CN106892435A - A kind of method that amino acid auxiliary prepares the Beta zeolite molecular sieve of chiral polymorph A enrichments - Google Patents
A kind of method that amino acid auxiliary prepares the Beta zeolite molecular sieve of chiral polymorph A enrichments Download PDFInfo
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- CN106892435A CN106892435A CN201710094696.2A CN201710094696A CN106892435A CN 106892435 A CN106892435 A CN 106892435A CN 201710094696 A CN201710094696 A CN 201710094696A CN 106892435 A CN106892435 A CN 106892435A
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- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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Abstract
A kind of method that amino acid auxiliary prepares the Beta zeolite molecular sieve of chiral polymorph A enrichments, belongs to Beta zeolite molecular sieve preparing technical field.The method is with silicon source, template tetraethyl ammonium hydroxide, solid Fluorine source, solid amino acid as raw material, first silicon source, template, deionized water are mixed after being fully hydrolyzed silicon source, water in removing gel obtains dry glue, homogeneous powder is obtained with solid Fluorine source, solid amino acid mixed grinding again, hydrothermal crystallizing is carried out.The hydrothermal crystallizing product that will be obtained is washed, separation of solid and liquid, drying and roasting, so as to obtain the Beta zeolite molecular sieve of chiral polymorph A enrichments of the present invention.The amino acid added in the present invention is the key factor of the Beta zeolites for generating the enrichment of A bodies, can be L histidines, L alanine, L lysines, glycine etc., the method of the present invention can prepare the Beta zeolite molecular sieve of A bodies enrichment, have huge application prospect in fields such as chiral catalysis, chiral separations.
Description
Technical field
The invention belongs to Beta zeolite molecular sieve preparing technical field, solid amino is added more particularly in initial dry glue
Sour mixed grinding, the method that the Beta zeolite molecular sieve of chiral polymorph A enrichments is prepared under given conditions.
Background technology
Inorganic microporous crystalline material with zeolite molecular sieve as representative is due to the duct suitable with small molecular size, rule
Pore-size distribution then, big specific surface area, heat endurance high and good chemical stability and be widely used in being catalyzed, inhale
The field such as attached, classification and ion exchange.It is solid that there is topological structure the molecular sieve of chiral space group symmetry to be considered to have
There is the molecular sieve of Chiral properties, this molecular sieve analog has pore size selectivity and chiral enantiomer selectivity simultaneously, in chirality
The aspects such as absorption, chiral separation and asymmetry catalysis have important application prospect and receive much concern.In having for having been found that
In the molecular sieve of inherent chirality structure, Beta zeolites are that uniquely there is three-dimensional twelve-ring to intersect pore passage structure and realize extensively
The silica-rich zeolite molecular sieve of the applications such as catalysis, adsorbing separation, is one of most possible molecular sieve for realizing chiral application.Beta boils
Stone is formed by the close polymorph A of two kinds of structures and polymorph B fault symbiosis, and wherein polymorph A skeleton structures have P4122
And P4322 space group symmetries, are chiral polymorph, and polymorph B skeleton structures have C2/c space group symmetries, are non-hand
Property polymorph.Polymorph A and polymorph B almost occur with equal probability, Beta zeolite molecular sieve is had the fault of height
Defect, A bodies and B bodies ratio are 44 in common Beta zeolites:56, without Chiral properties.
The selective crystallization of Beta zeolite polymorphs A is always that people extremely crave for.CN102190314A discloses one
The method for synthesizing pure silicon or metal-doped Beta zeolites under given conditions using organic formwork agent is planted, the synthetic method is first by silicon
Source, template and water are stirred at room temperature mixing, optionally mix with doping metals source, and use infrared light irradiation, or
The mode of baking oven heating is further heated, and then carries out hydrothermal crystallizing, and the final product Beta zeolites for obtaining have
More A bodies.Template can be set to decompose yet with infrared light irradiation or baking oven heating, condition is harsh and experiment is heavy
Renaturation is poor.CN103601212A discloses a kind of using the chiral polymorph A enrichments Beta zeolites of specific self-control template preparation
Method, the method use specific template agent N, N, N- dimethyl ethyl cyclohexyl ammonium hydroxide, N, N, N- trimethylcyclohexyl
Ammonium hydroxide or dimethyidicyclohexyl ammonium hydroxide, complex operation and relatively costly.CN104909382A also discloses one kind
The method of the Beta zeolites of synthesis A bodies enrichment, adds acid additive lemon in acid condition in party's normal direction Primogel
Acid, acetic acid, oxalic acid, hydrofluoric acid or phosphoric acid.But, Beta zeolite crystallizations speed is slow in acid condition, and the crystallization cycle is long.
If taking specific process to prepare the Beta zeolites or even single chiral polymorph A of chiral polymorph A enrichment
Crystal chiral will be catalyzed, chiral resolution field has great impetus.
The content of the invention
It is an object of the invention on the basis of existing technology, there is provided a kind of amino acid auxiliary prepares chiral polymorph A
The method of the Beta zeolite molecular sieve of enrichment, can be high with synthetic crystallization degree using the method and chiral polymorph A contents are up to
70% Beta zeolite molecular sieve.
The method of the invention is comprised the following steps that：
(1) silicon source, template and deionized water are proportionally added into reaction vessel, are stirred under closed, room temperature condition
Mix uniform, make silicon source complete hydrolysis；
(2) said mixture is stirred under room temperature condition, unlimited system, the volatilizable thing such as aqueous solvent is volatilized, stirring
To forming homogeneous gel；
(3) gel of gained is further dehydrated and obtains block dry glue, by gained bulk dry glue and solid amino acid,
Into homogeneous powder, load reactor carries out hydrothermal crystallizing to solid Fluorine source mixed grinding；
(4) crystallization product is transferred out from the reactor for being cooled to room temperature, the solid for obtaining is entered with deionized water
Row washing, separation, dry roasting, so as to obtain the Beta zeolite molecular sieve of chiral polymorph A enrichments of the present invention.
In the above method, silicon source used is tetraethyl orthosilicate, Ludox or white carbon etc.；Template used is quality
The tetraethyl ammonium hydroxide aqueous solution of fraction 30~40%；Amino acid used be L-Histidine, ALANINE, 1B,
Glycine etc.；Solid Fluorine source used is ammonium fluoride, ammonium acid fluoride etc.；
The present invention is by the way that to solid amino acid and solid Fluorine source is added in initial dry glue, it is many that solid-phase sequencing prepares chirality
The Beta zeolite molecular sieve of body A enrichments, A body contents exceed in obtained Beta zeolites during with L-Histidine as auxiliary agent
70%.
What deserves to be explained is, the present invention has no particular limits to the condition for hydrolyzing in step (1), any known suitable
Condition can be used, and the mol ratio of silicon source, template and deionized water is 1:0.25~0.5:12~20.
Gel is further dehydrated the process for being made dry glue, it is dry that dehydrating and drying method is preferably freezing in step (3)
Dry, the temperature of the freeze-drying can be 0 DEG C~-60 DEG C, it is ensured that H in system after drying2O and SiO2Mol ratio be less than 1：1
.Dry glue powder is obtained after dried block dry glue and solid amino acid, solid Fluorine source mixed grinding, the present invention is to described
The granularity of dry glue powder is not particularly limited, below preferably 300 mesh.In dry glue powder silicon source, amino acid and Fluorine source mole
Than being 1:0.075~0.12:0.2~0.5.Described hydrothermal crystallizing temperature is 130~170 DEG C, and the hydrothermal crystallizing time is 6~10
My god.
In step (4), the separate mode can be using modes such as suction filtration or centrifugations；The drying temperature is 60~100 DEG C,
The drying time is 2~12 hours；The sintering temperature is 550~600 DEG C, and roasting time is 4~8 hours.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with following tool
Body implementation method is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1：The XRD and DIFFaX program moulds of the Beta zeolite molecular sieve of chiral polymorph A enrichments obtained in embodiment 1
The chiral polymorph A contents of plan are 72% (being the shared ratio in Beta zeolites of A bodies, can see mass fraction as)
The standard x RD of Beta zeolite molecular sieve compares figure；
Fig. 2：The XRD and DIFFaX program moulds of the Beta zeolite molecular sieve of chiral polymorph A enrichments obtained in embodiment 2
The chiral polymorph A contents of plan are that the standard x RD of 64% Beta zeolite molecular sieve compares figure；
Fig. 3：The XRD and DIFFaX program moulds of the Beta zeolite molecular sieve of chiral polymorph A enrichments obtained in embodiment 3
The chiral polymorph A contents of plan are that the standard x RD of 65% Beta zeolite molecular sieve compares figure；
Fig. 4：The XRD and DIFFaX program moulds of the Beta zeolite molecular sieve of chiral polymorph A enrichments obtained in embodiment 4
The chiral polymorph A contents of plan are that the standard x RD of 60% Beta zeolite molecular sieve compares figure；
Fig. 5：The XRD of Beta zeolite molecular sieve obtained in comparative example 1 contains with the chiral polymorph A that DIFFaX programs are simulated
The standard x RD for measuring the Beta zeolite molecular sieve for 44% compares figure.
Specific embodiment
Embodiment 1：With L-Histidine as auxiliary agent
By 4.51g tetraethyl orthosilicates, the tetraethyl ammonium hydroxide aqueous solution of 2.22g mass fractions 35%, 4.5g deionizations
Water mixes in beaker, and beaker sealed membrane is sealed and stirred 5 hours, makes tetraethyl orthosilicate complete hydrolysis.Remove sealed membrane,
Gained mixed liquor is continued into stirring 6 hours in fume hood, makes the ethanol in system evaporate into form jelly with water, be transferred to
Freezed 3 days in freezing (20 DEG C of temperature of charge, -60 DEG C of condenser temperature) drying machine, the now H of system2O and SiO2Mol ratio is less than
1, dry glue quality 2.16g.2.16g dry glues are mixed and ground to form with the solid fluorinated ammoniums of 0.19g, 0.24g solid L-Histidines
Even powder (100 mesh), gained powder is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, is placed in 150 DEG C of baking ovens
Crystallization 7 days.Crystallization completes that product is washed with deionized to neutrality, suction filtration, 60 DEG C of baking ovens after product is cooled to room temperature dries
Dry, 550 DEG C of Muffle kiln roastings remove the Beta zeolite molecular sieve that template obtains final product chiral A bodies body enrichment, product for 6 hours
Quality 1.3g.
The Beta zeolite molecular sieve that will be obtained carries out X-ray diffraction analysis, and XRD spectra is shown in Fig. 1, and institute is obtained by XRD analysis
Chirality A body relative amounts are about 72% in the Beta zeolite molecular sieve sample of preparation.
Embodiment 2：With ALANINE as auxiliary agent
By 4.51g tetraethyl orthosilicates, the tetraethyl ammonium hydroxide aqueous solution of 2.22g mass fractions 35%, 7.5g deionizations
Water mixes in beaker, and beaker sealed membrane is sealed and stirred 5 hours, makes tetraethyl orthosilicate complete hydrolysis.Remove sealed membrane,
Gained mixed liquor is continued into stirring 6 hours in fume hood, makes the ethanol in system evaporate into form jelly with water, be transferred to
Freezed 3 days in freezing (20 DEG C of temperature of charge, -60 DEG C of condenser temperature) drying machine, the now H of system2O and SiO2Mol ratio is less than
1, dry glue quality 2.16g.2.16g dry glues are mixed and ground to form with the solid fluorinated ammoniums of 0.20g, 0.23g solid ALANINEs
, then be transferred to gained powder in the stainless steel cauldron of polytetrafluoroethyllining lining by even powder (100 mesh), is placed in 150 DEG C of bakings
Crystallization 7 days in case.Crystallization completes that product is washed with deionized to neutrality, suction filtration, 60 DEG C of bakings after product is cooled to room temperature
Case drying, 550 DEG C of Muffle kiln roastings remove the Beta zeolite molecular sieve that template obtains final product chiral A bodies body enrichment for 6 hours,
Product quality 1.3g.
The Beta zeolite molecular sieve that will be obtained carries out X-ray diffraction analysis, and XRD spectra is shown in Fig. 2, and institute is obtained by XRD analysis
Chirality A body relative amounts are about 64% in the Beta zeolite molecular sieve sample of preparation.
Embodiment 3：With 1B as auxiliary agent
By 4.51g tetraethyl orthosilicates, the tetraethyl ammonium hydroxide aqueous solution of 4.42g mass fractions 35%, 5.0g deionizations
Water mixes in beaker, and beaker sealed membrane is sealed and stirred 4 hours, makes tetraethyl orthosilicate complete hydrolysis.Remove sealed membrane,
Gained mixed liquor is continued into stirring 6 hours in fume hood, makes the ethanol in system evaporate into form jelly with water, be transferred to
Freezed 3 days in freezing (20 DEG C of temperature of charge, -60 DEG C of condenser temperature) drying machine, the now H of system2O and SiO2Mol ratio is less than
1, dry glue quality 2.16g.2.16g dry glues are mixed with the solid fluorinated ammoniums of 0.39g, 0.37g 1Bs and homogeneous powder is ground to form
Last (100 mesh), gained powder is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, is placed in crystallization 7 in 150 DEG C of baking ovens
My god.Crystallization completes that product is washed with deionized to neutrality, suction filtration, 60 DEG C of oven for drying, 550 after product is cooled to room temperature
It is to obtain Beta zeolite molecular sieve that DEG C Muffle kiln roasting removes template for 6 hours, product quality 1.3g.
The Beta zeolite molecular sieve that will be obtained carries out X-ray diffraction analysis, and XRD spectra is shown in Fig. 3, and institute is obtained by XRD analysis
Chirality A body relative amounts are about 65% in the Beta zeolite molecular sieve sample of preparation.
Embodiment 4：With glycine as auxiliary agent
By 4.50g tetraethyl orthosilicates, the tetraethyl ammonium hydroxide aqueous solution of 2.22g mass fractions 35%, 4.5g deionizations
Water mixes in beaker, and beaker sealed membrane is sealed and stirred 4 hours, makes tetraethyl orthosilicate complete hydrolysis.Remove sealed membrane,
Gained mixed liquor is continued into stirring 6 hours in fume hood, makes the ethanol in system evaporate into form jelly with water, be transferred to
Freezed 3 days in freezing (20 DEG C of temperature of charge, -60 DEG C of condenser temperature) drying machine, the now H of system2O and SiO2Mol ratio is less than
1, dry glue quality 2.17g.2.17g dry glues are mixed with the solid fluorinated ammoniums of 0.16g, 0.16g glycine and uniform powder is ground to form
(100 mesh), gained powder is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, is placed in crystallization 7 in 150 DEG C of baking ovens
My god.Crystallization completes that product is washed with deionized to neutrality, suction filtration, 60 DEG C of oven for drying, 550 after product is cooled to room temperature
It is to obtain Beta zeolite molecular sieve that DEG C Muffle kiln roasting removes template for 6 hours, product quality 1.3g.
The Beta zeolite molecular sieve that will be obtained carries out X-ray diffraction analysis, and XRD spectra is shown in Fig. 4, and institute is obtained by XRD analysis
Chirality A body relative amounts are about 60% in the Beta zeolite molecular sieve sample of preparation.
Comparative example 1：
This comparative example is used for the reference preparation method of the Beta zeolite molecular sieve for illustrating chiral polymorph A enrichments.
Method according to embodiment 1 prepares the Beta zeolite molecular sieve that chiral polymorph A is enriched with, unlike, it is added without
L-Histidine, and obtained 2.16g dry glues are directly mixed with 0.19g ammonium fluorides and uniform powder (100 mesh) is ground to form, shift
To in the stainless steel cauldron of polytetrafluoroethyllining lining, crystallization 7 days in 150 DEG C of baking ovens are placed in.Crystallization completes to treat that product is cooled to
After room temperature by product suction filtration, be washed with deionized to neutral, 80 DEG C of oven for drying, 550 DEG C of Muffle kiln roastings and remove for 6 hours
Template is to obtain Beta zeolite molecular sieve.
The Beta zeolite molecular sieve that will be obtained carries out X-ray diffraction analysis, and XRD spectra is shown in Fig. 5, and institute is obtained by XRD analysis
What is prepared is common Beta zeolites, and chirality A body relative amounts are about 44% in Beta zeolite molecular sieve sample.
The above, is only several case study on implementation of the invention, and any formal limitation is not done to the present invention,
Although the present invention is disclosed as above with preferable case study on implementation, but is not limited to the present invention, any to be familiar with this professional skill
Art personnel, without departing from the scope of the present invention, when the structure and technology contents using the disclosure above make a little
Change or be modified to the equivalence enforcement case of equivalent variations.But every content without departing from technical solution of the present invention, foundation
Any simple modification, equivalent variations and modification that technical spirit of the invention is made to above case study on implementation, still belong to the present invention
In the range of technical scheme.
Claims (10)
1. a kind of method that amino acid auxiliary prepares the Beta zeolite molecular sieve of chiral polymorph A enrichments, its step is as follows：
(1) silicon source, template and deionized water are proportionally added into reaction vessel, stir equal under closed, room temperature condition
It is even, make silicon source complete hydrolysis；
(2) by step (1) gained mixture in room temperature condition, open wide under system and stir to forming homogeneous gel；
(3) step (2) gained gel is further dehydrated and obtains block dry glue, by gained bulk dry glue and solid amino
, into homogeneous powder, loading reactor carries out hydrothermal crystallizing for acid, solid Fluorine source mixed grinding；
(4) step (3) crystallization product is transferred out from the reactor for being cooled to room temperature, the solid deionized water that will be obtained
Washed, separated, dry roasting, so as to obtain the Beta zeolite molecular sieve of chiral polymorph A enrichment.
2. a kind of amino acid auxiliary as claimed in claim 1 prepares the side of the Beta zeolite molecular sieve of chiral polymorph A enrichments
Method, it is characterised in that：Silicon source used in step (1) is tetraethyl orthosilicate, Ludox or white carbon, and template is quality point
The tetraethyl ammonium hydroxide aqueous solution of number 30~40%.
3. a kind of amino acid auxiliary as claimed in claim 1 prepares the side of the Beta zeolite molecular sieve of chiral polymorph A enrichments
Method, it is characterised in that：The mol ratio of silicon source, template and deionized water is 1 in step (1):0.25~0.5:12~20.
4. a kind of amino acid auxiliary as claimed in claim 1 prepares the side of the Beta zeolite molecular sieve of chiral polymorph A enrichments
Method, it is characterised in that：Amino acid used in step (3) is L-Histidine, ALANINE, 1B or glycine；Institute
The Fluorine source for using is ammonium fluoride or ammonium acid fluoride.
5. a kind of amino acid auxiliary as claimed in claim 1 prepares the side of the Beta zeolite molecular sieve of chiral polymorph A enrichments
Method, it is characterised in that：Dehydrating and drying method described in step (3) is freeze-drying, and the temperature of freeze-drying is 0 DEG C~-60
DEG C, H in system after the time guarantee of freeze-drying is dry2O and SiO2Mol ratio be less than 1：1.
6. a kind of amino acid auxiliary as claimed in claim 1 prepares the side of the Beta zeolite molecular sieve of chiral polymorph A enrichments
Method, it is characterised in that：The particle diameter of homogeneous powder is below 300 mesh in step (3).
7. a kind of amino acid auxiliary as claimed in claim 1 prepares the side of the Beta zeolite molecular sieve of chiral polymorph A enrichments
Method, it is characterised in that：The mol ratio of silicon source, amino acid and Fluorine source is 1 in step (3) homogeneous powder:0.075~0.12:0.2~
0.5。
8. a kind of amino acid auxiliary as claimed in claim 1 prepares the side of the Beta zeolite molecular sieve of chiral polymorph A enrichments
Method, it is characterised in that：Hydrothermal crystallizing temperature is 130~170 DEG C in step (3), and the hydrothermal crystallizing time is 6~10 days.
9. a kind of amino acid auxiliary as claimed in claim 1 prepares the side of the Beta zeolite molecular sieve of chiral polymorph A enrichments
Method, it is characterised in that：Separate mode described in step (4) is suction filtration or centrifugation.
10. a kind of amino acid auxiliary as claimed in claim 1 prepares the side of the Beta zeolite molecular sieve of chiral polymorph A enrichments
Method, it is characterised in that：Drying temperature described in step (4) is 60~100 DEG C, and drying time is 2~12 hours；Sintering temperature
It it is 550~600 DEG C, roasting time is 4~8 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109607560A (en) * | 2019-01-17 | 2019-04-12 | 大连理工大学 | A kind of flake hetero-atom molecular-sieve and its green synthesis method |
| CN110180603A (en) * | 2019-05-31 | 2019-08-30 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method and products thereof of porous amino-acid modified molecular sieve |
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| 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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2017
- 2017-02-22 CN CN201710094696.2A patent/CN106892435A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (1)
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| 张健: "手性金属有机骨架材料的合成与性能研究", 《中国化学会第七届全国分子手性学术研讨会论文集》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109607560A (en) * | 2019-01-17 | 2019-04-12 | 大连理工大学 | A kind of flake hetero-atom molecular-sieve and its green synthesis method |
| CN110180603A (en) * | 2019-05-31 | 2019-08-30 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method and products thereof of porous amino-acid modified molecular sieve |
| CN110180603B (en) * | 2019-05-31 | 2021-12-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of porous amino acid modified molecular sieve and product thereof |
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Application publication date: 20170627 |