CN104556114B - A kind of method of the micro- mesoporous composite material of synthesis of titanium silicon - Google Patents

A kind of method of the micro- mesoporous composite material of synthesis of titanium silicon Download PDF

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CN104556114B
CN104556114B CN201410561925.3A CN201410561925A CN104556114B CN 104556114 B CN104556114 B CN 104556114B CN 201410561925 A CN201410561925 A CN 201410561925A CN 104556114 B CN104556114 B CN 104556114B
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ammonium
silicon source
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CN104556114A (en
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夏长久
林民
朱斌
彭欣欣
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above

Abstract

A kind of method of the micro- mesoporous composite material of synthesis of titanium silicon, forms crystallization mixture, crystallization including by titanium source, template, water, polyhydric alcohol, peroxide and silicon source, optional inorganic source of ammonium, reclaims HTS；Described template includes quaternary organic ammonium compounds, chain alkyl ammonium compoundss and optional organic amine compound.The method can improve the activity of synthesized HTS.

Description

A kind of method of the micro- mesoporous composite material of synthesis of titanium silicon
Technical field
The present invention relates to a kind of HTS synthetic method, furtherly it is related to a kind of micro- mesoporous molecular of synthesis of titanium silicon The method of sieve composite.
Background technology
HTS is the new hetero-atom molecular-sieve starting the early 1980s to develop.Synthesize at present The TS-1 having MFI type structure, the MCM-22 and the TS- with larger pore structure of the TS-2 of MEL type structure, MWW type structure 48 etc..Wherein TS-1 is that Italian EniChem company develops synthesis earliest, is to introduce transition metal titanium to have ZSM- A kind of novel titanosilicate with superior catalytic selective oxidation performance formed in the framework of molecular sieve of 5 structures, TS- 1 catalysed oxidn not only with titanium, but also there is the shape-selective effect of ZSM-5 molecular sieve and excellent stability.Using This HTS, as catalyst, can be catalyzed polytype organic oxidizing reaction, such as the epoxidation of alkene, alkane Partial oxidation, the oxidation of alcohols, the hydroxylating of phenols, ammoxidation of cyclic ketones etc..Because TS-1 molecular sieve is in the oxidation of Organic substance In reaction, can be using free of contamination low concentration hydrogen peroxide as oxidant, it is to avoid oxidizing process complex process and pollution ring The problem in border, has the unrivaled energy-conservation of conventional oxidation system, economy and advantages of environment protection, and has good reaction Selectivity.HTS is as Organic substance catalyst for selective oxidation it is considered to be a mileage in molecular sieve catalytic field Upright stone tablet, can overcome the drawbacks such as conventional catalyst oxidation system reaction process complexity, condition harshness and serious environment pollution from source, Therefore it, in today of environmental protection requirement increasingly stringent, receives the especially great attention of people.
Nineteen eighty-three Taramasso reported first hydrothermal crystallization method synthesis of titanium silicon molecular sieve in patent US 4410501 Method.This method is the classical way of synthesis TS-1, and mainly point glue and crystallization two step are carried out, and building-up process is as follows：By positive silicic acid Ethyl ester (TEOS) puts into nitrogen protection no CO2Container in, be slowly added to TPAOH (template), then slowly Deca metatitanic acid four Ethyl ester (TEOT), stirs 1h, and a kind of reactant mixture containing silicon source, titanium source and organic base be obtained, heating, except alcohol, moisturizing, 175 DEG C under self-generated pressure kettle stir under, crystallization 10 days, be then peeled off, wash, being dried, roasting and obtain TS-1 molecular sieve.But In this technique, titanium insertion skeleton process influence factor is numerous, and the condition of hydrolysis and nucleation is all wayward, and therefore this method synthesizes TS-1 molecular sieve has that catalysis activity is low, stability is poor, is difficult to the drawback such as synthesize and reappear.
Disclosed HTS (Zeolites, page 1992, Vol.12 the 943rd～950) the preparation side of Thangaraj et al. In method, in order to balance the hydrolysis rate of organosilicon and titanium, in the hydrolytic process of titanium, introduce isopropanol, but what the method obtained HTS activity is not high.
Chinese patent CN98101357.0 (CN1260241A) discloses HTS reordering technique, has synthesized and has had solely The novel titanosilicate of special hollow-core construction, not only makes the repeatability of synthesis TS-1 greatly enhance, also add molecular sieve hole body Long-pending, substantially increase mass transfer diffusion rate in molecular sieve pore passage for the reactant molecule, catalytic performance increases.Disclosed in this patent Method by the hydrating solution of titanium with the TS-1 molecular sieve that synthesized according to molecular sieve (gram)：Ti (mole)=200～1500: 1 ratio mix homogeneously, gained mixture is reacted 1～8 day with 120～200 DEG C in a kettle., filters, washs and do Dry.At present, HTS molecular sieve is applied to the processes such as oxidation phenol hydroxylating, cyclohexanone oxamidinating and has been carried out industrialization, tool Have the advantages that reaction condition is gentle, atom utilization is high, technical process is simple and by-product is water clean and effective.
Content of the invention
The technical problem to be solved in the present invention is to provide a kind of micro- mesopore molecular sieve of titanium silicon (the also referred to as micro- mesoporous molecular of titanium silicon Sieve composite, the micro- mesoporous composite molecular sieve of titanium silicon, the micro- mesoporous composite material of titanium silicon or the micro- mesoporous material of titanium silicon) synthesis side Method.
A kind of synthetic method of the micro- mesopore molecular sieve of titanium silicon, including by titanium source, template, water, polyhydric alcohol, peroxide and Silicon source, optional inorganic source of ammonium form crystallization mixture, crystallization, the micro- mesopore molecular sieve of recovery Pd silicon；Described template includes Machine quaternary ammonium compound, long-chain organoammonium compound (also referred to as chain alkyl ammonium compoundss) and optional organic amine compound.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, introduces polyhydric alcohol and peroxidating in building-up process Thing, polyhydric alcohol is 0.01～0.8: 1, preferably 0.05～0.7: 1 for example, 0.05～0.5: 1 with the mol ratio of silicon source, peroxidating Thing is 0.01～0.25: 1, for example, 0.05～0.25: 1 or 0.05～0.15: 1 with the mol ratio of silicon source.Described polyhydric alcohol For the alcohols containing two or more hydroxyls in molecule；Preferably, in described polyol molecule, carbon atom number is 2～8 Individual, described hydroxyl for example, 2 or 3, in described polyhydric alcohols such as glycerol, ethylene glycol, hexanediol, diethylene glycol Plant or multiple.Described peroxide is the compound containing peroxide bridge, for example hydrogen peroxide, tert-butyl peroxide, peracetic acid, One or more of trifluoro peracetic acid etc..Introduce polyhydric alcohol and peroxide so that obtained HTS has Less crystallite dimension (or claiming grain size, the size of crystal grain short-axis direction), has higher activity.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, described silicon source is organic silicon source and/or solid silicon Source.Described titanium source is organic titanium source and/or inorganic ti sources.Described template is conventional in HTS building-up process One or more of template, for example, organic base, organic quaternary ammonium salt, described organic bases such as quaternary ammonium base and/or Organic amine.Water is 5～100: 1 with the mol ratio of silicon source (also referred to as total silicon source)；Template is 0.04～0.6 with the mol ratio of silicon source ∶1；Polyhydric alcohol is 0.01～0.8 with the mol ratio of silicon source, and peroxide is 0.01～0.25: 1 with the mol ratio of silicon source；Titanium source Mol ratio with silicon source is 0.005～0.05: 1.Peroxide is 0.01～0.25: 1 with the mol ratio of silicon source.Described silicon source It is with SiO2Organic silicon source of meter and the summation of solid silicon source.Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, institute State in the first embodiment, the mol ratio of described titanium source and silicon source is 0.005～0.05: 1, for example, 0.008～0.3: 1 Or 0.01～0.025: 1, further titanium source is, for example, 0.015～0.025: 1 with the mol ratio of silicon source.Described template and with SiO2Meter silicon source mol ratio be 0.08～0.6: 1, for example, 0.1～0.5: 1 or 0.1～0.3: 1 or be 0.1～0.2: 1； Described water is 5～100: 1, for example, 5～80: 1 or 6～50: 1 or 6～30: 1 or 6～15: 1 with the mol ratio of silicon source.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, described inorganic source of ammonium is inorganic ammonium salt and/or ammonia Water, preferably ammonia, with NH4 +The inorganic source of ammonium of meter and the mol ratio of titanium source are 0～5: 1, for example, 0.01～4: 1, preferably 0.05 ～0.5: 1.In the context of the present invention, introduce inorganic source of ammonium and be conducive to improving the oxidation activity of synthesized molecular sieve, improve skeleton Titanium silicon ratio.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, described organic silicon source is organo-silicon ester, described Organo-silicon ester, its formula is Si (OR1)4, R1Selected from the alkyl such as R with 1～6 carbon atom1For C1-C4Alkyl, described Alkyl can be branched alkyl or straight chained alkyl.Described organo-silicon ester such as quanmethyl silicate, tetraethyl orthosilicate, silicic acid four One or more of butyl ester, dimethyl diethyl estersil；Wherein preferred quanmethyl silicate, tetraethyl orthosilicate, dimethyl diethyl One or more of base estersil.Solid silicon source described in the present invention is highly purified silica solid or powder, for example Can be white carbon and/or high-purity silica gel.Under preferable case, SiO in described solid silicon source on the basis of butt weight2 Content is not less than 99.99 weight %, and the gross mass content of Fe, Al and Na impurity is less than 10ppm in terms of element；Such as SiO2Contain Measure as 99.99～100 weight %, typically greater than 99.99 and be less than 100 weight %.Described solid silicon source can be high-purity Degree silica gel and/or white carbon, preferably white carbon；SiO in wherein said silica gel2Content is preferably greater than or equal to 99.99 weight % examples As for more than 99.99 weight % and be less than 100 weight %, and the gross mass content of Fe, Al and Na impurity be less than 10ppm.Described The specific surface area of white carbon is preferably between 20-1000m2It is, for example, 50-400m between/g2/ g, with the butt weight of white carbon as base Standard, SiO in described white carbon2It is, for example, that 99.99～100 weight % are for example, big that content is preferably greater than or equal to 99.99 weight % In 99.99 weight % and less than 100 weight %, in described white carbon in terms of atom, the gross mass content of Fe, Al and Na impurity is little In 10ppm.Described white carbon can be commercially available, or according to existing method preparation, such as according to patent CN200910227646.2 The method preparation providing, a kind of preparation method is to occur combustion reaction to obtain with hydrogen and oxygen in Silicon chloride..
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, described titanium source is organic titanic compound or inorganic titanium Compound, such as tetraalkyl titanate (Ti (alkoxy)4、TiCl4、Ti(SO4)2And one of their hydrolyzate or Multiple.The carbon number of the alkyl wherein in tetraalkyl titanate is 1～6, for example, 1,2,3,4,5 or 6.
The present invention provide titanium silicon micro- mesopore molecular sieve synthetic method, described template agent include quaternary organic ammonium compounds and Chain alkyl ammonium compoundss, can optionally contain organic amine compound, and quaternary organic ammonium compounds are 0.04 with the mol ratio of total silicon source ～0.45: 1, the mol ratio of chain alkyl ammonium compoundss and total silicon source is 0.04～0.45: 1, organic amine and total silicon source mole Than for 0～0.4: 1.Described quaternary organic ammonium compounds are, for example, organic quaternary amine alkali and/or organic quaternary ammonium salt.Described organic amine For one or more of fatty amine, aromatic amine and hydramine, described fatty amine (also referred to as fat amine compound), its formula is R3(NH2)n, wherein R3For having alkyl or the alkylidene of 1～4 carbon atom, n=1 or 2；Described hydramine (the present invention Alcamine compound) its formula is called (HOR4)mN(3-m), wherein R4For having the alkyl of 1～4 carbon atom, m=1,2 or 3.Institute The fatty amine stated such as one or more of ethamine, n-butylamine, butanediamine or hexamethylene diamine；Described aromatic amine refers to there is one The amine of individual armaticity substituent group, such as one or more of aniline, toluidines, p-phenylenediamine；The for example single second of described hydramine One or more of hydramine, diethanolamine or triethanolamine.Described quaternary ammonium base for example TPAOH, four One or more of butyl ammonium hydroxide or tetraethyl ammonium hydroxide；Described organic quaternary ammonium salt such as 4-propyl bromide, One of tetrabutyl ammonium bromide, tetraethylammonium bromide, 4-propyl ammonium chloride, tetrabutylammonium chloride or tetraethylammonium chloride or many Kind.
The synthetic method of the micro- mesopore molecular sieve of titanium silicon that the present invention provides, a kind of specific embodiment, described titanium silicon is micro- Mesoporous composite molecular sieve has MFI structure, and described quaternary organic ammonium compounds include TPAOH, tetrapropyl chlorination One or more of ammonium, 4-propyl bromide.In TPAOH, 4-propyl ammonium chloride, 4-propyl bromide one Plant or multiple mol ratio with total silicon source is 0.01～0.5: 1, preferably 0.02～0.45: 1.
The synthetic method of the micro- mesopore molecular sieve of titanium silicon that the present invention provides, the titanium silicon described in a kind of embodiment is micro- mesoporous multiple Close molecular sieve and there is MEL structure, described quaternary organic ammonium compounds include TBAH, tetrabutyl ammonium bromide or four fourths One or more of ammonium chloride.One of TBAH, tetrabutyl ammonium bromide or tetrabutylammonium chloride or many The summation planted is 0.01～0.5: 1, preferably 0.02～0.45: 1 with the mol ratio of total silicon source.
The synthetic method of the micro- mesopore molecular sieve of titanium silicon that the present invention provides, a kind of embodiment, described titanium silicon is micro- mesoporous Composite molecular screen has BEA structure, described quaternary organic ammonium compounds include tetraethyl ammonium hydroxide, tetraethylammonium bromide, four One or more of ethyl ammonium chloride.Described quaternary organic ammonium compounds include tetraethyl ammonium hydroxide, tetraethylammonium bromide, The summation of one or more of tetraethylammonium chloride with the mol ratio of total silicon source be 0.01～0.5: 1, preferably 0.02～ 0.45∶1.
The synthetic method of the micro- mesopore molecular sieve of titanium silicon that the present invention provides, described its formula of chain alkyl ammonium compoundss is R5NH3X or R5N(R6)3X, wherein R5For alkyl between 12～18 for the carbon number, R6For carbon number between 1～4 Alkyl；X is, for example, OH for univalent anion-、Cl-、Br-；When X is OH-When, the present invention is referred to as alkali formula chain alkyl ammonium compoundss； Described organic silicon source is organo-silicon ester, described organo-silicon ester, and its formula is Si (OR1)4, R1Former selected from having 1～6 carbon The alkyl of son, described alkyl is branched-chain or straight-chain alkyl.Described quaternary ammonium base such as TPAOH, the tetrabutyl One or more of ammonium hydroxide or tetraethyl ammonium hydroxide；Described organic quaternary ammonium salt such as 4-propyl bromide, four fourths One or more of base ammonium bromide, tetraethylammonium bromide, 4-propyl ammonium chloride, tetrabutylammonium chloride or tetraethylammonium chloride； Described chain alkyl ammonium compoundss such as cetyl trimethylammonium bromide, cetyl chloride ammonium, cetyl trimethyl Ammonium hydroxide, chain alkyl ammonium compoundss are Tetradecyl Trimethyl Ammonium Bromide, tetradecyl ammonium chloride, CPC Base ammonium hydroxide, Dodecyl trimethyl ammonium chloride, lauryl ammonium chloride, trimethyl ammonium hydroxide, octadecane One or more of base trimethylammonium bromide, octadecyl ammonium chloride, octadecyl trimethyl ammonium hydroxide.
The mol ratio of the synthetic method of the micro- mesopore molecular sieve of titanium silicon that the present invention provides, quaternary organic ammonium compounds and total silicon source For 0.05～0.45: 1, long-chain organic amine compound is 0.05～0.45: 1 with the mol ratio of total silicon source.In the case of preferably, institute The template stated at least includes a kind of organic base, and described organic base is quaternary ammonium base, organic amine, alkali formula chain alkyl ammonium One or more in compound, the organic base in described template agent is 0.04～0.5: 1, such as 0.05 with the mol ratio of total silicon source ～0.45: 1.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, by titanium source, template, water, polyhydric alcohol and optional silicon Source, optional inorganic source of ammonium form crystallization mixture, then by described crystallization mixture crystallization, form crystallization product, crystallization Product obtains HTS through recovery.Described crystallization, can adopt existing method, and for example, the temperature of crystallization is 110～ 200 DEG C, crystallization time 0.2～20 day, carry out crystallization under self-generated pressure.A step crystallization can be adopted, it would however also be possible to employ substep is brilliant Change.A kind of embodiment, the temperature of described crystallization is 140～180 DEG C such as 160～180 DEG C, and crystallization time is 0.5～10 day For example, 0.5～6 day, crystallization pressure was self-generated pressure.A kind of embodiment, described crystallization is：At 100～130 DEG C for example 110～130 DEG C of crystallization 0.5～1.5 day, then crystallization 1～3 day at 160～180 DEG C, crystallization pressure is self-generated pressure.
The micro- mesopore molecular sieve of described recovery Pd silicon is existing method, for example, generally include crystallization product is filtered, wash and Roasting or crystallization product is filtered, washs, be dried then roasting.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, the first embodiment, comprise the following steps：
(1) by titanium source, template, water, polyhydric alcohol and optionally organic silicon source mixing, alcohol is caught up with hydrolysis；It is subsequently adding peroxidating Thing；
(2) product that step (1) obtains is aging；
(3) add or be added without solid silicon source, crystallization in the product that step (2) obtains, reclaim HTS；
Wherein, introduce described silicon source at least one step in step (1) and step (3), described template includes Machine quaternary ammonium compound, chain alkyl ammonium compoundss and optional organic amine compound.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, in the first embodiment described, the silicon that used Source is organic silicon source and/or solid silicon source, and the silicon source present invention wherein introducing in step (1) is referred to as first time silicon source, in step Suddenly the silicon source introducing in (3), the present invention is referred to as second silicon source.Wherein it is preferable that organic silicon source introduces in step (1), solid Silicon source (for inorganic silicon source) introduces in step (3).Organic silicon source can be simply used it is also possible to simply use solid silicon source, Using solid silicon source under preferable case.Described silicon source (also referred to as total silicon source) is with SiO2Meter organic silicon source and with SiO2Meter The summation of inorganic silicon source；When simply using organic silicon source, then described silicon source is organic silicon source, when simply using described solid Silicon source, then described silicon source is solid silicon source；When using solid silicon source and organic silicon source, then described silicon source be solid silicon source and Organic silicon source sum.It is preferred that described silicon source includes solid silicon source in the first embodiment described, introduce in step (3) Solid silicon source, wherein with SiO2Organic silicon source in meter step (1) with SiO2In meter step (3), the solid silicon source of introducing rubs That ratio for example, 0～1: 20, preferably 1: 0.1～20, the HTS of surface Silicon-rich can be obtained.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, in the first embodiment described, in building-up process Middle introducing polyhydric alcohol and peroxide, polyhydric alcohol is 0.01～0.8: 1 with the mol ratio of total silicon source, peroxide and total silicon source Mol ratio is 0.01～0.25: 1 for example, 0.05～0.25: 1.Introduce polyhydric alcohol and peroxide so that obtained titanium silicon Molecular sieve has higher activity, has less crystallite dimension (or claiming grain size, the size of crystal grain short-axis direction).Wherein Polyhydric alcohol is 0.01～0.8: 1 with the mol ratio of total silicon source, and peroxide is 0.01～0.25: 1 with the mol ratio of total silicon source, has Machine amine is 0～0.4: 1 with the mol ratio of total silicon source, and quaternary organic ammonium compounds are 0.05～0.45: 1 with the mol ratio of total silicon source, Chain alkyl ammonium compoundss are 0.05～0.25: 1 with the mol ratio of total silicon source；Described total silicon source is with SiO2The organosilicon of meter Source and the summation of solid silicon source.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, in the first embodiment described, will in step (1) Titanium source, template, water, polyhydric alcohol, optional organic silicon source and optional inorganic source of ammonium mixing, can in any way by Organic silicon source optionally, titanium source, template, optional inorganic source of ammonium, water and polyhydric alcohol mixing, are hydrolyzed and catch up with alcohol, made Machine silicon source and titanium source hydrolysis, reduce the content of the monohydric alcohol that hydrolysis produces.It can be will to include organic silicon source that alcohol is caught up with described hydrolysis And/or the mixture of titanium source and water stirs at least 10 minutes at 0～150 DEG C such as 0～100 DEG C preferably 50～95 DEG C and for example stirs Mix 10～3000 minutes, so that organic silicon source and titanium source hydrolysis, and reduce the monohydric alcohol of organic silicon source and titanium source hydrolysis generation Content.Generally, the content hydrolyzing the monohydric alcohol catching up with the water in products solution that alcohol obtains to produce is less than 10ppm (quality).Preferably, water Solution catches up with the content of monohydric alcohol in the product that alcohol obtains to be less than 10ppm (quality).
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, in the first embodiment described, in step (2), Will be aging for step (1) products therefrom, described aging be at room temperature～50 DEG C by step (1) products therefrom stand 1～60 hour. Described room temperature is 15～40 DEG C；Ageing time is 1～60 hour for example, 3～50 hours preferably 3～15 hours, in ageing process It is not stirred, described material is step (1) products therefrom standing.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, described crystallization, existing method can be adopted, for example, The temperature of crystallization is 110～200 DEG C, and crystallization time 0.2～20 day carries out crystallization under self-generated pressure.A step crystallization can be adopted, Fractional crystallization can also be adopted.A kind of embodiment, the temperature of described crystallization is 140～180 DEG C such as 160～180 DEG C, crystallization Time is 0.5～10 day for example, 0.5～6 day, and crystallization pressure is self-generated pressure.A kind of embodiment, described crystallization is：? 100～130 DEG C of such as 110～130 DEG C crystallization 0.5～1.5 day, then crystallization 1～3 day at 160～180 DEG C, crystallization pressure For self-generated pressure.
The micro- mesopore molecular sieve of titanium silicon of the present invention, has microcellular structure, also has meso-hole structure, the aperture of described micropore Less than 1nm, described mesoporous aperture (diameter) is between 2-8nm.2 θ angles in the micro- mesoporous composite molecular sieve XRD spectra of described titanium silicon For 0～3 ° and 5～35 °, there is diffraction maximum.The XRD spectra of molecular sieve has diffraction maximum at 2 θ angles for 5～35 degree, shows molecular sieve In there is microcellular structure；2 θ angles of molecular sieve have diffraction maximum for 0～3 degree, show to exist meso-hole structure in molecular sieve.
The micro- mesopore molecular sieve of titanium silicon of the present invention, the volume that aperture is less than the micropore of 1nm be micro pore volume be 0.12～ 0.19mL/g, aperture be the mesoporous volume of 2-8nm be mesopore volume be 0.3～0.8mL/g.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, can improve the oxidation activity of synthesized molecular sieve, Improve the utilization rate of titanium, synthesized HTS can have less crystal grain.
Brief description
(titanium silicon TS-1 is combined micro- Jie to the micro- mesopore molecular sieve of titanium silicon of MFI structure of having that Fig. 1 is prepared for the embodiment of the present invention Porous materials) XRD spectra.
(TS-1 molecular sieve is combined micro- the micro- mesopore molecular sieve of titanium silicon of MFI structure of having that Fig. 2 is prepared for the embodiment of the present invention Mesoporous material) little angle XRD (0.5-3 °) spectrogram.
Titanium silicon micro- mesopore molecular sieve (the titanium silicon with MFI structure through rearrangement that Fig. 3 is prepared for the embodiment of the present invention TS-1 molecular sieve is combined micro- mesoporous material) TEM figure.
Fig. 4 is surface silicon titanium than the measuring method schematic diagram with body phase silicon titanium ratio.It is to measure body phase silicon titanium using TEM-EDX The silicon titanium ratio of measurement particle surface illustrated by the schematic diagram with surface silicon titanium ratio for the ratio, wherein square frame 1, and square frame 2 is illustrated in measurement granule The silicon titanium ratio in heart district domain.Because particle surface territorial unit volume has higher external surface area, and the unit bodies of central area In long-pending, corresponding external surface area is relatively low, and therefore in square frame 1 and square frame 2, EDX measurement result can reflect the silicon titanium ratio on surface and body phase Difference.
(also referred to as titaniferous silicon is micro- composite mesoporous for the micro- mesopore molecular sieve of titanium silicon of MFI structure of having that the present invention synthesizes for Fig. 5 TS-1 molecular sieve) (embodiment 1 step (3) gained) nitrogen absorption under low temperature desorption curve.
Specific embodiment
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, one kind preferred embodiment, comprises the steps：
(1) by template, titanium source, organic silicon source, water, polyhydric alcohol and optional inorganic source of ammonium mixing, hydrolysis catches up with alcohol, then Add peroxide；Alcohol is caught up with described hydrolysis, generally at 0～150 DEG C such as 0～100 DEG C such as 50～95 DEG C by gained Mixture stirs at least 10 minutes, and the wherein mixing time of stirring is 10 minutes～50 hours；Wherein inorganic source of ammonium is (with NH4 + Meter)：Titanium source is (with TiO2Meter) mol ratio be 0～5: 1；
(2) will be aging for step (1) products therefrom, described aging be will be quiet at room temperature～50 DEG C for step (1) products therefrom Put 1～60 hour such as 2～50 hours or 3～30 hours, such as 3～15 hours further；
(3) ageing products obtained by step (2) are mixed homogeneously according to 1: 0.1～20 weight ratio with solid silicon source, Then crystallization (crystallization for example in closed reactor), reclaims HTS；In wherein said part by weight, step (2) Obtained ageing products and solid silicon source are all with SiO2Meter；
Wherein, water and the mol ratio of total silicon source are 5～100: 1；Template is 0.08～0.6: 1 with the mol ratio of total silicon source For example, 0.1～0.5: 1 for example, 0.15～0.3: 1 or be 0.1～0.2: 1；The mol ratio of titanium source and total silicon source is 0.005～ 0.05: 1 for example, 0.01～0.03: 1, further for 0.01～0.025: 1；Described template be quaternary organic ammonium compounds, Chain alkyl ammonium compoundss and optional organic amine, organic amine is 0～0.4: 1 with the mol ratio of total silicon source, organic quaternary ammonium chemical combination Thing is 0.05～0.45: 1 with the mol ratio of total silicon source, and chain alkyl ammonium compoundss are 0.05～0.45 with the mol ratio of total silicon source : 1 such as 0.05～0.25: 1.
Wherein, in described mol ratio, total silicon source is with SiO2Meter, described total silicon source is with SiO2Meter organic silicon source and with SiO2The summation of the solid silicon source of meter, inorganic source of ammonium is with NH4 +Meter；Described inorganic source of ammonium is inorganic ammonium salt and/or ammonia, titanium source With TiO2Meter, water is with H2O counts.
The present invention provide titanium silicon micro- mesopore molecular sieve synthetic method, described preferred embodiment, first time silicon source is Organic silicon source, second silicon source is solid silicon source, prepared zeolite crystal surface Silicon-rich, and grain surface silicon titanium ratio is substantially high In body phase silicon titanium ratio, the ratio of grain surface silicon titanium mol ratio and body phase silicon titanium mol ratio is 1.1～5: 1, for example, 1.2～4: 1 Or be 1.3～3: 1.Obtained HTS, has higher surface silicon titanium than the ratio with body phase silicon titanium ratio, has higher Oxidation activity, for hydrogen peroxide participate in oxidation reaction, it is possible to reduce the decomposition to hydrogen peroxide for the titanium in surface layer, be conducive to drop The activity of the decomposition side reaction of low hydrogen peroxide, improves raw material availability.Additionally, the micro- mesoporous molecular of titanium silicon that the present invention provides Sieve synthetic method, preferred embodiment using the relatively inexpensive solid silicon source being easy to get such as high-purity silica gel or/and white carbon, Part replace expensive organic silicon source, can reduce process of producing molecular sieve waste discharge and economize in raw materials cost while Obtain high performance HTS, can in the case of relatively low template agent consumption and relatively low water silicon ratio synthesis of titanium silicon molecule Sieve, can reduce the synthesis cost of HTS, improve the solid content of synthesis of molecular sieve crystallization product, improve one-pot molecular sieve Yield.
Wherein surface silicon titanium can be using TEM-EDX or ion excitation corrosion XPS method or XRF side than with body phase silicon titanium ratio Method measures and obtains, and wherein, surface silicon titanium ratio can be measured and be obtained using TEM-EDX or ion excitation corrosion XPS means, be that distance is brilliant Grain surface is less than the silicon titanium ratio of the atomic layer of 5nm such as 1～5nm；Body phase titanium silicon ratio can be obtained by chemico-analytic method Arrive, or the area measure more than 20nm obtains for example apart from grain surface distance in the central area of crystal grain by TEM-EDX, or Person is obtained by XRF measurement.
The present invention provide HTS synthetic method, described preferred embodiment, can be in lower template agent Synthesis of titanium silicon molecular sieve in the case of consumption, thus template agent consumption can reduce, such as template agent and having in terms of silicon dioxide The mol ratio of machine silicon source is 0.1～0.3: 1, further for 0.1～0.20: 1；In the method that the present invention provides, can be in Gao Gu Synthesis of titanium silicon molecular sieve under content, from can and reduce the usage amount of water, improve output per single reactor i.e. in same synthetic reaction body The more molecular sieves of long-pending lower synthesis, the mol ratio of therefore described water and total silicon source (being counted with silicon dioxide) can be for 5～50: 1, For example, 5～30: 1 or be 6～15: 1.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment in, described titanium source It is preferably 0.01～0.03: 1 for example, 0.01～0.025: 1 with the mol ratio of total silicon source.
The present invention provide titanium silicon micro- mesopore molecular sieve synthetic method, described preferred embodiment in, inorganic source of ammonium with The mol ratio of titanium source is 0～5: 1, for example, 0.01～4: 1, preferably 0.05～0.5: 1.Add inorganic source of ammonium, can improve The activity of synthesized molecular sieve, improves framework titania silicon ratio.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment in, described template Agent is not less than 0.08: 1 preferably 0.1～0.3: 1 with the mol ratio of described total silicon source.
The present invention provide titanium silicon micro- mesopore molecular sieve synthetic method, described preferred embodiment described in organic silicon source With the mol ratio of solid silicon source (with SiO2Meter first time silicon source and the mol ratio of second silicon source) it is preferably 1: 1～19, for example For 1: 2～18, or 3～17, or be 5～15: 1.Ageing products generally obtained by step (2) are equal to solid silicon source Organic silicon source and the mol ratio of solid silicon source.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment in, step (1) is described Template agent include quaternary organic ammonium compounds and chain alkyl ammonium compoundss, optionally also can contain organic amine compound, organic Quaternary ammonium compound is 0.04～0.45: 1 with the mol ratio of total silicon source, and chain alkyl ammonium compoundss with the mol ratio of total silicon source are 0.04～0.45: 1, organic amine is 0～0.4: 1 with the mol ratio of total silicon source.Described quaternary organic ammonium compounds are for example, organic Quaternary amine alkali and/or organic quaternary ammonium salt.Described organic amine is one or more of fatty amine, aromatic amine and hydramine, described Fatty amine (also referred to as fat amine compound), its formula is R3(NH2)n, wherein R3For have 1～4 carbon atom alkyl or Alkylidene, n=1 or 2；Described hydramine (present invention is also referred to as alcamine compound) its formula is (HOR4)mNH(3-m), wherein R4For There are the alkyl of 1～4 carbon atom, m=1,2 or 3.In described fatty amine such as ethamine, n-butylamine, butanediamine or hexamethylene diamine One or more；Described aromatic amine refers to the amine with an armaticity substituent group, for example aniline, toluidines, to benzene two One or more of amine；Described hydramine such as one or more of monoethanolamine, diethanolamine or triethanolamine.Described Quaternary ammonium base such as one or more of TPAOH, TBAH or tetraethyl ammonium hydroxide； Described organic quaternary ammonium salt such as 4-propyl bromide, tetrabutyl ammonium bromide, tetraethylammonium bromide, 4-propyl ammonium chloride, four fourths One or more of ammonium chloride or tetraethylammonium chloride.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, described its formula of chain alkyl ammonium compoundss is R5NH3X or R5N(R6)3X, wherein R5For alkyl between 12～18 for the carbon number, R6For carbon number between 1～4 Alkyl；X is, for example, OH for univalent anion-、Cl-、Br-；When X is OH-When, the present invention is referred to as alkali formula chain alkyl ammonium compoundss； Described organic silicon source is organo-silicon ester, described organo-silicon ester, and its formula is Si (OR1)4, R1Former selected from having 1～6 carbon The alkyl of son, described alkyl is branched-chain or straight-chain alkyl.Described quaternary ammonium base such as TPAOH, the tetrabutyl One or more of ammonium hydroxide or tetraethyl ammonium hydroxide；Described organic quaternary ammonium salt such as 4-propyl bromide, four fourths One or more of base ammonium bromide, tetraethylammonium bromide, 4-propyl ammonium chloride, tetrabutylammonium chloride or tetraethylammonium chloride； Described chain alkyl ammonium compoundss such as cetyl trimethylammonium bromide, cetyl chloride ammonium, cetyl trimethyl Ammonium hydroxide, chain alkyl ammonium compoundss are Tetradecyl Trimethyl Ammonium Bromide, tetradecyl ammonium chloride, tetradecyltrimethylammonium Ammonium hydroxide, Dodecyl trimethyl ammonium chloride, lauryl ammonium chloride, trimethyl ammonium hydroxide, octadecyl One or more of trimethylammonium bromide, octadecyl ammonium chloride, octadecyl trimethyl ammonium hydroxide.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, a kind of specific embodiment, described micro- Jie of titanium silicon Porous molecular sieve has MFI structure, described quaternary organic ammonium compounds include TPAOH, 4-propyl ammonium chloride, 4 third One or more of base ammonium bromide.One of TPAOH, 4-propyl ammonium chloride, 4-propyl bromide or many Kind is 0.01～0.45: 1 preferably 0.02～0.45: 1 with the mol ratio of total silicon source.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, the micro- mesoporous molecular of titanium silicon described in a kind of embodiment Sifter device has MEL structure, and described quaternary organic ammonium compounds include TBAH, tetrabutyl ammonium bromide or tetrabutyl chlorination One or more of ammonium.One or more of TBAH, tetrabutyl ammonium bromide or tetrabutylammonium chloride total And it is preferably 0.02～0.45: 1 with the mol ratio of total silicon source for 0.01～0.45: 1.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, a kind of embodiment, micro- mesoporous point of described titanium silicon Sub- sifter device has BEA structure, and described quaternary organic ammonium compounds include tetraethyl ammonium hydroxide, tetraethylammonium bromide, tetraethyl chlorine Change one or more of ammonium.Described quaternary organic ammonium compounds include tetraethyl ammonium hydroxide, tetraethylammonium bromide, tetraethyl The summation of one or more of ammonium chloride and the mol ratio with total silicon source are 0.01～0.45: 1 preferably 0.02～0.45: 1.
The mol ratio of the synthetic method of the micro- mesopore molecular sieve of titanium silicon that the present invention provides, quaternary organic ammonium compounds and total silicon source For 0.05～0.45: 1, long-chain organic amine compound is 0.05～0.45: 1 with the mol ratio of total silicon source.In the case of preferably, institute The template stated at least includes a kind of organic base, and described organic base is quaternary ammonium base, organic amine, alkali formula chain alkyl ammonium One or more in compound, the organic base in described template agent is 0.04～0.5: 1, such as 0.05 with the mol ratio of total silicon source ～0.45: 1.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment in, in step (1) Described organic silicon source is organo-silicon ester, described organo-silicon ester, and its formula is Si (OR1)4, R1Former selected from having 1～6 carbon The alkyl such as R of son1For C1-C4Alkyl, described alkyl can be branched alkyl or straight chained alkyl.Described organo-silicon ester Such as one or more of quanmethyl silicate, tetraethyl orthosilicate, silicic acid four butyl ester, dimethyl diethyl estersil；Wherein preferred One or more of quanmethyl silicate, tetraethyl orthosilicate, dimethyl diethyl estersil.Described solid silicon source is highly purified Silica solid or powder, for example, can be white carbon and/or high-purity silica gel.Under preferable case, with butt weight On the basis of SiO in described solid silicon source2Content is not less than 99.99 weight %, and in terms of atom Fe, Al and Na impurity gross mass Content is less than 10ppm；Such as SiO2Content be 99.99～100 weight %, typically greater than 99.99 and be less than 100 weight %. Described solid silicon source can be high-purity silica gel and/or white carbon, preferably white carbon；In wherein said high-purity silica gel SiO2Content is preferably greater than or equal to 99.99 weight % and is for example, more than 99.99 weight % and is less than 100 weight %, and Fe, Al and The mass content of the impurity such as Na is less than 10ppm；The specific surface area of described white carbon is preferably between 20-1000m2Between/g for example, 50-400m2/ g, on the basis of the butt weight of white carbon, SiO in described white carbon2Content is preferably greater than or equal to 99.99 weights Amount % is, for example, that 99.99～100 weight % are for example, more than 99.99 weight % and are less than 100 weight %, in terms of atom, described In white carbon, the quality total content of Fe, Al and Na is less than 10ppm.Described white carbon can be commercially available, or according to existing method system Method preparation that is standby, for example providing according to patent CN200910227646.2, a kind of preparation method is by Silicon chloride. and hydrogen Combustion reaction is occurred to obtain with oxygen.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment in, described titanium Source is organic titanic compound or inorganic titanium compound, such as tetraalkyl titanate (Ti (alkoxy)4、TiCl4、Ti(SO4)2And One or more of their hydrolyzate.The carbon number of the alkyl wherein in tetraalkyl titanate is 1～6, for example, 1st, 2,3,4,5 or 6.The mol ratio of titanium source and silicon source (total silicon source) preferably 0.01～0.03: 1 such as 0.015～0.025: 1.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment in, described titanium Source is organic titanic compound or inorganic titanium compound, such as tetraalkyl titanate (Ti (alkoxy)4、TiCl4、Ti(SO4)2And One or more of their hydrolyzate, described titanium source is preferably organic titanic compound.Wherein in tetraalkyl titanate Alkyl carbon number be 1～6, for example, 1,2,3 or 4.The mol ratio of titanium source and silicon source (total silicon source) is preferably 0.01～ 0.025: 1 such as 0.015～0.025: 1.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment in, in step (1) Described inorganic source of ammonium is inorganic ammonium salt and/or ammonia, described inorganic ammonium salt for example ammonium chloride, ammonium nitrate, in ammonium sulfate To one or more.Described inorganic source of ammonium is preferably ammonia, with NH4 +Meter ammonia with TiO2The mol ratio of titanium source of meter is 0～5: 1 for example, 0.01～4: 1 or be 0.05～0.5: 1.Add described inorganic quaternary ammonium salts, synthesized molecular sieve can be improved Activity, improve described surface silicon titanium than the ratio with body phase silicon titanium ratio.
The present invention provide titanium silicon micro- mesopore molecular sieve synthetic method in, described preferred embodiment in, step (1) in, titanium source, template, organic silicon source, inorganic source of ammonium and water are pressed mixing, alcohol is caught up with row hydrolysis.Alcohol is caught up with described hydrolysis, is 0 ～150 DEG C preferably 0～100 DEG C such as 50～90 DEG C are stirred at least 10 minutes, so that organic silicon source and titanium source hydrolysis, and reduce institute Obtain the unitary alcohol content in mixture.Generally mixing time is 10～3000 minutes, for example, 2～30 hours.Caught up with by hydrolysis Alcohol, obtains the organosilicon hydrolyzation liquid of clear.In the mixture that step (1) obtains, the content of monohydric alcohol is not preferably not higher than 10ppm (quality).Alcohol is caught up with by hydrolysis, obtains the organosilicon hydrolyzation liquid of clear.It is subsequently adding peroxide to stir, Generally mixing time is 10～60 minutes.Described polyhydric alcohol is the alcohols containing two or more hydroxyls in molecule, excellent Choosing, in described polyol molecule, carbon atom number is 2～8, described hydroxyl for example, 2 or 3, described polyhydric alcohols As one or more of glycerol, ethylene glycol, hexanediol, diethylene glycol.Described peroxide is the chemical combination containing peroxide bridge Thing, one of the preferred hydrogen peroxide of described peroxide, tert-butyl peroxide, peracetic acid, trifluoro peracetic acid etc. or many Kind.Polyhydric alcohol is 0.01～0.8, preferably 0.05～0.5: 1 with the mol ratio of silicon source, and peroxide with the mol ratio of silicon source is 0.01～0.25: 1, for example, 0.05～0.25: 1 or 0.05～0.15: 1.
Described polyhydric alcohols such as one or more of glycerol, ethylene glycol, diethylene glycol.Described peroxide is preferred One or more of hydrogen peroxide, tert-butyl peroxide, peracetic acid, trifluoro peracetic acid etc..Polyhydric alcohol and silicon source mole For 0.01～0.8, preferably 0.05～0.5: 1, peroxide is 0.01～0.25: 1, for example, 0.05 with the mol ratio of silicon source to ratio ～0.25: 1 such as 0.05～0.15: 1.
The present invention provide titanium silicon micro- mesopore molecular sieve synthetic method, described preferred embodiment in, in step (2), Will be aging for step (1) products therefrom, described aging be at room temperature～50 DEG C by step (1) products therefrom stand 1～60 hour. Described room temperature is 15～40 DEG C；Ageing time is 1～60 hour for example, 2～50 hours, preferably 3～30 hours for example, 3 ～15 hours, it is not stirred in ageing process, described material is step (1) products therefrom standing.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment in, will in step (3) The ageing products that step (2) obtains are mixed with solid silicon source, with SiO2Meter, the product that step (2) obtains is rubbed with solid silicon source Your ratio is 1: 0.1～20, for example, can be 1: 1～19 (i.e. the mol ratio of described organic silicon source and solid silicon source is 1: 1～19), Or be 1: 2～18 or 1: 3～17, further for 1: 5～15, with SiO2Preferred with the mol ratio of solid silicon source in respect of machine silicon source For 1: 5～15.The method that the present invention provides, it is possible to use the solid silicon source of higher proportion, can improve consolidating of synthetic product and contain Amount, thus improve the yield of single synthesis compared with being used alone organic silicon source in the case that synthesis reaction vessel is constant.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment in, step (3) is described Crystallization, the temperature of crystallization is 110～200 DEG C, and crystallization pressure is self-generated pressure, and the time of crystallization is 2 hours～20 days, usual institute The time stating crystallization is 0.5～20 day, and such as crystallization time is 0.5～10 day, the temperature of the crystallization described in further step (3) For 140～180 DEG C for example, 160～180 DEG C, crystallization time is 0.5～6 day for example, 1～6 day, further for example, 1～3 My god.Crystallization pressure is self-generated pressure.Described crystallization can be carried out in rustless steel stirred tank.Crystallization heats up can one section of intensification Can be with multistage heating mode.Heating rate can be carried out according to existing crystallization temperature-rising method, for example, 0.5-1 DEG C/min.Described crystalline substance Change can be carried out in rustless steel stirred tank.A kind of embodiment, the crystallization temperature of described crystallization is 160～180 DEG C, during crystallization Between be 1～6 day such as 0.5～3 day, crystallization pressure be self-generated pressure.A kind of embodiment, the crystallization described in step (3) is: Crystallization 0.5～1.5 day at 100～130 DEG C such as 110～130 DEG C, then crystallization 1～3 day at 160～180 DEG C, crystallization pressure Power is self-generated pressure.
The present invention provide titanium silicon micro- mesopore molecular sieve synthetic method, described preferred embodiment in, institute in step (3) Stating recovery HTS is existing method, including filtering crystallization product, wash and roasting or filter crystallization product, wash Wash, be dried and then roasting.The purpose filtering is that the HTS obtaining crystallization is separated with crystallization mother liquor, and the purpose of washing is Wash away the template solution on sieve particle surface for the absorption, for example, can be room temperature～50 DEG C in temperature, molecular sieve and water Weight compares 1: 1～20 such as 1: carries out mixing, washing or drip washing under (1-15).The purpose being dried is the big portion removing in molecular sieve Divide moisture, to reduce water evaporation quantity when roasting, the temperature being dried can be 100～200 DEG C.The purpose of roasting is to remove Template in molecular sieve, example as mentioned roasting temperature be 350～650 DEG C, roasting time be 2-10 hour.By reclaiming Obtain the micro- mesopore molecular sieve product of titanium silicon provided by the present invention.
In titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, reclaim the micro- mesopore molecular sieve of titanium silicon obtaining and also may be used Through processing further, titanium silicon micro- mesopore molecular sieve synthetic method that is, present invention provides, rearrangement step can also be included：
By reclaim the micro- mesopore molecular sieve of titanium silicon that obtains in organic alkali solution Crystallizing treatment preferably in organic quaternary ammonium alkali soluble Crystallizing treatment in liquid, the then micro- mesopore molecular sieve of recovery Pd silicon.The micro- mesopore molecular sieve of titanium silicon obtained by this process makes has sky Core structure, the present invention is referred to as molecular sieve and resets.Generally include for example preferably real by reclaiming the micro- mesopore molecular sieve of titanium silicon obtaining Apply the micro- mesopore molecular sieve of titanium silicon that the step (3) of mode obtains (with SiO2Meter) with organic base, water according to 1：0.02～0.5: 2～ 50 mol ratio forms mixture, in closed reactor and under self-generated pressure in 100～200 DEG C such as 110～150 DEG C or 120～200 DEG C of crystallization 0.1～10 day, then reclaim product, the micro- mesopore molecular sieve of titanium silicon after being reset.Wherein titanium silicon is micro- Mesopore molecular sieve is (with SiO2Meter) it is 1: 0.02～0.5 for example, 1: 0.02～0.2 with the mol ratio of organic base, with SiO2Meter HTS is, for example, 1: 5～10 with the mol ratio of water for 1: 2～50 for example, 1: 2～30 further, and crystallization temperature is 100 ～200 DEG C such as 120～200 DEG C, crystallization pressure is self-generated pressure, crystallization time 0.5～10 day, for example, 0.5～8 day or 1 ～6 days.Preferably, the crystallization temperature described in rearrangement step is 150-200 DEG C, and crystallization time is 0.5～6 day.Recovery method is existing There is method, can refer to foregoing recovery method, generally include and crystallization product is filtered, washs, right and roasting is dried.Reset Organic base described in step is quaternary ammonium base and/or organic amine, described quaternary ammonium base for example TPAOH, four The mixture of one or more of butyl ammonium hydroxide or tetraethyl ammonium hydroxide.Described organic base be quaternary ammonium base, One or more of organic amine；Described organic amine is one or more of fatty amine, aromatic amine and hydramine, described fat Fat amine (present invention is also referred to as fat amine compound), its formula is R3(NH2)n, wherein R3For having the alkyl of 1～4 carbon atom Or alkylidene, n=1 or 2；Described hydramine (present invention is also referred to as alcamine compound) its formula is (HOR4)mNH(3-m), its Middle R4 is the alkyl with 1～4 carbon atom, m=1,2 or 3.Described fatty amine such as ethamine, n-butylamine, butanediamine or own One or more of diamidogen；Described aromatic amine refers to the amine with an armaticity substituent group, for example aniline, toluidines, One or more of p-phenylenediamine；Described hydramine such as one of monoethanolamine, diethanolamine or triethanolamine or many Kind.A kind of embodiment, the HTS described in rearrangement step has MFI structure, and described quaternary ammonium base is 4 third Base ammonium hydroxide.A kind of embodiment, described HTS has MEL structure, the organic quaternary ammonium described in rearrangement step Alkali is TBAH.A kind of embodiment, described HTS has BEA structure for total silicon, in rearrangement step Described quaternary ammonium base is tetraethyl ammonium hydroxide.
Molecular sieve rearrangement process can be carried out once it is also possible to be repeated one or more times, and described repetition will be reset and be obtained The micro- mesopore molecular sieve of titanium silicon processed according still further to above-mentioned rearrangement method.Processed by rearrangement, can obtain with secondary pore The HTS of structure, the crystal grain of the micro- mesopore molecular sieve of gained titanium silicon is that (also referred to as described molecular sieve has hollow hollow-core construction Structure), there is bigger pore volume and specific surface area；The radical length of the chamber portion of this hollow crystal grain is 5～300nm, 25 DEG C, P/P0=0.10, the benzene adsorbance that adsorption time recorded under conditions of 1 hour is at least 70 milligrams per gram, this molecular sieve There is hysteresis loop between the adsorption isotherm of nitrogen absorption under low temperature and desorption isotherm.
Titanium silicon micro- mesopore molecular sieve synthetic method that the present invention provides, can be used for that synthesis has micropore and 2～8nm is mesoporous Titanium-silicon molecular screen material (the micro- mesoporous composite material of titanium silicon), described HTS for example has MFI structure, BEA, knot One or more of structure, MEL structure structure.
The present invention is further illustrated for the following examples, but and is not so limited the present invention.
Grain size in embodiment and surface silicon titanium adopt TEM-EDX, TEM electricity than the measuring method with body phase silicon titanium ratio Mirror experiment is carried out on FEI Co.'s Tecnai F20 G2 S-TWIN type transmission electron microscope, is furnished with the energy of Gatan company Filtration system GIF2001, adnexa is equipped with X-ray energy spectrometer.Electron microscopic sample adopts the method for suspended dispersed to prepare diameter 3mm's In micro-grid.In embodiment, each sample randomly selects its surface silicon titanium of 20 particle sizings ratio and body phase silicon titanium ratio, gauging surface , than the ratio with body phase silicon titanium ratio, the meansigma methodss then taking its 20 samples are as described sample surfaces silicon titanium ratio and body phase for silicon titanium The ratio of silicon titanium ratio.
XRD measuring method：The X-ray diffraction (XRD) of sample is carried out on Siemens D5005 type x-ray diffractometer Crystalline phase figure measures, and radiographic source is CuK αTube voltage 40kV, tube current 40mA, 0.5 °/min of scanning speed, Sweep limitss 2 θ=4 °～40 °.
The method of testing of BET specific surface area and pore volume adopts N2 adsorption volumetric method, according to BJH computational methods.(referring to stone Oily chemical analysis method (RIPP test method), RIPP151-90, Science Press, nineteen ninety publishes)
In embodiment and comparative example, raw materials used property is as follows：
Butyl titanate, analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group.
Titanium sulfate, analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group.
TPAOH, Guangdong great You chemical plant.
Tetraethyl orthosilicate, analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group.
Ammonia, analyzes pure, concentration 20 weight %.
Glycerol, analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group.
Diethylene glycol, analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group.
White carbon, Zhejiang Ju Hua group product, model AS-150；Solid content is more than 95 weight %, silicon dioxide in butt Content is more than 99.99 weight %, and the total content of ferrum, sodium and Al is less than 10ppm, and specific surface area is 195m2/g.
Remaining reagent is unexplained, is commercially available product, and analysis is pure.
Comparative example 1
This comparative example illustrate the conventional HTS of method preparation according to Thangaraj et al. (Zeolites, 1992, Vol.12 page 943～950).
22.5g tetraethyl orthosilicate is mixed with 7.0g TPAOH aqueous solution (concentration 25.05 weight %), adds 59.8g deionized water uniformly mixes；Then hydrolyze 1.0h at 60 DEG C, obtain the hydrating solution of tetraethyl orthosilicate.Again violent In the presence of stirring, it is slowly dropped into the solution being made up of 1.1g butyl titanate and 5.0g isopropanol in above-mentioned solution, will This mixture stirs 3h at 75 DEG C, obtains the colloid of clear.Again this colloid is moved in rustless steel closed reactor, Thermostatic crystallization 3 days at 170 DEG C, you can obtain conventional TS-1 molecular sieve.Its XRD analysis spectrogram is as shown in a in Fig. 1.
Comparative example 2
This comparative example explanation HTS molecular sieve used is according to prepared by patent CN98101357.0.
22.5g tetraethyl orthosilicate is mixed with 9.0g TPAOH aqueous solution (concentration 25.05 weight %), adds 64.5g deionized water uniformly mixes；Then hydrolyze 1.0h at 60 DEG C, obtain the hydrating solution of tetraethyl orthosilicate.Again violent In the presence of stirring, it is slowly dropped into the solution being made up of 0.6g butyl titanate and 7.0g isopropanol in above-mentioned solution, will This mixture stirs 7h at 75 DEG C, obtains the colloid of clear.Again this colloid is moved in rustless steel closed reactor, Thermostatic crystallization 3 days at 170 DEG C, you can obtain conventional TS-1 molecular sieve.
Again by butyl titanate, anhydrous isopropyl alcohol, TPAOH and deionized water according to 1: 15: 2.4: 350 Molar ratio uniformly mixes, and hydrolyzes 30 minutes, obtain the hydrating solution of butyl titanate at lower 45 DEG C of normal pressure.Take above-mentioned preparation TS-1 molecular sieve, according to molecular sieve (g): the ratio of Ti (mol)=600: 1 is uniform with the hydrating solution of above-mentioned butyl titanate Mixing, uniform stirring 12h under room temperature, finally puts into scattered suspension in stainless steel cauldron, places at 165 DEG C 3 days, you can obtain described HTS molecular sieve.
Embodiment 1
By 8.5g tetraethyl orthosilicate, 0.44g glycerol and 2.66g TPAOH aqueous solution (25.05 weight %), 1.12g cetyltrimethylammonium hydroxide, the mixing of 0.24g ethylenediamine, add 24.35g deionized water uniformly to mix；Then in Hydrolyze 1.0h at 60 DEG C, obtain the hydrating solution of tetraethyl orthosilicate.Again in the presence of being stirred vigorously, slow in above-mentioned solution Slowly instill the solution being made up of 0.41g butyl titanate and 5.0g isopropanol, this mixture is stirred 3h at 75 DEG C, obtains The colloid of clear, adds 0.39 gram of concentration to be 30 weight % hydrogen peroxide.Again this colloid is moved into rustless steel closed reactor In, thermostatic crystallization 3 days at 170 DEG C, you can obtain TS-1 molecular sieve.6g TS-1 sample and concentration are 25.05 weight % TPAOH aqueous solution uniformly mixes, the weight of described TS-1 and TPAOH aqueous solution than for 1: 5,170 DEG C in airtight reactor Crystallization 3 days, filters, washing, is dried 24 hours, 550 DEG C of roastings 6 hours, you can must reset product at 120 DEG C.
Comparative example 3
According to the method for embodiment 1, except for the difference that it is added without described glycerol.
Comparative example 4
By the method according to embodiment 1, except for the difference that it is added without described hydrogen peroxide.
Embodiment 2
(1) the TPAOH aqueous solution being 25.05 weight % by 15g concentration, 2.04g butyl titanate, 5.49g Cetyltrimethylammonium hydroxide (being represented with MSDS), 8.5g tetraethyl orthosilicate, 4.87g glycerol, 2.38g triethylamine, 1.96g Concentration is the ammonia of 20 weight % and 46.87g water is added sequentially in the beaker of 500ml, puts into heating and agitating function Magnetic stirring apparatuss on mix homogeneously, and at 80 DEG C heat 4 hours, at any time supplement evaporation moisture, obtain water white transparency water Solution liquid, is subsequently adding the hydrogen peroxide that 1.18g concentration is 30 weight %, stirs；
(2) step (1) products therefrom is stood 12 hours at room temperature carry out aging, obtain ageing products；
(3) in above-mentioned ageing products, stirring is lower to add 9.36g white carbon powder, stirs 1 hour, form one after adding Kind of " viscous body ", is transferred in rustless steel closed reactor, in 165 DEG C of thermostatic crystallizations 2 days, obtains crystallization sample, will The crystallization sample filtering that arrives, washing, are dried 24 hours at 120 DEG C, 550 DEG C of roastings 6 hours, you can titanium silicon of the present invention Titanium silicon micro- mesopore molecular sieve product is designated as TS-1F1；Its BET specific surface area is 431m2/ g, external surface area is 59m2/g.Its XRD divides Analysis spectrogram as shown in Figure 1, 2, has MFI structure.
(4) the TPAOH aqueous solution that TS-1F1 sample described in 6g is 25.05 weight % with concentration is uniformly mixed, described TS- The weight of 1F1 and TPAOH aqueous solution ratio for 1: 5,150 DEG C of crystallization 3 days in airtight reactor, filter, washing, at 120 DEG C It is dried 24 hours, 550 DEG C of roastings 6 hours, you can product must be reset, be designated as TS-1P1.Its XRD analysis spectrogram have as Fig. 1,2 Shown feature, its BET specific surface area is 457m2/ g, external surface area is 60m2/g.In transmission electron microscope photo, it is hollow Structure.There is MFI structure.
Embodiment 3
(1) by 19.96g concentration be 25.05 weight % TPAOH, 3.26g butyl titanate, 8.75g ten Six alkyl trimethyl ammonium bromides (being represented with CTMAB), 8.5g tetraethyl orthosilicate, 23.91 grams of diethylene glycol, 4.71g triethylamine, 0.05g concentration is the ammonia of 20 weight % and 50.32g water is added sequentially in the beaker of 500ml, puts into heating and stirs Mix homogeneously on the magnetic stirring apparatuss of function, and heat at 90 DEG C 1 hour, supplement the moisture of evaporation at any time, obtain colourless Bright basic hydrolysises liquid, is subsequently adding 10.37g tert-butyl hydroperoxide (being represented with TBHP), stirs；
(2) product of (1) gained is stood 12 hours at room temperature, obtain ageing products；
(3) in obtained ageing products, under stirring, it is slowly added to 26.4g white carbon powder, after adding, stirring 1.5 is little When, form uniform " viscous body ", be transferred in rustless steel closed reactor, in 165 DEG C of thermostatic crystallizations 2 days, filter, wash Wash, be dried 24 hours at 120 DEG C, 550 DEG C of roastings 6 hours, that is, obtain titanium silicon micro- mesopore molecular sieve sample, be designated as TS-1F2.Tool There is MFI structure.BET specific surface area is 435m2/ g, external surface area is 59m2/g；
(4) by the TPAOH aqueous solution of 6g TS-1F2 sample and 36 grams of concentration 22.05% uniformly, in airtight reaction 150 DEG C of crystallization 3 days in kettle, filter, washing, are dried 24 hours at 120 DEG C, 550 DEG C of roastings 6 hours, obtain hollow titanium silicon micro- mesoporous Zeolite product, is designated as TS-1P2.Its BET specific surface area is 456m2/ g, external surface area is 60m2/ g, transmission electron microscope shines In piece, it is hollow-core construction.
Embodiment 4
(1) by 104.76g concentration be 25.05% 4-propyl bromide aqueous solution, 1.02g titanyl sulfate, 15.03g ten Six alkyltrimethylammonium hydroxide, 7.63g triethylamine, 8.5g tetraethyl orthosilicate, 0.79g ethylene glycol, 1.09g concentration is 20 weights The ammonia of amount % and 168.21g water are added sequentially in the beaker of 500ml, put into the magnetic agitation with heating and agitating function Uniformly mix on device, and heat at 70 DEG C 3 hours, supplement the moisture of evaporation at any time, obtain basic hydrolysises liquid, be subsequently adding 8.71g concentration is the hydrogen peroxide solution of 30 weight %,
(2) (1) products therefrom is stood 24 hours at room temperature, obtain ageing products；
(3) in the beaker filling ageing products, under stirring, it is slowly added to 36g white carbon powder, stirs one hour, formed More uniform " viscous body ", it is transferred in rustless steel closed reactor, in 165 DEG C of thermostatic crystallizations 2 days, filter, washing, Be dried 24 hours at 120 DEG C, 550 DEG C of roastings 6 hours, you can titanium silicon micro- mesopore molecular sieve product of providing of the present invention, be designated as TS-1F3.There is MFI structure.
(4) by the TPAOH aqueous solution of 6g TS-1F3 sample and 40 gram 22.05%, stir, in airtight anti- Answer in kettle 150 DEG C of crystallization 3 days, filter, washing, at 120 DEG C, be dried 24 hours, 550 DEG C of roastings 6 hours, you can micro- Jie of titanium silicon Porous molecular sieve hollow specimen, is designated as TS-1P3.Its BET specific surface area is 453m2/ g, external surface area is 59m2/ g, transmitted electron shows In micro mirror photo, it is hollow-core construction.There is MFI structure.
Embodiment 5
According to the method for embodiment 2, except for the difference that it is added without ammonia.
Embodiment 6
According to the method for embodiment 2, in step (3), except for the difference that only use solid silicon source, step has been added without in (1) Machine silicon source.
Embodiment 7
Method according to embodiment 2 prepares HTS, its proportioning and synthesis condition, the results are shown in Table 1.
Embodiment 8
According to the method for embodiment 2, except for the difference that first crystallization 1 day at 120 DEG C in step (3), then brilliant at 170 DEG C Change 2 days, its proportioning and synthesis condition, the results are shown in Table 1.
Embodiment 9
According to the method for embodiment 2, adjust proportioning, other conditions and characterization result are shown in Table 1.
Embodiment 10
Change template, preparation has the micro- mesopore molecular sieve of MEL microcellular structure titanium silicon.With reference to the side according to embodiment 2 Method, changes proportioning and template, its proportioning and synthesis condition, the results are shown in Table 1.
Embodiment 11
Change template, preparation has the micro- mesopore molecular sieve of titanium silicon of BEA microcellular structure.The method of reference implementation example 2, changes Become proportioning and template, its proportioning and synthesis condition, the results are shown in Table 1.
Embodiment 12
According to the method for embodiment 3, except for the difference that the white carbon in step (3) is in order to SiO2Organic silicon source water of meter equivalent Solution catches up with alcohol product to replace, and wherein, organic silicon source hydrolysis catches up with the unitary alcohol content in alcohol product to be less than 10ppm mass.
Embodiment 13
This example demonstrates that the embodiment sample that the present invention provides is used for oxidation of phenol hydroxyl with the sample of comparative example preparation The reaction effect of Benzodiazepiness and preparing cyclohexanone oxime by ammoximation of cyclohexanone is prepared in change.
In the present embodiment, reagent used is commercially available chemically pure reagent.After reaction, the concentration of each material uses gas phase color Spectrometry carries out quantitative analyses.The 6890 type gas chromatograpies that Agilent company used produces；Analysis chromatographic column used is FFAP Post.
In embodiment, the conversion ratio of phenol, Ketohexamethylene conversion ratio, cyclohexanone-oxime selectivity are to count according to the following equation respectively Calculate：
The each 1.25g of the sample prepared by above-described embodiment 1-9 and comparative example (rearrangement) is taken to be added to containing phenol respectively In the three-neck flask reaction vessel of 25g and acetone 20ml, add hydrogen peroxide 9.81g (concentration 30 after temperature stabilization to setting value Weight %), (phenol：Hydrogen peroxide (H2O2) mol ratio is 3), in 80 DEG C of temperature, pressure 0.1MPa (normal pressure), reaction was adopted after 2 hours Sample, phenol carries out hydroxylating and generates Benzodiazepiness.
The HTS in above-mentioned comparative example and embodiment is taken to prepare sample respectively, according to TS-1 molecular sieve：Tertiary fourth Alcohol：25 weight % ammonia=1: 7.5: 7.5 mass ratio uniform stirring mixing, quality of TS-1 molecular sieve in slurry bed 2.4g, is warming up to 75 DEG C, then adds 30 weight % hydrogen peroxide with the speed of 6ml/h at this temperature, with the speed of 8.6ml/h Add the mixture (volume ratio of Ketohexamethylene and the tert-butyl alcohol is 1: 2.5) of Ketohexamethylene and the tert-butyl alcohol, added with the speed of 6ml/h simultaneously Enter 25 weight % ammonia spirits, volume space velocity is 8.59h-1.Above-mentioned three strands of materials are simultaneously introduced, and are continuously gone out with corresponding speed simultaneously Material, 4 hours after stable reaction, sampling, carry out chromatography, the results are shown in Table 2.
The decomposition run of hydrogen peroxide
Take H2O2Concentration is 15 grams of the hydrogen peroxide of 30 weight %, adds 2 grams of HTSs, and at temperature is 80 DEG C, stirring 1 is little When, the concentration of analysis hydrogen peroxide.The results are shown in Table 2
From table 2, under identical condition, the molecular sieve that the present invention provides has lower decomposing hydrogen dioxide solution speed, Thus improving the utilization rate of hydrogen peroxide in the oxidation reaction participating in for hydrogen peroxide, dioxygen water consumption can be reduced.
As can be seen from Table 2：The phenol hydroxylation of gained sample of the present invention and Ketohexamethylene activity are apparently higher than comparative sample Conventional TS-1 molecular sieve.
It should be noted that combination in any can also be carried out between the various different embodiment of the present invention, as long as its Without prejudice to the thought of the present invention, it equally should be considered as content disclosed in this invention.
Table 1 Zeolite synthesis condition and properties of product
TEA represents triethylamine, and EEA represents diethylamine, and CTMAB is cetyl trimethylammonium bromide, and TTAB is the tetradecane Base trimethyl amine bromide,；DTAB is trimethyl ammonium hydroxide, and MSDS is cetyltrimethylammonium hydroxide, TBAOH is TBAH, and TEAOH is tetraethyl ammonium hydroxide.
The characterization result of the micro- mesopore molecular sieve of titanium silicon of table 2 present invention preparation and catalysis of phenol hydroxylating conversion ratio and hexamethylene Ketone oxamidinating data and decomposing hydrogen dioxide solution evaluation result
In table 2, micro pore volume refers to the volume less than 1nm hole, and the mesopore volume of embodiment 1～9 and comparative example 3-4 refers to Aperture is the volume in 2～8nm hole, the volume that the mesopore volume of comparative example 1 and 2 is 2～50nm hole for aperture.
For comparative example 1,2,3,4, in table 1,2, step (3) products therefrom refers to without the titanium silicon molecule reset Sieve, step (4) product refers to through resetting the titanium silicon phenol sieve obtaining.

Claims (49)

1. the synthetic method of the micro- mesopore molecular sieve of a kind of titanium silicon, including by titanium source, template, water, polyhydric alcohol, peroxide and silicon Source, optional inorganic source of ammonium form crystallization mixture, crystallization, reclaim HTS；Described template includes organic quaternized Compound, chain alkyl ammonium compoundss and optional organic amine compound.
2. in accordance with the method for claim 1 it is characterised in that the synthetic method of the micro- mesopore molecular sieve of described titanium silicon, including Following steps:
(1) by titanium source, template, water, polyhydric alcohol and optionally organic silicon source, optional inorganic source of ammonium mixing, alcohol is caught up with hydrolysis；Then Add peroxide；
(2) product that step (1) obtains is aging；
(3) add or be added without organic silicon source and/or solid silicon source, crystallization, recovery Pd silicon molecule in the product that step (2) obtains Sieve；
Wherein, introduce described silicon source at least one step in step (1) and step (3), described template includes organic season Ammonium compoundss, chain alkyl ammonium compoundss and optional organic amine compound.
3. according to the method described in claim 1 or 2 it is characterised in that the mol ratio of polyhydric alcohol and total silicon source be 0.01～ 0.8：1, peroxide is 0.01～0.25 with the mol ratio of total silicon source:1；Organic amine is 0～0.4 with the mol ratio of total silicon source: 1, quaternary organic ammonium compounds are 0.05～0.45 with the mol ratio of total silicon source:1, chain alkyl ammonium compoundss and total silicon source mole Than for 0.01～0.25:1；Described total silicon source is with SiO2Organic silicon source of meter and the summation of solid silicon source.
4. according to the method described in claim 1 or 2 it is characterised in that polyhydric alcohol is 0.1～0.7 with the mol ratio of total silicon source: 1, peroxide is 0.05～0.25 with the mol ratio of total silicon source:1.
5. in accordance with the method for claim 2 it is characterised in that introducing in organic silicon source, and step (3) in step (1) Introduce solid silicon source；With SiO2Meter, the organic silicon source being introduced in step (1) with step (3) solid silicon source of introducing mole Than for 1:0.1～20.
6. in accordance with the method for claim 5 it is characterised in that the method comprises the steps：
(1) by titanium source, template, organic silicon source, optional inorganic source of ammonium, the mixing of polynary alcohol and water, alcohol is caught up with hydrolysis；Add peroxide Compound, wherein, inorganic source of ammonium：The mol ratio of titanium source is 0～5:1；
(2) will be aging for step (1) products therefrom, described aging be step (1) products therefrom is stood at room temperature～50 DEG C 1～ 60 hours；
(3) by the ageing products obtained by step (2) and solid silicon source according to 1：0.1～20 weight than mix homogeneously, crystallization, Reclaim HTS；In wherein said part by weight, the ageing products obtained by described step (2) are with SiO2Meter, solid Silicon source is with SiO2Meter；
Wherein, water and the mol ratio of total silicon source are 5～100:1；Template is 0.08～0.6 with the mol ratio of total silicon source:1；Many First alcohol is 0.01～0.8 with the mol ratio of total silicon source, and peroxide is 0.01～0.25 with the mol ratio of total silicon source:1；Titanium source with The mol ratio of total silicon source is 0.005～0.05:1；Quaternary organic ammonium compounds are 0.05～0.45 with the mol ratio of total silicon source:1, long Alkyl group ammonium compoundss are 0.05～0.25 with the mol ratio of total silicon source:1, organic amine is 0～0.4 with the mol ratio of total silicon source: 1；
Wherein, in described mol ratio, total silicon source is with SiO2Meter, described total silicon source is with SiO2Meter organic silicon source and with SiO2 The summation of the solid silicon source of meter, inorganic source of ammonium is with NH4 +Meter；Described inorganic source of ammonium be inorganic ammonium salt and/or ammonia, titanium source with TiO2Meter.
7. according to the method described in any one of claim 1～2 it is characterised in that the mol ratio of described titanium source and total silicon source For 0.005～0.05:1.
8. in accordance with the method for claim 1 it is characterised in that the mol ratio of template, total silicon source, titanium source and water is (0.08～0.6):1:(0.005～0.05):(5～100).
9. in accordance with the method for claim 8 it is characterised in that described template with the mol ratio of described total silicon source is 0.1～0.5:1.
10. in accordance with the method for claim 8 it is characterised in that the mol ratio of water and total silicon source is 5～50:1.
11. according to the method described in claim 1 or 2 it is characterised in that in described crystallization mixture introduce or do not introduce inorganic Source of ammonium, with NH4 +Meter inorganic source of ammonium with TiO2The mol ratio of the titanium source of meter is 0～5:1.
12. in accordance with the method for claim 5 it is characterised in that the mol ratio of described organic silicon source and solid silicon source is 1:1 ～19.
13. in accordance with the method for claim 2 it is characterised in that described aging, aging temperature be room temperature to 50 DEG C, always The change time is 1～60 hour.
14. in accordance with the method for claim 2 it is characterised in that step (2) described aging be room temperature～50 DEG C stand 2 ～50 hours.
15. in accordance with the method for claim 2 it is characterised in that monohydric alcohol in the product that alcohol obtains is caught up with step (1) hydrolysis Mass content is less than 10ppm.
16. according to the method described in claim 1 or 2 it is characterised in that described crystallization, the temperature of crystallization is 110～200 DEG C, Crystallization pressure is self-generated pressure, and the time of crystallization is 2 hours～20 days.
17. in accordance with the method for claim 16 it is characterised in that the crystallization temperature of described crystallization is 140～180 DEG C.
18. in accordance with the method for claim 17 it is characterised in that the time of described crystallization is 0.5～10 day.
19. according to the method described in claim 1 or 2 it is characterised in that described crystallization is：In 100～130 DEG C of crystallization 0.5 ～1.5 days, then crystallization 1～3 day at 160～180 DEG C, crystallization pressure is self-generated pressure.
20. in accordance with the method for claim 1 it is characterised in that the carbon atom number having in described polyol molecule is 2 ～8.
21. in accordance with the method for claim 1 it is characterised in that described peroxide is hydrogen peroxide, the tertiary fourth of peroxidating One or more of base, peracetic acid, trifluoro peracetic acid, described polyhydric alcohol is glycerol, ethylene glycol, hexanediol, two One or more of glycol.
22. in accordance with the method for claim 2 it is characterised in that described organic silicon source is organo-silicon ester, and described is organic Estersil, its formula is Si (OR1)4, R1Selected from the alkyl with 1～6 carbon atom, described alkyl is branched-chain or straight-chain alkyl； Described solid silicon source is high-purity silicon dioxide granule or SiO 2 powder, on the basis of butt weight, described solid silicon The SiO in source2Content is more than 99.99 weight %, and the total content of Fe, Al and Na in terms of atom is less than the silica gel of 10ppm, described Titanium source is organic titanium source or inorganic ti sources.
23. in accordance with the method for claim 22, and described organo-silicon ester is quanmethyl silicate, tetraethyl orthosilicate, silicic acid four One or more of butyl ester, dimethyl diethyl estersil.
24. in accordance with the method for claim 2 it is characterised in that described solid silicon source is white carbon, described white carbon Specific surface area is 20～1000m2/g.
25. according to the method described in claim 1 or 2 it is characterised in that quaternary organic ammonium compounds with the mol ratio of total silicon source are 0.05～0.3：1, chain alkyl ammonium compoundss are 0.05～0.3 with the mol ratio of total silicon source：1；In template, organic base is with always The mol ratio of silicon source is 0.05～0.3：1, described organic base is quaternary ammonium base, organic amine and the length with hydroxide ion Alkyl group ammonium compoundss.
26. according to the method described in claim 1 or 2 it is characterised in that described quaternary organic ammonium compounds be quaternary ammonium base And/or organic quaternary ammonium salt；Described its formula of chain alkyl ammonium compoundss is R5NH3X or R5N(R6)3X, wherein R5For carbon atom Alkyl between 12～18 for the number, R6For alkyl between 1～4 for the carbon number；X is univalent anion.
27. in accordance with the method for claim 25 it is characterised in that described quaternary organic ammonium compounds be quaternary ammonium base and/ Or organic quaternary ammonium salt, described quaternary ammonium base is TPAOH, TBAH or tetraethyl ammonium hydroxide One or more of；Described organic quaternary ammonium salt be 4-propyl bromide, tetrabutyl ammonium bromide, tetraethylammonium bromide, 4 third One or more of ammonium chloride, tetrabutylammonium chloride or tetraethylammonium chloride；Described chain alkyl ammonium compoundss are ten Six alkyl trimethyl ammonium bromides, cetyl chloride ammonium, cetyltrimethylammonium hydroxide, tetradecyltrimethylammonium bromination Ammonium, tetradecyl ammonium chloride, tetradecyltrimethylammonium ammonium hydroxide, Dodecyl trimethyl ammonium chloride, lauryl ammonium chloride, Trimethyl ammonium hydroxide, Cetyltrimethylammonium bromide, octadecyl ammonium chloride, octadecyl trimethyl hydrogen-oxygen Change one or more of ammonium.
28. according to the method described in claim 1 or 2 it is characterised in that the described micro- mesoporous composite molecular sieve of titanium silicon has MFI structure, described quaternary organic ammonium compounds include TPAOH, 4-propyl ammonium chloride, in 4-propyl bromide One or more；Or, the described micro- mesoporous composite molecular sieve of titanium silicon has a MEL structure, described quaternary organic ammonium compounds bag Include one or more of TBAH, tetrabutyl ammonium bromide or tetrabutylammonium chloride；Or, described micro- Jie of titanium silicon Hole composite molecular screen has BEA structure, described quaternary organic ammonium compounds include tetraethyl ammonium hydroxide, tetraethylammonium bromide, One or more of tetraethylammonium chloride.
29. according to the method described in claim 1 or 2 it is characterised in that described template includes organic base, described has Machine alkali is quaternary ammonium base and/or organic amine, and described quaternary organic ammonium compounds are quaternary ammonium base and/or organic quaternary ammonium salt, institute The organic amine stated is one or more of fatty amine, aromatic amine and hydramine；The formula of described fatty amine is R3(NH2)n, its Middle R3For having alkyl or the alkylidene of 1～4 carbon atom, n=1 or 2；Its formula of described hydramine is (HOR4)mNH(3-m), Wherein R4For having the alkyl of 1～4 carbon atom, m=1,2 or 3；Described aromatic amine is to have an armaticity substituent group Amine, described quaternary ammonium base be one of TPAOH, TBAH or tetraethyl ammonium hydroxide or Multiple, described organic quaternary ammonium salt is 4-propyl ammonium chloride, 4-propyl bromide, tetrabutylammonium chloride, tetrabutyl ammonium bromide, four One or more of ethyl ammonium chloride, tetraethylammonium bromide.
30. in accordance with the method for claim 29 it is characterised in that described fatty amine be ethamine, n-butylamine, butanediamine or One or more of hexamethylene diamine；Described hydramine is one or more of monoethanolamine, diethanolamine or triethanolamine；Institute The aromatic amine stated is one or more of aniline, toluidines, p-phenylenediamine.
31. according to the method described in claim 1 or 2 it is characterised in that described titanium source be tetraalkyl titanate Ti (alkoxy)4、TiCl4、Ti(SO4)2One or more of and their hydrolyzate, wherein in tetraalkyl titanate The carbon number of alkyl is 1,2,3,4,5 or 6.
32. in accordance with the method for claim 1 it is characterised in that the described micro- mesopore molecular sieve of titanium silicon has less than 1nm's Microcellular structure and the meso-hole structure that aperture is 2～8nm, aperture is the mesopore volume of 2～8nm is 0.3～0.8mL/g, porous body Amass as 0.12～0.19mL/g.
33. according to the method described in any one of claim 1～2 it is characterised in that described method also includes rearrangement step： By the HTS obtaining in organic aqueous alkali crystallization 0.5～10 day, the temperature of crystallization is 110～200 DEG C；Wherein with SiO2The described HTS of meter is 1 with the mol ratio of described organic base:0.02-0.5, with SiO2The described titanium silicon molecule of meter Sieve is 1 with the mol ratio of water:2～50；Described organic base is quaternary ammonium base and/or organic amine.
34. according to the method described in claim 33 it is characterised in that the temperature of crystallization described in rearrangement step be 150～200 DEG C, described HTS is 1 with the mol ratio of water:2～30, pressure is self-generated pressure, HTS and organic base Mol ratio is 1:0.02～0.2.
35. according to the method described in any one of claim 1～2 it is characterised in that the mol ratio of described titanium source and total silicon source For 0.008～0.03:1.
36. according to the method described in any one of claim 1～2 it is characterised in that the mol ratio of described titanium source and total silicon source For 0.01～0.025:1.
37. in accordance with the method for claim 8 it is characterised in that the mol ratio of described template and described total silicon source For 0.1～0.3:1.
38. in accordance with the method for claim 8 it is characterised in that the mol ratio of described template and described total silicon source For 0.1～0.2:1.
39. in accordance with the method for claim 8 it is characterised in that the mol ratio of water and total silicon source is 5～30:1.
40. in accordance with the method for claim 8 it is characterised in that the mol ratio of water and total silicon source is 6～15:1.
41. in accordance with the method for claim 2 it is characterised in that introduce inorganic source of ammonium in step (1), with NH4 +That counts is inorganic Source of ammonium with TiO2The mol ratio of the titanium source of meter is 0.01～4:1.
42. in accordance with the method for claim 2 it is characterised in that introduce inorganic source of ammonium in step (1), with NH4 +That counts is inorganic Source of ammonium with TiO2The mol ratio of the titanium source of meter is 0.05～0.5:1.
43. in accordance with the method for claim 5 it is characterised in that the mol ratio of described organic silicon source and solid silicon source is 1:2 ～18.
44. in accordance with the method for claim 5 it is characterised in that the mol ratio of described organic silicon source and solid silicon source is 1:5 ～15.
45. in accordance with the method for claim 2 it is characterised in that described solid silicon source is white carbon, described white carbon Specific surface area is 50～400m2/g.
46. in accordance with the method for claim 2 it is characterised in that step (2) described aging be room temperature～50 DEG C stand 3 ～30 hours.
47. in accordance with the method for claim 2 it is characterised in that step (2) described aging be room temperature～50 DEG C stand 3 ～15 hours.
48. in accordance with the method for claim 16 it is characterised in that the crystallization temperature of described crystallization is 160～180 DEG C.
49. in accordance with the method for claim 2 it is characterised in that described organic silicon source is organo-silicon ester, and described is organic Estersil, its formula is Si (OR1)4, R1Selected from the alkyl with 1～6 carbon atom, described alkyl is branched-chain or straight-chain alkyl.
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