CN104709918A - Titanium silicon molecular sieve with MWW topological structure and preparation and application thereof - Google Patents
Titanium silicon molecular sieve with MWW topological structure and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a titanium silicon molecular sieve with a MWW topological structure and a synthesis method thereof. The silicon-titanium ratio (atomic ratio) of the Ti-MWW molecular sieve is in the range of 10 to 1000, and a method for preparation of the Ti-MWW molecular sieve by ionothermal secondary synthesis is provided. A titanium source, ionic liquid and MWW molecular sieve rich in Si-OH groups are evenly mixed according to a certain proportion and feeding method for crystallization for a certain time at a certain temperature, and the Ti-MWW molecular sieve can be obtained by separation, washing and drying, and the crystallization product can be directly used as a catalyst or catalyst carrier. The Ti-MWW molecular sieve has excellent catalytic oxidation performance in the phenol hydroxylation, olefin epoxidation and aldehyde ketone compound ammoximationreaction processes.
Description
Technical field
The present invention relates to and a kind of there is HTS of MWW topological features and preparation method thereof.Especially, the present invention relates to a kind of method adopting the hot secondary synthesis of ion to prepare Ti-MWW molecular sieve.
Background technology
Molecular sieve, by essentially consist classification, is mainly silicate-base molecular sieve and phosphate base molecular sieve two class.Because different chemical reactions has different requirements to the pore passage structure of porous catalyst material and surface property, therefore, on the one hand the synthesis of novel structure molecular sieve material is the important research contents of Materials science and catalytic science all the time, on the other hand, the functionalized design of molecular screen material, synthesis and modification expand definition and the category of molecular sieve too.Wherein especially the introducing of transition metal hetero-atom makes molecular sieve have multifunctionality in skeleton, and having further expanded its range of application, is the catalytic material that academia and industry member are paid close attention to jointly.
Framework of molecular sieve introducing hetero-atoms, the hetero-atom molecular-sieve that the transition metal ion isomorphous substitution particularly with specific catalytic performance obtains, because metal ion is in isolated high dispersion state on framework of molecular sieve, simultaneously also due to the interaction between molecular sieve precursor skeleton, the unexistent special catalysis of transition metal oxide that they are possessed is conventional, its performance is also obviously different from the original function of parent molecule sieve, not only to the acidity of zeolite catalyst, surface property plays regulating effect, be conducive to zeolite catalyst simultaneously and realize multi-functional catalysis.
In this respect, most typical example is HTS.Nineteen eighty-three, titanium is successfully introduced in MFI topological framework silicate systems by gondola Taramasso, synthesis obtains TS-1 molecular sieve, thus make the application of molecular sieve from traditional acid-base catalysis process spread to catalytic oxidation process, be considered to a milestone of the molecular sieve catalytic research field 1980s.As everyone knows, the production of oxygenatedchemicals is very important process in petrochemical complex and fine chemistry industry always, and traditional catalytic oxidation process does not meet the needs of human kind sustainable development because effect is low, seriously polluted.The catalytic oxidation system developed on HTS basis, because its reaction conditions is gentle, selectivity is good, and whole catalytic process only has water byproduct and non-pollution discharge, be considered to eco-friendly green chemistry process, and then cause synthesis and the applied research upsurge of HTS for a long time.TS-1 molecular sieve is applied to the Industrial demonstration process of phenol hydroxylation and cyclohexanone oxamidinating by Eni company the earliest, the cyclohexanone-oxime that Sinopec is 70,000 tons/year is installed on 2003 and is constructed and put into operation, worldwide first has been carried out the large-scale industrial application of HTS, and Sumitomo, BASF, DOW, Evonik etc. also build up number cover and produce propylene oxide new device based on the cyclohexanone oxamidinating of titanium molecular sieve catalysis oxidising process and epoxidation of propylene subsequently.
Although have important industrial application value, be difficult to synthesis and catalytic performance is unstable constrains further developing of TS-1 molecular sieve research.The main following points of reason: (1), the study mechanism incorporation way of titanium in initial silicon titanium sol system and existing forms and follow-up crystallization process titanium being entered to framework of molecular sieve are all undistinct.Different titanium sources can affect the existing forms of titanium in starting sol, but years of researches show, even if only adopt butyl (tetra) titanate to be titanium source, due to complicacy and the susceptibility of the hydrolysis-polymerization-depolymerization reaction in titanium, silicon source in colloidal sol preparation process, with the high pressure of crystallization process and the limitation of closed state and characterization method, people still can not grasp completely to committed step wherein.It is generally acknowledged, by accurately controlling titanium, that the hydrolysis reaction in the silicon source silicon titanium sol system of preparing stable homogeneous successfully enters framework of molecular sieve to follow-up crystallization process titanium is most important.The hydrolysis rate of butyl (tetra) titanate is more faster than tetraethoxy in aqueous, therefore needs the hydrolysis rate controlling butyl (tetra) titanate, itself and tetraethoxy is matched, could obtain the silicon titanium sol system of stable homogeneous like this.At present mainly through butyl (tetra) titanate is dissolved in Virahol, or add hydrogen peroxide in the butyl (tetra) titanate aqueous solution, and carry out at low temperatures reacting to control, but wherein still cause because there is uncontrollable factor synthesizing poor repeatability.(2), synthesis condition is harsh, requires high to material purity.The impurity of trace is enough to suppress titanium to enter framework of molecular sieve, especially alkali and alkaline earth metal ions element, and high titanium content is the guarantee of HTS high catalytic activity.The impurity such as aluminium, iron suppresses titanium to enter skeleton on the one hand, and their existence also can produce acidic site on framework of molecular sieve on the other hand, thus causes the generation of acid catalysis side reaction.(3), cost intensive.This mainly must adopt caused by a large amount of high purity TPAOH template and expensive organosilicon titanium material owing to synthesizing.
Therefore, under the state that study mechanism is still undistinct, most research all concentrates on how to reduce production cost, as selected cheap silicon, titanium material, screening alternative low cost template, and developing new synthetic method etc.But though cheap raw material such as silicon sol can synthesize TS-1, catalytic activity is lower; In addition, environmental pollution can be caused in fluorine-containing titanium source; Although use titanous chloride and titanium tetrachloride that TS-1 can be synthesized, cause the very big consumption of TPAOH because their hydrolysis produce the neutralization of hydrogenchloride needs; Small part is then only had to enter framework of molecular sieve using oxide compound as titanium source; The TS-1 particle of low cost template synthesis is comparatively large, thus causes activity lower, and to make its active raising, need increase subsequent activation treatment step, trivial operations, cost increases simultaneously.Such as the method such as secondary synthesis, machinery synthesis does not then have practicality at present.
But due to the steric hindrance effect of the 3 D pore canal of TS-1 molecular sieve, make all kinds of macromolecular reaction thing fully cannot contact with the active centre of admiring be distributed in skeleton, catalyzed reaction cannot be carried out smoothly, and the absolute yield of oxidation products is lower.In order to the development of satisfied following fine chemistry industry and intermediate chemical industry, further development of new is admired the application of si molecular sieves in catalytic oxidation, and development of new molecular sieve containing titanium becomes a new research direction.
MCM-22 molecular sieve is the lamellar zeolite with MWW topological framework found the earliest, is synthesized first in nineteen ninety by Mobil company.Found successively again afterwards and synthesized MCM-49, MCM-56, MCM-36, ITQ-l and ITQ-2 equimolecular sieve.They all have certain sibship with the MCM-22 found at first, therefore can be summarized as MCM-22 family molecular sieves together with MCM-22.Molecular sieve MCM-36, ITQ-2 mono-group that current existing MCM-22 family molecular sieves is roughly divided into three groups: MCM-22 by the distance with MCM-22 molecular sieve sibship and is derived by its presoma; The ITQ-1 mono-group that pure silicon is formed; MCM-49 and intermediate product MCM-56 thereof is one group.The matrix topology of MCM-22 overlaps independently pore canal system by three and forms: supercage (0.7lx0.71xl.82nm) the ten-ring two dimension in the pore canal system of (0.40x0.54nm), layer that is connected with interlayer ten-ring intersects sinusoidal reticulated channel system (0.40xO.59nm) and be positioned at the 12 ring holes (0.70x0.7lx0.7lnm) that the crystal outside surface degree of depth is 0.70nm.The structure of the molecular sieve uniqueness of MWW topological framework and acidity, make it in the reactions such as hydro carbons alkylation, alkane aromatization and catalytic cracking, all show excellent catalytic performance.
Until 1999, the people such as Corma [Chem.Commun., (1999) 77] adopt the mode of grafting active centre titanium species to be incorporated into the MCM-22 molecular sieve peeled off through layer, obtain Ti-ITQ-2.2000, Ti-MCM-22 [US6114551,2000] prepared by the MCM-22 of TiC14 steam isomorphous substitution after dealuminzation in Mobil company.Above-mentioned two kinds of methods all belong to the category of two-step fabrication, and the HTS that this method obtains is in liquid phase reaction, and active centre titanium species is easier to run off, and catalyst performance is poor, and not can be recycled.Near to calendar year 2001, Wu Peng etc. add a large amount of boric acid as crystallization in motion agent preparing in gelation process, with hexamethylene imine or hexahydropyridine for structure directing agent, successfully synthesized Ti-MWW molecular sieve [J.Phys.Chem.B, 105 (2001) 289 of excellent performance by hydrothermal method; J.Catal., 202 (2001) 24], but this synthetic system uses a large amount of boric acid, cause combined coefficient too low on the one hand, on the other hand because the acidity of boric acid causes consuming a large amount of organic amine template, from and result in serious environmental pollution, the acidic site that the boron that exists in third aspect molecular sieve produces is the side reaction active centre of oxidizing reaction, and then causes the selectivity of reacting to decline.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, obtain a kind of HTS with MWW topological features, and the hot secondary synthesis of a kind of ion prepares the method for Ti-MWW molecular sieve, the ion thermal synthesis method of the method has the feature of extremely-low vapor pressure, has abandoned the restriction of conventional hydrothermal synthetic method Intermediate High Pressure for synthesis device.
The HTS with MWW topological features provided by the invention, silicon titanium ratio (atomic ratio) scope of this kind of Ti-MWW molecular sieve is within 10 ~ 1000.
The invention provides the method that the hot secondary synthesis of a kind of ion prepares Ti-MWW molecular sieve.Ionic liquid is as novel eco-friendly " green solvent " of a class, there is the character of many uniquenesses: (1) ionic liquid body fluid journey is wide, volatility is low, nonflammable, therefore ion thermal synthesis can be carried out at ambient pressure, thus reduces the pressure risk of Zeolite synthesis; (2) the organic amine structure directing agent structure that ionic liquid and Zeolite synthesis are conventional is close, can double as solvent and structure directing agent, and it is of a great variety, molecular structure can design, add the variable controlled variable of synthesis, for initiative novel material provides new platform; (3) ionic liquid is as a kind of ion solvent, new characteristic is dissolved with to inorganic salt, and ion thermal synthesis is carried out in anhydrous system, can avoid the fast hydrolyzing of some transition metal salt under water existence condition and form the phenomenon that precipitation is difficult to enter skeleton, therefore the hot method of ion has very large development space in Zeolite synthesis.
The feature of this ion process for thermosynthesizing is: titanium source, ionic liquid and the MWW molecular sieve that is rich in Si-OH group are mixed according to certain ratio and feeding method, crystallization certain hour at a certain temperature, obtains Ti-MWW molecular sieve through separation, washing, drying;
Its process comprises:
1), by the MWW molecular sieve being used as precursor material via acid treatment or alkaline purification or hydrothermal treatment consists or be the MWW molecular sieve that the combined method of wherein any two kinds of even all three kinds of methods of aforementioned three kinds of methods obtains being rich in Si-OH group;
2), by the MWW molecular sieve being rich in Si-OH group obtained in titanium source, ionic liquid and step 1) be made into the body phase mixed, obtain crystallization mixture;
3), by step 2) in prepared crystallization mixture mix after transfer in reactor, crystallization 2 ~ 240 hours under 100 ~ 280 DEG C of conditions; After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain Ti-MWW molecular sieve after drying.
Synthetic method provided by the invention, is characterized in that: the MWW molecular sieve being used as precursor material in described step 1) can be the composition of one or more of sial MWW molecular sieve, borosilicate MWW molecular sieve or pure silicon MWW molecular sieve.
Synthetic method provided by the invention, it is characterized in that: required for the MWW molecular sieve being used as precursor material in described step 1), the treatment process of process can adopt and take traditional conventional heating mode, can also select intensified by ultrasonic wave or microwave reinforced type of heating.
Synthetic method provided by the invention, described step 2) in synthesis titanium source used be one or the mixture of the inorganic ti sources such as titanium tetrachloride, titanous chloride, and the mixture of one or more in the organic titanium source such as alkoxy titanates.Preferred titanium tetrachloride, titanous chloride.
Synthetic method provided by the invention, described step 2) in synthesis ionic liquid used be tetraalkyl ammonium salt class, alkyl imidazole salt, alkyl pyridine salt, Alkylpiperidine salt, alkyl pyrroles salt, alkyl croak salt, tetraalkyl season phosphonium salt compounds etc. a kind of combined system of or its any category.Be preferably the combined system of a kind of or its any category of tetraalkyl ammonium salt class, alkyl imidazole salt compounds etc., be more preferably R
1r
2r
3r
4n
+x
-(wherein R
1, R
2, R
3, R
4for C1 ~ C4 alkyl substituent, X is Cl, Br), R
1r
2im
+x
-(wherein R
1, R
2for C1 ~ C4 alkyl substituent, Im is imidazole ring, and X is Cl, Br) combined system of a kind of or its any category of compound etc.
Because ionic liquid body fluid journey is wide, volatility is low, therefore ion thermal synthesis can be carried out at ambient pressure, thus reduces the pressure risk of Zeolite synthesis.Therefore synthetic method provided by the invention, in described step 3), reactor can be open state, can also be closure state; Crystallization process can take traditional conventional heating mode, can also select intensified by ultrasonic wave or microwave reinforced type of heating.
Synthetic method provided by the invention, the Ti-MWW molecular sieve obtained can directly use as catalyzer or support of the catalyst, also or through peracid treatment or alkaline purification or hydrothermal treatment consists to improve the catalytic efficiency of titanium active sites in molecular sieve.
Ti-MWW molecular sieve of the present invention adopts Dutch Philips X ' Pert Pro type X-ray diffractometer to measure the crystal phase structure of synthetic sample.Condition determination: Cu target, K alpha-ray (λ=0.15418nm), Ni filtering, voltage 40kV, electric current 40mA, sweep limit 5 ~ 65 °, sweep velocity 10 °/min.
Ti-MWW molecular sieve of the present invention adopts Japanese HITACHI U3900H ultraviolet-visible spectrophotometer to carry out UV-Vis sign.
The catalyzer of Ti-MWW molecular sieve of the present invention all has excellent oxidation catalytic property in phenolic hydroxy group, alkene epoxidation and group compounds of aldehydes and ketones Ammoximation reaction process.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of Ti-MWW molecular sieve prepared by embodiment 1.
Fig. 2 is the UV-Vis spectrogram of Ti-MWW molecular sieve prepared by embodiment 1.
Embodiment
The present invention is described further for following embodiment, but the present invention is not limited in following embodiment.Any those skilled in the art, are not departing within the scope of technical solution of the present invention, and the technology contents that the present invention can be utilized to disclose is made a little change or is modified to the equivalent case study on implementation of equivalent variations; Every content not departing from technical solution of the present invention, any simple modification done following case study on implementation according to technological core thought of the present invention, equivalent variations and modification, all still belong within the scope of technical solution of the present invention.
Embodiment 1
By MCM-22 molecular sieve (silica alumina ratio=25) 3g adopt concentrated nitric acid (concentration 65%) in liquid: solid be 20 ratio (weight ratio) at 100 DEG C, process 24 hours, obtain the MWW molecular sieve (silica alumina ratio >1900) being rich in Si-OH.
Then in a reactor, take the 1-butyl-3-methyl chloride of dissolving for imidazolium ionic liquid 100g, add titanium tetrachloride 0.7g violent stirring and react 4 hours, again the MWW molecular sieve being rich in Si-OH obtained above is added, violent stirring reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.1TiO
2.
Transfer in open reactor after prepared crystallization mixture is mixed, crystallization 20 hours under 200 DEG C of conditions.After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain Ti-MWW molecular sieve after drying.Reaction product has carried out the sign of X-ray diffraction spectrum, and result as shown in Figure 1, shows that product is consistent with the X-ray diffraction spectrogram of the MWW molecular sieve of standard.UV-Vis characterization result as shown in Figure 2, show that the titanium in product is mostly present in framework of molecular sieve with the form of four-coordination titanium, and these are all the active sites that HTS has oxidation catalysis function, this also and then show the superiority of the hot secondary synthesis method of this ion.
Embodiment 2
Adopt concentrated nitric acid (concentration 65%) in liquid borosilicate MWW-49 molecular sieve (silicon boron than=25) 3g: solid be 20 ratio (weight ratio) under 100 DEG C of heating conditions of intensified by ultrasonic wave, process 10 hours, obtain the MWW molecular sieve (silicon boron is than >800) being rich in Si-OH.
Then in a reactor, take the 1-ethyl-3-methyl chloride of dissolving for imidazole salts and etamon chloride mixture (weight ratio 1:1) ionic liquid 100g, add titanium tetrachloride 0.07g violent stirring and react 4 hours, again the MWW molecular sieve being rich in Si-OH obtained above is added, violent stirring reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.01TiO
2.
Transfer in the reactor of closed type after prepared crystallization mixture is mixed, crystallization 240 hours under 100 DEG C of conditions.After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain Ti-MWW molecular sieve after drying.Reaction product has carried out the sign of X-ray diffraction spectrum, shows that product is consistent with the X-ray diffraction spectrogram of the MWW molecular sieve of standard.
Embodiment 3
MCM-56 (silica alumina ratio=25) 3g is first processed 4 hours under the hydrothermal condition of 550 DEG C, adopt concentrated nitric acid (concentration 65%) in liquid again: solid be 20 ratio (weight ratio) at 80 DEG C, process 4 hours, obtain the MWW molecular sieve (silica alumina ratio >920) being rich in Si-OH.
Then in a reactor, take the 1-heptyl-3-methyl chloride of dissolving for piperidinium salt ionic liquid 100g, add titanium tetrachloride 0.18g violent stirring and react 4 hours, again the MWW molecular sieve being rich in Si-OH obtained above is added, violent stirring reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.025TiO
2.
Transfer in open reactor after prepared crystallization mixture is mixed, crystallization 10 hours under 150 DEG C of conditions.After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain Ti-MWW molecular sieve after drying.Reaction product has carried out the sign of X-ray diffraction spectrum, shows that product is consistent with the X-ray diffraction spectrogram of the MWW molecular sieve of standard.
Embodiment 4
First adopted by MCM-36 molecular sieve (silica alumina ratio=25) 3g trimethylammonium adamantyl ammonium hydroxide (concentration 25%) in liquid: solid be 20 ratio (weight ratio) under microwave reinforced 80 DEG C of heating conditions, process 0.5 hour, adopt concentrated nitric acid (concentration 65%) in liquid again: solid be 20 ratio (weight ratio) under microwave reinforced 80 DEG C of heating conditions, process 1 hour, obtain the MWW molecular sieve (silica alumina ratio >340) being rich in Si-OH.
Then in a reactor, take the 1-Butyryl Chloride of dissolving for pyridinium salt ionic liquid 50g, add titanium tetrachloride 0.09g violent stirring and react 4 hours, again the MWW molecular sieve being rich in Si-OH obtained above is added, violent stirring reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.0125TiO
2.
Transfer in open reactor after prepared crystallization mixture is mixed, crystallization 10 hours under 120 DEG C of heating conditions of intensified by ultrasonic wave.After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain Ti-MWW molecular sieve after drying.Reaction product has carried out the sign of X-ray diffraction spectrum, shows that product is consistent with the X-ray diffraction spectrogram of the MWW molecular sieve of standard.
Embodiment 5
By MCM-22 molecular sieve (silica alumina ratio=25) 3g adopt concentrated nitric acid (concentration 65%) in liquid: solid be 20 ratio (weight ratio) at 100 DEG C, process 24 hours, obtain the MWW molecular sieve (silica alumina ratio >1900) being rich in Si-OH.
Then in a reactor; take the 1-butyl-3-methyl chloride of dissolving for pyrroles's ionic liquid 100g; add titanous chloride 0.14g violent stirring under nitrogen protection and react 4 hours; again the MWW molecular sieve being rich in Si-OH obtained above is added; violent stirring reacts 4 hours; obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.025TiO
2.
Transfer in open reactor under nitrogen protection after prepared crystallization mixture is mixed, crystallization 5 hours under microwave reinforced 160 DEG C of heating conditions.After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain Ti-MWW molecular sieve after drying.Reaction product has carried out the sign of X-ray diffraction spectrum, shows that product is consistent with the X-ray diffraction spectrogram of the MWW molecular sieve of standard.
Embodiment 6
By pure silicon ITQ-1 molecular sieve 3g adopt trimethylammonium adamantyl ammonium hydroxide (concentration 25%) in liquid: solid be 20 ratio (weight ratio) under microwave reinforced 50 DEG C of heating conditions, process 10 hours, obtain the MWW molecular sieve being rich in Si-OH.
Then in a reactor, take the 1-butyl-3-methyl chloride of dissolving for pyrroles's ionic liquid 100g, add titanium tetrachloride 0.18g violent stirring and react 4 hours, again the MWW molecular sieve being rich in Si-OH obtained above is added, violent stirring reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.025SnO
2.
Transfer in open reactor after prepared crystallization mixture is mixed, crystallization 5 hours under microwave reinforced 160 DEG C of heating conditions.After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain Ti-MWW molecular sieve after drying.Reaction product has carried out the sign of X-ray diffraction spectrum, shows that product is consistent with the X-ray diffraction spectrogram of the MWW molecular sieve of standard.
Claims (10)
1. have the HTS of MWW topological framework, silicon titanium ratio (atomic ratio) scope of this kind of Ti-MWW molecular sieve is within 10 ~ 1000.
2. the hot secondary synthesis of ion prepares a method for MWW molecular sieve, it is characterized in that: titanium source, ionic liquid and MWW molecular sieve are mixed, crystallization, obtains Ti-MWW molecular sieve through crystallization, separation, washing, drying;
Its process comprises:
1), directly use being used as the MWW molecular sieve of precursor material or obtain required MWW molecular sieve via acid treatment or alkaline purification or hydrothermal treatment consists;
2), the MWW molecular sieve obtained in titanium source, ionic liquid and step 1) is made into the body phase mixed, obtain crystallization mixture, molecular sieve and ionic liquid are by weight being 1:20 ~ 100, and the amount in titanium source presses the metering of products therefrom silicon titanium ratio (atomic ratio) scope 10 ~ 1000;
3), by step 2) in prepared crystallization mixture mix after transfer in reactor, crystallization 2 ~ 240 hours under 100 ~ 280 DEG C of conditions; After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain Ti-MWW molecular sieve after drying.
3. in accordance with the method for claim 2, it is characterized in that:
The MWW molecular sieve being used as precursor material in described step 1) can be the composition of one or two or more kinds in sial MWW molecular sieve, borosilicate MWW molecular sieve or pure silicon MWW molecular sieve.
4., according to the method described in Claims 2 or 3, it is characterized in that:
Required for the MWW molecular sieve being used as precursor material in described step 1), the treatment process of process can adopt and take traditional conventional heating mode, can also select intensified by ultrasonic wave or microwave reinforced type of heating.
5. in accordance with the method for claim 2, it is characterized in that:
Described step 2) in synthesis titanium source used be in inorganic ti sources (titanium tetrachloride or titanous chloride etc.) one or two or more kinds mixture, or the mixture of one or two or more kinds of organic titanium source (alkoxy titanates etc.).
6. in accordance with the method for claim 2, it is characterized in that:
Described step 2) in synthesis ionic liquid used be the combined system of a kind of or its more than the two kinds any categories in tetraalkyl ammonium salt class, alkyl imidazole salt, alkyl pyridine salt, Alkylpiperidine salt, alkyl pyrroles salt, alkyl croak salt, tetraalkyl season phosphonium salt compounds.
7., according to the method described in claim 2 or 6, it is characterized in that:
Described step 2) in synthesis ionic liquid used be preferably the combined system of a kind of or its more than the two kinds any categories in tetraalkyl ammonium salt class, alkyl imidazole salt compounds.
8., according to the method described in claim 2,6 or 7, it is characterized in that:
Described step 2) in synthesis ionic liquid used be more preferably R
1r
2r
3r
4n
+x
-(wherein R
1, R
2, R
3, R
4for C1 ~ C4 alkyl substituent, X is Cl or Br), R
1r
2im
+x
-(wherein R
1, R
2for C1 ~ C4 alkyl substituent, Im is imidazole ring, and X is Cl or Br) combined system of a kind of or its more than two kinds any categories in compound.
9. in accordance with the method for claim 2, it is characterized in that:
In described step 3), reactor can be open state, can also be closure state; Crystallization process can take traditional conventional heating mode, can also select intensified by ultrasonic wave or microwave reinforced type of heating.
10. the application of molecular sieve described in a claim 1, it is characterized in that: the Ti-MWW molecular sieve obtained can directly use as catalyzer or support of the catalyst, also or before using through peracid treatment or alkaline purification or hydrothermal treatment consists to improve the catalytic efficiency of titanium active sites in molecular sieve.
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| CN110054198A (en) * | 2019-05-26 | 2019-07-26 | 福州大学 | A kind of preparation method of Ti-MWW molecular sieve |
| CN112158856A (en) * | 2020-08-25 | 2021-01-01 | 郑州大学 | Method for preparing Ti-MWW molecular sieve |
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| CN114160193A (en) * | 2021-12-06 | 2022-03-11 | 厦门大学 | CoAPO-11 molecular sieve, preparation method and application thereof, alkane hydroisomerization catalyst and application thereof |
| CN114931974A (en) * | 2022-05-25 | 2022-08-23 | 华东师范大学 | Composite titanium-aluminum silicate catalyst and preparation method and application thereof |
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