CN107954439A - A kind of preparation method of chirality A bodies enrichment Beta zeolite molecular sieve - Google Patents
A kind of preparation method of chirality A bodies enrichment Beta zeolite molecular sieve Download PDFInfo
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- CN107954439A CN107954439A CN201610900998.XA CN201610900998A CN107954439A CN 107954439 A CN107954439 A CN 107954439A CN 201610900998 A CN201610900998 A CN 201610900998A CN 107954439 A CN107954439 A CN 107954439A
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- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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Abstract
The present invention relates to Beta zeolite molecular sieve preparing technical field, discloses a kind of preparation method of chirality A bodies enrichment Beta zeolite molecular sieve, wherein, this method includes：(1) silicon source, template tetraethyl ammonium hydroxide and water are mixed, gained mixed liquor is hydrolyzed；(2) gel and drying is made in the mixed liquor after hydrolysis, dry glue is made；(3) dry glue, polyethylene glycol and Fluorine source are mixed, gained mixture is subjected to hydrothermal crystallizing；(4) obtained hydrothermal crystallizing product is subjected to separation of solid and liquid, obtained solid phase is dried and is optionally roasted.The method of the present invention can prepare the Beta zeolite molecular sieve that A body contents reach more than 70%.
Description
Technical field
The present invention relates to the technology of preparing of Beta zeolite molecular sieve, more particularly to a kind of chirality A bodies enrichment Beta zeolites
The preparation method of molecular sieve.
Background technology
1967, Wadlinger of Mobil companies of the U.S. etc. have developed with three-dimensional ten binary pore passage structures first
Macropore silica-rich zeolite, and it is named as Beta zeolites.Due to its special pore passage structure, Beta zeolites are provided simultaneously with acid catalysis characteristic
And structure selectivity, it is being hydrocracked, is having extensively in isomerization, alkylation, the petroleum refining such as dewaxing and petrochemical process
Using.The structure of Beta zeolites was determined by Treacy, Newsam and Higgins in 1988 years respectively.It is (also referred to as more by A bodies
Body A) and B bodies (also referred to as polymorph B) with 44:56 ratio symbiosis is formed.A bodies have chirality, and in c-axis direction, there are spiral shell
Trepanning road, B bodies are without chirality.At present, B bodies content is up to 90% Beta zeolites and has been synthesized, and chirality A
The Beta zeolites of body are not still reported.There is chiral multiform as only one in Beta zeolite polymorphs family
Body, A bodies have particularly important application prospect in chiral catalysis and chiral separation etc..However, synthesis or the A of pure A bodies
The selective crystallization of the Beta zeolites of body enrichment is still one of ultimate challenge in current Beta zeolites study on the synthesis.
In the relevant every research of Beta zeolites, the selective crystallization synthesis of each polymorph is that people study all the time
One of important directions.
For example, CN102190314A discloses one kind using organic formwork agent tetraethyl ammonium hydroxide, N, N, 2,6- tetramethyls
Phenylpiperidines hydroxide or dimethyl diisopropyl ammonium hydroxide, synthesize pure silicon or metal-doped Beta zeolites under given conditions
Method, which includes：Mixing is stirred at room temperature in silicon source, template and water, and it is optionally golden with doping
Category source mixes, and uses infrared light irradiation, or the mode of baking oven heating is further heated, and it is brilliant then to carry out hydro-thermal
Change, obtained final product Beta zeolites have more A bodies.Harsh yet with its condition, experimental repeatability is poor.
And for example, CN103601212A discloses a kind of method for preparing chiral A bodies enrichment Beta zeolites, this method bag
Include：Mixing is stirred at room temperature in silicon source, template and water, then dries, reheat, obtain blob of viscose shape solid abrasive into powder
End, Fluorine source is added into the powder, and carries out hydrothermal crystallizing.This method uses specific template agent N, N, N- dimethyl ethyl ring
Hexyl ammonium hydroxide, N, N, N- trimethylcyclohexyls ammonium hydroxide or dimethyidicyclohexyl ammonium hydroxide, but this method is grasped
It is higher to make complicated and cost.
And for example, CN104909382A discloses a kind of method for synthesizing A bodies enrichment Beta zeolites in acid condition, institute
It is citric acid, acetic acid, oxalic acid, hydrofluoric acid or phosphoric acid to state acid additive.But crystallization velocity is slow in acid condition, crystallization week
Phase is grown.
There is the Beta zeolite molecular sieve of chiral structure as first case, before its chiral helical duct is due to huge application
Scape and paid close attention to by people, therefore, probe into Beta zeolite molecular sieve influence A body contents key factor, and then synthesize A shapes
Body enrichment Beta zeolite molecular sieve has prior meaning.
The content of the invention
It is an object of the invention on the basis of existing technology, there is provided a kind of chirality A bodies are enriched with Beta zeolite molecules
The preparation method of sieve.
To achieve these goals, the present invention provides a kind of preparation method of chirality A bodies enrichment Beta zeolite molecular sieve,
Wherein, this method includes：
(1) silicon source, template tetraethyl ammonium hydroxide and water are mixed, gained mixed liquor is hydrolyzed；
(2) gel and drying is made in the mixed liquor after hydrolysis, dry glue is made；
(3) dry glue, polyethylene glycol and Fluorine source are mixed, gained mixture is subjected to hydrothermal crystallizing；
(4) obtained hydrothermal crystallizing product is subjected to separation of solid and liquid, obtained solid phase is dried and is optionally roasted
Burn.
The method of the present invention can prepare the higher Beta zeolite molecular sieve of A body contents, such as embodiment 3 and 4, prepare
A bodies content can reach more than 70% in the Beta zeolite molecular sieve gone out.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the XRD diagram that Beta zeolite molecular sieve is enriched with using chirality A bodies made from the method for the embodiment of the present invention 1；
Fig. 2 is the XRD diagram that Beta zeolite molecular sieve is enriched with using chirality A bodies made from the method for the embodiment of the present invention 2；
Fig. 3 is the XRD diagram that Beta zeolite molecular sieve is enriched with using chirality A bodies made from the method for the embodiment of the present invention 3；
Fig. 4 is the XRD diagram that Beta zeolite molecular sieve is enriched with using chirality A bodies made from the method for the embodiment of the present invention 4；
Fig. 5 is the XRD diagram using Beta zeolite molecular sieve made from the method for comparative example 1.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
Technical term in the present invention, provides being defined from it for definition, does not provide then usually the containing by this area of definition
Reason and good sense solution.
Template in the present invention, in the art also referred to as structure directing agent or Organic structure directing agent.
According to the present invention, there is provided a kind of preparation method of chirality A bodies enrichment Beta zeolite molecular sieve, wherein, the party
Method includes：
(1) silicon source, template tetraethyl ammonium hydroxide and water are mixed, gained mixed liquor is hydrolyzed；
(2) gel and drying is made in the mixed liquor after hydrolysis, dry glue is made；
(3) dry glue, polyethylene glycol and Fluorine source are mixed, gained mixture is subjected to hydrothermal crystallizing；
(4) obtained hydrothermal crystallizing product is subjected to separation of solid and liquid, obtained solid phase is dried and is optionally roasted
Burn.
The method of the present invention by adding polyethylene glycol and Fluorine source into obtained initial dry glue, and by gained mixture into
Row hydrothermal crystallizing, so as to prepare the higher Beta zeolite molecular sieve of A body contents.
Herein, " at least one " represents one or more kinds of.
In step (1), the silicon source is with SiO2Meter, under preferable case, silicon source, template tetraethyl ammonium hydroxide and water
Molar ratio is 1:0.2-0.35:15-30.
The present invention is not particularly limited for the species of silicon source, can be conventional selection.
Usually, the silicon source can be at least one of silicon-containing compound, Ludox and white carbon shown in Formulas I,
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl, such as methyl, ethyl, propyl group and its isomers and butyl and
Its isomers.
Preferably, the silicon source is at least one of ethyl orthosilicate, Ludox and white carbon.
In step (1), the hydrolysis is to instigate the hydrolysis of silicon source.The present invention does not limit the condition of hydrolysis particularly
System, any known suitable condition can use, for example, the temperature of hydrolysis can be 0 DEG C -150 DEG C, hydrolysis time can be
- 3000 minutes 10 minutes.Preferably, in step (1), " in confined conditions, under agitation, at room temperature described is hydrolyzed to
When progress 4-8 is small ".Wherein, the room temperature is usually 15-25 DEG C, is preferably 20-25 DEG C.
In step (2), the mixed liquor after hydrolysis is made to the process of gel, preferably under agitation, will be mixed after hydrolysis
Close liquid carry out at room temperature 6-10 it is small when, mixed liquor is stirred to viscous gel.Wherein, the room temperature is usually 15-25 DEG C, excellent
Elect 20-25 DEG C as.
In step (2), in order to further ensure the Beta zeolites prepared have higher A body contents, preferable case
Under, the condition that obtained gel is dried is caused into dried dry glue Zhong Shui and with SiO2The molar ratio of the silicon source of meter is less than
3:1.Wherein, the method for the drying and the condition of drying can be conventional method and condition, as long as ensureing body after drying
Be Zhong Shui with SiO2The molar ratio of the silicon source of meter is preferably shorter than 3:1, in a kind of embodiment of the present invention, be
Preferably template is avoided to decompose, the method for the drying is freeze-drying, and the temperature of the freeze-drying can be 0 DEG C
To -60 DEG C.
In step (3), the Fluorine source is with F-Meter, the molar ratio of silicon source, polyethylene glycol and Fluorine source is 1:0.02-0.5:
0.05-0.5, it is further preferred that the molar ratio of silicon source, polyethylene glycol and Fluorine source is 1:0.02-0.5:0.2-0.35.
The present invention is not particularly limited for the species of Fluorine source, can be conventional selection.The Fluorine source can be ammonium fluoride
At least one of with hydrofluoric acid.
In step (3), the mode that foregoing obtained dry glue, polyethylene glycol and Fluorine source are mixed can use conventional method will
Foregoing obtained dry glue, polyethylene glycol and Fluorine source mixing, obtain uniform mixture.In order to enable dry glue is preferably uniformly divided
Dissipate, preferably the dry glue is ground before mixing dry glue powder is made, or ground after dry glue, polyethylene glycol and Fluorine source are mixed
Clay into power.The granularity of the dry glue powder is not particularly limited in the present invention, as long as ensureing dry glue and polyethylene glycol and Fluorine source
It is sufficiently mixed uniformly.For example, in the specific embodiment of the present invention, by the dry glue, polyethylene glycol and Fluorine source
Granularity is ground into after mixing as less than 150 microns, is preferably 50-150 microns of powder.Wherein, the polyethylene glycol is preferably
Average molecular weight is the polyethylene glycol of 400-10000.For example, embodiment according to the present invention, the polyvinyl alcohol
Average molecular weight can be 400,2000,4000,10000.
In step (3), the hydrothermal crystallizing can carry out at conventional temperatures, be carried out such as at a temperature of 130-170 DEG C,
It is preferred that carried out at a temperature of 140-150 DEG C.The time of the hydrothermal crystallizing can also be conventional selection, however, according to this hair
Bright method, using previously described method, can shorten the hydrothermal crystallizing time, moreover, even if shortening the hydrothermal crystallizing time,
The higher Beta zeolite molecular sieve of A body contents can be prepared.The method according to the invention, time of the hydrothermal crystallizing can be with
It it is preferably 7-8 days for 6-10 days.
In step (4), the solid phase that the hydrothermal crystallizing product progress separation of solid and liquid that hydrothermal crystallizing obtains is obtained can be normal
It is dried under the conditions of rule and optionally roasts, so as to obtains chiral A bodies enrichment Beta zeolite molecular sieve.In the present invention,
It is " optional " represent it is inessential, it can be understood as including or do not include.Specifically, the drying can be at a temperature of 60-100 DEG C
Carry out, the time of the drying can make choice according to dry temperature, when generally can be 2-12 small.The mesh of the roasting
Essentially consist in removing sieve synthesis procedure in remain in the template in molecular sieve pore passage, can be according to specifically used requirement
Determine whether to be roasted.It is preferred that roasted after the completion of drying.The roasting can at a temperature of 550-600 DEG C into
OK, the duration of the roasting can make choice according to the temperature of roasting, when generally can be 4-8 small.The roasting one
As carried out in air atmosphere.Further, it is also possible to the solid phase that separation of solid and liquid is obtained is washed before the drying, i.e. by water
The hydrothermal crystallizing product that thermal crystallisation obtains carries out separation of solid and liquid, washing (optional) and drying, can obtain molecular screen primary powder；Alternatively, will
The hydrothermal crystallizing product that hydrothermal crystallizing obtains carries out separation of solid and liquid, washing (optional), dry (optional) and roasts, after must can roasting
Molecular sieve.Generally in room temperature to being mixed or being eluted with water at 50 DEG C, water is generally hydrothermal crystallizing product quality for washing
1-20 times.The method of the separation of solid and liquid can use conventional method to carry out, such as filtering, centrifugation etc..
According to the present invention, the heating of either step in Beta zeolite molecular sieve preparation method is enriched with to the chirality A bodies
Mode is without particular limitation, can be by the way of temperature programming, such as 0.5 DEG C -2 DEG C/min.
According to the present invention, the hydrothermal crystallizing pressure being enriched with to the chirality A bodies in Beta zeolite molecular sieve preparation method
Have no particular limits, can be the self-generated pressure of crystallization system.
The present invention will be described in detail by way of examples below.
In following embodiments and comparative example, X-ray powder diffraction material phase analysis (XRD) uses Rigaku D/MAX-2550
Type diffractometer.Test condition：Cu targets, K α radiation, Ni filter plates, tube voltage 50kV, tube current 200mA, 4 ° -40 ° of scanning range.
Embodiment 1
The present embodiment is used for the preparation for illustrating chirality A bodies enrichment Beta zeolite molecular sieve of the present invention.
The tetraethyl ammonium hydroxide aqueous solution of 4.50g ethyl orthosilicates and 2.22g mass fractions 35% and 4.5g are distilled
Water mixes in reaction vessel, by container sealed membrane seal and stir 5 it is small when, make ethyl orthosilicate complete hydrolysis.
Remove sealed membrane, in fume hood by gained mixed liquor continue stirring 6 it is small when, ethanol in system is volatilized with water
To forming jelly, 3 days lyophilized, system at this time is transferred in freezing (20 DEG C of temperature of charge, -60 DEG C of condenser temperature) drying machine
H2O and SiO2Molar ratio is less than 1, dry glue quality 2.15g.
2.15g dry glues are mixed with 3.6g PEG-400 and 0.2g ammonium fluorides and are ground into uniform powder (100 mesh), then
It is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, is placed in crystallization 7 days in 150 DEG C of baking ovens.
Product is filtered after the completion of crystallization, is washed with distilled water to neutrality, 80 DEG C of oven for drying, Muffle furnace in 550 DEG C of temperature
The lower calcining 6 of degree removes template when small and obtains Beta zeolite molecular sieve, product quality 1.3g.
Obtained Beta zeolite molecular sieve is subjected to X-ray diffraction analysis, XRD spectra is shown in Fig. 1, institute is obtained by XRD analysis
The A bodies relative amount of the Beta zeolite molecular sieve sample of preparation is 64%.
Embodiment 2
The present embodiment is used for the preparation for illustrating chirality A bodies enrichment Beta zeolite molecular sieve of the present invention.
The tetraethyl ammonium hydroxide aqueous solution of 4.50g ethyl orthosilicates and 2.23g mass fractions 35% and 4.5g are distilled
Water mixes in reaction vessel, by container sealed membrane seal and stir 5 it is small when, make ethyl orthosilicate complete hydrolysis.
Remove sealed membrane, in fume hood by gained mixed liquor continue stirring 6 it is small when, ethanol in system is volatilized with water
To jelly is formed, it is transferred in freeze drier (20 DEG C of temperature of charge, -60 DEG C of condenser temperature) and freezes 3 days, at this time system
H2O and SiO2Molar ratio is less than 1, dry glue quality 2.14g.
2.14g dry glues are mixed with 1.7g PEG-2000 and 0.19g ammonium fluorides and are ground into uniform powder (100 mesh), so
It is transferred to afterwards in the stainless steel cauldron of polytetrafluoroethyllining lining, is placed in crystallization 7 days in 150 DEG C of baking ovens.
Product is filtered after the completion of crystallization, is washed with distilled water to neutrality, 80 DEG C of oven for drying, Muffle furnace in 550 DEG C of temperature
The lower calcining 6 of degree removes template when small and obtains Beta zeolite molecular sieve, product quality 1.4g.
Obtained Beta zeolite molecular sieve is subjected to X-ray diffraction analysis, XRD spectra is shown in Fig. 2, institute is obtained by XRD analysis
The A body relative amounts of the Beta zeolite molecular sieve sample of preparation are about 68%.
Embodiment 3
The present embodiment is used for the preparation for illustrating chirality A bodies enrichment Beta zeolite molecular sieve of the present invention.
The tetraethyl ammonium hydroxide aqueous solution of 4.50g ethyl orthosilicates and 2.22g mass fractions 35% and 4.5g are distilled
Water mixes in reaction vessel, by container sealed membrane seal and stir 5 it is small when, make ethyl orthosilicate complete hydrolysis.
Remove sealed membrane, in fume hood by gained mixed liquor continue stirring 6 it is small when, ethanol in system is volatilized with water
To jelly is formed, it is transferred in freeze drier (20 DEG C of temperature of charge, -60 DEG C of condenser temperature) and freezes 3 days, at this time system
H2O and SiO2Molar ratio is less than 1, dry glue quality 2.15g.
2.15g dry glues are mixed with 4.2g PEG-4000 and 0.19g ammonium fluorides and are ground into uniform powder (100 mesh), are turned
Move on in the stainless steel cauldron of polytetrafluoroethyllining lining, be placed in crystallization 7 days in 150 DEG C of baking ovens.
Product is filtered after the completion of crystallization, is washed with distilled water to neutrality, 80 DEG C of oven for drying, Muffle furnace in 550 DEG C of temperature
The lower calcining 6 of degree removes template when small and obtains Beta zeolite molecular sieve.Product quality 1.5g.
Obtained Beta zeolite molecular sieve is subjected to X-ray diffraction analysis, XRD spectra is shown in Fig. 3, institute is obtained by XRD analysis
The A body relative amounts of the Beta zeolite molecular sieve sample of preparation are about 70%.
Embodiment 4
The present embodiment is used for the preparation for illustrating chirality A bodies enrichment Beta zeolite molecular sieve of the present invention.
The tetraethyl ammonium hydroxide aqueous solution of 4.51g ethyl orthosilicates and 2.22g mass fractions 35% and 4.5g are distilled
Water mixes in reaction vessel, by container sealed membrane seal and stir 4 it is small when, make ethyl orthosilicate complete hydrolysis.
Remove sealed membrane, in fume hood by gained mixed liquor continue stirring 6 it is small when, the ethanol in system is evaporated into water
Jelly is formed, is transferred in freeze drier (20 DEG C of temperature of charge, -60 DEG C of condenser temperature) and freezes 3 days, at this time system
H2O and SiO2Molar ratio is less than 1, product quality 2.14g.
2.14g dry glues are mixed with 6.3g PEG-10000 and 0.19g ammonium fluorides and are ground into uniform powder (100 mesh),
It is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, is placed in crystallization 7 days in 150 DEG C of baking ovens.
Product is filtered after the completion of crystallization, is washed with distilled water to neutrality, 80 DEG C of oven for drying, Muffle furnace in 550 DEG C of temperature
The lower calcining 6 of degree removes template when small and obtains Beta zeolite molecular sieve.Product quality 1.4g.
Obtained Beta zeolite molecular sieve is subjected to X-ray diffraction analysis, XRD spectra is shown in Fig. 4, institute is obtained by XRD analysis
The A body relative amounts of the Beta zeolite molecular sieve sample of preparation are about 72%.
Embodiment 5
The present embodiment is used for the preparation for illustrating chirality A bodies enrichment Beta zeolite molecular sieve of the present invention.
Method according to embodiment 1 prepares chirality A bodies enrichment Beta zeolite molecular sieve, unlike, mass fraction
35% tetraethyl ammonium hydroxide aqueous solution is 2.53g, distilled water 5.2g, ammonium fluoride 0.3g.
The A body relative amounts that prepared Beta zeolite molecular sieve sample is obtained by XRD analysis are about 64%.
Comparative example 1
This comparative example is used for the reference preparation method for illustrating chiral A bodies enrichment Beta zeolite molecular sieve.
Method according to embodiment 1 prepares chirality A bodies enrichment Beta zeolite molecular sieve, unlike, it is added without poly- second
Glycol, and dry glue made from 2.14g is directly mixed with 0.19g ammonium fluorides and is ground into uniform powder (100 mesh), it is transferred to poly-
In the stainless steel cauldron of tetrafluoroethene liner, crystallization 7 days in 150 DEG C of baking ovens are placed in.Product is filtered after the completion of crystallization, with steaming
Distilled water, which is washed, to be removed template when 550 DEG C of temperature lower calcinations 6 are small to neutrality, 80 DEG C of oven for drying, Muffle furnace and obtains Beta
Zeolite molecular sieve.
Obtained Beta zeolite molecular sieve is subjected to X-ray diffraction analysis, XRD spectra is shown in Fig. 5, institute is obtained by XRD analysis
Prepare for common Beta zeolites, the A body relative amounts of Beta zeolite molecular sieve sample are about 50% or so.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of preparation method of chirality A bodies enrichment Beta zeolite molecular sieve, it is characterised in that this method includes：
(1) silicon source, template tetraethyl ammonium hydroxide and water are mixed, gained mixed liquor is hydrolyzed；
(2) gel and drying is made in the mixed liquor after hydrolysis, dry glue is made；
(3) dry glue, polyethylene glycol and Fluorine source are mixed, gained mixture is subjected to hydrothermal crystallizing；
(4) obtained hydrothermal crystallizing product is subjected to separation of solid and liquid, obtained solid phase is dried and is optionally roasted.
2. the preparation method of chirality A bodies enrichment Beta zeolite molecular sieve according to claim 1, wherein, the silicon source
With SiO2Meter, the molar ratio of silicon source, template tetraethyl ammonium hydroxide and water is 1:0.2-0.35:15-30.
3. the preparation method of chirality A bodies enrichment Beta zeolite molecular sieve according to claim 1 or 2, wherein, by gained
The process of mixed liquor hydrolysis, in confined conditions, under agitation, when progress 4-8 is small at room temperature.
4. the preparation method of chirality A bodies enrichment Beta zeolite molecular sieve according to claim 1 or 2, wherein, it will hydrolyze
The process of gel is made in mixed liquor afterwards, under agitation, the mixed liquor after hydrolysis is carried out at room temperature 6-10 it is small when.
5. the preparation method of chirality A bodies enrichment Beta zeolite molecular sieve according to claim 1, wherein, after hydrolysis
Mixed liquor be made dry glue Zhong Shui that the condition of the drying after gel makes with SiO2The molar ratio of the silicon source of meter is less than 3:
1, the drying is preferably to be freeze-dried.
6. the preparation method of chirality A bodies enrichment Beta zeolite molecular sieve according to claim 1, wherein, the Fluorine source
With F-Meter, the molar ratio of silicon source, polyethylene glycol and Fluorine source is 1:0.02-0.5:0.05-0.5, is preferably 1:0.02-0.5:0.2-
0.35。
7. the preparation method of the chiral A bodies enrichment Beta zeolite molecular sieve according to claim 1 or 6, wherein, it is described poly-
The average molecular weight of ethylene glycol is 400-10000, is preferably 4000-10000.
8. the preparation method of chirality A bodies enrichment Beta zeolite molecular sieve according to claim 1, wherein, the hydro-thermal
Crystallization carries out at a temperature of 130-170 DEG C, is carried out preferably at a temperature of 140-150 DEG C；The time of hydrothermal crystallizing is 6-10
My god, it is preferably 7-8 days.
9. the preparation method of chirality A bodies enrichment Beta zeolite molecular sieve according to claim 1, wherein, by what is obtained
The temperature that solid phase is dried is 60-100 DEG C, and the temperature of the roasting is 550-600 DEG C.
10. the preparation method of the chiral A bodies enrichment Beta zeolite molecular sieve according to claim 1,2 or 6, wherein, institute
Silicon source is stated as at least one of silicon-containing compound, Ludox and white carbon shown in Formulas I,
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl,
The silicon-containing compound is preferably ethyl orthosilicate；
The Fluorine source is at least one of ammonium fluoride and hydrofluoric acid.
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| CN102190314A (en) * | 2011-04-06 | 2011-09-21 | 吉林大学 | Method for preparing beta-zeolite molecular sieve containing excess chiral polymorph A |
| CN102211779A (en) * | 2010-04-07 | 2011-10-12 | 中国石油天然气股份有限公司 | Method for preparing beta zeolite |
| CN103601212A (en) * | 2013-11-11 | 2014-02-26 | 吉林大学 | Method for preparing chiral polymorph A-shaped excessive Beta zeolite molecular sieve |
| CN104291351A (en) * | 2014-09-28 | 2015-01-21 | 山东齐鲁华信高科有限公司 | Method for synthesizing beta molecular sieve by utilizing beta molecular sieve mother solution |
| CN104909382A (en) * | 2015-05-21 | 2015-09-16 | 吉林大学 | Method for preparing Beta zeolite molecular sieve with excessive chiral polymorph A under acidic condition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102211779A (en) * | 2010-04-07 | 2011-10-12 | 中国石油天然气股份有限公司 | Method for preparing beta zeolite |
| CN102190314A (en) * | 2011-04-06 | 2011-09-21 | 吉林大学 | Method for preparing beta-zeolite molecular sieve containing excess chiral polymorph A |
| CN103601212A (en) * | 2013-11-11 | 2014-02-26 | 吉林大学 | Method for preparing chiral polymorph A-shaped excessive Beta zeolite molecular sieve |
| CN104291351A (en) * | 2014-09-28 | 2015-01-21 | 山东齐鲁华信高科有限公司 | Method for synthesizing beta molecular sieve by utilizing beta molecular sieve mother solution |
| CN104909382A (en) * | 2015-05-21 | 2015-09-16 | 吉林大学 | Method for preparing Beta zeolite molecular sieve with excessive chiral polymorph A under acidic condition |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109806909A (en) * | 2019-03-06 | 2019-05-28 | 中国科学院大连化学物理研究所 | A kind of preparation method and applications for methanol and/or dimethyl ether propylene catalyst |
| CN109806909B (en) * | 2019-03-06 | 2020-08-11 | 中国科学院大连化学物理研究所 | Preparation method and application of catalyst for preparing propylene from methanol and/or dimethyl ether |
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