CN115504482A - Titanium-silicon molecular sieve, preparation method and application thereof - Google Patents
Titanium-silicon molecular sieve, preparation method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 93
- 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 93
- 238000002360 preparation method Methods 0.000 title abstract description 9
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims description 32
- 239000002243 precursor Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 26
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 21
- 229910017604 nitric acid Inorganic materials 0.000 claims description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000000527 sonication Methods 0.000 claims 2
- 238000006735 epoxidation reaction Methods 0.000 abstract description 14
- 150000001336 alkenes Chemical class 0.000 abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 21
- 238000003917 TEM image Methods 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- -1 aldehyde ketone Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 2
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 2
- 229940117927 ethylene oxide Drugs 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 1
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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- 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
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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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- 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
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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Abstract
The invention discloses a titanium-silicon molecular sieve, a preparation method and application thereof, wherein the titanium-silicon molecular sieve is a stripped Ti-MWW molecular sieve, and the thickness of crystal grains is 5-10 nm; the preparation method of the catalyst comprises the following steps: (1) mixing the raw materials to prepare a reaction solution; (2) And (2) carrying out ultrasonic treatment, washing, drying and roasting on a product obtained after the reaction of the reaction liquid obtained in the step (1) is finished to obtain the Ti-MWW molecular sieve which is stripped and has the grain thickness of 5-10 nm. The prepared stripped Ti-MWW molecular sieve is particularly suitable for catalyzing the reaction of olefin and hydrogen peroxide for epoxidation to prepare olefin oxide, and can simultaneously obtain high effective utilization rate of hydrogen peroxide and yield of olefin oxide.
Description
Technical Field
The invention relates to a catalyst, in particular to a preparation method of a titanium silicalite molecular sieve and a catalytic application thereof.
Background
The Ti-MWW molecular sieve has an MWW topological structure, belongs to a hexagonal crystal system, has a space group of P6/mmm, is a nano material with a layered structure formed by connecting MWW nano layers through oxygen bridges, and is provided with two sets of mutually independent ten-membered ring channel systems, wherein one set of the mutually independent ten-membered ring channel systems is a sinusoidal ten-membered ring channel (0.40 nm multiplied by 0.59 nm) positioned in the nano layers, and the other set of the mutually independent ten-membered ring channel systems (0.40 nm multiplied by 0.54 nm) is positioned between the nano layers and contains a twelve-membered ring super cage (0.71 nm multiplied by 1.81 nm); further, twelve-membered ring bowl-shaped pores (0.71 nm. Times.0.71 nm) were present in the crystal surface.
The Ti-MWW molecular sieve is applied to olefin epoxidation reaction, aldehyde ketone ammoxidation reaction and oxidation reaction of pyridine and thioether by using a unique pore structure. Wherein, the Ti-MWW/H2O2 catalytic system is utilized to firstly realize the industrial application of butanone oxime preparation by butanone ammoxidation (MWW-Type Titanosilicate, springer-Verlag: berlin Heidelberg,2013,65). For the special layered structure of the Ti-MWW molecular sieve, more open pore channels can be obtained through stripping, the contact efficiency of reactant molecules and active centers is improved, and the catalytic performance of the Ti-MWW molecular sieve is further improved. Wu Peng group (The Journal of Physical Chemistry B,2004, 19126).
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a titanium silicalite molecular sieve, a preparation method and application thereof, the catalyst overcomes the defects in the prior art, shows excellent catalytic performance in olefin epoxidation reaction, and is simple in preparation method.
In order to achieve the purpose, the invention adopts the technical scheme that:
the titanium-silicon molecular sieve is an exfoliated Ti-MWW molecular sieve, and the thickness of crystal grains is 5-10 nm
In an embodiment of the present invention, the Ti-MWW molecular sieve precursor has a two-dimensional layered structure, and the titanium content is 1 to 4wt.%.
The preparation method of the titanium silicalite molecular sieve comprises the following steps:
step (1): mixing raw materials to prepare reaction liquid, wherein the raw materials comprise a Ti-MWW molecular sieve precursor, a nitric acid aqueous solution and a hydrogen peroxide aqueous solution;
step (2): and (2) carrying out ultrasonic treatment, washing, drying and roasting on a product obtained after the reaction of the reaction liquid obtained in the step (1) is finished to obtain the stripped Ti-MWW molecular sieve.
In an embodiment of the present invention, the concentration of the nitric acid aqueous solution in the step (1) is 2 to 14M.
In one embodiment of the present invention, the concentration of the aqueous hydrogen peroxide solution in step (1) is 1 to 30wt.%.
In an embodiment of the invention, the weight ratio of the Ti-MWW molecular sieve precursor in the step (1) to the nitric acid aqueous solution is 1 (5-50).
In an embodiment of the invention, the weight ratio of the Ti-MWW molecular sieve precursor in the step (1) to the aqueous hydrogen peroxide solution is 1 (1-10).
In one embodiment of the present invention, the reaction conditions in step (2) are 80-160 ℃ for 0.5-24 hours.
In one embodiment of the present invention, the ultrasonic condition in the step (2) is ultrasonic treatment at 30 ℃ for 1-12 hours.
The titanium-silicon molecular sieve is applied to catalytic reaction.
The titanium silicalite molecular sieve is applied to preparing epoxy alkane by catalyzing epoxidation of olefin and hydrogen peroxide.
The technical scheme has the following beneficial effects:
the stripped Ti-MWW molecular sieve prepared by the invention has high activity, is particularly suitable for catalyzing the reaction of olefin and hydrogen peroxide for epoxidation to prepare olefin oxide, and can obtain high yield of olefin oxide.
Drawings
FIG. 1 is a TEM image of an exfoliated Ti-MWW molecular sieve in example 1 of the present invention;
FIG. 2 is a TEM image of a non-exfoliated Ti-MWW molecular sieve in comparative example 1 of the present invention.
Detailed Description
The invention will now be further described with reference to the following examples and figures 1 and 2.
The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
All the embodiments are operated according to the operation steps of the technical scheme.
In The examples and comparative examples, ti-MWW molecular sieve precursors were prepared according to literature procedures (The Journal of Physical Chemistry B,2001, 105.
Example 1
(1) Mixing the raw materials to prepare a reaction solution: firstly, raw materials are weighed according to the weight ratio of a Ti-MWW molecular sieve precursor to a nitric acid aqueous solution of 1;
(2) And (2) reacting the reaction solution obtained in the step (1) at 100 ℃ for 6 hours, and performing ultrasonic treatment, washing, drying and roasting on the product after the reaction is finished to obtain the Ti-MWW molecular sieve, wherein the ultrasonic treatment is performed at 30 ℃ for 6 hours.
TEM image results (FIG. 1) show that the Ti-MWW molecular sieve is exfoliated and has a grain thickness of 5nm.
Example 2
(1) Mixing the raw materials to prepare a reaction solution: firstly, weighing raw materials according to the weight ratio of a Ti-MWW molecular sieve precursor to a nitric acid aqueous solution of 1:5 and the weight ratio of the Ti-MWW molecular sieve precursor to a hydrogen peroxide aqueous solution of 1:5 for later use, then adding the hydrogen peroxide aqueous solution into the nitric acid aqueous solution, and finally adding the Ti-MWW molecular sieve precursor and fully stirring to prepare a reaction solution, wherein the Ti-MWW molecular sieve precursor has a two-dimensional layered structure, the titanium content is 3.5wt.%, the concentration of the nitric acid aqueous solution is 14M, and the concentration of the hydrogen peroxide aqueous solution is 1wt.%;
(2) And (2) reacting the reaction solution obtained in the step (1) at 140 ℃ for 12 hours, and performing ultrasonic treatment, washing, drying and roasting on the reaction product to obtain the stripped Ti-MWW molecular sieve, wherein the ultrasonic treatment is performed at 30 ℃ for 8 hours.
TEM image results show that the Ti-MWW molecular sieve is in an exfoliated state, and the grain thickness of the Ti-MWW molecular sieve is 7.5nm.
Example 3
(1) Mixing the raw materials to prepare a reaction solution: firstly, raw materials are weighed according to the weight ratio of a Ti-MWW molecular sieve precursor to a nitric acid aqueous solution of 1:50 and the weight ratio of the Ti-MWW molecular sieve precursor to a hydrogen peroxide aqueous solution of 1:1 for later use, then the hydrogen peroxide aqueous solution is added into the nitric acid aqueous solution, and finally the Ti-MWW molecular sieve precursor is added and fully stirred to prepare a reaction solution, wherein the Ti-MWW molecular sieve precursor has a two-dimensional layered structure, the titanium content is 4wt.%, the concentration of the nitric acid aqueous solution is 8M, and the concentration of the hydrogen peroxide aqueous solution is 15wt.%;
(2) And (2) reacting the reaction solution obtained in the step (1) at 80 ℃ for 24 hours, and performing ultrasonic treatment, washing, drying and roasting on the product after the reaction is finished to obtain the Ti-MWW molecular sieve, wherein the ultrasonic treatment is performed at 30 ℃ for 12 hours.
TEM image results show that the Ti-MWW molecular sieve is in an exfoliated state, and the grain thickness of the Ti-MWW molecular sieve is 5nm.
Example 4
(1) Mixing the raw materials to prepare a reaction solution: firstly, raw materials are weighed according to the weight ratio of a Ti-MWW molecular sieve precursor to a nitric acid aqueous solution of 1;
(2) And (2) reacting the reaction solution obtained in the step (1) at 160 ℃ for 0.5 hour, and performing ultrasonic treatment, washing, drying and roasting on the product after the reaction is finished to obtain the Ti-MWW molecular sieve, wherein the ultrasonic treatment is performed at 30 ℃ for 1 hour.
TEM image results show that the Ti-MWW molecular sieve is in an exfoliated state, and the grain thickness of the Ti-MWW molecular sieve is 10nm.
Example 5
(1) Mixing the raw materials to prepare a reaction solution: firstly, raw materials are weighed according to the weight ratio of a Ti-MWW molecular sieve precursor to a nitric acid aqueous solution of 1;
(2) And (2) reacting the reaction liquid obtained in the step (1) at 120 ℃ for 12 hours, and performing ultrasonic treatment, washing, drying and roasting on a product after the reaction is finished to obtain the Ti-MWW molecular sieve, wherein the ultrasonic treatment is performed at 30 ℃ for 10 hours.
TEM image results show that the Ti-MWW molecular sieve is in an exfoliated state, and the grain thickness of the Ti-MWW molecular sieve is 7.5nm.
Example 6
(1) Mixing the raw materials to prepare a reaction solution: firstly, raw materials are weighed according to the weight ratio of a Ti-MWW molecular sieve precursor to a nitric acid aqueous solution of 1;
(2) And (2) reacting the reaction liquid obtained in the step (1) at 80 ℃ for 6 hours, and performing ultrasonic treatment, washing, drying and roasting on a product after the reaction is finished to obtain the Ti-MWW molecular sieve, wherein the ultrasonic treatment is performed at 30 ℃ for 12 hours.
TEM image results show that the Ti-MWW molecular sieve is in an exfoliated state, and the grain thickness of the Ti-MWW molecular sieve is 5nm.
Example 7
(1) Mixing the raw materials to prepare a reaction solution: firstly, raw materials are weighed according to the weight ratio of a Ti-MWW molecular sieve precursor to a nitric acid aqueous solution of 1:50 and the weight ratio of the Ti-MWW molecular sieve precursor to a hydrogen peroxide aqueous solution of 1:1 for later use, then the hydrogen peroxide aqueous solution is added into the nitric acid aqueous solution, and finally the Ti-MWW molecular sieve precursor is added and fully stirred to prepare a reaction solution, wherein the Ti-MWW molecular sieve precursor has a two-dimensional layered structure, the titanium content is 3.5wt.%, the concentration of the nitric acid aqueous solution is 8M, and the concentration of the hydrogen peroxide aqueous solution is 25wt.%;
(2) And (2) reacting the reaction solution obtained in the step (1) at 160 ℃ for 8 hours, and performing ultrasonic treatment, washing, drying and roasting on the reaction product to obtain the Ti-MWW molecular sieve, wherein the ultrasonic treatment is performed at 30 ℃ for 12 hours.
TEM image results show that the Ti-MWW molecular sieve is in an exfoliated state, and the grain thickness of the Ti-MWW molecular sieve is 5nm.
Comparative example 1
(1) Mixing the raw materials to prepare a reaction solution: firstly, raw materials are weighed for later use according to the weight ratio of a Ti-MWW molecular sieve precursor to a nitric acid aqueous solution of 1;
(2) And (2) reacting the reaction solution obtained in the step (1) at 100 ℃ for 6 hours, and performing ultrasonic treatment, washing, drying and roasting on the product after the reaction is finished to obtain the Ti-MWW molecular sieve, wherein the ultrasonic treatment is performed at 30 ℃ for 6 hours.
TEM image results (FIG. 2) show that the Ti-MWW molecular sieve is in a non-exfoliated state, and the grain thickness is 30nm.
Comparative example 2
(1) Mixing the raw materials to prepare a reaction solution: firstly, raw materials are weighed according to the weight ratio of a Ti-MWW molecular sieve precursor to a sulfuric acid aqueous solution of 1;
(2) And (2) reacting the reaction solution obtained in the step (1) at 100 ℃ for 6 hours, and performing ultrasonic treatment, washing, drying and roasting on the product after the reaction is finished to obtain the Ti-MWW molecular sieve, wherein the ultrasonic treatment is performed at 30 ℃ for 6 hours.
TEM image results show that the Ti-MWW molecular sieve is in a non-exfoliated state, and the grain thickness of the Ti-MWW molecular sieve is 30nm.
Comparative example 3
(1) Mixing the raw materials to prepare a reaction solution: firstly, weighing raw materials for later use according to the weight ratio of a Ti-MWW molecular sieve precursor to aqueous hydrogen peroxide of 1:8, and then adding the Ti-MWW molecular sieve precursor into the aqueous hydrogen peroxide for fully stirring to prepare a reaction solution, wherein the Ti-MWW molecular sieve precursor has a two-dimensional layered structure, the titanium content is 3.5wt.%, and the concentration of the aqueous hydrogen peroxide is 30wt.%;
(2) And (2) reacting the reaction solution obtained in the step (1) at 100 ℃ for 6 hours, and performing ultrasonic treatment, washing, drying and roasting on the product after the reaction is finished to obtain the Ti-MWW molecular sieve, wherein the ultrasonic treatment is performed at 30 ℃ for 6 hours.
TEM image results show that the Ti-MWW molecular sieve is in a non-exfoliated state, and the grain thickness of the Ti-MWW molecular sieve is 30nm.
Comparative example 4
(1) Mixing the raw materials to prepare a reaction solution: firstly, raw materials are weighed according to the weight ratio of a Ti-MWW molecular sieve precursor to a nitric acid aqueous solution of 1;
(2) And (2) reacting the reaction solution obtained in the step (1) at 100 ℃ for 6 hours, and washing, drying and roasting a product after the reaction is finished to obtain the Ti-MWW molecular sieve, wherein the ultrasonic condition is ultrasonic at 30 ℃ for 6 hours.
TEM image results show that the Ti-MWW molecular sieve is in a non-exfoliated state, and the grain thickness of the Ti-MWW molecular sieve is 30nm.
Catalytic reaction
All the examples and comparative examples are applied to the epoxidation of ethylene, propylene, n-hexene and cyclohexene with hydrogen peroxide to obtain alkylene oxide. The analysis of the reactants and products was carried out by gas chromatography (Agilent 7890B, DB-Wax capillary column 30m × 0.25mm × 0.25 μm) with isopropanol as internal standard; the residual amount of hydrogen peroxide was titrated with a cerium sulfate solution having a concentration of 0.05M.
Ethylene and hydrogen peroxide epoxidation to ethylene oxide: first, 0.1g of catalyst, 1.13g of 30wt.% aqueous hydrogen peroxide and 10g of acetonitrile were added to a high-pressure autoclave equipped with a 45mL teflon liner, respectively; then, introducing ethylene into the reaction kettle to replace the air in the reaction kettle, repeating the steps for three times and maintaining the reaction pressure at 2.0MPa; finally, after reacting at 60 ℃ for 2 hours under vigorous stirring, a liquid mixture was obtained by centrifugation.
Epoxidation of propene with hydrogen peroxide to propylene oxide: first, 0.1g of catalyst, 3.39g of 30wt.% aqueous hydrogen peroxide and 10g of acetonitrile were added to a high-pressure autoclave equipped with a 45mL polytetrafluoroethylene liner, respectively; then, introducing propylene into the reaction kettle to replace the air in the reaction kettle, repeating the steps for three times and maintaining the reaction pressure at 0.4MPa; finally, after reacting at 60 ℃ for 2 hours under vigorous stirring, a liquid mixture was obtained by centrifugation.
Epoxidation of n-hexene with hydrogen peroxide to produce epoxy n-hexane: first, 0.1g of catalyst, 1.13g of 30wt.% aqueous hydrogen peroxide and 10g of acetonitrile were added to a high-pressure autoclave equipped with a 45mL teflon liner, respectively; then 0.8416g n-hexene is added into the reaction kettle; finally, after reacting at 60 ℃ for 2 hours under vigorous stirring, a liquid mixture was obtained by centrifugation.
Epoxidation of cyclohexene with hydrogen peroxide to cyclohexene oxide: first, 0.2g of catalyst, 1.13g of 30wt.% aqueous hydrogen peroxide and 10g of acetonitrile were added to a high-pressure autoclave equipped with a 45mL teflon liner, respectively; then 0.8214g of cyclohexene is added into the reaction kettle; finally, after reacting at 60 ℃ for 2 hours under vigorous stirring, a liquid mixture was obtained by centrifugation.
The results of the epoxidation reaction of ethylene with hydrogen peroxide in the examples and comparative examples are shown in table 1.
TABLE 1
The results of the epoxidation reaction of propylene with hydrogen peroxide in the examples and comparative examples are shown in Table 2.
TABLE 2
| Sources of molecular sieves (examples and comparative examples) | Effective utilization rate of hydrogen peroxide | Yield of propylene oxide |
| Example 1 | 90.1％ | 87.3％ |
| Example 2 | 89.5％ | 84.3％ |
| Example 3 | 88.1％ | 85.4％ |
| Example 4 | 88.4％ | 85.6％ |
| Example 5 | 90.0％ | 87.0％ |
| Example 6 | 89.1％ | 86.2％ |
| Example 7 | 88.7％ | 86.1％ |
| Comparative example 1 | 81.5％ | 30.5％ |
| Comparative example 2 | 80.7％ | 28.2％ |
| Comparative example 3 | 82.7％ | 31.2％ |
| Comparative example 4 | 80.8％ | 27.9％ |
The results of the epoxidation reaction of n-hexene with hydrogen peroxide in the examples and comparative examples are shown in table 3.
TABLE 3
The results of the epoxidation reaction of cyclohexene with hydrogen peroxide in the examples and comparative examples are shown in Table 4.
TABLE 4
| Sources of molecular sieves (examples and comparative examples) | Effective utilization rate of hydrogen peroxide | Yield of cyclohexene oxide |
| Example 1 | 92.7％ | 85.3％ |
| Example 2 | 87.2％ | 83.3％ |
| Example 3 | 89.5％ | 86.9％ |
| Example 4 | 91.4％ | 82.6％ |
| Example 5 | 90.7％ | 88.7％ |
| Example 6 | 88.8％ | 85.6％ |
| Example 7 | 90.7％ | 84.9％ |
| Comparative example 1 | 75.4％ | 30.0％ |
| Comparative example 2 | 73.5％ | 28.9％ |
| Comparative example 3 | 77.7％ | 31.9％ |
| Comparative example 4 | 74.8％ | 29.8％ |
The above-described embodiments are intended to illustrate rather than to limit the invention, and any changes and alterations made without inventive step within the spirit and scope of the claims are intended to fall within the scope of the invention.
Claims (10)
1. The titanium silicalite molecular sieve is characterized in that the titanium silicalite molecular sieve is an exfoliated Ti-MWW molecular sieve, and the thickness of crystal grains is 5-10 nm.
2. The titanium silicalite molecular sieve of claim 1, wherein the Ti-MWW molecular sieve precursor has a two-dimensional layered structure with a titanium content of 1 to 4wt.%.
3. The method of preparing a titanium silicalite molecular sieve of claim 1 or 2, comprising the steps of:
step (1): mixing raw materials to prepare reaction liquid, wherein the raw materials comprise a Ti-MWW molecular sieve precursor, a nitric acid aqueous solution and a hydrogen peroxide aqueous solution;
step (2): and (2) carrying out ultrasonic treatment, washing, drying and roasting on a product obtained after the reaction of the reaction liquid obtained in the step (1) is finished to obtain the stripped Ti-MWW molecular sieve.
4. The method according to claim 3, wherein the concentration of the aqueous nitric acid solution in the step (1) is 2 to 14M.
5. A method according to claim 3, characterized in that the concentration of the aqueous hydrogen peroxide solution in step (1) is 1-30 wt.%.
6. The method of claim 3, wherein the weight ratio of the Ti-MWW molecular sieve precursor to the nitric acid aqueous solution in the step (1) is 1 (5-50).
7. The method of claim 3, wherein the weight ratio of the Ti-MWW molecular sieve precursor to the aqueous hydrogen peroxide solution in the step (1) is 1 (1-10).
8. The method according to claim 3, wherein the reaction conditions in the step (2) are 80 to 160 ℃ for 0.5 to 24 hours.
9. The method according to claim 3, wherein the sonication conditions in step (2) are sonication at 30 ℃ for 1 to 12 hours.
10. Catalytic use of the titanium silicalite molecular sieve of claim 1 or 2.
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