CN104556112A - Titanium-silicon micro-mesoporous molecular sieve composite material and synthetic method thereof - Google Patents
Titanium-silicon micro-mesoporous molecular sieve composite material and synthetic method thereof Download PDFInfo
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Abstract
The invention relates to a titanium-silicon micro-mesoporous molecular sieve composite material and a synthetic method thereof. The titanium-silicon micro-mesoporous molecular sieve composite material is rich in silicon on the surfaces of crystal grains, wherein the surface silicon-titanium ratio is higher than that of a bulk phase. The synthetic method of the titanium-silicon micro-mesoporous molecular sieve composite material comprises the following steps: mixing a titanium source, a template, an organic silicon source, an inorganic ammonium source and water; hydrolyzing to propel alcohol, aging, and mixing with a solid silicon source; and then crystallizing in a closed reaction kettle and recovering the titanium-silicon micro-mesoporous molecular sieve composite material. The titanium-silicon micro-mesoporous molecular sieve composite material provided by the invention has high oxidative activity and the noneffective decomposition activity of hydrogen peroxide in side reaction is remarkably reduced.
Description
Technical field
The present invention relates to the method for the micro-mesoporous molecular sieve composite material of a kind of synthesis of titanium silicon.
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 US4410501.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 1h, 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.
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 HTS of existing method synthesis is mainly based on micropore above, and mesopore volume is not high.
Summary of the invention
The technical problem to be solved in the present invention is to provide the micro-mesoporous molecular sieve composite material of a kind of titanium silicon (also referred to as the micro-mesoporous composite molecular sieve of titanium silicon, the micro-mesopore molecular sieve of titanium silicon, the micro-mesoporous composite material of titanium silicon or the micro-mesoporous material of titanium silicon), the micro-mesoporous molecular sieve composite material of this titanium silicon has micropore and composite mesoporous structure, and the other technical problem that the present invention will solve is to provide the synthetic method of the micro-mesoporous molecular sieve composite material of a kind of described titanium silicon.
The invention provides the synthetic method of the micro-mesoporous molecular sieve composite material of a kind of titanium silicon, 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; Described template comprises quaternary organic ammonium compounds and chain alkyl ammonium compound and optional organic amine;
(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, the micro-mesoporous molecular sieve composite material of recovery Pd silicon.
The micro-mesoporous molecular sieve composite material synthetic method of titanium silicon provided by the invention, preferably includes following steps:
(1) by template, titanium source, organosilicon source, optional 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 preferably 50 ~ 95 DEG C by gained mixture stir at least 10 minutes; The churning 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 that step (1) products therefrom is left standstill 1 ~ 60 hour such as 2 ~ 50 hours or 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 ~ 10, then crystallization in closed reactor, the micro-mesoporous molecular sieve composite material of recovery Pd silicon; 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 0.1 ~ 0.3:1 that the mol ratio template in template and total silicon source and the mol ratio in total silicon source are not less than 0.08 ~ 0.6:1; 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 micro-mesoporous molecular sieve composite material synthetic method of titanium silicon 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.Described template is quaternary organic ammonium compounds, chain alkyl ammonium compound and optional organic amine, the mol ratio in quaternary organic ammonium compounds and total silicon source is 0.04 ~ 0.45:1, the mol ratio in chain alkyl ammonium compound and total silicon source is 0.04 ~ 0.45:1, and the mol ratio in organic amine and total silicon source is 0 ~ 0.40:1.
The present invention also provides a kind of titanium silicon micro-mesoporous molecular sieve composite material, this molecular sieve has following characteristics: described titanium silicon micro-mesoporous molecular sieve composite material grain surface Silicon-rich, 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 shell 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 zone of crystal grain.
The micro-mesoporous molecular sieve composite material of described titanium silicon, have microvoid structure, also have meso-hole structure, the aperture of described micropore is less than 1nm, and described mesoporous aperture (diameter) is between 2-8nm.In the micro-mesoporous composite molecular sieve XRD spectra of described titanium silicon, 2 θ angles are 0 ~ 3 ° and 5 ~ 35 ° and have diffraction peak.The XRD spectra of molecular sieve is 5 ~ 35 degree at 2 θ angles and has diffraction peak, shows to there is microvoid structure in molecular sieve; 2 θ angles of molecular sieve are 0 ~ 3 ° and have diffraction peak, show to there is meso-hole structure in molecular sieve.
The micro-mesoporous molecular sieve composite material of titanium silicon of the present invention, aperture is less than the volume of the micropore of 1nm and micro pore volume is 0.12 ~ 0.19mL/g, and aperture is the mesoporous volume of 2-8nm and mesopore volume is 0.3 ~ 0.8mL/g.
The micro-mesoporous molecular sieve composite material synthetic method of titanium silicon provided by the invention, prepared titanium silicon micro-mesoporous molecular sieve composite material grain surface Silicon-rich, grain surface silicon titanium ratio is apparently higher than body phase silicon titanium ratio.In addition, the micro-mesoporous molecular sieve composite material synthetic method of titanium silicon 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 black, 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 the micro-mesoporous molecular sieve composite material of high performance titanium silicon, prepared molecular sieve has higher oxidation activity.The micro-mesoporous molecular sieve composite material synthetic method of titanium silicon provided by the invention, can at lower template consumption and lower water silicon mesoporous molecular sieve composite material more micro-than synthesis of titanium silicon in situation, the synthesis cost of the micro-mesoporous molecular sieve composite material of titanium silicon can be reduced, improve the solid content of synthesis of molecular sieve crystallization product, improve single still molecular sieve output.
The micro-mesoporous molecular sieve composite material of titanium silicon provided by the invention (also claiming titanium silicon micro-mesoporous composite molecular sieve), 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.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the micro-mesopore molecular sieve of titanium silicon (the micro-composite mesoporous TS-1 molecular sieve of titaniferous) with MFI structure of embodiment of the present invention synthesis.
Fig. 2 is the little angle XRD spectra of the micro-mesopore molecular sieve of titanium silicon (the micro-composite mesoporous TS-1 molecular sieve of titaniferous) with MFI structure of embodiment of the present invention synthesis.
Fig. 3 is the SEM scintigram of the micro-mesopore molecular sieve of titanium silicon (the micro-composite mesoporous beta molecule of titaniferous) with BEA structure of embodiment of the present invention synthesis
Fig. 4 be titanium silicon that embodiment of the present invention step (4) obtains have micro-mesopore molecular sieve of MFI structure TEM figure.
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 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 to embody and compares difference with the silicon titanium on surface.
Fig. 6 is the nitrogen absorption under low temperature desorption curve of the micro-mesopore molecular sieve of titanium silicon (the micro-composite mesoporous TS-1 molecular sieve of titaniferous) (embodiment 1 step (3) gained) with MFI structure of embodiment of the present invention synthesis.
Embodiment
The synthetic method of the micro-mesoporous molecular sieve composite material of titanium silicon provided by the invention, can in lower template agent consumption situation the micro-mesoporous molecular sieve composite material of synthesis of titanium silicon, thus template agent consumption can be lower, such as the mol ratio in template agent and total silicon source is 0.1 ~ 0.3:1, is 0.1 ~ 0.25:1 further; In method provided by the invention, can at the micro-mesoporous molecular sieve composite material of synthesis of titanium silicon 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 and the mol ratio in total silicon source (silicon-dioxide) can be 5 ~ 80:1 or 5 ~ 50:1 or 5 ~ 30:1 or 6 ~ 20 or 6 ~ 15:1.
The synthetic method of the micro-mesoporous molecular sieve composite material of titanium silicon provided by the invention, the mol ratio in described titanium source and total silicon source is 0.005 ~ 0.05:1 be such as 0.01 ~ 0.03:1 is such as 0.01 ~ 0.025:1.
The synthetic method of the micro-mesoporous molecular sieve composite material of titanium silicon 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 ratio (higher framework titania silicon ratio can be had in same titanium source usage quantity situation) in titanium source can be improved, reduce the usage quantity in titanium source.
The synthetic method of the micro-mesoporous molecular sieve composite material of titanium silicon provided by the invention, the mol ratio in described template and described total silicon source is not less than 0.08:1, and being such as that 0.08 ~ 0.6:1 is preferably 0.1 ~ 0.3:1, such as, is 0.1 ~ 0.2:1.
The synthetic method of the micro-mesoporous molecular sieve composite material of titanium silicon 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 the micro-mesoporous molecular sieve composite material of titanium silicon provided by the invention, template agent described in step (1) comprises quaternary organic ammonium compounds and chain alkyl ammonium compound, can optionally also containing organic amine compound, the mol ratio in quaternary organic ammonium compounds and total silicon source is 0.04 ~ 0.45:1, the mol ratio in chain alkyl ammonium compound and total silicon source is 0.04 ~ 0.45:1, and the mol ratio in organic amine and total silicon source is 0 ~ 0.4:1.Described quaternary organic ammonium compounds is such as organic quaternary amine alkali and/or organic quaternary ammonium salt.Described organic amine is one or more in aliphatic amide, aromatic amine and hydramine, and described aliphatic amide (also claiming 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.
The synthetic method of the micro-mesoporous molecular sieve composite material of titanium silicon provided by the invention, described its general formula of chain alkyl ammonium compound is R
5nH
3x or R
5n (R
6)
3x, wherein R
5for the alkyl of carbonatoms between 12 ~ 18, R
6for the alkyl of carbonatoms between 1 ~ 4; X is univalent anion is such as OH
-, C1
-, Br
-; When X is OH
-time, the present invention is called alkali formula chain alkyl ammonium compound; 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.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, described chain alkyl ammonium compound such as cetyl trimethylammonium bromide, cetyl chloride ammonium, cetyltrimethylammonium hydroxide, chain alkyl ammonium compound is Tetradecyl Trimethyl Ammonium Bromide, tetradecyl ammonium chloride, tetradecyltrimethylammonium ammonium hydroxide, Trimethyllaurylammonium bromide, lauryl ammonium chloride, trimethyl ammonium hydroxide, Cetyltrimethylammonium bromide, octadecyl ammonium chloride, one or more in octadecyl trimethyl ammonium hydroxide.
The synthetic method of the micro-mesoporous molecular sieve composite material of titanium silicon provided by the invention, a kind of embodiment, the described micro-mesoporous composite molecular sieve of titanium silicon has MFI structure, described quaternary organic ammonium compounds comprise in TPAOH, 4-propyl ammonium chloride, 4-propyl bromide one or more.The mol ratio in one or more and total silicon source in TPAOH, 4-propyl ammonium chloride, 4-propyl bromide is not less than 0.01:1, is preferably 0.02 ~ 0.45:1.
The synthetic method of the micro-mesoporous molecular sieve composite material of titanium silicon provided by the invention, the micro-mesoporous composite molecular sieve of titanium silicon described in embodiment has a MEL structure, described quaternary organic ammonium compounds comprise in TBAH, Tetrabutyl amonium bromide or tetrabutylammonium chloride one or more.One or more summation in TBAH, Tetrabutyl amonium bromide or tetrabutylammonium chloride be not less than 0.01:1 with the mol ratio in total silicon source, be preferably 0.02 ~ 0.45:1.
The synthetic method of the micro-mesoporous molecular sieve composite material of titanium silicon provided by the invention, a kind of embodiment, the described micro-mesoporous composite molecular sieve of titanium silicon has BEA structure, described quaternary organic ammonium compounds comprise in tetraethyl ammonium hydroxide, tetraethylammonium bromide, etamon chloride one or more.Described quaternary organic ammonium compounds comprises one or more the summation in tetraethyl ammonium hydroxide, tetraethylammonium bromide, etamon chloride and is not less than 0.01:1 with the mol ratio in total silicon source, is preferably 0.02 ~ 0.45:1.
The synthetic method of the micro-mesoporous composite molecular sieve of titanium silicon provided by the invention, the mol ratio in quaternary organic ammonium compounds and total silicon source is 0.05 ~ 0.45:1, and the mol ratio in long-chain organic amine compound and total silicon source is 0.05 ~ 0.45:1.In preferred situation, described template at least comprises a kind of organic bases, described organic bases be in quaternary ammonium base, organic amine, alkali formula chain alkyl ammonium compound one or more, the mol ratio in the organic bases in described template agent and total silicon source is 0.04 ~ 0.5:1, such as 0.05 ~ 0.45:1.
The micro-mesoporous molecular sieve composite material synthetic method of titanium silicon 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-chain 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 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 the total mass content of Fe, Al and Na impurity is less than 10ppm; 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 mass content of Fe, Al and Na impurity is less than 10ppm.The specific surface area of described white carbon black is preferably between 50-400m
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 described white carbon black, the total mass content of Fe, Al and Na impurity 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.
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 carbonatoms of the alkyl wherein in tetraalkyl titanate molecule is 1 ~ 6, and such as carbonatoms is 1,2,3,4,5 or 6.。The molar ratio in titanium source and total silicon source (being called for short silicon source) is as being such as 0.01 ~ 0.03:1 or 0.01 ~ 0.025:1 or 0.015 ~ 0.025:1 for 0.008 ~ 0.035:1.
The micro-mesoporous molecular sieve composite material synthetic method of titanium silicon 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 the micro-mesoporous molecular sieve composite material synthetic method of titanium silicon 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, 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 alcohol (the being generally monohydroxy-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 churning time is 10 ~ 3000 minutes, such as, be 2 ~ 30 hours.Catch up with alcohol by hydrolysis, obtain organosilicon source and the titanium source hydrolyzed solution of clear.Under preferable case, in the product that step (1) obtains, the mass content of the monohydroxy-alcohol alcohol that organosilicon source and the hydrolysis of organic titanium source produce is no more than 10ppm, and in the mixture that preferred steps (1) obtains, the content of monohydroxy-alcohol is not higher than 10ppm (quality).
The micro-mesoporous molecular sieve composite material synthetic method of titanium silicon 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; Digestion time is 1 ~ 60 hour is such as 2 ~ 50 hours, preferably 3 ~ 30 hours, such as 3 ~ 15 hours, does not stir in weathering process, described material and step (1) products therefrom is left standstill.
The micro-mesoporous molecular sieve composite material synthetic method of titanium silicon 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 that (namely the mol ratio of 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 in 1:0.1 ~ 10.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.
The micro-mesoporous molecular sieve composite material synthetic method of titanium silicon provided by the invention, 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 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, crystallization time is preferably 0.5 ~ 10 day 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 0.5 ~ 6 day such as 1 ~ 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.
The micro-mesoporous molecular sieve composite material synthetic method of titanium silicon provided by the invention, described in step (3), the micro-mesoporous molecular sieve composite material of recovery Pd silicon 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 the micro-mesoporous molecular sieve composite material of titanium silicon 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.The micro-mesoporous molecular sieve composite material product of titanium silicon provided by the present invention is obtained by reclaiming.
In the micro-mesoporous molecular sieve composite material synthetic method of titanium silicon provided by the invention, step (3) reclaims the micro-mesoporous molecular sieve composite material of titanium silicon obtained and also can be passed through further process, the i.e. micro-mesoporous molecular sieve composite material synthetic method of titanium silicon provided by the invention, can also comprise step (4):
(4) the micro-mesoporous molecular sieve composite material of the titanium silicon Crystallizing treatment in organic alkali solution step (3) obtained, the then micro-mesoporous molecular sieve composite material of recovery Pd silicon.The micro-mesoporous molecular sieve composite material of titanium silicon that this process obtains has hollow structure, and the present invention is referred to as molecular sieve and resets.Wherein the micro-mesoporous molecular sieve composite material of titanium silicon is (with SiO
2meter) be 1:0.02 ~ 0.5 with the molar ratio of organic bases 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 autogenous pressure, the preferred quaternary ammonium base of wherein said organic bases.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 bases is organic amine and/or quaternary ammonium base; Described organic amine is one or more in aliphatic amide, aromatic amine and hydramine, and described aliphatic amide (also claiming 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.A kind of embodiment, step (4), the described micro-mesoporous molecular sieve composite material of titanium silicon has MFI structure, and described quaternary ammonium base is TPAOH.A kind of embodiment, the described micro-mesoporous molecular sieve composite material of titanium silicon has MEL structure, and the quaternary ammonium base described in step (4) is TBAH.A kind of embodiment, the described micro-mesoporous molecular sieve composite material of titanium silicon has BEA structure, and the quaternary ammonium base described in step (4) is tetraethyl ammonium hydroxide.
Step (4) the present invention is referred to as molecular sieve and resets, this process can be carried out once, also one or many can be repeated, described repetition, the molecular sieve that the micro-mesoporous molecular sieve composite material of the titanium silicon obtained by described process replaces step (3) to obtain carries out the process of step (4).By resetting process, the micro-mesoporous molecular sieve composite material of titanium silicon with secondary pore structure can be obtained, the crystal grain that the micro-mesoporous molecular sieve composite material of gained titanium silicon has hollow structure and described HTS is hollow structure, the radical length of the chamber portion of this hollow crystal grain is 5 ~ 300nm, at 25 DEG C, 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.After resetting, molecular sieve has larger pore volume and specific surface 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 described 20 particles 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 (λ=1.5418
), 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.
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.
Other reagent, without what further illustrate, is commercial goods, analytical pure.
Comparative example 1
This comparative example illustrates that the method for giving prominence to according to people such as Thangaraj prepares the micro-mesoporous molecular sieve composite material of conventional titanium silicon (Zeolites, 1992, Vol.12 943rd ~ 950 pages).
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 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.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 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.Its XRD analysis spectrogram as shown in Figure 1.
Embodiment 1
(1) by 15g concentration be 25.05 % by weight the TPAOH aqueous solution, 2.04g tetrabutyl titanate, 5.62g cetyltrimethylammonium hydroxide (code name MSDS), 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 hydrolyzed solution;
(2) within 12 hours, carry out aging by standing under room temperature (26 DEG C) for gained hydrolyzed solution, obtain ageing products;
(3) in above-mentioned ageing products, add 9.6g white carbon black powder 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 crystallization sample, filter, washing, drying 24 hours at 120 DEG C, 550 DEG C of roastings 6 hours, the micro-mesoporous molecular sieve composite material product of titanium silicon of the present invention, be designated as TS-1F1; Mesopore volume is 0.385mL.g
-1, micro pore volume 0.152mL.g
-1.Its BET specific surface area is 449m
2/ g, outer surface area is 58m
2/ g.There is MFI structure.Its XRD analysis spectrogram as shown in Figure 1, 2.
(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 the micro-mesoporous molecular sieve composite material product of titanium silicon, be designated as TS-1P1.Its XRD analysis spectrogram feature as shown in Figure 1, 2, its BET specific surface area is 477m
2/ g, outer surface area is 62m
2/ g mesopore volume is 0.388mL.g
-1, micro pore volume 0.153mL.g
-1.In transmission electron microscope photo, it is hollow structure (see Fig. 4).
Embodiment 2
(1) by 7.4g concentration be 25.05 % by weight TPAOH, 1.23g tetrabutyl titanate, 3.29g cetyl trimethylammonium bromide (code name CTMAB), 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 alkaline hydrolysis liquid.
(2) hydrolyzed solution of gained is at room temperature left standstill 3 hours, obtain ageing products;
(3) in obtained ageing products, 9.6g white carbon black powder is slowly added under stirring, add rear stirring 1.5 hours, transferred in stainless steel closed reactor, in 165 DEG C of thermostatic crystallizations 2 days, filtered, washing, drying 24 hours at 120 DEG C, 550 DEG C of roastings 6 hours, namely obtain the micro-mesoporous molecular sieve composite material sample of titanium silicon, are designated as TS-1F2.Mesopore volume is 0.365mL.g
-1, micro pore volume 0.157mL.g
-1.There is MFI structure; Its XRD analysis spectrogram has feature as shown in Figure 1, 2;
(4) by even for the TPAOH aqueous solution of 6g TS-1F2 sample and 36 grams of concentration 22.05%, 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, the micro-mesoporous molecular sieve composite material product of titanium silicon must be reset, be designated as TS-1P2.Its XRD analysis spectrogram has feature as shown in Figure 1, 2, and surface has MFI structure.In transmission electron microscope photo, it is hollow structure.Mesopore volume is 0.372mL.g
-1, micro pore volume 0.154mL.g
-1.
Embodiment 3
(1) by 43g concentration be 25.05% the 4-propyl bromide aqueous solution, 1.68g titanyl sulfate, 5.62g cetyltrimethylammonium hydroxide, 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 heat 3 hours at 65 DEG C, supplement the moisture of evaporation at any time, obtain alkaline hydrolysis liquid.
(2) gained hydrolyzed solution is at room temperature left standstill 9 hours, obtain ageing products.
(3) in the beaker filling ageing products, 9.6g 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, the micro-mesoporous molecular sieve composite material product of titanium silicon provided by the invention, be designated as TS-1F3.Mesopore volume is 0.374mL.g
-1, micro pore volume 0.146mL.g
-1.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, wash, drying 24 hours at 120 DEG C, 550 DEG C of roastings 6 hours, the micro-mesoporous molecular sieve composite material sample of hollow titanium silicon, be designated as TS-1P3.In transmission electron microscope photo, it is hollow structure.Mesopore volume is 0.380mL.g
-1, micro pore volume 0.149mL.g
-1.XRD shows that it has MFI structure.
Embodiment 4 ~ 7
Prepare the micro-mesoporous molecular sieve composite material of titanium silicon according to the method for embodiment 1, its proportioning and synthesis condition, characterization result are in table 1,2.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 1,2.
Embodiment 10
Preparation has the micro-mesopore molecular sieve of titanium silicon of MEL structure.With reference to according to the method for embodiment 1, change proportioning and template, its proportioning and synthesis condition, the results are shown in Table 1,2.
Embodiment 11
Preparation has the micro-mesopore molecular sieve of titanium silicon of BEA structure.The method of reference example 1, changes proportioning and template, its proportioning and synthesis condition, the results are shown in Table 1.XRD the results are shown in Table 2, and its SEM figure is see Fig. 3.
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 1 ~ 11, contrast 1 ~ 2 and comparative example 1 ~ 3 synthesis condition, characterization result is in table 1,2.
Embodiment 12
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 micro-mesoporous molecular sieve composite material of titanium silicon got 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, be warming up to 75 DEG C, the quality of TS-1 molecular sieve is 2.6g.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 8.6ml/h, add 25 % by weight ammonia solns with the speed of 6ml/h, volume space velocity is 7.92h simultaneously
-1.。Above-mentioned three strands of materials add simultaneously, and simultaneously with corresponding speed continuous discharge, after stable reaction 3 hours, stratographic analysis was 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 micro-mesoporous molecular sieve composite materials of titanium silicon, 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 improve the transformation efficiency of reactant.
As can be seen from Table 1: 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.
Table 1 Zeolite synthesis condition and product performance
CTMAB and cetyl trimethylammonium bromide, TTAB and Tetradecyl Trimethyl Ammonium Bromide, DTAB is trimethyl ammonium hydroxide, and MSDS is cetyltrimethylammonium hydroxide, and TBAOH is TBAH, and TEAOH is tetraethyl ammonium hydroxide.
Table 2 different titanium silicon micro-mesoporous molecular sieve composite material catalysis of phenol hydroxylation transformation efficiency and cyclohexanone oxamidinating data and decomposing hydrogen dioxide solution
In table 2, micro pore volume refers to the volume being less than lnm hole, and the mesopore volume of embodiment 1 ~ 9 and comparative example 3-4 refers to that aperture is the volume in 2 ~ 8nm hole.The volume in the mesopore volume of comparative example 1 and 2 to be aperture be 2 ~ 50nm hole.
For comparative example, in table 1,2, step (3) product refers to the micro-mesoporous molecular sieve composite material of titanium silicon without resetting.Step (4) product refers to the HTS through resetting.
Claims (32)
1. the micro-mesoporous molecular sieve composite material of titanium silicon, is characterized in that, the surface silicon titanium of the micro-mesoporous molecular sieve composite material crystal grain of described titanium silicon is than being greater than 1.1 with the ratio of body phase silicon titanium ratio and being less than 5.
2. according to the micro-mesoporous molecular sieve composite material of titanium silicon 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 the micro-mesoporous molecular sieve composite material of titanium silicon according to claim 1, it is characterized in that, the titanium silicon of the micro-mesoporous molecular sieve composite material of described titanium silicon is 0.01 ~ 0.025:1 than mol ratio.
4. according to the micro-mesoporous composite molecular sieve of total silicon according to claim 1, it is characterized in that, the micro-mesoporous composite molecular sieve of described total silicon has the microvoid structure that is less than 1nm and aperture is the meso-hole structure of 2 ~ 8nm, aperture is the mesopore volume of 2 ~ 8nm is 0.3 ~ 0.8ml/g, and micro pore volume is for being 0.12 ~ 0.19ml/g.
5., according to the micro-mesoporous molecular sieve composite material of titanium silicon according to claim 1, it is characterized in that, the micro-mesoporous molecular sieve composite material of described titanium silicon have in MFI structure, MEL structure, BEA structure one or more.
6. according to the micro-mesoporous molecular sieve composite material of titanium silicon described in any one of Claims 1 to 5, the crystal grain of described HTS is hollow structure, 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 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.After resetting, molecular sieve has larger pore volume and specific surface area.
7. a synthetic method for the micro-mesoporous molecular sieve composite material of titanium silicon, 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; Described template comprises quaternary organic ammonium compounds, chain alkyl ammonium compound and optional organic amine;
(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, the micro-mesoporous molecular sieve composite material of recovery Pd silicon.
8. in accordance with the method for claim 7, 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;
In step (3), the weight ratio of the ageing products that described step (2) obtains and solid silicon source is 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;
Described template is quaternary organic ammonium compounds, chain alkyl ammonium compound and optional organic amine, the mol ratio in organic amine and total silicon source is 0 ~ 0.40:1, the mol ratio in quaternary organic ammonium compounds and total silicon source is 0.04 ~ 0.45:1, and the mol ratio in chain alkyl ammonium compound and total silicon source is 0.04 ~ 0.45:1; The mol ratio in water and total silicon source is 5 ~ 100:1; The mol ratio in titanium source and total silicon source is 0.005 ~ 0.05:1; Inorganic Ammonium source: the mol ratio in titanium source is 0 ~ 5:1; 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.
9. in accordance with the method for claim 8, 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.
10. 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 0.08 ~ 0.6:1 or 0.05 ~ 0.3:1 or 0.05 ~ 0.25:1 or 0.05 ~ 0.2:1.
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 or 6 ~ 30:1 or 6 ~ 15:1.
12. in accordance with the method for claim 8, 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.
13. in accordance with the method for claim 8, 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.
14. in accordance with the method for claim 7, it is characterized in that, step (3) 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 or 0.5 ~ 10 day.
15. in accordance with the method for claim 14, it is characterized in that the crystallization temperature of crystallization described in step (3) is 140 ~ 180 DEG C or is 160 ~ 180.
16. in accordance with the method for claim 7, 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 autogenous pressure.
17. in accordance with the method for claim 7, it is characterized in that, 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.
18. in accordance with the method for claim 8, it is characterized in that, the mol ratio in the organic bases in described template agent and total silicon source is 0.05 ~ 0.5:1; The mol ratio in quaternary organic ammonium compounds and total silicon source is 0.05 ~ 0.45:1, and the mol ratio in long-chain organoammonium compound and total silicon source is 0.05 ~ 0.45:1.
19. in accordance with the method for claim 18, 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.
20. in accordance with the method for claim 7, it is characterized in that, described solid silicon source is white carbon black, and the specific surface area of described white carbon black is 50 ~ 400m2/g.
21. in accordance with the method for claim 7, it is characterized in that, 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, and described quaternary ammonium base is one or more in TPAOH, TBAH or tetraethyl ammonium hydroxide.
22. in accordance with the method for claim 21, 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.
23. in accordance with the method for claim 7, it is characterized in that, described quaternary organic ammonium compounds is quaternary ammonium base and/or organic quaternary ammonium salt; Described its general formula of chain alkyl ammonium compound is R
5nH
3x or R
5n(R
6)
3x, wherein R
5for the alkyl of carbonatoms between 12 ~ 18, R
6for the alkyl of carbonatoms between 1 ~ 4; X is univalent anion; 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.
24. in accordance with the method for claim 23, 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 bromide, Tetrabutyl amonium bromide, tetraethylammonium bromide, 4-propyl ammonium chloride, tetrabutylammonium chloride or etamon chloride, described chain alkyl ammonium compound is cetyl trimethylammonium bromide, cetyl chloride ammonium, cetyltrimethylammonium hydroxide, chain alkyl ammonium compound is Tetradecyl Trimethyl Ammonium Bromide, tetradecyl ammonium chloride, tetradecyltrimethylammonium ammonium hydroxide, Trimethyllaurylammonium bromide, lauryl ammonium chloride, trimethyl ammonium hydroxide, Cetyltrimethylammonium bromide, octadecyl ammonium chloride, one or more in octadecyl trimethyl ammonium hydroxide.
25. in accordance with the method for claim 7, it is characterized in that, the described micro-mesoporous composite molecular sieve of titanium silicon has MFI structure, described quaternary organic ammonium compounds comprise in TPAOH, 4-propyl ammonium chloride, 4-propyl bromide one or more; Or the described micro-mesoporous composite molecular sieve of titanium silicon has MEL structure, described quaternary organic ammonium compounds comprise in TBAH, Tetrabutyl amonium bromide or tetrabutylammonium chloride one or more; Or the described micro-mesoporous composite molecular sieve of titanium silicon has BEA structure, described quaternary organic ammonium compounds comprise in tetraethyl ammonium hydroxide, tetraethylammonium bromide, etamon chloride one or more.
26. in accordance with the method for claim 7, 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.
27. in accordance with the method for claim 7, 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 churning time is 2 ~ 30 hours.
28. in accordance with the method for claim 7, it is characterized in that, in the product that step (1) obtains, the mass content of monohydroxy-alcohol alcohol is no more than 10ppm.
29. in accordance with the method for claim 7, it is characterized in that, the described aging digestion time of step (2) is 2 ~ 50 hours or 3 ~ 30 hours or 3 ~ 15 hours.
30. in accordance with the method for claim 7, 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 carbonatoms of the alkyl wherein in tetraalkyl titanate is 1,2,3,4,5 or 6.
31. according to the method described in any one of claim 7 ~ 30, it is characterized in that, described method also comprises step (4): the micro-mesoporous molecular sieve composite material of titanium silicon step (3) obtained crystallization 0.5 ~ 10 day in the organic bases aqueous solution, and the temperature of crystallization is 110 ~ 200 DEG C; The wherein said micro-mesoporous molecular sieve composite material of titanium silicon is (with SiO
2meter) be 1:0.02-0.5 with the mol ratio of described organic bases, the described micro-mesoporous molecular sieve composite material of titanium silicon 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.
32., according to method according to claim 31, is characterized in that, the temperature of step (4) described crystallization is 150 ~ 200 DEG C, and the mol ratio of the micro-mesoporous molecular sieve composite material of titanium silicon and water is 1:2 ~ 30, and pressure is autogenous pressure.
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| 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. |
| DE201410222042 DE102014222042A1 (en) | 2013-10-29 | 2014-10-29 | Titanium silicalite molecular sieve and its synthesis |
| TW103137439A TWI637912B (en) | 2013-10-29 | 2014-10-29 | Titanium bismuth molecular sieve and synthesis method thereof |
| JP2014220736A JP6517001B2 (en) | 2013-10-29 | 2014-10-29 | Titanium silicate molecular sieve and its synthesis |
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