the titanium-tungsten powder is more than 90 weight percent; preferably, in TiO2The content of titanium in the titanium-tungsten powder is more than 95 wt%.
According to the invention, WO3The content of tungsten in the titanium-tungsten powder is more than 2 weight percent; preferably, WO is used3The content of tungsten in the titanium-tungsten powder is 2.5-3 wt%.
The fourth aspect of the present invention provides a method for preparing a denitration catalyst, wherein the titanium tungsten powder prepared by the method of the first aspect of the present invention or the titanium tungsten powder provided by the second aspect of the present invention is used as a raw material.
According to the fourth aspect of the present invention, the preparation of the denitration catalyst can be performed by using the steps conventionally used in the art for preparing the denitration catalyst, for example, the titanium tungsten powder provided by the present invention can be mixed with the vanadium-containing compound and the solvent, and after the steps of molding, drying, calcining and the like, a new denitration catalyst can be obtained.
The vanadium-containing compound may be conventionally selected in the art for preparing a denitration catalyst, and may be, for example, ammonium metavanadate, vanadyl sulfate, vanadyl acetylacetonate, vanadyl oxalate, etc., without particular limitation.
In a fifth aspect, the present invention provides a denitration catalyst, which is prepared by the method of the fourth aspect.
The present invention will be described in detail below by way of examples. However, the present invention is not limited to the following examples.
In the following examples and comparative examples, the contents of each component in the waste denitration catalyst and the titanium tungsten powder prepared were measured by X-ray fluorescence spectrometry.
In the following examples and comparative examples, the used denitration catalyst was V-containing2O5、WO3、TiO2The content of each main component of the spent denitration catalyst of (1) is shown in table 1.
TABLE 1
| Composition (I) | Na2O | Al2O3 | SiO2 | SO3 | K2O | CaO | TiO2 | V2O5 | Fe2O3 | As2O3 | MoO3 | WO3 |
| Content (wt.) | 0.87 | 1.09 | 3.50 | 1.78 | 0.17 | 1.31 | 86.64 | 1.08 | 0.21 | 0.23 | 0.27 | 2.7 |
Note: the contents in Table 1 are% by weight.
Example 1
1) Crushing the waste denitration catalyst by a ball mill, wherein the particle size of the crushed material is 40 meshes;
2) adding the crushed material obtained in the step 1) and ammonium fluoride into deionized water to obtain a mixed solution, wherein the weight ratio of the crushed material to the deionized water is 1:40, the using amount of the ammonium fluoride is 0.26mol relative to 1L of the deionized water, then adding a sulfuric acid solution (with the concentration of 98 wt%, the same below) into the mixed solution until the pH of the mixed solution is 2, and then carrying out contact reaction for 1h at 25 ℃ under the stirring condition;
3) performing suction filtration on the contacted material obtained in the step 2) to obtain a solid, washing the obtained solid with deionized water with the volume 5 times that of the solid for three times, drying at 120 ℃ for 5 hours after washing to obtain titanium tungsten powder S1, wherein the content of each main component in the obtained titanium tungsten powder S1 is shown in Table 2.
Example 2
1) Crushing the waste denitration catalyst by a ball mill, wherein the particle size of the crushed material is 30 meshes;
2) adding the crushed material obtained in the step 1) and ammonium fluoride into deionized water to obtain a mixed solution, wherein the weight ratio of the crushed material to the deionized water is 1:30, the using amount of the ammonium fluoride is 1mol relative to 1L of the deionized water, then adding a sulfuric acid solution into the mixed solution until the pH of the mixed solution is 2.5, and then carrying out contact reaction for 1h at 25 ℃ under the stirring condition;
3) performing suction filtration on the contacted material obtained in the step 2) to obtain a solid, washing the obtained solid with deionized water with the volume 5 times that of the solid for three times, drying at 120 ℃ for 5 hours after washing to obtain titanium tungsten powder S2, wherein the content of each main component in the obtained titanium tungsten powder S2 is shown in Table 2.
Example 3
1) Crushing the waste denitration catalyst by a ball mill, wherein the particle size of the crushed material is 18 meshes;
2) adding the crushed material obtained in the step 1) and ammonium fluoride into deionized water to obtain a mixed solution, wherein the weight ratio of the crushed material to the deionized water is 1:20, the using amount of the ammonium fluoride is 0.5mol relative to 1L of the deionized water, then adding a sulfuric acid solution into the mixed solution until the pH of the mixed solution is 1.5, and then carrying out contact reaction for 1h at 25 ℃ under the stirring condition;
3) performing suction filtration on the contacted material obtained in the step 2) to obtain a solid, washing the obtained solid with deionized water with the volume 5 times that of the solid for three times, drying at 120 ℃ for 5 hours after washing to obtain titanium tungsten powder S3, wherein the content of each main component in the obtained titanium tungsten powder S3 is shown in Table 2.
Example 4
The procedure is as in example 1, except that,
in step 2), the pH of the mixture was 3.5.
Titanium tungsten powder S4 was obtained, and the contents of the respective main components in the obtained titanium tungsten powder S4 are shown in Table 2.
Example 5
The procedure is as in example 1, except that,
in the step 2), the weight ratio of the crushed material to deionized water is 1:100, the amount of ammonium fluoride is 3mol relative to 1L of deionized water, and then sulfuric acid solution is added into the mixed solution until the pH value of the mixed solution is 4;
titanium tungsten powder S5 was obtained, and the contents of the respective main components in the obtained titanium tungsten powder S5 are shown in Table 2.
Comparative example 1
The procedure is as in example 1, except that,
in step 2), the pH of the mixed solution is adjusted to 5.
Titanium tungsten powder D1 was obtained, and the contents of the respective main components in the obtained titanium tungsten powder D1 are shown in Table 2.
Comparative example 2
The procedure is as in example 1, except that,
in the step 2), the pH value of the mixed solution is adjusted to 8.5 by NaOH.
Titanium tungsten powder D2 was obtained, and the contents of the respective main components in the obtained titanium tungsten powder D2 are shown in Table 2.
TABLE 2
| Composition (I) | Al2O3 | SiO2 | SO3 | TiO2 | V2O5 | WO3 |
| S1 | 0％ | 0.1％ | 0.2％ | 95.8％ | 0.7％ | 2.7％ |
| S2 | 0.1％ | 0.1％ | 0.3％ | 95.4％ | 0.6％ | 2.6％ |
| S3 | 0.1％ | 0.2％ | 0.4％ | 95.3％ | 0.6％ | 2.7％ |
| S4 | 0.3％ | 0.6％ | 0.3％ | 93.9％ | 0.9％ | 2.7％ |
| S5 | 0.4％ | 0.7％ | 0.4％ | 92.3％ | 0.9％ | 2.7％ |
| D1 | 1.0％ | 3.3％ | 0.4％ | 89.5％ | 1.1％ | 2.7％ |
| D2 | 1.0％ | 3.3％ | 0.4％ | 89.7％ | 1.1％ | 2.7％ |
As can be seen from the results in table 2, when the waste denitration catalyst is treated under the pH condition defined in the present invention, impurities such as aluminum, silicon, vanadium, etc. in the waste denitration catalyst can be effectively removed at one time, titanium and tungsten are retained, the content of titanium therein is significantly increased, and when the pH is 5, the treatment effect is greatly reduced, which is almost the same as that when the waste denitration catalyst is treated under the alkaline condition (pH is 8.5).
The titanium tungsten powder prepared by the method of the invention contains titanium (in terms of TiO)2Calculated by weight) can reach more than 95 percent, and the content of titanium and tungsten (calculated by TiO)2With WO3Total amount) up to more than 98 percent by weight, extremely low content of other impurities and excellent quality.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for treating a spent denitration catalyst, comprising the steps of:
1) crushing the waste denitration catalyst to obtain a crushed material;
2) the pulverized material is contacted with a fluoride in the presence of a solvent under a condition of pH of 4 or less.
2. The method according to claim 1, wherein in step 2), the contact of the pulverized material, fluoride, acid and solvent is performed;
preferably, the fluoride is one or more of ammonium fluoride, sodium fluoride and tetramethylammonium fluoride;
more preferably, the fluoride is ammonium fluoride;
preferably, the acid is one or more of sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, acetic acid, oxalic acid, citric acid, formic acid and trichloroacetic acid;
preferably, the solvent is an inorganic solvent and/or other polar organic solvent;
more preferably, the solvent is water and/or ethanol.
3. The process according to claim 1 or 2, wherein in step 2) the pH is between 1 and 4,
preferably, in step 2), the pH is 1.5 to 3;
preferably, in step 2), the contacting conditions include: the contact temperature is 0-40 ℃, and the contact time is 0.5-5 h;
more preferably, in step 2), the contacting conditions include: the contact temperature is 25-40 ℃, and the contact time is 0.5-2 h.
4. A method according to any one of claims 1 to 3, wherein in step 1), the particle size of the comminuted material is in the range of from 10 to 200 mesh;
preferably, the particle size of the crushed material is 18-40 meshes.
5. A method according to any one of claims 1 to 3, wherein in step 2), the weight ratio of the crushed material to the solvent is from 1: 0.3 to 100;
preferably, the weight ratio of the crushed material to the solvent is 1: 20-40 parts of;
preferably, the fluoride is used in an amount of 0.1 to 3mol in terms of fluorine element with respect to 1L of the solvent;
more preferably, the fluoride is used in an amount of 0.2 to 1mol in terms of fluorine element with respect to 1L of the solvent.
6. The method according to any one of claims 1 to 3, wherein the method further comprises the steps of subjecting the contacted material to solid-liquid separation, washing and drying.
7. A method for producing titanium tungsten powder, characterized by being carried out according to any one of claims 1 to 7, wherein the component of the spent denitration catalyst contains V2O5、TiO2And WO3。
8. A titanium tungsten powder produced by the method for producing a titanium tungsten powder according to claim 7,
preferably, in TiO2The content of titanium in the titanium tungsten powder is more than 90 wt%.
9. A method for producing a denitration catalyst, characterized by producing a denitration catalyst from the titanium-tungsten powder produced by the method for producing titanium-tungsten powder according to claim 7 or the titanium-tungsten powder according to claim 8 as a raw material.
10. A denitration catalyst, characterized in that the denitration catalyst is prepared by the method of claim 9.
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| CN109295313A (en) * | 2018-10-26 | 2019-02-01 | 中国科学院过程工程研究所 | A method and application of recycling waste SCR denitration catalyst to prepare titanium and tungsten powder |
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