CN107952477A - Application of the multi-stage porous SAPO molecular sieve in methanol to olefins reaction - Google Patents
Application of the multi-stage porous SAPO molecular sieve in methanol to olefins reaction Download PDFInfo
- Publication number
- CN107952477A CN107952477A CN201610895837.6A CN201610895837A CN107952477A CN 107952477 A CN107952477 A CN 107952477A CN 201610895837 A CN201610895837 A CN 201610895837A CN 107952477 A CN107952477 A CN 107952477A
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- China
- Prior art keywords
- molecular sieve
- reaction
- porous structure
- sapo molecular
- hierarchical porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 46
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 46
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 241000269350 Anura Species 0.000 title claims abstract description 31
- 150000001336 alkenes Chemical class 0.000 title abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract 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 33
- 239000003054 catalyst Substances 0.000 claims description 33
- 229910052593 corundum Inorganic materials 0.000 claims description 27
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 27
- 239000011148 porous material Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- HHQMYHMTYIPFEG-UHFFFAOYSA-M [O-2].[O-2].[O-2].[OH-].O.[Al+3].[Si+4].P Chemical compound [O-2].[O-2].[O-2].[OH-].O.[Al+3].[Si+4].P HHQMYHMTYIPFEG-UHFFFAOYSA-M 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 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 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- WENLKAKVZDPNQX-UHFFFAOYSA-N methanetetrol silicic acid Chemical compound C(O)(O)(O)O.[Si](O)(O)(O)O WENLKAKVZDPNQX-UHFFFAOYSA-N 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims 1
- 235000019797 dipotassium phosphate Nutrition 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract 1
- -1 solves the problems Chemical compound 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000376 reactant Substances 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical class [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
The present invention relates to application of the hierarchical porous structure SAPO molecular sieve in reaction for preparing light olefins from methanol, mainly solves the problems, such as that prior art SAPO molecular sieve is used for poor-performing in methanol to olefins reaction.The present invention hydrolyzes under the conditions of 20 DEG C~100 DEG C by using the mixture of template R1, structure directing agent R2, water, phosphorus source, silicon source and silicon source and obtains colloidal sol, is then placed in reaction kettle and carries out crystallization；Sample is washed after crystallization, dried and is roasted to obtain the technical solution of multi-stage porous SAPO molecular sieve, preferably solves the problems, such as this, in the industrial production available for hierarchical porous structure molecular sieve.
Description
Technical field
The present invention relates to a kind of hierarchical porous structure SAPO molecular sieve, preparation method, and its in reaction for preparing light olefins from methanol
In application.
Background technology
SAPO-34 molecular sieves are the molecular sieves of the silicoaluminophosphate series of U.S. combinating carbide company (UCC) exploitation, it has
There are suitable acidity and pore passage structure, larger specific surface area, preferable absorption property and heat endurance and hydrothermal stability,
It can be described as promoting the optimal catalyst of methanol-to-olefins reaction process at present.It is however, typical gas-solid heterogeneous as one
React, easily carbon distribution is produced because of inside and outside diffusional resistance in SAPO-34 molecular sieve pore passages, plus the strongly exothermic spy of reaction itself
Property, so as to cause rapid catalyst deactivation.
To solve problem above, Recent study person takes a series of means from the different angle such as pore structure and crystalline size
To improve the performance of catalyst, result of study shows：The SAPO-34 molecular sieves of hierarchical porous structure are conducive to carrying for catalytic performance
Height, particularly mesoporous presence, it is conducive to shorten the diffusion path of reactant and product molecule, weakens the limitation of diffusion
(Selvin R., Hsu H.L, Her T.M.Catalysis Communications [J], 2008,10,169；Bi Y.Sh., L
ü G.X..Chem.J.Chinese Universities [J], 2009,30 (1), 129), it is anti-in MTO reactions to improve it
Coking deactivation ability is so as to extend catalyst life.At present, the report in relation to hierarchical porous structure SAPO-34 molecular sieves is less, main
There are following methods：Chen Lu etc. use multi-functional long chain organic silanes have for mesoporous template one-step synthesis multistage pore canal and
Compared with SAPO-34 molecular sieves (the Chemical Journal of Chinese Universities such as Chen Lu, Wang Runwei, fourth pair, 2010,31 (9) of low in acidity：1693-
1696.).Zhu and Liu et al. have studied has micropore-mesopore multistage using kaolin and SBA-15 as raw material hydro-thermal one-step synthesis method
Structure SAPO-34 molecular sieves (Zhu Jie, Gui Yu, Wang Yao, et al.Chem.Commun., 2009,3282-
3284；Liu Yuanlin,Wang Lingzhi,Zhang Jinlong,et al.Microporous and Mesoporous
Materials 145(2011)150-156)。
It is combined by organic formwork agent R1 and nano carbon black R2 in addition, CN105460945A discloses one kind and prepares multi-stage porous
The technical solution of structure SAPO molecular sieve, successfully prepares while has mesoporous and micropore SAPO molecular sieve material, but institute
Obtain the mesoporous intracrystalline pore for zeolite crystal of material.Although the presence of intracrystalline pore has delayed carbon distribution, but cannot thoroughly solve
Certainly inside diffusional resistance and the carbon distribution that produces.Relative to intracrystalline pore, the SAPO molecular sieve for having perforation mesoporous has preferable diffusion,
But the preparation at present with the mesoporous SAPO molecular sieve of perforation is still one of difficult point in synthesis field.It can be seen from the above that exploitation one
Kind preparation process is simple, the preparation side of hierarchical porous structure aluminium silicophosphate molecular sieve environmentally friendly and with preferable mass-transfer performance
Method is realization and expands the key point of its practical application.
The content of the invention
The first technical problem to be solved by the present invention is that existing SAPO molecular sieve is used for methanol to olefins reaction neutrality
Can be poor the problem of.The present invention provides a kind of new hierarchical porous structure SAPO molecular sieve, which has preferable diffusivity
Can, it is functional in methanol to olefins reaction.
The two of technology to be solved by this invention are to provide a kind of hierarchical porous structure of one of new solution technical problem
The preparation method of SAPO molecular sieve.
The three of technology to be solved by this invention are to provide a kind of hierarchical porous structure of one of new solution technical problem
The purposes of SAPO molecular sieve.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of hierarchical porous structure SAPO points
Son sieve, it is characterised in that micropore size is distributed as 0.3~0.7 nanometer；Transgranular mesoporous pore size is distributed as 2~60 nanometers；Compare surface
Product is 250~1350m2·g-1；Pore volume is 0.09~2.5cm3·g–1；It is described it is transgranular it is mesoporous be transgranular through hole.
The transgranular through hole refers to that mesopore orbit is located at crystals, and aperture is directly connected with crystal outer.
In above-mentioned technical proposal, preferable technical solution is distributed as 0.31~0.65 nanometer for micropore size；Mesoporous pore size
It is distributed as 2.5~48 nanometers；Specific surface area is 300~1200m2·g-1；Pore volume is 0.1~2.3cm3·g–1.It is above-mentioned to solve
The two of technical problem, the technical solution adopted by the present invention is as follows：A kind of preparation method of hierarchical porous structure SAPO molecular sieve, including
Following steps：
A) template R1 is handled in an acidic solution；
B) by water, phosphorus source, silicon source, silicon source and structure directing agent R2 be added separately to a) obtained by mixed solution in, -20
DEG C~100 DEG C under the conditions of, hydrolysis obtains silicon phosphorus aluminum oxide colloidal sol, wherein, phosphorus source is by theoretical generation P2O5Gauge, silicon source are according to reason
By generation Al2O3Gauge, silicon source are by theoretical generation SiO2Gauge, mixture weight are than composition：R1/Al2O3=0.001~1.0；
R2/Al2O3=0.1~10；H2O/Al2O3=2.56~30.79；SiO2/Al2O3=0.1~0.8；P2O5/Al2O3=0.08~
2.0；
C) above-mentioned silicon phosphorus aluminum oxide is placed in reaction kettle, the crystallization 0.1~4 day at 90 DEG C~220 DEG C；Reaction terminates
Sample is washed afterwards, dry and roasting obtains hierarchical porous structure SAPO molecular sieve；
Silicon source is selected from Ludox, positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid orthocarbonate, four butyl ester of positive silicic acid or
At least one of Ludox；Silicon source is in aluminium isopropoxide, boehmite, aluminium oxide, aluminum nitrate, aluminium chloride or aluminum sulfate
At least one；Phosphorus source is selected from phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium hydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, phosphoric acid hydrogen
At least one of potassium, sodium phosphate, disodium hydrogen phosphate or dibastic sodium phosphate.
In above-mentioned technical proposal, template R1 is selected from least one of nano-carbon materials such as carbon nanotubes in step a).
The effect of carbon nanotubes is to aid in the formation of transgranular through hole.
In above-mentioned technical proposal, in step a) acid solution in hydrochloric acid, nitric acid, phosphoric acid, citric acid, sulfuric acid at least
It is a kind of.
In above-mentioned technical proposal, acid solution processing in step a) is specifically, 0-100 DEG C of stirring 0.5-48h.By template
The effect that R1 is handled in an acidic solution is to aid in the formation of transgranular through hole.
In above-mentioned technical proposal, mixture weight is selected from than composition in step b)：R1/Al2O3=0.02~0.9；R2/
Al2O3=0.5~20；H2O/Al2O3=3.00~13.00；SiO2/Al2O3=0.15~0.60；P2O5/Al2O3=0.1~1.9
Between.
In above-mentioned technical proposal, structure directing agent R2 preferred solutions are tetraethyl oxyammonia, tetrem bromide in step b)
Change at least one of ammonium, triethylamine or ethylenediamine.
In above-mentioned technical proposal, crystallization temperature is 130~200 DEG C in step c), and crystallization time is 0.2~3 day.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：
A kind of method of methanol-to-olefins reaction, is 300~650 DEG C in reaction temperature using methanol as raw material, reaction
Meter pressure is 0.01MPa~1MPa, and reaction weight space velocity is 0.1~6h-1, under conditions of water/raw material weight ratio is 0~6, raw material
Contacted by catalyst bed with catalyst, reaction generation low-carbon alkene, catalyst used is hierarchical porous structure SAPO molecules
Sieve, its micropore size are distributed as 0.31~0.65 nanometer；Mesoporous pore size is distributed as 2.5~48 nanometers；Specific surface area for 300~
1200m2·g-1；Pore volume is 0.1~2.3cm3·g–1。。
In above-mentioned technical proposal, preferable technical solution is that reaction temperature is 350~600 DEG C；Reacting meter pressure is
0.1MPa~0.8MPa；When reaction weight space velocity is 0.2~5 small-1；Water/raw material weight ratio is 0.1~5.
At present, the molecular sieve of hierarchical porous structure is concentrated mainly on Si-Al molecular sieve, for the silicon phosphorus aluminium of hierarchical porous structure
The preparation method report of Zn-Al-P-Si-oxide molecular sieve is less.The present invention first by carbon nanotubes carry out acid treatment, then by with
Silicon source, phosphorus source and template are mixed to get with the mesoporous aluminium silicophosphate molecular sieve of perforation, and by adjusting the ruler in carbon pore footpath
The very little multi-stage porous molecular screen material with perforation duct that can obtain different pore size.This method preparation process is simple, easily
Control, crystallinity is high, achieves preferable technique effect.
At present, the fireballing problem of generally existing catalyst inactivation in methanol to olefins reaction.This is mainly due to catalysis
Agent diffusion is poor, causes caused by easy carbon distribution.Carbon distribution mainly influences the activity of catalyst in terms of two:On the one hand it is that carbon distribution covers
The active sites of lid catalyst cause to inactivate；On the other hand it is the duct of clogged with soot catalyst so that reactant can not be diffused into
Catalyst duct can not be diffused out up to active sites or product.The present invention is using the SAPO molecular sieve of hierarchical porous structure as methanol
The catalyst of alkene processed, contacts since its meso-hole structure is conducive to reactant molecule with the activated centre of catalyst, while also has
The duct of catalyst is quickly diffused out beneficial to reaction product, so as to reduce the generation of carbon deposit, its catalytic performance is catalyzed than ever
Agent, which has, to be obviously improved, while by adjusting reaction condition, the selectivity and yield that make propylene significantly improve, and is achieved preferable
Technique effect.
Brief description of the drawings
Fig. 1 is【Embodiment 1】The TEM figures of obtained hierarchical porous structure SAPO molecular sieve.
Fig. 2 is【Embodiment 1】The XRD diagram of obtained hierarchical porous structure SAPO molecular sieve.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Embodiment 1】
Carbon nanotubes is stirred into 24h for 40 DEG C in the acid solution containing hydrochloric acid, obtains uniform mixed solution A, then
By 12.3 grams of aluminium isopropoxides, 45 grams of deionized waters, 60 grams of tetraethyl ammonium hydroxides (25% weight), 5.5 grams of phosphoric acid (85% weights
Amount), 6 grams of Ludox (40% weight) be added sequentially in mixed solution A, be stirred at room temperature 24 it is small when obtain synthesis SAPO-
The crystallization liquid of 34 molecular sieves；Ageing 24h is stirred at room temperature in prepared crystallization liquid, the crystallization liquid being aged loads with poly-
In the crystallizing kettle of tetrafluoroethene liner, when crystallization 6 is small at 180 DEG C；
The weight ratio of each component is：R1/Al2O3=0.1；TEAOH/Al2O3=10；H2O/Al2O3=7；SiO2/Al2O3
=0.4；P2O5/Al2O3=1.1.
Products therefrom is washed, centrifugation, 110 DEG C dry to obtain solid sample, XRD the result shows that, products obtained therefrom SAPO-34
Molecular screen primary powder.TEM is shown in that Fig. 1, XRD are shown in Fig. 2.
【Embodiment 2~14】
According to【Embodiment 1】Each Step By Condition, hierarchical porous structure molecular sieve is made, simply feed change (table 1)
The parameters such as proportioning, Template Types, are specifically listed in table 1.The product of synthesis through characterization illustrate its result have with【Embodiment 1】、
The similar crystal structure of product, its specific physico-chemical parameter are shown in Table 2.
Table 1
Table 2
【Embodiment 15】
Using fixed-bed catalytic reactor, reactor is stainless steel tube, and methanol is carried out to catalyst prepared by embodiment 1
Reaction for preparing light olefins activity rating is converted, investigating process conditions used is：Loaded catalyst 0.5g, reaction temperature are
450 DEG C, reaction pressure 0.1MPa, water/raw material weight ratio is 0.25, weight space velocity 1h-1.Full product on-line analysis.Examination
The results are shown in Table 3.
Table 3
【Embodiment 16~18】
According to【Embodiment 32】The catalyst that process conditions used prepare embodiment 3 carries out methanol and converts low-carbon alkene processed
Hydrocarbon reaction activity rating, simply changes reaction temperature, and appraisal result is as shown in table 4.
Table 4
【Embodiment 19~21】
According to【Embodiment 15】The catalyst that process conditions used prepare embodiment 1 carries out methanol and converts low-carbon alkene processed
Hydrocarbon reaction activity rating, simply changes reaction pressure, and appraisal result is as shown in table 5.
Table 5
【Embodiment 22~24】
According to【Embodiment 15】The catalyst that process conditions used prepare embodiment 1 carries out methanol and converts low-carbon alkene processed
Hydrocarbon reaction activity rating, simply changes weight space velocity, and appraisal result is as shown in table 6.
Table 6
【Embodiment 25~27】
According to【Embodiment 15】The catalyst that process conditions used prepare embodiment 1 carries out methanol and converts low-carbon alkene processed
Hydrocarbon reaction activity rating, simply changes water/raw material weight ratio, and appraisal result is as shown in table 7.
Table 7
【Comparative example 1】It is catalyst with traditional SAPO-34 molecular sieves
First by 12.3 grams of aluminium isopropoxides, 5.5 grams of phosphoric acid (85% weight), 45 grams of deionized waters, 60 grams of tetraethyl hydrogen-oxygens
Change ammonium (25% weight), 6 grams of Ludox (40% weight) are added sequentially in 45 grams of deionized waters, stir evenly postposition at room temperature
In reaction kettle, crystallization 1 day at 180 DEG C；Sample is washed after reaction, dry and roasting obtains traditional SAPO points
Son sieve.
According to【Embodiment 15】Prepared by the catalyst (A) and conventional method that process conditions used prepare embodiment 1
Catalyst (B) carries out methanol to olefins reaction activity rating.Appraisal result is as shown in table 8.
As shown in table 8
【Comparative example 2】SAPO-34 molecular sieves prepared by few step (a) are catalyst
According to【Embodiment 15】The catalyst (A) and few step (a) that process conditions used prepare embodiment 1 prepare institute
Obtained material carries out methanol to olefins reaction activity rating for catalyst (B).Appraisal result is as shown in table 9.
As shown in table 9
【Comparative example 3】Template in step a is that SAPO-34 molecular sieves prepared by nanometer carbon black are catalyst
According to【Embodiment 15】Template in catalyst (A) and step (a) that process conditions used prepare embodiment 1
Agent is that to prepare obtained material be that catalyst (B) carries out the evaluation of C4 olefins by catalytic cracking reactivity to nanometer carbon black.Examination knot
Fruit is as shown in table 10.
As shown in table 10
Claims (9)
1. a kind of hierarchical porous structure SAPO molecular sieve, it is characterised in that micropore size is distributed as 0.3~0.7 nanometer；It is transgranular mesoporous
Pore-size distribution is 2~60 nanometers；Specific surface area is 250~1350m2·g-1；Pore volume is 0.09~2.5cm3·g–1；It is described transgranular
Mesoporous is transgranular through hole.
2. hierarchical porous structure SAPO molecular sieve according to claim 1, it is characterised in that micropore size is distributed as 0.31~
0.65 nanometer；Mesoporous pore size is distributed as 2.5~48 nanometers；Specific surface area is 300~1200m2·g-1；Pore volume for 0.1~
2.3cm3·g–1。
3. a kind of preparation method of the hierarchical porous structure SAPO molecular sieve described in claim 1, comprises the following steps：
A) template R1 is handled in an acidic solution；
B) by water, phosphorus source, silicon source, silicon source and structure directing agent R2 be added separately to a) obtained by mixed solution in, -20 DEG C~
Under the conditions of 100 DEG C, hydrolysis obtains silicon phosphorus aluminum oxide colloidal sol, wherein, phosphorus source is by theoretical generation P2O5Gauge, silicon source are by theoretical raw
Into Al2O3Gauge, silicon source are by theoretical generation SiO2Gauge, mixture weight are than composition：R1/Al2O3=0.001~1.0；R2/
Al2O3=0.1~10；H2O/Al2O3=2.56~30.79；SiO2/Al2O3=0.1~0.8；P2O5/Al2O3=0.08~2.0；
C) above-mentioned silicon phosphorus aluminum oxide is placed in reaction kettle, the crystallization 0.1~4 day at 90 DEG C~220 DEG C；It is right after reaction
Sample is washed, dry and roasting obtains hierarchical porous structure SAPO molecular sieve；
Silicon source is selected from Ludox, and positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid orthocarbonate, four butyl ester of positive silicic acid or silicon are molten
At least one of glue；Silicon source in aluminium isopropoxide, boehmite, aluminium oxide, aluminum nitrate, aluminium chloride or aluminum sulfate extremely
Few one kind；Phosphorus source is selected from phosphoric acid, ammonium phosphate, diammonium hydrogen phosphate, ammonium hydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium hydrogen phosphate, phosphorus
At least one of sour sodium, disodium hydrogen phosphate or dibastic sodium phosphate.
4. the preparation method of hierarchical porous structure SAPO molecular sieve according to claim 3, it is characterised in that template in step a)
Agent R1 is carbon nanotubes.
5. the preparation method of hierarchical porous structure SAPO molecular sieve according to claim 3, it is characterised in that mixing in step b)
Thing weight ratio forms：R1/Al2O3=0.02~0.9；R2/Al2O3=0.5~20；H2O/Al2O3=3.00~13.00；
SiO2/Al2O3=0.15~0.60；P2O5/Al2O3=0.1~1.9.
6. the preparation method of hierarchical porous structure SAPO molecular sieve according to claim 3, it is characterised in that structure in step c)
Directed agents R2 is selected from least one of tetraethyl oxyammonia, tetraethylammonium bromide, triethylamine or ethylenediamine.
7. the preparation method of hierarchical porous structure SAPO molecular sieve according to claim 3, it is characterised in that crystallization in step c)
Temperature is 130~200 DEG C, and crystallization time is 0.2~3 day.
8. a kind of method of methanol-to-olefins reaction, is 300~650 DEG C in reaction temperature using methanol as raw material, reaction table
Pressure is 0.01MPa~1MPa, and reaction weight space velocity is 0.1~6h-1, under conditions of water/raw material weight ratio is 0~6, raw material leads to
Cross catalyst bed to contact with any one of claim 1~2 catalyst, reaction generation low-carbon alkene, catalyst used
For hierarchical porous structure SAPO molecular sieve.
9. the method for methanol-to-olefins reaction according to claim 8, it is characterised in that reaction temperature is 350~600
℃；Reaction meter pressure is 0.1MPa~0.8MPa；When reaction weight space velocity is 0.2~5 small-1；Water/raw material weight ratio for 0.1~
5。
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| CN112250083A (en) * | 2019-07-22 | 2021-01-22 | 青岛科技大学 | Micro-mesoporous composite aluminum phosphate molecular sieve and preparation method thereof |
| CN112279270A (en) * | 2019-07-22 | 2021-01-29 | 青岛科技大学 | Aluminum phosphate molecular sieve and preparation method thereof |
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