CN107285334B - A kind of method and catalyst of synthesis in solid state AEI type molecular sieve - Google Patents
A kind of method and catalyst of synthesis in solid state AEI type molecular sieve Download PDFInfo
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- CN107285334B CN107285334B CN201710618009.2A CN201710618009A CN107285334B CN 107285334 B CN107285334 B CN 107285334B CN 201710618009 A CN201710618009 A CN 201710618009A CN 107285334 B CN107285334 B CN 107285334B
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- molecular sieve
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- aei
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 47
- 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 47
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 26
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 title description 29
- 239000007787 solid Substances 0.000 title description 5
- 238000002425 crystallisation Methods 0.000 claims abstract description 36
- 230000008025 crystallization Effects 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000009415 formwork Methods 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 39
- 239000007790 solid phase Substances 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 9
- 229910052906 cristobalite Inorganic materials 0.000 claims description 9
- 229910052682 stishovite Inorganic materials 0.000 claims description 9
- 229910052905 tridymite Inorganic materials 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- LLSKXGRDUPMXLC-UHFFFAOYSA-N 1-phenylpiperidine Chemical class C1CCCCN1C1=CC=CC=C1 LLSKXGRDUPMXLC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 230000035935 pregnancy Effects 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- -1 alkyl piperidine Pyridine class organic compound Chemical class 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 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 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 239000002904 solvent Substances 0.000 abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 4
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 239000010457 zeolite Substances 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 150000001768 cations Chemical class 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 239000010949 copper Substances 0.000 description 12
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229910002089 NOx Inorganic materials 0.000 description 8
- 238000005342 ion exchange Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentaoxide Chemical compound [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 4
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001272 nitrous oxide Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 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 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- LZDSILRDTDCIQT-UHFFFAOYSA-N dinitrogen trioxide Chemical compound [O-][N+](=O)N=O LZDSILRDTDCIQT-UHFFFAOYSA-N 0.000 description 2
- 238000001570 ionothermal synthesis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- XCWPUUGSGHNIDZ-UHFFFAOYSA-N Oxypertine Chemical compound C1=2C=C(OC)C(OC)=CC=2NC(C)=C1CCN(CC1)CCN1C1=CC=CC=C1 XCWPUUGSGHNIDZ-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- IOYNQIMAUDJVEI-BMVIKAAMSA-N Tepraloxydim Chemical compound C1C(=O)C(C(=N/OC\C=C\Cl)/CC)=C(O)CC1C1CCOCC1 IOYNQIMAUDJVEI-BMVIKAAMSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229960002841 oxypertine Drugs 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010887 waste solvent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
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Abstract
The invention discloses a kind of molecular sieve solid phase synthesis process of AEI type structure, silicon source and Alkylpiperidine class organic formwork agent are subjected to hybrid reaction processing, excessive moisture is removed in vacuum distillation, meta-aluminic acid ammonium compounds gelinite is obtained, then crystallization is carried out with the mixture of silicon source, alkali source and molecular sieve seed mixed grinding and obtains AEI type structure molecular screen original powder.This Zeolite synthesis yield provided by the invention is high, required crystallization time is short, reduces the dosage of solvent and template, is suitable for large-scale industrial application.AEI molecular screen primary powder is swapped with metal cation, available metal-AEI molecular sieve can be used for tail gas NOx catalytic reduction reaction；AEI molecular screen primary powder is exchanged with ammonium ion, activate after obtain the AEI molecular sieve of Hydrogen, can be used for MTO and react to obtain the low-carbon alkene of high yield.
Description
Technical field
The invention belongs to porous orderly microporous inorganic materials synthesis fields, and in particular to have AEI type molecular sieve to a kind of
Solid phase synthesis process and catalyst.
Background technique
Molecular sieve primary synthetic methods include hydro-thermal or organic solvent thermal synthesis method, xerogel transformation approach, ionothermal synthesis.Water
Heat and solvent-thermal process method are to prepare the most classic method of molecular sieve, but the method low yield, environmental pollution are big；Xerogel conversion
Method preparation process is complicated, and ionothermal synthesis has significant improvement in terms of reducing reaction pressure, but the price of ionic liquid valuableness makes
This extensive industrial application of method is restricted.In addition, these methods require the effect of a large amount of solvents, it can not be fundamentally
Solve waste solvent, pollution this major issue of environment.
2012, Ren etc. reported a kind of and need to not need to add any by solid material mixed grinding, heating crystallization
Solvent, 10~20min of grinding can directly fill new method-solid phase thermal method that kettle crystallization prepares molecular sieve, for synthesize it is more cheap,
More green novel molecular sieve opens new air route.
Traditional water (solvent) thermal synthesis zeolite molecular sieve process, needs to consume a large amount of solvent (water or alcohols), product is washed
Wash the wastes and pollution for also resulting in great lot of water resources.On the other hand, due to the presence of a large amount of solvents, high-temperature heating process can draw
The pressure in kettle that reacts is higher, increases the quality requirement for equipment.
By the way that solid material is carried out simple physical mixed, grinding, crystallization in kettle, crystallization time can be shortened, greatly
Ground increases one-pot utilization rate, this can not only be conducive to the more products of plant produced, can also reduce the production cost of each product.
The zeolite product being prepared shows the physicochemical properties consistent with solvent structure sample, and this method
Material yield is high, reduces energy consumption, saves time and the energy, reduces solvent contamination.
Solid phase molecules sieve synthetic method does not need a kind of synthetic method that a large amount of solvents participate in, it is only needed in raw material containing few
It measures the crystallization water to participate in, and avoids generating reaction high pressure completely in reaction.A kind of energy conservation and environmental protection, safety non-pollution it is green
Color synthetic route.This provides very favorable support for the industrialized production of zeolite molecular sieve.
Summary of the invention
The object of the present invention is to provide a kind of methods of solid-phase grinding mixing method synthesis AEI molecular sieve, improve AEI molecular sieve
Combined coefficient and yield reduce the usage amount of template, solvent, reduce discharge of wastewater and reduce AEI Zeolite synthesis cost.
The invention is realized by the following technical scheme:
A kind of method of solid-phase sequencing synthesis AEI structure molecular screen, synthetic method are characterized in that:
(1) silicon source is reacted 6~24 at a temperature of 100~180 DEG C with the organic compound aqueous solution of Alkylpiperidine class
Hour, preferably 120~180 DEG C of reaction temperature, then 30~80 DEG C of vacuum distillations remove extra moisture, obtain gelatinous inclined
Aluminic acid ammonium compounds.
(2) meta-aluminic acid ammonium compounds gelatinous in (1) and silicon source, alkali source, crystal seed mixed grinding is uniform, obtain solid phase
Mixture, which is placed in crystallizing kettle, divides temperature section dynamic crystallization to react, and 125~200 DEG C of temperature range, the reaction time 48~96 hours.
Sudden cold suspension crystallization, isolates solid product, is filtered, washed with deionized water to neutrality, at 100~130 DEG C after the completion of crystallization
It air drying 12~48 hours, is roasted 2~10 hours in 400~600 DEG C of air, obtains AEI molecular screen primary powder.
Further, in the above-mentioned technical solutions, Alkylpiperidine class organic compound described in synthesis step of the present invention
Selected from 1,1,2,2,6,6- pregnancy phenylpiperidines, 1,1,2,2,6,6- hexamethyl -4- oxo-piperidine, acetyl group -2,2 1-,
6,6- tetramethyl -4- oxo-piperidine, 1,1,3,5- tetramethyl -4- oxo-piperidine, 1- hydroxyl -1,1,2,2,6,6- hexamethyl piperazine
Pyridine, 1,1- dimethyl -4,4- dipropoxy piperidines, 3,5- dimethoxy -1,1- lupetidine, 3,5- dihydroxy -
1,1- lupetidine, 4- ethyl -1,1- dimethyl -3,5- dioxopiperidine.1- ethyl -1- methyl -2,2,6,6- six
It is one or more in methyl piperidine, 1- glycidyl -1- methyl -2,2,6,6- pregnancy phenylpiperidines.
Further, in the above-mentioned technical solutions, silicon source described in synthesis step of the present invention is selected from boehmite, SB
One or more of powder, Aluminum sol, pseudobochmite, aluminium isopropoxide and aluminium hydroxide.
Further, in the above-mentioned technical solutions, silicon source described in synthesis step of the present invention may come from white carbon black, big
It is one or more in hole silica gel, silochrom, Kiselgel A, tlc silica gel, Type B silica gel, sodium metasilicate and diatomite.
The organic compound aqueous solution mass concentration of the Alkylpiperidine class is 5.0~50wt%.
Further, in the above-mentioned technical solutions, following groups centimorgans in crystallization predecessor solid-phase mixture of the present invention
Your ratio is silicon source (SiO2Calculate), silicon source (Al2O3Calculate), alkali source (Na2O calculate) and organic formwork agent (OSDA) according to
Na2O:SiO2:Al2O3: OSDA=0.1~0.5:1.0:0.004~0.083:0.05~0.5, it is mixed that crystal seed accounts for the crystallization solid that feeds intake
0.1~20wt% of polymer weight, wherein H2O content accounts for the 2.0~20.0% of solid-phase mixture weight.
Further, in the above-mentioned technical solutions, synthetic method of the present invention divides temperature section crystallization using dynamic, and first segment is brilliant
Changing temperature is 125~150 DEG C, and crystallization time is 12~72 hours；Second segment crystallization temperature is that 170~200 DEG C of crystallization times are
12~96 hours.
The present invention provides a kind of catalyst, carries out ion using the AEI molecular sieve and soluble metal solution of above-mentioned synthesis
Exchange, obtains the AEI molecular sieve catalyst of metal promoted, can be used as a kind of NOx selective catalytic reduction catalyst.The rush
Copper, iron, cobalt, tungsten, nickel, zinc, molybdenum, vanadium, tin, titanium, zirconium, manganese, chromium, niobium, bismuth, antimony, ruthenium, germanium, palladium, indium, platinum, gold are selected from into agent metal
Or silver one or more of combination in these.The preferred copper of the promoter metals, iron, cobalt, nickel, zinc, tungsten, molybdenum；Further preferably
Copper and iron.Nitrogen oxides (NOx), including multiple compounds, such as nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide
(NO2), nitrogen trioxide (N2O3), dinitrogen tetroxide (N2O4) and dinitrogen pentoxide (N2O5) etc..
The present invention provides another catalyst, using the AEI molecular sieve and soluble ammonium salting liquid of above-mentioned synthesis carry out from
Then son exchange obtains the AEI molecular sieve of Hydrogen by dry, roasting, can be used as a kind of preparation for MTO catalyst.
Soluble ammonium salting liquid is the aqueous solution of ammonium nitrate, ammonium sulfate, ammonium chloride or ammonium hydrogen carbonate, the concentration of ammonium ion is 0.5~
5.0mol/L, preferably 0.5~1.5mol/L.
The method of synthesis AEI molecular sieve of the present invention is relative to conventional method advantage:
(1) shorten generated time, reduce organic formwork agent usage amount, reduce synthesis cost；
(2) the AEI molecular sieve yield that synthesis obtains is high, and grain size distribution is more uniform；
(3) by carried metal promotor, it is also original for the catalysis of NOx to obtain the SCR catalyst containing AEI molecular sieve
Relatively high activity；
(4) after by ammonium ion exchange roasting, obtained Hydrogen AEI molecular sieve can be used for MTO reaction, have good
Activity and selectivity.
Detailed description of the invention
The invention will be further described with reference to the accompanying drawings and embodiments:
Fig. 1 is the XRD diffraction pattern of 1 method of embodiment synthesis AEI molecular sieve；
Fig. 2 is the SEM figure of 1 method of embodiment synthesis AEI molecular sieve.
Specific embodiment
Embodiment of the present invention and generated effect are further illustrated by embodiment and comparative example, but of the invention
Protection scope is not limited to content listed by embodiment.
Embodiment 1
(1) by quantitative boehmite (Al2O3: 65.1wt%) and 1- ethyl -1- methyl -2,2,6,6- hexamethyl piperazine
Pyridine aqueous solution (concentration: 20.0wt%), is stirred to react 12 hours at a temperature of 150 DEG C, by 60 DEG C of mixture after reaction into
Row vacuum distillation, removes extra moisture, obtains gelatinous meta-aluminic acid ammonium compounds.
(2) by gelatinous meta-aluminic acid ammonium compounds and silochrom (SiO2: 91.40wt%), NaOH (purity:
It 96wt%) mixes and grinds uniformly with AEI molecular sieve seed, then mixture moves toLining 2000ml crystallizing kettle
In, and stirred under 60rpm speed, 130 DEG C crystallization 24 hours, then 175 DEG C crystallization 60 hours.Wherein AEI molecular sieve seed
The 5.0% of the total butt quality of Zhan, following component molar ratios of crystallization forerunner's solid-phase mixture:
Na2O:SiO2: Al2O3: OSDA=0.27:1.0:0.0562:0.24；
After crystallization is complete, product is cooled down rapidly, is to dry at 8.0~9.0,120 DEG C by filtering separation, washing to pH value
4 hours are roasted at 12 hours and 540 DEG C dry, can be obtained AEI molecular screen primary powder, product is denoted as A.
The 10.0g AEI molecular screen primary powder of above-mentioned synthesis is added to the Cu that 100.0g concentration is 0.2mol/L
(CH3COO)2·H2In O aqueous solution, its pH to 6.5 is adjusted, is placed in heatproof container after stirring evenly 1 hour, and be put into togerther
In drier with pressure reducing valve；After the pressure in drier is extracted into 10Torr or less with vacuum pump, room temperature is carried out 1 hour
Degassing process, it is 12 hours dry to be then warming up to 90 DEG C of conditions, by the sample after drying under normal atmosphere pressure 500 DEG C of temperature
Roasting 4 hours；It obtains the copper and is modified AEI molecular sieve, in the catalyst prepared according to icp analysis result, copper (II) ion
The 2.1% of molecular sieve catalyst total weight is accounted for, i.e. copper load capacity is 2.1wt%, and Na ion concentration is lower than 200ppm, and product is denoted as
A1。
By AEI molecular screen primary powder with 1.0 DEG C/min heating rate, it is warming up to 550 DEG C of roastings in Muffle furnace and removes within 6 hours
Template.The ammonium nitrate solution ratio that the 10.0wt% of 10.0g is corresponded to every gram of AEI molecular screen primary powder is small in 80 DEG C of exchanges 1
When, an ammonium ion exchange is repeated after solid is recovered by filtration.Na ion is removed by ion exchange, solid product is again 120
DEG C drying 12 hours, 550 DEG C roasted 2 hours, obtain the Hydrogen AEI molecular sieve of high-crystallinity, and it is 11.5 that XRF, which measures silica alumina ratio,
Product is denoted as A2
Embodiment 2~10
The process of Solid phase synthesis AEI molecular sieve, Cu ion exchange and ammonium ion exchange is analogous to embodiment 1, institute
Unlike the type of silicon source in step (1), organic base Template Types, the type of silicon source, crystallization forerunner's solid-phase mixture
Component ratio, crystallization temperature and crystallization time etc., as shown in Tables 1 and 2.
Table 1
Table 2
Table 3
Comparative example 1
The AEI molecular sieve powder that SAR is 19.4 is synthesized according to US2017128921A1 patent Example 1:
It is the USY molecular sieve (Al of 10.7 de-aluminates by the molecule silica alumina ratio (SAR) of 35.0g2O3: 11.79wt%,
SiO2: 74.31%) it is stirred in stainless steel kettle with 945.7g deionized water, then under stiring by the N of 303.15g, N-
Diethyl -3,5- lupetidine solution (20.0wt%) and 416.15g sodium silicate solution (Na2O:9.00wt%, SiO2:
It 28.8wt%) is taken up in order of priority and slowly pours into said mixture, the mixed sols finally obtained is placed in 2L crystallizing kettle instead
It answers.Under 60rpm revolving speed stirring state, crystallizing kettle is heated to 145 DEG C of set temperature in 40min, and keeps this temperature,
49 hours completion crystallization, solid product are recovered by filtration, and are rinsed until pH value less than 10 with deionized water hereinafter, the filter of filtering
It is 12 hours dry in 120 DEG C of baking ovens of cake, obtain the AEI molecular screen primary powder containing organic formwork agent.
The 10.0g AEI molecular screen primary powder of above-mentioned synthesis is added to the Cu (NO that 100.0g concentration is 0.3mol/L3)2·
In 3H2O aqueous solution, its pH to 6.5 is adjusted, is placed in heatproof container after stirring evenly 1 hour, and be put into togerther with pressure reducing valve
Drier in；After the pressure in drier is extracted into 10Torr or less with vacuum pump, room temperature carries out 1 hour degassing process,
Then it is 12 hours dry that 90 DEG C of conditions are warming up to, 500 DEG C of temperature calcinations 4 are small under normal atmosphere pressure by the sample after drying
When；The modified AEI molecular sieve of the copper is obtained, according in the catalyst of icp analysis result preparation, copper (II) ion accounts for molecular sieve
The 2.5% of total catalyst weight, i.e. copper load capacity are 2.1wt%, and Na ion concentration is lower than 200ppm, and product is denoted as CP-1.
By molecular screen primary powder with 1.0 DEG C/min heating rate, 550 DEG C of roastings, 6 hours removing moulds are warming up in Muffle furnace
Plate agent.The ammonium acetate solution ratio that the 10.0wt% of 10.0g is corresponded to every gram molecule sieve powder, exchanges 1 hour, filtering at 80 DEG C
An ammonium ion exchange is repeated after recycling solid.Na ion is removed by ion exchange, solid product dries 12 at 120 DEG C again
Hour, 550 DEG C roast 2 hours, obtain the Hydrogen AEI molecular sieve of high-crystallinity, and it is 19.4 that XRF, which measures silica alumina ratio, is named as VS-
1。
Comparative example 2
3.94g NaOH (purity: 98%) is dissolved into 49.5g deionized water, is stirred in rustless steel container, then
Continue the business HY molecular sieve powder (Al for being 5.4 by the molecule silica alumina ratio (SAR) of 13.83g under stirring2O3: 18.32wt%,
SiO2: 58.71%, Na2O:0.08wt% the slurries for forming white uniformity) are added, next, by 9.29g N, diethyl -3 N-,
5- dimethyl hydrogen Oxypertine (concentration: 55.8wt% is denoted as OSDA) and 324.3g sodium silicate solution (Na2O:9.00wt%, SiO2:
It 28.8wt%) sequentially adds in above-mentioned mixed serum.The colloidal sol eventually formed, corresponding mole of composition are as follows:
68.0SiO2: 1.00Al2O3: 21.0Na2O:1.00OSDA:580H2O
Continue to stir 30min, be subsequently placed in 120 DEG C of stirring crystallization in 0.6L kettle, crystallization is completed after 45 hours, solid product
Recycling, and the progress of the program as described in comparative example 1 Cu ion exchange obtains copper (II) ion accounts for molecular sieve catalyst total weight
2.5%, product is denoted as CP-2.
Na ion is activated and removed with AEI molecular screen primary powder of the technical process identical in comparative example 1 to synthesis, is obtained
To the Hydrogen AEI molecular sieve of high-crystallinity, it is 11.7 that XRF, which measures silica alumina ratio, is named as VS-2.
Embodiment 11~18
SCR catalyst test:
10~20 mesh A1~F1 catalyst granules prepared in Example 1~6 and comparative example 1~2 are mounted in reactorIn, it include 500ppm NO, 500ppm NH3, 10 volume %O2, 5 volume % steam and Ar be Balance Air
Mixed airflow 160mL/min first passes through preheater (being set as 250 DEG C), subsequently into SCR reactor.At 150~650 DEG C
Reaction temperature and be based on 48000h-1Sample is tested under volume gas hourly space velocity.The temperature is by being located at sample position
Interior thermocouple monitoring.
Fresh SCR catalyst each in used above-described embodiment and comparative example is carried out the durable processing of hydro-thermal to be aged
SCR catalyst, hydro-thermal it is durable processing test condition are as follows:
Space velocity SV:30000/h, temperature: 800 DEG C, the time: 16 hours, moisture concentration: 10%, oxygen concentration: 10%,
Nitrogen concentration: balance.
After carrying out hydro-thermal ripening according to above-mentioned parameter, continue to comment as SCR catalyst for NOx catalytic reduction reaction
Valence test:
NO conversion ratio or " de- NOx " activity are under steady state conditions, a reactor by using 55 type FT-IR spectrum of Bruker EQUINOX
Instrument measures NOx, NH3 and N2O concentration in exit and determines.
Using above-mentioned SCR catalyst activity laboratory evaluation device, the loaded Cu that embodiment and comparative example is prepared
SCR catalyst carry out NOx selective catalytic reduction performance evaluation, the results are shown in Table 4.
Table 4
Can be as seen from Table 4 under all test temperatures, the SCR of A1~F1 catalyst sample of preparation of the embodiment of the present invention is living
Property is substantially better than CP-1 the and CP-2 catalyst sample in comparative example, no matter its " fresh " state or " ageing " state.Therefore,
Cu-AEI molecular sieve catalytic agent material of the invention is clearly shown by the result that embodiment 11~18 obtains and is obtained with it
Catalyst have improveds SCR catalytic activity, especially such as diesel locomotive application in processing NOx when cold start
Under specific low conversion temperature.
Embodiment 19~26
The evaluation of catalyst: A2~F2 catalyst raw powder obtained in Examples 1 to 6 is subjected to tabletting, is crushed to 20
~40 mesh.It weighs 0.5g catalyst (20~40 mesh) to be packed into stainless steel tubular reactor (length 45cm, internal diameter 8mm), both ends
Suitable quartz sand and silica wool are filled respectively, carry out MTO evaluation.Before test, first purged with carrier gas N2, on temperature of reactor
500 DEG C are risen to, is kept for 2 hours.After pretreatment, reactor is cooled to required reaction temperature i.e. 350 DEG C and keeps.Methanol is by nitrogen
It carries, nitrogen flow rate 15ml/min, methanol weight air speed 4.0h-1.Product gas composition uses 7890 chromatography of Agilent GC
On-line analysis, chromatograph are equipped with fid detector and HP-PONA chromatographic column.Selectivity of product, which is that the specific product is shared, removes diformazan
The mass percent of the outer total overall reaction product of ether (DME), the results are shown in Table 5.
Table 5
t50: conversion ratio was reduced to for 50% time experienced from 100%；t98: conversion ratio is reduced to 98% institute from 100%
The time of experience.
As can be seen from Table 5, the AEI molecular sieve catalyst of method preparation provided by the invention has more in MTO reaction
High low-carbon alkene (C2 =+C3 =) selectivity up to 85%, and conversion ratio drop to 50% before conversion life-span 13 hours with
On, conversion ratio was reduced to for 98% time experienced at 7.0 hours or more, illustrated the AEI molecular sieve catalyst that embodiment obtains
Compared with comparative example, there is better MTO reactivity worth and durability.
Examples detailed above is technical conception and technical characteristics to illustrate the invention, can not be limited with this of the invention
Protection scope.Without departing from the premise in the spirit of the present invention, all essence according to the present invention is made equivalent transformation changes or repairs
Decorations, appended claims should all cover within the protection scope of spirit of that invention.
Claims (5)
1. a kind of method of solid-phase grinding mixing method synthesis AEI type molecular sieve, it is characterised in that:
(1) silicon source reacted at a temperature of 100~180 DEG C to 6 with the organic formwork agent compound water solution of Alkylpiperidine class~
24 hours, then room temperature~80 DEG C vacuum distillation removed extra moisture, obtained gelatinous meta-aluminic acid ammonium compounds；
(2) meta-aluminic acid ammonium compounds gelatinous in (1) and silicon source, alkali source, crystal seed mixed grinding is uniform, obtain solid phase mixing
Object, which is placed in crystallizing kettle, divides temperature section dynamic crystallization to react, and 125~200 DEG C of temperature range, the reaction time 48~96 hours；Crystallization
Sudden cold suspension crystallization after the completion, isolates solid product, is filtered, washed with deionized water to neutrality, in 100~130 DEG C of air
Middle drying 12~48 hours roasts 2~10 hours in 400~600 DEG C of air, obtains AEI molecular screen primary powder；
Following component molar ratios are silicon source with SiO in the crystallization predecessor solid-phase mixture2It calculates, silicon source is with Al2O3Meter
It calculates, alkali source is with Na2O is calculated and the organic formwork agent compound water solution of Alkylpiperidine class is calculated with OSDA, according to Na2O:
SiO2:Al2O3: OSDA=0.1~0.5:1.0:0.004~0.083:0.05~0.5 molar ratio is mixed, and crystal seed accounts for
0.1~20wt% of the crystallization that feeds intake predecessor solid-phase mixture weight, wherein H2O content account for solid-phase mixture weight 2.0~
20.0%.
2. the method for solid-phase grinding mixing method synthesis AEI type molecular sieve according to claim 1, it is characterised in that: alkyl piperidine
Pyridine class organic compound is selected from 1,1,2,2,6,6- pregnancy phenylpiperidines, 1,1,2,2,6,6- hexamethyl -4- oxo-piperidine
, 1,1,3,5- tetramethyl -4- oxo-piperidine, 1- hydroxyl -1,1,2,2,6,6- pregnancy phenylpiperidines, dimethyl -4 1,1-,
4- dipropoxy piperidines, 3,5- dimethoxy -1,1- lupetidine, 3,5- dihydroxy -1,1- lupetidine, 4-
Ethyl -1,1- dimethyl -3,5- dioxopiperidine, 1- ethyl -1- methyl -2,2,6,6- pregnancy phenylpiperidines, 1- epoxy third
It is one or more in base -1- methyl -2,2,6,6- pregnancy phenylpiperidines.
3. the method for solid-phase grinding mixing method synthesis AEI type molecular sieve according to claim 1, it is characterised in that: silicon source choosing
From one or more of boehmite, SB powder, Aluminum sol, boehmite, aluminium isopropoxide and aluminium hydroxide.
4. the method for solid-phase grinding mixing method synthesis AEI type molecular sieve according to claim 1, it is characterised in that: silicon source can
From white carbon black, macro porous silica gel, silochrom, Kiselgel A, tlc silica gel, Type B silica gel, sodium metasilicate and diatom
It is one or more in soil.
5. the method for solid-phase grinding mixing method synthesis AEI type molecular sieve according to claim 1, it is characterised in that: use and divide
Temperature section dynamic crystallization, first segment crystallization temperature are 120~160 DEG C, and crystallization time is 12~72 hours；Second segment crystallization temperature
Be 170~200 DEG C of crystallization times be 12~96 hours.
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| JP2021535883A (en) * | 2018-08-29 | 2021-12-23 | パシフィック インダストリアル デベロップメント コーポレイション | Method for producing AEI-type zeolite having a high silica / alumina ratio (SAR) |
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| CN109336131B (en) * | 2018-11-01 | 2022-02-22 | 山东国瓷功能材料股份有限公司 | Method for quickly synthesizing AEI type molecular sieve |
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| CN106745031A (en) * | 2016-11-28 | 2017-05-31 | 中海亚环保材料有限公司 | A kind of zeolites of high silica alumina ratio SSZ 39 and its synthesis and application |
| CN106745057A (en) * | 2017-03-10 | 2017-05-31 | 中触媒新材料股份有限公司 | The AEI/MFI eutectics Si-Al molecular sieve and synthetic method of a kind of binder free and application |
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