CN104709920A - Tin-containing heteroatomic functional molecular sieve and synthesis and application thereof - Google Patents
Tin-containing heteroatomic functional molecular sieve and synthesis and application thereof Download PDFInfo
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Abstract
The present invention discloses a tin-containing heteroatomic functional molecular sieve 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) is in the range of 80 to 1000, and the synthesis method of the tin-containing beta molecular sieve is a boric acid-assisted hydrothermal synthesis technology. A tin source, a silicon source, boric acid, a template agent, water and a crystal seed 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 heteroatoms functional molecular sieve and synthetic method thereof.Particularly, this kind of stanniferous heteroatoms functional molecular sifter device has BEA topological features, and silicon tin ratio (atomic ratio) scope is within 80 ~ 1000, and a kind of Hydrothermal Synthesis technology adopting boric acid to assist prepares the synthetic method of stanniferous Beta 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.
Removing HTS, 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 supersiliceous 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 catalytic material to be widely used in refining of petroleum 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 catalytic 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 catalyzer, 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 study group.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 catalyzer has excellent catalytic performance to Baeyer-Viiliger reaction and is close to product ester or the lactone selectivity of 100%.They have carried out system, lasting and deep research [Corma A., Renz M., Angew.Chem.Int.Ed.2007,46,298 – 300] to the application of Sn-Beta molecular sieve in fields such as fine chemistry industries.
The application progress of nearest stanniferous molecular sieve in Wood Adhesives from Biomass 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 renewable energy source important component part needs the innovation relying on advanced catalysis material to support.At present, directly utilize biomass or carbohydrate containing the feature enriching functional group, by mode that is chemical and bio-transformation, obtain up till now based on the chemical that fossil resource is produced, become one of worldwide great heat subject.
Recently, Danish scientist has delivered carbohydrate is catalytically conveted to lactic acid derivatives novel process [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 Wood Adhesives from Biomass process equally, can be used for preparing large chemical productss such as poly(lactic acid), vinylformic 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 biomass as raw material, the research being obtained lactic acid by the synthesis of heterogeneous catalyst 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 catalyzer 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 hydroxide template, thus cause cost height enterprise, simultaneous reactions system adopts the fluorine-containing system with quaternary ammonium hydroxide 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, Beta molecular sieve through nitric acid dealuminzation adopts gas phase SnCl4 isomorphous substitution to carry out the research [P.Li of post-synthesis by P.Wu etc., G.Liu, H.Wu, 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 isomorphous substitution 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, provide a kind of stanniferous heteroatoms functional molecular sieve, this stanniferous heteroatoms functional molecular sifter device has BEA topological features, and silicon tin ratio (atomic ratio) scope is within 80 ~ 1000.
The invention provides the synthetic method that a kind of Hydrothermal Synthesis technology adopting boric acid to assist prepares stanniferous Beta molecular sieve.Xi Yuan, silicon source, boric acid, template, water and crystal seed are mixed according to certain ratio and feeding method, at a certain temperature crystallization certain hour, obtain Sn-Beta heteroatoms functional molecular sieve through separation, washing, drying.
Its process comprises:
1), by treated for precursor material Beta molecular sieve obtain the Beta molecular sieve being used as crystal seed, then in water, dispersion obtains crystal seed liquid completely;
2), Jiang Xiyuan, silicon source, boric acid, template, the crystal seed liquid mixing that obtains in water and step 1) be made into uniform body phase, obtains crystallization mixture;
3), by step 2) in prepared crystallization mixture mix after transfer in autoclave, crystallization 2 ~ 40 days under 130 ~ 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.
Synthetic method provided by the invention, is characterized in that: the Beta molecular sieve being used as crystal seed 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, the treating processes of carrying out needed for described step 1) precursor material Beta molecular sieve is via acid treatment, alkaline purification, hydrothermal treatment consists, ion-exchange or is the combined method of preceding method, treating processes can adopt takes 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 Xi Yuan used be one or the mixture in the inorganic tin such as tin tetrachloride, tin protochloride source, and the mixture of one or more in the organotin source such as tin alkyl, alkoxyl group tin, organotin acid esters.
Synthetic method provided by the invention, described step 2) in synthesis silicon source used be Trimethylsiloxysilicate, gas-phase silica, silicon sol.
Synthetic method provided by the invention, described step 2) in synthesis template used be tetraethyl ammonium hydroxide or tetraethyl ammonium hydroxide and many vinyl polyamines NH
2cH
2cH
2(NCH
2cH
2) nNH
2, the mixture of n=1 ~ 5.
Synthetic method provided by the invention, described step 2) in synthesize the crystallization mixture obtained mol ratio be 1.0SiO
2: (0.001 ~ 0.0125) SnO
2: (0.05 ~ 1.0) B
2o
3: (0.15 ~ 1.0) SDA1:(0 ~ 2.0) SDA2:(5 ~ 100) H
2o:(0.01 ~ 0.2) seed, wherein, SDA1 is tetraethyl ammonium hydroxide, and SDA2 is many vinyl polyamines, and seed is crystal seed.
Synthetic method provided by the invention, is characterized in that: synthesize crystallization condition used crystallization 3 ~ 30 days under 150 ~ 180 DEG C of conditions in described step 3).
Synthetic method provided by the invention, the stanniferous Beta hetero-atom 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 tin active sites in molecular sieve.
The crystal phase structure of Beta heteroatoms functional molecular sieve employing Dutch Philips X ' the Pert Pro 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 limit 5 ~ 65 °, sweep velocity 10 °/min.
The standby catalyzer of the stanniferous Beta heteroatoms functional molecular sieve series of the present invention transforms at biomass catalyzing and to react etc. many fine chemistry industry reaction process 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.
Fig. 5 is the XRD spectra of Sn-Beta molecular sieve prepared by embodiment 5.
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 Beta molecular sieve (silica alumina ratio=21) 3g adopt concentrated nitric acid (concentration 65%) in liquid: solid be 20 ratio (weight ratio) at 100 DEG C, process 24 hours, obtain Beta molecular sieve crystal seed (silica alumina ratio >2000).
0.15gBeta molecular sieve crystal seed is joined in 30g deionized water, keeps 24 hours under high degree of agitation, obtain fully decentralized crystal seed liquid.
Tetraethyl ammonium hydroxide (concentration 50%) 10.4g and water 120g is added in another reactor, then tetraethoxy 12.3g is added, 50 DEG C of reactions 24 hours are warming up under stirring, then add boric acid 1.6g and continue reaction 5 hours, the solution again tin tetrachloride 0.17g being dissolved in the preparation of 20g water was added dropwise in above-mentioned reaction system in 1 hour, react 4 hours under violent stirring, then crystal seed liquid is added continuation reaction 2 hours.Finally reaction system is heated to 80 DEG C to remove water unnecessary in system and alcohol, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.008SnO
2: 0.3B
2o
3: 0.6SDA1:0SDA2:15H
2o:0.03seed.
Transfer in autoclave after prepared crystallization mixture is mixed, crystallization 25 days under 140 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.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 Beta molecular sieve of standard.
Embodiment 2
Adopt concentrated nitric acid (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 Beta molecular sieve crystal seed (silicon boron is than >1300).
0.7gBeta molecular sieve crystal seed is joined in 60g deionized water, keeps 24 hours under high degree of agitation, obtain fully decentralized crystal seed liquid.
Water 200g is added in another reactor, take tetraethyl ammonium hydroxide (concentration 50%) 2.6g and diethylene triamine 12.3g to add, then add boric acid 5.3g and continue reaction 5 hours, the solution again tin tetrachloride 0.02g being dissolved in the preparation of 20g water was added dropwise in above-mentioned reaction system in 1 hour, react 4 hours under violent stirring, again crystal seed liquid is added and continue reaction 2 hours, finally add tetraethoxy 12.3g, 50 DEG C of reactions 24 hours are warming up under stirring, reaction system is heated to 80 DEG C to remove water unnecessary in system and alcohol, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.001SnO
2: 1.0B
2o
3: 0.15SDA1:2.0SDA2:100H
2o:0.2seed.
Transfer in autoclave after prepared crystallization mixture is mixed, crystallization 2 days 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.Reaction 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 Beta molecular sieve crystal seed.
0.05gBeta molecular sieve crystal seed is joined in 60g deionized water, keeps 24 hours under high degree of agitation, obtain fully decentralized crystal seed liquid.
Water 200g is added in another reactor, take tetraethyl ammonium hydroxide (concentration 50%) 2.6g and diethylene triamine 12.3g to add, then add boric acid 5.3g and continue reaction 5 hours, the solution again tin tetrachloride 0.02g being dissolved in the preparation of 20g water was added dropwise in above-mentioned reaction system in 1 hour, react 4 hours under violent stirring, again crystal seed liquid is added and continue reaction 2 hours, finally add tetraethoxy 12.3g, 50 DEG C of reactions 24 hours are warming up under stirring, reaction system is heated to 80 DEG C to remove water unnecessary in system and alcohol, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.001SnO
2: 1.0B
2o
3: 0.15SDA1:2.0SDA2:100H
2o:0.2seed.
Transfer in autoclave after prepared crystallization mixture is mixed, crystallization 30 days under 160 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.Reaction 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, then adopts concentrated nitric acid (concentration 65%) in liquid: solid be 20 ratio (weight ratio) at 80 DEG C, process 4 hours, obtain Beta molecular sieve crystal seed.
0.25gBeta molecular sieve crystal seed is joined in 60g deionized water, keeps 24 hours under high degree of agitation, obtain fully decentralized crystal seed liquid.
Water 120g is added in another reactor, take tetraethyl ammonium hydroxide (concentration 25%) 10.4g and triethylene tetraamine 2.5g to add, then add boric acid 1.33g and continue reaction 5 hours, the solution again tin tetrachloride 0.02g being dissolved in the preparation of 20g water was added dropwise in above-mentioned reaction system in 1 hour, react 4 hours under violent stirring, again crystal seed liquid is added and continue reaction 2 hours, finally add tetraethoxy 12.3g, 50 DEG C of reactions 24 hours are warming up under stirring, reaction system is heated to 80 DEG C to remove water unnecessary in system and alcohol, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.001SnO
2: 0.25B
2o
3: 0.3SDA1:0.4SDA2:20H
2o:0.05seed.
Transfer in autoclave after prepared crystallization mixture is mixed, crystallization 18 days under 180 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.Reaction 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
By Beta molecular sieve (silica alumina ratio=21) 3g adopt concentrated nitric acid (concentration 65%) in liquid: solid be 20 ratio (weight ratio) at 100 DEG C, process 24 hours, obtain Beta molecular sieve crystal seed (silica alumina ratio >2000).
0.2gBeta molecular sieve crystal seed is joined in 60g deionized water, keeps 24 hours under high degree of agitation, obtain fully decentralized crystal seed liquid.
Water 120g is added in another reactor, take tetraethyl ammonium hydroxide (concentration 25%) 10.4g and tetraethylenepentamine 3.2g to add, then add boric acid 0.8g and continue reaction 5 hours, the solution again tin tetrachloride 0.10g being dissolved in the preparation of 20g water was added dropwise in above-mentioned reaction system in 1 hour, react 4 hours under violent stirring, again crystal seed liquid is added and continue reaction 2 hours, then add gas-phase silica 3.55g, stirring reaction 24 hours.Finally reaction system is heated to 80 DEG C to remove water unnecessary in system, obtain the crystallization mixture mixed, its mol ratio is 1.0SiO
2: 0.005SnO
2: 0.15B
2o
3: 0.3SDA1:0.4SDA2:20H
2o:0.04seed.
Transfer in autoclave after prepared crystallization mixture is mixed, crystallization 22 days under 160 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.Reaction product has carried out the sign of X-ray diffraction spectrum, and result as shown in Figure 5, shows that product is consistent with the X-ray diffraction spectrogram of the Beta molecular sieve of standard.
Claims (8)
1. a stanniferous heteroatoms functional molecular sieve, this stanniferous heteroatoms functional molecular sifter device has BEA topological features, and silicon tin ratio (atomic ratio) scope is within 80 ~ 1000.
2. the Hydrothermal Synthesis technology adopting boric acid to assist prepares the synthetic method of stanniferous Beta molecular sieve, it is characterized in that: Jiang Xiyuan, silicon source, boric acid, template, water and crystal seed mix, obtain Sn-Beta heteroatoms functional molecular sieve through crystallization, separation, washing, drying;
Its process comprises:
1), precursor material Beta molecular sieve is obtained through (acid such as nitric acid, hydrochloric acid) process the Beta molecular sieve being used as crystal seed;
2), Jiang Xiyuan, silicon source, boric acid, template, the crystal seed mixing that obtains in water and step 1) be made into uniform body phase, obtains crystallization mixture;
Template used is tetraethyl ammonium hydroxide or tetraethyl ammonium hydroxide and many vinyl polyamines NH
2cH
2cH
2(NCH
2cH
2) nNH
2, n=1 ~ 5 mixture;
The mol ratio of crystallization mixture is 1.0SiO
2: (0.001 ~ 0.0125) SnO
2: (0.05 ~ 1.0) B
2o
3: (0.15 ~ 1.0) SDA1:(0 ~ 2.0) SDA2:(5 ~ 100) H
2o:(0.01 ~ 0.2) seed, wherein, SDA1 is tetraethyl ammonium hydroxide, and SDA2 is many vinyl polyamines, and seed is crystal seed;
3), by step 2) in prepared crystallization mixture mix after transfer in autoclave, crystallization 2 ~ 40 days under 130 ~ 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.
3. in accordance with the method for claim 2, it is characterized in that:
The Beta molecular sieve being used as crystal seed precursor material in described step 1) can be the composition of one or two or more kinds of sial Beta molecular sieve, borosilicate Beta molecular sieve or pure silicon Beta molecular sieve.
4., according to the method described in claim 2 and 3, it is characterized in that:
The treating processes of carrying out needed for described step 1) precursor material Beta molecular sieve is press down or the combined method of preceding method more than two kinds via acid treatment, alkaline purification, hydrothermal treatment consists or ion-exchange, treating processes can adopt takes 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 Xi Yuan used be one or two or more kinds mixture in tin tetrachloride, tin protochloride, or tin alkyl, alkoxyl group 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 silicon source used be one or two or more kinds of Trimethylsiloxysilicate, gas-phase silica or silicon sol.
7. in accordance with the method for claim 2, it is characterized in that:
Crystallization condition used crystallization 3 ~ 30 days under 150 ~ 180 DEG C of conditions is synthesized in described step 3).
8. 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 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 tin active sites in molecular sieve.
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|---|---|---|---|---|
| EP3178788A1 (en) * | 2015-12-08 | 2017-06-14 | Basf Se | A tin-containing zeolitic material having a bea framework structure |
| WO2017097806A1 (en) * | 2015-12-08 | 2017-06-15 | Basf Se | A tin-containing zeolitic material having a bea framework structure |
| 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 |
| CN112551538A (en) * | 2020-12-23 | 2021-03-26 | 中触媒新材料股份有限公司 | Synthesis method of nanoscale Sn-Beta |
| CN112645347A (en) * | 2020-12-23 | 2021-04-13 | 中触媒新材料股份有限公司 | Nanoscale Sn-Beta molecular sieve and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5518708A (en) * | 1987-12-15 | 1996-05-21 | Uop | Substitution of Sn in place of Al in the framework of molecular sieve via treatment with fluoride salts |
| CN1430616A (en) * | 2000-04-25 | 2003-07-16 | 环球油品公司 | Oxidation of ketones to esters using tin substituted zeolith beta |
| CN102249258A (en) * | 2011-05-06 | 2011-11-23 | 大连理工大学 | Method for synthesizing heteroatom Sn-beta zeolite |
| CN102452895A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Method for catalyzing cycloalkane by utilizing Sn-containing Ti-Si molecular sieve |
-
2013
- 2013-12-16 CN CN201310695102.5A patent/CN104709920B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5518708A (en) * | 1987-12-15 | 1996-05-21 | Uop | Substitution of Sn in place of Al in the framework of molecular sieve via treatment with fluoride salts |
| CN1430616A (en) * | 2000-04-25 | 2003-07-16 | 环球油品公司 | Oxidation of ketones to esters using tin substituted zeolith beta |
| CN102452895A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Method for catalyzing cycloalkane by utilizing Sn-containing Ti-Si molecular sieve |
| CN102249258A (en) * | 2011-05-06 | 2011-11-23 | 大连理工大学 | Method for synthesizing heteroatom Sn-beta zeolite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019502629A (en) * | 2015-12-08 | 2019-01-31 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Tin-containing zeolite material having a BEA framework structure |
| WO2017097806A1 (en) * | 2015-12-08 | 2017-06-15 | Basf Se | A tin-containing zeolitic material having a bea framework structure |
| EP3178788A1 (en) * | 2015-12-08 | 2017-06-14 | Basf Se | A tin-containing zeolitic material having a bea framework structure |
| CN108367930A (en) * | 2015-12-08 | 2018-08-03 | 巴斯夫欧洲公司 | Stanniferous zeolitic material with BEA frame structures |
| CN108367931A (en) * | 2015-12-08 | 2018-08-03 | 巴斯夫欧洲公司 | Stanniferous zeolitic material with BEA frame structures |
| JP2018536614A (en) * | 2015-12-08 | 2018-12-13 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Tin-containing zeolite material having a BEA framework structure |
| US20180362351A1 (en) * | 2015-12-08 | 2018-12-20 | Basf Se | A tin-containing zeolitic material having a bea framework structure |
| WO2017097835A1 (en) | 2015-12-08 | 2017-06-15 | Basf Se | A tin-containing zeolitic material having a bea framework structure |
| US10737944B2 (en) | 2015-12-08 | 2020-08-11 | Basf Se | Tin-containing zeolitic material having a BEA framework structure |
| JP7039472B2 (en) | 2015-12-08 | 2022-03-22 | ビーエーエスエフ ソシエタス・ヨーロピア | Tin-containing zeolite material with BEA skeleton structure |
| US10766781B2 (en) | 2015-12-08 | 2020-09-08 | Basf Se | Tin-containing zeolitic material having a BEA framework structure |
| CN108367931B (en) * | 2015-12-08 | 2022-01-18 | 巴斯夫欧洲公司 | Tin-containing zeolitic materials having a BEA framework structure |
| 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 |
| CN112744833A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Preparation method of tin-containing molecular sieve and oximation reaction method of tin-containing molecular sieve and cyclohexanone produced by method |
| CN112645347A (en) * | 2020-12-23 | 2021-04-13 | 中触媒新材料股份有限公司 | Nanoscale Sn-Beta molecular sieve and preparation method thereof |
| CN112551538A (en) * | 2020-12-23 | 2021-03-26 | 中触媒新材料股份有限公司 | Synthesis method of nanoscale Sn-Beta |
| CN112645347B (en) * | 2020-12-23 | 2022-10-25 | 中触媒新材料股份有限公司 | Nanoscale Sn-Beta molecular sieve and preparation method thereof |
| CN113457654A (en) * | 2021-06-02 | 2021-10-01 | 江西省科学院应用化学研究所 | Carbon-based solid acid catalyst, and preparation method and use method thereof |
| CN114604878A (en) * | 2022-03-18 | 2022-06-10 | 大连理工大学 | Preparation method and application of bifunctional Sn-B-BEA molecular sieve with hierarchical pore structure |
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