CN104707649A - Tin-containing molecular sieve with BEA topological structure and preparation and application thereof - Google Patents
Tin-containing molecular sieve with BEA topological structure and preparation and application thereof Download PDFInfo
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Abstract
The present invention discloses a tin-containing heteroatomic functional molecular sieve with a BEA topologic structure and a synthesis method thereof, the tin-containing heteroatomic functional molecular sieve has the characteristics of the BEA topologic structure, silicon-tin ratio (atomic ratio) of the Sn-beta heteroatomic functional molecular sieve is in the range of 10 to 1000, and the synthesis method of the tin-containing beta molecular sieve is an ionothermal secondary synthesis preparation method. A tin source, ionic liquid and a beta 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, the Sn-beta heteroatomic functional molecular sieve can be obtained by separation, washing and drying, and a crystallization product can be directly used as a catalyst or catalyst carrier. The Sn-beta heteroatomic functional molecular sieve has good catalytic performance in the catalytic conversion of biomass and a plurality of fine chemical reaction processes.
Description
Technical field
The present invention relates to a kind of stanniferous hetero atom functional molecular sieve with BEA topological features and preparation method thereof.Especially, the present invention relates to the method that the hot secondary synthesis of a kind of ion prepares stanniferous Beta molecular sieve.
Background technology
Molecular sieve, by basic composition 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 material 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 catalysis material that academia and industrial quarters are paid close attention to jointly.
Framework of molecular sieve introducing hetero-atoms, the hetero-atom molecular-sieve that the transition metal ions same order elements 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 action, 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 structure 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 industry 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 condition is gentle, selective 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 application study 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 expoxy propane new equipment based on the cyclohexanone oxamidinating of titanium molecular sieve catalysis oxidizing process and epoxidation of propylene subsequently.
In addition, benzene is applied to via N
2the Fe-ZSM-5 catalyst that O catalytic oxidation produces phenol is the hetero-atom molecular-sieve system with unique catalytic performance equally, and research finds that the active sites of catalytic reaction is not merely the acidic site in zeolite molecular sieve, and the Fe in framework of molecular sieve will cause N
2o decomposes and forms active oxygen at catalyst surface, and the active oxygen species formed like this can not pass through O
2simply adsorb at catalyst surface and obtain.With this Fe-ZSM-5(containing Al) for catalyst, phenol selectivity is 100%, phenol yield is 20% ~ 25%, and this result is that one-step synthesis method phenol new technology is laid a good foundation.This technique industrialization already at present, becomes the another example of functional hetero-atom molecular-sieve application.
Remove above-mentioned two molecular sieve analogs, what functional hetero-atom molecular-sieve had research value and application potential most is stanniferous hetero-atom molecular-sieve, especially Sn-Beta hetero-atom molecular-sieve.As everyone knows, Beta molecular sieve is a kind of micro pore high silicon molecular sieve, and its skeleton forms by three-dimensional twelve-ring duct is staggered, X, Y direction are linear path, its aperture is about 0.66 × 0.76nm, and Z-direction is the bending channel of through X, Y-axis straight channel, and its aperture is about 056 × 0.65nm.Beta molecular sieve is synthesized in 1967 first by Mobil company, but its structure fails to be determined for a long time, until the late nineteen eighties are just verified by people such as Higgins and Newsam gradually.Beta zeolite synthesized under general condition is polymorph A, polymorph B, polymorph C symbiosis, it is the silica-rich zeolite uniquely with three-dimensional twelve-ring straight channel system, and pure polymorph A type Beta zeolite is the zeolite of unique a kind of chiral structure, and it probably has potential application foreground in chirality adsorption selection, asymmetry catalysis.The pore passage structure of Beta zeolite molecular sieve uniqueness, good heat and hydrothermal stability and suitable acidity make it can be used as catalysis material to be widely used in petroleum refining and petroleum chemical engineering, as the amination of Alkylation benzene with propylene, alcohols, olefin hydration, toluene disproportionation and methylate, hydrocracking and catalytic dewaxing etc., be a kind of catalysis material with broad prospect of application.
Tin due to its acidity moderate, oxidation susceptibility is superior makes its research at catalytic field comparatively active, but the easy inactivation of stanniferous catalyst, and reusability is poor.Tin is introduced framework of molecular sieve, synthesizes stanniferous hetero-atom molecular-sieve, thus utilized the catalytic performance of the uniqueness of tin, become a focus of molecular sieve research field.Also get more and more to the report that the preparations and applicatio of Sn-Beta heteroatom zeolite is probed in recent years, wherein representative and breakthrough is that Hispanic Corma teaches seminar.People's reported first such as the calendar year 2001 Corma synthetic method of Sn-Beta molecular sieve [Corma A., Nemeth L., Renz M., Valencia S., Nature, 2001,412,423-425], they adopt tetraethyl orthosilicate as silicon source, add HF as mineralizer, successfully synthesize the Sn-Beta without aluminium in fluorine-containing system, by probing into its catalytic performance, find that this catalyst has excellent catalytic performance to Baeyer-Viiliger reaction selective with the product ester or lactone being close to 100%.They have carried out system, lasting and deep research [Corma A., RenzM., Angew.Chem.Int.Ed.2007,46,298 – 300] to the application of Sn-Beta molecular sieve in fields such as fine chemistry industries.
Living beings can experience polyalcohol path and be converted into HC fuel and chemicals, and the research of this respect with the work of the people such as Dumesic representatively.Polyalcohol has abundant functional group, can obtain hydrogen, liquid hydrocarbon fuel and various chemicals and important chemical intermediate to its trans-utilization, and therefore biomass-based polyalcohol is considered to biomass conversion and utilizes plateform molecules important in process.
What current biomass conversion research on utilization was more also has another kind of important platform chemicals---5 hydroxymethyl furfural (HMF).HMF is mainly Material synthesis with fructose at present, can be used as the additive etc. in the intermediate of newtype drug synthesis, the monomer preparing macrocyclic compound polymer, biofuel production process.
The application progress of nearest stanniferous molecular sieve in biomass conversion and renewable energy utilization allows people attract attention.The energy is the significant problem of international community's common concern, and the conversion preparation as the biomass energy of regenerative resource important component part needs the innovation relying on advanced catalysis material to support.At present, directly utilize living beings or carbohydrate containing the feature enriching functional group, by chemistry and the biological mode transformed, obtain up till now based on the chemicals that fossil resource is produced, become one of worldwide great heat subject.
Recently, Danish scientist has delivered carbohydrate is catalytically conveted to lactic acid derivative new technology [Holm M., Saravanamurugan S. via hetero-atom molecular-sieve Sn-Beta on Science, Taarning E., Science, 2010,328,602-605].Lactic acid is considered to the important platform chemicals of biomass conversion process equally, can be used for preparing large chemical products such as PLA, acrylic acid, 1,2-PD.Method mainly fermentation method and the chemical synthesis of current industrial production lactic acid, but the fermentation method cycle is long, can only interval or semi-continuous production; The raw material of chemical synthesis generally has toxicity, does not meet Green Chemistry requirement.Therefore, using living beings as raw material, the research being obtained lactic acid by the synthesis of heterogeneous catalysis approach is significant.
Research finds, center Sn atom enters the space structure of Beta zeolite in a particular manner, after Sn occupies these specific positions, for catalyst coordination after molecule, they show special electronics form and steric strain, and therefore have excellent catalytic performance.But synthetic method complexity is a shortcoming of this molecular sieve system, because the excessive Sn-O of the causing key of tin atom radius and Si-O key very do not mate, therefore the synthesis difficulty of stanniferous molecular sieve is very large.Up to now, hydrothermal synthesis method all adopts fluorine-containing system to synthesize Sn-Beta molecular sieve.Synthesize this molecular sieve and use a large amount of quaternary ammonium base templates, thus cause cost height enterprise, simultaneous reactions system adopts the fluorine-containing system with quaternary ammonium base a great deal of, very big pollution can be caused to environment, and synthesized by its Theil indices of Sn-Beta molecular sieve of obtaining lower, silicon tin can reach 125 ~ 200 [Corma A., Nemeth L. than only, Renz M., Valencia S., Nature, 2001,412,423-425].
Except adopting the synthesis of hydrothermal system, the synthesis adopting secondary synthesis method to carry out being difficult to the hetero-atom molecular-sieve synthesized is studied always widely, the such as secondary synthesis of titaniferous hetero-atom molecular-sieve.For stanniferous hetero-atom molecular-sieve, the Beta molecular sieve through nitric acid dealuminzation is adopted gas phase SnCl by P.Wu etc.
4same order elements carries out research [P.Li, G.Liu, the H.Wu of post-synthesis, Y.Liu, J.Jiang, and P.Wu, J.Phys.Chem.C, dx.doi.org/10.1021/jp1076966], but the existence of the method for this gas phase same order elements is difficult to operation and unmanageable shortcoming.Beta molecular sieve through nitric acid dealuminzation then adopts the mode of solid liposome nanoparticle to carry out the research [C.Hammond of post-synthesis by I.Hermans etc., S.Conrad, and I.Hermans, Angew.Chem.Int.Ed., DOI:10.1002/anie.201206193], the party's rule also exists the distinct disadvantage that Xi Yuan used easily reunites, not easily disperses.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, obtain a kind of stanniferous hetero atom functional molecular sieve with BEA topological features, and the hot secondary synthesis of a kind of ion prepares the method for stanniferous Beta molecular sieve, the ion thermal synthesis method of the method has the feature of extremely-low vapor pressure, abandon the restriction of conventional hydrothermal synthetic method Intermediate High Pressure for synthesis device, the Heavy environmental pollution that the use that simultaneously it also avoid fluorine brings.
The stanniferous hetero atom functional molecular sieve with BEA topological features provided by the invention, silicon tin ratio (atomic ratio) scope of this kind of Sn-Beta hetero atom functional molecular sieve is within 10 ~ 1000.
The invention provides the method that the hot secondary synthesis of a kind of ion prepares stanniferous Beta 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 controlled variable of synthesis, for initiative new material provides new platform; (3) ionic liquid is as a kind of ion solvent, new characteristic is dissolved with to inorganic salts, 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: Jiang Xiyuan, ionic liquid and the Beta molecular sieve being rich in Si-OH group mix according to certain ratio and feeding method, crystallization certain hour at a certain temperature, obtains Sn-Beta hetero atom functional molecular sieve through separation, washing, drying;
Its process comprises:
1), by the Beta molecular sieve being used as precursor material via acid treatment or alkali treatment or hydrothermal treatment consists or be the Beta 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), the Beta molecular sieve being rich in Si-OH group that obtains in Jiang Xiyuan, ionic liquid and step 1) is made into the body phase mixed, and obtains 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 stanniferous Beta hetero-atom molecular-sieve after drying.
Synthetic method provided by the invention, the Beta molecular sieve being used as precursor material in described step 1) can be the composition of one or more of sial Beta molecular sieve, borosilicate Beta molecular sieve or pure silicon Beta molecular sieve.
Synthetic method provided by the invention, required for the Beta molecular sieve being used as precursor material in described step 1), the processing method of process can adopt and take traditional conventional heating mode, can also select intensified by ultrasonic wave or microwave reinforced mode of heating.
Synthetic method provided by the invention, described step 2) in synthesis Xi Yuan used be one or the mixture in the inorganic tin such as butter of tin, stannous chloride source, and the mixture of one or more in the organotin source such as tin alkyl, alkoxyl tin, organotin acid esters.Preferred butter of tin, stannous chloride.
Synthetic method provided by the invention, is characterized in that: 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, 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 mode of heating.
Synthetic method provided by the invention, it is characterized in that: the stanniferous Beta hetero-atom molecular-sieve obtained can directly use as catalyst or catalyst carrier, also or through peracid treatment or alkali treatment or hydrothermal treatment consists to improve the catalytic efficiency of tin active sites in molecular sieve.
The crystal phase structure of Beta hetero atom functional molecular sieve employing Dutch Philips X ' the PertPro type X-ray diffractometer mensuration synthetic sample that the present invention is stanniferous.Condition determination: Cu target, K alpha ray (λ=0.15418nm), Ni filtering, voltage 40kV, electric current 40mA, sweep limits 5 ~ 65 °, sweep speed 10 °/min.
The standby catalyst of the stanniferous Beta hetero atom functional molecular sieve series of the present invention transforms at biomass catalyzing and to react etc. many fine chemistry industry courses of reaction as Baeyer-Viiliger all has good catalytic performance.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of Sn-Beta molecular sieve prepared by embodiment 1.
Fig. 2 is the XRD spectra of Sn-Beta molecular sieve prepared by embodiment 2.
Fig. 3 is the XRD spectra of Sn-Beta molecular sieve prepared by embodiment 3.
Fig. 4 is the XRD spectra of Sn-Beta molecular sieve prepared by embodiment 4.
Detailed description of the invention
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 Beta molecular sieve (silica alumina ratio=21) 3g adopt red fuming nitric acid (RFNA) (concentration 65%) in liquid: solid be 20 ratio (weight ratio) at 100 DEG C, process 24 hours, obtain the Beta molecular sieve (silica alumina ratio >2000) being rich in Si-OH.
Then in a reactor, take the 1-butyl-3-methyl chloride of dissolving for imidazolium ionic liquid 100g, add butter of tin 1.5g strong agitation and react 4 hours, again the Beta molecular sieve being rich in Si-OH obtained above is added, strong agitation reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.1SnO
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 stanniferous Beta hetero-atom molecular-sieve after drying.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 Beta molecular sieve of standard.
Embodiment 2
Adopt red fuming nitric acid (RFNA) (concentration 65%) in liquid borosilicate Beta 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 Beta molecular sieve (silicon boron is than >1300) 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 butter of tin 0.15g strong agitation and react 4 hours, again the Beta molecular sieve being rich in Si-OH obtained above is added, strong agitation reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.01SnO
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 stanniferous Beta hetero-atom molecular-sieve after drying.Product has carried out the sign of X-ray diffraction spectrum, and result as shown in Figure 2, shows that product is consistent with the X-ray diffraction spectrogram of the Beta molecular sieve of standard.
Embodiment 3
By pure silicon Beta molecular sieve 3g adopt tetraethyl 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 Beta molecular sieve being rich in Si-OH.
Then in a reactor, take the 1-butyl-3-bromic ether of dissolving for imidazolium ionic liquid 100g, add butter of tin 0.02g strong agitation and react 4 hours, again the Beta molecular sieve being rich in Si-OH obtained above is added, strong agitation reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.001SnO
2.
Transfer in open reactor after prepared crystallization mixture is mixed, crystallization 2 hours under microwave reinforced 180 DEG C of heating conditions.After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain stanniferous Beta hetero-atom molecular-sieve after drying.Product has carried out the sign of X-ray diffraction spectrum, and result as shown in Figure 3, shows that product is consistent with the X-ray diffraction spectrogram of the Beta molecular sieve of standard.
Embodiment 4
Beta molecular sieve (silica alumina ratio=21) 3g is first processed 4 hours under the hydrothermal condition of 550 DEG C, adopt red fuming nitric acid (RFNA) (concentration 65%) in liquid again: solid be 20 ratio (weight ratio) at 80 DEG C, process 4 hours, obtain the Beta 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 butter of tin 0.33g strong agitation and react 4 hours, again the Beta molecular sieve being rich in Si-OH obtained above is added, strong agitation 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 10 hours under 150 DEG C of conditions.After crystallization terminates, reactant be cooled to room temperature, filter, wash and obtain stanniferous Beta hetero-atom molecular-sieve after drying.Product has carried out the sign of X-ray diffraction spectrum, and result as shown in Figure 4, shows that product is consistent with the X-ray diffraction spectrogram of the Beta molecular sieve of standard.
Embodiment 5
First adopted by Beta molecular sieve (silica alumina ratio=21) 3g tetraethyl 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 red fuming nitric acid (RFNA) (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 Beta molecular sieve (silica alumina ratio >230) being rich in Si-OH.
Then in a reactor, take the 1-butyl chloride of dissolving for pyridiniujm ionic liquid 50g, add butter of tin 0.16g strong agitation and react 4 hours, again the Beta molecular sieve being rich in Si-OH obtained above is added, strong agitation reacts 4 hours, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.0125SnO
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 stanniferous Beta hetero-atom molecular-sieve after drying.Product has carried out the sign of X-ray diffraction spectrum, shows that product is consistent with the X-ray diffraction spectrogram of the Beta molecular sieve of standard.
Embodiment 6
By Beta molecular sieve (silica alumina ratio=21) 3g adopt red fuming nitric acid (RFNA) (concentration 65%) in liquid: solid be 20 ratio (weight ratio) at 100 DEG C, process 24 hours, obtain the Beta molecular sieve (silica alumina ratio >2000) 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 stannous chloride 0.22g strong agitation and react 4 hours, again the Beta molecular sieve being rich in Si-OH obtained above is added, strong agitation 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 stanniferous Beta hetero-atom molecular-sieve after drying.Product has carried out the sign of X-ray diffraction spectrum, shows that product is consistent with the X-ray diffraction spectrogram of the Beta molecular sieve of standard.
Claims (10)
1. have the stanniferous molecular sieve of BEA topological structure, it is the stanniferous hetero atom functional molecular sieve with BEA topological features, and silicon tin ratio (atomic ratio) scope of this kind of Sn-Beta hetero atom functional molecular sieve is within 10 ~ 1000.
2. the hot secondary synthesis of ion prepares a method for stanniferous Beta molecular sieve, it is characterized in that: Jiang Xiyuan, ionic liquid and Beta molecular sieve mix, obtain Sn-Beta hetero atom functional molecular sieve through crystallization, separation, washing, drying;
Its process comprises:
1), the Beta molecular sieve being used as precursor material is obtained required Beta molecular sieve via methods such as acid treatment, alkali treatment or hydrothermal treatment consists;
2) the Beta molecular sieve, obtained in Jiang Xiyuan, 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 of Xi Yuan presses the metering of products therefrom silicon tin 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 stanniferous Beta hetero-atom molecular-sieve after drying.
3. in accordance with the method for claim 2, it is characterized in that:
The Beta molecular sieve being used as precursor material in described step 1) can be the composition of one or two or more kinds in sial Beta molecular sieve, borosilicate Beta molecular sieve or pure silicon Beta molecular sieve.
4., according to the method described in Claims 2 or 3, it is characterized in that:
Required for the Beta molecular sieve being used as precursor material in described step 1), the processing method of process can adopt and take traditional conventional heating mode, can also select intensified by ultrasonic wave or microwave reinforced mode of heating.
5. in accordance with the method for claim 2, it is characterized in that:
Described step 2) in synthesis Xi Yuan used be one or two or more kinds mixture in butter of tin, stannous chloride, and tin alkyl, alkoxyl tin, the mixture of one or two or more kinds in organotin acid esters.
6. in accordance with the method for claim 2, it is characterized in that:
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 more than two kinds any categories.
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 of tetraalkyl ammonium salt class, alkyl imidazole salt compounds etc. or its more than two kinds any categories.
8., according to the method described in claim 2,6 and 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, 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 more than two kinds any categories of compound etc.
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 mode of heating.
10. the application of molecular sieve described in a claim 1, it is characterized in that: the stanniferous Beta hetero-atom molecular-sieve obtained can directly use as catalyst or catalyst carrier, also or before using through peracid treatment or alkali treatment or hydrothermal treatment consists to improve the catalytic efficiency of tin active sites in molecular sieve.
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| CN108609632A (en) * | 2016-12-09 | 2018-10-02 | 中国科学院大连化学物理研究所 | A kind of stanniferous Beta molecular sieves and preparation method thereof |
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