CN116139851A - Resource utilization method of waste denitration catalyst - Google Patents
Resource utilization method of waste denitration catalyst Download PDFInfo
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- CN116139851A CN116139851A CN202310088061.7A CN202310088061A CN116139851A CN 116139851 A CN116139851 A CN 116139851A CN 202310088061 A CN202310088061 A CN 202310088061A CN 116139851 A CN116139851 A CN 116139851A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 111
- 239000002699 waste material Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 59
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000002386 leaching Methods 0.000 claims abstract description 36
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 20
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 20
- 239000011734 sodium Substances 0.000 claims abstract description 20
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000706 filtrate Substances 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 235000017550 sodium carbonate Nutrition 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 235000002639 sodium chloride Nutrition 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- DLCOPLYGCSRNAY-UHFFFAOYSA-N molybdenum titanium vanadium Chemical compound [Ti][Mo][V] DLCOPLYGCSRNAY-UHFFFAOYSA-N 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 239000004071 soot Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical group [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 claims description 3
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 3
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 3
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 37
- 229910052721 tungsten Inorganic materials 0.000 abstract description 23
- 239000010937 tungsten Substances 0.000 abstract description 23
- 238000005516 engineering process Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000011084 recovery Methods 0.000 description 13
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 11
- 229910052750 molybdenum Inorganic materials 0.000 description 11
- 239000011733 molybdenum Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- NWJUARNXABNMDW-UHFFFAOYSA-N tungsten vanadium Chemical compound [W]=[V] NWJUARNXABNMDW-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 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 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005496 tempering Methods 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000001038 titanium pigment Substances 0.000 description 2
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- UCKLMHXLCUEQPZ-UHFFFAOYSA-N [O-2].[Ti+4].[V+5].[W+4] Chemical compound [O-2].[Ti+4].[V+5].[W+4] UCKLMHXLCUEQPZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/28—Molybdenum
-
- 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
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1218—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
- C22B34/225—Obtaining vanadium from spent catalysts
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/34—Obtaining molybdenum
- C22B34/345—Obtaining molybdenum from spent catalysts
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
- C22B34/365—Obtaining tungsten from spent catalysts
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/95—Waste catalysts; Waste ion exchange materials; Waste adsorbents
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Abstract
The invention relates to the technical field of resource utilization of waste SCR denitration catalysts, and discloses a resource utilization method of waste denitration catalysts. The method comprises the following steps: (1) Crushing the pretreated waste SCR denitration catalyst, mixing with a sodium source, roasting, crushing the roasted material, and leaching with water according to a liquid-solid ratio of 5-8 mL to 1 g; (2) Carrying out solid-liquid separation on the slurry to obtain filtrate and filter residue, washing the filter residue, and combining the washing liquid and the filtrate; (3) Adding monoethanolamine, an active component source and a co-catalytic component source into the combined solution to enable the weight of active component metal elements in the solution to be 3-5% and the weight of co-catalytic component metal elements to be 1-8%, and stirring; (4) Mixing the raw material solution with a titanium source, pre-extruding, forming, drying and roasting the mixed mud to obtain the new denitration catalyst. The method has high leaching rate of vanadium and tungsten, and 100% of leached vanadium and tungsten can be used for preparing the novel denitration catalyst.
Description
Technical Field
The invention relates to the technical field of resource utilization of waste SCR denitration catalysts, in particular to a resource utilization method of waste denitration catalysts.
Background
The Selective Catalytic Reduction (SCR) denitration technology is an efficient, reliable and mature flue gas denitration technology, is widely applied to a coal-fired flue gas denitration system in China, and an SCR denitration catalyst is a key component of the technology. Millions of tons of SCR denitration catalysts are put into use since the denitration of coal-fired flue gas in thermal power and non-electric industries in China, and more than 4 ten thousand tons of non-renewable waste SCR denitration catalysts are generated each year along with the arrival of the replacement period of the SCR denitration catalysts. At present, waste SCR denitration catalysts are classified as dangerous wastes in China, the traditional landfill method cannot meet the requirements, and companies with related professional technical qualification are required to process the waste SCR denitration catalysts. Typical waste SCR denitration catalyst contains 0.5% -2%V 2 O 5 、＜10％WO 3 And 80 to 90 percent of TiO 2 The method can not be classified into the waste vanadium catalyst, and the existing technology of the professional engaged in the waste vanadium catalyst resource recovery enterprises can not realize the efficient separation and purification of vanadium and tungsten, so the recycling of the waste SCR denitration catalyst belongs to the new field in China. The waste SCR denitration catalytic resource utilization has great economic and social benefits for saving resources and protecting environment.
Currently, aiming at waste SCR denitration catalyst, most of domestic enterprisesThe vanadium-tungsten-titanium oxide powder is prepared by impurity removal and grinding processes according to the low-cost raw materials, and is applied to the manufacture of new catalysts or other products. In order to solve the problems of low impurity removal efficiency, poor powder quality and the like of the method, part of enterprises extract metal elements in the waste SCR denitration catalyst by adopting sodium (calcium) roasting-water leaching, wet acid leaching, alkaline leaching, electrolytic method and other technologies, and prepare chemical products containing vanadium, tungsten and titanium. Chinese patent application CN 102936049A, CN 101921916A, CN 102936039A, CN102557142a et al describe recovery of V from spent SCR denitration catalysts using a strong base roasting-water leaching process 2 O 5 、WO 3 And TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Chinese patent application CN 103088217a describes the recovery of tungsten components from spent SCR denitration catalysts using a roasting-extraction process; chinese patent application CN 102732730a describes the recovery of vanadium components from spent SCR denitration catalysts using an electrolytic process. The patent technology verifies that V is extracted from waste SCR denitration catalyst 2 O 5 、WO 3 、TiO 2 Or the feasibility of the related chemicals, but does not relate to the recycling of the extract or recovered product. At the same time, due to V in the catalyst 2 O 5 、WO 3 Or MoO 3 The above patent techniques all aim at pursuing high extraction yield and high purity of the product, but cannot achieve 100% extraction and separation. In order to improve the extraction rate and the product purity, the patent technology adopts a longer process flow, and the large wastewater yield and the high wastewater treatment cost become important factors for limiting the industrial application of the technology.
In order to solve the problems of difficult separation of vanadium and tungsten (molybdenum), low product purity, large wastewater production amount and long production period in the prior recovery technology, and to explore the recycling utilization way and utilization rate of the extract or the recovered product, the invention provides a recycling utilization method of a waste SCR denitration catalyst. Therefore, the technology makes up the defects of the prior art, can bring remarkable economic benefit and social benefit, and has great popularization and application value.
Disclosure of Invention
The invention provides a new idea of comprehensively utilizing the valuable elements in the waste SCR denitration catalyst in order to realize low-cost and high-efficiency recycling of the waste SCR denitration catalyst, not only can fully utilize the heavy metal components in the waste SCR denitration catalyst and reduce the production cost of the new denitration catalyst, but also creates considerable economic benefits, and solves the problems of difficult separation and purification of vanadium and tungsten (molybdenum), large wastewater production amount and the like.
In order to achieve the above purpose, the present invention provides a method for recycling waste denitration catalyst, which comprises the following steps:
(1) Crushing the pretreated waste SCR denitration catalyst, mixing the crushed waste SCR denitration catalyst with a sodium source for roasting, crushing the roasted material, and carrying out water leaching reaction according to the liquid-solid ratio of 5-8 mL to 1 g;
(2) Carrying out solid-liquid separation on the slurry obtained in the step (1) to obtain filtrate and filter residue, washing the filter residue with water, and then combining the obtained washing solution and filtrate to obtain a combined solution;
(3) Adding monoethanolamine, an active component source and a co-catalytic component source into the combined solution obtained in the step (2) to enable the weight of active component metal elements in the solution to be 3-5% and the weight of co-catalytic component metal elements to be 1-8%, and then stirring for reaction to obtain a raw material solution;
(4) Mixing the raw material solution obtained in the step (3) with a titanium source, and then pre-extruding, extrusion molding, drying and roasting the mixed pug to obtain the new denitration catalyst.
Preferably, in the step (1), the waste SCR denitration catalyst is a vanadium tungsten titanium denitration catalyst or a vanadium molybdenum titanium denitration catalyst.
Preferably, in the step (1), the waste SCR denitration catalyst is a honeycomb type or a corrugated type denitration catalyst.
PreferablyIn the step (1), the waste SCR denitration catalyst contains 0.5 to 2 weight percent of V 2 O 5 WO < 10% by weight 3 Or MoO 3 80 to 90 wt% of TiO 2 。
Preferably, in step (1), the pretreatment includes: and (3) carrying out soot blowing, soaking and drying on the waste SCR denitration catalyst.
Preferably, in the step (1), the pretreated waste SCR denitration catalyst is crushed to the particle size d 90 And less than or equal to 300 meshes.
Preferably, in the step (1), the total weight of the crushed waste SCR denitration catalyst and the sodium source is 100 wt%, and the crushed waste SCR denitration catalyst is 84-94 wt% and the sodium source is 6-16 wt%.
Preferably, in step (1), the sodium source is selected from one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium chloride and sodium sulfite.
Preferably, in step (1), the roasting conditions include: the roasting temperature is 850-900 ℃; the roasting time is 4-6 hours.
Preferably, in step (1), the calcined material is crushed to a particle size d 90 Less than or equal to 1000 meshes.
Preferably, in step (1), the water leaching reaction is carried out under stirring.
Preferably, in step (1), the conditions of the water leaching reaction include: the liquid-solid ratio is 6-7 mL/1 g, the temperature is 60-100 ℃ and the time is 3-5 h.
Preferably, in the step (2), the solid-liquid separation mode is suction filtration.
Preferably, in step (2), the process of washing the filter residue with water comprises: washing 3-5 times with deionized water at 60-80 ℃.
Preferably, the active ingredient source is selected from ammonium metavanadate and/or vanadyl sulfate.
Preferably, the source of the co-catalytic component is selected from one or more of ammonium tungstate, ammonium metatungstate and ammonium molybdate.
Preferably, in step (3), the stirred reaction is carried out in a water bath; the temperature of the stirring reaction is 40-50 ℃.
Preferably, in step (3), the process of adding monoethanolamine and the active component source and the co-catalytic component source includes: after monoethanolamine is added, stirring is carried out in a water bath at 40-50 ℃, and then an active component source and a catalysis assisting component source are added.
Preferably, in step (3), the monoethanolamine is used in an amount of 3-5 wt% of the combined liquid.
Preferably, in step (4), the raw material solution is used in an amount of 1 to 30% by weight of the titanium source.
Preferably, in step (4), the mixing conditions include: the mixing temperature is 50-100 ℃, and the mixing time is 1-3 hours.
Preferably, in step (4), the roasting conditions include: the roasting temperature is 550-650 ℃ and the roasting time is 4-10 hours.
Preferably, the new denitration catalyst contains less than or equal to 2.5 weight percent of V 2 O 5 WO (WO) in an amount of less than or equal to 7% by weight 3 Or MoO 3 81-83 wt% TiO 2 。
Compared with the prior art, the invention has the following advantages:
(1) The invention prepares a multipurpose raw material solution after extracting vanadium and tungsten (molybdenum) in the waste SCR denitration catalyst, and compared with the prior recovery technology, shortens the recovery process of vanadium and tungsten (molybdenum), reduces energy consumption, improves recovery production efficiency and reduces recovery cost.
(2) The invention solves the problems of difficult separation of vanadium and tungsten (molybdenum), low product purity, large wastewater yield and long production period in the prior recovery technology, and has the characteristics of high recovery efficiency, high product purity and environmental protection.
(3) Compared with the prior recovery technology, the invention extracts vanadium and tungsten (molybdenum) and then uses the extracted vanadium and tungsten (molybdenum) as raw material solution for preparing a new denitration catalyst, and the recovery utilization rate of the recovered metal elements is up to 100%.
(4) The method has high leaching rate of vanadium and tungsten (molybdenum), and 100% of leached vanadium and tungsten (molybdenum) can be used for preparing the novel denitration catalyst.
Drawings
FIG. 1 is a flow chart of a waste SCR denitration catalyst recycling process.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a resource utilization method of a waste denitration catalyst, which comprises the following steps:
(1) Crushing the pretreated waste SCR denitration catalyst, mixing the crushed waste SCR denitration catalyst with a sodium source for roasting, crushing the roasted material, and carrying out water leaching reaction according to the liquid-solid ratio of 5-8 mL to 1 g;
(2) Carrying out solid-liquid separation on the slurry obtained in the step (1) to obtain filtrate and filter residue, washing the filter residue with water, and then combining the obtained washing solution and filtrate to obtain a combined solution;
(3) Adding monoethanolamine, an active component source and a co-catalytic component source into the combined solution obtained in the step (2) to enable the weight of active component metal elements in the solution to be 3-5% and the weight of co-catalytic component metal elements to be 1-8%, and then stirring for reaction to obtain a raw material solution;
(4) Mixing the raw material solution obtained in the step (3) with a titanium source, and then pre-extruding, extrusion molding, drying and roasting the mixed pug to obtain the new denitration catalyst.
Crushing and sodium roasting a waste SCR denitration catalyst to obtain vanadium, tungsten (molybdenum) and sodium salt of titanium, leaching under specific conditions to enable the vanadium, tungsten (molybdenum) to exist in a solution, enabling titanium to exist in filter residues, separating titanium from the vanadium and tungsten (molybdenum), enabling impurities to exist in filtrate to obtain vanadium, tungsten (molybdenum) solution with higher purity, adding monoethanolamine, an active component source and a co-catalytic component source to enable the combined solution to have specific concentration of vanadium, tungsten (molybdenum), continuously stirring until the solution is clarified to obtain a raw material solution, mixing the raw material solution with the titanium source, and obtaining the novel denitration catalyst through a series of subsequent processes.
In the method of the invention, the waste SCR denitration catalyst is a common type SCR denitration catalyst in the field. In a specific embodiment, in the step (1), the waste SCR denitration catalyst is a vanadium tungsten titanium denitration catalyst or a vanadium molybdenum titanium denitration catalyst. Further, in the step (1), the waste SCR denitration catalyst is a honeycomb type or a corrugated type denitration catalyst. Preferably, in the step (1), the waste SCR denitration catalyst contains 0.5 to 2 weight percent of V 2 O 5 WO < 10% by weight 3 Or MoO 3 80 to 90 wt% of TiO 2 。
In the method of the present invention, the pretreatment is an operation conventionally performed in the art. In a specific embodiment, in step (1), the preprocessing includes: and carrying out soot blowing, soaking, drying and other operations on the waste SCR denitration catalyst.
In a preferred embodiment, in order to utilize vanadium, tungsten (molybdenum) in the spent catalyst to bake as much as possible to soluble sodium salts, the spent SCR denitration catalyst needs to be crushed to a specific particle size. In the specific implementation process, in the step (1), the pretreated waste SCR denitration catalyst can be crushed to the particle size d 90 And less than or equal to 300 meshes.
In a specific embodiment, in order to fully convert vanadium and tungsten (molybdenum) in the waste SCR denitration catalyst into sodium salt, leaching is performed during subsequent operation, and the proportion of the waste SCR denitration catalyst to a sodium source needs to be reasonably controlled. In particular embodiments, in step (1), the crushed waste SCR denitration catalyst may be 84 to 94 wt%, for example 84 wt%, 86 wt%, 88 wt%, 90 wt%, 92 wt%, or 94 wt%, based on 100 wt% of the total weight of the crushed waste SCR denitration catalyst and the sodium source; the sodium source may be 6 to 16 wt%, for example 6 wt%, 8 wt%, 10wt%, 12 wt%, 14 wt%, or 16 wt%.
In the method of the present invention, in step (1), the sodium source may be a substance well known to those skilled in the art. In a specific embodiment, the sodium source is selected from one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium chloride and sodium sulfite.
In order to obtain sodium salts which facilitate leaching of vanadium and tungsten (molybdenum), sodium roasting is required under suitable conditions in the method of the invention. In a specific embodiment, in step (1), the roasting conditions include: the firing temperature may be 850-900 ℃, such as 850 ℃, 860 ℃, 870 ℃, 880 ℃, 890 ℃, or 900 ℃; the calcination time may be 4 to 6 hours, for example 4 hours, 4.5 hours, 5 hours, 5.5 hours or 6 hours.
Further, in step (1), the roasted mass may be crushed to a particle size d in order to maximize leaching of vanadium, tungsten (molybdenum) while at the same time leaching faster 90 Less than or equal to 1000 meshes.
In the method of the invention, in order to improve the leaching efficiency of vanadium and tungsten (molybdenum), in the step (1), the water leaching reaction is carried out under the condition of stirring. In order to leach vanadium and tungsten (molybdenum) to the greatest extent and improve leaching efficiency, the liquid-solid ratio of leaching needs to be reasonably controlled. In particular embodiments, the liquid to solid ratio may be 5mL:1g, 5.5mL:1g, 6mL:1g, 6.5mL:1g, 7mL:1g, 7.5mL:1g, or 8mL:1g. In a preferred embodiment, in the step (1), the liquid-solid ratio of the water leaching reaction is 6 to 7 mL/1 g.
In particular embodiments, the temperature of the water leaching reaction may be 60 to 100 ℃, e.g., 60 ℃, 70 ℃, 80 ℃, 90 ℃, or 100 ℃. In specific embodiments, the time of the water leaching reaction may be 3 to 5 hours, for example 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours.
In the process of the present invention, in step (2), the solid-liquid separation may be carried out in a manner well known to those skilled in the art. In a preferred embodiment, the solid-liquid separation mode may be suction filtration.
Further, in order to recover vanadium and tungsten (molybdenum) entrained on the filter residue and prevent damage of the vanadium and tungsten (molybdenum), after solid-liquid separation, the filter residue needs to be washed with water and a washing solution is recovered to obtain a combined solution. In a specific embodiment, in step (2), the process of washing the filter residue with water includes: washing 3-5 times with deionized water at 60-80 ℃.
In the method of the present invention, to obtain a new denitration catalyst having a target component, monoethanolamine, and an active component source and a co-catalyst component source are added to the combined liquid to adjust a solute component. In a specific embodiment, the active ingredient source is selected from vanadium sources, such as ammonium metavanadate and/or vanadyl sulfate. In particular embodiments, the source of the co-catalytic component is selected from a tungsten source and/or a molybdenum source, such as one or more of ammonium tungstate, ammonium metatungstate, and ammonium molybdate.
In the process of the present invention, after the monoethanolamine is added, along with the active component source and the co-catalytic component source, stirring is continued until the solution is clear. In a specific embodiment, in step (3), the stirring reaction is carried out in a water bath, preferably the temperature of the stirring reaction may be 40-50 ℃, for example 40 ℃, 45 ℃ or 50 ℃.
In a specific embodiment, in step (3), the process of adding monoethanolamine and the active component source and the co-catalytic component source includes: after monoethanolamine is added, stirring is carried out in a water bath at 40-50 ℃, and then an active component source and a catalysis assisting component source are added.
In a preferred embodiment, in step (3), the monoethanolamine is used in an amount of 3-5 wt% of the combined liquid, for example 3wt%, 3.5 wt%, 4wt%, 4.5 wt% or 5 wt%.
In the method of the present invention, in order to prepare a raw material solution into a new denitration catalyst according to a kneading process and obtain a new denitration catalyst of a target component, it is necessary to control the ratio and concentration of an active component metal element and a co-catalytic component metal element in the solution.
In particular embodiments, the active component source and the co-catalyst component source are added such that the active component metal element in the solution is 3 to 5wt%, for example 3wt%, 3.5 wt%, 4wt%, 4.5 wt%, or 5 wt%; the metal element of the co-catalytic component may be 1 to 8 wt%, for example 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6 wt%, 7wt% or 8 wt%.
In the method of the present invention, in order to prepare a new denitration catalyst according to a kneading step and obtain a new denitration catalyst of a target component, it is necessary to control the amount ratio of the raw material solution to the titanium source.
In particular embodiments, in step (4), the feedstock solution may be used in an amount of 1 to 30 wt%, such as 1wt%, 2wt%, 5wt%, 8 wt%, 10wt%, 12 wt%, 15 wt%, 18 wt%, 20 wt%, 22 wt%, 25 wt%, 28 wt%, or 30 wt%, of the titanium source.
In the method of the present invention, in step (4), the kneading conditions include: the mixing temperature may be 50 to 100 ℃, for example 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃; the mixing time may be 1 to 3 hours, for example 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours. In a specific embodiment, in step (4), the roasting conditions include: the firing temperature may be 550 to 650 ℃, such as 550 ℃, 600 ℃, or 650 ℃; the calcination time may be 4 to 10 hours, for example 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours.
The novel denitration catalyst obtained by the method contains less than or equal to 2.5 weight percent of V 2 O 5 WO (WO) in an amount of less than or equal to 7% by weight 3 Or MoO 3 81-83 wt% TiO 2 。
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
Example 1
Sodium roasting-water leaching: taking a waste honeycomb SCR denitration catalyst (component: V) 2 O 5 -WO 3 /TiO 2 ，V 2 O 5 Is 2%, WO 3 The content of (2) is 5%, tiO 2 The content of (3%) is 80%), the surface and the pore channels are purged by a compressed air gun, after all the pore channels are ash-free and blocked, the catalyst is washed, soaked and dried, and then is put into an automatic crushing device to be crushed into the particle size (d) 90 ) And less than or equal to 300 meshes. According to the mass ratio of 10wt% of sodium carbonate, 1wt% of sodium chloride to 89wt% of catalyst powder, weighing 56.18g of sodium carbonate, 5.62g of sodium carbonate and 500g of catalyst powder, placing in a dry vibration ball mill, ball milling for 30min, placing the mixture into an alumina crucible, placing into a muffle furnace, preserving heat for 6h at 850 ℃, and cooling to room temperature along with the furnace. Pulverizing the baked block to particle size (d) 90 ) Placing the powder into a reaction kettle, adding hot water at 80 ℃ according to the liquid-solid ratio (mL: g) of 7:1, and continuously stirring for 3h at 80 ℃.
(2) And (3) filtering: and introducing the slurry in the reaction kettle into a vacuum suction filter for filtering to obtain filtrate and filter residue, washing the filter residue with deionized water at 60 ℃ for 5 times, and then combining the obtained washing liquid and the filtrate to obtain the vanadium-tungsten combined liquid.
(3) Tempering: taking 1kg of vanadium-tungsten combined solution, adding 30g of monoethanolamine, and uniformly stirring in a water bath at 45 ℃; according to the concentration of V and W in the filtrate, according to the solution with the concentration of V of 3wt% and the concentration of W of 1wt%, the amount of ammonium metavanadate and ammonium tungstate added is calculated, and after the respective addition, the solution is continuously stirred until the solution is clarified, so as to obtain a raw material solution.
(4) Mixing: in the mixing procedure, titanium dioxide is added into a mixing mill according to the target V of the product 2 O 5 The content is 2.5wt%, WO 3 The content is 7wt%, the weight of the added raw material solution is calculated, the raw material solution is added in a plurality of times, and then is stirred uniformly, and is mixed for 3 hours at 100 ℃, wherein the dosage of the raw material solution is 30 wt% of the dosage of the titanium pigment.
(5) And (5) forming and roasting: and (3) pre-extruding, forming, drying and roasting the mixed pug at 630 ℃ for 8 hours to prepare the novel honeycomb denitration catalyst.
Example 2
(1) Sodium roasting-water leaching: taking a waste honeycomb SCR denitration catalyst (component: V) 2 O 5 -WO 3 /TiO 2 ，V 2 O 5 Is 1%, WO 3 The content of (2) is 4%, tiO 2 The content of (1%) is 81%), the surface and the pore canal are purged by a compressed air gun, after all pore canals are ash-free and blocked, the catalyst is washed, soaked and dried, and then is put into an automatic crushing device to be crushed into the particle size (d) 90 ) And less than or equal to 300 meshes. According to the mass ratio of 10wt% to 1wt% to 89wt% of sodium carbonate, 5.62g of sodium bicarbonate and 500g of catalyst powder, placing the mixture into a dry vibration ball mill, ball-milling for 30min, placing the mixture into an alumina crucible, placing the alumina crucible into a muffle furnace, preserving heat for 4h at 900 ℃, and cooling to room temperature along with the furnace. Pulverizing the baked block to particle size (d) 90 ) The powder is put into a reaction kettle, hot water with the temperature of 80 ℃ is added according to the liquid-solid ratio (mL: g) of 5:1, and the stirring is continued for 5 hours at the temperature of 80 ℃.
(2) And (3) filtering: and introducing the slurry in the reaction kettle into a vacuum suction filter for filtering to obtain filtrate and filter residue, flushing the filter residue with deionized water at 80 ℃ for 3 times, and then combining the obtained washing liquid and the filtrate to obtain the vanadium-tungsten combined liquid.
(3) Tempering: taking 1kg of vanadium-tungsten combined solution, adding 40g of monoethanolamine, and uniformly stirring in a water bath at 45 ℃; according to the concentration of V and W in the filtrate, according to the solution with the concentration of V of 4wt% and the concentration of W of 4wt%, the amount of ammonium metavanadate and ammonium tungstate added is calculated, and after the ammonium metavanadate and the ammonium tungstate are respectively added, the solution is continuously stirred until the solution is clarified, so as to obtain a raw material solution.
(4) Mixing: in the mixing procedure, titanium dioxide is added into a mixing mill according to the target V of the product 2 O 5 The content is 2wt%, WO 3 The content is 5wt%, the weight of the added raw material solution is calculated, the raw material solution is added in several times, and the mixture is stirred uniformly at 80 DEG CRefining for 2 hours, wherein the amount of the raw material solution is 18 weight percent of the amount of the titanium dioxide.
(5) And (5) forming and roasting: and (3) pre-extruding, forming, drying and roasting the mixed pug at 600 ℃ for 6 hours to prepare the novel honeycomb denitration catalyst.
Example 3
(1) Sodium roasting-water leaching: taking a waste honeycomb SCR denitration catalyst (component: V) 2 O 5 -WO 3 /TiO 2 ，V 2 O 5 The content of (C) is 0.5%, WO 3 The content of (3%), tiO 2 The content of (2%) is 82%), the surface and the pore canal are purged by a compressed air gun, after all pore canals are ash-free and blocked, the catalyst is washed, soaked and dried, and then is put into an automatic crushing device to be crushed into the particle size (d) 90 ) And less than or equal to 300 meshes. According to the mass ratio of 10wt% to 1wt% to 89wt% of sodium carbonate, 56.18g of sodium carbonate, 5.62g of sodium hydroxide and 500g of catalyst powder are weighed, placed in a dry vibration ball mill, ball-milled for 30min, the mixture is placed in an alumina crucible, placed in a muffle furnace, kept at 900 ℃ for 3h, and cooled to room temperature along with the furnace. Pulverizing the baked block to particle size (d) 90 ) The powder is put into a reaction kettle, hot water with the temperature of 80 ℃ is added according to the liquid-solid ratio (mL: g) of 6:1, and the stirring is continued for 4 hours at the temperature of 80 ℃.
(2) And (3) filtering: and introducing the slurry in the reaction kettle into a vacuum suction filter for filtering to obtain filtrate and filter residue, flushing the filter residue with deionized water at 80 ℃ for 4 times, and then combining the obtained washing liquid and the filtrate to obtain the vanadium-tungsten combined liquid.
(3) Tempering: taking 1kg of vanadium-tungsten combined solution, adding 50g of monoethanolamine, and uniformly stirring in a water bath at 50 ℃; according to the concentration of V and W in the filtrate, according to the solution with the concentration of V of 5wt% and the concentration of W of 7wt%, the amount of ammonium metavanadate and ammonium tungstate added is calculated, and after the ammonium metavanadate and the ammonium tungstate are respectively added, the solution is continuously stirred until the solution is clarified, so as to obtain a raw material solution.
(4) Mixing: in the mixing procedure, titanium dioxide is added into a mixing mill according to the target V of the product 2 O 5 The content is 1wt%, WO 3 The content is 5wt%,and calculating the weight of the added raw material solution, adding the raw material solution in batches, stirring uniformly, and mixing at 50 ℃ for 1 hour, wherein the dosage of the raw material solution is 5% by weight of the dosage of the titanium pigment.
(5) And (5) forming and roasting: the mixed pug is pre-extruded, formed and dried, and baked for 4 hours at 550 ℃ to prepare the new honeycomb denitration catalyst.
Comparative example 1
The procedure of example 2 was followed, except that in step (1), the liquid-solid ratio (mL: g) was 3mL:1g.
Test example 1
The leaching rates of vanadium and tungsten in examples 1 to 3 and comparative example 1 were measured and calculated, and the results are shown in Table 1.
The determination and calculation process of the leaching rates of vanadium and tungsten comprises the following steps: leaching rate of vanadium (tungsten) =vanadium (tungsten) content in filtrate/vanadium (tungsten) content in spent catalyst x 100%.
TABLE 1
| Leaching rate of vanadium/% | Leaching rate of tungsten/% | |
| Example 1 | 91.2 | 92.3 |
| Example 2 | 89.5 | 90.0 |
| Example 3 | 92.0 | 91.5 |
| Comparative example 1 | 86.5 | 88.9 |
As can be seen from Table 1, the leaching rates of vanadium and tungsten can be greatly improved by adopting the methods of examples 1-3.
Test example 2
The components and the activity K values of the novel denitration catalysts prepared in examples 1 to 3 and comparative example 1 were measured according to GB/T31587-2015 "honeycomb flue gas denitration catalyst", and the results are shown in Table 2.
TABLE 2
It can be seen from table 2 that the denitration catalyst products produced by leaching vanadium and tungsten have higher activity.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A resource utilization method of a waste denitration catalyst is characterized by comprising the following steps:
(1) Crushing the pretreated waste SCR denitration catalyst, mixing the crushed waste SCR denitration catalyst with a sodium source for roasting, crushing the roasted material, and carrying out water leaching reaction according to the liquid-solid ratio of 5-8 mL to 1 g;
(2) Carrying out solid-liquid separation on the slurry obtained in the step (1) to obtain filtrate and filter residue, washing the filter residue with water, and then combining the obtained washing solution and filtrate to obtain a combined solution;
(3) Adding monoethanolamine, an active component source and a co-catalytic component source into the combined solution obtained in the step (2) to enable the weight of active component metal elements in the solution to be 3-5% and the weight of co-catalytic component metal elements to be 1-8%, and then stirring for reaction to obtain a raw material solution;
(4) Mixing the raw material solution obtained in the step (3) with a titanium source, and then pre-extruding, extrusion molding, drying and roasting the mixed pug to obtain the new denitration catalyst.
2. The method of claim 1, wherein in step (1), the spent SCR denitration catalyst is a vanadium tungsten titanium denitration catalyst or a vanadium molybdenum titanium denitration catalyst;
preferably, in the step (1), the waste SCR denitration catalyst is a honeycomb type or corrugated type denitration catalyst;
preferably, in the step (1), the waste SCR denitration catalyst contains 0.5 to 2 weight percent of V 2 O 5 WO < 10% by weight 3 Or MoO 3 80 to 90 wt% of TiO 2 。
3. The method according to claim 1 or 2, wherein in step (1), the pre-treatment comprises: soot blowing, soaking and drying are carried out on the waste SCR denitration catalyst;
preferably, in the step (1), the pretreated waste SCR denitration catalyst is crushed to the particle size d 90 And less than or equal to 300 meshes.
4. A method according to any one of claims 1 to 3, wherein in step (1), the crushed waste SCR denitration catalyst is 84 to 94% by weight and the sodium source is 6 to 16% by weight, based on 100% by weight of the total weight of the crushed waste SCR denitration catalyst and the sodium source;
preferably, in step (1), the sodium source is selected from one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium chloride and sodium sulfite;
preferably, in step (1), the roasting conditions include: the roasting temperature is 850-900 ℃; roasting time is 4-6 hours;
preferably, in step (1), the calcined material is crushed to a particle size d 90 Less than or equal to 1000 meshes.
5. The process according to any one of claims 1 to 4, wherein in step (1), the water leaching reaction is carried out under stirring;
preferably, in step (1), the conditions of the water leaching reaction include: the liquid-solid ratio is 6-7 mL/1 g, the temperature is 60-100 ℃ and the time is 3-5 h.
6. The method according to any one of claims 1 to 5, wherein in step (2), the solid-liquid separation is performed by suction filtration;
preferably, in step (2), the process of washing the filter residue with water comprises: washing 3-5 times with deionized water at 60-80 ℃.
7. The method according to any one of claims 1 to 6, wherein the active ingredient source is selected from ammonium metavanadate and/or vanadyl sulfate;
preferably, the source of the co-catalytic component is selected from one or more of ammonium tungstate, ammonium metatungstate and ammonium molybdate.
8. The process according to any one of claims 1 to 7, wherein in step (3) the stirred reaction is carried out in a water bath; the temperature of the stirring reaction is 40-50 ℃;
preferably, in step (3), the process of adding monoethanolamine and the active component source and the co-catalytic component source includes: adding monoethanolamine, stirring in a water bath at 40-50 ℃, and then adding an active component source and/or a co-catalytic component source;
preferably, in step (3), the monoethanolamine is used in an amount of 3-5 wt% of the combined liquid.
9. The method according to any one of claims 1 to 8, wherein in step (4), the raw material solution is used in an amount of 1 to 30% by weight of the titanium source.
10. The method according to any one of claims 1 to 9, wherein in step (4), the mixing conditions include: the mixing temperature is 50-100 ℃, and the mixing time is 1-3 hours;
preferably, in step (4), the roasting conditions include: the roasting temperature is 550-650 ℃ and the roasting time is 4-10 hours;
preferably, the new denitration catalyst contains less than or equal to 2.5 weight percent of V 2 O 5 WO (WO) in an amount of less than or equal to 7% by weight 3 Or MoO 3 81-83 wt% TiO 2 。
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