CN104556111A - Ti-Si molecular sieve and synthesis method thereof - Google Patents
Ti-Si molecular sieve and synthesis method thereof Download PDFInfo
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- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
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Abstract
The invention provides a Ti-Si molecular sieve and a synthesis method thereof. The crystal surface of the Ti-Si molecular sieve is rich in Si, and the surface Ti-Si ratio of the Ti-Si molecular sieve is higher than the bulk-phase Ti-Si ratio of the Ti-Si molecular sieve. The synthesis method of the Ti-Si molecular sieve comprises the steps as follows: mixing a Ti source, a template agent, an organic Si source, an inorganic Si source and water, removing alcohol by hydrolysis, aging, mixing an aged product with a solid Si source, performing crystallization in an airtight reaction kettle, and recycling the Ti-Si molecular sieve. The Ti-Si molecular sieve provided by the invention has higher oxidative activity, and the activity in non-effective decomposition of hydrogen peroxide in side reaction is obviously reduced.
Description
Technical field
The present invention relates to a kind of HTS and synthetic method thereof.
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 catalyst, can the polytype organic oxidizing reaction of catalysis, as the epoxidation of alkene, the partial oxidation of alkane, the oxidation of alcohols, the hydroxylating of phenols, the ammoxidation etc. of cyclic ketones.Because TS-1 molecular sieve is in organic oxidation reaction, free of contamination low concentration hydrogen peroxide can be adopted as oxidant, avoid the problem of oxidizing process complex process and contaminated environment, there is unrivaled energy-conservation, the advantage such as economy and environment is friendly of conventional oxidation system, and there is good reaction selectivity.HTS is as organic matter 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: ethyl orthosilicate (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 reactant mixture containing silicon source, titanium source and organic base, heating, except alcohol, moisturizing, 175 DEG C under self-generated 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.
Chinese patent CN 98101357.0(CN 1260241A) disclose HTS reordering technique, synthesize the novel titanosilicate with unique hollow structure, the reappearance of synthesis TS-1 is not only made greatly to strengthen, also add molecular sieve pores, substantially increase the mass transfer diffusion rate of reactant molecule in molecular sieve pore passage, catalytic performance increases.Method disclosed in this patent by the hydrating solution of titanium with the TS-1 molecular sieve synthesized according to molecular sieve (gram): Ti(mole) ratio of=200 ~ 1500:1 mixes, 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 hydroxylating, cyclohexanone oxamidinating and has realized industrialization, has reaction condition gentleness, atom utilization is high, technical process is simple and accessory substance is the advantages such as water clean and effective.
Disclosed HTS direct hydrothermal synthesis method, uses organosilicon source and/or inorganic silicon source usually at present.Organosilicon source is organo-silicon ester TEOS such as, price comparison is expensive, and its active constituent content forming molecular sieve is also lower, is difficult to the solid content improving Zeolite synthesis crystallization product, and a large amount of ethanol that volatilizees in process of producing molecular sieve, and these ethanol is difficult to collect recycling.In order to reduce costs, researcher studies and adopts inorganic silicon source to replace part or all of organosilicon source, but uses the HTS that inorganic silicon source (solid silicon source) is synthesized at present, and the active HTS of organosilicon source synthesis that more all uses is low.In addition, the activity problems improving HTS further is not related in prior art.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of new HTS for the deficiency of existing HTS, and the other technical problem that the present invention will solve is to provide a kind of synthetic method of described HTS.
The invention provides a kind of synthetic method of HTS, comprise the steps:
(1) by titanium source, template, organosilicon source, water and the mixing of optional Inorganic Ammonium source, alcohol is caught up with in hydrolysis;
(2) step (1) products therefrom is aging at room temperature ~ 50 DEG C;
(3) ageing products that step (2) obtains is mixed with solid silicon source, then crystallization in closed reactor, recovery Pd si molecular sieves.
HTS synthetic method provided by the invention, the mol ratio in titanium source and total silicon source is preferably 0.01 ~ 0.05:1.The ageing products that described in step (3), step (2) obtains and the mol ratio of solid silicon source are 1:0.1 ~ 10; In wherein said mol ratio, the ageing products that described step (2) obtains is with SiO
2meter, solid silicon source is with SiO
2meter.
HTS synthetic method provided by the invention, preferably includes following steps:
(1) by template, titanium source, organosilicon source, Inorganic Ammonium source and water mixing, alcohol is caught up with in hydrolysis; Described hydrolysis catch up with alcohol usually at 0 ~ 150 DEG C such as 0 ~ 100 DEG C by gained mixture stir at least 10 minutes; The mixing time of described stirring such as stirs 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 by step (1) products therefrom in left at room temperature 1 ~ 60 hour such as 2 ~ 50 hours or 3 ~ 30 hours, such as 3 ~ 15 hours further;
(3) ageing products that step (2) obtains is mixed with the weight ratio of solid silicon source according to 1:0.1 ~ 10, then 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 titanium source and total silicon source is 0.005 ~ 0.05:1, the mol ratio in water and total silicon source is 5 ~ 100:1; It is such as 0.05 ~ 0.3:1 that the mol ratio in template and total silicon source is not less than 0.05 ~ 0.5:1; 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.
The present invention also provides a kind of HTS, and this molecular sieve has following characteristics: described HTS grain surface Silicon-rich, and grain surface silicon titanium mol ratio is greater than 1.1 with the ratio of body phase silicon titanium mol ratio, such as, be 1.1 ~ 5.Its surface silicon titanium compares with the proportionality of body phase silicon titanium ratio as being 1.2 ~ 4:1.
Wherein, surface silicon titanium ratio can adopt TEM-EDX or ion excitation corrosion XPS method to measure and obtain, for distance grain surface is no more than the silicon titanium ratio of the atomic layer of 5nm such as 1 ~ 5nm, body phase silicon titanium obtains than by chemico-analytic method, or is obtained by TEM-EDX or the XPS area measure that such as distance grain surface distance is greater than 20nm in the central area of crystal grain.
HTS synthetic method provided by the invention, prepared HTS grain surface Silicon-rich, grain surface silicon titanium ratio is apparently higher than body phase silicon titanium ratio.In addition, HTS synthetic method provided by the invention, use the relatively inexpensive solid silicon source be easy to get such as high-purity silica gel or/and white carbon, part replaces expensive organosilicon source, can reduce the waste discharge of process of producing molecular sieve and economize in raw materials while cost and obtain high performance HTS.HTS synthetic method provided by the invention, 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.
HTS provided by the invention, there is higher surface silicon titanium ratio and the ratio of body phase silicon titanium ratio, there is higher oxidation activity, for the oxidation reaction that hydrogen peroxide participates in, titanium can be reduced in superficial layer to the decomposition of hydrogen peroxide, be conducive to the activity of the decomposition side reaction reducing hydrogen peroxide, improve raw material availability.
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 the TEM figure of the hollow titanium silicon TS-1 molecular sieve that embodiment of the present invention step (4) obtains.
Fig. 4 is HTS hydrogen peroxide test prepared by prior art and embodiment 6, hydrogen peroxide concentration time history plot.
Fig. 5 is the schematic diagram utilizing TEM-EDX to measure body phase silicon titanium ratio and surface silicon titanium ratio, and 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 external surface area, and in the unit volume of central area, corresponding external surface area is lower, and therefore in square frame 1 and square frame 2, EDX measurement result can reflect to embody and compares difference with the silicon titanium on surface.
Detailed description of the invention
The synthetic method of HTS provided by the invention, can in lower template agent consumption situation synthesis of titanium silicon molecular sieve, thus template agent consumption can be lower, and such as the mol ratio in template agent and total silicon source is 0.05 ~ 0.3:1, is 0.05 ~ 0.25:1 or 0.05 ~ 0.2:1 further; In method provided by the invention, can at synthesis of titanium silicon molecular sieve under high solids content, from can and reduce the use amount of water, improve output per single reactor and namely under same synthesis reactor volume, synthesize more molecular sieve, therefore described water and the mol ratio in total silicon source (silica) can be 5 ~ 80:1 or 5 ~ 50:1 be such as 5 ~ 30:1 to be such as 6 ~ 20 or to be 6 ~ 15:1.Such as, the mol ratio in template and total silicon source is 0.05 ~ 0.2:1, and the mol ratio in water and total silicon source is 6 ~ 15:1.
The synthetic method of HTS provided by the invention, the mol ratio in described titanium source and total silicon source is that to be preferably 0.01 ~ 0.03:1 be such as 0.01 ~ 0.025:1 to 0.005 ~ 0.05:1.
The synthetic method of HTS provided by the invention, the mol ratio in Inorganic Ammonium source and titanium source is 0 ~ 5:1 is such as that 0.01 ~ 4:1 is preferably 0.01 ~ 0.5:1.Add Inorganic Ammonium source, the oxidation activity of synthesized molecular sieve can be improved, the utilization rate (higher framework titania silicon ratio can be had in same titanium source use amount situation) in titanium source can be improved, reduce the use amount in titanium source.
The synthetic method of HTS provided by the invention, the mol ratio in described template and described total silicon source is not less than 0.05:1, and being preferably 0.05 ~ 0.3:1, such as, is 0.05 ~ 0.2:1.
The synthetic method of HTS provided by the invention, the mol ratio of described organosilicon source and solid silicon source is that 1:0.1 ~ 10 are preferably 1:1 ~ 9 such as 1:2 ~ 8 or be 1:3 ~ 7.With SiO
2namely the ageing products that the step (2) counted obtains and the ratio of solid silicon source equal the mol ratio of organosilicon source and solid silicon source.Described solid silicon source is inorganic silicon source.
The synthetic method of HTS provided by the invention, the template agent described in step (1) is organic base or for organic base and organic quaternary ammonium salt mixture, and described organic base is one or more in quaternary ammonium base, organic amine; Such as described template can be the mixture of the mixture of organic quaternary amine alkali, organic quaternary amine alkali and organic amine, organic quaternary amine alkali and organic quaternary ammonium salt, organic amine and the mixture of organic quaternary ammonium salt or the mixture of organic quaternary amine alkali and organic quaternary ammonium salt and organic amine.Described organic amine is one or more in fatty amine, aromatic amine and hydramine, and described fatty amine (also claiming fat amine compound), its general formula is R
3(NH
2)
n, wherein R
3for there is alkyl or the alkylidene 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 fatty amine such as ethamine, n-butylamine, butanediamine or hexamethylene diamine; Described aromatic amine refers to have the substituent amine of armaticity, such as, in aniline, toluidines, p-phenylenediamine (PPD) one or more; One or more in described hydramine such as MEA, diethanol amine or triethanolamine.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, TBAB, tetraethylammonium bromide, 4-propyl ammonium chloride, tetrabutylammonium chloride or etamon chloride.
A kind of embodiment, described template comprises organic base, comprises quaternary organic ammonium compounds, and it is such as 0.05 ~ 0.45 that the mol ratio in the organic base introduced in template and silicon source is not less than 0.05:1; 1, described organic base is quaternary ammonium base and/or organic amine; Quaternary organic ammonium compounds be not less than 0.05:1 with the mol ratio in silicon source, be such as 0.05 ~ 0.45:1, described quaternary organic ammonium compounds is quaternary ammonium base and/or organic quaternary ammonium salt.
A kind of implementation method, described template agent, comprise quaternary ammonium base, can be quaternary ammonium base or the mixture comprising quaternary ammonium base, such as described template agent be the mixture of quaternary ammonium base and organic amine, quaternary ammonium base and the mixture of organic quaternary ammonium salt or the mixture of quaternary ammonium base and organic quaternary ammonium salt and organic amine.Under preferable case, the mol ratio of quaternary ammonium base and organic ammonium is such as 1:0 ~ 8,1:0 ~ 10, and the mol ratio of quaternary ammonium base and organic quaternary ammonium salt is such as 1:0 ~ 8,1:0 ~ 10.The mol ratio in quaternary ammonium base and total silicon source is 0.05 ~ 0.45:1, such as, be 0.05 ~ 0.3:1, such as, be 0.05 ~ 0.2:1.
HTS synthetic method provided by the invention, a kind of embodiment, described HTS is TS-1 molecular sieve, described template agent for TPAOH or for TPAOH be selected from one or more in organic amine, 4-propyl ammonium chloride, 4-propyl bromide mixtures of forming.A kind of embodiment, described HTS is TS-2 molecular sieve, and described template is for TBAH or for TBAH be selected from one or more in organic amine, tetrabutylammonium chloride, TBAB mixtures of forming.。
HTS synthetic method provided by the invention, a kind of embodiment, described HTS is Ti-beta-molecular sieve, and described template is tetraethyl ammonium hydroxide or is tetraethyl ammonium hydroxide and one or more the mixture be selected from organic amine, etamon chloride, tetraethylammonium bromide.
HTS synthetic method provided by the invention, the organosilicon source described in step (1) is organic silicone grease, 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 alkyl or straight chained alkyl.One or more in described organic silicone grease such as silicic acid four formicester, 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 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 gross mass content of Fe, Al and Na impurity of element; 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, preferred white carbon, 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 gross mass content of Fe, Al and Na impurity is less than 10ppm.The specific area of described white carbon is preferably between 50-400m
2between/g, with the butt weight of white carbon for benchmark, SiO in described white carbon
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 described white carbon, the quality total content of Fe, Al and Na impurity is less than 10ppm.Described white carbon 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 reaction obtain by a kind of preparation method.
Described titanium source is organic titanic compound or inorganic titanium compound, such as, be tetraalkyl titanate (Ti (alkoxy)
4, TiCl
4, Ti (SO
4)
2and one or more in their hydrolysate.The carbon number of the alkyl wherein in tetraalkyl titanate molecule is 1 ~ 6, and such as carbon number is 1,2,3,4,5 or 6.The molar ratio in titanium source and total silicon source (also claiming silicon source) as being 0.008 ~ 0.035:1, such as, is 0.01 ~ 0.03:1 or 0.01 ~ 0.025:1, or 0.015 ~ 0.025:1.
HTS synthetic method provided by the invention, the 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 the titanium source of meter is 0 ~ 5:1, and being such as 0.01 ~ 4:1, such as, is 0.01 ~ 0.5:1.Add described inorganic quaternary ammonium salts, the content of the framework titania of synthesized molecular sieve can be improved, improve the activity of molecular sieve.
In HTS synthetic method provided by the invention, in step (1), titanium source, template, organosilicon source, Inorganic Ammonium source and water are pressed mixing, be hydrolyzed and catch up with alcohol.Alcohol is caught up with in described hydrolysis, can be 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 alcohol (the being generally monohydric alcohol) content that in gained mixture, organosilicon source and the hydrolysis of organic titanium source produce, be namely hydrolyzed and catch up with alcohol.Usual mixing time is 10 ~ 3000 minutes, such as, be 2 ~ 30 hours.Catch up with alcohol by hydrolysis, obtain organosilicon source and the titanium source hydrolyzate of clear.Under preferable case, in the product that step (1) obtains, the mass content of the monohydric alcohol that organosilicon source and the hydrolysis of organic titanium source produce is no more than 10ppm, and preferably, in the mixture that step (1) obtains, the content of monohydric alcohol is not higher than 10ppm(quality).
HTS synthetic method provided by the invention, in step (2), by aging for step (1) products therefrom, described aging be, at room temperature to 50 DEG C, step (1) products therefrom is left standstill 1 ~ 60 hour.Described room temperature is 15 ~ 40 DEG C; Ageing time is 1 ~ 60 hour is such as 2 ~ 50 hours, preferably 3 ~ 30 hours, such as 3 ~ 15 hours, does not stir in ageing process, described material and step (1) products therefrom is left standstill.
HTS synthetic method provided by the invention, mixes the ageing products that step (2) obtains with solid silicon source, with SiO in step (3)
2meter, the mol ratio of the product that step (2) obtains and solid silicon source is the mol ratio of 1:0.1 ~ 10(and described organosilicon source and solid silicon source is 1:0.1 ~ 10, such as, can be 1:1 ~ 9,1:2 ~ 8,1:1 ~ 7 or 1:3 ~ 6.Method provided by the invention, can use the solid silicon source of higher proportion, can improve the solid content of synthetic product, thus improves the output of single synthesis when synthesis reaction vessel is constant.
HTS synthetic method provided by the invention, step (3) described crystallization, the temperature of crystallization is 110 ~ 200 DEG C, crystallization pressure is self-generated pressure, and the time of crystallization is 2 hours ~ 20 days, and the time of usual described crystallization is 0.5 ~ 20 day, such as crystallization time is 0.5 ~ 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, and crystallization time is preferably 0.5 ~ 10 day such as 1 ~ 6 day, is such as 1 ~ 3 day further.Crystallization pressure is self-generated pressure.Described crystallization can be carried out in stainless steel stirred tank.Crystallization heat up can one section heat up also can multistage heating mode.Heating 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 stirred tank.A kind of embodiment, the crystallization temperature of described crystallization is 160 ~ 180 DEG C, and crystallization time is 0.5 ~ 6 day such as 1 ~ 3 day, and crystallization pressure is self-generated pressure.A kind of embodiment, the crystallization described in step (3) is: crystallization 0.5 ~ 1.5 day at 100 ~ 130 DEG C such as 110 ~ 130 DEG C, then crystallization 1 ~ 3 day at 160 ~ 180 DEG C, and crystallization pressure is self-generated pressure.
HTS synthetic method provided by the invention, 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 siliceous 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 and then filter or use water wash.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, step (3) reclaims the HTS obtained and also can be passed through further process, i.e. HTS synthetic method provided by the invention, can also comprise step (4):
(4) the HTS Crystallizing treatment in organic alkali solution step (3) obtained, then recovery Pd si molecular sieves.The HTS that this process obtains has hollow-core construction, and the present invention is referred to as molecular sieve and resets.Wherein HTS is (with SiO
2meter) be 1:0.02 ~ 0.5 with the molar ratio of organic base be such as 1:0.02 ~ 0.2; With SiO
2the mol ratio of molecular sieve and the water of meter be 1:2 ~ 50 such as 1:2 ~ 30 or be 1:2 ~ 20, or be 1:5 ~ 10; Crystallization temperature is 120 ~ 200 DEG C, and the time is 0.5 ~ 10 day such as 0.5 ~ 8 day; Crystallization pressure is self-generated pressure, the preferred quaternary ammonium base of wherein said organic base.Preferably, the crystallization temperature described in step (4) is 150-200 DEG C, and crystallization time is 0.5 ~ 10 day or is 1 ~ 6 day, and the mol ratio of molecular sieve and water is 1:2 ~ 30.Recovery method is existing method, generally includes crystallization product filtration, washing, so dry and roasting, can refer to the recovery method described in step (3).Described organic base is organic amine and/or quaternary ammonium base; Described organic amine is one or more in fatty amine, aromatic amine and hydramine, and described fatty amine (also claiming fat amine compound), its general formula is R
3(NH
2)
n, wherein R
3for there is alkyl or the alkylidene 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 fatty amine such as ethamine, n-butylamine, butanediamine or hexamethylene diamine; Described aromatic amine refers to have the substituent amine of armaticity, such as, in aniline, toluidines, p-phenylenediamine (PPD) one or more; One or more in described hydramine such as MEA, diethanol amine or triethanolamine.One or more in described quaternary ammonium base such as TPAOH, TBAH or tetraethyl ammonium hydroxide.A kind of embodiment, described HTS is TS-1 molecular sieve, and described quaternary ammonium base is TPAOH.A kind of embodiment, described HTS is TS-2 molecular sieve, and described quaternary ammonium base is TBAH.A kind of embodiment, described HTS is titanium silicon beta molecular sieve (titanium silicon beta-molecular sieve), and described quaternary ammonium base is tetraethyl ammonium hydroxide.
Step (4) the present invention is referred to as molecular sieve and resets, and this process can be carried out once, also can repeat one or many, described repetition, and the molecular sieve that the HTS obtained by described process replaces step (3) to obtain carries out the process of step (4).By resetting process, can obtain the HTS with secondary pore structure, the crystal grain that gained HTS has hollow-core construction and described HTS is hollow-core construction, and 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 adsorbance recorded under the adsorption time condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isotherm of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm.After resetting, molecular sieve has larger pore volume and specific area.
The present invention is further illustrated for the following examples, but therefore do not limit the present invention.
The measuring method of the grain size 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 radiographic source is CuK α (λ=1.5418
), tube voltage 40kV, tube current 40mA, sweep speed 0.5 °/min, sweep limits 2 θ=4 ° ~ 40 °.
The method of testing of BET specific surface area adopts N2 adsorption volumetric method, according to BJH computational methods.(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:
Butyl titanate, analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group.
Titanyl sulfate, analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group.
TPAOH, great You chemical plant, Guangdong.
Tetraethyl orthosilicate, analyzes pure, Chemical Reagent Co., Ltd., Sinopharm Group.
Ammoniacal liquor, analyzes pure, concentration 20 % by weight.
White carbon, 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 area is 195m
2/ g.
What other reagent did not further illustrate is commercial goods, analyzes 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 7.0g TPAOH, 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 butyl titanate and 5.0g isopropyl alcohol, 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.Its XRD analysis spectrogram as shown in Figure 1.
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 9.0g TPAOH, 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 butyl titanate and 7.0g isopropyl alcohol, 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 butyl 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 butyl 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 butyl titanate, uniform stirring 12h under normal temperature, finally scattered suspension is put into stainless steel cauldron, place 3 days at 165 DEG C, described HTS molecular sieve.Its XRD analysis spectrogram as shown in Figure 1.
Embodiment 1
(1) by 15g concentration be 25.05 % by weight TPAOH (TPAOH) aqueous solution, 2.04g butyl titanate, 8.5g tetraethyl orthosilicate, 2g concentration be 20 % by weight ammoniacal liquor and 38g water join successively in the beaker of 500ml, put into heating and agitating function magnetic stirring apparatus on mix, and stir 4 hours at 80 DEG C, supplement the moisture of evaporation at any time, obtain water white transparency hydrolyzate;
(2) within 12 hours, carry out aging by standing under room temperature (26 DEG C) for gained hydrolyzate, obtain ageing products;
(3) in above-mentioned ageing products, 9.6g white carbon 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 426m
2/ g, external surface area is 60m
2/ g; Micro pore volume 0.166mL/g, mesopore volume 0.086mL/g.XRD analysis its there is MFI. structure, XRD spectra is 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.As shown in Figure 1, its BET specific surface area is 457m to its XRD analysis spectrogram
2/ g, external surface area is 68m
2/ g, micro pore volume 0.152mL/g, mesopore volume 0.168mL/g, in transmission electron microscope photo, it is hollow-core construction (see Fig. 3).
Embodiment 2
(1) by 7.4g concentration be 25.05 % by weight TPAOH, 1.23g butyl titanate, 4.16g tetraethyl orthosilicate, 0.67g concentration be 20 % by weight ammoniacal liquor and 14g water join successively in the beaker of 500ml, put into heating and agitating function magnetic stirring apparatus on mix, and stir 1 hour at 90 DEG C, supplement the moisture of evaporation at any time, obtain water white transparency basic hydrolysis liquid.
(2) hydrolyzate of gained is at room temperature left standstill 3 hours, obtain ageing products;
(3) in obtained ageing products, 9.6g white carbon powder is slowly added under stirring, add rear stirring 1.5 hours, transferred in stainless steel closed reactor, in 145 DEG C of thermostatic crystallizations 6 days, filter, wash, at 120 DEG C dry 24 hours, 550 DEG C of roastings 6 hours, namely obtained TS-1 sieve sample, be designated as TS-1F2, its specific area is 435m
2/ g, external surface area is 61m
2/ g, micro pore volume 0.159mL/g, mesopore volume 0.083mL/g; XRD analysis of spectra has feature as shown in Figure 1
(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 XRD analysis spectrogram has feature as shown in Figure 1.BET specific surface area is 429m
2/ g, external surface area is 60m
2/ g, micro pore volume 0.150mL/g, mesopore volume 0.177mL/g; In transmission electron microscope photo, it is hollow-core construction.
Embodiment 3
(1) by 43g concentration be 25.05% 4-propyl bromide (TPABr) aqueous solution, 1.68g titanyl sulfate, 2.4g triethylamine, 33.3g tetraethyl orthosilicate, 0.05g concentration be 20 % by weight ammoniacal liquor and 26g water join successively in the beaker of 500ml, put into heating and agitating function magnetic stirring apparatus on Homogeneous phase mixing, and stir 3 hours at 65 DEG C, supplement the moisture of evaporation at any time, obtain basic hydrolysis liquid.
(2) gained hydrolyzate is at room temperature left standstill 9 hours, obtain ageing products.
(3) in the beaker filling ageing products, slowly add 9.6g white carbon powder 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, to 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, its specific area is 427m
2/ g, external surface area is 60m
2/ g, micro pore volume 0.173mL/g, mesopore volume 0.079mL/g
(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, wash, 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 438m
2/ g, external surface area is 59m
2/ g, micro pore volume 0.162mL/g, mesopore volume 0.183mL/g.In transmission electron microscope photo, it is hollow-core construction.
Embodiment 4 ~ 7
Prepare HTS according to the method for embodiment 1, its proportioning and synthesis condition, the results are shown in Table 1.Other conditioned reference embodiment 1.
Embodiment 8
According to the method for embodiment 1, unlike not adding ammonium source.
Embodiment 9
According to the method for embodiment 1, 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 10
Preparation TS-2 molecular sieve.With reference to according to the method for embodiment 1, change proportioning and template, template used dose is TBAH (TBAOH), its proportioning and synthesis condition, the results are shown in Table 1.
Embodiment 11
Preparation Ti-beta-molecular sieve.The method of reference example 1, change proportioning and template, template used dose is TBAH (TEAOH), its proportioning and synthesis condition, the results are shown in Table 1.Its SEM figure is see Fig. 4
Comparative example 1
According to the method for embodiment 1, unlike not adding ammoniacal liquor, and do not carry out aging.
Comparative example 2
According to the method for embodiment 1, it is 75 DEG C unlike aging temperature.
Comparative example 3
According to the method for embodiment 1, add in step (1) unlike solid silicon source.
Embodiment 12
The present embodiment illustrates that the reaction effect of benzenediol 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 hydroxylating.
The present embodiment reagent used is commercially available chemically pure reagent, and after reaction, the concentration of each material uses gas 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 phenol conversion ratio, cyclohexanone conversion ratio, cyclohexanone oxime is selective calculates according to the following equation respectively:
Sample (rearrangement) each 1.25g got respectively prepared by above-described embodiment 1-9 and comparative example joins in the three-neck flask reaction vessel containing phenol 25g and acetone 20ml, hydrogen peroxide 9.81g(concentration 30 % by weight is added after temperature stabilization to setting value), (phenol: hydrogen peroxide (H
2o
2) mol ratio is 3), temperature 80 DEG C, pressure 0.1MPa(normal pressure), react 2 hours post-samplings, phenol carries out hydroxylating and generates benzenediol.
The HTS got respectively in above-mentioned comparative example and embodiment prepares sample, according to TS-1 molecular sieve: the tert-butyl alcohol: mass ratio uniform stirring mixing in slurry bed of 25 % by weight ammoniacal liquor=1:7.5:7.5, the consumption of TS-1 molecular sieve is 3.2g.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 cyclohexanone and the tert-butyl alcohol is for 1:2.5) of cyclohexanone and the tert-butyl alcohol is added with the speed of 8.6ml/h, add 25 % by weight ammonia spirits with the speed of 6ml/h, volume space velocity is 6.4h simultaneously
-1.Above-mentioned three strands of materials add simultaneously, and simultaneously with corresponding speed continuous discharge, stable reaction 4 hours, sample analysis, 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 HTSs, 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 oxidation reaction participated in for hydrogen peroxide, improve the utilization rate of hydrogen peroxide, can improve the conversion ratio of reactant.
Fig. 4 is the time dependent curve of middle hydrogen peroxide concentration of TS-1 molecular sieve (step 3 obtain do not reset molecular sieve) the decomposing hydrogen dioxide solution test of embodiment 6 and the synthesis of existing method.
As can be seen from Table 1: the phenol hydroxylation of gained sample of the present invention and cyclohexanone activity are apparently higher than the conventional TS-1 molecular sieve of comparative sample.
It should be noted that, also can be combined 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.
For comparative example, in table 1,2, step (3) product refers to the HTS without resetting, and step (4) product refers to the HTS through resetting.
Claims (31)
1. a HTS, is characterized in that, the surface silicon titanium of described HTS crystal grain is than being greater than 1.1 with the ratio of body phase silicon titanium ratio and being less than 5.
2. according to HTS according to claim 1, it is characterized in that, described surface silicon titanium is 1.2 ~ 4:1 than with the ratio of body phase silicon titanium ratio.
3. according to HTS according to claim 1, it is characterized in that, the titanium silicon of described HTS is that 0.005 ~ 0.03:1 is preferably 0.01 ~ 0.025:1 than mol ratio.
4. according to HTS according to claim 1, it is characterized in that, described HTS is TS-1 molecular sieve, TS-2 molecular sieve or Ti-beta-molecular sieve.
5. according to the HTS described in any one of Claims 1 to 4, it is characterized in that, the crystal grain of described HTS is hollow-core construction, and 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 adsorbance recorded under the adsorption time condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isotherm of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm.
6. a synthetic method for HTS, comprises the following steps:
(1) by titanium source, template, organosilicon source, water and the mixing of optional Inorganic Ammonium source, alcohol is caught up with in hydrolysis;
(2) step (1) products therefrom is aging at room temperature ~ 50 DEG C;
(3) ageing products that step (2) obtains is mixed with solid silicon source, then crystallization in closed reactor, recovery Pd si molecular sieves.
7. in accordance with the method for claim 6, it is characterized in that, step (2) described aging be that step (1) products therefrom is left standstill 1 ~ 60 hour at room temperature ~ 50 DEG C;
The ageing products that described in step (3), step (2) obtains and the weight ratio of solid silicon source are 1:0.1 ~ 10, and 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;
Inorganic Ammonium source: the mol ratio in titanium source is 0 ~ 5:1; The mol ratio in water and total silicon source is 5 ~ 100:1; The mol ratio in template and total silicon source is 0.05 ~ 0.5:1; The mol ratio in titanium source and total silicon source is 0.005 ~ 0.05:1; Wherein, 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; Titanium source is with TiO
2meter; Described Inorganic Ammonium source is inorganic ammonium salt and/or ammoniacal liquor.
8. in accordance with the method for claim 7, it is characterized in that, the mol ratio in described titanium source and total silicon source is 0.005 ~ 0.04:1 or 0.01 ~ 0.03:1 or 0.01 ~ 0.025:1.
9. in accordance with the method for claim 7, it is characterized in that, the mol ratio in described template and described total silicon source is 0.05 ~ 0.3:1 or 0.05 ~ 0.25:1 or 0.05 ~ 0.2:1.
10. in accordance with the method for claim 7, it is characterized in that, the mol ratio in water and total silicon source is 5 ~ 50 or 6 ~ 30:1; Or the mol ratio in water and total silicon source is 6 ~ 15:1.
11. in accordance with the method for claim 7, it is characterized in that, the mol ratio in Inorganic Ammonium source and titanium source is 0.01 ~ 4:1 or 0.05 ~ 0.5:1.
12. in accordance with the method for claim 7, it is characterized in that, the mol ratio of described organosilicon source and solid silicon source is 1:1 ~ 9 or is 1:2 ~ 8.
13. in accordance with the method for claim 6, it is characterized in that, step (3) described crystallization, and 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 or 0.5 ~ 10 day.
14. in accordance with the method for claim 13, it is characterized in that the crystallization temperature of crystallization described in step (3) is 140 ~ 180 DEG C or is 160 ~ 180 DEG C.
15. in accordance with the method for claim 6, it is characterized in that, the crystallization described in step (3) 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 self-generated pressure.
16. in accordance with the method for claim 6, it is characterized in that, described template is organic base or is organic base and organic quaternary ammonium salt; Described organosilicon source is organic silicone grease, 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.
17. in accordance with the method for claim 6, it is characterized in that, in step (1), described template agent comprises quaternary ammonium base and optional organic amine and/or organic quaternary ammonium salt, wherein, the mol ratio of quaternary ammonium base and organic amine is 1:0 ~ 10, and the mol ratio of quaternary ammonium base and organic quaternary ammonium salt is 1:0 ~ 10.
18. in accordance with the method for claim 16, it is characterized in that, described organic silicone grease is one or more in silicic acid four formicester, tetraethyl orthosilicate, silicic acid four butyl ester, dimethyl diethyl silicone grease.
19. in accordance with the method for claim 6, it is characterized in that, described solid silicon source is white carbon, and the specific area of described white carbon is 50 ~ 400m
2/ g.
20. in accordance with the method for claim 17, it is characterized in that, described organic amine is one or more in fatty amine, aromatic amine and hydramine; The general formula of described fatty amine is R
3(NH
2)
n, wherein R
3for there is alkyl or the alkylidene 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 armaticity, and described quaternary ammonium base is one or more in TPAOH, TBAH or tetraethyl ammonium hydroxide.
21. in accordance with the method for claim 20, it is characterized in that, described fatty amine is one or more in ethamine, n-butylamine, butanediamine or hexamethylene diamine; Described hydramine is one or more in MEA, diethanol amine or triethanolamine; Described aromatic amine is one or more in aniline, toluidines, p-phenylenediamine (PPD).
22. in accordance with the method for claim 6, it is characterized in that, described HTS is TS-1 molecular sieve, described template agent for TPAOH or for TPAOH be selected from one or more in organic amine, 4-propyl ammonium chloride, 4-propyl bromide mixtures of forming; Or described HTS is TS-2 molecular sieve, described template is for TBAH or for TBAH be selected from one or more in organic amine, tetrabutylammonium chloride, TBAB mixtures of forming; Or described HTS is Ti-beta-molecular sieve, described template is tetraethyl ammonium hydroxide or is tetraethyl ammonium hydroxide and one or more the mixture be selected from organic amine, etamon chloride, tetraethylammonium bromide.
23. in accordance with the method for claim 6, it is characterized in that, step (1) described hydrolysis catches up with alcohol to be stir at least 10 minutes at 0 ~ 150 DEG C.
24. in accordance with the method for claim 6, it is characterized in that, alcohol is caught up with in step (1) described hydrolysis, and the temperature of stirring is 50 ~ 95 DEG C, and mixing time is 2 ~ 30 hours.
25., according to the method described in claim 6 or 24, is characterized in that, in the product that step (1) obtains, the mass content of the alcohol that organosilicon source and the hydrolysis of organic titanium source produce is no more than 10ppm.
26. in accordance with the method for claim 6, it is characterized in that, the described aging ageing time of step (2) is 2 ~ 50 hours or 3 ~ 30 hours or 3 ~ 15 hours.
27., according to the method described in any one of claim 6 ~ 26, is characterized in that, described method also comprises step (4): HTS step (3) obtained crystallization 0.5 ~ 10 day in the organic base aqueous solution, and 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 base, described HTS is (with SiO
2meter) be 1:2 ~ 50 with the mol ratio of water; Described organic base is quaternary ammonium base and/or organic amine.
28. in accordance with the method for claim 27, it is characterized in that, the temperature of step (4) described crystallization is 150 ~ 200 DEG C, and the mol ratio of HTS and water is 1:2 ~ 30, and pressure is self-generated pressure.
29. in accordance with the method for claim 6, it is characterized in that, described titanium source is tetraalkyl titanate (Ti (alkoxy)
4, TiCl
4, Ti (SO
4)
2and one or more in their hydrolysate, the carbon number of the alkyl wherein in tetraalkyl titanate is 1,2,3,4,5 or 6.
30. in accordance with the method for claim 6, it is characterized in that, the mass content that step (1) is hydrolyzed monohydric alcohol in the product catching up with alcohol to obtain is no more than 10ppm.
31. in accordance with the method for claim 6, it is characterized in that, step (2) described aging be leave standstill 1 ~ 60 hour in room temperature ~ 50 DEG C; Described time of repose is such as 2 ~ 50 hours, 3 ~ 30 hours or 3 ~ 15 hours.
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| JP2014220736A JP6517001B2 (en) | 2013-10-29 | 2014-10-29 | Titanium silicate molecular sieve and its synthesis |
| US14/527,657 US9896343B2 (en) | 2013-10-29 | 2014-10-29 | Titanium silicalite molecular sieve and its synthesis |
| NL2013705A NL2013705B1 (en) | 2013-10-29 | 2014-10-29 | A titanium silicalite molecular sieve and its synthesis. |
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