CN106145143A

CN106145143A - A kind of method synthesizing the micro-mesoporous composite material of hetero atom

Info

Publication number: CN106145143A
Application number: CN201510181923.6A
Authority: CN
Inventors: 舒兴田; 夏长久; 林民; 朱斌; 彭欣欣
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2015-04-17
Filing date: 2015-04-17
Publication date: 2016-11-23
Anticipated expiration: 2035-04-17
Also published as: CN106145143B

Abstract

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

Description

A kind of method synthesizing the micro-mesoporous composite material of hetero atom

Technical field

The present invention relates to a kind of hetero-atom molecular-sieve synthetic method, relate to a kind of conjunction furtherly Become containing selected from Fe, Co, Cu, Sn, Zr, B, Ge, V, Cr, Mn cage heteroatom and The method of micro-mesoporous molecular sieve composite material of silicon.

Background technology

The skeleton of hetero-atom molecular-sieve also has in addition to containing silica other hetero atom, also The part framework silicon that may be considered in silica zeolite is replaced formation by other hetero atom Molecular sieve containing cage heteroatom.Synthesized at present has a MFI type structure, such as Fe-ZSM-5, Sn-ZSM-5 and TS-1 molecular sieve, the such as TS-2 of MEL type structure, FeS-2, ZrS-2 molecular sieve, and Ti-MCM-22 and B-MWW of MWW type structure, There is TS-48 and the Sn-beta-molecular sieve etc. of macroporous structure.Initial stage in this century is Hispanic A.Corma et al. synthesis Sn-beta-molecular sieve also comes into operation, and they find to apply this molecular sieve Catalysis of pimelinketone and 35%H under the conditions of 56 DEG C respectively₂O₂Reactant aqueous solution obtains corresponding interior Ester.

CN102757066A discloses a kind of method synthesizing B-β hetero-atom molecular-sieve, by than Example, by boron source, template, alkali source, fluoride and water at room temperature mechanical agitation, treats that solid is complete Molten, add crystal seed and silicon source forms Primogel, fill still after stirring certain time and seal, Crystallization 2～5 days at 120 DEG C～170 DEG C, Hydrothermal Synthesis has the B-β hetero atom of BEA structure Molecular sieve.This patent application does not provide the synthesis method that hetero atom divides micro-mesoporous sub-sieve.

Summary of the invention

The technical problem to be solved in the present invention is to provide a kind of micro-mesopore molecular sieve of hetero atom (also referred to as For the micro-mesoporous molecular sieve composite material of hetero atom, the micro-mesoporous composite molecular sieve of hetero atom, hetero atom Micro-mesoporous composite material or the micro-mesoporous material of hetero atom) synthetic method.

A kind of synthetic method of the micro-mesopore molecular sieve of hetero atom, including by hetero atom source, template, Water, peroxide, polyhydric alcohol and silicon source, optional inorganic source of ammonium form crystallization mixture, brilliant Change, reclaim the micro-mesopore molecular sieve of hetero atom；Described template includes quaternary organic ammonium compounds, length Alkyl group ammonium compounds (also referred to as long-chain organoammonium compound) and optional organic amine compound； Described hetero atom is selected from Fe, Co, Cu, Sn, Zr, B, Ge, V, Cr, Mn Plant or multiple.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, introduces in building-up process Polyhydric alcohol and peroxide, the mol ratio in polyhydric alcohol and silicon source is 0.01～0.8:1, preferably 0.05～ 0.7:1 for example, 0.05～0.5:1, peroxide is 0.01～0.25:1 with the mol ratio in silicon source, For example, 0.05～0.25:1 or 0.05～0.15:1.Described polyhydric alcohol is containing two in molecule Or the alcohols of two or more hydroxyl；Preferably, in described polyol molecule, carbon atom number is 2～8 Individual, described hydroxyl for example, 2 or 3, described polyhydric alcohols such as glycerol, ethylene glycol, One or more in hexanediol, diethylene glycol.Described peroxide is the change containing peroxide bridge Compound, such as in hydrogen peroxide, tert-butyl peroxide, peracetic acid, trifluoro peracetic acid etc. One or more.Introduce polyhydric alcohol and peroxide so that obtained hetero-atom molecular-sieve tool There is less crystallite dimension (or claiming grain size, the size of crystal grain short-axis direction), have more High activity.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described silicon source is organic Silicon source and/or solid silicon source.Described hetero atom source is organic hetero atom source and/or inorganic miscellaneous former Component.Described template is template conventional in hetero-atom molecular-sieve building-up process.Water with The mol ratio in silicon source (also referred to as total silicon source) is 5～100:1；Template with the mol ratio in silicon source is 0.04～0.6:1；Polyhydric alcohol is 0.01～0.8 with the mol ratio in silicon source, and peroxide rubs with silicon source Your ratio is 0.01～0.25:1；Hetero atom source is 0.005～0.05:1 with the mol ratio in silicon source.Peroxide Compound is 0.01～0.25:1 with the mol ratio in silicon source.Described silicon source is with SiO₂That counts is organic Silicon source and the summation of solid silicon source.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, in a kind of embodiment, Described hetero atom source and the mol ratio in silicon source are 0.005～0.05:1, for example, 0.008～0.03:1 Or 0.01～0.025:1, the mol ratio in further hetero atom source and silicon source is for example, 0.015～0.025:1.Described template and with SiO₂The mol ratio in the silicon source of meter is 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 and the mol ratio in silicon source It is 5～100:1, for example, 5～80:1 or 6～50:1 or 6～30:1 or 6～15:1.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described inorganic source of ammonium is Inorganic ammonium salt and/or ammonia, preferably ammonia, with NH₄ ⁺The inorganic source of ammonium of meter and hetero atom source Mol ratio is 0～5:1, for example, 0.01～4:1, preferably 0.05～0.5:1.In situation of the present invention Under, introduce inorganic source of ammonium and be conducive to improving the oxidation activity of synthesized molecular sieve, improve skeleton miscellaneous Atomic ratio.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described organosilicon source is Organo-silicon ester, described organo-silicon ester, its formula is Si (OR¹)₄, R¹Selected from having 1～6 The alkyl of carbon atom such as R¹For 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 fourth One or more in ester, dimethyl diethyl estersil；Wherein preferred quanmethyl silicate, silicic acid One or more in tetra-ethyl ester, dimethyl diethyl estersil.Solid silicon source described in the present invention For highly purified silica solid or powder, such as, it can be white carbon and/or high-purity Degree silica gel.Under preferable case, SiO in described solid silicon source on the basis of butt weight₂Content It is not less than 99.99 weight %, and the gross mass content of Fe, Al and Na impurity is little in terms of element In 10ppm；Such as SiO₂Content is 99.99～100 weight %, typically greater than 99.99 and Less than 100 weight %.Described solid silicon source can be high-purity silica gel and/or white carbon, excellent Select white carbon；SiO in wherein said silica gel₂Content is preferably greater than or equal to 99.99 weight % such as For more than 99.99 weight % and less than 100 weight %, and total matter of Fe, Al and Na impurity Amount content is less than 10ppm.The specific surface area of described white carbon is preferably between 20-1000m²/ g it Between for example, 50-400m²/ g, on the basis of the butt weight of white carbon, in described white carbon SiO₂Content is preferably greater than or equal to 99.99 weight % for example, 99.99～100 weight % for example, More than 99.99 weight % and less than 100 weight %, Fe, Al in described white carbon in terms of atom It is less than 10ppm with the gross mass content of Na impurity.Described white carbon can be purchased, or presses Prepare according to existing method, the method system such as provided according to patent CN200910227646.2 Standby, a kind of preparation method is to be obtained with hydrogen and oxygen generation combustion reaction by Silicon chloride..

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described hetero atom source is When heteroatomic organic compound or heteroatomic inorganic compound, such as hetero atom are metal, Described hetero atom source can be inorganic metal salt or organic metal acid esters.Preferably, described miscellaneous Atomic source is for being dissolved in water or react the generation hydrolysis heteroatomic oxide of generation with water Containing described heteroatomic compound.The most heteroatomic organic acid of described organic compound Salt, alkoxide, alkyl compound, phenyl compound, benzyl compounds, carbonyl compound, carboxylic Based compound, alcoholic compound, alkenyl compound, alkoxide compound, organohalogen compounds, acyl Based compound, tetraalkoxy hetero atom acid esters are (such as M (alkoxy)₄Described in wherein M represents Hetero atom) in one or more；Heteroatomic inorganic compound can be containing described miscellaneous former The inorganic salt of son or acid, the most heteroatomic chloride, heteroatomic sulfate, heteroatomic Nitrate, heteroatomic hydroxide, heteroatomic oxychlorination thing, heteroatomic oxide, One or more in heteroatomic acid, it is preferred that described heteroatomic inorganic salt or acid can It is dissolved in water or reacts formation hydrolyzate with water.Preferably, described hetero atom source is four alcoxyls Base hetero atom acid esters M (alkoxy)₄, heteroatomic alkyl compound, heteroatomic alcoholic compound, Heteroatomic carboxyl compound, heteroatomic chloride, heteroatomic sulfate, heteroatomic One in nitrate, heteroatomic acetate, heteroatomic acid and their hydrolyzate Or multiple, wherein the carbon number of the alkoxyl in tetraalkoxy hetero atom acid ester molecules is 1～6, such as carbon number is 1,2,3,4,5 or 6.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described template agent includes Quaternary organic ammonium compounds and chain alkyl ammonium compounds, can optionally contain organic amine compound, have The mol ratio in machine quaternary ammonium compound and total silicon source is 0.04～0.45:1, chain alkyl ammonium compounds with The mol ratio in total silicon source is 0.04～0.45:1, and organic amine is 0～0.4:1 with the mol ratio in total silicon source. The most organic quaternary amine alkali of described quaternary organic ammonium compounds and/or organic quaternary ammonium salt.Described Organic amine is one or more in fatty amine, aromatic amine and hydramine, and described fatty amine is (also Claim fat amine compound), its formula is R³(NH₂)_n, wherein R³Former for having 1～4 carbon The alkyl of son or alkylidene, n=1 or 2；(present invention is also referred to as alcamines to described hydramine Compound) its formula is (HOR⁴)_mNH_(3-m), wherein R⁴For having 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, such as One or more in aniline, toluidines, p-phenylenediamine；Described hydramine such as monoethanolamine, One or more in diethanolamine or triethanolamine.Described quaternary ammonium base such as tetrapropyl One or more in ammonium hydroxide, TBAH or tetraethyl ammonium hydroxide；Described Organic quaternary ammonium salt such as 4-propyl bromide, tetrabutyl ammonium bromide, tetraethylammonium bromide, four One or more in propyl ammonium chloride, tetrabutylammonium chloride or tetraethylammonium chloride.

The synthetic method of the micro-mesopore molecular sieve of hetero atom that the present invention provides, a kind of specific embodiment party Formula, the micro-mesopore molecular sieve of described hetero atom has MFI structure, described organic quaternary ammonium Compound include the one in TPAOH, 4-propyl ammonium chloride, 4-propyl bromide or Multiple.One or many in TPAOH, 4-propyl ammonium chloride, 4-propyl bromide Planting the 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 hetero atom that the present invention provides, a kind of embodiment institute The micro-mesopore molecular sieve of hetero atom stated has MEL structure, described quaternary organic ammonium compounds bag Include one or more in TBAH, tetrabutyl ammonium bromide or tetrabutylammonium chloride. One or more in TBAH, tetrabutyl ammonium bromide or tetrabutylammonium chloride total And be 0.01～0.5:1 with the mol ratio in total silicon source, preferably 0.02～0.45:1.

The synthetic method of the micro-mesopore molecular sieve of hetero atom that the present invention provides, a kind of embodiment, The micro-mesopore molecular sieve of described hetero atom has BEA structure, described quaternary organic ammonium compounds Including one or more in tetraethyl ammonium hydroxide, tetraethylammonium bromide, tetraethylammonium chloride. Described quaternary organic ammonium compounds includes tetraethyl ammonium hydroxide, tetraethylammonium bromide, tetraethyl The summation of one or more in ammonium chloride is 0.01～0.5:1 with the mol ratio with total silicon source, excellent Elect 0.02～0.45:1 as.

The synthetic method of the micro-mesopore molecular sieve of hetero atom that the present invention provides, described chain alkyl Its formula of ammonium compounds is R⁵NH₃X or R⁵N(R⁶)₃X, wherein R⁵For carbon number Alkyl between 12～18, R⁶For carbon number alkyl between 1～4；X is monovalence Anion for example, OH^-、Cl^-、Br^-；When X is OH^-Time, the present invention is referred to as alkali formula long-chain Alkyl ammonium compound；Described organosilicon source is organo-silicon ester, described organo-silicon ester, and it leads to Formula is Si (OR¹)₄, R¹Being selected from the alkyl with 1～6 carbon atom, described alkyl is side chain Or straight chained alkyl.Described quaternary ammonium base such as TPAOH, tetrabutylammonium hydroxide One or more in ammonium or tetraethyl ammonium hydroxide；Described organic quaternary ammonium salt such as tetrapropyl Ammonium bromide, tetrabutyl ammonium bromide, tetraethylammonium bromide, 4-propyl ammonium chloride, tetrabutyl chlorination One or more in ammonium or tetraethylammonium chloride；Described chain alkyl ammonium compounds such as ten Six alkyl trimethyl ammonium bromides, cetyl chloride ammonium, cetyltrimethylammonium hydroxide, Chain alkyl ammonium compounds be Tetradecyl Trimethyl Ammonium Bromide, tetradecyl ammonium chloride, 14 Alkyltrimethylammonium hydroxide, Dodecyl trimethyl ammonium chloride, lauryl ammonium chloride, ten Dialkyl group trimethylammonium hydroxide, Cetyltrimethylammonium bromide, octadecyl ammonium chloride, One or more in octadecyl trimethyl ammonium hydroxide.

The synthetic method of the micro-mesopore molecular sieve of hetero atom that the present invention provides, quaternary organic ammonium compounds Being 0.05～0.45:1 with the mol ratio in total silicon source, long-chain organic amine compound rubs with total silicon source Your ratio is 0.05～0.45:1.In the case of You Xuan, described template at least includes that one has Machine alkali, described organic base is quaternary ammonium base, organic amine, alkali formula chain alkyl ammonium compounds In one or more, the described organic base in template agent with the mol ratio in total silicon source is 0.04～0.5:1, such as 0.05～0.45:1.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, by hetero atom source, template Agent, water, polyhydric alcohol and optionally silicon source, optional inorganic source of ammonium form crystallization mixture, then By described crystallization mixture crystallization, forming crystallization product, crystallization product obtains miscellaneous through recovery Atom and molecule sieves.Described crystallization, can use existing method, and such as, the temperature of crystallization is 110～200 DEG C, crystallization time 0.2～20 days, carry out crystallization under self-generated pressure.One can be used Step crystallization, it would however also be possible to employ fractional crystallization.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, Crystallization pressure is self-generated pressure.A kind of embodiment, described crystallization is: at 100～130 DEG C Such as 110～130 DEG C crystallization 0.5～1.5 days, then crystallization 1～3 days at 160～180 DEG C, brilliant Change pressure is self-generated pressure.

The described micro-mesopore molecular sieve of recovery hetero atom is existing method, such as, generally includes crystalline substance Change product filtration, washing and roasting or crystallization product filtered, wash, be dried then roasting.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, the first embodiment, Comprise the following steps:

(1) by hetero atom source, template, water, polyhydric alcohol and optionally organosilicon source mixing, Alcohol is caught up with in hydrolysis；It is subsequently adding peroxide；

(2) product that step (1) obtains is aging；

(3) product that step (2) obtains adds or is added without solid silicon source, crystallization, Reclaim hetero-atom molecular-sieve；

Wherein, step (1) and step (3) introduce described silicon source at least one step, Described template includes quaternary organic ammonium compounds, chain alkyl ammonium compounds and optional organic Amines.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, the first embodiment party described In formula, the silicon source used is organosilicon source and/or solid silicon source, wherein in step (1) The silicon source present invention introduced is referred to as silicon source for the first time, the silicon source of introducing in step (3), this Invention is referred to as second time silicon source.Wherein, it is preferable that organosilicon source introduces in step (1), Solid silicon source (for inorganic silicon source) introduces in step (3).Organosilicon source can be simply used, Solid silicon source can also be simply used, under preferable case, use solid silicon source.Described silicon source is (also Total silicon source) it is called with SiO₂Meter organosilicon source and with SiO₂The summation in the inorganic silicon source of meter； When simply using organosilicon source, then described silicon source is organosilicon source, described when simply using Solid silicon source, then described silicon source is solid silicon source；When using solid silicon source and organosilicon source, Then described silicon source is solid silicon source and organosilicon source sum.In the first embodiment described, Preferably, described silicon source includes solid silicon source, introduces solid silicon source in step (3), its In with SiO₂Count the organosilicon source introduced in step (1) and with SiO₂Meter step (3) draws The mol ratio of the solid silicon source entered for example, 0～1:20, preferably 1:0.1～20, can obtain table The hetero-atom molecular-sieve of face Silicon-rich.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, the first embodiment party described In formula, building-up process introduces polyhydric alcohol and peroxide, polyhydric alcohol and total silicon source mole Ratio is 0.01～0.8:1, and the mol ratio in peroxide and total silicon source is 0.01～0.25:1 for example, 0.05～0.25:1.Introduce polyhydric alcohol and peroxide so that obtained hetero-atom molecular-sieve tool There is higher activity, there is less crystallite dimension and (or claim grain size, crystal grain short-axis direction Size).Wherein polyhydric alcohol is 0.01～0.8:1 with the mol ratio in total silicon source, and peroxide is with total The mol ratio in silicon source is 0.01～0.25:1, and organic amine is 0～0.4:1 with the mol ratio in total silicon source, Quaternary organic ammonium compounds is 0.05～0.45:1 with the mol ratio in total silicon source, chain alkyl ammonium compounds It is 0.05～0.25:1 with the mol ratio in total silicon source；Described total silicon source is with SiO₂The organosilicon of meter Source and the summation of solid silicon source.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, the first embodiment party described In formula, by hetero atom source, template, water, polyhydric alcohol, optional organic in step (1) Silicon source and the mixing of optional inorganic source of ammonium, can be in any way by optional organosilicon Source, hetero atom source, template, optional inorganic source of ammonium, water and polyhydric alcohol mixing, carried out Alcohol is caught up with in hydrolysis, makes organosilicon source and the hydrolysis of hetero atom source, containing of the monohydric alcohol that reduction hydrolysis produces Amount.Described hydrolysis catches up with alcohol can be the mixing by including organosilicon source and/or hetero atom source and water Thing stirs at least 10 minutes at 0～150 DEG C such as 0～100 DEG C preferably 50～95 DEG C and such as stirs 10～3000 minutes, so that organosilicon source and the hydrolysis of hetero atom source, and reduce organosilicon source and miscellaneous The content of the monohydric alcohol that atomic source hydrolysis produces.Generally, the water in products solution that alcohol obtains is caught up with in hydrolysis The content of the monohydric alcohol produced is less than 10ppm (quality).Preferably, hydrolysis catches up with alcohol to obtain In product, the content of monohydric alcohol is less than 10ppm (quality).

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, the first embodiment party described In formula, in step (2), by aging for step (1) products therefrom, described aging be in room temperature ～at 50 DEG C, step (1) products therefrom is stood 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 i.e. step (1) products therefrom is stood.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described crystallization, can adopt Using existing method, such as, the temperature of crystallization is 110～200 DEG C, crystallization time 0.2～20 days, Crystallization is carried out under self-generated pressure.A step crystallization can be used, it would however also be possible to employ fractional crystallization.One Planting embodiment, the temperature of described crystallization is 140～180 DEG C such as 160～180 DEG C, during crystallization Between be 0.5～10 day for example, 0.5～6 day, 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 days, then exist Crystallization 1～3 days at 160～180 DEG C, crystallization pressure is self-generated pressure.

The micro-mesopore molecular sieve of hetero atom of the present invention, has microcellular structure, also has mesoporous knot Structure, the aperture of described micropore be less than 1nm, described mesoporous aperture (diameter) 2-8nm it Between.In described hetero atom micro-mesoporous composite molecular sieve XRD spectra 2 θ angles be 0～3 ° and 5～ 35 ° have diffraction maximum.The XRD spectra of molecular sieve is 5～35 degree at 2 θ angles and has diffraction Peak, shows to exist in molecular sieve microcellular structure；2 θ angles of molecular sieve are 0～3 degree to be had and spreads out Penetrate peak, show molecular sieve exists meso-hole structure.

The micro-mesopore molecular sieve of hetero atom of the present invention, the volume of the aperture micropore less than 1nm I.e. micro pore volume is 0.12～0.19mL/g, and aperture is volume mesoporous for 2-8nm i.e. mesopore volume It is 0.3～0.8mL/g.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, synthesized hetero atom divides Son sieve can have less crystal grain, can improve the oxidation activity of synthesized molecular sieve, improves Heteroatomic utilization rate.

Accompanying drawing explanation

Fig. 1 is the micro-mesoporous composite molecular of stanniferous hetero atom prepared by the step (3) of embodiment 4 The XRD spectra of sieve.

Fig. 2 is the micro-mesoporous composite material of stanniferous hetero atom prepared by the step (3) of embodiment 4 XRD spectra (0-5 °).

Fig. 3 is the micro-mesoporous composite molecular of stanniferous hetero atom prepared by the step (4) of embodiment 4 The TEM photo of sieve.

Fig. 4 is that surface silicon titanium is than the measuring method schematic diagram with body phase silicon titanium ratio.For utilizing TEM-EDX measures body phase silicon titanium ratio and the schematic diagram of surface silicon titanium ratio, and wherein square frame 1 is illustrated Measuring the silicon titanium ratio in grain edges region, the silicon titanium in granular center region is measured in square frame 2 signal Ratio.Owing to grain edges territorial unit volume has a higher external surface area, and central area In unit volume, corresponding external surface area is relatively low, and therefore in square frame 1 and square frame 2, EDX measures knot Fruit can reflect that the silicon titanium embodied with surface compares difference.

Micro-composite mesoporous point of stanniferous hetero atom prepared by the step (3) that Fig. 5 is embodiment 4 Son sieve low temperature N₂The pore distribution curve that adsorption-desorption records, shows there is mesoporous existence in molecular sieve.

Detailed description of the invention

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, a kind of preferably embodiment party Formula, comprises the steps:

(1) by template, hetero atom source, organosilicon source, water, polyhydric alcohol and optional Inorganic Ammonium Source mixes, and alcohol is caught up with in hydrolysis, is subsequently adding peroxide；Alcohol is caught up with in described hydrolysis, generally exists At 0～150 DEG C such as 0～100 DEG C such as 50～95 DEG C by gained mixture stirring at least 10 Minute, the mixing time wherein stirred is 10 minutes～50 hours；The most inorganic source of ammonium (with NH₄ ⁺Meter): hetero atom source is (with TiO₂Meter) mol ratio be 0～5:1；

(2) by aging for step (1) products therefrom, described aging be by step (1) products therefrom 1～60 hour such as 2～50 hours or 3～30 hours are stood, further example at room temperature～50 DEG C Such as 3～15 hours；

(3) by the ageing products obtained by step (2) and solid silicon source according to the weight of 1:0.1～20 Amount ratio mix homogeneously, then crystallization (such as crystallization in closed reactor), reclaim hetero atom Micro-mesopore molecular sieve；Aging product in wherein said part by weight, obtained by step (2) Thing and solid silicon source are all with SiO₂Meter；

Wherein, water is 5～100:1 with the mol ratio in total silicon source；Template and the mol ratio in total silicon source It is 0.08～0.6:1 for example, 0.1～0.5:1,0.15～0.3:1 or 0.1～0.2:1；Hetero atom source with The mol ratio in total silicon source be 0.005～0.05:1 for example, 0.01～0.03:1 the most for example, 0.01～0.025:1；Described template is quaternary organic ammonium compounds, chain alkyl ammonium compounds With optional organic amine, organic amine is 0～0.4:1 with the mol ratio in total silicon source, organic quaternary ammonium Compound is 0.05～0.45:1 with the mol ratio in total silicon source, chain alkyl ammonium compounds and total silicon source Mol ratio is 0.05～0.45:1 such as 0.05～0.25:1.

Wherein, in described mol ratio, total silicon source is with SiO₂Meter, described total silicon source be with SiO₂Meter organosilicon 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, hetero atom source in terms of hetero atom, Water is with H₂O counts.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment party Formula, silicon source is organosilicon source for the first time, and silicon source is solid silicon source for the second time, prepared molecule Sieve grain surface Silicon-rich, grain surface silicon ratio is apparently higher than body phase silicon ratio, brilliant The ratio of grain surface silicon hetero atom mol ratio and body phase silicon mol ratio is 1.1～5:1, such as It is 1.2～4:1 or is 1.3～3:1.Obtained hetero-atom molecular-sieve, has higher surface silicon Hetero atom, than the ratio with body phase silicon ratio, has higher oxidation activity, for hydrogen peroxide The oxidation reaction participated in, it is possible to reduce the hetero atom decomposition to hydrogen peroxide in surface layer, is conducive to Reduce the activity of the decomposition side reaction of hydrogen peroxide, improve raw material availability.Additionally, this Hetero atom micro-mesopore molecular sieve synthetic method of bright offer, preferred embodiment uses the most honest and the cleanest The solid silicon source that valency is easy to get such as high-purity silica gel is or/and white carbon, and part replaces expensive Organosilicon source, it is possible to reduce the waste discharge of process of producing molecular sieve and the same of cost that economize in raw materials Time obtain high performance hetero-atom molecular-sieve, can be at relatively low template agent consumption and relatively low water Synthesize hetero-atom molecular-sieve in the case of silicon ratio, the synthesis cost of hetero-atom molecular-sieve can be reduced, Improve the solid content of synthesis of molecular sieve crystallization product, improve one-pot molecular sieve yield.

Surface silicon hetero atom can use TEM-EDX or ion to swash than with body phase silicon ratio Sending out corrosion XPS method or XRF method measures and obtains, wherein, surface silicon hetero atom ratio can TEM-EDX or ion excitation corrosion XPS means are used to measure and obtain, for distance crystal grain table The silicon ratio of the face atomic layer less than 5nm such as 1～5nm；Body phase hetero atom ratio can Obtained by chemico-analytic method, or by TEM-EDX in the central area of crystal grain such as The distance grain surface distance area measure more than 20nm obtains, or is measured by XRF Obtain.

The present invention provide hetero-atom molecular-sieve synthetic method, described preferred embodiment, can To synthesize hetero-atom molecular-sieve in the case of lower template agent consumption, thus template agent consumption can To reduce, such as template agent with the mol ratio in the organosilicon source in terms of silicon dioxide is 0.1～0.3:1, it is 0.1～0.20:1 further；In the method that the present invention provides, can be at Gao Gu Synthesize hetero-atom molecular-sieve under content, from can and reduce the usage amount of water, improve output per single reactor i.e. More molecular sieve, therefore described water and total silicon is synthesized under same synthesis reactor volume The mol ratio in source (in terms of silicon dioxide) can be 5～50:1, for example, 5～30:1 or be 6～15:1.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment party In formula, described hetero atom source is preferably 0.01～0.03:1 for example, with the mol ratio in total silicon source 0.01～0.025:1.The method that the present invention provides can use inorganic heteroatoms source, has with use Machine hetero atom source is compared, and can reduce synthesis cost.Described hetero atom (representing with M) is One or more in Fe, Co, Cu, Sn, Zr, B, Ge, V, Cr, Mn.

The organic compound of ferrum is such as: Ferrous acetate, acrylic acid ferrum, ethanol ferrum, isopropyl oxygen ferrum, One or more in ammonium ferric oxalate etc., the inorganic compound of ferrum such as iron chloride, protochloride One or more in ferrum, ferrum oxide, ferrous oxide, five water iron sulfate etc..

The organic compound of stannum is such as: tributyltin chloride, bis-acetylacetonate base dibutyl tin, Trioctylphosphine stannic chloride, tributylvinyl tin, three normal-butyl hydrogen stannum, tetravinyl stannum, propylene Base triphenyltin, three normal-butyl Tin tetrabromide .s, dibutyl tin dichloride, allyl tributyltin, Trimethyltin chloride, dimethyltin chloride, tetraphenyltin, tetramethyl tin, three normal-butyl first Epoxide stannum, butyl tin trichloride, tetra allylic tin, triphenyl tin chloride, tetra isopropyl stannum, Methacrylic acid tributyl tin, tetrabutyltin, tetraethyl tin, ethanol stannum, stannous acetate, two One or more in phenyl dichloro stannum, isopropoxy stannum；The inorganic compound of stannum is such as SnCl₄、SnCl₄·5H₂O、SnCl₂、SnCl₂·2H₂O、SnSO₄In one or more.

The organic compound of zirconium is such as: zirconium iso-propoxide, tetrabenzyl zirconium, tetrabutyl zirconate, acetyl Acetone zirconium, tetramethyl acrylic acid zirconium, zirconium-n-propylate, acetic acid zirconium, zirconium tert-butoxide, four ethoxies One or more in base zirconium；The inorganic compound of zirconium is such as: zirconium oxychloride, zirconium hydroxide, One or more in zirconium nitrate, Zirconium tetrachloride., Zr (SO4) 2 4H2O.

The organic compound of germanium is such as: benzyl tri-chlorination germanium, ethyl tri-chlorination germanium, trichloromethyl Germanium, four n-butoxy germanes, tributyl germanium chloride, tetraethyl germanium, trimethyl ammonia chloride germanium, three Butylethylene germanium, tetra-n-butyl germanium, tetramethyl germanium, trimethyl ammonia chloride germanium, triethyl group germanium chloride, In tetraethoxy germanium, dichloro-dimethyl germanium, methoxyl group germanium, isopropanol germanium, isobutyl group germane One or more；The inorganic compound of germanium is such as: the one in germanium tetrachloride, germanium dioxide Or it is multiple.

The organic compound of vanadium is such as: oxidation diacetyl acetone closes vanadium, vanadium acetylacetonate, three different One or more in propoxyl group vanadium oxide, three propanol vanadium oxides, oxidation triethyl group vanadium；Vanadium Inorganic compound such as: vanadium tetrachloride, vanadium oxytrichloride, vanadium oxysulfate, vanadyl oxalate, just One or more in vanadic acid sodium, sodium metavanadate, ammonium metavanadate, potassium metavanadate.

The organic compound of chromium is such as: in chromium acetylacetonate, benzoyl acetone chromium, isopropanol chromium One or more；The inorganic compound of chromium such as chromium chloride hexahydrate, Cr (NO₃)₃·9H₂O In one or more.

The organic compound of boron is such as: Trialkylboron compounds such as trimethyl borine, boron triethyl, One or more in tripropylborane, tri butyl boron；The inorganic compound of boron such as boric acid, One or more in metaboric acid, diboron trioxide.

The organic compound of manganese is such as: manganese acetylacetonate, manganese acetate, two acetate hydrate manganese, four One or more in acetate hydrate manganese；The inorganic compound of manganese such as MnSO₄·7H₂O、 MnCl₂·4H₂O、Mn(NO₃)₂·6H₂O,Mn(ClO₄)₂·6H₂One or more in O.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment party In formula, inorganic source of ammonium is 0～5:1 with the mol ratio in hetero atom source, and for example, 0.01～4:1 are excellent Elect 0.05～0.5:1 as.Add inorganic source of ammonium, the activity of synthesized molecular sieve can be improved, carry High cage heteroatom silicon ratio.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described preferred enforcement In mode, the inorganic source of ammonium described in step (1) is inorganic ammonium salt and/or ammonia, described Inorganic ammonium salt such as ammonium chloride, ammonium nitrate, ammonium sulfate obtain one or more.Described nothing Machine source of ammonium is preferably ammonia, with NH₄ ⁺Meter ammonia with TiO₂Meter hetero atom source mole Than being 0～5:1 for example, 0.01～4:1 or be 0.05～0.5:1.Add described inorganic quaternary ammonium salts, The activity of synthesized molecular sieve can be improved, improve described surface silicon hetero atom than with body phase sila The ratio of atomic ratio.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment party In formula, described template is not less than 0.08:1 preferably with the mol ratio in described total silicon source 0.1～0.3:1.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment party The mol ratio of organosilicon source described in formula and solid silicon source is (with SiO₂Meter for the first time silicon source and the The mol ratio in secondary silicon source) it is preferably 1:1～19, for example, 1:2～18, or 3～17, or Person is 5～15:1.Generally the ageing products obtained by step (2) and solid silicon source be equal to have Machine silicon source and the mol ratio of solid silicon source.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment party In formula, the template agent described in step (1) includes quaternary organic ammonium compounds and chain alkyl ammonium Compound, can be optionally possibly together with organic amine compound, and quaternary organic ammonium compounds is rubbed with total silicon source Your ratio is 0.04～0.45:1, and chain alkyl ammonium compounds with the mol ratio in total silicon source is 0.04～0.45:1, organic amine is 0～0.4:1 with the mol ratio in total silicon source.Described organic quaternary ammonium The most organic quaternary amine alkali of compound and/or organic quaternary ammonium salt.Described organic amine be fatty amine, One or more in aromatic amine and hydramine, described fatty amine (also referred to as fatty amines chemical combination Thing), its formula is R³(NH₂)_n, wherein R³For having alkyl or the Asia of 1～4 carbon atom Alkyl, n=1 or 2；Described hydramine (present invention is also referred to as alcamine compound) its formula is (HOR⁴)_mNH_(3-m), wherein R⁴For having the alkyl of 1～4 carbon atom, m=1,2 or 3. One or more in described fatty amine such as ethamine, n-butylamine, butanediamine or hexamethylene diamine； Described aromatic amine refers to the amine with an armaticity substituent group, such as aniline, toluidines, One or more in p-phenylenediamine；Described hydramine such as monoethanolamine, diethanolamine or three One or more in ethanolamine.Described quaternary ammonium base such as TPAOH, four One or more in butyl ammonium hydroxide or tetraethyl ammonium hydroxide；Described organic quaternary ammonium salt Such as 4-propyl bromide, tetrabutyl ammonium bromide, tetraethylammonium bromide, 4-propyl ammonium chloride, One or more in tetrabutylammonium chloride or tetraethylammonium chloride.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described chain alkyl ammonium Its formula of compound is R⁵NH₃X or R⁵N(R⁶)₃X, wherein R⁵Exist for carbon number Alkyl between 12～18, R⁶For carbon number alkyl between 1～4；X be monovalence cloudy from Son for example, OH^-、Cl^-、Br^-；When X is OH^-Time, the present invention is referred to as alkali formula chain alkyl Ammonium compounds；Described organosilicon source is organo-silicon ester, described organo-silicon ester, and its formula is Si(OR¹)₄, R¹Being selected from the alkyl with 1～6 carbon atom, described alkyl is side chain or straight Alkyl group.Described quaternary ammonium base such as TPAOH, TBAH or One or more in tetraethyl ammonium hydroxide；Described organic quaternary ammonium salt such as tetrapropyl bromination Ammonium, tetrabutyl ammonium bromide, tetraethylammonium bromide, 4-propyl ammonium chloride, tetrabutylammonium chloride or One or more in tetraethylammonium chloride；Described chain alkyl ammonium compounds such as hexadecane Base trimethylammonium bromide, cetyl chloride ammonium, cetyltrimethylammonium hydroxide, long-chain Alkyl ammonium compound is Tetradecyl Trimethyl Ammonium Bromide, tetradecyl ammonium chloride, myristyl Trimethylammonium hydroxide, Dodecyl trimethyl ammonium chloride, lauryl ammonium chloride, dodecane Base trimethylammonium hydroxide, Cetyltrimethylammonium bromide, octadecyl ammonium chloride, 18 One or more in alkyltrimethylammonium hydroxide.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, a kind of specific embodiment party Formula, the micro-mesopore molecular sieve of described hetero atom has MFI structure, described organic quaternary ammonium Compound include the one in TPAOH, 4-propyl ammonium chloride, 4-propyl bromide or Multiple.One or many in TPAOH, 4-propyl ammonium chloride, 4-propyl bromide Kind it is 0.01～0.45:1 to be preferably 0.02～0.45:1 with the mol ratio in total silicon source.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described in a kind of embodiment The micro-mesopore molecular sieve of hetero atom there is MEL structure, described quaternary organic ammonium compounds includes One or more in TBAH, tetrabutyl ammonium bromide or tetrabutylammonium chloride.Four The summation of one or more in butyl ammonium hydroxide, tetrabutyl ammonium bromide or tetrabutylammonium chloride It is 0.01～0.45:1 to be preferably 0.02～0.45:1 with the mol ratio in total silicon source.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, a kind of embodiment, institute The micro-mesopore molecular sieve of hetero atom stated has BEA structure, described quaternary organic ammonium compounds bag Include one or more in tetraethyl ammonium hydroxide, tetraethylammonium bromide, tetraethylammonium chloride. Described quaternary organic ammonium compounds includes tetraethyl ammonium hydroxide, tetraethylammonium bromide, tetraethyl The summation of one or more in ammonium chloride be 0.01～0.45:1 excellent with the mol ratio in total silicon source Elect 0.02～0.45:1 as.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described preferred enforcement In mode, the organosilicon source described in step (1) 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-C₄ Alkyl, described alkyl can be branched alkyl or straight chained alkyl.Described organo-silicon ester example Such as in quanmethyl silicate, tetraethyl orthosilicate, silicic acid four butyl ester, dimethyl diethyl estersil Plant or multiple；Wherein in preferred quanmethyl silicate, tetraethyl orthosilicate, dimethyl diethyl estersil One or more.Described solid silicon source is highly purified silica solid or powder, Can be such as white carbon and/or high-purity silica gel.Under preferable case, with butt weight it is SiO in solid silicon source described in benchmark₂Content is not less than 99.99 weight %, and Fe in terms of atom, The gross mass content of Al and Na impurity is less than 10ppm；Such as SiO₂Content is 99.99～100 Weight %, typically greater than 99.99 and less than 100 weight %.Described solid silicon source is permissible It is high-purity silica gel and/or white carbon, preferably white carbon；SiO in wherein said high-purity silica gel₂ Content is preferably greater than or equal to 99.99 weight % for example, more than 99.99 weight % and less than 100 Weight %, and the mass content of the impurity such as Fe, Al and Na is less than 10ppm；Described white carbon Specific surface area be preferably between 20-1000m²For example, 50-400m between/g²/ g, with Linesless charcoal On the basis of black butt weight, SiO in described white carbon₂Content is preferably greater than or equal to 99.99 weights Amount % for example, 99.99～100 weight % is for example, more than 99.99 weight % and less than 100 weight %, in terms of atom, in described white carbon, the quality total content of Fe, Al and Na is less than 10ppm. Described white carbon can be purchased, or prepares according to existing method, such as according to patent Prepared by the method that CN200910227646.2 provides, a kind of preparation method be by Silicon chloride. with Hydrogen and oxygen generation combustion reaction obtain.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described preferred enforcement In mode, described hetero atom source is heteroatomic organic compound or heteroatomic inorganic chemical When thing, such as hetero atom are metal, described hetero atom source can be inorganic metal salt or organic Metal acid esters.Preferably, described hetero atom source hydrolyzes for being dissolved in water or react with water Reaction produce heteroatomic oxide containing described heteroatomic compound.Described organic compound The most heteroatomic acylate of thing, alkoxide, alkyl compound, phenyl compound, Benzylation Compound, carbonyl compound, carboxyl compound, alcoholic compound, alkenyl compound, alkoxylate Compound, organohalogen compounds, acyl compounds, tetraalkoxy hetero atom acid esters are (such as M (alkoxy)₄ Wherein M represent described in hetero atom) in one or more；Heteroatomic inorganic compound Can be containing described heteroatomic inorganic salt or acid, the most heteroatomic chloride, hetero atom Sulfate, heteroatomic nitrate, heteroatomic hydroxide, heteroatomic oxychlorination thing, One or more in heteroatomic oxide, heteroatomic acid, it is preferred that described hetero atom Inorganic salt or acid can be dissolved in water or with water react formation hydrolyzate.Preferably, described Hetero atom source is tetraalkoxy hetero atom acid esters M (alkoxy)₄, heteroatomic alkyl compound, Tetraalkyl heteroatomic compound, heteroatomic alcoholic compound, heteroatomic carboxyl compound, miscellaneous The chloride of atom, heteroatomic sulfate, heteroatomic nitrate, heteroatomic acetate, One or more in heteroatomic acid and their hydrolyzate, wherein tetraalkoxy is miscellaneous former The carbon number of the alkoxyl in sub-acid ester molecules is 1～6, such as carbon number is 1,2,3, 4,5 or 6.Hetero atom source is preferably 0.01～0.03:1 with the mol ratio in silicon source (total silicon source) Such as 0.015～0.025:1.

In hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described preferred enforcement In mode, in step (1) by hetero atom source, template, organosilicon source, inorganic source of ammonium and Water is by mixing, and alcohol is caught up with in row hydrolysis.Alcohol is caught up with in described hydrolysis, at 0～150 DEG C preferably 0～100 DEG C Such as 50～90 DEG C are stirred at least 10 minutes, so that organosilicon source and the hydrolysis of hetero atom source, and Reduce the monohydric alcohol content in gained mixture.Generally mixing time is 10～3000 minutes, example As for 2～30 hours.Catch up with alcohol by hydrolysis, obtain the organosilicon hydrolyzation liquid of clear.Step Suddenly in the mixture that (1) obtains, the content of monohydric alcohol is not the most not higher than 10ppm (quality). Catch up with alcohol by hydrolysis, obtain the organosilicon hydrolyzation liquid of clear.It is subsequently adding peroxide to stir Mixing uniformly, usual mixing time is 10～60 minutes.Described polyhydric alcohol is containing two in molecule Individual or the alcohols of two or more hydroxyl, it is preferable that in described polyol molecule, carbon atom number is 2～8, described hydroxyl for example, 2 or 3, described polyhydric alcohols such as glycerol, second One or more in glycol, hexanediol, diethylene glycol.Described peroxide is containing peroxide The compound of key, the preferred hydrogen peroxide of described peroxide, tert-butyl peroxide, peracetic acid, One or more in trifluoro peracetic acid etc..Polyhydric alcohol with the mol ratio in silicon source is 0.01～0.8, preferably 0.05～0.5:1, peroxide is 0.01～0.25 with the mol ratio in silicon source: 1, for example, 0.05～0.25:1 or 0.05～0.15:1.

One or more in described polyhydric alcohols such as glycerol, ethylene glycol, diethylene glycol.Institute The preferred hydrogen peroxide of peroxide stated, tert-butyl peroxide, peracetic acid, trifluoro peracetic acid One or more in Deng.The mol ratio in polyhydric alcohol and silicon source is 0.01～0.8, preferably 0.05～ 0.5:1, peroxide is 0.01～0.25:1 with the mol ratio in silicon source, for example, 0.05～0.25:1 Such as 0.05～0.15:1.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment party In formula, in step (2), by aging for step (1) products therefrom, described aging be in room temperature ～at 50 DEG C, step (1) products therefrom is stood 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 Hour, ageing process is not stirred, by quiet for described material i.e. step (1) products therefrom Put.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment party In formula, the ageing products that step (2) obtains is mixed by step (3) with solid silicon source, with SiO₂Meter, the product that step (2) obtains is 1:0.1～20 with the mol ratio of solid silicon source, example Being 1:1～19 (mol ratio of organosilicon source and solid silicon source as described in i.e. is 1:1～19), Or be 1:2～18 or 1:3～17, it is 1:5～15 further, with SiO₂Meter organosilicon source with The mol ratio of solid silicon source is preferably 1:5～15.The method that the present invention provides, it is possible to use higher The solid silicon source of ratio, can improve the solid content of synthetic product, thus organic with being used alone The yield improving single synthesis in the case of synthesis reaction vessel is constant is compared in silicon source.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described preferred embodiment party In formula, step (3) described crystallization, the temperature of crystallization is 110～200 DEG C, and crystallization pressure is Self-generated pressure, the time of crystallization is 2 hours～20 days, and the time of usual described crystallization is 0.5～20 My god, such as crystallization time is 0.5～10 day, the temperature of the crystallization described in further step (3) Being 140～180 DEG C for example, 160～180 DEG C, crystallization time is 0.5～6 day for example, 1～6 day, The most for example, 1～3 day.Crystallization pressure is self-generated pressure.Described crystallization can be at rustless steel Stirred tank is carried out.Crystallization heat up can one section of intensification can also multistage heating mode.Heat up speed Rate can be carried out according to existing crystallization temperature-rising method, for example, 0.5-1 DEG C/min.Described crystallization can To carry out in rustless steel stirred tank.A kind of embodiment, the crystallization temperature of described crystallization is 160～180 DEG C, crystallization time is 1～6 day such as 0.5～3 day, and crystallization pressure is self-generated pressure. A kind of embodiment, the crystallization described in step (3) is: at 100～130 DEG C such as 110～130 Crystallization 0.5～1.5 days at DEG C, then crystallization 1～3 days at 160～180 DEG C, crystallization pressure is Self-generated pressure.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, described preferred enforcement In mode, reclaiming the micro-mesopore molecular sieve of hetero atom described in step (3) is existing method, bag Include crystallization product filtration, washing and roasting or crystallization product filtered, wash, be dried so Rear roasting.The purpose filtered is the micro-mesopore molecular sieve of hetero atom crystallization obtained and crystallization mother liquor Separating, the purpose of washing is the template solution washing away absorption on sieve particle surface, such as Can be room temperature～50 DEG C in temperature, weight ratio 1:1～the 20 such as 1:(1-15 of molecular sieve and water) Under carry out mixing, washing or drip washing.The purpose being dried is to remove the most of moisture in molecular sieve, To reduce water evaporation quantity when roasting, dry temperature can be 100～200 DEG C.Roasting Purpose be to remove the template in molecular sieve, the temperature of example roasting as mentioned is 350～650 DEG C, roasting time is 2-10 hour.Obtained provided by the present invention miscellaneous by recovery Atom micro-mesopore molecular sieve product.

In hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, it is miscellaneous former that recovery obtains The micro-mesopore molecular sieve of son is also may pass through processing further, and the hetero atom that i.e. present invention provides is micro-mesoporous Zeolite synthesis method, it is also possible to include rearrangement step:

The hetero atom micro-mesopore molecular sieve Crystallizing treatment in organic alkali solution recovery obtained is excellent It is selected in Crystallizing treatment in organic quaternary ammonium aqueous slkali, then reclaims the micro-mesopore molecular sieve of hetero atom.Should Process makes the micro-mesopore molecular sieve of obtained hetero atom have hollow-core construction, and the present invention referred to as divides Son sieve is reset.Generally include the micro-mesopore molecular sieve of hetero atom recovery obtained the most described preferably The micro-mesopore molecular sieve of hetero atom that obtains of embodiment step (3) (with SiO₂Meter) with organic Alkali, water form mixture, at closed reactor according to the mol ratio of 1:0.02～0.5:2～50 Neutralize 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 hetero atom after being reset.Wherein The micro-mesopore molecular sieve of hetero atom is (with SiO₂Meter) it is 1:0.02～0.5 with the mol ratio of organic base For example, 1:0.02～0.2, with SiO₂The hetero-atom molecular-sieve of meter is 1:2～50 with the mol ratio of water For example, 1:2～30 the most for example, 1:5～10, the crystallization temperature of rearrangement is 100～200 DEG C Such as 120～200 DEG C, crystallization pressure is self-generated pressure, crystallization time 0.5～10 days, for example, 0.5～8 day or 1～6 day.Preferably, the crystallization temperature described in rearrangement step is 150-200 DEG C, Crystallization time is 0.5～6 day.Recovery method is existing method, can refer to foregoing recovery Method, generally includes and is filtered by crystallization product, washs, is dried so and roasting.Rearrangement step institute The organic base stated is quaternary ammonium base and/or organic amine, described quaternary ammonium base such as 4 third Mixing of one or more in base ammonium hydroxide, TBAH or tetraethyl ammonium hydroxide Compound.Described organic base is one or more in quaternary ammonium base, organic amine；Described Organic amine is one or more in fatty amine, aromatic amine and hydramine, described fatty amine (this Invention also referred to as fat amine compound), its formula is R³(NH₂)_n, wherein R³For having 1～4 The alkyl of individual carbon atom or alkylidene, n=1 or 2；(present invention is also referred to as alcohol to described hydramine Aminated compounds) its formula is (HOR⁴)_mNH_(3-m), wherein R⁴For having 1～4 carbon atom Alkyl, m=1,2 or 3.Described fatty amine such as ethamine, n-butylamine, butanediamine or own One or more in diamidogen；Described aromatic amine refers to have an armaticity substituent group One or more in amine, such as aniline, toluidines, p-phenylenediamine；Described hydramine is such as One or more in monoethanolamine, diethanolamine or triethanolamine.A kind of embodiment, weight Hetero-atom molecular-sieve described in row's step has MFI structure, and described quaternary ammonium base is TPAOH.A kind of embodiment, described hetero-atom molecular-sieve has MEL knot Structure, the quaternary ammonium base described in rearrangement step is TBAH.A kind of embodiment, Described hetero-atom molecular-sieve is that total silicon has BEA structure, organic described in rearrangement step Quaternary ammonium base is tetraethyl ammonium hydroxide.

Molecular sieve rearrangement process can be carried out once, it is also possible to is repeated one or more times, described heavy Multiple, will reset the micro-mesopore molecular sieve of the hetero atom obtained according still further to above-mentioned rearrangement method at Reason.Processed by rearrangement, the hetero-atom molecular-sieve with secondary pore structure, gained can be obtained The crystal grain of the micro-mesopore molecular sieve of hetero atom is that (the most described molecular sieve is free hearty cord to hollow-core construction Structure), there is bigger pore volume and specific surface area；The radial direction of the chamber portion of this hollow crystal grain A length of 5～300nm, at 25 DEG C, P/P₀=0.10, adsorption time recorded under conditions of 1 hour Benzene adsorbance be at least 70 milligrams per gram, the adsorption isotherm of the nitrogen absorption under low temperature of this molecular sieve And between desorption isotherm, there is hysteresis loop.

Hetero atom micro-mesopore molecular sieve synthetic method that the present invention provides, may be used for synthesis tool Micropore and 2～8nm mesoporous hetero-atom molecular-sieve materials are had (or to claim hetero atom micro-composite mesoporous Material), the micro-mesopore molecular sieve of described hetero atom such as have MFI structure, BEA, structure, One or more structures in the molecular sieve of MEL structure.

The present invention is further illustrated for the following examples, but and is not so limited this Bright.

Grain size and surface silicon hetero atom in embodiment compare the survey with body phase silicon ratio Metering method uses TEM-EDX, TEM electron microscope experiment at FEI Co. Tecnai F20G2 Carry out on S-TWIN type transmission electron microscope, be furnished with the energy filter system of Gatan company GIF2001, adnexa is equipped with X-ray energy spectrometer.Electron microscopic sample uses the method system of suspended dispersed Standby on micro-grid of diameter 3mm.In embodiment, each sample randomly selects 20 particle sizings Its surface silicon hetero atom ratio and body phase silicon ratio, gauging surface silicon ratio and body phase silicon The ratio of hetero atom ratio, then takes the meansigma methods of its 20 samples as described sample surfaces silicon Hetero atom is than the ratio with body phase silicon ratio.

XRD measuring method: carry out sample on Siemens D5005 type x-ray diffractometer X-ray diffraction (XRD) crystalline phase figure measure, radiographic source is CuK α, Tube voltage 40kV, tube current 40mA, 0.5 °/min of scanning speed, sweep limits 2 θ=4 °～ 40°。

The method of testing of BET specific surface area and pore volume uses N2 adsorption volumetric method, according to BJH Computational methods.(see Petrochemical Engineering Analysis method (RIPP test method), RIPP151-90, Science Press, nineteen ninety publication)

In embodiment and comparative example, raw materials used character is as follows:

TPAOH, great You chemical plant, Guangdong.

Tetraethyl orthosilicate, analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group.

Ammonia, analytical pure, concentration 20 weight %.

Glycerol, analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group.

Diethylene glycol, analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group.

White carbon, Zhejiang Ju Hua group product, model AS-150；Solid content is more than 95 weight %, in butt, dioxide-containing silica is more than 99.99 weight %, and the total content of ferrum, sodium and Al is little In 10ppm, specific surface area is 195m²/g。

Remaining reagent is unexplained, is commercially available product, analytical pure.

Embodiment 1

(1) by TPAOH (TPAOH) aqueous solution that concentration is 20 weight %, Cetyl trimethylammonium bromide (CTMAB), five water iron sulfate, tetraethyl orthosilicate (TEOS), Glycerol, concentration are the ammonia of 20 weight % and water is added sequentially in beaker, put into Mix homogeneously on the magnetic stirring apparatus of heating and agitating function, and stir 3 hours at 60 DEG C, Supplement the moisture of evaporation at any time, obtain water white transparency hydrolyzed solution, be subsequently adding hydrogen peroxide water-soluble Liquid, stirs；

(2) gained hydrolyzed solution is stood under uniform temperature (aging temperature) within 12 hours, carry out Aging, obtain ageing products；

(3) in the ageing products that step (2) obtains, stirring is lower adds white carbon powder, Stir 1 hour mix homogeneously after adding, form a kind of " viscous body ", be transferred into rustless steel In closed reactor, in 150 DEG C of thermostatic crystallizations 36 hours, crystallization product was through filtering, using 10 times of crystallization product weight deionized water wash, wash 10 times, filter cake are placed in 120 DEG C Under be dried 24 hours, then be placed in 550 DEG C of roastings 6 hours, ferrum of the present invention Hetero atom micro-mesopore molecular sieve product, is designated as Fe-MFI-1；22 °-25 ° appearance of XRD spectra " Five Fingers Peak ", shows that it has MFI structure；

(4) by TPAOH water that Fe-MFI-1 sample described in 6g and concentration are 20 weight % Solution uniformly mixes, and the weight ratio of described Fe-MFI-1 Yu TPAOH aqueous solution is 1:5, In airtight reactor, 150 DEG C of crystallization 3 days, filter, wash, and are dried 24 little at 120 DEG C Time, 550 DEG C of roastings 6 hours, reset hetero-atom molecular-sieve product, be designated as Fe-MFI-1-C.In embodiment 1, proportioning and the synthesis condition of each raw material are as shown in table 1.Implement The surface silicon iron atom ratio of example 1 step (3) and step (4) products therefrom is former with body phase ferrosilicon The ratio of son ratio is shown in Table 2.

Embodiment 2～3

Micro-mesopore molecular sieve Han iron heteroatoms, its proportioning and conjunction is prepared according to the method for embodiment 1 One-tenth condition is shown in Table 1, characterizes and evaluation result is shown in Table 2.The synthesis condition ginseng being not directed in table 1 Examine embodiment 1.

Comparative example 1

List of references (Journal of Catalysis 2014,312,263 270) carries out Fe-MFI Zeolite synthesis.Specifically comprise the following steps that

(1) 0.46g five water iron sulfate, 5.5g sulphuric acid (mass fraction 95%-98%) are weighed And 25g deionized water mix homogeneously is placed in beaker I.

(2) in beaker II, weigh 21.32g nine water sodium silicate and be dissolved in 40.85g deionization In water.Under the effect of stirring, slowly the solution of beaker II is added in beaker I.It follows that Weigh 3.33gTPABr (mass fraction 98%) to add in said mixture, finally give light The mixture of yellow.

(3) mixture of last for step (2) gained is placed in the crystallizing kettle of 170 DEG C of band stirrings Interior crystallization 3 days, the product of gained, through filtering, washs, is dried 24 at ambient temperature little Time, then be placed in Muffle furnace with 2K/min^-1Speed rise to 480 DEG C of roastings 4 hours, Obtain sieve sample eventually.

Embodiment 4～11

The micro-mesopore molecular sieve of stanniferous hetero atom, its proportioning and conjunction is prepared according to the method for embodiment 1 One-tenth condition is shown in Table 1, characterizes and evaluation result is shown in Table 2.The synthesis condition ginseng being not directed in table 1 Examine embodiment 1.

Comparative example 2

List of references (Microporous Materials, 1997,12,331-340) carries out Sn-MFI Zeolite synthesis.Specifically comprise the following steps that

(1) weigh 1.9gSnCl4 5H2O, be dissolved in 10gH2O and obtain solution A, then Weigh 5.34gNH4F to be dissolved in 25g water and obtain solution B, under the effect of stirring by this two Plant solution A, B mix homogeneously obtains solution C, more just 9.78gTPABr adds 56g water In obtain solution D, then solution D is added solution C and stirs 30 minutes and obtain solution E；

(2) weigh 8.64g white carbon to be gradually added in solution E under the effect of stirring, and Stir and obtain homogeneous colloidal sol in 4 hours；

(3) colloidal sol of step (2) gained is filled still and is placed in 200 DEG C of static crystallizations 6 days, The product of gained, through filtering, washs, and is dried 5 hours at 120 DEG C, then 550 DEG C of roastings Burn 3 hours, final score sieve sample.

Comparative example 1～3

The micro-mesopore molecular sieve of stanniferous hetero atom, its proportioning and conjunction is prepared according to the method for embodiment 4 One-tenth condition is shown in Table 1, characterizes and evaluation result is shown in Table 2.The synthesis condition ginseng being not directed in table 1 Examine embodiment 1.

Embodiment 12～14

Micro-mesopore molecular sieve in zircona atom, its proportioning and conjunction is prepared according to the method for embodiment 1 One-tenth condition is shown in Table 1, characterizes and evaluation result is shown in Table 2.The synthesis condition ginseng being not directed in table 1 Examine embodiment 1.

Comparative example 3

List of references (Catalysis Letters, 1997,45,41-50) carries out Zr-MFI molecular sieve Synthesis.Specifically comprise the following steps that

(1) 0.16g ZrCl is weighed₄It is dissolved in 5g deionized water, this solution is added In 21.25gTEOS, it is slowly stirred 20 minutes,

(2) in above-mentioned solution, 40.72gTPAOH aqueous solution it is added dropwise over, to be mixed 1 After hour, add 8g deionized water, and stir 30 minutes, obtain the colloidal sol of clear.

(3) colloidal sol of step (2) gained is filled still and is placed in 160 DEG C of static crystallizations 48 hours, The product of gained through filtering, washing, and being dried at 110 DEG C, 550 DEG C of roastings totally 16 hours, Final score sieve sample.

Embodiment 15

Prepare the boracic micro-mesopore molecular sieve of germa atom according to the method for embodiment 1, its proportioning and Synthesis condition is shown in Table 1, characterizes and evaluation result is shown in Table 2.The synthesis condition being not directed in table 1 Reference example 1.

Comparative example 4

List of references (Microporous and Mesoporous Materials, 2013,170, 131 140) B-Ge-MFI Zeolite synthesis is carried out.Specifically comprise the following steps that

(1) weigh 0.1g boric acid to be dissolved in 5g deionized water, add 12.2g white carbon, And stir, then it is added dropwise over TPAOH solution that 3.3g mass fraction is 20% also 15 minutes Stir 15 minutes, then weigh 0.1699gGeO₂Add in the solution of gained, and persistently stir Mix 20 minutes；

(2) 3.75gTPABr is dissolved in 8.61g deionized water, then this solution is added In the product of step (1) gained, and stir 1.5 hours；

(3) product of step (2) gained is filled still, and the stirring speed of 60 revs/min Under rate, crystallization 6 days under the conditions of 160 DEG C, crystallization product through filtration, washing, 110 DEG C Dried overnight, after 550 DEG C of roastings 6 hours, final score sieve sample.

Embodiment 16,17

The micro-mesopore molecular sieve of germanic hetero atom, its proportioning and conjunction is prepared according to the method for embodiment 1 One-tenth condition is shown in Table 1, characterizes and evaluation result is shown in Table 2.The synthesis condition ginseng being not directed in table 1 Examine embodiment 1.

Comparative example 5

List of references (J.Phys.Chem.1993,97,5678-5684) carries out Ge-MFI and divides Son sieve synthesis.Specifically comprise the following steps that

(1) TEOS16.67g, TPABr0.66g, methylamine 12.43g, HF (quality are weighed The aqueous solution of mark 40%) 2.5g, deionized water 30g add mix homogeneously in beaker, and acute Strong stirring 30 minutes is to obtain uniform colloidal sol；

(2) weigh in the colloidal sol that germanium tetrachloride 0.43g is slowly added to step (1) gained, And stir 2 hours；

(3) product of step (2) gained is filled still, crystallization under the conditions of being placed in 170 DEG C 18 hours, the product of gained, through filtering, washed, and in 110 DEG C of dry 24h, 550 DEG C of roastings Burn 5 hours, final score sieve sample.

Embodiment 18

The micro-mesopore molecular sieve of the atom Han vanada, its proportioning and conjunction is prepared according to the method for embodiment 1 One-tenth condition is shown in Table 1, characterizes and evaluation result is shown in Table 2.The synthesis condition ginseng being not directed in table 1 Examine embodiment 1.

Comparative example 6

List of references (Thermochimica Acta, 2004,420,145 154) carries out V-MFI Zeolite synthesis.Specifically comprise the following steps that

(1) (quality forms: 8%Na to weigh 22.22g sodium silicate solution₂O, 27%SiO₂, 65%H₂O) with 0.10g mass fraction be 50% NaOH aqueous solution, obtain alkalescence Solution A；

(2) weigh 2.44g sodium fluoride to be dissolved in 24.57g deionized water, claim the most respectively Take 0.38g vanadium oxysulfate (VOSO₄), 4.53gTPABr is dissolved in and wherein obtains acid solution B；

(3) solution B is poured into solution A, and to obtain continuous stirring 5 hours homogeneous to obtain Colloidal sol, crystallization 3 days under the conditions of this colloidal sol dress still is placed in 190 DEG C, the product of gained passes through Filter, washing, and at 110 DEG C of dry 24h, 550 DEG C of roastings 5 hours, final score sieve sample Product.

Embodiment 19

The micro-mesopore molecular sieve of the atom Han chroma, its proportioning and conjunction is prepared according to the method for embodiment 1 One-tenth condition is shown in Table 1, characterizes and evaluation result is shown in Table 2.The synthesis condition ginseng being not directed in table 1 Examine embodiment 1.

Comparative example 7

List of references (Applied Catalysis A:General, 1996,134, L197-L201) Carry out Cr-MFI Zeolite synthesis.Specifically comprise the following steps that

(1) 20gTEOS is slowly added into by 26g deionized water and 0.96gCr (NO₃)· 9H₂In the solution of O composition, and it is stirred vigorously half an hour, obtains solution A.Weigh 2.4g again Mass fraction is the HF aqueous solution of 40%, 35g deionized water, 0.32g NaOH, 48.6g matter Measure the TPAOH aqueous solution that mark is 20% uniform, obtain solution B；

(2) the mixture B of gained in step (1) is slowly dropped in A product, and Maintaining the product temperatur in step (1) is 0 DEG C, and stirring 2 hours afterproduct pH value is 5.3；

(3) by step (3) gained product dress still and under the conditions of 170 DEG C static brilliant Change 4 days, crystallization complete after gained product through washing, filter, filter cake be placed in 120 DEG C do Dry 6 hours, then be placed under 550 DEG C of air atmospheres dry 12 hours, finally give molecular sieve Sample.

Embodiment 20

The micro-mesopore molecular sieve of the atom Han mangana, its proportioning and conjunction is prepared according to the method for embodiment 1 One-tenth condition is shown in Table 1, characterizes and evaluation result is shown in Table 2.The synthesis condition ginseng being not directed in table 1 Examine embodiment 1.

Comparative example 8

List of references (J.Am.Chem.Soc.2013,135,8594-8605) carries out Mn-MFI Zeolite synthesis.Specifically comprise the following steps that

(1) weigh 25gTEOS to be added drop-wise in 25g deionized water, and stir half an hour.So Rear dropping 24gTPAOH aqueous solution (mass fraction is 25%), as structure directing agent, is continued Continuous stirring 3 hours.This mixture is referred to as solution A.

(2) weigh 0.44g manganese acetylacetonate (III) to be dissolved in 20mL ethanol, then by this second Alcoholic solution is added drop-wise in solution A, and stirs 3 hours, obtains the claret solution B of clarification.

(3) solution B is filled still, crystallization 48h under the conditions of 180 DEG C, the product warp of gained Filter, washing, dried overnight under the conditions of 120 DEG C, then be placed in 550 DEG C of roastings in Muffle furnace Burn 5 hours, finally give pale pink sieve sample.

Embodiment 21

Micro-to the hetero atom of embodiment 1～20, comparative example 1～8 and comparative example 1～5 preparation respectively Mesopore molecular sieve carries out the epoxidation oxidation reaction evaluation of cyclohexene, and oxidant used is hydrogen peroxide Or tert-butyl hydroperoxide is oxidant, and appreciation condition is as follows: use the heating of 250ml band to stir The there-necked flask mixing and stirring condensing reflux is reactor, and reaction temperature is 80 DEG C, H₂O₂(or Tert-butyl hydroperoxide)/cyclohexene=3:1 (mol ratio), cyclohexene quality 30g, solvent is Acetone, quality is 40g, and catalyst amount 1.5g, response time 4h, product is performing centrifugal separation on After going out molecular sieve, liquid phase uses Agilent GC6890N to analyze, cyclohexene conversion rate and epoxide ring Hexane selectivity computing formula is as follows, the results are shown in Table 2.

Cyclohexene conversion rate=(after 1-reaction the front cyclohexene of molal quantity/reaction of cyclohexene mole Number) × 100%

The 7-oxa-bicyclo[4.1.0 molal quantity of 7-oxa-bicyclo[4.1.0 selectivity=generation/(the front cyclohexene of reaction The molal quantity of cyclohexene after molal quantity-reaction) × 100%

Embodiment 22

Respectively prepared by embodiment 1～20, comparative example 1～8 and comparative example 1～5 step (3) Hetero-atom molecular-sieve carries out hydrogen peroxide (concentration, 30 weight %) decomposition run, and experimental condition is such as Under: hydrogen peroxide 15g, molecular sieve 2g, reaction temperature 80 DEG C, in 1 hour response time, adopt With analyzing purity remnants hydrogen peroxide concentration, result is as shown in table 2.

It should be noted that can also carry out between the various different embodiment of the present invention appointing Meaning combination, as long as it is without prejudice to the thought of the present invention, it should be considered as presently disclosed equally Content.

Claims

1. a synthetic method for the micro-mesopore molecular sieve of hetero atom, including by hetero atom source, template Agent, water, peroxide, polyhydric alcohol, silicon source and optional inorganic source of ammonium formation crystallization mixture, Crystallization, reclaims the micro-mesopore molecular sieve of hetero atom；Described template include quaternary organic ammonium compounds, Chain alkyl ammonium compounds and optional organic amine compound, described hetero atom is Fe, Co, One or more in Cu, Sn, Zr, B, Ge, V, Cr, Mn.

The most in accordance with the method for claim 1, it is characterised in that described hetero atom is micro-mesoporous The synthetic method of molecular sieve, comprises the following steps:

(1) by hetero atom source, template, water, polyhydric alcohol and optional organosilicon source, optionally Inorganic source of ammonium mixing, hydrolysis catch up with alcohol；It is subsequently adding peroxide；

(2) product that step (1) obtains is aging；

(3) product that step (2) obtains add or be added without organosilicon source and/or solid Silicon source, crystallization, reclaims the micro-mesopore molecular sieve of hetero atom；

Wherein, step (1) and step (3) introduce described silicon at least one step Source, described template include quaternary organic ammonium compounds, chain alkyl ammonium compounds and Optional organic amine compound.

3. according to the method described in claim 1 or 2, it is characterised in that polyhydric alcohol and total silicon The mol ratio in source is 0.01～0.8:1, and peroxide is 0.01～0.25:1 with the mol ratio in total silicon source； Organic amine is 0～0.4:1 with the mol ratio in total silicon source, and quaternary organic ammonium compounds is rubbed with total silicon source Your ratio is 0.05～0.45:1, and chain alkyl ammonium compounds with the mol ratio in total silicon source is 0.01～0.25:1；Described total silicon source is with SiO₂The organosilicon source of meter and solid silicon source total With.

4. according to the method described in claim 1 or 2, it is characterised in that polyhydric alcohol and total silicon The mol ratio in source is 0.1～0.7:1, and peroxide is 0.05～0.25:1 with the mol ratio in total silicon source.

The most in accordance with the method for claim 2, it is characterised in that step (1) introduces Organosilicon source, and step (3) introduce solid silicon source；With SiO₂Meter, step (1) The organosilicon source of middle introducing with the mol ratio of the solid silicon source of introducing in step (3) is 1:0.1～20.

The most in accordance with the method for claim 5, it is characterised in that the method includes walking as follows Rapid:

(1) by hetero atom source, template, organosilicon source, optional inorganic source of ammonium, polyhydric alcohol and Water mixes, and alcohol is caught up with in hydrolysis；Add peroxide, wherein, inorganic source of ammonium: rubbing of hetero atom source Your ratio is 0～5:1；

(2) by aging for step (1) products therefrom, described aging be by step (1) products therefrom 1～60 hour is stood at room temperature～50 DEG C；

(3) by the ageing products obtained by step (2) and solid silicon source according to the weight of 1:0.1～20 Amount ratio mix homogeneously, crystallization, reclaims the micro-mesopore molecular sieve of hetero atom；Wherein said weight In ratio, the ageing products obtained by described step (2) is with SiO₂Meter, solid silicon source is with SiO₂ Meter；

Wherein, water is 5～100:1 with the mol ratio in total silicon source；Template and total silicon source mole Ratio is 0.08～0.6:1；The mol ratio in polyhydric alcohol and total silicon source is 0.01～0.8, peroxide with The mol ratio in total silicon source is 0.01～0.25:1；Hetero atom source with the mol ratio in total silicon source is 0.005～0.05:1；Quaternary organic ammonium compounds is 0.05～0.45:1 with the mol ratio in total silicon source, long Alkyl group ammonium compounds is 0.05～0.25:1 with the mol ratio in total silicon source, organic amine and total silicon source Mol ratio be 0～0.4:1；

Wherein, in described mol ratio, total silicon source is with SiO₂Meter, described total silicon source be with SiO₂Meter organosilicon 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, and hetero atom source is in terms of hetero atom.

7. according to the method described in any one of claim 1～6, it is characterised in that described is miscellaneous The mol ratio in atomic source and total silicon source be 0.005～0.05:1,0.008～0.03:1 or 0.01～0.025:1.

The most in accordance with the method for claim 1, it is characterised in that template, total silicon source, The mol ratio of hetero atom source and water is (0.08～0.6): 1:(0.005～0.05): (5～100).

The most in accordance with the method for claim 8, it is characterised in that described template and institute The mol ratio in the total silicon source stated is 0.1～0.5:1 or 0.1～0.3:1 or 0.1～0.2:1.

The most in accordance with the method for claim 8, it is characterised in that water and total silicon source mole Ratio is 5～50:1,5～30:1 or 6～15:1.

11. according to the method described in claim 1 or 2, it is characterised in that in step (1) Introduce or do not introduce inorganic source of ammonium, with NH₄ ⁺Miscellaneous former with in terms of hetero atom of the inorganic source of ammonium of meter The mol ratio of component is 0～5:1,0.01～4:1 or 0.05～0.5:1.

12. in accordance with the method for claim 5, it is characterised in that described organosilicon source is with solid The mol ratio in body silicon source is 1:1～19 or for 1:2～18 or for 1:5～15.

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, ageing time is 1～60 hour.

14. in accordance with the method for claim 2, it is characterised in that step (2) is described always Turn to stand 2～50 hours, 3～30 hours or 3～15 hours room temperature～50 DEG C.

15. in accordance with the method for claim 2, it is characterised in that step (1) hydrolysis is caught up with In the product that alcohol obtains, the mass content of monohydric alcohol is less than 10ppm.

16. according to the method described in claim 1 or 2, it is characterised in that described crystallization, brilliant The temperature changed is 110～200 DEG C, and 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 of described crystallization Temperature is 140～180 DEG C or 160～180 DEG C.

18. in accordance with the method for claim 17, it is characterised in that the time of described crystallization It it is 0.5～10 day.

19. according to the method described in claim 1 or 2, it is characterised in that described crystallization is: 100～130 DEG C of crystallization 0.5～1.5 days, then crystallization 1～3 days 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 described polyhydric alcohol is molecule In there is the alcohol of 2 or more than 2 hydroxyls, the carbon atom having in described polyol molecule Number is preferably 2～8；Described peroxide is the compound in molecule with peroxide bridge.

21. in accordance with the method for claim 1, it is characterised in that described peroxide is One or more in hydrogen peroxide, tert-butyl peroxide, peracetic acid, trifluoro peracetic acid, Described polyhydric alcohol is one or more in glycerol, ethylene glycol, hexanediol, diethylene glycol.

22. in accordance with the method for claim 2, it is characterised in that described organosilicon source is Organo-silicon ester, described organo-silicon ester, its formula is Si (OR¹)₄, R¹Selected from having 1～6 The alkyl of carbon atom, described alkyl is branched-chain or straight-chain alkyl；Described solid silicon source is high Purity silica granule or SiO 2 powder, on the basis of butt weight, described solid silicon The SiO in source₂Content is more than 99.99 weight %, the total content of Fe, Al and Na in terms of atom Less than the silica gel of 10ppm, described hetero atom source is organic hetero atom and/or inorganic heteroatoms Source.

23. in accordance with the method for claim 22, described organo-silicon ester be quanmethyl silicate, One or more in tetraethyl orthosilicate, silicic acid four 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, the specific surface area of described white carbon is 20～1000m²/ g for example, 50～400m²/g。

25. according to the method described in claim 1 or 2, it is characterised in that organic quaternary ammonium chemical combination Thing is 0.05～0.3:1 with the mol ratio in total silicon source, chain alkyl ammonium compounds and total silicon source Mol ratio is 0.05～0.3:1；In template, organic base is 0.05～0.3 with the mol ratio in total silicon source: 1, described organic base is quaternary ammonium base, organic amine and the long alkane with hydroxide ion One or more in base ammonium compounds.

26. according to the method described in claim 1 or 2, it is characterised in that described organic season Ammonium compounds is quaternary ammonium base and/or organic quaternary ammonium salt；Described chain alkyl ammonium compounds its Formula is R⁵NH₃X or R⁵N(R⁶)₃X, wherein R⁵For carbon number 12～18 it Between alkyl, R⁶For carbon number alkyl between 1～4；X is univalent anion；Described Organosilicon source be organo-silicon ester, described organo-silicon ester, its formula is Si (OR¹)₄, R¹ Being selected from the alkyl with 1～6 carbon atom, described alkyl is branched-chain or straight-chain alkyl.

27. in accordance with the method for claim 25, it is characterised in that described organic quaternary ammonium Alkali be the one in TPAOH, TBAH or tetraethyl ammonium hydroxide or Multiple；Described organic quaternary ammonium salt is 4-propyl bromide, tetrabutyl ammonium bromide, tetrem bromide Change one or more in ammonium, 4-propyl ammonium chloride, tetrabutylammonium chloride or tetraethylammonium chloride； Described chain alkyl ammonium compounds is cetyl trimethylammonium bromide, cetyl chloride Ammonium, cetyltrimethylammonium hydroxide, chain alkyl ammonium compounds are tetradecyltrimethylammonium Ammonium bromide, tetradecyl ammonium chloride, tetradecyltrimethylammonium ammonium hydroxide, dodecyl front three Base ammonium bromide, lauryl ammonium chloride, trimethyl ammonium hydroxide, octadecyl three One in methyl bromide ammonium, octadecyl ammonium chloride, octadecyl trimethyl ammonium hydroxide or Multiple.

28. according to the method described in claim 1 or 2, it is characterised in that described hetero atom Micro-mesopore molecular sieve has MFI structure, and described quaternary organic ammonium compounds includes tetrapropyl hydrogen One or more in amine-oxides, 4-propyl ammonium chloride, 4-propyl bromide；Or, described The micro-mesopore molecular sieve of hetero atom there is MEL structure, described quaternary organic ammonium compounds includes One or more in TBAH, tetrabutyl ammonium bromide or tetrabutylammonium chloride；Or Person, the micro-mesopore molecular sieve of described hetero atom has BEA structure, described organic quaternary ammonium Compound include the one in tetraethyl ammonium hydroxide, tetraethylammonium bromide, tetraethylammonium chloride or Multiple.

29. according to the method described in claim 1 or 2, it is characterised in that described organic base For quaternary ammonium base and/or organic amine, described organic amine is fatty amine, aromatic amine and hydramine In one or more；The formula of described fatty amine is R³(NH₂)_n, wherein R³For having The alkyl of 1～4 carbon atom or alkylidene, 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 the amine with an armaticity substituent group, and described quaternary ammonium base is four One or more in propyl group ammonium hydroxide, TBAH or tetraethyl ammonium hydroxide, Described organic quaternary ammonium salt be 4-propyl ammonium chloride, 4-propyl bromide, tetrabutylammonium chloride, One or more in tetrabutyl ammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide.

30. in accordance with the method for claim 29, it is characterised in that described fatty amine is One or more in ethamine, n-butylamine, butanediamine or hexamethylene diamine；Described hydramine is single second One or more in hydramine, diethanolamine or triethanolamine；Described aromatic amine be aniline, One or more in toluidines, p-phenylenediamine.

31. according to the method described in claim 1 or 2, it is characterised in that described hetero atom Source is tetraalkoxy hetero atom acid esters M (alkoxy)₄, tetraalkyl heteroatomic compound, hetero atom Alcoholic compound, heteroatomic acyl compounds, hetero atom carboxyl compound, heteroatomic have Machine hydrochlorate, heteroatomic alkoxide, heteroatomic alkyl compound, heteroatomic phenyl compound, Heteroatomic benzyl compounds, heteroatomic carbonyl compound, heteroatomic alkenyl compound, Heteroatomic alkoxide compound, heteroatomic organohalogen compounds, heteroatomic chloride, miscellaneous The sulfate of atom, heteroatomic nitrate, heteroatomic acetate, heteroatomic acid and One or more in their hydrolyzate, the wherein alkyl in tetraalkoxy hetero atom acid esters Carbon number be 1,2,3,4,5 or 6.

32. in accordance with the method for claim 1, it is characterised in that micro-Jie of described hetero atom Porous molecular sieve has the microcellular structure less than 1nm and meso-hole structure that aperture is 2～8nm, hole Footpath be the mesopore volume of 2～8nm be 0.3～0.8ml/g, micro pore volume for for 0.12～ 0.19ml/g。

33. according to the method described in any one of claim of right1~32, it is characterised in that described Method also includes rearrangement step: by the micro-mesopore molecular sieve of hetero atom that obtains in organic base aqueous solution Middle crystallization 0.5～10 days, the temperature of crystallization is 110～200 DEG C；Wherein with SiO₂Described in meter Hetero-atom molecular-sieve is 1:0.02-0.5 with the mol ratio of described organic base, with SiO₂Described in meter Hetero-atom molecular-sieve is 1:2～50 with the mol ratio of water；Organic base described in rearrangement step is organic Quaternary ammonium base and/or organic amine.

34. according to the method described in claim 33, it is characterised in that brilliant described in rearrangement step The temperature changed is 150～200 DEG C, and the micro-mesopore molecular sieve of described hetero atom with the mol ratio of water is 1:2～30, pressure is self-generated pressure, and the micro-mesopore molecular sieve of hetero atom with the mol ratio of organic base is 1:0.02～0.2.