CN104556104A - 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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CN104556104A
CN104556104A CN201410562400.1A CN201410562400A CN104556104A CN 104556104 A CN104556104 A CN 104556104A CN 201410562400 A CN201410562400 A CN 201410562400A CN 104556104 A CN104556104 A CN 104556104A
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silicon source
mol ratio
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CN104556104B (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
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    • 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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  • 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 using 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 novel hetero-atom molecular-sieve starting the early 1980s to develop.The TS-1 having MFI type structure synthesized at present, the TS-2 of MEL type structure, the MCM-22 of MWW type structure and the TS-48 etc. had compared with macroporous structure.Wherein TS-1 is that Italian EniChem company develops synthesis the earliest, transition metal titanium is introduced there is a kind of novel titanosilicate with superior catalytic selective oxidation performance formed in the framework of molecular sieve of ZSM-5 structure, TS-1 not only has the catalysed oxidn of titanium, but also the shape of selecting with ZSM-5 molecular sieve acts on and excellent stability.Adopt this HTS as catalyzer, can the polytype organic oxidizing reaction of catalysis, as the epoxidation of alkene, the partial oxidation of alkane, the oxidation of alcohols, the hydroxylation of phenols, the ammonia oxidation etc. of cyclic ketones.Because TS-1 molecular sieve is in organic oxidizing reaction, free of contamination lower concentration hydrogen peroxide can be adopted as oxygenant, avoid the problem of oxidising process complex process and contaminate environment, there is unrivaled energy-conservation, the advantage such as economy and environment is friendly of conventional oxidation system, and there is good reaction preference.HTS is as organism catalyst for selective oxidation; be considered to a milestone in molecular sieve catalytic field; can overcome from source that conventional catalyst oxidation system reaction process is complicated, condition is harsh and the drawback such as serious environment pollution; therefore it is in today of environmental protection requirement increasingly stringent, receives the especially great attention of people.
Nineteen eighty-three Taramasso is the reported first method of hydrothermal crystallization method synthesis of titanium silicon molecular sieve in patent US 4410501.This method is the classical way of synthesis TS-1, and main point glue and crystallization two step are carried out, and building-up process is as follows: tetraethoxy (TEOS) is put into nitrogen protection without CO 2container in, slowly add TPAOH (template), then slowly drip tetraethyl titanate (TEOT), stir lh, obtained a kind of reaction mixture containing silicon source, titanium source and organic bases, heating, except alcohol, moisturizing, 175 DEG C under autogenous pressure still stir under, crystallization 10 days, be then separated, wash, dry, roasting and TS-1 molecular sieve.But in this technique titanium to insert skeleton process influence factor numerous, the condition of hydrolysis and nucleation is all wayward, and the TS-1 molecular sieve of therefore this method synthesis exists that catalytic activity is low, poor stability, be difficult to synthesize and the drawback such as reproduction.
HTS (Zeolites disclosed in the people such as Thangaraj, 1992, Vol.12 943rd ~ 950 pages) in preparation method, in order to balance the hydrolysis rate of organosilicon and titanium, in the hydrolytic process of titanium, introduce Virahol, but the HTS activity that the method obtains is not high.
Chinese patent CN98101357.0 (CN1260241A) discloses HTS reordering technique, synthesize the novel titanosilicate with unique hollow structure, the circulation ratio of synthesis TS-1 is not only made greatly to strengthen, also add molecular sieve pores, substantially increase the mass transfer rate of diffusion of reactant molecule in molecular sieve pore passage, catalytic performance increases.The hydrating solution of titanium mixes according to the ratio of molecular sieve (gram): Ti (mole)=200 ~ 1500:1 with the TS-1 molecular sieve synthesized by method disclosed in this patent, gained mixture reacted 1 ~ 8 day in a kettle. with at 120 ~ 200 DEG C, filters, wash and drying.At present, HTS molecular sieve is applied to the processes such as oxidation phenol hydroxylation, cyclohexanone oxamidinating and has realized industrialization, has reaction conditions gentleness, atom utilization is high, technological process is simple and by product is the advantages such as water clean and effective.
The synthesis of current HTS uses quaternary ammonium base usually, but has quaternary ammonium hydroxide cost higher, and research consideration organic quaternary ammonium salt and organic bases are with the use of replacing quaternary ammonium base, but the HTS activity using organic quaternary ammonium salt to prepare at present is not high.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of new HTS synthetic method.
A synthetic method for HTS, comprise and titanium source, template, water, polyvalent alcohol, superoxide, silicon source and optional Inorganic Ammonium source are formed crystallization mixture, crystallization, recovery Pd si molecular sieves, described template is organic quaternary ammonium salt and organic bases.
HTS synthetic method provided by the invention, introduces polyvalent alcohol and superoxide in building-up process, and the mol ratio in polyvalent alcohol and silicon source is 0.01 ~ 0.8:1, and the mol ratio in superoxide and silicon source is 0.01 ~ 0.25:1.It is such as 0.05 ~ 0.5:1 that the mol ratio in polyvalent alcohol and total silicon source is preferably 0.05 ~ 0.7:1, and the mol ratio in superoxide and total silicon source can be 0.05 ~ 0.25:1 is such as 0.05 ~ 0.15:1.Described polyvalent alcohol is the alcohols containing two or more hydroxyls in molecule, preferably, in described polyol molecule, carbon atom number is 2 ~ 8, and described hydroxyl is such as 2 or 3, and described polyhydric alcohols is as one or more in glycerol, ethylene glycol, hexylene glycol, glycol ether.Described superoxide is the compound containing peroxide bridge, such as, in hydrogen peroxide, tert-butyl peroxide, Peracetic Acid, trifluoro Peracetic Acid etc. one or more.Introduce polyvalent alcohol and superoxide, make obtained HTS have less grain-size (or claiming grain size, the size of crystal grain short-axis direction), there is higher activity.
HTS synthetic method provided by the invention, described silicon source is organosilicon source and/or solid silicon source.Described titanium source is organic titanium source and/or inorganic ti sources.Described template is organic bases and organic quaternary ammonium salt, and described organic bases is as quaternary ammonium base and/or organic amine.The mol ratio in water, silicon Yuan Shui and total silicon source is 5 ~ 100:1; The mol ratio in template and total silicon source is 0.04 ~ 0.6:1; The mol ratio in polyvalent alcohol and total silicon source is 0.01 ~ 0.8, and the mol ratio in superoxide and total silicon source is 0.01 ~ 0.25:1; The mol ratio in titanium source and total silicon source is 0.005 ~ 0.05:1.In described mol ratio, described total silicon source (silicon source) is with SiO 2the organosilicon source of meter and the summation of solid silicon source.
HTS synthetic method provided by the invention, described silicon source is organosilicon source and/or solid silicon source.Described organosilicon source is organo-silicon ester, described organo-silicon ester, and its general formula is Si (OR 1) 4, R 1be selected from the alkyl such as R with 1 ~ 6 carbon atom 1for C 1-C 4alkyl, described alkyl can be branched-chain alkyl or straight chained alkyl.One or more in described organo-silicon ester such as quanmethyl silicate, tetraethyl orthosilicate, silicic acid four butyl ester, dimethyl diethyl estersil; One or more wherein preferably in quanmethyl silicate, tetraethyl orthosilicate, dimethyl diethyl estersil.The said solid silicon source of the present invention is highly purified silica solid or powder, such as, can be white carbon black and/or high-purity silica gel.Under preferable case, with butt weight for SiO in solid silicon source described in benchmark 2content is not less than 99.99 % by weight, and is less than 10ppm in the total mass content of element Fe, Al and Na impurity; Such as SiO 2content is 99.99 ~ 100 % by weight, is generally and is greater than 99.99 and is less than 100 % by weight.Described solid silicon source can be high-purity silica gel and/or white carbon black, preferred white carbon black; SiO in wherein said silica gel 2content is preferably greater than or equal to 99.99 % by weight such as being greater than 99.99 % by weight and being less than 100 % by weight, and the total mass content of Fe, Al and Na impurity is less than 10ppm.The specific surface area of described white carbon black is preferably between 20-1000m 2be such as 50-400m between/g 2/ g, with the butt weight of white carbon black for benchmark, SiO in described white carbon black 2it is such as 99.99 ~ 100 % by weight such as being greater than 99.99 % by weight and being less than 100 % by weight that content is preferably greater than or equal to 99.99 % by weight, is less than 10ppm in the total mass content of Fe, Al and Na impurity in the described white carbon black of atom.Described white carbon black can be purchased, or prepares according to existing method, the method preparation such as provided according to patent CN200910227646.2, and silicon tetrachloride and hydrogen and oxygen generation combustion reactions obtain by a kind of preparation method.
Described titanium source is organic titanic compound or inorganic titanium compound, such as tetraalkyl titanate (Ti (alkoxy) 4), TiCl 4, Ti (SO 4) 2and one or more in their hydrolysate.The carbonatoms of the alkyl wherein in tetraalkyl titanate is 1 ~ 6, such as, be 1,2,3,4,5 or 6.
HTS synthetic method provided by the invention, described template agent is organic bases and organic quaternary ammonium salt.Described organic bases is one or more in quaternary ammonium base, organic amine; Described organic amine is aliphatic amide, aromatic amine and/or hydramine, and described aliphatic amide (the present invention also claims fat amine compound), its general formula is R 3(NH 2) n, wherein R 3for there is alkyl or the alkylidene group of 1 ~ 4 carbon atom, n=1 or 2; Described hydramine (the present invention also claims alcamine compound) its general formula is (HOR 4) mnH (3-m), wherein R 4for having the alkyl of 1 ~ 4 carbon atom, m=1,2 or 3.One or more in described aliphatic amide such as ethamine, n-Butyl Amine 99, butanediamine or hexanediamine; Described aromatic amine refers to have the substituent amine of aromaticity, such as, in aniline, Tolylamine, Ursol D one or more; One or more in described hydramine such as monoethanolamine, diethanolamine or trolamine.One or more in described quaternary ammonium base such as TPAOH, TBAH or tetraethyl ammonium hydroxide; One or more in described organic quaternary ammonium salt such as 4-propyl bromide, Tetrabutyl amonium bromide, tetraethylammonium bromide, 4-propyl ammonium chloride, tetrabutylammonium chloride or etamon chloride.Under preferable case, described template comprises quaternary organic ammonium compounds, and containing organic bases.Described quaternary organic ammonium compounds such as quaternary ammonium base and/or organic quaternary ammonium salt, described organic bases is as quaternary ammonium base and/or organic amine.The mol ratio in organic quaternary ammonium salt and total silicon source is preferably 0.05 ~ 0.45:1, the mol ratio in organic bases and total silicon source is preferably 0.05 ~ 0.45:1, the mol ratio in preferred described organic quaternary ammonium salt and total silicon source is 0.05 ~ 0.3:1 such as 0.05 ~ 0.2:1, the mol ratio in described organic bases and total silicon source is 0.05 ~ 0.3:1, such as 0.05 ~ 0.2:1.
HTS synthetic method provided by the invention, a kind of embodiment, described HTS is TS-1 molecular sieve, and described organic quaternary ammonium salt is one or more in 4-propyl ammonium chloride, 4-propyl bromide; Described organic bases is TPAOH and/or organic amine
HTS synthetic method provided by the invention, a kind of embodiment, described HTS is TS-2 molecular sieve, and described organic quaternary ammonium salt is one or more in tetrabutylammonium chloride, Tetrabutyl amonium bromide; Described organic bases is TBAH and/or organic amine.
HTS synthetic method provided by the invention, a kind of embodiment, described HTS is Ti-beta-molecular sieve, and described organic quaternary ammonium salt is one or more in etamon chloride, tetraethylammonium bromide; Described organic bases is tetraethyl ammonium hydroxide and/or organic amine.
HTS synthetic method provided by the invention, described Inorganic Ammonium source is inorganic ammonium salt and/or ammoniacal liquor, and preferred ammoniacal liquor, with NH 4 +the Inorganic Ammonium source of meter and the mol ratio in titanium source are 0 ~ 5:1, such as, be 0.01 ~ 4:1, preferably 0.05 ~ 0.5:1.In the context of the present invention, introduce Inorganic Ammonium source and be conducive to the oxidation activity improving synthesized molecular sieve, improve framework titania silicon ratio.
HTS synthetic method provided by the invention, titanium source, template, water, polyvalent alcohol, superoxide and silicon source, optional Inorganic Ammonium source are formed crystallization mixture, then by described crystallization mixture crystallization, form crystallization product, crystallization product obtains HTS through recovery.Described crystallization, can adopt existing method, and such as, the temperature of crystallization is 110 ~ 200 DEG C, and crystallization time 0.2 ~ 20 day, carries out crystallization under autogenous pressure.A step crystallization can be adopted, also can adopt fractional crystallization.A kind of embodiment, the temperature of described crystallization is 140 ~ 180 DEG C such as 160 ~ 180 DEG C, and crystallization time is 0.5 ~ 10 day is such as 0.5 ~ 6 day, and crystallization pressure is autogenous pressure.A kind of embodiment, described crystallization is: 100 ~ 130 DEG C of such as 110 ~ 130 DEG C of crystallization 0.5 ~ 1.5 day, then crystallization 1 ~ 3 day at 160 ~ 180 DEG C, and crystallization pressure is autogenous pressure.
HTS synthetic method provided by the invention, described recovery Pd si molecular sieves is existing method, such as, generally includes by crystallization product filtration, washing and roasting or by crystallization product filtration, washing, drying then roasting.
HTS synthetic method provided by the invention, the first embodiment, comprises the following steps:
(1) by titanium source, template, water, polyvalent alcohol and the silicon source mixing of optional first time, alcohol is caught up with in hydrolysis; Then superoxide is added; Described first time silicon source is organosilicon source;
(2) product that obtains of step (1) is aging;
(3) add or do not add second time silicon source in the product that step (2) obtains, crystallization, recovery Pd si molecular sieves; Described second time silicon source is organosilicon source and/or solid silicon source;
Wherein, introduce described silicon source at least one step in step (1) and step (3), described template is organic quaternary ammonium salt and organic bases.
HTS synthetic method provided by the invention, in the first embodiment, the silicon source the present invention introduced in step (1) is called first time silicon source, the silicon source of introducing in step (3), and the present invention is called second time silicon source.The silicon source used is organosilicon source and/or solid silicon source, can only use organosilicon source, also only can use solid silicon source, use solid silicon source under preferable case.In the first embodiment described, preferably, described silicon source comprises organosilicon source and solid silicon source, and organosilicon source is introduced in step (1), and solid silicon source (inorganic silicon source) is introduced in step (3), wherein with SiO 2meter organosilicon source with SiO 2the molar ratio of the solid silicon source of meter is as being 0 ~ 1:20; Preferably with SiO 2meter organosilicon source with SiO 2the mol ratio of the solid silicon source of meter is 1:0.1 ~ 20, can obtain the HTS of surperficial Silicon-rich.
HTS synthetic method provided by the invention, in the first described embodiment, introduces polyvalent alcohol and superoxide in step (1).Introduce polyvalent alcohol and superoxide, make obtained HTS have higher activity, there is less grain-size (or claiming grain size, the size of crystal grain short-axis direction).Wherein the mol ratio in polyvalent alcohol and total silicon source is 0.01 ~ 0.8:1, the mol ratio in superoxide and total silicon source is 0.01 ~ 0.25:1 is such as 0.05 ~ 0.25:1, the mol ratio in organic quaternary ammonium salt and total silicon source is 0.04 ~ 0.56:1, organic bases be 0.04 ~ 0.5:1 with the mol ratio in total silicon source.In the present invention, described total silicon source is with SiO 2meter organosilicon source and with SiO 2the summation of the solid silicon source of meter; When only using organosilicon source, then described total silicon source is organosilicon source, and when only using described solid silicon source, then described total silicon source is solid silicon source; When use solid silicon source and organosilicon source, then described total silicon source is solid silicon source and organosilicon source sum.
HTS synthetic method provided by the invention, in the first described embodiment, the mol ratio in described titanium source and total silicon source is 0.005 ~ 0.05:1, such as, be 0.008 ~ 0.3:1 or 0.01 ~ 0.025:1, and the molar ratio in further titanium source and total silicon source is as 0.015 ~ 0.025:1.Described total silicon source (silicon source) is organosilicon source and solid silicon source, described template and with SiO 2the mol ratio in total silicon source of meter is 0.08 ~ 0.6:1, such as, be 0.1 ~ 0.5:1 or 0.1 ~ 0.3:1 or be 0.1 ~ 0.2:1; The mol ratio in described water and total silicon source is 5 ~ 100:1, such as, be 5 ~ 80:1 or 6 ~ 50:1 or 6 ~ 30:1 or 6 ~ 15:1.
HTS synthetic method provided by the invention, in the first described embodiment, the Inorganic Ammonium source described in step (1) is inorganic ammonium salt and/or ammoniacal liquor, and preferred ammoniacal liquor, with NH 4 +the Inorganic Ammonium source of meter and the mol ratio in titanium source are 0 ~ 5:1, such as, be 0.01 ~ 4:1, preferably 0.05 ~ 0.5:1.In the context of the present invention, introduce Inorganic Ammonium source and be conducive to the oxidation activity improving synthesized molecular sieve, improve framework titania silicon ratio.
HTS synthetic method provided by the invention, in the first described embodiment, by titanium source, template, water, polyvalent alcohol, optional organosilicon source and the mixing of optional Inorganic Ammonium source in step (1), optional organosilicon source, titanium source, template, optional Inorganic Ammonium source, water and polyvalent alcohol can be mixed, be hydrolyzed and catch up with alcohol according to any method, make organosilicon source and the hydrolysis of titanium source, reduce the content of the monohydroxy-alcohol that hydrolysis produces.Described hydrolysis catches up with alcohol within least 10 minutes, such as can stir 10 ~ 3000 minutes for being stirred at 0 ~ 150 DEG C such as 0 ~ 100 DEG C preferably 50 ~ 95 DEG C by the mixture comprising organosilicon source and/or titanium source and water, to make organosilicon source and the hydrolysis of titanium source, and reduce the content of the alcohol of organosilicon source and titanium source (if hydrolysis produces monohydroxy-alcohol) hydrolysis generation.Preferably, the content being hydrolyzed the monohydroxy-alcohol of the water in products solution generation of catching up with alcohol to obtain is no more than 10ppm (quality), and preferably, described hydrolysis catches up with the mass content of monohydroxy-alcohol in alcohol product to be no more than 10ppm.
HTS synthetic method provided by the invention, in the first described embodiment, in step (2), by aging for step (1) products therefrom, described aging be, at room temperature ~ 50 DEG C, step (1) products therefrom is left standstill 1 ~ 60 hour.Described room temperature is 15 ~ 40 DEG C; Digestion time is 1 ~ 60 hour is such as 3 ~ 50 hours preferably 3 ~ 15 hours, does not stir in weathering process, described material and step (1) products therefrom is left standstill.
HTS synthetic method provided by the invention, in the first described embodiment, described crystallization, can adopt existing method, and such as, the temperature of crystallization is 110 ~ 200 DEG C, and crystallization time 0.2 ~ 20 day, carries out crystallization under autogenous pressure.A step crystallization can be adopted, also can adopt fractional crystallization.A kind of embodiment, the temperature of described crystallization is 140 ~ 180 DEG C such as 160 ~ 180 DEG C, and crystallization time is 0.5 ~ 10 day is such as 0.5 ~ 6 day, and crystallization pressure is autogenous pressure.A kind of embodiment, described crystallization is: 100 ~ 130 DEG C of such as 110 ~ 130 DEG C of crystallization 0.5 ~ 1.5 day, then crystallization 1 ~ 3 day at 160 ~ 180 DEG C, and crystallization pressure is autogenous pressure.
HTS synthetic method provided by the invention, can improve the oxidation activity of synthesized molecular sieve, and improve the utilization ratio of titanium, synthesized HTS can have less crystal grain.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of titanium silicon TS-1 molecular sieve prepared by the embodiment of the present invention.
Fig. 2 is the XRD spectra of Ti-beta-molecular sieve prepared by the embodiment of the present invention.
Fig. 3 is titaniferous beta-molecular sieve (also known as Ti-beta-molecular sieve) the SEM scintigram of embodiment of the present invention synthesis.
Fig. 4 is that the TEM through the titanium silicon TS-1 molecular sieve reset prepared by the embodiment of the present invention schemes.
Fig. 5 is the measuring method schematic diagram of surface silicon titanium ratio and body phase silicon titanium ratio.For the schematic diagram utilizing TEM-EDX to measure body phase silicon titanium ratio and surface silicon titanium ratio, wherein square frame 1 illustrates that the silicon titanium ratio in measurement grain edges region, square frame 2 illustrate to measure the silicon titanium ratio in granular center region.Because grain edges area unit volume has higher outer surface area, and in the unit volume of central zone, corresponding outer surface area is lower, and therefore in square frame 1 and square frame 2, EDX measuring result can reflect that difference is compared with the silicon titanium of body phase in surface.
Embodiment
HTS synthetic method provided by the invention, one preferred embodiment, comprises the steps:
(1) by template, titanium source, organosilicon source, water, polyvalent alcohol and the mixing of optional Inorganic Ammonium source, alcohol is caught up with in hydrolysis, then adds superoxide; Alcohol is caught up with in described hydrolysis, and usually stirred at least 10 minutes by the mixture of gained at 0 ~ 150 DEG C such as 0 ~ 100 DEG C such as 50 ~ 95 DEG C, the churning time wherein stirred is 10 minutes ~ 50 hours; Wherein Inorganic Ammonium source is (with NH 4 +meter): titanium source is (with TiO 2meter) mol ratio be 0 ~ 5:1;
(2) by aging for step (1) products therefrom, described aging be that step (1) products therefrom is left standstill 1 ~ 60 hour such as 3 ~ 30 hours, such as 3 ~ 15 hours further at room temperature ~ 50 DEG C;
(3) ageing products that step (2) obtains is mixed with the weight ratio of solid silicon source according to 1:0.1 ~ 20, then crystallization such as crystallization in closed reactor, recovery Pd si molecular sieves; In wherein said part by weight, the ageing products that step (2) obtains and solid silicon source are all with SiO 2meter;
Wherein, the mol ratio in water and total silicon source is 5 ~ 100:1; The mol ratio in template and total silicon source is 0.08 ~ 0.6:1 be such as 0.1 ~ 0.5:1 to be such as 0.15 ~ 0.3:1 or to be 0.1 ~ 0.2:1; The mol ratio in titanium source and total silicon source is 0.005 ~ 0.05:1 is such as 0.01 ~ 0.03:1, is 0.01 ~ 0.025:1 further; Described template is organic quaternary ammonium salt and organic bases, and the mol ratio in organic quaternary ammonium salt and total silicon source is 0.04 ~ 0.6:1, and the mol ratio in organic bases and total silicon source is 0.04 ~ 0.5:1, and described organic bases is as organic amine;
Wherein, in described mol ratio, total silicon source is with SiO 2meter, described total silicon source is with SiO 2meter organosilicon source and with SiO 2the summation of the solid silicon source of meter, Inorganic Ammonium source is with NH 4 +meter; Described Inorganic Ammonium source is inorganic ammonium salt and/or ammoniacal liquor, and titanium source is with TiO 2meter, water is with H 2o counts.
HTS synthetic method provided by the invention, preferred embodiment described, prepared zeolite crystal surface Silicon-rich, grain surface silicon titanium ratio is apparently higher than body phase silicon titanium ratio, the ratio of grain surface silicon titanium mol ratio and body phase silicon titanium mol ratio is 1.1 ~ 5:1, such as, be 1.2 ~ 4:1 or be 1.3 ~ 3:1.The HTS obtained, there is higher surface silicon titanium ratio and the ratio of body phase silicon titanium ratio, there is higher oxidation activity, for the oxidizing reaction that hydrogen peroxide participates in, titanium can be reduced in upper layer to the decomposition of hydrogen peroxide, be conducive to the activity of the decomposition side reaction reducing hydrogen peroxide, improve raw material availability.In addition, HTS synthetic method provided by the invention, preferred embodiment use the relatively inexpensive solid silicon source be easy to get such as high-purity silica gel or/and white carbon black, part replaces expensive organosilicon source, the waste discharge of process of producing molecular sieve can be reduced and economize in raw materials while cost and obtain high performance HTS, can at lower template agent consumption and lower water silicon than synthesis of titanium silicon molecular sieve in situation, the synthesis cost of HTS can be reduced, improve the solid content of synthesis of molecular sieve crystallization product, improve single still molecular sieve output.
Surface silicon titanium ratio and body phase silicon titanium ratio can adopt TEM-EDX or ion excitation corrosion XPS means to measure and obtain, wherein, surface silicon titanium ratio can adopt TEM-EDX or ion excitation corrosion XPS means to measure and obtain, for distance grain surface is no more than the silicon titanium ratio of the atomic shell of 5nm such as 1 ~ 5nm; Body phase titanium silicon obtains than by chemico-analytic method, or is obtained by the TEM-EDX area measure that such as distance grain surface distance is greater than 20nm in the central zone of crystal grain, or is obtained by XRF analysis.
HTS synthetic method provided by the invention, preferred embodiment described, can in lower template agent consumption situation synthesis of titanium silicon molecular sieve, thus template agent consumption can reduce, such as template agent with in the mol ratio in total silicon source of silicon-dioxide for 0.1 ~ 0.3:1, be 0.1 ~ 0.20:1 further; In method provided by the invention, can at synthesis of titanium silicon molecular sieve under high solids content, from can and reduce the usage quantity of water, improve output per single reactor and namely under same synthesis reactor volume, synthesize more molecular sieve, therefore described water is with can be 5 ~ 50:1 in the mol ratio in total silicon source of silicon-dioxide be such as 5 ~ 30 or for 6 ~ 15:1.
HTS synthetic method provided by the invention, described preferred embodiment in, it is such as 0.01 ~ 0.025:1 that the mol ratio in described titanium source and total silicon source is preferably 0.01 ~ 0.03:1.
HTS synthetic method provided by the invention, described preferred embodiment in, the mol ratio in Inorganic Ammonium source and titanium source is 0 ~ 5:1, such as, be 0.01 ~ 4:1, be preferably 0.05 ~ 0.5:1.Add Inorganic Ammonium source, the activity of synthesized molecular sieve can be improved, improve framework titania silicon ratio.
The synthetic method of HTS provided by the invention, described preferred embodiment in, the mol ratio in described template and described total silicon source is not less than 0.08:1, and to be preferably 0.1 ~ 0.3:1 be such as 0.1 ~ 0.2:1.
HTS synthetic method provided by the invention, described preferred embodiment described in the mol ratio in solid silicon source and organosilicon source be preferably 1 ~ 19:1, be such as 2 ~ 18:1, or 3 ~ 17:1, or be 5 ~ 15:1.The ageing products that usual step (2) obtains equals the mol ratio of organosilicon source and solid silicon source with the ratio of solid silicon source.
HTS synthetic method provided by the invention, described preferred embodiment in, the template agent described in step (1) is organic bases and organic quaternary ammonium salt, and described organic bases is one or more in quaternary ammonium base, organic amine; Such as, described template is the mixture of quaternary ammonium base and organic quaternary ammonium salt, organic amine and the mixture of organic quaternary ammonium salt or the mixture of quaternary ammonium base and organic quaternary ammonium salt and organic amine.Described organic amine is aliphatic amide, aromatic amine and/or hydramine, and described aliphatic amide (the present invention also claims fat amine compound), its general formula is R 3(NH 2) n, wherein R 3for there is alkyl or the alkylidene group of 1 ~ 4 carbon atom, n=1 or 2; Described hydramine (the present invention also claims alcamine compound) its general formula is (HOR 4) mnH (3-m), wherein R 4for having the alkyl of 1 ~ 4 carbon atom, m=1,2 or 3.One or more in described aliphatic amide such as ethamine, n-Butyl Amine 99, butanediamine or hexanediamine; Described aromatic amine refers to have the substituent amine of aromaticity, such as, in aniline, Tolylamine, Ursol D one or more; One or more in described hydramine such as monoethanolamine, diethanolamine or trolamine.One or more in described quaternary ammonium base such as TPAOH, TBAH or tetraethyl ammonium hydroxide; One or more in described organic quaternary ammonium salt such as 4-propyl bromide, Tetrabutyl amonium bromide, tetraethylammonium bromide, 4-propyl ammonium chloride, tetrabutylammonium chloride or etamon chloride.
HTS synthetic method provided by the invention, described preferred embodiment in, a kind of embodiment, described HTS is TS-1 molecular sieve, described organic bases is TPAOH and/or organic amine, and described organic quaternary ammonium salt is one or more in 4-propyl ammonium chloride, 4-propyl bromide.
HTS synthetic method provided by the invention, described preferred embodiment in, a kind of embodiment, described HTS is TS-2 molecular sieve, described organic bases is TBAH and/or organic amine, and described organic quaternary ammonium salt is tetrabutylammonium chloride, one or more mixtures formed in Tetrabutyl amonium bromide.。
HTS synthetic method provided by the invention, described preferred embodiment in, a kind of embodiment, described HTS is Ti-beta-molecular sieve, described organic bases is tetraethyl ammonium hydroxide and/or organic amine, and described organic quaternary ammonium salt is one or more in etamon chloride, tetraethylammonium bromide.
HTS synthetic method provided by the invention, described preferred embodiment in, the organosilicon source described in step (1) is organo-silicon ester, described organo-silicon ester, and its general formula is Si (OR 1) 4, R 1be selected from the alkyl such as R with 1 ~ 6 carbon atom 1for C 1-C 4alkyl, described alkyl can be branched-chain alkyl or straight chained alkyl.One or more in described organo-silicon ester such as quanmethyl silicate, tetraethyl orthosilicate, silicic acid four butyl ester, dimethyl diethyl estersil; One or more wherein preferably in quanmethyl silicate, tetraethyl orthosilicate, dimethyl diethyl estersil.Said solid silicon source is highly purified silica solid or powder, such as, can be white carbon black and/or high-purity silica gel.Under preferable case, with butt weight for SiO in solid silicon source described in benchmark 2content is not less than 99.99 % by weight, and is less than 10ppm in the total mass content of atom Fe, Al and Na impurity; Such as SiO 2content is 99.99 ~ 100 % by weight, is generally and is greater than 99.99 and is less than 100 % by weight.Described solid silicon source can be high-purity silica gel and/or white carbon black, preferred white carbon black; SiO in wherein said high-purity silica gel 2content is preferably greater than or equal to 99.99 % by weight such as being greater than 99.99 % by weight and being less than 100 % by weight, and the mass content of the impurity such as Fe, Al and Na is less than 10ppm; The specific surface area of described white carbon black is preferably between 20-1000m 2/ g is 50-400m such as 2between/g, with the butt weight of white carbon black for benchmark, SiO in described white carbon black 2it is such as 99.99 ~ 100 % by weight such as being greater than 99.99 % by weight and being less than 100 % by weight that content is preferably greater than or equal to 99.99 % by weight, and in atom, in described white carbon black, the quality total content of Fe, Al and Na is less than 10ppm.Described white carbon black can be purchased, or prepares according to existing method, the method preparation such as provided according to patent CN200910227646.2, and silicon tetrachloride and hydrogen and oxygen generation combustion reactions obtain by a kind of preparation method.
HTS synthetic method provided by the invention, described preferred embodiment in, described titanium source is organic titanic compound or inorganic titanium compound, such as tetraalkyl titanate (Ti (alkoxy) 4, TiCl 4, Ti (SO 4) 2and one or more in their hydrolysate, described titanium source is preferably organic titanic compound.The carbonatoms of the alkyl wherein in tetraalkyl titanate is 1 ~ 6, such as, be 1,2,3,4,5 or 6.The mol ratio in titanium source and silicon source (total silicon source) is preferably 0.01 ~ 0.025:1 such as 0.015 ~ 0.025:1.
HTS synthetic method provided by the invention, described preferred embodiment in, Inorganic Ammonium source described in step (1) is inorganic ammonium salt and/or ammoniacal liquor, obtains one or more in described inorganic ammonium salt such as ammonium chloride, ammonium nitrate, ammonium sulfate.Described Inorganic Ammonium source is preferably ammoniacal liquor, with NH 4 +meter ammoniacal liquor with TiO 2the mol ratio in titanium source of meter is 0 ~ 5:1 to be such as 0.01 ~ 4:1 or to be 0.05 ~ 0.5:1.Add described inorganic quaternary ammonium salts, the activity of synthesized molecular sieve can be improved, improve described surface silicon titanium than the ratio with body phase silicon titanium ratio.
In HTS synthetic method provided by the invention, described preferred embodiment in, in step (1) by titanium source, template, organosilicon source, Inorganic Ammonium source and water by mixing, be hydrolyzed and catch up with alcohol.Alcohol is caught up with in described hydrolysis, for 0 ~ 150 DEG C preferably 0 ~ 100 DEG C such as 50 ~ 95 DEG C stir at least 10 minutes, to make organosilicon source and the hydrolysis of titanium source, and reduce the alcohol content in gained mixture.Usual churning time is 10 ~ 3000 minutes, such as, be 2 ~ 30 hours.Catch up with alcohol by hydrolysis, obtain the hydrolyzed solution of clear.In the mixture that step (1) obtains, the content of monohydroxy-alcohol is not preferably higher than 10ppm (quality).Catch up with alcohol by hydrolysis, obtain organosilicon source and the titanium source hydrolyzed solution of clear, then add superoxide and stir, usual churning time is 10 ~ 60 minutes.Described polyvalent alcohol is the alcohols containing two or more hydroxyls in molecule, in preferably described polyol molecule, carbon atom number is 2 ~ 8, described hydroxyl is such as 2 or 3, and described polyhydric alcohols is as one or more in glycerol, ethylene glycol, hexylene glycol, glycol ether.Described superoxide is the compound containing peroxide bridge, one or more in the preferred hydrogen peroxide of described superoxide, tert-butyl peroxide, Peracetic Acid, trifluoro Peracetic Acid etc.The mol ratio in polyvalent alcohol and silicon source is 0.01 ~ 0.8:1, and being preferably 0.01 ~ 0.7:1 is such as 0.05 ~ 0.5:1; The mol ratio in superoxide and silicon source is 0.01 ~ 0.25:1, such as, be 0.05 ~ 0.25:1 or 0.05 ~ 0.15:1.
HTS synthetic method provided by the invention, described preferred embodiment in, in step (2), by aging for step (1) products therefrom, described aging be, at room temperature ~ 50 DEG C, step (1) products therefrom is left standstill 1 ~ 60 hour.Described room temperature is 15 ~ 40 DEG C; Digestion time is 1 ~ 60 hour is such as 2 ~ 50 hours, and preferably 3 ~ 30 hours is such as 3 ~ 15 hours, does not stir in weathering process, described material and step (1) products therefrom is left standstill.
HTS synthetic method provided by the invention, described preferred embodiment in, in step (3), the ageing products that step (2) obtains is mixed with solid silicon source, with SiO 2meter, the mol ratio of the product that step (2) obtains and solid silicon source is 1:0.1 ~ 20, such as, can be 1:1 ~ 19 (namely the mol ratio of described organosilicon source and solid silicon source is 1:1 ~ 19), or be 1:2 ~ 18 or 1:3 ~ 17, be 1:5 ~ 15 further, with SiO 2the mol ratio of meter organosilicon source and solid silicon source is preferably 1:5 ~ 15.Method provided by the invention, can use the solid silicon source of higher proportion, can improve the solid content of synthetic product, thus be used alone the output improving single compared with organosilicon source when synthesis reaction vessel is constant and synthesize.
HTS synthetic method provided by the invention, described preferred embodiment in, step (3) described crystallization, the temperature of crystallization is 110 ~ 200 DEG C, crystallization pressure is autogenous pressure, the time of crystallization is 2 hours ~ 20 days, the time of usual described crystallization is 0.5 ~ 20 day, such as crystallization time is 1 ~ 10 day, the temperature of the crystallization described in further step (3) is 140 ~ 180 DEG C and is such as 160 ~ 180 DEG C, crystallization time is 0.5 ~ 6 day is such as 1 ~ 6 day, is such as 1 ~ 3 day further.Crystallization pressure is autogenous pressure.Described crystallization can be carried out in stainless steel stirring tank.Crystallization heat up can one section heat up also can multistage heating mode.Temperature rise rate can carry out according to existing crystallization temperature-rising method, such as, be 0.5-1 DEG C/min.Described crystallization can be carried out in stainless steel stirring tank.A kind of embodiment, the crystallization temperature of described crystallization is 160 ~ 180 DEG C, and crystallization time is 1 ~ 6 day such as 0.5 ~ 3 day, and crystallization pressure is autogenous pressure.A kind of embodiment, the crystallization described in step (3) is: crystallization 0.5 ~ 1.5 day at 100 ~ 130 DEG C such as 110 ~ 130 DEG C, then crystallization 1 ~ 3 day at 160 ~ 180 DEG C, and crystallization pressure is autogenous pressure.
HTS synthetic method provided by the invention, described preferred embodiment in, described in step (3), recovery Pd si molecular sieves is existing method, comprises by crystallization product filtration, washing and roasting or by crystallization product filtration, washing, drying then roasting.The object of filtering is that HTS crystallization obtained is separated with crystallization mother liquor, the object of washing washes away the template being adsorbed on sieve particle surface, can be such as room temperature ~ 50 DEG C in temperature, the weight ratio 1:1 ~ 20 such as 1:(1-15 of molecular sieve and water) under carry out mixing, washing or drip washing.Dry object is the most of moisture in removing molecular sieve, and to reduce water evaporation quantity when roasting, dry temperature can be 100 ~ 200 DEG C.The object of roasting is the template in removing molecular sieve, and the temperature of such as described roasting is 350 ~ 650 DEG C, and roasting time is 2-10 hour.HTS product provided by the present invention is obtained by reclaiming.
In HTS synthetic method provided by the invention, reclaim the HTS obtained and also can be passed through further process, i.e. HTS synthetic method provided by the invention, can also comprise following rearrangement step (for the first embodiment of the present invention or preferred embodiment for, the present invention is also referred to as step (4)):
HTS Crystallizing treatment preferably Crystallizing treatment in organic quaternary ammonium alkaline solution, then the recovery Pd si molecular sieves in organic alkali solution obtained will be reclaimed.This process makes obtained HTS have hollow structure, and the present invention is referred to as molecular sieve and resets.This process comprises and will reclaim the HTS that obtains and organic bases, water form mixture according to the mol ratio of 1:0.02 ~ 0.5:2 ~ 50, in 100 ~ 200 DEG C such as 110 ~ 150 DEG C or 120 ~ 200 DEG C of crystallization 0.1 ~ 10 day in closed reactor and under autogenous pressure, then reclaim product.Wherein HTS is (with SiO 2meter) be 1:0.02 ~ 0.5 with the mol ratio of organic bases be such as 1:0.02 ~ 0.2, with SiO 2the HTS of meter and the mol ratio of water are that 1:2 ~ 50 are such as 1:2 ~ 30 are such as 1:5 ~ 10 further, crystallization temperature is 100 ~ 200 DEG C such as 120 ~ 200 DEG C, crystallization pressure is autogenous pressure, crystallization time 0.5 ~ 10 day, such as, be 0.5 ~ 8 day or 1 ~ 6 day.Preferably, the crystallization temperature described in rearrangement step is 150-200 DEG C, and crystallization time is 0.5 ~ 6 day.Recovery method is existing method, can refer to the recovery method preferred embodiment described in step (3), generally includes crystallization product filtration, washing, so dry and roasting.Organic bases described in rearrangement step is quaternary ammonium base and/or organic amine, one or more the mixture in described quaternary ammonium base such as TPAOH, TBAH or tetraethyl ammonium hydroxide.Described organic bases is one or more in quaternary ammonium base, organic amine; Described organic amine is one or more in aliphatic amide, aromatic amine and hydramine, and described aliphatic amide (the present invention also claims fat amine compound), its general formula is R 3(NH 2) n, wherein R 3for there is alkyl or the alkylidene group of 1 ~ 4 carbon atom, n=1 or 2; Described hydramine (the present invention also claims alcamine compound) its general formula is (HOR 4) mnH (3-m), wherein R 4for having the alkyl of 1 ~ 4 carbon atom, m=1,2 or 3.One or more in described aliphatic amide such as ethamine, n-Butyl Amine 99, butanediamine or hexanediamine; Described aromatic amine refers to have the substituent amine of aromaticity, such as, in aniline, Tolylamine, Ursol D one or more; One or more in described hydramine such as monoethanolamine, diethanolamine or trolamine.A kind of embodiment, the HTS described in rearrangement step is TS-1 molecular sieve, and described quaternary ammonium base is TPAOH.A kind of embodiment, described HTS is TS-2 molecular sieve, and the quaternary ammonium base described in rearrangement step is TBAH.A kind of embodiment, described HTS is Ti-beta molecular sieve (Ti-beta-molecular sieve), and the quaternary ammonium base described in rearrangement step is tetraethyl ammonium hydroxide.
Molecular sieve rearrangement step, this process can be carried out once, also can repeat one or many, described repetition, processes the HTS obtained process according to the method for rearrangement step by rearrangement.By resetting process, can obtain the HTS with secondary pore structure, the crystal grain of gained HTS is hollow structure (also claiming described molecular sieve to have hollow structure), has larger pore volume and specific surface area; The radical length of the chamber portion of this hollow crystal grain is 5 ~ 300nm, at 25 DEG C, and P/P 0=0.10, the benzene adsorptive capacity recorded under the adsorption time condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm.
HTS synthetic method provided by the invention, may be used for synthesis of titanium silicon molecular sieve, and described HTS is TS-1 molecular sieve, TS-2 molecular sieve, Ti-MCM-22, TS-48 or Ti-beta-molecular sieve such as.
The present invention is further illustrated for the following examples, but therefore do not limit the present invention.Reagent used in embodiment is unaccounted is commercially available analytical reagent.
The measuring method of the grain size (short-axis direction) in embodiment and surface silicon titanium ratio and body phase silicon titanium ratio adopts TEM-EDX, TEM electron microscope experiment carries out on FEI Co. Tecnai F20G2S-TWIN type transmission electron microscope, be furnished with the energy filter system GIF2001 of Gatan company, annex is equipped with X-ray energy spectrometer.Electron microscopic sample adopts the method for suspended dispersed to be prepared on micro-grid of diameter 3mm.Its surface silicon titanium of each sample random selecting 20 particle sizings ratio and body phase silicon titanium ratio in embodiment, gauging surface silicon titanium than and the ratio of body phase silicon titanium ratio, the mean value then getting its 20 samples compares as described sample surfaces silicon titanium and the ratio of body phase silicon titanium ratio.
XRD measuring method: X-ray diffraction (XRD) the crystalline phase figure carrying out sample on Siemens D5005 type x-ray diffractometer measures, and gamma ray source is CuK α tube voltage 40kV, tube current 40mA, sweep velocity 0.5 °/min, sweep limit 2 θ=4 ° ~ 40 °.
The testing method of BET specific surface area and pore volume adopts N2 adsorption volumetry, according to BJH method of calculation.(see Petrochemical Engineering Analysis method (RIPP test method), RIPP151-90, Science Press, nineteen ninety publishes)
In embodiment and comparative example, raw materials used character is as follows:
Tetrabutyl titanate, analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group.
Titanyl sulfate, analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group.
TPAOH, great You chemical plant, Guangdong.
Tetraethyl orthosilicate, analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group.
Ammoniacal liquor, analytical pure, concentration 20 % by weight.
Glycerine, analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group.
Glycol ether, analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group.
White carbon black, Zhejiang Ju Hua group product, model AS-150; Solid content is greater than 95 % by weight, and in butt, dioxide-containing silica is greater than 99.99 % by weight, and the total content of iron, sodium and Al is less than 10ppm, and specific surface area is 195m 2/ g.
All the other reagent are commercially available product without what further illustrate, analytical pure
Comparative example 1
This comparative example illustrates prepares conventional HTS (Zeolites, 1992, Vol.12 943rd ~ 950 pages) according to the method for the people such as Thangaraj.
22.5g tetraethyl orthosilicate is mixed with the 7.0g TPAOH aqueous solution (concentration 25.05 % by weight), adds 59.8g deionized water Homogeneous phase mixing; Then at 60 DEG C, be hydrolyzed 1.0h, obtain the hydrating solution of tetraethyl orthosilicate.Again under the effect of vigorous stirring, in above-mentioned solution, slowly instill the solution be made up of 1.1g tetrabutyl titanate and 5.0g Virahol, this mixture is stirred 3h at 75 DEG C, obtains the colloid of clear.Moved in stainless steel closed reactor by this colloid, thermostatic crystallization 3 days at 170 DEG C, can obtain conventional TS-1 molecular sieve again.
Comparative example 2
This comparative example illustrates that HTS molecular sieve used is according to prepared by patent CN98101357.0.
22.5g tetraethyl orthosilicate is mixed with the 9.0g TPAOH aqueous solution (concentration 25.05 % by weight), adds 64.5g deionized water Homogeneous phase mixing; Then at 60 DEG C, be hydrolyzed 1.0h, obtain the hydrating solution of tetraethyl orthosilicate.Again under the effect of vigorous stirring, in above-mentioned solution, slowly instill the solution be made up of 0.6g tetrabutyl titanate and 7.0g Virahol, this mixture is stirred 7h at 75 DEG C, obtains the colloid of clear.Moved in stainless steel closed reactor by this colloid, thermostatic crystallization 3 days at 170 DEG C, can obtain conventional TS-1 molecular sieve again.
Again by tetrabutyl titanate, anhydrous isopropyl alcohol, TPAOH and the deionized water molar ratio Homogeneous phase mixing according to 1:15:2.4:350, at lower 45 DEG C of normal pressure, be hydrolyzed 30 minutes, obtain the hydrating solution of tetrabutyl titanate.Get the TS-1 molecular sieve of above-mentioned preparation, according to molecular sieve (g): the ratio of Ti (mol)=600:1 and the hydrating solution Homogeneous phase mixing of above-mentioned tetrabutyl titanate, uniform stirring 12h under normal temperature, finally scattered suspension liquid is put into stainless steel cauldron, place 3 days at 165 DEG C, described HTS molecular sieve.
Embodiment 1
8.5g tetraethyl orthosilicate, 0.45g glycerine are mixed with the 3.4g 4-propyl bromide aqueous solution (concentration 25.05 % by weight), 0.33g triethylamine, adds 24.34g deionized water Homogeneous phase mixing; Then at 60 DEG C, be hydrolyzed 1.0h, obtain the hydrating solution of tetraethyl orthosilicate.Acutely stirring againunder the effect of mixing, slowly instill the solution be made up of 1.1g tetrabutyl titanate and 5.0g Virahol, this mixture is stirred 3h at 75 DEG C, obtains the colloid of clear in above-mentioned solution, adding 0.36 gram of concentration is 30 % by weight hydrogen peroxide.Moved in stainless steel closed reactor by this colloid, at 170 DEG C, thermostatic crystallization 3 days, can obtain TS-1 molecular sieve again.Its XRD analysis spectrogram as shown in Figure 1, has MFI structure.
Comparative example 3
According to the method for embodiment 1, unlike not adding described glycerine.
Comparative example 4
By the method according to embodiment 1, unlike not adding described hydrogen peroxide.
Embodiment 2
(1) by 19.6g concentration be 25.05 % by weight the 4-propyl bromide aqueous solution, 2.18g triethylamine, 2.04g tetrabutyl titanate, 8.5g tetraethyl orthosilicate, 4.87g glycerine, 2g concentration be 20 % by weight ammoniacal liquor and 49.04g water join successively in the beaker of 500ml, put into heating and agitating function magnetic stirring apparatus on mix, and heat 4 hours at 80 DEG C, supplement the moisture of evaporation at any time, obtain water white transparency hydrolyzed solution, then add the hydrogen peroxide that 1.16g concentration is 30 % by weight, stir;
(2) within 12 hours, carry out aging by room temperature standing for step (1) products therefrom, obtain ageing products;
(3) in above-mentioned ageing products, 9.36g white carbon black powder is added under stirring, add rear stirring 1 hour, formed a kind of " viscous body ", transferred in stainless steel closed reactor, in 165 DEG C of thermostatic crystallizations 2 days, obtain TS-1 sample, by obtain TS-1 sample filtering, washing, at 120 DEG C dry 24 hours, 550 DEG C of roastings 6 hours, titanium silicon TS-1 zeolite product of the present invention is designated as TS-1F1; Its BET specific surface area is 430m 2/ g, outer surface area is 59m 2/ g, micro pore volume is 0.170mL.g -1, mesopore volume is 0.083mL.g -1, its XRD analysis spectrogram as shown in Figure 1;
(4) by TS-1F1 sample described in 6g and concentration be 22.05 % by weight TPAOH aqueous solution Homogeneous phase mixing, the weight ratio of described TS-1F1 and the TPAOH aqueous solution is 1:5,150 DEG C of crystallization 3 days in airtight reactor, filter, wash, drying 24 hours at 120 DEG C, 550 DEG C of roastings 6 hours, reset TS-1 product, be designated as TS-1P1.Its BET specific surface area is 448m 2/ g, outer surface area is 60m 2/ g, micro pore volume is 0.155mL.g -1, mesopore volume is 0.176mL.g -1in transmission electron microscope photo, it is hollow structure (shown in Fig. 4).
Embodiment 3
(1) by 25.45g concentration be 25.05 % by weight 4-propyl bromide, 3.34g tetrabutyl titanate, 2.43g triethylamine, 8.5g tetraethyl orthosilicate, 35.66 grams of glycol ethers, 0.05g concentration be 20 % by weight ammoniacal liquor and 51.84g water join successively in the beaker of 500ml, put into heating and agitating function magnetic stirring apparatus on mix, and heat 1 hour at 90 DEG C, supplement the moisture of evaporation at any time, obtain water white transparency alkaline hydrolysis liquid, then add 10.61g tertbutyl peroxide (TBHP), stir;
(2) product of (1) gained is at room temperature left standstill 12 hours, obtain ageing products;
(3) in obtained ageing products, slowly add 26.4g white carbon black powder under stirring, add rear stirring 1.5 hours, formed uniform " viscous body ", transferred in stainless steel closed reactor, in 165 DEG C of thermostatic crystallizations 2 days, to filter, washing, at 120 DEG C dry 24 hours, 550 DEG C of roastings 6 hours, namely obtain TS-1 sieve sample, be designated as TS-1F2, XRD analysis shows to have MFI structure;
(4) the TPAOH aqueous solution of 6g TS-1F2 sample and 36 grams of concentration 22.05% is even, 150 DEG C of crystallization 3 days in airtight reactor, filter, washing, drying 24 hours at 120 DEG C, 550 DEG C of roastings 6 hours, obtain TS-1 zeolite product, are designated as TS-1P2.Its BET specific surface area is 452m 2/ g, outer surface area is 61m 2/ g, XRD analysis shows to have MFI structure; In transmission electron microscope photo, it is hollow structure.
Embodiment 4
(1) by 104.67g concentration be 25.05% the 4-propyl bromide aqueous solution, 0.33g titanyl sulfate, 7.63g triethylamine, 8.5g tetraethyl orthosilicate, 0.79g ethylene glycol, 0.36g concentration be 20 % by weight ammoniacal liquor and 172.8g water join successively in the beaker of 500ml, put into heating and agitating function magnetic stirring apparatus on Homogeneous phase mixing, and heat 3 hours at 70 DEG C, supplement the moisture of evaporation at any time, obtain alkaline hydrolysis liquid, then the hydrogen peroxide solution that 8.7g concentration is 15 % by weight is added
(2) (1) products therefrom is at room temperature left standstill 24 hours, obtain ageing products;
(3) in the beaker filling ageing products, 36g white carbon black powder is slowly added under stirring, stir one hour, formed comparatively uniform " viscous body ", transferred in stainless steel closed reactor, in 165 DEG C of thermostatic crystallizations 2 days, filter, washing, at 120 DEG C dry 24 hours, 550 DEG C of roastings 6 hours, TS-1 zeolite product provided by the invention, be designated as TS-1F3; XRD shows that it has MFI structure;
(4) by the TPAOH aqueous solution of 6g TS-1F3 sample and 40 gram 22.05%, stir, 150 DEG C of crystallization 3 days in airtight reactor, filter, washing, at 120 DEG C dry 24 hours, 550 DEG C of roastings 6 hours, hollow TS-1 sample, be designated as TS-1P3.Its BET specific surface area is 455m 2/ g, outer surface area is 60m 2/ g, in transmission electron microscope photo, it is hollow structure, and XRD shows that it has MFI structure; .
Embodiment 5
HTS is prepared, unlike not adding ammoniacal liquor according to the method for embodiment 2.
Embodiment 6
HTS is prepared according to the method for embodiment 2, unlike only using solid silicon source, step
Suddenly organosilicon source is not added in (1).
Embodiment 7
Prepare HTS according to the method for embodiment 2, its proportioning and synthesis condition, the results are shown in Table 1.
Embodiment 8
According to the method for embodiment 2, unlike first crystallization 1 day at 120 DEG C in step (3), then crystallization 2 days at 170 DEG C, its proportioning and synthesis condition, the results are shown in Table 1.
Embodiment 9
According to the method for embodiment 2, adjustment proportioning, other condition and characterization result are in table 1.
Embodiment 10
Preparation TS-2 molecular sieve.With reference to according to the method for embodiment 2, change proportioning and template, its proportioning and synthesis condition, the results are shown in Table 1.
Embodiment 11
Preparation Ti-beta-molecular sieve.The method of reference example 2, changes proportioning and template, its proportioning and synthesis condition, the results are shown in Table 1.
Embodiment 12
According to the method for embodiment 4, unlike the white carbon black in step (3) in order to SiO 2the organosilicon source hydrolysis of meter equivalent catches up with alcohol product to replace, and wherein, the hydrolysis of organosilicon source catches up with the monohydroxy-alcohol content in alcohol product to be no more than 10ppm quality.
Embodiment 13
The present embodiment illustrates that the reaction effect of dihydroxy-benzene and preparing cyclohexanone oxime by ammoximation of cyclohexanone prepared by sample prepared by embodiment sample provided by the invention and comparative example for oxidation of phenol hydroxylation.
The present embodiment reagent used is commercially available chemically pure reagent.After reaction, the concentration of each material uses vapor-phase chromatography to carry out quantitative analysis.The 6890 type gas chromatographs that Agilent company used produces; Analysis chromatographic column used is FFAP post.
In embodiment, the transformation efficiency of phenol, pimelinketone transformation efficiency, cyclohexanone-oxime selectivity calculate respectively according to the following equation:
Sample (rearrangement) each 1.25g got respectively prepared by above-described embodiment 1-9 and comparative example joins in the three-necked flask reaction vessel containing phenol 25g and acetone 20ml, hydrogen peroxide 9.81g (concentration 30 % by weight) is added, (phenol: hydrogen peroxide (H after temperature-stable to set(ting)value 2o 2) mol ratio is 3), temperature 80 DEG C, pressure 0.1MPa (normal pressure), reacts 2 hours post-samplings, and phenol carries out hydroxylating and generates dihydroxy-benzene.
The HTS of getting respectively in above-mentioned comparative example and embodiment prepares sample, according to TS-1 molecular sieve: the trimethyl carbinol: mass ratio uniform stirring mixing in slurry bed of 25 % by weight ammoniacal liquor=1:7.5:7.5, the weight of molecular sieve is 2.7g, be warming up to 75 DEG C, then 30 % by weight hydrogen peroxide are added with the speed of 6ml/h at this temperature, the mixture (volume ratio of pimelinketone and the trimethyl carbinol is for 1:2.5) of pimelinketone and the trimethyl carbinol is added with the speed of 8.4ml/h, add 25 % by weight ammonia solns with the speed of 6ml/h, volume space velocity is 7.56h simultaneously -1.Above-mentioned three strands of materials add simultaneously, and simultaneously with corresponding speed continuous discharge, stable reaction 3 hours, stratographic analysis is carried out in sampling, the results are shown in Table 2.
The decomposition run of hydrogen peroxide
Get H 2o 2concentration is 15 grams, the hydrogen peroxide of 30 % by weight, adds 2 grams of HTS, and temperature is stir 1 hour at 80 DEG C, analyzes the concentration of hydrogen peroxide.The results are shown in Table 2
From table 2, under identical condition, molecular sieve provided by the invention has lower decomposing hydrogen dioxide solution speed, thus in the oxidizing reaction participated in for hydrogen peroxide, improve the utilization ratio of hydrogen peroxide, can reduce hydrogen peroxide consumption.
As can be seen from Table 2: the phenol hydroxylation of gained sample of the present invention and pimelinketone activity are apparently higher than the conventional TS-1 molecular sieve of comparative sample.
It should be noted that, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims (31)

1. a synthetic method for HTS, comprises and titanium source, template, water, polyvalent alcohol, superoxide, silicon source and optional Inorganic Ammonium source is formed crystallization mixture, crystallization, recovery Pd si molecular sieves; Described template is organic quaternary ammonium salt and organic bases, and described silicon source is organosilicon source and/or solid silicon source.
2., according to the synthetic method of HTS according to claim 1, comprise the following steps:
(1) mixed in titanium source, template, water, polyvalent alcohol and optional organosilicon source, optional Inorganic Ammonium source, alcohol is caught up with in hydrolysis; Then superoxide is added;
(2) product that obtains of step (1) is aging;
(3) add in the product that step (2) obtains or do not add organosilicon source and/or solid silicon source, crystallization, recovery Pd si molecular sieves;
Wherein, introduce described silicon source at least one step in step (1) and step (3), described template is organic quaternary ammonium salt and organic bases.
3. according to the method described in claim 1 or 2, it is characterized in that, the mol ratio in polyvalent alcohol and total silicon source is 0.01 ~ 0.8:1, the mol ratio in superoxide and total silicon source is 0.01 ~ 0.25:1, the mol ratio in organic quaternary ammonium salt and total silicon source is 0.04 ~ 0.6:1, organic bases be 0.04 ~ 0.5:1 with the mol ratio in total silicon source, described total silicon source is with SiO 2the organosilicon source of meter and the summation of solid silicon source.
4. in accordance with the method for claim 3, it is characterized in that, the mol ratio in polyvalent alcohol and total silicon source is 0.1 ~ 0.7:1, and the mol ratio in superoxide and total silicon source is 0.05 ~ 0.25:1.
5. in accordance with the method for claim 2, it is characterized in that, in step (1), introduce organosilicon source, and introduce solid silicon source in step (3); With SiO 2meter, the mol ratio of the organosilicon source of introducing in step (1) and the middle solid silicon source introduced of step (3) is 1:0.1 ~ 20.
6. in accordance with the method for claim 5, it is characterized in that, the method comprises the steps:
(1) by titanium source, template, organosilicon source, optional Inorganic Ammonium source, the mixing of polynary alcohol and water, alcohol is caught up with in hydrolysis; Add superoxide, wherein, Inorganic Ammonium source: the mol ratio in titanium source is 0 ~ 5:1;
(2) by aging for step (1) products therefrom, described aging be that step (1) products therefrom is left standstill 1 ~ 60 hour at room temperature ~ 50 DEG C;
(3) ageing products that step (2) obtains is mixed with the weight ratio of solid silicon source according to 1:0.1 ~ 20, crystallization, recovery Pd si molecular sieves; In wherein said part by weight, the ageing products that described step (2) obtains is with SiO 2meter, solid silicon source is with SiO 2meter;
Wherein, the mol ratio in water and total silicon source is 5 ~ 100:1; The mol ratio in template and total silicon source is 0.08 ~ 0.6:1; The mol ratio in polyvalent alcohol and total silicon source is 0.01 ~ 0.8:1, and the mol ratio in superoxide and total silicon source is 0.01 ~ 0.25:1; The mol ratio in titanium source and total silicon source is 0.005 ~ 0.05:1; The mol ratio in organic quaternary ammonium salt and total silicon source is 0.04 ~ 0.56:1, organic bases be 0.04 ~ 0.5:1 with the mol ratio in total silicon source;
Wherein, in described mol ratio, total silicon source is with SiO 2meter, described total silicon source is with SiO 2meter organosilicon source and with SiO 2the summation of the solid silicon source of meter, Inorganic Ammonium source is with NH 4 +meter; Described Inorganic Ammonium source is inorganic ammonium salt and/or ammoniacal liquor, and titanium source is with TiO 2meter.
7. according to the method described in any one of claim 1 ~ 6, it is characterized in that, the mol ratio in described titanium source and total silicon source is 0.005 ~ 0.05:1,0.008 ~ 0.03:1 or 0.01 ~ 0.025:1.
8. according to the method described in any one of claim 1 ~ 6, it is characterized in that, the mol ratio of template, total silicon source, titanium source and water is (0.08 ~ 0.6): 1:(0.005 ~ 0.05): (5 ~ 100).
9. in accordance with the method for claim 8, it is characterized in that, the mol ratio in described template and described total silicon source is 0.1 ~ 0.5:1 or 0.1 ~ 0.3:1 or 0.1 ~ 0.2:1.
10. in accordance with the method for claim 9, it is characterized in that, the mol ratio in described organic quaternary ammonium salt and total silicon source is 0.05 ~ 0.3:1, and the mol ratio in described organic bases and total silicon source is 0.05 ~ 0.3:1, and described organic bases is quaternary ammonium base and/or organic amine.
11. in accordance with the method for claim 8, it is characterized in that, the mol ratio in water and total silicon source is 5 ~ 50:1,5 ~ 30:1 or is 6 ~ 15:1.
12., according to the method described in claim 2 or 6, is characterized in that, introduce or do not introduce Inorganic Ammonium source, with NH in step (1) 4 +meter Inorganic Ammonium source with TiO 2the mol ratio in the titanium source of meter is 0 ~ 5:1, is preferably 0.01 ~ 4:1 or 0.05 ~ 0.5:1.
13., according to the method described in any one of claim 1 ~ 6, is characterized in that, the mol ratio of described organosilicon source and solid silicon source is 1:1 ~ 19 or for 1:2 ~ 18 or be 1:5 ~ 15.
14., according to the method described in any one of claim 1 ~ 6, is characterized in that, described aging, and aging temperature is room temperature to 50 DEG C, and digestion time is 1 ~ 60 hour.
15., according to the method described in any one of claim 1 ~ 6, is characterized in that, described crystallization, and the temperature of crystallization is 110 ~ 200 DEG C, and crystallization pressure is autogenous pressure, and the time of crystallization is 2 hours ~ 20 days.
16. in accordance with the method for claim 15, it is characterized in that, the time of described crystallization is 0.5 ~ 10 day.
17. in accordance with the method for claim 16, it is characterized in that, the crystallization temperature of described crystallization is 140 ~ 180 DEG C or 160 ~ 180 DEG C.
18., according to the method described in any one of claim 1 ~ 6, is characterized 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, and crystallization pressure is autogenous pressure.
19. according to the method described in any one of claim 1 ~ 6, it is characterized in that, described method also comprises rearrangement step: will reclaim the HTS that obtains crystallization 0.5 ~ 10 day in the organic bases aqueous solution, the temperature of crystallization is 110 ~ 200 DEG C; Wherein said HTS is (with SiO 2meter) be 1:0.02-0.5 with the mol ratio of described organic bases, described HTS is (with SiO 2meter) be 1:2 ~ 50 with the mol ratio of water; Described organic bases is quaternary ammonium base and/or organic amine.
20. in accordance with the method for claim 19, it is characterized in that, the temperature of crystallization described in rearrangement step is 150 ~ 200 DEG C, and described HTS and the mol ratio of water are 1:2 ~ 30, pressure is autogenous pressure, and the mol ratio of organic bases and HTS is 0.02 ~ 0.2:1.
21., according to the method described in any one of claim 1 ~ 6, is characterized in that, described polyvalent alcohol is the alcohol in molecule with more than 2 or 2 hydroxyls, and the carbon atom number had in described polyol molecule is 2 ~ 8; Described superoxide is the compound in molecule with peroxide bridge.
22. according to the method described in any one of claim 1 ~ 6, it is characterized in that, described superoxide is one or more in hydrogen peroxide, tert-butyl peroxide, Peracetic Acid, trifluoro Peracetic Acid, and described polyvalent alcohol is one or more in glycerol, ethylene glycol, hexylene glycol, glycol ether.
23., according to the method described in any one of claim 1 ~ 6, is characterized in that, described template is organic bases and organic quaternary ammonium salt; Described organosilicon source is organo-silicon ester, described organo-silicon ester, and its general formula is Si (OR 1) 4, R 1be selected from the alkyl with 1 ~ 6 carbon atom, described alkyl is branched-chain or straight-chain alkyl; Described solid silicon source is high-purity silicon dioxide granule or SiO 2 powder, with butt weight for benchmark, and the SiO of described solid silicon source 2content is greater than 99.99 % by weight, is less than the silica gel of 10ppm in the total content of Fe, Al and Na of atom, and described titanium source is organic titanium source and/or inorganic ti sources.
24., according to the method described in any one of claim 1 ~ 6, is characterized in that, described solid silicon source is white carbon black, and the specific surface area of described white carbon black is 20 ~ 1000m 2/ g is preferably 50 ~ 400m 2/ g.
25. in accordance with the method for claim 23, it is characterized in that, described organo-silicon ester is one or more in quanmethyl silicate, tetraethyl orthosilicate, silicic acid four butyl ester, dimethyl diethyl estersil.
26., according to the method described in any one of claim 1 ~ 6, is characterized in that, described organic bases is quaternary ammonium base and/or organic amine, and described organic amine is one or more in aliphatic amide, aromatic amine and hydramine; The general formula of described aliphatic amide is R 3(NH 2) n, wherein R 3for there is alkyl or the alkylidene group of 1 ~ 4 carbon atom, n=1 or 2; Its general formula of described hydramine is (HOR 4) mnH (3-m), wherein R 4for having the alkyl of 1 ~ 4 carbon atom, m=1,2 or 3; Described aromatic amine is for having the substituent amine of aromaticity.
27. in accordance with the method for claim 26, it is characterized in that, described aliphatic amide is one or more in ethamine, n-Butyl Amine 99, butanediamine or hexanediamine; Described hydramine is one or more in monoethanolamine, diethanolamine or trolamine; Described aromatic amine is one or more in aniline, Tolylamine, Ursol D.
28. in accordance with the method for claim 26, it is characterized in that, described quaternary ammonium base is one or more in TPAOH, TBAH or tetraethyl ammonium hydroxide; Described organic quaternary ammonium salt is one or more in 4-propyl ammonium chloride, 4-propyl bromide, tetrabutylammonium chloride, Tetrabutyl amonium bromide, etamon chloride, tetraethylammonium bromide.
29. according to the method described in any one of claim 1 ~ 6, it is characterized in that, described HTS is TS-1 molecular sieve, and described organic quaternary ammonium salt is one or more in 4-propyl ammonium chloride, 4-propyl bromide, and described organic bases is TPAOH and/or organic amine; Or described HTS is TS-2 molecular sieve, described organic quaternary ammonium salt is one or more in tetrabutylammonium chloride, Tetrabutyl amonium bromide, and described organic bases is TBAH and/or organic amine; Or described HTS is Ti-beta-molecular sieve, described organic quaternary ammonium salt is one or more in etamon chloride, tetraethylammonium bromide, and described organic bases is tetraethyl ammonium hydroxide and/or organic amine.
30., according to the method described in any one of claim 1 ~ 6, is characterized in that, described titanium source is tetraalkyl titanate, TiCl 4, Ti (SO 4) 2and one or more in their hydrolysate, the carbonatoms of the alkyl wherein in tetraalkyl titanate is 1,2,3,4,5 or 6.
31., according to the method described in claim 2 or 6, is characterized in that, the mass content that step (1) is hydrolyzed monohydroxy-alcohol in the product catching up with alcohol to obtain is no more than 10ppm.
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