CN113209984A - Catalyst for treating VOCs (volatile organic compounds) through microwave-enhanced catalytic oxidation and preparation method and application thereof - Google Patents
Catalyst for treating VOCs (volatile organic compounds) through microwave-enhanced catalytic oxidation and preparation method and application thereof Download PDFInfo
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- CN113209984A CN113209984A CN202010451675.3A CN202010451675A CN113209984A CN 113209984 A CN113209984 A CN 113209984A CN 202010451675 A CN202010451675 A CN 202010451675A CN 113209984 A CN113209984 A CN 113209984A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 131
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 35
- 230000003647 oxidation Effects 0.000 title claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 25
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 12
- 229910021472 group 8 element Inorganic materials 0.000 claims abstract description 9
- 239000006255 coating slurry Substances 0.000 claims description 50
- 239000000843 powder Substances 0.000 claims description 47
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 40
- 239000002184 metal Substances 0.000 claims description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 30
- 229910052684 Cerium Inorganic materials 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical group [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 28
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 23
- 229910052746 lanthanum Inorganic materials 0.000 claims description 20
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- 229910052878 cordierite Inorganic materials 0.000 claims description 18
- 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 18
- 238000000034 method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 229910017052 cobalt Inorganic materials 0.000 claims description 15
- 239000010941 cobalt Substances 0.000 claims description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 229910052720 vanadium Inorganic materials 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- -1 alcohol amine compound Chemical class 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- 238000010304 firing Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 150000002696 manganese Chemical class 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 150000003681 vanadium Chemical class 0.000 claims description 5
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 3
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 16
- NXGASACSZHOEHS-UHFFFAOYSA-N cerium lanthanum zirconium Chemical compound [Zr].[La].[Ce] NXGASACSZHOEHS-UHFFFAOYSA-N 0.000 description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 8
- 238000003618 dip coating Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229910010271 silicon carbide Inorganic materials 0.000 description 8
- 229910001961 silver nitrate Inorganic materials 0.000 description 8
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 6
- 229910052748 manganese Inorganic materials 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 4
- 229910000428 cobalt oxide Inorganic materials 0.000 description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 229910001923 silver oxide Inorganic materials 0.000 description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 description 4
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 229910000480 nickel oxide Inorganic materials 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or rhenium
-
- 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
- B01D53/007—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 by irradiation
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/898—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with vanadium, tantalum, niobium or polonium
-
- B01J35/23—
-
- B01J35/613—
-
- B01J35/633—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0228—Coating in several steps
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/806—Microwaves
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- 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
Abstract
The invention relates to the technical field of catalysts, and discloses a catalyst for treating VOCs (volatile organic compounds) by microwave-enhanced catalytic oxidation and a preparation method and application thereof, wherein the catalyst comprises a carrier, and a binder and an active component which are loaded on the carrier, wherein the active component comprises a component A, a component B and a component C; based on the total weight of the catalyst, the content of the carrier is 75.8-84.2 wt%, the content of the binder is 10-12 wt%, the content of the component A is 1-1.2 wt%, the content of the component B is 3.8-8.2 wt%, and the content of the component C is 0.8-3 wt%; wherein the A component is selected from rare earth elements and/or group IVB elements; the component B is selected from at least one of group VB elements, group VIIB elements and group VIII elements; the C component is selected from group IB elements. The catalyst prepared by the invention has more excellent wave-absorbing and temperature-raising capability and higher VOCs removal rate.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst for treating VOCs (volatile organic compounds) through microwave-enhanced catalytic oxidation and a preparation method and application thereof.
Background
As a novel catalytic oxidation technology, the microwave-enhanced catalytic oxidation treatment technology has the advantages of high heating speed, low installed power and energy consumption, low reaction temperature, high reaction efficiency and the like compared with the traditional catalytic oxidation technology, and can effectively promote the activity of the catalyst and prolong the service life of the catalyst compared with the traditional catalytic oxidation technology. However, the catalysts used in the microwave enhanced catalytic oxidation technology are different from the catalysts used in the conventional catalytic oxidation technology. The catalyst used for the microwave-enhanced catalytic oxidation is required to have good VOCs treatment capacity, and meanwhile, the catalyst is required to have good wave absorbing capacity.
At present, the catalyst for microwave reinforcement is mainly used for achieving the purpose of heating active elements of the catalyst by adding SiC into a coating layer or adopting a SiC honeycomb carrier in the preparation process of the catalyst. However, the addition of SiC in the coating reduces the efficiency of the existing catalyst for treating VOCs, while the use of SiC honeycomb ceramics as the carrier increases microwave energy consumption.
Therefore, there is a need to provide a new catalyst for microwave-enhanced catalytic oxidation treatment of VOCs.
Disclosure of Invention
The invention aims to solve the problems of improving the wave-absorbing and temperature-raising capability of a microwave-enhanced catalyst and the treatment efficiency of VOCs, and provides a catalyst for treating VOCs by microwave-enhanced catalytic oxidation and a preparation method and application thereof. The catalyst has more excellent wave-absorbing and temperature-raising capability and higher VOCs removal rate.
In order to achieve the above object, a first aspect of the present invention provides a catalyst for microwave-enhanced catalytic oxidation treatment of VOCs, comprising a carrier, and a binder and an active component supported on the carrier, the active component comprising an a component, a B component, and a C component; based on the total weight of the catalyst, the content of the carrier is 75.8-84.2 wt%, the content of the binder is 10-12 wt%, the content of the component A is 1-1.2 wt%, the content of the component B is 3.8-8.2 wt%, and the content of the component C is 0.8-3 wt%;
wherein the A component is selected from rare earth elements and/or group IVB elements; the component B is selected from at least one of group VB elements, group VIIB elements and group VIII elements; the C component is selected from group IB elements.
In a second aspect, the present invention provides a method for preparing a catalyst for microwave-enhanced catalytic oxidation treatment of VOCs, the method comprising:
(1) mixing the binder, the metal powder corresponding to the component A and an organic solvent to obtain first coating slurry;
(2) performing first coating on a carrier by using the first coating slurry, and then performing first drying and first roasting to obtain a first carrier coated with a binder and an A component;
(3) mixing the metal salt corresponding to the component B with water to obtain second coating slurry;
(4) performing second coating on the first carrier by using the second coating slurry, and then performing second drying and second roasting to obtain a second carrier coated with a binder, an A component and a B component;
(5) mixing the metal salt corresponding to the component C with water to obtain third coating slurry;
(6) performing third coating on the second carrier by using the third coating slurry, and then performing third drying and third roasting to obtain a catalyst;
wherein the A component is selected from rare earth elements and/or group IVB elements; the component B is selected from at least one of group VB elements, group VIIB elements and group VIII elements; the C component is selected from group IB elements.
The third aspect of the present invention provides the use of the catalyst provided in the first aspect of the present invention and/or the catalyst prepared by the preparation method provided in the second aspect of the present invention in the microwave-enhanced catalytic oxidation treatment of VOCs.
By the technical scheme, the catalyst provided by the invention has more excellent wave-absorbing and temperature-raising capability by adjusting the formula and the preparation method of the active component; the catalyst is applied to the treatment of VOCs by microwave-enhanced catalytic oxidation, and the removal rate of VOCs is higher.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a catalyst for treating VOCs (volatile organic compounds) by microwave-enhanced catalytic oxidation, which comprises a carrier, a binder and active components, wherein the binder and the active components are loaded on the carrier; based on the total weight of the catalyst, the content of the carrier is 75.8-84.2 wt%, the content of the binder is 10-12 wt%, the content of the component A is 1-1.2 wt%, the content of the component B is 3.8-8.2 wt%, and the content of the component C is 0.8-3 wt%;
wherein the A component is selected from rare earth elements and/or group IVB elements; the component B is selected from at least one of group VB elements, group VIIB elements and group VIII elements; the C component is selected from group IB elements.
Preferably, the rare earth element is cerium and/or lanthanum, the group IVB element is zirconium, the group VB element is vanadium, the group VIIB element is manganese, the group VIII element is at least one selected from iron, cobalt and nickel, and the group IB element is silver and/or copper.
Preferably, in the component A, the weight ratio of cerium to zirconium to lanthanum is 6: (1-3): (0-3).
Preferably, in the component B, the weight ratio of cobalt, manganese, iron, vanadium and nickel is 1: (0-1): 1: 1: (0-1).
In the present invention, the active component in the catalyst is present in the form of a metal oxide.
Preferably, the support has a CPSI value of 200-400, where "CPSI" represents the number of channels per square inch of cross-section, i.e., the pore density.
According to the present invention, the selection of the carrier is not particularly limited, and includes, for example, but not limited to, a honeycomb carrier, preferably, the carrier is selected from a mica honeycomb carrier, a cordierite honeycomb carrier or a quartz honeycomb carrier.
According to the present invention, the binder contains alumina, the selection range of the alumina is wide, and preferably, the alumina is at least one selected from alpha-alumina, beta-alumina and gamma-alumina having an average particle diameter of 50 to 60 nm.
Preferably, the catalyst has a dielectric constant of 4 to 4.7 and a loss tangent of 0.01 to 0.15; more preferably, the catalyst has a dielectric constant of 4.44 to 4.55 and a loss tangent of 0.07 to 0.13 at 150 ℃. The catalyst provided by the invention has larger loss tangent, so that the catalyst has more excellent wave-absorbing and temperature-raising capability.
Preferably, the specific surface area of the catalyst is 16-20m2Per g, pore volume of 0.04-0.2cm3(iv)/g, the average particle diameter is 8-12 nm.
In a second aspect, the present invention provides a method for preparing a catalyst for microwave-enhanced catalytic oxidation treatment of VOCs, the method comprising:
(1) mixing the binder, the metal powder corresponding to the component A and an organic solvent to obtain first coating slurry;
(2) performing first coating on a carrier by using the first coating slurry, and then performing first drying and first roasting to obtain a first carrier coated with a binder and an A component;
(3) mixing the metal salt corresponding to the component B with water to obtain second coating slurry;
(4) performing second coating on the first carrier by using the second coating slurry, and then performing second drying and second roasting to obtain a second carrier coated with a binder, an A component and a B component;
(5) mixing the metal salt corresponding to the component C with water to obtain third coating slurry;
(6) performing third coating on the second carrier by using the third coating slurry, and then performing third drying and third roasting to obtain a catalyst;
wherein the A component is selected from rare earth elements and/or group IVB elements; the component B is selected from at least one of group VB elements, group VIIB elements and group VIII elements; the C component is selected from group IB elements.
In the present invention, the metal powder corresponding to the component a means that the metal element represented by the component a is provided in the form of a metal simple substance, such as rare earth metal powder, metal powder of group IVB element, and provides the component a for the finally obtained catalyst. The metal salt corresponding to the component B means that the metal element represented by the component B is provided in the form of metal salt, such as salt containing VB group element, VIIB group element and VIII group element, and the component B is provided for the finally obtained catalyst. The metal salt corresponding to the C component means that the metal element represented by the C component is provided in the form of a metal salt, such as a group IB element-containing salt, which provides the C component for the finally obtained catalyst.
According to the present invention, the selection range of the elements is wide, preferably, the rare earth element is cerium and/or lanthanum, the group IVB element is zirconium, the group VB element is vanadium, the group VIIB element is manganese, the group VIII element is at least one selected from iron, cobalt and nickel, and the group IB element is silver and/or copper.
According to the present invention, in step (1), in the first coating slurry, the content of the binder is 16.39 to 19.61 wt%, and the total content of the metal powders corresponding to the a component is 1.64 to 1.96 wt%.
Preferably, in the metal powder corresponding to the component A, the average particle size of cerium powder, zirconium powder or lanthanum powder is 50-60 nm.
Preferably, in the metal powder corresponding to the component a, the ratio of the cerium powder, the zirconium powder and the lanthanum powder is 6: (1-3): (0-3).
In the present invention, the binder contains alumina, the selection range of the alumina is wide, preferably, the alumina is selected from at least one of α -alumina, β -alumina and γ -alumina having an average particle diameter of 50 to 60nm, and more preferably, γ -alumina.
In the invention, the organic solvent is obtained by mixing organic acid, alcohol amine compound and water, wherein the concentration of the organic acid in the organic solvent is 2.5-4.5mol/L, and the concentration of the alcohol amine compound is 3.5-5 mol/L.
The organic acid is selected from a wide range, for example, but not limited to, dicarboxylic acids or tricarboxylic acids, and preferably, the organic acid is at least one selected from the group consisting of citric acid, oxalic acid, acetic acid, nitric acid, and sulfuric acid.
The selection range of the alcohol amine compound is wide, and preferably, the alcohol amine compound is at least one selected from ethanolamine, diethanolamine and triethanolamine.
According to the present invention, in the step (3), the total content of the metal salts corresponding to the B component in terms of metal oxide in the second coating slurry is 10 to 25% by weight.
Preferably, in the metal salts corresponding to the component B, the dosage ratio of cobalt salt, manganese salt, iron salt, vanadium salt and nickel salt is 1: (0-1): 1: 1: (0-1).
In the present invention, the cobalt salt, manganese salt, iron salt, vanadium salt or nickel salt is selected from a wide range, and preferably, the cobalt salt, manganese salt, iron salt or nickel salt is selected from at least one of nitrate, acetate and sulfate of the corresponding metal, and more preferably, cobalt nitrate, manganese nitrate, iron nitrate and nickel nitrate; the vanadium salt is selected from ammonium metavanadate.
According to the present invention, in the step (5), the total content of the metal salts corresponding to the C component in the third coating slurry is 1.5 to 10% by weight in terms of metal oxide.
In the present invention, the selection range of the copper salt or the silver salt is wide, preferably, the copper salt is selected from at least one of copper nitrate, copper acetate and copper sulfate, and more preferably, the copper nitrate; the silver salt is selected from at least one of silver nitrate, silver acetate and silver sulfate, more preferably silver nitrate.
According to the present invention, in the steps (2), (4) and (6), the drying manner is not particularly limited, and a drying manner conventional in the art may be adopted, and drying is preferable.
Preferably, the conditions of the first drying, the second drying and the third drying include: the temperature is 100-150 ℃, and the time is 2-3 h;
preferably, the conditions of the first firing, the second firing and the third firing include: the temperature is 500-550 ℃, and the time is 2-3 h.
Preferably, the first coating, the second coating and the third coating are each independently selected from the group consisting of dip coating, brush coating, spray coating, electrocoat coating and co-precipitation coating, more preferably dip coating.
According to the invention, before coating the support, the method further comprises a pre-treatment of the support, said pre-treatment comprising:
soaking the carrier in acid liquor, and then carrying out fourth drying; then the dried carrier is soaked in alkali liquor, and then is dried in a fifth way.
Preferably, the pH value of the acid solution is 3-4; the pH value of the alkali liquor is 8-10.
In the invention, the selection range of the acid solution and the alkali solution is wide, for example, the acid solution is a nitric acid solution, a hydrochloric acid solution and the like; the alkali liquor is sodium hydroxide solution, potassium hydroxide solution, etc.
Preferably, the fourth drying adopts natural airing or air blowing, and the time is 2-5 h.
Preferably, the fifth drying condition includes: the temperature is 100 ℃ and 150 ℃, and the time is 2-3 h.
In order to clearly describe the method for preparing the catalyst of the present invention, a preferred embodiment is provided below for illustration:
(1) soaking a carrier with the CPSI value of 200-400 in acid liquor with the pH value of 3-4 for 1h, blowing the carrier with compressed air for 2-5h, then soaking the carrier in alkali liquor with the pH value of 8-10 for 1h, and then drying the carrier at the temperature of 100-150 ℃ for 2-3h for later use;
(2) mixing gamma-alumina and metal powder corresponding to component A with an organic solvent to obtain first coating slurry (the content of the gamma-alumina is 16.39-19.61 wt%, and the total content of the metal powder corresponding to component A is 1.64-1.96 wt%), wherein in the metal powder corresponding to component A, the dosage ratio of cerium powder, zirconium powder and lanthanum powder is 6: (1-3): (0-3);
(3) placing the carrier treated in the step (1) in first coating slurry for dip coating for 1h, drying at 100-150 ℃ for 2-3h, and roasting at 500-550 ℃ for 2-3h to obtain a first carrier coated with gamma-alumina and the component A;
(4) and (2) mixing the metal salt corresponding to the component B with water to obtain second coating slurry (the total content of the metal salt corresponding to the component B calculated by metal oxides is 10-25 wt%), wherein the dosage ratio of cobalt salt, manganese salt, ferric salt, vanadium salt and nickel salt in the metal salt corresponding to the component B is 1: (0-1): 1: 1: (0-1);
(5) placing the first carrier obtained in the step (3) in second coating slurry for dip coating for 2h, drying at 100-150 ℃ for 2-3h, and roasting at 500-550 ℃ for 2-3h to obtain a second carrier coated with gamma-alumina, the component A and the component B;
(6) mixing the metal salt corresponding to the component C with water to obtain third coating slurry (the total content of the metal salt corresponding to the component C is 1.5-10 wt% calculated by metal oxide), wherein the metal salt corresponding to the component C is silver salt and/or copper salt;
(7) and (4) placing the second carrier obtained in the step (5) in the third coating slurry for dip coating for 1h, drying at the temperature of 100 ℃ and 150 ℃ for 2-3h, and roasting at the temperature of 500 ℃ and 550 ℃ for 2-3h to obtain the catalyst.
The third aspect of the present invention provides the use of the catalyst provided in the first aspect of the present invention and/or the catalyst prepared by the preparation method provided in the second aspect of the present invention in the microwave-enhanced catalytic oxidation treatment of VOCs.
Preferably, the conditions of the microwave-enhanced catalytic oxidation treatment include: the frequency of the microwave is 915MHz or 2450 MHz; the reaction temperature is 150-450 ℃; space velocity of 2000-20000h-1。
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available without specific description.
Cordierite honeycomb carrier: purchased from China petrochemical catalyst Shanghai division;
gamma-alumina: purchased from alatin;
cerium powder, zirconium powder, lanthanum powder: purchased from alatin;
cobalt nitrate, manganese nitrate, ferric nitrate, ammonium metavanadate, nickel nitrate, silver nitrate, copper nitrate: purchased from alatin;
citric acid, ethanolamine: from alatin.
In the following examples, the specific surface area of the catalyst was measured using a specific surface area measuring instrument; measuring the aperture of the catalyst by adopting a nitrogen physical adsorption instrument; measuring the average particle size of the catalyst by adopting a transmission electron microscope; and measuring the content of each component in the catalyst by adopting atomic fluorescence emission spectroscopy.
Example 1
This example serves to illustrate the preparation of the catalyst of the invention.
(1) Soaking a cordierite honeycomb carrier with a CPSI value of 400 in a nitric acid solution with a pH value of 3 for 1h, purging with compressed air for 2h, then soaking in a sodium hydroxide solution with a pH value of 10 for 1h, purging with compressed air for 2h, and then drying at 100 ℃ for 2h for later use;
(2) mixing gamma-alumina with the average particle size of 50nm, cerium-zirconium-lanthanum powder with the average particle size of 60nm (the dosage ratio of the cerium powder to the zirconium powder is 1: 0.5: 0.5) and an organic solvent (the concentration of citric acid is 3mol/L and the concentration of ethanolamine is 4mol/L) to obtain first coating slurry, wherein the content of the gamma-alumina is 19.61 wt%, and the total content of the cerium-zirconium-lanthanum powder is 1.96 wt%;
(3) placing the cordierite honeycomb carrier treated in the step (1) into first coating slurry for dip coating for 1h, drying for 2h at 100 ℃, and roasting for 2h at 500 ℃ to obtain the cordierite honeycomb carrier coated with gamma-alumina and cerium-zirconium-lanthanum;
(4) cobalt nitrate, manganese nitrate, ferric nitrate, ammonium metavanadate and nickel nitrate are mixed according to the dosage ratio of 1: 1: 1: 1: 1 with water to obtain a second coating slurry in which the total content of cobalt nitrate, manganese nitrate, iron nitrate, ammonium metavanadate and nickel nitrate in terms of metal oxides (cobalt oxide, manganese oxide, iron oxide, vanadium oxide and nickel oxide) is 15% by weight;
(5) placing the cordierite honeycomb carrier coated with the gamma-alumina and the cerium-zirconium-lanthanum in the step (3) into second coating slurry for dip coating for 2h, drying for 2h at 150 ℃, and roasting for 3h at 550 ℃ to obtain the cordierite honeycomb carrier coated with the gamma-alumina, the cerium-zirconium-lanthanum, the cobalt, the manganese, the iron, the vanadium and the nickel;
(6) mixing silver nitrate with water to obtain a third coating slurry, wherein the content of silver nitrate calculated by silver oxide is 10 wt%;
(7) and (3) placing the cordierite honeycomb carrier coated with the gamma-alumina, the cerium-zirconium-lanthanum, the cobalt, the manganese, the iron, the vanadium and the nickel obtained in the step (5) into third coating slurry for dip coating for 1h, drying for 2h at the temperature of 150 ℃, and roasting for 3h at the temperature of 550 ℃ to obtain the catalyst.
The resulting catalyst had a cordierite honeycomb carrier content of 80 wt%, based on the total weight of the catalyst; the content of gamma-alumina was 12% by weight; the content of cerium was 0.6% by weight; the content of zirconium was 0.3 wt%; the lanthanum content was 0.3 wt%; the cobalt content was 0.76 wt%; the manganese content was 0.76 wt%; the iron content was 0.76 wt%; the vanadium content was 0.76 wt%; the nickel content was 0.76 wt%; the silver content was 3 wt%.
The resulting catalyst had a specific surface area of 18m2Per g, pore volume of 0.18cm3(iv)/g, average particle diameter is 10 nm.
Example 2
This example serves to illustrate the preparation of the catalyst of the invention.
A catalyst was prepared in the same manner as in example 1, except that:
in the step (2), the average particle size of the gamma-alumina is 60nm, the average particle size of the cerium-zirconium-lanthanum powder (the using amount ratio of the cerium powder to the zirconium powder is 1.5: 0.25: 0.25) is 50nm, the content of the gamma-alumina in the first coating slurry is 16.39 wt%, and the total content of the cerium-zirconium-lanthanum powder is 1.64 wt%;
in the step (4), the total content of cobalt nitrate, manganese nitrate, iron nitrate, ammonium metavanadate and nickel nitrate in the second coating slurry is 25% by weight in terms of metal oxides (cobalt oxide, manganese oxide, iron oxide, vanadium oxide and nickel oxide);
in the step (6), the content of silver nitrate in terms of silver oxide in the third coating slurry was 1.5% by weight.
The resulting catalyst had a cordierite honeycomb carrier content of 80 wt%, based on the total weight of the catalyst; the content of gamma-alumina was 10% by weight; the content of cerium was 0.75 wt%; the zirconium content was 0.125 wt%; the lanthanum content was 0.125 wt%; the cobalt content was 1.64 wt%; the manganese content was 1.64 wt%; the iron content was 1.64 wt%; the vanadium content was 1.64 wt%; the nickel content was 1.64 wt%; the silver content was 0.8 wt%.
The resulting catalyst had a specific surface area of 16m2Per g, pore volume of 0.17cm3(iv)/g, average particle diameter 9 nm.
Example 3
This example serves to illustrate the preparation of the catalyst of the invention.
A catalyst was prepared in the same manner as in example 1, except that:
in the step (2), the average particle size of the gamma-alumina is 60nm, the average particle size of the cerium-zirconium-lanthanum powder (the using amount ratio of the cerium powder to the zirconium powder is 1.5: 0.25: 0.25) is 50nm, the content of the gamma-alumina in the first coating slurry is 16.39 wt%, and the total content of the cerium-zirconium-lanthanum powder is 1.64 wt%;
in the step (4), the total content of cobalt nitrate, manganese nitrate, iron nitrate, ammonium metavanadate and nickel nitrate in the second coating slurry is 10% by weight in terms of metal oxides (cobalt oxide, manganese oxide, iron oxide, vanadium oxide and nickel oxide);
in the step (6), the content of silver nitrate in terms of silver oxide in the third coating slurry was 3% by weight.
The resulting catalyst had a cordierite honeycomb carrier content of 80 wt%, based on the total weight of the catalyst; the content of gamma-alumina was 10% by weight; the content of cerium was 0.75 wt%; the zirconium content was 0.125 wt%; the lanthanum content was 0.125 wt%; the cobalt content was 1.4 wt%; the manganese content was 1.4 wt%; the iron content was 1.4 wt%; the vanadium content was 1.4 wt%; the nickel content was 1.4 wt%; the silver content was 2 wt%.
The resulting catalyst had a specific surface area of 16m2Per g, pore volume of 0.17cm3(iv)/g, average particle diameter 9 nm.
Example 4
This example serves to illustrate the preparation of the catalyst of the invention.
A catalyst was prepared in the same manner as in example 1, except that:
in the step (6), copper nitrate was mixed with water to obtain a third coating slurry in which the content of copper nitrate was 10% by weight in terms of copper oxide.
The resulting catalyst had a cordierite honeycomb carrier content of 80 wt%, based on the total weight of the catalyst; the content of gamma-alumina was 12% by weight; the content of cerium was 0.6% by weight; the content of zirconium was 0.3 wt%; the lanthanum content was 0.3 wt%; the cobalt content was 0.76 wt%; the manganese content was 0.76 wt%; the iron content was 0.76 wt%; the vanadium content was 0.76 wt%; the nickel content was 0.76 wt%; the copper content was 3 wt%.
The resulting catalyst had a specific surface area of 18m2Per g, pore volume of 0.1cm3(ii)/g, average particle diameter 11 nm.
Example 5
This example serves to illustrate the preparation of the catalyst of the invention.
A catalyst was prepared in the same manner as in example 2, except that:
in the step (6), copper nitrate was mixed with water to obtain a third coating slurry in which the content of copper nitrate was 1.5% by weight in terms of copper oxide.
The resulting catalyst had a cordierite honeycomb carrier content of 80 wt%, based on the total weight of the catalyst; the content of gamma-alumina was 10% by weight; the content of cerium was 0.75 wt%; the zirconium content was 0.125 wt%; the lanthanum content was 0.125 wt%; the cobalt content was 1.64 wt%; the manganese content was 1.64 wt%; the iron content was 1.64 wt%; the vanadium content was 1.64 wt%; the nickel content was 1.64 wt%; the copper content was 0.8 wt%.
The resulting catalyst had a specific surface area of 16m2Per g, pore volume of 0.12cm3(iv)/g, average particle diameter 12 nm.
Example 6
This example serves to illustrate the preparation of the catalyst of the invention.
A catalyst was prepared in the same manner as in example 3, except that:
in the step (6), copper nitrate was mixed with water to obtain a third coating slurry in which the content of copper nitrate was 3% by weight in terms of copper oxide.
The resulting catalyst had a cordierite honeycomb carrier content of 80 wt%, based on the total weight of the catalyst; the content of gamma-alumina was 10% by weight; the content of cerium was 0.75 wt%; the zirconium content was 0.125 wt%; the lanthanum content was 0.125 wt%; the cobalt content was 1.4 wt%; the manganese content was 1.4 wt%; the iron content was 1.4 wt%; the vanadium content was 1.4 wt%; the nickel content was 1.4 wt%; the copper content was 2 wt.%.
The resulting catalyst had a specific surface area of 16m2Per g, pore volume of 0.11cm3(iv)/g, average particle diameter 12 nm.
Example 7
This example serves to illustrate the preparation of the catalyst of the invention.
A catalyst was prepared in the same manner as in example 1, except that:
in the step (2), cerium-zirconium-lanthanum powder (the dosage ratio of cerium powder to zirconium powder is 1: 0.5: 0.5) is replaced by cerium-zirconium powder (the mass ratio of cerium powder to zirconium powder is 1.5: 0.5);
in the step (4), cobalt nitrate, ferric nitrate and ammonium metavanadate are mixed according to the dosage ratio of 1: 1: 1 with water to obtain a second coating slurry in which the total content of cobalt nitrate, iron nitrate and ammonium metavanadate is 12% by weight in terms of metal oxides (cobalt oxide, iron oxide and vanadium oxide);
in the step (6), the content of silver nitrate in terms of silver oxide in the third coating slurry was 1.6% by weight.
The resulting catalyst had a cordierite honeycomb carrier content of 80 wt%, based on the total weight of the catalyst; the content of gamma-alumina was 12% by weight; the content of cerium was 0.9 wt%; the content of zirconium was 0.3 wt%; the cobalt content was 2 wt%; the iron content was 2 wt%; the vanadium content was 2 wt%; the silver content was 0.8 wt%.
The resulting catalyst had a specific surface area of 20m2Per g, pore volume of 0.11cm3(iv)/g, average particle diameter 9 nm.
Comparative example 1
A catalyst was prepared in a similar manner to example 1, except that step (4) was omitted and silicon carbide was added in step (2), specifically:
mixing gamma-alumina with an average particle size of 50nm, cerium lanthanum powder with an average particle size of 60nm (the using amount ratio of the cerium powder to the lanthanum powder is 1: 0.25), silicon carbide powder and an organic solvent (the concentration of citric acid is 3mol/L and the concentration of ethanolamine is 4mol/L) to obtain first coating slurry, wherein the content of the gamma-alumina is 18.6 wt%, and the total content of the cerium lanthanum powder is 1.25 wt%; the content of silicon carbide was 1.57% by weight.
The resulting catalyst had a cordierite honeycomb carrier content of 78.5 wt%, based on the total weight of the catalyst; the content of gamma-alumina was 17.8 wt%; the content of cerium was 0.96% by weight; the lanthanum content was 0.24 wt%; the content of silicon carbide was 1.5% by weight; the silver content was 1 wt%.
The resulting catalyst had a specific surface area of 14m2Per g, pore volume of 0.2cm3(iv)/g, average particle diameter is 14 nm.
Comparative example 2
A catalyst was prepared in a similar manner to example 1, except that step (4) was omitted, and in step (2), cerium-zirconium-lanthanum powder (cerium powder, zirconium powder and lanthanum powder in a use ratio of 1: 0.5: 0.5) was replaced with cerium-zirconium powder (cerium powder and zirconium powder in a mass ratio of 1: 0.25), to give a first coating slurry having a content of γ -alumina of 20.6 wt% and a total content of cerium-zirconium powder of 1.47 wt%;
in the step (6), copper nitrate was mixed with water to obtain a third coating slurry in which the content of copper nitrate was 7% by weight in terms of copper oxide.
The resulting catalyst had a cordierite honeycomb carrier content of 80 wt%, based on the total weight of the catalyst; the content of gamma-alumina was 14% by weight; the content of cerium was 0.8 wt%; the content of zirconium was 0.2 wt%; the copper content was 5 wt%.
The resulting catalyst had a specific surface area of 24m2Per g, pore volume of 0.18cm3(ii)/g, average particle diameter 13 nm.
Test example
The catalyst obtained in the above example was placed in a microwave reactor, microwaves were generated using a microwave source of 3kW, 2450MHz, and the microwaves were fed into the microwave reactor. The inlet of the reactor is filled with simulated gas (comprising 1000 mg/m)3Butane, 1000mg/m3Pentane, 1000mg/m3Hexane) with a volume space velocity of 10000h-1The gas inlet temperature was normal temperature (25 ℃ C.), and the gas inflow was 10m3And h, the dosage of the catalyst is 1L, and relevant performance tests are carried out.
The surface temperature of the catalyst was measured by a thermocouple, the dielectric constant and loss tangent of the catalyst were measured by a dielectric constant analysis tester, and the skin depth of the catalyst was measured by a microwave penetration depth tester, and the results are shown in table 1.
TABLE 1
Note: t is50Surface temperature, T, of the catalyst representing a VOCs removal rate of 50%90Represents the catalyst surface temperature at which the removal rate of VOCs was 90%.
Skin depth refers to the depth of penetration of a material by microwaves of a certain frequency.
As can be seen from Table 1, the catalyst prepared according to the present invention has a better temperature rise rate, T, than the prior art50And T90The catalyst prepared by the method has better effect of absorbing microwaves and more excellent wave-absorbing and temperature-raising capability.
Testing the surface temperature of the catalyst by a thermocouple, starting microwaves to maintain the surface temperature of the catalyst at 250 ℃, and testing the removal rate (eta) of VOCs according to the following formula:
η＝(Cin-Cout)/Cin×100％，
wherein the content of the first and second substances,
eta represents the removal rate of VOCs, and the unit is%;
Cinthe concentration of the mixed gas at the inlet of the reactor is expressed in mg/m3；
CoutThe concentration of the mixed gas at the outlet of the reactor is expressed in mg/m3；
The concentrations of the mixed gas at the inlet and outlet of the reactor were measured using a FID portable analyzer, and the results are shown in Table 2.
Meanwhile, 1L of the catalyst was placed in an electric heating furnace of 5kW, the surface temperature of the catalyst was measured by a thermocouple, the catalyst was heated while maintaining the surface temperature at 250 ℃, and then normal temperature gas was introduced, the gas flow rate and concentration were the same as those under the microwave heating condition, and the removal rate (η) of VOCs was measured, and the results are shown in Table 2.
TABLE 2
As can be seen from table 2, the removal rate of VOCs of the catalyst prepared in accordance with the present invention under microwave heating was significantly superior to that of the catalyst of comparative example 1 in which silicon carbide was added and the conventional catalyst of comparative example 2.
Moreover, as can be seen from table 2, at the same reaction temperature, the catalyst prepared by the present invention generally has higher efficiency under microwave heating than that under conventional heating, which indicates that the interaction between the microwave and the catalyst is significant, the number of times of effective collisions between the catalyst and VOCs molecules under microwave radiation is increased, and the apparent activation energy required for the reaction is further reduced, thereby significantly increasing the reaction efficiency of the catalysts prepared in examples 1 to 7 under microwave heating, and making the catalysts of the present invention more suitable for microwave-enhanced catalytic oxidation processes. Whereas comparative examples 1 and 2 show no significant comparative change in the removal rate of VOCs under conventional heating and microwave heating.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (15)
1. The catalyst for treating VOCs by microwave-enhanced catalytic oxidation is characterized by comprising a carrier, a binder and active components, wherein the binder and the active components are loaded on the carrier, and the active components comprise an A component, a B component and a C component; based on the total weight of the catalyst, the content of the carrier is 75.8-84.2 wt%, the content of the binder is 10-12 wt%, the content of the component A is 1-1.2 wt%, the content of the component B is 3.8-8.2 wt%, and the content of the component C is 0.8-3 wt%;
wherein the A component is selected from rare earth elements and/or group IVB elements; the component B is selected from at least one of group VB elements, group VIIB elements and group VIII elements; the C component is selected from group IB elements.
2. The catalyst of claim 1, wherein the rare earth element is cerium and/or lanthanum, the group IVB element is zirconium;
preferably, the group VB element is vanadium, the group VIIB element is manganese, and the group VIII element is at least one selected from iron, cobalt and nickel;
preferably, the group IB element is silver and/or copper.
3. The catalyst of claim 2, wherein the weight ratio of cerium, zirconium and lanthanum in component a is 6: (1-3): (0-3);
preferably, in the component B, the weight ratio of cobalt, manganese, iron, vanadium and nickel is 1: (0-1): 1: 1: (0-1).
4. The catalyst according to any one of claims 1-3, wherein the support has a CPSI value of 200-400, preferably the support is selected from a mica honeycomb support, a cordierite honeycomb support or a quartz honeycomb support;
preferably, the binder contains alumina selected from at least one of alpha-alumina, beta-alumina and gamma-alumina, more preferably gamma-alumina.
5. The catalyst of any one of claims 1-4, wherein the catalyst has a dielectric constant of 4-4.7, a loss tangent of 0.01-0.15; preferably, the catalyst has a dielectric constant of 4.44 to 4.55 and a loss tangent of 0.07 to 0.13 at 150 ℃;
preferably, the specific surface area of the catalyst is 16-20m2Per g, pore volume of 0.04-0.2cm3(iv)/g, the average particle diameter is 8-12 nm.
6. A preparation method of a catalyst for treating VOCs by microwave-enhanced catalytic oxidation is characterized by comprising the following steps:
(1) mixing the binder, the metal powder corresponding to the component A and an organic solvent to obtain first coating slurry;
(2) performing first coating on a carrier by using the first coating slurry, and then performing first drying and first roasting to obtain a first carrier coated with a binder and an A component;
(3) mixing the metal salt corresponding to the component B with water to obtain second coating slurry;
(4) performing second coating on the first carrier by using the second coating slurry, and then performing second drying and second roasting to obtain a second carrier coated with a binder, an A component and a B component;
(5) mixing the metal salt corresponding to the component C with water to obtain third coating slurry;
(6) performing third coating on the second carrier by using the third coating slurry, and then performing third drying and third roasting to obtain a catalyst;
wherein the A component is selected from rare earth elements and/or group IVB elements; the component B is selected from at least one of elements in VB group, elements in VIIB group and elements in VIII group; the C component is selected from group IB elements.
7. The method of claim 6, wherein the rare earth element is cerium and/or lanthanum, and the group IVB element is zirconium;
the VB group element is vanadium, the VIIB group element is manganese, and the VIII group element is at least one selected from iron, cobalt and nickel;
the group IB element is silver and/or copper.
8. The method according to claim 7, wherein in step (1), in the first coating slurry, the content of the binder is 16.39-19.61 wt%, and the total content of the metal powders corresponding to the A component is 1.64-1.96 wt%;
preferably, in the metal powder corresponding to the component a, the ratio of the cerium powder, the zirconium powder and the lanthanum powder is 6: (1-3): (0-3);
preferably, the binder contains alumina selected from at least one of alpha-alumina, beta-alumina and gamma-alumina, more preferably gamma-alumina;
preferably, the organic solvent comprises an organic acid and an alcohol amine compound, the concentration of the organic acid is 2.5-4.5mol/L, and the concentration of the alcohol amine compound is 3.5-5 mol/L;
preferably, the organic acid is selected from at least one of citric acid, oxalic acid, acetic acid, sulfuric acid and nitric acid;
preferably, the alkanolamine compound is at least one selected from the group consisting of ethanolamine, diethanolamine and triethanolamine.
9. The method according to claim 7 or 8, wherein in step (3), the total content of the metal salts corresponding to the B component in terms of metal oxide in the second coating slurry is 10 to 25% by weight;
preferably, in the metal salts corresponding to the component B, the dosage ratio of cobalt salt, manganese salt, iron salt, vanadium salt and nickel salt is 1: (0-1): 1: 1: (0-1).
10. The method according to any one of claims 6 to 9, wherein in step (5), the total content of the metal salts corresponding to the C component in terms of metal oxide in the third coating slurry is 1.5 to 10% by weight.
11. The method of any one of claims 6-10, wherein the conditions of the first, second, and third drying comprise: the temperature is 100-150 ℃, and the time is 2-3 h;
preferably, the conditions of the first firing, the second firing and the third firing include: the temperature is 500-550 ℃, and the time is 2-3 h.
12. A method according to any one of claims 6 to 11, wherein prior to coating the support, the method further comprises pre-treating the support, the pre-treating comprising:
soaking the carrier in acid liquor, and then carrying out fourth drying; then the dried carrier is soaked in alkali liquor, and then is dried in a fifth way.
13. The process as claimed in claim 12, wherein the acid solution has a pH of 3-4; the pH value of the alkali liquor is 8-10;
preferably, the fourth drying is natural airing or air blowing, and the time is 2-5 h;
preferably, the fifth drying condition includes: the temperature is 100 ℃ and 150 ℃, and the time is 2-3 h.
14. Use of a catalyst according to any one of claims 1 to 5 and/or a catalyst prepared by a method according to any one of claims 6 to 13 in the microwave-enhanced catalytic oxidation treatment of VOCs.
15. The use according to claim 14, wherein the microwave-enhanced catalysis isThe conditions of the chemical oxidation treatment include: the frequency of the microwave is 915MHz or 2450 MHz; the reaction temperature is 150-450 ℃; the volume space velocity is 2000-20000h-1。
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