CN116332200A - Titanium silicon molecular sieve, preparation method thereof, method for preparing cyclohexanone oxime and method for preparing caprolactone - Google Patents
Titanium silicon molecular sieve, preparation method thereof, method for preparing cyclohexanone oxime and method for preparing caprolactone Download PDFInfo
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- CN116332200A CN116332200A CN202111579946.4A CN202111579946A CN116332200A CN 116332200 A CN116332200 A CN 116332200A CN 202111579946 A CN202111579946 A CN 202111579946A CN 116332200 A CN116332200 A CN 116332200A
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- titanium
- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 84
- 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 84
- 238000000034 method Methods 0.000 title claims abstract description 53
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 title claims abstract description 34
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract description 22
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 100
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 91
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 89
- 239000010936 titanium Substances 0.000 claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 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 22
- 239000010703 silicon Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000005216 hydrothermal crystallization Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 11
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 6
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 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
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- -1 aliphatic alcohol amine Chemical class 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 238000002444 silanisation Methods 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000006220 Baeyer-Villiger oxidation reaction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000010812 external standard method Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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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
- C01B39/085—Group IVB- metallosilicates
-
- 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
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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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
- C07D313/02—Seven-membered rings
- C07D313/04—Seven-membered rings not condensed with other rings
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- 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
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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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
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Abstract
The invention relates to the technical field of cyclohexanone catalytic oxidation, in particular to a titanium-silicon molecular sieve, a preparation method thereof, a method for preparing cyclohexanone oxime and a method for preparing caprolactone, wherein the method comprises the following steps: (1) Uniformly mixing a silicon source, an alkaline template agent, a titanium source and water to obtain titanium silicasol; (2) Adding a silanization reagent into the titanium silicasol, and carrying out hydrothermal crystallization and roasting on the obtained mixture. According to the invention, the titanium silicasol precursor is treated by the specific silanization reagent, so that the prepared titanium silicasol molecular sieve has high catalytic activity when being applied to catalytic oxidation of cyclohexanone and cyclohexanone ammoximation reaction, and the conversion rate of cyclohexanone can be improved to more than 91%.
Description
Technical Field
The invention relates to the technical field of cyclohexanone catalytic oxidation and ammoximation, in particular to a titanium-silicon molecular sieve, a preparation method thereof, a method for preparing cyclohexanone oxime and a method for preparing caprolactone.
Background
Fine chemicals are widely focused by researchers in the chemical industry because of the advantages of high added value of products, wide application fields and the like. And with the rapid development of society, the demand for fine chemicals has increased. Among them, caprolactone is an important intermediate in organic chemical industry, and its production and development have undergone a long research period. Caprolactone, colorless liquid, has aromatic smell, is easily dissolved in water, ethanol, benzene, etc. and is insoluble in petroleum ether. The degradable plastic prepared from caprolactone has good biocompatibility and degradability, has wide application prospect in the fields of biological medicines, plastic tableware, mulching film materials and the like, and meets the current green development requirement. Caprolactone can also be used as a synthetic raw material for automotive primers, adhesives, cast elastomers, etc. In addition, cyclohexanone oxime is a white prismatic crystal, is dissolved in solvents such as water, ethanol, methanol and the like, and is an intermediate for producing caprolactam.
At present, caprolactone can be prepared by Baeyer-Villiger oxidation, hexanediol dehydrogenation and 6-hydroxycaproic acid intramolecular condensation. The Baeyer-Villiger oxidation process of cyclohexanone and peroxycarboxylic acid is mainly adopted in industry to prepare caprolactone. However, the use of peroxyacids as oxidizing agents and catalysts has a number of disadvantages: a large amount of organic carboxylic acid waste is generated, and the environmental pollution is serious; the product is difficult to purify and separate, and the atom economy is poor; the organic peroxyacid is produced by using high-concentration hydrogen peroxide, the property is unstable, and the risk in the transportation process is high. Therefore, researchers use hydrogen peroxide as an oxidizing agent instead of peroxy acid. When the hydrogen peroxide participates in the reaction, the byproduct is only water, and the utilization rate of the active oxygen is high. The hydrogen peroxide oxidant and the titanium-silicon molecular sieve catalyst can form an excellent Ti-OOH catalytic oxidation system.
The conventional industrial production of cyclohexanone oxime adopts a hydroxylamine method, and the process requires hydroxylamine and a large amount of sulfuric acid, which results in serious environmental pollution. Researchers at home and abroad have made a great deal of research work for improving the process, and have found that the titanium-silicon molecular sieve catalyzed cyclohexanone to prepare cyclohexanone oxime has the advantages of mild reaction conditions, few byproducts and the like. The titanium-silicon molecular sieve is a molecular sieve formed by substituting silicon atoms with a small part of titanium atoms to enter a tetrahedral framework structure. Wherein, the skeleton titanium atom is taken as a catalytic active center and plays a critical role in catalytic reaction.
CN107840344a discloses a titanium-silicon molecular sieve, a preparation method and application thereof, and mesoporous pore canals with a certain proportion can be introduced into the titanium-silicon molecular sieve through treatment of a silanization reagent, but the introduction of the mesoporous pore canals can cause loss of part of active centers of skeleton titanium atoms, thereby affecting the activity of cyclohexanone catalytic oxidation.
Disclosure of Invention
The invention aims to improve the catalytic performance of a titanium silicalite molecular sieve in the catalysis of cyclohexanone reaction and ammoximation, and provides a titanium silicalite molecular sieve, a preparation method thereof, a method for preparing cyclohexanone oxime and a method for preparing caprolactone.
To achieve the above object, a first aspect of the present invention provides a method for preparing a titanium silicalite molecular sieve, the method comprising:
(1) Uniformly mixing a silicon source, an alkaline template agent, a titanium source and water to obtain titanium silicasol;
(2) Adding a compound shown in a formula (I) into the titanium silicasol, and carrying out hydrothermal crystallization and roasting on the obtained mixture;
wherein i is an integer of 1 to 10; r is R 1 、R 2 And R is 3 Each independently selected from C 1 -C 6 Alkyl of R 4 Selected from C 1 -C 6 Alkyl or hydrogen.
In a second aspect, the invention provides a titanium silicalite molecular sieve prepared according to the method of the first aspect.
In a third aspect, the present invention provides a process for preparing cyclohexanone oxime, the process comprising: the cyclohexanone, alcohol, ammonia and hydrogen peroxide are contacted to react in the presence of a catalyst comprising the titanium silicalite molecular sieve of the second aspect.
In a fourth aspect, the present invention provides a process for preparing caprolactone, the process comprising: cyclohexanone, alcohol and hydrogen peroxide are contacted in the presence of a catalyst comprising the titanium silicalite molecular sieve of the second aspect.
According to the technical scheme, the titanium silicasol precursor is treated by the specific silanization reagent, so that the prepared titanium silicasol molecular sieve has high catalytic activity when being applied to the catalytic oxidation of cyclohexanone, and the conversion rate of cyclohexanone can be improved to more than 91%.
Drawings
FIG. 1 is an XRD pattern of a titanium silicalite molecular sieve obtained in example 1 of the present invention;
FIG. 2 is a UV-Vis spectrum of a titanium silicalite molecular sieve obtained in example 1 of the present invention;
FIG. 3 is a TEM image of a titanium silicalite molecular sieve obtained in example 1 of the present invention;
FIG. 4 is an XRD pattern of the titanium silicalite molecular sieve obtained in comparative example 1;
FIG. 5 is an XRD pattern of a titanium silicalite molecular sieve obtained in example 21 of the present invention;
FIG. 6 is a UV-Vis spectrum of a titanium silicalite molecular sieve obtained in example 21 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.
As previously described, a first aspect of the present invention provides a process for preparing a titanium silicalite molecular sieve, the process comprising:
(1) Uniformly mixing a silicon source, an alkaline template agent, a titanium source and water to obtain titanium silicasol;
(2) Adding a compound shown in a formula (I) into the titanium silicasol, and carrying out hydrothermal crystallization and roasting on the obtained mixture;
wherein i is an integer of 1 to 10; r is R 1 、R 2 And R is 3 Each independently selected from C 1 -C 6 Alkyl of R 4 Selected from C 1 -C 6 Alkyl or hydrogen.
In the invention, C 1 -C 6 The alkyl group of (a) means an alkyl group having 1 to 6 carbon atoms in total, and may be, for example, one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl and n-hexyl.
In some preferred embodiments of the invention i is an integer from 1 to 5, which may be 1, 2, 3, 4 or 5, for example.
In some preferred embodiments of the invention, R 1 、R 2 And R is 3 Each independently selected from C 1 -C 3 Alkyl group of said C 1 -C 3 The alkyl group of (a) may be methyl, ethyl, n-propyl or isopropyl, preferably R 1 、R 2 And R is 3 Each independently selected from methyl, ethyl or n-propyl. In the present invention, R 1 、R 2 And R is 3 May be the same or different, and R is preferably selected from 1 、R 2 And R is 3 All the same.
According to the invention, R is preferably 4 Selected from one of hydrogen, methyl, ethyl or n-propyl.
In the present invention, the amino-linked outer terminal single-chain alkyl group (R 4 ) The flexible acting force of the titanium silicalite molecular sieve can ensure that the prepared titanium silicalite molecular sieve has a full microporous structure, and simultaneously can also obviously increase the micropore volume and the specific surface area of the titanium silicalite molecular sieve.
According to the invention, too high an amount of silylating agent (compound represented by formula (I)) can result in poor crystallization properties of the titanium silicasol, and the framework structure of the molecular sieve contains more defects; the use level of the silylation reagent (the compound shown in the formula (I)) is too low, so that the specific surface area of the obtained titanium-silicon molecular sieve can be reduced, and the activity of catalyzing cyclohexanone is affected; preferably, in step (1), the silicon source is selected from the group consisting of SiO 2 The molar ratio of the silicon source to the compound represented by formula (I) is 1: (0.01-0.3), preferably 1: (0.01-0.2); more preferably 1: (0.05-0.2).
In some preferred embodiments of the invention, the silicon source is in the form of SiO 2 Calculated by N when the alkaline template agent contains nitrogen element, and calculated by OH when the alkaline template agent does not contain nitrogen element - The molar ratio of the silicon source to the alkaline template to the water is 1: (0.05-0.4): (5-40); preferably 1: (0.1-0.3): (5-25).
According to the present invention, preferably, the silicon source is at least one selected from the group consisting of tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate, tetrabutyl silicate, silica gel, white carbon black, and silica sol;
according to the present invention, preferably, the basic template is at least one selected from the group consisting of quaternary ammonium base, aliphatic amine and aliphatic alcohol amine, preferably at least one selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide;
in some preferred embodiments of the invention, the silicon source is in the form of SiO 2 The titanium source is calculated as TiO 2 A gauge, the silicon source and the titanium sourceThe molar ratio of (2) is 1: (0.001-0.04), preferably 1: (0.005-0.025).
According to the present invention, preferably, the titanium source is selected from an organic titanium source and/or an inorganic titanium source; further preferably, the titanium source is selected from at least one of titanium tetrachloride, titanium sulfate, titanium nitrate, tetraethyl titanate, tetrapropyl titanate, and tetrabutyl titanate.
In a preferred embodiment of the present invention, step (1) further comprises: mixing a silicon source, an alkaline template agent and water, stirring for 0.1-2h at room temperature, adding a titanium source in the stirring process, and stirring for 0.5-6h to obtain the titanium silicasol. Preferably, the second stirring time is 0.5-3h.
According to the present invention, preferably, step (1) further comprises: alcohol is removed after the mixing; alcohol removal can remove alcohol generated by hydrolysis of a silicon source and a titanium source, in the invention, the alcohol generated in a system is preferably removed by adopting an azeotropic distillation mode, and meanwhile, water lost by azeotropic distillation is supplemented in the alcohol removal process, so that the proportion of each substance in the titanium silicasol is ensured to meet the requirements; preferably, the alcohol expelling conditions include: the temperature is 30-100 ℃ and the time is 2-10h; more preferably: the temperature is 40-90 ℃ and the time is 4-10h.
According to the present invention, in order to enable the silylating agent (the compound represented by formula (I)) to be uniformly dispersed in the titanium silicasol, the step (1) preferably further comprises: the compound shown in the formula (I) is added into the titanium silicasol for third stirring for 0.1-24h, preferably for 0.5-10h, and more preferably for 0.5-5h.
The inventor of the present invention found that too long a hydrothermal time would increase the crystallinity of the molecular sieve, but the specific surface area of the molecular sieve would decrease; too short hydrothermal time can result in imperfect growth of the framework structure of the molecular sieve. In some preferred embodiments of the present invention, in step (2), the conditions for hydrothermal crystallization include: heating the mixture to 50-200 ℃ within 0.1-1h, and crystallizing at 50-200 ℃ for 10-100h; preferably crystallization is carried out at a temperature of 100-200 ℃ for 20-80 hours; more preferably, the conditions for hydrothermal crystallization include: the temperature is 120-180 ℃ and the time is 20-80h; under the above preferred conditions, the specific surface area and pore volume of the molecular sieve can be balanced; the molecular sieve with good crystallization, specific surface area and pore volume is prepared.
The pressure of the hydrothermal crystallization is not particularly limited, and may be the autogenous pressure of the crystallization system.
According to the present invention, preferably, the method further comprises: washing, filtering and drying a product obtained by hydrothermal crystallization; wherein the washing, filtering and drying processes may be known to those skilled in the art, respectively. Illustratively, the temperature of the washing may be 20-50 ℃, the solvent for washing may be water, and the amount of the solvent for washing is 1-20 times the mass of the crystallized product; the drying conditions may be: the temperature is 40-150 ℃ and the time is 0.5-24h.
In some preferred embodiments of the invention, the firing conditions include: the temperature is 400-800 ℃ and the time is 1-15h; preferably 500-600deg.C for 4-10 hr.
In a second aspect, the invention provides a titanium silicalite molecular sieve prepared according to the method of the first aspect.
According to the invention, under the preferred condition, the pore diameter of the titanium silicalite molecular sieve is 0.5-0.6nm; specific surface area of 550-650m 2 /g; the micropore volume is 0.2-0.3cm 3 /g。
In the invention, the titanium silicon molecular sieve can be used as a catalyst for cyclohexanone reaction, such as catalyzing cyclohexanone Baeyer-Villiger reaction to prepare caprolactone and cyclohexanone ammoximation reaction to prepare cyclohexanone oxime.
In a third aspect, the present invention provides a process for preparing caprolactone, the process comprising: contacting cyclohexanone, alcohol and hydrogen peroxide in the presence of a catalyst comprising the titanium silicalite molecular sieve of the second aspect; preferably, the reaction conditions include: the molar ratio of titanium silicon molecular sieve, cyclohexanone and alcohol is 1: (10-30): (50-150); preferably, the reaction conditions further comprise: the temperature is 30-120 ℃ and the time is 2-8h.
In accordance with the present invention,preferably, the alcohol is selected from C 1 -C 6 Preferably at least one of methanol, ethanol and t-butanol.
According to a fourth aspect of the present invention, there is provided a process for preparing cyclohexanone oxime, the process comprising: the cyclohexanone, alcohol, ammonia and hydrogen peroxide are contacted to react in the presence of a catalyst comprising the titanium silicalite molecular sieve of the second aspect.
According to the present invention, preferably, the reaction conditions include: the weight ratio of the titanium silicon molecular sieve to the alcohol to the ammonia water is 1: (10-30): (10-30); the volume ratio of the cyclohexanone to the alcohol is 1 (1-5); further preferably, the reaction conditions further include: the temperature is 30-120 ℃ and the time is 2-8h; more preferably, the alcohol is selected from C 1 -C 6 Preferably at least one of methanol, ethanol and t-butanol.
In the invention, the catalyst can be a full molecular sieve and also can comprise a carrier; when the titanium silicon molecular sieve particles are used for catalyzing and oxidizing cyclohexanone and cyclohexanone ammoximation reaction, the titanium silicon molecular sieve particles are directly used as a catalyst.
According to a particularly preferred embodiment of the present invention, the method for preparing a titanium silicalite molecular sieve comprises:
(1) The silicon source, the alkaline template agent and water are mixed according to the mole ratio of 1: (0.1-0.3): (5-25), mixing, performing first stirring at room temperature for 0.1-2h, adding a titanium source in the stirring process, and performing second stirring for 0.5-3h to obtain a mixed system; wherein the molar ratio of the silicon source to the titanium source is 1: (0.005-0.025);
then alcohol is removed from the mixed system to obtain titanium silicasol; the alcohol expelling temperature is 40-90 ℃ and the time is 4-10h;
(2) Adding a compound shown in a formula (I) into the titanium silicasol, carrying out third stirring for 1-3h, and carrying out hydrothermal crystallization and roasting on the obtained mixture; wherein the molar ratio of the silicon source to the compound represented by formula (I) is 1: (0.05-0.2), the crystallization conditions are: heating the mixture to 150-180 ℃ within 0.1-1h, and then carrying out hydrothermal crystallization for 20-70h at 150-180 ℃;
wherein i is an integer of 1 to 10; r is R 1 、R 2 And R is 3 Selected from methyl, ethyl, n-propyl or isopropyl, n-butyl, R 4 Selected from hydrogen, methyl, ethyl, n-propyl or isopropyl.
The present invention will be described in detail by examples. In the examples below, room temperature is 25.+ -. 5 ℃.
In the following examples and comparative examples, X-ray diffraction (XRD) pattern measurement of the samples was performed on a Siemens D5005 type X-ray diffractometer with a Cu ka tube voltage of 40kV, a tube current of 40mA, a scanning speed of 0.5 °/min, and a scanning range of 2θ=5 ° -35 °; the ultraviolet-visible spectrum diagram (UV-Vis) of the sample is obtained by testing an Agilent Cary 300 ultraviolet spectrophotometer, the wavelength interval is 3nm, and the scanning range is 190-800nm;
specific surface area was measured for static N of the sample at liquid nitrogen temperature (77.4K) using an ASAP2405J static nitrogen adsorber from Micromeritics 2 After the absorption and desorption curve, P/P 0 Adsorption curves in the range of=0.05-0.35 were BET fitted;
pore volume was measured according to the method described in RIPP 151-90 in petrochemical analysis method (first edition, published by scientific Press 1990, 9) written by Yang Cuiding et al;
the pore size distribution is calculated according to the BJH formula;
the particle size was determined by JEOL JEM-2100 Transmission Electron Microscope (TEM).
In the following examples, the silylating agents used are shown in table 1; among them, compounds 1 to 6 are all commercially available.
TABLE 1
Example 1
(1) Stirring tetrapropyl silicate, tetrapropyl ammonium hydroxide and water for 0.5h at room temperature, adding tetraethyl titanate in the stirring process, and stirring for 1h for the second time to obtain a mixed system; wherein, tetrapropyl silicate is prepared by SiO 2 Tetrapropylammonium hydroxide in N and tetraethyltitanate in TiO 2 The molar ratio of tetrapropyl silicate, tetrapropyl ammonium hydroxide, water and tetraethyl titanate is 1:0.25:10:0.02
Then alcohol expelling is carried out on the mixed system for 5 hours at the temperature of 80 ℃ to obtain titanium silicasol;
(2) Adding the compound (1) into titanium silicasol, and carrying out third stirring at room temperature for 1h to obtain a mixture, wherein the molar ratio of the compound (1) to tetrapropyl silicate is 0.12:1;
(3) Heating the mixture to 180 ℃ for 0.8h, and performing hydrothermal crystallization for 60h at 180 ℃ to obtain a crystallized product;
sequentially leaching the crystallized product with water, filtering, and drying at 120 ℃ for 2 hours;
roasting the dried product at 550 ℃ for 6 hours to obtain a titanium-silicon molecular sieve;
the XRD spectrum of the titanium silicalite molecular sieve obtained in this example is shown in FIG. 1, the UV-Vis spectrum is shown in FIG. 2, the TEM spectrum is shown in FIG. 3, and the physical properties and catalytic performance are shown in Table 3. In fig. 1, it can be seen that the titanium silicalite molecular sieve prepared in this example has an MFI structure; FIG. 2 illustrates that the titanium silicalite molecular sieve prepared in this example has framework titanium active centers; as can be seen from FIG. 3, the particle size of the titanium silicalite molecular sieve prepared in this example is about 100-200nm.
Examples 2 to 20
Titanium silicalite molecular sieves were prepared according to the procedure of example 1, the proportions and synthesis conditions of which are shown in Table 2, and the physical properties and catalytic properties of the molecular sieves prepared are shown in Table 3.
Comparative example 1
The titanium-silicon molecular sieve is prepared according to the method for preparing the titanium-silicon micro-mesoporous molecular sieve composite material disclosed in Zeolite, 1992, vol.12, pages 943-950, and the specific method is as follows:
22.5g of tetraethyl silicate, 7.0g of tetrapropylammonium hydroxide and 59.8g of deionized water were mixed well and hydrolyzed at 60℃for 1.0h. Then, a solution of 1.1g of tetrabutyl titanate and 5.0g of isopropyl alcohol was slowly dropped into the above solution under vigorous stirring, and the mixture was stirred at 75℃for 3 hours to give a clear and transparent colloid. And transferring the colloid into a stainless steel closed reaction kettle, and crystallizing at the constant temperature of 170 ℃ for 72 hours to obtain the conventional TS-1 molecular sieve. The XRD analysis spectrum is shown in FIG. 4.
Comparative examples 2 to 6
Titanium silicalite molecular sieves were prepared according to the procedure of example 1, the proportions and synthesis conditions of which are shown in Table 2, and the physical properties and catalytic properties of the molecular sieves prepared are shown in Table 3.
Comparative example 7
Titanium silicalite molecular sieves were prepared as in example 1 except that the silylating agent (compound 7) had a molecular structural formula shown in formula (II); the physical properties of the molecular sieve are shown in Table 3;
comparative example 8
Titanium silicalite molecular sieves were prepared as in example 1 except that the silylating agent was N-phenyl-3-aminopropyl trimethoxysilane (compound 8) having the structural formula shown in formula (III) and the physical properties of the molecular sieves prepared were as shown in table 3;
test example 1
This test example demonstrates the reaction effect of the molecular sieves prepared in examples 1-20 and comparative examples 1-8 provided herein for catalyzing the Baeyer-Villiger reaction of cyclohexanone to caprolactone. The reagents used in this test example were all commercially available chemically pure reagents. The concentration of each substance after the reaction was quantitatively analyzed by gas chromatography. 6890 type gas chromatograph manufactured by Agilent company is used; the analytical chromatographic column used was an FFAP column. The concentration of the components is quantified by an external standard method. Firstly, measuring the peak area of each component, searching the concentration of the component through a standard working curve, and calculating each index.
In the test examples, cyclohexanone conversion and caprolactone selectivity were calculated according to the following formulas, respectively:
cyclohexanone conversion% = (moles of cyclohexanone remaining after 1-reaction/moles of cyclohexanone charged before reaction) ×100%
Caprolactone selectivity% = moles of caprolactone after reaction/(moles of cyclohexanone charged before reaction-moles of cyclohexanone remaining after reaction) ×100%
The titanium silicalite molecular sieves prepared in examples 1-20 and comparative examples 1-8 were added to a three-necked flask reaction vessel containing cyclohexanone and methanol, respectively, wherein the molar ratio of titanium silicalite molecular sieve, cyclohexanone, methanol was 1:20:100. After the temperature is stabilized to a set value, adding hydrogen peroxide (concentration of 30 wt.%), cyclohexanone and hydrogen peroxide (H) 2 O 2 ) The molar ratio of (2) is 1:1. The experiment was stopped after 3 hours at 70℃and 0.1MPa (normal pressure), the catalyst was removed by filtration, and the sample was taken for chromatographic analysis, and the reaction results are shown in Table 3.
TABLE 3 Table 3
As can be seen from Table 3, the titanium silicalite molecular sieve obtained in the examples of the present invention has high cyclohexanone Baeyer-Villiger reactivity, wherein the conversion rate of cyclohexanone is up to 98%, and the selectivity of caprolactone is up to 98%.
Example 21
(1) Tetrabutyl silicate and tetrabutyl hydrogen are treatedThe method comprises the steps of (1) carrying out first stirring on ammonium oxide and water for 0.5h at room temperature, adding titanium tetrachloride in the stirring process, and carrying out second stirring for 0.5h to obtain a mixed system; wherein, tetrabutyl silicate is prepared by SiO 2 Tetrabutylammonium hydroxide in N, titanium tetrachloride in TiO 2 The molar ratio of tetrabutyl silicate, tetrabutyl ammonium hydroxide, water and titanium tetrachloride is 1:0.1:15:0.005;
then alcohol expelling is carried out on the mixed system at 80 ℃ for 6 hours to obtain titanium silicasol;
(2) Adding the compound (4) into the titanium silicasol, and carrying out third stirring for 1.5 hours at room temperature to obtain a mixture, wherein the molar ratio of the compound (4) to the tetrabutyl silicate is 0.12:1;
(3) Heating the mixture to 170 ℃ for 0.5h, and performing hydrothermal crystallization for 24h at 170 ℃ to obtain a crystallized product;
sequentially leaching the crystallized product with water, filtering, and drying at 120 ℃ for 2 hours;
roasting the dried product at 550 ℃ for 6 hours to obtain a titanium-silicon molecular sieve;
XRD spectra of the titanium silicalite molecular sieve obtained in the embodiment are shown in figure 5, UV-Vis spectra are shown in figure 6, and physical parameters are shown in table 5; in fig. 5, it can be seen that the titanium silicalite molecular sieve prepared in this example has an MFI structure; fig. 6 illustrates that the titanium silicalite molecular sieve prepared in this example has framework titanium active centers.
Examples 22 to 40
Titanium silicalite molecular sieves were prepared according to the procedure of example 21, the proportions and synthesis conditions of which are shown in Table 4, and the physical properties and catalytic properties of the molecular sieves prepared are shown in Table 5.
Comparative examples 9 to 13
Titanium silicalite molecular sieves were prepared according to the procedure of example 21, the proportions and synthesis conditions of which are shown in Table 4, and the physical properties and catalytic properties of the molecular sieves prepared are shown in Table 5.
Test example 2
This test example demonstrates the reaction effect of the molecular sieves prepared in examples 21-40 and comparative example 1, comparative examples 9-15 provided in the present invention for cyclohexanone ammoximation reaction to prepare cyclohexanone oxime. The reagents used in this test example were all commercially available chemically pure reagents. The concentration of each substance after the reaction was quantitatively analyzed by gas chromatography. 6890 type gas chromatograph manufactured by Agilent company is used; the analytical chromatographic column used was an FFAP column. The concentration of the components is quantified by an external standard method. Firstly, measuring the peak area of each component, searching the concentration of the component through a standard working curve, and calculating each index.
The cyclohexanone conversion and cyclohexanone oxime selectivity in the test cases were calculated according to the following formulas, respectively:
cyclohexanone conversion% = (moles of cyclohexanone remaining after 1-reaction/moles of cyclohexanone charged before reaction) ×100%
Cyclohexanone oxime selectivity% = moles of cyclohexanone oxime after reaction/(moles of cyclohexanone charged before reaction-moles of cyclohexanone remaining after reaction) ×100%.
The titanium silicalite molecular sieves prepared in examples 21 to 40 and comparative examples 9 to 15 were used as catalysts, respectively, and the catalysts, t-butanol and aqueous ammonia (25 wt%) were uniformly stirred and mixed in a slurry bed at a mass ratio of 1:10:10, followed by heating to 70 ℃. After the temperature had stabilized to 70 ℃, hydrogen peroxide (30 wt%) was added at a rate of 5mL/h, a mixture of cyclohexanone and t-butanol (volume ratio of cyclohexanone to t-butanol 1:3) was added at a rate of 8mL/h, and an aqueous ammonia solution (25 wt%) was added at a rate of 5 mL/h. Three materials are added simultaneously, and simultaneously, the materials are continuously discharged at a corresponding speed, the reaction is stable for 3 hours, sampling is carried out for chromatographic analysis, and the reaction results are shown in Table 5.
TABLE 5
As can be seen from Table 5, the titanium-silicon molecular sieve prepared by the embodiment of the invention has high cyclohexanone ammoximation reaction activity, the cyclohexanone conversion rate is up to 98%, and the cyclohexanone oxime selectivity is also up to 98%.
The preferred embodiments of the present invention have been described in detail above, 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 (12)
1. A method of making a titanium silicalite molecular sieve, the method comprising:
(1) Uniformly mixing a silicon source, an alkaline template agent, a titanium source and water to obtain titanium silicasol;
(2) Adding a compound shown in a formula (I) into the titanium silicasol, and carrying out hydrothermal crystallization and roasting on the obtained mixture;
wherein i is an integer of 1 to 10; r is R 1 、R 2 And R is 3 Each independently selected from C 1 -C 6 Alkyl of R 4 Selected from hydrogen or C 1 -C 6 Is a hydrocarbon group.
2. The method of claim 1, wherein i is an integer from 1 to 5;
preferably, R 1 、R 2 And R is 3 Each independently selected from methyl, ethyl or propyl;
preferably, R 4 Selected from hydrogen, methyl, ethyl or n-propyl.
3. The method of claim 1 or 2, wherein the silicon source is in SiO 2 Meter, the silicon source and the meter(I) The molar ratio of the compounds shown is 1: (0.01-0.3), preferably 1: (0.05-0.2).
4. A method according to any one of claims 1-3, wherein the silicon source is in SiO 2 Calculated by N when the alkaline template agent contains nitrogen element, and calculated by OH when the alkaline template agent does not contain nitrogen element - The titanium source is calculated as TiO 2 The meter is used for measuring the number of the wires,
the molar ratio of the silicon source to the alkaline template to the water is 1: (0.05-0.4): (5-40); preferably 1: (0.1-0.3): (5-25);
preferably, the molar ratio of the silicon source to the titanium source is 1: (0.001-0.04), preferably 1: (0.005-0.025).
5. The method of any of claims 1-4, wherein the silicon source is selected from at least one of tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate, tetrabutyl silicate, silica gel, white carbon black, and silica sol;
preferably, the basic template is selected from at least one of quaternary ammonium base, aliphatic amine and aliphatic alcohol amine, preferably at least one of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide and tetrabutyl ammonium hydroxide;
preferably, the titanium source is selected from an organic titanium source and/or an inorganic titanium source;
preferably, the titanium source is selected from at least one of titanium tetrachloride, titanium sulfate, titanium nitrate, tetraethyl titanate, tetrapropyl titanate, and tetrabutyl titanate.
6. The method of any one of claims 1-5, wherein step (1) further comprises the step of mixing followed by alcohol expelling; preferably, the alcohol expelling conditions include: the temperature is 30-100 ℃ and the time is 2-10h; preferably at 40-90deg.C for 4-10 hr.
7. The method according to any one of claims 1 to 6, wherein in step (2), the conditions for hydrothermal crystallization include: heating the mixture to 50-200 ℃ within 0.1-1h, and crystallizing at 50-200 ℃ for 10-100h; preferably crystallization is carried out at a temperature of 100-200 ℃ for 20-80 hours;
preferably, the roasting conditions include: the temperature is 400-800 ℃ and the time is 1-15h.
8. A titanium silicalite molecular sieve prepared according to the method of any one of claims 1-7;
preferably, the pore diameter of the titanium silicalite molecular sieve is 0.5-0.6nm; specific surface area of 550-650m 2 /g; the micropore volume is 0.2-0.3cm 3 /g。
9. A process for preparing cyclohexanone oxime, the process comprising: cyclohexanone, alcohol, ammonia and hydrogen peroxide are contacted in the presence of a catalyst, wherein the catalyst comprises the titanium silicalite molecular sieve of claim 8.
10. The method of claim 9, wherein the reaction conditions comprise: the weight ratio of the titanium silicon molecular sieve to the alcohol to the ammonia water is 1: (10-30): (10-30); the volume ratio of the cyclohexanone to the alcohol is 1 (1-5);
preferably, the reaction conditions further comprise: the temperature is 30-120 ℃ and the time is 2-8h.
11. A method of preparing caprolactone, the method comprising: cyclohexanone, alcohol and hydrogen peroxide are contacted in the presence of a catalyst, wherein the catalyst comprises the titanium silicalite molecular sieve of claim 8.
12. The method of claim 11, wherein the reaction conditions comprise: the molar ratio of titanium silicon molecular sieve, cyclohexanone and alcohol is 1: (10-30): (50-150);
preferably, the reaction conditions further comprise: the temperature is 30-120 ℃ and the time is 2-8h.
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| PCT/CN2022/133454 WO2023116315A1 (en) | 2021-12-22 | 2022-11-22 | Titanium silicate molecular sieve, and nano-gold-loaded titanium silicate molecular sieve catalyst and preparation method therefor and use thereof |
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