CN112827505A - Integral catalyst for catalyzing ozone to degrade VOCs (volatile organic compounds), and preparation and application thereof - Google Patents
Integral catalyst for catalyzing ozone to degrade VOCs (volatile organic compounds), and preparation and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 29
- 239000011248 coating agent Substances 0.000 claims abstract description 108
- 238000000576 coating method Methods 0.000 claims abstract description 108
- 239000002808 molecular sieve Substances 0.000 claims abstract description 81
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000000919 ceramic Substances 0.000 claims abstract description 60
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 39
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 18
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- 239000000243 solution Substances 0.000 claims description 62
- 238000001035 drying Methods 0.000 claims description 38
- 238000002791 soaking Methods 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 33
- 239000012298 atmosphere Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 29
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 26
- 238000007664 blowing Methods 0.000 claims description 26
- 229910017604 nitric acid Inorganic materials 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 25
- 229910044991 metal oxide Inorganic materials 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
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- 230000015556 catabolic process Effects 0.000 claims description 14
- 238000006731 degradation reaction Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 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 claims description 12
- 229910052878 cordierite Inorganic materials 0.000 claims description 11
- 238000010926 purge Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- -1 tetrapropylammonium ion Chemical class 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000012546 transfer Methods 0.000 abstract description 6
- 230000000593 degrading effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 74
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 239000000843 powder Substances 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011148 porous material Substances 0.000 description 11
- 238000004901 spalling Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 229940071125 manganese acetate Drugs 0.000 description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000006385 ozonation reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
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- 239000010815 organic waste Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
- 239000010457 zeolite Substances 0.000 description 1
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Classifications
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- 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
- B01D53/76—Gas phase processes, e.g. by using aerosols
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/104—Ozone
Abstract
The invention discloses a monolithic catalyst for degrading VOCs (volatile organic compounds) by catalyzing ozone, belongs to the technical field of catalyzing ozone to oxidize VOCs, and comprises inorganic ceramic and a molecular sieve, wherein the molecular sieve is loaded on the inorganic ceramic, and the specific surface area of the inorganic ceramic is 30-250 m2(ii)/g; the surface of the inorganic ceramic comprises micropores, and the aperture of each micropore is 5-10 microns; the specific surface area of the molecular sieve is 300-600 m2The silicon-aluminum ratio of the molecular sieve is not less than 5; and non-noble metal is loaded on the molecular sieveOxides, wherein the non-noble metal oxides account for 0.5-10% of the mass fraction of the molecular sieve; the surface of the inorganic ceramic is coated with silica sol, and an organic pore-forming agent is used in the preparation process of the catalyst; the treatment that the surface of the inorganic ceramic is coated with silica sol and an organic pore-forming agent is adopted, so that the catalytic action of active components is fully exerted, and the mass transfer efficiency and the mechanical stability of the coating are improved.
Description
Technical Field
The invention belongs to the technical field of catalyzing ozone to oxidize VOCs, and particularly relates to an integral catalyst for catalyzing ozone to degrade VOCs, and preparation and application thereof.
Background
The catalyst is one of the key concerns in the field of catalytic research as the core of the catalytic process. Although noble metal catalysts represented by Pt, Pb, Au and Ag have the advantages of low ignition temperature, high catalytic activity and difficulty in generating secondary pollutants, the noble metal catalysts have the disadvantages of high cost, poor thermal stability, easy loss in the using process and easy occurrence of catalyst poisoning phenomenon, so that the application of the noble metal catalysts in industry is greatly limited. At present, non-noble metal oxides are often used to replace noble metals so as to reduce the preparation cost of the catalyst and improve the application stability. The non-noble metal oxide catalyst mainly comprises transition metal oxides, perovskite oxides, spinel composite oxides and the like, and oxygen vacancies are provided in a transition metal valence change or lattice distortion mode and the like in the catalysis process to achieve the catalysis effect. Among them, the transition metal catalyst is widely used in industry by virtue of abundant metal species and high catalytic activity.
In a common carrier of a transition metal catalyst, a Y-type molecular sieve is paid extensive attention by virtue of a proper pore channel structure and adjustable chemical properties, and researches show that non-noble metal oxides can obtain better dispersion degree on the surface of the Y-type molecular sieve and show higher catalytic activity. However, when the metal is oxidized and loaded on the Y-type molecular sieve by adopting the traditional impregnation method, the metal oxide is often agglomerated on the surface of the carrier, which is not beneficial to the exposure of the catalytic active sites; moreover, the catalytic effect of the Y-type molecular sieve loaded with metal oxide is usually further reduced in the process of coating the Y-type molecular sieve to prepare the monolithic catalyst. In addition, the Y-type molecular sieve coating loaded with metal oxides is easy to fall off in application due to low adhesive force.
Through search, the patent name with publication number CN104190433A is a catalytic ozonation catalyst for treating volatile organic waste gas, and a preparation method and application thereof. The patent discloses a catalytic ozonation catalyst for organic waste gas treatment, which consists of a carrier and an active component, wherein the carrier is alumina, silicon oxide, zeolite or ceramic balls; the active component consists of manganese oxide and an auxiliary agent, wherein the auxiliary agent is an oxide of at least one element of iron, nickel, cobalt, chromium and vanadium.
Disclosure of Invention
Aiming at the technical problem that the stability and the mass transfer efficiency of the active component of the existing catalyst for catalyzing the ozone oxidation of VOCs are difficult to balance on a substrate, the monolithic catalyst for catalyzing the ozone degradation of VOCs is provided, and the mass transfer efficiency and the mechanical stability of a coating are improved while the catalytic action of the active component is fully exerted through silica sol and an organic pore-forming agent;
in addition, a preparation method of the monolithic catalyst for catalyzing the ozone degradation of VOCs is provided; the active component is mixed with silica sol and an organic pore-forming agent to form a coating solution, and the coating solution is coated on the surface of the modified cordierite ceramic substrate, so that the mass transfer efficiency of the active component and the mechanical stability of the coating are further improved.
The invention provides an integral catalyst for catalyzing ozone degradation of VOCs (volatile organic compounds), which comprises inorganic ceramic and a molecular sieve, wherein the molecular sieve is loaded on the inorganic ceramic, and the specific surface area of the inorganic ceramic is 30-250 m2(ii)/g; the surface of the inorganic ceramic comprises micropores, and the aperture of each micropore is 5-10 microns; the specific surface area of the molecular sieve is 300-600 m2The silicon-aluminum ratio of the molecular sieve is not less than 5; and non-noble metal oxide is loaded on the molecular sieve, and the non-noble metal oxide accounts for 0.5-10% of the mass fraction of the molecular sieve(ii) a The surface of the inorganic ceramic is coated with silica sol, and an organic pore-forming agent is used in the preparation process of the catalyst.
Preferably, the mass ratio of the inorganic ceramic to the coating is (80-98): 2-20).
Preferably, the inorganic ceramic is cordierite ceramic; and/or the molecular sieve is a Y-type molecular sieve.
Preferably, the non-noble metal oxide is one of manganese oxide, chromium oxide, cobalt oxide, copper oxide, iron oxide, cerium oxide, and nickel oxide.
Preferably, the silica sol is an acidic silica sol having an average particle diameter of 10nm to 200 nm. Compared with the common neutral silica sol, the acidic silica sol introduces more siloxy groups and silicon hydroxyl groups on the surface of the coating, and the groups can provide adsorption sites in the process of catalyzing ozone to oxidize VOCs (volatile organic chemicals), so that the groups can play a role in adsorbing reactants to promote the reaction, and can adsorb products to release metal oxide active sites, thereby solving the problem that the ozone is easy to inactivate in room-temperature catalysis.
Preferably, the pore-forming agent comprises one or more of CTAB, CTEOS, TPABr, tetrapropylammonium ion, tri-quaternary ammonium, tri-n-propylamine, di-n-propylamine. The organic pore-forming agent can effectively avoid the problems of coating blockage and active site coverage caused by the introduction of an adhesive, the organic pore-forming agent can move to the gaps among the particles and the surface of the coating due to the action of capillary force in the drying process, and a pore structure for mass transfer diffusion is still left among the coating particles after roasting, so that the coating catalyst is fully utilized. Meanwhile, the pore-forming agent on the surface of the coating can damage a silica sol layer formed by the accumulation of local excessive silica sol, so that the silica sol is prevented from completely covering active sites.
The invention relates to a preparation method of an integral catalyst for catalyzing ozone degradation of VOCs, which comprises the following preparation steps
(1) Substrate pretreatment
Taking inorganic ceramic as a matrix, and pretreating the matrix by using an alkali washing and/or acid etching and/or heat treatment mode;
(2) preparation of the catalytic component
Carrying out water vapor treatment on the Y-shaped molecular sieve, then placing the treated Y-shaped molecular sieve in an acid solution, and dropwise adding a metal oxide salt solution onto the acid-leached Y-shaped molecular sieve to load the metal oxide onto the Y-shaped molecular sieve;
(3) coating of substrates
The preparation method comprises the following steps of (1) mixing Y-type molecular sieve loaded with metal oxide, silica sol, organic pore-forming agent and deionized water according to the ratio of (0.02-0.2): (0.03-0.18): (3-50) mixing the components in the mass ratio to form a coating solution, and coating the coating solution on the pretreated substrate.
Preferably, the specific preparation steps of the matrix pretreatment are as follows:
putting the substrate in an air atmosphere, activating for 4 hours at the temperature of 350 ℃, cooling, soaking in 10-25% strong base solution for 1-10 minutes, cleaning, soaking in boiling oxidizing acid for 2-5 hours, and replacing the acid liquor every 1 hour; blowing off residual liquid, and washing the residual liquid to be neutral by using deionized water; the method increases the specific surface area of the inorganic ceramic, and generates uniform 5-10 micron macropores on the surface of the substrate for anchoring the coating. Meanwhile, a layer of silica particles with oxygen-containing functional groups is formed on the surface of cordierite corroded by strong alkali and oxidizing acid, and the particles containing rich-OH, COOH and other functional groups provide a large number of ozone adsorption sites for the oxidation process of ozone to promote the catalytic process on one hand, and are combined with silica sol particles in the coating through hydrogen bonds to strengthen the adhesive force of the coating on the other hand.
And/or the preparation of the catalytic component comprises the following specific steps:
heating a Y-type molecular sieve to 200-300 ℃ in an air atmosphere, introducing steam, raising the temperature to 650-850 ℃, keeping for 4-6 hours, then reducing the temperature to 200-400 ℃, stopping introducing the steam, and taking out a sample when the temperature is reduced to below 100 ℃ in the air atmosphere; then preparing a nitric acid solution with the concentration of 0.5-2 mol/L, and mixing the Y-type molecular sieve treated by using the water vapor and the nitric acid solution according to the solid-to-liquid ratio of 1: (8-12) putting the mixture into a three-neck flask, stirring and reacting for 4-6 h in a reflux device at the temperature of 60-100 ℃, washing the sample for 3-5 times by using water after the reaction is finished, and drying and standing; dropwise adding the metal oxide salt solution onto the acid-leached Y-shaped molecular sieve, standing for 8-14 h, drying at 80-140 ℃ for 8-16 h, and taking out; then calcining the mixture at 500-600 ℃ for 3-5 h, and taking out;
and/or the substrate is coated by the specific steps of
The preparation method comprises the following steps of (1) mixing Y-type molecular sieve loaded with metal oxide, silica sol, organic pore-forming agent and deionized water according to the ratio of (0.02-0.2): (0.03-0.18): (3-50) mixing the components in the mass ratio to form a coating solution, placing the substrate in the coating solution, soaking for 2-10 minutes, purging to remove residual liquid, and drying at the temperature of 90-130 ℃ for 1-5 hours to form a coating; soaking, blowing and drying are used as a coating period, the coating is repeated for 1-10 times to obtain the required coating amount, the average thickness of the coating is 5-50 mu m, and finally the coating is placed in an inert gas atmosphere and roasted at 500-600 ℃ for 4-8 hours.
Preferably, the acid solution for treating the Y-type molecular sieve is one of oxalic acid, citric acid and hydrochloric acid; and/or the metal oxide salt solution dripped on the Y-shaped molecular sieve after acid leaching is one or two of acetate, sulfate, nitrate and chloride solution of Mn, Cr, Co, Cu, Fe, Ce and Ni.
The invention relates to an application of an integral catalyst for catalyzing ozone to degrade VOCs, which is applied to the treatment of exhaust gas discharged in petrochemical industry, electronic industry, automobile manufacturing, pharmacy and solvent manufacturing industries.
Drawings
FIG. 1 is a statistical plot of toluene conversion for a catalytic ozonation VOCs monolith catalyst of the present invention;
FIG. 2 is a statistical plot of the selectivity of a monolithic catalyst for catalyzing the degradation of VOCs by ozone to COx in accordance with the present invention.
Detailed Description
The following detailed description of exemplary embodiments of the invention refers to the accompanying drawings, which, although described in sufficient detail to enable those skilled in the art to practice the invention, it is to be understood that other embodiments may be realized and that various changes to the invention may be made without departing from the spirit and scope of the invention. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is presented for purposes of illustration only and not limitation to describe the features and characteristics of the invention, to set forth the best mode of carrying out the invention, and to sufficiently enable one skilled in the art to practice the invention. Accordingly, the scope of the invention is to be limited only by the following claims.
The invention relates to a VOCs monolithic catalyst for catalyzing ozone degradation, which comprises inorganic ceramic and a molecular sieve, wherein the inorganic ceramic is cordierite ceramic in the embodiment, and the molecular sieve is a Y-type molecular sieve; the molecular sieve is loaded on inorganic ceramic, and the specific surface area of the inorganic ceramic is 30-250 m2(ii)/g; the surface of the inorganic ceramic comprises micropores, and the aperture of each micropore is 5-10 microns; the molecular sieve is loaded with non-noble metal oxide, the non-noble metal oxide is one of manganese oxide, chromium oxide, cobalt oxide, copper oxide, iron oxide, cerium oxide and nickel oxide, and the non-noble metal oxide accounts for 0.5-10% of the mass fraction of the molecular sieve; the surface of the inorganic ceramic is coated with silica sol, and an organic pore-forming agent is used in the preparation process of the catalyst; the mass ratio of the inorganic ceramic to the coating is (80-98): 2-20), the silica sol is acidic silica sol with the average particle size of 10-200 nm, and the pore-forming agent comprises one or more of CTAB, CTEOS, TPABr, tetrapropylammonium ion, tri-quaternary ammonium, tri-n-propylamine and di-n-propylamine.
Compared with the common neutral silica sol, the acidic silica sol introduces more siloxy groups and silicon hydroxyl groups on the surface of the coating, and the groups can provide adsorption sites in the process of catalyzing ozone to oxidize VOCs (volatile organic chemicals), so that the groups can play a role in adsorbing reactants to promote the reaction, and can adsorb products to release metal oxide active sites, thereby solving the problem that the ozone is easy to inactivate in room-temperature catalysis.
The organic pore-forming agent can effectively avoid the problems of coating blockage and active site coverage caused by the introduction of an adhesive, the organic pore-forming agent can move to the gaps among the particles and the surface of the coating due to the action of capillary force in the drying process, and a pore structure for mass transfer diffusion is still left among the coating particles after roasting, so that the coating catalyst is fully utilized. Meanwhile, the pore-forming agent on the surface of the coating can damage a silica sol layer formed by the accumulation of local excessive silica sol, so that the silica sol is prevented from completely covering active sites.
The invention relates to a preparation method of an integral catalyst for catalyzing ozone degradation of VOCs, which comprises the following preparation steps
(1) Substrate pretreatment
Taking inorganic ceramic as a matrix, and pretreating the matrix by using an alkali washing and/or acid etching and/or heat treatment mode; specifically, the method comprises the steps of heating a Y-type molecular sieve to 200-300 ℃ in an air atmosphere, introducing steam, raising the temperature to 650-850 ℃, keeping for 4-6 hours, then reducing the temperature to 200-400 ℃, stopping introducing the steam, and taking out a sample when the temperature is reduced to below 100 ℃ in the air atmosphere; then preparing a nitric acid solution with the concentration of 0.5-2 mol/L, and mixing the Y-type molecular sieve treated by using the water vapor and the nitric acid solution according to the solid-to-liquid ratio of 1: (8-12) putting the mixture into a three-neck flask, stirring and reacting for 4-6 h in a reflux device at the temperature of 60-100 ℃, washing the sample for 3-5 times by using water after the reaction is finished, and drying and standing; dropwise adding the metal oxide salt solution onto the acid-leached Y-shaped molecular sieve, standing for 8-14 h, drying at 80-140 ℃ for 8-16 h, and taking out; then calcining the mixture at 500-600 ℃ for 3-5 h, and taking out.
(2) Preparation of the catalytic component
Carrying out water vapor treatment on the Y-shaped molecular sieve, then placing the treated Y-shaped molecular sieve in an acid solution, and dropwise adding a metal oxide salt solution onto the acid-leached Y-shaped molecular sieve, wherein the metal oxide is loaded onto the Y-shaped molecular sieve; specifically, the method comprises the steps of heating a Y-type molecular sieve to 200-300 ℃ in an air atmosphere, introducing steam, raising the temperature to 650-850 ℃, keeping for 4-6 hours, then reducing the temperature to 200-400 ℃, stopping introducing the steam, and taking out a sample when the temperature is reduced to below 100 ℃ in the air atmosphere; then preparing a nitric acid solution with the concentration of 0.5-2 mol/L, and mixing the Y-type molecular sieve treated by using the water vapor and the nitric acid solution according to the solid-to-liquid ratio of 1: (8-12) putting the mixture into a three-neck flask, stirring and reacting for 4-6 h in a reflux device at the temperature of 60-100 ℃, washing the sample for 3-5 times by using water after the reaction is finished, and drying and standing; dropwise adding the metal oxide salt solution onto the acid-leached Y-shaped molecular sieve, standing for 8-14 h, drying at 80-140 ℃ for 8-16 h, and taking out; then calcining the mixture at 500-600 ℃ for 3-5 h, and taking out;
(3) coating of substrates
The preparation method comprises the following steps of (1) mixing Y-type molecular sieve loaded with metal oxide, silica sol, organic pore-forming agent and deionized water according to the ratio of (0.02-0.2): (0.03-0.18): (3-50) mixing the components in the mass ratio to form a coating solution, and coating the coating solution on the pretreated substrate. Specifically, the method comprises the following steps of mixing a Y-type molecular sieve loaded with metal oxide, silica sol, an organic pore-forming agent and deionized water according to the ratio of 1 (0.02-0.2): (0.03-0.18): (3-50), placing the substrate in the coating solution, soaking for 2-10 minutes, purging to remove residual liquid to form a coating, wherein the thickness of the coating is 3-20 microns, and drying at 90-130 ℃ for 1-5 hours; soaking, blowing and drying are taken as a coating period, the coating is repeated for 1-10 times to obtain the required coating amount, and finally the obtained product is placed in an inert gas atmosphere and roasted at 500-600 ℃ for 4-8 hours.
Example 1
Pretreatment of a carrier: a honeycomb cordierite ceramic carrier with the pore density of 600cpsi and the wall thickness of 3mil is selected, and is activated for 4 hours in an air atmosphere at 350 ℃ after being washed to remove impurities. After roasting, placing the mixture in 20% sodium hydroxide solution for soaking for 2 minutes, blowing off residual liquid, washing the residual liquid with deionized water until the residual liquid is neutral, soaking the mixture in 10% nitric acid solution, controlling the temperature of an oil bath to boil the acid liquid, changing the acid every 1 hour, carrying out acid etching for 3 hours, and washing the mixture with deionized water until the residual liquid is neutral.
Preparation of powder catalyst: heating a commercial Y-type molecular sieve to 200 ℃ in an air atmosphere; blowing high-purity nitrogen into water, heating to 100 ℃, introducing the nitrogen into a quartz tube after airflow is stable, raising the temperature to 850 ℃ and keeping the temperature for 4 hours, then reducing the temperature to 400 ℃, stopping injecting water, and reducing the temperature to below 100 ℃ in an air atmosphere to take out a sample; preparing a 1mol/L nitric acid solution, and mixing the dealuminized sample treated by the water vapor with the prepared nitric acid solution according to a solid-to-liquid ratio of 1: 10, putting the mixture into a three-neck flask, stirring the mixture in a reflux device at the temperature of 80 ℃ for reaction for 6 hours, washing the sample with water for 5 times after the reaction is finished, and drying the sample overnight; and (3) dropwise adding the completely dissolved manganese acetate solution into the sample treated in the step, so that the mass fraction of manganese in the dealuminized Y-type molecular sieve carrier is 1%. The obtained sample was allowed to stand at room temperature for 12 hours, and then dried at 110 ℃ for 12 hours and taken out. And finally, calcining the obtained sample at 500 ℃ for 3h, and taking out the sample.
Coating of a coating: mixing the prepared powder with acidic silica sol, CTAB and deionized water according to a mass ratio of 1: 0.1: 0.12: 3.78 to form a coating liquid, soaking the treated honeycomb ceramic in the coating liquid for 10 minutes, blowing for 10 seconds under the pressure of 0.1mPa of an air compressor, drying for 2 hours at 110 ℃, repeating the soaking, blowing and drying processes for 3 times, and roasting for 4 hours at 550 ℃ to form the monolithic catalyst.
The catalyst of this example was cut to specification
Length of 30mm, evaluation temperature of 30 ℃, gas ratio of [ toluene ]]＝200ppm，[O3]＝3600ppm，[O2]20 percent of the total weight of the catalyst, the balance of nitrogen and an evaluation space velocity of 100000h～1The detected toluene conversion, COx selectivity, and coating spalling rate data are shown in table 1.
Example 2
Pretreatment of a carrier: a honeycomb cordierite ceramic carrier with the pore density of 400cpsi and the wall thickness of 4mil is selected, and is activated for 4 hours in an air atmosphere at 350 ℃ after being washed to remove impurities. After roasting, placing the mixture in 20% sodium hydroxide solution for soaking for 2 minutes, blowing off residual liquid, washing the residual liquid with deionized water until the residual liquid is neutral, soaking the residual liquid in 26% nitric acid solution, controlling the temperature of an oil bath to boil the acid liquid, changing the acid every 1 hour, carrying out acid etching for 2 hours, and washing the residual liquid with deionized water until the residual liquid is neutral.
Preparation of powder catalyst: heating a commercial Y-type molecular sieve to 300 ℃ in an air atmosphere; blowing high-purity nitrogen into water, heating to 100 ℃, introducing the nitrogen into a quartz tube after airflow is stable, raising the temperature to 750 ℃, keeping the temperature for 5 hours, then reducing the temperature to 400 ℃, stopping injecting water, and reducing the temperature to below 100 ℃ in an air atmosphere to take out a sample; preparing a 1.5mol/L nitric acid solution, and mixing the dealuminized sample treated by the water vapor and the prepared nitric acid solution according to a solid-to-liquid ratio of 1: 10, putting the mixture into a three-neck flask, stirring the mixture in a reflux device at the temperature of 80 ℃ for reaction for 5 hours, washing a sample for 4 times by using water after the reaction is finished, and drying the sample overnight; and (3) dropwise adding the completely dissolved manganese acetate solution into the sample treated in the step, so that the mass fraction of manganese in the dealuminized Y-type molecular sieve carrier is 1%. The obtained sample was allowed to stand at room temperature for 12 hours, and then dried at 110 ℃ for 12 hours and taken out. And finally, calcining the obtained sample at 500 ℃ for 3h, and taking out the sample.
Coating of a coating: mixing the prepared powder with acidic silica sol, CTAB and deionized water according to a mass ratio of 1: 0.1: 0.12: 3.78 to form a coating liquid, soaking the treated honeycomb ceramic in the coating liquid for 3 minutes, blowing for 10 seconds under the pressure of 0.2mPa of an air compressor, drying for 2 hours at 110 ℃, repeating the soaking, blowing and drying processes for 4 times, and roasting for 4 hours at 500 ℃ to form the monolithic catalyst.
The catalyst of this example was cut to specification
Length of 30mm, evaluation temperature of 30 ℃, gas ratio of [ toluene ]]＝200ppm，[O3]＝3600ppm，[O2]20 percent of the total weight of the catalyst, the balance of nitrogen and an evaluation space velocity of 100000h～1The detected toluene conversion, COx selectivity, and coating spalling rate data are shown in table 1.
Example 3
Pretreatment of a carrier: a honeycomb cordierite ceramic carrier with the pore density of 600cpsi and the wall thickness of 3mil is selected, and is activated for 4 hours in an air atmosphere at 350 ℃ after being washed to remove impurities. After roasting, the mixture is placed in a 10% sodium hydroxide solution for soaking for 3 minutes, residual liquid is blown off and washed to be neutral by deionized water, the mixture is soaked in a mixed solution of 10% nitric acid and 10% perchloric acid, the temperature of an oil bath is controlled to boil acid liquor, the acid is changed every 1 hour, the acid etching is carried out for 2 hours, and the deionized water is washed to be neutral.
Preparation of powder catalyst: heating a commercial Y-type molecular sieve to 200 ℃ in an air atmosphere; blowing high-purity nitrogen into water, heating to 100 ℃, introducing the nitrogen into a quartz tube after airflow is stable, raising the temperature to 650 ℃, keeping the temperature for 4 hours, then reducing the temperature to 400 ℃, stopping injecting water, and taking out a sample after the temperature is reduced to below 100 ℃ in an air atmosphere; preparing a 2mol/L nitric acid solution, and mixing the dealuminized sample treated by the water vapor with the prepared nitric acid solution according to a solid-to-liquid ratio of 1: 10, putting the mixture into a three-neck flask, stirring the mixture in a reflux device at the temperature of 80 ℃ for reaction for 4 hours, washing the sample with water for 5 times after the reaction is finished, and drying the sample overnight; and (3) dropwise adding the completely dissolved manganese acetate solution into the sample treated in the step, so that the mass fraction of manganese in the dealuminized Y-type molecular sieve carrier is 1%. The obtained sample was allowed to stand at room temperature for 12 hours, and then dried at 110 ℃ for 12 hours and taken out. And finally, calcining the obtained sample at 550 ℃ for 4 hours and taking out the sample.
Coating of a coating: mixing the prepared powder with acidic silica sol, CTAB and deionized water according to a mass ratio of 1: 0.08: 0.12: 3.8, fully mixing and uniformly stirring to form a coating solution, soaking the treated honeycomb ceramic in the coating solution for 5 minutes, blowing for 10 seconds under the pressure of 0.1mPa of an air compressor, drying for 2 hours at 110 ℃, repeating the soaking, blowing and drying processes for 3 times, and roasting for 4 hours at 500 ℃ to form the monolithic catalyst.
The catalyst of this example was cut to specification
Length of 30mm, evaluation temperature of 30 ℃, gas ratio of [ toluene ]]＝200ppm，[O3]＝3600ppm，[O2]20 percent of the total weight of the catalyst, the balance of nitrogen and an evaluation space velocity of 100000h～1The detected toluene conversion, COx selectivity, and coating spalling rate data are shown in table 1.
Example 4
Pretreatment of a carrier: a honeycomb cordierite ceramic carrier with the pore density of 600cpsi and the wall thickness of 3mil is selected, and is activated for 4 hours in an air atmosphere at 350 ℃ after being washed to remove impurities. After roasting, placing the mixture in 20% sodium hydroxide solution for soaking for 2 minutes, blowing off residual liquid, washing the residual liquid with deionized water until the residual liquid is neutral, soaking the residual liquid in 26% nitric acid solution, controlling the temperature of an oil bath to boil the acid liquid, changing the acid every 1 hour, carrying out acid etching for 3 hours, and washing the residual liquid with deionized water until the residual liquid is neutral.
Preparation of powder catalyst: heating a commercial Y-type molecular sieve to 200 ℃ in an air atmosphere; blowing high-purity nitrogen into water, heating to 100 ℃, introducing the nitrogen into a quartz tube after airflow is stable, raising the temperature to 850 ℃ and keeping the temperature for 4 hours, then reducing the temperature to 400 ℃, stopping injecting water, and reducing the temperature to below 100 ℃ in an air atmosphere to take out a sample; preparing a 1mol/L nitric acid solution, and mixing the dealuminized sample treated by the water vapor with the prepared nitric acid solution according to a solid-to-liquid ratio of 1: 10, putting the mixture into a three-neck flask, stirring the mixture in a reflux device at the temperature of 80 ℃ for reaction for 6 hours, washing the sample with water for 5 times after the reaction is finished, and drying the sample overnight; and (3) dropwise adding the completely dissolved manganese acetate solution into the sample treated in the step, so that the mass fraction of manganese in the dealuminized Y-type molecular sieve carrier is 2%. The obtained sample was allowed to stand at room temperature for 12 hours, and then dried at 110 ℃ for 12 hours and taken out. And finally, calcining the obtained sample at 550 ℃ for 4 hours and taking out the sample.
Coating of a coating: mixing the prepared powder with acidic silica sol, CTAB and deionized water according to a mass ratio of 1: 0.1: 0.12: 3.78 to form a coating liquid, soaking the treated honeycomb ceramic in the coating liquid for 2 minutes, blowing for 10 seconds under the pressure of 0.1mPa of an air compressor, drying for 2 hours at 110 ℃, repeating the soaking, blowing and drying processes for 3 times, and roasting for 4 hours at 500 ℃ to form the monolithic catalyst.
The catalyst of this example was cut to specification
Length of 30mm, evaluation temperature of 30 ℃, gas ratio of [ toluene ]]＝200ppm，[O3]＝3600ppm，[O2]20 percent of the total weight of the catalyst, the balance of nitrogen and an evaluation space velocity of 100000h～1The detected toluene conversion, COx selectivity, and coating spalling rate data are shown in table 1.
Example 5
Pretreatment of a carrier: a honeycomb cordierite ceramic carrier with the pore density of 600cpsi and the wall thickness of 3mil is selected, and is activated for 4 hours in an air atmosphere at 350 ℃ after being washed to remove impurities. After roasting, placing the mixture in 20% sodium hydroxide solution for soaking for 2 minutes, blowing off residual liquid, washing the residual liquid with deionized water until the residual liquid is neutral, soaking the residual liquid in a mixed solution of 20% nitric acid and 5% perchloric acid, controlling the temperature of an oil bath to boil the acid liquid, changing the acid every 1 hour, carrying out acid etching for 2 hours altogether, and washing the residual liquid with deionized water until the residual liquid is neutral.
Preparation of powder catalyst: heating a commercial Y-type molecular sieve to 300 ℃ in an air atmosphere; blowing high-purity nitrogen into water, heating to 100 ℃, introducing the nitrogen into a quartz tube after airflow is stable, raising the temperature to 850 ℃ and keeping the temperature for 4 hours, then reducing the temperature to 400 ℃, stopping injecting water, and reducing the temperature to below 100 ℃ in an air atmosphere to take out a sample; preparing a 1mol/L nitric acid solution, and mixing the dealuminized sample treated by the water vapor with the prepared nitric acid solution according to a solid-to-liquid ratio of 1: 10, putting the mixture into a three-neck flask, stirring the mixture in a reflux device at the temperature of 80 ℃ for reaction for 6 hours, washing a sample for 4 times by using water after the reaction is finished, and drying the sample overnight; and (3) dropwise adding the completely dissolved manganese acetate solution into the sample treated in the step, so that the mass fraction of manganese in the dealuminized Y-type molecular sieve carrier is 5%. The obtained sample was allowed to stand at room temperature for 12 hours, and then dried at 110 ℃ for 12 hours and taken out. And finally, calcining the obtained sample at 550 ℃ for 4 hours and taking out the sample.
Coating of a coating: mixing the prepared powder with acidic silica sol, CTAB and deionized water according to a mass ratio of 1: 0.2: 0.24: 8.56 are fully mixed and stirred to form coating liquid, the treated honeycomb ceramics are soaked in the coating liquid for 5 minutes, the pressure of an air compressor is 0.25mPa to purge for 10 seconds, the honeycomb ceramics are dried for 2 hours at 110 ℃, the soaking, purging and drying processes are repeated for 6 times, and the honeycomb ceramics are roasted for 4 hours at 550 ℃ to form the monolithic catalyst.
The catalyst of this example was cut to specification
Length of 30mm, evaluation temperature of 30 ℃, gas ratio of [ toluene ]]＝200ppm，[O3]＝3600ppm，[O2]20 percent of the total weight of the catalyst, the balance of nitrogen and an evaluation space velocity of 100000h～1The detected toluene conversion, COx selectivity, and coating spalling rate data are shown in table 1.
Example 6
Pretreatment of a carrier: 10g of honeycomb cordierite ceramic carrier with the porosity of 80% and the pore diameter of 0.2-0.5 mm is selected, and is activated for 4 hours in an air atmosphere at 350 ℃ after being washed to remove impurities. After roasting, placing the mixture in 20% sodium hydroxide solution for soaking for 2 minutes, blowing off residual liquid, washing the residual liquid with deionized water until the residual liquid is neutral, soaking the residual liquid in 26% nitric acid solution, controlling the temperature of an oil bath to boil the acid liquid, changing the acid every 1 hour, carrying out acid etching for 2 hours, and washing the residual liquid with deionized water until the residual liquid is neutral.
Preparation of powder catalyst: heating a commercial Y-type molecular sieve to 200 ℃ in an air atmosphere; blowing high-purity nitrogen into water, heating to 100 ℃, introducing the nitrogen into a quartz tube after airflow is stable, raising the temperature to 850 ℃ and keeping the temperature for 4 hours, then reducing the temperature to 400 ℃, stopping injecting water, and reducing the temperature to below 100 ℃ in an air atmosphere to take out a sample; preparing a 1mol/L nitric acid solution, and mixing the dealuminized sample treated by the water vapor with the prepared nitric acid solution according to a solid-to-liquid ratio of 1: 10, putting the mixture into a three-neck flask, stirring the mixture in a reflux device at the temperature of 80 ℃ for reaction for 6 hours, washing the sample with water for 5 times after the reaction is finished, and drying the sample overnight; and (3) dropwise adding the completely dissolved manganese acetate solution into the sample treated in the step, so that the mass fraction of manganese in the dealuminized Y-type molecular sieve carrier is 1%. The obtained sample was allowed to stand at room temperature for 12 hours, and then dried at 110 ℃ for 12 hours and taken out. And finally, calcining the obtained sample at 500 ℃ for 3h, and taking out the sample.
Coating of a coating: mixing the prepared powder with acidic silica sol, CTAB and deionized water according to a mass ratio of 1: 0.2: 0.24: 8.56 are fully mixed and stirred to form coating liquid, the processed foamed ceramics are soaked in the coating liquid for 10 minutes, the pressure of an air compressor is 0.3mPa to purge for 10 seconds, the foamed ceramics are dried for 2 hours at 110 ℃, the soaking, purging and drying processes are repeated for 3 times, and the foamed ceramics are roasted for 4 hours at 550 ℃ to form the monolithic catalyst.
The catalyst of this example was cut to specification
Length of 30mm, evaluation temperature of 30 ℃, gas ratio of [ toluene ]]＝200ppm，[O3]＝3600ppm，[O2]20 percent of the total weight of the catalyst, the balance of nitrogen and an evaluation space velocity of 100000h～1The detected toluene conversion, COx selectivity, and coating spalling rate data are shown in table 1.
Comparative example 1
Pretreatment of a carrier: a honeycomb cordierite ceramic carrier with the pore density of 600cpsi and the wall thickness of 3mil is selected, and is activated for 4 hours in an air atmosphere at 350 ℃ after being washed to remove impurities.
Preparation of powder catalyst: preparing 130mL of 0.14mol/L manganese acetate solution, dispersing and dripping the solution into 100g Y type molecular sieve powder, performing ultrasonic treatment for 1 hour, standing at 25 ℃ for 4 hours, drying at 110 ℃ for 2 hours after complete diffusion, roasting at 550 ℃ for 4 hours, performing wet ball milling for 15 minutes by using ethanol as a solvent, and drying to obtain the molecular sieve powder.
Coating of a coating: mixing the prepared powder with neutral silica sol and deionized water according to a mass ratio of 1: 0.1: 3.9 are fully mixed and stirred to form coating liquid, the treated honeycomb ceramics is soaked in the coating liquid for 5 minutes, the pressure of an air compressor is 0.1mPa to purge for 10 seconds, the honeycomb ceramics is dried for 2 hours at 110 ℃, the soaking, purging and drying processes are repeated for 4 times, and the honeycomb ceramics is roasted for 4 hours at 550 ℃ to form the monolithic catalyst.
The catalyst of this comparative example was cut to specification
Length of 30mm, evaluation temperature of 30 ℃, gas ratio of [ toluene ]]＝200ppm，[O3]＝3600ppm，[O2]20 percent of the total weight of the catalyst, the balance of nitrogen and an evaluation space velocity of 100000h～1The detected toluene conversion, COx selectivity, and coating spalling rate data are shown in table 1.
Comparative example 2
Pretreatment of a carrier: a honeycomb iron-chromium-aluminum alloy carrier with the pore density of 600cpsi and the wall thickness of 3mil is selected, and is activated for 4 hours in the air atmosphere at 350 ℃ to remove impurities after being washed.
The powder catalyst preparation method and the coating application method were the same as in example 1.
The catalyst of this comparative example was cut to specification
Length of 30mm, evaluation temperature of 30 ℃, gas ratio of [ toluene ]]＝200ppm，[O3]＝3600ppm，[O2]20 percent of the total weight of the catalyst, the balance of nitrogen and an evaluation space velocity of 100000h～1The detected toluene conversion, COx selectivity, and coating spalling rate data are shown in table 1.
Comparative example 3
The carrier pretreatment and powder catalyst preparation were the same as in example 1.
Coating of a coating: mixing the prepared powder with alkaline silica sol, CTAB and deionized water according to a mass ratio of 1: 0.1: 0.12: 3.78 to form a coating liquid, soaking the treated honeycomb ceramic in the coating liquid for 10 minutes, blowing for 10 seconds under the pressure of 0.1mPa of an air compressor, drying for 2 hours at 110 ℃, repeating the soaking, blowing and drying processes for 3 times, and roasting for 4 hours at 550 ℃ to form the monolithic catalyst.
The catalyst of this comparative example was cut to specification
Length of 30mm, evaluation temperature of 30 ℃, gas ratio of [ toluene ]]＝200ppm，[O3]＝3600ppm，[O2]20 percent of the total weight of the catalyst, the balance of nitrogen and an evaluation space velocity of 100000h～1The detected toluene conversion, COx selectivity, and coating spalling rate data are shown in table 1.
Comparative example 4
The carrier pretreatment and powder catalyst preparation were the same as in example 1.
Coating of a coating: mixing the prepared powder with acidic silica sol and deionized water according to a mass ratio of 1: 0.1: 3.9 are fully mixed and stirred to form coating liquid, the treated honeycomb ceramics is soaked in the coating liquid for 10 minutes, the pressure of an air compressor is 0.1mPa to purge for 10 seconds, the honeycomb ceramics is dried for 2 hours at 110 ℃, the soaking, purging and drying processes are repeated for 3 times, and the honeycomb ceramics is roasted for 4 hours at 550 ℃ to form the monolithic catalyst.
The catalyst of this comparative example was cut to specification
Length of 30mm, evaluation temperature of 30 ℃, gas ratio of [ toluene ]]＝200ppm，[O3]＝3600ppm，[O2]20 percent of the total weight of the catalyst, the balance of nitrogen and an evaluation space velocity of 100000h～1The detected toluene conversion, COx selectivity, and coating spalling rate data are shown in table 1.
TABLE 1 comparison of catalytic Activity
| Group of | Toluene conversion rate,% | COx selectivity,% | The rate of coating peeling off% |
| Example 1 | 97.1 | 98.5 | 0.8 |
| Example 2 | 98.4 | 98.2 | 0.5 |
| Example 3 | 97.0 | 98.8 | 0.7 |
| Example 4 | 95.6 | 97.9 | 0.7 |
| Example 5 | 93.1 | 97.0 | 0.4 |
| Example 6 | 89.5 | 95.2 | 1.1 |
| Comparative example 1 | 67.4 | 52.5 | 8.2 |
| Comparative example 2 | 81.8 | 91.6 | 6.8 |
| Comparative example 3 | 77.9 | 93.1 | 1.0 |
| Comparative example 4 | 50.3 | 96.3 | 0.6 |
As can be seen from the table, the toluene conversion rate, the COx selectivity and the coating peeling rate of the examples 1 to 6 are better improved compared with the comparative examples 1 to 4.
Further, the catalyst of example 2 was used as an example to evaluate the application conditions, and the catalytic effects were measured when the toluene concentration was 30ppm, 200ppm and 500ppm, respectively, and the effects are shown in FIG. 1 and FIG. 2. Therefore, the catalyst prepared by the invention has good conversion rate and CO for catalyzing the oxidation of the ozone with low-concentration and high-concentration methylbenzene on the basis of ensuring the binding powerxSelectivity and industrial application value.
The invention has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description and drawings are to be regarded as illustrative rather than restrictive, and any such modifications and variations are intended to be included within the scope of the present invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.
More specifically, although exemplary embodiments of the invention have been described herein, the invention is not limited to these embodiments, but includes any and all embodiments modified, omitted, combined (e.g., between various embodiments), adapted and/or substituted as would be recognized by those skilled in the art from the foregoing detailed description, and which may be combined as desired. The limitations in the claims are to be interpreted broadly based the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.
Claims (10)
1. The integral catalyst for catalyzing ozone degradation of VOCs is characterized by comprising inorganic ceramic and a molecular sieve, wherein the molecular sieve is loaded on the inorganic ceramic, and the specific surface area of the inorganic ceramic is 30-250 m2(ii)/g; the surface of the inorganic ceramic comprises micropores, and the aperture of each micropore is 5-10 microns; the specific surface area of the molecular sieve is 300-600 m2The silicon-aluminum ratio of the molecular sieve is not less than 5; non-noble metal oxide is loaded on the molecular sieve, and the non-noble metal oxide accounts for 0.5-10% of the mass fraction of the molecular sieve; the surface of the inorganic ceramic is coated with silica sol.
2. The monolithic catalyst as recited in claim 1, wherein the mass ratio of the inorganic ceramic to the coating is (80-98): 2-20).
3. The monolithic catalyst for catalyzing the degradation of VOCs by ozone of claim 1, wherein the inorganic ceramic is cordierite ceramic; and/or the molecular sieve is a Y-type molecular sieve.
4. The monolithic catalyst as recited in claim 1, wherein the non-noble metal oxide is one of manganese oxide, chromium oxide, cobalt oxide, copper oxide, iron oxide, cerium oxide, and nickel oxide.
5. The monolithic catalyst for catalyzing the degradation of VOCs by ozone of claim 1, wherein the silica sol is an acidic silica sol having an average particle size of 10nm to 200 nm.
6. The preparation method of the monolithic catalyst for catalyzing ozone degradation of VOCs is characterized by comprising the following preparation steps
(1) Substrate pretreatment
Taking inorganic ceramic as a matrix, and pretreating the matrix by using an alkali washing and/or acid etching and/or heat treatment mode;
(2) preparation of the catalytic component
Carrying out water vapor treatment on the Y-shaped molecular sieve, then placing the treated Y-shaped molecular sieve in an acid solution, and dropwise adding a metal oxide salt solution onto the acid-leached Y-shaped molecular sieve to load the metal oxide onto the Y-shaped molecular sieve;
(3) coating of substrates
The preparation method comprises the following steps of (1) mixing Y-type molecular sieve loaded with metal oxide, silica sol, organic pore-forming agent and deionized water according to the ratio of (0.02-0.2): (0.03-0.18): (3-50) mixing the components in the mass ratio to form a coating solution, and coating the coating solution on the pretreated substrate.
7. The preparation method of the monolithic catalyst for catalyzing the degradation of VOCs by ozone according to claim 6,
the specific preparation steps of the matrix pretreatment are as follows:
putting the substrate in an air atmosphere, activating for 4 hours at the temperature of 350 ℃, cooling, soaking in 10-25% strong base solution for 1-10 minutes, cleaning, soaking in boiling oxidizing acid for 2-5 hours, and replacing the acid liquor every 1 hour; blowing off residual liquid, and washing the residual liquid to be neutral by using deionized water;
and/or the preparation of the catalytic component comprises the following specific steps:
heating a Y-type molecular sieve to 200-300 ℃ in an air atmosphere, introducing steam, raising the temperature to 650-850 ℃, keeping for 4-6 hours, then reducing the temperature to 200-400 ℃, stopping introducing the steam, and taking out a sample when the temperature is reduced to below 100 ℃ in the air atmosphere; then preparing a nitric acid solution with the concentration of 0.5-2 mol/L, and mixing the Y-type molecular sieve treated by using the water vapor and the nitric acid solution according to the solid-to-liquid ratio of 1: (8-12) putting the mixture into a three-neck flask, stirring and reacting for 4-6 h in a reflux device at the temperature of 60-100 ℃, washing the sample for 3-5 times by using water after the reaction is finished, and drying and standing; dropwise adding the metal oxide salt solution onto the acid-leached Y-shaped molecular sieve, standing for 8-14 h, drying at 80-140 ℃ for 8-16 h, and taking out; then calcining the mixture at 500-600 ℃ for 3-5 h, and taking out;
and/or the substrate is coated by the specific steps of
The preparation method comprises the following steps of (1) mixing Y-type molecular sieve loaded with metal oxide, silica sol, organic pore-forming agent and deionized water according to the ratio of (0.02-0.2): (0.03-0.18): (3-50) mixing the components in the mass ratio to form a coating solution, placing the substrate in the coating solution, soaking for 2-10 minutes, purging to remove residual liquid, and drying at the temperature of 90-130 ℃ for 1-5 hours to form a coating; soaking, blowing and drying are used as a coating period, the coating is repeated for 1-10 times to obtain the required coating amount, the average thickness of the coating is 5-50 mu m, and finally the coating is placed in an inert gas atmosphere and roasted at 500-600 ℃ for 4-8 hours.
8. The method of claim 6, wherein the pore-forming agent comprises one or more of CTAB, CTEOS, TPABr, tetrapropylammonium ion, tri-quaternary ammonium, tri-n-propylamine, and di-n-propylamine.
9. The method for preparing the monolithic catalyst for catalyzing ozone degradation of VOCs according to claim 6, wherein the acid solution for treating the Y-type molecular sieve is one of oxalic acid, citric acid and hydrochloric acid; and/or the metal oxide salt solution dripped on the Y-shaped molecular sieve after acid leaching is one or two of acetate, sulfate, nitrate and chloride solution of Mn, Cr, Co, Cu, Fe, Ce and Ni.
10. The application of the monolithic catalyst for catalyzing ozone degradation of VOCs is characterized in that the catalyst is the catalyst according to any one of claims 1-6, and is applied to exhaust gas treatment in petrochemical industry, electronic industry, automobile manufacturing, pharmacy and solvent manufacturing industries.
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