CN112844441A - Ion exchange type montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning and preparation method thereof - Google Patents
Ion exchange type montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning and preparation method thereof Download PDFInfo
- Publication number
- CN112844441A CN112844441A CN202110035105.0A CN202110035105A CN112844441A CN 112844441 A CN112844441 A CN 112844441A CN 202110035105 A CN202110035105 A CN 202110035105A CN 112844441 A CN112844441 A CN 112844441A
- Authority
- CN
- China
- Prior art keywords
- montmorillonite
- titanium dioxide
- catalyst
- heavy metal
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 206
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 194
- 239000003054 catalyst Substances 0.000 title claims abstract description 131
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 75
- 238000005342 ion exchange Methods 0.000 title claims abstract description 65
- 206010027439 Metal poisoning Diseases 0.000 title claims abstract description 38
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 37
- 208000010501 heavy metal poisoning Diseases 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 145
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 72
- 239000002253 acid Substances 0.000 claims abstract description 47
- 239000000725 suspension Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims description 72
- 229910017604 nitric acid Inorganic materials 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 239000007787 solid Substances 0.000 claims description 40
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 39
- 238000001035 drying Methods 0.000 claims description 36
- 229910001868 water Inorganic materials 0.000 claims description 36
- -1 iron ions Chemical class 0.000 claims description 32
- 238000001354 calcination Methods 0.000 claims description 28
- 150000002500 ions Chemical class 0.000 claims description 27
- 238000000227 grinding Methods 0.000 claims description 24
- 239000012535 impurity Substances 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 24
- 238000000967 suction filtration Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- 229910052791 calcium Inorganic materials 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 150000005837 radical ions Chemical class 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000000703 Cerium Chemical class 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001844 chromium Chemical class 0.000 claims description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- 229910001430 chromium ion Inorganic materials 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 38
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 37
- 238000005245 sintering Methods 0.000 abstract description 13
- 239000002028 Biomass Substances 0.000 abstract description 12
- 239000010881 fly ash Substances 0.000 abstract description 12
- 239000000446 fuel Substances 0.000 abstract description 12
- 239000011521 glass Substances 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 12
- 238000003837 high-temperature calcination Methods 0.000 abstract description 10
- 239000002243 precursor Substances 0.000 abstract description 10
- 238000003980 solgel method Methods 0.000 abstract description 10
- 239000003546 flue gas Substances 0.000 abstract description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 208000005374 Poisoning Diseases 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910006287 γ-MnO2 Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an ion exchange type montmorillonite-based denitration catalyst and a preparation method thereof. The denitration catalyst is mainly characterized in that raw montmorillonite ore is modified by dilute acid, a titanium dioxide precursor prepared by a sol-gel method is added into acid-modified montmorillonite suspension, and the titanium dioxide pillared montmorillonite catalyst is obtained by high-temperature calcination. Finally, active metal ions are exchanged to the pillared montmorillonite by an ion exchange method to obtain the catalyst. The catalyst has the advantages of low raw material price, simple preparation method, excellent denitration performance, strong sintering resistance, good alkali metal and heavy metal poisoning resistance and the like, and can be used for denitration of fixed source flue gas containing alkali/heavy metal fly ash in biomass fuel boilers, coal-fired power plants, glass plants, garbage incineration plants and the like.
Description
Technical Field
The invention relates to a denitration catalyst and a preparation method thereof, in particular to an ion exchange type montmorillonite-based denitration catalyst and a preparation method thereof, which are applied to the technical field of nitrogen oxide control and purification in environmental protection.
Background
Nitrogen Oxides (NO) produced in coal combustion flue gasx) Including NO, NO2、N2O, is extremely harmful to human and ecological systems, can cause urban smog, acid rain and ozone depletion, and is still one of the main environmental problems at present. Currently, the industry primarily reduces the fixed source NO by Selective Catalytic Reduction (SCR) techniquesxDischarge of (2) at V2O5-WO3/MoO3-TiO2For commercial denitration catalysts, it is converted to nitrogen and water. Although vanadium-based catalysts have high activity, their disadvantages, such as biotoxicity, high SO, remain significant2Oxidation to SO3Activity, narrow temperature window (300-400 ℃), and the like.
In recent years, CeO is used2Excellent oxygen storage capacity and excellent redox performance, Ce-based catalysts are widely studied as catalysts that may replace V-based commercial catalysts. Wherein, CeO taking montmorillonite (MMT) as carrier2The MMT supported catalyst is receiving increasing attention due to wide material source and low cost. However, the catalyst still has certain disadvantages, such as CeO loaded on the surface of montmorillonite2The catalyst is easy to sinter at high temperature, so that active components are agglomerated, and the performance of the catalyst is influenced; montmorillonite does not have strong acidity, and the performance of montmorillonite used as a carrier is poor. Meanwhile, alkali/heavy metals (K, Na, Ca, As, Pb and the like) in the industrial flue gas occupy acid sites on the catalyst, so that the adsorption of ammonia is reduced, the SCR catalyst has a poisoning effect, and the activity of the catalyst is reduced. The active component of the supported catalyst is positioned on the outer surface of the carrier, so that the supported catalyst is very easy to be attacked by alkali/heavy metal ions to cause the deactivation of the catalyst. Therefore, the method develops the dehydration with low price, excellent activity at medium and low temperature, sintering resistance and alkali/heavy metal co-poisoning resistanceThe nitro catalyst has important significance.
CN106423192A discloses a method for supporting interlayer column by using layered montmorillonite as carrier and selecting different metals and loading gamma-MnO2A low-temperature denitration catalyst as an active component. However, MnSO is used in the preparation of the catalyst4·H2O and (NH)4)2S2O8Reacting to obtain an active component gamma-MnO2The effect of sulfate residues on the catalyst activity cannot be excluded. Meanwhile, the catalyst is obtained without calcination, active components can be sintered and even subjected to crystal transformation in the medium-high temperature reaction process, and the stability is poor. In addition, the active components of the catalyst are exposed on the surface of the carrier and are seriously poisoned by alkali/heavy metal in flowing gas, and the invention patent does not relate to the research of the aspect. CN102225335A relates to a flue gas denitration catalyst and a preparation method thereof, wherein the loading capacity of the active component copper of the catalyst is 5-10 wt% calculated by CuO, and the loading capacity of the auxiliary agent cerium is CeO2The amount is 1 to 2 wt%. However, the catalyst is mainly prepared by adopting a loading mode, the specific surface area of the catalyst is low, the acid sites are insufficient, the denitration performance of the catalyst is researched only at a low space velocity, and the activity of the catalyst after alkali/heavy metal poisoning is not involved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an ion exchange type montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning and a preparation method thereof. The catalyst developed by the invention enhances the alkali/heavy metal resistance of the catalyst on the basis of ensuring the excellent medium and low temperature activity of the catalyst, and can greatly prolong the service life of the catalyst in fixed source flue gas denitration.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
an ion-exchange montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning takes montmorillonite modified by dilute acid and supported by titanium dioxide columns as an ion exchange material and takes different exchanged metal ions as active components. The dispersion degree of the active components is improved, and the catalytic activity and alkali/heavy metal tolerance of the catalyst are also greatly improved.
As a preferable technical scheme of the invention, the dilute acid is at least one of hydrochloric acid, nitric acid and sulfuric acid.
In a preferred embodiment of the present invention, the metal ion is at least one of a copper ion, an iron ion, a cerium ion, a manganese ion, a cobalt ion, and a chromium ion.
The invention relates to a preparation method of an ion exchange type montmorillonite-based denitration catalyst capable of resisting alkali metal and heavy metal poisoning, which comprises the following steps:
a. the preparation of the titanium dioxide pillared montmorillonite by dilute acid modification:
adding raw montmorillonite ore into dilute acid, carrying out oil bath stirring for 3-5 hours at 80-100 ℃ to wash out impurity ions including Na, Mg and Ca in the raw montmorillonite ore, carrying out suction filtration until acid radical ions and separated impurity ions are cleaned, drying a filter cake after suction filtration at 70-80 ℃ overnight, and grinding for later use;
dropwise adding a titanium source into a dilute acid solution under vigorous stirring, wherein the molar ratio of titanium to dilute acid is 1-5, and continuously stirring at room temperature for 12-24 hours after dropwise adding is finished to prepare a titanium dioxide pillared solution;
stirring the acid modified montmorillonite in deionized water at room temperature for 12-24 hours to ensure that the montmorillonite fully absorbs water and swells, wherein the ratio of the montmorillonite to water is 1-2 g/100 mL;
dropwise adding the prepared titanium dioxide pillared liquid into a montmorillonite suspension, carrying out oil bath stirring at the temperature of 60-80 ℃ for 5-7 hours, then carrying out centrifugal separation on the solid and the solution, centrifugally washing the obtained precipitate for 5-7 times, drying at the temperature of 70-80 ℃ overnight, grinding, and calcining at the temperature of 350-500 ℃ for 4-5 hours to prepare acid-modified titanium dioxide pillared montmorillonite;
b. dilute acid modification and titanium dioxide pillared montmorillonite ion exchange modification:
dispersing the acid-modified titanium dioxide pillared montmorillonite obtained after calcination in the step a into a metal salt solution, carrying out oil bath stirring for 5-7 hours at the temperature of 60-80 ℃, separating the solid from the solution through centrifugal separation, washing the obtained solid for 5-7 times, drying the solid at the temperature of 70-80 ℃ overnight, and calcining the solid at the temperature of 350-500 ℃ for 4-5 hours by using a muffle furnace to obtain a product, namely the ion exchange type montmorillonite-based catalyst resistant to alkali metal and heavy metal poisoning.
Preferably, in the step a, the titanium source is at least one of tetra-n-butyl titanate, titanium tetrachloride and titanyl sulfate.
Preferably, in the step a, the concentration of the dilute acid solution is 1-5 mol/L, and the ratio of titanium to soil is 5-15 mmol/g.
Preferably, in the step b, the metal salt is at least one of copper salt, iron salt, cerium salt, manganese salt, cobalt salt and chromium salt.
Preferably, the copper salt is at least one of copper nitrate, copper acetate and copper chloride; preferably, the ferric salt is at least one of ferric nitrate, ferric acetate and ferric chloride; preferably, the cerium salt is at least one of cerium nitrate, cerium acetate and cerium chloride; preferably, the manganese salt is at least one of manganese nitrate, manganese acetate and manganese chloride; preferably, the cobalt salt is at least one of cobalt nitrate, cobalt acetate and cobalt chloride; preferably, the chromium salt is at least one of chromium nitrate, chromium acetate and chromium chloride.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the denitration catalyst takes the montmorillonite modified by dilute acid and supported by titanium dioxide columns as an ion exchange material, so that the specific surface area and the surface acid sites of the montmorillonite are greatly increased through acid treatment and column support modification, the capture capability of the montmorillonite on alkali/heavy metal is enhanced, and the activity and the alkali/heavy metal resistance of the montmorillonite are improved;
2. the denitration catalyst exchanges active components to ion exchange sites among montmorillonite layers in an ion exchange mode, so that the active components are not easy to sinter, and meanwhile, abundant cation exchange sites among the montmorillonite layers can anchor alkali/heavy metal ions in flowing gas, so that the influence of the alkali/heavy metal ions on the active components is reduced, and the alkali/heavy metal resistance of the catalyst is improved;
3. the catalyst disclosed by the invention has the advantages of low raw material price, simple preparation method, excellent denitration performance, strong sintering resistance, good alkali/heavy metal resistance and the like, and can be used for denitration of tail gas of a biomass fuel boiler, a coal-fired power plant, a glass plant, a garbage incineration plant and other fixed source containing alkali/heavy metal fly ash.
Drawings
FIG. 1 shows Ce exchanged TiO prepared in example 1 of the present invention2SEM image of pillared acid montmorillonite catalyst.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
example 1
In this embodiment, a preparation method of an ion-exchange montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning includes the following steps:
modifying with nitric acid, and preparing titanium dioxide pillared montmorillonite:
adding montmorillonite raw ore into 3mol/L dilute nitric acid, performing oil bath stirring at 90 ℃ for 4 hours to wash out impurity ions including Na, Mg and Ca in the montmorillonite raw ore, performing suction filtration until acid radical ions and the separated impurity ions are cleaned, drying a filter cake after suction filtration at 70 ℃ overnight, and grinding for later use;
dropwise adding 2.04g of tetrabutyl titanate into 5.5mL of 3mol/L dilute nitric acid solution under vigorous stirring, and continuously stirring at room temperature for 12 hours after dropwise adding is finished to prepare titanium dioxide pillared solution;
stirring the nitric acid modified montmorillonite in deionized water for 12 hours at room temperature to ensure that the montmorillonite fully absorbs water and swells, wherein the ratio of the montmorillonite to the water is 1g/100 mL;
dropwise adding the prepared titanium dioxide pillared liquid into 1% montmorillonite suspension, carrying out oil bath stirring at 60 ℃ for 6 hours, then carrying out centrifugal separation on the solid and the solution, centrifugally washing the obtained precipitate for 5-7 times, drying at 70 ℃ overnight, grinding, and calcining at 400 ℃ for 4 hours to prepare nitric acid modified titanium dioxide pillared montmorillonite;
modifying by nitric acid and ion exchange of titanium dioxide pillared montmorillonite: dispersing 1g of calcined nitric acid modified titanium dioxide pillared montmorillonite in 100mL of 0.05mol/L cerium nitrate solution, carrying out oil bath stirring at 60 ℃ for 6 hours, separating the solid from the solution through centrifugal separation, washing the obtained solid with water for 5-7 times, drying at 70 ℃ overnight, and calcining at 400 ℃ for 4 hours by using a muffle furnace to obtain a product, namely the ion exchange type montmorillonite-based catalyst resistant to alkali metal and heavy metal poisoning.
Experimental test analysis:
testing the denitration performance of the catalyst: granulating the prepared catalyst into 20-40 meshes, putting the granules into a reaction furnace for activity and N2Selectivity test, reaction temperature of 270 ℃ and 450 ℃ and space velocity of 50000m3·g-1·h-1The denitration efficiency is stabilized to be more than 90 percent under the condition of (1), N2The O yield was less than 10 ppm. Simulated flue gas is O25％，NO 500ppm，NH3500 ppm，N2Is diluent gas. The catalyst sample was tested, and FIG. 1 shows Ce exchanged TiO prepared in this example2SEM image of pillared acid montmorillonite catalyst, it can be seen that the Ce exchanged TiO prepared in this example2The pillared acid montmorillonite catalyst has an obvious layered structure.
Alkali metal poisoning resistance test: 1% potassium nitrate is loaded on the catalyst by adopting a dipping method, and the simulated poisoned catalyst obtained after calcining for 4 hours at 400 ℃ is subjected to SCR denitration activity test, wherein the reaction temperature is 300-450 ℃, and the space velocity is 50000m3·g-1·h-1The denitration efficiency is stabilized to be more than 80 percent under the condition of (1), N2The amount of O produced is very small. The catalyst of the embodiment is a selective reduction denitration catalyst with good performance, and simultaneously has high alkali/heavy metal resistance, and the catalyst can improve the poisoning effect when alkali/heavy metal coexists. The true bookThe embodiment catalyst enhances the alkali/heavy metal resistance of the catalyst on the basis of ensuring excellent medium and low temperature activity of the catalyst, and can greatly prolong the service life of the catalyst in fixed source flue gas denitration. The catalyst has the advantages of low raw material price, simple preparation method, excellent denitration performance, strong sintering resistance, good alkali/heavy metal resistance and the like, and can be used for denitration of tail gas of a biomass fuel boiler, a coal-fired power plant, a glass plant, a garbage incineration plant and other fixed source containing alkali/heavy metal fly ash.
Example 2
This embodiment is substantially the same as embodiment 1, and is characterized in that:
in this embodiment, a preparation method of an ion-exchange montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning includes the following steps:
modifying with nitric acid, and preparing titanium dioxide pillared montmorillonite: adding montmorillonite raw ore into 3mol/L dilute nitric acid, performing oil bath stirring at 90 ℃ for 4 hours to wash out impurity ions including Na, Mg and Ca in the montmorillonite raw ore, performing suction filtration until acid radical ions and the separated impurity ions are cleaned, drying a filter cake after suction filtration at 70 ℃ overnight, and grinding for later use;
dropwise adding 2.04g of tetrabutyl titanate into 5.5mL of 3mol/L dilute nitric acid solution under vigorous stirring, and continuously stirring at room temperature for 12 hours after dropwise adding is finished to prepare titanium dioxide pillared solution;
stirring the nitric acid modified montmorillonite in deionized water for 12 hours at room temperature to ensure that the montmorillonite fully absorbs water and swells, wherein the ratio of the montmorillonite to the water is 1g/100 mL;
dropwise adding the prepared titanium dioxide pillared liquid into 1% montmorillonite suspension, carrying out oil bath stirring at 60 ℃ for 6 hours, then carrying out centrifugal separation on the solid and the solution, centrifugally washing the obtained precipitate for 5-7 times, drying at 70 ℃ overnight, grinding, and calcining at 400 ℃ for 4 hours to prepare nitric acid modified titanium dioxide pillared montmorillonite;
modifying by nitric acid and ion exchange of titanium dioxide pillared montmorillonite: dispersing 1g of calcined nitric acid modified titanium dioxide pillared montmorillonite in 100mL of 0.05mol/L copper nitrate solution, carrying out oil bath stirring at 60 ℃ for 6 hours, separating the solid from the solution through centrifugal separation, washing the obtained solid with water for 5-7 times, drying at 70 ℃ overnight, and calcining at 400 ℃ for 4 hours by using a muffle furnace to obtain a product, namely the ion exchange montmorillonite-based catalyst resistant to alkali metal and heavy metal poisoning.
The denitration catalyst is mainly characterized in that raw montmorillonite ore is modified by dilute acid, a titanium dioxide precursor prepared by a sol-gel method is added into acid-modified montmorillonite suspension, and the titanium dioxide pillared montmorillonite catalyst is obtained by high-temperature calcination. Finally, active metal ions are exchanged to the pillared montmorillonite by an ion exchange method to obtain the catalyst. The catalyst in the embodiment has the advantages of low raw material price, simple preparation method, excellent denitration performance, strong sintering resistance, good alkali/heavy metal resistance and the like, and can be used for denitration of tail gas of a biomass fuel boiler, a coal-fired power plant, a glass plant, a garbage incineration plant and other fixed source containing alkali/heavy metal fly ash.
Example 3
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of an ion-exchange montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning includes the following steps:
modifying with nitric acid, and preparing titanium dioxide pillared montmorillonite: adding montmorillonite raw ore into 3mol/L dilute nitric acid, performing oil bath stirring at 90 ℃ for 4 hours to wash out impurity ions including Na, Mg and Ca in the montmorillonite raw ore, performing suction filtration until acid radical ions and the separated impurity ions are cleaned, drying a filter cake after suction filtration at 70 ℃ overnight, and grinding for later use;
dropwise adding 2.04g of tetrabutyl titanate into 5.5mL of 3mol/L dilute nitric acid solution under vigorous stirring, and continuously stirring at room temperature for 12 hours after dropwise adding is finished to prepare titanium dioxide pillared solution;
stirring the nitric acid modified montmorillonite in deionized water for 12 hours at room temperature to ensure that the montmorillonite fully absorbs water and swells, wherein the ratio of the montmorillonite to the water is 1g/100 mL;
dropwise adding the prepared titanium dioxide pillared liquid into 1% montmorillonite suspension, carrying out oil bath stirring at 60 ℃ for 6 hours, then carrying out centrifugal separation on the solid and the solution, centrifugally washing the obtained precipitate for 5-7 times, drying at 70 ℃ overnight, grinding, and calcining at 400 ℃ for 4 hours to prepare nitric acid modified titanium dioxide pillared montmorillonite;
modifying by nitric acid and ion exchange of titanium dioxide pillared montmorillonite: dispersing 1g of calcined nitric acid modified titanium dioxide pillared montmorillonite in 100mL of 0.05mol/L ferric nitrate solution, carrying out oil bath stirring at 60 ℃ for 6 hours, separating the solid from the solution through centrifugal separation, washing the obtained solid with water for 5-7 times, drying at 70 ℃ overnight, and calcining at 400 ℃ for 4 hours by using a muffle furnace to obtain a product, namely the ion exchange montmorillonite-based catalyst resistant to alkali metal and heavy metal poisoning.
The denitration catalyst is mainly characterized in that raw montmorillonite ore is modified by dilute acid, a titanium dioxide precursor prepared by a sol-gel method is added into acid-modified montmorillonite suspension, and the titanium dioxide pillared montmorillonite catalyst is obtained by high-temperature calcination. Finally, active metal ions are exchanged to the pillared montmorillonite by an ion exchange method to obtain the catalyst. The catalyst in the embodiment has the advantages of low raw material price, simple preparation method, excellent denitration performance, strong sintering resistance, good alkali/heavy metal resistance and the like, and can be used for denitration of tail gas of a biomass fuel boiler, a coal-fired power plant, a glass plant, a garbage incineration plant and other fixed source containing alkali/heavy metal fly ash.
Example 4
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of an ion-exchange montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning includes the following steps:
modifying with nitric acid, and preparing titanium dioxide pillared montmorillonite: adding montmorillonite raw ore into 3mol/L dilute nitric acid, performing oil bath stirring at 90 ℃ for 4 hours to wash out impurity ions including Na, Mg and Ca in the montmorillonite raw ore, performing suction filtration until acid radical ions and the separated impurity ions are cleaned, drying a filter cake after suction filtration at 70 ℃ overnight, and grinding for later use;
dropwise adding 2.04g of tetrabutyl titanate into 5.5mL of 3mol/L dilute nitric acid solution under vigorous stirring, and continuously stirring at room temperature for 12 hours after dropwise adding is finished to prepare titanium dioxide pillared solution;
stirring the nitric acid modified montmorillonite in deionized water for 12 hours at room temperature to ensure that the montmorillonite fully absorbs water and swells, wherein the ratio of the montmorillonite to the water is 1g/100 mL;
dropwise adding the prepared titanium dioxide pillared liquid into 1% montmorillonite suspension, carrying out oil bath stirring at 60 ℃ for 6 hours, then carrying out centrifugal separation on the solid and the solution, centrifugally washing the obtained precipitate for 5-7 times, drying at 70 ℃ overnight, grinding, and calcining at 400 ℃ for 4 hours to prepare nitric acid modified titanium dioxide pillared montmorillonite;
modifying by nitric acid and ion exchange of titanium dioxide pillared montmorillonite: dispersing 1g of calcined nitric acid modified titanium dioxide pillared montmorillonite into 100mL of 0.05mol/L manganese nitrate solution, carrying out oil bath stirring at 60 ℃ for 6 hours, separating the solid from the solution through centrifugal separation, washing the obtained solid with water for 5-7 times, drying at 70 ℃ overnight, and calcining at 400 ℃ for 4 hours by using a muffle furnace to obtain a product, namely the ion exchange type montmorillonite-based catalyst resistant to alkali metal and heavy metal poisoning.
The denitration catalyst is mainly characterized in that raw montmorillonite ore is modified by dilute acid, a titanium dioxide precursor prepared by a sol-gel method is added into acid-modified montmorillonite suspension, and the titanium dioxide pillared montmorillonite catalyst is obtained by high-temperature calcination. Finally, active metal ions are exchanged to the pillared montmorillonite by an ion exchange method to obtain the catalyst. The catalyst in the embodiment has the advantages of low raw material price, simple preparation method, excellent denitration performance, strong sintering resistance, good alkali/heavy metal resistance and the like, and can be used for denitration of tail gas of a biomass fuel boiler, a coal-fired power plant, a glass plant, a garbage incineration plant and other fixed source containing alkali/heavy metal fly ash.
Example 5
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of an ion-exchange montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning includes the following steps:
modifying with nitric acid, and preparing titanium dioxide pillared montmorillonite: adding montmorillonite raw ore into 3mol/L dilute nitric acid, performing oil bath stirring at 90 ℃ for 4 hours to wash out impurity ions including Na, Mg and Ca in the montmorillonite raw ore, performing suction filtration until acid radical ions and the separated impurity ions are cleaned, drying a filter cake after suction filtration at 70 ℃ overnight, and grinding for later use;
dropwise adding 2.04g of tetrabutyl titanate into 5.5mL of 3mol/L dilute nitric acid solution under vigorous stirring, and continuously stirring at room temperature for 12 hours after dropwise adding is finished to prepare titanium dioxide pillared solution;
stirring the nitric acid modified montmorillonite in deionized water for 12 hours at room temperature to ensure that the montmorillonite fully absorbs water and swells, wherein the ratio of the montmorillonite to the water is 1g/100 mL;
dropwise adding the prepared titanium dioxide pillared liquid into 1% montmorillonite suspension, carrying out oil bath stirring at 60 ℃ for 6 hours, then carrying out centrifugal separation on the solid and the solution, centrifugally washing the obtained precipitate for 5-7 times, drying at 70 ℃ overnight, grinding, and calcining at 400 ℃ for 4 hours to prepare nitric acid modified titanium dioxide pillared montmorillonite;
modifying by nitric acid and ion exchange of titanium dioxide pillared montmorillonite: dispersing 1g of calcined nitric acid modified titanium dioxide pillared montmorillonite into 100mL of 0.05mol/L mixed solution of ferric nitrate and cerium nitrate, carrying out oil bath stirring at 60 ℃ for 6 hours, separating the solid from the solution through centrifugal separation, washing the obtained solid for 5-7 times with water, drying at 70 ℃ overnight, and calcining at 400 ℃ for 4 hours by using a muffle furnace to obtain a product, namely the ion exchange type montmorillonite-based catalyst resistant to alkali metal and heavy metal poisoning.
The denitration catalyst is mainly characterized in that raw montmorillonite ore is modified by dilute acid, a titanium dioxide precursor prepared by a sol-gel method is added into acid-modified montmorillonite suspension, and the titanium dioxide pillared montmorillonite catalyst is obtained by high-temperature calcination. Finally, active metal ions are exchanged to the pillared montmorillonite by an ion exchange method to obtain the catalyst. The catalyst in the embodiment has the advantages of low raw material price, simple preparation method, excellent denitration performance, strong sintering resistance, good alkali/heavy metal resistance and the like, and can be used for denitration of tail gas of a biomass fuel boiler, a coal-fired power plant, a glass plant, a garbage incineration plant and other fixed source containing alkali/heavy metal fly ash.
Example 6
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of an ion-exchange montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning includes the following steps:
modifying with nitric acid, and preparing titanium dioxide pillared montmorillonite: adding montmorillonite raw ore into 3mol/L dilute nitric acid, performing oil bath stirring at 90 ℃ for 4 hours to wash out impurity ions including Na, Mg and Ca in the montmorillonite raw ore, performing suction filtration until acid radical ions and the separated impurity ions are cleaned, drying a filter cake after suction filtration at 70 ℃ overnight, and grinding for later use;
dropwise adding 2.04g of tetrabutyl titanate into 5.5mL of 3mol/L dilute nitric acid solution under vigorous stirring, and continuously stirring at room temperature for 12 hours after dropwise adding is finished to prepare titanium dioxide pillared solution;
stirring the nitric acid modified montmorillonite in deionized water for 12 hours at room temperature to ensure that the montmorillonite fully absorbs water and swells, wherein the ratio of the montmorillonite to the water is 1g/100 mL;
dropwise adding the prepared titanium dioxide pillared liquid into 1% montmorillonite suspension, carrying out oil bath stirring at 60 ℃ for 6 hours, then carrying out centrifugal separation on the solid and the solution, centrifugally washing the obtained precipitate for 5-7 times, drying at 70 ℃ overnight, grinding, and calcining at 400 ℃ for 4 hours to prepare nitric acid modified titanium dioxide pillared montmorillonite;
modifying by nitric acid and ion exchange of titanium dioxide pillared montmorillonite: dispersing 1g of calcined nitric acid modified titanium dioxide pillared montmorillonite into 100mL of 0.05mol/L mixed solution of copper nitrate and cerium nitrate, carrying out oil bath stirring at 60 ℃ for 6 hours, separating the solid from the solution through centrifugal separation, washing the obtained solid for 5-7 times with water, drying at 70 ℃ overnight, and calcining at 400 ℃ for 4 hours by using a muffle furnace to obtain a product, namely the ion exchange type montmorillonite-based catalyst resistant to alkali metal and heavy metal poisoning.
The denitration catalyst is mainly characterized in that raw montmorillonite ore is modified by dilute acid, a titanium dioxide precursor prepared by a sol-gel method is added into acid-modified montmorillonite suspension, and the titanium dioxide pillared montmorillonite catalyst is obtained by high-temperature calcination. Finally, active metal ions are exchanged to the pillared montmorillonite by an ion exchange method to obtain the catalyst. The catalyst in the embodiment has the advantages of low raw material price, simple preparation method, excellent denitration performance, strong sintering resistance, good alkali/heavy metal resistance and the like, and can be used for denitration of tail gas of a biomass fuel boiler, a coal-fired power plant, a glass plant, a garbage incineration plant and other fixed source containing alkali/heavy metal fly ash.
Example 7
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of an ion-exchange montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning includes the following steps:
modifying with hydrochloric acid, and preparing titanium dioxide pillared montmorillonite: adding montmorillonite raw ore into 3mol/L dilute hydrochloric acid, stirring in oil bath at 90 ℃ for 4 hours to wash out impurity ions including Na, Mg and Ca in the montmorillonite raw ore, then carrying out suction filtration until acid radical ions and the separated impurity ions are cleaned, drying a filter cake after suction filtration at 70 ℃ overnight, and grinding for later use;
dropwise adding 2.04g of tetrabutyl titanate into 5.5mL of 3mol/L dilute hydrochloric acid solution under vigorous stirring, and continuously stirring at room temperature for 12 hours after dropwise adding is finished to prepare titanium dioxide pillared solution;
stirring montmorillonite modified by hydrochloric acid in deionized water for 12 hours at room temperature to ensure that the montmorillonite fully absorbs water and swells, wherein the ratio of the montmorillonite to the water is 1g/100 mL;
dropwise adding the prepared titanium dioxide pillared liquid into 1% montmorillonite suspension, carrying out oil bath stirring at 60 ℃ for 6 hours, then carrying out centrifugal separation on the solid and the solution, centrifugally washing the obtained precipitate for 5-7 times, drying at 70 ℃ overnight, grinding, and calcining at 400 ℃ for 4 hours to prepare hydrochloric acid modified titanium dioxide pillared montmorillonite;
hydrochloric acid modification and ion exchange modification of titanium dioxide pillared montmorillonite: dispersing 1g of calcined hydrochloric acid modified and titanium dioxide pillared montmorillonite in 100mL of 0.05mol/L cerium nitrate solution, carrying out oil bath stirring at 60 ℃ for 6 hours, separating the solid from the solution through centrifugal separation, washing the obtained solid with water for 5-7 times, drying at 70 ℃ overnight, and calcining at 400 ℃ for 4 hours by using a muffle furnace to obtain a product, namely the ion exchange montmorillonite-based catalyst resistant to alkali metal and heavy metal poisoning.
The denitration catalyst is mainly characterized in that raw montmorillonite ore is modified by dilute acid, a titanium dioxide precursor prepared by a sol-gel method is added into acid-modified montmorillonite suspension, and the titanium dioxide pillared montmorillonite catalyst is obtained by high-temperature calcination. Finally, active metal ions are exchanged to the pillared montmorillonite by an ion exchange method to obtain the catalyst. The catalyst in the embodiment has the advantages of low raw material price, simple preparation method, excellent denitration performance, strong sintering resistance, good alkali/heavy metal resistance and the like, and can be used for denitration of tail gas of a biomass fuel boiler, a coal-fired power plant, a glass plant, a garbage incineration plant and other fixed source containing alkali/heavy metal fly ash.
Example 8
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of an ion-exchange montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning includes the following steps:
modifying with nitric acid, and preparing titanium dioxide pillared montmorillonite: adding montmorillonite raw ore into 3mol/L dilute nitric acid, performing oil bath stirring at 90 ℃ for 4 hours to wash out impurity ions including Na, Mg and Ca in the montmorillonite raw ore, performing suction filtration until acid radical ions and the separated impurity ions are cleaned, drying a filter cake after suction filtration at 70 ℃ overnight, and grinding for later use;
dropwise adding a titanium tetrachloride solution into a dilute nitric acid solution of 3mol/L under vigorous stirring, wherein the molar ratio of titanium tetrachloride to nitric acid is 3, and continuously stirring at room temperature for 12 hours after the dropwise addition is finished to prepare a titanium dioxide pillared solution;
stirring the nitric acid modified montmorillonite in deionized water for 12 hours at room temperature to ensure that the montmorillonite fully absorbs water and swells, wherein the ratio of the montmorillonite to the water is 1g/100 mL;
dropwise adding the prepared titanium dioxide pillared liquid into 1% montmorillonite suspension, carrying out oil bath stirring at 60 ℃ for 6 hours, then carrying out centrifugal separation on the solid and the solution, centrifugally washing the obtained precipitate for 5-7 times, drying at 70 ℃ overnight, grinding, and calcining at 400 ℃ for 4 hours to prepare nitric acid modified titanium dioxide pillared montmorillonite;
modifying by nitric acid and ion exchange of titanium dioxide pillared montmorillonite: dispersing 1g of calcined nitric acid modified titanium dioxide pillared montmorillonite in 100mL of 0.05mol/L cerium nitrate solution, carrying out oil bath stirring at 60 ℃ for 6 hours, separating the solid from the solution through centrifugal separation, washing the obtained solid with water for 5-7 times, drying at 70 ℃ overnight, and calcining at 400 ℃ for 4 hours by using a muffle furnace to obtain a product, namely the ion exchange type montmorillonite-based catalyst resistant to alkali metal and heavy metal poisoning.
The denitration catalyst is mainly characterized in that raw montmorillonite ore is modified by dilute acid, a titanium dioxide precursor prepared by a sol-gel method is added into acid-modified montmorillonite suspension, and the titanium dioxide pillared montmorillonite catalyst is obtained by high-temperature calcination. Finally, active metal ions are exchanged to the pillared montmorillonite by an ion exchange method to obtain the catalyst. The catalyst in the embodiment has the advantages of low raw material price, simple preparation method, excellent denitration performance, strong sintering resistance, good alkali/heavy metal resistance and the like, and can be used for denitration of tail gas of a biomass fuel boiler, a coal-fired power plant, a glass plant, a garbage incineration plant and other fixed source containing alkali/heavy metal fly ash.
Example 9
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of an ion-exchange montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning includes the following steps:
modifying with nitric acid, and preparing titanium dioxide pillared montmorillonite: adding montmorillonite raw ore into 3mol/L dilute nitric acid, performing oil bath stirring at 90 ℃ for 4 hours to wash out impurity ions including Na, Mg and Ca in the montmorillonite raw ore, performing suction filtration until acid radical ions and the separated impurity ions are cleaned, drying a filter cake after suction filtration at 70 ℃ overnight, and grinding for later use;
dropwise adding 3.4g of tetrabutyl titanate into 9.17mL of 3mol/L dilute nitric acid solution under vigorous stirring, and continuously stirring at room temperature for 12 hours after dropwise adding is finished to prepare titanium dioxide pillared solution;
stirring the nitric acid modified montmorillonite in deionized water for 12 hours at room temperature to ensure that the montmorillonite fully absorbs water and swells, wherein the ratio of the montmorillonite to the water is 1g/100 mL;
dropwise adding the prepared titanium dioxide pillared liquid into 1% montmorillonite suspension, carrying out oil bath stirring at 60 ℃ for 6 hours, then carrying out centrifugal separation on the solid and the solution, centrifugally washing the obtained precipitate for 5-7 times, drying at 70 ℃ overnight, grinding, and calcining at 400 ℃ for 4 hours to prepare nitric acid modified titanium dioxide pillared montmorillonite;
modifying by nitric acid and ion exchange of titanium dioxide pillared montmorillonite: dispersing 1g of calcined nitric acid modified titanium dioxide pillared montmorillonite in 100mL of 0.05mol/L cerium nitrate solution, carrying out oil bath stirring at 60 ℃ for 6 hours, separating the solid from the solution through centrifugal separation, washing the obtained solid with water for 5-7 times, drying at 70 ℃ overnight, and calcining at 400 ℃ for 4 hours by using a muffle furnace to obtain a product, namely the ion exchange type montmorillonite-based catalyst resistant to alkali metal and heavy metal poisoning.
The denitration catalyst is mainly characterized in that raw montmorillonite ore is modified by dilute acid, a titanium dioxide precursor prepared by a sol-gel method is added into acid-modified montmorillonite suspension, and the titanium dioxide pillared montmorillonite catalyst is obtained by high-temperature calcination. Finally, active metal ions are exchanged to the pillared montmorillonite by an ion exchange method to obtain the catalyst. The catalyst in the embodiment has the advantages of low raw material price, simple preparation method, excellent denitration performance, strong sintering resistance, good alkali/heavy metal resistance and the like, and can be used for denitration of tail gas of a biomass fuel boiler, a coal-fired power plant, a glass plant, a garbage incineration plant and other fixed source containing alkali/heavy metal fly ash.
Example 10
This embodiment is substantially the same as the previous embodiment, and is characterized in that:
in this embodiment, a preparation method of an ion-exchange montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning includes the following steps:
modifying with nitric acid, and preparing titanium dioxide pillared montmorillonite: adding raw montmorillonite ore into 5mol/L dilute nitric acid, stirring in an oil bath at 90 ℃ for 4 hours to wash out impurity ions including Na, Mg and Ca in the raw montmorillonite ore, then carrying out suction filtration until acid radical ions and the separated impurity ions are cleaned, drying a filter cake after suction filtration at 70 ℃ overnight, and grinding for later use;
dropwise adding 2.04g of tetrabutyl titanate into 5.5mL of 3mol/L dilute nitric acid solution under vigorous stirring, and continuously stirring at room temperature for 12 hours after dropwise adding is finished to prepare titanium dioxide pillared solution;
stirring the nitric acid modified montmorillonite in deionized water for 12 hours at room temperature to ensure that the montmorillonite fully absorbs water and swells, wherein the ratio of the montmorillonite to the water is 1g/100 mL;
dropwise adding the prepared titanium dioxide pillared liquid into 1% montmorillonite suspension, carrying out oil bath stirring at 60 ℃ for 6 hours, then carrying out centrifugal separation on the solid and the solution, centrifugally washing the obtained precipitate for 5-7 times, drying at 70 ℃ overnight, grinding, and calcining at 400 ℃ for 4 hours to prepare nitric acid modified titanium dioxide pillared montmorillonite;
modifying by nitric acid and ion exchange of titanium dioxide pillared montmorillonite: dispersing 1g of calcined nitric acid modified titanium dioxide pillared montmorillonite in 100mL of 0.05mol/L cerium nitrate solution, carrying out oil bath stirring at 60 ℃ for 6 hours, separating the solid from the solution through centrifugal separation, washing the obtained solid with water for 5-7 times, drying at 70 ℃ overnight, and calcining at 400 ℃ for 4 hours by using a muffle furnace to obtain a product, namely the ion exchange type montmorillonite-based catalyst resistant to alkali metal and heavy metal poisoning.
The denitration catalyst is mainly characterized in that raw montmorillonite ore is modified by dilute acid, a titanium dioxide precursor prepared by a sol-gel method is added into acid-modified montmorillonite suspension, and the titanium dioxide pillared montmorillonite catalyst is obtained by high-temperature calcination. Finally, active metal ions are exchanged between the pillared montmorillonite layers by an ion exchange method to obtain the catalyst. The catalyst disclosed by the invention has the advantages of low raw material price, simple preparation method, excellent denitration performance, strong sintering resistance, good alkali/heavy metal resistance and the like, and can be used for denitration of tail gas of a biomass fuel boiler, a coal-fired power plant, a glass plant, a garbage incineration plant and other fixed source containing alkali/heavy metal fly ash.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitution ways, as long as the purpose of the present invention is met, and the ion exchange type anti-poisoning montmorillonite-based denitration catalyst and the preparation method thereof shall fall within the protection scope of the present invention without departing from the technical principle and inventive concept of the present invention.
Claims (8)
1. An ion exchange type montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning is characterized in that: the montmorillonite modified by dilute acid and supported by titanium dioxide column is used as an ion exchange material, and different exchanged metal ions are used as active components.
2. The ion-exchange type montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning according to claim 1, characterized in that: the dilute acid is at least one of hydrochloric acid, nitric acid and sulfuric acid.
3. The ion-exchange type montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning according to claim 1, characterized in that: the metal ions are at least one of copper ions, iron ions, cerium ions, manganese ions, cobalt ions and chromium ions.
4. A method for preparing the ion-exchange montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning according to claim 1, which is characterized in that: the method comprises the following steps:
a. the preparation of the titanium dioxide pillared montmorillonite by dilute acid modification:
adding raw montmorillonite ore into dilute acid, carrying out oil bath stirring for 3-5 hours at 80-100 ℃ to wash out impurity ions including Na, Mg and Ca in the raw montmorillonite ore, carrying out suction filtration until acid radical ions and separated impurity ions are cleaned, drying a filter cake after suction filtration at 70-80 ℃ overnight, and grinding for later use;
dropwise adding a titanium source into a dilute acid solution under vigorous stirring, wherein the molar ratio of titanium to dilute acid is 1-5, and after dropwise adding is finished, continuously stirring at room temperature for 12-24 hours to prepare a titanium dioxide pillared solution;
stirring the acid modified montmorillonite in deionized water at room temperature for 12-24 hours to ensure that the montmorillonite fully absorbs water and swells, wherein the ratio of the montmorillonite to water is 1-2 g/100 mL;
dropwise adding the prepared titanium dioxide pillared liquid into a montmorillonite suspension, carrying out oil bath stirring at the temperature of 60-80 ℃ for 5-7 hours, then carrying out centrifugal separation on the solid and the solution, centrifugally washing the obtained precipitate for 5-7 times, drying at the temperature of 70-80 ℃ overnight, grinding, and calcining at the temperature of 350-500 ℃ for 4-5 hours to prepare acid-modified titanium dioxide pillared montmorillonite;
b. dilute acid modification and titanium dioxide pillared montmorillonite ion exchange modification:
dispersing the acid-modified titanium dioxide pillared montmorillonite obtained after calcination in the step a into a metal salt solution, carrying out oil bath stirring for 5-7 hours at the temperature of 60-80 ℃, separating the solid from the solution through centrifugal separation, washing the obtained solid for 5-7 times, drying the solid at the temperature of 70-80 ℃ overnight, and calcining the solid at the temperature of 350-500 ℃ for 4-5 hours by using a muffle furnace to obtain a product, namely the ion exchange type montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning.
5. The method for preparing an ion-exchange montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning according to claim 4, wherein: in the step a, the titanium source is at least one of tetra-n-butyl titanate, titanium tetrachloride and titanyl sulfate.
6. The method for preparing an ion-exchange montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning according to claim 4, wherein: in the step a, the concentration of the dilute acid solution is 1-5 mol/L, and the ratio of titanium to soil is 5-15 mmol/g.
7. The method for preparing an ion-exchange montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning according to claim 4, wherein: in the step b, the metal salt is at least one of copper salt, iron salt, cerium salt, manganese salt, cobalt salt and chromium salt.
8. The method for preparing an ion-exchange montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning according to claim 7, wherein: the copper salt is at least one of copper nitrate, copper acetate and copper chloride;
or the ferric salt is at least one of ferric nitrate, ferric acetate and ferric chloride;
or the cerium salt is at least one of cerium nitrate, cerium acetate and cerium chloride;
or the manganese salt is at least one of manganese nitrate, manganese acetate and manganese chloride;
or the cobalt salt is at least one of cobalt nitrate, cobalt acetate and cobalt chloride;
or the chromium salt is at least one of chromium nitrate, chromium acetate and chromium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110035105.0A CN112844441A (en) | 2021-01-12 | 2021-01-12 | Ion exchange type montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110035105.0A CN112844441A (en) | 2021-01-12 | 2021-01-12 | Ion exchange type montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112844441A true CN112844441A (en) | 2021-05-28 |
Family
ID=76002756
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110035105.0A Pending CN112844441A (en) | 2021-01-12 | 2021-01-12 | Ion exchange type montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112844441A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114797858A (en) * | 2022-06-08 | 2022-07-29 | 辽宁工业大学 | Method for improving catalytic hydrogen production performance of copper-based catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5415850A (en) * | 1993-02-24 | 1995-05-16 | The Research Foundation Of State Univeristy Of New York | Pillared interlayered clay catalysts for the selective reduction of nitrogen oxides with ammonia |
| CN102225335A (en) * | 2011-04-28 | 2011-10-26 | 武汉大学 | Denitration catalyst for flue gas and preparation method thereof |
| CN106423192A (en) * | 2016-09-19 | 2017-02-22 | 常州大学 | Metal pillared montmorillonite supported gamma-MnO2 low-temperature denitration catalyst and preparation method thereof |
| CN108452796A (en) * | 2018-03-12 | 2018-08-28 | 北京科技大学 | A kind of preparation method of the modified montmorillonite used base SCR denitration of Supported Manganese and cerium |
| CN110013846A (en) * | 2018-12-22 | 2019-07-16 | 北京工业大学 | Aluminium manganese is total to the preparation method and application of pillared montmorillonite load C e-Cu or Eu-Ce composite catalyst |
-
2021
- 2021-01-12 CN CN202110035105.0A patent/CN112844441A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5415850A (en) * | 1993-02-24 | 1995-05-16 | The Research Foundation Of State Univeristy Of New York | Pillared interlayered clay catalysts for the selective reduction of nitrogen oxides with ammonia |
| CN102225335A (en) * | 2011-04-28 | 2011-10-26 | 武汉大学 | Denitration catalyst for flue gas and preparation method thereof |
| CN106423192A (en) * | 2016-09-19 | 2017-02-22 | 常州大学 | Metal pillared montmorillonite supported gamma-MnO2 low-temperature denitration catalyst and preparation method thereof |
| CN108452796A (en) * | 2018-03-12 | 2018-08-28 | 北京科技大学 | A kind of preparation method of the modified montmorillonite used base SCR denitration of Supported Manganese and cerium |
| CN110013846A (en) * | 2018-12-22 | 2019-07-16 | 北京工业大学 | Aluminium manganese is total to the preparation method and application of pillared montmorillonite load C e-Cu or Eu-Ce composite catalyst |
Non-Patent Citations (2)
| Title |
|---|
| DONG XU ET AL.: ""Boosting the Alkali/Heavy Metal Poisoning Resistance for NO Removal by Using Iron-Titanium Pillared Montmorillonite Catalysts"", 《JOURNAL OF HAZARDOUS MATERIALS》 * |
| 商平等: "《环境矿物材料》", 31 January 2008, 化学工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114797858A (en) * | 2022-06-08 | 2022-07-29 | 辽宁工业大学 | Method for improving catalytic hydrogen production performance of copper-based catalyst |
| CN114797858B (en) * | 2022-06-08 | 2023-12-19 | 辽宁工业大学 | Method for improving catalytic hydrogen production performance of copper-based catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108722477B (en) | Anti-alkalosis efficient denitration catalyst and preparation method and application thereof | |
| CN102114424B (en) | Low-temperature smoke denitration SCR (silicon controlled rectifier) catalyst and preparation method | |
| CN104492446B (en) | A kind of catalyst and preparation method for ammonia selective reducing nitrogen oxide | |
| CN105833894B (en) | Have both the denitrating catalyst and its preparation method and application of alkali resistant (soil) metal and sulfur resistive water resistant function | |
| CN102658161B (en) | Supported iron-based composite oxide catalyst and preparation method thereof | |
| Kang et al. | Insights into the co-doping effect of Fe3+ and Zr4+ on the anti-K performance of CeTiOx catalyst for NH3-SCR reaction | |
| CN102500358B (en) | Denitration catalyst with excellent alkali metal and alkaline-earth metal poisoning resistance | |
| US6521559B1 (en) | Superior pillared clay catalysts for selective catalytic reduction of nitrogen oxides for power plant emission control | |
| CN107552043B (en) | Supported low-temperature SCR denitration catalyst and preparation method thereof | |
| CN107308944B (en) | A kind of TiO 2-based catalyst and its preparation method and application | |
| EP0457480B1 (en) | Catalytic reduction | |
| CN110773153B (en) | Supported manganese-based medium-low temperature denitration catalyst, preparation method and application thereof | |
| CN104888795A (en) | Titanium oxide loaded vanadate denitration catalyst as well as preparation method and application thereof | |
| CN109351358A (en) | A kind of transition metal oxide composite catalyst and its preparation method and application | |
| CN103230813A (en) | Preparation method of alkali-poisoning-resistant denitrifying catalyst applicable to cement kilns | |
| CN112495369B (en) | Medium-low temperature vanadium-tungsten titanium-based SCR denitration catalyst and preparation method thereof | |
| CN103894185A (en) | Method for preparing selective catalytic reduction (SCR) denitration catalyst by taking TiO2-ZnO as composite carrier | |
| CN105233814A (en) | Cerium oxide catalyst for catalyzing and purifying nitric oxides, preparation method and application | |
| CN106268779A (en) | A kind of middle high temperature SCR denitration with alkali resistant metal poisoning and preparation method thereof | |
| CN106111123A (en) | A kind of support type manganio composite oxides selective denitrification catalyst containing tourmaline | |
| CN105457646B (en) | A kind of middle low-temperature denitration catalyst and preparation method thereof with protective layer | |
| CN112844441A (en) | Ion exchange type montmorillonite-based denitration catalyst resistant to alkali metal and heavy metal poisoning and preparation method thereof | |
| CN107376934B (en) | Iron oxide pillared layered manganese oxide catalyst and preparation method and application thereof | |
| CN103623814B (en) | A kind of manganese vanadium oxides composite catalyst for ammine selectivity catalytic reduction nitrous oxides | |
| CN109012703A (en) | A kind of new method preparing iron sulphur titanium group high temperature NH3-SCR denitrating catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210528 |
|
| RJ01 | Rejection of invention patent application after publication |