CN114700106A - 一种多级孔道结构分子筛脱硝催化剂的制备方法 - Google Patents
一种多级孔道结构分子筛脱硝催化剂的制备方法 Download PDFInfo
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- CN114700106A CN114700106A CN202210546236.XA CN202210546236A CN114700106A CN 114700106 A CN114700106 A CN 114700106A CN 202210546236 A CN202210546236 A CN 202210546236A CN 114700106 A CN114700106 A CN 114700106A
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- molecular sieve
- zsm
- catalyst
- denitration catalyst
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 65
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000011148 porous material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 16
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 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 description 24
- 239000000243 solution Substances 0.000 claims description 19
- 239000011572 manganese Substances 0.000 claims description 18
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000005342 ion exchange Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 150000000703 Cerium Chemical class 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims 3
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000005216 hydrothermal crystallization Methods 0.000 abstract description 4
- 238000005470 impregnation Methods 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000003738 black carbon Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 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 2
- 150000002603 lanthanum Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000002751 molybdenum Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 150000003657 tungsten Chemical class 0.000 description 2
- 150000003754 zirconium Chemical class 0.000 description 2
- 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 description 2
- 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 1
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- FUECGUJHEQQIFK-UHFFFAOYSA-N [N+](=O)([O-])[O-].[W+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[W+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] FUECGUJHEQQIFK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 1
- HKVFISRIUUGTIB-UHFFFAOYSA-O azanium;cerium;nitrate Chemical compound [NH4+].[Ce].[O-][N+]([O-])=O HKVFISRIUUGTIB-UHFFFAOYSA-O 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- 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 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 description 1
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- LITQZINTSYBKIU-UHFFFAOYSA-F tetracopper;hexahydroxide;sulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[O-]S([O-])(=O)=O LITQZINTSYBKIU-UHFFFAOYSA-F 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明公开了一种多级孔道结构分子筛脱硝催化剂的制备方法，包括以下步骤，S1：对碳纳米管进行酸化处理；S2：制备多级结构ZSM‑5分子筛；S3：制备H型ZSM‑5分子筛；S4：制备多级孔道结构ZSM‑5脱硝催化剂；本发明通过变温水热晶化法，合成ZSM‑5分子筛，有效引入均匀的多级孔道，并通过浸渍法将Mn、Ce负载在多级孔道分子筛上，解决了普通分子筛孔道小，大直径分子进入孔道困难，孔道内形成的大分子不能快速溢出，容易积炭，导致催化效果低，容易失活等问题，同时提高了催化剂的稳定性，提高了分子筛催化剂的脱硝催化效率及抗硫性能，提高了NOx去除率，同时催化剂使用时间可延长一倍，提高了催化剂的使用效率。
Description
技术领域
本发明涉及一种多级孔道结构分子筛脱硝催化剂的制备方法。
背景技术
氮氧化物(NOx)是大气中主要的污染物。NOx的大量排放会给人类的身体健康、生活活动和自然生态环境带来严重的危害，包括对人体的致毒作用、形成的酸雨或酸雾对植物的损害作用、与碳氢化合物形成光化学烟雾对臭氧层的破坏等。因此，对烟气进行脱硝以及开发高效的脱硝催化剂显得至关重要。沸石分子筛以及改性分子筛是目前研究比较活跃的一类催化剂，具有较宽的活性温度窗口、较高的催化活性和较好的热稳定性等优点，近年来受到大量关注。
目前，用于脱硝的传统ZSM-5分子筛具有微孔结构，但这种微孔结构的分子筛催化作用并不理想，不利于大分子反应物进入活性位点，也不利于反应物、中间产物、目标产物的流通，容易造成转化率降低以及焦炭沉积，制约了它在大分子催化转化中的应用。如果能够采取一定方法缩短分子筛扩散路径，提高孔道大小，即可推动分子筛在催化方向的新发展。此外，催化剂中的活性组分常常会因为团聚成团簇或大纳米粒子而导致其无法均匀地分散在催化剂表面，进而造成催化活性降低，影响脱硝效果，所以实现催化剂中活性组分的高度分散尤为重要。
多级孔道分子筛通过同时加入微孔结构和介孔结构的导向剂，获得了兼具微孔和介孔的结构，可以结合微孔分子筛的可调变酸性、良好水热稳定性和介孔材料的优异传质扩散性能等优点。且在不需要任何的化学改性的情况下，孔径的增大有助于催化活性的提高且大大减少催化剂表面焦炭的沉积。
过渡金属Ce、Mn具有多种可变价态，具有较强的氧化还原性能，Mn基分子筛催化剂在催化反应中表现出良好的低温脱硝活性，Ce有优良的储氧能力，展现了很强的应用潜力。所以研制Ce、Mn负载的多级孔道的分子筛并研究其在脱硝催化剂领域的应用是非常有意义的。
发明内容
为解决现有技术中存在的上述缺陷，本发明的目的在于提供一种多级孔道结构分子筛脱硝催化剂的制备及其在脱硝方面的应用。通过采用四丙基氢氧化铵为模板剂，碳纳米管为第二模板，通过变温水热晶化法，合成ZSM-5分子筛，有效引入均匀的多级孔道，并通过浸渍法将Mn、Ce负载在多级孔道分子筛上，解决了普通分子筛孔道单一，催化性能不佳的问题。
一种多级孔道结构分子筛脱硝催化剂的制备方法，包括S1：对碳纳米管进行酸化处理；
S2：制备多级结构ZSM-5分子筛；
称取重量份为260-390份四丙基氢氧化铵加入到水中，搅拌均匀，加入重量份为5-8份异丙醇铝并搅拌至溶解，逐滴加入重量份为160-250份正硅酸乙酯，室温下搅拌16-24h后加入重量份为8-12份S1中酸化处理的碳纳米管，继续搅拌10-12h，陈化2-4h，然后将合成液转移至高压釜中，密封，在170℃晶化20-24h，再于100℃晶化20-24h，最后再升温至170℃继续晶化20-24h，晶化结束后，冷却至室温，将合成的产物反复洗涤至滤液pH为9-10，100℃烘干，于500-550℃下焙烧6-8h，得到多级结构ZSM-5分子筛；
S3：制备H型ZSM-5分子筛；
将S2中制备的多级结构ZSM-5分子筛用1mol/L的硝酸铵溶液进行离子交换，再经洗涤、干燥后，再升温至500-550℃焙烧6-8h，得到H型分子筛；
S4：制备多级孔道结构ZSM-5脱硝催化剂；
取S3中制备的H型ZSM-5分子筛浸渍在化学盐水溶液中，所述的化学盐水溶液中的盐为锰盐或铈盐中的一种或多种，充分搅拌20-24h后在100-120℃下烘干，于500-550℃下焙烧6-8h，得到多级孔道结构ZSM-5脱硝催化剂。
优选地，S4中所述的锰盐是硫酸锰、乙酸锰、碳酸锰和硝酸锰中的至少一种。
优选地，S4所述的化学盐水溶液还可以包含其他盐，如钼盐、钨盐、铁盐、钴盐、铜盐、镧盐、铈盐、锆盐和锡盐的一种或多种。钼盐为正钼酸铵、仲钼酸铵、二钼酸铵、四钼酸铵、硝酸钼和硫酸钼中的至少一种；钨盐为偏钨酸铵、仲钨酸铵、钨酸铵和硝酸钨中的的至少一种；铁盐为硝酸铁、硫酸亚铁、硫酸铁和乙酸铁中的至少一种；钴盐为硝酸钴、硫酸钴和乙酸钴中的至少一种；铜盐为硝酸铜、硫酸铜、氯化铜、碱式碳酸铜和碱式硫酸铜中的至少一种；镧盐为硝酸镧、硫酸镧和乙酸镧中的至少一种；铈盐为硝酸铈、硝酸铈铵和硫酸铈中的至少一种；锆盐为硝酸锆、氯化锆、氧氯化锆和硫酸锆中的至少一种；锡盐为氯化亚锡、结晶四氯化锡和草酸亚锡中的至少一种。
优选地，S4中所述的化学盐水溶液中的铈盐是指硝酸铈。
优选地，所述得硝酸盐水溶液的浓度为20％～50％。
优选地，所述硝酸锰和硝酸铈的混合溶液的质量浓度为20％～50％。
优选地，所述含硝酸锰和硝酸铈的混合溶液中锰与铈摩尔比为1：0.2。
优选地，在进行离子交换时，温度为70～90℃。
优选地，在进行离子交换时，温度为80℃，离子交换的次数为4次。
有益效果：
本发明通过采用四丙基氢氧化铵为模板剂，碳纳米管为第二模板，通过变温水热晶化法，合成ZSM-5分子筛，有效引入均匀的多级孔道，并通过浸渍法将Mn、Ce负载在多级孔道分子筛上，解决了普通分子筛孔道小，大直径分子进入孔道困难，孔道内形成的大分子不能快速溢出，容易积炭，导致催化效果低，容易失活等问题。同时，尺寸极小的纳米棒和存在于晶间的介孔有利于产物分子的传递扩散,因而提高了催化剂的稳定性。
本发明方法制备的分子筛同时具有介孔和微孔结构，且同时可负载Mn、Cu、Ce等金属，提高了分子筛催化剂的脱硝催化效率及抗硫性能。
本发明制备的分子筛在氮氧化物去除方面，NOx转化率在95％以上，提高了NOx去除率，同时催化剂使用时间可延长一倍，提高了催化剂的使用效率。
具体实施方式
为了加深对本发明的理解，下面将结合实施例对本发明作进一步详述，该实施例仅用于解释本发明，并不构成对本发明保护范围的限定。
实施例1
第一步：对碳纳米管进行酸化处理
取1.5g原始碳纳米管，加入200mL质量浓度为68％的硝酸溶液，超声30min，加热至80℃回流处理24h，冷却至室温，倒去上层溶液，将底部的碳纳米管用稀硝酸溶液清洗至溶液不显示黑色，倒去上层溶液得到黑色的碳纳米管，用去离子水洗涤至中性，于120℃烘干备用。
第二步：制备多级结构ZSM-5分子筛
以碳纳米管为第二模板剂，以正硅酸乙酯为硅源，以异丙醇铝为铝源，以四丙基氢氧化铵为结构导向剂，采用水热晶化法合成得到多级结构ZSM-5分子筛。
称取32.5g四丙基氢氧化铵(25％水溶液)加入到50g水中，搅拌均匀，加入0.68g异丙醇铝并搅拌至完全溶解变澄清，逐滴加入20.8g正硅酸乙酯，室温下搅拌24h后加入1.2g第一步酸化处理好的碳纳米管，继续搅拌10h，停止搅拌，陈化3h，然后将合成液转移至高压釜中，密封，将高压釜转移至烘箱中进行晶化，晶化条件为170℃晶化24h，再于100℃晶化24h，最后再升温至170℃继续晶化24h，晶化结束后取出高压釜，冷却至室温，将合成的产物用水反复洗涤至滤液pH为9-10，100℃烘干，在马弗炉中升温至500℃焙烧8h，去除有机模板和碳纳米管，得到多级结构ZSM-5分子筛。
第三步：制备H型ZSM-5分子筛
将所述多级结构ZSM-5分子筛用20倍体积的1mol/L的NH4NO3溶液在80℃下进行离子交换，共进行4次离子交换，每次时间不少于2h，交换完毕再用沸水洗涤、干燥过夜，在马弗炉中升温至550℃焙烧6h，得到H型分子筛。
第四步：制备Mn/HZSM-5催化剂
用浸渍法制备。取所述多级结构ZSM-5分子筛浸渍在含Mn(NO3)2的水溶液中，硝酸锰水溶液的质量浓度为50％，充分搅拌24h后在120℃下烘干，在马弗炉中升温至550℃焙烧6h，制的含Mn的多级孔道结构ZSM-5脱硝催化剂。
实施例2
第一步至第三步与实施例1相同，仅第四步不同。
第四步：制备Ce/HZSM-5催化剂
取所述多级结构ZSM-5分子筛浸渍在含Ce(NO3)3的水溶液中，硝酸铈水溶液的质量浓度为50％，充分搅拌24h后在120℃下烘干，在马弗炉中升温至550℃焙烧6h，制的含Ce的多级孔道结构ZSM-5脱硝催化剂。
实施例3
第一步至第三步与实施例1相同，仅第四步不同。
第四步：制备Mn-Ce/HZSM-5催化剂
取所述多级结构ZSM-5分子筛浸渍在含Ce(NO3)3的水溶液中，硝酸锰和硝酸铈混合水溶液的质量浓度为50％，且金属元素Mn与Ce摩尔比为1：0.2，充分搅拌24h后在120℃下烘干，在马弗炉中升温至550℃焙烧6h，制的含Ce的多级孔道结构ZSM-5脱硝催化剂。
实施例4
步骤与实施例1相同，仅硝酸锰的浓度不同。
取所述多级结构ZSM-5分子筛浸渍在含Mn(NO3)2的水溶液中，硝酸锰水溶液的质量浓度为20％，充分搅拌24h后在120℃下烘干，在马弗炉中升温至550℃焙烧6h，制的含Mn的多级孔道结构ZSM-5脱硝催化剂。
实施例5
步骤与实施例1相同，仅硝酸锰的浓度不同。
取所述多级结构ZSM-5分子筛浸渍在含Mn(NO3)2的水溶液中，硝酸锰水溶液的质量浓度为40％，充分搅拌24h后在120℃下烘干，在马弗炉中升温至550℃焙烧6h，制的含Mn的多级孔道结构ZSM-5脱硝催化剂。
对比例1
将普通市售的HZSM-5分子筛(厂家：南开催化剂厂)用20倍体积的1mol/L的NH4NO3溶液在80℃下进行离子交换，共进行4次离子交换，每次时间不少于2h，交换完毕再用沸水洗涤、干燥过夜，在马弗炉中升温至550℃焙烧6h，然后再浸渍在含Mn(NO3)2的水溶液中，硝酸锰水溶液的质量浓度为50％，充分搅拌24h后在120℃下烘干，在马弗炉中升温至550℃焙烧6h，制的普通的含Mn的ZSM-5脱硝催化剂。
催化剂脱硝活性测试方法如下：
将制备的催化剂用于固定床反应测试活性，包括以下步骤：上述实施案例1得到的催化剂A经压片、过筛后，取20～40目的催化剂颗粒进行活性评价。催化剂的活性评价装置为常压式微型固定床反应装置，由气体混合预热炉和反应炉组成反应系统，反应器为内径7mm的石英管。在实验过程中采用程序升温的方式进行反应，用温度控制仪控制加热炉的温度。到达数据采集点时停留30min进行数据处理并记录数据。反应条件为：500ppm NO、500ppm NH3、5v％O2、N2为平衡气、气体总流量为600mL/min、催化剂用量为200mg，反应体积空速为180000h-1。NO、NH3和NO2的浓度均由烟气分析仪(德国德图仪器testo340)进行在线定性，定量分析，N2O的浓度则由配有2m光程气体池的傅里叶变换红外光谱仪(NicoletiS50)测得。
将实施例1-5制备的分子筛催化剂与对比例1的分子筛催化剂进行脱硝活性测试，具体对比结果如表1所示。
表1不同催化剂在不同温度下的脱硝效果
由表1可以看出，本发明提供的多级孔道结构ZSM-5脱硝催化剂具有更宽的温度窗口、优异的脱硝活性和较好的稳定性等特点。本发明还创造性的发现Mn-Ce/HZSM-5催化剂在较低温度时依然表现良好的催化活性，可以适用于低温脱硝。本发明方法不仅具有成本低、工艺简单、操作简便，而且具有良好的经济效益和环境效益。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (7)
1.一种多级孔道结构分子筛脱硝催化剂的制备方法，其特征在于，包括以下步骤：
S1：对碳纳米管进行酸化处理；
S2：制备多级结构ZSM-5分子筛；
称取重量份为260-390份四丙基氢氧化铵加入到水中，搅拌均匀，加入重量份为5-8份异丙醇铝并搅拌至溶解，逐滴加入重量份为160-250份正硅酸乙酯，室温下搅拌16-24h后加入重量份为8-12份S1中酸化处理的碳纳米管，继续搅拌10-12h，陈化2-4h，然后将合成液转移至高压釜中，密封，在170℃晶化20-24h，再于100℃晶化20-24h，最后再升温至170℃继续晶化20-24h，晶化结束后，冷却至室温，将合成的产物反复洗涤至滤液pH为9-10，100℃烘干，于500-550℃下焙烧6-8h，得到多级结构ZSM-5分子筛；
S3：制备H型ZSM-5分子筛；
将S2中制备的多级结构ZSM-5分子筛用1mol/L的硝酸铵溶液进行离子交换，再经洗涤、干燥后，再升温至500-550℃焙烧6-8h，得到H型分子筛；
S4：制备多级孔道结构ZSM-5脱硝催化剂；
取S3中制备的H型ZSM-5分子筛浸渍在化学盐水溶液中，所述的化学盐水溶液中的盐为锰盐或铈盐中的一种或多种，充分搅拌20-24h后在100-120℃下烘干，于500-550℃下焙烧6-8h，得到多级孔道结构ZSM-5脱硝催化剂。
2.根据权利要求1所述的一种多级孔道结构分子筛脱硝催化剂的制备方法，其特征在于，S4中所述的化学盐水溶液是指硝酸锰的水溶液。
3.根据权利要求2所述的一种多级孔道结构分子筛脱硝催化剂的制备方法，其特征在于，所述的硝酸锰的水溶液的浓度为20％～50％。
4.根据权利要求1所述的一种多级孔道结构分子筛脱硝催化剂的制备方法，其特征在于，S4中所述的化学盐水溶液是指硝酸铈的水溶液。
5.根据权利要求1所述的一种多级孔道结构分子筛脱硝催化剂的制备方法，其特征在于，S4中所述的化学盐水溶液是指硝酸锰和硝酸铈的混合溶液。
6.根据权利要求5所述的一种多级孔道结构分子筛脱硝催化剂的制备方法，其特征在于，所述的硝酸锰和硝酸铈的混合溶液中锰与铈的摩尔比为1：0.2。
7.根据权利要求1所述的一种多级孔道结构分子筛脱硝催化剂的制备方法，其特征在于，进行离子交换的温度为70～90℃。
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