CN109317188A - 一种介孔FeCu-ZSM-5分子筛的制备方法及应用 - Google Patents
一种介孔FeCu-ZSM-5分子筛的制备方法及应用 Download PDFInfo
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- CN109317188A CN109317188A CN201811355699.8A CN201811355699A CN109317188A CN 109317188 A CN109317188 A CN 109317188A CN 201811355699 A CN201811355699 A CN 201811355699A CN 109317188 A CN109317188 A CN 109317188A
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- molecular sieve
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- acid
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 83
- 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 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000005342 ion exchange Methods 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 72
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 58
- 239000000377 silicon dioxide Substances 0.000 claims description 30
- 238000002425 crystallisation Methods 0.000 claims description 28
- 230000008025 crystallization Effects 0.000 claims description 28
- 229910052681 coesite Inorganic materials 0.000 claims description 27
- 229910052906 cristobalite Inorganic materials 0.000 claims description 27
- 229910052682 stishovite Inorganic materials 0.000 claims description 27
- 229910052905 tridymite Inorganic materials 0.000 claims description 27
- 229910052742 iron Inorganic materials 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 230000032683 aging Effects 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 25
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 21
- 239000010703 silicon Substances 0.000 claims description 21
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- 229910001868 water Inorganic materials 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 8
- -1 4-propyl bromide Chemical compound 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000010189 synthetic method Methods 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 235000019353 potassium silicate Nutrition 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 238000001994 activation Methods 0.000 claims description 4
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 4
- 229910001570 bauxite Inorganic materials 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 229940051250 hexylene glycol Drugs 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- 241000907663 Siproeta stelenes Species 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052934 alunite Inorganic materials 0.000 claims description 2
- 239000010424 alunite Substances 0.000 claims description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 2
- 229910052955 covellite Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 239000011019 hematite Substances 0.000 claims description 2
- 229910052595 hematite Inorganic materials 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 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 claims description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000011022 opal Substances 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052683 pyrite Inorganic materials 0.000 claims description 2
- 239000011028 pyrite Substances 0.000 claims description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 2
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 claims 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000007598 dipping method Methods 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract description 2
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- 238000013480 data collection Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910052691 Erbium Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 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
- 230000001195 anabolic effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- 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
- B01D53/90—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本发明属于环保催化剂的绿色制备技术领域,公开一种介孔FeCu‑ZSM‑5分子筛的制备方法及应用,特别涉及一种以一锅法合成介孔FeCu‑ZSM‑5分子筛的方法及其在选择性催化还原(SCR)脱硝反应中的应用,并首次提出将脱模与离子交换后的两次焙烧合二为一,即将合成的原粉进行交换后经一次焙烧即可直接制备具有温窗宽、成本低、水热稳定性好及SCR脱硝活性高等特点的FeCu‑ZSM‑5分子筛,克服了传统浸渍或离子交换法步骤繁琐、成本高、污染排放大的缺点,且合成过程不使用介(大)孔模板剂,也不采用后处理的方法来构造介孔,因此,本发明方法不仅具有工艺简单、操作简便等优势,而且具有良好的经济和环境效益。
Description
技术领域
本发明属于环保催化剂领域,具体涉及一种介孔FeCu-ZSM-5分子筛的制备方法及其在氮氧化物选择性催化还原反应中的应用。
背景技术
目前氮氧化物已成为仅次于可吸入颗粒物和二氧化硫的重要大气污染物,主要来自于催化裂化(FCC)烟气、汽车尾气和火电厂废气排放。近些年来NH3-SCR脱硝技术逐渐成为研究的焦点,并被大量专家学者认为是最具有潜力的脱硝技术。分子筛由于具有规则有序的结构、可调变的骨架组成、较高的比表面积、吸附容量和阳离子可交换性、良好的孔道择形性、优异的热稳定性和化学稳定性等特点,已被广泛应用于石油化工、精细化工和绿色化工等领域。近些年来,杂原子修饰的ZSM-5分子筛成为环保领域研究的热点之一,尤其以Fe或Cu修饰的ZSM-5分子筛在脱硝领域具有广阔的应用前景。
CN201610320403.3公开了一种Fe-ZSM-5掺杂Rh和Er复合型催化剂的制备方法和应用。通过水热法制备出钠型高硅铝比Na-ZSM-5分子筛,将其与NH4Cl溶液交换,制备出NH4-ZSM-5分子筛,随后将NH4-ZSM-5分子筛加入硝酸铁溶液,通过离子交换法制备出Fe-ZSM-5分子筛,再通过浸渍法掺杂少量Rh和Er,制备出高比表面积(350~420 m2/g)的复合型Rh/Er/Fe/ZSM-5催化剂。其催化剂虽然在一定的温度范围下具有较高的NO初始转化率,但其制备过程较为复杂,并且其通过钠型分子筛转变为氨型分子筛的焙烧,不仅存在高能耗,同时面临环保问题,随着我国环保要求的不断提高,氨的排放面临着巨大挑战,同时稀有金属的使用依然面临成本和资源匮乏的一系列问题。
CN201711364463.6公开了一种离子交换制备Cu-ZSM-5的方法:采用液相离子交换法和固相分散法相结合的方法,具体是:按质量比称取硝酸铜固体和HZSM-5分子筛原粉,在研钵中充分研磨混合;移入无水乙醇/蒸馏水中,搅拌使其快速混合,制得悬浊液;于超声波中加热进行离子交换;减压蒸馏至少量液体,移至坩埚中,放进烘箱干燥至固态;称取田菁粉和上述固体研磨后置于容器中,滴加无水乙醇/蒸馏水混合液揉至团状,将其压成厚度均匀的片状固体,置于烘箱中干燥;将干燥后的片状固体破碎、过筛,放入微波马弗炉中升温焙烧,自然冷却。此发明具有铜离子分散性好、NO分解率高的特点,但其复杂制备方法在工业化的道路上必然面对一系列阻碍,同时存在原子利用率低,其采用固相液相分离的方法依然面临着工业化的挑战。
CN201310371632.4公开了Cu-Fe-ZSM-5-凹土复合烟气脱硝催化剂的制备方法,首先,凹土经煅烧、热酸液处理,抽滤、水洗得到酸化凹土,随后添加碱液、有机模板剂,陈化、水热晶化、抽滤、水洗、烘干、煅烧制备ZSM-5分子筛;然后,将ZSM-5分子筛、凹土、铜盐和铁盐的混合液混合搅拌,加热回流处理,烘干、挤条、煅烧成型制备Cu-Fe-ZSM-5-凹土复合烟气脱硝催化剂。虽然利用凹土载体和粘性特性,引用ZSM-5对NO的吸附特性,引入廉价铁盐,降低成本,但其温窗较窄,仅在250~330 oC区间内表现出脱硝活性,其温窗显然不符合未来脱硝领域的发展趋势。
目前FeCu-ZSM-5分子筛的制备均是通过将合成的分子筛与Fe盐和Cu盐进行离子交换方法制得,不仅步骤繁琐、能耗物耗高,且脱硝温窗较窄(主要是低温脱硝活性较差),同时浸渍杂原子容易在分子筛表面产生团聚、阻碍孔道、遮挡活性位等不可忽视的缺点。因此,若能在使用廉价模板剂基础上,发展高性能介孔FeCu-ZSM-5型分子筛的一锅法低成本原位合成新技术,有望得到活性位分布较为适宜,同时降低分子筛的生产成本,并提高其脱硝性能,具有重要的科学研究价值和广阔的工业应用前景。
发明内容
为解决上述问题,本发明提供了一种介孔FeCu-ZSM-5分子筛的制备方法,在不使用介(大)孔模板剂、不采用后处理的条件下,采用分段调控合成体系pH值的一锅法原位合成介孔FeCu-ZSM-5分子筛,无需脱除微孔模板剂即可直接进行离子交换,且具有较宽的温窗和可调的Fe和Cu含量,并且分子筛骨架内Fe含量远高于孔道及表面,且铜主要以二价形式存在,不存在团聚的氧化铜,即分子筛中的铁与铜绝大部分均以脱硝活性位的形式存在。
一种介孔FeCu-ZSM-5分子筛,包括以下原料:去离子水、铝源、硅源、铁源、铜源、酸源和模板剂。
一种介孔FeCu-ZSM-5分子筛的制备方法,制备方法为化学试剂合成法或矿物合成法中的一种。
所述化学合成法具体包括如下步骤:
(1)在20~90 oC下,将去离子水、铝源、硅源、铁源、铜源和模板剂在搅拌条件下混合均匀,控制各种原料的投料量使得合成体系中各物质的摩尔比为SiO2/Al2O3=10~∞,SiO2/Fe2O3=10~350,SiO2/CuO=10~150,Na2O/SiO2=0.1~0.5,H2O/SiO2=10~50,模板剂/SiO2=0.01~0.5;混合后加入酸源,进行第一次老化,再加入酸源,调节体系pH为7~8.5,进行第二次老化,即获得老化后的凝胶;
(2)将步骤(1)中获得的老化后的凝胶转移至含聚四氟乙烯内衬的反应釜中密封晶化,待晶化结束后,将晶化产物冷却、过滤除去母液,滤饼用去离子水洗涤至中性,干燥得到固体,之后将固体进行离子交换,并过滤、洗涤、干燥得到粉末;所述干燥条件为80-150℃,干燥过夜;
(3)将步骤(2)中获得粉末置于马弗炉中焙烧得到FeCu-ZSM-5分子筛。
所述铁源为硝酸铁、氯化铁和硫酸铁中的一种或几种,所述的铜源为硝酸铜、三水硝酸铜、九水硝酸铜、二水氯化铜中的一种或者几种的混合物,所述的酸源为2-羟基-均丙三羧酸、亚硫酸、亚硝酸、硫酸、盐酸、硝酸、草酸、醋酸中的一种或几种的混合物;所述的硅源为水玻璃、硅溶胶、正硅酸乙酯、固体硅胶中的一种或几种;所述的铝源为铝酸钠或者硫酸铝中的一种或者两种的混合物,中所述的模板剂为四辛基溴化铵、四丁基溴化铵、十六烷基三甲基溴化铵、四丙基氢氧化铵、四丙基溴化铵、己二醇、正丁胺、乙胺中的一种或几种的混合物。
所述矿物合成法具体包括如下步骤:
(1)矿物的活化:将铝源、硅源、铁源、铜源分别进行活化;
(2)将步骤(1)活化后的后的矿物与氢氧化钠、去离子水和晶种混合均匀后,控制各种原料的投料量使得合成体系中各物质的摩尔比为SiO2/Al2O3=10~∞,SiO2/Fe2O3=10~350,SiO2/CuO=10~150,Na2O/SiO2=0.1~0.5,H2O/SiO2=10~50,模板剂/SiO2=0.01~0.5;混合后加入酸源,调节体系pH为5~13,进行老化,即获得老化后的凝胶;
(3)将步骤(2)中获得的老化后的凝胶转移至含聚四氟乙烯内衬的反应釜中密封晶化,待晶化结束后,将晶化产物冷却、过滤除去母液,滤饼用去离子水洗涤至中性,干燥得到固体,之后将固体进行离子交换,并过滤、洗涤、干燥得到粉末;所述干燥条件为80-150℃,干燥过夜;
(4)将步骤(3)中获得粉末置于马弗炉中焙烧得到FeCu-ZSM-5分子筛。
所述的铁源为铝土矿、硅藻土、累托土、黄铁矿、云母赤铁矿、赤泥中的一种或几种,所述的铜源为磁铁矿、孔雀石、铜蓝、黄铜矿中的一种或者几种的混合,所述的酸源为2-羟基-均丙三羧酸、亚硫、和亚硝酸、硫酸、盐酸、硝酸、草酸、醋酸中的一种或几种的混合物,所述的硅源为铝土矿、硅藻土、累托土、天然沸石或蛋白石中的一种或两种,所述的铝源为云母、明矾石、铝土矿、硅藻土、累托土、天然沸石中的一种或几种的混合物,所述的模板剂为四辛基溴化铵、四丁基溴化铵、十六烷基三甲基溴化铵、四丙基氢氧化铵、四丙基溴化铵、己二醇、正丁胺、乙胺中的一种或几种的混合物。
所述老化是在60~90 oC条件下进行,老化时间为2~12 h;所述晶化是在100~190 oC条件下进行,晶化时间为12~96 h。
所述离子交换具体的具体方法为:将所述干燥得到的固体与0.1~2 M的NH4Cl溶液按照质量比1:10~1:30的比例混合进行离子交换,于10~80 oC加热搅拌处理3~8 h。
所述焙烧时间为4~10 h,焙烧温度为500~600 oC。
将制备得到的FeCu-ZSM-5催化剂应用于氮氧化物选择性催化还原反应中。
综上所述,本发明提供了一种FeCu-ZSM-5分子筛及其合成方法。本发明的FeCu-ZSM-5分子筛具有如下优点:
(1)克服了传统浸渍或离子交换制备方法步骤繁琐和成本高的缺点,采用分段调控合成体系pH值的一锅法原位合成介孔FeCu-ZSM-5分子筛,且无需脱除微孔模板剂即可进行离子交换,经济环保高效地合成SCR脱硝性能优良的介孔FeCu-ZSM-5分子筛,其在较宽的温度窗口(150-700 oC)NO转化率高于90%,具备较高的N2选择性(>99%)。
(2)解决了传统浸渍法所面临的工艺复杂、流程长、Fe或Cu容易团聚合成周期长等难题,同时避免了介(大)孔模板剂的使用,有效缓解了在脱模时大量氨气等污染气体的释放以及脱除模板剂对分子筛自身孔道造成坍塌等损害,短周期经济环保高效地合成SCR脱硝性能优良的介孔FeCu-ZSM-5分子筛。
(3)本发明方法制备的FeCu-ZSM-5属于梯级孔催化材料,其摩尔硅铝比为10~∞,具有比表面积大、吸附容量大、酸性位丰富的优势,有利于反应物质与活性位的充分接触,同时也解决了内部传质扩散等困扰传统微孔分子筛的问题。
(4)本发明所提供的合成工艺路线不仅可大幅降低分子筛合成的生产成本,而且可极大地提高合成过程的绿色性,所得到的分子筛具有更优的物理化学性质,且其合成成本更低。
(5)短周期制备所得产品介孔分布集中在5~50 nm,比表面积为380~700 m2/g,外比表面积为120~400 m2/g,分子筛中Fe2O3含量为分子筛总重量的0.1~10%,其中骨架Fe的含量占总铁含量的95%以上,且在骨架内分布均匀;分子筛中CuO含量为分子筛总重量的0.1~10%,其中Cu2+的含量占总铜含量的90%以上,且其在分子筛内表面分布较为均匀。
附图说明
图1是本发明实施例1制备得到的FeCu-ZSM-5分子筛的X射线衍射(XRD)谱图。
图2是本发明实施例1制备得到的FeCu-ZSM-5分子筛的N2吸附-脱附等温线。
具体实施方式
以下通过具体实施例详细说明本发明的实施过程和产生的有益效果,旨在有助于更好地理解本发明的实质和特点,不作为对本案可实施范围的限定。
实施例1
将1.32 g Fe(NO3)3·9H2O、0.26 g Cu(NO3)2·3H2O、36.55 g H2O、1.473 g TPABr,14.18 g水玻璃(27.6 wt% SiO2)、2.2 g 2-羟基-均丙三羧酸加入烧杯中调pH至12,30 oC下老化4 h,再加入1.2 g 2-羟基-均丙三羧酸调pH至9,70 oC老化4 h,然后转移至带有聚四氟乙烯内衬的不锈钢高压釜中于170 oC晶化48 h,待晶化结束后,将晶化产物冷却、过滤和洗涤至中性后,放入烘箱于120 oC过夜干燥,得到钠型分子筛。
将钠型分子筛与1 M的NH4Cl溶液按照质量比1:20的比例进行离子交换,于70 oC的恒温水浴锅中搅拌4 h,经抽滤、洗涤、烘干,520 oC焙烧5 h后,即制得氢型FeCu-ZSM-5分子筛,记为催化剂A。图1和图2分别为催化剂A的XRD谱图和N2吸附-脱附等温线,由XRD谱图可知所得产品为高结晶度的ZSM-5分子筛,由N2吸附-脱附等温线可以看出所的样品含有明显的介孔,其中介孔孔径主要集中在10 nm处,比表面积为441 m2/g,外比表面积为151 m2/g,Fe2O3含量为分子筛总重量的3.1%,其中骨架铁的含量占总铁含量的96%。CuO含量为分子筛总重量的1.8%,其中二价铜离子占总铜含量的91%。
实施例2
本实施例提供一种FeCu-ZSM-5催化剂,制备步骤同实施例1,仅调变部分参数,具体如下:
分子筛制备:将2.18 g Fe(NO3)3·9H2O、0.13 g Cu(NO3)2·3H2O、10 g H2O、5.20 g十六烷基三甲基溴化铵、1.069 g铝酸钠、14.18 g水玻璃(27.6 wt% SiO2)、2.2 g H2SO4加入烧杯中调pH至11,40 oC下老化2 h,再加入1.2 g硫酸调pH至8,80 oC老化4 h,然后转移至带有聚四氟乙烯内衬的不锈钢高压釜中于160 oC晶化24 h,待晶化结束后,将晶化产物冷却、过滤和洗涤至中性后,放入烘箱于120 oC过夜干燥,得到钠型分子筛。
将钠型分子筛与1 M的NH4Cl溶液按照质量比1:20的比例进行离子交换,于70 oC的恒温水浴锅中搅拌4 h,经抽滤、洗涤、烘干,530 oC焙烧6 h后,即制得氢型FeCu-ZSM-5分子筛,记为催化剂B。所得样品介孔孔径主要集中在15 nm处,比表面积为470 m2/g,外比表面积为160 m2/g,Fe2O3含量为分子筛总重量的5.4%,其中骨架铁的含量占总铁含量的95.5%。CuO含量为分子筛总重量的0.7%,其中二价铜离子占总铜含量的90%。
实施例3
本实施例提供一种FeCu-ZSM-5催化剂,制备步骤同实施例1,仅调变部分参数,具体如下:
分子筛制备:将5.2 g Fe(NO3)3·9H2O、0.11 g Cu(NO3)2·3H2O、18.3 g H2O、8.67 gTPABr,2.27 g硫酸铝、14.18 g水玻璃(27.6 wt% SiO2)、2.2 g H2SO4加入烧杯中调pH至13,50 oC下老化5 h,再加入3.2 g硫酸调pH至7,60 oC老化6 h,然后转移至带有聚四氟乙烯内衬的不锈钢高压釜中于170 oC晶化48 h,待晶化结束后,将晶化产物冷却、过滤和洗涤至中性后,放入烘箱于90 oC过夜干燥,得到钠型分子筛。
将钠型分子筛与1 M的NH4Cl溶液按照质量比1:15的比例进行离子交换,于70 oC的恒温水浴锅中搅拌3 h,经抽滤、洗涤、烘干,550 oC焙烧7 h后,即制得氢型FeCu-ZSM-5分子筛,记为催化剂C。所得样品介孔孔径主要集中在30 nm处,比表面积为550 m2/g,外比表面积为300 m2/g,Fe2O3含量为分子筛总重量的9.4%,其中骨架铁的含量占总铁含量的97%。CuO含量为分子筛总重量的0.6%,其中二价铜离子占总铜含量的90%。
实施例4
本实施例提供一种FeCu-ZSM-5催化剂,制备方法具体如下:
矿物的活化:将市售的硅藻土烘干、粉碎成粉末,称取50.00 g硅藻土粉末在800 oC焙烧4 h,备用。称取60.00 g累托土、72 g氢氧化钠、300 g水,常温下机械搅拌1 h,之后在255oC烘箱中活化12 h,之后粉碎备用。
分子筛制备:将0.79 g氢氧化钠,加入52.2 g去离子水,混合均匀,加入0.30 g Cu(NO3)2·H2O、4.7 g热活化的硅藻土,加入0.24 g活化后的累托土和0.52 g正丁胺,加入盐酸2 g调节pH至13,转移至60 oC水浴搅拌30 min,,加入盐酸0.5 g调节pH至12,在70 oC水浴搅拌老化4 h,转移至带聚四氟乙烯内衬的高压反应釜,旋转烘箱170 oC晶化72 h,待晶化结束后,将晶化产物冷却、过滤和洗涤至中性后,放入烘箱于110 oC过夜干燥,得到钠型分子筛。
将钠型分子筛与1 M的NH4Cl溶液按照质量比1:30的比例进行离子交换,于80 oC的恒温水浴锅中搅拌4 h,经抽滤、洗涤、烘干,560 oC焙烧8 h后,即制得氢型FeCu-ZSM-5分子筛,记为催化剂D。所得样品介孔孔径主要集中在35 nm处,比表面积为470 m2/g,外比表面积为215m2/g,Fe2O3含量为分子筛总重量的1%,其中骨架铁的含量占总铁含量的98%。CuO含量为分子筛总重量的0.87%,其中二价铜离子占总铜含量的93%。
实施例5
本实施例,将实施案例1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7 mm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30 min进行数据处理并记录数据。反应条件为:500 ppm NO、500 ppm NH3、5 v% O2、N2为平衡气、气体总流量为600 mL/min、催化剂用量为200 mg,反应体积空速为180000 h-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2 m光程气体池的傅里叶变换红外光谱仪(Nicolet iS50)测得。
实施例6
本实施例,将催化剂用于固定床反应测试活性,步骤同实施例5,参数不同之处在于:催化剂更替为实施案例2制备的催化剂B。
实施例7
本实施例,将催化剂用于固定床反应测试活性,步骤同实施例5,参数不同之处在于:催化剂更替为实施案例3制备的催化剂C。
实施例8
本实施例,将催化剂用于固定床反应测试活性,步骤同实施例5,参数不同之处在于:催化剂更替为实施案例4制备的催化剂D。
实施例9
本实施例,将催化剂用于固定床反应测试活性,步骤同实施例5,参数不同之处在于:催化剂更替为实施案例4制备的催化剂经过700 oC下水热处理4 h,记为催化剂E。
对比例1
(1)为了证明本发明所述技术方案的技术效果,本发明还设置了对比例,本对比例中采用的分子筛为南开催化剂厂购买的商业HZSM-5。
(2)称取0.62 g Cu(NO3)2·3H2O和3.22 g Fe(NO3)3·9H2O、5 g去离子水,将其混合均匀后,缓慢滴加到10 g步骤(1)中的分子筛,超声2 h,室温晾干,再将其放置于烘箱中120 oC下干燥8 h,最后于马弗炉中520 oC下焙烧5 h,冷却至室温。记为催化剂F。
上述对比例1得到的催化剂F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7 mm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30 min进行数据处理并记录数据。反应条件为:500 ppm NO、500 ppm NH3、5 v% O2、N2为平衡气、气体总流量为600 mL/min、催化剂用量为200 mg,反应体积空速为180000 h-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2 m光程气体池的傅里叶变换红外光谱仪(Nicolet iS50)测得。
对比例2
(1)为了证明本发明所述技术方案的技术效果,本发明还设置了对比例,本对比例中采用的分子筛为对比案例1制备的催化剂经过700oC下水热老化处理4 h,记为催化剂G。
上述实对比例2得到的催化剂G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7 mm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30 min进行数据处理并记录数据。反应条件为:500 ppm NO、500 ppm NH3、5 v% O2、N2为平衡气、气体总流量为600 mL/min、催化剂用量为200 mg,反应体积空速为180000 h-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2 m光程气体池的傅里叶变换红外光谱仪(Nicolet iS50)测得。
表1 各实施例和固定床反应测试活性的测定结果
注:温窗为NO的转化率>90%时对应的温度区间.
由表1可以看出,本发明提供的介孔FeCu-ZSM-5具有超宽的温度窗口(特别是低温活性)、优异的N2选择性和较好的水热稳定性等特点,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。
尽管以上结合附图对本发明进行了描述,但是本发明并不局限于上述的具体实施方式,上述的具体实施方式仅仅是示意性的,而不是限制性的,本领域的普通技术人员在本发明的启示下,在不脱离本发明宗旨的情况下,还可以做出很多变形,这些均属于本发明的保护之内。
Claims (10)
1.一种介孔FeCu-ZSM-5分子筛,其特征在于,包括以下原料:去离子水、铝源、硅源、铁源、铜源、酸源和模板剂;所述分子筛中Fe2O3含量为分子筛总重量的0.1~10%,其中骨架Fe的含量占总铁含量的95%以上,且在骨架内分布均匀;分子筛中CuO含量为分子筛总重量的0.1~10%,其中Cu2+的含量占总铜含量的90%以上,且其在分子筛内表面分布均匀。
2.如权利要求1所述一种介孔FeCu-ZSM-5分子筛的制备方法,其特征在于,制备方法为化学试剂合成法或矿物合成法中的一种。
3.根据权利要求2所述一种介孔FeCu-ZSM-5分子筛的制备方法,其特征在于,所述化学合成法具体包括如下步骤:
(1)在20~90 oC下,将去离子水、铝源、硅源、铁源、铜源和模板剂在搅拌条件下混合均匀,控制各种原料的投料量使得合成体系中各物质的摩尔比为SiO2/Al2O3=10~∞,SiO2/Fe2O3=10~350,SiO2/CuO=10~150,Na2O/SiO2=0.1~0.5,H2O/SiO2=10~50,模板剂/SiO2=0.01~0.5;混合后加入酸源,调节体系pH为5~13,进行第一次老化,再加入酸源,调节体系pH为5~13,进行第二次老化,即获得老化后的凝胶;
(2)将步骤(1)中获得的老化后的凝胶转移至含聚四氟乙烯内衬的反应釜中密封晶化,待晶化结束后,将晶化产物冷却、过滤除去母液,滤饼用去离子水洗涤至中性,干燥得到固体,之后将固体进行离子交换,并过滤、洗涤、干燥得到粉末;所述干燥条件为80-150℃,干燥过夜;
(3)将步骤(2)中获得粉末置于马弗炉中焙烧得到FeCu-ZSM-5分子筛。
4.根据权利要求3所述一种介孔FeCu-ZSM-5分子筛的制备方法,其特征在于,所述铁源为硝酸铁、氯化铁和硫酸铁中的一种或几种,所述的铜源为硝酸铜、三水硝酸铜、九水硝酸铜、二水氯化铜中的一种或者几种的混合物,所述的酸源为2-羟基-均丙三羧酸、亚硫酸、亚硝酸、硫酸、盐酸、硝酸、草酸、醋酸中的一种或几种的混合物;所述的硅源为水玻璃、硅溶胶、正硅酸乙酯、固体硅胶中的一种或几种;所述的铝源为铝酸钠或者硫酸铝中的一种或者两种的混合物,中所述的模板剂为四辛基溴化铵、四丁基溴化铵、十六烷基三甲基溴化铵、四丙基氢氧化铵、四丙基溴化铵、己二醇、正丁胺、乙胺中的一种或几种的混合物。
5.根据权利要求2所述一种介孔FeCu-ZSM-5分子筛的制备方法,其特征在于,所述矿物合成法具体包括如下步骤:
(1)矿物的活化:将铝源、硅源、铁源、铜源分别进行活化;
(2)将步骤(1)活化后的后的矿物与氢氧化钠、去离子水和晶种混合均匀后,控制各种原料的投料量使得合成体系中各物质的摩尔比为SiO2/Al2O3=10~∞,SiO2/Fe2O3=10~350,SiO2/CuO=10~150,Na2O/SiO2=0.1~0.5,H2O/SiO2=10~50,模板剂/SiO2=0.01~0.5;混合后加入酸源,调节体系pH为5~13,进行老化,即获得老化后的凝胶;
(3)将步骤(2)中获得的老化后的凝胶转移至含聚四氟乙烯内衬的反应釜中密封晶化,待晶化结束后,将晶化产物冷却、过滤除去母液,滤饼用去离子水洗涤至中性,干燥得到固体,之后将固体进行离子交换,并过滤、洗涤、干燥得到粉末;所述干燥条件为80-150℃,干燥过夜;
(4)将步骤(3)中获得粉末置于马弗炉中焙烧得到FeCu-ZSM-5分子筛。
6.根据权利要求4所述一种介孔FeCu-ZSM-5分子筛的制备方法,其特征在于,所述的铁源为铝土矿、硅藻土、累托土、黄铁矿、云母赤铁矿、赤泥中的一种或几种,所述的铜源为磁铁矿、孔雀石、铜蓝、黄铜矿中的一种或者几种的混合,所述的酸源为2-羟基-均丙三羧酸、亚硫、和亚硝酸、硫酸、盐酸、硝酸、草酸、醋酸中的一种或几种的混合物,所述的硅源为铝土矿、硅藻土、累托土、天然沸石或蛋白石中的一种或两种,所述的铝源为云母、明矾石、铝土矿、硅藻土、累托土、天然沸石中的一种或几种的混合物,所述的模板剂为四辛基溴化铵、四丁基溴化铵、十六烷基三甲基溴化铵、四丙基氢氧化铵、四丙基溴化铵、己二醇、正丁胺、乙胺中的一种或几种的混合物。
7.根据权利要求3或5任一所述的一种介孔FeCu-ZSM-5分子筛的制备方法,其特征在于所述老化是在60~90 oC条件下进行,老化时间为2~12 h;所述晶化是在100~190 oC条件下进行,晶化时间为12~96 h。
8.根据权利要求3或5任一所述的一种介孔FeCu-ZSM-5分子筛的制备方法,其特征在于所述离子交换具体的具体方法为:将所述干燥得到的固体与0.1~2 M的NH4Cl溶液按照质量比1:10~1:30的比例混合进行离子交换,于10~80 oC加热搅拌处理3~8 h。
9.根据权利要求3或5任一所述的一种介孔FeCu-ZSM-5分子筛的制备方法,其特征在于所述焙烧时间为4~10 h,焙烧温度为500~600 oC。
10.如权利要求1-9所述的FeCu-ZSM-5催化剂在氮氧化物选择性催化还原反应中的应用。
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Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103183359A (zh) * | 2013-03-20 | 2013-07-03 | 中国科学院青岛生物能源与过程研究所 | 一种纳米级FeZSM-5分子筛及其制备方法和应用 |
CN103447079A (zh) * | 2013-08-23 | 2013-12-18 | 淮阴工学院 | Cu-Fe-ZSM-5-凹土复合烟气脱硝催化剂的制备方法 |
CN105413652A (zh) * | 2015-11-06 | 2016-03-23 | 中国第一汽车股份有限公司 | 含有硅藻泥的颗粒过滤器载体材料混合物的制备方法 |
CN105523566A (zh) * | 2015-12-13 | 2016-04-27 | 定州市荣鼎水环境生化技术有限公司 | 以氨为还原剂的选择性催化还原氮氧化物的沸石分子筛及其制备方法和应用 |
CN105731492A (zh) * | 2016-01-28 | 2016-07-06 | 中国石油大学(华东) | 一种低成本绿色合成Fe-ZSM-5分子筛的方法 |
CN105833717A (zh) * | 2009-04-17 | 2016-08-10 | 约翰逊马西有限公司 | 小孔分子筛负载铜催化剂 |
CN106111183A (zh) * | 2016-06-24 | 2016-11-16 | 碗海鹰 | 一种选择性催化还原氮氧化物的催化剂及其制备方法 |
CN106881148A (zh) * | 2017-03-31 | 2017-06-23 | 国家电投集团远达环保催化剂有限公司 | 一种蜂窝式宽温度脱硝催化剂及其制备方法 |
CN107597177A (zh) * | 2017-09-18 | 2018-01-19 | 中节能万润股份有限公司 | 一种铁‑铜氧化物和分子筛复合蜂窝式脱硝催化剂及其制备方法 |
CN108217681A (zh) * | 2018-01-19 | 2018-06-29 | 山东齐鲁华信高科有限公司 | 一种高铁含量的Fe-ZSM-5分子筛的制备方法 |
CN108273544A (zh) * | 2017-12-28 | 2018-07-13 | 凯龙蓝烽新材料科技有限公司 | 挤出式铜铁混合基分子筛脱硝催化剂及其制备方法 |
CN108295891A (zh) * | 2018-01-10 | 2018-07-20 | 绍兴文理学院 | 柴油车尾气净化用Cu基分子筛脱硝催化剂的原位再生系统与方法 |
CN108435235A (zh) * | 2018-03-26 | 2018-08-24 | 福州大学 | 一种介孔Zn-ZSM-5分子筛及低成本制备方法 |
CN108452841A (zh) * | 2018-02-07 | 2018-08-28 | 浙江大学 | 一种Cu和Fe共改性的SSZ-13分子筛催化剂的制备方法 |
CN108722409A (zh) * | 2018-04-27 | 2018-11-02 | 石河子大学 | 介孔铜基氧化铝催化剂、制备方法及应用 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100937594B1 (ko) * | 2007-10-19 | 2010-01-20 | 한국화학연구원 | 아산화질소 및 질소산화물 분해용 제올라이트 촉매 및 이 촉매를 이용하여 아산화질소 및 질소산화물의 분해제거방법 |
CN102240570B (zh) * | 2010-05-11 | 2013-09-18 | 北京化工大学 | 一种具有介孔特征催化剂及其应用 |
CN104492471B (zh) * | 2014-12-24 | 2017-04-26 | 中南大学 | 一种中低温scr脱硝介孔分子筛催化剂及其制备和应用方法 |
CN107126973A (zh) * | 2017-05-31 | 2017-09-05 | 江南大学 | 一种CuFe‑SAPO‑34催化剂的原位合成方法及其应用 |
CN108579800A (zh) * | 2018-05-18 | 2018-09-28 | 西南林业大学 | 一种汽车尾气净化催化剂及其制备方法 |
-
2018
- 2018-11-14 CN CN201811355699.8A patent/CN109317188A/zh active Pending
- 2018-12-27 WO PCT/CN2018/124493 patent/WO2020098103A1/zh active Application Filing
- 2018-12-27 US US16/613,193 patent/US20210331932A1/en not_active Abandoned
Patent Citations (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105833717A (zh) * | 2009-04-17 | 2016-08-10 | 约翰逊马西有限公司 | 小孔分子筛负载铜催化剂 |
CN103183359A (zh) * | 2013-03-20 | 2013-07-03 | 中国科学院青岛生物能源与过程研究所 | 一种纳米级FeZSM-5分子筛及其制备方法和应用 |
CN103447079A (zh) * | 2013-08-23 | 2013-12-18 | 淮阴工学院 | Cu-Fe-ZSM-5-凹土复合烟气脱硝催化剂的制备方法 |
CN105413652A (zh) * | 2015-11-06 | 2016-03-23 | 中国第一汽车股份有限公司 | 含有硅藻泥的颗粒过滤器载体材料混合物的制备方法 |
CN105523566A (zh) * | 2015-12-13 | 2016-04-27 | 定州市荣鼎水环境生化技术有限公司 | 以氨为还原剂的选择性催化还原氮氧化物的沸石分子筛及其制备方法和应用 |
CN105731492A (zh) * | 2016-01-28 | 2016-07-06 | 中国石油大学(华东) | 一种低成本绿色合成Fe-ZSM-5分子筛的方法 |
CN106111183A (zh) * | 2016-06-24 | 2016-11-16 | 碗海鹰 | 一种选择性催化还原氮氧化物的催化剂及其制备方法 |
CN106881148A (zh) * | 2017-03-31 | 2017-06-23 | 国家电投集团远达环保催化剂有限公司 | 一种蜂窝式宽温度脱硝催化剂及其制备方法 |
CN107597177A (zh) * | 2017-09-18 | 2018-01-19 | 中节能万润股份有限公司 | 一种铁‑铜氧化物和分子筛复合蜂窝式脱硝催化剂及其制备方法 |
CN108273544A (zh) * | 2017-12-28 | 2018-07-13 | 凯龙蓝烽新材料科技有限公司 | 挤出式铜铁混合基分子筛脱硝催化剂及其制备方法 |
CN108295891A (zh) * | 2018-01-10 | 2018-07-20 | 绍兴文理学院 | 柴油车尾气净化用Cu基分子筛脱硝催化剂的原位再生系统与方法 |
CN108217681A (zh) * | 2018-01-19 | 2018-06-29 | 山东齐鲁华信高科有限公司 | 一种高铁含量的Fe-ZSM-5分子筛的制备方法 |
CN108452841A (zh) * | 2018-02-07 | 2018-08-28 | 浙江大学 | 一种Cu和Fe共改性的SSZ-13分子筛催化剂的制备方法 |
CN108435235A (zh) * | 2018-03-26 | 2018-08-24 | 福州大学 | 一种介孔Zn-ZSM-5分子筛及低成本制备方法 |
CN108722409A (zh) * | 2018-04-27 | 2018-11-02 | 石河子大学 | 介孔铜基氧化铝催化剂、制备方法及应用 |
Non-Patent Citations (4)
Title |
---|
ASIMA SULTANA ET AL.: "Tuning the NOx conversion of Cu-Fe/ZSM-5 catalyst in NH3-SCR", 《CATALYSIS COMMUNICATIONS》 * |
YUANYUAN YUE ET AL.: "One-pot synthesis of hierarchical FeZSM-5 zeolites from natural aluminosilicates for selective catalytic reduction of NO by NH3", 《SCIENTIFIC REPORTS》 * |
胡海鹏等: "Fe-Cu/ZSM-5催化剂的NH3-SCR脱硝性能", 《燃料化学学报》 * |
郑春满等: "《高等合成化学方法与实践》", 30 September 2018, 国防工业出版社 * |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
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