CN106660027B - 杂化sapo-34/zsm-5催化剂、其制备及其使用 - Google Patents
杂化sapo-34/zsm-5催化剂、其制备及其使用 Download PDFInfo
- Publication number
- CN106660027B CN106660027B CN201580047785.0A CN201580047785A CN106660027B CN 106660027 B CN106660027 B CN 106660027B CN 201580047785 A CN201580047785 A CN 201580047785A CN 106660027 B CN106660027 B CN 106660027B
- Authority
- CN
- China
- Prior art keywords
- zsm
- sapo
- catalyst
- mixture
- reaction mixture
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000011541 reaction mixture Substances 0.000 claims abstract description 11
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims abstract description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract 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 abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 235000011007 phosphoric acid Nutrition 0.000 claims abstract description 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- -1 ethylene, propylene Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000006069 physical mixture Substances 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000269350 Anura Species 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229940075614 colloidal silicon dioxide Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- 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
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/023—Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J2029/062—Mixtures of different aluminosilicates
-
- 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
-
- 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
- B01J2229/30—After treatment, characterised by the means used
-
- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
-
- 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
- B01J2229/60—Synthesis on support
- B01J2229/62—Synthesis on support in or on other molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
本发明涉及依序经由如下步骤制备杂化SAPO‑34/ZSM‑5催化剂：a)形成主要由作为唯一硅原子源的ZSM‑5、异丙醇铝及正磷酸溶液组成的混合物；b)将所述混合物与四乙基氢氧化铵的水溶液组合以形成反应混合物；及c)使所述反应混合物经历水热条件一段足以将所述反应混合物转化成杂化SAPO‑34/ZSM‑5催化剂的时间。使用所述杂化催化剂将含氧物(甲醇和/或二甲醚)转化成烯烃。
Description
本申请要求2014年9月19日提交的美国临时申请第62/052,533号的权益。
本发明大体上涉及一种杂化SAPO-34/ZSM-5催化剂，并且确切地说，涉及在ZSM-5上原位生长SAPO-34所制备的催化剂。本发明还涉及所述杂化催化剂在将醇转化成烯烃，确切地说，将甲醇转化成烯烃中的用途。
Ho-Jeong Chae等人在“用于MTO反应的ZSM-5/SAPO-34复合催化剂的物理化学特征(Physicochemical characteristics of ZSM-5/SAPO-34composite catalyst for MTOreaction)”，《固体物理学与化学杂志(Journal of Physics and Chemistry of Solids)》71(2010)，第600-603页提供了有关标题催化剂及其在高压釜中的水热合成的教示。第一种水热合成技术涉及在ZSM-5结晶之后进行SAPO-34合成凝胶的连续结晶。第二种水热合成技术是使用商购的ZSM-5粉末作为晶种进行SAPO-34合成凝胶的一步结晶。在第一种技术中，合成ZSM-5并且接着使其结晶以形成ZSM-5浆液，然后将所述浆液与包括二氧化硅源(烟雾状二氧化硅)的SAPO-34凝胶组份混合，形成SAPO-34凝胶，并且接着使SAPO-34结晶。这些教示包括由这两种技术制备的复合催化剂与单独ZSM-5、单独SAPO-34以及ZSM-5与SAPO-34的物理混合物的比较。
美国专利申请公开案(United States Patent Application Publication，USPAP)2006/0106270(Glover等人)披露使用双功能催化剂将含氧物转化成丙烯。所述催化剂含有结构对应于ZSM-5或ZSM-11的沸石分子筛或结构对应于SAPO-34的ELAPO分子筛，或这些物质的混合物。“含氧物”包括脂肪醇、醚、羰基化合物(例如，醛、酮及羧酸)及这些物质的混合物。当EL是硅时，优选来源包括烟雾状二氧化硅、胶态二氧化硅或沉淀二氧化硅。沸石催化剂(例如，ZSM-5)与非沸石催化剂(例如，SAPO-34)的混合物的制备涉及以物理方式将含有沸石材料的粒子与含有非沸石材料的粒子混合，以及将这两种类型材料混入磷改性的铝基质中以形成其中存在这两种类型材料的粒子。
美国专利(US)4,499,327(Kaiser)教示使用硅磷酸铝(silicoaluminophosphate，SAPO)分子筛催化剂将如甲醇、乙醇、二甲醚、乙醚或其混合物等原料转化成轻(C2、C3和/或C4)烯烃。SAPO分子筛包含由[AlO2]、[PO2]及[SiO2]四面体单元构成的分子框架。
US 7,230,151(Martens等人)披露使用两种或多于两种沸石催化剂，由含氧物馈料制备烯烃，尤其乙烯和丙烯的方法。这些催化剂之一可以是ZSM-5并且另一种可以是10环分子筛，如ZSM-22、ZSM-23、ZSM-35、ZSM-48及其混合物。
US 3,702,886(Argauer)描述ZSM-5及其制备。另参见US 4,582,815、US 5,053,374及US 5,182,242。ZSM-5是具有根据IZA(国际沸石协会(InternationalZeoliteAssociation))的MFI框架结构并且组成可以表示为Mn/m[AlnSi96-nO192]～16H2O(其中n<27并且M是阳离子，及m是所述阳离子的价态)的结晶沸石家族。ZSM-5的合成可以涉及制备含有四丙基氢氧化铵、氧化钠、铝氧化物、二氧化硅的氧化物及水的溶液，使所述溶液经历由100℃至175℃的温度及在温度下6小时至60天的时间组成的反应条件。
在一些方面，本发明是一种用于制备杂化SAPO-34/ZSM-5催化剂的方法，所述方法依序包括如下步骤：a)形成主要由作为唯一硅原子源的ZSM-5、异丙醇铝及正磷酸溶液组成的混合物；b)将所述混合物与四乙基氢氧化铵的水溶液组合以形成反应混合物；及c)使所述反应混合物经历水热条件一段足以将所述反应混合物转化成杂化SAPO-34/ZSM-5催化剂的时间，所述水热条件包含在190摄氏度(℃)至210摄氏度范围内，优选200℃±5℃的温度，及自生压力。
在一些方面，所述方法在步骤c)之后另外依序包括步骤d)，其中所述杂化SAPO-34/ZSM-5催化剂在含氧气氛中在550℃至650℃范围内的温度下经历煅烧，保持在一小时至12小时范围内的时间。
在一些方面，本发明是一种用于将包含甲醇和二甲醚并且任选包含乙醇的含氧物转化成至少一种烯烃的方法，所述方法包括将所述含氧物与以上杂化SAPO-34/ZSM-5催化剂操作性接触放置。
在一些方面，ZSM-5是以超过50:50，优选在96:4至85:15范围内，并且更优选在94:6至90:10范围内的SAPO-34比ZSM-5重量比存在于所述催化剂中。
所述杂化催化剂可用于将含氧物(例如，甲醇、乙醇和/或二甲醚)转化成烯烃，优选乙烯、丙烯及丁烯中的至少一种，确切地说，相较于SAPO-34比ZSM-5的比率相同的SAPO-34与ZSM-5的物理混合物，在转化中具有改善的使用寿命及较高的C2/C3烯烃比率，同时对C2至C4烯烃维持至少相同的总体选择性。
比较实例(CEx A)-物理混合物
在研钵中用研杵以物理方式将1.5克(g)新鲜煅烧的SAPO-34与1.5g煅烧的ZSM-5(Si/Al2＝280)混合。使所得催化剂经历如以下所提供的催化剂测试并且将结果概述于下表1中。
CEx B-物理混合物
在研钵中用研杵以物理方式将1.5克(g)新鲜煅烧的SAPO-34与0.17g煅烧的ZSM-5(Si/Al2＝280)混合。使所得催化剂经历如以下所提供的催化剂测试并且将结果概述于下表1中。
CEx C-物理混合物
在研钵中用研杵以物理方式将1.5克(g)新鲜煅烧的SAPO-34与0.1g煅烧的ZSM-5(Si/Al2＝280)混合。使所得催化剂经历如以下所提供的催化剂测试并且将结果概述于下表1中。
CEx D-杂化物
在搅拌下，将8.2g异丙醇铝(Al(OC3H7)3)与4.6g 85wt％的正磷酸于8.4g水中的溶液组合以形成初始混合物。将3g未煅烧的ZSM-5(NH4形式，SiO2/Al2O3＝280)添加至初始混合物中并继续搅拌30分钟(min)。在持续搅拌下，添加16.8g的35wt％四乙基氢氧化铵(tetraethylammonium hydroxide，TEAOH)的水溶液以形成反应混合物。将反应混合物放入内衬有聚四氟乙烯的不锈钢压力容器中并将所述容器和其内含物放入在200℃设定点温度下以自生压力操作的烘箱中，保持120小时(hr)。通过离心从容器内含物中回收固体催化性反应产物。用水洗涤催化性反应产物，接着在空气中在100℃下对其进行干燥。使所述催化性反应产物经历如以下所提供的催化剂测试并且将结果概述于下表1中。
实例(Ex)1-杂化物
重复CEx D，但未煅烧的ZSM-5的量变为1g。结果概述于下表1中。
Ex 2-杂化物
重复CEx D，但未煅烧的ZSM-5的量变为0.8g。结果概述于下表1中。
表1
催化剂测试
在连续流微量反应器系统中评价催化剂性能(不锈钢管(1/4英寸×6英寸(6.35毫米(mm)×15.24厘米(cm))，夹在两等份(2.5英寸(6.4cm))20目至50目的石英片之间的200克(g)20目至50目(295微米(μm)至853μm)催化剂，环境压力(标称一个大气压(101.32千帕(KPa))。在起始馈送甲醇之前，在氦气(20ml/min流动速率)中，在500℃温度下热处理催化剂两小时(hr)以去除催化剂中吸附的水和易挥发的有机材料。在热处理之后，在标准温度和压力(STP)(标称一个大气压(101.32千帕(KPa)和25℃))下，使用ISCO泵(100DM)以6微升/分钟(μl/min)速率将甲醇与20ml/min的He和N2的混合气体(5vol％)一起馈送至反应器系统中。
表1中呈现的数据展示，相较于SAPO-34比ZSM-5的比率相同的SAPO-34和ZSM-5的物理混合物(CEx B和CEx C)，Ex 1和Ex 2的杂化催化剂显示改善的使用寿命和较高的C2/C3烯烃比率，同时对C2至C4烯烃维持至少相同的总体选择性。
Claims (5)
1.一种用于制备杂化SAPO-34/ZSM-5催化剂的方法，所述方法依序包括如下步骤：a)形成混合物，所述混合物主要由作为唯一硅原子源的ZSM-5、异丙醇铝及正磷酸溶液组成；b)将所述混合物与四乙基氢氧化铵的水溶液组合以形成反应混合物；及c)使所述反应混合物经历水热条件一段时间，所述时间足以将所述反应混合物转化成杂化SAPO-34/ZSM-5催化剂，所述水热条件包含在190摄氏度至210摄氏度范围内的温度及自生压力，
其中ZSM-5是以在96:4至85:15范围内的SAPO-34比ZSM-5重量比存在。
2.如权利要求1所述的方法，其中ZSM-5是以在94:6至90:10范围内的SAPO-34比ZSM-5重量比存在。
3.如权利要求1所述的方法，所述方法在步骤c)之后另外依序包括步骤d)，其中所述杂化SAPO-34/ZSM-5催化剂在含氧气氛中在550℃至650℃范围内的温度下经历煅烧，保持在1小时至12小时范围内的时间。
4.一种用于将包含甲醇和二甲醚的含氧物进料流转化成至少一种烯烃的方法，所述方法包括将所述含氧物与如权利要求1至3中任一权利要求所述的催化剂操作性接触放置。
5.如权利要求4所述的方法，其中所述烯烃是乙烯、丙烯及丁烯中的至少一种。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201462052533P | 2014-09-19 | 2014-09-19 | |
| US62/052,533 | 2014-09-19 | ||
| PCT/US2015/049068 WO2016044010A1 (en) | 2014-09-19 | 2015-09-09 | Hybrid sapo-34/zsm-5 catalyst, its preparation and its use |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| CN106660027A CN106660027A (zh) | 2017-05-10 |
| CN106660027A8 CN106660027A8 (zh) | 2017-07-11 |
| CN106660027B true CN106660027B (zh) | 2019-12-03 |
Family
ID=54238530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201580047785.0A Active CN106660027B (zh) | 2014-09-19 | 2015-09-09 | 杂化sapo-34/zsm-5催化剂、其制备及其使用 |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US10207259B2 (zh) |
| EP (1) | EP3194071B1 (zh) |
| CN (1) | CN106660027B (zh) |
| BR (1) | BR112017004342B1 (zh) |
| CA (1) | CA2961479C (zh) |
| WO (1) | WO2016044010A1 (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022005770A1 (en) * | 2020-06-30 | 2022-01-06 | Dow Global Technologies Llc | Processes for preparing c2 to c3 hydrocarbons in the presence of a hybrid catalyst |
| CN113477274A (zh) * | 2021-07-05 | 2021-10-08 | 南京工业大学 | 一种负载有金属氧化物的zsm-5/sapo-34分子筛的制备方法 |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3702886A (en) | 1969-10-10 | 1972-11-14 | Mobil Oil Corp | Crystalline zeolite zsm-5 and method of preparing the same |
| US4499327A (en) | 1982-10-04 | 1985-02-12 | Union Carbide Corporation | Production of light olefins |
| US4582815A (en) | 1984-07-06 | 1986-04-15 | Mobil Oil Corporation | Extrusion of silica-rich solids |
| US5053374A (en) | 1987-05-01 | 1991-10-01 | Mobil Oil Corporation | Method for preparing a zeolite catalyst bound with a refractory oxide of low acidity |
| US5182242A (en) | 1992-06-02 | 1993-01-26 | Mobil Oil Corp. | Catalysts bound with low acidity refractory oxide |
| US6797851B2 (en) | 2001-08-30 | 2004-09-28 | Exxonmobil Chemical Patents Inc. | Two catalyst process for making olefin |
| US7663012B2 (en) | 2004-06-25 | 2010-02-16 | Uop Llc | Conversion of dimethylether to propylene using moving bed technology |
| US7408092B2 (en) | 2004-11-12 | 2008-08-05 | Uop Llc | Selective conversion of oxygenate to propylene using moving bed technology and a hydrothermally stabilized dual-function catalyst |
| US20080100308A1 (en) | 2006-10-25 | 2008-05-01 | Robert Crick | Apparatus for detecting imbalances in a paired line |
-
2015
- 2015-09-09 CA CA2961479A patent/CA2961479C/en active Active
- 2015-09-09 WO PCT/US2015/049068 patent/WO2016044010A1/en active Application Filing
- 2015-09-09 CN CN201580047785.0A patent/CN106660027B/zh active Active
- 2015-09-09 EP EP15772073.1A patent/EP3194071B1/en active Active
- 2015-09-09 BR BR112017004342-4A patent/BR112017004342B1/pt active IP Right Grant
- 2015-09-09 US US15/501,873 patent/US10207259B2/en active Active
Non-Patent Citations (3)
| Title |
|---|
| Hydrothermally Synthesized HZSM-5/SAPO-34 Composite Zeolite Catalyst for Ethanol Conversion to Propylene;Chao Duan等;《CATALYSIS LETTERS》;20111027;第141卷(第12期);第1821-1827页 * |
| Physicochemical characteristics of ZSM-5/SAPO-34 composite catalyst for MTO reaction;Ho-Jeong Chae等;《Journal of Physics and Chemistry of Solids》;20101231;第600-603页 * |
| Synthesis and application of ZSM-5/SAPO-34 and SAPO-34/ZSM-5 composite systems for propylene yield enhancement in propane dehydrogenation process;Marjan Razavian等;《Microporous and Mesoporous Materials》;20140916;第176-189页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2961479C (en) | 2022-10-18 |
| EP3194071A1 (en) | 2017-07-26 |
| BR112017004342B1 (pt) | 2022-02-22 |
| CN106660027A (zh) | 2017-05-10 |
| US10207259B2 (en) | 2019-02-19 |
| EP3194071B1 (en) | 2018-12-26 |
| CA2961479A1 (en) | 2016-03-24 |
| CN106660027A8 (zh) | 2017-07-11 |
| WO2016044010A1 (en) | 2016-03-24 |
| US20180178204A1 (en) | 2018-06-28 |
| BR112017004342A2 (pt) | 2017-12-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DK2660203T3 (en) | PROCEDURE FOR SYNTHETIZING SAPO MOLECULE SIGNS USING A SOLVOTERMAL PROCEDURE | |
| EP2528881B1 (en) | Method for making a catalyst comprising a phosphorus modified zeolite to be used in an alcohols dehydration process | |
| TW380121B (en) | Zeolite bound zeolite catalyst and process for hydrocarbon conversion using said catalyst | |
| EP1485323B1 (en) | High silica chabazite, its synthesis and its use in the conversion of oxygenates to olefins | |
| WO2012071889A1 (zh) | 一种低硅sapo-34分子筛的合成方法 | |
| TW200804230A (en) | Process for the preparation of an olefin | |
| WO2008022532A1 (fr) | Procédé destiné à synthétiser rapidement un tamis moléculaire de silicoaluminophosphate sapo-34 | |
| RU2563648C2 (ru) | Улучшенный способ получения катализатора на основе цеолита для превращения метанола в олефины | |
| JP2004530619A (ja) | 合成多孔質結晶性物質ｉｔｑ−１２、その合成および用途 | |
| EP2300370A2 (en) | Synthesis and use of mse-framework type molecular sieves | |
| JP2007291076A (ja) | プロピレンの製造方法 | |
| RU2563649C2 (ru) | Способ получения катализатора на основе цеолита для превращения метанола в олефины | |
| EP1451106B1 (en) | Process for manufacture of molecular sieves | |
| JP2019525877A (ja) | 高シリカａｆｘフレームワーク型ゼオライト | |
| WO2007114195A1 (ja) | プロピレンの製造方法 | |
| CN106660027B (zh) | 杂化sapo-34/zsm-5催化剂、其制备及其使用 | |
| WO2012071891A1 (zh) | 一种小晶粒sapo-34分子筛的合成方法 | |
| JPH04308536A (ja) | シリカ変性ゼオライトを用いたプロピレンのオリゴマー化方法 | |
| JPS5955838A (ja) | ポリメチル置換ベンゼンの製造方法 | |
| RU2396116C2 (ru) | Обработанный водой катализатор для получения легких олефинов | |
| JP6407154B2 (ja) | ホウ素ゼオライトをベースとする触媒の製造 | |
| CN113966251A (zh) | Iwr骨架结构类型的硅铝酸盐沸石材料的直接合成及其在催化中的用途 | |
| EP3558904A1 (en) | Method for stable operation of microporous structures in an oxygenate conversion process | |
| Razavian et al. | Investigation the role of polyethylene glycol (PEG) as a co-template in synthesis of SAPO-34 catalyst | |
| RU2343114C1 (ru) | Способ регулирования структуры кристаллических микропористых силикоалюмофосфатов |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| CI01 | Publication of corrected invention patent application | ||
| CI01 | Publication of corrected invention patent application |
Correction item: Priority Correct: 62/052,533 2014.09.19 US Number: 19 Volume: 33 |
|
| CI02 | Correction of invention patent application | ||
| CI02 | Correction of invention patent application |
Correction item: Priority Correct: 62/052,533 2014.09.19 US Number: 19 Page: The title page Volume: 33 |
|
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |