CN104707649B - A kind of have the stanniferous molecular sieve of BEA topological structures and its preparation and application - Google Patents
A kind of have the stanniferous molecular sieve of BEA topological structures and its preparation and application Download PDFInfo
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Abstract
A kind of stanniferous hetero atom functional molecular sieve with BEA topological features and preparation method thereof.The silicon tin ratio of this kind of Sn Beta hetero atoms functional molecular sieve（Atomic ratio）Scope is within 10～1000, and the method that a kind of hot secondary synthesis of ion prepare stanniferous Beta molecular sieves.Xi Yuan, ionic liquid and Beta molecular sieves rich in Si OH groups are well mixed according to certain ratio and feeding method, crystallization certain time at a certain temperature, separating, washing, drying obtains Sn Beta hetero atoms functional molecular sieve, and crystallization product can be used directly as catalyst or catalyst carrier.The Sn Beta hetero atoms functional molecular sieve is converted in biomass catalyzing and many fine chemistry industry courses of reaction are respectively provided with good catalytic performance.
Description
Technical field
The present invention relates to a kind of stanniferous hetero atom functional molecular sieve and its preparation side with BEA topological features
Method.Especially, the present invention relates to a kind of hot secondary synthesis of ion method for preparing stanniferous Beta molecular sieves.
Background technology
Molecular sieve is by basic group constituent class, predominantly two class of silicate-base molecular sieve and phosphate base molecular sieve.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, on the other hand, molecular screen material all the time
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 that there is multifunctionality, has further expanded its range of application, is that academia and industrial quarters are common
Catalysis material with concern.
Framework of molecular sieve introducing hetero-atoms, the transition metal ions same order elements 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, not only to the acidity of 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
It is introduced in MFI topological structure silicate systems, synthesis has obtained TS-1 molecular sieves, so that the application of molecular sieve is from traditional acid
Base catalysis process expands to catalytic oxidation process, it is considered to be of 1980s molecular sieve catalytic research field
Milestone.It is well known that the production of oxygenatedchemicals is always very important process in petrochemical industry and fine chemistry industry, tradition
The catalytic oxidation process needs that do not meet human kind sustainable development as effect is low, seriously polluted.In HTS base
The catalytic oxidation system that develops on plinth, selective good because of its reaction condition gently, and whole catalytic process only has water byproduct
And non-pollution discharge, it is considered to be eco-friendly green chemistry process, and then caused HTS for a long time
Synthesis and application study upsurge.TS-1 molecular sieves are applied to the work of phenol hydroxylation and cyclohexanone oxamidinating earliest for Eni companies
Industry demonstration program, the cyclohexanone oxime that 70,000 tons/year of Sinopec are installed on 2003 and are constructed and put into operation, worldwide first
Carry out the large-scale industrial application of HTS, subsequent Sumitomo, BASF, DOW, Evonik etc. and also all build up number set base
Expoxy propane new equipment is produced in the cyclohexanone oxamidinating and epoxidation of propylene of titanium molecular sieve catalysis oxidizing process.
Additionally, being applied to benzene via N2O catalysis oxidations produce the Fe-ZSM-5 catalyst of phenol is urged with uniqueness
Change the hetero-atom molecular-sieve system of performance, research finds that the active sites of catalytic reaction are not merely the acidity in zeolite molecular sieve
Position, the Fe in framework of molecular sieve will cause N2O decomposes and forms active oxygen, and the active oxygen thing for so being formed in catalyst surface
Plant and can not pass through O2Obtain in catalyst surface simply absorption.With the Fe-ZSM-5（Contain Al）For catalyst, phenol selection
Property be 100%, phenol yield be 20%～25%, this result is laid a good foundation for one-step synthesis method phenol new technology.At present
The technique was industrialized already, became the another example of feature hetero-atom molecular-sieve application.
Remove above-mentioned two molecular sieve analog, 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 silicons
Molecular sieve, its skeleton are staggeredly formed by three-dimensional twelve-ring duct, and X, Y direction are linear path, and its aperture is about 0.66
× 0.76nm, Z-direction are insertion X, the bending channel of Y-axis straight channel, and its aperture is about 056 × 0.65nm.Beta molecular sieves
Synthesized in 1967 first by Mobil companies, but its structure fail to be determined for a long time, until the late nineteen eighties just gradually by
Higgins and Newsam et al. are verified.Under general condition synthesized Beta zeolites be polymorph A, polymorph B, polymorph C altogether
Raw, it is unique silica-rich zeolite with three-dimensional twelve-ring straight channel system, and pure polymorph A type Beta zeolite is unique one
The zeolite of chiral structure is planted, which is likely to have potential application foreground in terms of chiral selection absorption, asymmetry catalysis.Beta zeolites
The unique pore passage structure of molecular sieve, good heat and hydrothermal stability and suitable acidity make which extensively use as catalysis material
In petroleum refining and petroleum chemical engineering, such as Alkylation benzene with propylene, the amination of alcohols, alkene hydration, the disproportionation of toluene and
Methylate, be hydrocracked with catalytic dewaxing etc., it is a kind of catalysis material with broad prospect of application.
Tin is moderate due to its acidity, and oxidation susceptibility is superior to cause which more to enliven in the research of catalytic field, but stanniferous
Catalyst easily inactivate, reusability is poor.Tin is introduced framework of molecular sieve, synthesizes stanniferous hetero-atom molecular-sieve, so as to
The catalytic performance of the uniqueness using tin is able to, becomes a focus of molecular sieve research field.In recent years to Sn-Beta hetero atoms
The report of the preparation of zeolite and probe into application is also more and more, and that wherein 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,
Add HF as mineralizer, successfully synthesize the Sn-Beta without aluminium 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].
Biomass can experience polyalcohol path and be converted into HC fuel and chemicals, and the research of this respect is with Dumesic
Et al. work be representative.Polyalcohol has abundant functional group, its trans-utilization can be obtained hydrogen, liquid hydrocarbon fuel and
Various chemicals and important chemical intermediate, during therefore biomass-based polyalcohol is considered as biomass trans-utilization
Important plateform molecules.
Biomass trans-utilization studies the more platform chemicals 5- methylol chaffs for also having another kind important at present
Aldehyde（HMF）.HMF is presently mainly to can act as the intermediate of newtype drug synthesis with fructose as Material synthesis, prepare big cyclisation
Additive in the monomer of compound polymer, biofuel production process etc..
Application progress of the stanniferous molecular sieve in terms of biomass conversion and renewable energy utilization allows people to attract attention recently.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 the chemicals for being currently based on 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 products such as acid, acrylic acid, 1,2- propane diols.The method of industrial production lactic acid is mainly fermentation method and chemistry conjunction at present
Cheng Fa, but the fermentation method cycle is long, can only interval or semi-continuous production；The raw material of chemical synthesis 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 catalysis approach has weight
Want meaning.
Research finds that center Sn atoms enter the space structure of Beta zeolites in a particular manner, 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
Excessive cause Sn-O keys and Si-O keys very not to mate, therefore the synthesis difficulty of stanniferous molecular sieve is very big.So far, Hydrothermal Synthesiss
Method synthesizes Sn-Beta molecular sieves using fluorine-containing system.Synthesize the molecular sieve using substantial amounts of quaternary ammonium base template, so as to make
Look forward to into high cost, simultaneous reactions system can cause greatly pollution using fluorine-containing system considerable amount of with quaternary ammonium base to environment, and
Synthesized Sn-Beta molecular sieves its Theil indices for obtaining than relatively low, silicon tin ratio be only capable of reaching 125～200 [Corma A.,
Nemeth L., Renz M., Valencia S., Nature, 2001,412,423-425].
Except the synthesis using hydrothermal system, the conjunction of the hetero-atom molecular-sieve carried out being difficult to synthesizing 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,
Beta molecular sieves through nitric acid dealuminzation are adopted gas phase SnCl by P.Wu etc.4Same order elements 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 same order elements is difficult to operation and unmanageable shortcoming.I.Hermans etc.
Beta molecular sieves through nitric acid dealuminzation are then carried out by the way of solid liposome nanoparticle the research of post-synthesis
[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.
Content of the invention
It is an object of the invention to overcoming the deficiencies in the prior art, obtain a kind of with the stanniferous of BEA topological features
Hetero atom functional molecular is sieved, and the method that a kind of hot secondary synthesis of ion prepare stanniferous Beta molecular sieves, the method from
The characteristics of sub- thermal synthesis method has extremely-low vapor pressure, has abandoned conventional hydrothermal synthetic method Intermediate High Pressure for the limit of synthesis device
System, while the Heavy environmental pollution that the use that it also avoid fluorine brings.
The stanniferous hetero atom functional molecular sieve with BEA topological features that the present invention is provided, this kind of Sn-Beta are miscellaneous
The silicon tin ratio of atomic function molecular sieve（Atomic ratio）Scope is within 10～1000.
The invention provides the method that a kind of hot secondary synthesis of ion prepare stanniferous Beta molecular sieves.Ionic liquid is used as one
Class new eco-friendly " green solvent ", with many unique properties：(1) ionic liquid body fluid journey width, volatility are low, no
Inflammable, therefore ion thermal synthesis can be carried out at ambient pressure, so as to reduce the pressure risk of Zeolite synthesis；(2) ionic liquid
The body organic amine structure directing agent structure conventional with Zeolite synthesis is close, can double as solvent and structure directing agent, Er Qieqi
Species is various, and molecular structure can be designed, and increased the controlled variable of synthesis, provides new platform for formulating new material；(3) ion
Liquid is carried out in anhydrous system as a kind of ion solvent, the new characteristic that is dissolved with to inorganic salts, and ion thermal synthesis,
Fast hydrolyzing of some transition metal salts under water existence condition can be avoided and form the phenomenon that precipitation is difficult to enter skeleton, because
The hot method of this ion has very big development space in terms of Zeolite synthesis.
The ion process for thermosynthesizing is characterized in that：Xi Yuan, ionic liquid and Beta molecular sieves rich in Si-OH groups are pressed
It is well mixed according to certain ratio and feeding method, at a certain temperature crystallization certain time, separating, washing, drying is obtained
Sn-Beta hetero atoms functional molecular is sieved；
Its process includes：
1）, the Beta molecular sieves that will act as precursor material via acid treatment or alkali process or hydro-thermal process or be
The combined method of the even all three method of wherein any two kinds of aforementioned three kinds of methods obtains Beta point rich in Si-OH groups
Son sieve；
2）, Jiang Xiyuan, ionic liquid and step 1）In the Beta molecular sieves rich in Si-OH groups that obtain be made into mixing
Even body phase, obtains crystallization mixture；
3）, by step 2）In prepared crystallization mixture be well mixed after be transferred in reactor, at 100～280 DEG C
Under the conditions of crystallization 2～240 hours；After crystallization terminates, reactant is cooled to room temperature, is obtained after being filtered, washed and dried stanniferous
Beta hetero-atom molecular-sieves.
The synthetic method that the present invention is provided, described step 1）In to be used as the Beta molecular sieves of precursor material can be silicon
The composition of one or more of aluminium Beta molecular sieves, borosilicate Beta molecular sieves or pure silicon Beta molecular sieves.
The synthetic method that the present invention is provided, described step 1）In be used as warp required for the Beta molecular sieves of precursor material
The processing method that crosses can be using traditional conventional heating mode is taken, can also selecting intensified by ultrasonic wave or microwave reinforced
Mode of heating.
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 one kind or the mixture in inorganic tin source, and one or more of the organotin source such as tin alkyl, alkoxyl tin, organotin acid esters
Mixture.It is preferred that butter of tin, stannous chloride.
The synthetic method that the present invention is provided, it is characterised in that：Described step 2）Ionic liquid used by middle synthesis is four
Alkyl quaternaries, alkyl imidazole salt, alkyl pyridine salt, Alkylpiperidine salt, alkyl pyrroles's salt, alkyl croak salt,
Tetraalkyl season phosphine salt compounds etc. one kind or its any category combined system.Preferably tetraalkyl ammonium salt class, alkyl
One kind of imidazole salt compound etc. or the combined system of its any category, more preferably R1R2R3R4N+X-（Wherein R1、R2、R3、
R4For C1～C4 alkyl substituents, X is Cl, Br）、R1R2Im+X-（Wherein R1、R2For C1～C4 alkyl substituents, Im is imidazoles
Ring, X are Cl, Br）One kind of compound etc. or the combined system of its any category.
As ionic liquid body fluid journey width, volatility are low, therefore ion thermal synthesis can be carried out at ambient pressure, so as to reduce
The pressure risk of Zeolite synthesis.Therefore the synthetic method that the present invention is provided, it is characterised in that：Described step 3）Middle 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.
The synthetic method that the present invention is provided, it is characterised in that：Obtained stanniferous Beta hetero-atom molecular-sieves can be straight
Connect and use as catalyst or catalyst carrier, also or through peracid treatment or alkali process or hydro-thermal process improving in molecular sieve
The catalytic efficiency of tin active sites.
The stanniferous Beta hetero atoms functional molecular sieve of the present invention is spread out using Holland's Philips X ' Pert Pro type X ray
Penetrate the crystal phase structure that instrument determines synthetic sample.Condition determination：Cu targets, K alpha rays (λ=0.15418nm), Ni are filtered, voltage
40kV, electric current 40mA, 5～65 ° of sweep limits, 10 °/min of sweep 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.
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；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 red fuming nitric acid (RFNA)（Concentration 65%）Press liquid：Solid is 20 ratio（Weight
Amount ratio）Process 24 hours at 100 DEG C, obtain the Beta molecular sieve (silica alumina ratios rich in Si-OH>2000).
Then, in a reactor, the 1- butyl -3- methyl chlorides of dissolving are weighed for imidazolium ionic liquid 100g, is added
Butter of tin 1.5g strong agitations are reacted 4 hours, then the Beta molecular sieves rich in Si-OH being previously obtained are added, and stir strongly
Reaction 4 hours, the crystallization mixture being uniformly mixed is mixed, its mol ratio is 1.0SiO2:0.1SnO2.
It is transferred to after prepared crystallization mixture is well mixed in open reactor, brilliant under the conditions of 200 DEG C
Change 20 hours.After crystallization terminates, reactant is cooled to room temperature, after being filtered, washed and dried, obtains stanniferous Beta hetero atoms
Molecular sieve.Product has carried out the sign of X-ray diffraction spectra, as a result as shown in figure 1, showing Beta point of product and standard
The X-ray diffraction spectrogram of son sieve is consistent.
Embodiment 2
Borosilicate Beta molecular sieves (silicon boron ratio=25) 3g is adopted red fuming nitric acid (RFNA)（Concentration 65%）Press liquid：Solid is 20 ratio
（Weight ratio）Process 10 hours under 100 DEG C of heating conditions of intensified by ultrasonic wave, obtain the Beta molecular sieve (silicon rich in Si-OH
Boron ratio>1300).
Then, in a reactor, the 1- ethyl -3- methyl chlorides for weighing dissolving are mixed with etamon chloride for imidazole salts
Compound（Weight compares 1：1）Ionic liquid 100g, add butter of tin 0.15g strong agitations to react 4 hours, then will be previously obtained
Beta molecular sieves rich in Si-OH are added, and strong agitation is reacted 4 hours, and the crystallization mixture being uniformly mixed, its mole are matched somebody with somebody
Than for 1.0SiO2:0.01SnO2.
It is transferred in the reactor of closed type after prepared crystallization mixture is well mixed, brilliant under the conditions of 100 DEG C
Change 240 hours.After crystallization terminates, reactant is cooled to room temperature, after being filtered, washed and dried, obtains stanniferous Beta hetero atoms
Molecular sieve.Product has carried out the sign of X-ray diffraction spectra, as a result as shown in Fig. 2 showing Beta point of product and standard
The X-ray diffraction spectrogram of son sieve is consistent.
Embodiment 3
Pure silicon Beta molecular sieve 3g are adopted tetraethyl ammonium hydroxide（Concentration 25%）Press liquid：Solid is 20 ratio（Weight
Amount ratio）Process 10 hours under 50 DEG C of microwave reinforced heating conditions, obtain the Beta molecular sieves rich in Si-OH.
Then, in a reactor, the 1- butyl -3- bromic ethers of dissolving are weighed for imidazolium ionic liquid 100g, is added
Butter of tin 0.02g strong agitations are reacted 4 hours, then the Beta molecular sieves rich in Si-OH being previously obtained are added, and stir strongly
Reaction 4 hours, the crystallization mixture being uniformly mixed is mixed, its mol ratio is 1.0SiO2:0.001SnO2.
It is transferred to after prepared crystallization mixture is well mixed in open reactor, microwave reinforced 180
Crystallization 2 hours under DEG C heating condition.After crystallization terminates, reactant is cooled to room temperature, is obtained after being filtered, washed and dried stanniferous
Beta hetero-atom molecular-sieves.Product has carried out the sign of X-ray diffraction spectra, as a result as shown in figure 3, show product with
The X-ray diffraction spectrogram of the Beta molecular sieves of standard 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 adopts red fuming nitric acid (RFNA)
（Concentration 65%）Press liquid：Solid is 20 ratio（Weight ratio）Process 4 hours at 80 DEG C, obtain Beta point rich in Si-OH
Son sieve (silica alumina ratio>920).
Then, in a reactor, the 1- heptyl -3- methyl chlorides of dissolving are weighed for piperidines ionic liquid 100g, is added
Butter of tin 0.33g strong agitations are reacted 4 hours, then the Beta molecular sieves rich in Si-OH being previously obtained are added, and stir strongly
Reaction 4 hours, the crystallization mixture being uniformly mixed is mixed, its mol ratio is 1.0SiO2:0.025SnO2.
It is transferred to after prepared crystallization mixture is well mixed in open reactor, brilliant under the conditions of 150 DEG C
Change 10 hours.After crystallization terminates, reactant is cooled to room temperature, after being filtered, washed and dried, obtains stanniferous Beta hetero atoms
Molecular sieve.Product has carried out the sign of X-ray diffraction spectra, as a result as shown in figure 4, showing Beta point of product and standard
The X-ray diffraction spectrogram of son sieve is consistent.
Embodiment 5
Beta molecular sieves (silica alumina ratio=21) 3g is first adopted tetraethyl ammonium hydroxide（Concentration 25%）Press liquid：Solid is 20
Ratio（Weight ratio）Process 0.5 hour under 80 DEG C of microwave reinforced heating conditions, then adopt red fuming nitric acid (RFNA)（Concentration 65%）Press liquid
Body：Solid is 20 ratio（Weight ratio）Process 1 hour under 80 DEG C of microwave reinforced heating conditions, obtain rich in Si-OH's
Beta molecular sieve (silica alumina ratios>230).
Then, in a reactor, the 1- butyl chlorides of dissolving is weighed for pyridine ionic liquid 50g, butter of tin is added
0.16g strong agitations are reacted 4 hours, then the Beta molecular sieves rich in Si-OH being previously obtained are added, strong agitation reaction 4
Hour, the crystallization mixture being uniformly mixed, its mol ratio are 1.0SiO2:0.0125SnO2.
It is transferred in open reactor, in intensified by ultrasonic wave after prepared crystallization mixture is well mixed
Crystallization 10 hours under 120 DEG C of heating conditions.After crystallization terminates, reactant is cooled to room temperature, is obtained after being filtered, washed and dried
Stanniferous Beta hetero-atom molecular-sieves.Product has carried out the sign of X-ray diffraction spectra, shows the Beta of product and standard
The X-ray diffraction spectrogram of molecular sieve is consistent.
Embodiment 6
Beta molecular sieves (silica alumina ratio=21) 3g is adopted red fuming nitric acid (RFNA)（Concentration 65%）Press liquid：Solid is 20 ratio（Weight
Amount ratio）Process 24 hours at 100 DEG C, obtain the Beta molecular sieve (silica alumina ratios rich in Si-OH>2000).
Then, in a reactor, the 1- butyl -3- methyl chlorides of dissolving are weighed for pyrroles ionic liquid 100g, is added
Stannous chloride 0.22g strong agitations are reacted 4 hours, then the Beta molecular sieves rich in Si-OH being previously obtained are added, and stir strongly
Reaction 4 hours, the crystallization mixture being uniformly mixed is mixed, its mol ratio is 1.0SiO2:0.025SnO2.
It is transferred to after prepared crystallization mixture is well mixed in open reactor, microwave reinforced 160
Crystallization 5 hours under DEG C heating condition.After crystallization terminates, reactant is cooled to room temperature, is obtained after being filtered, washed and dried stanniferous
Beta hetero-atom molecular-sieves.Product has carried out the sign of X-ray diffraction spectra, shows the Beta molecules of product and standard
The X-ray diffraction spectrogram of sieve is consistent.
Claims (8)
1. the method that a kind of hot secondary synthesis of ion prepare stanniferous Beta molecular sieves, is characterized in that：By Xi Yuan, ionic liquid and
Beta molecular sieves are well mixed, and through crystallization, separation, wash, be dried to obtain Sn-Beta hetero atoms functional molecular sieve；Which is one
Plant and there is the stanniferous molecular sieve of BEA topological structures, that is, there is the stanniferous hetero atom functional molecular sieve of BEA topological features, should
The silicon tin atom of kind of Sn-Beta hetero atoms functional molecular sieve is than scope within 10～1000；
Its process includes：
1), will act as needed for the Beta molecular sieves of precursor material are obtained via acid treatment, alkali process or hydro-thermal treatment method
Beta molecular sieves；
2), Jiang Xiyuan, ionic liquid and step 1) in the Beta molecular sieves that obtain be made into the body phase being well mixed, obtain crystallization and mix
Compound, molecular sieve and ionic liquid are 1 by weight：The amount of 20～100, Xi Yuan press products therefrom silicon tin atom than scope 10～
1000 meterings；
3), by step 2) in prepared crystallization mixture be well mixed after be transferred in reactor, in 100～280 DEG C of conditions
Lower crystallization 2～240 hours；After crystallization terminates, reactant is cooled to room temperature, is obtained after being filtered, washed and dried stanniferous
Beta hetero-atom molecular-sieves.
2. in accordance with the method for claim 1, it is characterised in that：
Described step 1) in be used as precursor material Beta molecular sieves be sial Beta molecular sieves, borosilicate Beta molecular sieves,
Or the composition of one or two or more kinds in pure silicon Beta molecular sieves.
3. in accordance with the method for claim 1, it is characterised in that：
Described step 2) in synthesis Xi Yuan used be butter of tin, one or two or more kinds mixture in stannous chloride,
And the mixture of one or two or more kinds in tin alkyl, alkoxyl tin, organotin acid esters.
4. in accordance with the method for claim 1, it is characterised in that：
Described step 2) in synthesis ionic liquid used be tetraalkyl ammonium salt class, alkyl imidazole salt, Fixanol
Class, Alkylpiperidine salt, alkyl pyrroles's salt, alkyl croak salt, one kind of tetraalkyl season phosphine salt compounds or its two kinds with
The combined system of upper any category.
5. according to the method described in claim 1 or 4, it is characterised in that：
Described step 2) in synthesis ionic liquid used be preferably tetraalkyl ammonium salt class, alkyl imidazole salt compounds
A kind of combined system of or its two kinds of any of the above categories.
6. according to the method described in claim 1 or 4, it is characterised in that：
Described step 2) in synthesis ionic liquid used be more preferably R1R2R3R4N+X-、R1R2Im+X-One kind of compound or
The combined system of its two kinds of any of the above categories；
R1R2R3R4N+X-, wherein R1、R2、R3、R4For C1～C4 alkyl substituents, X is Cl, Br；
R1R2Im+X-, wherein R1、R2For C1～C4 alkyl substituents, Im is imidazole ring, and X is Cl, Br.
7. in accordance with the method for claim 1, it is characterised in that：
Described step 3) in reactor be open state, or closure state；Crystallization process takes traditional conventional heating side
Formula, or select intensified by ultrasonic wave or microwave reinforced mode of heating.
8. the application of the stanniferous Beta molecular sieves that a kind of method according to claim 1 is prepared, it is characterised in that：Institute
The stanniferous Beta hetero-atom molecular-sieves for obtaining are used directly as catalyst or catalyst carrier, also or using front through peracid at
Reason or alkali process or hydro-thermal process are improving the catalytic efficiency of tin active sites in molecular sieve.
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| CN107244678B (en) * | 2017-07-04 | 2019-03-12 | 江西师范大学 | Sn- beta-molecular sieve and its hydrothermal synthesis method and method for hydroxylation of phenol |
| CN107311201B (en) * | 2017-07-04 | 2019-08-06 | 江西师范大学 | The method of nanometer Sn- beta-molecular sieve and preparation method thereof and phenol hydroxylation reaction |
| CN112742468B (en) * | 2019-10-30 | 2023-07-11 | 中国石油化工股份有限公司 | Titanium-containing molecular sieve, preparation method thereof, catalyst and method for selectively oxidizing hydrocarbon |
| CN112742453B (en) * | 2019-10-30 | 2023-07-14 | 中国石油化工股份有限公司 | Preparation method of titanium-containing molecular sieve, catalyst and selective oxidation method |
| CN113083359B (en) * | 2019-12-23 | 2023-07-25 | 中国石油化工股份有限公司 | Hydrotalcite modified titanium-silicon molecular sieve catalyst, preparation method and application |
| CN115722259B (en) * | 2021-08-26 | 2024-02-09 | 中国科学院广州能源研究所 | Synthesis method of space adjacent bimetallic heteroatom molecular sieve |
| 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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| CN102101681A (en) * | 2009-12-16 | 2011-06-22 | 中国科学院大连化学物理研究所 | Ionothermal synthesis method of microporous aluminum phosphate 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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| CN102101681A (en) * | 2009-12-16 | 2011-06-22 | 中国科学院大连化学物理研究所 | Ionothermal synthesis method of microporous aluminum phosphate 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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