CN114653364A - Noble metal coating-carrier catalyst, preparation method and application thereof - Google Patents
Noble metal coating-carrier catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN114653364A CN114653364A CN202011531798.4A CN202011531798A CN114653364A CN 114653364 A CN114653364 A CN 114653364A CN 202011531798 A CN202011531798 A CN 202011531798A CN 114653364 A CN114653364 A CN 114653364A
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- Prior art keywords
- coating
- noble metal
- component
- combination
- carrier
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 131
- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 171
- 239000011248 coating agent Substances 0.000 claims abstract description 170
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910001868 water Inorganic materials 0.000 claims abstract description 31
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 30
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 84
- 239000002002 slurry Substances 0.000 claims description 68
- 229910052878 cordierite Inorganic materials 0.000 claims description 64
- 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 64
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 58
- 239000002243 precursor Substances 0.000 claims description 57
- 239000002253 acid Substances 0.000 claims description 55
- 229910052625 palygorskite Inorganic materials 0.000 claims description 55
- 229910052697 platinum Inorganic materials 0.000 claims description 55
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 54
- 229960000892 attapulgite Drugs 0.000 claims description 53
- 239000011148 porous material Substances 0.000 claims description 53
- 229910052684 Cerium Inorganic materials 0.000 claims description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 46
- 239000000725 suspension Substances 0.000 claims description 43
- 239000005995 Aluminium silicate Substances 0.000 claims description 39
- 235000012211 aluminium silicate Nutrition 0.000 claims description 39
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 39
- 229910052746 lanthanum Inorganic materials 0.000 claims description 38
- 229910052763 palladium Inorganic materials 0.000 claims description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 33
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 25
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 25
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 24
- 229910017604 nitric acid Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 229910052748 manganese Inorganic materials 0.000 claims description 21
- 239000012752 auxiliary agent Substances 0.000 claims description 20
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 229910052797 bismuth Inorganic materials 0.000 claims description 17
- 239000002808 molecular sieve Substances 0.000 claims description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000000395 magnesium oxide Substances 0.000 claims description 16
- 229910052804 chromium Inorganic materials 0.000 claims description 15
- 229910052737 gold Inorganic materials 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 13
- 229910052741 iridium Inorganic materials 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 150000007522 mineralic acids Chemical class 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910052788 barium Inorganic materials 0.000 claims description 9
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 9
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910052702 rhenium Inorganic materials 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052745 lead Inorganic materials 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052701 rubidium Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 150000005846 sugar alcohols Chemical class 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- -1 group A: li Inorganic materials 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 229920002678 cellulose Chemical class 0.000 claims description 4
- 239000001913 cellulose Chemical class 0.000 claims description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 229920000768 polyamine Chemical class 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910000505 Al2TiO5 Inorganic materials 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 238000003556 assay Methods 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000000391 magnesium silicate Substances 0.000 claims description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 2
- 235000019792 magnesium silicate Nutrition 0.000 claims description 2
- 235000019359 magnesium stearate Nutrition 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims 1
- UYHTVWHUVIXPOF-UHFFFAOYSA-N N(=O)C(CCN)N=O Chemical compound N(=O)C(CCN)N=O UYHTVWHUVIXPOF-UHFFFAOYSA-N 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 95
- 238000001035 drying Methods 0.000 description 60
- 239000007864 aqueous solution Substances 0.000 description 40
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 39
- 238000002791 soaking Methods 0.000 description 32
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 30
- 239000000203 mixture Substances 0.000 description 24
- 239000002585 base Substances 0.000 description 22
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 22
- 238000000498 ball milling Methods 0.000 description 21
- 239000011572 manganese Substances 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 16
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 13
- 239000011651 chromium Substances 0.000 description 13
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- 235000015165 citric acid Nutrition 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 10
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- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
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- 238000002156 mixing Methods 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 6
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000007605 air drying Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 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 4
- 239000010410 layer Substances 0.000 description 4
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
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- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
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- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [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 description 2
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- KWGRBVOPPLSCSI-UHFFFAOYSA-N d-ephedrine Natural products CNC(C)C(O)C1=CC=CC=C1 KWGRBVOPPLSCSI-UHFFFAOYSA-N 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
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- QWDUNBOWGVRUCG-UHFFFAOYSA-N n-(4-chloro-2-nitrophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(Cl)C=C1[N+]([O-])=O QWDUNBOWGVRUCG-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
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- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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- 238000000643 oven drying Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical class [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- UXMRNSHDSCDMLG-UHFFFAOYSA-J tetrachlororhenium Chemical compound Cl[Re](Cl)(Cl)Cl UXMRNSHDSCDMLG-UHFFFAOYSA-J 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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Abstract
The invention relates to a noble metal coating-carrier catalyst, a preparation method and application thereof. The noble metal coating-carrier catalyst has the advantages of simple preparation method, high mechanical strength, good coating wear resistance, difficult shedding, strong water and heat resistance stability, good catalytic degradation performance of volatile organic compounds, long service life and the like.
Description
Technical Field
The invention relates to a noble metal coating-carrier catalyst. More particularly, the present invention relates to a noble metal coating-supported catalyst coated with a noble metal coating on a support and a method for preparing the same. The invention also relates to the application of the noble metal coating-carrier catalyst in the catalytic oxidation treatment of volatile organic compounds (VOC or VOCs).
Background
With the increasing national requirements for environmental protection in recent years, recovery technologies such as adsorption, absorption, condensation, membrane separation, high temperature incineration, and catalytic oxidation have been widely used for the recovery/treatment of various waste gases containing volatile organic compounds (VOCs or VOCs). Wherein the adsorption method is suitable for 500-3000 h-1The method is characterized in that low-concentration volatile organic pollutants in the waste gas are removed at a low airspeed, a high-boiling-point component (more than C5) is adsorbed on the surface or pore canal of the waste gas in a porous matrix adsorption and interception mode, the process hardly generates chemical reaction, the saturated adsorption matrix needs to be regenerated and desorbed to obtain re-adsorption performance, and the service cycle of the matrix is treated as dangerous solid waste after 1-2 years. The absorption method is based on the principle of similar phase dissolution, and adopts high boiling point solvent (such as low temperature diesel oil) to absorb high boiling point components in VOCs to form rich solution, and the rich solution is dissolvedAfter absorption, the mixture returns to the system for absorption again. The condensation method is a process of condensing organic substances into liquid by cooling and/or pressurizing according to different saturated vapor pressures of the organic substances at different temperatures, and removing and purifying the liquid from a gas phase. The membrane separation process can adopt organic polymeric membranes, inorganic membranes and biological membranes, but the membrane materials have the defects of low flux, poor selectivity, unsuitability for high space velocity treatment and the like. The high-temperature incineration has high requirement on the temperature, generally exceeds 800 ℃, although the high-temperature incineration can reach the standard for treatment, a large amount of auxiliary agents such as natural gas and the like are needed to be supplemented to keep the combustion temperature, and the energy consumption is high.
Compared with the above methods, the catalytic oxidation method causes the organic waste gas to generate flameless combustion under the action of the catalyst, has the advantages of high selectivity, low reaction temperature and the like, the reaction temperature is generally lower than 500 ℃, and the product is nontoxic CO2And H2O, catalytic Oxidation non-methane Total hydrocarbons in volatile organics suitable for processing are generally above 500mg/m3. The most central of catalytic oxidation is a catalyst, which is divided into a noble metal catalyst and a transition metal oxide catalyst. Noble metal catalysts have the advantages of high activity, low light-off temperature, good stability, long service life and the like, but are expensive and not suitable for treating organic gases containing sulfur. The non-noble metal mainly takes transition metal oxide as a main component, and has better anti-poisoning performance and oxidation activity, but the catalyst has the defects of short service life, low activity, high ignition temperature and the like. ZL200510060542.9 discloses a preparation method of a rare earth composite porous alumina supported palladium catalyst, which takes honeycomb matrix ceramic as a carrier, adopts a sol dip coating method to coat hydrated alumina, a thermal adsorption method to support cerium-zirconium oxide and a supported metal palladium active component, and is used for 10000-30000 h-1Under the space velocity, the complete oxidation temperatures of the catalyst for toluene and ethyl acetate are 180-200 ℃ and 260-280 ℃, respectively, but the patent does not mention the influence of bromide on the activity and the service life of the catalyst. US4983366 discloses a process for the catalytic conversion of exhaust gases containing hydrocarbons and carbon monoxide and a related purification unit, by passing the exhaust gases through a zeolite containing alumina, silica and/or oxides or barium, manganese, copper, chromium and nickel, and then through a catalyst containing platinum and nickelAnd/or palladium or rhodium, which is particularly suitable for treating the exhaust gases from vinyl chloride production plants, but which does not mention the effect of a high-strength substrate on the life of the noble metal catalyst. CN95197182.4 discloses a catalyst and a method for treating a gas containing halogenated organic compounds, non-halogenated organic compounds, carbon monoxide or mixtures thereof, the catalyst being characterized by containing at least one platinum group metal, zirconia and at least one oxide of manganese, cerium or cobalt. CN200610047791.9 provides a method for purifying organic waste gas, especially for purifying organic waste gas containing acetaldehyde, ethylene glycol and PTA dust, such as polyester waste gas treatment method, wherein catalytic combustion adopts platinum, palladium or CuO, MnO containing2The honeycomb catalyst of (1). The clariant corporation in CN201810125199.9 discloses low cost ruthenium oxide based catalysts for VOC and halogenated VOC emission control, which catalysts include noble metals platinum based metals such as ruthenium and platinum, cerium zirconium solid solution, and tin oxide and silicon oxide, among other components. According to reports, the Envicat VOC catalyst developed by Craine has high efficiency of removing harmful Volatile Organic Compounds (VOCs) and carbon monoxide (CO), and simultaneously, the thermal energy consumption can be saved by 40 percent. CN201410455174.7 describes a catalyst comprising iron oxide, cobaltosic oxide, nickel oxide, copper oxide, vanadium oxide, chromium oxide, manganese dioxide or cerium oxide as non-noble metal oxide components, which are coated on a carrier to prepare a catalytic combustion catalyst for methane and other VOC gases.
In the above patent publications, alumina and titania are used as primary coating components in the catalyst coating process, and then active metal or active metal oxide is loaded, the stability of the coating not only affects the service life of the catalyst, but also the pressure drop of the fixed bed layer is increased and uncontrollable reaction factors are increased due to pulverization of the cracked and fallen coating. Therefore, much attention has been paid to the development of a coated catalyst which has good thermal stability, high scour strength and good bonding effect with a substrate.
Attapulgite clay (Attapulgite), also called Palygorskite (Palygorskite), is Attapulgite for short, and is rich in magnesium aluminum silicate with a layer chain structureThe natural hydrated clay material has a sandwich structure of two layers of silica tetrahedron and one layer of Mg (Al) O octahedron as basic structural unit, and the optimal unit cell molecular formula is (Mg)5Si8O20(OH)2(OH2)4·4H2And O. The modified attapulgite clay has higher specific surface area, open meso-microporous composite pore canals and good thermal stability, and is mixed with a molecular sieve and SiO2、Al2O3The materials belong to inorganic mineral materials, have good adhesion performance, and play a good role in enhancing and toughening organic and inorganic materials. The natural one-dimensional nano material attapulgite is used as an inner coating material of a honeycomb carrier and then precious metal is loaded for VOCs treatment, which is rarely reported in literatures.
Disclosure of Invention
As a result of diligent research based on the prior art, the present inventors have found that a noble metal coated-supported catalyst (referred to as "catalyst of the present invention" or "catalyst" for short in the present invention) exhibiting good catalytic oxidation conversion performance and thermal stability of VOCs is prepared by coating a support with a coating layer containing a noble metal component and an auxiliary component, wherein the coating substrate is at least one selected from the group consisting of attapulgite, kaolin, and montmorillonite, and thus the present invention has been accomplished
Specifically, the present invention relates to the following aspects.
A noble metal coating-carrier catalyst is characterized by comprising a carrier and a coating covering the carrier, wherein the coating comprises a coating component and an active metal component, the active metal component comprises a noble metal component and an auxiliary agent component, the coating component comprises at least one base material selected from attapulgite, kaolin and montmorillonite,
wherein the noble metal is at least one element selected from Pt, Pd, Ru, Rh, Au, Ir and Ag, preferably at least one combination selected from the combination of Pt and Pd, the combination of Pt and Ru, the combination of Pt and Au and the combination of Pt and Ir,
the additive component is at least one selected from the group A elements, the additive is preferably selected from at least one combination of Ce and Mo, Ce and Mn, Ce and Co, Ce and Fe, Ce and Ni, Ce and Bi, Ce and Cr, La and Mn, La and Fe, La and Co, La and Ni, La and Bi,
group A: li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce;
based on the total volume of the noble metal coating-carrier catalyst, the content of noble metal (calculated by noble metal simple substance) is 100-1300 g/m3Preferably 150 to 1000 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200 kg/m3Preferably 15 to 150 kg/m3The content of the coating component is 30-200 kg/m3Preferably 60 to 200kg/m3。
The invention also provides a preparation method of the noble metal coating-carrier catalyst, which comprises the following steps:
(1) contacting at least one base material selected from attapulgite, kaolin and montmorillonite, peptizing agent and water to prepare coating component slurry;
(2) contacting the coating component slurry, a solution or suspension of at least one noble metal component precursor, a solution or suspension of at least one auxiliary component precursor with a support to obtain a contact product, and
(3) a step of calcining the contact product to obtain the noble metal coating-supported catalyst.
The invention also provides the application of the noble metal coating-carrier catalyst in the catalytic oxidation treatment of volatile organic compounds.
Effects of the invention
Compared with the existing coating catalyst, the noble metal coating-carrier catalyst has the advantages of high mechanical strength, good coating wear resistance, difficult shedding, strong water and heat resistance stability, good catalytic degradation performance of volatile organic compounds, long service life and the like, and is particularly suitable for treating VOCs.
In addition, the preparation method of the noble metal coating-carrier catalyst of the invention is simple, and the amount of the active metal component contained in the coating can be adjusted according to the requirement, thereby adjusting the activity of the catalyst.
Detailed Description
Embodiments of the present invention will be described in more detail below with reference to specific embodiments, but those skilled in the art will understand that the following description of the embodiments is only for illustrating the present invention and should not be construed as limiting the scope of the present invention. On the contrary, the invention is intended to cover all alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims.
Unless otherwise specified, the embodiments of the present invention may be combined in any manner, and the resulting changes, modifications, and alterations of the technical solutions are also included in the scope of the present invention, and do not exceed the scope of the present invention.
The invention provides a noble metal coating-carrier catalyst, which is characterized by comprising a carrier and a coating covering the carrier, wherein the coating comprises a coating component and an active metal component, the active metal component comprises a noble metal component and an auxiliary agent component, the coating component comprises at least one base material selected from attapulgite, kaolin and montmorillonite,
wherein the noble metal is at least one element selected from the group consisting of Pt, Pd, Ru, Rh, Au, Ir and Ag, preferably at least one combination selected from the group consisting of a combination of Pt and Pd, a combination of Pt and Ru, a combination of Pt and Au and a combination of Pt and Ir,
the additive component is at least one selected from the group A elements, the additive is preferably selected from at least one combination of Ce and Mo, Ce and Mn, Ce and Co, Ce and Fe, Ce and Ni, Ce and Bi, Ce and Cr, La and Mn, La and Fe, La and Co, La and Ni, La and Bi,
group A: li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce;
based on the total volume of the noble metal coating-carrier catalyst, the content of noble metal (calculated by noble metal simple substance) is 100-1300 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200 kg/m3The content of the coating component is 30-200 kg/m3。
In one embodiment of the invention, the catalyst consists essentially of a support, a coating component, and an active metal component. In one embodiment of the invention, the catalyst consists only of the support, the coating component and the active metal component. In one embodiment of the invention, the catalyst does not contain carbonaceous materials (including but not limited to activated carbon, carbon fibers, etc.).
In the present invention, "support" means a material on which additional compounds and/or elements are supported, which is preferably composed of an inert material. In the present invention, the carrier is not particularly limited, and a carrier that is common in the art, specifically, an inorganic carrier can be used. For example, as the inorganic carrier, the carrier may be at least one selected from cordierite, alumina, magnesia, silicon carbide, aluminum titanate, silica, zirconia, ceria, titania, zirconium silicate, magnesium silicate, layered silicate, and ceramics, but is not limited thereto.
In the present invention, the carrier may be porous or non-porous. Preferably non-porous. The carrier may be composed of particles having a regular or irregular shape. The shape of the carrier can be, for example, spherical, plate-shaped, cylindrical, cubic, rectangular, solid or hollow cylindrical, annular, star-shaped, raschig ring or other shapes.
In one embodiment of the present invention, the support is a support material (inert support) having no substantial oxidation effect on the distribution of the oxidation reaction products, and the BET specific surface area is 0.1 to 5m2·g-1Pore volume of less than 0.02 ml.g-1。
In one embodiment of the invention, the support has N at-196 deg.C2Little microscopic pore volume was detectable in the BJH method assay of the adsorption test.
In one embodiment of the present invention, the support preferably has macroscopic channels, which may be one or more of circular, square, triangular, hexagonal or rhombic. The arrangement of these macro-channels on the support may be ordered or disordered, preferably uniformly ordered, honeycomb channels. In general, to reduce adsorption resistance, the macroscopic pores of the support are open.
In one embodiment of the present invention, the cross-sectional area of the individual macrochannels on the support is 1mm2~80mm2Preferably 1mm2~35mm2. The thickness of the hole wall is 1-4 mm, preferably 1-2.5 mm.
In the present invention, the coating component comprises at least one base material selected from the group consisting of attapulgite, kaolin and montmorillonite.
In one embodiment of the present invention, the coating composition may further comprise at least one material selected from the group consisting of molecular sieves, alumina, silica, magnesia, and titania.
In one embodiment of the present invention, the coating component preferably comprises attapulgite. In one embodiment of the present invention, the coating component preferably comprises attapulgite and at least one selected from kaolin, montmorillonite, molecular sieve, alumina, silica, magnesia, titania, in which case the content of attapulgite is 50% to 98%, preferably 60% to 95%, relative to the total mass of the coating component.
In one embodiment of the invention, the coating composition consists essentially of at least one substrate selected from the group consisting of attapulgite, kaolin, and montmorillonite, and optionally at least one material selected from the group consisting of molecular sieves, alumina, silica, magnesia, titania. In one embodiment of the invention, the coating component consists solely of at least one substrate selected from the group consisting of attapulgite, kaolin, and montmorillonite, and optionally at least one material selected from the group consisting of molecular sieves, alumina, silica, magnesia, titania.
In one embodiment of the invention, the coating composition consists essentially of attapulgite and optionally at least one material selected from the group consisting of kaolin, montmorillonite, molecular sieves, alumina, silica, magnesia, titania. In one embodiment of the invention, the coating component consists only of attapulgite and optionally at least one material selected from kaolin, montmorillonite, molecular sieve, alumina, silica, magnesia, titania.
In one embodiment of the present invention, the base material selected from at least one of attapulgite, kaolin and montmorillonite in the coating component accounts for 50 to 100%, preferably 50 to 95%, and more preferably 55 to 90% of the total mass of the coating component.
In one embodiment of the present invention, the content of the coating component is 30 to 200kg/m based on the total volume of the noble metal coating-supported catalyst3Preferably 60 to 200kg/m3。
In one embodiment of the present invention, the BET specific surface area of the coating component is 80 to 600m2·g-1Preferably 100 to 600m2·g-1An average pore diameter of 2 to 12nm, preferably 4 to 12nm, and a pore volume of 0.15 to 1.0 ml/g-1Preferably 0.2 to 1.0 ml/g-1。
In the present invention, the BET specific surface area, pore size and pore volume of the coating component are values measured by uniformly mixing the coating materials. For example, when the coating composition comprises attapulgite and a molecular sieve, the attapulgite and the molecular sieve are mixed uniformly by ball milling or other dispersion methods, and then the mixture is tested to obtain a value.
In one embodiment of the present invention, the noble metal is at least one element selected from Pt, Pd, Ru, Rh, Au, Ir, and Ag.
In one embodiment of the present invention, the noble metal is at least one selected from the group consisting of a combination of Pt and Pd, a combination of Pt and Ru, a combination of Pt and Au, and a combination of Pt and Ir, and preferably, the mass ratio of the two elements (the former to the latter) (in terms of the simple substance of the element) in each combination is 0.2 to 5, and preferably 0.4 to 4.
In one embodiment of the invention, the adjuvant component is at least one selected from the group consisting of group a elements, group a: li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce.
In one embodiment of the present invention, the auxiliary is preferably at least one selected from the group consisting of a combination of Ce and Mo, a combination of Ce and Mn, a combination of Ce and Co, a combination of Ce and Fe, a combination of Ce and Ni, a combination of Ce and Bi, a combination of Ce and Cr, a combination of La and Mn, a combination of La and Fe, a combination of La and Co, a combination of La and Ni, and a combination of La and Bi, and the mass ratio of the two elements (the former to the latter) (in terms of the element) in each combination is preferably 0.1 to 10, preferably 0.5 to 5.
In one embodiment of the present invention, the noble metal content (calculated by the simple noble metal) is 100-1300 g/m based on the total volume of the noble metal coating-carrier catalyst3Preferably 150 to 1000 g/m3。
In one embodiment of the invention, the content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200 kg/m based on the total volume of the noble metal coating-carrier catalyst3Preferably 15 to 150 kg/m3。
In one embodiment of the present invention, in the noble metal catalyst, the mass ratio of the noble metal Pt to other noble metals is 0.7:1 to 8: 1.
In the invention, most of the auxiliary metal may be in the highest oxidation state after high-temperature calcination, but a process of coexistence of multiple states and interconversion of multiple states may exist in the reaction process, and the process maintains the activity and stability of the catalyst.
The invention also provides a preparation method of the noble metal coating-carrier catalyst, which is characterized by comprising the following steps:
(1) contacting at least one base material selected from attapulgite, kaolin and montmorillonite, peptizing agent and water to prepare coating component slurry;
(2) a step of bringing the coating component slurry, a solution or suspension of at least one precursor of a noble metal component, a solution or suspension of at least one precursor of an auxiliary component into contact with a support to obtain a contact product, and
(3) a step of calcining the contact product to obtain the noble metal coating-supported catalyst.
In one embodiment of the present invention, in the step (1) of the above preparation method, at least one substrate selected from the group consisting of attapulgite, kaolin and montmorillonite is not subjected to any pretreatment.
In one embodiment of the present invention, at least one substrate selected from the group consisting of attapulgite, kaolin, and montmorillonite may be pretreated with an acid or the like. As a mode of the pretreatment, the substrate may be mixed with an inorganic acid to perform an activation treatment. In this case, the mass ratio of the base material to the solute in the inorganic acid is preferably 1:1 to 10, and more preferably 1:3 to 7. Wherein the inorganic acid is preferably dilute sulfuric acid, nitric acid or hydrochloric acid; the mass concentration of the inorganic acid is preferably 1 to 10%, and more preferably 4 to 8%. The temperature of the activation treatment is preferably 20-80 ℃, and more preferably 30-50 ℃; the time of the activation treatment is preferably 1 to 10 hours, and more preferably 4 to 8 hours. During the activation treatment, stirring can be performed, and the stirring speed is preferably 200-500 r/min. In the present invention, the activation treatment can increase the specific surface area of the base material and improve the adsorption capacity. And after the activation treatment, roasting the base material to obtain the treated base material. In the present invention, for convenience, both the substrate subjected to the pretreatment and the substrate not subjected to the pretreatment will be simply referred to as substrates hereinafter.
In the preparation method of the present invention, the attapulgite known in the art may be used, and may be a commercially available attapulgite. The kaolin may employ kaolin known in the art, which may be commercially available. The montmorillonite may be one known in the art, and may be commercially available.
In the preparation method, at least one of the attapulgite, kaolin and montmorillonite in the base material accounts for 50-100%, preferably 50-95%, and more preferably 55-90% of the total mass of the base material. In the preparation method of the present invention, the base material may further include at least one material selected from the group consisting of molecular sieves, alumina, silica, magnesia, and titania. In one embodiment of the present invention, the substrate is,the substrate preferably comprises attapulgite. In one embodiment of the present invention, the substrate preferably includes attapulgite and at least one selected from kaolin, montmorillonite, molecular sieve, alumina, silica, magnesia, and titania, and in this case, the content of the attapulgite is 50% to 98%, preferably 60% to 95%, with respect to the total mass of the substrate. In the present invention, the amount of the base material is a predetermined amount such that the base material is contained in an amount of 30 to 200kg/m with respect to the total volume of the carrier3Preferably 60 to 200kg/m3。
In the production method of the present invention, in the step (1), the peptizing agent may be an organic or inorganic substance as long as it can disperse the base material, and examples thereof include inorganic acids, inorganic bases, organic acids, monohydric alcohols, polyhydric alcohols, ethers, organic bases, cellulose derivatives, and carboxylates. These peptizers may be used alone or in combination of two or more. The amount of the peptizing agent is not particularly limited, and may be adjusted according to the total amount of the base material, and is preferably 1 to 20 parts by mass, more preferably 1.2 to 10 parts by mass, and still more preferably 1.5 to 5 parts by mass, based on 100 parts by mass of the total amount of the base material.
As the inorganic acid, various types of inorganic acids known in the art can be used, and for example, one or a combination of two or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and perchloric acid can be cited.
The inorganic base may be an alkali metal hydroxide or an alkaline earth metal hydroxide, and examples thereof include one or a combination of two or more of sodium hydroxide, calcium hydroxide, potassium hydroxide, magnesium hydroxide, and lithium hydroxide.
As the organic acid, various monocarboxylic acids and polycarboxylic acids known in the art can be used, and examples thereof include C having 2 to 10 (preferably 3 to 6) carboxyl groups2-20Examples of the alkane include oxalic acid, succinic acid, and adipic acid. The carboxylic acid may be C optionally having one or more hydroxyl groups (for example, 1 to 6) and 1 to 10 (preferably 3 to 6) carboxyl groups2-20Examples of the alkane include malic acid, tartaric acid, citric acid and stearic acidAnd the like. Alternatively, the polycarboxylic acid may be one represented by the formula C2-20Examples of the polycarboxyalkyl (poly) amine obtained by inserting one or more N atoms into an alkane chain include nitrilotriacetic acid and ethylenediaminetetraacetic acid.
As the monohydric alcohol, various monohydric alcohols known in the art can be used, and examples thereof include C having 1 hydroxyl group1-20Examples of the alkane include methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol.
As the polyol, various polyols known in the art can be used, and examples thereof include C having 2 to 10 (preferably 3 to 6) hydroxyl groups2-20Examples of the alkane include ethylene glycol, diethylene glycol, propylene glycol, glycerin and pentaerythritol, and examples of the polymer of the polyhydric alcohol include polyethylene glycol and polyvinyl alcohol, and the alkane may be at C2-20Examples of the polyhydroxyalkyl (poly) amine obtained by inserting one or more N atoms into an alkane chain include monoethanolamine and triethanolamine.
As the ether, a compound of the formula RO (CH) may be used2CH2O)nH (R is C3-C9 alkyl, and n is an integer of 1-12) fatty alcohol-polyoxyethylene ether; molecular formula is RC6H4O(CH2CH2O)nH (R is C3-C9 alkyl, n is an integer of 1-12) alkylphenol ethoxylates; molecular formula C8H17(CH2CH2O)nH (n is an integer of 1-12) and polyoxyethylene secondary octanol.
As the organic base, various polyamines and various nitrogen-containing basic organic compounds known in the art can be used, and examples thereof include urea, pyridine, ephedrine, ethylenediamine, diethylenetriamine, triethylenetetramine, dopamine, and the like.
As the cellulose derivative, those known in the art can be used, and examples thereof include methyl cellulose, hydroxymethyl propyl cellulose, carboxymethyl cellulose and the like.
As the carboxylate, those known in the art can be used, and examples thereof include magnesium stearate, sodium stearate, and the like.
In the step (1), the amount of water to be added is not particularly limited as long as the base material can be dispersed. The amount of water used is preferably 20 to 120 parts by mass per 100 parts by mass of the total amount of the base material.
In the step (1), a kneader may be used for stirring to prepare a contact body, or the base material may be subjected to ball milling to prepare a slurry.
In the step (2), in the contacting step, there is no particular limitation on the order of contacting the respective raw material components (i.e., the support, the coating component, the noble metal component precursor, and the auxiliary component precursor). Also, according to the present invention, the manner in which the contacting step is carried out is not particularly limited as long as sufficient contact of the respective raw material components with the support can be achieved and a uniform contact product is formed. For example, the raw material components may be mixed (if necessary, stirred) in any manner known in the art until homogeneous.
For example, the coating component slurry may be contacted with the support, optionally after heat treatment, and then contacted with the noble metal component precursor and the promoter component precursor as the active metal component. It is also possible to simultaneously contact the coating component slurry, the noble metal component precursor as the active metal component, and the auxiliary component precursor with the support.
In one embodiment of the present invention, the step (2) may include the steps of:
(2-1) first contacting the coating component slurry with a carrier; and
(2-2) optionally heat-treating the contact product of step (2-1), and then contacting with a solution or suspension of at least one noble metal component precursor and a solution or suspension of at least one auxiliary component precursor.
In one embodiment of the present invention, the step (2) may include the steps of:
(2-1') bringing a solution or suspension of at least one precursor of a noble metal component, a solution or suspension of at least one precursor of an auxiliary component, and a support into contact; and
(2-2') the contact product of the step (2-1') is optionally heat-treated and then contacted with the slurry of the coating component.
In one embodiment of the present invention, the step (2) may include the steps of:
(2') contacting the coating component slurry, the solution or suspension of the precursor of the at least one noble metal component, and the solution or suspension of the precursor of the at least one auxiliary component simultaneously with the support.
In the step (2), the noble metal is at least one element selected from the group consisting of Pt, Pd, Ru, Rh, Au, Ir, and Ag. The noble metal is preferably at least one combination selected from the group consisting of a combination of Pt and Pd, a combination of Pt and Ru, a combination of Pt and Au, and a combination of Pt and Ir, and the mass ratio of the two elements (the former to the latter) (in terms of the simple substance of the element) in each combination is preferably 0.2 to 5, and more preferably 0.4 to 4.
In step (2), the auxiliary agent component is at least one selected from group a elements, group a: li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce. Preferably, the auxiliary agent is at least one combination selected from the group consisting of a combination of Ce and Mo, a combination of Ce and Mn, a combination of Ce and Fe, a combination of Ce and Co, a combination of Ce and Ni, a combination of Ce and Bi, a combination of Ce and Cr, a combination of La and Mn, a combination of La and Fe, a combination of La and Co, a combination of La and Ni, and a combination of La and Bi, and preferably, the mass ratio of the two elements (the former to the latter) (in terms of the elements) in each combination is 0.1 to 10, preferably 0.5 to 5.
In the present invention, the precursor of the noble metal component is a precursor of a noble metal commonly used in the art, for example, the precursor of the noble metal may be preferably a soluble salt and/or an acid of the noble metal, and further preferably a chloride, a nitrate, an acetate, a sulfate, an ammonia salt, and the like, but is not limited thereto. For example, the palladium metal precursor may be selected from palladium chloride, palladium nitrate, palladium acetate, palladium diammine dichloride, etc., and the platinum metal precursor may be selected from chloroplatinic acid, platinum chloride, dinitroso diammine platinum, tetraammine platinum dichloride, etc.
In the present invention, the precursor of the auxiliary component is a precursor of an auxiliary metal commonly used in the art, for example, the precursor of the auxiliary metal may be preferably a soluble salt of the auxiliary component, and further preferably a chloride salt, a nitrate, an acetate, a sulfate, an ammonia salt, or a phosphate. For example, cerium nitrate, cerium chloride, cerium ammonium nitrate, and the like can be selected as the cerium precursor.
In the present invention, when a solution or suspension of a precursor of the noble metal component and/or a solution or suspension of a precursor of the auxiliary component is prepared, the pH can be adjusted using the pH adjuster described below.
In the present invention, the solvent used for preparing the solution or suspension of the precursor of the noble metal component and the solution or suspension of the precursor of the auxiliary component is not particularly limited, and various solvents known in the art may be used as long as the precursor of the noble metal component and the precursor of the auxiliary component can be dissolved or suspended and the effect of the present invention is not impaired. It can be various organic solvents or water, preferably deionized water. To the solvent, various kinds of inorganic acids (e.g., hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.), organic acids (e.g., formic acid, acetic acid, propionic acid, oxalic acid, etc.), and the like can be optionally added. The inorganic acid and the organic acid can function as a complexing agent, a stabilizer, and a pH adjuster as described below.
In the present invention, when the precursor of the noble metal component and the precursor of the auxiliary component are prepared as a solution or a suspension, the concentration of the solution or the suspension is not particularly limited, and may be usually 10 to 300 g/L.
In the present invention, when a solution or suspension of a precursor of the noble metal component or a solution or suspension of a precursor of the auxiliary component is prepared, various additives such as a complexing agent, a stabilizer, and a pH adjuster may be further added as necessary.
Examples of the complexing agent include polycarboxylic acids, monohydric alcohols, polyhydric alcohols, and polyamines. These complexing agents may be used alone or in combination of two or more, as required. Examples of the polycarboxylic acid include C2-20 alkanes having 2 to 10 (preferably 3 to 6) carboxyl groups, and examples thereof include oxalic acid, succinic acid, and adipic acid. The polycarboxylic acid may be a C2-20 alkane having one or more hydroxyl groups (for example, 1 to 6) and 2 to 10 (preferably 3 to 6) carboxyl groups, and examples thereof include malic acid, tartaric acid, and citric acid. Alternatively, the polycarboxylic acid may be a polycarboxyalkyl (poly) amine obtained by inserting one or more N atoms into the C2-20 alkane chain, and examples thereof include nitrilotriacetic acid and ethylenediaminetetraacetic acid. Examples of the monohydric alcohol include C1-20 alkanes having 1 hydroxyl group, and examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol. Examples of the polyhydric alcohol include C2-20 alkanes having 2 to 10 (preferably 3 to 6) hydroxyl groups, such as ethylene glycol and glycerol, and polymers of the polyhydric alcohol, such as polyethylene glycol, and polyhydroxyalkyl (poly) amines obtained by inserting one or more N atoms into the hydrocarbon chain of the C2-20 alkane, such as monoethanolamine and triethanolamine. Examples of the polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine, and the like.
As the stabilizer, various stabilizers known in the art may be used, and for example, oxides of metals selected from barium, calcium, magnesium, strontium, and mixtures thereof may be used. The stabilizer preferably comprises one or more barium and/or strontium oxides.
As the pH adjuster, various pH adjusters known in the art can be used, and examples thereof include various water-soluble acids and water-soluble bases, such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydroxymonocarboxylic acid, polyhydroxymonocarboxylic acid, hydroxypolycarboxylic acid, polyhydroxypolycarboxylic acid, monocarboxylic acid, and the like; alkaline substances such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, ethylenediamine, and ammonia water.
When the complexing agent having acidity or basicity is used, it can also function as a pH adjuster.
In step (2) of the present invention, the coating composition slurry and the carrierThe contacting of the body may be performed by coating the support with the slurry using a conventional coating apparatus, or may be performed by immersing the support in the slurry. The concentration of the coating component slurry, the coating amount of the coating component slurry and the contact time of the carrier and the coating component slurry can be adjusted, so that the content of the coating component in the finally prepared catalyst is 30-200 kg/m relative to the total volume of the catalyst3Preferably 60 to 200kg/m3。
In the step (2) of the present invention, the contact between the solution or suspension of the precursor of the active metal and the support may be performed by spraying or showering the solution or suspension onto the support, or by immersing the support in the solution or suspension. Preferably by impregnation. The contacting may be carried out at any temperature, for example at room temperature. The contact time is not particularly limited as long as the content of the noble metal (in terms of the simple noble metal) in the finally prepared catalyst is 100 to 1300g/m relative to the total volume of the catalyst3Preferably 150 to 1000 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200 kg/m3Preferably 15 to 150 kg/m3And (4) finishing.
In the step (2) of the present invention, the order of contacting the solution or suspension of the precursor of the noble metal component, the solution or suspension of the precursor of the auxiliary component and the support is not limited at all. The solution or suspension of the precursor of the noble metal component may be contacted with the support first, and then the solution or suspension of the precursor of the auxiliary component may be contacted with the support, or the order may be reversed. Alternatively, after preparing a solution or suspension of a precursor of the noble metal component and a solution or suspension of a precursor of the auxiliary component, respectively, the two solutions or suspensions may be mixed and simultaneously brought into contact with the carrier. In addition, between the two contact steps, a heat treatment step such as drying may be optionally interposed, for example, drying, airing, and air-drying at 50 to 180 ℃, preferably 60 to 150 ℃, and more preferably 70 to 120 ℃.
In the step (2) of the present invention, a solution of a precursor of a noble metal component orWhen the suspension, the solution of the precursor of the auxiliary component or the suspension contacts the carrier, the concentration of the solution of the precursor of the noble metal component or the suspension, the concentration of the solution of the precursor of the auxiliary component or the suspension, and the contact time of the carrier and the solution of the carrier or the suspension can be adjusted, so that the content of the noble metal (in terms of noble metal simple substance) in the finally prepared catalyst is 100-1300 g/m3Preferably 150 to 1000 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200 kg/m3Preferably 15 to 150 kg/m3And (4) finishing.
In the present invention, after the contact or immersion treatment is completed, the heat treatment such as air drying and air drying may be performed within one step or between two steps, and the heat treatment may be performed at 20 to 150 ℃, preferably 30 to 120 ℃, and more preferably 50 to 100 ℃.
In the present invention, the contacting step may also be carried out in the presence of a dispersion medium such as water, if necessary, for the purpose of making the contact more uniform and sufficient, or for the purpose of facilitating the contact. The contact product obtained at this time may be in the form of a slurry or a pasty liquid.
In the present invention, the contacting step may be carried out at any temperature of 0 ℃ to 150 ℃, for example, at room temperature. When the temperature is above the boiling point of the dispersion medium, it can be carried out in a pressure vessel so that the corresponding boiling point at this pressure is above said temperature. From the viewpoint of convenience, ordinary temperature is preferable, but the temperature is not limited to this in some cases. The contact time is generally 0.5 to 5 hours, but is not limited thereto, based on the desired contact product.
According to the invention, the contact product after its preparation, in particular when it is a slurry, may sometimes be dried by any means known in the art, for example by drying, airing, air-drying at 50 to 180 ℃, preferably at 60 to 150 ℃, more preferably at 70 to 120 ℃, in order to remove any dispersion medium (such as water) that may be introduced during its preparation. According to the invention, the dried contact product is also referred to simply as contact product.
In the present invention, in the step (3), the contact product obtained in the step (2) is calcined to obtain the noble metal coating-supported catalyst of the present invention.
In the step (3), the roasting temperature is 200 to 580 ℃, preferably 200 to 550 ℃, and further preferably 250 to 550 ℃. The calcination may be performed in an air atmosphere or an inert gas atmosphere. The baking time is not particularly limited, and may be 2 to 20 hours, preferably 4 to 16 hours.
The invention also provides an application of the noble metal coating-carrier catalyst or the noble metal coating-carrier catalyst prepared by the preparation method in the catalytic oxidation treatment of volatile organic compounds.
In the application of the noble metal coating-carrier catalyst, the noble metal coating-carrier catalyst is filled in a reactor, gas containing volatile organic compounds is introduced, and the gas volume airspeed is 4000-25000 h-1And removing volatile organic gas by catalytic oxidation at 150-550 ℃.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
In the examples of the present invention, unless otherwise specified, the parts are "parts by mass". Unless otherwise specified, the content of each metal element is calculated as a simple substance.
In the present invention, the surface area is measured by a BET specific surface area measurement method.
The pore volume was determined by the BJH (Barrett-Joyner-Halenda) method.
The average pore size was determined by the BJH method.
The cordierite used in the examples was a cordierite having a single-pore cross-sectional area of 4.5mm2A macroscopic honeycomb pore support.
Example 1
Adding a proper amount of water into 10 parts of attapulgite, 1 part of gamma-alumina, 0.3 part of urea and 1 part of 65% nitric acid, ball-milling the mixture into slurry, coating the slurry on the surface of 100 parts of 10cm multiplied by 5cm cordierite, and drying the slurry for 4 hours at the temperature of 80 ℃ to obtain a honeycomb internal coating carrier, wherein the ratio of the coating componentsSurface is 192m2Per g, pore volume 0.26cm3Per g, mean pore diameter of 4.8nm, coating content per unit volume of 82kg/m3. Pt content per cubic cordierite of 400g/m3Ru content of 120g/m3Preparing a chloroplatinic acid solution and an oxalic acid aqueous solution of ruthenium chloride according to the proportion, wherein the mass ratio of oxalic acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic cordierite is 20kg/m3Sn content of 18kg/m3Preparing aqueous solution of cerium nitrate and stannous chloride according to the proportion, firstly dipping Pt and Ru solution on a coating carrier, drying for 4 hours at the temperature of 150 ℃, then further dipping Ce and Sn solution, drying for 2 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 550 ℃ to obtain the noble metal coating-carrier catalyst A.
Example 2
Adding a proper amount of water into 10 parts of attapulgite, 1 part of gamma-alumina, 0.3 part of hydroxymethyl cellulose and 1 part of nitric acid with the mass concentration of 65%, ball-milling the mixture into slurry, coating the slurry on the surface of 80 parts of 10cm multiplied by 5cm cordierite, and drying the slurry for 4 hours at the temperature of 150 ℃ to obtain a honeycomb internal coating carrier, wherein the specific surface of the coating component is 192m2Per g, pore volume 0.26cm3Per g, mean pore diameter of 4.8nm, coating content per unit volume of 102kg/m3. Pt content per cubic cordierite is 500g/m3The Pd content is 120g/m3Preparing a chloroplatinic acid solution and an oxalic acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of oxalic acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic cordierite is 40kg/m3Mn content of 18kg/m3Preparing aqueous solution of cerium nitrate and manganese nitrate, firstly soaking Pt and Pd solution on a coating carrier, drying for 4 hours at the temperature of 150 ℃, then further soaking Ce and Mn solution, drying for 2 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 550 ℃ to obtain the noble metal coating-carrier catalyst B.
Comparative example 1
Adding a proper amount of water into 11 parts of gamma-alumina, 0.3 part of hydroxymethyl cellulose and 1 part of nitric acid with the mass concentration of 65%, ball-milling the mixture into slurry, coating the slurry on the surface of 80 parts of 10cm multiplied by 5cm cordierite, drying the slurry for 4 hours at the temperature of 150 ℃ to obtain a honeycomb internal coating carrier, wherein the coating carrier is prepared by coatingThe unit volume content is 102kg/m3. The Pt content of each cubic cordierite is 500g/m3The Pd content is 120g/m3Preparing a chloroplatinic acid solution and an oxalic acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of oxalic acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic cordierite is 40kg/m3Mn content of 18kg/m3Preparing aqueous solution of cerium nitrate and manganese nitrate, firstly soaking Pt and Pd solution on a coating carrier, drying for 4 hours at the temperature of 150 ℃, then further soaking Ce and Mn solution, drying for 2 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 550 ℃ to obtain the noble metal coating-carrier catalyst B1.
Example 3
Mixing 10 parts of attapulgite and 1 part of SiO2And 0.3 part of hydroxymethyl cellulose and 1 part of nitric acid with the mass concentration of 65%, adding a proper amount of water, ball-milling the mixture into slurry, coating the slurry on the surface of 80 parts of 10cm multiplied by 5cm cordierite, and drying the mixture for 4 hours at the temperature of 150 ℃ to obtain a honeycomb internal coating carrier, wherein the specific surface of the coating component is 205m2Per g, pore volume of 0.41cm3Per g, mean pore diameter of 6.2nm, coating content per unit volume of 102kg/m3. Pt content per cubic cordierite is 500g/m3The Au content is 150g/m3Preparing a chloroplatinic acid solution and an oxalic acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of oxalic acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic cordierite is 40kg/m3The content of Co is 18kg/m3Preparing aqueous solution of cerium nitrate and cobalt nitrate, firstly soaking Pt and Au solution on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further soaking Ce and Co solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 550 ℃ to obtain the noble metal coating-carrier catalyst C.
Comparative example 2
Mixing 11 parts of SiO2And 0.3 part of hydroxymethyl cellulose and 1 part of nitric acid with the mass concentration of 65%, adding a proper amount of water, ball-milling the mixture into slurry, coating the slurry on the surface of 80 parts of 10cm multiplied by 5cm cordierite, and drying the mixture for 4 hours at the temperature of 150 ℃ to obtain a honeycomb internal coating carrier, wherein the unit volume content of the coating is 102kg/m3. Pt content per cubic cordierite is 500g/m3The Au content is 150g/m3Preparing a chloroplatinic acid solution and an oxalic acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of oxalic acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic cordierite is 40kg/m3The content of Co is 18kg/m3Preparing aqueous solution of cerium nitrate and cobalt nitrate, firstly soaking Pt and Au solution on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further soaking Ce and Co solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 550 ℃ to obtain the noble metal coating-carrier catalyst C1.
Example 4
Mixing 10 parts of attapulgite, 1 part of kaolin and 1 part of SiO2And 0.3 part of hydroxymethyl cellulose and 1 part of nitric acid with the mass concentration of 65%, adding a proper amount of water, ball-milling the mixture into slurry, coating the slurry on the surface of 80 parts of 10cm multiplied by 5cm cordierite, and drying the mixture for 4 hours at the temperature of 150 ℃ to obtain a honeycomb internal coating carrier, wherein the specific surface of the coating component is 189m2Per g, pore volume of 0.39cm3Per g, an average pore diameter of 8.2nm and a coating content per unit volume of 112kg/m3. Pt content per cubic cordierite is 500g/m3The Ir content is 210g/m3The mass ratio of citric acid to chloroplatinic acid is 3:1, and the content of Ce per cubic cordierite is 40kg/m3The Fe content is 8kg/m3Preparing aqueous solution of cerium nitrate and ferric nitrate, firstly dipping Pt and Ir solution on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further dipping Ce and Fe solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 550 ℃ to obtain the noble metal coating-carrier catalyst D.
Example 5
Mixing 11 parts of kaolin and 1 part of SiO2And 0.3 part of hydroxymethyl cellulose and 1 part of nitric acid with the mass concentration of 65%, adding a proper amount of water, ball-milling the mixture into slurry, coating the slurry on the surface of 80 parts of 10cm multiplied by 5cm cordierite, and drying the mixture for 4 hours at the temperature of 150 ℃ to obtain a honeycomb internal coating carrier, wherein the specific surface of the coating component is 186m2Per g, pore volume of 0.42cm3Per g, an average pore diameter of 8.4nm, a coating content per unit volume of 112kg/m3. Pt content per cubic cordierite is 500g/m3The Pd content is 210g/m3The citric acid aqueous solution of the chloroplatinic acid solution and the citric acid aqueous solution of the palladium chloride are prepared according to the proportion, wherein the mass ratio of the citric acid to the chloroplatinic acid is 3:1, and the content of each cubic cordierite Ce is 40kg/m3Ni content of 11kg/m3Preparing aqueous solution of cerium nitrate and nickel nitrate, firstly soaking Pt and Pd solution on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further soaking Ce and Ni solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 530 ℃ to obtain the noble metal coating-carrier catalyst E.
Example 6
Mixing 11 parts of montmorillonite and 1 part of SiO2And 0.3 part of hydroxymethyl cellulose and 1 part of nitric acid with the mass concentration of 65%, adding a proper amount of water, ball-milling the mixture into slurry, coating the slurry on the surface of 80 parts of 10cm multiplied by 5cm cordierite, and drying the mixture for 4 hours at the temperature of 150 ℃ to obtain a honeycomb internal coating carrier, wherein the specific surface of the coating component is 193m2Per g, pore volume 0.40cm3G, average pore diameter of 7.9nm, coating unit volume content of 112kg/m3. Pt content per cubic cordierite is 500g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a citric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of citric acid to chloroplatinic acid is 3:1, and the content of each cubic cordierite Ce is 80kg/m3The Bi content is 11kg/m3Preparing aqueous solutions of cerium nitrate and bismuth nitrate, firstly soaking Pt and Pd solutions on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further soaking Ce and Bi solutions, drying for 3 hours at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 520 ℃ to obtain the noble metal coating-carrier catalyst F.
Example 7
Mixing 10 parts of attapulgite, 1 part of kaolin and 1 part of SiO2And 0.3 part of hydroxymethyl cellulose and 1 part of nitric acid with the mass concentration of 65%, adding a proper amount of water, ball-milling the mixture into slurry, coating the slurry on the surface of 80 parts of 10cm multiplied by 5cm cordierite, and drying the mixture for 4 hours at the temperature of 150 ℃ to obtain a honeycomb internal coating carrier, wherein the specific surface of the coating component is 189m2Per g, pore volume of 0.39cm3G, averageThe pore diameter is 8.2nm, and the unit volume content of the coating is 112kg/m3. Pt content per cubic cordierite is 500g/m3The Pd content is 150g/m3Preparing a chloroplatinic acid solution and a citric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of citric acid to chloroplatinic acid is 3:1, and the content of each cubic cordierite Ce is 80kg/m3The Cr content is 20kg/m3Preparing aqueous solution of cerium nitrate and chromium nitrate, firstly soaking Pt and Pd solution on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further soaking Ce and Cr solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 500 ℃ to obtain the noble metal coating-carrier catalyst G.
Example 8
12 parts of attapulgite, 2 parts of kaolin and 1 part of SiO2Adding a proper amount of water, ball-milling the mixture into slurry, coating the slurry on the surface of 80 parts of 10cm multiplied by 5cm cordierite, drying the mixture for 4 hours at the temperature of 150 ℃ to obtain a honeycomb internal coating carrier, wherein the specific surface of the coating component is 145m2Per g, pore volume of 0.33cm3Per g, mean pore diameter of 8.9nm, coating content per unit volume of 140kg/m3. The Pt content of each cubic cordierite is 500g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of the hydrochloric acid to the chloroplatinic acid is 3:1, and the content of La in each cubic cordierite is 80kg/m3Mn content of 20kg/m3Preparing aqueous solution of lanthanum nitrate and manganese nitrate, firstly soaking Pt and Pd solution on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further soaking La and Mn solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 500 ℃ to obtain the noble metal coating-carrier catalyst H.
Example 9
Grinding 10 parts of attapulgite, 2 parts of kaolin, 1 part of SBA-15 molecular sieve, 2 parts of urea and 4 parts of nitric acid with the mass concentration of 65% into slurry by adding a proper amount of water and triethylene glycol, coating the slurry on the surface of 80 parts of 10cm multiplied by 5cm cordierite, and drying the slurry for 4 hours at the temperature of 150 ℃ to obtain a honeycomb internal coating carrier, wherein the specific surface of the coating component is298m2Per g, pore volume of 0.43cm3G, average pore diameter of 9.8nm, coating content per unit volume of 121 kg/m3. Pt content per cubic cordierite is 500g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the content of each cubic cordierite La is 80kg/m3Co content of 30kg/m3Preparing aqueous solution of lanthanum nitrate and cobalt nitrate, firstly dipping Pt and Pd solution on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further dipping La and Co solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 500 ℃ to obtain the noble metal coating-carrier catalyst I.
Example 10
Adding a proper amount of water and triethylene glycol into 10 parts of attapulgite, 2 parts of kaolin, 1 part of SBA-15 molecular sieve, 2 parts of urea and 1 part of nitric acid with the mass concentration of 65%, ball-milling to form slurry, coating the slurry on the surface of 80 parts of 10cm multiplied by 5cm cordierite, and drying for 4 hours at the temperature of 150 ℃ to obtain a honeycomb internal coating carrier, wherein the specific surface of the coating component is 298m2Per g, pore volume of 0.43cm3G, average pore diameter of 9.8nm, and coating content per unit volume of 121 kg/m3. Pt content per cubic cordierite is 500g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of the hydrochloric acid to the chloroplatinic acid is 3:1, and the content of La in each cubic cordierite is 90kg/m3The Fe content is 18kg/m3Preparing aqueous solution of lanthanum nitrate and ferric nitrate, firstly soaking Pt and Pd solution on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further soaking La and Fe solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 500 ℃ to obtain the noble metal coating-carrier catalyst J.
Example 11
Adding a proper amount of water and triethylene glycol into 10 parts of attapulgite, 2 parts of kaolin, 2 parts of SAPO molecular sieve, 2 parts of urea and 1 part of nitric acid with the mass concentration of 65%, ball-milling the mixture into slurry, coating the slurry on the surface of 80 parts of 10cm multiplied by 5cm cordierite, and performing ball milling at the temperature of 150 DEG CDrying for 4 hours to obtain a honeycomb internal coating carrier, wherein the specific surface of the coating component is 208m2Per g, pore volume of 0.46cm3G, average pore diameter of 7.1nm, unit volume content of coating of 131 kg/m3. Pt content per cubic cordierite is 500g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the content of each cubic cordierite La is 90kg/m3Ni content of 20kg/m3Preparing aqueous solution of lanthanum nitrate and nickel nitrate, firstly soaking Pt and Pd solution on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further soaking La and Ni solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 500 ℃ to obtain the noble metal coating-carrier catalyst K.
Example 12
Grinding 10 parts of attapulgite, 1 part of kaolin, 1 part of alumina, 2 parts of urea and 1 part of 65 mass percent nitric acid into slurry by adding a proper amount of water and triethylene glycol, coating the slurry on the surface of 80 parts of 10cm multiplied by 5cm cordierite, and drying for 4 hours at the temperature of 150 ℃ to obtain a honeycomb internal coating carrier, wherein the specific surface of the coating component is 156m2Per g, pore volume of 0.42cm3G, average pore diameter of 7.7nm, coating unit volume content of 112kg/m3. Pt content per cubic cordierite is 500g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the content of each cubic cordierite La is 90kg/m3And a Bi content of 20kg/m3Preparing aqueous solution of lanthanum nitrate and bismuth nitrate, firstly soaking Pt and Pd solution on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further soaking La and Bi solution, drying for 3 hours again at the temperature of 150 ℃, and roasting for 5 hours at the temperature of 500 ℃ to obtain the noble metal coating-carrier catalyst L.
Example 13
10 parts of attapulgite, 1 part of kaolin, 1 part of alumina, 2 parts of urea and 1 part of nitric acid with the mass concentration of 65 percent, adding a proper amount of water and triethylene glycol, ball-milling into slurry, and coating the slurry on a coating80 portions of 10cm multiplied by 5cm cordierite surface, drying for 4 hours at the temperature of 150 ℃ to obtain the carrier of the honeycomb internal coating, wherein the specific surface of the coating component is 156m2Per g, pore volume 0.42cm3G, average pore diameter of 7.7nm, coating unit volume content of 112kg/m3. Pt content per cubic cordierite is 500g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the content of each cubic cordierite La is 90kg/m3Preparing lanthanum nitrate aqueous solution, firstly dipping Pt and Pd solution on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further dipping La solution, drying for 3 hours again at the temperature of 180 ℃, and roasting for 5 hours at the temperature of 530 ℃ to obtain the noble metal coating-carrier catalyst M.
Example 14
Adding a proper amount of water and triethylene glycol into 10 parts of attapulgite, 1 part of kaolin, 1 part of alumina, 2 parts of urea and 1 part of nitric acid with the mass concentration of 65%, ball-milling the mixture into slurry, coating the slurry on the surface of 80 parts of 10cm multiplied by 5cm cordierite, and drying the slurry for 4 hours at the temperature of 150 ℃ to obtain a honeycomb internal coating carrier, wherein the specific surface of the coating component is 156m2Per g, pore volume of 0.42cm3G, average pore diameter of 7.7nm, coating unit volume content of 112kg/m3. The Pt content of each cubic cordierite is 500g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of hydrochloric acid to chloroplatinic acid is 3:1, and the content of Ce in each cubic cordierite is 90kg/m3Preparing a cerium nitrate aqueous solution, firstly soaking a Pt and Pd solution on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further soaking a Ce solution, drying for 3 hours again at the temperature of 180 ℃, and roasting for 5 hours at the temperature of 530 ℃ to obtain the noble metal coating-carrier catalyst N.
Example 15
10 parts of attapulgite, 1 part of kaolin, 1 part of alumina, 2 parts of urea and 1 part of 65% nitric acid by mass, adding a proper amount of water and triethylene glycol, ball-milling into slurry, coating the slurry on the surface of 80 parts of 10cm × 10cm × 5cm cordierite, and performing ball milling at 150 DEG CDrying for 4 hours under the condition of (1) to obtain a honeycomb internal coating carrier, wherein the specific surface of the coating component is 156m2Per g, pore volume of 0.42cm3G, average pore diameter of 7.7nm, coating unit volume content of 112kg/m3. Pt content per cubic cordierite is 500g/m3Pd content of 150g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of the hydrochloric acid to the chloroplatinic acid is 3:1, and the content of Cr in each cubic cordierite is 90kg/m3Mo content of 20kg/m3Preparing aqueous solution of chromium nitrate and ammonium molybdate, firstly soaking Pt and Pd solution on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further soaking Cr and Mo solution, drying for 3 hours again at the temperature of 180 ℃, and roasting for 4 hours at the temperature of 530 ℃ to obtain the noble metal coating-carrier catalyst O.
Example 16
Adding a proper amount of water and triethylene glycol into 10 parts of attapulgite, 1 part of kaolin, 1 part of alumina, 2 parts of urea and 1 part of nitric acid with the mass concentration of 65%, ball-milling the mixture into slurry, coating the slurry on the surface of 80 parts of 10cm multiplied by 5cm cordierite, and drying the slurry for 4 hours at the temperature of 150 ℃ to obtain a honeycomb internal coating carrier, wherein the specific surface of the coating component is 156m2Per g, pore volume 0.42cm3G, average pore diameter of 7.7nm, coating unit volume content of 112kg/m3. The Pt content of each cubic cordierite is 500g/m3The Pd content is 150g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of the hydrochloric acid to the chloroplatinic acid is 3:1, and the content of each cubic cordierite K is 10kg/m3The Re content was 30kg/m3W content of 20kg/m3Preparing aqueous solutions of potassium nitrate, rhenium chloride and ammonium tungstate, firstly soaking Pt and Pd solutions on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further soaking K, Re and W solutions, drying for 3 hours again at the temperature of 180 ℃, and roasting for 4 hours at the temperature of 530 ℃ to obtain the noble metal coating-carrier catalyst P.
Example 17
Adding 10 parts of attapulgite, 1 part of kaolin, 1 part of titanium oxide, 2 parts of urea and 1 part of nitric acid with the mass concentration of 65 percentAdding appropriate amount of water and triethylene glycol, ball-milling into slurry, coating on 80 parts of 10cm × 10cm × 5cm cordierite surface, oven drying at 150 deg.C for 4 hr to obtain honeycomb internal coating carrier with specific surface of coating component 121m2Per g, pore volume of 0.35cm3Per g, an average pore diameter of 8.1nm, a coating content per unit volume of 112kg/m3. Pt content per cubic cordierite is 500g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of the hydrochloric acid to the chloroplatinic acid is 3:1, and the content of Sn in each cubic cordierite is 15kg/m3The V content is 10kg/m3Zn content of 20kg/m3Preparing aqueous solutions of stannous chloride, ammonium metavanadate and zinc nitrate, firstly soaking Pt and Pd solutions on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further soaking Sn, V and Zn solutions, drying for 3 hours again at the temperature of 180 ℃, and roasting for 4 hours at the temperature of 530 ℃ to obtain the noble metal coating-carrier catalyst Q.
Example 18
Grinding 10 parts of attapulgite, 1 part of kaolin, 1 part of magnesium oxide, 2 parts of urea and 1 part of 65 mass percent nitric acid into slurry by adding a proper amount of water and triethylene glycol, coating the slurry on the surface of 80 parts of 10cm multiplied by 5cm cordierite, and drying for 4 hours at the temperature of 150 ℃ to obtain a honeycomb internal coating carrier, wherein the specific surface of the coating component is 123m2Per g, pore volume 0.32cm3Per g, mean pore diameter of 6.1nm, coating content per unit volume of 112kg/m3. The Pt content of each cubic cordierite is 500g/m3The Pd content is 200g/m3Preparing a chloroplatinic acid solution and a hydrochloric acid aqueous solution of palladium chloride according to the proportion, wherein the mass ratio of the hydrochloric acid to the chloroplatinic acid is 3:1, and the Ga content of each cubic cordierite is 11kg/m3W content 18kg/m3The Co content is 60kg/m3Preparing aqueous solutions of gallium nitrate, ammonium tungstate and cobalt nitrate, firstly soaking Pt and Pd solutions on a coating carrier, drying for 4 hours at the temperature of 130 ℃, then further soaking Ga, W and Co solutions, drying for 3 hours again at the temperature of 180 ℃, and roasting for 4 hours at the temperature of 530 ℃ to obtain the noble metal coating-carrier catalyst R.
Example 19
The noble metal-coated supported catalysts of examples 1 to 18 and comparative examples 1 to 2 were charged in a fixed bed reactor and charged with non-methane total hydrocarbons in an amount of 1200mg/m3The reaction temperature of the VOCs gas is 350 ℃ and the space velocity of the VOCs gas is 10000h-1The reaction was carried out under the conditions described above, and the results of the detection of VOCs at the outlet by gas chromatography are shown in Table 1.
TABLE 1 comparison of catalytic reaction Performance of noble Metal coating-Supported catalyst
| Catalyst and process for preparing same | The reaction time is 1h, and the concentration (mg/m) of VOCs at the outlet is3） | The reaction is carried out for 500h, and the concentration (mg/m) of VOCs at the outlet is3） | The reaction time is 1000h, and the concentration (mg/m) of VOCs at the outlet is3） |
| A | 30.1 | 30.3 | 31.1 |
| B | 4.2 | 4.3 | 4.5 |
| C | 7.1 | 8.1 | 8.5 |
| D | 9.0 | 9.4 | 9.8 |
| E | 8.1 | 8.9 | 9.3 |
| F | 8.6 | 8.8 | 9.3 |
| G | 9.1 | 9.3 | 9.7 |
| H | 8.7 | 8.8 | 9.4 |
| I | 10.3 | 10.8 | 11.8 |
| J | 9.8 | 10.4 | 11.2 |
| K | 9.3 | 9.7 | 10.1 |
| L | 8.6 | 8.8 | 9.7 |
| M | 39.8 | 40.2 | 41.1 |
| N | 42.1 | 42.0 | 43.1 |
| O | 36.1 | 36.4 | 37.7 |
| P | 37.6 | 38.1 | 39.0 |
| Q | 42.0 | 42.5 | 43.1 |
| R | 42.7 | 42.9 | 43.3 |
| B1 | 45.2 | 49.4 | 58.1 |
| C1 | 49.2 | 50.9 | 55.3 |
Example 20
The catalysts of examples 2 and 3 and comparative examples 1 and 2 were subjected to elemental analysis of metals, and the samples obtained after 1000 hours of the above reaction of treating the VOCs gas were subjected to elemental analysis, in terms of the metal content per volume of the catalyst, as shown in table 2. The comparison shows that the active metal component of the internal coating catalyst has low shedding rate and good stability.
TABLE 2 analysis of key elements after catalytic reaction of noble metal coating-supported catalyst
Although the invention is described in detail herein with reference to exemplary embodiments, it should be understood that the invention is not limited to the described embodiments. Those having ordinary skill in the art and access to the teachings herein will recognize additional variations, modifications, and embodiments within the scope thereof. Accordingly, the invention is to be broadly construed, consistent with the claims which are appended hereto.
Claims (17)
1. A noble metal coating-carrier catalyst is characterized by comprising a carrier and a coating covering the carrier, wherein the coating comprises a coating component and an active metal component, the active metal component comprises a noble metal component and an auxiliary agent component, and the coating component comprises at least one base material selected from attapulgite, kaolin and montmorillonite;
wherein the noble metal is at least one element selected from Pt, Pd, Ru, Rh, Au, Ir and Ag, preferably at least one combination selected from the combination of Pt and Pd, the combination of Pt and Ru, the combination of Pt and Au and the combination of Pt and Ir,
the additive component is at least one selected from the group A elements, the additive is preferably selected from at least one combination of Ce and Mo, Ce and Mn, Ce and Co, Ce and Fe, Ce and Ni, Ce and Bi, Ce and Cr, La and Mn, La and Fe, La and Co, La and Ni, La and Bi,
group A: li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce;
based on the total volume of the noble metal coating-carrier catalyst, the content of noble metal (calculated by noble metal simple substance) is 100-1300 g/m3Preferably 150 to 1000 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200 kg/m3Preferably 15 to 150 kg/m3The content of the coating component is 30-200 kg/m3Preferably 60 to 200kg/m3。
2. The noble metal washcoat-supported catalyst of claim 1, wherein the coated catalyst consists essentially of a support, a coating component and an active metal component, preferably the catalyst consists only of a support, a coating component and an active metal component.
3. The noble metal washcoat-supported catalyst of claim 1 or 2, wherein the washcoat component further comprises at least one material selected from the group consisting of molecular sieves, alumina, silica, magnesia, titania; preferably, the coating component comprises attapulgite and at least one selected from kaolin, montmorillonite, molecular sieve, alumina, silica, magnesia and titania, wherein the content of the attapulgite is 50-98%, preferably 60-95%, relative to the total mass of the coating component; preferably the coating component consists essentially of at least one substrate selected from the group consisting of attapulgite, kaolin and montmorillonite and optionally at least one material selected from the group consisting of molecular sieves, alumina, silica, magnesia, titania; more preferably, the coating component consists essentially of attapulgite and optionally at least one material selected from the group consisting of kaolin, montmorillonite, molecular sieves, alumina, silica, magnesia, titania.
4. The noble metal coating-supported catalyst of any of claims 1 to 3, wherein the substrate selected from at least one of attapulgite, kaolin and montmorillonite in the coating component accounts for 50 to 100%, preferably 50 to 95%, and more preferably 55 to 90% of the total mass of the coating component.
5. The noble metal coating-carrier catalyst according to claim 1 to 4, wherein the mass ratio of the noble metal Pt to the other noble metal is 0.7:1 to 8: 1.
6. The noble metal coating-supported catalyst as claimed in claim 1 to 5, wherein the BET specific surface area of the coating component is 80 to 600m2·g-1Preferably 100 to 600m2·g-1An average pore diameter of 2 to 12nm, preferably 4 to 12nm, and a pore volume of 0.15 to 1.0 ml/g-1Preferably 0.2 to 1.0 ml/g-1。
7. The noble metal coating-carrier catalyst as claimed in claim 1 to 6, wherein the carrier is at least one selected from the group consisting of cordierite, alumina, magnesia, silicon carbide, aluminum titanate, silica, zirconia, ceria, titania, zirconium silicate, magnesium silicate, layered silicate and ceramics, and preferably the BET specific surface area of the carrier is 0.1 to 5m2·g-1Pore volume of less than 0.02 ml.g-1Preferably the support is N at-196 ℃2Little microscopic pore volume was detectable in the BJH method assay of the adsorption test.
8. The noble metal washcoat-supported catalyst of claims 1-7, wherein the support is shaped as a sphere, a sheet, a cylinder, a cube, a cuboid, a solid in appearanceAt least one of a cylinder or a hollow cylinder, a ring, a star and a Raschig ring, preferably the carrier is provided with a macropore, the macropore is one or more of a circle, a square, a triangle, a hexagon or a rhombus, and the cross section of a single macropore is preferably 1mm2~80mm2Preferably 1mm2~35mm2The thickness of the hole wall is 1-4 mm, preferably 1-2.5 mm.
9. A preparation method of a noble metal coating-carrier catalyst is characterized by comprising the following steps:
(1) contacting at least one base material selected from attapulgite, kaolin and montmorillonite, peptizing agent and water to prepare coating component slurry, wherein the base material is used in an amount such that the content of the base material is 30-200 kg/m relative to the total volume of the carrier3Preferably 60 to 200kg/m3；
(2) A step of bringing the coating component slurry, a solution or suspension of at least one precursor of a noble metal component, a solution or suspension of at least one precursor of an auxiliary component into contact with a support to obtain a contact product, and
(3) a step of calcining the contact product to obtain the noble metal coating-supported catalyst.
10. The method according to claim 9, wherein the at least one selected from the group consisting of attapulgite, kaolin, and montmorillonite is present in the base material in an amount of 50 to 100%, preferably 50 to 95%, and more preferably 55 to 90% by mass of the total mass of the base material, and preferably the base material further comprises at least one selected from the group consisting of molecular sieves, alumina, silica, magnesia, and titania.
11. The production method according to claim 9 or 10, wherein the peptizing agent is at least one selected from the group consisting of inorganic acids, inorganic bases, polycarboxylic acids, monohydric alcohols, polyhydric alcohols, polyamines, cellulose derivatives, and carboxylates, preferably at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, sodium hydroxide, calcium hydroxide, potassium hydroxide, magnesium hydroxide, lithium hydroxide, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, pentaerythritol, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, urea, methylcellulose, hydroxymethylcellulose, hydroxymethylpropylcellulose, carboxymethylcellulose, magnesium stearate, and sodium stearate.
12. The production method according to any one of claims 9 to 11, wherein the step (2) comprises the steps of:
(2-1) first contacting the coating component slurry with a carrier; and
(2-2) optionally heat-treating the contact product of the step (2-1), and then contacting with a solution or suspension of at least one noble metal component precursor and a solution or suspension of at least one auxiliary component precursor;
or
(2-1') bringing a solution or suspension of at least one precursor of a noble metal component, a solution or suspension of at least one precursor of an auxiliary component, and a support into contact; and
(2-2') contacting the contact product of step (2-1'), optionally after heat treatment, with a slurry of a coating component;
or
(2') contacting the coating component slurry, the solution or suspension of the precursor of the at least one noble metal component, and the solution or suspension of the precursor of the at least one auxiliary component simultaneously with the support.
13. The production method according to any one of claims 9 to 12, wherein the auxiliary component is at least one selected from the group A elements, the auxiliary is preferably at least one selected from the group consisting of a combination of Ce and Mo, a combination of Ce and Mn, a combination of Ce and Co, a combination of Ce and Fe, a combination of Ce and Ni, a combination of Ce and Bi, a combination of Ce and Cr, a combination of La and Mn, a combination of La and Fe, a combination of La and Co, a combination of La and Ni, a combination of La and Bi,
group A: li, Na, K, Rb, Cs, Ca, Mg, Ba, Sr, Ti, Cr, Mo, W, Fe, Co, Ni, Re, Zn, Mn, Ga, Al, Sn, Pb, Bi, Sb, La, Ce,
the noble metal is at least one selected from Pt, Pd, Ru, Rh, Au, Ir and Ag, preferably at least one selected from Pt and Pd combination, Pt and Ru combination, Pt and Au combination and Pt and Ir combination,
the precursor of the noble metal is soluble salt and/or acid of the noble metal, preferably at least one selected from chloride, nitrate, acetate, sulfate and ammonium salt, and further preferably at least one selected from palladium chloride, palladium nitrate, palladium acetate, dichlorodiammine palladium, chloroplatinic acid, platinum chloride, dinitrosopropylamine and dichlorotetrammonium;
the precursor of the auxiliary component is at least one of chloride, nitrate, acetate, sulfate, ammonia salt and phosphate of the auxiliary component,
in the obtained catalyst, the content of the noble metal (calculated by the simple substance of the noble metal) is 100-1300 g/m relative to the total volume of the catalyst3Preferably 150 to 1000 g/m3The content of the auxiliary agent (calculated by the simple substance of the auxiliary agent) is 10-200 kg/m3Preferably 15 to 150 kg/m3。
14. The production method according to any one of claims 9 to 13, wherein at least one of a complexing agent, a stabilizer and a pH adjuster may be added to the solution or suspension of the precursor of the noble metal component and/or the solution or suspension of the precursor of the auxiliary component.
15. The production method according to any one of claims 9 to 14, wherein in the step (3), the temperature of the calcination is 200 to 580 ℃, preferably 200 to 550 ℃, and more preferably 250 to 550 ℃; the roasting time is 2-20 hours, preferably 4-16 hours.
16. Use of a noble metal coating-supported catalyst according to any one of claims 1 to 8 or a noble metal coating-supported catalyst prepared according to the preparation process of any one of claims 9 to 15 for the catalytic oxidation of volatile organic compounds.
17. The use of claim 16, wherein said conditions are: the gas containing volatile organic compounds is enabled to have a gas volume space velocity of 4000-25000 h-1And contacting the noble metal coating-carrier catalyst at 150-550 ℃.
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