CN104556104B - Method for synthesizing titanium-silicalite molecular sieve employing organic quaternary ammonium salt template agent - Google Patents

Method for synthesizing titanium-silicalite molecular sieve employing organic quaternary ammonium salt template agent Download PDF

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CN104556104B
CN104556104B CN201410562400.1A CN201410562400A CN104556104B CN 104556104 B CN104556104 B CN 104556104B CN 201410562400 A CN201410562400 A CN 201410562400A CN 104556104 B CN104556104 B CN 104556104B
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silicon source
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CN104556104A (en
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舒兴田
夏长久
林民
朱斌
彭欣欣
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
    • C01B39/085—Group IVB- metallosilicates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM

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  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention discloses a method for synthesizing a titanium-silicalite molecular sieve employing an organic quaternary ammonium salt template agent. The method comprises the following steps: forming a crystallized mixture from a titanium source, a template agent, water, polyhydric alcohols, peroxide, a silicon source and an optional inorganic ammonium source; crystallizing, and recovering the titanium-silicalite molecular sieve, wherein the template agent is an organic quaternary ammonium salt and organic alkali; and the silicon source is an organic silicon source and/or solid silicon source. According to the method disclosed by the invention, the oxidation activity of the synthesized titanium-silicalite molecular sieve can be improved; and the sizes of crystal grains are reduced.

Description

A kind of method of use organic quaternary ammonium salt template synthesis of titanium silicon molecular sieve
Technical field
The present invention relates to a kind of synthetic method of HTS.
Background technology
HTS is the new hetero-atom molecular-sieve for starting 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 and the TS- with larger pore structure of MWW type structures 48 etc..Wherein TS-1 is that Italian EniChem companies develop synthesis earliest, is to introduce transition metal titanium to have ZSM- A kind of novel titanosilicate with superior catalytic selective oxidation performance formed in the framework of molecular sieve of 5 structures, TS- 1 catalysed oxidn not only with titanium, but also the shape-selective effect with ZSM-5 molecular sieve and excellent stability.Using This HTS can be catalyzed polytype organic oxidizing reaction as catalyst, such as the epoxidation of alkene, alkane Partial oxidation, the oxidation of alcohols, the hydroxylating of phenols, ammoxidation of cyclic ketones etc..Because TS-1 molecular sieves are in the oxidation of organic matter In reaction, can be using free of contamination low concentration hydrogen peroxide as oxidant, it is to avoid oxidizing process complex process and pollution ring The problem in border, with the unrivaled energy-conservation of conventional oxidation system, economy and advantages of environment protection, and with good reaction Selectivity.HTS is used 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 severe contamination 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 first in patent US 4410501 Method.The method is the classical way for synthesizing TS-1, is mainly divided to glue and the step of crystallization two to carry out, and 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), then slowly be added dropwise metatitanic acid four Ethyl ester (TEOT), stirs lh, is obtained a kind of reactant 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 is then peeled off, washs, dries, is calcined and obtains TS-1 molecular sieves.But Titanium insertion skeleton process influence factor is numerous in the technique, and the condition of hydrolysis and nucleation is difficult to control, therefore method synthesis The drawback such as TS-1 molecular sieves have that catalysis activity is low, stability is poor, be difficult to synthesize and reappear.
The disclosed HTSs of Thangaraj et al. (Zeolites, page 1992, Vol.12 the 943rd~950) preparation side In method, in order to balance the hydrolysis rate of organosilicon and titanium, isopropanol is introduced in the hydrolytic process of titanium, but what the method was obtained HTS activity is not high.
Chinese patent CN98101357.0 (CN1260241A) discloses HTS reordering technique, has synthesized with only The novel titanosilicate of special hollow-core construction, not only greatly enhances the reappearance of synthesis TS-1, also add molecular sieve hole body Product, substantially increases mass transfer diffusion rate of the reactant molecule in molecular sieve pore passage, and catalytic performance increases.Disclosed in the patent Method is by the hydrating solution of titanium with the TS-1 molecular sieves for having synthesized according to molecular sieve (gram)：Ti (mole)=200~1500： 1 ratio is well mixed, and gained mixture is reacted 1~8 day with 120~200 DEG C in a kettle., is filtered, is washed and does It is dry.At present, HTS molecular sieves are applied to the processes such as oxidation phenol hydroxylating, cyclohexanone oxamidinating and have been carried out industrialization, tool Have the advantages that reaction condition is gentle, atom utilization is high, technical process is simple and accessory substance is water clean and effective.
The synthesis of current HTS has quaternary ammonium base relatively costly usually using quaternary ammonium base, and research considers Used cooperatively with organic quaternary ammonium salt and organic base and replace quaternary ammonium base, but the titanium silicon molecule for being prepared using organic quaternary ammonium salt at present Sieve activity is not high.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of new HTS synthetic method.
A kind of synthetic method of HTS, including by titanium source, template, water, polyalcohol, peroxide, silicon source and Optional inorganic source of ammonium forms crystallization mixture, crystallization, reclaims HTS, described template for organic quaternary ammonium salt with have Machine alkali.
The HTS synthetic method that the present invention is provided, introduces polyalcohol and peroxide in building-up process, polynary Alcohol is 0.01~0.8 with the mol ratio of silicon source:1, peroxide is 0.01~0.25 with the mol ratio of silicon source:1.Polyalcohol with it is total The mol ratio of silicon source is preferably 0.05~0.7:1 is, for example, 0.05~0.5:1, peroxide can be with the mol ratio of total silicon source 0.05~0.25:1 is, for example, 0.05~0.15:1.Described polyalcohol is the alcohol containing two or more hydroxyls in molecule Class, it is preferable that carbon atom number is 2~8 in described polyol molecule, and described hydroxyl is, for example, 2 or 3, and described is more One or more in first alcohol such as glycerine, ethylene glycol, hexylene glycol, diethylene glycol (DEG).Described peroxide is to contain peroxide bridge Compound, such as one or more in hydrogen peroxide, tert-butyl peroxide, Peracetic acid, trifluoro Peracetic acid etc..Introduce many First alcohol and peroxide so that resulting HTS has smaller crystallite dimension (or grain size, crystal grain short axle The size in direction), with activity higher.
The HTS synthetic method that the present invention is provided, described silicon source is organic silicon source and/or solid silicon source.It is described Titanium source be organic titanium source and/or inorganic ti sources.Described template is organic base and organic quaternary ammonium salt, described organic bases Such as quaternary ammonium base and/or organic amine.Water, silicon source water are 5~100 with the mol ratio of total silicon source:1；Template and total silicon source Mol ratio is 0.04~0.6:1；The mol ratio of polyalcohol and total silicon source is 0.01~0.8, peroxide and total silicon source mole Than being 0.01~0.25:1；Titanium source is 0.005~0.05 with the mol ratio of total silicon source:1.In described mol ratio, described is total Silicon source (silicon source) is with SiO2Organic silicon source of meter and the summation of solid silicon source.
The HTS synthetic method that the present invention is provided, described silicon source is organic silicon source and/or solid silicon source.It is described Organic silicon source be organo-silicon ester, described organo-silicon ester, its formula be Si (OR1)4, R1Selected from 1~6 carbon atom Alkyl such as R1It is C1-C4Alkyl, described alkyl can be branched alkyl or straight chained alkyl.Described organo-silicon ester is for example One or more in quanmethyl silicate, tetraethyl orthosilicate, the butyl ester of silicic acid four, dimethyl diethyl estersil；Wherein preferred silicic acid One or more in four methyl esters, tetraethyl orthosilicate, dimethyl diethyl estersil.Solid silicon source described in the present invention is high-purity Silica solid or powder, for example can be white carbon and/or high-purity silica gel.Under preferable case, with dry basis SiO in the solid silicon source on the basis of amount2Content is not less than 99.99 weight %, and in terms of element Fe, Al and Na impurity total matter Amount content is less than 10ppm；Such as SiO2Content is 99.99~100 weight %, typically greater than 99.99 and less than 100 weights Amount %.Described solid silicon source can be high-purity silica gel and/or white carbon, preferably white carbon；SiO in wherein described silica gel2 It is, for example, that, more than 99.99 weight % and less than 100 weight %, and Fe, Al and Na are miscellaneous that content is preferably greater than or equal to 99.99 weight % The gross mass content of matter is less than 10ppm.The specific surface area of the white carbon is preferably between 20-1000m2It is, for example, 50- between/g 400m2/ g, on the basis of the butt weight of white carbon, SiO in the white carbon2Content is preferably greater than or equal to 99.99 weight % Such as 99.99~100 weight % are, for example, more than 99.99 weight % and less than 100 weight %, in terms of atom in the white carbon The gross mass content of Fe, Al and Na impurity is less than 10ppm.The white carbon with commercially available, or can be prepared according to existing method, Prepared by the method for for example being provided according to patent CN200910227646.2, a kind of preparation method is by silicon tetrachloride and hydrogen and oxygen There is combustion reaction and obtain in gas.
Described titanium source is organic titanic compound or inorganic titanium compound, such as tetraalkyl titanate (Ti (alkoxy)4)、 TiCl4、Ti(SO4)2And one or more in their hydrolysate.The carbon of the alkyl wherein in tetraalkyl titanate is former Subnumber is 1~6, for example, 1,2,3,4,5 or 6.
The HTS synthetic method that the present invention is provided, described template agent is organic base and organic quaternary ammonium salt.It is described Organic base be one or more in quaternary ammonium base, organic amine；Described organic amine is fatty amine, aromatic amine and/or alcohol Amine, described fatty amine (present invention is also referred to as fat amine compound), its formula is R3(NH2)n, wherein R3It is with 1~4 The alkyl or alkylidene of carbon atom, n=1 or 2；Described hydramine (present invention is also referred to as alcamine compound) its formula is (HOR4)mNH(3-m), wherein R4It is with 1~4 alkyl of carbon atom, m=1,2 or 3.Described fatty amine such as ethamine, just One or more in butylamine, butanediamine or hexamethylene diamine；Described aromatic amine refers to the amine for replacing base with an armaticity, example Such as one or more in aniline, toluidines, p-phenylenediamine；Described hydramine such as MEA, diethanol amine or three ethanol One or more in amine.Described quaternary ammonium base such as TPAOH, TBAH or tetraethyl hydrogen One or more in amine-oxides；Described organic quaternary ammonium salt such as 4-propyl bromide, TBAB, tetraethyl bromination One or more in ammonium, 4-propyl ammonium chloride, tetrabutylammonium chloride or etamon chloride.Under preferable case, described mould Plate agent includes quaternary organic ammonium compounds, and contains organic base.Described quaternary organic ammonium compounds such as quaternary ammonium base and/or have Machine quaternary ammonium salt, described organic bases such as quaternary ammonium base and/or organic amine.Organic quaternary ammonium salt is preferred with the mol ratio of total silicon source It is 0.05~0.45:1, organic base is preferably 0.05~0.45 with the mol ratio of total silicon source:1, preferred described organic quaternary ammonium Salt is 0.05~0.3 with the mol ratio of total silicon source:1 such as 0.05~0.2:1, described organic base is with the mol ratio of total silicon source 0.05~0.3:1, such as 0.05~0.2:1.
The HTS synthetic method that the present invention is provided, a kind of specific embodiment, described HTS is TS- 1 molecular sieve, described organic quaternary ammonium salt is one or more in 4-propyl ammonium chloride, 4-propyl bromide；Described is organic Alkali is TPAOH and/or organic amine.
The HTS synthetic method that the present invention is provided, a kind of specific embodiment, described HTS is TS- 2 molecular sieves, described organic quaternary ammonium salt is one or more in tetrabutylammonium chloride, TBAB；Described is organic Alkali is TBAH and/or organic amine.
The HTS synthetic method that the present invention is provided, a kind of specific embodiment, described HTS is Ti- Beta-molecular sieve, described organic quaternary ammonium salt is one or more in etamon chloride, tetraethylammonium bromide；Described is organic Alkali is tetraethyl ammonium hydroxide and/or organic amine.
The HTS synthetic method that the present invention is provided, described inorganic source of ammonium is inorganic ammonium salt and/or ammoniacal liquor, preferably Ammoniacal liquor, with NH4 +The inorganic source of ammonium of meter is 0~5 with the mol ratio of titanium source:1, for example, 0.01~4:1, preferably 0.05~0.5:1. In the context of the present invention, the oxidation activity that inorganic source of ammonium is conducive to improving synthesized molecular sieve is introduced, improves framework titania silicon ratio.
The HTS synthetic method that the present invention is provided, by titanium source, template, water, polyalcohol, peroxide and silicon Source, optional inorganic source of ammonium form crystallization mixture, then by described crystallization mixture crystallization, form crystallization product, crystallization Product obtains HTS by recovery.Described crystallization, can use existing method, for example, the temperature of crystallization be 110~ 200 DEG C, crystallization time 0.2~20 day carries out crystallization under self-generated pressure.A step crystallization can be used, it would however also be possible to employ substep is brilliant Change.A kind of implementation method, the temperature of the crystallization is 140~180 DEG C such as 160~180 DEG C, and crystallization time is 0.5~10 day For example, 0.5~6 day, crystallization pressure was self-generated pressure.A kind of implementation method, described crystallization is：At 100~130 DEG C for example 110~130 DEG C of crystallization 0.5~1.5 day, then crystallization 1~3 day at 160~180 DEG C, crystallization pressure is self-generated pressure.
The HTS synthetic method that the present invention is provided, the recovery HTS is existing method, for example, generally Including crystallization product being filtered, being washed and be calcined or filtered crystallization product, wash, dry and then be calcined.
The HTS synthetic method that the present invention is provided, the first implementation method is comprised the following steps：
(1) titanium source, template, water, polyalcohol and optional first time silicon source are mixed, alcohol is caught up with hydrolysis；It is subsequently adding peroxide Compound；The first time silicon source is organic silicon source；
(2) product that step (1) is obtained is aging；
(3) added in the product that step (2) is obtained or be added without second silicon source, crystallization reclaims HTS；It is described Second silicon source is organic silicon source and/or solid silicon source；
Wherein, described silicon source is introduced in step (1) and step (3) at least one step, described template is to have Machine quaternary ammonium salt and organic base.
The HTS synthetic method that the present invention is provided, in the first implementation method, the silicon source introduced in step (1) The present invention is referred to as first time silicon source, and the silicon source introduced in step (3), the present invention is referred to as second silicon source.The silicon source for being used It is organic silicon source and/or solid silicon source, organic silicon source can be simply used, it is also possible to simply uses solid silicon source, preferable case Lower use solid silicon source.In described the first implementation method, it is preferred that described silicon source includes organic silicon source and solid silicon source, Organic silicon source is introduced in step (1), and solid silicon source (inorganic silicon source) is introduced in step (3), wherein with SiO2That counts is organic Silicon source with SiO2The mol ratio of the solid silicon source of meter is, for example, 0~1:20；It is preferred that with SiO2Meter organic silicon source with SiO2Meter Solid silicon source mol ratio be 1:0.1~20, the HTS of surface Silicon-rich can be obtained.
The HTS synthetic method that the present invention is provided, introduces many in the first described implementation method, in step (1) First alcohol and peroxide.Introduce polyalcohol and peroxide so that resulting HTS has activity higher, has Smaller crystallite dimension (or grain size, the size of crystal grain short-axis direction).Wherein polyalcohol is with the mol ratio of total silicon source 0.01~0.8:1, peroxide is 0.01~0.25 with the mol ratio of total silicon source:1 is, for example, 0.05~0.25:1, organic quaternary ammonium Salt is 0.04~0.56 with the mol ratio of total silicon source:1, organic base is 0.04~0.5 with the mol ratio with total silicon source:1.The present invention In, described total silicon source is with SiO2Meter organic silicon source and with SiO2The summation of the solid silicon source of meter；When simply using organosilicon Source, then described total silicon source is organic silicon source, and when described solid silicon source is simply used, then described total silicon source is solid silicon Source；When solid silicon source and organic silicon source is used, then described total silicon source is solid silicon source and organic silicon source sum.
The HTS synthetic method that the present invention is provided, in the first described implementation method, described titanium source and total The mol ratio of silicon source is 0.005~0.05:1, for example, 0.008~0.3:1 or 0.01~0.025:1, further titanium source with it is total The molar ratio of silicon source such as 0.015~0.025:1.Described total silicon source (silicon source) is organic silicon source and solid silicon source, the mould Plate agent and with SiO2The mol ratio of total silicon source of meter is 0.08~0.6:1, for example, 0.1~0.5:1 or 0.1~0.3:1 is 0.1~0.2:1；The water is 5~100 with the mol ratio of total silicon source:1, for example, 5~80:1 or 6~50:1 or 6~30:1 or 6~15:1.
The HTS synthetic method that the present invention is provided, in the first described implementation method, described in step (1) Inorganic source of ammonium is inorganic ammonium salt and/or ammoniacal liquor, preferred ammoniacal liquor, with NH4 +The inorganic source of ammonium of meter is 0~5 with the mol ratio of titanium source:1, For example, 0.01~4:1, preferably 0.05~0.5:1.In the context of the present invention, inorganic source of ammonium is introduced to be conducive to improving synthesized point The oxidation activity of son sieve, improves framework titania silicon ratio.
The HTS synthetic method that the present invention is provided, in the first described implementation method, by titanium in step (1) Source, template, water, polyalcohol, optional organic silicon source and optional inorganic source of ammonium mixing, will can appoint in any way Organic silicon source, titanium source, template, optional inorganic source of ammonium, water and the polyalcohol for selecting mix, are hydrolyzed and catch up with alcohol, make organic Silicon source and titanium source are hydrolyzed, and reduce the content of the monohydric alcohol that hydrolysis is produced.It is described hydrolysis catch up with alcohol can be will include organic silicon source and/ Or the mixture of titanium source and water is for example stirred in being stirred at least 10 minutes at 0~150 DEG C such as 0~100 DEG C preferably 50~95 DEG C 10~3000 minutes, so that organic silicon source and titanium source hydrolysis, and organic silicon source and titanium source are reduced (if hydrolysis produces monohydric alcohol Words) hydrolysis produce alcohol content.It is preferred that, the content for hydrolyzing the monohydric alcohol that the water in products solution for catching up with alcohol to obtain is produced is no more than 10ppm (quality), it is preferable that described hydrolysis catches up with the mass content of monohydric alcohol in alcohol product to be no more than 10ppm.
The HTS synthetic method that the present invention is provided, in the first described implementation method, in step (2), will walk Suddenly (1) products therefrom is aging, it is described it is aging be at room temperature~50 DEG C by step (1) products therefrom stand 1~60 hour.It is described Room temperature is 15~40 DEG C；Ageing time is for example, preferably 3~15 hours 3~50 hours 1~60 hour, is not entered in ageing process Row stirring, is that step (1) products therefrom stands by the material.
The HTS synthetic method that the present invention is provided, in the first described implementation method, described crystallization can be adopted With existing method, for example, the temperature of crystallization is 110~200 DEG C, crystallization time 0.2~20 day carries out crystallization under self-generated pressure. A step crystallization can be used, it would however also be possible to employ fractional crystallization.A kind of implementation method, the temperature of the crystallization is 140~180 DEG C of examples Such as 160~180 DEG C, it 0.5~10 day is, for example, 0.5~6 day that crystallization time is, crystallization pressure is self-generated pressure.A kind of embodiment party Formula, described crystallization is：In 100~130 DEG C of such as 110~130 DEG C crystallization 0.5~1.5 day, then at 160~180 DEG C Crystallization 1~3 day, crystallization pressure is self-generated pressure.
The HTS synthetic method that the present invention is provided, can improve the oxidation activity of synthesized molecular sieve, improve titanium Utilization rate, synthesized HTS can have smaller crystal grain.
Brief 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 titaniferous beta-molecular sieve (also known as Ti- beta-molecular sieves) SEM scanning figures of embodiment of the present invention synthesis.
Fig. 4 is the TEM figures of the titanium silicon TS-1 molecular sieves by resetting prepared by the embodiment of the present invention.
Fig. 5 be surface silicon titanium than with body phase silicon titanium than measuring method schematic diagram.It is to measure body phase silicon titanium using TEM-EDX Than with surface silicon titanium than schematic diagram, wherein square frame 1 illustrates the silicon titanium ratio in measurement grain edges region, square frame 2 to illustrate measurement The silicon titanium ratio of grain central area.Because grain edges area unit volume is with external surface area higher, and the list of central area Correspondence external surface area is relatively low in the volume of position, therefore EDX measurement results can reflect the silicon on surface and body phase in square frame 1 and square frame 2 Titanium compares difference.
Specific embodiment
The HTS synthetic method that the present invention is provided, one kind preferred embodiment, comprises the following steps：
(1) template, titanium source, organic silicon source, water, polyalcohol and optional inorganic source of ammonium are mixed, alcohol is caught up with hydrolysis, then Add peroxide；Alcohol is caught up with the hydrolysis, by the mixed of gained generally at 0~150 DEG C such as 0~100 DEG C such as 50~95 DEG C Compound is stirred at least 10 minutes, wherein the mixing time for stirring is 10 minutes~50 hours；Wherein inorganic source of ammonium is (with NH4 +Meter)： Titanium source is (with TiO2Meter) mol ratio be 0~5:1；
(2) it is step (1) products therefrom is aging, it is described it is aging be in quiet at room temperature~50 DEG C by step (1) products therefrom Put 1~60 hour such as 3~30 hours, further such as 3~15 hours；
(3) by the ageing products obtained by step (2) and solid silicon source according to 1：0.1~20 weight ratio is well mixed, Then crystallization crystallization for example in closed reactor, reclaims HTS；In wherein described part by weight, step (2) institute The ageing products and solid silicon source for obtaining are with SiO2Meter；
Wherein, water and the mol ratio of total silicon source are 5~100:1；Template is 0.08~0.6 with the mol ratio of total silicon source:1 For example, 0.1~0.5:1 is, for example, 0.15~0.3:1 is 0.1~0.2:1；The mol ratio of titanium source and total silicon source for 0.005~ 0.05:1 is, for example, 0.01~0.03:1, it is further 0.01~0.025:1；Described template be organic quaternary ammonium salt with it is organic Alkali, organic quaternary ammonium salt is 0.04~0.6 with the mol ratio of total silicon source:1, organic base is 0.04~0.5 with the mol ratio of total silicon source: 1, the organic bases such as organic amine；
Wherein, in described mol ratio, total silicon source is with SiO2Meter, total silicon source is with SiO2Meter organic silicon source and with SiO2The summation of the solid silicon source of meter, inorganic source of ammonium is with NH4 +Meter；Described inorganic source of ammonium is inorganic ammonium salt and/or ammoniacal liquor, titanium source With TiO2Meter, water is with H2O is counted.
The present invention provide HTS synthetic method, it is described preferred embodiment, prepared zeolite crystal Surface Silicon-rich, grain surface silicon titanium ratio apparently higher than body phase silicon titanium ratio, grain surface silicon titanium mol ratio and body phase silicon titanium mol ratio Ratio be 1.1~5:1, for example, 1.2~4:1 is 1.3~3:1.Resulting HTS, with surface silicon higher The ratio between titanium ratio and body phase silicon titanium ratio, with oxidation activity higher, for the oxidation reaction that hydrogen peroxide is participated in, it is possible to reduce surface Decomposition of the titanium to hydrogen peroxide in layer, advantageously reduces the activity of the decomposition side reaction of hydrogen peroxide, improves raw material availability.This Outward, the HTS synthetic method that the present invention is provided, preferred embodiment uses the relatively inexpensive solid silicon source example being easy to get Such as high-purity silica gel or/and white carbon, partly instead of expensive organic silicon source, the waste of process of producing molecular sieve can be reduced Discharge and economize in raw materials cost while obtain high performance HTS, can be in relatively low template agent consumption and relatively low Synthesis of titanium silicon molecular sieve in the case of water silicon ratio, can reduce the synthesis cost of HTS, improve synthesis of molecular sieve crystallization and produce The solid content of thing, improves one-pot molecular sieve yield.
Surface silicon titanium ratio and body phase silicon titanium ratio can be determined and obtained using TEM-EDX or ion excitation corrosion XPS means, its In, surface silicon titanium ratio can be determined and obtained using TEM-EDX or ion excitation corrosion XPS means, be to be no more than apart from grain surface The silicon titanium ratio of the atomic layer of 5nm such as 1~5nm；Body phase titanium silicon than can be obtained by the method for chemical analysis, or by TEM- EDX is for example obtained in the central area of crystal grain apart from grain surface area measure of the distance more than 20nm, or is obtained by XRF analysis Arrive.
The present invention provide HTS synthetic method, it is described preferred embodiment, can be in lower template agent Synthesis of titanium silicon molecular sieve in the case of consumption, thus template agent consumption can reduce, such as template agent with it is total in terms of silica The mol ratio of silicon source is 0.1~0.3:1, it is further 0.1~0.20:1；In the method that the present invention is provided, can be in large arch dam The lower synthesis of titanium silicon molecular sieve of amount, from can and reduce the usage amount of water, it is in same synthesis reactor volume to improve output per single reactor The more molecular sieves of lower synthesis, therefore described water and the mol ratio of the total silicon source in terms of silica can be 5~50:1 It is such as 5~30 or be 6~15:1.
The HTS synthetic method that the present invention is provided, it is described preferred embodiment in, described titanium source and total silicon The mol ratio in source is preferably 0.01~0.03:1 is, for example, 0.01~0.025:1.
The HTS synthetic method that the present invention is provided, it is described preferred embodiment in, inorganic source of ammonium and titanium source Mol ratio is 0~5:1, for example, 0.01~4:1, preferably 0.05~0.5:1.Inorganic source of ammonium is added, can improve synthesized The activity of molecular sieve, improves framework titania silicon ratio.
The synthetic method of the HTS that the present invention is provided, it is described preferred embodiment in, described template with The mol ratio of described total silicon source is not less than 0.08:1 is preferably 0.1~0.3:1 is, for example, 0.1~0.2:1.
The HTS synthetic method that the present invention is provided, it is described preferred embodiment described in solid silicon source and organic The mol ratio of silicon source is preferably 1~19:1, for example, 2~18:1, or 3~17:1, or be 5~15:1.Usual step (2) The ratio between resulting ageing products and solid silicon source are equal to organic silicon source and the mol ratio of solid silicon source.
The present invention provide HTS synthetic method, it is described preferred embodiment in, the masterplate described in step (1) Agent is organic base and organic quaternary ammonium salt, and described organic base is one or more in quaternary ammonium base, organic amine；For example, institute The template stated is mixture, the mixture of organic amine and organic quaternary ammonium salt or organic of quaternary ammonium base and organic quaternary ammonium salt The mixture of quaternary ammonium base and organic quaternary ammonium salt and organic amine.Described organic amine is fatty amine, aromatic amine and/or hydramine, institute The fatty amine (present invention is also referred to as fat amine compound) stated, its formula is R3(NH2)n, wherein R3It is with 1~4 carbon atom Alkyl or alkylidene, n=1 or 2；Described hydramine (present invention is also referred to as alcamine compound) its formula is (HOR4)mNH(3-m), wherein R4It is with 1~4 alkyl of carbon atom, m=1,2 or 3.Described fatty amine for example ethamine, n-butylamine, One or more in butanediamine or hexamethylene diamine；Described aromatic amine refers to the amine for replacing base with an armaticity, such as benzene One or more in amine, toluidines, p-phenylenediamine；In described hydramine such as MEA, diethanol amine or triethanolamine One or more.Described quaternary ammonium base such as TPAOH, TBAH or tetraethyl hydroxide One or more in ammonium；Described organic quaternary ammonium salt for example 4-propyl bromide, TBAB, tetraethylammonium bromide, One or more in 4-propyl ammonium chloride, tetrabutylammonium chloride or etamon chloride.
The present invention provide HTS synthetic method, it is described preferred embodiment in, a kind of specific embodiment, Described HTS is TS-1 molecular sieves, and described organic base is TPAOH and/or organic amine, and described has Machine quaternary ammonium salt is one or more in 4-propyl ammonium chloride, 4-propyl bromide.
The present invention provide HTS synthetic method, it is described preferred embodiment in, a kind of specific embodiment, Described HTS is TS-2 molecular sieves, and described organic base is TBAH and/or organic amine, and described has The mixture that machine quaternary ammonium salt is made up of one or more in tetrabutylammonium chloride, TBAB.
The present invention provide HTS synthetic method, it is described preferred embodiment in, a kind of specific embodiment, Described HTS is Ti- beta-molecular sieves, and described organic base is tetraethyl ammonium hydroxide and/or organic amine, and described has Machine quaternary ammonium salt is one or more in etamon chloride, tetraethylammonium bromide.
The HTS synthetic method that the present invention is provided, it is described preferred embodiment in, described in step (1) Organic silicon source is organo-silicon ester, and described organo-silicon ester, its formula is Si (OR1)4, R1Selected from 1~6 alkane of carbon atom Base such as R1It is C1-C4Alkyl, described alkyl can be branched alkyl or straight chained alkyl.Described organo-silicon ester such as silicon One or more in sour four methyl esters, tetraethyl orthosilicate, the butyl ester of silicic acid four, dimethyl diethyl estersil；Wherein preferred silicic acid four One or more in methyl esters, tetraethyl orthosilicate, dimethyl diethyl estersil.Described solid silicon source is the titanium dioxide of high-purity Silicon solid or powder, for example, can be white carbon and/or high-purity silica gel.Under preferable case, on the basis of butt weight SiO in the solid silicon source2Content is not less than 99.99 weight %, and the gross mass content of Fe, Al and Na impurity is small in terms of atom 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, preferably white carbon；SiO in wherein described high-purity silica gel2Content is excellent Choosing is, for example, and the impurity such as Fe, Al and Na more than 99.99 weight % and less than 100 weight % more than or equal to 99.99 weight % Mass content be less than 10ppm；The specific surface area of the white carbon is preferably between 20-1000m2/ g such as 50-400m2Between/g, On the basis of the butt weight of white carbon, SiO in the white carbon2Content is preferably greater than or equal to 99.99 weight % 99.99~100 weight % be, for example, more than 99.99 weight % and less than 100 weight %, in terms of atom, Fe in the white carbon, The quality total content of Al and Na is less than 10ppm.The white carbon with commercially available, or can be prepared according to existing method, for example according to Prepared by the method that patent CN200910227646.2 is provided, a kind of preparation method is that silicon tetrachloride is fired with hydrogen and oxygen Reaction is burnt to obtain.
The HTS synthetic method that the present invention is provided, it is described preferred embodiment in, described titanium source is to have Machine titanium compound or inorganic titanium compound, such as tetraalkyl titanate (Ti (alkoxy)4、TiCl4、Ti(SO4)2And they One or more in hydrolysate, described titanium source is preferably organic titanic compound.Alkyl wherein in tetraalkyl titanate Carbon number be 1~6, for example, 1,2,3,4,5 or 6.The mol ratio of titanium source and silicon source (total silicon source) is preferably 0.01~ 0.025:1 such as 0.015~0.025:1.
The HTS synthetic method that the present invention is provided, it is described preferred embodiment in, described in step (1) Inorganic source of ammonium is inorganic ammonium salt and/or ammoniacal liquor, and one kind is obtained in described inorganic ammonium salt such as ammonium chloride, ammonium nitrate, ammonium sulfate Or it is various.Described inorganic source of ammonium is preferably ammoniacal liquor, with NH4 +The ammoniacal liquor of meter with TiO2The mol ratio of the titanium source of meter is 0~5:1 For example, 0.01~4:1 is 0.05~0.5:1.The inorganic quaternary ammonium salts are added, the activity of synthesized molecular sieve can be improved, Improve the surface silicon titanium than with body phase silicon titanium than ratio.
The present invention provide HTS synthetic method in, it is described preferred embodiment in, by titanium in step (1) Source, template, organic silicon source, inorganic source of ammonium and water are hydrolyzed and are caught up with alcohol by mixing.Alcohol is caught up with the hydrolysis, is at 0~150 DEG C It is preferred that 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 gained mixing Alcohol content in thing.Usual mixing time is 10~3000 minutes, for example, 2~30 hours.Alcohol is caught up with by hydrolysis, is clarified Transparent hydrolyzate.The content of monohydric alcohol is not preferably not higher than 10ppm (quality) in the mixture that step (1) is obtained.By water Solution catches up with alcohol, obtains organic silicon source and titanium source hydrolyzate of clear, is subsequently adding peroxide and stirs, when generally stirring Between be 10~60 minutes.Described polyalcohol is the alcohols containing two or more hydroxyls in molecule, and preferably described is more Carbon atom number is 2~8 in first alcohol molecule, and described hydroxyl is, for example, 2 or 3, described polyhydric alcohols such as glycerine, One or more in ethylene glycol, hexylene glycol, diethylene glycol (DEG).Described peroxide is the compound containing peroxide bridge, described One or more in the preferred hydrogen peroxide of peroxide, tert-butyl peroxide, Peracetic acid, trifluoro Peracetic acid etc..Polyalcohol It is 0.01~0.8 with the mol ratio of silicon source:1, preferably 0.01~0.7:1 is, for example, 0.05~0.5:1；Peroxide and silicon source Mol ratio be 0.01~0.25：1, for example, 0.05~0.25:1 or 0.05~0.15:1.
The present invention provide HTS synthetic method, it is described preferred embodiment in, in step (2), by step (1) products therefrom is aging, it is described it is aging be at room temperature~50 DEG C by step (1) products therefrom stand 1~60 hour.The room Temperature is 15~40 DEG C；It 1~60 hour is, for example, 2~50 hours that ageing time is, is, for example, within preferably 3~30 hours 3~15 hours, It is not stirred in ageing process, is that step (1) products therefrom stands by the material.
The present invention provide HTS synthetic method, it is described preferred embodiment in, by step in step (3) (2) ageing products for obtaining mix with solid silicon source, with SiO2Meter, product and the mol ratio of solid silicon source that step (2) is obtained It is 1:0.1~20, for example can be 1:1~19 (mol ratio of i.e. described organic silicon source and solid silicon source be 1：1~19), or be 1:2~18 or 1:3~17, it is further 1：5~15, with SiO2Mol ratio in respect of machine silicon source and solid silicon source is preferably 1: 5~15.The method that the present invention is provided, it is possible to use the solid silicon source of higher proportion, can improve the solid content of synthetic product, from And the yield of single synthesis is improved in the case where synthesis reaction vessel is constant compared with organic silicon source is used alone.
The present invention provide HTS synthetic method, it is described preferred embodiment in, step (3) described crystallization, The temperature of crystallization is 110~200 DEG C, and crystallization pressure is self-generated pressure, and the time of crystallization is 2 hours~20 days, the usual crystalline substance The time of change is 0.5~20 day, and such as crystallization time is 1~10 day, and the temperature of the crystallization described in further step (3) is 140 ~180 DEG C is, for example, 160~180 DEG C, and it 0.5~6 day is, for example, 1~6 day, further for example, 1~3 day that crystallization time is.It is brilliant Change pressure is self-generated pressure.The crystallization can be carried out in stainless steel stirred tank.Crystallization intensification can be heated up with one section can also Multistage heating mode.Heating rate can be carried out according to existing crystallization temperature-rising method, for example, 0.5-1 DEG C/min.The crystallization can Carried out with stainless steel stirred tank.A kind of implementation method, the crystallization temperature of the crystallization is 160~180 DEG C, and crystallization time is Such as 0.5~3 day 1~6 day, crystallization pressure was self-generated pressure.A kind of implementation method, the crystallization described in step (3) is：100 Crystallization 0.5~1.5 day at~130 DEG C such as 110~130 DEG C, then crystallization 1~3 day at 160~180 DEG C, crystallization pressure It is self-generated pressure.
The present invention provide HTS synthetic method, it is described preferred embodiment in, described in step (3) reclaim HTS is existing method, including crystallization product is filtered, wash and is calcined or filter crystallization product, washs, done Dry and then roasting.The purpose of filtering is that the HTS that crystallization is obtained is separated with crystallization mother liquor, and the purpose of washing is to wash away The template on sieve particle surface is adsorbed, for example, can be room temperature~50 DEG C in temperature, molecular sieve compares 1 with the weight of water:1 ~20 such as 1:Mixing, washing or drip washing are carried out under (1-15).Dry purpose is to remove the most of moisture in molecular sieve, with Water evaporation quantity when roasting is reduced, dry temperature can be 100~200 DEG C.The purpose of roasting be remove molecular sieve in Template, the temperature that example is calcined as mentioned be 350~650 DEG C, roasting time be 2-10 hours.This hair is obtained by reclaiming Bright provided HTS product.
In the HTS synthetic method that the present invention is provided, the HTS that recovery is obtained can also be by further place Reason, i.e., the HTS synthetic method that the present invention is provided can also include following rearrangement step (for of the present invention first Kind of implementation method or preferred embodiment for, the present invention is also referred to as step (4))：
The HTS for obtaining Crystallizing treatment in organic alkali solution will be reclaimed brilliant preferably in organic quaternary ammonium aqueous slkali Change is processed, and then reclaims HTS.HTS obtained by the process makes has hollow-core construction, and the present invention is referred to as Molecular sieve is reset.The process includes that the HTS for obtaining will be reclaimed with organic base, water according to 1：0.02~0.5：2~50 Mol ratio forms mixture, in the closed reactor and under self-generated pressure in 100~200 DEG C such as 110~150 DEG C or 120~ 200 DEG C of crystallization 0.1~10 day, then reclaim product.Wherein HTS is (with SiO2Meter) with the mol ratio of organic base it is 1: 0.02~0.5 is, for example, 1:0.02~0.2, with SiO2The HTS of meter is 1 with the mol ratio of water:2~50 is, for example, 1:2 ~30 is, for example, further 1:5~10, crystallization temperature is 100~200 DEG C such as 120~200 DEG C, and crystallization pressure is spontaneous pressure Power, crystallization time 0.5~10 day, for example, 0.5~8 day or 1~6 day.It is preferred that, the crystallization temperature described in rearrangement step is 150- 200 DEG C, crystallization time is 0.5~6 day.Recovery method is existing method, be can refer to described in preferred embodiment step (3) Recovery method, generally includes crystallization product filtering, washing, dries right and roasting.Organic base described in rearrangement step is organic Quaternary ammonium base and/or organic amine, described quaternary ammonium base such as TPAOH, TBAH or tetraethyl hydrogen One or more in amine-oxides of mixture.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, and (present invention is also referred to as fatty amine to described fatty amine Class compound), its formula is R3(NH2)n, wherein R3It is with 1~4 alkyl or alkylidene of carbon atom, n=1 or 2；Institute Hydramine (present invention is also referred to as alcamine compound) its formula stated is (HOR4)mNH(3-m), wherein R4It is with 1~4 carbon atom Alkyl, m=1,2 or 3.One or more in described fatty amine such as ethamine, n-butylamine, butanediamine or hexamethylene diamine；Institute The aromatic amine stated refers to the amine for replacing base with an armaticity, such as one kind or many in aniline, toluidines, p-phenylenediamine Kind；One or more in described hydramine such as MEA, diethanol amine or triethanolamine.A kind of implementation method, resets HTS described in step is TS-1 molecular sieves, and described quaternary ammonium base is TPAOH.One kind is implemented Mode, described HTS is TS-2 molecular sieves, and the quaternary ammonium base described in rearrangement step is TBAH.One Implementation method is planted, described HTS is Ti-beta molecular sieves (Ti- beta-molecular sieves), the organic season described in rearrangement step Ammonium alkali is tetraethyl ammonium hydroxide.
Molecular sieve rearrangement step, this process can be carried out once, it is also possible to be repeated one or more times, and the repetition will The HTS that rearrangement treatment is obtained is processed according still further to the method for rearrangement step.Processed by rearrangement, can be had There is the HTS of secondary pore structure, the crystal grain of gained HTS for hollow-core construction (have time by also referred to as described molecular sieve Core structure), with bigger pore volume and specific surface area；The radical length of the chamber portion of the hollow crystal grain is 5~300nm, In 25 DEG C, P/P0=0.10, the benzene adsorbance that adsorption time is measured under conditions of 1 hour is at least 70 milligrams per grams, the molecular sieve Nitrogen absorption under low temperature adsorption isotherm and desorption isotherm between there is hysteresis loop.
The HTS synthetic method that the present invention is provided, can be used for synthesis of titanium silicon molecular sieve, described titanium silicon molecule Sieve such as TS-1 molecular sieves, TS-2 molecular sieves, Ti-MCM-22, TS-48 or Ti- beta-molecular sieve.
The present invention is further illustrated for the following examples, but and is not so limited the present invention.Institute in embodiment The reagent used is unaccounted to be commercially available AR.
Grain size (short-axis direction) and surface silicon titanium in embodiment than with body phase silicon titanium than measuring method use TEM-EDX, TEM electron microscope experiment are carried out on FEI Co.'s Tecnai F20G2S-TWIN type transmission electron microscopes, are furnished with The energy filter system GIF2001 of Gatan companies, annex is equipped with X-ray energy spectrometer.Electron microscopic sample uses the side of suspended dispersed Method is prepared in the micro-grid of diameter 3mm.Each sample randomly selects its surface silicon titanium ratio of 20 particle sizings and body in embodiment Phase silicon titanium ratio, gauging surface silicon titanium than with body phase silicon titanium than ratio, then take its 20 average values of sample as the sample Product surface silicon titanium than with body phase silicon titanium than ratio.
XRD measuring methods：The X-ray diffraction (XRD) of sample is carried out on Siemens D5005 type x-ray diffractometers Crystalline phase figure is determined, and radiographic source is CuK αTube voltage 40kV, tube current 40mA, 0.5 °/min of sweep speed, θ=4 °~40 ° of sweep limits 2.
The method of testing of BET specific surface area and pore volume uses N2 adsorption volumetric method, according to BJH computational methods.(referring to stone Oily chemical analysis method (RIPP test methods), RIPP151-90, Science Press, nineteen ninety publishes)
Raw materials used property is as follows in embodiment and comparative example：
Butyl titanate, analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group.
Titanyl sulfate, analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group.
TPAOH, Guangdong great You chemical plant.
Tetraethyl orthosilicate, analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group.
Ammoniacal liquor, analyzes pure, the weight % of concentration 20.
Glycerine, analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group.
Diethylene glycol (DEG), analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group.
White carbon, Zhejiang Ju Hua groups product, model AS-150；Solid content is more than 95 weight %, silica in butt Content is more than 99.99 weight %, and the total content of iron, sodium and Al is less than 10ppm, and specific surface area is 195m2/g。
Remaining reagent is analyzed pure without the commercially available product that is for further illustrating
Comparative example 1
This comparative example illustrate according to the method for Thangaraj et al. prepare conventional HTS (Zeolites, 1992, Vol.12 pages 943~950).
22.5g tetraethyl orthosilicates are mixed with the 7.0g TPAOHs aqueous solution (the weight % of concentration 25.05), is added 59.8g deionized waters uniformly mix；Then in 1.0h is hydrolyzed at 60 DEG C, the hydrating solution of tetraethyl orthosilicate is obtained.Again violent In the presence of stirring, to the solution that is made up of 1.1g butyl titanates and 5.0g isopropanols is slowly dropped into above-mentioned solution, will The mixture stirs 3h at 75 DEG C, obtains the colloid of clear.Again by the colloid move into stainless steel closed reactor in, Thermostatic crystallization 3 days at 170 DEG C, you can obtain conventional TS-1 molecular sieves.
Comparative example 2
This comparative example explanation HTS molecular sieves used are according to prepared by patent CN98101357.0.
22.5g tetraethyl orthosilicates are mixed with the 9.0g TPAOHs aqueous solution (the weight % of concentration 25.05), is added 64.5g deionized waters uniformly mix；Then in 1.0h is hydrolyzed at 60 DEG C, the hydrating solution of tetraethyl orthosilicate is obtained.Again violent In the presence of stirring, to the solution that is made up of 0.6g butyl titanates and 7.0g isopropanols is slowly dropped into above-mentioned solution, will The mixture stirs 7h at 75 DEG C, obtains the colloid of clear.Again by the colloid move into stainless steel closed reactor in, Thermostatic crystallization 3 days at 170 DEG C, you can obtain conventional TS-1 molecular sieves.
Again by butyl titanate, anhydrous isopropyl alcohol, TPAOH and deionized water according to 1:15:2.4:350 Molar ratio uniformly mixes, and in being 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 is uniform with the hydrating solution of above-mentioned butyl titanate , in uniform stirring 12h under normal temperature, finally be put into scattered suspension in stainless steel cauldron by mixing, is placed at 165 DEG C 3 days, you can obtain described HTS molecular sieves.
Embodiment 1
By 8.5g tetraethyl orthosilicates, 0.45g glycerine and the 3.4g 4-propyl bromides aqueous solution (the weight % of concentration 25.05), 0.33g triethylamines mix, and add 24.34g deionized waters uniformly to mix；Then in 1.0h is hydrolyzed at 60 DEG C, silicic acid tetrem is obtained Ester hydrolysis solution.Again in the presence of being stirred vigorously, to being slowly dropped into by 1.1g butyl titanates and 5.0g in above-mentioned solution The solution that isopropanol is constituted, 3h is stirred by the mixture at 75 DEG C, obtains the colloid of clear, adds 0.36 gram of concentration It is 30 weight % hydrogen peroxide.Again by the colloid move into stainless steel closed reactor in, thermostatic crystallization 3 days at 170 DEG C, you can To TS-1 molecular sieves.Its XRD analysis spectrogram is as shown in figure 1, have MFI structure.
Comparative example 3
According to the method for embodiment 1, the difference is that being added without described glycerine.
Comparative example 4
By the method according to embodiment 1, the difference is that being added without described hydrogen peroxide.
Embodiment 2
(1) by the 4-propyl bromide aqueous solution, 2.18g triethylamines, 2.04g metatitanic acids that 19.6g concentration is 25.05 weight % Four butyl esters, 8.5g tetraethyl orthosilicates, 4.87g glycerine, 2g concentration are that the ammoniacal liquor and 49.04g water of 20 weight % are added sequentially to In the beaker of 500ml, it is put on the magnetic stirring apparatus with heating and agitating function and is well mixed, and heating 4 is small at 80 DEG C When, the moisture of evaporation is supplemented at any time, water white transparency hydrolyzate is obtained, the hydrogen peroxide that 1.16g concentration is 30 weight % is subsequently adding, Stir；
(2) step (1) products therefrom is stood 12 hours at room temperature carry out aging, obtain ageing products；
(3) in above-mentioned ageing products, stirring is lower to add 9.36g white carbon powder, is stirred 1 hour after adding, and forms one Kind of " viscous body ", is transferred into stainless steel closed reactor, in 165 DEG C of thermostatic crystallizations 2 days, obtains TS-1 samples, will TS-1 sample filterings, the washing arrived, dry 24 hours at 120 DEG C, and 550 DEG C are calcined 6 hours, you can obtain titanium silicon of the present invention TS-1 zeolite products are designated as TS-1F1；Its BET specific surface area is 430m2/ g, external surface area is 59m2/ g, micro pore volume is 0.170mL.g-1, mesopore volume is 0.083mL.g-1, its XRD analysis spectrogram is as shown in Figure 1；
(4) the TPAOH aqueous solution that TS-1F1 samples described in 6g and concentration are 22.05 weight % is uniformly mixed, the TS- 1F1 is 1 with the weight ratio of the TPAOH aqueous solution：5,150 DEG C of crystallization 3 days in closed reactor, filtering, washing, at 120 DEG C Dry 24 hours, 550 DEG C are calcined 6 hours, you can must reset TS-1 products, be designated as TS-1P1.Its BET specific surface area is 448m2/ g, external surface area is 60m2/ g, micro pore volume is 0.155mL.g-1, mesopore volume is 0.176mL.g-1Transmitted electron shows It is hollow-core construction in micro mirror photo (shown in Fig. 4).
Embodiment 3
(1) by 4-propyl bromide, 3.34g butyl titanates, the second of 2.43g tri- that 25.45g concentration is 25.05 weight % Amine, 8.5g tetraethyl orthosilicates, 35.66 grams of diethylene glycol (DEG)s, 0.05g concentration are that the ammoniacal liquor and 51.84g water of 20 weight % are added sequentially to In the beaker of 500ml, it is put on the magnetic stirring apparatus with heating and agitating function and is well mixed, and heating 1 is small at 90 DEG C When, the moisture of evaporation is supplemented at any time, water white transparency basic hydrolysis liquid is obtained, it is subsequently adding 10.61g TBHPs (TBHP), stir；
(2) product obtained by (1) is stood 12 hours at room temperature, obtains ageing products；
(3) in resulting ageing products, 26.4g white carbon powder is slowly added under stirring, 1.5 is stirred after adding small When, uniform " viscous body " is formed, it is transferred into stainless steel closed reactor, in 165 DEG C of thermostatic crystallizations 2 days, filter, wash Wash, dried at 120 DEG C 24 hours, 550 DEG C are calcined 6 hours, that is, obtain TS-1 sieve samples, are designated as TS-1F2, XRD analysis table It is bright with MFI structure；
(4) 6g TS-1F2 samples are well mixed with the TPAOH aqueous solution of 36 grams of concentration 22.05%, in closed reaction 150 DEG C of crystallization 3 days in kettle, filtering, washing are dried 24 hours at 120 DEG C, and 550 DEG C are calcined 6 hours, obtain TS-1 zeolite products, It is designated as TS-1P2.Its BET specific surface area is 452m2/ g, external surface area is 61m2/ g, XRD analysis show with MFI structure；Transmission It is hollow-core construction in electron micrograph.
Embodiment 4
(1) by the 4-propyl bromide aqueous solution, 0.33g titanyl sulfates, the second of 7.63g tri- that 104.67g concentration is 25.05% Amine, 8.5g tetraethyl orthosilicates, 0.79g ethylene glycol, 0.36g concentration are that the ammoniacal liquor and 172.8g water of 20 weight % are added sequentially to In the beaker of 500ml, it is put on the magnetic stirring apparatus with heating and agitating function and uniformly mixes, and heating 3 is small at 70 DEG C When, the moisture of evaporation is supplemented at any time, basic hydrolysis liquid is obtained, the hydrogen peroxide solution that 8.7g concentration is 15 weight % is subsequently adding,
(2) (1) products therefrom is stood 24 hours at room temperature, obtains ageing products；
(3) in the beaker for filling ageing products, 36g white carbon powder is slowly added under stirring, is stirred one hour, formed More uniform " viscous body ", is transferred into stainless steel closed reactor, in 165 DEG C of thermostatic crystallizations 2 days, filtering, washing, Dried at 120 DEG C 24 hours, 550 DEG C are calcined 6 hours, you can obtain the TS-1 zeolite products of offer of the present invention, be designated as TS-1F3； XRD shows that it has MFI structure；
(4) the TPAOH aqueous solution by 6g TS-1F3 samples with 40 gram 22.05% mixes, and stirs, in closed anti- Answer in kettle 150 DEG C of crystallization 3 days, filtering, washing are dried 24 hours at 120 DEG C, and 550 DEG C are calcined 6 hours, you can hollow TS-1 Sample, is designated as TS-1P3.Its BET specific surface area is 455m2/ g, external surface area is 60m2/ g, in transmission electron microscope photo its It is hollow-core construction, XRD shows that it has MFI structure；.
Embodiment 5
Method according to embodiment 2 prepares HTS, the difference is that being added without ammoniacal liquor.
Embodiment 6
Method according to embodiment 2 prepares HTS, the difference is that using only solid silicon source, step
Suddenly it is added without organic silicon source in (1).
Embodiment 7
Method according to embodiment 2 prepares HTS, its proportioning and synthesis condition, the results are shown in Table 1.
Embodiment 8
According to the method for embodiment 2, the difference is that first crystallization 1 day at 120 DEG C in step (3), then brilliant at 170 DEG C Change 2 days, its proportioning and synthesis condition, the results are shown in Table 1.
Embodiment 9
According to the method for embodiment 2, adjustment proportioning, other conditions and characterization result are shown in Table 1.
Embodiment 10
Prepare TS-2 molecular sieves.With reference to the method according to embodiment 2, change proportioning and template, it is matched and synthesis bar Part, the results are shown in Table 1.
Embodiment 11
Prepare Ti- beta-molecular sieves.The method of reference implementation example 2, changes proportioning and template, and it is matched and synthesis condition, knot Fruit is shown in Table 1.
Embodiment 12
According to the method for embodiment 4, the difference is that the white carbon in step (3) is used to SiO2Count organic silicon source water of equivalent Solution catches up with alcohol product to replace, wherein, organic silicon source hydrolysis catches up with the unitary alcohol content in alcohol product to be no more than 10ppm mass.
Embodiment 13
This example demonstrates that the present invention embodiment sample for providing and sample prepared by comparative example are used for oxidation of phenol hydroxyl Change prepares the reaction effect of benzenediol and preparing cyclohexanone oxime by ammoximation of cyclohexanone.
Reagent used by the present embodiment is commercially available chemically pure reagent.The concentration of each material 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 Post.
The conversion ratio of phenol, cyclohexanone conversion ratio, cyclohexanone oxime selectivity are respectively to count according to the following equation in embodiment Calculate：
Above-described embodiment 1-9 is taken respectively and sample (rearrangement) each 1.25g prepared by comparative example is added to and contains phenol In the three-neck flask reaction vessel of 25g and acetone 20ml, after addition hydrogen peroxide 9.81g (concentration 30 after temperature stabilization to setting value Weight %), (phenol：Hydrogen peroxide (H2O2) mol ratio for 3), in 80 DEG C of temperature, after 2 hours adopt by pressure 0.1MPa (normal pressure), reaction Sample, phenol carries out hydroxylating generation benzenediol.
The HTS taken respectively in above-mentioned comparative example and embodiment prepares sample, according to TS-1 molecular sieves：The tert-butyl alcohol： 25 weight % ammoniacal liquor=1:7.5:The uniform stirring mixing in slurry bed of 7.5 mass ratio, the weight of molecular sieve is 2.7g, is heated up To 75 DEG C, 30 weight % hydrogen peroxide are then added with the speed of 6ml/h at this temperature, hexamethylene is added with the speed of 8.4ml/h (volume ratio of cyclohexanone and the tert-butyl alcohol is 1 to the mixture of ketone and the tert-butyl alcohol:2.5), while adding 25 weights with the speed of 6ml/h Amount % ammonia spirits, volume space velocity is 7.56h-1.Above-mentioned three strands of materials are added simultaneously, while with corresponding speed continuous discharge, instead Should stablize 3 hours, sampling carries out chromatography, the results are shown in Table 2.
The decomposition run of hydrogen peroxide
Take H2O2Concentration is 15 grams of the hydrogen peroxide of 30 weight %, adds 2 grams of HTSs, and temperature is small to stir 1 at 80 DEG C When, analyze the concentration of hydrogen peroxide.The results are shown in Table 2
From table 2, under identical condition, the molecular sieve that the present invention is provided has lower decomposing hydrogen dioxide solution speed, So as to improve the utilization rate of hydrogen peroxide in the oxidation reaction participated in for hydrogen peroxide, dioxygen water consumption can be reduced.
As can be seen from Table 2：The phenol hydroxylation and cyclohexanone of gained sample of the invention are active apparently higher than comparative sample Conventional TS-1 molecular sieves.
It should be noted that can also be combined between a variety of implementation methods of the invention, as long as its Without prejudice to thought of the invention, it should equally be considered as content disclosed in this invention.

Claims (43)

1. a kind of synthetic method of HTS, including titanium source, template, water, polyalcohol, peroxide, silicon source are formed Titanium source, template, water, polyalcohol, peroxide, silicon source and inorganic source of ammonium are formed crystallization mixture by crystallization mixture, Crystallization, reclaims HTS；Described template is organic quaternary ammonium salt and organic base, described silicon source for organic silicon source and/ Or solid silicon source, described solid silicon source is the silica dioxide granule or SiO 2 powder of high-purity.
2., according to the synthetic method of the HTS described in claim 1, comprise the following steps:
(1) by titanium source, template, water, polyalcohol and optionally organic silicon source, optional inorganic source of ammonium mixing, alcohol is caught up with hydrolysis；Then Add peroxide；
(2) product that step (1) is obtained is aging；
(3) added in the product that step (2) is obtained or be added without organic silicon source and/or solid silicon source, crystallization, recovery Pd silicon molecule Sieve；
Wherein, described silicon source is introduced in step (1) and step (3) at least one step, described template is organic season Ammonium salt and organic base.
3. according to the method described in claim 1 or 2, it is characterised in that the mol ratio of polyalcohol and total silicon source for 0.01~ 0.8:1, peroxide is 0.01~0.25 with the mol ratio of total silicon source:1, organic quaternary ammonium salt is 0.04 with the mol ratio of total silicon source ~0.6:1, organic base is 0.04~0.5 with the mol ratio with total silicon source:1, described total silicon source is with SiO2The organosilicon of meter Source and the summation of solid silicon source.
4. in accordance with the method for claim 3, it is characterised in that polyalcohol is 0.1~0.7 with the mol ratio of total silicon source:1, Peroxide is 0.05~0.25 with the mol ratio of total silicon source:1.
5. in accordance with the method for claim 2, it is characterised in that organic silicon source is introduced in step (1), and in step (3) Introduce solid silicon source；With SiO2Meter, the organic silicon source being introduced into step (1) with step (3) solid silicon source of introducing mole Than being 1:(0.1~20).
6. in accordance with the method for claim 5, it is characterised in that the method comprises the following steps：
(1) titanium source, template, organic silicon source, optional inorganic source of ammonium, polynary alcohol and water are mixed, alcohol is caught up with hydrolysis；Add peroxide Compound, wherein, inorganic source of ammonium：The mol ratio of titanium source is 0~5:1；
(2) it is step (1) products therefrom is aging, it is described it is aging be by step (1) products therefrom at room temperature~50 DEG C stand 1~ 60 hours；
(3) by the ageing products obtained by step (2) and solid silicon source according to 1:The weight of (0.1~20) is brilliant than well mixed Change, reclaim HTS；In wherein described part by weight, the ageing products obtained by the step (2) are with SiO2Meter, Gu Body silicon source is with SiO2Meter；
Wherein, water and the mol ratio of total silicon source are 5~100:1；Template is 0.08~0.6 with the mol ratio of total silicon source:1；It is many First alcohol is 0.01~0.8 with the mol ratio of total silicon source:1, peroxide is 0.01~0.25 with the mol ratio of total silicon source:1；Titanium source It is 0.005~0.05 with the mol ratio of total silicon source:1；Organic quaternary ammonium salt is 0.04~0.56 with the mol ratio of total silicon source:1, it is organic Alkali is 0.04~0.5 with the mol ratio with total silicon source:1；
Wherein, in described mol ratio, total silicon source is with SiO2Meter, total silicon source is with SiO2Meter organic silicon source and with SiO2 The summation of the solid silicon source of meter, inorganic source of ammonium is with NH4 +Meter；Described inorganic source of ammonium be inorganic ammonium salt and/or ammoniacal liquor, titanium source with TiO2Meter.
7. according to the method described in claim 1~2,5,6 any one, it is characterised in that described titanium source is rubbed with total silicon source You are than being 0.005~0.05:1.
8. according to the method described in claim 1~2,5,6 any one, it is characterised in that template, total silicon source, titanium source and water Mol ratio be (0.08~0.6):1:(0.005~0.05):(5~100).
9. in accordance with the method for claim 8, it is characterised in that described template is with the mol ratio of described total silicon source 0.1~0.5:1.
10. in accordance with the method for claim 9, it is characterised in that described organic quaternary ammonium salt is with the mol ratio of total silicon source 0.05~0.3:1, described organic base and the mol ratio of total silicon source is 0.05~0.3：1, described organic base is organic quaternary ammonium Alkali and/or organic amine.
11. in accordance with the method for claim 8, it is characterised in that the mol ratio of water and total silicon source is 5~50:1.
12. according to the method described in claim 2 or 6, it is characterised in that is introduced in step (1) or does not introduce inorganic source of ammonium, with NH4 +Meter inorganic source of ammonium with TiO2The mol ratio of the titanium source of meter is 0~5:1.
13. according to the method described in claim 1~2,5,6 any one, it is characterised in that organic silicon source and solid silicon source Mol ratio be 1:(1~19).
14. according to the method described in any one of claim 2,5,6, it is characterised in that described aging, and aging temperature is room temperature To 50 DEG C, ageing time is 1~60 hour.
15. according to the method described in claim 1~2,5,6 any one, it is characterised in that the crystallization, and the temperature of crystallization is 110~200 DEG C, crystallization pressure is self-generated pressure, and the time of crystallization is 2 hours~20 days.
16. in accordance with the method for claim 15, it is characterised in that the time of the crystallization is 0.5~10 day.
17. in accordance with the method for claim 16, it is characterised in that the crystallization temperature of the crystallization is 140~180 DEG C.
18. according to the method described in claim 1~2,5,6 any one, it is characterised in that described crystallization is：100~ 130 DEG C of crystallization 0.5~1.5 day, then crystallization 1~3 day at 160~180 DEG C, crystallization pressure is self-generated pressure.
19. according to the method described in claim 1~2,5,6 any one, it is characterised in that described method also includes resetting walking Suddenly：The HTS for obtaining crystallization 0.5~10 day in organic aqueous alkali will be reclaimed, the temperature of crystallization is 110~200 ℃；Wherein described HTS is (with SiO2Meter) with the mol ratio of the organic base it is 1:(0.02-0.5), described titanium Si molecular sieves are (with SiO2Meter) with the mol ratio of water it is 1：(2~50)；Described organic base is quaternary ammonium base and/or organic Amine.
20. in accordance with the method for claim 19, it is characterised in that the temperature of crystallization described in rearrangement step is 150~200 DEG C, described HTS and the mol ratio of water is 1：(2~30), pressure is self-generated pressure, organic base and HTS Mol ratio be 0.02~0.2:1.
21. according to the method described in claim 1~2,5,6 any one, it is characterised in that the polyalcohol be molecule in have 2 or more than 2 alcohol of hydroxyl, the carbon atom number having in the polyol molecule is 2~8；Described peroxide It is the compound with peroxide bridge in molecule.
22. according to the method described in claim 1~2,5,6 any one, it is characterised in that described peroxide is dioxygen One or more in water, tert-butyl peroxide, Peracetic acid, trifluoro Peracetic acid, described polyalcohol is glycerine, second two One or more in alcohol, hexylene glycol, diethylene glycol (DEG).
23. according to the method described in claim 1~2,5,6 any one, it is characterised in that described template be organic base and Organic quaternary ammonium salt；Described organic silicon source is organo-silicon ester, and described organo-silicon ester, its formula is Si (OR1)4, R1Selected from having 1~6 alkyl of carbon atom, described alkyl is branched-chain or straight-chain alkyl；Described solid silicon source is high-purity silicon dioxide Particle or SiO 2 powder, on the basis of butt weight, the SiO of the solid silicon source2Content is more than 99.99 weight %, with The total content of Fe, Al and Na of atom meter is less than 10ppm, and described titanium source is organic titanium source and/or inorganic ti sources.
24. according to the method described in claim 1~2,5,6 any one, it is characterised in that described solid silicon source is hard charcoal Black, the specific surface area of the white carbon is 20~1000m2/g。
25. in accordance with the method for claim 23, it is characterised in that described organo-silicon ester is quanmethyl silicate, silicic acid four One or more in ethyl ester, the butyl ester of silicic acid four, dimethyl diethyl estersil.
26. according to the method described in claim 1~2,5,6 any one, it is characterised in that described organic base is organic quaternary ammonium Alkali and/or organic amine, described organic amine are one or more in fatty amine, aromatic amine and hydramine；Described fatty amine Formula is R3(NH2)n, wherein R3It is with 1~4 alkyl or alkylidene of carbon atom, n=1 or 2；Described hydramine its lead to Formula is (HOR4)mNH(3-m), wherein R4It is with 1~4 alkyl of carbon atom, m=1,2 or 3；Described aromatic amine is with one Individual armaticity replaces the amine of base.
27. in accordance with the method for claim 26, it is characterised in that described fatty amine be ethamine, n-butylamine, butanediamine or One or more in hexamethylene diamine；Described hydramine is one or more in MEA, diethanol amine or triethanolamine；Institute The aromatic amine stated is one or more in aniline, toluidines, p-phenylenediamine.
28. in accordance with the method for claim 26, it is characterised in that described quaternary ammonium base be TPAOH, One or more in TBAH or tetraethyl ammonium hydroxide；Described organic quaternary ammonium salt be 4-propyl ammonium chloride, One kind or many in 4-propyl bromide, tetrabutylammonium chloride, TBAB, etamon chloride, tetraethylammonium bromide Kind.
29. according to the method described in claim 1~2,5,6 any one, it is characterised in that described HTS is TS-1 Molecular sieve, described organic quaternary ammonium salt is one or more in 4-propyl ammonium chloride, 4-propyl bromide, described organic base It is TPAOH and/or organic amine；Or, described HTS is TS-2 molecular sieves, described organic quaternary ammonium Salt is one or more in tetrabutylammonium chloride, TBAB, described organic base for TBAH and/or Organic amine；Or, described HTS is Ti- beta-molecular sieves, and described organic quaternary ammonium salt is etamon chloride, tetrem One or more in base ammonium bromide, described organic base is tetraethyl ammonium hydroxide and/or organic amine.
30. according to the method described in claim 1~2,5,6 any one, it is characterised in that described titanium source is tetraalkyl metatitanic acid Ester, TiCl4、Ti(SO4)2And one or more in their hydrolysate, the wherein carbon of the alkyl in tetraalkyl titanate Atomicity is 1,2,3,4,5 or 6.
31. according to the method described in claim 2 or 6, it is characterised in that unitary in the product that alcohol is obtained is caught up with step (1) hydrolysis The mass content of alcohol is no more than 10ppm.
32. in accordance with the method for claim 12, it is characterised in that inorganic source of ammonium is introduced in step (1), with NH4 +The nothing of meter Machine source of ammonium with TiO2The mol ratio of the titanium source of meter is 0.01~4:1.
33. according to the method described in claim 32, it is characterised in that with NH4 +Meter inorganic source of ammonium with TiO2The titanium source of meter Mol ratio be 0.05~0.5:1.
34. in accordance with the method for claim 24, it is characterised in that the specific surface area of the white carbon is 50~400m2/g。
35. in accordance with the method for claim 7, it is characterised in that the mol ratio of described titanium source and total silicon source for 0.008~ 0.03:1。
36. in accordance with the method for claim 7, it is characterised in that the mol ratio of described titanium source and total silicon source for 0.01~ 0.025:1。
37. in accordance with the method for claim 9, it is characterised in that the mol ratio of described template and described total silicon source It is 0.1~0.3:1.
38. in accordance with the method for claim 9, it is characterised in that the mol ratio of described template and described total silicon source It is 0.1~0.2:1.
39. in accordance with the method for claim 11, it is characterised in that the mol ratio of water and total silicon source is 5~30:1.
40. in accordance with the method for claim 11, it is characterised in that the mol ratio of water and total silicon source is 6~15:1.
41. in accordance with the method for claim 13, it is characterised in that the mol ratio of organic silicon source and solid silicon source is 1: (2~18).
42. in accordance with the method for claim 13, it is characterised in that the mol ratio of organic silicon source and solid silicon source is 1: (5~15).
43. in accordance with the method for claim 17, it is characterised in that the crystallization temperature of the crystallization is 160~180 DEG C.
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