CN115445604B - Recycling recovery method of waste denitration catalyst - Google Patents
Recycling recovery method of waste denitration catalyst Download PDFInfo
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- CN115445604B CN115445604B CN202211073570.4A CN202211073570A CN115445604B CN 115445604 B CN115445604 B CN 115445604B CN 202211073570 A CN202211073570 A CN 202211073570A CN 115445604 B CN115445604 B CN 115445604B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 239000002699 waste material Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000011084 recovery Methods 0.000 title claims abstract description 37
- 238000004064 recycling Methods 0.000 title claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 39
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 32
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007791 liquid phase Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000011259 mixed solution Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 24
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 23
- 239000010937 tungsten Substances 0.000 claims abstract description 23
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 23
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011858 nanopowder Substances 0.000 claims abstract description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 16
- 239000007790 solid phase Substances 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000012716 precipitator Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 32
- 238000000605 extraction Methods 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 23
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 20
- 230000003647 oxidation Effects 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 150000003973 alkyl amines Chemical class 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000003350 kerosene Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 6
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000010668 complexation reaction Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- NWJUARNXABNMDW-UHFFFAOYSA-N tungsten vanadium Chemical compound [W]=[V] NWJUARNXABNMDW-UHFFFAOYSA-N 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 239000004408 titanium dioxide Substances 0.000 abstract description 4
- 239000002920 hazardous waste Substances 0.000 abstract description 2
- 238000002386 leaching Methods 0.000 description 29
- GXTVJIIYRCYTNM-UHFFFAOYSA-N [V].[Mo].[W] Chemical compound [V].[Mo].[W] GXTVJIIYRCYTNM-UHFFFAOYSA-N 0.000 description 19
- 239000012535 impurity Substances 0.000 description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 13
- 239000012065 filter cake Substances 0.000 description 13
- 229910052750 molybdenum Inorganic materials 0.000 description 13
- 239000011733 molybdenum Substances 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000011734 sodium Substances 0.000 description 8
- 208000008316 Arsenic Poisoning Diseases 0.000 description 6
- 239000011280 coal tar Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000004537 pulping Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 4
- 101000889329 Conus textile Conotoxin tx5d Proteins 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910000413 arsenic oxide Inorganic materials 0.000 description 3
- 229960002594 arsenic trioxide Drugs 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- JPGXOMADPRULAC-UHFFFAOYSA-N 1-[butoxy(butyl)phosphoryl]oxybutane Chemical compound CCCCOP(=O)(CCCC)OCCCC JPGXOMADPRULAC-UHFFFAOYSA-N 0.000 description 1
- YXHUEGLTOGMNPE-UHFFFAOYSA-N 3-methyl-1-[methyl(3-methylbutoxy)phosphoryl]oxybutane Chemical compound CC(C)CCOP(C)(=O)OCCC(C)C YXHUEGLTOGMNPE-UHFFFAOYSA-N 0.000 description 1
- RMBBSOLAGVEUSI-UHFFFAOYSA-H Calcium arsenate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-][As]([O-])([O-])=O.[O-][As]([O-])([O-])=O RMBBSOLAGVEUSI-UHFFFAOYSA-H 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910017625 MgSiO Inorganic materials 0.000 description 1
- 229910020264 Na2TiO3 Inorganic materials 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- -1 and in step (2) Chemical compound 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229940103357 calcium arsenate Drugs 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment 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
- B01J38/68—Liquid treating or treating in liquid phase, e.g. dissolved or suspended including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the 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
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
-
- 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
-
- 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
-
- 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
- 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
- B01J38/70—Wet oxidation of material submerged in liquid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
Abstract
The invention relates to the technical field of hazardous waste recovery, and discloses a recycling recovery method of a waste denitration catalyst, which comprises the following steps: (1) Oxidizing and cleaning powder obtained by pretreatment of the waste denitration catalyst to obtain mixed solution; (2) Reacting the mixed solution with strong alkali, and carrying out solid-liquid separation to obtain a first solid phase and a first liquid phase; (3) Acidolysis of the first solid phase, solid-liquid separation to obtain solid materialWashing with water, drying, calcining to obtain TiO 2 A nano powder; (4) And (3) regulating the pH value of the first liquid phase to 9-11, then reacting with a precipitator, and then carrying out solid-liquid separation to obtain a second liquid phase containing vanadium and tungsten and a second solid phase containing arsenic. The method provided by the invention not only can fully remove arsenic in the waste denitration catalyst, but also can efficiently recycle vanadium, tungsten and titanium in the waste denitration catalyst, and the obtained titanium dioxide powder has high purity, large pore volume and large specific surface area, and can prepare the denitration catalyst with good denitration effect.
Description
Technical Field
The invention relates to the technical field of hazardous waste recovery, in particular to a recycling recovery method of a waste denitration catalyst.
Background
The thermal power generation system is a largest thermal power generation country in the world, the installed thermal power capacity still reaches 13 hundred million kilowatts by the 2021 year, and the installed thermal power capacity accounts for 54.7% of the installed thermal power capacity of the whole country, so that the thermal power can still play an important role in guaranteeing the electric power safety in a longer period in the future. Arsenic is an element commonly existing in coal in China, and the content of the arsenic is concentrated at 0.4-10 mug/g; in southwest and Mongolian regions of China, the arsenic content of the mined coal is even up to 2000 mug/g.
Selective Catalytic Reduction (SCR) denitration technology is the most widely used flue gas denitration technology in coal-fired power plants at present, wherein the catalyst is the core of the SCR denitration system. When high arsenic coal is burned, gaseous As is generated in flue gas 2 O 3 Will deposit and oxidize on the surface of the catalystCausing the blocking of catalyst pore channels, breaking acid sites of the catalyst, changing the form of active groups, reducing the ammonia adsorption and oxidation-reduction capability of the catalyst, thereby causing serious catalyst poisoning and further affecting the performance of the catalyst and the operation efficiency of a denitration system. After the denitration catalyst is deactivated, a large amount of arsenic oxide is adhered to the surface of the denitration catalyst, so that the denitration catalyst is defined as dangerous waste, and the harmless and recycling treatment and utilization of the denitration catalyst become the pain problem of the operation of a thermal power plant. At present, the denitration catalyst regeneration technology capability is mature, and the regenerated catalyst is accepted by users such as coal-fired power plants. But TiO in denitration catalyst 2 In the using process of the carrier, irreversible microstructure change can be caused by high-temperature sintering, so that the pore volume and the specific surface area are reduced, and the reactivity of the denitration catalyst is further influenced. In general, the deactivated denitration catalyst is regenerated no more than 3 times. Under the condition of high price of raw materials such as titanium dioxide, how to realize deep resource utilization of the waste denitration catalyst with lost regeneration capacity becomes an important research direction.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a recycling method of a waste denitration catalyst, which can realize recycling of the waste denitration catalyst.
In order to achieve the above object, according to one aspect of the present invention, there is provided a recycling method of a waste denitration catalyst, comprising the steps of:
(1) Oxidizing and cleaning powder obtained by pretreatment of the waste denitration catalyst to obtain mixed solution;
(2) Reacting the mixed solution with strong alkali, and then carrying out solid-liquid separation to obtain a first solid phase containing titanium and a first liquid phase containing arsenic, vanadium and tungsten;
(3) Acidolysis is carried out on the first solid phase, then solid-liquid separation is carried out, and the obtained solid substance is washed, dried and calcined to obtain TiO 2 A nano powder;
(4) And regulating the pH value of the first liquid phase to 9-11, then reacting with a precipitator, and then carrying out solid-liquid separation to obtain a second liquid phase containing vanadium and tungsten and a second solid phase containing arsenic.
Preferably, in step (1), the oxidative cleaning is performed under the cooperation of ultrasonic waves or ultraviolet light.
Preferably, in the step (1), the oxidizing cleaning solution used in the oxidizing cleaning step is one or more selected from hydrogen peroxide, ozone, sodium hypochlorite and sodium persulfate;
and/or the concentration of the oxidized cleaning liquid used for the oxidized cleaning is 1-10wt%;
and/or the mass ratio of the oxidation cleaning liquid to the waste denitration catalyst powder used for the oxidation cleaning is 1-10: 1, a step of;
and/or the time of the oxidation cleaning is 0.5-3 h.
Preferably, in the step (1), the pretreatment process of the waste denitration catalyst powder comprises the following steps: deashing, crushing, grinding and sieving the waste denitration catalyst;
and/or the effective component of the waste denitration catalyst is TiO 2 、V 2 O 5 、WO 3 And/or MoO 3 。
Preferably, in step (2), the strong base is sodium hydroxide or potassium hydroxide.
Preferably, in the step (2), a strong base is added to the mixed solution, and the concentration of the strong base in the mixed solution is 10-30wt%;
and/or, in step (2), the reaction conditions include: the temperature is 100-150 ℃, the pressure is 0.1-0.2 MPa, and the time is 1-5 h.
Preferably, in the step (3), the acid solution used for acidolysis is one or more selected from hydrochloric acid, sulfuric acid and nitric acid;
and/or the concentration of the acid solution used for acidolysis is 1-15 wt%;
and/or the mass ratio of the acid liquor used for acidolysis to the first solid phase is 1-10: 1, a step of;
and/or, the acidolysis conditions include: the temperature is 60-100 ℃, the time is 1-3 h, and the pH value of the reaction solution is controlled within 5.
Preferably, in the step (3), the obtained solid matter is washed with desalted water;
and/or, in the step (3), washing the obtained solid substance with water until the conductivity is less than 10 mu S/cm;
and/or in the step (3), the drying mode is flash drying, and the drying temperature is 100-160 ℃;
and/or in the step (3), in the calcining step, the calcining temperature is 500-650 ℃ and the calcining time is 3-7 h.
Preferably, in the step (4), an acid solution is adopted to adjust the pH value of the first liquid phase, wherein the acid solution is one or more than two of hydrochloric acid, sulfuric acid and nitric acid;
and/or in the step (4), the precipitating agent is selected from one or more than two of magnesium sulfate, magnesium chloride and calcium chloride;
and/or in the step (4), the reaction temperature of the reaction is 50-80 ℃ and the reaction time is 1-2 h.
Preferably, step (4) further comprises: and regulating the pH value of the second liquid phase to 2-7, and then performing complexation extraction-back extraction to obtain refined solution containing vanadium-tungsten.
Preferably, in the extraction step, the extractant used contains an alkylamine, a neutral phosphine extractant, a higher alcohol and a sulfonated kerosene.
And/or, in the extractant used for extraction, the content of alkylamine is 5-25wt%, the content of neutral phosphine extractant is 5-15wt%, the content of high-carbon alcohol is 5-10wt%, and the content of sulfonated kerosene is 60-85wt%;
and/or, the extractant used for extraction is acidified before use, wherein the volume ratio O/A of the acidified extractant to the second liquid phase is 1-4: 20.
preferably, in the stripping step, the stripping agent is ammonia water, and the concentration of the ammonia water is 5-20wt%.
And/or the volume ratio O/A of the organic phase obtained by extraction to the back extractant is 1-3: 1.
according to the method provided by the invention, through the design of the preparation steps and parameters, arsenic in the waste denitration catalyst can be fully removed, vanadium, tungsten and titanium in the waste denitration catalyst can be efficiently recovered, the obtained titanium dioxide powder is high in purity, large in pore volume and specific surface area, and can be reused for production of a denitration catalyst, and the denitration effect of the prepared denitration catalyst is good.
Drawings
Fig. 1 is a schematic flow chart of an embodiment of a method for recycling a waste denitration catalyst provided by the invention.
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. In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "A and/or B", including the A scheme, or the B scheme, or the scheme where A and B are satisfied simultaneously. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The invention provides a recycling method of a waste denitration catalyst, referring to fig. 1, in an embodiment, the method comprises the following steps:
(1) Oxidizing and cleaning powder obtained by pretreatment of the waste denitration catalyst to obtain mixed solution;
(2) Reacting the mixed solution with strong alkali, and then carrying out solid-liquid separation to obtain a first solid phase containing titanium and a first liquid phase containing arsenic, vanadium and tungsten;
(3) Acidolysis is carried out on the first solid phase, then solid-liquid separation is carried out, and the obtained solid substance is washed, dried and calcined to obtain TiO 2 A nano powder;
(4) And regulating the pH value of the first liquid phase to 9-11, then reacting with a precipitator, and then carrying out solid-liquid separation to obtain a second liquid phase containing vanadium and tungsten and a second solid phase containing arsenic.
In the present invention, in step (1), the pretreatment process includes: the waste denitration catalyst is subjected to ash removal, crushing, grinding and sieving, and preferably is sieved by a 100-400-mesh sieve. In the specific implementation, the waste honeycomb denitration catalyst is firstly purged by compressed air and then is washed by process water to remove fly ash attached to the surface and pore canal of the catalyst, and then is dried, crushed and ground by a ball mill to obtain waste denitration catalyst powder.
The invention does not limit the specific source of the waste denitration catalyst, and can be obtained after the common denitration catalyst is subjected to arsenic poisoning and deactivation, and at the moment, the active components of the waste denitration catalyst comprise TiO 2 、V 2 O 5 And WO 3 The method comprises the steps of carrying out a first treatment on the surface of the It can be understood that the waste denitration catalyst is also attached with arsenic oxide and SiO 2 Impurities such as phosphorus and coal tar. In the invention, the waste denitration catalyst is obtained by arsenic poisoning and deactivation of the arsenic poisoning resistant denitration catalyst, and at the moment, the effective component of the waste denitration catalyst is TiO 2 、V 2 O 5 、WO 3 And MoO 3 The method comprises the steps of carrying out a first treatment on the surface of the Specifically, the waste denitration catalyst uses TiO 2 Is a carrier, V 2 O 5 As active ingredient, WO 3 And MoO 3 Is a composite auxiliary agent and is attached with arsenic oxide and SiO 2 Impurities such as phosphorus and coal tar.
In a preferred embodiment, in step (1), the oxidative cleaning is performed under the cooperation of ultrasonic waves or ultraviolet light, so that hydroxyl radicals (OH) can be excited to generate, to further improve the oxidizing ability and promote the conversion of As (III) into As (V); meanwhile, macromolecular organic matters such as coal tar and the like attached to the surface of the catalyst and in the pore canal are subjected to ring opening and chain breaking under the action of OH to form micromolecular organic matters or inorganic matters, so that the removal rate of the coal tar and the biodegradability of the wastewater are remarkably improved, and the operation load of a terminal wastewater treatment system is reduced.
In the present invention, the oxidizing cleaning liquid used in the oxidizing cleaning step is one or more selected from hydrogen peroxide, ozone, sodium hypochlorite and sodium persulfate. Further, the concentration of the oxidized cleaning liquid is 1-10wt%.
In the invention, the mass ratio of the oxidation cleaning liquid to the waste denitration catalyst powder is 1-10: 1, preferably 1 to 5:1, in particular, may be, for example, 1:1, 2:1, 4:1 or 5:1.
In the invention, the time of the oxidation cleaning is 0.5-3 h. In a preferred embodiment, after the oxidation cleaning is completed, the mixture is left to stand and then floating oil or scum floating on the surface of the mixture is removed to remove organic matters such as coal tar which may be present on the surface.
In the present invention, in step (2), the strong base is sodium hydroxide or potassium hydroxide. In specific implementation, strong base is added into the mixed solution, and the concentration of the strong base in the mixed solution is 10-30wt%.
In a specific embodiment, in the step (2), the reaction temperature of the alkaline leaching reaction of the mixed solution and the strong base may be 100 ℃, 110 ℃, 130 ℃, 140 ℃ or 150 ℃; the reaction pressure may be 0.1 to 0.2MPa, preferably 0.12 to 0.18MPa, specifically, for example, 0.12MPa, 0.13MPa, 0.15MPa or 0.18MPa; the reaction time may be 1 to 5 hours.
Wherein step (2) mainly occurs the following chemical reaction (here exemplified by strong base sodium hydroxide):
TiO 2 +2NaOH→Na 2 TiO 3 +H 2 O
V 2 O 5 +2NaOH→2NaVO 3 +H 2 O
WO 3 +2NaOH→Na 2 WO 4 +H 2 O
MoO 3 +2NaOH→Na 2 MoO 4 +H 2 O
SiO 2 +2NaOH→Na 2 SiO 3 +H 2 O
As 2 O 5 +6NaOH→2Na 3 AsO 4 +3H 2 O
P 2 O 5 +6NaOH→2Na 3 PO 4 +3H 2 O
the invention is not limited to the specific mode of the solid-liquid separation in the step (2). In a specific embodiment, filtration is performed to obtain a first solid phase comprising titanium (i.e., an alkaline leaching cake) and a first liquid phase comprising arsenic, vanadium, molybdenum and tungsten (i.e., an alkaline leaching liquor).
In a preferred embodiment, in the step (3), the acid solution used for the acidolysis is one or more selected from hydrochloric acid, sulfuric acid and nitric acid.
In a preferred embodiment, the concentration of the acid solution is 1 to 15wt%, preferably 5 to 12wt%, and specifically, for example, may be 5wt%, 7wt%, 8wt%, 10wt% or 12wt%.
Further, the mass ratio of the acid liquor to the first solid phase is 1-10: 1, preferably 1 to 5:1, in particular, may be, for example, 1:1, 2:1, 3:1 or 5:1.
In the invention, in the step (3), the acidolysis temperature is 60-100 ℃, the acidolysis time is 1-3 h, and the pH value of the reaction solution is controlled within 5.
Wherein the acidolysis mainly occurs the following chemical reactions (here the acid liquor is sulfuric acid as an example):
Na 2 TiO 3 +H 2 SO 4 →H 2 TiO 3 +Na 2 SO 4
in a specific embodiment, the resulting solid material (meta-titanic acid, H 2 TiO 3 ) And (5) cleaning.
The invention does not limit the time and the times of the water washing, and preferably the obtained solid substance is washed until the conductivity is less than 10 mu S/cm to obtain the meta-titanic acid powder.
In a preferred embodiment, in the step (3), the obtained meta-titanic acid powder is dried by flash drying. More preferably, the drying temperature is 100 to 160 ℃.
In a preferred embodiment, in the step (3), the calcination is performed by heating to 500 to 650 ℃ for 3 to 7 hours. Wherein, in the calcination process, the following chemical reactions mainly occur:
H 2 TiO 3 →TiO 2 +H 2 O
in the invention, the step (4) is used for chemically removing impurities from the first liquid phase obtained in the step (2). In a specific embodiment, in the step (4), an acid solution is used to adjust the pH value of the first liquid phase to 9-11, where the acid solution is one or more than two selected from hydrochloric acid, sulfuric acid and nitric acid. Preferably, when the pH of the first liquid phase is >12, an acid solution having a concentration of 40 to 60wt% may be used, and when the pH of the first liquid phase is <12, an acid solution having a concentration of 2 to 8wt% should be used.
In a preferred embodiment, in step (4), the precipitating agent is selected from one or more of magnesium sulfate, magnesium chloride and calcium chloride. More preferably, a precipitant is added to the first liquid phase, and the concentration of the precipitant in the resulting reaction solution is 10 to 40wt%.
In a specific embodiment, in the step (4), the reaction temperature of the reaction is 50-80 ℃ and the reaction time is 1-2 h.
Wherein in step (4), the first liquid phase and the precipitant mainly undergo the following chemical reaction (here, the precipitant is magnesium sulfate as an example):
Na 2 SiO 3 +MgSO 4 ＝MgSiO 3 ↓+Na 2 SO 4
2Na 3 AsO 4 +3MgSO 4 ＝Mg 3 (AsO 4 ) 2 ↓+3Na 2 SO 4
2Na 3 PO 4 +3MgSO 4 ＝Mg 3 (PO 4 ) 2 ↓+3Na 2 SO 4
therefore, in the step (4), magnesium arsenate and/or calcium arsenate which are difficult to dissolve in water can be formed, and then solid-liquid separation is carried out, so that the impurity depth removal of pollutants characterized by arsenic is realized; meanwhile, the process can also cooperatively remove impurity elements such as silicon, phosphorus and the like.
Because the invention selects the waste arsenic-resistant denitration catalyst, the obtained second liquid phase contains vanadium-tungsten-molybdenum. In order to further remove impurities in the second liquid phase, the catalyst can be reused for the production of the arsenic poisoning resistant denitration catalyst. In a preferred embodiment, step (4) further comprises: and regulating the pH value of the second liquid phase to 2-7, and then performing complexation extraction-back extraction to obtain a refined solution containing vanadium-tungsten-molybdenum.
In a preferred embodiment, the extractant used in the extraction step comprises an alkylamine, a neutral phosphine extractant, a higher alcohol and a sulfonated kerosene.
Further preferably, in the extractant, the content of the alkylamine is 5 to 25wt%, the content of the neutral phosphine extractant is 5 to 15wt%, the content of the high carbon alcohol is 5 to 10wt%, and the content of the sulfonated kerosene is 60 to 85wt%. Wherein the alkylamine is selected from one or more of primary amine, secondary amine, tertiary amine and quaternary ammonium salt, the neutral phosphine extractant is selected from one or more of diisoamyl methylphosphonate, dibutyl butylphosphonate, diisomixed ester of methylphosphonate and tributyl phosphate, and the higher alcohol is selected from saturated monohydric alcohols of C8-C10.
More preferably, the extractant is acidified prior to use. The acid liquid is one or more of hydrochloric acid, sulfuric acid and nitric acid. Wherein the concentration of the acid liquor is 0.1-0.3 mol/L.
In the invention, the vanadium-tungsten-molybdenum extraction in the second liquid phase is performed by adopting a centrifugal separation technology, and in a specific embodiment, the volume ratio O/A of the acidified extractant to the second liquid phase is 1-4: 20.
through the extraction step, the vanadium, tungsten and molybdenum active components in the second liquid phase are extracted into the organic phase, and then the back extraction step is performed.
In the back extraction step, a centrifugal separation technology is adopted, the back extractant is ammonia water, and the concentration of the ammonia water is 5-20wt%.
In a specific embodiment, the volume ratio O/a of the extracted organic phase to the stripping agent is 1 to 3:1.
the extraction-back extraction process in the step (4) realizes the selective separation and enrichment of active components of vanadium, tungsten and molybdenum by optimizing the components of the extractant under the condition of less acid and alkali consumption, finally obtains the ammonium salt solution of vanadium-tungsten-molybdenum, and can be used for the production of the anti-arsenic poisoning denitration catalyst.
According to the method provided by the invention, on one hand, a hot alkali reaction coupling acid washing process is adopted, and the new phase of meta-titanic acid is generated, so that the sintered carrier is dissociated and reconstructed to form a new microscopic pore canal, the pore volume and the specific surface area of the carrier are effectively improved, and the problem of recycling the waste catalyst carrier losing the regeneration capacity is solved; on the other hand, the oxidation capacity is further improved by adopting an oxidation cleaning process in combination with ultrasonic waves and ultraviolet light, so that the arsenic removal rate, the coal tar removal rate and the biodegradability of the wastewater are improved.
The present invention will be described in detail by way of examples, but the scope of the present invention is not limited thereto.
In the following examples, the pretreatment process of the waste arsenic poisoning resistant catalyst is: purging by compressed air and flushing by process water in sequence; then drying, crushing, grinding and screening (100 meshes) to obtain waste denitration catalyst powder, wherein the main components of the waste denitration catalyst powder are as follows:
| composition of the components | TiO 2 | V 2 O 5 | MoO 3 | WO 3 | As 2 O 3 | SiO 2 | Others |
| Mass fraction/wt% | 83.7 | 0.85 | 8.7 | 1.8 | 2.1 | 2.3 | 0.55 |
And the specific surface area of the waste denitration catalyst powder is only 41.5m 2 Per g, pore volume of 0.23cm 3 /g。
Example 1
(1) Mixing and pulping the waste denitration catalyst powder with hydrogen peroxide with the concentration of 4wt%, and performing oxidation cleaning to obtain mixed liquid, wherein the mass ratio of the hydrogen peroxide to the waste denitration catalyst powder is 1:1, and the oxidation cleaning time is 0.5h;
(2) Adding NaOH flake alkali into the mixed solution, enabling the concentration of NaOH in the mixed solution to be 20wt%, carrying out alkaline leaching reaction at 130 ℃ and 0.15MPa for 2.5 hours, and filtering and separating after the reaction is finished to obtain an alkaline leaching filter cake containing titanium and an alkaline leaching filtrate containing vanadium-tungsten-molybdenum respectively;
(3) Mixing and pulping the alkaline leaching filter cake with 10wt% of sulfuric acid, wherein the mass ratio of the alkaline leaching filter cake to the sulfuric acid is 1:1, and the alkaline leaching filter cake is subjected to 80 ℃ conditionThen acidolysis reaction is carried out for 2 hours, the pH value of the solution is always controlled within 5 during the reaction process, then filtration and separation are carried out, the obtained filter cake is washed by desalted water until the electric conductivity of the leaching solution is less than 10 mu S/cm, thus obtaining meta-titanic acid powder, the meta-titanic acid powder is flash-evaporated and dried at 120 ℃, then the temperature is raised to 600 ℃ for calcination for 6 hours, thus obtaining TiO 2 A nano powder;
(4) Regulating the pH value of the alkaline leaching filtrate in the step (2) to 10-10.5 by sulfuric acid, adding magnesium sulfate, enabling the concentration of the magnesium sulfate in the obtained reaction solution to be 25wt%, carrying out chemical impurity removal reaction at 65 ℃ for 1h, and filtering and separating after the reaction is finished to obtain precipitation containing arsenic and other impurities and vanadium-tungsten-molybdenum impurity removal filtrate; adjusting the pH value of the vanadium-tungsten-molybdenum impurity removal filtrate to 4-5 by using 50wt% sulfuric acid, wherein the volume ratio of O/A is 1:10, adding an extractant, and performing vanadium-tungsten-molybdenum centrifugal separation extraction, wherein the extractant comprises the following components in percentage by mass: 15wt% of alkylamine (tri Xin Guiwan-tertiary amine), 10wt% of neutral phosphine extractant (tributyl phosphate), 5wt% of higher alcohol (sec-octanol) and 70wt% of sulfonated kerosene, and acidizing the extractant with 0.1mol/L dilute sulfuric acid before use; and after the extraction is finished, taking an organic phase for back extraction, taking 12.5wt% ammonia water as a back extractant, and obtaining a vanadium-tungsten-molybdenum refined solution after centrifugal separation, wherein the volume ratio O/A of the organic phase to the back extractant is 2:1.
TiO obtained in the step (2) 2 The purity of the nano powder is 97.9 percent, and the specific surface area is 87.2m 2 Per g, pore volume 0.35cm 3 /g；
In this example, the recovery rate of vanadium was 94.6%, the recovery rate of tungsten was 93.8%, the recovery rate of molybdenum was 95.2%, and the arsenic removal rate was 88.5%.
Example 2
The procedure of example 1 was followed, except that in step (1), the oxidized cleaning liquid used was 2wt% hydrogen peroxide, and in step (2), naOH flake alkali was added to the mixed solution, and the concentration of NaOH in the mixed solution was 10wt%, and the alkaline leaching reaction was carried out at 110℃and 0.12 MPa.
TiO obtained in the step (2) 2 The purity of the nano powder is 97.4 percent, and the specific surface area is 85.3m 2 /g，Pore volume 0.34cm 3 /g；
In this example, the recovery rate of vanadium was 92.4%, the recovery rate of tungsten was 91.8%, the recovery rate of molybdenum was 93.2%, and the arsenic removal rate was 85.3%.
Example 3
The procedure of example 1 was followed, except that in step (2), naOH flake alkali was added to the mixed solution so that the concentration of NaOH in the mixed solution was 30% by weight, and the alkaline leaching reaction was carried out at 150℃and 0.18 MPa.
TiO obtained in the step (2) 2 The purity of the nano powder is 98.4 percent, and the specific surface area is 90.8m 2 Per g, pore volume 0.36cm 3 /g；
In this example, the recovery rate of vanadium was 96.3%, the recovery rate of tungsten was 95.4%, the recovery rate of molybdenum was 97.8%, and the arsenic removal rate was 91.0%.
Example 4
The procedure of example 3 was followed, except that in step (1), the oxidation cleaning was performed under the cooperation of ultrasonic waves having a frequency of 40kHz.
TiO obtained in the step (2) 2 The purity of the nano powder is 98.7 percent, and the specific surface area is 93.6m 2 Per g, pore volume 0.39cm 3 /g；
In this example, the recovery rate of vanadium was 97.3%, the recovery rate of tungsten was 96.4%, the recovery rate of molybdenum was 98.9%, and the arsenic removal rate was 99.8%.
Example 5
The procedure of example 3 was followed, except that in step (1), the oxidation cleaning was performed under the cooperation of ultraviolet light.
TiO obtained in the step (2) 2 The purity of the nano powder is 98.6 percent, and the specific surface area is 93.1m 2 Per g, pore volume 0.37cm 3 /g；
In this example, the recovery rate of vanadium was 96.6%, the recovery rate of tungsten was 95.7%, the recovery rate of molybdenum was 98.1%, and the arsenic removal rate was 97.6%.
Example 6
The procedure was carried out as in example 1, except that the alkaline leaching reaction was carried out at 70℃under normal pressure in step (2).
Step (2) to obtainTiO of (C) 2 The purity of the nano powder is 95.5 percent, and the specific surface area is 58.3m 2 Per g, pore volume 0.28cm 3 /g；
In this example, the recovery rate of vanadium was 78.2%, the recovery rate of tungsten was 75.6%, the recovery rate of molybdenum was 80.4%, and the arsenic removal rate was 70.3%.
Example 7
(1) Mixing and pulping the waste denitration catalyst powder with sodium hypochlorite with the concentration of 5wt%, and performing oxidation cleaning to obtain a mixed solution, wherein the mass ratio of the sodium hypochlorite to the waste denitration catalyst powder is 5:1, and the oxidation cleaning time is 2 hours;
(2) Adding KOH flake alkali into the mixed solution, enabling the concentration of KOH in the mixed solution to be 10wt%, carrying out alkaline leaching reaction at 110 ℃ and 0.12MPa for 4 hours, and filtering and separating after the reaction is finished to obtain an alkaline leaching filter cake containing titanium and an alkaline leaching filtrate containing vanadium-tungsten-molybdenum respectively;
(3) Mixing and pulping the alkaline leaching filter cake with 5wt% hydrochloric acid, enabling the mass ratio of the alkaline leaching filter cake to nitric acid to be 5:1, enabling acidolysis reaction to be carried out for 3 hours at 60 ℃, controlling the pH value of a solution to be within 5 all the time in the reaction process, filtering and separating, washing the obtained filter cake with desalted water until the conductivity of the leaching solution is less than 10 mu S/cm to obtain meta-titanic acid powder, flash drying the meta-titanic acid powder at 150 ℃, and then heating to 650 ℃ for calcination for 4 hours to obtain TiO 2 A nano powder;
(4) Regulating the pH value of the alkaline leaching filtrate in the step (2) to 9-9.5 by sulfuric acid, then adding magnesium chloride, enabling the concentration of the magnesium chloride in the obtained reaction solution to be 10wt%, carrying out chemical impurity removal reaction at 55 ℃ for 2 hours, and filtering and separating after the reaction is finished to obtain precipitation containing arsenic and other impurities and vanadium-tungsten-molybdenum impurity removal filtrate; adjusting the pH value of the vanadium-tungsten-molybdenum impurity removal filtrate to 4-5 by using 50wt% sulfuric acid, wherein the volume ratio of O/A is 1:20, adding an extractant, and performing vanadium-tungsten-molybdenum centrifugal separation extraction, wherein the extractant comprises the following components in percentage by mass: 5wt% alkylamine (tri Xin Guiwan-tertiary amine), 5wt% neutral phosphine extractant (tributyl phosphate), 5wt% higher alcohol (sec-octanol) and 85wt% sulfonated kerosene, the extractant being acidified with 0.1mol/L dilute sulfuric acid prior to use; and after the extraction is finished, taking an organic phase for back extraction, taking 8wt% ammonia water as a back extractant, and obtaining a vanadium-tungsten-molybdenum refined solution after centrifugal separation, wherein the volume ratio O/A of the organic phase to the back extractant is 1:1.
TiO obtained in the step (2) 2 The purity of the nano powder is 97.3 percent, the specific surface area is 73.5m2/g, and the pore volume is 0.30cm3/g;
in this example, the recovery rate of vanadium was 91.9%, the recovery rate of tungsten was 91.2%, the recovery rate of molybdenum was 92.6%, and the arsenic removal rate was 84.3%.
Example 8
(1) Mixing and pulping the waste denitration catalyst powder with sodium persulfate with the concentration of 6wt%, and performing oxidation cleaning to obtain a mixed solution, wherein the mass ratio of the sodium persulfate to the waste denitration catalyst powder is 2:1, and the oxidation cleaning time is 1h;
(2) Adding NaOH flake alkali into the mixed solution, enabling the concentration of NaOH in the mixed solution to be 10wt%, carrying out alkaline leaching reaction at 110 ℃ and 0.12MPa for 1h, and filtering and separating after the reaction is finished to obtain a titanium-containing alkaline leaching filter cake and vanadium-tungsten-molybdenum-containing alkaline leaching filtrate respectively;
(3) Mixing and pulping the alkaline leaching filter cake with 7wt% of nitric acid, wherein the mass ratio of the alkaline leaching filter cake to the nitric acid is 3:1, carrying out acidolysis reaction for 1h at 100 ℃, controlling the pH value of the solution to be within 5 all the time in the reaction process, filtering and separating, washing the obtained filter cake with desalted water until the conductivity of the leaching solution is less than 10 mu S/cm to obtain meta-titanic acid powder, carrying out flash evaporation drying on the meta-titanic acid powder at 130 ℃, and then heating to 550 ℃ for calcination for 7h to obtain TiO 2 A nano powder;
(4) Regulating the pH value of the alkaline leaching filtrate in the step (2) to 10.5-11 by sulfuric acid, then adding calcium chloride, enabling the concentration of the calcium chloride in the obtained reaction solution to be 35wt%, carrying out chemical impurity removal reaction at 80 ℃ for 1h, and filtering and separating after the reaction is finished to obtain precipitation containing arsenic and other impurities and vanadium-tungsten-molybdenum impurity removal filtrate; adjusting the pH value of the vanadium-tungsten-molybdenum impurity removal filtrate to 4-5 by using 50wt% sulfuric acid, wherein the volume ratio of O/A is 3:20, adding an extractant, and performing vanadium-tungsten-molybdenum centrifugal separation extraction, wherein the extractant comprises the following components in percentage by mass: 20wt% of alkylamine (tri Xin Guiwan-tertiary amine), 10wt% of neutral phosphine extractant (tributyl phosphate), 10wt% of higher alcohol (sec-octanol) and 60wt% of sulfonated kerosene, and acidizing the extractant with 0.1mol/L dilute sulfuric acid before use; and after the extraction is finished, taking an organic phase for back extraction, taking 17wt% ammonia water as a back extractant, and obtaining a vanadium-tungsten-molybdenum refined solution after centrifugal separation, wherein the volume ratio O/A of the organic phase to the back extractant is 3:1.
TiO obtained in the step (2) 2 The purity of the nano powder is 97.2 percent, and the specific surface area is 91.8m 2 Per g, pore volume 0.36cm 3 /g；
In this example, the recovery rate of vanadium was 91.7%, the recovery rate of tungsten was 91.1%, the recovery rate of molybdenum was 92.4%, and the arsenic removal rate was 80.7%.
Comparative example 1
The procedure of example 1 was followed, except that in step (3), the acidolysis reaction was not performed.
TiO obtained in the step (2) 2 The purity of the nano powder is 82.7 percent, and the specific surface area is 36.3m 2 Per g, pore volume 0.2cm 3 /g; it should be noted that the above TiO 2 The nano powder contains a large amount of Na2TiO3 impurities and cannot be used as a raw material of a denitration catalyst.
In this comparative example, the recovery rate of vanadium was 94.2%, the recovery rate of tungsten was 93.3%, the recovery rate of molybdenum was 94.8%, and the arsenic removal rate was 88.2%.
Comparative example 2
The procedure of example 1 was followed, except that in step (4), the pH of the alkaline leaching solution was not adjusted.
TiO obtained in the step (2) 2 The purity of the nano powder is 97.6 percent, and the specific surface area is 86.5m 2 Per g, pore volume 0.34cm 3 /g；
In this comparative example, the recovery rate of vanadium was 50.6%, the recovery rate of tungsten was 48.9%, the recovery rate of molybdenum was 53.3%, and the arsenic removal rate was 78.8%.
The test results in the above examples 1-8 and comparative examples 1-2 are shown in Table 1 below.
TABLE 1
As can be seen from the results in Table 1, the method provided by the invention not only can fully remove arsenic in the waste denitration catalyst, but also can efficiently recover vanadium, tungsten and titanium in the waste denitration catalyst, and the obtained titanium dioxide powder has high purity, large pore volume and large specific surface area, can be reused for production of the denitration catalyst, and has good denitration effect.
Comparing example 3 with examples 4 and 5, it can be seen that the arsenic removal rate can be further improved by the co-oxidation cleaning using ultrasonic waves or ultraviolet light.
In addition, as can be seen by comparing example 1 with example 6 and comparative examples 1-2, the invention optimizes the parameters to make the recycling effect of the waste denitration catalyst better.
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. The recycling recovery method of the waste denitration catalyst is characterized by comprising the following steps of:
(1) Oxidizing and cleaning powder obtained by pretreatment of the waste denitration catalyst to obtain mixed solution;
(2) Reacting the mixed solution with strong alkali, and then carrying out solid-liquid separation to obtain a first solid phase containing titanium and a first liquid phase containing arsenic, vanadium and tungsten;
(3) Acidolysis is carried out on the first solid phase, then solid-liquid separation is carried out, and the obtained solid substance is washed, dried and calcined to obtain TiO 2 A nano powder;
(4) Adjusting the pH value of the first liquid phase to 9-11, then reacting with a precipitator, and then carrying out solid-liquid separation to obtain a second liquid phase containing vanadium and tungsten and a second solid phase containing arsenic;
wherein, in the step (1), the oxidation cleaning is performed under the cooperation of ultrasonic waves or ultraviolet light;
in the step (2), a strong base is added to the mixed solution, and the concentration of the strong base in the mixed solution is 10-30wt%, and the reaction conditions include: the temperature is 130-150 ℃, the pressure is 0.15-0.2 MPa, and the time is 2.5-5 h;
in the step (3), the acid solution used for acidolysis is one or more selected from hydrochloric acid, sulfuric acid and nitric acid, and the acidolysis conditions comprise: the temperature is 60-100 ℃, the time is 1-3 h, and the pH value of the reaction solution is controlled within 5.
2. The method according to claim 1, wherein in the step (1), the oxidizing cleaning liquid used in the oxidizing cleaning step is one or more selected from the group consisting of hydrogen peroxide, ozone, sodium hypochlorite and sodium persulfate;
and/or the concentration of the oxidized cleaning liquid used for the oxidized cleaning is 1-10wt%;
and/or the mass ratio of the oxidation cleaning liquid to the waste denitration catalyst powder used for the oxidation cleaning is 1-10: 1, a step of;
and/or the time of the oxidation cleaning is 0.5-3 h.
3. The method of claim 1, wherein in step (1), the preprocessing comprises: deashing, crushing, grinding and sieving the waste denitration catalyst;
and/or the effective component of the waste denitration catalyst is TiO 2 、V 2 O 5 、WO 3 And/or MoO 3 。
4. A method according to any one of claims 1 to 3, wherein in step (2) the strong base is sodium hydroxide or potassium hydroxide.
5. The method according to claim 1, wherein the acid solution used for acidolysis has a concentration of 1 to 15wt%;
and/or the mass ratio of the acid liquor used for acidolysis to the first solid phase is 1-10: 1.
6. the method according to claim 1, wherein in step (3), the obtained solid matter is washed with desalted water;
and/or, in the step (3), washing the obtained solid substance with water until the conductivity is less than 10 mu S/cm;
and/or in the step (3), the drying mode is flash drying, and the drying temperature is 100-160 ℃;
and/or in the step (3), in the calcining step, the calcining temperature is 500-650 ℃ and the calcining time is 3-7 h.
7. The method according to claim 1, wherein in step (4), the pH value of the first liquid phase is adjusted with an acid solution, wherein the acid solution is one or more selected from the group consisting of hydrochloric acid, sulfuric acid, and nitric acid;
and/or in the step (4), the precipitating agent is selected from one or more than two of magnesium sulfate, magnesium chloride and calcium chloride;
and/or in the step (4), the reaction temperature of the reaction is 50-80 ℃ and the reaction time is 1-2 h.
8. The method of claim 1, wherein step (4) further comprises: and regulating the pH value of the second liquid phase to 2-7, and then performing complexation extraction-back extraction to obtain refined solution containing vanadium-tungsten.
9. The method of claim 8, wherein the extractant used in the extraction step comprises an alkylamine, a neutral phosphine extractant, a higher alcohol, and a sulfonated kerosene;
and/or, in the extractant used for extraction, the content of alkylamine is 5-25wt%, the content of neutral phosphine extractant is 5-15wt%, the content of high-carbon alcohol is 5-10wt%, and the content of sulfonated kerosene is 60-85wt%;
and/or, the extractant used for extraction is acidified before use, wherein the volume ratio O/A of the acidified extractant to the second liquid phase is 1-4: 20.
10. the method according to claim 8, wherein in the stripping step, the stripping agent is ammonia water, and the concentration of the ammonia water is 5-20wt%;
and/or the volume ratio O/A of the organic phase obtained by extraction to the back extractant is 1-3: 1.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86105274A (en) * | 1986-08-05 | 1988-04-13 | 中南工业大学 | The method of from wolframic acid is received solution, separating Pb, As Si |
| CN101613805A (en) * | 2009-07-13 | 2009-12-30 | 湖南有色金属研究院 | A kind of comprehensive recovery bismuth is smelted the method for tungsten, molybdenum in the reflection slag |
| CN102936039B (en) * | 2012-11-15 | 2014-08-13 | 曾瑞 | Recovery process of honeycomb type selective catalytic reduction (SCR) waste catalyst containing tungsten, vanadium and titanium |
| WO2016187994A1 (en) * | 2015-05-22 | 2016-12-01 | 北京赛科康仑环保科技有限公司 | Recycling and remanufacturing method for spent scr denitrification catalyst |
| CN109317221A (en) * | 2017-08-01 | 2019-02-12 | 神华集团有限责任公司 | Inactivate the regeneration method of denitrating catalyst |
| CN109750156A (en) * | 2019-03-15 | 2019-05-14 | 华北电力大学 | A method of recycling vanadium, tungsten/molybdenum and titanium elements from discarded SCR denitration |
| CN110218881A (en) * | 2018-03-01 | 2019-09-10 | 国家能源投资集团有限责任公司 | The method of active component in extractant composition and its application and recycling solution |
| CN110817944A (en) * | 2019-11-06 | 2020-02-21 | 北京华电光大环境股份有限公司 | Recovery method of waste SCR denitration catalyst |
| CN111054451A (en) * | 2019-12-02 | 2020-04-24 | 中节能清洁技术发展有限公司 | Arsenic removal method of waste SCR denitration catalyst and preparation method of regenerated powder of waste SCR denitration catalyst |
| CN113249595A (en) * | 2021-06-01 | 2021-08-13 | 中国科学院过程工程研究所 | Method for recovering tungsten from waste alkali liquor generated by regenerating waste SCR catalyst and application of method |
-
2022
- 2022-09-02 CN CN202211073570.4A patent/CN115445604B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86105274A (en) * | 1986-08-05 | 1988-04-13 | 中南工业大学 | The method of from wolframic acid is received solution, separating Pb, As Si |
| CN101613805A (en) * | 2009-07-13 | 2009-12-30 | 湖南有色金属研究院 | A kind of comprehensive recovery bismuth is smelted the method for tungsten, molybdenum in the reflection slag |
| CN102936039B (en) * | 2012-11-15 | 2014-08-13 | 曾瑞 | Recovery process of honeycomb type selective catalytic reduction (SCR) waste catalyst containing tungsten, vanadium and titanium |
| WO2016187994A1 (en) * | 2015-05-22 | 2016-12-01 | 北京赛科康仑环保科技有限公司 | Recycling and remanufacturing method for spent scr denitrification catalyst |
| CN109317221A (en) * | 2017-08-01 | 2019-02-12 | 神华集团有限责任公司 | Inactivate the regeneration method of denitrating catalyst |
| CN110218881A (en) * | 2018-03-01 | 2019-09-10 | 国家能源投资集团有限责任公司 | The method of active component in extractant composition and its application and recycling solution |
| CN109750156A (en) * | 2019-03-15 | 2019-05-14 | 华北电力大学 | A method of recycling vanadium, tungsten/molybdenum and titanium elements from discarded SCR denitration |
| CN110817944A (en) * | 2019-11-06 | 2020-02-21 | 北京华电光大环境股份有限公司 | Recovery method of waste SCR denitration catalyst |
| CN111054451A (en) * | 2019-12-02 | 2020-04-24 | 中节能清洁技术发展有限公司 | Arsenic removal method of waste SCR denitration catalyst and preparation method of regenerated powder of waste SCR denitration catalyst |
| CN113249595A (en) * | 2021-06-01 | 2021-08-13 | 中国科学院过程工程研究所 | Method for recovering tungsten from waste alkali liquor generated by regenerating waste SCR catalyst and application of method |
Non-Patent Citations (6)
| Title |
|---|
| Efficient recovery of scrapped V2O5-WO3/TiO2 SCR catalyst by cleaner hydrometalurgical process;Lou Wenbo 等;《HYDROMETALLURGY》;第187卷;第45-53页 * |
| 废SCR脱硝催化剂再生与金属回收及载体回用技术;毕冬雪 等;《电力科技与环保》;第38卷(第3期);第232-237页 * |
| 废弃SCR催化剂中钒和钨的浸出及回收;闫巍 等;《化工环保》;第38卷(第4期);第471-475页 * |
| 废钒-钛系脱硝催化剂回收利用策略与技术进展;王宝冬 等;《材料导报》;第35卷(第15期);第15001-15010页 * |
| 沈旭.《化学选矿技术》.冶金工业出版社,2011,第194页. * |
| 碱溶法回收废SCR脱硝催化剂中的二氧化钛;武文粉 等;《过程工程学报》;第19卷(第S1期);第74页2.3.1、2.3.2，第76页表3 * |
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