CN107999124A - A kind of core shell structure Ti-MWW@Si molecular sieves and its preparation and application - Google Patents

A kind of core shell structure Ti-MWW@Si molecular sieves and its preparation and application Download PDF

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CN107999124A
CN107999124A CN201711338727.0A CN201711338727A CN107999124A CN 107999124 A CN107999124 A CN 107999124A CN 201711338727 A CN201711338727 A CN 201711338727A CN 107999124 A CN107999124 A CN 107999124A
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CN107999124B (en
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王志光
李进
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Dalian Heterogeneous Catalyst Co Ltd
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    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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    • 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
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    • 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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    • C07—ORGANIC CHEMISTRY
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    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
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    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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Abstract

The invention discloses a kind of Ti MWW@Si molecular sieves with core shell structure, kernel is the Titanium Sieve Molecular Sieve that micropore has MWW topological structures, and shell is Si mesopore molecular sieves.Specific preparation process is using glucose solution dipping Ti MWW molecular sieves, and then anaerobic carbonization is deposited on molecular sieve outer surface and forms C Ti MWW molecular sieves, then the solution mixing low temp crystallization with the formation such as CTAB, P123, alkyl silicate, forms SiO2The shell of mesoporous molecular sieve structure, removes surface deposition carbon, CTAB, P123 etc. finally by roasting, obtains the Ti MWW Si molecular sieves with microporous mesoporous core shell structure.This Titanium Sieve Molecular Sieve of the present invention can be applied to oxidation catalyst of cyclopropene, its unique texture can increase surface hydrophobic, reduces inactivation probability, improves reactivity, selectivity and catalyst life, have good application prospect.

Description

A kind of core shell structure Ti-MWW@Si molecular sieves and its preparation and application
Technical field
The present invention relates to a kind of Titanium Sieve Molecular Sieve of core shell structure and its preparation and application, and in particular to a kind of core shell structure Ti-MWW@Si molecular sieve catalysts and preparation method thereof and propylene ring oxidation reaction production propylene oxide application, belong to nothing Machine field of chemical material synthesis.
Background technology
Propylene oxide (PO) is a kind of important large industrial chemicals, because it is with the very big oxygen-containing three-membered ring of tension force, is changed It is very active to learn property, it is widely used, mainly for the production of polyethers, further produce polyurethane plastics, foam stabiliser, papermaking Industrial defoaming agent, crude oil demulsifier, oil well acid treatment wetting agent and high-effective low foam detergent etc..Propylene oxide is also used for producing third Glycol, and then produce unsaturated polyester resin etc..As the expansion of propylene oxide purposes and the continuous of downstream product dosage increase, The particularly prosperity of the industry such as automobile, building household, increases considerably polyurethane and nonionic surfactant demand, Cause the market demand of propylene oxide vigorous.
At present, in the world the industrial process of propylene oxide mainly have chlorohydrination method, conjugated oxidation (also referred to as co-production method, Indirect oxidation method), production phenols (CHP methods) and hydrogen peroxide direct oxidation method (HPPO methods), wherein HPPO methods be because ring Protect pollution-free and become the emphasis researched and developed now, and tend to be ripe, show good industrial prospect.
HPPO methods are by hydrogen peroxide (H2O2) propylene oxide propylene oxide new process.In the relatively mild bar that compares Under part, propylene and H2O2In methanol/water mixed liquor, occurred directly in fixed bed reactors using special Ti-Si catalyst Oxidation reaction prepares propylene oxide.The technique overcomes chlorohydrination serious corrosion of equipment, waste liquid, the shortcomings that waste residue is more, technique stream Journey is simple, and product yield is high.
To TS-1 and Ti-MWW catalyst system and catalyzings, the optimum solvent of propylene liquid phase epoxidation process is respectively methanol and acetonitrile, Principal product is propylene oxide.Accessory substance is mainly the 1,2- propane diols that ring opening hydrolysis of the propylene oxide under acid act on is formed Deng, this mainly by complex compound Ti-OOH that the silicone hydroxyl in catalyst, titanium hydroxyl, titanium activated centre and hydrogen peroxide are formed and Caused by the weak acid position of formation.
What patent CN101397282B was disclosed is that propylene, oxygen, hydrogen, methanol equal solvent are mixed in TS-1 molecular sieve catalysts Haptoreaction is closed, propylene conversion and hydrogen effective rate of utilization are all very low, and catalytic reaction produces a large amount of accessory substances, catalyst inactivation It hurry up, short life, the Efficient Conversion of unsuitable epoxidation of propylene.
Patent CN103121982B is disclosed in propylene ring oxidation reaction on MFI structure titanium-silicon molecular sieve catalyst, using having The hydrophobicity on machine silicon increase Titanium Sieve Molecular Sieve surface, but propylene conversion, propylene oxide selectivity etc. is relatively low, it is difficult to Reach the level of commercial Application.
Patent CN03805131 and CN100441572C by the use of Ti-MWW molecular sieves as catalyst, alcohol, ketone, ether, ester, The epoxidation reaction of propylene and hydrogen peroxide generates 1,2- propylene oxide under nitrile, hydrocarbon, halogenated hydrocarbons equal solvent, due to surface hydroxyl parent The problems such as water-based, cannot reach higher propylene conversion, the relatively high usage of hydrogen peroxide and longer catalyst and use the longevity Life.
Epoxidation of propylene process is catalyzed to TS-1, has higher yield of propylene oxide to reaction process with methanol as solvent, But for Ti-MWW catalyst system and catalyzings, yield of propylene oxide is still to much lower, illustrates that Ti-MWW has more epoxidation of propylene process High catalytic activity.The structure of Ti-MWW uniquenesses makes the titanium activity that reaction substrate molecule is more easy in contact Ti-MWW framework of molecular sieve Position.
Ti-MWW has as comprising interlayer silicone hydroxyl and the intralayer defects position such as hydroxyl cave as caused by boron removal so that have compared with Strong hydrophily, thus the hydroxyl in Ti-MWW understands Preferential adsorption as first alcohol and water isopolarity molecule, and hinder reaction molecular Diffusion to titanium active sites, causes the productivity ratio in water and methanol solvate oxypropylene relatively low.Acetonitrile is molten as aprotic Agent, Epoxidation activity is relatively low compared with when using alcohols solvent in Ti-MWW systems, its inertia and weak base performance effectively suppress ring The open loop of Ethylene Oxide, so as to avoid generation etherificate and hydrolysising by-product.
The content of the invention
The present invention produces stronger hydrophily for the problem that Ti-MWW surface silanol groups exist, and reduces selectivity, this hair A kind of bright provided core shell structure Ti-MWW@Si molecular sieves, make by the use of organic surface active agent as directed agents, alkyl silicate class The Ti-MWW molecular sieves that conventional method synthesizes are modified for silicon source, improve the surface hydrophobic of molecular sieve, promote reaction point Sub- diffuser efficiency, shell are the mesoporous molecular sieve structure of SiO2, a kind of Ti-MWW Si molecular sieves of core shell structure are obtained, in second The yield and H of propylene oxide are improved in nitrile to liquid propylene epoxidation process2O2Utilization rate, and improve the service life of catalyst.
The invention discloses a kind of Ti-MWW@Si molecular sieves with core shell structure, kernel is that micropore has MWW topology knots The Titanium Sieve Molecular Sieve of structure, shell are SiO2Mesopore molecular sieve；Kernel Ti-MWW framework of molecular sieve is made of Ti, Si, O element, The weight content wherein calculated using TiO2 is 2.0wt%~5.2wt%；The SiO of the shell2Mesopore molecular sieve accounts for whole nucleocapsid 2.0wt%~10.0wt% of structure molecular screen weight.
The Ti-MWW@Si molecular sieve preparations that the present invention relates to are characterized in that：
(1) Ti-MWW zeolite crystals are dispersed in 5wt%~35wt% glucose solutions and form suspension slurry, its Middle molecular sieve quality accounts for 10wt%~40wt% of mixture quality；
(2) 50~90 DEG C of rotatory vacuum drying removing moisture of mixed serum that will be obtained in (1), are enriched with glucose molecule On Ti-MWW zeolite crystals surface, then in N2When 400~600 DEG C of roastings 1~10 are small under atmosphere, C-Ti-MWW molecules are obtained Sieve；
(3) by template CTAB, template P123, ammonium hydroxide (NH3·H2O), absolute ethyl alcohol (EtOH) and deionized water ultrasound It is dispersed, in 30~50 DEG C of 0.5~4.0h of mechanical agitation, then cool to 25 DEG C add alkyl silicates be vigorously stirred 1~ 10min obtains mixed solution, then mixes the C-Ti-MWW molecular sieves obtained in (2) with above-mentioned mixed solution, C- in solution Ultrasonic dispersed 0.5~4.0h obtains mixing slurry to mass percent 4%~17% shared by Ti-MWW molecular sieves in the solution Liquid, is placed at 25 DEG C of 12~48h of crystallization in closed vessel, carries out the solid product that separation of solid and liquid obtains and is washed till neutrality, drying, In air atmosphere with the rate of heat addition of 2~5 DEG C/min from room temperature rise at 500~600 DEG C roasting 4~10 it is small when removed template method With carbon distribution component, the Ti-MWW@Si molecular sieves with core shell structure are obtained.
Further, in the above-mentioned technical solutions, alkyl silicate includes in the step (3)：Methyl orthosilicate, positive silicon Any one in acetoacetic ester, positive silicic acid propyl ester, positive isopropyl silicate, butyl silicate.
Further, in the above-mentioned technical solutions, in the step (3) mixed serum component according to mol ratio Si： CTAB：P123：EtOH：NH3：H2O=1：0.08~0.20：0.004~0.01：50~100：15~35：600~800, wherein Alkyl silicate is calculated with the molal quantity of Si.
The Ti-MWW@Si molecular sieves of above-mentioned core shell structure provided by the invention should as propylene ring oxidation reaction catalyst With.
Propylene ring oxidation reaction of the present invention is that propylene, hydrogen peroxide, acetonitrile, water are input to epoxy as charging Change to react under epoxidation reaction condition in reactor and obtain propene oxide product.
The amount of each component in propylene ring oxidation reaction charging is characterized in that：Gross weight based on liquid feed stream Gauge, ethane nitrile content are 50~75wt%, and content of hydrogen peroxide is 6~28wt%；The molar ratio of propylene and hydrogen peroxide is 2.0~5.0；
Using mode is operated batch-wise or continuously, epoxidation reaction temperature is propylene ring oxidation reaction of the present invention 25~100 DEG C, preferably 30~80 DEG C, more preferably 35~65 DEG C；Epoxidation reaction pressure is 14~100bar, preferably 15~ 50bar。
This compound titanium silicon molecular sieve provided by the present invention is the effective modified of conventional Ti-MWW molecular sieves, is not only improved The hydrophobicity on molecular sieve catalyst surface, and the core shell structure formed has the hierarchical porous structure of mesoporous-micropore, well Improve the diffusion rate of reaction molecular, improve reactivity, reduce the inactivation of molecular sieve catalyst, prolong the service life, have Good application prospect.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and embodiments：
Fig. 1 is the XRD diagram for the Ti-MWW molecular sieves that 1 method of comparative example example synthesizes；
Fig. 2 is the XRD diagram for the Ti-MWW@Si molecular sieves that 1 method of embodiment synthesizes.
Embodiment
Embodiment of the present invention and caused effect are further illustrated by embodiment and comparison example, but the present invention Protection domain is not limited to the content listed by embodiment.
H is calculated by following calculating formula respectively2O2Conversion ratio, PO (propylene oxide) selectivity, H2O2Effective rate of utilization, C3H6(propylene) conversion ratio and PO yields.
H2O2Conversion ratio：
PO selectivity：
H2O2Effective rate of utilization：
C3H6Conversion ratio：
PO yields：
C in formula0 H2O2And Ci H2O2The mass concentration of hydrogen peroxide, n before and after Wei not reacting0 C3H6And ni C3H6Third before and after Wei not reacting The molal quantity of alkene, n0 H2O2And ni H2O2Oxydol H before and after Wei not reacting2O2Molal quantity, npo, nNMEAnd nPGRing after respectively reacting The amount of the material of Ethylene Oxide, propylene glycol monomethyl ether and propane diols generation.As the index of evaluation response performance, XH2O2, Spo, YpoAdopt With reaction 6 it is small when after, test sample when 2 is small, make continuous three samples test sample result three scale errors be less than 2%, at the same time Reactivity worth index is used as using the average value of these three sample results.
Comparative example 1
Ti-MWW molecular sieves are synthesized according to document (J.Phys.Chem.B, 2001,105 (15), 2897-2905) method.
TiO in titanium source in molar ratio2：SiO in silicon source2：B in boron source2O3：F- in Fluorine source：Organic formwork agent： H2O is 0.033：1：0.67：1：1.4：19 prepare reaction mixture, and the titanium source is butyl titanate, and the silicon source is Silica gel, the boron source are boric acid, and the Fluorine source is HF, and the organic formwork agent is piperidines, the reaction mixture It is filtered, washing, dry in 170 DEG C of hydrothermal crystallizings 7 days, obtain Ti-MWW molecular screen primary powders；By Ti-MWW molecular screen primary powders with Concentration is that 2mol/l salpeter solutions according to weight ratio are 1：50 prepare reaction mixture, when processing 20 is small at 100 DEG C, pass through Filter, washing, drying, obtain acid-treated product；By acid-treated product when 550 DEG C of roastings 10 are small, obtained Ti-MWW molecular sieves Product may be used as the catalyst of propylene ring oxidation reaction, be denoted as VS-1, its XRD diffraction analysis spectrogram is as shown in Figure 1.
Comparative example 2
TS-l molecular sieves are synthesized according to the method for document (zeolites, 1992,12 (8), 943-950), by the positive silicon of 22.5g Sour tetra-ethyl ester is mixed with 7.0g tetrapropylammonium hydroxide, and adds 59.8g distilled water, is uniformly mixed after water at normal pressure and 60 DEG C Solve 1.0 it is small when, obtain the hydrating solution of tetraethyl orthosilicate, be slowly added into vigorous stirring by 1.1g butyl titanates with The solution that 5.0g anhydrous isopropyl alcohols are formed, gained mixture is stirred at 75 DEG C 3 it is small when, obtain clear colloid.Will This colloid is put into stainless steel sealing reaction kettle, and constant temperature is placed 6 days at 170 DEG C of temperature and self-generated pressure, obtains crystallization product Mixture；It is 6~8 that this mixture, which is filtered, is washed with water to pH, and 60 minutes dry in 110 DEG C, is not roasted TS-1 original powders, when air atmosphere roasting 4 is small at 550 DEG C, obtains TS-1 molecular sieves, may be used as the catalysis of propylene ring oxidation reaction Agent, product are denoted as VS-2.
Embodiment 1
(1) it is 15wt%'s the Ti-MWW zeolite crystals 10.0g prepared according to comparative example 1 to be dispersed in 18.57g concentration Suspension slurry is formed in glucose solution, then mixed serum is rotated to vacuum drying removing moisture at 60 DEG C, make grape Glycan molecule is enriched in Ti-MWW zeolite crystals surface, then in N2When the lower 500 DEG C of roastings 2 of atmosphere are small, Carbon deposition C-Ti- is obtained MWW molecular sieves.
(2) by template CTAB, template P123, ammonium hydroxide NH3·H2O, absolute ethyl alcohol EtOH and deionized water ultrasound are uniform It is scattered, in 40 DEG C of mechanical agitation 1h, then cool to 25 DEG C add TEOS and 1000rpm rotating speeds be vigorously stirred 5min obtain mixing it is molten Liquid, its component is according to mol ratio TEOS：CTAB：P123：EtOH：NH3：H2O=1：0.16：0.005：81：20：665, then By the C-Ti-MWW molecular sieves obtained in (1) and the dispersed 1h of above-mentioned solution ultrasound, C-Ti-MWW molecular sieves account for whole mixing Liquid mass percent is 8%.25 DEG C of crystallization 24h in closed vessel afterwards, Synthesis liquid centrifuge, and obtained solid product is washed To neutrality, dried in 50 DEG C of vacuum drying ovens, risen at 500 DEG C and roasted from room temperature with the rate of heat addition of 2 DEG C/min in air atmosphere Burn 8 it is small when removed template method and carbon distribution component, obtain Ti-MWW Si products, may be used as the catalyst of propylene ring oxidation reaction, It is as shown in Figure 2 to be denoted as product A, XRD diffraction pattern.
Embodiment 2~8
(1) it is same as Example 1 to take Ti-MWW zeolite crystals 10.0g to be dispersed in formation suspension slurry in glucose solution Liquid, glucose concentration and quality are as shown in table 1.Then by mixed serum at 50~90 DEG C (the actual temp such as institute of table 1 Show) rotatory vacuum drying removing moisture, glucose molecule is enriched in Ti-MWW zeolite crystals surface, then in N2Under atmosphere Roast (temperature and roasting time are as shown in table 1), obtain Carbon deposition C-Ti-MWW molecular sieves.
(2) it is same as Example 1 by template CTAB, template P123, ammonium hydroxide (NH3·H2O), absolute ethyl alcohol (EtOH) It is dispersed in 40 DEG C of ultrasounds with deionized water H2O, and mechanical agitation 1h, then cool to 25 DEG C and add alkyl silicate (difference Embodiment species is as shown in table 2) and 1000rpm rotating speeds be vigorously stirred 5min and obtain mixed solution, in the mixed liquor component according to Mol ratio is as shown in table 2, and the C-Ti-MWW molecular sieves obtained in (1) then are placed in the dispersed 1h of above-mentioned solution ultrasound (ratios of the C-Ti-MWW in mixed solution is as shown in table 2 in different embodiments).25 DEG C of crystallization in closed vessel afterwards 36h, Synthesis liquid centrifuge, and obtained solid product is washed till neutrality, is dried in 80 DEG C of vacuum drying ovens, with 4 in air atmosphere DEG C/rate of heat addition of min from room temperature rise to that roasting 6 is small at 550 DEG C when removed template method and carbon distribution component, obtain Ti-MWW Si Molecular sieve, the titanium-silicon molecular sieve catalyst product obtained in each embodiment, name are as shown in table 2.
Table 1
Embodiment Concentration of glucose/% Glucose Liquid quality/g Revolving temperature/DEG C Calcination temperature in N2/DEG C Roasting time/h in N2
Embodiment 1 15.0% 18.57 60 500 2
Embodiment 2 35.0% 30.00 60 400 8
Embodiment 3 25.0% 56.67 70 550 4
Embodiment 4 20.0% 15.00 90 450 8
Embodiment 5 20.0% 56.67 80 500 6
Embodiment 6 35.0% 40.00 50 550 4
Embodiment 7 25.0% 30.00 50 550 4
Embodiment 8 5.0% 15.00 80 600 2
Table 2
*：It is represented as the molar ratio of alkyl silicate.
**：C-Ti-MWW molecular sieves are put into the mass percent in the mixed solution of alkyl silicate.
Embodiment 9~16 and comparative example 3~7
Propylene ring oxidation reaction carries out in stainless steel cauldrons of the 1000mL with teflon lined.
It is 30.0wt%'s by titanium-silicon molecular sieve catalyst, 30ml concentration in 150mg embodiments 1~8 and comparative example 1~2 H2O2And 60ml pure solvents are added in reaction kettle, reaction kettle is sealed, leads to air in propylene replacement reaction kettle three times, Ran Housheng Temperature starts the continuous propylene that is passed through and reacts (reaction pressure, propylene decompression maximum pressure 3.0MPa), after reacting 2h to 40 DEG C.Stop Reaction, reaction kettle is put into frozen water and is cooled to 15 DEG C, to reaction after isopropanol is added in mixture as internal standard and solvent Solution, after mixing with gas chromatographic analysis, the results are shown in Table 3.Reaction solution ceriometry is remaining to cross H2O2, really H used in fixed2O2Amount.
Table 3
From table 3 it is observed that 9~16 Ti-MWW@Si molecular sieves being modified using surface are relative to contrast in embodiment Using use TS-1 molecular sieves in Ti-MWW molecular sieves and comparative example 4 in example 3, propylene oxide (PO), propylene oxide selectively, H2O2Conversion ratio and H2O2The index parameters such as effective rate of utilization all have clear improvement, and Ti-MWW molecular sieves are selecting acetonitrile as molten Catalytic effect is substantially better than in comparative example 5~7 using methanol, acetone, 1,3- dichloroethanes equal solvents during agent, this illustrates this hair The core shell structure Titanium Sieve Molecular Sieve Ti-MWW@Si of bright micropore-mesopore can improve liquid propylene epoxidation process in acetonitrile Yield, selectivity and the H of propylene oxide2O2Utilization rate.
The embodiment only technical concepts and features to illustrate the invention, its object is to allow person skilled in the art Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention The equivalent change or modification that Spirit Essence is made, should be covered by the protection scope of the present invention.

Claims (8)

1. a kind of Ti-MWW@Si molecular sieves with core shell structure, kernel is the titanium silicon molecule that micropore has MWW topological structures Sieve, shell is SiO2Mesopore molecular sieve；Kernel Ti-MWW framework of molecular sieve is made of Ti, Si, O element, wherein in terms of TiO2 The weight content of calculation is 2.0wt%~5.2wt%；The shell SiO2Mesopore molecular sieve accounts for whole core shell structure molecular sieve 2.0wt%~10.0wt%.
2. the preparation method of molecular sieve as claimed in claim 1, it is characterised in that：
(1) Ti-MWW zeolite crystals are dispersed in 5wt%~35wt% glucose solutions and form suspension slurry, wherein dividing Son sieve quality accounts for 10wt%~40wt% of mixture quality；
(2) 50~90 DEG C of rotatory vacuum drying removing moisture of mixed serum that will be obtained in (1), are enriched in glucose molecule Ti-MWW zeolite crystals surface, then in N2When 400~600 DEG C of roastings 1~10 are small under atmosphere, C-Ti-MWW molecules are obtained Sieve；
(3) it is template CTAB, template P123, ammonium hydroxide absolute ethyl alcohol and deionized water ultrasound is dispersed, at 30~50 DEG C 0.5~4.0h of mechanical agitation, then cool to 25 DEG C and add alkyl silicates and be vigorously stirred 1~10min and obtain mixed solution, then The C-Ti-MWW molecular sieves obtained in (2) are mixed with above-mentioned mixed solution, the quality in solution shared by C-Ti-MWW molecular sieves Ultrasonic dispersed 0.5~4.0h obtains mixed serum to percentage 4%~17% in the solution, is placed in closed vessel 25 DEG C 12~48h of crystallization, carries out the obtained solid product of separation of solid and liquid and is washed till neutrality, drying, in air atmosphere with 2~5 DEG C/min The rate of heat addition from room temperature rise at 500~600 DEG C roasting 4~10 it is small when removed template method and carbon distribution component, obtain with core The Ti-MWW@Si molecular sieves of shell structure.
3. preparation method according to claim 2, it is characterised in that：Alkyl silicate includes positive silicic acid first in step (3) Any one in ester, ethyl orthosilicate, positive silicic acid propyl ester, positive isopropyl silicate, butyl silicate.
4. preparation method according to claim 2, it is characterised in that：Mixed serum component is according to mole matching somebody with somebody in step (3) Compare Si：CTAB：P123：EtOH：NH3：H2O=1：0.08~0.20：0.004~0.01：50~100：15~35：600~800, Wherein alkyl silicate is calculated with the molal quantity of Si.
5. the Ti-MWW@Si molecular sieves with core shell structure that such as Claims 1 to 4 any one preparation method obtains are as third The application of alkene epoxidation catalysts.
6. application according to claim 5, it is characterised in that：Propylene, hydrogen peroxide, acetonitrile, water are inputted as charging Into epoxidation reactor, reaction obtains propene oxide product under epoxidation reaction condition.
7. application according to claim 6, it is characterised in that：Gross weight meter based on liquid feed stream, ethane nitrile content are 50~75wt%, content of hydrogen peroxide are 6~28wt%；The molar ratio of propylene and hydrogen peroxide is 2.0~5.0.
8. application according to claim 5, it is characterised in that：Reaction uses and is operated batch-wise or continuously mode, epoxy It is 25~100 DEG C to change reaction temperature,；Epoxidation reaction pressure is 14~100bar.
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Cited By (3)

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CN112007690A (en) * 2019-05-31 2020-12-01 中国石油化工股份有限公司 Core-shell structure titanium-silicon material, preparation method thereof and method for producing ketoxime through macromolecular ketone ammoximation reaction
CN112138703A (en) * 2019-06-27 2020-12-29 中国石油化工股份有限公司 Modified SBA-15 molecular sieve material and preparation method thereof, isobutane dehydrogenation catalyst and preparation method and application thereof
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CN112007690A (en) * 2019-05-31 2020-12-01 中国石油化工股份有限公司 Core-shell structure titanium-silicon material, preparation method thereof and method for producing ketoxime through macromolecular ketone ammoximation reaction
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