CN114832859A - Catalyst for purifying CVOCs and preparation method thereof - Google Patents
Catalyst for purifying CVOCs and preparation method thereof Download PDFInfo
- Publication number
- CN114832859A CN114832859A CN202210637473.7A CN202210637473A CN114832859A CN 114832859 A CN114832859 A CN 114832859A CN 202210637473 A CN202210637473 A CN 202210637473A CN 114832859 A CN114832859 A CN 114832859A
- Authority
- CN
- China
- Prior art keywords
- ruthenium
- catalyst
- mass ratio
- auxiliary agent
- roasting
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 claims abstract description 58
- 238000003756 stirring Methods 0.000 claims abstract description 56
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 52
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 40
- 239000010703 silicon Substances 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 16
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims description 36
- 238000000576 coating method Methods 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 36
- 239000002243 precursor Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 14
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 12
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000005751 Copper oxide Substances 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 238000007792 addition Methods 0.000 claims description 7
- 229910000431 copper oxide Inorganic materials 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- NSNVGCNCRLAWOJ-UHFFFAOYSA-N [N+](=O)([O-])[O-].N(=O)[Ru+2].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].N(=O)[Ru+2].[N+](=O)([O-])[O-] NSNVGCNCRLAWOJ-UHFFFAOYSA-N 0.000 claims description 4
- GBDZMMXUOBAJMN-UHFFFAOYSA-K azane;ruthenium(3+);trichloride Chemical compound N.N.N.N.N.N.[Cl-].[Cl-].[Cl-].[Ru+3] GBDZMMXUOBAJMN-UHFFFAOYSA-K 0.000 claims description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 claims 1
- 238000001354 calcination Methods 0.000 claims 1
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000012010 growth Effects 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 230000002779 inactivation Effects 0.000 abstract description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000002002 slurry Substances 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000002912 waste gas Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910000420 cerium oxide Inorganic materials 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002671 adjuvant Substances 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- ZWYCMWUUWAFXIA-UHFFFAOYSA-N iron(2+);5,10,15,20-tetraphenylporphyrin-22,23-diide Chemical compound [Fe+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C2=CC=C([N-]2)C(C=2C=CC=CC=2)=C2C=CC3=N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 ZWYCMWUUWAFXIA-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000004045 organic chlorine compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- DDRQVDNHTVCAGJ-UHFFFAOYSA-K [Cl-].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[Ru+3].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] Chemical compound [Cl-].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[Ru+3].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] DDRQVDNHTVCAGJ-UHFFFAOYSA-K 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002906 medical waste Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- -1 printing Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004056 waste incineration 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
-
- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/206—Organic halogen compounds
- B01D2257/2064—Chlorine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (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 relates to a catalyst for purifying CVOCs and a preparation method thereof, wherein the preparation method comprises the following steps: mixing and stirring a silicon-containing auxiliary agent, a ruthenium-containing polyvinyl imidazole complex and a catalytic auxiliary agent, and then carrying out solid-liquid separation and first roasting to obtain the catalyst; the silicon-containing auxiliary agent is obtained by carrying out a first stirring reaction on methyl triethoxysilane, ethyl orthosilicate and alcohol in a water phase, then sequentially adding acid and n-butyl titanate to carry out a second stirring reaction, and then carrying out solid-liquid separation and second roasting. According to the preparation method provided by the invention, the preparation of the high water resistance catalyst is realized by adopting a specific preparation process, the target compound can be continuously and efficiently adsorbed and catalyzed, and the inactivation and invalidation of the catalyst are prevented; meanwhile, the method can also inhibit the migration, aggregation and growth of metal ions in the high-temperature roasting process.
Description
Technical Field
The invention relates to the field of waste gas treatment, in particular to a catalyst for purifying CVOCs and a preparation method thereof.
Background
At present, chlorine-Containing Volatile Organic Compounds (CVOCs) are one kind of Volatile Organic Compounds (VOCs), and are widely applied to the industries such as medicine, leather, paint, printing, dye, rubber, chemical industry and the like. CVOCs have the characteristics of high chemical stability, low biodegradability, strong fat solubility and the like. CVOCs are seriously harmful, and the human body can cause the symptoms of decreased immune level, dysfunction of the central nervous system and the like after being exposed to the CVOCs for a long time; furthermore, CVOCs are also important precursors that cause overproof ozone and PM2.5 concentrations in the atmosphere.
On the other hand, CVOCs such as chlorobenzene or chlorophenol are important precursors of primary carcinogen dioxin, and are commonly present in flue gas discharged from industries such as household garbage and medical waste incineration, steel smelting, heating and power supply and the like. In recent years, with the year-by-year importance of our country on ecological environment protection and the direction of people to good life, accelerating waste gas treatment construction, particularly CVOCs treatment engineering construction, is one of the important means for improving the environmental air quality of our country. The method not only can reduce the CVOCs pollutants, but also can reduce the generation of a byproduct dioxin, thereby achieving the purpose of harmlessness and having extremely high environmental, social and economic values.
The catalytic oxidation technology is one of the most effective and economic methods for treating CVOCs, and particularly relates to a method for realizing the directional removal of pollutants by reducing the reaction activation energy under the action of a catalyst to ensure that target pollutants are subjected to an oxidation-reduction reaction on the surface of the catalyst. The technology has the advantages of low energy consumption, high efficiency, less secondary pollution and the like.
For example, CN110038407A discloses a method for purifying and treating waste gas containing hydrogen chloride gas and organic chlorine compound gas, comprising the following steps: introducing a mixed gas of waste gas and air into a graphite preheater for preheating, then introducing a shell pass of a heat exchanger and a high-temperature gas discharged from a fixed bed reactor for heat exchange and temperature rise, then introducing the mixed gas into the fixed bed reactor for catalytic oxidation reaction, introducing the reacted high-temperature gas into a tube pass of the heat exchanger for heat exchange and cooling, introducing the cooled gas into a spray scrubber for absorbing acid gas, and then introducing the cooled gas into a gas-liquid separator for directly discharging the gas. The method adopts a fixed bed reactor catalytic oxidation method, efficiently treats the waste gas containing hydrogen chloride gas and organic chlorine compound gas at low cost, preheats the mixed gas through a graphite preheater, reduces the dew point corrosion of HCl gas on pipelines and a heat exchanger, exchanges heat between the high-temperature tail gas after catalytic oxidation and the waste gas to be treated through the heat exchanger, fully utilizes the reaction heat, and has better economic benefit.
CN102698751A A catalyst for eliminating chlorine-containing volatile organic compounds by low-temperature catalytic combustion is mainly composed of a transition metal oxide-cerium oxide composite oxide carrier and ruthenium oxide loaded on the carrier, wherein transition metal elements are Ti, Mn, Co, Fe, Cu and Ni. Air as an oxidant is brought into the reactor, so that the chlorine-containing volatile organic compounds are converted into carbon dioxide, hydrogen chloride and chlorine, and the tail gas of complete combustion can be absorbed by dilute alkali solution and then is discharged. The catalyst has high catalytic activity, strong chlorine poisoning resistance and long service life, and is particularly suitable for eliminating chlorine-containing organic compounds by low-temperature catalytic combustion.
However, the technology has the following challenges when treating CVOCs at present: firstly, the CVOCs conversion rate is low when purifying high-concentration CVOCs due to the weak performance of the catalyst, and CO is generated 2 The generation rate is not high, so that the treated tail gas can hardly meet the pollutant emission standard; secondly, the catalyst is difficult to realize the directional adsorption, catalysis and removal of the CVOCs under the condition of high water vapor content, and the purification efficiency is forced to be difficult to meet the industrial requirement.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a catalyst for purifying CVOCs and a preparation method thereof, and solves the problems that the existing catalyst has poor treatment effect on organochlorine-containing gas under high water vapor content and the purification efficiency does not reach the standard.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a catalyst for purifying CVOCs, the method comprising the steps of: mixing and stirring a silicon-containing auxiliary agent, a ruthenium-containing polyvinyl imidazole complex and a catalytic auxiliary agent, and then carrying out solid-liquid separation and first roasting to obtain the catalyst;
the silicon-containing auxiliary agent is obtained by carrying out a first stirring reaction on methyl triethoxysilane, ethyl orthosilicate and alcohol in a water phase, then sequentially adding acid and n-butyl titanate to carry out a second stirring reaction, and then carrying out solid-liquid separation and second roasting.
According to the preparation method provided by the invention, the preparation of the high water resistance catalyst is realized by adopting a specific preparation process, the target compound can be continuously and efficiently adsorbed and catalyzed, and the inactivation and invalidation of the catalyst are prevented; meanwhile, the preparation method provided by the invention can also inhibit the migration, aggregation and growth of noble metal ions in the high-temperature roasting process.
In the invention, the high water vapor content is more than or equal to 5 percent of the water vapor content in the organochlorine gas, and is preferably 5-10 percent.
In the invention, the solid-liquid separation can be specifically performed by aging, drying and other operations in sequence.
In the present invention, the acid may be hydrochloric acid, nitric acid, sulfuric acid or the like.
In a preferred embodiment of the present invention, the mass ratio of the silicon-containing auxiliary agent to the ruthenium precursor in the ruthenium polyvinylimidazole complex during the mixing is (50-200: 1), and may be, for example, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, 110:1, 120:1, 130:1, 140:1, 150:1, 160:1, 170:1, 180:1, 190:1 or 200:1, but is not limited to the above-mentioned values, and other values not specified in the above-mentioned range are also acceptable.
Preferably, the mass ratio of the catalyst promoter to the ruthenium precursor in the ruthenium polyvinylimidazole complex during the mixing is (3-8):1, and may be, for example, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1, 5:1, 5.2:1, 5.4:1, 5.6:1, 5.8:1, 6:1, 6.2:1, 6.4:1, 6.6:1, 6.8:1, 7:1, 7.2:1, 7.4:1, 7.6:1, 7.8:1 or 8:1, but is not limited to the recited values, and other values not recited in the range are also acceptable.
Preferably, the catalyst promoter comprises 1 or a combination of at least 2 of copper oxide, cobaltosic oxide, cerium oxide or manganese oxide, such as a combination of copper oxide and cobaltosic oxide, a combination of cerium oxide and manganese oxide or a combination of copper oxide and cerium oxide, and the like.
Preferably, the mixing and stirring time is 1 to 3 hours, for example, 1 hour, 1.1 hour, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.8 hours, 1.9 hours, 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours or 3 hours, etc., but not limited to the enumerated values, and other unrecited values in the range are also acceptable.
As a preferred embodiment of the present invention, the temperature of the first baking is 300-.
Preferably, the first baking time is 2 to 5 hours, such as 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours, 3 hours, 3.1 hours, 3.2 hours, 3.3 hours, 3.4 hours, 3.5 hours, 3.6 hours, 3.7 hours, 3.8 hours, 3.9 hours, 4 hours, 4.1 hours, 4.2 hours, 4.3 hours, 4.4 hours, 4.5 hours, 4.6 hours, 4.7 hours, 4.8 hours, 4.9 hours or 5 hours, etc., but not limited to the recited values, and other values not recited in the range are also satisfactory.
In a preferred embodiment of the present invention, the mass ratio of methyltriethoxysilane to tetraethoxysilane in the process of producing the silicon-containing auxiliary agent is (3-6: 1), and examples thereof include, but are not limited to, 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1, 4:1, 4.1:1, 4.2:1, 4.3:1, 4.4:1, 4.5:1, 4.6:1, 4.7:1, 4.8:1, 4.9:1, 5:1, 5.1:1, 5.2:1, 5.3:1, 5.4:1, 5.5:1, 5.6:1, 5.7:1, 5.8:1, 5.9:1, and 6:1, and other values are not limited thereto.
Preferably, the mass ratio of the alcohol to the methyltrimethoxy in the preparation process of the silicon-containing auxiliary agent is (5-10):1, and may be, for example, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1 or 10:1, but is not limited to the recited values, and other unrecited values within the range are also acceptable.
Preferably, the mass ratio of alcohol to water in the preparation process of the silicon-containing auxiliary agent is (2-5):1, and may be, for example, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1 or 5:1, etc., but is not limited to the enumerated values, and other unrecited values in the range are also satisfactory.
Preferably, the amount of acid added during the preparation of the silicon-containing adjuvant is 0.5-2% of the amount of water added, and may be, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, or 2%, but is not limited to the recited values, and other values not recited within this range are also acceptable.
In the present invention, the acid may be an organic acid or an inorganic acid, and may be acetic acid, sulfuric acid, hydrochloric acid, nitric acid, or the like.
Preferably, the molar concentration of the acid during the preparation of the silicon-containing adjuvant is 9 to 12mol/L, and may be, for example, 9mol/L, 9.2mol/L, 9.4mol/L, 9.6mol/L, 9.8mol/L, 10mol/L, 10.2mol/L, 10.4mol/L, 10.6mol/L, 10.8mol/L, 11mol/L, 11.2mol/L, 11.4mol/L, 11.6mol/L, 11.8mol/L or 12mol/L, etc., but is not limited to the recited values, and other unrecited values within the range are also acceptable.
Preferably, the mass ratio of n-butyl titanate to methyltriethoxysilane in the preparation of the silicon-containing adjuvant is (1-5):1, and may be, for example, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1 or 5:1, but is not limited to the recited values, and other unrecited values within the range are also acceptable.
In a preferred embodiment of the present invention, the time of the first stirring reaction in the process of preparing the silicon-containing auxiliary agent is 0.5 to 1 hour, for example, 0.5 hour, 0.55 hour, 06. hour, 0.65 hour, 0.7 hour, 0.75 hour, 0.8 hour, 0.85 hour, 0.9 hour, 0.95 hour or 1 hour, but is not limited to the recited values, and other values not recited in the range are also acceptable.
Preferably, the time of the second stirring reaction in the preparation process of the silicon-containing auxiliary agent is 0.5-1h, for example, 0.5h, 0.55h, 06.h, 0.65h, 0.7h, 0.75h, 0.8h, 0.85h, 0.9h, 0.95h or 1h, etc., but not limited to the enumerated values, and other unrecited values in the range are also acceptable.
In a preferred embodiment of the present invention, the temperature of the second baking in the preparation process of the silicon-containing auxiliary agent is 300-600 ℃, and may be, for example, 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃ or 600 ℃, but not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also included.
Preferably, the time of the second baking in the preparation process of the silicon-containing assistant is 2 to 6 hours, for example, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours, 5 hours, 5.2 hours, 5.4 hours, 5.6 hours, 5.8 hours or 6 hours, etc., but not limited to the enumerated values, and other unrecited values in the range are also satisfactory.
According to a preferred technical scheme of the invention, the ruthenium-polyvinyl imidazole complex is obtained by carrying out a third stirring reaction on polyvinyl imidazole, a ruthenium precursor and a liquid phase.
In the present invention, the polyvinylimidazole can be referred to as: the preparation method of Journal-Maria, san Sinena, Jerzy, et al. effects of Axial coding of the Metal Center on the Activity of Iron Tetraphenylporphyrin as a NPrecious Catalyst for Oxygen Reduction [ J ]. Journal of Physical Chemistry C,2014,118(33), 19139-19149.
Preferably, the mass ratio of the polyvinylimidazole to the ruthenium precursor in the preparation of the ruthenium polyvinylimidazole complex is (5-20):1, and may be, for example, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 10.5:1, 11:1, 11.5:1, 12:1, 12.5:1, 13:1, 13.5:1, 14:1, 14.5:1, 15:1, 15.5:1, 16:1, 16.5:1, 17:1, 17.5:1, 18:1, 18.5:1, 19:1, 19.5:1 or 20:1, etc., but not limited to the recited values, and other values not recited in the range are also acceptable.
Preferably, the liquid phase in the preparation of the ruthenium polyvinylimidazole complex comprises water and alcohol in a mass ratio of (1-3):1, which may be, for example, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1 or 3:1, etc., but is not limited to the recited values, and other values not recited in this range are also desirable.
In the present invention, the alcohol may be methanol, ethanol, glycerol, ethylene glycol, or the like.
Preferably, the mass ratio of alcohol to polyvinylimidazole in the preparation of the ruthenium polyvinylimidazole complex is (5-10):1, and may be, for example, 5:1, 5.2:1, 5.4:1, 5.6:1, 5.8:1, 6:1, 6.2:1, 6.4:1, 6.6:1, 6.8:1, 7:1, 7.2:1, 7.4:1, 7.6:1, 7.8:1, 8:1, 8.2:1, 8.4:1, 8.6:1, 8.8:1, 9:1, 9.2:1, 9.4:1, 9.6:1, 9.8:1 or 10:1, and the like, but is not limited to the recited values, and other values not recited in the range are also acceptable.
Preferably, the ruthenium precursor in the preparation process of the ruthenium polyvinyl imidazole complex comprises 1 or a combination of at least 2 of ruthenium chloride, ruthenium nitrosyl nitrate or ruthenium hexaammonium trichloride.
Preferably, the third stirring reaction time during the preparation of the ruthenium polyvinyl imidazole complex is 0.5 to 2 hours, for example, 0.5 hour, 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour, 1 hour, 1.1 hour, 1.2 hour, 1.3 hour, 1.4 hour, 1.5 hour, 1.6 hour, 1.7 hour, 1.8 hour, 1.9 hour or 2 hours, etc., but not limited to the enumerated values, and other unrecited values within the range are also acceptable.
As a preferable technical scheme of the invention, the preparation method further comprises the steps of mixing and ball-milling the catalyst, the sol, the coating auxiliary agent and water to obtain a coating material, then coating the coating material on the surface of the carrier, and then drying and carrying out third roasting to obtain the monolithic catalyst.
Preferably, the sol comprises a nano-silica sol.
Preferably, the coating aid comprises 1 or a combination of at least 2 of cetyltrimethylammonium bromide, polyethylene glycol, sodium lauryl sulfate.
In the invention, the molecular weight of the polyethylene glycol is less than or equal to 400.
Preferably, the mass ratio of the catalyst to the sol is (9.5-10.5):1, and may be, for example, 9.5:1, 9.55:1, 9.6:1, 9.65:1, 9.7:1, 9.75:1, 9.8:1, 9.85:1, 9.9:1, 9.95:1, 10:1, 10.05:1, 10.1:1, 10.15:1, 10.2:1, 10.25:1, 10.3:1, 10.35:1, 10.4:1, 10.45:1 or 10.5:1, etc., but is not limited to the recited values, and other unrecited values within this range are also acceptable.
Preferably, the mass ratio of the catalyst to the coating assistant is (5-10):1, and may be, for example, 5:1, 5.2:1, 5.4:1, 5.6:1, 5.8:1, 6:1, 6.2:1, 6.4:1, 6.6:1, 6.8:1, 7:1, 7.2:1, 7.4:1, 7.6:1, 7.8:1, 8:1, 8.2:1, 8.4:1, 8.6:1, 8.8:1, 9:1, 9.2:1, 9.4:1, 9.6:1, 9.8:1 or 10:1, and the like, but is not limited to the recited values, and other unrecited values within this range are also satisfactory.
Preferably, the mass ratio of water to catalyst is (5-15):1, and may be, for example, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 10.5:1, 11:1, 11.5:1, 12:1, 12.5:1, 13:1, 13.5:1, 14:1, 14.5:1 or 15:1, but is not limited to the recited values, and other values not recited within this range are also acceptable.
Preferably, the ball milling time is 2-5h, for example, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h or 5h, etc., but not limited to the recited values, and other values not recited in the range are also acceptable.
Preferably, the drying temperature is 120-.
Preferably, the drying time is 2 to 8 hours, for example, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours, 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours, 5 hours, 5.2 hours, 5.4 hours, 5.6 hours, 5.8 hours, 6 hours, 6.2 hours, 6.4 hours, 6.6 hours, 6.8 hours, 7 hours, 7.2 hours, 7.4 hours, 7.6 hours, 7.8 hours or 8 hours, etc., but not limited to the recited values, and other values not recited in the range are also satisfactory.
Preferably, the temperature of the third baking is 300-500 ℃, for example, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃ or 500 ℃ and so on, but not limited to the enumerated values, and other unrecited values in the range are also satisfactory.
Preferably, the third baking time is 1-5h, such as 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h or 5h, etc., but not limited to the recited values, and other values not recited in the range are also acceptable.
As a preferred technical scheme of the invention, the preparation method comprises the following steps: mixing and stirring a silicon-containing auxiliary agent, a ruthenium-containing polyvinyl imidazole complex and a catalytic auxiliary agent, then carrying out solid-liquid separation and first roasting to obtain a catalyst, mixing and ball-milling the catalyst, sol, the coating auxiliary agent and water to obtain a coating material, then coating the coating material on the surface of a carrier, and then drying and carrying out third roasting to obtain an integral catalyst;
the mass ratio of the silicon-containing auxiliary agent to the ruthenium precursor in the ruthenium polyvinyl imidazole complex in the mixing and stirring process is (50-200): 1; the mass ratio of the catalytic assistant to the ruthenium precursor in the ruthenium polyvinyl imidazole complex in the mixing and stirring process is (3-8) to 1; the catalytic promoter comprises 1 or the combination of at least 2 of copper oxide, cobaltosic oxide, cerium dioxide or manganese oxide; the mixing and stirring time is 1-3 h; the first roasting temperature is 300-500 ℃, and the time is 2-5 h; the sol comprises nano-silica sol; the coating auxiliary agent comprises 1 or at least 2 of cetyl trimethyl ammonium bromide, polyethylene glycol and lauryl sodium sulfate; the mass ratio of the catalyst to the sol is (9.5-10.5) to 1; the mass ratio of the catalyst to the coating auxiliary agent is (5-10) to 1; the mass ratio of the water to the catalyst is (5-15) to 1; the ball milling time is 2-5 h; the drying temperature is 120-220 ℃, and the drying time is 2-8 h; the temperature of the third roasting is 300-500 ℃, and the time is 1-5 h;
the silicon-containing auxiliary agent is obtained by mixing methyltriethoxysilane, ethyl orthosilicate, alcohol and water for a first stirring reaction, then sequentially adding acid and n-butyl titanate for a second stirring reaction, and then performing solid-liquid separation and second roasting; the mass ratio of the methyl triethoxysilane to the ethyl orthosilicate is (3-6) to 1; the mass ratio of the ethanol to the methyl trimethoxy is (5-10) to 1; the mass ratio of the ethanol to the water is (2-5) to 1; the addition amount of the acid is 0.5-2% of the addition amount of the water; the mass concentration of the acid is 9-12 mol/L; the mass ratio of the n-butyl titanate to the methyltriethoxysilane is (1-5) to 1; the first stirring reaction time is 0.5-1 h; the second stirring reaction time is 0.5-1 h; the temperature of the second roasting is 300-600 ℃, and the time is 2-6 h;
the ruthenium-polyvinyl imidazole complex is obtained by carrying out a third stirring reaction on polyvinyl imidazole, a ruthenium precursor and a liquid phase; the mass ratio of the polyvinyl imidazole to the ruthenium precursor is (5-20) to 1; the liquid phase comprises water and alcohol in a mass ratio of (1-3) to 1; the mass ratio of the alcohol to the polyvinyl imidazole is (5-10) to 1; the ruthenium precursor comprises 1 or at least 2 of ruthenium chloride, nitrosyl ruthenium nitrate or hexaammonium ruthenium trichloride; the time of the third stirring reaction is 0.5-2 h.
In a second aspect, the invention provides a catalyst for purifying CVOCs, which is obtained by the preparation method in the first aspect and is used for treating organic chlorine-containing gas with water vapor content of more than or equal to 5%.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the preparation method provided by the invention, the introduced polyvinylimidazole can effectively inhibit the migration, aggregation and growth of the noble metal component in the high-temperature roasting process, ensure that the roasted ruthenium component is uniformly distributed on the surface of the catalyst in a microparticle form, and ensure that the catalyst has enough catalytic active sites in unit volume, thereby ensuring that the catalyst has higher catalytic efficiency and stability.
(2) According to the preparation method provided by the invention, the silicon-titanium material phase is introduced and matched with the polyvinyl imidazole, so that the catalyst has high water resistance, the water poisoning is prevented, and the surface of the catalyst can continuously and efficiently adsorb and catalyze target compounds.
(3) The monolithic catalyst provided by the invention can effectively solve the problems of difficult treatment of high-concentration CVOCs waste gas and the like, realizes directional removal of target pollutants, and ensures higher CVOCs conversion rate and CO 2 The generation rate, CVOCs conversion rate is more than or equal to 98 percent, and CO 2 The generation rate is more than or equal to 98 percent.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
This example provides a method for preparing a catalyst for purifying CVOCs, which includes the following steps: mixing and stirring a silicon-containing auxiliary agent, a ruthenium-containing polyvinyl imidazole complex and a catalytic auxiliary agent, then carrying out solid-liquid separation and first roasting to obtain a catalyst, mixing and ball-milling the catalyst, sol, the coating auxiliary agent and water to obtain a coating material, then coating the coating material on the surface of a carrier, and then drying and carrying out third roasting to obtain an integral catalyst;
the method specifically comprises the following steps: (1) 30g of methyltriethoxysilane and 10g of tetraethoxysilane are dissolved in ethanol (180g), then 50g of water is added and fully mixed, 0.5g of hydrochloric acid (12mol/L) is slowly dropped, the mixture is stirred for 0.5h, 60g of n-butyl titanate is added, the mixture is slowly stirred for 0.5h, then the mixture is aged for 12h, a product is collected and placed in a drying oven to be dried for 5h at 120 ℃, and finally the product is placed in a muffle furnace to be roasted for 3h at 450 ℃, so that the silicon-containing auxiliary agent is prepared.
(2) Fully dissolving 10g of polyvinyl imidazole and 1g of ruthenium trichloride in 100g of ethanol, stirring for 30 minutes, then adding 200g of deionized water, and continuously stirring for 1 hour to obtain a ruthenium-polyvinyl imidazole complex solution.
(3) 200g of a silicon-containing assistant was added to the ruthenium-polyvinylimidazole complex solution obtained in the step (2), and 4g of cerium oxide was added, stirred for 2 hours, and then dried at 150 ℃ for 5 hours and calcined at 450 ℃ for 3 hours to obtain a powder catalyst.
(4) Adding 20g of powder catalyst into 100g of deionized water, adding 2g of nano silica sol, 1g of sodium dodecyl sulfate and 1g of polyethylene glycol (molecular weight is 300), and performing ball milling for 2 hours to prepare slurry; the honeycomb cordierite substrate was then immersed in the slurry, and the slurry remaining in the channels was removed by ear washing, dried at 120 ℃ for 4 hours, and then calcined at 450 ℃ for 3 hours to obtain a monolithic catalyst capable of purifying CVOCs.
Example 2
This example provides a method for preparing a catalyst for purifying CVOCs, which includes the following steps: mixing and stirring a silicon-containing auxiliary agent, a ruthenium-containing polyvinyl imidazole complex and a catalytic auxiliary agent, then carrying out solid-liquid separation and first roasting to obtain a catalyst, mixing and ball-milling the catalyst, sol, the coating auxiliary agent and water to obtain a coating material, then coating the coating material on the surface of a carrier, and then drying and carrying out third roasting to obtain an integral catalyst;
the method specifically comprises the following steps: (1) 40g of methyltriethoxysilane and 10g of tetraethoxysilane are dissolved in ethanol (300g), then 80g of water is added and fully mixed, 0.8g of hydrochloric acid (12mol/L) is slowly dripped, stirring is carried out for 0.5h, 100g of n-butyl titanate is added, slow stirring is carried out for 0.5h, then aging is carried out for 12h, a product is collected and is placed in a drying oven to be dried for 5h at 120 ℃, and finally the product is placed in a muffle furnace to be roasted for 3h at 450 ℃, thus obtaining the silicon-containing auxiliary agent.
(2) Fully dissolving 10g of polyvinyl imidazole and 1g of hexaammonium chloride ruthenium trichloride in 100g of ethanol, stirring for 30 minutes, then adding 100g of deionized water, and continuously stirring for 1 hour to obtain a ruthenium-polyvinyl imidazole complex solution.
(3) And (3) adding 100g of silicon-containing auxiliary agent into the ruthenium-polyvinyl imidazole complex solution obtained in the step (2), adding 4g of copper oxide, stirring for 2 hours, drying at 150 ℃ for 5 hours, and roasting at 450 ℃ for 3 hours to obtain the powder catalyst.
(4) Adding 20g of powder catalyst into 100g of water, adding 2g of nano silica sol and 2g of sodium dodecyl sulfate, and carrying out ball milling for 2 hours to prepare slurry; the honeycomb cordierite substrate was then immersed in the slurry, and the slurry remaining in the channels was removed by ear washing, dried at 120 ℃ for 4 hours, and then calcined at 450 ℃ for 3 hours to obtain a monolithic catalyst capable of purifying CVOCs.
Example 3
This example provides a method for preparing a catalyst for purifying CVOCs, which includes the following steps: mixing and stirring a silicon-containing auxiliary agent, a ruthenium-containing polyvinyl imidazole complex and a catalytic auxiliary agent, then carrying out solid-liquid separation and first roasting to obtain the catalyst, mixing and ball-milling the catalyst, sol, the coating auxiliary agent and water to obtain a coating material, then coating the coating material on the surface of a carrier, and then drying and carrying out third roasting to obtain an integral catalyst;
the method specifically comprises the following steps: (1) 50g of methyltriethoxysilane and 15g of ethyl orthosilicate are dissolved in ethanol (300g), then 80g of water is added and fully mixed, 1g of hydrochloric acid (12mol/L) is slowly dripped, stirring is carried out for 0.5h, 120g of tetrabutyl titanate is added, stirring is carried out for 0.5h, then aging is carried out for 12h, a product is collected and is dried in an oven at 120 ℃ for 5h, and finally, the product is roasted in a muffle furnace at 450 ℃ for 3h to obtain the silicon-containing auxiliary agent.
(2) Fully dissolving 10g of polyvinyl imidazole and 2g of nitrosyl ruthenium nitrate in 100g of ethanol, stirring for 30 minutes, then adding 100g of deionized water, and continuously stirring for 1 hour to prepare the ruthenium-polyvinyl imidazole complex solution.
(3) And (3) adding 100g of silicon-containing auxiliary agent into the ruthenium-polyvinyl imidazole complex solution obtained in the step (2), adding 8g of manganese oxide, stirring for 2 hours, drying for 5 hours at 150 ℃, and roasting for 2 hours at 480 ℃ to obtain the powder catalyst.
(4) Adding 20g of powder catalyst into 100g of deionized water, adding 2g of nano silica sol and 2g of polyethylene glycol (molecular weight is 400), and performing ball milling for 2 hours to prepare slurry; and then immersing the honeycomb mullite carrier into the slurry, taking out the slurry which is blown out of the pore channels by using an aurilave, drying the slurry at the temperature of 100 ℃ for 5 hours, and then roasting the dried slurry at the temperature of 500 ℃ for 1 hour to obtain the monolithic catalyst capable of purifying the CVOCs.
Example 4
The only difference in example 1 is that the preparation of the ruthenium polyvinylimidazole complex is carried out under a carbon monoxide atmosphere.
Example 5
The only difference from example 1 is that the ruthenium polyvinylimidazole complex is not added during mixing.
Example 6
The only difference from example 1 is that the ruthenium precursor was replaced with ruthenium carbonyl.
Example 7
The only difference from example 1 is that n-butyl titanate is not added.
Example 8
The only difference from example 1 is that no silicon containing adjuvant was added during mixing.
Example 9
The only difference from example 1 is that cobalt nitrate was added during the preparation of the ruthenium polyvinylimidazole complex in an amount equivalent to the ruthenium precursor.
Application example 1
The catalysts obtained in examples 1 to 9 and the catalysts obtained in CN111135816A, example A2 and example B2 were subjected to combustion treatment of methylene chloride having a steam-water content of 7% and chlorobenzene having a steam-water content of 7%, and the treatment results are shown in tables 1 and 2, wherein Table 1 shows the treatment results of methylene chloride and Table 2 shows the treatment results of chlorobenzene.
The polyvinylimidazoles used in the above examples were those described in the literature: the preparation method of Journal-Maria, san Sinena, Jerzy, et al. effects of Axial coding of the Metal Center on the Activity of Iron Tetraphenylporphyrin as a NPrecious Catalyst for Oxygen Reduction [ J ]. Journal of Physical Chemistry C,2014,118(33), 19139-19149.
TABLE 1
| CVOCs conversion/%) | CO 2 Production rate/%) | |
| Example 1 | 99％ | 99％ |
| Example 2 | 100％ | 99％ |
| Example 3 | 100％ | 100％ |
| Example 4 | 93％ | 92％ |
| Example 5 | 64％ | 42％ |
| Example 6 | 94％ | 93％ |
| Example 7 | 71％ | 61％ |
| Example 8 | 80％ | 78％ |
| Example 9 | 84％ | 65％ |
| CN111135816A example A2 | 65％ | 63％ |
| CN111135816A example B2 | 69％ | 71％ |
TABLE 2
In the above table, the CVOCs conversion is calculated as (content of organochlorine gas in feed gas-content of organochlorine gas in post-combustion gas)/content of organochlorine gas in feed gas, CO 2 The formation rate is calculated as the carbon dioxide content in the burned gas/the content of the chlorine-containing organic gas in the feed gas. Specifically, if the application example of the present invention is specifically combustion treatment of methylene chloride containing water vapor, the CVOCs conversion rate is calculated by (content of methylene chloride in feed gas-content of methylene chloride in burned gas)/content of methylene chloride in feed gas, CO 2 The formation rate was calculated as the carbon dioxide content in the combusted gas/the methylene chloride content in the fed gas. When the water vapor-containing chlorobenzene is burned, the CVOCs conversion rate is calculated in the manner of (the chlorobenzene content in the feed gas-the chlorobenzene content in the burned gas)/the chlorobenzene content in the feed gas, and CO 2 The formation rate was calculated as carbon dioxide content in the combusted gas x 6/chlorobenzene content in the feed gas.
According to the results, the preparation method provided by the invention realizes the preparation of the high water resistance catalyst by adopting a specific preparation process, can continuously and efficiently adsorb and catalyze target compounds, and prevents the deactivation and invalidation of the catalyst; meanwhile, the preparation method provided by the invention can also inhibit the migration, aggregation and growth of noble metal ions in the high-temperature roasting process.
It is to be noted that the present invention is described by the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the detailed structural features, that is, it is not meant to imply that the present invention must be implemented by relying on the detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A preparation method of a catalyst for purifying CVOCs is characterized by comprising the following steps: mixing and stirring a silicon-containing auxiliary agent, a ruthenium-containing polyvinyl imidazole complex and a catalytic auxiliary agent, and then carrying out solid-liquid separation and first roasting to obtain the catalyst;
the silicon-containing auxiliary agent is obtained by mixing methyltriethoxysilane, ethyl orthosilicate, alcohol and water to perform a first stirring reaction, then sequentially adding acid and n-butyl titanate to perform a second stirring reaction, and then performing solid-liquid separation and second roasting.
2. The preparation method according to claim 1, wherein the mass ratio of the silicon-containing auxiliary agent to the ruthenium precursor in the ruthenium polyvinyl imidazole complex during the mixing and stirring is (50-200): 1;
preferably, the mass ratio of the catalytic promoter to the ruthenium precursor in the ruthenium polyvinyl imidazole complex in the mixing and stirring process is (3-8): 1;
preferably, the promoter comprises 1 or a combination of at least 2 of copper oxide, tricobalt tetraoxide, ceria or manganese oxide;
preferably, the mixing and stirring time is 1-3 h.
3. The method according to claim 1 or 2, wherein the first roasting temperature is 300-500 ℃;
preferably, the time of the first roasting is 2-5 h.
4. The preparation method according to any one of claims 1 to 3, wherein the mass ratio of the methyltriethoxysilane to the ethyl orthosilicate in the preparation process of the silicon-containing auxiliary agent is (3-6): 1;
preferably, the mass ratio of the alcohol to the methyl trimethoxy in the preparation process of the silicon-containing auxiliary agent is (5-10): 1;
preferably, the mass ratio of alcohol to water in the preparation process of the silicon-containing auxiliary agent is (2-5): 1;
preferably, the addition amount of acid in the preparation process of the silicon-containing auxiliary agent is 0.5-2% of the addition amount of water;
preferably, the molar concentration of the acid in the preparation process of the silicon-containing auxiliary agent is 9-12 mol/L;
preferably, the mass ratio of the n-butyl titanate to the methyltriethoxysilane in the preparation process of the silicon-containing auxiliary agent is (1-5): 1.
5. The production method according to any one of claims 1 to 4, wherein the first stirring reaction is carried out for a period of time of 0.5 to 1 hour;
preferably, the time of the second stirring reaction is 0.5 to 1 h.
6. The method according to any one of claims 1 to 5, wherein the temperature of the second roasting is 300-600 ℃;
preferably, the time of the second roasting is 2-6 h.
7. The preparation method according to any one of claims 1 to 6, wherein the ruthenium-polyvinyl imidazole complex is obtained by subjecting polyvinyl imidazole, a ruthenium precursor and a liquid phase to a third stirring reaction;
preferably, the mass ratio of the polyvinyl imidazole to the ruthenium precursor in the preparation process of the ruthenium polyvinyl imidazole complex is (5-20): 1;
preferably, the liquid phase in the preparation process of the ruthenium polyvinyl imidazole complex comprises water and alcohol in a mass ratio of (1-3) to 1;
preferably, the mass ratio of the alcohol to the polyvinyl imidazole in the preparation process of the ruthenium-polyvinyl imidazole complex is (5-10): 1;
preferably, the ruthenium precursor in the preparation process of the ruthenium polyvinyl imidazole complex comprises 1 or at least 2 of ruthenium chloride, nitrosyl ruthenium nitrate or hexaammonium ruthenium trichloride;
preferably, the time of the third stirring reaction in the preparation process of the ruthenium polyvinyl imidazole complex is 0.5-2 h.
8. The preparation method according to any one of claims 1 to 7, further comprising mixing and ball-milling the catalyst, the sol, the coating aid and water to obtain a coating material, and then coating the coating material on the surface of the carrier, followed by drying and third calcination to obtain the monolithic catalyst;
preferably, the sol comprises a nano-silica sol;
preferably, the coating aid comprises 1 or a combination of at least 2 of cetyltrimethylammonium bromide, polyethylene glycol, sodium lauryl sulfate;
preferably, the mass ratio of the catalyst to the sol is (9.5-10.5): 1;
preferably, the mass ratio of the catalyst to the coating assistant is (5-10) to 1;
preferably, the mass ratio of water to catalyst is (5-15): 1;
preferably, the ball milling time is 2-5 h;
preferably, the temperature of the drying is 120-220 ℃;
preferably, the drying time is 2-8 h;
preferably, the temperature of the third roasting is 300-500 ℃;
preferably, the time of the third roasting is 1-5 h.
9. The method of any one of claims 1 to 8, comprising the steps of: mixing and stirring a silicon-containing auxiliary agent, a ruthenium-containing polyvinyl imidazole complex and a catalytic auxiliary agent, then carrying out solid-liquid separation and first roasting to obtain a catalyst, mixing and ball-milling the catalyst, sol, the coating auxiliary agent and water to obtain a coating material, then coating the coating material on the surface of a carrier, and then drying and carrying out third roasting to obtain an integral catalyst;
the mass ratio of the silicon-containing auxiliary agent to the ruthenium precursor in the ruthenium polyvinyl imidazole complex in the mixing and stirring process is (50-200): 1; the mass ratio of the catalytic assistant to the ruthenium precursor in the ruthenium polyvinyl imidazole complex in the mixing and stirring process is (3-8) to 1; the catalytic promoter comprises 1 or the combination of at least 2 of copper oxide, cobaltosic oxide, cerium dioxide or manganese oxide; the mixing and stirring time is 1-3 h; the temperature of the first roasting is 300-; the sol comprises nano-silica sol; the coating auxiliary agent comprises 1 or at least 2 of cetyl trimethyl ammonium bromide, polyethylene glycol and lauryl sodium sulfate; the mass ratio of the catalyst to the sol is (9.5-10.5) to 1; the mass ratio of the catalyst to the coating auxiliary agent is (5-10) to 1; the mass ratio of the water to the catalyst is (5-15) to 1; the ball milling time is 2-5 h; the drying temperature is 120-220 ℃, and the drying time is 2-8 h; the temperature of the third roasting is 300-500 ℃, and the time is 1-5 h;
the silicon-containing auxiliary agent is obtained by mixing methyltriethoxysilane, ethyl orthosilicate, alcohol and water for a first stirring reaction, then sequentially adding acid and n-butyl titanate for a second stirring reaction, and then performing solid-liquid separation and second roasting; the mass ratio of the methyl triethoxysilane to the ethyl orthosilicate is (3-6) to 1; the mass ratio of the ethanol to the methyl trimethoxy is (5-10) to 1; the mass ratio of the ethanol to the water is (2-5) to 1; the addition amount of the acid is 0.5-2% of the addition amount of the water; the molar concentration of the acid is 9-12 mol/L; the mass ratio of the n-butyl titanate to the methyltriethoxysilane is (1-5) to 1; the first stirring reaction time is 0.5-1 h; the second stirring reaction time is 0.5-1 h; the temperature of the second roasting is 300-600 ℃, and the time is 2-6 h;
the ruthenium-polyvinyl imidazole complex is obtained by carrying out a third stirring reaction on polyvinyl imidazole, a ruthenium precursor and a liquid phase; the mass ratio of the polyvinyl imidazole to the ruthenium precursor is (5-20) to 1; the liquid phase comprises water and alcohol in a mass ratio of (1-3) to 1; the mass ratio of the alcohol to the polyvinyl imidazole is (5-10) to 1; the ruthenium precursor comprises 1 or at least 2 of ruthenium chloride, nitrosyl ruthenium nitrate or hexaammonium ruthenium trichloride; the time of the third stirring reaction is 0.5-2 h.
10. A catalyst for purifying CVOCs, characterized in that the catalyst is obtained by the preparation method of any one of claims 1 to 9 and is used for treating organochlorine gases with the water vapor content of more than or equal to 5 percent.
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