CN114534779B - Large-size spherical titanium silicalite catalyst and preparation method and application thereof - Google Patents
Large-size spherical titanium silicalite catalyst and preparation method and application thereof Download PDFInfo
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- CN114534779B CN114534779B CN202210108818.XA CN202210108818A CN114534779B CN 114534779 B CN114534779 B CN 114534779B CN 202210108818 A CN202210108818 A CN 202210108818A CN 114534779 B CN114534779 B CN 114534779B
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- titanium silicalite
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- acetylcholine
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- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- 239000010936 titanium Substances 0.000 title claims abstract description 80
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OIPILFWXSMYKGL-UHFFFAOYSA-N acetylcholine Chemical compound CC(=O)OCC[N+](C)(C)C OIPILFWXSMYKGL-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229960004373 acetylcholine Drugs 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 238000002425 crystallisation Methods 0.000 claims abstract description 32
- 230000008025 crystallization Effects 0.000 claims abstract description 27
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims description 29
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 28
- 238000006735 epoxidation reaction Methods 0.000 claims description 17
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical group [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 29
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 40
- 239000000243 solution Substances 0.000 description 31
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 30
- 239000010457 zeolite Substances 0.000 description 22
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 18
- 229910021536 Zeolite Inorganic materials 0.000 description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910008051 Si-OH Inorganic materials 0.000 description 5
- 229910006358 Si—OH Inorganic materials 0.000 description 5
- -1 TS-1 Chemical compound 0.000 description 5
- 229910003089 Ti–OH Inorganic materials 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 4
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 229960004295 valine Drugs 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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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
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/32—Spheres
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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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
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a large-size spherical titanium silicalite catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: adding acetylcholine into sol obtained by mixing and aging a silicon source, a titanium source, a template agent and a solvent, carrying out crystallization reaction under the assistance of water vapor, and carrying out aftertreatment and calcination on a crystallized product to obtain the titanium silicalite catalyst; the molar ratio of the silicon source to the acetylcholine is 1: (0.03-0.15). The large-size spherical titanium silicalite catalyst is prepared by adding a proper amount of acetylcholine in the synthesis process of a steam assisted crystallization method, so that the problems of low catalytic activity and difficult separation and recovery of the conventional titanium silicalite catalyst are solved, and the method has wide industrial application prospect.
Description
Technical Field
The invention relates to the technical field of zeolite catalysts, in particular to a large-size spherical titanium silicalite catalyst and a preparation method and application thereof.
Background
With the development of society and the enhancement of environmental protection consciousness, green chemical products are also more and more popularIs concerned with (1). Among them, epichlorohydrin (ECH) is an important chemical intermediate, mainly used for producing epoxy resin, chlorohydrin rubber, glycerin, and the like. In the current industrial production, the ECH production methods mainly include a chlorohydrin method and an allyl alcohol method, but the chlorohydrin method can produce a large amount of calcium chloride (CaCl) 2 ) The by-products and the wastewater containing halogen have serious environmental pollution, and the allyl alcohol method has complex process and high production cost. Thus, the production of ECH using green and environmentally friendly catalyst materials remains a challenge.
Titanium-containing zeolite (e.g., TS-1, ti-MCM-41, ti-SBA-15, ti-MCM-48, ti-TUD, ti-MWW) catalysts have been widely used in olefin epoxidation reactions. The TS-1 zeolite is a material with a three-dimensional framework structure and regular micropore channels, has high specific surface area, high adsorption capacity, adjustable adsorption performance, good hydrothermal stability and strong corrosion resistance, and can be used for a series of organic reactions, such as olefin epoxidation, aromatic hydrocarbon hydroxylation, ketone ammoximation, alcohol oxidation and the like.
TS-1 as a green catalytic material has been applied to a reaction system for producing ECH by catalyzing the epoxidation of chloropropene (ACH) with methanol as a solvent and hydrogen peroxide as a clean oxidant. The reaction system has the advantages of environmental friendliness, simplicity in operation, easiness in product separation, high selectivity and the like, is increasingly and widely focused by researchers, and becomes a hotspot in the current research field. However, the conventional TS-1 zeolite has a grain diameter of about 230nm, low catalytic activity and complex synthesis process. Harris et al (Harris J W, jeremy A, garrett M, et al, propylene oxide inhibits propylene epoxidation over Au/TS-1[ J ] Journal of Catalysis,2018, 365:105-114.) propose a method for increasing the catalytic oxidation activity of a small-sized TS-1 catalyst by decreasing the grain size of the TS-1 zeolite to increase the specific surface area of the catalyst, but the separation and recovery of the small-sized TS-1 catalyst are difficult, and are severely limited in industrial application.
Disclosure of Invention
The primary purpose of the invention is to overcome the problems of small particle size and low catalytic activity of the large-size catalyst of the existing titanium silicalite catalyst and provide a preparation method of the large-size spherical titanium silicalite catalyst. The titanium silicalite catalyst prepared by the method has large particle size (320 nm-3 mu m), high catalytic activity and good catalytic stability.
It is another object of the present invention to provide a large-sized spherical titanium silicalite catalyst prepared by the method.
It is another object of the present invention to provide the use of large-size spherical titanium silicalite catalysts.
It is a further object of the present invention to provide a process for preparing epichlorohydrin using large-size spherical titanium silicalite catalysts.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of a large-size spherical titanium silicalite catalyst comprises the following steps:
adding acetylcholine into sol obtained by mixing and aging a silicon source, a titanium source, a template agent and a solvent, carrying out crystallization reaction under the assistance of water vapor, and carrying out aftertreatment and calcination on a crystallized product to obtain a large-size spherical titanium silicalite catalyst; the molar ratio of the silicon source to the acetylcholine is 1: (0.03-0.15).
Through multiple experiments, the inventor finds that a certain amount of acetylcholine is added into sol obtained by mixing and aging a silicon source, a titanium source, a template agent and a solvent, quaternary ammonium groups in the acetylcholine can interact with Si-OH or Ti-OH groups in a zeolite crystallization system to promote the combination of the Si-OH or Ti-OH groups and zeolite crystal nucleus of the surface modified quaternary ammonium groups, so that the growth of TS-1 crystals is accelerated, the grain size of the TS-1 zeolite catalyst is increased, and on the other hand, the addition of a proper amount of acetylcholine can enable the prepared zeolite material to have higher framework structure crystallinity and better four-coordination framework Ti species, so that the catalytic activity of the zeolite catalyst is improved. When the acetylcholine is excessive, the high concentration acetylcholine can severely wrap the crystal nucleus, so that Si-OH or Ti-OH can not be combined with the crystal nucleus, and the Si-OH or Ti-OH in the system is unfavorable for growing on the surface of the crystal nucleus.
Silicon sources, titanium sources, templates, and solvents conventional in the art may be used in the present invention.
Typically, the silicon source is selected from one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, butyl orthosilicate, silica gel; the titanium source is selected from one or more of tetrabutyl titanate, tetraethyl titanate, tetraisopropyl titanate, titanium trichloride and titanium tetrachloride; the template agent is selected from tetrapropylammonium hydroxide and/or tetrapropylammonium bromide; the solvent is selected from isopropanol and/or ethanol.
Specifically, the preparation method of the large-size spherical titanium silicalite catalyst comprises the following steps:
s1, mixing a silicon source and an aqueous solution of a template agent to obtain a solution A, and adding the solution obtained by mixing a titanium source and a solvent into the solution A to obtain a solution B;
s2, adding acetylcholine into the sol obtained by ageing the solution B, transferring the sol into a beaker, placing the beaker in a crystallization kettle after a bracket is supported by the beaker, adding water into the bottom of the crystallization kettle, performing crystallization reaction, and performing post-treatment and calcination on a crystallized product to obtain a large-size spherical titanium silicalite catalyst; the molar ratio of the silicon source to the acetylcholine is 1: (0.03-0.15).
Preferably, the mass ratio of the silicon source to the water at the bottom of the crystallization kettle is 1: (0.5-2.5).
Preferably, the silicon source is selected from tetraethyl orthosilicate (TEOS); the titanium source is selected from tetrabutyl titanate (TBOT); the template is selected from tetrapropylammonium hydroxide (TPAOH); the solvent is selected from isopropyl alcohol (IPA).
More preferably, the solvent is selected from mixed solvents of isopropanol and water.
Preferably, the molar ratio of the silicon source to acetylcholine is 1: (0.05-0.12). When the molar ratio of the silicon source to the acetylcholine is 1: (0.05-0.12), the grain diameter of the zeolite catalyst is distributed between 540nm and 3 mu m.
More preferably, the molar ratio of the silicon source to acetylcholine is 1: (0.075-0.1). When the molar ratio of the silicon source to the acetylcholine is 1: when (0.075-0.1), the zeolite catalyst crystal grain size can be further increased, and the zeolite catalyst crystal grain size is distributed between 900nm and 3 μm.
Preferably, the molar ratio of the silicon source, the titanium source and the template agent is 1: (0.02-0.1): (0.2-0.5).
Preferably, the aging time is 30 to 180 minutes. During this aging time, the mixed system of silicon source, titanium source, templating agent and solvent can be fully hydrolyzed.
Preferably, the crystallization reaction temperature is 150-200 ℃ and the time is 9-72 h.
More preferably, the crystallization reaction temperature is 160-180 ℃ and the time is 12-24 hours.
Preferably, the calcination temperature is 400-650 ℃ and the time is 3-8 h.
More preferably, the calcination temperature is 550 ℃ and the time is 5 hours.
The post-treatment of the invention comprises centrifugation, washing and drying in sequence.
The invention also provides a large-size spherical titanium silicalite catalyst prepared by the method, and the grain diameter of the obtained zeolite catalyst is distributed between 320nm and 3 mu m.
The invention also provides application of the large-size spherical titanium silicalite catalyst in olefin epoxidation reaction.
Preferably, the olefin epoxidation reaction is the epoxidation of chloropropene to produce epichlorohydrin.
The invention also provides a preparation method of the epoxy chloropropane, which comprises the following steps:
mixing chloropropene, a large-size spherical titanium silicalite catalyst, hydrogen peroxide and a solvent, and stirring and reacting for 2-6 h at 50-70 ℃.
Preferably, the molar ratio of chloropropene to hydrogen peroxide is 2:3.
Preferably, the large-size spherical titanium silicalite catalyst is used in an amount of 6.5wt% based on the mass of chloropropene.
Compared with the prior art, the invention has the beneficial effects that:
the invention prepares the large-size spherical titanium silicalite catalyst by adding a proper amount of acetylcholine in the process of synthesizing the titanium silicalite catalyst by steam assisted crystallization. On one hand, the large-size catalyst is easy to separate and recycle, and is more convenient for industrial application; on the other hand, due to the addition of a proper amount of acetylcholine, the prepared zeolite material has higher crystallinity of a framework structure and better four-coordination framework Ti species, so that the catalytic activity and stability of the zeolite material when the zeolite material is applied to olefin epoxidation reaction are improved, and the zeolite material has wide application prospect.
Drawings
Fig. 1 is an SEM image of the large-sized spherical titanium silicalite catalyst according to example 1 and comparative examples 1 to 4, wherein fig. 1a corresponds to example 1, fig. 1b corresponds to example 2, fig. 1c corresponds to example 1, fig. 1d corresponds to comparative example 3, and fig. 1e corresponds to comparative example 4.
FIG. 2 is an SEM image of a large-sized spherical titanium silicalite catalyst TS-1#0.05ACh of example 2.
FIG. 3 is an SEM image of a large size spherical titanium silicalite catalyst TS-1#0.075ACh of example 3.
Fig. 4 is an XRD pattern of the large-sized spherical titanium silicalite catalyst described in example 1 and comparative examples 1 to 4.
FIG. 5 is N of large-sized spherical titanium silicalite catalysts according to example 1 and comparative examples 1 to 3 2 Physical adsorption takes place from the figure.
FIG. 6 is an ultraviolet-visible absorption spectrum of the large-sized spherical titanium silicalite catalyst of example 1 and comparative examples 1 to 3.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples for the purpose of illustration and not limitation, and various modifications may be made within the scope of the present invention as defined by the appended claims.
The main raw materials in examples and comparative examples are commercially available, and are specifically as follows:
tetrabutyl titanate, analytically pure, tianjin, miou chemical Co., ltd;
ethyl orthosilicate, analytically pure, tianjin, miou chemical Co., ltd;
tetrapropylammonium hydroxide, 25%, kente catalyst technology limited;
isopropyl alcohol, analytically pure, chemical company, inc.
Example 1
A preparation method of a large-size spherical titanium silicalite catalyst comprises the following steps:
63g (0.3 mol) of ethyl orthosilicate solution was added dropwise to a mixed solution of 59.6g of a 25% tetrapropylammonium hydroxide solution and 40g of deionized water to obtain a solution A, and then a solution obtained by mixing 2.58g of a tetrabutyl titanate solution and 31.6g of an isopropyl alcohol solution was added dropwise to the solution A to obtain a solution B (TEOS, TBOT, TPAOH, IPA and H 2 O molar ratio of 1:0.025:0.24:1.74:15.67), sol was obtained under vigorous stirring, 0.03mol of acetylcholine (molar ratio of ethyl orthosilicate to acetylcholine of 1:0.1) was added after aging for 30min, then transferred into a polytetrafluoroethylene beaker, the support was placed into a stainless steel crystallization kettle liner after supporting the beaker, 50g of distilled water was added to the inner substrate portion, after crystallization at 170 ℃ for 18h, the mixture solution was centrifuged, the obtained solid was washed to neutrality, then dried overnight at 120 ℃ in an oven, finally calcined at 550 ℃ for 5h in a muffle furnace, and the obtained catalyst was designated TS-1#0.1ACh.
Example 2
This example provides a method for preparing a large-size spherical titanium silicalite catalyst, which differs from example 1 in that 0.015mol of acetylcholine (molar ratio of ethyl orthosilicate to acetylcholine is 1:0.05) is added, and the catalyst obtained is designated as TS-1#0.05ACh.
Example 3
This example provides a method for preparing a large-size spherical titanium silicalite catalyst, which differs from example 1 in that 0.0225mol of acetylcholine (molar ratio of ethyl orthosilicate to acetylcholine is 1:0.075) is added, and the catalyst obtained is recorded as TS-1#0.075ACh.
Example 4
This example provides a method for preparing a large-size spherical titanium silicalite catalyst, which differs from example 1 in that 0.036mol of acetylcholine (molar ratio of ethyl orthosilicate to acetylcholine is 1:0.12) is added, and the catalyst obtained is recorded as TS-1#0.12ACh.
Example 5
This example provides a method for preparing a large-size spherical titanium silicalite catalyst, which differs from example 1 in that 0.045mol of acetylcholine (molar ratio of ethyl orthosilicate to acetylcholine is 1:0.15) is added, and the catalyst obtained is recorded as TS-1#0.15ACh.
Example 6
This example provides a method for preparing a large-size spherical titanium silicalite catalyst, which differs from example 1 in that 0.009mol of acetylcholine (molar ratio of ethyl orthosilicate to acetylcholine 1:0.03) is added, and the catalyst thus obtained is designated as TS-1#0.03ACh.
Example 7
This example provides a method for preparing a large-size spherical titanium silicalite catalyst, which differs from example 1 in that the crystallization reaction temperature is 150 ℃ and the crystallization reaction time is 72 hours.
Example 8
This example provides a method for preparing a large-size spherical titanium silicalite catalyst, which is different from example 1 in that the crystallization reaction temperature is 200 ℃ and the crystallization reaction time is 9 hours.
Example 9
This example provides a method for preparing a large-sized spherical titanium silicalite catalyst, which differs from example 1 in that the calcination temperature is 400℃and the calcination time is 8 hours.
Example 10
This example provides a method for preparing a large-sized spherical titanium silicalite catalyst, which differs from example 1 in that the calcination temperature is 650 deg.c and the calcination time is 3 hours.
Comparative example 1
The comparative example provides a method for preparing a spherical titanium silicalite catalyst, comprising the following steps:
63g (0.3 mol) of ethyl orthosilicate solution were added dropwise to a mixture of 59.6g of 25% tetrapropylammonium hydroxide solution and 40g of deionized water to give solution A, followed by 2.58g of tetrabutyl titanate solution and 31.6g of deionized waterThe solution obtained by mixing the isopropanol solution is added into the solution A in a dropwise manner to obtain a solution B (TEOS, TBOT, TPAOH, IPA and H) 2 O molar ratio is 1:0.025:0.24:1.74:15.67), obtaining sol under the condition of intense stirring, transferring the mixed solution into a stainless steel crystallization kettle with a polytetrafluoroethylene lining after aging for 2 hours, centrifugally washing the obtained mixture after crystallization for 18 hours at 170 ℃ to neutrality, drying the obtained solid overnight at 120 ℃, grinding the dried solid into powder, and calcining for 5 hours at 550 ℃ to obtain the nano-sized traditional TS-1 solid catalyst.
Comparative example 2
The comparative example provides a method for preparing a spherical titanium silicalite catalyst, comprising the following steps:
63g (0.3 mol) of ethyl orthosilicate solution was added dropwise to a mixed solution of 59.6g of a 25% tetrapropylammonium hydroxide solution and 40g of deionized water to obtain a solution A, and then a solution obtained by mixing 2.58g of a tetrabutyl titanate solution and 31.6g of an isopropyl alcohol solution was added dropwise to the solution A to obtain a solution B (TEOS, TBOT, TPAOH, IPA and H 2 O molar ratio is 1:0.025:0.24:1.74:15.67), obtaining sol under the condition of intense stirring, after aging for 2 hours, placing the synthesized sol into a baking oven at 70-90 ℃, drying the sol for 12-48 hours to obtain solid particles, grinding the solid particles into powder, placing the powder into a polytetrafluoroethylene beaker, placing the powder into a stainless steel crystallization kettle lining after supporting the beaker by a bracket, adding 50g of distilled water into an inner substrate part, centrifugally washing a mixture obtained after crystallization for 18 hours at 170 ℃, drying the obtained solid at 120 ℃ overnight, grinding the dried solid into powder, calcining the powder at 550 ℃ for 5 hours, and marking the obtained catalyst as TS-1#0ACh.
Comparative example 3
This comparative example provides a method for preparing a spherical titanium silicalite catalyst, which is different from example 1 in that 0.12mol of acetylcholine (molar ratio of ethyl orthosilicate to acetylcholine is 1:0.4) is added, and the obtained catalyst is recorded as TS-1#0.4ACh.
Comparative example 4
This comparative example provides a method for preparing a spherical titanium silicalite catalyst, which is different from example 1 in that L-valine is used instead of acetylcholine (molar ratio of ethyl orthosilicate to L-valine is 1:0.1), and the obtained catalyst is named as TS-1#0.1Val.
Characterization of
The large-sized spherical titanium silicalite catalysts prepared in examples 1 to 10 and comparative examples 1 to 4 were characterized as follows.
The samples were characterized by scanning electron microscopy (SUPRA model 55, karl Zeiss Co., germany) under high vacuum and an accelerating voltage of 5 kV.
SEM images of the large-sized spherical titanium silicalite catalysts of example 1 and comparative examples 1 to 4 are shown in fig. 1, in which fig. 1a corresponds to comparative example 1, fig. 1b corresponds to comparative example 2, fig. 1c corresponds to example 1, fig. 1d corresponds to comparative example 3, and fig. 1e corresponds to comparative example 4. As can be seen from FIG. 1a, the catalyst TS-1 of the comparative example is a spherical grain with a diameter of about 230nm, and FIG. 1c shows that the titanium silicalite (TS-1#0.1ACh) to which acetylcholine is added has a diameter of 3 μm and also exhibits spherical grains, indicating that the addition of acetylcholine does not change the morphology of the titanium silicalite grains. However, FIG. 1b shows that the catalyst TS-1#0ACh of comparative example 2 has a diameter of about 120nm, indicating that acetylcholine can promote crystal growth. As can be seen from FIG. 1d, the catalyst TS-1#0.4ACh of comparative example 4 has a particle diameter of about 50nm, which indicates that the acetylcholine concentration is high to severely wrap the crystal nucleus, and is unfavorable for the growth of Si-OH or Ti-OH on the surface of the crystal nucleus in the system.
SEM images of catalyst TS-1#0.05ACh of example 2 and catalyst TS-1#0.075ACh of example 3 are shown in FIGS. 2 and 3, respectively. As can be seen from FIGS. 2 and 3, the catalyst TS-1#0.05ACh of example 2 has a diameter of about 540nm, and the catalyst TS-1#0.075ACh of example 3 has a diameter of about 900nm. It should be noted that the catalyst grain sizes in examples 4 to 10 are distributed between 320nm and 3 μm, and will not be described here again.
The sample was subjected to crystal structure observation by using an X-ray diffractometer (RIGAKU Ultima IV diffractometer, japan Physics Co., ltd.) with a Cu target in a scanning range of 5 DEG to 70 DEG, a scanning step number of 0.02 DEG, a 40kV operating voltage, and a 40mA operating current.
The XRD patterns of the catalysts described in example 1 and comparative examples 1 to 4 are shown in FIG. 4. As is evident from FIG. 4, the TS-1#0ACh (comparative example 2) and TS-1#0ACh (example 1) catalysts have distinct diffraction peaks at 7.9, 8.8, 23.1, 23.9, and 24.4, which are consistent with the diffraction peaks of the conventional TS-1 zeolite (comparative example 1), indicating that the addition of acetylcholine did not disrupt the crystalline structure of the titanium silicalite. In addition, in the X-ray diffraction pattern, it was found that the crystallinity of TS-1 was up to 142% with the crystallinity of TS-1#0.1ACh of the conventional TS-1, which suggests that the addition of acetylcholine accelerates the crystallization of the titanium silicalite under the condition of water vapor-assisted crystallization, indicating that the present invention prepares a large-particle titanium silicalite catalyst with good crystallinity. TS-1#0.4ACh (comparative example 3) and TS-1#0.1Val (comparative example 4) have no distinct characteristic peaks and therefore do not have MFI topology. The catalysts described in examples 2 to 10 have distinct characteristic peaks, and are not described in detail.
The catalysts described in example 1 and comparative examples 1 to 3 were placed on a Micromeritics ASAP2020 adsorber (America Michael company), pretreated with liquid nitrogen at-196℃and degassed at 200℃for 10 hours, and the samples were observed for N 2 Physical adsorption and desorption conditions in (3), N 2 The physical adsorption drawing is shown in fig. 5. As can be seen from FIG. 5, TS-1#0.1ACh has an adsorption and desorption curve similar to that of conventional TS-1, which indicates that TS-1#0.1ACh and TS-1 are microporous materials, but the smaller hysteresis loop shown in the figure is caused by pores formed by stacking catalyst grains. However, TS-1#0ACh and TS-1#0ACh exhibit similar adsorption and desorption curves, because the particles are relatively small, so that the inter-grain packing forms larger pores.
N of the catalysts described in examples 2 to 10 2 The physical adsorption and desorption curves are similar to those of example 1, and will not be described again.
The catalysts described in example 1 and comparative examples 1-3, respectively, were placed on a Shimadzu UV-3600 spectrometer using BaSO 4 As a background standard, a 200-600nm ultraviolet visible diffuse reflectance (UV-vis) spectrum was recorded, and an ultraviolet visible absorption spectrum is shown in FIG. 6.
As can be seen from the UV-visible absorption spectrum of FIG. 6, all zeolites (conventional TS-1, TS-1#0ACh, TS-1#0.1ACh and TS-1#0.4ACh) have similar absorption peaks at 210nm, which is attributed to tetra-coordinated framework titanium, indicating that all zeolites possess framework titanium structure, and TS-1#0.1ACh catalysts have stronger absorption peaks at 210nm and more stable structure, while conventional TS-1 zeolites have weaker absorption peaks at 330nm, demonstrating the presence of non-framework titanium, indicating that the use of steam-assisted crystallization method is more conducive to the formation of tetra-coordinated framework titanium. The ultraviolet-visible absorption spectrum of the catalysts described in examples 2 to 10 is similar to that of the catalyst described in example 1, and will not be described again.
Catalytic Activity test
The catalysts described in examples 1-3 and comparative examples 1-3 were used to catalyze epoxidation of chloropropene to prepare epichlorohydrin, respectively, by the following method:
1.53g of chloropropene and 20mL of methanol are weighed, and are added into a 25mL two-port bottle, 0.1g of the catalyst is added into the two-port bottle, the two-port bottle is placed in an oil bath at 70 ℃ for continuous stirring reaction for 4 hours, after the reaction is finished, the reaction liquid is taken out, transferred into a centrifugal machine, centrifuged for 4 minutes at 10000rpm, and the supernatant is taken for gas chromatography analysis.
The calculation method of the chloropropene conversion rate is as follows:
wherein X is ACH (%) is chloropropene conversion, n 0 ACH And n ACH Is the initial and final molar content of chloropropene.
The method for calculating the selectivity of the epichlorohydrin comprises the following steps:
wherein S is ECH (%) is the selectivity of epoxy chloropropane, n 0 ACH And n ACH Is the initial and final molar content of chloropropene, n ECH Is the molar content of epichlorohydrin.
The catalysts described in examples 1-3 and comparative examples 1-3 catalyze the epoxidation of chloropropene to produce epichlorohydrin, and the conversion of chloropropene and the selectivity of epichlorohydrin are shown in Table 1.
TABLE 1 chloropropene conversion and epichlorohydrin selectivity
| Conversion of chloropropene | Epichlorohydrin selectivity | |
| Example 1 | 92.30％ | 86.07％ |
| Example 2 | 88.52％ | 88.57％ |
| Example 3 | 91.97％ | 84.58％ |
| Comparative example 1 | 69.79％ | 86.48％ |
| Comparative example 2 | 71.98％ | 87.48％ |
| Comparative example 3 | 0 | 0 |
From the results of table 1, it is apparent that adding an appropriate amount of acetylcholine during the preparation of the titanium silicalite catalyst by the steam-assisted crystallization method can increase the catalytic activity of the catalyst for the epoxidation of chloropropene to prepare epichlorohydrin, and as the addition amount of acetylcholine increases, the catalytic activity of the catalyst also increases and decreases, since adding an appropriate amount of acetylcholine accelerates the crystallization of titanium silicalite and promotes the growth of titanium silicalite into large particles, while adding an excessive amount of acetylcholine (comparative example 3), high concentration of acetylcholine hinders the formation of MFI structure during the crystallization of titanium silicalite, even leads to the formation of MFI topology, thereby resulting in no catalytic activity. Wherein the chloropropene conversion reached a maximum of 92.3% at an acetylcholine addition of 0.03mol (example 1), which is about 1.3 times the catalytic activity of conventional TS-1 (comparative example 1), and which is also higher than the catalytic activity of the catalyst prepared by the conventional steam-assisted crystallization method (comparative example 2).
The catalysts described in examples 4 to 10 were also higher in catalytic activity than the conventional TS-1 catalyst and the catalyst prepared by the conventional steam assisted crystallization method (comparative example 2).
Catalytic stability test
Taking the reaction of catalyzing epoxidation of chloropropene to prepare epichlorohydrin by using the catalyst TS-1#0.1ACh as an example, testing the stability of the catalyst in the reaction of catalyzing epoxidation of chloropropene to prepare epichlorohydrin, repeatedly using the TS-1#0.1ACh catalyst in the reaction of preparing epichlorohydrin by epoxidation of chloropropene for five times during testing, cleaning with n-hexane after each use, and testing the catalytic activity after using five times and calcining once. The specific operation method of each reaction is as follows:
1.53g of chloropropene is weighed, 20mL of methanol is measured, the chloropropene and the methanol are added into a 25mL two-port bottle, 0.1g of TS-1#0.1ACh catalyst is added into the two-port bottle, the two-port bottle is placed in an oil bath at 70 ℃ for continuous stirring reaction for 4 hours, after the reaction is finished, the reaction liquid is taken out, the reaction liquid is transferred into a centrifugal machine, the centrifugal machine is centrifuged for 4 minutes at 10000rpm, and the supernatant liquid is taken for gas chromatography analysis.
The test result shows that the conversion rate of the propylene oxide is 92.3% and the selectivity of the epichlorohydrin is 86.07% in the first reaction; the conversion rate of chloropropene is 78.96% and the selectivity of epichlorohydrin is 86.85% in the second reaction; the conversion rate of chloropropene is 72.76% and the selectivity of epichlorohydrin is 89.8% in the third reaction; the conversion rate of chloropropene is 71.26 percent, and the selectivity of epichlorohydrin is 89.62 percent; the fifth reaction gave a chloropropene conversion of 68.07% and a epichlorohydrin selectivity of 90.34%. The catalyst was calcined and used in the reaction to give a chloropropene conversion of 93.081% and an epichlorohydrin selectivity of 87.50%.
From the above data, it can be seen that the TS-1#0.1ACh catalyst is stable after the epoxidation conversion rate is reduced to about 70% after repeating the reaction for five times after simple washing by an organic solvent in the reaction of preparing epichlorohydrin by catalyzing chloropropene epoxidation, which shows that the catalyst has good catalytic stability and can completely recover the catalytic activity after calcination.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (7)
1. The application of the large-size spherical titanium silicalite catalyst in olefin epoxidation reaction is characterized in that the large-size spherical titanium silicalite catalyst is prepared by the following preparation method:
adding acetylcholine into sol obtained by mixing and aging a silicon source, a titanium source, a template agent and a solvent, carrying out crystallization reaction under the assistance of water vapor, and carrying out aftertreatment and calcination on a crystallized product to obtain a large-size spherical titanium silicalite catalyst; the molar ratio of the silicon source to the acetylcholine is 1: (0.05-0.12);
the template agent is selected from tetrapropylammonium hydroxide and/or tetrapropylammonium bromide; the grain diameter of the large-size spherical titanium silicalite catalyst is 540 nm-3 mu m.
2. The use according to claim 1, wherein the molar ratio of silicon source to acetylcholine is 1: (0.075 to 0.1).
3. The use according to claim 1, wherein the molar ratio of the silicon source, the titanium source and the template agent is 1 (0.02-0.1): (0.2 to 0.5).
4. The use according to claim 1, wherein the aging time is 30-180 min.
5. The use according to claim 1, wherein the crystallization reaction temperature is 150-200 ℃ and the time is 9-72 h.
6. The use according to claim 1, wherein the calcination temperature is 400-650 ℃ and the time is 3-8 hours.
7. The preparation method of the epichlorohydrin is characterized by comprising the following steps:
mixing chloropropene, a large-size spherical titanium silicalite catalyst, hydrogen peroxide and a solvent, and stirring at 50-70 ℃ for reaction for 2-6 hours;
the large-size spherical titanium silicalite catalyst is prepared by the following preparation method:
adding acetylcholine into sol obtained by mixing and aging a silicon source, a titanium source, a template agent and a solvent, carrying out crystallization reaction under the assistance of water vapor, and carrying out aftertreatment and calcination on a crystallized product to obtain a large-size spherical titanium silicalite catalyst; the molar ratio of the silicon source to the acetylcholine is 1: (0.05-0.12);
the template agent is selected from tetrapropylammonium hydroxide and/or tetrapropylammonium bromide; the grain diameter of the large-size spherical titanium silicalite catalyst is 540 nm-3 mu m.
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