CN116459845A - Catalyst for treating volatile organic compounds and preparation method thereof - Google Patents
Catalyst for treating volatile organic compounds and preparation method thereof Download PDFInfo
- Publication number
- CN116459845A CN116459845A CN202310435209.XA CN202310435209A CN116459845A CN 116459845 A CN116459845 A CN 116459845A CN 202310435209 A CN202310435209 A CN 202310435209A CN 116459845 A CN116459845 A CN 116459845A
- Authority
- CN
- China
- Prior art keywords
- nitrate
- catalyst
- active material
- load carrier
- volatile organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000011149 active material Substances 0.000 claims abstract description 49
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 45
- 239000011248 coating agent Substances 0.000 claims abstract description 44
- 238000000576 coating method Methods 0.000 claims abstract description 44
- 239000013543 active substance Substances 0.000 claims abstract description 29
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 28
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract 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 claims abstract description 22
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims abstract description 22
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 22
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 22
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims abstract description 14
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims abstract description 14
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 14
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims abstract description 11
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 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 claims abstract description 11
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 11
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 11
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 11
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims description 55
- 238000001354 calcination Methods 0.000 claims description 45
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 239000002270 dispersing agent Substances 0.000 claims description 21
- 238000005507 spraying Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000004202 carbamide Substances 0.000 claims description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 16
- 230000009467 reduction Effects 0.000 claims description 16
- 239000004353 Polyethylene glycol 8000 Substances 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 15
- 229940085678 polyethylene glycol 8000 Drugs 0.000 claims description 15
- 235000019446 polyethylene glycol 8000 Nutrition 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000011159 matrix material Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000003618 dip coating Methods 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- 230000002829 reductive effect Effects 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000003349 gelling agent Substances 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000000630 rising effect Effects 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000005067 remediation Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 18
- 239000010815 organic waste Substances 0.000 abstract description 12
- 239000000243 solution Substances 0.000 description 35
- 229910000510 noble metal Inorganic materials 0.000 description 33
- 238000003756 stirring Methods 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000000694 effects Effects 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000002912 waste gas Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000007084 catalytic combustion reaction Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
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- 239000008213 purified water Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 206010010071 Coma Diseases 0.000 description 2
- 206010010904 Convulsion Diseases 0.000 description 2
- 206010019233 Headaches Diseases 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 206010067125 Liver injury Diseases 0.000 description 2
- 206010028813 Nausea Diseases 0.000 description 2
- 208000001738 Nervous System Trauma Diseases 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- 230000004913 activation Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
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- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
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- 238000004043 dyeing Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 231100000869 headache Toxicity 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 210000003734 kidney Anatomy 0.000 description 2
- 208000037806 kidney injury Diseases 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 210000004185 liver Anatomy 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000008693 nausea Effects 0.000 description 2
- 208000028412 nervous system injury Diseases 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
- 208000024891 symptom Diseases 0.000 description 2
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- 239000004753 textile Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 230000008673 vomiting Effects 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
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- PCWGTDULNUVNBN-UHFFFAOYSA-N 4-methylpentan-1-ol Chemical compound CC(C)CCCO PCWGTDULNUVNBN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- HYJODZUSLXOFNC-UHFFFAOYSA-N [S].[Cl] Chemical compound [S].[Cl] HYJODZUSLXOFNC-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
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Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
The application discloses a catalyst for treating volatile organic compounds and a preparation method thereof, and relates to the technical field of organic waste gas treatment. The catalyst comprises: a high load carrier; the modified coating film layer is coated on the surface of the high-load carrier, and consists of cerium nitrate, lanthanum nitrate, zirconium nitrate, praseodymium nitrate, yttrium nitrate, potassium nitrate, sodium nitrate, calcium nitrate and nano aluminum oxide solution, wherein the total concentration of metal ions is 1-5mol/L, and the coating amount of the modified coating film layer is 2-10% of the weight of the high-load carrier; an active material layer including a first active material and a second active material; the first active substance consists of manganese nitrate, cobalt nitrate, copper nitrate, chromium nitrate and ammonium metavanadate, ammonia water is used as a reducing agent, and the total concentration of metal ions is 1-10mol/L; the second active substance consists of platinum nitrate, palladium nitrate, rhodium nitrate, silver nitrate and ruthenium nitrate, and the total concentration of metal ions is 0.5-20mol/L.
Description
Technical Field
The application relates to the technical field of organic waste gas treatment, in particular to a catalyst for treating volatile organic compounds and a preparation method thereof.
Background
With the development of industry, organic waste gas generated by industries such as petrochemical industry, chemical industry, printing, paint production, rubber production, pharmacy, textile printing and dyeing and the like is increasingly increased, and organic waste gas with volatility such as benzene, toluene, xylene, ethyl acetate, acetone, styrene, formaldehyde, ethylene glycol diethyl ether, methylene dichloride and the like is generated. These volatile organic waste gases can cause symptoms such as headache, nausea, vomiting, weakness, etc., and even cause convulsions, coma, liver, kidney, brain and nervous system injury in severe cases, with serious consequences. Volatile organic compounds also form ozone and haze under the action of nitrogen oxides and ultraviolet rays, causing serious environmental impact, and the volatile organic compounds are the third largest pollutant which is harmful to the environment after the nitrogen oxides and sulfur dioxide.
Catalytic combustion is the most widely used technology for purifying volatile organic waste gas at present, and the working principle is that the volatile organic waste gas is subjected to oxidation reaction at a lower temperature under the action of a catalyst to generate harmless carbon dioxide and water. The catalytic combustion technology has wide application range on volatile organic compounds, almost can treat all volatile organic compounds, and has no secondary pollution. However, the existing catalyst has lower catalytic efficiency on volatile organic compounds.
Disclosure of Invention
The main purpose of the application is to provide a catalyst for treating volatile organic compounds and a preparation method thereof, and aims to solve the technical problem that the catalytic combustion effect of the existing catalyst on the volatile organic compounds is poor.
In order to solve the above technical problems, the embodiments of the present application provide: a catalyst for remediation of volatile organics, the catalyst comprising:
a high load carrier;
the modified coating film layer is coated on the surface of the high-load carrier, and consists of cerium nitrate, lanthanum nitrate, zirconium nitrate, praseodymium nitrate, yttrium nitrate, potassium nitrate, sodium nitrate, calcium nitrate and nano aluminum oxide solution, wherein the total concentration of metal ions is 1mol/L-5mol/L, and the coating amount of the modified coating film layer is 2% -10% of the weight of the high-load carrier;
an active material layer including a first active material and a second active material; wherein the first active substance consists of manganese nitrate, cobalt nitrate, copper nitrate, chromium nitrate and ammonium metavanadate, ammonia water is introduced as a reducing agent, and the total concentration of metal ions is 1mol/L-10mol/L; the second active substance consists of platinum nitrate, palladium nitrate, rhodium nitrate, silver nitrate and ruthenium nitrate, and the total concentration of metal ions is 0.5-20mol/L.
As some optional embodiments of the present application, the molar ratio of the metal ions in the cerium nitrate, lanthanum nitrate, zirconium nitrate, praseodymium nitrate, yttrium nitrate, potassium nitrate, sodium nitrate, calcium nitrate and nano aluminum oxide solution in the modified coating film layer is 30-80:5-12:2-7:0.5-3:0.1-0.3:0.1-0.5:0.1-0.3:0.1-0.3:1-5.
As some optional embodiments of the present application, the first active material has a metal ion molar ratio of manganese nitrate, cobalt nitrate, copper nitrate, chromium nitrate and ammonium metavanadate of 2 to 9:8-15:5-20:1-5:1-10, wherein the molar ratio of the ammonia water to the total metal ions is 0.1-5.
As some optional embodiments of the present application, the molar concentration ratio of the metal ions of the platinum nitrate, palladium nitrate, rhodium nitrate, silver nitrate and ruthenium nitrate in the second active material is 0.5-1:0.01-0.1:0.01-0.08:0.5-5:0.2-3.
As some optional embodiments of the present application, the second active material is in the form of a reductive dispersion gel solution and is supported by dip-coating;
wherein the reductive dispersion gel solution is prepared by using a reducing agent, a dispersing agent and a gelling agent to prepare platinum nitrate, palladium nitrate, rhodium nitrate, silver nitrate and ruthenium nitrate in the second active substance; the reducing agent is glucose, the dispersing agent is polyethylene glycol 200 and urea, and the gelling agent is citric acid.
As some optional embodiments of the present application, the high load carrier comprises a matrix material, a dispersant, a binder, and a pore former;
wherein, the matrix material comprises the following components by mass percent: 15% -50%:10% -20%:1% -5%:5% -15% of aluminum oxide, silicon dioxide, magnesium oxide, calcium oxide and pseudo-boehmite;
the dispersing agent is polyethylene glycol 200 and urea, and the mass of the polyethylene glycol 200 and the urea is 0.5% -1% of the mass of the matrix material;
the binder is polyethylene glycol 8000, the pore-forming agent is polyvinyl alcohol, and the total mass of the polyethylene glycol 8000 and the polyvinyl alcohol is 1% -3% of the total mass of the matrix material and the dispersing agent; wherein, the mass percentage of the polyethylene glycol 8000 and the polyvinyl alcohol is 20% -50%:50% -80%.
In order to solve the above technical problems, the embodiment of the present application further provides: a method for preparing the catalyst for treating volatile organic compounds, which comprises the following steps:
preparing a first high-load carrier;
preparing a modified coating film solution, coating the modified coating film solution on the high-load carrier, and performing a first drying treatment and a first calcination treatment to obtain a second high-load carrier;
preparing a first active material solution, and spraying the first active material solution on the surface of the second high-load carrier in a double-channel independent instantaneous high-temperature reduction spraying mode, so that the first active material is embedded into the second high-load carrier to obtain a first intermediate;
preparing a second active material solution, carrying the second active material solution on the first intermediate in a dip-coating mode, and performing a second drying treatment to obtain a second intermediate;
and (3) treating the second intermediate at a high temperature, wherein the treatment temperature is 250-350 ℃, the heating rate is 5-10 ℃/min, and the treatment time is 2-6 h.
As some optional embodiments of the present application, the first drying parameters are: the drying temperature is 80-120 ℃ and the drying time is 12-24 hours; the first calcination treatment parameters are as follows: the calcination temperature is 450-550 ℃, the heating rate is 5-10 ℃/min, and the calcination time is 2-6 h; the parameters of the secondary drying treatment are as follows: the drying temperature is 120-150 ℃ and the drying time is 12-24h.
As some optional embodiments of the present application, the preparing a first high load carrier includes:
mixing aluminum oxide, silicon dioxide, magnesium oxide, calcium oxide and pseudo-boehmite to obtain a mixed material A; mixing the mixture A with urea to obtain a mixture B; mixing the B mixed material with polyethylene glycol 8000 and polyvinyl alcohol, and then adding dilute nitric acid and acetic acid for hydrolysis to obtain a carrier mixed raw material C; and (3) carrying out extrusion molding treatment on the carrier mixed raw material C, and sequentially carrying out drying treatment and calcination treatment to obtain the first high-load carrier with the water absorption rate of 25% -30%.
As some optional embodiments of the present application, the drying parameters are: the drying temperature is 80-130 ℃ and the drying time is 8-16 h; the calcination treatment parameters are as follows: the calcination temperature is 1200-1400 ℃, the temperature rising rate is 5-20 ℃/min, and the calcination time is 2-4 h.
Compared with the prior art, the catalyst for treating volatile organic compounds in the embodiment of the application comprises the following components: a high load carrier; the modified coating film layer is coated on the surface of the high-load carrier, and consists of cerium nitrate, lanthanum nitrate, zirconium nitrate, praseodymium nitrate, yttrium nitrate, potassium nitrate, sodium nitrate, calcium nitrate and nano aluminum oxide solution, wherein the total concentration of metal ions is 1mol/L-5mol/L, and the coating amount of the modified coating film layer is 2% -10% of the weight of the high-load carrier; an active material layer including a first active material and a second active material; wherein the first active substance consists of manganese nitrate, cobalt nitrate, copper nitrate, chromium nitrate and ammonium metavanadate, ammonia water is introduced as a reducing agent, and the total concentration of metal ions is 1mol/L-10mol/L; the second active substance consists of platinum nitrate, palladium nitrate, rhodium nitrate, silver nitrate and ruthenium nitrate, and the total concentration of metal ions is 0.5-20mol/L.
The modified coating film layer is introduced with trace alkali metals such as potassium, sodium, calcium and the like, the composite oxide structure interface can be modified, the efficiency, airspeed, adaptability to broad spectrum and related resistance of the coating film layer can be improved after modification, the modified coating film layer can be compatible with the introduction of non-noble metal active units and noble metal active units, the maximum oxygen storage and release capacity and the activation oxidation capacity of active substances are excited, the conversion efficiency and the air-speed ratio are improved, the absolute value data reduction is further improved, the high temperature resistance of the interface can be improved by introducing the nano aluminum oxide solution, the high temperature treatment is carried out at the temperature of 700 ℃ for 24 hours, and the activity reduction range is smaller. The active material layer adopts two layers of independent reduction calcining embedding modes, so that two layers of active materials are effectively compatible in a high-efficiency composite oxide interface, the first active material adopts non-noble metal elements, and mainly aims at specific non-noble metal elements, so that the reaction efficiency of substances such as lipids, ethers, oxygen-containing substances, nitrogen-containing substances and the like is high, and meanwhile, chromium and vanadium elements are introduced for activity modification, so that the chlorine resistance and the overall oxidation performance of the catalyst are improved; the second active substance is noble metal element, which is mainly aimed at the high reaction efficiency of aromatic hydrocarbon, alkane, alcohol, aldehyde and other substances, the noble metal element is independently embedded into the high-efficiency composite oxide interface, and is independently reduced and calcined, finally the complementary enhancement and synergy effects of non-noble metal active element and noble metal active element are formed, so that the high-efficiency treatment of various waste gas components contained in waste gas components in the same temperature range can be realized through one catalyst, the purpose of energy saving is achieved, and the characteristics of low temperature, broad spectrum, high efficiency, poisoning resistance and energy saving of the catalyst for catalyzing comprehensive waste gas components are truly embodied. Through the modification of the molecular structure interface and the component improvement, the catalyst for treating the volatile organic compounds has high activity, high efficiency of catalytic combustion of the volatile organic compounds, lower conversion temperature, good stability, long service life, wide application range and lower energy consumption.
Drawings
FIG. 1 is a nanoscale electron micrograph image of a first intermediate according to an embodiment of the present application;
fig. 2 is a nanoscale electron micrograph image of a second intermediate designed in accordance with an embodiment of this application.
Detailed Description
It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the present application.
Volatile organic compounds refer to organic compounds with saturated vapor pressure higher than 133.32Pa at normal temperature and boiling point lower than 50-260 ℃ at normal pressure, or any volatile organic solid or liquid at normal temperature and normal pressure, and 300 or more have been identified at present. The most common are benzene, toluene, xylene, ethyl acetate, acetone, styrene, formaldehyde, ethylene glycol ethyl ether, methylene chloride, etc., which are mainly produced in petrochemical industry, chemical industry, printing, paint production, rubber production, pharmaceutical industry, textile printing and dyeing, etc. These volatile organic waste gases can cause symptoms such as headache, nausea, vomiting, weakness, etc., and even cause convulsions, coma, liver, kidney, brain and nervous system injury in severe cases, with serious consequences. Volatile organic compounds also form ozone and haze under the action of nitrogen oxides and ultraviolet rays, causing serious environmental impact, and the volatile organic compounds are the third largest pollutant which is harmful to the environment after the nitrogen oxides and sulfur dioxide.
Catalytic combustion is the most widely used technology for purifying volatile organic waste gas at present, and the working principle is that the volatile organic waste gas is subjected to oxidation reaction at a lower temperature under the action of a catalyst to generate harmless carbon dioxide and water. The catalytic combustion technology has wide application range on volatile organic compounds, almost can treat all volatile organic compounds, and has no secondary pollution. However, the existing catalyst has lower catalytic efficiency on volatile organic compounds. The existing catalyst has the following technical defects that the activity of a non-noble metal catalyst is low and the efficiency is low when the catalyst is used for treating benzene series, alkane and the like (such as styrene, toluene, xylene, trimethylbenzene, propane and the like); the noble metal catalyst has the problems of low oxygen-containing and nitrogen-containing organic matter efficiency, high conversion temperature and the like; the active substances are easy to fall off; expensive; the transition metal oxide has low catalytic activity on dichloroethane, cyclohexanone and the like, has single catalytic activity, and can only aim at specific partial volatile organic compounds, and has limited catalytic activity and the like; the existing catalyst has the problem of weak broad spectrum; it is difficult to decompose specific gases in the comprehensive atmosphere.
Based on this, the embodiment of the application provides a catalyst for treating volatile organic compounds, the catalyst includes: a high load carrier; the modified coating film layer is coated on the surface of the high-load carrier, and consists of cerium nitrate, lanthanum nitrate, zirconium nitrate, praseodymium nitrate, yttrium nitrate, potassium nitrate, sodium nitrate, calcium nitrate and nano aluminum oxide solution, wherein the total concentration of metal ions is 1mol/L-5mol/L, and the coating amount of the modified coating film layer is 2% -10% of the weight of the high-load carrier; an active material layer including a first active material and a second active material; wherein the first active substance consists of manganese nitrate, cobalt nitrate, copper nitrate, chromium nitrate and ammonium metavanadate, ammonia water is introduced as a reducing agent, and the total concentration of metal ions is 1mol/L-10mol/L; the second active substance consists of platinum nitrate, palladium nitrate, rhodium nitrate, silver nitrate and ruthenium nitrate, and the total concentration of metal ions is 0.5-20mol/L.
The modified coating film layer is introduced with trace alkali metals such as potassium, sodium, calcium and the like, the composite oxide structure interface can be modified, the efficiency, airspeed, adaptability to broad spectrum and related resistance of the coating film layer can be improved after modification, the modified coating film layer can be compatible with the introduction of non-noble metal active units and noble metal active units, the maximum oxygen storage and release capacity and the activation oxidation capacity of active substances are excited, the conversion efficiency and the air-speed ratio are improved, the absolute value data reduction is further improved, the high temperature resistance of the interface can be improved by introducing the nano aluminum oxide solution, the high temperature treatment is carried out at the temperature of 700 ℃ for 24 hours, and the activity reduction range is smaller. The active material layer adopts two layers of independent reduction calcining embedding modes, so that two layers of active materials are effectively compatible in a high-efficiency composite oxide interface, the first active material adopts non-noble metal elements, and mainly aims at specific non-noble metal elements, so that the reaction efficiency of substances such as lipids, ethers, oxygen-containing substances, nitrogen-containing substances and the like is high, and meanwhile, chromium and vanadium elements are introduced for activity modification, so that the chlorine resistance and the overall oxidation performance of the catalyst are improved; the second active substance is noble metal element, which is mainly aimed at the high reaction efficiency of aromatic hydrocarbon, alkane, alcohol, aldehyde and other substances, the noble metal element is independently embedded into the high-efficiency composite oxide interface, and is independently reduced and calcined, finally the complementary enhancement and synergy effects of non-noble metal active element and noble metal active element are formed, so that the high-efficiency treatment of various waste gas components contained in waste gas components in the same temperature range can be realized through one catalyst, the purpose of energy saving is achieved, and the characteristics of low temperature, broad spectrum, high efficiency, poisoning resistance and energy saving of the catalyst for catalyzing comprehensive waste gas components are truly embodied. Through the modification of the molecular structure interface and the component improvement, the catalyst for treating the volatile organic compounds has high activity, high efficiency of catalytic combustion of the volatile organic compounds, lower conversion temperature, good stability, long service life, wide application range and lower energy consumption.
Specifically, embodiments of the present application provide: a catalyst for remediation of volatile organics, the catalyst comprising: high load carriers, modified coating film layers, and active material layers.
Specifically, the high-load carrier comprises a matrix material, a dispersing agent, a binder and a pore-forming agent; wherein, the matrix material comprises the following components by mass percent: 15% -50%:10% -20%:1% -5%:5% -15% of aluminum oxide, silicon dioxide, magnesium oxide, calcium oxide and pseudo-boehmite; the dispersing agent is urea, and the mass of the urea is 0.5% -1% of the mass of the matrix material; the binder is polyethylene glycol 8000, the pore-forming agent is polyvinyl alcohol, and the total mass of the polyethylene glycol 8000 and the polyvinyl alcohol is 1% -3% of the total mass of the matrix material and the dispersing agent; wherein, the mass percentage of the polyethylene glycol and the polyvinyl alcohol is 20% -50%:50% -80%. The special pore-forming agent proportion enables the high-load carrier to have a nanoscale high-pass pore canal, realizes nanoscale pore canal molding, and provides technical support for the after-embedded modified coating film layer to enter the pore canal.
Specifically, the coating film layer is coated on the surface of the high-load carrier, the coating film layer consists of cerium nitrate, lanthanum nitrate, zirconium nitrate, praseodymium nitrate, yttrium nitrate, potassium nitrate, sodium nitrate, calcium nitrate and nano aluminum oxide solution, the total concentration of metal ions is 1mol/L-5mol/L, and the coating amount of the coating film layer is 2% -10% of the weight of the high-load carrier. More specifically, the molar ratio of metal ions in the cerium nitrate, lanthanum nitrate, zirconium nitrate, praseodymium nitrate, yttrium nitrate, potassium nitrate, sodium nitrate, calcium nitrate and nano aluminum oxide solution in the coating film layer is 30-80:5-12:2-7:0.5-3:0.1-0.3:0.1-0.5:0.1-0.3:0.1-0.3:1-5.
Specifically, the active material layer includes a first active material and a second active material; the first active substance consists of manganese nitrate, cobalt nitrate, copper nitrate, chromium nitrate and ammonium metavanadate, wherein the total concentration of metal ions is 1mol/L-10mol/L, and the molar ratio of ammonia water to total metal ions is 0.1-5; the second active substance consists of platinum nitrate, palladium nitrate, rhodium nitrate, silver nitrate and ruthenium nitrate, and the total concentration of metal ions is 0.5-20mol/L. More specifically, the metal ion molar ratio of the manganese nitrate, the cobalt nitrate, the copper nitrate, the chromium nitrate and the ammonium metavanadate in the first active substance is 2-9:8-15:5-20:1-5:1-10. More specifically, the molar concentration ratio of the metal ions of the platinum nitrate, the palladium nitrate, the rhodium nitrate, the silver nitrate and the ruthenium nitrate in the second active substance is 0.5-1:0.01-0.1:0.01-0.08:0.5-5:0.2-3. The second active material is in the form of a reductive dispersion gel solution and is loaded in a dip-coating mode; wherein the reductive dispersion gel solution is prepared by using a reducing agent, a dispersing agent and a gelling agent to prepare platinum nitrate, palladium nitrate, rhodium nitrate, silver nitrate and ruthenium nitrate in the second active substance; the reducing agent is glucose, the dispersing agent is polyethylene glycol 200 and urea, and the gelling agent is citric acid. Glucose is adopted as a reducing agent, so that the catalyst can be effectively and completely matched with a high-dispersion gel solution, the physical characteristics of the gel solution are not changed, the performance of the catalyst can be reduced while calcination can be realized, meanwhile, the dispersing agent, the gel and the like can be used for reducing and solid-state calcination of the catalyst at 300 ℃, and the energy consumption required by catalyst molding is greatly saved.
Meanwhile, the embodiment of the application also provides: a method for preparing the catalyst for treating volatile organic compounds, which comprises the following steps:
and S10, preparing a first high-load carrier. Specifically, the method comprises the following steps: mixing aluminum oxide, silicon dioxide, magnesium oxide, calcium oxide and pseudo-boehmite to obtain a mixed material A; mixing the mixture A with urea to obtain a mixture B; mixing the B mixed material with polyethylene glycol 8000 and polyvinyl alcohol, and then adding dilute nitric acid and acetic acid for hydrolysis to obtain a carrier mixed raw material C; and (3) carrying out extrusion molding treatment on the carrier mixed raw material C, and sequentially carrying out drying treatment and calcination treatment to obtain the first high-load carrier with the water absorption rate of 25% -30%. Wherein, the stoving processing parameters are: the drying temperature is 80-130 ℃ and the drying time is 8-16 h; the calcination treatment parameters are as follows: the calcination temperature is 1200-1400 ℃, the temperature rising rate is 5-20 ℃/min, and the calcination time is 2-4 h.
In practical applications, the steps may include: alumina, silicon dioxide, magnesium oxide, calcium oxide and pseudo-boehmite are mixed according to the mass percentage (35% -60%): (15% -50%): (10% -20%): (1% -5%): mixing (5% -15%) in a stirring tank to obtain a mixed material A, adding urea with the mass of 0.5% -1% of the mixed material A as a dispersing agent into the stirring tank, continuously stirring for 1-2 hours to obtain a highly dispersed mixed material B, continuously adding polyethylene glycol 8000 with the mass of 1% -3% of the mixed material B into the stirring tank, and continuously stirring for 1-2 hours with polyvinyl alcohol as a binder and a pore-forming agent, wherein the mixing ratio of the polyethylene glycol 8000 to the polyvinyl alcohol is (20% -50%): adding dilute nitric acid and acetic acid (50% -80%) into a stirring tank to hydrolyze, controlling the mass of the dilute nitric acid and acetic acid to be 1% -5% of the total solid mass, controlling the pH to be 3-6, controlling the stirring frequency of the stirring tank to be 30-60 r/min, controlling the stirring temperature to be 60-80 ℃ and the stirring time to be 1-2h, obtaining a uniformly mixed, highly dispersed and sticky carrier mixed raw material C with colloid, putting the carrier raw material C into honeycomb die forming equipment to carry out extrusion forming (100 x 50 or 100 x 100, unit mm) to 200 meshes or 400 meshes, and the like, then putting the formed carrier into a drying furnace to carry out drying, controlling the drying temperature to be 80-130 ℃, controlling the drying time to be 8-16h, putting the dried carrier into a high-temperature calciner to carry out calcination, controlling the calcination temperature to be 1200-1400 ℃ and the temperature rising rate to be 5-20 ℃/min, and controlling the calcination constant temperature time to be 2-4h, and finally opening the carrier with high load, wherein the first high-porosity high-water absorption carrier with high dispersion and high water absorption capacity of up to 25% can be achieved.
In specific application, the first high-load carrier adopts a customized formula and process, the carrier is more stable and has strong high-temperature resistance, wherein a pore-forming agent and a dispersing agent are added, nano-level pore canal molding is realized, the pore canal is rich and uniform, and technical support is provided for the after-embedded modified coating film layer to enter the pore canal. In addition, in specific application, the special pickling and washing treatment can effectively remove impurities, uniform pore channels and uniform surface adsorption capacity, provide uniform and adsorption capacity for active material loading, remove the influence of the impurities and further improve the overall conversion efficiency.
And step S20, preparing a coating film solution, coating the coating film solution on the high-load carrier, and performing a first drying treatment and a first calcination treatment to obtain a second high-load carrier. Wherein, the first drying treatment parameters are as follows: the drying temperature is 80-120 ℃ and the drying time is 12-24 hours; the first calcination treatment parameters are as follows: the calcination temperature is 450-550 ℃, the temperature rising rate is 5-10 ℃/min, and the calcination time is 2-6 h.
In practical applications, the steps may include: coating the first high-load carrier obtained in the step S10 into a film by using a mixed solution of cerium nitrate, lanthanum nitrate, zirconium nitrate, praseodymium nitrate, yttrium nitrate, potassium nitrate, sodium nitrate, calcium nitrate and nano aluminum oxide solution, wherein the metal ion molar ratio of the mixed solution is (30-80): (5-12): (2-7): (0.5-3): (0.1-0.3): (0.1-0.5): (0.1-0.3): (0.1-0.3): (1-5), controlling the total concentration of metal ions to be 1-5mol/L, controlling the coating amount to be 2% -10% of the weight of the carrier, then adopting constant temperature of 80-120 ℃ to dry for 12-24h, adopting temperature of 450-550 ℃ to calcine after drying, controlling the heating rate to be 5-10 ℃/min, and controlling the calcination time to be 2-6h, thus finally obtaining the modified second high-load carrier with a special interface structure, wherein the modified second high-load carrier has the characteristics of high oxygen storage and release, high temperature resistance, high dispersibility and high compatible activity.
In the specific application, the surface of the second high-load carrier adopts a plurality of alkali metals mixed in a special proportion to modify the rare earth auxiliary agent, so that a special auxiliary catalytic interface body is formed, the oxygen storage and release function of the interface is improved, the participation degree of catalytic oxidation oxygen is improved, the adsorption resolving power is improved, and the terminal conversion efficiency is further improved.
S30, preparing a first active material solution, spraying the first active material solution on the surface of the second high-load carrier in an independent double-channel instantaneous high-temperature reduction spraying mode, independently metering active liquid and a reducing agent in the process, spraying the active liquid and the reducing agent into the second carrier in 1-3 seconds at the temperature of 250-350 ℃, and simultaneously performing reduction treatment to embed the first active material into the second high-load carrier; the first intermediate is obtained without drying and calcining.
In practical applications, the steps may include: embedding non-noble metal activity into the second high-load carrier obtained in the step 2, wherein the non-noble metal activity material is mixed solution of four materials including manganese nitrate, cobalt nitrate, copper nitrate, chromium nitrate and ammonium metavanadate, and the metal ion mole ratio of the mixed solution is (2-9): (8-15): (5-20): (1-5): (1-10), controlling the total concentration of metal ions to be 1-10mol/L, carrying out instantaneous high-temperature reduction spraying on the surface of the second high-load carrier obtained in the step S20 by using an independent channel mixed solution, wherein the process temperature is 250-350 ℃, the spraying contact time is 1-3 seconds, and obtaining an embedded non-noble metal embedded intermediate after spraying is finished, wherein the embedding of the non-noble metal mainly plays a role in efficiently degrading oxygen-containing and nitrogen-containing organic matters, and meanwhile, the broad-spectrum treatment capability is enhanced and the synergistic effect is achieved. The two-channel independent instantaneous high-temperature reduction spraying has two independent metering channels, the first active mother liquor and the reducing agent can be independently metered and mixed, the sprayed mixed liquid is heated to 250-350 ℃ in 1-3s, the process does not need drying and calcining treatment, the instantaneous high-temperature reduction spraying technology is directly used, the production efficiency is improved, the robot operation can be completely used, the drying and calcining treatment is omitted, and the energy consumption is greatly saved.
In practical application, after the non-noble metal active embedding treatment is completed, the obtained first intermediate can be pretreated, namely the first intermediate is put into purified water with the pH value of 1-3, ultrasonic vibration is carried out for 1-2 hours, 3-5 times of purified water is replaced during the period, and in order to open all nano pore channels and redundant easy-falling powder, and then the obtained first intermediate is dried for 12-24 hours at the constant temperature of 120-150 ℃.
In a specific application, microscopic observation of the first intermediate can show that the first intermediate forms two heterogeneous catalysis-assisting interfaces in a pore channel and a non-pore channel, and the first carrier also participates in catalysis-assisting action in the non-pore channel interface and can improve the processing capacity of oxygen-containing organic matters. And moreover, the first active substances adopt a thermal spraying mode, so that various base metals can be effectively and uniformly embedded into the nano structure of the second carrier, the conversion efficiency of oxygen-containing and nitrogen-containing organic matters is effectively and synergistically improved, the participation of various base metals is greatly improved, and the application range is greatly increased.
And S40, preparing a second active material solution, carrying the second active material solution on the first intermediate in a dip-coating mode, and carrying out a second drying treatment to obtain a second intermediate. Wherein, the second drying treatment parameters are as follows: the drying temperature is 120-150 ℃ and the drying time is 12-24h.
In practical applications, the steps may include: carrying out noble active substance loading on the pretreated first intermediate, carrying out mixed solution preparation on noble metal active substances, wherein at least one of platinum nitrate, palladium nitrate, rhodium nitrate, silver nitrate and ruthenium nitrate is selected, carrying out stirring and heating at 60-80 ℃, controlling the pH value of the prepared solution to be 1-2, taking out and drying the solution, controlling the metal ion concentration ratio of the mixed solution to be 0.5-1, (0.01-0.1), (0.01-0.08), (0.5-5) and (0.2-3), controlling the total concentration of metal ions to be 0.5-20mol/L, adding 0.5-1% of reducing agent glucose, dispersing agent polyethylene glycol 200, urea and colloid forming agent citric acid into the metal ion solution, carrying out stirring and heating at 60-80 ℃, finally carrying out dip-coating on the surface of the prepared reducing dispersion gel solution in the first intermediate in the step 4, taking out and drying the solution, controlling the temperature rising rate to be 2-10 ℃/min, and controlling the time to be 5-12h, wherein the reducing dispersion gel is adopted in the process, the reducing dispersion gel mode, the reducing dispersion mode is improved in the conversion efficiency of the intermediate metal active substances and the uniform size and the adsorption capacity of the molecular transfer capability of the catalyst is greatly improved at 99.95%.
In specific application, the second active material adopts a mode of matching a plurality of noble metals in cooperation with a plurality of base metal points, and the load adopts a sol dip-coating mode, so that the noble metals can be uniformly riveted in lattices of a catalysis-assisting interface, and finally two heterogeneous phase special reaction mechanisms of the base metals, the noble metal rivets, the first carrier and the second carrier are formed.
Step S50, calcining the second intermediate at high temperature to obtain a catalyst for treating volatile organic compounds; wherein, the organic gas reduction treatment parameters are as follows: the treatment temperature is 250-350 ℃, the heating rate is 5-10 ℃/min, and the treatment time is 2-6 h.
In practical applications, the steps may include: the second intermediate is put into a drying and calcining furnace, the drying temperature is controlled at 80-130 ℃, the calcining temperature is controlled at 250-350 ℃, the heating rate is controlled at 5-10 ℃/min, and the high-activity catalyst with high dispersion, high temperature resistance, high performance, lower conversion temperature, good stability, broad spectrum, long service life, low cost, wide application range, no secondary pollution and strong recoverability is obtained after 2-6h of constant temperature. Wherein the reduction treatment and the calcination treatment at the process end are synchronously carried out, thereby reducing the energy consumption and improving the manufacturing efficiency.
The catalyst for treating volatile organic compounds described in the present application will be described in detail with reference to the following specific examples:
example 1
Alumina, silicon dioxide, magnesia, calcium oxide and pseudo-boehmite are mixed according to the mass percentage of 40 percent: 30%:10%:5%: mixing 15% in a stirring tank to obtain a mixed material A, adding 1% urea by mass of A into the stirring tank as a dispersing agent, continuously stirring for 2 hours to obtain a highly dispersed mixed material B, continuously adding 3% polyethylene glycol 8000 by mass of B and polyvinyl alcohol as a binder and a pore-forming agent into the stirring tank, and continuously stirring for 2 hours, wherein the mixing ratio of the polyethylene glycol 8000 and the polyvinyl alcohol is 50%:50% of the total solid mass, adding dilute nitric acid and acetic acid into a stirring tank for hydrolysis, controlling the mass of the dilute nitric acid and acetic acid to be 5% of the total solid mass, controlling the pH to be 3, controlling the stirring frequency of the stirring tank to be 60 r/min, controlling the stirring temperature to be 60 ℃ and the stirring time to be 2h, obtaining a carrier mixed raw material C which is uniformly mixed, highly dispersed, sticky and gelatinous, placing the carrier raw material C into honeycomb die forming equipment for extrusion forming (100 x 50) 200 meshes, placing the formed carrier into a drying furnace for drying, controlling the drying temperature to be 130 ℃ and the drying time to be 16h, placing the dried carrier into a high-temperature calciner for calcination, controlling the calcination temperature to be 1200-1400 ℃ and the heating rate to be 5 ℃/min, controlling the calcination constant temperature time to be 3h, and finally opening the furnace for cooling to obtain the high-load high-dispersion nano pore path high water absorption first high-load carrier, wherein the water absorption rate can reach 25% -30%.
Coating the obtained first high-load carrier with a mixed solution of cerium nitrate, lanthanum nitrate, zirconium nitrate, praseodymium nitrate, yttrium nitrate, potassium nitrate, sodium nitrate, calcium nitrate and nano aluminum oxide solution to form a film, wherein the molar ratio of metal ions of the mixed solution is 80:12:6:0.5:0.2:0.1:0.1:0.1:1, controlling the total concentration of metal ions at 5mol/L, controlling the coating amount at 8% of the weight of the carrier, then adopting a constant temperature of 120 ℃ to carry out drying for 24 hours, adopting 500 ℃ to carry out calcination after drying, controlling the heating rate at 5 ℃/min, and controlling the calcination time at 3 hours, thus obtaining the modified second high-load carrier with a special structure, wherein the modified second high-load carrier has high temperature resistance, high dispersibility and special resistance (chlorine sulfur resistance and the like).
Embedding non-noble metal activity into the obtained second high-load carrier, wherein the non-noble metal active substances are manganese nitrate, cobalt nitrate, copper nitrate, chromium nitrate and ammonium metavanadate, and the mixed solution is prepared by mixing the four substances, wherein the molar ratio of metal ions of the mixed solution is 2:8:5:1:1, controlling the total concentration of metal ions at 1mol/L and the molar ratio of total metal ions to reducer ammonia water at 0.3, spraying the mixed solution on the surface of a second high-load carrier through instantaneous high-temperature reduction spraying equipment, wherein the spraying contact time is 1-3 seconds, and obtaining an embedded non-noble metal embedded intermediate after spraying is completed, wherein the embedding of non-noble metal mainly plays a role in efficiently degrading oxygen-containing and nitrogen-containing organic matters, and meanwhile, the broad-spectrum treatment capacity is enhanced and the synergistic effect is achieved.
After the non-noble metal active embedding treatment is completed, the obtained first intermediate can be pretreated, namely the first intermediate is put into purified water with the pH value of 2, ultrasonic oscillation is carried out for 1 hour, the purified water is replaced for 5 times, and in order to open all nano pore channels and redundant easy-to-drop powder, the process is carried out for 12 hours by adopting constant temperature of 130 ℃.
Carrying out noble active substance loading on the pretreated first intermediate, carrying out mixed solution preparation on noble metal active substances selected from at least one of platinum nitrate, palladium nitrate, rhodium nitrate, silver nitrate and ruthenium nitrate, carrying out solvent selection by dilute nitric acid, controlling the PH at 2, controlling the concentration ratio of metal ions of the mixed solution to 0.5:0.01:0.01:0.5:0.2, controlling the total concentration of metal ions to 0.5mol/L, adding 0.5% of reducing agent glucose, dispersing agent urea and gelling agent citric acid into the metal ion solution, stirring and heating to 60 ℃, finally loading the prepared reducing dispersion gel solution on the surface of the first intermediate in a dip-coating mode, taking out and drying, controlling the temperature rising rate to 2 ℃/min, and controlling the drying time to 12h.
Calcining and reducing the second intermediate to obtain a catalyst for treating volatile organic compounds; wherein the treatment temperature is 300 ℃, the heating rate is 5 ℃/min, and the treatment time is 2h.
Experimental example 1
The test conditions were: the inlet air concentration is about 1000ppm, the inlet air flow is 1000mL/min, and the airspeed is 10000h -1 The volume of each catalyst was 6mL and the results are shown in Table 1:
table 1:
as can be seen from the above table, the catalyst prepared in example 1 of the present application has a lower conversion temperature for each organic exhaust gas. Meanwhile, it can be seen that the conversion rate of the catalyst in the embodiment 1 of the application to organic waste gases such as ethyl acetate, acetone, dimethylamide, n-hexane, toluene, cyclohexanone, styrene, butyl acetate, n-butyl acetate, isohexanol, ethanol, xylene, ethylene glycol diethyl ether and formaldehyde can reach 99%, so that the catalyst prepared in the embodiment 1 of the application has wider application range and higher conversion rate to different organic waste gases.
Experimental example 2
Test conditions: the exhaust gas amount of volatile organic compounds is 2000m 3 And/h, catalyst loading of 0.192m 3 The preheating temperature is 250 ℃ and the airspeed is 10416h -1 The concentration of the waste gas is 2800-3000mg/m 3 The packing mode is 4 layers by 96 blocks (100 by 50 per block specification, unit mm).
Project device: catalytic combustion device of Tianjin Tianmai limited company; monitoring instrument: hand-held portable analyzer for wary in the united states; waste gas source: paint spraying waste gas of a certain paint spraying factory; test airspeed: 10000h -1 The method comprises the steps of carrying out a first treatment on the surface of the Test concentration: 2800-3000mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the Test time: stable and continuous operation is carried out for 30 days; and (3) selecting a catalyst: the catalyst prepared in example 1.
The test results are shown in table 2:
table 2:
as can be seen from Table 2, the catalyst prepared in example 1 of the present application was used for 30 days at a gas inlet concentration of at least 2800mg/m 3 On the premise that the concentration of the discharged gas can be kept below 29.5mg/m 3 The conversion rate can be kept above 98.98%. Therefore, the catalyst disclosed by the application is good in stability and long in service life.
The foregoing description is only of the preferred embodiments of the present application, and is not intended to limit the scope of the claims, and all equivalent structures or equivalent processes using the descriptions and drawings of the present application, or direct or indirect application in other related technical fields are included in the scope of the claims of the present application.
Claims (10)
1. A catalyst for remediation of volatile organics, the catalyst comprising:
a high load carrier;
the modified coating film layer is coated on the surface of the high-load carrier, and consists of cerium nitrate, lanthanum nitrate, zirconium nitrate, praseodymium nitrate, yttrium nitrate, potassium nitrate, sodium nitrate, calcium nitrate and nano aluminum oxide solution, wherein the total concentration of metal ions is 1mol/L-5mol/L, and the coating amount of the modified coating film layer is 2% -10% of the weight of the high-load carrier;
an active material layer including a first active material and a second active material; wherein the first active substance consists of manganese nitrate, cobalt nitrate, copper nitrate, chromium nitrate and ammonium metavanadate, ammonia water is introduced as a reducing agent, and the total concentration of metal ions is 1mol/L-10mol/L; the second active substance consists of platinum nitrate, palladium nitrate, rhodium nitrate, silver nitrate and ruthenium nitrate, and the total concentration of metal ions is 0.5-20mol/L.
2. The catalyst for treating volatile organic compounds according to claim 1, wherein the molar ratio of metal ions in the cerium nitrate, lanthanum nitrate, zirconium nitrate, praseodymium nitrate, yttrium nitrate, potassium nitrate, sodium nitrate, calcium nitrate and nano aluminum oxide solution in the modified coating film layer is 30-80:5-12:2-7:0.5-3:0.1-0.3:0.1-0.5:0.1-0.3:0.1-0.3:1-5.
3. The catalyst for treating volatile organic compounds according to claim 1, wherein the first active material has a metal ion molar ratio of manganese nitrate, cobalt nitrate, copper nitrate, chromium nitrate and ammonium metavanadate of 2 to 9:8-15:5-20:1-5:1-10, wherein the molar ratio of the ammonia water to the total metal ions is 0.1-5.
4. The catalyst for treating volatile organic compounds according to claim 1, wherein the molar concentration ratio of metal ions of platinum nitrate, palladium nitrate, rhodium nitrate, silver nitrate and ruthenium nitrate in the second active material is 0.5 to 1:0.01-0.1:0.01-0.08:0.5-5:0.2-3.
5. The catalyst for the remediation of volatile organic compounds of claim 4 wherein the second active material is in the form of a reductive dispersion gel solution and is supported by dip coating;
wherein the reductive dispersion gel solution is prepared by using a reducing agent, a dispersing agent and a gelling agent to prepare platinum nitrate, palladium nitrate, rhodium nitrate, silver nitrate and ruthenium nitrate in the second active substance; the reducing agent is glucose, the dispersing agent is polyethylene glycol 200 and urea, and the gelling agent is citric acid.
6. The catalyst for remediation of volatile organic compounds of claim 1 wherein the high-load carrier comprises a matrix material, a dispersant, a binder, and a pore former;
wherein, the matrix material comprises the following components by mass percent: 15% -50%:10% -20%:1% -5%:5% -15% of aluminum oxide, silicon dioxide, magnesium oxide, calcium oxide and pseudo-boehmite;
the dispersing agent is polyethylene glycol 200 and urea, and the mass of the polyethylene glycol 200 and the urea is 0.5% -1% of the mass of the matrix material;
the binder is polyethylene glycol 8000, the pore-forming agent is polyvinyl alcohol, and the total mass of the polyethylene glycol 8000 and the polyvinyl alcohol is 1% -3% of the total mass of the matrix material and the dispersing agent; wherein, the mass percentage of the polyethylene glycol 8000 and the polyvinyl alcohol is 20% -50%:50% -80%.
7. A method for preparing the catalyst for treating volatile organic compounds according to any one of claims 1 to 6, comprising the steps of:
preparing a first high-load carrier;
preparing a modified coating film solution, coating the modified coating film solution on the high-load carrier, and performing a first drying treatment and a first calcination treatment to obtain a second high-load carrier;
preparing a first active material solution, and spraying the first active material solution on the surface of the second high-load carrier in a double-channel independent instantaneous high-temperature reduction spraying mode, so that the first active material is embedded into the second high-load carrier to obtain a first intermediate;
preparing a second active material solution, carrying the second active material solution on the first intermediate in a dip-coating mode, and performing a second drying treatment to obtain a second intermediate;
and (3) treating the second intermediate at a high temperature, wherein the treatment temperature is 250-350 ℃, the heating rate is 5-10 ℃/min, and the treatment time is 2-6 h.
8. The method for preparing a catalyst for treating volatile organic compounds according to claim 7, wherein the first drying treatment parameters are as follows: the drying temperature is 80-120 ℃ and the drying time is 12-24 hours; the first calcination treatment parameters are as follows: the calcination temperature is 450-550 ℃, the heating rate is 5-10 ℃/min, and the calcination time is 2-6 h; the parameters of the secondary drying treatment are as follows: the drying temperature is 120-150 ℃ and the drying time is 12-24h.
9. The method for preparing a catalyst for managing volatile organic compounds according to claim 7, wherein the preparing a first highly loaded carrier comprises:
mixing aluminum oxide, silicon dioxide, magnesium oxide, calcium oxide and pseudo-boehmite to obtain a mixed material A; mixing the mixture A with urea to obtain a mixture B; mixing the mixture B with polyethylene glycol 8000 and polyvinyl alcohol, and then adding dilute nitric acid and acetic acid for hydrolysis to obtain a carrier mixed raw material C; and (3) carrying out extrusion molding treatment on the carrier mixed raw material C, and sequentially carrying out drying treatment and calcination treatment to obtain the first high-load carrier with the water absorption rate of 25% -30%.
10. The method for preparing a catalyst for treating volatile organic compounds according to claim 9, wherein the drying treatment parameters are: the drying temperature is 80-130 ℃ and the drying time is 8-16 h; the calcination treatment parameters are as follows: the calcination temperature is 1200-1400 ℃, the temperature rising rate is 5-20 ℃/min, and the calcination time is 2-4 h.
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