CN104096591B - Mto catalyst and preparation method thereof - Google Patents
Mto catalyst and preparation method thereof Download PDFInfo
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- CN104096591B CN104096591B CN201310116349.7A CN201310116349A CN104096591B CN 104096591 B CN104096591 B CN 104096591B CN 201310116349 A CN201310116349 A CN 201310116349A CN 104096591 B CN104096591 B CN 104096591B
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- catalyst
- sapo
- molecular sieve
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002808 molecular sieve Substances 0.000 claims abstract description 41
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005977 Ethylene Substances 0.000 claims abstract description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 15
- 239000004927 clay Substances 0.000 claims abstract description 12
- 239000007767 bonding agent Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- 238000001935 peptisation Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 7
- 239000004005 microsphere Substances 0.000 claims abstract description 5
- 238000011084 recovery Methods 0.000 claims abstract 3
- 238000002425 crystallisation Methods 0.000 claims description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 230000008025 crystallization Effects 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 17
- 238000011065 in-situ storage Methods 0.000 claims description 15
- 235000011007 phosphoric acid Nutrition 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 229910052681 coesite Inorganic materials 0.000 claims description 14
- 229910052906 cristobalite Inorganic materials 0.000 claims description 14
- 229910052682 stishovite Inorganic materials 0.000 claims description 14
- 229910052905 tridymite Inorganic materials 0.000 claims description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- -1 molecular sieve Rare earth Chemical class 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 229910052779 Neodymium Inorganic materials 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 8
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical group O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- 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 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 241001494479 Pecora Species 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 4
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 3
- 125000004494 ethyl ester group Chemical group 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910001679 gibbsite Inorganic materials 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 abstract description 7
- 241000269350 Anura Species 0.000 abstract 2
- 239000000523 sample Substances 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 229910001868 water Inorganic materials 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 241000208340 Araliaceae Species 0.000 description 6
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 6
- 235000003140 Panax quinquefolius Nutrition 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 235000008434 ginseng Nutrition 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 5
- 239000010413 mother solution Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 4
- 238000010009 beating Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- ZYTJPPRBIGGXRO-UHFFFAOYSA-N propan-2-ylalumane Chemical compound C(C)(C)[AlH2] ZYTJPPRBIGGXRO-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910017498 Nd(NO3)3.6H2O Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical class CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Catalysts (AREA)
Abstract
The title of the present invention is MTO catalyst and preparation method thereof.The present invention provides the catalyst and the preparation method of active component SAPO 34 molecular sieve i.e. RE SAPO 34 molecular sieve containing rare earth thereof that a kind of methanol changes into low carbene (MTO), this catalyst is made into treats Gunning material with described active component and natural clay, peptization bonding agent, spray-dried make microsphere, its methanol conversion 100%, ethylene+propylene total recovery is more than 80%, triolefin total recovery is more than 90%, and propylene/ethylene is more than 0.9.
Description
Technical field
The present invention relates to be converted into the catalyst of low-carbon alkene (MTO) for methanol, being more particularly to active constituent is
The preparation method of the MTO catalyst of the RE-SAPO-34 molecular sieve containing rare earth and catalytic perfomance thereof.
Background technology
Methanol-to-olefins (MTO) is the important Coal Chemical Industry technique skill being expected to petroleum replacing raw material route preparing low-carbon olefins
Art.World head overlaps 1.0Mt/a stage arrangement and builds up in China, and the most successfully goes into operation, and new catalyst and improvement Technology are also
It is evolving.MTO technology of tracing to the source is union carbide corporation (UCC) first to be disclosed a kind of new patent US4440871 of 1984
Type silicoaluminophosphamolecular molecular sieves system SAPO-n, finds that the SAPO-34 of its small aperture shows excellent methanol and is converted into ethylene
Etc. the performance (US4499327,4677242,4873390,5095163,6166282) of low carbene, but poor stability, need to be changed
Enter.Research worker finds that the active component that can be used as MTO catalyst has each molecular sieve analog, but all not as good as SAPO-34, improves
The catalysis activity of SAPO-34 and stability are then research and development MTO raw catelyst and the core improving MTO new technology.
Metallic element modification SAPO-34 can improve the MTO reactivity worth of SAPO-34, and initially EXXON company utilizes alkali
Earth elements (Ca, Sr, Ba) modified SAPO-34, improves ethylene-propylene yield (US6040264), about the patent of this respect,
All report metal-modified SAPO-34 can carry such as US4567029, EP0159624, CN101301626A, WO2001US04502
High methanol is converted into performance and the stability of low carbene.The CN1167654A patent application of China's research worker also discloses
Cu, Co, Ni study on the modification obtains the effect improving low carbene yield, especially special in Dalian Chemiclophysics Inst., Chinese Academy of Sciences
Reporting in profit application CN1068574 and use nickel modified SAPO-34, when Si/Ni atomic ratio reaches 100, methanol is converted into ethylene
Yield can be brought up to 60% by 30%；The patent application CN1704390 of Sinopec Shanghai Petroleum Chemical Engineering Institute also discloses
Zinc modification SAPO-34 improves MTO reactivity worth.
Modifying element, in addition to common transition metal and alkaline earth, also has researcher to use rare-earth elements La to make modified SAPO-
34 researchs (CN101318667A), but reaction generates the performance of low carbene and is not improved, far away from the Ni-of the Dalian Chemistry and Physics Institute
SAPO-34。
Molecular sieve modified with catalysis relation research in terms of, if scholars find modified metal atom with tetrahedron list
Unit (MeO4) be inserted into and retain the former topological structure of molecular sieve among the skeleton of SAPO-34 molecular sieve, then due to the valence state of Me
Affecting framework of molecular sieve electrostatic charge, be possible not only to the port size of Molecular regulator sieve, the acidity of the most modulated molecular sieve, in order to change
The performance (Catal Let, 1998,53:171-176) of kind its catalyzed conversion low carbene of MTO.This is for improving SAPO-34 further
And catalyst performance indicates direction.Magnify after boehmite first mixes with phosphoric acid, Ludox by smelting, add template three second
Amine, adds the acetate of modified metal M g, and synthesis has obtained the Mg-SAPO-34 molecular sieve of skeleton magnesium, and its method is that Schilling changes
Property metal and template form complex, be re-introduced into aluminum source and the synthesis of silicon source crystallization.
Large-sized rare earth element ce is successfully introduced in disclosed CN101993094A patent application by the present inventor
SAPO-34 molecular sieve, it shown excellence MTO reactivity worth, can by methanol convert 100%, the yield of ethylene, propylene can
To bring up to 80%.But totally say that current MTO catalysis technique still haves much room for improvement in many-side, for catalyst, not only want
Ask (ethylene+propylene) yield and (ethylene+propylene+butylene) three yields to improve further, require to reduce further CO+CO simultaneously2+
The selectivity of dimethyl ether, and need especially to improve propylene/ethylene ratio, the physical property of catalyst also has the bigger sky that needs
Between.
Summary of the invention
Therefore, it is an object of the invention to provide a kind of yield of light olefins high, propylene/ethylene ratio is high, CO, CO2With two
MTO catalyst that methyl ether selectivity is low and preparation method thereof, more specifically, it is provided that rare earth modified point of a kind of MTO excellent performance
The synthetic method of son sieve RE-SAPO-34 and by it as active component can the MTO catalyst of commercial Application and preparation side thereof
Method.The scheme of solution problem is as follows:
1, a kind of methanol-to-olefin catalyst, it is characterised in that make with RE-SAPO-34 molecular sieve prepared by in-situ crystallization method
For active component, making substrate with natural clay, formulated with peptization bonding agent, methanol conversion 100%, ethylene+propylene is total
Yield is more than 80%, and propylene/ethylene ratio is more than 0.9.
2, according to the catalyst described in 1, it is characterised in that characterized by XRD, described RE-SAPO-34 molecular sieve middle rare earth
RE atom enters into SAPO-34 framework of molecular sieve, has CHA or CHA/AEI topological structure.
3, according to the catalyst described in 1, it is characterised in that described in-situ crystallization method is rare earth RE elemental cerium Ce or neodymium Nd
Soluble-salt and phosphorus source and fluoride prerotation turn to fluorine-containing RE phosphate, in situ with aluminum source and silicon source under the effect of template RN
Stir into gel crystallization synthesis RE-SAPO-34 molecular sieve.
4, according to the catalyst described in 1, it is characterised in that described in-situ crystallization method prepares each of RE-SAPO-34 molecular sieve
Planting raw material molar ratio is (0.01-0.5) F: (0.01-1.0) RE2O3∶(0.2-1.5)SiO2∶1.0Al2O3∶(0.2-2.0)
P2O5∶(2.0-5.0)RN∶(35-50)H2O。
5, according to the catalyst described in 1, it is characterised in that described RE-SAPO-34 molecular sieve, described natural clay and described
The mass ratio of colloidal sol bonding agent is 1.0: 0.10-1.0: 0.05-0.2.
6, according to the catalyst described in 3, it is characterised in that the soluble-salt of described cerium or neodymium be cerium or the nitrate of neodymium or
A kind of or their mixture in sulfate or acetate；Or, phosphorus source is orthophosphoric acid or Metaphosphoric acid or pyrophosphoric acid or has
A kind of or their mixture in machine phosphate ester；Or, described fluoride is any one in ammonium fluoride or sodium fluoride or fluohydric acid gas
Or combinations thereof；Or, source of aluminium be in boehmite or β-gibbsite or amorphous hydroted alumina any one or
Combinations thereof；Or, described silicon source is any one or combinations thereof in Ludox or white carbon or the positive ethyl ester of silicic acid；Or
Person, described template RN is triethylamine or diethylamine or n-butylamine or tetraethyl ammonium hydroxide TEAOH or tetraethylammonium bromide
Any one or combinations thereof in TEABr or morpholine；Or, their any combination.
7, according to the catalyst described in 3 or 6, it is characterised in that in-situ crystallization temperature is 100-220 DEG C.
8, according to the catalyst described in 1, it is characterised in that described natural clay is Kaolin or attapulgite or bentonite
Or sheep Montmorillonitum any one, or combinations thereof.
9, according to the catalyst described in 1, it is characterised in that described peptization bonding agent is aluminum chloride or aluminum nitrate or aluminium silicate
In any one, or combinations thereof.
10, according to the catalyst described in 1, it is characterised in that described active component, described natural clay glue with described peptization
Connect agent to be made into and treat Gunning material, spray-dried make microsphere.
11, according to the catalyst described in 10, it is characterised in that described in treat that the solid content of Gunning material is 20-50%.
12, according to the catalyst described in 10, it is characterised in that the outlet temperature of described spray drying is 200-400 DEG C.
Accompanying drawing explanation
Fig. 1 is the XRD spectrum of 2# Molecular Sieve Comparative's sample and embodiment 1# and 4# sample.
Detailed description of the invention
The present invention provides a kind of yield of light olefins high, and propylene/ethylene ratio is high, CO, CO2Low with dimethyl ether selectivity
MTO catalyst and preparation method thereof, more specifically, it is provided that the rare-earth modified molecular-sieve RE-SAPO-34 of a kind of MTO excellent performance
Synthetic method and by it as active component can the MTO catalyst and preparation method thereof of commercial Application.Described RE-SAPO-
34 is to use in-situ crystallization method that rare earth element ce or the Nd of thick atom size are introduced the rare earth modified of framework of molecular sieve synthesis
SPAO-34 molecular sieve, is characterized in that having CHA/AEI topological structure (see Fig. 1)；Described in-situ crystallization method is by rare earth element
Cerium (Ce) salt or neodymium (Nd) salt are converted into fluorine-containing RE phosphate in advance with phosphorus source, simultaneously with aluminum source and silicon under fluoride is assisted
Source stirs into gel in situ hydrothermal crystallizing under template effect, is then dried by the crystallization thing filtering off mother solution and mould is removed in roasting
After plate agent, obtain RE-SAPO-34 molecular screen primary powder.Described RE-SAPO-34 molecular sieve in-situ crystallization synthesizes feeding intake of each raw material
Mol ratio is (0.01-0.5) F: (0.01-1.0) RE2O3∶(0.2-1.5)SiO2∶1.0Al2O3∶(0.2-2.0)P2O5∶(2.0-
5.0)RN∶(35-50)H2O.Described rare earth (RE) is cerium (Ce) salt or neodymium (Nd) salt, such as nitrate or the sulfate of Ce or Nd
Or acetate, or their mixture.Described aluminum source is boehmite, or β-gibbsite, or amorphous hydroted alumina
In any one or combinations thereof.Described silicon source is Ludox or white carbon, or the group of any one or they in the positive ethyl ester of silicic acid
Close.Described template RN is triethylamine or diethylamine or n-butylamine, or tetraethyl ammonium hydroxide (TEAOH), or tetraethyl bromination
One in ammonium (TEABr) or morpholine or combinations thereof.Phosphorus source is orthophosphoric acid or Metaphosphoric acid or pyrophosphoric acid or organophosphor
Any one or combinations thereof in acid esters.Described fluoride is the group of any one or they in ammonium fluoride or sodium fluoride or fluohydric acid gas
Close.The temperature of described gel in situ hydrothermal crystallizing is 100-220 DEG C, best 120-180 DEG C；Crystallization time 5-72 hour, best
16-48 hour；The roasting of described crystallization thing is carried out in atmosphere, sintering temperature 400-780 DEG C, preferably 450-650 DEG C, during roasting
Between 2-8 hour, preferably 3-6 hour.
MTO catalyst of the present invention is by RE-SAPO-34 molecular sieve, natural clay and colloidal sol bonding agent example 1.0 in mass ratio
(RE-SAPO-34): 0.10-1.0 (natural clay): 0.05-0.2 (colloidal sol bonding agent) add water being sufficiently mixed making beating formed homogeneous
Treat Gunning material, make microsphere through being spray-dried roasting.Described natural clay be Kaolin or attapulgite or bentonite or
Sheep Montmorillonitum, or their mixture；Described colloidal sol bonding agent is aluminum chloride or aluminum nitrate or aluminium silicate；Treat solid (body) of Gunning material
Content 20-50%, preferably 30-40%, outlet temperature 200-400 DEG C of described spray drying.
MTO catalyst of the present invention, at 400-550 DEG C, preferred 470-500 DEG C, carries out methanol in normal pressure, fixed bed reactors
Convert the MTO evaluation response making low carbene, methanol feed liquid air speed 0.5-5.0h-1, preferably 1.0-2.0h-1, methanol converts
100%, (C2Two-C4Two) triolefin yield more than 90%, (C2Two+C3Two) alkene yield more than 85%, C3Two/C2TwoRatio more than 9/10, two
Methyl ether yield is less than 1.5%；Fixed fluidized bed evaluate time, 470 DEG C, normal pressure, air speed 2.0h-1Under the conditions of, methanol converts
100%, (C2Two+C3Two) yield is more than 80%, dimethyl ether is less than 1.5%, and propylene/ethylene ratio, more than 0.9, has the MTO of excellence
Conversion performance.
Embodiment
The following example is in order to illustrate the present invention, but is not limiting as the present invention in listed embodiment.
Comparative example 1
The patent application synthetically prepared SAPO-of CN1087292A method according to Dalian Inst of Chemicophysics, Chinese Academy of Sciences
34 molecular sieves.Weigh 141 grams of isopropyl aluminum, dissolve in 150 grams of deionized waters, 63.75 grams of orthophosphoric acid, be added sequentially after stirring
39.3 grams of methyl silicates, 52.5 grams of triethylamines and 137.1 grams of deionized waters, stir into gel, proceed to inner liner polytetrafluoroethylene
Autoclave in, be heated to 170 DEG C, thermostatic crystallization 120 hours, drop to room temperature, filter and wash crystallization product, 110 DEG C be dried 3
Hour, 550 DEG C of roastings obtain 1# Molecular Sieve Comparative's sample for 4 hours.
Comparative example 2
Prepare SAPO-34 molecular sieve according to the method for UCC publication USP4440871, take 141 grams of isopropyl aluminum and 150
Gram deionized water, the orthophosphoric acid mixing of 86 gram 85%, stir evenly, add 39.3 grams of tetraethyl orthosilicates, 181 grams of tetraethyl hydroxides
Ammonium, 0.56 gram of HF and 100 grams of deionized waters, be sufficiently stirred for obtaining gel, transfer in autoclave, at 200 DEG C of thermostatic crystallizations 48
Hour, it is filtrated to get crystallization product and passes through washing, 110 DEG C are dried 3 hours, 4 hours prepared 2# Molecular Sieve Comparative of 550 DEG C of roastings
Sample.
Embodiment 1 synthesizes RE-SAPO-34
According to molar ratio 0.5HF: 1.0CeO2∶0.6SiO2∶1.0Al2O3∶2.0P2O5∶3.0RN∶50H2O, first will
Aqueous solution and 46 gram of 85% orthophosphoric acid that 43.5 grams of cerous nitrates are made into are mixed into gel, after adding 15.2 grams of boehmites
Be sequentially added into 2.5 grams of HF under continued mixing, 13.8 grams containing 27%SiO2Ludox and joined by 65 grams of tetraethyl ammonium hydroxides
The aqueous solution become, and add water ion and reach the above-mentioned mol ratio that feeds intake, it is sufficiently stirred for into gel, transfers to liner poly-four
In the autoclave of fluorothene, 200 DEG C of crystallization 48 hours, product is through filtering, and washing and 110 DEG C are dried 4 hours, 550 DEG C of roastings
Burn 4 hours, obtain embodiment 1# sample.
Embodiment 2 synthesizes RE-SAPO-34
According to molar ratio 0.1HF: 0.05CeO2∶0.6SiO2∶1.0Al2O3∶4P2O5∶3.0RN∶5.0H2O, first by 46
Gram 85%wt orthophosphoric acid, aqueous solution containing 0.8 gram of cerous acetate and 8.5 grams of boehmites are mixed into gel, continue stirring
Under be sequentially added into 0.5 gram of HF, 0.9 gram of white carbon SiO2With the aqueous solution containing 65 grams of tetraethyl ammonium hydroxides supplementary deionized water
Reach molar ratio, be sufficiently stirred for forming homogeneous gel, proceed in the autoclave of inner liner polytetrafluoroethylene, 200 DEG C of crystallization
48 hours, crystallization product was washed through drainage and is dried with 110 DEG C, and 550 DEG C of roastings 5 hours obtain embodiment 2# sample.
Embodiment 3 synthesizes RE-SAPO-34
According to molar ratio 0.01HF: 0.01CeO2∶0.6SiO2∶1.0Al2O3∶2.0P2O5∶5.0RN∶50H2O, will
0.4 gram of cerous acetate, 46 grams of 85%wt orthophosphoric acid, the mixing of a small amount of deionized water, stir into gel, continue first to add the thin water of plan under stirring
Aluminum stone, stirs evenly, and sequentially adds the aqueous solution containing 0.05 gram of HF, and 13.8 grams contain 27%SiO2Silicon solution and 51 grams of triethylamines,
Finally supplement amount of deionized water to meeting the mol ratio that feeds intake, after being sufficiently stirred for forming gel, transfer to liner polyvinyl fluoride
In autoclave, 200 DEG C of crystallization 48 hours, product through filtering, washing, dry 4 hours for 120 DEG C, 550 DEG C of roastings 4 hours, obtain
Embodiment 3# sample.
Embodiment 4 synthesizes RE-SAPO-34
According to molar ratio 0.05NH4F∶0.1Nd2O3∶0.8SiO2∶1.0Al2O3∶1.5P2O5∶2.0RN∶50H2O, presses
Embodiment charging sequence, by 6.0 grams of rubidium nitrate [Nd (NO3)3.6H2O], 46 grams of 85%wt orthophosphoric acid, 20.2 grams of boehmites,
0.6 gram of NH4F, 24.6 grams containing 27%SiO2Ludox and 27.2 grams of triethylamines mix with the deionized water meeting rate of charge, stir
Mixing and uniformly become gel, proceed to autoclave, 200 DEG C of crystallization 48 hours, the crystallization product being filtrated to get was through washing, 120 DEG C of drying
After, in 550 DEG C of roastings 4 hours, obtain embodiment 4# sample.
Embodiment 5 synthesizes RE-SAPO-34
According to molar ratio 0.05NH4F∶0.8CeO2∶1.2SiO2∶1.0Al2O3∶1.2P2O5∶3.0RN∶50H2O, first will
58.3 grams of molten water of cerous nitrate, stir evenly, add 46 grams of 85%wt orthophosphoric acid, after stirring evenly formation gel, add 25.3 grams of aluminum isopropylate.,
Continue to stir, be then sequentially added into containing 0.8 gram of NH4F, 46 grams containing 27%SiO2Ludox and 51 grams of triethylamines water-soluble
Liquid, and add deionized water and reach molar ratio to its total Water, the gel stirred is transferred to autoclave, 200
DEG C crystallization 48 hours, after product is separated by filtration washing, dries 4 hours for 120 DEG C, 550 DEG C of roastings 4 hours, obtains embodiment 5#
Sample.
Embodiment 6 synthesizes RE-SAPO-34
According to molar ratio 0.1NH4F∶0.4CeO2∶1.5SiO2∶1.0Al2O3∶0.6P2O5∶3.0RN∶50H2O, takes
58.3 grams of molten water of cerous nitrate, add 39 grams of pyrophosphoric acids, stir evenly gel, add 50.6 grams of β-gibbsites, be stirred for into equal
After even gel, it is sequentially added into containing 3.1 grams of NH4F, 115.1 grams containing 27%SiO2Ludox and the solution of 102 grams of triethylamines, finally mend
Add amount of deionized water to molar ratio.After fully stirring evenly, gel being proceeded to autoclave, 200 DEG C of crystallization 48 hours, crystallization was produced
Thing is separated by filtration, washes, and after 120 DEG C dry 4 hours, 550 DEG C of roastings obtain embodiment 6# sample in 4 hours in atmosphere.
Embodiment 7 synthesizes RE-SAPO-34
According to molar ratio 0.01NH4F∶0.8CeO2∶0.2SiO2∶1.0Al2O3∶4P2O5∶3.0RN∶50H2O, takes 17.4
Gram molten water of cerous nitrate, adds 46 grams of 85%wt orthophosphoric acid and stirs gel, add 8.5 grams of boehmites, and stirring is extremely
After homogeneous gel, it is sequentially added into 0.02 gram of HF, 0.6 gram of white carbon SiO2Powder and 65 grams of tetraethyl ammonium hydroxides, then add
Deionized water is to meeting the mol ratio that feeds intake.It is sufficiently stirred for forming homogeneous gel, proceeds to the autoclave of liner tetrafluoroethene,
200 DEG C of crystallization 48 hours.The separated mother solution that goes of product, washing crystallization thing is in 110 DEG C of drying 6 hours, roasting 4 in 550 DEG C of air
Hour, obtain embodiment 7# sample.
Embodiment 8 synthesizes RE-SAPO-34
According to molar ratio 0.05NH4F∶0.4CeO2∶0.8SiO2∶1.0Al2O3∶1.0P2O5∶3.0RN∶50H2O, by 35
Gram molten water of cerous nitrate, adds 46 grams of 85%wt orthophosphoric acid, and stir gel, adds 30.4 grams of amorphous AL (OH)3, continue
Continuous stirring, to forming homogeneous gel, is then sequentially added into containing 0.9 gram of NH4F, 36.8 grams containing 27%SiO2Ludox and 61.2 grams
The aqueous solution of triethylamine, adds deionized water and reaches molar ratio, is sufficiently stirred for forming homogeneous gel and proceeds to rustless steel height
Pressure still, 200 DEG C of crystallization 48 hours, product separated and removes mother solution, through washing, dries 5 hours for 120 DEG C, roasts in 550 DEG C of air stream
Burn 4 hours, obtain embodiment 8# sample.
Embodiment 9 synthesizes RE-SAPO-34
According to molar ratio 0.01HF: 1.2CeO2∶∶0.6SiO2∶1.0Al2O3∶0.2P2O5∶(3.0TEABr+
0.5NH4OH)∶50H2O, by 43.5 grams of molten water of cerous nitrate, adds 46 grams of 85%wt orthophosphoric acid, and stir gel, adds
8.5 grams of boehmites, continue stirring to forming homogeneous gel, sequentially add containing 0.02 gram of HF, 9.2 grams containing 27%SiO2's
Ludox, 35 grams of tetraethylammonium bromides (TEABr) and 18 grams of ammonium hydroxide, supplementary deionized water is to reaching molar ratio.Fill
Point stirring mixture, to formation homogeneous gel, proceeds to autoclave, 200 DEG C of crystallization 48 hours.After crystallization product separation mother solution again
Through washing, drying 5 hours at 120 DEG C, in 550 DEG C of air, roasting 5 hours, obtains embodiment 9# sample.
Embodiment 10 synthesizes RE-SAPO-34
According to molar ratio 0.01HF: 1.2CeO2∶∶0.6SiO2∶1.0Al2O3∶0.2P2O5∶3.0RN∶50H2O, will
43.5 grams of cerous nitrates are dissolved in water, add 46 grams of 85%wt orthophosphoric acid, and stir gel, add 8.5 grams of boehmites,
Continue stirring to forming homogeneous gel, be sequentially added into containing 0.02 gram of HF, 9.2 grams containing 27%SiO2Ludox and 11.3 grams of positive fourths
Amine, then add deionized water and reach the water yield of molar ratio requirement.It is thoroughly mixed thing to forming homogeneous gel, then turns
Move on in teflon-lined autoclave, 200 DEG C of crystallization 48 hours.Crystallization product is after filtering, washing, at 110 DEG C
Drying 6 hours, in 550 DEG C of air, roasting 4 hours, obtains embodiment 10# sample.
Embodiment 11 synthesizes RE-SAPO-34
According to molar ratio 0.01HF: 1.2CeO2∶∶0.6SiO2∶1.0Al2O3∶0.2P2O5∶3.0RN∶50H2O, will
43.5 grams of cerous nitrates are dissolved in water and 21.5 grams of etherophosphoric acid mixing, stir into homogeneous gel shape, add 8.5 grams of boehmites,
Continue stirring to being formed after homogeneous gel, be sequentially added into 0.02 gram of HF, 9.2 grams containing 27%SiO2Ludox and 14 grams of morpholines,
Add deionized water again and reach the requirement of molar ratio to total Water.It is thoroughly mixed after thing reaches homogeneous gel, proceeds to
Autoclave, 200 DEG C of crystallization 48 hours, the separated mother solution that goes of product, washing and 120 DEG C dried 5 hours, 550 DEG C in atmosphere
Roasting 4 hours, obtains embodiment 11# sample.
Embodiment 12 prepares catalyst
Take 1# Molecular Sieve Comparative's sample, 2# Molecular Sieve Comparative's sample, embodiment 1# sample and embodiment 2# sample respectively and select 1 with Suzhou machine
Number Kaolin and aluminum chloride are pressed 1.2/1.0/0.2 mass and are pulled an oar than mixing and water adding, control solid content 40%, and spraying prepares microsphere and urges
Agent ginseng 1, catalyst ginseng 2, catalyst reality 1#, catalyst reality 2#, spray drying exit temperature 240 DEG C.Example 3# respectively
After sample, embodiment 4# sample, embodiment 5# sample select No. 1 Kaolin and aluminum chloride to mix by 1.0/1.0/0.3 mass ratio with Suzhou machine
Making beating, controls solid content 35% and spray drying exit temperature 250 DEG C, is spray-dried and prepares catalyst reality 3#, catalyst reality 4#
With catalyst reality 5#.
Embodiment 13 prepares catalyst
Example 6# sample, embodiment 7# sample add water with attapulgite and aluminum nitrate 2.0/1.0/0.5 in mass ratio respectively
Mixing making beating, controls solid content 38%, is spray-dried shaping and prepares microspherical catalyst reality 6# and catalyst reality 7#.
Embodiment 14 prepares catalyst
The silicate gel of Example 8# sample, embodiment 9# sample and bentonite and silica alumina ratio 3/1 is in mass ratio respectively
3.5/1/0.5 add water making beating, controls solid content 30%, and spraying shapes and prepares microspherical catalyst, outlet temperature 250 DEG C.Urged
Agent reality 8# and catalyst reality 9#.
Embodiment 15 prepares catalyst
Example 10# sample, embodiment 11# sample and Shanxi sheep Montmorillonitum and aluminum chloride 2.5/1.0/0.4 in mass ratio respectively
Mix, add water, pull an oar, control solid content 28%, be spray-dried and shape prepared catalyst reality 10# and catalyst reality 11#.
Embodiment 16 molecular sieve thing phase
Take 1# Molecular Sieve Comparative's sample, 2# Molecular Sieve Comparative's sample, embodiment 1# sample-embodiment 11# sample grinding and tabletting respectively
After on X-ray diffractometer, Cu K α source, 40kV, 60mA are set under the conditions of carry out XRD material phase analysis, each sample is all in typical case
CHA/AEI topological structure, XRD spectrum (Fig. 1) of optional 2# Molecular Sieve Comparative's sample and embodiment 1# and 4# sample testifies, each molecular sieve sample
Relative crystallinity be shown in Table 1, show that each example of embodiment all can synthesize SAPO-34 molecular sieve, the inventive method synthesis obtains RE-
SAPO-34 degree of crystallinity is superior to control sample.
Table 1 SAPO-34 molecular sieve crystallinity
Embodiment 17
Take catalyst ginseng 1, ginseng 2, catalyst reality 1#, real 2#, real 3#, real 4#, real 5#, real 6#, real 7#, real 8#, real 9#, reality
10# and real 11# carries out physical property measurement, the results are shown in Table 2, shows that RE-SAPO-34 molecular sieve of the present invention all can prepare physical property
Excellent is suitable to the microspherical catalyst that fluidized-bed reactor uses.
The physical property of table 2 catalyst
Embodiment 18 MTO reactivity worth
Fixed fluidized-bed reactor 100ml, catalyst to be evaluated is by charge door negative pressure sucting reaction device, the nitrogen of 40ml/min
Atmosphere is warming up to 500 DEG C of constant temperature 1 hour, is cooled to 470 DEG C, feed methanol flow 2.0ml/min i.e. air speed 2.0h-1.Intermittently
Sample analysis.Under these experimental conditions, respectively to catalyst ginseng 1, ginseng 2, real 1#, real 2#, real 3#, real 4#, real 5#, real 6#,
Real 7#, real 8#, real 9#, real 10#, real 11# carry out MTO reactivity worth evaluation, and result is converged to table 3, it is seen that MTO catalyst of the present invention
Having methanol and convert 100%, (ethylene+propylene) yield 80%, generation dimethyl ether is few, and especially propylene/ethylene is high, more than 0.9
Feature, significant for filling up alkene market propylene breach.
Table 3 catalyst MTO reactivity worth
Claims (9)
1. a methanol-to-olefin catalyst, it is characterised in that the RE-SAPO-34 molecular sieve prepared using in-situ crystallization method is as work
Property component, makees substrate with natural clay, formulated with peptization bonding agent, methanol conversion 100%, ethylene+propylene total recovery
More than 80%, propylene/ethylene ratio is more than 0.9；
The mass ratio of described RE-SAPO-34 molecular sieve, described natural clay and described peptization bonding agent is 1.0: 0.10-1.0:
0.05-0.2；
Described in-situ crystallization method is that the soluble-salt of rare earth RE elemental cerium Ce or neodymium Nd turns to fluorine-containing with phosphorus source and fluoride prerotation
RE phosphate, stirs into gel crystallization synthesis RE-SAPO-34 molecule in situ under the effect of template RN with aluminum source and silicon source
Sieve；
The molar ratio of the various raw materials that described in-situ crystallization method prepares RE-SAPO-34 molecular sieve is (0.01-0.5) F:
(0.01-1.0)RE2O3∶(0.2-1.5)SiO2∶1.0Al2O3∶(0.2-2.0)P2O5∶(2.0-5.0)RN∶(35-50)H2O。
Catalyst the most according to claim 1, it is characterised in that characterized by XRD, in described RE-SAPO-34 molecular sieve
Rare earth RE atom enters into SAPO-34 framework of molecular sieve, has CHA or CHA/AEI topological structure.
Catalyst the most according to claim 1, it is characterised in that the soluble-salt of described cerium or neodymium is the nitric acid of cerium or neodymium
A kind of or their mixture in salt or sulfate or acetate；Or, phosphorus source is orthophosphoric acid or Metaphosphoric acid or pyrophosphoric acid
Or a kind of or their mixture in organophosphorus ester；Or, described fluoride is to appoint in ammonium fluoride or sodium fluoride or fluohydric acid gas
One or combinations thereof；Or, source of aluminium is arbitrary in boehmite or β-gibbsite or amorphous hydroted alumina
Plant or combinations thereof；Or, described silicon source is any one or combinations thereof in Ludox or white carbon or the positive ethyl ester of silicic acid；
Or, described template RN is triethylamine or diethylamine or n-butylamine or tetraethyl ammonium hydroxide TEAOH or tetraethylammonium bromide
Any one or combinations thereof in TEABr or morpholine.
4. according to the catalyst described in claim 1 or 3, it is characterised in that in-situ crystallization temperature is 100-220 DEG C.
Catalyst the most according to claim 1, it is characterised in that described natural clay is Kaolin or attapulgite or swollen
Profit soil or sheep Montmorillonitum any one, or combinations thereof.
Catalyst the most according to claim 1, it is characterised in that described peptization bonding agent is aluminum chloride or aluminum nitrate or silicon
In acid aluminum any one, or combinations thereof.
Catalyst the most according to claim 1, it is characterised in that described active component, described natural clay and described peptization
Bonding agent is made into treats Gunning material, spray-dried makes microsphere.
Catalyst the most according to claim 7, it is characterised in that described in treat that the solid content of Gunning material is 20-50%.
Catalyst the most according to claim 7, it is characterised in that the outlet temperature of described spray drying is 200-400 DEG C.
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| CN108187736B (en) * | 2018-01-20 | 2020-03-24 | 辽宁金易化工有限公司 | Gibbsite @ SAPO molecular sieve compound with core-shell structure, preparation method and application thereof in catalyzing methanol to olefin |
| CN109052428B (en) * | 2018-07-26 | 2022-02-01 | 西北师范大学 | Method for preparing SAPO molecular sieve by using attapulgite of non-metal ore as raw material |
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| CN1683078A (en) * | 2004-04-16 | 2005-10-19 | 中国石油化工股份有限公司 | Synthetic method for metal ion containing silicon-phosphor-aluminium molecular shieve |
| CN101767800A (en) * | 2009-01-06 | 2010-07-07 | 神华集团有限责任公司 | Method for preparing SAPO-34 molecular sieve |
| CN101993094A (en) * | 2009-08-19 | 2011-03-30 | 汉能科技有限公司 | Cerium-containing silicoaluminophosphate (SAPO) type molecular sieve Ce-APO-34 and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5962762A (en) * | 1995-12-13 | 1999-10-05 | Sun; Hsian-Ning | Use of transition metal containing small pore molecular sieve catalysts in oxygenate conversion |
| CN1683078A (en) * | 2004-04-16 | 2005-10-19 | 中国石油化工股份有限公司 | Synthetic method for metal ion containing silicon-phosphor-aluminium molecular shieve |
| CN101767800A (en) * | 2009-01-06 | 2010-07-07 | 神华集团有限责任公司 | Method for preparing SAPO-34 molecular sieve |
| CN101993094A (en) * | 2009-08-19 | 2011-03-30 | 汉能科技有限公司 | Cerium-containing silicoaluminophosphate (SAPO) type molecular sieve Ce-APO-34 and preparation method and application thereof |
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