CN112934258B - Composite molecular sieve, preparation method thereof, hydroisomerization catalyst and hydroisomerization method for Fischer-Tropsch synthetic oil - Google Patents
Composite molecular sieve, preparation method thereof, hydroisomerization catalyst and hydroisomerization method for Fischer-Tropsch synthetic oil Download PDFInfo
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- CN112934258B CN112934258B CN201911176649.8A CN201911176649A CN112934258B CN 112934258 B CN112934258 B CN 112934258B CN 201911176649 A CN201911176649 A CN 201911176649A CN 112934258 B CN112934258 B CN 112934258B
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- 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 221
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 218
- 239000002131 composite material Substances 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003921 oil Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000011258 core-shell material Substances 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 25
- 238000002425 crystallisation Methods 0.000 claims description 25
- 230000008025 crystallization Effects 0.000 claims description 25
- 239000003513 alkali Substances 0.000 claims description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- 238000010306 acid treatment Methods 0.000 claims description 7
- 229910000510 noble metal Inorganic materials 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- 239000011550 stock solution Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- 229910021485 fumed silica Inorganic materials 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims 4
- 239000002199 base oil Substances 0.000 abstract description 11
- 239000010687 lubricating oil Substances 0.000 abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 28
- 239000002245 particle Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000012634 fragment Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000011410 subtraction method Methods 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/618—Surface area more than 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the field of hydroisomerization of Fischer-Tropsch synthetic oil, and discloses a composite molecular sieve, a preparation method thereof, a hydroisomerization catalyst and a hydroisomerization method of Fischer-Tropsch synthetic oil. The composite molecular sieve has a core-shell structure, wherein the core-shell structure comprises an inner core and an outer shell coating the inner core, the inner core contains a modified ZSM-48 molecular sieve, and the outer shell contains an MCM-41 molecular sieve; the content of the shell is 0.1-50 wt% and the content of the core is 50-99.9 wt% based on the total weight of the composite molecular sieve. The hydroisomerization catalyst prepared by the composite molecular sieve of the invention is used for hydroisomerization reaction of Fischer-Tropsch synthetic oil, has better isomerism selectivity, and can produce high-quality and high-yield lubricating oil base oil.
Description
Technical Field
The invention relates to the field of hydroisomerization of Fischer-Tropsch synthetic oil, in particular to a composite molecular sieve and a preparation method thereof, a hydroisomerization catalyst prepared by the composite molecular sieve and a hydroisomerization method of Fischer-Tropsch synthetic oil.
Background
Fischer-Tropsch synthesis is one of the important routes for converting coal, natural gas and biomass into synthetic liquid fuels. The molecular structure of fuel is modulated by hydroisomerization reaction using Fischer-Tropsch synthetic oil as raw material.
CN105800635a discloses a preparation method of a ZSM-48 molecular sieve with a mesoporous-microporous hierarchical structure, which specifically comprises the following steps: (1) Homogenizing and mixing an aluminum source, sodium hydroxide and deionized water; (2) Adding a template agent and a silicon source into the solution in the step (1), and homogenizing and mixing again to obtain a mixture; (3) Adding starch to the mixture of step (2) to obtain an initial gel mixture; (4) Aging, crystallizing, separating, washing, drying and roasting the crystallized solid product to obtain ZSM-48 molecular sieve raw powder; (5) And roasting the ZSM-48 molecular sieve raw powder to obtain the ZSM-48 molecular sieve with the mesoporous-microporous hierarchical structure.
CN104418341A discloses a ZSM-48/Silicalite-1 composite molecular sieve and a preparation method thereof, wherein the composite molecular sieve takes a ZSM-48 molecular sieve with low silicon-aluminum ratio as a core phase, silicalite-1 as a shell layer, and the total specific surface area of the composite molecular sieve is 330-400 m 2 Per gram, the total pore volume is 0.22-0.28 ml/g, the average pore diameter is 2.5-3.5 nm, and the content of the shell layer is 10-70% based on the total weight of the composite molecular sieve; wherein the mole ratio of the silicon oxide to the aluminum oxide of the ZSM-48 molecular sieve with low silicon-aluminum ratio is 25-50. The preparation method comprises the following steps: (1) Uniformly mixing seed crystal S, template agent R, silicon source, aluminum source, sodium hydroxide and water to obtain a reaction mixture, crystallizing, separating, drying and roasting the crystallized product to obtain a ZSM-48 molecular sieve with low silicon-aluminum ratio; (2) Uniformly mixing the ZSM-48 molecular sieve with low silicon-aluminum ratio obtained in the step (1), sodium hydroxide, a template agent and water, adding a silicon source to prepare a reaction mixture gel system, crystallizing the reaction mixture gel, and separating, drying and roasting the crystallized product to obtain the ZSM-48/Silicalite-1 composite molecular sieve.
CN106669814a discloses a preparation method of a ZSM-48/Y composite molecular sieve, which comprises the following contents: (1) Roasting a ZSM-48 molecular sieve at a high temperature, then contacting unsaturated olefin with the roasted ZSM-48 molecular sieve, carrying out roasting carbon deposition reaction in an inert gas atmosphere, and then carrying out surface dealumination treatment on the ZSM-48 molecular sieve to obtain a modified ZSM-48 molecular sieve; (2) Uniformly stirring the modified ZSM-48 molecular sieve powder, an aluminum source, sodium hydroxide and water to obtain a reaction mixture gel system, aging under a closed condition, crystallizing, and finally cooling, washing, drying and roasting to obtain the ZSM-48/Y composite molecular sieve. The composite zeolite molecular sieve prepared by the method organically combines the isomerism performance of the ZSM-48 molecular sieve with the cracking performance of the Y-type molecular sieve, and can be applied to the production of high-quality lubricating oil base oil in the hydrocracking petroleum refining process.
The hydrogenation catalyst prepared from the ZSM-48 molecular sieve disclosed in the prior art is easy to hydrocrack Fischer-Tropsch synthetic oil, is favorable for obtaining cracked products, and has poor isomerization effect.
Disclosure of Invention
The invention aims to solve the problem that the hydroisomerization effect of a hydrogenation catalyst on Fischer-Tropsch synthetic oil is poor in the prior art, and provides a composite molecular sieve, a preparation method thereof, a hydroisomerization catalyst and a hydroisomerization method of the Fischer-Tropsch synthetic oil.
In order to achieve the above object, a first aspect of the present invention provides a composite molecular sieve having a core-shell structure including a core and a shell coating the core, the core containing a modified ZSM-48 molecular sieve, the shell containing an MCM-41 molecular sieve; the content of the shell is 0.1-50 wt% and the content of the core is 50-99.9 wt% based on the total weight of the composite molecular sieve.
The second aspect of the present invention provides a method for preparing a composite molecular sieve, comprising:
(1) Modifying the ZSM-48 molecular sieve to obtain a modified ZSM-48 molecular sieve;
(2) And mixing the modified ZSM-48 molecular sieve, a solvent, a template agent, a silicon source and an aluminum source, and regulating the pH value to obtain a crystallization stock solution, and sequentially crystallizing, drying and roasting the crystallization stock solution.
In a third aspect, the present invention provides a composite molecular sieve made by the above-described method of preparation.
In a fourth aspect, the present invention provides a hydroisomerization catalyst comprising a support and an active component, said support comprising the composite molecular sieve described above.
In a fifth aspect the invention provides a process for hydroisomerisation of a Fischer-Tropsch oil comprising: under the hydroisomerization reaction condition, the hydroisomerization catalyst and the Fischer-Tropsch synthetic oil are subjected to hydroisomerization reaction.
According to the technical scheme, after the molecular sieve of ZSM-48 is modified, modified ZSM-48 with crystallinity and rich in hydroxyl ZSM-48 or structural fragments of ZSM-48 is generated, and then the composite molecular sieve with an MCM-41/ZSM-48 core-shell structure is prepared through crystallization, wherein the composite molecular sieve has a core-shell structure, the core-shell structure comprises a core and a shell coating the core, the core contains the modified ZSM-48 molecular sieve, the shell contains the MCM-41 molecular sieve, the interface regulation and the spatial position regulation of the microporous molecular sieve and the mesoporous molecular sieve are realized, and the spatial structure and the strong acid and weak acid center are provided for isomerization of Fischer-Tropsch synthetic oil. Compared with the traditional ZSM-48 molecular sieve, the molecular sieve has higher activity, selectivity and hydrothermal stability, and has strong acid and weak acid distribution. The catalyst prepared by the composite molecular sieve (MCM-41/ZSM-48 composite molecular sieve) has better isomerism selectivity when being used for hydroisomerization reaction of Fischer-Tropsch synthetic oil, can produce high-quality and high-yield lubricating oil base oil, and reduces the cloud point of the product.
Drawings
FIG. 1 is an XRD pattern of a modified ZSM-48 molecular sieve and a composite molecular sieve (MCM-41/ZSM-48) of example 1 of the invention;
FIG. 2 is an SEM image of a modified ZSM-48 molecular sieve of example 1 of the invention;
fig. 3 is an SEM image of the composite molecular sieve of example 1 of the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a composite molecular sieve, which has a core-shell structure, wherein the core-shell structure comprises an inner core and an outer shell for coating the inner core, the inner core contains a modified ZSM-48 molecular sieve, and the outer shell contains an MCM-41 molecular sieve; the content of the shell is 0.1-50 wt% and the content of the core is 50-99.9 wt% based on the total weight of the composite molecular sieve.
In the present invention, it is preferable that the content of the shell is 10 to 40% by weight and the content of the core is 60 to 90% by weight based on the total weight of the composite molecular sieve. Still more preferably, the shell is present in an amount of 30 to 40 weight percent and the inner core is present in an amount of 60 to 70 weight percent based on the total weight of the composite molecular sieve. In the preferred range of the invention, the composite molecular sieve is used in the hydroisomerization reaction process of Fischer-Tropsch synthetic oil, has better isomerism selectivity, and can produce high-quality and high-yield lubricating oil base oil. In the present invention, the contents of the outer shell and the inner core may be measured by an instrument or may be calculated by a subtraction method.
In the present invention, preferably, the modified ZSM-48 molecular sieve has SiO 2 With Al 2 O 3 The molar ratio is greater than 50:1, preferably 100-500:1. Such as 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, 400:1, 450:1, 500:1, and any value in the range of any two values recited above. In the present invention, siO 2 With Al 2 O 3 The molar ratio can be determined by X-ray fluorescence spectroscopy.
In the present invention, preferably, the modified ZSM-48 molecular sieve has a specific surface area of 100 to 1000m 2 And/g. For example 100m 2 /g、200m 2 /g、300m 2 /g、400m 2 /g、500m 2 /g、600m 2 /g、700m 2 /g、800m 2 /g、900m 2 /g、1000m 2 /g、100m 2 And/g, and any value in the range formed by any two values.
In the present invention, preferably, the modified ZSM-48 molecular sieve has a pore volume of from 0.05 to 0.5mL/g. For example, 0.05mL/g, 0.1mL/g, 0.2mL/g, 0.3mL/g, 0.4mL/g, 0.5mL/g, and any value in the range of any two values.
In the invention, the ZSM-48 molecular sieve is modified to obtain a structure with rough surface, so that the composite molecular sieve with a core-shell structure is easier to form. Further preferably, the shell contains SiO of MCM-41 molecular sieve 2 With Al 2 O 3 The molar ratio is 50-1000. The formed composite molecular sieve has better hydroisomerization effect on Fischer-Tropsch synthetic oil.
In the present invention, preferably, the specific surface area of the composite molecular sieve is 100 to 1200m 2 And/g. For example 100m 2 /g、200m 2 /g、300m 2 /g、400m 2 /g、500m 2 /g、600m 2 /g、700m 2 /g、800m 2 /g、900m 2 /g、1000m 2 /g、100m 2 /g、1100m 2 /g、1200m 2 And/g, and any value in the range formed by any two values.
In the present invention, preferably, the pore volume of the composite molecular sieve is 0.05 to 0.5mL/g. For example, 0.05mL/g, 0.1mL/g, 0.2mL/g, 0.3mL/g, 0.4mL/g, 0.5mL/g, and any value in the range of any two values.
In the present invention, it is preferable that the composite molecular sieve has an average pore diameter of 0.1 to 10nm. For example, 0.1nm, 0.5nm, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, and any value in the range of any two values.
In the present invention, the specific surface area, pore volume and average pore diameter can be determined by the physical adsorption BET method conventional in the art, and will not be described herein. In the present invention, "specific surface area" means the total specific surface area.
The composite molecular sieve provided by the invention is used in the hydroisomerization process of Fischer-Tropsch synthetic oil, and is beneficial to realizing the production of high-quality lubricating oil base oil from Fischer-Tropsch synthetic oil.
The second aspect of the present invention provides a method for preparing a composite molecular sieve, comprising:
(1) Modifying the ZSM-48 molecular sieve to obtain a modified ZSM-48 molecular sieve;
(2) And mixing the modified ZSM-48 molecular sieve, a solvent, a template agent, a silicon source and an aluminum source, and regulating the pH value to obtain a crystallization stock solution, and sequentially crystallizing, drying and roasting the crystallization stock solution.
According to the process of the present invention, preferably, the ZSM-48 molecular sieve is SiO 2 With Al 2 O 3 The molar ratio is greater than 50:1, preferably 100-500:1. Such as 100:1, 150:1, 200:1, 250:1, 300:1, 350:1, 400:1, 450:1, 500:1, and any value in the range of any two values recited above. Preferred SiO in the present invention 2 With Al 2 O 3 The modification treatment is more favorable in the molar ratio, and the structural fragments of the hydroxyl-rich ZSM-48 or ZSM-48 with a certain crystallinity are generated after the modification treatment.
According to the method of the present invention, preferably, the ZSM-48 molecular sieve has a specific surface area of 100 to 1000m 2 Preferably 200 to 500m 2 And/g. For example 200m 2 /g、300m 2 /g、400m 2 /g、500m 2 And/g, and any value in the range formed by any two values.
According to the process of the present invention, preferably, the ZSM-48 molecular sieve has a particle size of from 0.5 to 5. Mu.m. For example, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, and any value in the range of any two values.
According to the process of the present invention, preferably, the modified ZSM-48 molecular sieve has a particle size of from 0.1 to 5. Mu.m. For example, 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, and any value in the range of any two values. In the present invention, particle size may be determined by laser particle size analyzer analysis.
According to the method of the present invention, the modification treatment method aims at modifying the ZSM-48 molecular sieve to obtain hydroxyl-rich ZSM-48 or ZSM-48 structural fragments, preferably, in the step (1), the modification treatment method is acid treatment, alkali treatment or hydrothermal treatment.
According to the method of the present invention, preferably, the acid treatment process comprises: the ZSM-48 was acid treated with acid solution. The acid in the acid liquid can be one or more of hydrochloric acid, nitric acid and sulfuric acid, and the solvent in the acid liquid can be deionized water. For example, the acid solution is one or more of aqueous hydrochloric acid, aqueous nitric acid and aqueous sulfuric acid. More preferably, the acid concentration in the acid solution is 0.1 to 1mol/L. Further preferably, the weight ratio of ZSM-48 molecular sieve to acid solution in terms of acid is 1: (1-50). Still further preferably, the conditions of the acid treatment include: the time is 30-360 min, and the temperature is 30-100 ℃.
According to the method of the present invention, preferably, the alkali treatment process comprises: the ZSM-48 was alkali treated with alkali. Wherein, the alkali in the alkali liquor can be one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate and potassium carbonate, and the solvent in the alkali liquor can be deionized water. For example, the lye is one or more of aqueous sodium hydroxide, aqueous potassium hydroxide, aqueous sodium bicarbonate, aqueous potassium bicarbonate, aqueous sodium carbonate and aqueous potassium carbonate. More preferably, the concentration of the alkali in the alkali solution is 0.01 to 5mol/L. Further preferably, the weight ratio of ZSM-48 molecular sieve to lye calculated as alkali is 1: (1-50). Still further preferably, the conditions of the alkali treatment include: the time is 30-360 min, and the temperature is 30-100 ℃.
According to the method of the present invention, preferably, the conditions of the hydrothermal treatment include: the temperature is 100-500 ℃ and the time is 30-360 min. The hydrothermal treatment may be performed under closed conditions.
According to the method of the present invention,and (2) forming a shell layer of the MCM-41 molecular sieve on the outer layer of the modified ZSM-48 molecular sieve. In order to ensure that the obtained composite molecular sieve has a better isomerization effect, the feeding amount among the components is controlled to meet the limit relation in the preparation process. Preferably, the molar ratio of the silicon source, aluminum source, template agent, solvent and modified ZSM-48 molecular sieve is 1: (0.001-0.02): (0.01-10): (5-200), wherein the silicon source is SiO 2 The aluminum source is calculated as Al 2 O 3 And (5) counting.
According to the method of the invention, the weight ratio of the silicon source to the modified ZSM-48 molecular sieve is (0.01-50): 1, wherein the silicon source is SiO 2 And (5) counting.
According to the method of the invention, the template agent is suitable for preparing the MCM-41/ZSM-48 composite molecular sieve of the invention. Preferably, the template agent is cetyl trimethylammonium bromide and/or cetyl trimethylammonium chloride.
The silicon source used in the process according to the present invention is suitable for preparing the MCM-41/ZSM-48 composite molecular sieve of the present invention. Preferably, the silicon source is one or more of sodium silicate, white carbon black, silica sol, fumed silica and ethyl orthosilicate, and further preferably sodium silicate.
According to the method of the present invention, an aluminum source suitable for preparing the MCM-41/ZSM-48 composite molecular sieve of the present invention may be used. Preferably, the aluminum source is one or more of sodium metaaluminate, aluminum sulfate, pseudo-boehmite, and aluminum isopropoxide, and more preferably sodium metaaluminate.
According to the method of the present invention, the pH value is adjusted in the step (2) so that the crystallization stock solution is easier to perform crystallization treatment, and the composite molecular sieve of the present invention is obtained, preferably, the pH value is 9 to 10.5, and for example, may be any value in a range formed by 9, 9.5, 10, 10.5 and any two of these values.
According to the process of the present invention, the crystallization conditions are for the purpose of being suitable for the preparation of the MCM-41/ZSM-48 composite molecular sieve of the present invention, preferably the crystallization conditions include: the temperature is 10 to 150 ℃, preferably 30 to 120 ℃, and the time is 12 to 96 hours, preferably 12 to 72 hours. According to a specific embodiment of the present invention, the filtering and washing operations are performed after crystallization, and are conventional operations in the art, and are not described herein.
According to the process of the present invention, the drying conditions are for the purpose of being suitable for the preparation of the MCM-41/ZSM-48 composite molecular sieve of the present invention, preferably the drying conditions comprise: the temperature is 80-200 ℃ and the time is 12-36 h.
According to the process of the present invention, the calcination conditions are for the purpose of being suitable for the preparation of the MCM-41/ZSM-48 composite molecular sieve of the present invention, preferably the calcination conditions comprise: the temperature is 300-600 ℃, preferably 300-500 ℃; the time is 1 to 24 hours, preferably 4 to 10 hours.
According to the process of the present invention, preferably, the SiO of the MCM-41 molecular sieve formed in step (2) 2 With Al 2 O 3 The molar ratio is 50-1000.
In a third aspect, the present invention provides a composite molecular sieve made by the above-described method of preparation.
In a fourth aspect, the present invention provides a hydroisomerization catalyst comprising a support and an active component, said support comprising the composite molecular sieve described above.
In a preferred case, the active component is a noble metal, preferably platinum and/or palladium.
According to one embodiment of the present invention, the catalyst may contain a noble metal, a binder and the composite molecular sieve of the present invention, wherein the noble metal is platinum and/or palladium and the binder is alumina.
According to a specific embodiment of the present invention, the preparation method of the catalyst may be:
(1) Mixing a composite molecular sieve with an alumina binder to prepare a carrier, wherein the content of the composite molecular sieve is 10-90 wt% and the content of the alumina binder is 10-90 wt% based on the total amount of the carrier;
(2) The noble metal is loaded on the carrier by an impregnation method, wherein the noble metal can be platinum and/or palladium, the content of the platinum is 0.01-1 wt% and the content of the palladium is 0.01-1 wt% based on the total amount of the carrier.
Typical catalysts may be: on a carrier containing 65 wt% of the composite molecular sieve and 35 wt% of the alumina binder, platinum was supported in an amount of 0.35 wt% of the carrier. The foregoing is merely an example, and the specific catalyst is not limited thereto.
In a fifth aspect the invention provides a process for hydroisomerisation of a Fischer-Tropsch oil comprising: and (3) carrying out isomerization reaction on the Fischer-Tropsch synthetic oil in the presence of the hydroisomerization catalyst.
According to the process of the present invention, the conditions of the isomerization reaction may include, but are not limited to: the volume ratio of hydrogen to oil is 400-1000: 1, the temperature is 200-400 ℃, the pressure is 1-12 MPa, and the volume airspeed is 0.01-10 h -1 。
The present invention will be described in detail by examples.
1) Particle size was determined by laser particle size analysis (from Malvern, uk, model Mastersizer 2000E).
2) The specific surface area, pore volume and average pore size were determined by means of a physical adsorption BET tester (instrument available from Micromeritics, USA, model ASAP).
3)SiO 2 With Al 2 O 3 The molar ratio was determined by X-ray fluorescence spectroscopy.
4) SEM was purchased from FEI company under the model name Nova NanoSEM450.
5) XRD (X-ray diffractometer) was purchased from Bruker, germany, model D8ADVANCE;
6) Cloud points were measured by an HCP852 automated pour point/cloud point analyzer (Germany, origin) and tested according to the method of GB/T6986-2014.
7) Pour point was determined according to the method of GB/T3535-2006.
8) ZSM-48 molecular sieve was purchased from a molecular sieve synthesized by Beijing low carbon clean energy institute.
9) MCM-41 molecular sieves (for comparative example 1) were purchased from Tianjin Nanhua catalyst company.
Example 1
(1) 10g of ZSM-48 molecular sieve (SiO 2 With Al 2 O 3 Molar ratio of 120, specific surface area of 320m 2 Per gram, particle size of 1.5 μm) was mixed with 300mL of a 0.5mol/L aqueous NaOH solution, alkali treated for 60min at 80℃in a water bath, filtered, and washed with deionized water to give a modified ZSM-48 molecular sieve. The result is shown in figure 1 by XRD analysis, the obtained spectrogram is compared with a standard spectrogram, and the molecular sieve obtained is confirmed to have the structure of ZSM-48 molecular sieve. The modified ZSM-48 molecular sieve obtained by alkali treatment has a particle size of 1.2 μm by analysis by a laser particle sizer, and the particle size is reduced compared with the ZSM-48 molecular sieve (particle size of 1.5 μm). The results are shown in FIG. 2, which is observed by SEM. SiO of the modified ZSM-48 molecular sieve is measured 2 With Al 2 O 3 The molar ratio is 100, and the specific surface area of the modified ZSM-48 molecular sieve is 295m 2 And/g, the pore volume of the modified ZSM-48 molecular sieve is 0.12mL/g.
(2) Mixing 7.0g of the modified ZSM-48 molecular sieve with 120g of water, stirring uniformly, adding 18.0g of cetyltrimethylammonium bromide, 95g of sodium silicate and 0.27g of sodium metaaluminate, mixing and stirring, adjusting the pH value to 10 by using a sulfuric acid aqueous solution (the sulfuric acid concentration is 1 mol/L), transferring into a crystallization reaction kettle, crystallizing for 24 hours at 120 ℃ to obtain a crystallized product, filtering, washing the crystallized product by water, drying for 12 hours at 120 ℃, and roasting for 6 hours at 550 ℃ to obtain the composite molecular sieve S1. XRD analysis is carried out on the composite molecular sieve, the result is shown in figure 1, the obtained spectrogram is compared with a standard spectrogram, the molecular sieve has the structure of ZSM-48 molecular sieve and MCM-41, the SEM image of the composite molecular sieve is shown in figure 3, the composite molecular sieve has a core-shell structure which comprises a core and a shell coating the core, the core contains the modified ZSM-48 molecular sieve, and the shell contains the MCM-41 molecular sieve, as can be seen from figure 3. SiO of MCM-41 molecular sieve is measured 2 With Al 2 O 3 The molar ratio was 200. The shell content was 40 wt% and the core content was 60 wt% based on the total weight of the composite molecular sieve S1 by subtraction.
The total of the composite molecular sieve is determinedSpecific surface area of 350m 2 Per g, pore volume 0.2mL/g, average pore diameter 3nm.
Example 2
(1) 10g of ZSM-48 molecular sieve (SiO 2 With Al 2 O 3 The molar ratio is 100, the specific surface area is 300m 2 Per gram, particle size 1.5 μm) was mixed with 300mL of 1mol/L HCl solution, acid treated for 60min at 100deg.C in water bath, and filtered, washing with water to give a modified ZSM-48 molecular sieve. The modified ZSM-48 particles obtained by acid treatment were 1.5 μm in size by analysis with a laser particle sizer. SiO of the modified ZSM-48 molecular sieve is measured 2 With Al 2 O 3 The molar ratio is 95, and the specific surface area of the modified ZSM-48 molecular sieve is 285m 2 And/g, the pore volume of the modified ZSM-48 molecular sieve is 0.08mL/g.
(2) Mixing 7.0g of the modified ZSM-48 molecular sieve with 120g of water, stirring uniformly, adding 18.0g of cetyltrimethylammonium bromide, 95g of sodium silicate and 2.2g of aluminum sulfate, mixing and stirring, adjusting the pH value to 9 by using sulfuric acid solution (the concentration is 1 mol/L), transferring into a crystallization reaction kettle, crystallizing at 80 ℃ for 36h to obtain a crystallization product, filtering and washing the crystallization product by water, drying at 120 ℃ for 12h, and roasting at 550 ℃ for 4h to obtain the composite molecular sieve S2. XRD analysis is carried out on the composite molecular sieve, the result is similar to that of figure 1, the obtained molecular sieve is confirmed to have the structure of ZSM-48 molecular sieve and MCM-41, the SEM image of the composite molecular sieve is similar to that of figure 3, and the composite molecular sieve can be seen to have a core-shell structure which comprises a core and a shell coating the core, wherein the core contains the modified ZSM-48 molecular sieve, and the shell contains the MCM-41 molecular sieve. SiO of MCM-41 molecular sieve is measured 2 With Al 2 O 3 The molar ratio was 100. The shell content was 35 wt.% and the core content was 65 wt.% based on the total weight of the composite molecular sieve S2, calculated by the subtraction method.
The total specific surface area of the composite molecular sieve is 330m 2 Per g, pore volume 0.15mL/g, average pore diameter 3nm.
Example 3
(1) 10g of ZSM-48 molecular sieve was used(SiO 2 With Al 2 O 3 Molar ratio of 200, specific surface area of 330m 2 /g, particle size 1.5 μm) was hydrothermally treated at 300℃for 360min and filtered to give a modified ZSM-48 molecular sieve. The modified ZSM-48 obtained by hydrothermal treatment had a particle size of 1.5 μm by analysis with a laser particle sizer, and had no decrease in particle size compared with the ZSM-48 molecular sieve (particle size of 1.5 μm). SiO of the modified ZSM-48 molecular sieve is measured 2 With Al 2 O 3 The molar ratio is 190, and the specific surface area of the modified ZSM-48 molecular sieve is 315m 2 And/g, the pore volume of the modified ZSM-48 molecular sieve is 0.08mL/g.
(2) 8.0g of the modified ZSM-48 molecular sieve is mixed with 120g of water, stirred uniformly, 18.0g of cetyltrimethylammonium bromide, 20.0g of white carbon black and 0.2g of pseudo-boehmite are added, mixed and stirred, the pH value is regulated to 10.5 by sulfuric acid solution (the concentration is 1 mol/L), the mixture is transferred into a crystallization reaction kettle, the crystallization is carried out for 24 hours at 120 ℃, the crystallization product is obtained, and the crystallization product is dried for 12 hours at 150 ℃ after being filtered and washed, and then baked for 6 hours at 500 ℃ to obtain the composite molecular sieve S3. XRD analysis is carried out on the composite molecular sieve, the result is similar to that of figure 1, the obtained molecular sieve is confirmed to have the structure of ZSM-48 molecular sieve and MCM-41, the SEM image of the composite molecular sieve is similar to that of figure 3, and the composite molecular sieve can be seen to have a core-shell structure which comprises a core and a shell coating the core, wherein the core contains the modified ZSM-48 molecular sieve, and the shell contains the MCM-41 molecular sieve. SiO of MCM-41 molecular sieve is measured 2 With Al 2 O 3 The molar ratio was 200. The content of the shell was 30% by weight and the content of the core was 70% by weight, calculated by the difference method, based on the total weight of the composite molecular sieve S3.
The total specific surface area of the composite molecular sieve is 345m 2 Per g, pore volume 0.14mL/g, average pore diameter 3nm.
Example 4
The procedure of example 1 is followed except that the ZSM-48 molecular sieve is SiO 2 With Al 2 O 3 The molar ratio was 80.
Comparative example 1
10g of ZSM-48 molecular sieve was thoroughly mixed with 5g of commercially available MCM-41 to give a mixed molecular sieve D1.
Comparative example 2
(1) 10g of ZSM-48 molecular sieve (SiO 2 With Al 2 O 3 The molar ratio of (2) was 100 and the specific surface area was 200m 2 Per gram, particle size 1.5 μm) was mixed with 300mL of a 1.0mol/L NaOH solution, alkali treated for 60min at 80℃in a water bath, filtered and washed with water to give a modified ZSM-48 molecular sieve.
(2) Mixing 2.0g of the modified ZSM-48 molecular sieve with 120g of water, stirring uniformly, adding 18.0g of cetyltrimethylammonium bromide, 95g of sodium silicate and 7.5g of sodium metaaluminate, mixing and stirring, adjusting the pH value to 10 by using sulfuric acid solution (the concentration is 1 mol/L), transferring into a crystallization reaction kettle, crystallizing for 24 hours at 120 ℃ to obtain a crystallized product, filtering and washing the crystallized product, drying for 12 hours at 120 ℃, and roasting for 6 hours at 550 ℃ to obtain the composite molecular sieve D2.
Comparative example 3
The procedure of example 1 was followed except that the ZSM-48 molecular sieve was replaced with a ZSM-5 molecular sieve. The MCM-41/ZSM-5 composite molecular sieve D3 is prepared.
Comparative example 4
The procedure of example 1 was followed except that the ZSM-48 molecular sieve was replaced with a SAPO-34 molecular sieve. And preparing the MCM-41/SAPO34 composite molecular sieve D4.
Test example 1
The composite molecular sieves obtained in examples 1 to 4 and comparative examples 1 to 4 were mixed with high-purity macroporous alumina (SB powder) (the weight ratio of the composite molecular sieve to the SB powder is 75:25), and diluted nitric acid solution (nitric acid concentration: 3 wt%) was added thereto, followed by kneading, followed by extrusion, followed by crushing, drying and calcination, followed by immersing in 0.5 wt% of platinum nitrate, followed by drying and calcination, to obtain hydroisomerization catalysts of examples 1 to 4 and comparative examples 1 to 4, respectively.
Hydroisomerization of the hydroisomerization catalysts of examples 1-4 and comparative examples 1-4, respectively, with the Fischer-Tropsch oil is performed under hydroisomerization conditions. Wherein the properties and boiling point distribution of the Fischer-Tropsch oil are shown in Table 1.
The reaction conditions are as follows: the hydrogen oil volume ratio (volume ratio of hydrogen to Fischer-Tropsch oil) is 500:1, the temperature is 310 ℃, the pressure is 3.0MPa, and the volume space velocity is 1.0h -1 . The product was tested for the content of each component by liquid chromatography (model Agilent 1200, available from Agilent corporation), the yield of lube base oil was calculated according to formula (I), the cracking conversion was calculated according to formula (II), and the pour and cloud point tests were determined and the results are shown in table 2.
Yield% of lube base oil =weight of base oil in post-reaction product/total mass of post-reaction liquid x 100 (formula I);
cracking conversion% = weight of non-base oil in product/feed of liquid feedstock formula (II)
TABLE 1
TABLE 2
As can be seen from the results of Table 2, the catalyst prepared using the composite molecular sieve of the present invention (MCM-41/ZSM-48 composite molecular sieve) was used for the hydroisomerization reaction of Fischer-Tropsch synthesis oil, and the cracking conversion was low, i.e., the Fischer-Tropsch synthesis oil was less involved in the cracking reaction, but more was isomerized, resulting in more isomerized product, indicating better isomerism selectivity, and the yield of lube base oil was high, and the lube base oil pour point and cloud point were reduced, as compared to comparative example 1 (no change of ZSM-48), comparative example 2 (according to the method of example 1, except that the shell content was not within the scope of the present invention), comparative example 3 (MCM-41/ZSM-5 composite molecular sieve), and comparative example 4 (MCM-41/SAPO 34 composite molecular sieve).
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (23)
1. The composite molecular sieve is characterized by having a core-shell structure, wherein the core-shell structure comprises a core and a shell coating the core, the core contains a modified ZSM-48 molecular sieve, and the shell contains an MCM-41 molecular sieve; the content of the shell is 0.1-50 wt% and the content of the core is 50-99.9 wt% based on the total weight of the composite molecular sieve; siO of the modified ZSM-48 molecular sieve 2 With Al 2 O 3 The molar ratio is greater than 50:1.
2. The composite molecular sieve of claim 1, wherein the shell is present in an amount of 10 to 40 wt% and the core is present in an amount of 60 to 90 wt%, based on the total weight of the composite molecular sieve.
3. The composite molecular sieve of claim 2, wherein the shell is present in an amount of 30 to 40 wt% and the core is present in an amount of 60 to 70 wt%, based on the total weight of the composite molecular sieve.
4. The composite molecular sieve of claim 1, wherein the modified ZSM-48 molecular sieve has SiO 2 With Al 2 O 3 The molar ratio is 100-500:1;
and/or the specific surface area of the modified ZSM-48 molecular sieve is 100-1000 m 2 /g；
And/or the pore volume of the modified ZSM-48 molecular sieve is 0.05-0.5 mL/g.
5. According to claimThe composite molecular sieve according to any one of claims 1 to 4, wherein the composite molecular sieve has a specific surface area of 100 to 1200m 2 /g；
And/or the pore volume of the composite molecular sieve is 0.05-0.5 mL/g;
and/or the average pore diameter of the composite molecular sieve is 0.1-10 nm.
6. A method of preparing a composite molecular sieve comprising:
(1) Modifying the ZSM-48 molecular sieve to obtain a modified ZSM-48 molecular sieve;
(2) Mixing the modified ZSM-48 molecular sieve, a solvent, a template agent, a silicon source and an aluminum source, and regulating the pH value to obtain a crystallization stock solution, and sequentially crystallizing, drying and roasting the crystallization stock solution;
wherein, the SiO of the ZSM-48 molecular sieve 2 With Al 2 O 3 The molar ratio is greater than 50:1.
7. The method of claim 6, wherein the ZSM-48 molecular sieve is SiO 2 With Al 2 O 3 The molar ratio is 100-500:1;
and/or the specific surface area of the ZSM-48 molecular sieve is 100-1000 m 2 Per gram of 200-500 m 2 /g；
And/or the granularity of the ZSM-48 molecular sieve is 0.5-5 mu m;
and/or the granularity of the modified ZSM-48 molecular sieve is 0.1-5 mu m.
8. The method according to claim 6 or 7, wherein the modification treatment is an acid treatment, an alkali treatment or a hydrothermal treatment.
9. The method of claim 8, wherein the acid treatment comprises: the ZSM-48 was acid treated with acid solution.
10. The method of claim 9, wherein the acid in the acid solution has a concentration of 0.1-1 mol/L;
and/or the weight ratio of ZSM-48 molecular sieve to acid solution calculated as acid is 1: (1-50);
and/or, the conditions of the acid treatment include: the time is 30-360 min, and the temperature is 30-100 ℃.
11. The method of claim 8, wherein the alkali treatment comprises: the ZSM-48 was alkali treated with alkali.
12. The method according to claim 11, wherein the alkali concentration in the alkali liquor is 0.01-5 mol/L;
and/or the weight ratio of ZSM-48 molecular sieve to alkali solution calculated by alkali is 1: (1-50);
and/or, the conditions of the alkali treatment include: the time is 30-360 min, and the temperature is 30-100 ℃.
13. The method of claim 8, wherein the hydrothermal treatment conditions comprise: the temperature is 100-500 ℃ and the time is 30-360 min.
14. The method of any of claims 6-7 and 9-13, wherein the molar ratio of silicon source, aluminum source, templating agent, and solvent is 1: (0.001 to 0.02): (0.01-10): (5-200), wherein the silicon source is SiO 2 The aluminum source is calculated as Al 2 O 3 Counting;
and/or the weight ratio of the silicon source to the modified ZSM-48 molecular sieve is (0.01-50): 1, wherein the silicon source is SiO 2 Counting;
and/or, the template agent is cetyl trimethyl ammonium bromide and/or cetyl trimethyl ammonium chloride;
and/or the silicon source is one or more of sodium silicate, white carbon black, silica sol, fumed silica and tetraethoxysilane;
and/or the aluminum source is one or more of sodium metaaluminate, aluminum sulfate, pseudo-boehmite and aluminum isopropoxide;
and/or the solvent is deionized water;
and/or the pH value is 9-10.5;
and/or, the crystallization conditions include: the temperature is 10-150 ℃ and the time is 12-96 h;
and/or, the drying conditions include: the temperature is 80-200 ℃ and the time is 12-36 h;
and/or, the firing conditions include: the temperature is 300-600 ℃ and the time is 1-24 h.
15. The method of claim 8, wherein the crystallization conditions comprise: the temperature is 30-120 ℃; the time is 12-72 h;
and/or, the firing conditions include: the temperature is 300-500 ℃; the time is 4-10 h.
16. The method of claim 8, wherein the molar ratio of silicon source, aluminum source, templating agent, and solvent is 1: (0.001 to 0.02): (0.01-10): (5-200), wherein the silicon source is SiO 2 The aluminum source is calculated as Al 2 O 3 Counting;
and/or the weight ratio of the silicon source to the modified ZSM-48 molecular sieve is (0.01-50): 1, wherein the silicon source is SiO 2 Counting;
and/or, the template agent is cetyl trimethyl ammonium bromide and/or cetyl trimethyl ammonium chloride;
and/or the silicon source is one or more of sodium silicate, white carbon black, silica sol, fumed silica and tetraethoxysilane;
and/or the aluminum source is one or more of sodium metaaluminate, aluminum sulfate, pseudo-boehmite and aluminum isopropoxide;
and/or the solvent is deionized water;
and/or the pH value is 9-10.5;
and/or, the crystallization conditions include: the temperature is 10-150 ℃ and the time is 12-96 h;
and/or, the drying conditions include: the temperature is 80-200 ℃ and the time is 12-36 h;
and/or, the firing conditions include: the temperature is 300-600 ℃ and the time is 1-24 h.
17. The method of claim 16, wherein the crystallization conditions comprise: the temperature is 30-120 ℃; the time is 12-72 h;
and/or, the firing conditions include: the temperature is 300-500 ℃; the time is 4-10 h.
18. A composite molecular sieve made by the method of any one of claims 6-17.
19. A hydroisomerization catalyst, wherein the catalyst comprises a support and an active component, said support comprising the composite molecular sieve of any one of claims 1-5 and 18.
20. The hydroisomerization catalyst of claim 19, wherein the active component is a noble metal.
21. The hydroisomerization catalyst of claim 20, wherein the noble metal is platinum and/or palladium.
22. A process for hydroisomerizing a fischer-tropsch synthesis oil comprising: hydroisomerization of the hydroisomerization catalyst according to any one of claims 19 to 21 with a fischer-tropsch synthesis oil under hydroisomerization conditions.
23. The process of claim 22, wherein the hydroisomerization reaction conditions comprise: the volume ratio of hydrogen to oil is 400-1000: 1, the temperature is 200-400 ℃, the pressure is 1-12 MPa, and the volume airspeed is 0.01-10 h -1 。
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