CN113023745B - Beta/Al-SBA-15 composite molecular sieve and preparation method and application thereof - Google Patents
Beta/Al-SBA-15 composite molecular sieve and preparation method and application thereof Download PDFInfo
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- CN113023745B CN113023745B CN201911353957.3A CN201911353957A CN113023745B CN 113023745 B CN113023745 B CN 113023745B CN 201911353957 A CN201911353957 A CN 201911353957A CN 113023745 B CN113023745 B CN 113023745B
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 127
- 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 127
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 54
- 238000002425 crystallisation Methods 0.000 claims abstract description 52
- 230000008025 crystallization Effects 0.000 claims abstract description 51
- 239000002002 slurry Substances 0.000 claims abstract description 50
- 239000002253 acid Substances 0.000 claims abstract description 44
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000011148 porous material Substances 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 230000002378 acidificating effect Effects 0.000 claims description 37
- 239000007864 aqueous solution Substances 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000499 gel Substances 0.000 description 22
- 239000004115 Sodium Silicate Substances 0.000 description 21
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 21
- 229910052911 sodium silicate Inorganic materials 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 238000004537 pulping Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 14
- 229910001388 sodium aluminate Inorganic materials 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000002156 adsorbate Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000012258 stirred mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Classifications
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- 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
-
- 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
- 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
- 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
- B01J35/633—Pore volume less than 0.5 ml/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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/14—Pore volume
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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
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- Life Sciences & Earth Sciences (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a Beta/Al-SBA-15 composite molecular sieve and a preparation method and application thereof. The acid content of the medium strong acid of the composite molecular sieve is 0.6-1.2 mL/g, and the ratio of the B acid to the L acid is less than 0.80. The preparation method of the composite molecular sieve comprises the following steps: amorphous silica-alumina dry gel is used as a raw material, a P123 triblock copolymer is used as a template agent to carry out crystallization synthesis on the Al-SBA-15 molecular sieve, and then Beta molecular sieve slurry is added to carry out crystallization to obtain the Beta/Al-SBA-15 composite molecular sieve. The Beta/Al-SBA-15 composite molecular sieve not only has high content of medium-strong acid, but also has low ratio of B acid to L acid and good hydrothermal stability, and is suitable to be used as a hydrofining catalyst component.
Description
Technical Field
The invention relates to the field of molecular sieves, in particular to a mesoporous-microporous composite molecular sieve and a preparation method and application thereof.
Background
Hydrocracking catalysts are typically bifunctional catalysts having both an acidic function and a hydrogenation function. The conventional Beta molecular sieve has the characteristics of moderate pore structure, proper acidity and good stability, is often used as an acidic component of a hydrotreating catalyst, and is widely applied to the hydrocracking reaction process. However, the product properties of the hydrocracking catalyst prepared by using the conventional Beta molecular sieve can not meet the requirements of clean oil products, such as: the product naphtha has the defects of low aromatic hydrocarbon content, poor tail oil quality and the like, and the application range is limited. Especially, the quality of the crude oil is increasingly worsened at present, the diffusion of heavy oil in Beta molecular sieve pore channels is severely limited, the heavy oil is easy to coke on the surface, the operation period is shortened, and the operation cost of a refinery is increased. As is well known, mesoporous materials have large pore diameters and have wide application prospects in the fields of macromolecule catalysis, adsorption, separation and the like. However, the mesoporous molecular sieve is limited by the composition of amorphous pore walls, has poor hydrothermal stability, acid stability and strength, cannot meet the requirements of industrial application, and has no advantages yet reflected. How to better combine the mesoporous material and the microporous zeolite molecular sieve to exert the synergistic effect of the mesoporous material and the microporous zeolite molecular sieve to obtain the composite molecular sieve with better comprehensive performance, so as to solve the problems of poor crude oil quality, petrochemical product upgrading and updating, petrochemical industry development caused by stricter environmental regulations and the like, and is a research hotspot of technicians in the field.
CN1524617A discloses ZSM-5/AIPO 4 The method adopts a two-stage crystallization method to improve the distribution of AlPO4-5 on the surface of ZSM-5, but when the core-shell structure composite molecular sieve is synthesized by an embedding method, electropositive phosphorus aluminum hydrated ions can be adsorbed on the surface of electronegative ZSM-5 and can also be separated from the surface of ZSM-5, so that the integral stability of the composite molecular sieve is poor.
CN101905170A discloses a preparation method of a mesoporous-microporous core-shell composite molecular sieve catalyst. The synthesis process is carried out in an acid environment, although the defect that the synthesized composite molecular sieve has a small pore diameter can be overcome, an exogenous silicon source or a silica-alumina source is introduced, the pore channel of the molecular sieve is influenced, and the preparation cost is increased.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a Beta/Al-SBA-15 composite molecular sieve and a preparation method and application thereof, wherein the Beta/Al-SBA-15 composite molecular sieve not only has high content of medium strong acid, but also has low ratio of B acid to L acid and good hydrothermal stability, and is suitable for hydrotreating reaction; the preparation method has the advantages of simple flow, no need of introducing exogenous silicon source and aluminum source, low preparation cost, no special environmental protection requirement and the like.
Beta/Al-SBA-15 composite molecular sieve
The first aspect of the invention provides a Beta/Al-SBA-15 composite molecular sieve, wherein the medium-strong acid content of the molecular sieve is 0.6-1.2 mL/g, preferably 0.7-1.0 mL/g; the ratio of the B acid to the L acid in the molecular sieve is less than 0.80, preferably less than 0.75, more preferably less than 0.50, and even more preferably more than 0.22, and specifically may be 0.25, 0.30, 0.35 or 0.40.
Further, the Beta/Al-SBA-15 composite molecular sieve has the properties ofThe following: the specific surface area is 500-950 m 2 Preferably 650 to 850 m/g 2 The total pore volume is 0.4-1.1 mL/g, preferably 0.48-0.85 mL/g.
Further, the Beta/Al-SBA-15 composite molecular sieve has the following pore distribution: the pore volume of the pores with the pore diameter of 4-15nm accounts for 42-72%, preferably 45-65%, and more preferably 55-65% of the total pore volume.
Furthermore, in the Beta/Al-SBA-15 composite molecular sieve, the mass content of alumina is 2-85%, preferably 5-82%, and more preferably 7.3-77.5%. The Beta/Al-SBA-15 composite molecular sieve has the mass content of alumina which can be adjusted within a wide range, such as 10.3%, 15.5%, 16.5%, 18.6%, 20.4%, 25.5%, 30.5%, 32.5%, 35.5%, 40.5%, 45.2%, 50.5%, 55.3%, 60.5%, 73.5%, 77.5% and the like.
Further, in the composite molecular sieve, the mass content of the Beta molecular sieve is 10-90%, preferably 25-85%.
Preparation method of Beta/Al-SBA-15 composite molecular sieve
The second aspect of the invention provides a preparation method of a Beta/Al-SBA-15 composite molecular sieve, which comprises the following steps: amorphous silica-alumina dry gel is used as a raw material, a P123 triblock copolymer is used as a template agent to carry out crystallization synthesis on the Al-SBA-15 molecular sieve, and then Beta molecular sieve slurry is added to carry out crystallization to obtain the Beta/Al-SBA-15 composite molecular sieve.
Further, the amorphous silica-alumina dry gel has the following properties: the surface area is 400-650 m 2 Per g, preferably 450 to 600m 2 The pore volume is 0.52-1.8 ml/g, preferably 0.85-1.5 ml/g; the pore volume with the pore diameter of 4-15nm accounts for 85% -95% of the total pore volume, and the pore volume larger than 15nm accounts for less than 5% of the total pore volume.
Further, in the amorphous silica-alumina dry gel, the mass content of alumina is 2-85%. The mass content of the alumina can be adjusted within a wide range, and can be, for example, 5%, 10%, 15%, 16%, 18%, 20%, 25%, 30%, 32%, 35%, 40%, 45%, 50%, 55%, 60%, 70%, 75%, and the like.
Further, the Beta molecular sieve has the following properties：SiO 2 /Al 2 O 3 The molar ratio is 35-155, and the specific surface area is 510-850 m 2 (iv)/g, the total pore volume is 0.30-0.60 mL/g.
Furthermore, the Beta molecular sieve slurry can be prepared by adding water into a Beta molecular sieve for pulping, or can be crystallized Beta molecular sieve slurry, and the mass content of the Beta molecular sieve in the slurry is 20-40%.
Further, the specific preparation method of the Beta/Al-SBA-15 composite molecular sieve comprises the following steps:
(1) mixing amorphous silica-alumina and deionized water, and pulping to form slurry;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer;
(3) and (2) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2), performing first crystallization, then adding Beta molecular sieve slurry, and performing second crystallization to prepare the Beta/Al-SBA-15 composite molecular sieve.
According to the method, the amorphous silica-alumina in the step (1) is prepared by a carbonization method, and can be prepared by the following steps:
a. respectively preparing a sodium aluminate solution and a sodium silicate solution;
b. adding part or all of sodium silicate solution into sodium aluminate solution, and introducing CO 2 Controlling the reaction temperature of the gas to be 10-40 ℃, preferably 15-35 ℃, and controlling the pH value of the gel to be 8-11; wherein when CO is introduced 2 When the gas amount accounts for 40-100 percent of the total input amount, preferably 50-80 percent, adding the rest sodium silicate solution;
c. b, ventilating and stabilizing the mixture for 10-30 minutes under the temperature and pH value control of the step b;
d. c, filtering the solid-liquid mixture obtained in the step c, and washing a filter cake;
e. d, pulping the filter cake obtained in the step d, then carrying out hydro-thermal treatment, filtering and drying to obtain the amorphous silica-alumina dry gel; the hydrothermal treatment conditions were as follows: treating for 2-10 hours at 120-150 ℃ and under the water vapor pressure of 0.5-4.0 MPa.
Further, in the step a, the concentration of the sodium aluminate solution is 15-55 gAl 2 O 3 A further optional amount of 15 to 35gAl 2 O 3 L, the concentration of the sodium silicate solution is 50-200 gSiO 2 A further amount of 50 to 150g SiO 2 /L。
Further, in the step b, part or all of the sodium silicate solution is added, namely 5wt% -100 wt% of the total added sodium silicate solution. The CO is 2 The concentration of the gas is 30-60 v%. And c, ventilating and stirring in the gelling process in the step b.
Further, the specific process of step b is as follows: (1) adding all sodium silicate into sodium aluminate, and introducing CO 2 A gas; (2) adding part of sodium silicate into sodium aluminate, and introducing all CO 2 Gas, then adding the remaining sodium silicate solution to the mixture; (3) after adding part of sodium silicate to sodium aluminate, part of CO is introduced 2 Gas, then CO is introduced 2 The gas was added to the remaining sodium silicate solution.
Further, filtering the slurry obtained in the step d, washing the slurry with deionized water at the temperature of 50-95 ℃ until the slurry is nearly neutral,
and further, mixing the filter cake obtained in the step e according to a solid-liquid volume ratio of 8: 1-12: 1, adding water and pulping.
Further, the drying in the step e can be performed by a conventional method, and can be performed for 6-8 hours at 110-130 ℃.
Further, the mass ratio of the amorphous silica-alumina dry gel to water in the step (1) is 10: 90-30: 70, preferably 12: 88-25: 75.
further, the pH value of the acidic aqueous solution in the step (2) is 1-5, preferably 1.2-2.3, and the mass content of the P123 triblock copolymer in the acidic aqueous solution is 0.5-5.0%, preferably 0.8-2.8%.
Further, in step (2), the P123 triblock copolymer is added to a dilute acid (such as dilute hydrochloric acid) at a concentration of H + 0.05 to 0.3mol/L, preferably 0.1 to 0.2mol/L, and more preferably 0.13 to 0.18 mol/L; in order to co-polymerize the P123 triblockThe polymer is fully dissolved, and the temperature system is controlled to be 10-60 ℃, preferably 20-40 ℃, and further preferably 25-35 ℃.
Further, in the step (3), the slurry prepared in the step (1) is mixed with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2), and the amounts of the slurry prepared in the step (1) and the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2) are such that the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 0.5:1 to 5:1, preferably 1:1 to 5:1, and more preferably 1:1 to 3: 1.
Further, the conditions of the first crystallization in the step (3) are: the crystallization temperature is 80-120 ℃, and preferably 90-110 ℃; the crystallization time is 10-35 h, preferably 16-24 h; the pH value in the crystallization process is controlled to be 2.0-5.0, preferably 3.2-4.8.
Further, the conditions of the second crystallization in the step (3) are: the crystallization temperature is 80-130 ℃, and preferably 90-120 ℃; the crystallization time is 4-20 h, preferably 10-15 h; the pH value is controlled to be 2.0-5.0, preferably 4.2-5.0 in the crystallization process.
Further, after the crystallization step of step (3), the Beta/Al-SBA-15 composite molecular sieve may be separated from the obtained mixture by any conventionally known means, such as filtration, washing, drying, etc. The filtration can adopt suction filtration. The washing can be performed by using deionized water as a washing solution. The drying can be carried out at 80-150 ℃, preferably 90-130 ℃, and the drying time is 2-12 hours, preferably 3-6 hours. The drying may be carried out at atmospheric pressure.
Further, the composite molecular sieve prepared by the above method may be calcined to remove the template agent and water and the like if necessary. The roasting can be carried out according to any mode conventionally known in the field, the roasting temperature is controlled to be 450-600 ℃, preferably 480-580 ℃, further preferably 500-560 ℃, and the roasting time is 2-10 hours, preferably 3-6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.
Application of Beta/Al-SBA-15 composite molecular sieve
The Beta/Al-SBA-15 composite molecular sieve provided by the invention can be applied in any physical form, such as powder, granules or molded products (such as strips, clovers and the like). These physical forms can be obtained in any manner conventionally known in the art and are not particularly limited.
The third aspect of the invention provides a catalyst composition, which comprises the Beta/Al-SBA-15 composite molecular sieve or the Beta/Al-SBA-15 composite molecular sieve prepared according to the preparation method of the Beta/Al-SBA-15 composite molecular sieve. Other materials contained in the catalyst composition may be active materials and inactive materials. The active material may be other molecular sieve, amorphous silica-alumina, macroporous alumina, etc., or may be an active metal component, and the inactive material (generally referred to as a binder) may be clay, alumina, silica gel, etc. These other materials may be used singly or in combination of plural kinds in any ratio. As the amount of the other materials, those conventionally used in the art can be referred to, and there is no particular limitation.
The fourth aspect of the invention provides a Beta/Al-SBA-15 composite molecular sieve, a Beta/Al-SBA-15 composite molecular sieve prepared by the preparation method of the Beta/Al-SBA-15 composite molecular sieve or an application of the catalyst composition in a hydrotreating catalyst. For example, the catalyst can be used as an active component of a heavy oil hydrofining catalyst.
Compared with the prior art, the Beta/Al-SBA-15 composite molecular sieve and the preparation method thereof have the following advantages:
(1) the Beta/Al-SBA-15 composite molecular sieve has the ordered mesoporous-microporous composite molecular sieve with high hydrothermal stability, adjustable acid amount and reasonable pore distribution, wherein the composite molecular sieve has high strong acid content and small B acid/L acid ratio, and a hydrocracking catalyst prepared by using the composite molecular sieve as an acid component has the advantages of high middle oil selectivity, low diesel condensation point and small BMCI value of tail oil, and is beneficial to wide industrial application.
(2) In the method, the discharge of ammonia nitrogen wastewater and the use amount of hydrochloric acid in the preparation process of the composite molecular sieve in the current industrial production can be reduced, the process flow is shortened, and the production cost is reduced; the Beta/Al-SBA-15 composite molecular sieve synthesized by the method reacts in a weak acidic environment, so that the framework structure of the Beta molecular sieve is prevented from being damaged when the Beta molecular sieve is exposed in an acidic solution for a long time.
Detailed Description
In the present invention, the Al-SBA-15 molecular sieve means that aluminum atoms are introduced into the SBA-15 molecular sieve, the existence state of the aluminum atoms in the SBA-15 molecular sieve is not particularly limited, and a part of the aluminum atoms are generally distributed on the framework of the SBA-15 molecular sieve.
In the invention, the determination of the L acid or the B acid adopts an infrared spectroscopy, an instrument adopts an American Nicot Fourier infrared spectrometer-6700, and the determination method comprises the following steps: weighing 20mg of sample with granularity less than 200 meshes, pressing into sheet with diameter of 20mm, placing on sample rack of absorption cell, placing 200mg of sample in cup of instrument, connecting absorption cell and adsorption tube, vacuumizing until vacuum degree reaches 4 × 10 -2 And Pa, heating to 500 ℃, keeping for 1 hour to remove adsorbates on the surface of the sample, cooling to room temperature, adsorbing pyridine to saturation, continuously heating to 160 ℃, balancing for 1 hour, and desorbing the physically adsorbed pyridine to obtain the acid content of infrared total acid, B acid and L acid, wherein the unit of the B acid and the L acid is mmol/L.
In the invention, NH is adopted as the medium strong acid 3 TPD method. The adopted instrument is an Auto-Chem II 2920 chemical adsorption instrument of Mike instruments. Ammonia gas is used as an adsorption and desorption medium, helium gas is used as carrier gas, and the acid quantities of different desorption temperature areas are obtained by adopting temperature programming desorption and chromatographic analysis, wherein the ammonia gas desorption temperature corresponding to the acid quantity of the medium-strong acid is 250-400 ℃, and the acid quantity unit is as follows: mL/g is the amount of ammonia adsorbed per gram of molecular sieve.
In the invention, the specific surface area, the pore volume and the pore distribution are measured by adopting an ASAP2405 physical adsorption instrument, and the measuring method comprises the following steps: after the sample is processed, liquid N 2 Used as adsorbate, the adsorption temperature is-196 ℃, and analysis and test are carried out. Wherein the specific surface area is calculated by a BET method, and the pore volume and the pore distribution are calculated by a BJH method.
The action and effect of the present invention will be further described below with reference to examples and comparative examples. The scope of protection of the invention is not limited to these examples. In the present invention,% is mass fraction unless otherwise specified.
Example 1
(1) Preparation of amorphous silica-alumina dry gel powder A1 and slurry: sodium aluminate solution concentration 18gAl 2 O 3 Per L, sodium silicate solution concentration 80SiO 2 Putting 0.65L of sodium aluminate solution into a gelling tank, adding 0.30L of sodium silicate solution, controlling the reaction temperature to be 20 ℃, and introducing 35 v% CO 2 Gas, introduction of CO 2 When the gas accounts for 65 percent of the total input amount, 0.30L of sodium silicate solution is added while introducing gas, the pH value of the formed gel is controlled to be 9.2, then the ventilation is stabilized for 20 minutes, the slurry is filtered and washed to be neutral by deionized water at 65 ℃, a filter cake is added with water according to the solid-liquid volume ratio of 10: 1 for pulping, the treatment is carried out for 3 hours at the temperature of 130 ℃ and the water vapor pressure of 3.5MPa, and after the drying is carried out for 6 hours at the temperature of 120 ℃, the amorphous silica-alumina product A1 is obtained by crushing and sieving. The properties of the amorphous silica-alumina dry gel powder A1 are shown in Table 1. Mixing the prepared amorphous silica-alumina A1 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica-alumina dry gel to water is 21: 79;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of a dilute hydrochloric acid solution is 0.12mol/L, the pH value of an acidic aqueous solution containing the P123 triblock copolymer is 1.5, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 25 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 1.8 wt%;
(3) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 1.2:1, the crystallization temperature is 102 ℃, and the crystallization time is 18 hours; the pH value is controlled to be 3.3 in the crystallization process,
(4) slurry containing 34.3Beta molecular sieve (wherein the Beta molecular sieve has the following properties:specific surface area 793m 2 Per g, pore volume 0.52 mL. g -1 ，SiO 2 /Al 2 O 3 The mole ratio is 65, the Beta molecular sieve slurry is prepared by pulping the Beta molecular sieve and water), pumping the slurry into the mixed system prepared in the step (3) by using a vacuum pump, drying the slurry for 3h at 100 ℃ after the crystallization time is 12h at the pH value of 4.3 and the temperature of 95 ℃, and roasting the slurry for 3h at the temperature of 550 ℃ to obtain the finished product of BetaAS-1.
Example 2
(1) Preparation of amorphous silica-alumina dry gel powder A2 and slurry: sodium aluminate solution concentration 32gAl 2 O 3 Per L, sodium silicate solution concentration 115gSiO 2 Putting 0.8L of sodium aluminate solution into a gelling tank, adding 0.2L of sodium silicate solution, controlling the reaction temperature to be 22 ℃, and introducing 48 v% CO 2 Gas, introduction of CO 2 When the gas accounts for 55 percent of the total input amount, 0.25L of sodium silicate solution is added while introducing gas, the pH value of the formed gel is controlled to be 9.8, then the ventilation is stabilized for 20 minutes, the slurry is filtered and washed to be neutral by deionized water at 75 ℃, a filter cake is added with water according to the solid-liquid volume ratio of 8:1 for pulping, the obtained product is treated for 3 hours at the temperature of 110 ℃ and the water vapor pressure of 3.0MPa, after the obtained product is dried for 8 hours at the temperature of 120 ℃, the obtained product is crushed and sieved to obtain an amorphous silica-alumina product A2, and the properties of the amorphous silica-alumina dry gel powder A2 are shown in Table 1. Mixing the prepared amorphous silica-alumina A2 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica-alumina dry gel to water is 23: 77;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of a dilute hydrochloric acid solution is 0.15mol/L, the pH value of an acidic aqueous solution containing the P123 triblock copolymer is 1.4, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 28 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 2.5 wt%;
(3) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 1.5:1, the crystallization temperature is 92 ℃, and the crystallization time is 18 h; the pH value is controlled to be 3.6 in the crystallization process,
(4) a slurry containing 31.4g of Beta molecular sieve (wherein the Beta molecular sieve has the following properties: specific surface area 821 m) 2 Per g, pore volume 0.56 mL. g -1 ，SiO 2 /Al 2 O 3 The mole ratio is 55, the Beta molecular sieve slurry is prepared by pulping the Beta molecular sieve and water) and is pumped into the mixed system prepared in the step (3) by a vacuum pump, and after the crystallization time is 13h at the pH value of 2.8 and the temperature of 115 ℃, the Beta molecular sieve slurry is dried for 4h at the temperature of 110 ℃ and roasted for 3h at the temperature of 530 ℃ to obtain the finished product of the Beta AS-2.
Example 3
(1) Preparation of amorphous silica-alumina dry gel powder A3 and slurry: sodium aluminate solution concentration 20gAl 2 O 3 Per L, sodium silicate working solution concentration 85gSiO 2 L, putting 1.08L of sodium aluminate solution into a gel forming tank, adding 0.2L of sodium silicate solution, controlling the reaction temperature to be 32 ℃, and introducing 55 v% CO 2 Stopping gas when the pH value reaches 9.8, then ventilating and stabilizing for 20 minutes, washing to be neutral, adding water into a filter cake according to the solid-liquid volume ratio of 8:1 for pulping, treating for 2.5 hours at the temperature of 130 ℃ under the water vapor pressure of 3.9MPa, drying for 8 hours at the temperature of 120 ℃, crushing and sieving to obtain an amorphous silica-alumina product A3. The properties of the amorphous silica-alumina dry gel powder A3 are shown in Table 1. Mixing the prepared amorphous silica-alumina A3 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica-alumina dry gel to water is 18: 82;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of a dilute hydrochloric acid solution is 0.16mol/L, the pH value of an acidic aqueous solution containing the P123 triblock copolymer is 1.8, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 33 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 2.1 wt%;
(3) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 1.8:1, the crystallization temperature is 96 ℃, and the crystallization time is 12 hours; controlling the pH value to be 3.6 in the crystallization process;
(4) a slurry containing 35.9g of Beta molecular sieve (wherein the Beta molecular sieve has the following properties: specific surface area 778m 2 Per g, pore volume 0.53 mL. g -1 ，SiO 2 /Al 2 O 3 The mole ratio is 62, the Beta molecular sieve slurry is prepared by pulping the Beta molecular sieve and water) and pumping into the mixed system prepared in the step (3) by a vacuum pump, drying for 4h at 110 ℃ and roasting for 3h at 540 ℃ after the pH value is 4.5 and the temperature is 95 ℃ and the crystallization time is 10h, thus obtaining the finished product of the Beta AS-3.
Example 4
(1) Preparation of amorphous silica-alumina dry gel powder A4 and slurry: sodium aluminate solution concentration 25gAl 2 O 3 Per L, sodium silicate solution concentration 55gSiO 2 L, putting 0.65L of sodium aluminate solution into a gel forming tank, then adding 0.15L of sodium silicate solution, controlling the reaction temperature to be 35 ℃, and introducing 52 v% CO 2 Stopping gas when the pH value reaches 9.5, then ventilating and stabilizing for 20 minutes, washing to be neutral, adding water into a filter cake according to the solid-liquid volume ratio of 8:1 for pulping, treating for 2.5 hours at 130 ℃ under the water vapor pressure of 3.2MPa, drying for 8 hours at 120 ℃, crushing and sieving to obtain the amorphous silica-alumina product A4. The properties of the amorphous silica-alumina dry gel powder A4 are shown in Table 1. Mixing the prepared amorphous silica-alumina A4 with deionized water, and pulping to form slurry; wherein the mass ratio of the amorphous silica-alumina dry gel to water is 24: 76;
(2) preparing an acidic aqueous solution containing a P123 triblock copolymer; adding the P123 triblock copolymer into dilute hydrochloric acid, wherein the concentration of a dilute hydrochloric acid solution is 0.16mol/L, the pH value of an acidic aqueous solution containing the P123 triblock copolymer is 1.8, the temperature of the acidic aqueous solution containing the P123 triblock copolymer is 33 ℃, and the mass content of the P123 triblock copolymer in the acidic aqueous solution containing the P123 triblock copolymer is 1.9 wt%;
(3) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2); the mass ratio of the P123 triblock copolymer to the amorphous silica-alumina in the mixed system is 1.7:1, the crystallization temperature is 98 ℃, and the crystallization time is 13 hours; controlling the pH value to be 3.5 in the crystallization process;
(4) slurry containing 20g of Beta molecular sieve (wherein the Beta molecular sieve has the following properties: specific surface area 769 m 2 Per g, pore volume 0.55 mL. g -1 ，SiO 2 /Al 2 O 3 The mole ratio is 68, the Beta molecular sieve slurry is prepared by pulping the Beta molecular sieve and water) and is pumped into the mixed system prepared in the step (3) by a vacuum pump, and after the crystallization time is 13h at the pH value of 4.7 and the temperature of 98 ℃, the Beta molecular sieve slurry is dried for 4h at the temperature of 110 ℃ and roasted for 4h at the temperature of 550 ℃ to obtain the finished product of the Beta AS-4.
Comparative example 1
Respectively weighing template agent triblock copolymer P123 and silicon source tetraethoxysilane, wherein the mass of the template agent P123 is 5.5g, and the mass of tetraethoxysilane is 10.2 g; adding a template agent and a silicon source into an HCl solution with the pH value of 2.8, and fully stirring for 30 hours at the temperature of 28 ℃; standing and crystallizing the stirred mixture for 20h at 120 ℃, washing with deionized water, and drying to obtain SBA-15. Pulping the obtained SBA-15 molecular sieve with a solid-to-liquid ratio of 1:10, adding the obtained SBA-15 molecular sieve into hydrochloric acid solution containing 23g of aluminum isopropoxide, heating to 100 ℃, stirring for 20 hours, and cooling to room temperature to obtain a mixed system F.
Pumping slurry containing 34.3g of beta molecular sieve (same as example 1) into a mixed system of the mixed solution F by a vacuum pump, drying at 110 ℃ for 4h after crystallization time of 12h at the pH value of 3.7 and the temperature of 100 ℃, and roasting at 540 ℃ for 4h to obtain the finished product BetaAS-5.
Comparative example 2
Adding 5g of P123 into 2mol/L125mL hydrochloric acid solution, and stirring at 40 ℃ until the P123 is completely dissolved; adding 8.5g of tetraethoxysilane into hydrochloric acid solution containing P123, stirring for 4 hours, adding aluminum nitrate to enable the molar ratio of silicon to aluminum to be 35, continuing to stir for 20 hours, adding the solution into a 250mL reaction kettle, stirring for 48 hours at 100 ℃, cooling to room temperature, adjusting the pH value to 7.5 by using 4mol of ammonia water solution, continuously stirring, heating to 100 ℃, stirring for 72 hours, and cooling to 40 ℃ to obtain solution A for later use.
Pumping slurry containing 34.3g of beta molecular sieve (same as example 1) into a mixed system of A by a vacuum pump, drying at 110 ℃ for 4h after crystallization time of 13h at the pH value of 3.3 and the temperature of 98 ℃, and roasting at 550 ℃ for 4h to obtain a finished product of BetaAS-6.
TABLE 1 Properties of amorphous silica-alumina
| Item | A1 | A2 | A3 | A4 |
| Specific surface area, m 2 /g | 488 | 516 | 508 | 520 |
| Pore volume, mL/g | 1.32 | 1.28 | 1.33 | 1.30 |
| Hole distribution,% | ||||
| 4～15nm | 85.8 | 86.5 | 88.3 | 91.2 |
| ＞15nm | 3.6 | 4.3 | 2.8 | 4.1 |
TABLE 2 Properties of the composite molecular sieve obtained in examples and comparative examples
| Item | BetaAS-1 | BetaAS-2 | BetaAS-3 | BetaAS-4 | BetaAS-5 | BetaAS-6 |
| Alumina content, wt% | 20.50 | 33.39 | 56.78 | 66.92 | 18.15 | 16.95 |
| Specific surface area, m 2 /g | 755 | 758 | 772 | 768 | 712 | 719 |
| Pore volume, mL/g | 0.57 | 0.62 | 0.58 | 0.62 | 0.48 | 0.45 |
| Relative degree of crystallinity after firing at 900% | 97 | 98 | 97 | 99 | 88 | 85 |
| Acid amount of medium strong acid, mL/g | 0.70 | 0.71 | 0.75 | 0.77 | 0.52 | 0.48 |
| B/L | 0.225 | 0.228 | 0.235 | 0.253 | 1.05 | 1.25 |
| Hole distribution,% | ||||||
| 4～15nm | 55.35 | 56.29 | 64.78 | 56.68 | 30.47 | 35.32 |
| ＞15nm | 4.92 | 4.85 | 4.33 | 3.56 | 11.34 | 14.03 |
Example 5
The BetaAS-1 prepared in example 1 was used to prepare a hydrofinishing catalyst support and catalyst:
weighing alumina dry glue powder (the specific surface area is 308 m) 2 85g of water solution containing nitric acid and citric acid (the amount of the nitric acid is 12.6g and the amount of the citric acid is 4.5g), 15g of BetaAS-1 composite molecular sieve and 4g of sesbania powder, and the water solution is added with 120mL of aqueous solution containing nitric acid and citric acid, and is subjected to kneading, rolling, strip extrusion molding, drying at 120 ℃ for 3 hours and roasting at 550 ℃ for 4 hours to obtain the final carrier containing the composite molecular sieve, wherein the number is Z1.
Soaking Z1 in a soaking solution containing Mo, Ni and P in the same volume, drying at 130 ℃ for 2h, and roasting at 480 ℃ for 3h to finally obtain the catalyst C-1. In catalyst C1, the molybdenum oxide content was 23.5wt%, the nickel oxide content was 3.95wt%, and the phosphorus content was 1.25 wt%.
The catalyst C-1 is subjected to a catalyst activity evaluation experiment, and specifically comprises the following steps: the properties of the feed oil used in the one-stage series process carried out on a 200mL small scale hydrogenation unit are shown in Table 3. The operating conditions were as follows: hydrogen partial pressure 14.5MPa, hydrogen-oil volume ratio 1200: 1, space velocity of 1.5h －1 . The results of the catalyst activity tests are shown in Table 4.
Example 6
The BetaAS-3 prepared in example 3 was used to prepare a hydrofinishing catalyst carrier and catalyst:
weighing alumina dry glue powder (the specific surface area is 308 m) 2 85g of water solution containing nitric acid and citric acid (the amount of the nitric acid is 12.3g and the amount of the citric acid is 4.2g), 12g of BetaAS-3 composite molecular sieve and 4g of sesbania powder, and the water solution is added with 120mL of aqueous solution containing nitric acid and citric acid, and is subjected to kneading, rolling, strip extrusion molding, drying at 120 ℃ for 3 hours and roasting at 550 ℃ for 4 hours to obtain the final carrier containing the composite molecular sieve, wherein the number is Z2.
Soaking Z2 in a soaking solution containing Mo, Ni and P in the same volume, drying at 130 ℃ for 2h, and roasting at 480 ℃ for 3h to finally obtain the catalyst C-2. In catalyst C2, the molybdenum oxide content was 23.2wt%, the nickel oxide content was 3.85wt%, and the phosphorus content was 1.21 wt%.
The catalyst activity evaluation test was carried out for catalyst C-2 in the same manner as in example 6.
Comparative examples 3 to 4
The carrier and catalyst were prepared as in example 5 except that BetaAS-5 to BetaAS-6 prepared in comparative examples were used instead of BetaAS-1 in example 5, respectively, to prepare a carrier and a catalyst for a hydrorefining catalyst, and catalysts C-3 to C-4 were obtained accordingly.
The method for evaluating the activity of the catalyst was the same as in example 5 using catalysts C-3 to C-4, respectively. The properties of the raw oil are shown in Table 3, and the results of the activity evaluation are shown in Table 4.
TABLE 3 Properties of the feed oils
| Raw oil | Iran VGO |
| Density (20 ℃ C.), g.cm -3 | 0.916 |
| Nitrogen content, μ g -1 | 1210 |
| Distillation range, deg.C | 302-510 |
TABLE 4 evaluation results of catalyst Activity
| Catalyst numbering | C-1 | C-2 | C-3 | C-4 |
| Reaction temperature of | 383 | 383 | 383 | 383 |
| Nitrogen content, μ g -1 | 8.3 | 7.5 | 28.7 | 30.2 |
As can be seen from the evaluation results of the catalysts in Table 4, the denitrification activity of the hydrofining catalyst prepared by adopting the Beta/Al-SBA-15 composite molecular sieve is obviously improved.
Claims (27)
1. A Beta/Al-SBA-15 composite molecular sieve has a medium-strong acid content of 0.7-1.2 mL/g, and a ratio of B acid to L acid of 0.22-0.4; in the Beta/Al-SBA-15 composite molecular sieve, the mass content of alumina is 20.50-85%; the pore distribution of the Beta/Al-SBA-15 composite molecular sieve comprises the following steps: the pore volume occupied by pores with the pore diameter of 4-15nm is 42% -72% of the total pore volume;
the preparation method of the composite molecular sieve comprises the following steps: amorphous silica-alumina dry gel is used as a raw material, P123 triblock copolymer is used as a template agent to carry out first crystallization to synthesize the Al-SBA-15 molecular sieve, and then Beta molecular sieve slurry is added to carry out second crystallization to obtain the Beta/Al-SBA-15 composite molecular sieve.
2. The composite molecular sieve of claim 1, wherein the amount of the medium strong acid in the composite molecular sieve is 0.7-1.0 mL/g.
3. The composite molecular sieve of claim 1, wherein the composite molecular sieve has the following properties: the specific surface area is 550 to 950m 2 The total pore volume is 0.4-1.1 mL/g.
4. The composite molecular sieve of claim 3, wherein the composite molecular sieve has the following properties: the specific surface area is 650-850 m 2 The total pore volume is 0.48-0.85 mL/g.
5. The composite molecular sieve of claim 1, wherein the composite molecular sieve has an alumina content of 20.50 to 77.5% by mass.
6. The composite molecular sieve of claim 1, wherein the pore distribution of the composite molecular sieve comprises: the pore volume occupied by the pores with the pore diameters of 4-15nm is 45% -65% of the total pore volume.
7. The composite molecular sieve of claim 6, wherein the composite molecular sieve has a pore distribution comprising: the pore volume occupied by the pores with the pore diameters of 4-15nm is 55-65% of the total pore volume.
8. The composite molecular sieve of claim 1, wherein the mass content of the Beta molecular sieve in the composite molecular sieve is 10-90%.
9. The composite molecular sieve of claim 8, wherein the mass content of the Beta molecular sieve in the composite molecular sieve is 25-85%.
10. According to claim1, the composite molecular sieve is characterized in that the amorphous silica-alumina dry gel has the following properties: the specific surface area is 400-650 m 2 The pore volume is 0.52-1.8 mL/g, and the pore distribution is as follows: the pore volume with the pore diameter of 4-15nm accounts for 85% -95% of the total pore volume, and the pore volume with the pore diameter of more than 15nm accounts for less than 5% of the total pore volume.
11. The method of any one of claims 1-10, wherein the Beta/Al-SBA-15 composite molecular sieve comprises:
(1) mixing amorphous silica-alumina dry gel and water to form slurry;
(2) preparing an acidic solution containing a P123 triblock copolymer;
(3) and (2) mixing the slurry prepared in the step (1) with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2), performing first crystallization, then adding Beta molecular sieve slurry, and performing second crystallization to prepare the Beta/Al-SBA-15 composite molecular sieve.
12. The method according to claim 11, wherein the mass ratio of the amorphous silica-alumina dry gel to the water in the step (1) is 10: 90-30: 70.
13. the method according to claim 12, wherein the mass ratio of the amorphous silica-alumina dry gel to the water in the step (1) is 15: 85-25: 75.
14. the method according to claim 11, wherein the pH of the acidic aqueous solution in the step (2) is 1-5, and the mass content of the P123 triblock copolymer in the acidic aqueous solution is 0.5-5.0%.
15. The method according to claim 14, wherein the pH of the acidic aqueous solution in the step (2) is 1.2-2.3, and the mass content of the P123 triblock copolymer in the acidic aqueous solution is 0.8-2.8%.
16. The process of claim 11, wherein the P123 triblock copolymer is added to dilute acid in step (2), said dilute acid solution having a concentration of H + The amount is 0.05-0.3 mol/L; in the step (2), the temperature system is controlled to be 10-60 ℃.
17. The process of claim 16, wherein the P123 triblock copolymer is added to dilute acid in step (2), said dilute acid solution having a concentration of H + The amount is 0.1-0.2 mol/L; in the step (2), the temperature system is controlled to be 20-40 ℃.
18. The method according to claim 11, wherein the slurry prepared in the step (1) is mixed with the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2) in the step (3), and the amounts of the slurry prepared in the step (1) and the acidic aqueous solution containing the P123 triblock copolymer prepared in the step (2) are 0.5:1 to 5:1 by mass of the P123 triblock copolymer and the amorphous silica-alumina in the mixed system.
19. The method according to claim 18, wherein the amount of the slurry prepared in step (1) and the acidic aqueous solution containing the P123 triblock copolymer prepared in step (2) is 1: 1-5: 1 by mass of the P123 triblock copolymer and the amorphous silica-alumina in the mixed system.
20. The method according to claim 11, wherein the first crystallization temperature in the step (3) is 80 to 120 ℃; the crystallization time is 10-35 h; the pH value is controlled to be 2.0-5.0 in the crystallization process.
21. The method as claimed in claim 20, wherein the first crystallization temperature in the step (3) is 90 to 110 ℃; the crystallization time is 16-24 h; the pH value is controlled to be 3.2-4.8 in the crystallization process.
22. According toThe method of claim 11, wherein said Beta molecular sieve has the following properties: SiO 2 2 /Al 2 O 3 The molar ratio is 35-155, and the specific surface area is 510-850 m 2 (iv)/g, the total pore volume is 0.30-0.60 mL/g.
23. The method according to claim 11, wherein the Beta molecular sieve is present in the slurry at a mass content of 20% to 40%.
24. The method as claimed in claim 11, wherein the conditions of the second crystallization in the step (3) are: the crystallization temperature is 80-130 ℃; the crystallization time is 4-20 h; the pH value is controlled to be 2.0-5.0 in the crystallization process.
25. The method as claimed in claim 24, wherein the conditions of the second crystallization in the step (3) are: the crystallization temperature is 90-120 ℃; the crystallization time is 10-15 h; the pH value is controlled to be 4.2-5.0 in the crystallization process.
26. A catalyst composition comprising the Beta/Al-SBA-15 composite molecular sieve of any one of claims 1 to 10 or the Beta/Al-SBA-15 composite molecular sieve prepared according to the process of any one of claims 11 to 25.
27. Use of the Beta/Al-SBA-15 composite molecular sieve according to any one of claims 1 to 10, or the Beta/Al-SBA-15 composite molecular sieve prepared by the process according to any one of claims 11 to 25, or the catalyst composition according to claim 26 in a hydroprocessing catalyst.
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