CN109833905A - 分子筛催化剂及其制备方法和应用 - Google Patents
分子筛催化剂及其制备方法和应用 Download PDFInfo
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- CN109833905A CN109833905A CN201711232744.6A CN201711232744A CN109833905A CN 109833905 A CN109833905 A CN 109833905A CN 201711232744 A CN201711232744 A CN 201711232744A CN 109833905 A CN109833905 A CN 109833905A
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- catalyst
- molecular sieve
- methanol
- propylene
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- 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 63
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 72
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 9
- -1 dimethyl ether cyclopropene Chemical compound 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 7
- JZJZDEPVJPPXIG-UHFFFAOYSA-N methoxymethane;prop-1-ene Chemical group COC.CC=C JZJZDEPVJPPXIG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 14
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 6
- 229910000319 transition metal phosphate Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 40
- 230000015572 biosynthetic process Effects 0.000 description 37
- 238000003786 synthesis reaction Methods 0.000 description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 31
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 238000002425 crystallisation Methods 0.000 description 19
- 230000008025 crystallization Effects 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 239000012265 solid product Substances 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 239000000377 silicon dioxide Substances 0.000 description 18
- 238000010792 warming Methods 0.000 description 18
- 239000000376 reactant Substances 0.000 description 17
- 238000007605 air drying Methods 0.000 description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 15
- 229910052593 corundum Inorganic materials 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 14
- 229910001845 yogo sapphire Inorganic materials 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 12
- 229910052681 coesite Inorganic materials 0.000 description 12
- 229910052906 cristobalite Inorganic materials 0.000 description 12
- 229910052682 stishovite Inorganic materials 0.000 description 12
- 229910052905 tridymite Inorganic materials 0.000 description 12
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 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 description 7
- 230000008569 process Effects 0.000 description 7
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000002608 ionic liquid Substances 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- 229910001593 boehmite Inorganic materials 0.000 description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
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- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229940031098 ethanolamine Drugs 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- IVYKCKIFWVRWDM-UHFFFAOYSA-N 2-ethyl-1-methylimidazole;hydrobromide Chemical compound [Br-].CCC=1NC=C[N+]=1C IVYKCKIFWVRWDM-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 241000269350 Anura Species 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 2
- 229910002796 Si–Al Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012973 diazabicyclooctane Substances 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 235000001258 Cinchona calisaya Nutrition 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- CKLJMWTZIZZHCS-UWTATZPHSA-N D-aspartic acid Chemical compound OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 101150113959 Magix gene Proteins 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
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- 235000012211 aluminium silicate Nutrition 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 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
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-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
- 238000001816 cooling Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229960000948 quinine Drugs 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
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- B01J35/615—
-
- 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
-
- 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
-
- 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
-
- 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
- B01J29/7003—A-type
-
- 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
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates (APO compounds)
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
-
- B01J35/633—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
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Abstract
本申请公开了一种催化剂,所述催化剂含有分子筛,所述分子筛结构中具有至少一维8元环小孔通道,该8元环通道方向可扩散物质的直径不小于分子筛结构中可容纳物质直径不超过所述催化剂用于甲醇和/或二甲醚制丙烯反应。本申请还公开了一种甲醇和/或二甲醚制丙烯方法,包括将甲醇和/或二甲醚与甲醇制丙烯催化剂接触,得到丙烯,其中,所述催化剂为本申请提供的催化剂。
Description
技术领域
本申请涉及一种分子筛催化剂及其制备方法和应用,属于化工催化剂领域。
背景技术
丙烯是重要的化工原料,主要应用于生产聚丙烯(PP)、环氧丙烷(PO)、丙烯腈(AN)、丙烯酸(AA)等化工产品,终端应用涉及包装、建筑、汽车、纺织、日化等诸多领域。目前,全球对于丙烯的需求量逐年上涨,受益于中国经济的发展,中国丙烯消费量也快速增长。
目前,国内外丙烯的生产方法多以石油为原料,而我国的石油资源十分匮乏,石油储量与产量无法满足国民经济快速发展的需求,供需矛盾凸现。由煤经甲醇/二甲醚催化制取低碳烯烃(MTO)以及丙烯(MTP)技术可利用丰富的煤和天然气资源,是石油路线获取烯烃的有利替代与补充,因此受到研究者的广泛关注。
MTP技术的关键是高性能催化剂的研制。HZSM-5分子筛因其合适的孔径大小及酸性质成为MTP催化剂的首选。20世纪90年代,德国Lurgi公司基于一种改性高硅铝比ZSM-5分子筛开发出了一种具有高丙烯选择性的MTP固定床工艺过程。该工艺追求丙烯的收率最大化,流程中将乙烯与C4+烃类与丙烯分离,循环到MTP反应系统中,从而实现原料甲醇转化率大于99%,丙烯炭基收率高达71%。近年来,中石化和清华大学也相继开发了S-MTO/MTP和FMTP技术工艺。
目前工业上使用的MTP催化剂均使用ZSM-5作为分子筛催化剂,此外,还有关于SAPO-34和SAPO-18分子筛用MTP反应的相关报道。基于这些催化剂得到的丙烯选择性有限,提高丙烯单程选择性是当前对MTP反应研究的最重要挑战。
发明内容
根据本发明的一个方面提供一种催化剂,所述催化剂含有分子筛,所述分子筛结构中具有至少一维8元环小孔通道,该8元环通道方向可扩散物质的直径不小于,分子筛结构中可容纳物质直径不超过;
所述催化剂用于甲醇和/或二甲醚制丙烯反应。
优选地,所述分子筛结构中含有一维、二维或三维的8元环孔道,通道方向可扩散物质的直径不小于。
优选地,所述空间结构可容纳物质直径为。
优选地,所述分子筛的骨架类型选自AFN,DFT,PHI,SIV,THO,
APD,CAS,EDI,GIS和VNI中的至少一种。
优选地,所述分子筛选自磷酸硅铝分子筛、硅铝酸盐分子筛、过渡金属磷酸铝分子筛中的至少一种。
优选地,所述催化剂含有过渡金属磷酸铝分子筛,制备方法包括:
向合成釜中加入过渡金属原料、铝源、磷源、模板剂和溶剂,晶化后得到所述过渡金属磷酸铝分子筛;
所述溶剂为水、有机胺或离子液体。
根据本发明的又一个方面,提供一种甲醇和/或二甲醚制丙烯方法,将甲醇和/或二甲醚与甲醇制丙烯催化剂接触,得到丙烯;
所述甲醇制丙烯催化剂包括本申请中提供的所述催化剂。
优选地,所述甲醇制丙烯催化剂含有硅铝酸盐分子筛、磷酸硅铝分子筛或过渡金属磷酸铝分子筛中的至少一种。;
所述将甲醇和/或二甲醚与甲醇制丙烯催化剂接触的反应温度为300℃~500℃。
优选地,所述方法中,原料的转化率大于75%。
优选地,所述方法中,丙烯的单程选择性大于60%。
本申请能产生的有益效果包括:
1)本申请所提供的分子筛催化剂对MTP反应具有良好的催化作用,使用本发明提供的催化剂,可以使得甲醇的转化率高达80%以上,并且本发明的催化剂可以解决现有技术中心,MTP反应选择性差的问题,单程丙烯选择性高于60%;
2)本发明的催化剂分子筛组成灵活多样,只要能够驱动MTP反应即可,因此可以根据实际需要选择不同的分子筛。
附图说明
图1是实施例1合成样品的XRD谱图
图2是实施例6合成样品的XRD谱图
图3是实施例18合成样品的XRD谱图
图4是本申请一种实施方式中SAPO-APD分子筛的NH3-TPD曲线。
具体实施方式
下面结合实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法,通常按照常规条件或按照制造厂商所建议的条件。未做特殊说明的情况下,本申请所使用原料,均通过商业途径购买,不经特殊处理直接使用。
本申请的测试条件如下:
催化剂经压片、破碎至20-40目,于600℃下通入空气焙烧4小时。取0.3g该样品装入固定床反应器(自制)作为催化剂进行MTP反应评价,反应器为石英管。在550℃下通氮气活化1小时,然后降温至目标温度进行反应。甲醇由氮气携带。反应产物由在线气相色谱(安捷伦A7890)进行分析,PoraPlot-Q-HT色谱柱。
催化剂的元素组成采用Philips公司的Magix 2424X型射线荧光分析仪(XRF)测定。
催化剂的X射线粉末衍射物相分析(XRD)采用荷兰帕纳科(PANalytical)公司的X’Pert PRO X射线衍射仪,Cu靶,Kα辐射源(λ=0.15418nm),电压40KV,电流40mA。
采用美国Micromeritics公司ASAP 2020型物理吸附仪测定样品的比表面积和孔径分布。分析前,样品在350℃下抽真空加热预处理6h,以He为介质测量样品管自由体积。分析样品时,以氮气为吸附气体,在液氮温度(77K)下进行物理吸附和脱附测定。采用BET公式确定材料的比表面积;使用相对压力(P/P0)为0.99时的N2的吸附量计算材料的总孔容。用t-plot方法计算微孔表面积和微孔孔容。计算时,N2分子横截面积取0.162nm2。
采用美国Micromeritics公司Autochem2920型化学吸附仪测量样品饱和吸附NH3后的程序升温脱附。样品在600℃,40mL/min的He气氛下活化处理60min。待温度降至100℃后注入氨气使样品吸附饱和,经He吹扫除去物理吸附的NH3,然后以10℃/min的速度程序升温至600℃,利用TCD监测器记录NH3脱附信号。
以下结合实施例对本发明进行进一步的说明。
实施例1
MnAPO-AFN分子筛的合成
向100mL不锈钢反应釜中一次加入MnCl2·4H2O,去离子水,异丙醇铝,草酸,1,3-丙二胺(1,3-PDA)和磷酸(85%)。反应物摩尔比为MnCl2·4H2O∶Al(iPrO)3∶H3PO4∶H2C2O4∶1,3PDA∶H2O=(1.0∶1.4∶5.0∶1.6∶5.0∶920)。将原料混合物搅拌均匀,然后密封,在搅拌下升温至180℃,转动晶化72h。固体产物经离心分离、用去离子水洗涤样品至中性,在120℃空气中干燥后,得到待用的分子筛样品S1,命名为MnAPO-AFN。
实施例2
SAPO-AFN分子筛的合成
向100mL合成釜中依次加入一定量的异丙醇铝、去离子水、三乙烯二胺(DABCO)、正硅酸乙酯和磷酸(85%)。反应物摩尔比为Al2O3∶P2O5∶SiO2∶DABCO∶H2O=(1.0∶1.0∶0.3∶3.0∶50)。将原料混合物搅拌均匀,然后密封,在搅拌下升温至200℃,转动晶化40h。固体产物经离心分离、用去离子水洗涤样品至中性,在120℃空气中干燥后,得到待用的分子筛样品S2,命名为SAPO-AFN。
实施例3
CoAlPO-DFT分子筛的合成
将13.2g碳酸钴溶解于108.23g去离子水和26.78g磷酸(85%)中。在另一烧杯中将10g异丙醇铝,10.32g磷酸和53g乙二醇混合均匀,室温搅拌24h。将23.41g上述配置的乙二醇溶液与含钴的水溶液混合后,均匀搅拌20分钟后,取出30g溶液,加入1.05g奎宁和3.08g哌嗪和0.6ml乙二胺。将原料混合物搅拌均匀,然后密封,在搅拌下升温至180℃,转动晶化96h。固体产物经离心分离、用去离子水洗涤样品至中性,在100℃空气中干燥后,得到待用的分子筛样品S3,命名为CoAlPO-DFT。
实施例4
SAPO-DFT分子筛的合成
向100mL合成釜中依次加入一定量的拟薄水铝石(65重量%)、去离子水、1,3丙二胺(1,3-DPA)、硅溶胶(31重量%)和磷酸(85%)。反应物摩尔比为Al2O3∶P2O5∶SiO2∶1,3-DPA∶H2O=(1.0∶1.0∶0.3∶5.0∶50)。将原料混合物搅拌均匀,然后密封,在搅拌下升温至180℃,转动晶化12-72h。固体产物经离心分离、用去离子水洗涤样品至中性,在120℃空气中干燥后,得到待用的分子筛样品S4,命名为SAPO-DFT。
实施例5
ZnAlPO-PHI分子筛的合成
向100mL合成釜中依次加入氧化锌、氢氧化铝、去离子水、磷酸、乙二醇(EG)和N,N-二甲基-1,3-丙胺(C5H14N2)。反应物摩尔比为ZnO∶P2O5∶Al2O3∶C5H14N2∶20H2O∶100EG=(3∶5∶1∶8∶20∶100)。将原料混合物搅拌均匀,然后密封,在搅拌下升温至180℃,转动晶化48h。固体产物经离心分离、用去离子水洗涤样品至中性,在100℃空气中干燥后,得到待用的分子筛样品S5,命名为ZnAlPO-PHI。
实施例6
SiAl-PHI分子筛的合成
向100mL合成釜中依次加入一定量的KOH、去离子水、硅酸钠溶液(Na2O∶8.9%,SiO2∶28.7%)和偏铝酸钠(30.5%Na2O,45.6%Al2O3)。反应物摩尔比为Na2O∶K2O∶Al2O3∶SiO2∶H2O=(6.95∶3.5∶1.0∶22∶350)。将原料混合物搅拌均匀,然后密封,在搅拌下升温至120℃,转动晶化12h。固体产物经离心分离、用去离子水洗涤样品至中性,在100℃空气中干燥后,得到待用的分子筛样品S6,命名为SiAl-PHI。
实施例7
CoAlPO-SIV分子筛的合成
向100mL不锈钢合成釜中依次加入磷酸,异丙醇铝,Co(OH)2、乙基甲基咪唑溴盐离子液体(IL)和氢氟酸。反应物摩尔比为Al(iPrO)3∶H3PO4∶HF∶IL∶Co(OH)2∶6H2O=(1.0∶2.9∶0.69∶40∶1.6∶3.6)。将原料混合物搅拌均匀,然后密封,在搅拌下升温至170℃,转动晶化72h。固体产物经离心分离、用去离子水洗涤样品至中性,在100℃空气中干燥后,得到待用的分子筛样品S7,命名为CoAlPO-SIV。
实施例8
SAPO-SIV分子筛的合成
向100mL合成釜中依次加入一定量的氢氧化铝、去离子水、异丙胺(IPA)、白炭黑,乙基甲基咪唑溴盐离子液体(IL)、氢氟酸和磷酸(85%)。反应物摩尔比为Al2O3∶1.0P2O5∶0.3SiO2∶IL∶0.3HF∶IPA∶H2O=(1.0∶1.0∶0.3∶25∶0.3∶2.0∶10)。将原料混合物搅拌均匀,然后密封,在搅拌下升温至180℃,转动晶化48h。固体产物经离心分离、用去离子水洗涤样品至中性,在120℃空气中干燥后,得到待用的分子筛样品S8,命名为SAPO-SIV。将样品焙烧脱除模板剂后,测其比表面积及孔容,样品具有高的BET比表面积412.8m2g-1,及大的孔体积0.24cm3g-1,其中按照t-plot方法计算得到的微孔比表面积和微孔容积分别为360.5m2g-1和0.18cm3g-1。
实施例9
ZnAlPO-THO分子筛的合成
向100mL合成釜中依次加入氧化锌、异丙醇铝、磷酸、乙二醇(EG)和1,3丙二胺(1,3-DPA)。反应物摩尔比为ZnO∶P2O5∶Al2O3∶1,3-DPA∶EG=(3∶5∶1∶8∶120)。将原料混合物搅拌均匀,然后密封,在搅拌下升温至180℃,转动晶化96h。固体产物经离心分离、用去离子水洗涤样品至中性,在100℃空气中干燥后,得到待用的分子筛样品S9,命名为ZnAlPO-THO。
实施例10
SAPO-THO分子筛的合成
向100mL合成釜中依次加入拟薄水铝石、去离子水、哌啶(C5H11N)、白炭黑和磷酸(85%)。反应物摩尔比为1.0Al2O3∶1.0P2O5∶0.3SiO2∶3.0C5H11N∶40H2O=(1∶1∶0.3∶3.0∶40)。将原料混合物搅拌均匀,然后密封,在搅拌下升温至180℃,转动晶化12-72h。固体产物经离心分离、用去离子水洗涤样品至中性,在120℃空气中干燥后,得到待用的分子筛样品S10,命名为SAPO-THO。
实施例11
SAPO-APD分子筛的合成
向100mL合成釜中依次加入异丙醇铝、去离子水、乙醇胺(ETA)、硅溶胶(30%)和磷酸(85%)。反应物摩尔比为Al2O3∶P2O5∶SiO2∶ETA∶H2O=(1∶1.4∶0.3∶7∶140)。将原料混合物搅拌均匀,然后密封,在搅拌下升温至160℃,转动晶化72h。固体产物经离心分离、用去离子水洗涤样品至中性,在120℃空气中干燥后,得到待用的分子筛样品S11,命名为SAPO-APD。采用NH3-TPD方法研究了该分子筛的表面酸性。NH3-TPD曲线图见图1。样品在170℃左右出现一个很高的脱附峰,在370℃只存在一个比较矮的宽包,可见样品酸性很弱。
实施例12
SiA1-CAS分子筛的合成
向合成釜中依次加入哌嗪、去离子水、LudoxAS-40、铝酸钠和HF。反应混合物的摩尔比如下:Na2O∶Al2O3∶SiO2∶C4H10N2∶HF∶H2O=(1∶1∶10∶5.6∶77)。搅拌均匀后密封,升温至150℃,转动晶化48h。固体产物经离心分离、用去离子水洗涤样品至中性,在100℃空气中干燥后,得到分子筛前驱体1。将前驱体1置于管式炉中以1分钟/度的速度升温至1000摄氏度,加热10小时,得到目标产物分子筛S12,命名为SiAl-CAS。
实施例13
SAPO-CAS分子筛的合成
向100mL合成釜中依次加入拟薄水铝石、去离子水、哌嗪(PIP)、硅溶胶(30%)和磷酸(85%)。反应物摩尔比为Al2O3∶P2O5∶SiO2∶PIP∶H2O=(1∶1∶0.3∶3∶40)。将原料混合物搅拌均匀,然后密封,在搅拌下升温至160℃,转动晶化12h。固体产物经离心分离、用去离子水洗涤样品至中性,在120℃空气中干燥后,得到待用的分子筛样品S13,命名为SAPO-CAS。
实施例14
CoAlPO-EDI分子筛的合成
向200mL合成釜中依次加入12.8g硝酸钴、23.2g硝酸铝、27.16磷酸(2M)、8.9g 1,2丙二胺和100g去离子水。将原料混合物搅拌均匀,然后密封,在搅拌下升温至150℃,转动晶化48h。固体产物经离心分离、用去离子水洗涤样品至中性,在100℃空气中干燥后,得到待用的分子筛样品S14,命名为CoAlPO-EDI。
实施例15
SiA1-EDI分子筛的合成
向100mL合成釜中依次加入一定量的KOH、去离子水、铝粉和白炭黑。反应物摩尔比为K2O∶Al2O3∶SiO2∶H2O=(5∶1∶3∶100)。将原料混合物搅拌均匀,然后密封,在搅拌下升温至100℃,转动晶化96h。固体产物经离心分离、用去离子水洗涤样品至中性,在100℃空气中干燥后,得到待用的分子筛样品S15,命名为SiAl-EDI。
实施例16
SAPO-EDI分子筛的合成
向100mL合成釜中依次加入拟薄水铝石、去离子水、三甲胺(TMA)、四乙基氢氧化铵(35%)、硅溶胶(30%)和磷酸(85%)。反应物摩尔比为Al2O3∶P2O5∶SiO2∶TEA2O∶TMA∶H2O=(1∶1∶0.3∶1.5∶2∶40)。将原料混合物搅拌均匀,然后密封,在搅拌下升温至170℃,转动晶化12-72h。固体产物经离心分离、用去离子水洗涤样品至中性,在120℃空气中干燥后,得到待用的分子筛样品S16,命名为SAPO-EDI。
实施例17
SiA1-GIS分子筛的合成
向100mL合成釜中依次加入一定量的氟化钠、去离子水和高岭土(Al2O3∶SiO2∶H2O=1∶2∶2.2)。反应物摩尔比为Al2O3∶SiO2∶NaF∶H2O=(1∶3∶5∶120)。将原料混合物搅拌均匀,然后密封,在搅拌下升温至150℃,转动晶化24h。固体产物经离心分离、用去离子水洗涤样品至中性,在100℃空气中干燥后,得到待用的分子筛样品S17,命名为GIS。
实施例18
CoAPO-GIS分子筛的合成
向100mL合成釜中依次加入一定量的异丙醇铝、去离子水、磷酸、醋酸钴、二甲胺(C2H7N)和1,4-丁二酸(C4H7NO4)。反应物摩尔比为CoAc·4H2O∶Al(iPrO)3∶H3PO4∶C2H7N∶C4H7NO4∶200H2O=(0.7∶4∶1∶4∶6∶1.2∶200)。将原料混合物搅拌均匀,然后密封,在搅拌下升温至180℃,转动晶化48h。固体产物经离心分离、用去离子水洗涤样品至中性,在100℃空气中干燥后,得到待用的分子筛样品S18,命名为CoAPO-GIS。
实施例19
SAPO-GIS分子筛的合成
向合成釜中依次加入拟薄水铝石、去离子水、磷酸、硅溶胶(30%)、和丙胺。反应物摩尔比为:Al2O3∶P2O5∶SiO2∶4.0PA∶100H2O=(1∶1∶0.3∶4∶100)。将原料混合物搅拌均匀,然后密封,在搅拌下升温至160℃,转动晶化96h。固体产物经离心分离、用去离子水洗涤样品至中性,在100℃空气中干燥后,得到待用的分子筛样品S19,命名为SAPO-GIS。
实施例20
结构表征
对实施例1-19中制备的样品进行XRD表征,结果显示合成样品均为纯相,没有其它杂相分子筛存在。选择的实施例2,6和18的XRD衍射图见后面附图1-3。其他部分XRD表征数据2θ角度及相对强度见表1。对实施例11样品进行了NH3-TPD表征,结果见附图4。
表1
实施例21
SAPO分子筛的MTP性能评价
将上述实施例中合成的SAPO分子筛在400-800℃空气中焙烧2小时,即得到待用催化剂产品,用于MTP催化反应评价,催化性能评价操作见具体实施方式部分,考察所用的工艺条件及催化结果示于表2中,其中,本是实施例以及后文中有关内容提及计算转化率时,甲醇和二甲醚均视为反应物,选择性选取转化率最高点时值。由表2可以看出,乙烯、丙烯和C4的总选择性接近100%(受仪器检测误差影响,总选择性有可能等于或略超100%)。
表2
实施例22
硅铝分子筛的MTP的催化性能评价
上述实施例中合成的硅铝分子筛需要通过离子交换得到氢型分子筛。具体过程为,首先在400-800℃空气中焙烧3小时。然后,将100g硝酸铵溶于1300ml去离子水中,完全溶解后加入20g烧后分子筛样品,在85℃油浴下搅拌10h,静置冷却后离心分离、用去离子水洗涤样品至中性。重复上述离子交换步骤2-4次(S6两次,S12四次,其余交换三次),得到的铵型的分子筛样品。再在400-800℃空气中焙烧3小时,得到待用的MTP催化剂。催化性能评价操作见具体实施方式部分,考察所用的工艺条件及催化结果示于表3中。
表3
实施例23
过渡金属磷酸铝分子筛的MTP催化性能评价
上述实施例中合成的过渡金属磷酸铝分子筛需要通过仔细的焙烧除去模板剂得到酸性分子筛。分子筛样品置于管式炉中后通入O2气,以1度/分钟的升温速率升至400℃,保持2小时,再以0.5度/分钟的速度升至500焙烧4小时,即得到待用的MTP催化剂。催化性能操作见具体实施方式部分,考察所用的工艺条件及催化结果示于表4中。
表4
对比例1
选取常用MTP催化剂SAPO-18和ZSM-5进行MTP催化性能的对比实验。两催化剂样品均焙烧除去模板剂后备用。分子筛样品置于管式炉中后通入O2气,以1度/分钟的升温速率升至400℃,保持2小时,再以0.5度/分钟的速度升至500焙烧4小时,即得到待用的MTP催化剂。催化性能操作见具体实施方式部分,考察所用的工艺条件及催化结果示于表5中。
表5a
aZSM-5和SAPO-18均选取了低碳烯烃选择性最佳的点来进行比较。
由以上实施例可以看出,本发明的分子筛催化剂能够以高转化率和高选择性催化MTP反应,显著优于现有技术中的催化剂。
以上所述,仅是本申请的几个实施例,并非对本申请做任何形式的限制,虽然本申请以较佳实施例揭示如上,然而并非用以限制本申请,任何熟悉本专业的技术人员,在不脱离本申请技术方案的范围内,利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例,均属于技术方案范围内。
Claims (10)
1.一种催化剂,其特征在于,所述催化剂含有分子筛,所述分子筛结构中具有至少一维8元环小孔通道,该8元环通道方向可扩散物质的直径不小于分子筛结构中可容纳物质直径不超过
所述催化剂用于甲醇和/或二甲醚制丙烯反应。
2.根据权利要求1所述的催化剂,其特征在于,所述分子筛结构中含有一维、二维或三维的8元环孔道,通道方向可扩散物质的直径不小于
3.根据权利要求1所述的催化剂,其特征在于,所述分子筛结构中可容纳物质直径为
4.根据权利要求1所述的催化剂,其特征在于,所述分子筛的骨架类型选自AFN,DFT,PHI,SIV,THO,APD,CAS,EDI,GIS和VNI中的至少一种。
5.根据权利要求1所述的催化剂,其特征在于,所述分子筛选自磷酸硅铝分子筛、硅铝酸盐分子筛和过渡金属磷酸铝分子筛中的至少一种。
6.一种甲醇和/或二甲醚制丙烯方法,其特征在于,将甲醇和/或二甲醚与甲醇制丙烯催化剂接触,得到丙烯;
所述甲醇制丙烯催化剂包括权利要求1至5任一项所述催化剂。
7.根据权利要求6所述的方法,其特征在于,所述甲醇制丙烯催化剂含有硅铝酸盐分子筛、磷酸硅铝分子筛或过渡金属磷酸铝分子筛中的至少一种。
8.根据权利要求7所述的方法,其特征在于,所述将甲醇和/或二甲醚与甲醇制丙烯催化剂接触的反应温度为300℃~500℃。
9.根据权利要求7所述的方法,其特征在于,所述方法中,原料的转化率大于75%。
10.根据权利要求7所述的方法,其特征在于,所述方法中,丙烯的单程选择性大于60%。
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CN113912080A (zh) * | 2021-11-08 | 2022-01-11 | 吉林大学 | 一种sapo-14分子筛及其制备方法和应用 |
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