CN104556111B - A kind of Titanium Sieve Molecular Sieve and its synthetic method - Google Patents
A kind of Titanium Sieve Molecular Sieve and its synthetic method Download PDFInfo
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- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
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Abstract
A kind of Titanium Sieve Molecular Sieve and its synthetic method, the Titanium Sieve Molecular Sieve grain surface Silicon-rich, surface silicon titanium ratio are higher than body phase silicon titanium ratio.The synthetic method of the Titanium Sieve Molecular Sieve includes mixing in titanium source, template, organic silicon source, inorganic source of ammonium and water, and hydrolysis catches up with alcohol, aging, mixed with solid silicon source, then the crystallization in closed reactor, recycles Titanium Sieve Molecular Sieve.Titanium Sieve Molecular Sieve provided by the invention has higher oxidation activity, and side reaction hydrogen peroxide decomposition activity is substantially reduced.
Description
Technical field
The present invention relates to a kind of Titanium Sieve Molecular Sieve and its synthetic methods.
Background technology
Titanium Sieve Molecular Sieve is to start the new hetero-atom molecular-sieve of exploitation the early 1980s.Synthesize at present
The TS-1 for having MFI type structure, the TS-2 of MEL type structures, the MCM-22 of MWW type structures and with larger pore structure TS-
48 etc..Wherein TS-1 is that Italian EniChem companies develop synthesis earliest, is to introduce transition metal element titanium to have ZSM-
A kind of novel titanosilicate with superior catalytic selective oxidation performance formed in the framework of molecular sieve of 5 structures, TS-
1 not only has the catalysed oxidn of titanium, but also the shape-selective effect with ZSM-5 molecular sieve and excellent stability.Using
This Titanium Sieve Molecular Sieve can be catalyzed polytype organic oxidizing reaction as catalyst, such as the epoxidation of alkene, alkane
Partial oxidation, the oxidation of alcohols, the ammoxidation etc. of the hydroxylating of phenols, cyclic ketones.Since TS-1 molecular sieves are in the oxidation of organic matter
In reaction, free of contamination low concentration hydrogen peroxide can be used as oxidant, avoid oxidation process complex process and pollution ring
The problem of border, has the unrivaled energy saving, economy of conventional oxidation system and advantages of environment protection, and with good reaction
Selectivity.Titanium Sieve Molecular Sieve is as organic matter catalyst for selective oxidation, it is considered to be a mileage in molecular sieve catalytic field
Upright stone tablet can overcome the drawbacks such as complicated conventional catalyst oxidation system reaction process, condition harshness and serious pollution environment from source,
Therefore it receives the especially great attention of people in environmental protection requirement increasingly strict today.
Nineteen eighty-three Taramasso reports hydrothermal crystallization method synthesis of titanium silicon molecular sieve for the first time in patent US 4410501
Method.The method is to synthesize the classical way of TS-1, glue and two step of crystallization is mainly divided to carry out, building-up process is as follows:By positive silicic acid
Ethyl ester (TEOS) is put into nitrogen protection without CO2Container in, be slowly added to TPAOH（Template）, metatitanic acid four is then slowly added dropwise
Ethyl ester (TEOT) stirs lh, is made a kind of reaction mixture containing silicon source, titanium source and organic base, heating, except alcohol, moisturizing,
Under 175 DEG C are stirred under self-generated pressure kettle, crystallization 10 days, then separate, wash, is dry, roasting and TS-1 molecular sieves.However
Titanium insertion skeleton process influence factor is numerous in the technique, and the condition of hydrolysis and nucleation is not easy to control, therefore method synthesis
There are catalytic activity is low, stability is poor, be difficult to synthesize and the drawbacks such as reappears for TS-1 molecular sieves.
Chinese patent CN 98101357.0（CN 1260241A）Titanium Sieve Molecular Sieve reordering technique is disclosed, having synthesized has
The novel titanosilicate of unique hollow structure not only greatly enhances the reappearance of synthesis TS-1, also adds molecular sieve pores
Volume, substantially increases mass transfer diffusion rate of the reactant molecule in molecular sieve pore passage, and catalytic performance increases.The patent discloses
Method by the hydrating solution of titanium and the TS-1 molecular sieves that have synthesized according to molecular sieve（Gram）：Ti（Mole）=200~
1500：1 ratio is uniformly mixed, by gained mixture in a kettle with being reacted 1~8 day at 120~200 DEG C, filtering, washing
It is and dry.At present, HTS molecular sieves have been carried out industry applied to processes such as oxidation phenol hydroxylating, cyclohexanone oxamidinatings
Change, have many advantages, such as that reaction condition is mild, atom utilization is high, technical process is simple and by-product is water clean and effective.
Presently disclosed Titanium Sieve Molecular Sieve direct hydrothermal synthesis method, usually using organic silicon source and/or inorganic silicon source.Have
Machine silicon source such as organo-silicon ester TEOS, costly, the active constituent content for forming molecular sieve is relatively low, it is difficult to improve for price
The solid content of Zeolite synthesis crystallization product, and a large amount of ethyl alcohol that volatilize in process of producing molecular sieve, and these ethyl alcohol are difficult to collect
It recycles.In order to reduce cost, researcher studies replaces part or all of organic silicon source using inorganic silicon source, but uses at present
Inorganic silicon source（Solid silicon source）The Titanium Sieve Molecular Sieve of synthesis, the Titanium Sieve Molecular Sieve that activity is relatively all synthesized using organic silicon source are low.
In addition, in the prior art without reference to the activity problems for further improving Titanium Sieve Molecular Sieve.
The content of the invention
The technical problem to be solved by the present invention is to be directed to the deficiency of existing Titanium Sieve Molecular Sieve to provide a kind of new titanium silicon molecule
Sieve, the invention solves other technical problem be to provide a kind of synthetic method of the Titanium Sieve Molecular Sieve.
The present invention provides a kind of synthetic method of Titanium Sieve Molecular Sieve, includes the following steps：
（1）Titanium source, template, organic silicon source, water and optional inorganic source of ammonium are mixed, alcohol is caught up in hydrolysis；
（2）By step（1）Products therefrom aging at room temperature~50 DEG C；
（3）By step（2）Obtained ageing products are uniformly mixed with solid silicon source, then brilliant in closed reactor
Change, recycle Titanium Sieve Molecular Sieve.
Titanium Sieve Molecular Sieve synthetic method provided by the invention, the molar ratio of titanium source and total silicon source is preferably 0.01~0.05:
1.Step（3）Described in step（2）The molar ratio of obtained ageing products and solid silicon source is 1:0.1~10；It is wherein described
Molar ratio in, the step（2）Obtained ageing products are with SiO2Meter, solid silicon source is with SiO2Meter.
Titanium Sieve Molecular Sieve synthetic method provided by the invention, preferably includes following steps：
（1）Template, titanium source, organic silicon source, inorganic source of ammonium and water are mixed, alcohol is caught up in hydrolysis；The hydrolysis catches up with alcohol usual
The mixture of gained is stirred at least 10 minutes at 0~150 DEG C such as 0~100 DEG C；The mixing time of the stirring is for example
When stirring 10 minutes~50 is small；Wherein, inorganic source of ammonium（With NH4 +Meter）：Titanium source（With TiO2Meter）Molar ratio be 0~5:1；
（2）By step（1）Products therefrom aging, the aging are by step（1）Products therefrom stands 1~60 at room temperature
Hours such as 2~50 it is small when or 3~30 it is small when, further such as 3~15 it is small when；
（3）By step（2）Obtained ageing products are with solid silicon source according to 1：0.1~10 weight ratio is uniformly mixed,
Then the crystallization in closed reactor recycles Titanium Sieve Molecular Sieve；In the wherein described weight ratio, step（2）It is obtained old
Change product and solid silicon source with SiO2Meter；Wherein, the molar ratio of titanium source and total silicon source is 0.005~0.05:1st, water and total silicon
The molar ratio in source is 5~100:1;Template and the molar ratio of total silicon source are not less than 0.05~0.5:1 is, for example, 0.05~0.3:
1；Wherein, in the molar ratio, total silicon source is with SiO2Meter, total silicon source are with SiO2Meter organic silicon source and with SiO2Meter
Solid silicon source summation, inorganic source of ammonium is with NH4 +Meter；The inorganic source of ammonium is inorganic ammonium salt and/or ammonium hydroxide, and titanium source is with TiO2
Meter, water is with H2O is counted.
The present invention also provides a kind of Titanium Sieve Molecular Sieve, which has following characteristics：The Titanium Sieve Molecular Sieve crystal grain table
Face Silicon-rich, grain surface silicon titanium molar ratio and the ratio of body phase silicon titanium molar ratio are more than 1.1, are, for example, 1.1~5.Its surface silicon
Titanium than with body phase silicon titanium than ratio be, for example, 1.2~4:1.
Wherein, TEM-EDX can be used in surface silicon titanium ratio or ion excitation corrosion XPS methods measure to obtain, and is apart from crystal grain
The silicon titanium ratio of atomic layer of the surface no more than 5nm such as 1~5nm, body phase silicon titanium than can be obtained by the method for chemical analysis or
It is for example obtained by TEM-EDX or XPS in the central area of crystal grain apart from region measurement of the grain surface distance more than 20nm.
Titanium Sieve Molecular Sieve synthetic method provided by the invention, prepared Titanium Sieve Molecular Sieve grain surface Silicon-rich, crystal grain table
Face silicon titanium ratio is apparently higher than body phase silicon titanium ratio.In addition, Titanium Sieve Molecular Sieve synthetic method provided by the invention, using relatively inexpensive easy
The solid silicon source such as high-purity silica gel or/and white carbon obtained, partly instead of expensive organic silicon source, can reduce molecular sieve
High performance Titanium Sieve Molecular Sieve is obtained while the waste discharge of production process and saving cost of material.Titanium silicon provided by the invention
Zeolite synthesis method, can be in relatively low template agent dosage and relatively low water silicon ratio synthesis of titanium silicon molecular sieve, can be with
The synthesis cost of Titanium Sieve Molecular Sieve is reduced, improves the solid content of synthesis of molecular sieve crystallization product, improves one-pot molecular sieve yield.
Titanium Sieve Molecular Sieve provided by the invention has the ratio between higher surface silicon titanium ratio and body phase silicon titanium ratio, has higher
Oxidation activity, for hydrogen peroxide participate in oxidation reaction, it is possible to reduce decomposition of the titanium to hydrogen peroxide in superficial layer is conducive to drop
The activity of the decomposition side reaction of low hydrogen peroxide improves raw material availability.
Description of the drawings
Fig. 1 is the XRD spectra of titanium silicon TS-1 molecular sieves prepared by the embodiment of the present invention.
Fig. 2 is the XRD spectra of Ti- beta-molecular sieves prepared by the embodiment of the present invention.
Fig. 3 is step of the embodiment of the present invention（4）The TEM figures of obtained hollow titanium silicon TS-1 molecular sieves.
Fig. 4 is Titanium Sieve Molecular Sieve dioxygen water test prepared by the prior art and embodiment 6, and hydrogen peroxide concentration changes over time
Graph.
Fig. 5 is to measure body phase silicon titanium than the schematic diagram with surface silicon titanium ratio, the wherein signal of box 1 measurement using TEM-EDX
The silicon titanium ratio in grain edges region, the silicon titanium ratio in the signal measurement granular center of box 2 region.Due to grain edges area unit body
Product has higher external surface area, and corresponding outer surface product is relatively low in the unit volume of central area, therefore box 1 and box 2
Interior EDX measurement results can reflect that the silicon titanium on embodiment and surface compares difference.
Specific embodiment
The synthetic method of Titanium Sieve Molecular Sieve provided by the invention, can be in relatively low template agent dosage synthesis of titanium silicon
Molecular sieve, thus template agent dosage can be relatively low, such as the molar ratio of template agent and total silicon source is 0.05~0.3:1, further
For 0.05~0.25:1 or 0.05~0.2:1；It, can be in synthesis of titanium silicon molecule under high solids content in method provided by the invention
Sieve, from can and reduce the usage amount of water, improve output per single reactor and under same synthesis reactor volume synthesize more molecules
Sieve, therefore the water and total silicon source（Silica）Molar ratio can be 5~80:1 or 5~50:1 is, for example, 5~30:1
For example, 6~20 or for 6~15:1.For example, the molar ratio of template and total silicon source is 0.05~0.2:1, water and total silicon source
Molar ratio be 6~15:1.
The synthetic method of Titanium Sieve Molecular Sieve provided by the invention, the molar ratio of the titanium source and total silicon source for 0.005~
0.05:1 is preferably 0.01~0.03:1 is, for example, 0.01~0.025:1.
The molar ratio of the synthetic method of Titanium Sieve Molecular Sieve provided by the invention, inorganic source of ammonium and titanium source is 0~5:1 is, for example,
0.01~4:1 is preferably 0.01~0.5:1.Inorganic source of ammonium is added in, the oxidation activity of synthesized molecular sieve, Ke Yiti can be improved
The utilization rate of high titanium source（There can be higher framework titania silicon ratio in same titanium source usage amount）, reduce making for titanium source
Dosage.
The molar ratio of the synthetic method of Titanium Sieve Molecular Sieve provided by the invention, the template and total silicon source is not
Less than 0.05:1, it is preferably 0.05~0.3:1, it is, for example, 0.05~0.2:1.
The molar ratio of the synthetic method of Titanium Sieve Molecular Sieve provided by the invention, organic silicon source and solid silicon source is 1:
0.1~10 is preferably 1:1~9 is, for example, 1:2~8 or for 1:3~7.With SiO2The step of meter（2）Obtained ageing products
With the ratio between solid silicon source i.e. equal to organic silicon source and the molar ratio of solid silicon source.The solid silicon source is inorganic silicon source.
The synthetic method of Titanium Sieve Molecular Sieve provided by the invention, step（1）The template agent is organic base or is organic
Alkali and organic quaternary ammonium salt mixture, the organic base is quaternary ammonium base, the one or more in organic amine；Example is as mentioned
Template can be the mixed of organic quaternary amine alkali, the mixture of organic quaternary amine alkali and organic amine, organic quaternary amine alkali and organic quaternary ammonium salt
Conjunction object, the mixture of organic amine and organic quaternary ammonium salt or organic quaternary amine alkali and the mixture of organic quaternary ammonium salt and organic amine.
The organic amine is the one or more in fatty amine, aromatic amine and hydramine, and the fatty amine (is also referred to as fatty amines chemical combination
Object), general formula R3(NH2)n, wherein R3To have the alkyl or alkylidene of 1~4 carbon atom, n=1 or 2；The alcohol
Amine（The present invention is also referred to as alcamine compound）Its general formula is (HOR4)mNH(3-m), wherein R4To have the alkyl of 1~4 carbon atom,
M=1,2 or 3.One or more in the fatty amine such as ethamine, n-butylamine, butanediamine or hexamethylene diamine；The fragrance
Amine refers to amine of the tool there are one armaticity substituent group, such as the one or more in aniline, toluidines, p-phenylenediamine；Described
One or more in hydramine such as monoethanolamine, diethanol amine or triethanolamine.The quaternary ammonium base such as tetrapropyl
One or more in ammonium hydroxide, tetrabutylammonium hydroxide or tetraethyl ammonium hydroxide；The organic quaternary ammonium salt such as four
Propyl ammonium bromide, tetrabutylammonium bromide, tetraethylammonium bromide, 4-propyl ammonium chloride, tetrabutylammonium chloride or etamon chloride
In one or more.
A kind of embodiment, the template include organic base, including quaternary organic ammonium compounds, are introduced in template
Organic base and silicon source molar ratio be not less than 0.05:1 is, for example, 0.05~0.45;1, the organic base is quaternary ammonium base
And/or organic amine；Quaternary organic ammonium compounds with the molar ratio of silicon source with being not less than 0.05:1, it is, for example, 0.05~0.45:1, institute
The quaternary organic ammonium compounds stated are quaternary ammonium base and/or organic quaternary ammonium salt.
A kind of implementation, the template agent can be that quaternary ammonium base either includes including quaternary ammonium base
The mixture of machine quaternary ammonium base, template agent for the mixture of quaternary ammonium base and organic amine, quaternary ammonium base and has example as mentioned
The mixture or quaternary ammonium base and organic quaternary ammonium salt of machine quaternary ammonium salt and the mixture of organic amine.It is organic under preferable case
The molar ratio of quaternary ammonium base and organic ammonium is 1:0~10 such as 1:0~8, the molar ratio of quaternary ammonium base and organic quaternary ammonium salt is 1:0
~10 such as 1:0~8.The molar ratio of quaternary ammonium base and total silicon source is 0.05~0.45:1, it is, for example, 0.05~0.3:1, example
Such as it is 0.05~0.2:1.
Titanium Sieve Molecular Sieve synthetic method provided by the invention, a kind of embodiment, the Titanium Sieve Molecular Sieve are TS-1 points
Son sieve, the template agent are tetrapropylammonium hydroxide or are tetrapropylammonium hydroxide and are selected from organic amine, tetrapropyl chlorination
The mixture that one or more in ammonium, 4-propyl bromide are formed.A kind of embodiment, the Titanium Sieve Molecular Sieve are
TS-2 molecular sieves, the template are tetrabutylammonium hydroxide or are tetrabutylammonium hydroxide and selected from organic amine, four fourths
The mixture that one or more in ammonium chloride, tetrabutylammonium bromide are formed..
Titanium Sieve Molecular Sieve synthetic method provided by the invention, a kind of embodiment, the Titanium Sieve Molecular Sieve are divided for Ti- β
Son sieve, the template are tetraethyl ammonium hydroxide or are tetraethyl ammonium hydroxide and selected from organic amine, tetraethyl chlorination
One or more mixtures in ammonium, tetraethylammonium bromide.
Titanium Sieve Molecular Sieve synthetic method provided by the invention, step（1）Described in organic silicon source for organic silicone grease, it is described
Organo-silicon ester, general formula be Si (OR1)4, R1Selected from such as R of the alkyl with 1~6 carbon atom1For C1-C4Alkyl, institute
The alkyl stated can be branched alkyl or straight chained alkyl.Organic silicone grease such as four formicester of silicic acid, tetraethyl orthosilicate, silicic acid
One or more in four butyl esters, dimethyl diethyl estersil；Wherein preferred quanmethyl silicate, tetraethyl orthosilicate, dimethyl two
One or more in ethyl estersil.Solid silicon source described in the present invention is the silica solid or powder of high-purity, example
Such as can be white carbon and/or high-purity silica gel.Under preferable case, the SiO in the solid silicon source on the basis of butt weight2
Content is not less than 99.99 weight %, and the gross mass content of Fe, Al and Na impurity based on the element is less than 10ppm；Such as SiO2
Content is 99.99~100 weight %, is typically greater than 99.99 and less than 100 weight %.The solid silicon source can be high-purity
Silica gel and/or white carbon, preferably white carbon are spent, wherein SiO in the silica gel2Content is preferably greater than or equal to 99.99 weight % for example
To be more than 99.99 weight % and being less than 100 weight %, and the gross mass content of Fe, Al and Na impurity is less than 10ppm.The hard charcoal
Black specific surface area is preferably between 50-400m2Between/g, on the basis of the butt weight of white carbon, SiO in the white carbon2Contain
It is, for example, that 99.99~100 weight % are, for example, more than 99.99 weight % and less than 100 weights that amount, which is preferably greater than or equal to 99.99 weight %,
% is measured, the quality total content of Fe, Al and Na impurity is less than 10ppm in the white carbon.The white carbon can be commercially available or be pressed
It is prepared according to existing method, such as it is prepared by the method provided according to patent CN200910227646.2, a kind of preparation method is by four
Silicon chloride occurs combustion reaction with hydrogen and oxygen and obtains.
The titanium source is organic titanic compound or inorganic titanium compound, is, for example, tetraalkyl titanate（Ti
(alkoxy)4、TiCl4、Ti(SO4)2And the one or more in their hydrolysate.Wherein tetraalkyl titanate molecule
In alkyl carbon number for 1~6, such as carbon number is 1,2,3,4,5 or 6.Titanium source and total silicon source（Also referred to as silicon source）
Molar ratio be, for example, 0.008~0.035:1, it is, for example, 0.01~0.03:1 or 0.01~0.025:1 or 0.015~
0.025:1。
Titanium Sieve Molecular Sieve synthetic method provided by the invention, step（1）Described in inorganic source of ammonium for inorganic ammonium salt and/or
Ammonium hydroxide obtains one or more in the inorganic ammonium salt such as ammonium chloride, ammonium nitrate, ammonium sulfate.The inorganic source of ammonium is excellent
Ammonium hydroxide is elected as, with NH4 +The ammonium hydroxide of meter with TiO2The molar ratio of the titanium source of meter is 0~5:1, it is, for example, 0.01~4:1, be, for example,
0.01~0.5:1.The inorganic quaternary ammonium salts are added in, the content of the framework titania of synthesized molecular sieve can be improved, improve molecular sieve
Activity.
In Titanium Sieve Molecular Sieve synthetic method provided by the invention, step（1）It is middle by titanium source, it is template, organic silicon source, inorganic
Source of ammonium and water are hydrolyzed by mixing and are caught up with alcohol.Alcohol is caught up in the hydrolysis, can be 0~150 DEG C preferably 0~100 DEG C such as 50~
95 DEG C are stirred at least 10 minutes, so that organic silicon source and titanium source hydrolysis, and reduce organic silicon source and organic titanium in gained mixture
The alcohol that source hydrolysis generates（Usually monohydric alcohol）Content is hydrolyzed and catches up with alcohol.Usual mixing time is 10~3000 minutes, example
When being such as 2~30 small.Alcohol is caught up with by hydrolysis, obtains organic silicon source of clear and titanium source hydrolyzate.Under preferable case, step
（1）The mass content for the monohydric alcohol that organic silicon source and organic titanium source hydrolysis generate is no more than 10ppm in obtained product, it is preferable that
Step（1）The content of monohydric alcohol is not higher than 10ppm in obtained mixture（Quality）.
Titanium Sieve Molecular Sieve synthetic method provided by the invention, step（2）In, by step（1）Products therefrom aging, it is described old
Turn to room temperature at 50 DEG C by step（1）When products therefrom standing 1~60 is small.The room temperature is 15~40 DEG C；Ageing time
For 1~60 it is small when for example, 2~50 it is small when, preferably 3~30 it is small when, such as 3~15 it is small when, without stirring in ageing process,
By the material, that is, step（1）Products therefrom is stood.
Titanium Sieve Molecular Sieve synthetic method provided by the invention, step（3）It is middle by step（2）Obtained ageing products and solid
Silicon source mixes, with SiO2Meter, step（2）Obtained product and the molar ratio of solid silicon source is 1：0.1~10（I.e. described organosilicon
The molar ratio of source and solid silicon source is 1：0.1~10, such as can be 1:1~9,1:2~8,1:1~7 or 1：3~6.The present invention
The method of offer can use the solid silicon source of higher proportion, the solid content of synthetic product can be improved, so as in synthetic reaction
The yield of single synthesis is improved in the case that kettle is constant.
Titanium Sieve Molecular Sieve synthetic method provided by the invention, step（3）The crystallization, the temperature of crystallization is 110~200
DEG C, crystallization pressure is self-generated pressure, when the time of crystallization is 2 small~20 days, the time of the usual crystallization is 0.5~20 day,
Such as crystallization time is 0.5~10 day, further step（3）The temperature of the crystallization for 140~180 DEG C be, for example, 160~
180 DEG C, crystallization time is preferably such as 1~6 day 0.5~10 day, further for example, 1~3 day.Crystallization pressure is spontaneous pressure
Power.The crystallization can carry out in stainless steel stirred tank.Crystallization heating can be heated up with one section can also multistage heating mode.It rises
Warm rate can be carried out according to existing crystallization temperature-rising method, be, for example, 0.5-1 DEG C/min.The crystallization can be in stainless steel stirred tank
Middle progress.A kind of embodiment, the crystallization temperature of the crystallization is 160~180 DEG C, and crystallization time is 0.5~6 day such as 1~3
My god, crystallization pressure is self-generated pressure.A kind of embodiment, step（3）The crystallization is：100~130 DEG C such as 110~
Crystallization 0.5~1.5 day at 130 DEG C, then crystallization 1~3 day at 160~180 DEG C, crystallization pressure are self-generated pressure.
Titanium Sieve Molecular Sieve synthetic method provided by the invention, step（3）Described in recycle Titanium Sieve Molecular Sieve be existing method,
Including crystallization product is filtered, wash and is roasted or filters crystallization product, is washed, is dried and then is roasted.The purpose of filtering
Titanium Sieve Molecular Sieve for crystallization is obtained is separated with crystallization mother liquor, and the purpose of washing washes away absorption on sieve particle surface
Siliceous template, such as can be in the weight ratio 1 that temperature is room temperature~50 DEG C, molecular sieve and water:1~20 such as 1:（1-15）
Then lower progress mixing, washing filters or uses water wash.Dry purpose is the most of moisture removed in molecular sieve, to reduce
Water evaporation quantity when roasting, dry temperature can be 100~200 DEG C.The purpose of roasting is the mould removed in molecular sieve
Plate agent, the temperature that example roasts as mentioned are 350~650 DEG C, when roasting time is 2-10 small.Institute of the present invention is obtained by recycling
The Titanium Sieve Molecular Sieve product of offer.
In Titanium Sieve Molecular Sieve synthetic method provided by the invention, step（3）Recycling obtained Titanium Sieve Molecular Sieve can also pass through
It is further processed, i.e., Titanium Sieve Molecular Sieve synthetic method provided by the invention can also include step（4）：
（4）By step（3）Obtained Titanium Sieve Molecular Sieve Crystallizing treatment in organic alkali solution, then recovery Pd silicon molecule
Sieve.The obtained Titanium Sieve Molecular Sieve of the process has hollow-core construction, and the present invention is referred to as molecular sieve and resets.Wherein Titanium Sieve Molecular Sieve
（With SiO2Meter）Molar ratio with organic base is 1：0.02~0.5 is, for example, 1：0.02~0.2；With SiO2The molecular sieve of meter with
The molar ratio of water is 1:2~50 be, for example, 1:2~30 or for 1:2~20 or for 1:5~10；Crystallization temperature for 120~
200 DEG C, the time is such as 0.5~8 day 0.5~10 day；Crystallization pressure is self-generated pressure, wherein the organic base is preferably organic
Quaternary ammonium base.It is preferred that step（4）The crystallization temperature is 150-200 DEG C, and crystallization time is 0.5~10 day or is 1~6 day, point
The molar ratio of son sieve and water is 1:2~30.Recovery method is existing method, generally includes to filter crystallization product, washs, dries
It so and roasts, can refer to step（3）The recovery method.The organic base is organic amine and/or quaternary ammonium base；It is described
Organic amine be the one or more in fatty amine, aromatic amine and hydramine, the fatty amine (also referred to as fat amine compound),
Its general formula is R3(NH2)n, wherein R3To have the alkyl or alkylidene of 1~4 carbon atom, n=1 or 2；The hydramine
（The present invention is also referred to as alcamine compound）Its general formula is (HOR4)mNH(3-m), wherein R4To have the alkyl of 1~4 carbon atom, m
=1,2 or 3.One or more in the fatty amine such as ethamine, n-butylamine, butanediamine or hexamethylene diamine；The fragrance
Amine refers to amine of the tool there are one armaticity substituent group, such as the one or more in aniline, toluidines, p-phenylenediamine；Described
One or more in hydramine such as monoethanolamine, diethanol amine or triethanolamine.The quaternary ammonium base such as tetrapropyl
One or more in ammonium hydroxide, tetrabutylammonium hydroxide or tetraethyl ammonium hydroxide.A kind of embodiment, the titanium silicon
Molecular sieve is TS-1 molecular sieves, and the quaternary ammonium base is tetrapropylammonium hydroxide.A kind of embodiment, the titanium silicon point
Son sieve is TS-2 molecular sieves, and the quaternary ammonium base is tetrabutylammonium hydroxide.A kind of embodiment, the titanium silicon molecule
It sieves as titanium silicon beta molecular sieves（Titanium silicon beta-molecular sieve）, the quaternary ammonium base is tetraethyl ammonium hydroxide.
Step（4）The present invention is referred to as molecular sieve and resets, this process can be carried out once, can also be repeated once or more
It is secondary, the repetition, i.e., by the obtained Titanium Sieve Molecular Sieve that handles instead of step（3）Obtained molecular sieve carries out step（4）'s
Processing.It is handled by rearrangement, the Titanium Sieve Molecular Sieve with secondary pore structure can be obtained, gained Titanium Sieve Molecular Sieve has hollow knot
The crystal grain of structure, that is, Titanium Sieve Molecular Sieve is hollow-core construction, and the radical length of the chamber portion of the hollow crystal grain is 5~300nm,
At 25 DEG C, P/P0=0.10, when adsorption time 1 is small under conditions of the benzene adsorbance that measures be at least 70 milligrams per grams, the molecular sieve
Nitrogen absorption under low temperature adsorption isotherm and desorption isotherm between there are hysteresis loops.Molecular sieve has the hole body of bigger after rearrangement
Product and specific surface area.
The present invention is further illustrated for the following examples, but is not intended to limit the present invention.
The measuring method of grain size and surface silicon titanium ratio and body phase silicon titanium ratio in embodiment uses TEM-EDX, TEM electricity
Mirror experiment carries out on FEI Co.'s Tecnai F20G2S-TWIN type transmission electron microscopes, the energy mistake equipped with Gatan companies
Filter system GIF2001, attachment are equipped with X-ray energy spectrometer.Electron microscopic sample is prepared using the method for suspended dispersed in the micro- of diameter 3mm
On grid.Each sample randomly selects its surface silicon titanium ratio of 20 particle sizings and body phase silicon titanium ratio, gauging surface silicon in embodiment
Then titanium takes the average value of its 20 samples as the sample surfaces silicon titanium ratio and body phase silicon than the ratio with body phase silicon titanium ratio
Titanium than ratio.
XRD measuring methods：The X-ray diffraction of sample is carried out on Siemens D5005 type x-ray diffractometers（XRD）
Crystalline phase figure measures, and radiographic source is CuK α（λ=1.5418）, tube voltage 40kV, tube current 40mA, 0.5 °/min of sweep speed sweeps
Retouch 2 θ=4 °~40 ° of scope.
The test method of BET specific surface area uses N2 adsorption volumetric method, according to BJH computational methods.（Referring to petrochemical industry point
Analysis method（RIPP test methods）, RIPP151-90, Science Press, nineteen ninety publication）
Raw materials used property is as follows in embodiment and comparative example：
Butyl titanate analyzes pure, Sinopharm Chemical Reagent Co., Ltd..
Titanyl sulfate analyzes pure, Sinopharm Chemical Reagent Co., Ltd..
Tetrapropylammonium hydroxide, Guangdong great You chemical plant.
Tetraethyl orthosilicate analyzes pure, Sinopharm Chemical Reagent Co., Ltd..
Ammonium hydroxide analyzes pure, 20 weight % of concentration.
White carbon, Zhejiang Ju Hua groups product, model AS-150；Solid content is more than 95 weight %, and silica contains in butt
Amount is more than 99.99 weight %, and the total content of iron, sodium and Al is less than 10ppm, specific surface area 195m2/g。
What other reagents did not further illustrated is commercial goods, and analysis is pure.
Comparative example 1
This comparative example illustrates to prepare conventional Titanium Sieve Molecular Sieve according to the method for Thangaraj et al.（Zeolites, 1992,
Vol.12 pages 943~950）.
22.5g tetraethyl orthosilicates with 7.0g tetrapropylammonium hydroxide are mixed, 59.8g deionized waters is added in and uniformly mixes；
Then 1.0h is hydrolyzed at 60 DEG C, obtains the hydrating solution of tetraethyl orthosilicate.Again under the action of being vigorously stirred, to above-mentioned solution
In be slowly dropped into the solution being made of 1.1g butyl titanates and 5.0g isopropanols, which is stirred into 3h at 75 DEG C,
Obtain the colloid of clear.The colloid is moved into stainless steel closed reactor again, thermostatic crystallization 3 days at 170 DEG C, you can
Obtain conventional TS-1 molecular sieves.Its XRD analysis spectrogram is as shown in Figure 1.
Comparative example 2
This comparative example illustrates HTS molecular sieves used according to prepared by patent CN98101357.0.
22.5g tetraethyl orthosilicates with 9.0g tetrapropylammonium hydroxide are mixed, 64.5g deionized waters is added in and uniformly mixes；
Then 1.0h is hydrolyzed at 60 DEG C, obtains the hydrating solution of tetraethyl orthosilicate.Again under the action of being vigorously stirred, to above-mentioned solution
In be slowly dropped into the solution being made of 0.6g butyl titanates and 7.0g isopropanols, which is stirred into 7h at 75 DEG C,
Obtain the colloid of clear.The colloid is moved into stainless steel closed reactor again, thermostatic crystallization 3 days at 170 DEG C, you can
Obtain conventional TS-1 molecular sieves.
Again by butyl titanate, anhydrous isopropyl alcohol, tetrapropylammonium hydroxide and deionized water according to 1:15:2.4:350
Molar ratio uniformly mixes, and is hydrolyzed 30 minutes at lower 45 DEG C of normal pressure, obtains the hydrating solution of butyl titanate.Take above-mentioned preparation
TS-1 molecular sieves, according to molecular sieve（g）:Ti(mol)=600:1 ratio and the hydrating solution of above-mentioned butyl titanate are uniform
Scattered suspension is finally put into stainless steel cauldron, is placed at 165 DEG C by mixing, the uniform stirring 12h under room temperature
3 days, you can obtain the HTS molecular sieves.Its XRD analysis spectrogram is as shown in Figure 1.
Embodiment 1
（1）By the tetrapropylammonium hydroxide that 15g concentration is 25.05 weight %（TPAOH）Aqueous solution, four fourth of 2.04g metatitanic acids
Ester, 8.5g tetraethyl orthosilicates, the ammonium hydroxide that 2g concentration is 20 weight % and 38g water are added sequentially in the beaker of 500ml, are put into band
Have and be uniformly mixed on the magnetic stirring apparatus of heating and agitating function, and when stirring 4 is small at 80 DEG C, supplement the water of evaporation at any time
Point, obtain water white transparency hydrolyzate；
（2）By gained hydrolyzate in room temperature（26℃）It is lower stand 12 it is small when carry out aging, obtain ageing products；
（3）In above-mentioned ageing products, 9.6g white carbon powder is added with stirring, when stirring 1 is small after adding, is formed a kind of
" viscous body " is transferred into stainless steel closed reactor, in 165 DEG C of thermostatic crystallizations 2 days, is obtained TS-1 samples, will be obtained
TS-1 sample filterings, washing, at 120 DEG C it is dry 24 it is small when, when 550 DEG C of roastings 6 are small, you can titanium silicon of the present invention
TS-1 zeolite products are denoted as TS-1F1；Its BET specific surface area is 426m2/ g, external surface area 60m2/g；Micro pore volume
0.166mL/g, mesopore volume 0.086mL/g.XRD analysis its with MFI. structures, XRD spectra is as shown in Figure 1；
（4）TS-1F1 samples described in 6g are uniformly mixed with the TPAOH aqueous solutions that concentration is 22.05 weight %, the TS-
The weight ratio of 1F1 and TPAOH aqueous solutions is 1：5,150 DEG C of crystallization 3 days in closed reaction kettle, filtering, washing, at 120 DEG C
When drying 24 is small, when 550 DEG C of roastings 6 are small, you can TS-1 products must be reset, be denoted as TS-1P1.Its XRD analysis spectrogram such as Fig. 1 institutes
Show, BET specific surface area 457m2/ g, external surface area 68m2/ g, micro pore volume 0.152mL/g, mesopore volume 0.168mL/
G, its in transmission electron microscope photo are hollow-core construction（Referring to Fig. 3）.
Embodiment 2
（1）It is the tetrapropylammonium hydroxide of 25.05 weight %, 1.23g butyl titanates, 4.16g silicic acid four by 7.4g concentration
Ethyl ester, the ammonium hydroxide that 0.67g concentration is 20 weight % and 14g water are added sequentially in the beaker of 500ml, are put into heating and are stirred
Mix on the magnetic stirring apparatus of function be uniformly mixed, and at 90 DEG C stirring 1 it is small when, supplement the moisture of evaporation at any time, obtain colourless
Transparent basic hydrolyzate.
（2）By the hydrolyzate of gained stand at room temperature 3 it is small when, obtain ageing products；
（3）In acquired ageing products, 9.6g white carbon powder is slowly added under stirring, when stirring 1.5 is small after adding,
Be transferred into stainless steel closed reactor, in 145 DEG C of thermostatic crystallizations 6 days, filtering, washing, at 120 DEG C it is dry 24 it is small when,
To get to TS-1 sieve samples when 550 DEG C of roastings 6 are small, TS-1F2, specific surface area 435m are denoted as2/ g, external surface area are
61m2/ g, micro pore volume 0.159mL/g, mesopore volume 0.083mL/g；XRD analysis spectrogram has feature as shown in Figure 1
（4）6g TS-1F2 samples are uniformly mixed with the TPAOH aqueous solutions of 36 grams of concentration 22.05%, in closed reaction
150 DEG C of crystallization 3 days in kettle, filtering, washing, at 120 DEG C it is dry 24 it is small when, when 550 DEG C of roastings 6 are small, obtain TS-1 zeolite products,
It is denoted as TS-1P2.Its XRD analysis spectrogram has feature as shown in Figure 1.BET specific surface area is 429m2/ g, external surface area 60m2/
G, micro pore volume 0.150mL/g, mesopore volume 0.177mL/g；Its in transmission electron microscope photo is hollow-core construction.
Embodiment 3
（1）By the 4-propyl bromide that 43g concentration is 25.05%（TPABr）Aqueous solution, 1.68g titanyl sulfates, 2.4g tri-
Ethamine, 33.3g tetraethyl orthosilicates, the ammonium hydroxide that 0.05g concentration is 20 weight % and 26g water are added sequentially in the beaker of 500ml,
Be put into heating and agitating function magnetic stirring apparatus on uniformly mix, and at 65 DEG C stirring 3 it is small when, at any time supplement evaporation
Moisture, obtain basic hydrolysis liquid.
（2）By gained hydrolyzate stand at room temperature 9 it is small when, obtain ageing products.
（3）In the beaker for filling ageing products, 9.6g white carbon powder is slowly added under stirring, is stirred one hour, shape
It into more uniform " viscous body ", is transferred into stainless steel closed reactor, in 165 DEG C of thermostatic crystallizations 2 days, filters, washes
It washs, when drying 24 is small at 120 DEG C, when 550 DEG C of roastings 6 are small, you can obtain TS-1 zeolite products provided by the invention, be denoted as TS-
1F3, specific surface area 427m2/ g, external surface area 60m2/ g, micro pore volume 0.173mL/g, mesopore volume 0.079mL/g
（4）6g TS-1F3 samples with 40 gram 22.05% of TPAOH aqueous solutions are mixed, are stirred evenly, in closed reaction
150 DEG C of crystallization 3 days in kettle, filtering, washing, at 120 DEG C it is dry 24 it is small when, when 550 DEG C of roastings 6 are small, you can hollow TS-1 samples
Product are denoted as TS-1P3, BET specific surface area 438m2/ g, external surface area 59m2/ g, micro pore volume 0.162mL/g, mesoporous body
Product 0.183mL/g.Its in transmission electron microscope photo is hollow-core construction.
Embodiment 4~7
Method according to embodiment 1 prepares Titanium Sieve Molecular Sieve, and proportioning and synthesis condition the results are shown in Table 1.Other condition ginsengs
Examine embodiment 1.
Embodiment 8
According to the method for embodiment 1, the difference is that being added without source of ammonium.
Embodiment 9
According to the method for embodiment 1, the difference is that step（3）Middle elder generation crystallization 1 day at 120 DEG C, it is then brilliant at 170 DEG C
Change 2 days, proportioning and synthesis condition the results are shown in Table 1.
Embodiment 10
Prepare TS-2 molecular sieves.With reference to the method according to embodiment 1, change proportioning and template, template used dose is four
Butyl ammonium hydroxide（TBAOH）, proportioning and synthesis condition the results are shown in Table 1.
Embodiment 11
Prepare Ti- beta-molecular sieves.The method of reference implementation example 1 changes proportioning and template, and template used dose is the tetrabutyl
Ammonium hydroxide（TEAOH）, proportioning and synthesis condition the results are shown in Table 1.Its SEM figure is referring to Fig. 4
Comparative example 1
According to the method for embodiment 1, the difference is that ammonium hydroxide is added without, and without aging.
Comparative example 2
According to the method for embodiment 1, the difference is that aging temperature is 75 DEG C.
Comparative example 3
According to the method for embodiment 1, the difference is that solid silicon source is in step（1）Middle addition.
Embodiment 12
This example demonstrates that embodiment sample provided by the invention is used for oxidation of phenol hydroxyl with sample prepared by comparative example
Change prepares the reaction effect of benzenediol and preparing cyclohexanone oxime by ammoximation of cyclohexanone.
Reagent used in the present embodiment is commercially available chemically pure reagent, and the concentration of each substance uses gas-chromatography after reaction
Method carries out quantitative analysis.6890 type gas chromatographs of Agilent companies production used；Analysis chromatographic column used is FFAP
Column.
The conversion ratio of phenol, cyclohexanone conversion ratio, cyclohexanone oxime selectivity are to count according to the following equation respectively in embodiment
It calculates：
Above-described embodiment 1-9 and the sample prepared by comparative example are taken respectively（It does not reset）Each 1.25g is added to containing phenol
In the three-neck flask reaction vessel of 25g and acetone 20ml, hydrogen peroxide 9.81g is added in after temperature stabilization to setting value（Concentration 30
Weight %）,（Phenol：Hydrogen peroxide（H2O2）Molar ratio is 3）, in 80 DEG C of temperature, pressure 0.1MPa（Normal pressure）, reaction 2 it is small when after adopt
Sample, phenol carry out hydroxylating generation benzenediol.
The Titanium Sieve Molecular Sieve in above-mentioned comparative example and embodiment is taken to prepare sample respectively, according to TS-1 molecular sieves：The tert-butyl alcohol：
25 weight % ammonium hydroxide=1:7.5:7.5 mass ratio uniform stirring in slurry bed mixes, and the dosage of TS-1 molecular sieves is 3.2g.It rises
Then temperature adds in 30 weight % hydrogen peroxide with the rate of 6ml/h at this temperature to 75 DEG C, hexamethylene is added in the rate of 8.6ml/h
The mixture of ketone and the tert-butyl alcohol（The volume ratio of cyclohexanone and the tert-butyl alcohol is 1:2.5）, while 25 weights are added in the rate of 6ml/h
Measure % ammonia spirits, volume space velocity 6.4h-1.Above-mentioned three strands of materials add in simultaneously, while with corresponding speed continuous discharge, reaction
Stablize 4 it is small when, sampling analysis the results are shown in Table 2.
The decomposition run of hydrogen peroxide
Take H2O2Concentration is 15 grams of the hydrogen peroxide of 30 weight %, adds in 2 grams of Titanium Sieve Molecular Sieve, and temperature is that stirring 1 is small at 80 DEG C
When, analyze the concentration of hydrogen peroxide.It the results are shown in Table 2.
By table 2 as it can be seen that under identical condition, molecular sieve provided by the invention has lower decomposing hydrogen dioxide solution rate,
So as to improve the utilization rate of hydrogen peroxide in the oxidation reaction participated in for hydrogen peroxide, the conversion ratio of reactant can be improved.
Fig. 4 is the TS-1 molecular sieves that embodiment 6 and existing method synthesize（What step 3 obtained does not reset molecular sieve）Hydrogen peroxide
The curve that the middle hydrogen peroxide concentration of decomposition run changes over time.
As can be seen from Table 1：The phenol hydroxylation of gained sample of the invention and cyclohexanone activity are apparently higher than comparison sample
Conventional TS-1 molecular sieves.
It should be noted that various embodiments of the present invention can be combined randomly, as long as its
Without prejudice to the thought of the present invention, it should also be regarded as the disclosure of the present invention.
Claims (47)
1. a kind of Titanium Sieve Molecular Sieve, which is characterized in that the surface silicon titanium of the Titanium Sieve Molecular Sieve crystal grain than with body phase silicon titanium than
Ratio is 1.2 ~ 5, and the surface silicon titanium is than for apart from silicon titanium ratio of the grain surface no more than 5nm atomic layers；The titanium silicon molecule
The preparation method of sieve includes the following steps：
（1）Titanium source, template, organic silicon source, water and optional inorganic source of ammonium are mixed, alcohol is caught up in hydrolysis；
（2）By step（1）Products therefrom aging at room temperature ~ 50 DEG C；
（3）By step（2）Obtained ageing products are uniformly mixed with solid silicon source, then the crystallization in closed reactor, are returned
Receive Titanium Sieve Molecular Sieve；Step（2）The weight ratio of obtained ageing products and solid silicon source is 1:0.1 ~ 10, wherein the weight
In amount ratio, the step（2）Obtained ageing products are with SiO2Meter, solid silicon source is with SiO2Meter.
2. Titanium Sieve Molecular Sieve described in accordance with the claim 1, which is characterized in that the surface silicon titanium than with body phase silicon titanium than ratio
It is worth for 1.2 ~ 4:1.
3. Titanium Sieve Molecular Sieve described in accordance with the claim 1, which is characterized in that the titanium silicon of the Titanium Sieve Molecular Sieve is than molar ratio
0.005~0.03:1。
4. Titanium Sieve Molecular Sieve described in accordance with the claim 1, which is characterized in that the Titanium Sieve Molecular Sieve is TS-1 molecular sieves, TS-
2 molecular sieves or Ti- beta-molecular sieves.
5. according to claim 1 ~ 4 any one of them Titanium Sieve Molecular Sieve, which is characterized in that the crystal grain of the Titanium Sieve Molecular Sieve is
Hollow-core construction, the radical length of the chamber portion of the hollow crystal grain are 5 ~ 300nm, at 25 DEG C, P/P0=0.10, adsorption time 1 is small
When under conditions of the benzene adsorbance that measures be at least 70 milligrams per grams, the adsorption isotherm of the nitrogen absorption under low temperature of the molecular sieve and de-
There are hysteresis loops between attached thermoisopleth.
6. Titanium Sieve Molecular Sieve described in accordance with the claim 1, which is characterized in that the titanium silicon of the Titanium Sieve Molecular Sieve is than molar ratio
0.01~0.025:1。
7. a kind of synthetic method of Titanium Sieve Molecular Sieve, comprises the following steps:
（1）Titanium source, template, organic silicon source, water and optional inorganic source of ammonium are mixed, alcohol is caught up in hydrolysis；
（2）By step（1）Products therefrom aging at room temperature ~ 50 DEG C；
（3）By step（2）Obtained ageing products are uniformly mixed with solid silicon source, then the crystallization in closed reactor, are returned
Receive Titanium Sieve Molecular Sieve；Step（2）The weight ratio of obtained ageing products and solid silicon source is 1:0.1 ~ 10, wherein the weight
In amount ratio, the step（2）Obtained ageing products are with SiO2Meter, solid silicon source is with SiO2Meter.
8. according to the method for claim 7, which is characterized in that step（2）The aging is by step（1）Products therefrom in
When standing 1 ~ 60 is small at room temperature ~ 50 DEG C;
Step（3）Described in step（2）The weight ratio of obtained ageing products and solid silicon source is 1:0.1 ~ 10, wherein described
Weight ratio in, the step（2）Obtained ageing products are with SiO2Meter, solid silicon source is with SiO2Meter；
Inorganic source of ammonium：The molar ratio of titanium source is 0 ~ 5:1；The molar ratio of water and total silicon source is 5 ~ 100:1；Template and total silicon source
Molar ratio is 0.05 ~ 0.5:1；The molar ratio of titanium source and total silicon source is 0.005 ~ 0.05:1;Wherein, total silicon source be with
SiO2Meter organic silicon source and with SiO2The summation of the solid silicon source of meter, inorganic source of ammonium is with NH4 +Meter；Titanium source is with TiO2Meter；Described
Inorganic source of ammonium is inorganic ammonium salt and/or ammonium hydroxide.
9. according to the method for claim 8, which is characterized in that the molar ratio of the titanium source and total silicon source for 0.005 ~
0.04:1。
10. according to the method for claim 8, which is characterized in that the template and the molar ratio of total silicon source
For 0.05 ~ 0.3:1.
11. according to the method for claim 8, which is characterized in that the molar ratio of water and total silicon source is 5 ~ 50.
12. according to the method for claim 8, which is characterized in that the molar ratio of inorganic source of ammonium and titanium source is 0.01 ~ 4:1.
13. according to the method for claim 8, which is characterized in that the molar ratio of organic silicon source and solid silicon source is 1:1
~9。
14. according to the method for claim 7, which is characterized in that step（3）The crystallization, the temperature of crystallization is 110 ~ 200
DEG C, crystallization pressure is self-generated pressure, when the time of crystallization is 2 small ~ 20 days.
15. according to the method for claim 14, it is characterised in that step（3）Described in crystallization crystallization temperature for 140 ~
180℃。
16. according to the method for claim 7, which is characterized in that step（3）The crystallization is：In 100 ~ 130 DEG C of crystallization
0.5 ~ 1.5 day, then crystallization 1 ~ 3 day at 160 ~ 180 DEG C, crystallization pressure were self-generated pressure.
17. according to the method for claim 7, which is characterized in that the template is organic base or is organic base and to have
Machine quaternary ammonium salt；Organic silicon source is organic silicone grease, and the organo-silicon ester, general formula is Si (OR1)4, R1Selected from 1 ~
The alkyl of 6 carbon atoms, the alkyl are branched-chain or straight-chain alkyls；The solid silicon source is high-purity silicon dioxide granule
Or SiO 2 powder, on the basis of butt weight, the SiO of the solid silicon source2Content is more than 99.99 weight %, in terms of atom
Fe, Al and Na total content be less than 10ppm, the titanium source be organic titanium source and/or inorganic ti sources.
18. according to the method for claim 7, which is characterized in that step（1）In, the template includes organic quaternary ammonium
Alkali and optional organic amine and/or organic quaternary ammonium salt, wherein, the molar ratio of quaternary ammonium base and organic amine is 1:0 ~ 10, it is organic
The molar ratio of quaternary ammonium base and organic quaternary ammonium salt is 1:0~10.
19. according to the method for claim 17, which is characterized in that the organo-silicon ester is quanmethyl silicate, silicic acid four
One or more in ethyl ester, four butyl ester of silicic acid, dimethyl diethyl estersil.
20. according to the method for claim 7, which is characterized in that the solid silicon source is white carbon, the white carbon
Specific surface area is 50 ~ 400m2/g。
21. according to the method for claim 18, which is characterized in that the organic amine is fatty amine, aromatic amine and hydramine
In one or more；The general formula of the fatty amine is R3(NH2)n, wherein R3For have the alkyl of 1 ~ 4 carbon atom or
Alkylidene, n=1 or 2；Its general formula of the hydramine is (HOR4)mNH(3-m), wherein R4To have the alkyl of 1 ~ 4 carbon atom, m
=1,2 or 3；For the aromatic amine to have the amine there are one armaticity substituent group, the quaternary ammonium base is tetrapropyl hydrogen-oxygen
Change the one or more in ammonium, tetrabutylammonium hydroxide or tetraethyl ammonium hydroxide.
22. according to the method for claim 21, which is characterized in that the fatty amine for ethamine, n-butylamine, butanediamine or
One or more in hexamethylene diamine；The hydramine is the one or more in monoethanolamine, diethanol amine or triethanolamine；Institute
The aromatic amine stated is aniline, the one or more in toluidines, p-phenylenediamine.
23. according to the method for claim 7, which is characterized in that the Titanium Sieve Molecular Sieve is TS-1 molecular sieves, described
Template is tetrapropylammonium hydroxide or is tetrapropylammonium hydroxide and is selected from organic amine, 4-propyl ammonium chloride, tetrapropyl bromine
Change the mixture that the one or more in ammonium are formed；Alternatively, the Titanium Sieve Molecular Sieve is TS-2 molecular sieves, the template
Agent is tetrabutylammonium hydroxide or is tetrabutylammonium hydroxide and selected from organic amine, tetrabutylammonium chloride, tetrabutylammonium bromide
In the mixture that is formed of one or more；Alternatively, the Titanium Sieve Molecular Sieve is Ti- beta-molecular sieves, the template is
Tetraethyl ammonium hydroxide is tetraethyl ammonium hydroxide and in organic amine, etamon chloride, tetraethylammonium bromide
One or more mixtures.
24. according to the method for claim 7, which is characterized in that step（1）It is in 0 ~ 150 DEG C of stirring that alcohol is caught up in the hydrolysis
At least 10 minutes.
25. according to the method for claim 7, which is characterized in that step（1）Alcohol is caught up in the hydrolysis, the temperature of stirring for 50 ~
95 DEG C, when mixing time is 2 ~ 30 small.
26. according to the method for claim 7, which is characterized in that step（1）Organic silicon source and organic titanium in obtained product
The mass content for the alcohol that source hydrolysis generates is no more than 10ppm.
27. according to the method for claim 7, which is characterized in that step（2）The ageing time of the aging is small for 2 ~ 50
When.
28. according to claim 7 ~ 27 any one of them method, which is characterized in that the method further includes step（4）：It will
Step（3）Obtained Titanium Sieve Molecular Sieve crystallization 0.5 ~ 10 day in organic aqueous alkali, the temperature of crystallization is 110 ~ 200 DEG C；Its
Described in Titanium Sieve Molecular Sieve with SiO2The molar ratio of meter and the organic base is 1:0.02-0.5, the Titanium Sieve Molecular Sieve with
SiO2The molar ratio of meter and water is 1:2~50;The organic base is quaternary ammonium base and/or organic amine.
29. according to the method for claim 28, which is characterized in that step（4）The temperature of the crystallization is 150 ~ 200 DEG C,
Titanium Sieve Molecular Sieve and the molar ratio of water are 1:2 ~ 30, pressure is self-generated pressure.
30. according to the method for claim 7, which is characterized in that the titanium source is tetraalkyl titanate Ti (alkoxy)4、
TiCl4、Ti(SO4)2And the one or more in their hydrolysate, the wherein carbon of the alkyl in tetraalkyl titanate are former
Subnumber is 1,2,3,4,5 or 6.
31. according to the method for claim 7, which is characterized in that step（1）Monohydric alcohol in the product that alcohol obtains is caught up in hydrolysis
Mass content is no more than 10ppm.
32. according to the method for claim 7, which is characterized in that step（2）The aging be room temperature ~ 50 DEG C stand 1 ~
60 it is small when.
33. according to the method described in claim 32, which is characterized in that when the time of repose is 2 ~ 50 small.
34. according to the method for claim 8, which is characterized in that the molar ratio of the titanium source and total silicon source for 0.01 ~
0.03:1。
35. according to the method for claim 8, which is characterized in that the molar ratio of the titanium source and total silicon source for 0.01 ~
0.025:1。
36. according to the method for claim 8, which is characterized in that the template and the molar ratio of total silicon source
For 0.05 ~ 0.25:1.
37. according to the method for claim 8, which is characterized in that the template and the molar ratio of total silicon source
For 0.05 ~ 0.2:1.
38. according to the method for claim 11, which is characterized in that the molar ratio of water and total silicon source is 6 ~ 30:1.
39. according to the method for claim 8, which is characterized in that the molar ratio of inorganic source of ammonium and titanium source is 0.05 ~ 0.5:1.
40. according to the method for claim 8, which is characterized in that the molar ratio of organic silicon source and solid silicon source is 1:2
~8。
41. according to the method for claim 14, which is characterized in that step（3）The crystallization, the time of crystallization is 0.5 ~ 10
My god.
42. according to the method for claim 14, it is characterised in that step（3）Described in crystallization crystallization temperature for 160 ~
180℃。
43. according to the method for claim 7, which is characterized in that step（2）The ageing time of the aging is small for 3 ~ 30
When.
44. according to the method for claim 7, which is characterized in that step（2）The ageing time of the aging is small for 3 ~ 15
When.
45. according to the method described in claim 32, which is characterized in that when the time of repose is 3 ~ 30 small.
46. according to the method described in claim 32, which is characterized in that when the time of repose is 3 ~ 15 small.
47. according to the method for claim 8, which is characterized in that the molar ratio of water and total silicon source is 6 ~ 15:1.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310523080.4A CN104556111B (en) | 2013-10-29 | 2013-10-29 | A kind of Titanium Sieve Molecular Sieve and its synthetic method |
| NL2013705A NL2013705B1 (en) | 2013-10-29 | 2014-10-29 | A titanium silicalite molecular sieve and its synthesis. |
| JP2014220736A JP6517001B2 (en) | 2013-10-29 | 2014-10-29 | Titanium silicate molecular sieve and its synthesis |
| TW103137439A TWI637912B (en) | 2013-10-29 | 2014-10-29 | Titanium bismuth molecular sieve and synthesis method thereof |
| DE201410222042 DE102014222042A1 (en) | 2013-10-29 | 2014-10-29 | Titanium silicalite molecular sieve and its synthesis |
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| CN112744838B (en) * | 2019-10-31 | 2023-02-21 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve, preparation method thereof and method for producing ketoxime by macromolecular ketone ammoximation reaction |
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| CN112028085A (en) * | 2020-06-08 | 2020-12-04 | 江西师范大学 | Molybdenum-containing hollow titanium-silicon molecular sieve and preparation method and application thereof |
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