CN104096591A - Mto catalyst and preparation method thereof - Google Patents
Mto catalyst and preparation method thereof Download PDFInfo
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- CN104096591A CN104096591A CN201310116349.7A CN201310116349A CN104096591A CN 104096591 A CN104096591 A CN 104096591A CN 201310116349 A CN201310116349 A CN 201310116349A CN 104096591 A CN104096591 A CN 104096591A
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- sapo
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- molecular sieve
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 45
- 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 42
- 239000002808 molecular sieve Substances 0.000 claims abstract description 41
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 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
- 239000007767 bonding agent Substances 0.000 claims abstract description 12
- 239000004927 clay Substances 0.000 claims abstract description 12
- 239000005977 Ethylene Substances 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims description 38
- 230000008025 crystallization Effects 0.000 claims description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 31
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 235000011007 phosphoric acid Nutrition 0.000 claims description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 12
- 238000011065 in-situ storage Methods 0.000 claims description 12
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 229910052779 Neodymium Inorganic materials 0.000 claims description 9
- 239000004411 aluminium Substances 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 9
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 9
- 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
- 150000002910 rare earth metals Chemical class 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 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
- 238000001935 peptisation Methods 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
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- 229910001593 boehmite Inorganic materials 0.000 claims description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- 241001494479 Pecora Species 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229960000892 attapulgite Drugs 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 235000009508 confectionery Nutrition 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000002689 soil 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-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
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 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
- 150000002148 esters Chemical class 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
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 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
- 239000011159 matrix material Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 238000005507 spraying Methods 0.000 abstract description 7
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract 1
- 150000005671 trienes Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000000047 product Substances 0.000 description 13
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 12
- -1 ethylene, propylene Chemical group 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 8
- 239000007864 aqueous solution Substances 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
- 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
- 238000005516 engineering process Methods 0.000 description 5
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 238000010009 beating Methods 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 229910052622 kaolinite Inorganic materials 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
- 150000003839 salts Chemical class 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 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
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007921 spray Substances 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
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 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
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical class [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 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
- 238000002156 mixing Methods 0.000 description 1
- 150000002780 morpholines Chemical class 0.000 description 1
- 150000003941 n-butylamines Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel 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
Abstract
The invention discloses an MTO catalyst and a preparation method thereof. The invention provides the MTO catalyst (methanol to olefins) and a preparation method for rear-earth-containing SAPO-34 molecular sieve (RE-SAPO-34) which is the active composition of the catalyst. According to the catalyst, a to-be sprayed slurry is prepared from the active composition, natural clay and a peptizing bonding agent, and is subjected to spraying drying to prepare microballons. The methanol conversion rate is 100%, the total yield of ethylene and propylene is larger than 80%, the total yield of triene is larger than 90%, and the ratio of propylene to ethylene is larger than 0.9.
Description
Technical field
The present invention relates to generate for methanol conversion the catalyst of low-carbon alkene (MTO), more specifically relating to active constituent is preparation method and the catalytic perfomance thereof that contains the MTO catalyst of the RE-SAPO-34 molecular sieve of rare earth.
Background technology
Methanol-to-olefins (MTO) is the important Coal Chemical Industry technology that is expected to petroleum replacing raw material route preparing low-carbon olefins.The world's first cover 1.0Mt/a stage arrangement builds up in China, and successfully goes into operation, and new catalyst and improvement technology are also at development.The MTO technology of tracing to the source is that first to disclose a kind of Novel phosphoric acid Si-Al molecular sieve at the patent US4440871 of 1984 be SAPO-n in union carbide corporation (UCC), find that the SAPO-34 of its small aperture shows the performance (US4499327,4677242,4873390,5095163,6166282) of the low carbenes such as excellent methanol conversion generation ethene, but poor stability, haves much room for improvement.Researcher 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, the catalytic activity and the stability that improve SAPO-34 are research and development MTO raw catelyst and the core of improving MTO new technology.
Metallic element upgrading SAPO-34 can improve the MTO reactivity worth of SAPO-34, originally be that EXXON company utilizes alkaline earth element (Ca, Sr, Ba) modified SAPO-34, improve ethylene-propylene yield (US6040264), about the patent of this respect, as having reported metal-modified SAPO-34, US4567029, EP0159624, CN101301626A, WO2001US04502 can improve methanol conversion and generate performance and the stability of low carbene.China researcher's CN1167654A patent application also discloses Cu, Co, Ni study on the modification obtains the effect that improves low carbene yield, especially in the patent application CN1068574 of Dalian Chemiclophysics Inst., Chinese Academy of Sciences, reported and used nickel modified SAPO-34, in the time that Si/Ni atomic ratio reaches 100, methanol conversion generates the yield of ethene can bring up to 60% by 30%; The patent application CN1704390 of Sinopec Shanghai Petroleum Chemical Engineering Institute also discloses zinc modification SAPO-34 and has improved MTO reactivity worth.
Modifying element is except common transition metal and alkaline earth, also there is researcher to adopt rare-earth elements La to do modified SAPO-34 research (CN101318667A), but reaction generates the performance of low carbene and is not improved, far away from the Ni-SAPO-34 of the Dalian Chemistry and Physics Institute.
Be related to aspect research in molecular sieve modified and catalysis, if scholars find modified metal atom with tetrahedron element (MeO
4) be inserted among the skeleton of SAPO-34 molecular sieve and retain the former topological structure of molecular sieve, because the valence state of Me affects framework of molecular sieve electrostatic charge, not only can Molecular regulator the port size of sieve, also can modulate the acidity of molecular sieve, in order to improve performance (the Catal Let of the low carbene of its catalyzed conversion MTO, 1998,53:171-176).This is for further improving SAPO-34 and catalyst performance has been indicated direction.Magnify smelting first mixes boehmite with phosphoric acid, Ludox after, add template triethylamine, add again the acetate of modified metal M g, the synthetic Mg-SAPO-34 molecular sieve that has obtained skeleton magnesium, its method is that shilling modified metal and template form complex compound, then it is synthetic to introduce He Gui source, aluminium source crystallization.
The inventor has successfully introduced SAPO-34 molecular sieve by large-sized rare earth element ce in disclosed CN101993094A patent application, and it shows excellent MTO reactivity worth, can be by methanol conversion 100%, and the yield of ethylene, propylene can bring up to 80%.But totally say that current MTO catalysis technique still haves much room for improvement in many-side, with regard to catalyst, not only require (ethene+propylene) yield and (ethene+propylene+butylene) three yields further to improve, require further to reduce CO+CO simultaneously
2+ dimethyl ether selective, and need to improve especially propylene/ethylene ratio, the physical property of catalyst also has the larger space that needs.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of yield of light olefins high, propylene/ethylene is than high, CO, CO
2with the selective low MTO Catalysts and its preparation method of dimethyl ether, more specifically, provide a kind of MTO excellent performance rare-earth modified molecular-sieve RE-SAPO-34 synthetic method and by it as active component can commercial Application MTO Catalysts and its preparation method.The scheme of dealing with problems is as follows:
1, a methanol-to-olefins catalyst, is characterized in that, using the standby RE-SAPO-34 molecular sieve of in-situ crystallization legal system as active component, making matrix with natural clay, formulated with peptization bonding agent, methanol conversion 100%, ethene+propylene total recovery is greater than 80%, and propylene/ethylene ratio is greater than 0.9.
2, according to the catalyst described in 1, it is characterized in that characterizing 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 characterized in that described in-situ crystallization method is that the soluble-salt of rare earth RE elemental cerium Ce or neodymium Nd and phosphorus source and fluoride prerotation turn to fluorine-containing RE phosphate, original position and He Gui source, aluminium source stir into the synthetic RE-SAPO-34 molecular sieve of gel crystallization under template RN effect.
4,, according to the catalyst described in 1, it is characterized in that described in-situ crystallization legal system is (0.01-0.5) F for the various raw material molar ratios of RE-SAPO-34 molecular sieve: (0.01-1.0) RE
2o
3: (0.2-1.5) SiO
2: 1.0Al
2o
3: (0.2-2.0) P
2o
5: (2.0-5.0) RN: (35-50) H
2o.
5,, according to the catalyst described in 1, the mass ratio that it is characterized in that described RE-SAPO-34 molecular sieve, described natural clay and described colloidal sol bonding agent is 1.0: 0.10-1.0: 0.05-0.2.
6,, according to the catalyst described in 3, the soluble-salt that it is characterized in that described cerium or neodymium is a kind of in the nitrate of cerium or neodymium or sulfate or acetate or their mixture; Or described phosphorus source is a kind of in orthophosphoric acid or metaphosphoric acid or pyrophosphoric acid or organophosphorus ester or their mixture; Or described fluoride is the combination of any or they in ammonium fluoride or sodium fluoride or hydrogen fluoride; Or described aluminium source is the combination of any or they in boehmite or β-gibbsite or amorphous hydroted alumina; Or described silicon source is the combination of any or they in Ludox or white carbon or the positive ethyl ester of silicic acid; Or described template RN is the combination of any or they in triethylamine or diethylamine or n-butylamine or tetraethyl ammonium hydroxide TEAOH or tetraethylammonium bromide TEABr or morpholine; Or, their any combination.
7,, according to the catalyst described in 3 or 6, it is characterized in that in-situ crystallization temperature is 100-220 DEG C.
8, according to the catalyst described in 1, it is characterized in that described natural clay be kaolin or attapulgite or bentonite or the sweet soil of sheep any, or their combination.
9, according to the catalyst described in 1, it is characterized in that described peptization bonding agent be in aluminium chloride or aluminum nitrate or alumina silicate any, or their combination.
10,, according to the catalyst described in 1, it is characterized in that described active component, described natural clay and described peptization bonding agent are made into treat Gunning material, the spray-dried microballoon of making.
11,, according to the catalyst described in 10, the solid content for the treatment of Gunning material described in it is characterized in that is 20-50%.
12,, according to the catalyst described in 10, it is characterized in that described spray-dired outlet temperature is 200-400 DEG C.
Brief description of the drawings
Fig. 1 is the XRD spectrum of 2# molecular sieve contrast sample and embodiment 1# and 4# sample.
Detailed description of the invention
The invention provides a kind of yield of light olefins high, propylene/ethylene is than high, CO, CO
2with the selective low MTO Catalysts and its preparation method of dimethyl ether, more specifically, provide a kind of MTO excellent performance rare-earth modified molecular-sieve RE-SAPO-34 synthetic method and by it as active component can commercial Application MTO Catalysts and its preparation method.Described RE-SAPO-34 adopts in-situ crystallization method that the rare earth element ce of thick atom size or Nd are introduced to the synthetic rare earth modified SPAO-34 molecular sieve of framework of molecular sieve, it is characterized in that having CHA/AEI topological structure (seeing Fig. 1); Described in-situ crystallization method is that rare-earth element cerium (Ce) salt or neodymium (Nd) salt and phosphorus source are converted in advance to fluorine-containing RE phosphate under fluoride is assisted, under template effect, stir into gel in situ hydrothermal crystallizing with He Gui source, aluminium source simultaneously, then the crystallization thing of elimination mother liquor is dried to also roasting and remove after template, obtain RE-SAPO-34 molecular screen primary powder.The molar ratio of the synthetic each raw material of described RE-SAPO-34 molecular sieve original position crystallization is (0.01-0.5) F: (0.01-1.0) RE
2o
3: (0.2-1.5) SiO
2: 1.0Al
2o
3: (0.2-2.0) P
2o
5: (2.0-5.0) RN: (35-50) H
2o.Described rare earth (RE) is cerium (Ce) salt or neodymium (Nd) salt, as the nitrate of Ce or Nd or sulfate or acetate, or their mixture.Described aluminium source is boehmite, or β-gibbsite, or the combination of any or they in amorphous hydroted alumina.Described silicon source is Ludox or white carbon, or the combination of any or they in the positive ethyl ester of silicic acid.Described template RN is triethylamine or diethylamine or n-butylamine, or tetraethyl ammonium hydroxide (TEAOH), or a kind of in tetraethylammonium bromide (TEABr) or morpholine or their combination.Described phosphorus source is the combination of any or they in orthophosphoric acid or metaphosphoric acid or pyrophosphoric acid or organophosphorus ester.Described fluoride is the combination of any or they in ammonium fluoride or sodium fluoride or hydrogen fluoride.The temperature of described gel in situ hydrothermal crystallizing is 100-220 DEG C, preferably 120-180 DEG C; Crystallization time 5-72 hour, preferably 16-48 hour; The roasting of described crystallization thing is carried out in air, sintering temperature 400-780 DEG C, preferably 450-650 DEG C, roasting time 2-8 hour, preferably 3-6 hour.
MTO catalyst of the present invention by RE-SAPO-34 molecular sieve, natural clay and colloidal sol bonding agent in mass ratio example 1.0 (RE-SAPO-34): 0.10-1.0 (natural clay): 0.05-0.2 (colloidal sol bonding agent) add water and fully mix making beating and forms the homogeneous Gunning material for the treatment of, through spraying, drying and roasting is made microballoon.Described natural clay is kaolin or attapulgite or bentonite or the sweet soil of sheep, or their mixture; Described colloidal sol bonding agent is aluminium chloride or aluminum nitrate or alumina silicate; Treat solid (body) content 20-50% of Gunning material, preferably 30-40%, described spray-dired outlet temperature 200-400 DEG C.
MTO catalyst of the present invention, at 400-550 DEG C, preferred 470-500 DEG C, carries out the MTO evaluation response of the low carbene of methanol conversion system, methanol feeding liquid air speed 0.5-5.0h in normal pressure, fixed bed reactors
-1, preferably 1.0-2.0h
-1, methanol conversion 100%, (C2
two-C4
two) triolefin yield is greater than 90%, (C2
two+ C3
two) alkene yield is greater than 85%, C3
two/ C2
twothan being greater than 9/10, yield of dimethyl ether is less than 1.5%; When fixed fluidized bed evaluation, at 470 DEG C, normal pressure, air speed 2.0h
-1under condition, methanol conversion 100%, (C2
two+ C3
two) yield is greater than 80%, dimethyl ether is less than 1.5%, and propylene/ethylene ratio is greater than 0.9, has excellent MTO conversion performance.
Embodiment
The following example is in order to the present invention to be described, but do not limit the invention to listed embodiment.
Comparative example 1
According to the synthetic preparation of the patent application CN1087292A method of Dalian Inst of Chemicophysics, Chinese Academy of Sciences SAPO-34 molecular sieve.Take 141 grams of isopropyl aluminium, dissolve in 150 grams of deionized waters, 63.75 grams of orthophosphoric acid, add 39.3 grams of methyl silicates, 52.5 grams of triethylamines and 137.1 grams of deionized waters in turn after stirring, stir into gel, proceed in the autoclave of inner liner polytetrafluoroethylene, be heated to 170 DEG C, thermostatic crystallization 120 hours, drop to room temperature, filter and wash crystallization product, 110 DEG C are dried 3 hours, and 550 DEG C of roastings obtain 1# molecular sieve contrast sample for 4 hours.
Comparative example 2
Method according to UCC publication USP4440871 is prepared SAPO-34 molecular sieve, get 141 grams of isopropyl aluminium and 150 grams of deionized waters, the orthophosphoric acid of 86 gram 85% mixes, stir evenly, add again 39.3 grams of tetraethyl orthosilicates, 181 grams of tetraethyl ammonium hydroxides, 0.56 gram of HF and 100 grams of deionized waters, fully stir and obtain gel, transfer in autoclave, 200 DEG C of thermostatic crystallizations 48 hours, filtration obtains crystallization product through washing, 110 DEG C are dried 3 hours, and 550 DEG C of roastings make 2# molecular sieve contrast sample for 4 hours.
The synthetic RE-SAPO-34 of embodiment 1
According to molar ratio 0.5HF: 1.0CeO
2: 0.6SiO
2: 1.0Al
2o
3: 2.0P
2o
5: 3.0RN: 50H
2o, the aqueous solution first 43.5 grams of cerous nitrates being made into and 46 gram of 85% orthophosphoric acid are mixed into gel, add after 15.2 grams of boehmites and under continuing to stir, to add successively 2.5 grams of HF, 13.8 grams containing 27%SiO
2ludox and the aqueous solution being made into by 65 grams of tetraethyl ammonium hydroxides, and add the ion that anhydrates and reach the above-mentioned mole proportioning that feeds intake, fully stir into gel, transfer in the autoclave of inner liner polytetrafluoroethylene, 200 DEG C of crystallization 48 hours, product was through filtering, washing and 110 DEG C of oven dry 4 hours, 550 DEG C of roastings 4 hours, obtain embodiment 1# sample.
The synthetic RE-SAPO-34 of embodiment 2
According to molar ratio 0.1HF: 0.05CeO
2: 0.6SiO
2: 1.0Al
2o
3: 4P
2o
5: 3.0RN: 5.0H
2o, first by 46 grams of 85%wt orthophosphoric acid, be mixed into gel containing the aqueous solution and 8.5 grams of boehmites of 0.8 gram of cerous acetate, adds 0.5 gram of HF, 0.9 gram of white carbon SiO under continuing to stir successively
2reach molar ratio with the aqueous solution supplementary deionized water containing 65 grams of tetraethyl ammonium hydroxides, fully stir and form even gel, proceed in the autoclave of inner liner polytetrafluoroethylene, 200 DEG C of crystallization 48 hours, crystallization product is washed with 110 DEG C dry after filtration, 550 DEG C of roastings 5 hours, obtain embodiment 2# sample.
The synthetic RE-SAPO-34 of embodiment 3
According to molar ratio 0.01HF: 0.01CeO
2: 0.6SiO
2: 1.0Al
2o
3: 2.0P
2o
5: 5.0RN: 50H
2o, mixes 0.4 gram of cerous acetate, 46 grams of 85%wt orthophosphoric acid, a small amount of deionized waters, stirs into gel, under continuing to stir, first adds boehmite, stirs evenly, then adds successively the aqueous solution containing 0.05 gram of HF, and 13.8 grams containing 27%SiO
2silicon solution and 51 grams of triethylamines, finally supplement amount of deionized water to meeting mole proportioning that feeds intake, fully stir and form after gel, transfer in the autoclave of liner polyvinyl fluoride, 200 DEG C of crystallization 48 hours, product after filtration, washing, dry 4 hours for 120 DEG C, 550 DEG C of roastings 4 hours, obtain embodiment 3# sample.
The synthetic RE-SAPO-34 of embodiment 4
According to molar ratio 0.05NH
4f: 0.1Nd
2o
3: 0.8SiO
2: 1.0Al
2o
3: 1.5P
2o
5: 2.0RN: 50H
2o, by embodiment charging sequence, by 6.0 grams of rubidium nitrate [Nd (NO
3)
3.6H
2o], 46 grams of 85%wt orthophosphoric acid, 20.2 grams of boehmites, 0.6 gram of NH
4f, 24.6 grams are containing 27%SiO
2ludox and 27.2 grams of triethylamines mix with the deionized water that meets rate of charge, be stirred into gel, proceed to autoclave, 200 DEG C of crystallization 48 hours, the crystallization product that filtration obtains, after washing, 120 DEG C of oven dry, in 550 DEG C of roastings 4 hours, obtains embodiment 4# sample.
The synthetic RE-SAPO-34 of embodiment 5
According to molar ratio 0.05NH
4f: 0.8CeO
2: 1.2SiO
2: 1.0Al
2o
3: 1.2P
2o
5: 3.0RN: 50H
2o, first by 58.3 grams of molten water of cerous nitrate, stir evenly, add 46 grams of 85%wt orthophosphoric acid, stir evenly and form after gel, add 25.3 grams of aluminium isopropoxides, continue to stir, then add successively containing 0.8 gram of NH
4f, 46 grams are containing 27%SiO
2ludox and the aqueous solution of 51 grams of triethylamines, and add deionized water to its total Water and reach molar ratio, the gel stirring is transferred to autoclave, 200 DEG C of crystallization 48 hours, product is separated by filtration after washing, dry 4 hours for 120 DEG C, 550 DEG C of roastings 4 hours, obtain embodiment 5# sample.
The synthetic RE-SAPO-34 of embodiment 6
According to molar ratio 0.1NH
4f: 0.4CeO
2: 1.5SiO
2: 1.0Al
2o
3: 0.6P
2o
5: 3.0RN: 50H
2o, gets 58.3 grams of molten water of cerous nitrate, adds 39 grams of pyrophosphoric acids, stirs evenly gel, adds 50.6 grams of β-gibbsites, then stirs into after even gel, adds successively containing 3.1 grams of NH
4f, 115.1 grams are containing 27%SiO
2the solution of Ludox and 102 grams of triethylamines, finally adds amount of deionized water to molar ratio.After fully stirring evenly, gel is proceeded to autoclave, 200 DEG C of crystallization 48 hours, crystallization product was separated by filtration, washes, dry after 4 hours for 120 DEG C, in air 550 DEG C of roastings 4 hours embodiment 6# sample.
The synthetic RE-SAPO-34 of embodiment 7
According to molar ratio 0.01NH
4f: 0.8CeO
2: 0.2SiO
2: 1.0Al
2o
3: 4P
2o
5: 3.0RN: 50H
2o, gets 17.4 grams of molten water of cerous nitrate, adds 46 grams of 85%wt orthophosphoric acid gel that stirs, and adds 8.5 grams of boehmites, is stirred to and is after even gel, adds successively 0.02 gram of HF, 0.6 gram of white carbon SiO
2powder and 65 grams of tetraethyl ammonium hydroxides, then add deionized water to meeting mole proportioning that feeds intake.Fully stir and form even gel, proceed to the autoclave of liner tetrafluoroethene, 200 DEG C of crystallization 48 hours.Product is through dividing the mother liquor of leaving away, and washing crystallization thing is dried 6 hours at 110 DEG C, and roasting 4 hours in 550 DEG C of air, obtains embodiment 7# sample.
The synthetic RE-SAPO-34 of embodiment 8
According to molar ratio 0.05NH
4f: 0.4CeO
2: 0.8SiO
2: 1.0Al
2o
3: 1.0P
2o
5: 3.0RN: 50H
2o, by 35 grams of molten water of cerous nitrate, adds 46 grams of 85%wt orthophosphoric acid, and the gel that stirs, adds 30.4 grams of amorphous AL (OH)
3, continue to be stirred to the even gel of formation, then add successively containing 0.9 gram of NH
4f, 36.8 grams are containing 27%SiO
2ludox and the aqueous solution of 61.2 grams of triethylamines, add deionized water and reach molar ratio, fully be stirred to the even gel of formation and proceed to stainless steel autoclave, 200 DEG C of crystallization 48 hours, product separation removes mother liquor, through washing, dries 5 hours for 120 DEG C, roasting 4 hours in 550 DEG C of air streams, obtains embodiment 8# sample.
The synthetic RE-SAPO-34 of embodiment 9
According to molar ratio 0.01HF: 1.2CeO
2:: 0.6SiO
2: 1.0Al
2o
3: 0.2P
2o
5: (3.0TEABr+0.5NH
4oH): 50H
2o, by 43.5 grams of molten water of cerous nitrate, adds 46 grams of 85%wt orthophosphoric acid, and the gel that stirs, adds 8.5 grams of boehmites, continues to be stirred to form even gel, then adds successively containing 0.02 gram of HF, 9.2 grams containing 27%SiO
2ludox, 35 grams of tetraethylammonium bromides (TEABr) and 18 grams of ammonium hydroxide, supplementary deionized water is to reaching molar ratio.Fully stir the mixture to and form even gel, proceed to autoclave, 200 DEG C of crystallization 48 hours.After crystallization product separation mother liquor, again through washing, dry 5 hours at 120 DEG C, roasting 5 hours in 550 DEG C of air, obtains embodiment 9# sample.
The synthetic RE-SAPO-34 of embodiment 10
According to molar ratio 0.01HF: 1.2CeO
2:: 0.6SiO
2: 1.0Al
2o
3: 0.2P
2o
5: 3.0RN: 50H
2o, by water-soluble 43.5 grams of cerous nitrates, adds 46 grams of 85%wt orthophosphoric acid, and the gel that stirs, adds 8.5 grams of boehmites, continues to be stirred to form even gel, adds successively containing 0.02 gram of HF, 9.2 grams containing 27%SiO
2ludox and 11.3 grams of n-butylamines, then add deionized water and reach the water yield of molar ratio requirement.Fully stir the mixture to forming even gel, then transfer in teflon-lined autoclave, 200 DEG C of crystallization 48 hours.Crystallization product after filtration, washing after, 110 DEG C dry 6 hours, roasting 4 hours in 550 DEG C of air, obtains embodiment 10# sample.
The synthetic RE-SAPO-34 of embodiment 11
According to molar ratio 0.01HF: 1.2CeO
2:: 0.6SiO
2: 1.0Al
2o
3: 0.2P
2o
5: 3.0RN: 50H
2o, mixes with 21.5 grams of etherophosphoric acids water-soluble 43.5 grams of cerous nitrates, stirs into even gel, adds 8.5 grams of boehmites, continues to be stirred to form after even gel, adds successively 0.02 gram of HF, 9.2 grams containing 27%SiO
2ludox and 14 grams of morpholines, then add deionized water and reach to total Water the requirement of molar ratio.Fully stir the mixture and reach after even gel, proceed to autoclave, 200 DEG C of crystallization 48 hours, product was through point leaving away mother liquor, washing and 120 DEG C of oven dry 5 hours, and in air, 550 DEG C of roastings 4 hours, obtain embodiment 11# sample.
Embodiment 12 Kaolinite Preparation of Catalysts
Getting respectively 1# molecular sieve contrast sample, 2# molecular sieve contrast sample, embodiment 1# sample and embodiment 2# sample and Suzhou machine selects No. 1 kaolin and aluminium chloride to pull an oar than mixing and water adding by 1.2/1.0/0.2 quality, control solid content 40%, spraying makes microspherical catalyst ginseng 1, catalyst ginseng 2, the real 1# of catalyst, the real 2# of catalyst, 240 DEG C of the dry outlet temperatures of spraying.Making beating after getting respectively embodiment 3# sample, embodiment 4# sample, embodiment 5# sample and Suzhou machine and selecting No. 1 kaolin and aluminium chloride to mix by 1.0/1.0/0.3 mass ratio, control 250 DEG C of the dry outlet temperatures of solid content 35% and spraying, the dry real 3# of catalyst, the real 4# of catalyst and the real 5# of catalyst of making of spraying.
Embodiment 13 Kaolinite Preparation of Catalysts
Get respectively embodiment 6# sample, embodiment 7# sample and attapulgite and aluminum nitrate in mass ratio 2.0/1.0/0.5 add water and mix making beating, control solid content 38%, be spray dried to shape and make the real 6# of microspherical catalyst and the real 7# of catalyst.
Embodiment 14 Kaolinite Preparation of Catalysts
The silicate gel of getting respectively embodiment 8# sample, embodiment 9# sample and bentonite and the silica alumina ratio 3/1 3.5/1/0.5 making beating that adds water in mass ratio, controls solid content 30%, and spraying is shaped and makes microspherical catalyst, 250 DEG C of outlet temperatures.Obtain the real 8# of catalyst and the real 9# of catalyst.
Embodiment 15 Kaolinite Preparation of Catalysts
Get respectively embodiment 10# sample, embodiment 11# sample and the sweet soil of Shanxi sheep and aluminium chloride in mass ratio 2.5/1.0/0.4 mix, add water, pull an oar, control solid content 28%, be spray dried to shape and make the real 10# of catalyst and the real 11# of catalyst.
Embodiment 16 molecular sieve thing phases
Get respectively that 1# molecular sieve contrast sample, 2# molecular sieve contrast sample, embodiment 1# sample-embodiment 11# sample grind and compressing tablet after on X-ray diffractometer, arrange under Cu K α source, 40kV, 60mA condition and carry out XRD material phase analysis, each sample is all typical CHA/AEI topological structure, the XRD spectrum (Fig. 1) of optional 2# molecular sieve contrast sample and embodiment 1# and 4# sample is testified, the relative crystallinity of each molecular sieve sample is in table 1, show that the each example of embodiment all can synthesize SAPO-34 molecular sieve, the inventive method is synthetic to be obtained RE-SAPO-34 degree of crystallinity and is all better than contrasting sample.
Table 1 SAPO-34 molecular sieve crystallinity
Embodiment 17
Get catalyst ginseng 1, ginseng 2, catalyst real 1#, real 2#, real 3#, real 4#, real 5#, real 6#, real 7#, real 8#, real 9#, real 10# and real 11# and carry out physical property measurement, the results are shown in Table 2, show RE-SAPO-34 molecular sieve of the present invention all can prepare physical property good be suitable for fluidized-bed reactor use microspherical catalyst.
The physical property of table 2 catalyst
Embodiment 18 MTO reactivity worth
Fixed fluidized-bed reactor 100ml, catalyst to be evaluated, by charge door negative pressure sucting reaction device, is warming up to 500 DEG C of constant temperature 1 hour in the blanket of nitrogen of 40ml/min, be cooled to 470 DEG C, and charging methyl alcohol flow 2.0ml/min is air speed 2.0h
-1.Intermittent sampling is analyzed.Under above-mentioned experiment condition, respectively 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# are carried out to the evaluation of MTO reactivity worth, result is converged to table 3, visible MTO catalyst of the present invention has methanol conversion 100%, (ethene+propylene) yield 80%, generates dimethyl ether few, and especially propylene/ethylene is high, be greater than 0.9 feature, for filling up, alkene market propylene breach is significant.
Table 3 catalyst MTO reactivity worth
Claims (12)
1. a methanol-to-olefins catalyst, is characterized in that, using the standby RE-SAPO-34 molecular sieve of in-situ crystallization legal system as active component, making matrix with natural clay, formulated with peptization bonding agent, methanol conversion 100%, ethene+propylene total recovery is greater than 80%, and propylene/ethylene ratio is greater than 0.9.
2. catalyst according to claim 1, is characterized in that characterizing by XRD, and 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. catalyst according to claim 1, it is characterized in that described in-situ crystallization method is that the soluble-salt of rare earth RE elemental cerium Ce or neodymium Nd and phosphorus source and fluoride prerotation turn to fluorine-containing RE phosphate, original position and He Gui source, aluminium source stir into the synthetic RE-SAPO-34 molecular sieve of gel crystallization under template RN effect.
4. catalyst according to claim 1, is characterized in that described in-situ crystallization legal system is (0.01-0.5) F for the various raw material molar ratios of RE-SAPO-34 molecular sieve: (0.01-1.0) RE
2o
3: (0.2-1.5) SiO
2: 1.0Al
2o
3: (0.2-2.0) P
2o
5: (2.0-5.0) RN: (35-50) H
2o.
5. catalyst according to claim 1, the mass ratio that it is characterized in that described RE-SAPO-34 molecular sieve, described natural clay and described colloidal sol bonding agent is 1.0: 0.10-1.0: 0.05-0.2.
6. catalyst according to claim 3, the soluble-salt that it is characterized in that described cerium or neodymium is a kind of in the nitrate of cerium or neodymium or sulfate or acetate or their mixture; Or described phosphorus source is a kind of in orthophosphoric acid or metaphosphoric acid or pyrophosphoric acid or organophosphorus ester or their mixture; Or described fluoride is the combination of any or they in ammonium fluoride or sodium fluoride or hydrogen fluoride; Or described aluminium source is the combination of any or they in boehmite or β-gibbsite or amorphous hydroted alumina; Or described silicon source is the combination of any or they in Ludox or white carbon or the positive ethyl ester of silicic acid; Or described template RN is the combination of any or they in triethylamine or diethylamine or n-butylamine or tetraethyl ammonium hydroxide TEAOH or tetraethylammonium bromide TEABr or morpholine; Or, their any combination.
7. according to the catalyst described in claim 3 or 6, it is characterized in that in-situ crystallization temperature is 100-220 DEG C.
8. catalyst according to claim 1, it is characterized in that described natural clay be kaolin or attapulgite or bentonite or the sweet soil of sheep any, or their combination.
9. catalyst according to claim 1, it is characterized in that described peptization bonding agent be in aluminium chloride or aluminum nitrate or alumina silicate any, or their combination.
10. catalyst according to claim 1, is characterized in that described active component, described natural clay and described peptization bonding agent are made into treat Gunning material, the spray-dried microballoon of making.
11. catalyst according to claim 10, the solid content for the treatment of Gunning material described in it is characterized in that is 20-50%.
12. catalyst according to claim 10, is characterized in that described spray-dired outlet temperature is 200-400 DEG C.
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| CN108187736A (en) * | 2018-01-20 | 2018-06-22 | 辽宁金易化工有限公司 | Gibbsite@SAPO molecular sieves compound and preparation method with nucleocapsid and the application in catalysis methanol alkene |
| 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 |
| CN109052428A (en) * | 2018-07-26 | 2018-12-21 | 西北师范大学 | The method for preparing SAPO molecular sieve as raw material using nonmetallic ore attapulgite |
| 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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