CN104709920B - 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 hetero atom functional molecular sieve and its synthetic method.Specifically, this kind is former containing stanna
Sub-functionality molecular sieve has BEA topological features, silicon stannum ratio（Atomic ratio）Scope is within 80～1000, and one kind is adopted
The Hydrothermal Synthesiss technology aided in boric acid prepares the synthetic method of stanniferous Beta molecular sieves.
Background technology
Molecular sieve is by basic composition classification, predominantly silicate-base molecular sieve and the class of phosphate base molecular sieve two.Due to not
Same chemical reaction has different requirements to the pore passage structure and surface property of porous catalyst material, therefore, one side new construction
The synthesis of molecular screen material is the important research contents of material science and catalytic science all the time, on the other hand, molecular screen material
Functionalized design, synthesis and modified definition and the category for similarly expanding molecular sieve.Wherein especially transition metal in skeleton
Heteroatomic introducing causes molecular sieve to have multifunctionality, has further expanded its range of application, is that academia and industrial quarters are common
With the catalysis material of concern.
Framework of molecular sieve introducing hetero-atoms, the transition metal ionss isomorphous substitution gained particularly with specific catalytic performance
The hetero-atom molecular-sieve for arriving because metal ion on framework of molecular sieve in isolated high dispersion state, as well as with
Interaction between molecular sieve precursor skeleton so that the transition metal oxide that they possess routine unexistent special is urged
Change function, its performance is also clearly distinguishable from the original function of parent molecule sieve, acidity not only to zeolite catalyst, surface property
Adjustment effect is played, while being conducive to zeolite catalyst to realize multi-functional catalysis.
In this respect, most typical example is HTS.Nineteen eighty-three, the Taramasso of Italy is successfully by titanium
In being introduced into MFI topological structure silicate systems, synthesis has obtained TS-1 molecular sieves, so that the application of molecular sieve is from traditional acid
Base catalysiss process expands to catalytic oxidation process, it is considered to be of 1980s molecular sieve catalytic research field
Milestone.
HTS is removed, what feature hetero-atom molecular-sieve most had research value and application potential is stanniferous
Hetero-atom molecular-sieve, especially Sn-Beta hetero-atom molecular-sieves.
It is well known that Beta molecular sieves are a kind of micro pore high silicon molecular sieves, its skeleton is interlocked by three-dimensional twelve-ring duct
Form, X, Y direction are linear path, its aperture is about 0.66 × 0.76nm, and Z-direction is insertion X, Y-axis straight channel
Bending channel, its aperture is about 056 × 0.65nm.Beta molecular sieves were synthesized first by Mobil companies in 1967, but its structure
Fail for a long time to be determined, just gradually verified by Higgins and Newsam et al. until the late nineteen eighties.Institute under generic condition
The Beta zeolites of synthesis are polymorph A, polymorph B, the symbiosis of polymorph C, are uniquely have three-dimensional twelve-ring straight channel system
Silica-rich zeolite, and pure polymorph A type Beta zeolite is a kind of unique zeolite of chiral structure, and it is likely in chiral selection
Absorption, asymmetry catalysis aspect have potential application foreground.The unique pore passage structure of Beta zeolite molecular sieve, good heat and hydro-thermal
During stability and suitable acidity make it to be widely used in petroleum refining and petroleum chemical engineering as catalysis material, such as benzene and third
Allylic alkylation, the amination of alcohols, alkene hydration, the disproportionation of toluene and methylate, be hydrocracked with catalytic dewaxing etc., being a kind of tool
There is the catalysis material of broad prospect of application.
Stannum is moderate due to its acidity, and oxidation susceptibility is superior to cause it more to enliven in the research of catalytic field, but stanniferous
Catalyst easily inactivate, reusability is poor.Stannum is introduced into framework of molecular sieve, synthesizes stanniferous hetero-atom molecular-sieve, so as to
It is able to, using unique catalytic performance of stannum, become a focus of molecular sieve research field.In recent years to Sn-Beta hetero atoms
The preparation of zeolite and the report of probe into application are also more and more, wherein that representative and breakthrough is Hispanic Corma
Professor seminar.Calendar year 2001 Corma et al. reported first synthetic method [Corma A., the Nemeth of Sn-Beta molecular sieves
L., Renz M., Valencia S., Nature, 2001,412,423-425], they adopt tetraethyl orthosilicate as silicon source,
HF is used as mineralizer for addition, and the Sn-Beta of aluminum-free is successfully synthesized in fluorine-containing system, by probing into its catalytic performance,
It was found that the catalyst has excellent catalytic performance and intimate 100% product ester or lactone choosing to Baeyer-Viiliger reactions
Selecting property.Their applications to Sn-Beta molecular sieves in fields such as fine chemistry industries have carried out system, have continued and in-depth study
[Corma A.,Renz M.,Angew.Chem.Int.Ed.2007,46,298–300]。
Recently application progress of the stanniferous molecular sieve in terms of biomass conversion and renewable energy utilization allows people to attract attention.The energy
It is the significant problem of international community's common concern, prepared by the conversion as the biomass energy of regenerative resource important component part
The innovation for relying on advanced catalysis material is needed to support.At present, directly using biomass or carbohydrate containing abundant functional group
Feature, by way of chemistry and bioconversion, obtains being currently based on the chemicals of fossil resource production, has become world's model
One of great heat subject in enclosing.
Recently, Danish scientist has been delivered carbohydrate on Science and has been catalyzed via hetero-atom molecular-sieve Sn-Beta
Be converted into lactic acid derivative new technology [Holm M., Saravanamurugan S., Taarning E., Science, 2010,
328,602-605].Lactic acid is also considered as the important platform chemicals of biomass transformation process, can be used for preparing poly- breast
Large chemical productss such as acid, acrylic acid, 1,2- Propylene Glycol.At present the method for commercial production lactic acid is mainly fermentation method and chemistry conjunction
Cheng Fa, but the fermentation method cycle is long, can only interval or semi-continuous production；The raw material of chemical synthesiss typically has toxicity, is not inconsistent
Close Green Chemistry to require.Therefore, using biomass as raw material, the research for obtaining lactic acid by the synthesis of heterogeneous catalysiss approach has weight
Want meaning.
Research finds that center Sn atoms enter in a particular manner the space structure of Beta zeolites, when Sn occupies these spies
After fixed position, for the molecule after being coordinated with catalyst, they show special electronics form and steric strain, and because
This and there is excellent catalytic performance.But synthetic method complexity is a shortcoming of this molecular sieve system, due to tin atom radius
It is excessive to cause Sn-O keys and Si-O keys very not to match, therefore the synthesis difficulty of stanniferous molecular sieve is very big.
So far, hydrothermal synthesis method synthesizes Sn-Beta molecular sieves using fluorine-containing system.Synthesize the molecular sieve to use
Substantial amounts of quaternary ammonium base template, so as to cause high cost to look forward to, simultaneous reactions system adopts fluorine-containing system considerable amount of with quaternary ammonium base,
Can cause greatly pollution to environment, and synthesized its Theil indices of Sn-Beta molecular sieves for obtaining, than relatively low, silicon stannum ratio is only capable of reaching
To 125～200 [Corma A., Nemeth L., Renz M., Valencia S., Nature, 2001,412,423-425].
Except the synthesis using hydrothermal system, carry out being difficult to the conjunction of the hetero-atom molecular-sieve of synthesis using secondary synthesis method
Into widely being studied always, the such as secondary synthesis of titaniferous hetero-atom molecular-sieve.For stanniferous hetero-atom molecular-sieve,
P.Wu etc. by the Beta molecular sieves of Jing nitric acid dealuminzations using gas phase SnCl4 isomorphous substitution carry out post-synthesis research [P.Li,
G.Liu,H.Wu,Y.Liu,J.Jiang,and P.Wu,J.Phys.Chem.C,dx.doi.org/10.1021/
Jp1076966], but the presence of the method for the gas phase isomorphous substitution is difficult to operation and unmanageable shortcoming.I.Hermans etc.
The Beta molecular sieves of Jing nitric acid dealuminzations are then carried out the research of post-synthesis by the way of solid liposome nanoparticle
[C.Hammond,S.Conrad,and I.Hermans,Angew.Chem.Int.Ed.,DOI:10.1002/
Anie.201206193], party's rule has Xi Yuan used and easily reunites, is difficult scattered distinct disadvantage.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of stanniferous hetero atom functional molecular sieve, should
Stanniferous hetero atom functional molecular sifter device has BEA topological features, silicon stannum ratio（Atomic ratio）Scope is within 80～1000.
The invention provides a kind of Hydrothermal Synthesiss technology of employing boric acid auxiliary prepares the synthesis side of stanniferous Beta molecular sieves
Method.By Xi Yuan, silicon source, boric acid, template, water and crystal seed according to certain ratio and feeding method mix homogeneously, in a constant temperature
The lower crystallization certain hour of degree, separating, washing, drying obtains Sn-Beta hetero atoms functional molecular sieve.
Its process includes：
1）, by the molecular sieve Jing process of precursor material Beta obtain be used as crystal seed Beta molecular sieves, it is then complete in water
Full dispersion obtains crystal seed liquid；
2）, Jiang Xiyuan, silicon source, boric acid, template, water and step 1）In the crystal seed liquid mixing that obtains with uniformly body
Phase, obtains crystallization mixture；
3）, by step 2）In be transferred in autoclave after prepared crystallization mixture mix homogeneously, at 130～200 DEG C
Under the conditions of crystallization 2～40 days；After crystallization terminates, reactant is cooled to into room temperature, obtains stanniferous after being filtered, washed and dried
Beta hetero-atom molecular-sieves.
The synthetic method that the present invention is provided, it is characterised in that：Described step 1）In be used as crystal seed precursor material
Beta molecular sieves can be one or more of sial Beta molecular sieves, borosilicate Beta molecular sieves or pure silicon Beta molecular sieves
Compositionss.
The synthetic method that the present invention is provided, described step 1）The process carried out needed for precursor material Beta molecular sieve
Journey be via acid treatment, alkali process, hydrothermal treatment consists, ion exchange or be preceding method combined method, processing procedure can be with
Using traditional conventional heating mode is taken, intensified by ultrasonic wave or microwave reinforced mode of heating can also be selected.
The synthetic method that the present invention is provided, described step 2）Xi Yuan used by middle synthesis is butter of tin, stannous chloride
Deng the one kind or mixture in inorganic tin source, and one or more of the organotin source such as tin alkyl, alkoxyl stannum, organotin acid esters
Mixture.
The synthetic method that the present invention is provided, described step 2）Silicon source used by middle synthesis is Trimethylsiloxysilicate, gas phase
White carbon, Ludox.
The synthetic method that the present invention is provided, described step 2）Template used by middle synthesis be tetraethyl ammonium hydroxide or
Tetraethyl ammonium hydroxide and many vinyl polyamines NH2CH2CH2(NCH2CH2)nNH2, the mixture of n=1～5.
The synthetic method that the present invention is provided, described step 2）The mol ratio of the crystallization mixture obtained by middle synthesis is
1.0SiO2：(0.001～0.0125) SnO2：(0.05～1.0) B2O3：(0.15～1.0) SDA1：(0～2.0) SDA2：(5～
100)H2O：(0.01～0.2) seed, wherein, SDA1 is tetraethyl ammonium hydroxide, and SDA2 is many vinyl polyamines, and seed is crystalline substance
Kind.
The synthetic method that the present invention is provided, it is characterised in that：Described step 3）Crystallization condition used by middle synthesis is 150
Crystallization 3～30 days under the conditions of～180 DEG C.
The synthetic method that the present invention is provided, resulting stanniferous Beta hetero-atom molecular-sieves can be directly as catalyst
Or catalyst carrier is used, stannum active sites urges also or in acid treatment or alkali process or hydrothermal treatment consists are to improve molecular sieve
Change efficiency.
The stanniferous Beta hetero atoms functional molecular sieve of the present invention is spread out using Holland's Philips X ' Pert Pro type X-rays
Penetrate the crystal phase structure that instrument determines synthetic sample.Condition determination：Cu targets, K alpha rays (λ=0.15418nm), Ni filtering, voltage
40kV, electric current 40mA, 5～65 ° of sweep limitss, 10 °/min of scanning speed.
The standby catalyst of the stanniferous Beta hetero atom functional molecular sieve series of the present invention is in biomass catalyzing conversion and such as
Baeyer-Viiliger reactions etc. many fine chemistry industry courses of reaction are respectively provided with good catalytic performance.
Description of the drawings
Fig. 1 is the XRD spectra of Sn-Beta molecular sieves prepared by embodiment 1.
Fig. 2 is the XRD spectra of Sn-Beta molecular sieves prepared by embodiment 2.
Fig. 3 is the XRD spectra of Sn-Beta molecular sieves prepared by embodiment 3.
Fig. 4 is the XRD spectra of Sn-Beta molecular sieves prepared by embodiment 4.
Fig. 5 is the XRD spectra of Sn-Beta molecular sieves prepared by embodiment 5.
Specific embodiment
The present invention is described further for below example, but the invention is not limited in below example.
Any those skilled in the art, in the range of without departing from technical solution of the present invention, using the technology that the present invention is disclosed
Content is made a little change or is modified to the equivalence enforcement case of equivalent variations；It is every without departing from technical solution of the present invention
Hold, any simple modification, equivalent variations and modification that foundation technological core thought of the invention is made to following case study on implementation,
Still belong in the range of technical solution of the present invention.
Embodiment 1
Beta molecular sieves (silica alumina ratio=21) 3g is adopted into concentrated nitric acid（Concentration 65%）By liquid：Solid is 20 ratio（Weight
Amount ratio）Process 24 hours at 100 DEG C, obtain Beta molecular sieve seed (silica alumina ratios>2000).
0.15gBeta molecular sieve seeds are added in 30g deionized waters, are kept for 24 hours under high degree of agitation, obtained
Complete scattered crystal seed liquid.
Tetraethyl ammonium hydroxide is added in another reactor（Concentration 50%）10.4g and water 120g, is subsequently adding positive silicon
50 DEG C are warming up under acetoacetic ester 12.3g, stirring to react 24 hours, are subsequently adding boric acid 1.6g and are continued to react 5 hours, then by tetrachloro
Change stannum 0.17g is dissolved in the solution of 20g water preparation and was added dropwise in 1 hour in above-mentioned reaction system, and reaction 4 is little under strong agitation
When, then add continuation to react 2 hours crystal seed liquid.Finally reaction system is heated to into 80 DEG C with unnecessary in removing system
Water and alcohol, the crystallization mixture being uniformly mixed, its mol ratio is 1.0SiO2:0.008SnO2:0.3B2O3：0.6SDA1：
0SDA2：15H2O：0.03seed.
To be transferred in autoclave after prepared crystallization mixture mix homogeneously, crystallization 25 days under the conditions of 140 DEG C.It is brilliant
After change terminates, reactant is cooled to into room temperature, stanniferous Beta hetero-atom molecular-sieves are obtained after being filtered, washed and dried.Reaction
Product has carried out the sign of X-ray diffraction spectra, as a result as shown in figure 1, showing the X-ray of product and the Beta molecular sieves of standard
Diffraction spectrogram is consistent.
Embodiment 2
Borosilicate Beta molecular sieves (silicon boron ratio=25) 3g is adopted into concentrated nitric acid（Concentration 65%）By liquid：Solid is 20 ratio
（Weight ratio）Process 10 hours under 100 DEG C of heating conditions of intensified by ultrasonic wave, obtain Beta molecular sieve seeds (silicon boron ratio>
1300)。
0.7gBeta molecular sieve seeds are added in 60g deionized waters, are kept for 24 hours under high degree of agitation, obtained completely
Scattered crystal seed liquid.
Water 200g is added in another reactor, tetraethyl ammonium hydroxide is weighed（Concentration 50%）2.6g and divinyl
Triamine 12.3g is added, and is subsequently adding boric acid 5.3g and is continued to react 5 hours, then butter of tin 0.02g is dissolved in into 20g water and prepares
Solution be added dropwise in 1 hour in above-mentioned reaction system, react 4 hours under strong agitation, then crystal seed liquid is added continue anti-
Answer 2 hours, be eventually adding under tetraethyl orthosilicate 12.3g, stirring be warming up to 50 DEG C react 24 hours, by reaction system heat temperature raising
To 80 DEG C with water and alcohol unnecessary in removing system, the crystallization mixture being uniformly mixed, its mol ratio is 1.0SiO2:
0.001SnO2:1.0B2O3：0.15SDA1：2.0SDA2：100H2O：0.2seed.
To be transferred in autoclave after prepared crystallization mixture mix homogeneously, crystallization 2 days under the conditions of 200 DEG C.It is brilliant
After change terminates, reactant is cooled to into room temperature, stanniferous Beta hetero-atom molecular-sieves are obtained after being filtered, washed and dried.Reaction
Product has carried out the sign of X-ray diffraction spectra, as a result as shown in Fig. 2 showing the X-ray of product and the Beta molecular sieves of standard
Diffraction spectrogram is consistent.
Embodiment 3
Pure silicon Beta molecular sieve 3g are adopted into tetraethyl ammonium hydroxide（Concentration 25%）By liquid：Solid is 20 ratio（Weight
Amount ratio）Process 10 hours under 50 DEG C of microwave reinforced heating conditions, obtain Beta molecular sieve seeds.
0.05gBeta molecular sieve seeds are added in 60g deionized waters, are kept for 24 hours under high degree of agitation, obtained
Complete scattered crystal seed liquid.
Water 200g is added in another reactor, tetraethyl ammonium hydroxide is weighed（Concentration 50%）2.6g and divinyl
Triamine 12.3g is added, and is subsequently adding boric acid 5.3g and is continued to react 5 hours, then butter of tin 0.02g is dissolved in into 20g water and prepares
Solution be added dropwise in 1 hour in above-mentioned reaction system, react 4 hours under strong agitation, then crystal seed liquid is added continue anti-
Answer 2 hours, be eventually adding under tetraethyl orthosilicate 12.3g, stirring be warming up to 50 DEG C react 24 hours, by reaction system heat temperature raising
To 80 DEG C with water and alcohol unnecessary in removing system, the crystallization mixture being uniformly mixed, its mol ratio is 1.0SiO2:
0.001SnO2:1.0B2O3：0.15SDA1：2.0SDA2：100H2O：0.2seed.
To be transferred in autoclave after prepared crystallization mixture mix homogeneously, crystallization 30 days under the conditions of 160 DEG C.It is brilliant
After change terminates, reactant is cooled to into room temperature, stanniferous Beta hetero-atom molecular-sieves are obtained after being filtered, washed and dried.Reaction
Product has carried out the sign of X-ray diffraction spectra, as a result as shown in figure 3, showing the X-ray of product and the Beta molecular sieves of standard
Diffraction spectrogram is consistent.
Embodiment 4
Beta molecular sieves (silica alumina ratio=21) 3g is first processed 4 hours under 550 DEG C of hydrothermal condition, then using concentrated nitric acid
（Concentration 65%）By liquid：Solid is 20 ratio（Weight ratio）Process 4 hours at 80 DEG C, obtain Beta molecular sieve seeds.
0.25gBeta molecular sieve seeds are added in 60g deionized waters, are kept for 24 hours under high degree of agitation, obtained
Complete scattered crystal seed liquid.
Water 120g is added in another reactor, tetraethyl ammonium hydroxide is weighed（Concentration 25%）10.4g and trivinyl
Tetramine 2.5g is added, and is subsequently adding boric acid 1.33g and is continued to react 5 hours, then butter of tin 0.02g is dissolved in into 20g water and prepares
Solution be added dropwise in 1 hour in above-mentioned reaction system, react 4 hours under strong agitation, then crystal seed liquid is added continue anti-
Answer 2 hours, be eventually adding under tetraethyl orthosilicate 12.3g, stirring be warming up to 50 DEG C react 24 hours, by reaction system heat temperature raising
To 80 DEG C with water and alcohol unnecessary in removing system, the crystallization mixture being uniformly mixed, its mol ratio is 1.0SiO2:
0.001SnO2:0.25B2O3：0.3SDA1：0.4SDA2：20H2O：0.05seed.
To be transferred in autoclave after prepared crystallization mixture mix homogeneously, crystallization 18 days under the conditions of 180 DEG C.It is brilliant
After change terminates, reactant is cooled to into room temperature, stanniferous Beta hetero-atom molecular-sieves are obtained after being filtered, washed and dried.Reaction
Product has carried out the sign of X-ray diffraction spectra, as a result as shown in figure 4, showing the X-ray of product and the Beta molecular sieves of standard
Diffraction spectrogram is consistent.
Embodiment 5
Beta molecular sieves (silica alumina ratio=21) 3g is adopted into concentrated nitric acid（Concentration 65%）By liquid：Solid is 20 ratio（Weight
Amount ratio）Process 24 hours at 100 DEG C, obtain Beta molecular sieve seed (silica alumina ratios>2000).
0.2gBeta molecular sieve seeds are added in 60g deionized waters, are kept for 24 hours under high degree of agitation, obtained completely
Scattered crystal seed liquid.
Water 120g is added in another reactor, tetraethyl ammonium hydroxide is weighed（Concentration 25%）10.4g and tetravinyl
Five amine 3.2g are added, and are subsequently adding boric acid 0.8g and are continued to react 5 hours, then butter of tin 0.10g is dissolved in into the preparation of 20g water
Solution was added dropwise in above-mentioned reaction system in 1 hour, reacted 4 hours under strong agitation, then added continuation to react 2 crystal seed liquid
Hour, add gas-phase silica 3.55g, stirring reaction 24 hours.Finally reaction system is heated to 80 DEG C to remove
Unnecessary water in system, the crystallization mixture being uniformly mixed, its mol ratio is 1.0SiO2:0.005SnO2:
0.15B2O3：0.3SDA1：0.4SDA2：20H2O：0.04seed.
To be transferred in autoclave after prepared crystallization mixture mix homogeneously, crystallization 22 days under the conditions of 160 DEG C.It is brilliant
After change terminates, reactant is cooled to into room temperature, stanniferous Beta hetero-atom molecular-sieves are obtained after being filtered, washed and dried.Reaction
Product has carried out the sign of X-ray diffraction spectra, as a result as shown in figure 5, showing the X-ray of product and the Beta molecular sieves of standard
Diffraction spectrogram is consistent.
Claims (6)
1. a kind of Hydrothermal Synthesiss technology of employing boric acid auxiliary prepares the synthetic method of stanniferous Beta molecular sieves, it is characterized in that：Will
Xi Yuan, silicon source, boric acid, template, water and crystal seed mix homogeneously, Jing crystallization, separate, wash, being dried to obtain Sn-Beta hetero atoms
Functional molecular is sieved；
Its process includes：
1), precursor material Beta molecular sieve is pressed down or aforementioned via acid treatment, alkali process, hydrothermal treatment consists or ion exchange
The combined method that more than two kinds of method processes the Beta molecular sieves for obtaining being used as crystal seed；
2), Jiang Xiyuan, silicon source, boric acid, template, water and step 1) in the crystal seed mixing that obtains with uniformly body phase, obtain
Crystallization mixture；
Template used is tetraethyl ammonium hydroxide or tetraethyl ammonium hydroxide and many vinyl polyamines NH2CH2CH2
(NCH2CH2)nNH2, n=1～5 mixture；
The mol ratio of crystallization mixture is 1.0SiO2：(0.001～0.0125) SnO2：(0.05～1.0) B2O3：(0.15～
1.0)SDA1：(0～2.0) SDA2：(5～100) H2O：(0.01～0.2) seed, wherein, SDA1 is tetraethyl ammonium hydroxide,
SDA2 is many vinyl polyamines, and seed is crystal seed；
3), by step 2) in be transferred in autoclave after prepared crystallization mixture mix homogeneously, in 130～200 DEG C of conditions
Lower crystallization 2～40 days；After crystallization terminates, reactant is cooled to into room temperature, stanniferous Beta is obtained after being filtered, washed and dried miscellaneous
Atom and molecule is sieved.
2. in accordance with the method for claim 1, it is characterised in that：
Described step 1) in be used as the Beta molecular sieves of crystal seed precursor material be sial Beta molecular sieves, borosilicate Beta molecules
The compositionss of one or two or more kinds of sieve or pure silicon Beta molecular sieves.
3. according to the method described in claim 1 or 2, it is characterised in that：
Described step 1) the processing procedure processing procedure that carries out needed for precursor material Beta molecular sieve takes traditional
Conventional heating mode, also selects intensified by ultrasonic wave or microwave reinforced mode of heating.
4. in accordance with the method for claim 1, it is characterised in that：
Described step 2) in the used Xi Yuan of synthesis be one or two or more kinds mixture in butter of tin, stannous chloride,
Or the mixture of one or two or more kinds in tin alkyl, alkoxyl stannum, organotin acid esters.
5. in accordance with the method for claim 1, it is characterised in that：
Described step 2) middle one kind or two for synthesizing silicon source used for Trimethylsiloxysilicate, gas-phase silica or Ludox
More than kind.
6. in accordance with the method for claim 1, it is characterised in that：
Described step 3) middle synthesis crystallization condition used crystallization 3～30 days under the conditions of 150～180 DEG C.
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| 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 |
| EP3178788A1 (en) | 2015-12-08 | 2017-06-14 | 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 |
| CN112744833B (en) * | 2019-10-30 | 2023-02-21 | 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 |
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| CN113457654B (en) * | 2021-06-02 | 2023-06-09 | 江西省科学院应用化学研究所 | Carbon-based solid acid catalyst and preparation method and application method thereof |
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