Preparation method and application of chiral enantiomer of Beta zeolite molecular sieve

Abstract

According to the invention, a hydrothermal synthesis method is adopted to prepare the chiral enantiomer of the Beta zeolite molecular sieve with optical rotation. The molecular sieve has a chiral pore channel with a single enantiomer structure, shows excellent selectivity and stability in selective adsorption and resolution of chiral molecules, and has great potential application value in the fields of fine chemical engineering, drug separation and the like.

Description

Technical Field

[0001] This invention belongs to the field of zeolite molecular sieve preparation technology, specifically relating to a method for preparing chiral enantiomers of Beta zeolite molecular sieves and their application in the preparation of organic molecular enantiomers. Background Technology

[0002] Chiral zeolite molecular sieves possess chiral channel structures, enabling them to recognize guest molecules with a combination of size selectivity, shape selectivity, and enantioselectivity, making them ideal for chiral adsorption, enantiomeric separation, and asymmetric catalysis. Therefore, the search for and development of chiral zeolite molecular sieves with superior performance is of great significance. However, most known chiral zeolite molecular sieves are racemic, and synthesizing enantiomeric chiral zeolite molecular sieves with single mirror-image isomers has remained one of the major challenges for synthetic chemists.

[0003] Currently, only eight known zeolite molecular sieves possess inherent chiral structures, including *BEA, CZP, GOO, ITV, JRY, LTJ, OSO, and STW (these three-letter abbreviations are structure codes named by the International Molecular Sieve Association). Beta zeolite molecular sieves with the *BEA structure have three-dimensional intersecting twelve-membered ring channels. The a-axis and b-axis directions have straight channels with a pore size of 0.67 nm × 0.66 nm, while the z-axis direction has curved channels with a pore size of 0.56 nm × 0.56 nm. Due to its continuous three-dimensional channels and good thermal and hydrothermal stability, Beta molecular sieves are widely used in the adsorption and separation of aromatics, alkylation, acylation, and cracking reactions, making it one of the few molecular sieves currently used in industrial applications. Beta zeolite molecular sieves have various crystal forms, among which crystal form A has 12-membered ring chiral helical channels in the c-axis direction, with chiral space groups P4322 or P4122, and it has great application potential in enantioselective catalysis and separation processes. Generally, synthesized Beta molecular sieves are a coexistence of chiral crystalline form A and achiral crystalline form B, with a ratio of 44:56 [MMJTreacy, JMNewsam. Two new three-dimensional twelve-ring zeolite frameworks of which zeolite beta is a disordered intergrowth[J].Nature,1988,332,249-251; Lu T,Yan W,Xu R.Chiralzeolite beta:Structure,synthesis,andapplication[J].Inorganic ChemistryFrontiers,2019,6,1938-1951]. Earlier, researchers synthesized Beta zeolites rich in crystalline form A using chiral organic templates and obtained a 5% enantiomeric excess in chiral organic enantioselective catalysis [MEDavis, RFLobo.Zeolite and molecular sieve synthesis[J].Chemistry of Materials,1992,4,756-768].In recent years, researchers have made great progress in synthesizing beta zeolites rich in crystalline form A [M. Tong, D. Zhang, W. Fan, et al. Synthesis of chiral polymorph A-enriched zeolite Beta with an extremely concentrated fluoride route [J]. Scientific Reports, 2015, 5, 11521; M. Tong, D. Zhang, L. Zhu, et al. An elaborate structure investigation of the chiral polymorph A-enriched zeolite beta [J]. CrystEngComm, 2016, 18, 1782-1789; Du Hongbin, Jiao Feng. A method for preparing a single-crystal hierarchical porous chiral crystalline form A-enriched beta molecular sieve, Chinese Invention Patent, Application No.: 202310455924.X]. However, the synthesized Beta zeolite molecular sieves and the crystalline type A Beta zeolite molecular sieves mentioned above are all racemates or racemates with a slight excess of one mirror-image enantiomer, exhibiting poor performance in enantiomeric resolution of chiral organic molecules and asymmetric catalytic synthesis. Therefore, developing enantiomers of Beta zeolite molecular sieves with chiral resolution properties has significant economic value. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing chiral enantiomers of Beta zeolite molecular sieves with chiral separation properties, by using a chiral silicon source to prepare the chiral enantiomers of Beta zeolite molecular sieves. This invention also provides the use of Beta zeolite molecular sieve chiral enantiomers in the preparation of enantiomers of small organic molecules, which exhibit excellent chiral resolution selectivity.

[0005] The technical solution of the present invention is as follows: A method for preparing chiral enantiomers of Beta zeolite molecular sieves includes the following steps: (1) The silicon source material, boron group element compound, tetravalent element compound (excluding silicon), organic template agent, fluorine source material, chiral silicon source material and water are mixed evenly under stirring to obtain a reaction gel. The chemical composition of the reaction gel is: rR 1 OH:aHF:xX2O3:yYO2:SiO2:zR 2 Si(OR 3 )3:wH2O, where R 1 The positively charged group representing the organic template agent is a nitrogen-containing organic cation; X represents one or more trivalent boron group elements; Y represents one or more tetravalent elements other than silicon; R2 Si(OR 3 )3 represents a chiral silicon source material; r = 0.1-1, a = 0-1, x = 0-0.2, y = 0-0.2, z = 0.01-0.3, w = 1-50; (2) Transfer the reaction gel to a stainless steel reactor and react at 120-200℃ for 1-30 days under sealed conditions; (3) After washing and drying the crystallized product from step (2), calcining it in an air atmosphere at 500-650℃ for 2-5 hours to obtain the chiral enantiomer of Beta zeolite molecular sieve with organic matter removed.

[0006] The above-mentioned method for preparing chiral enantiomers of Beta zeolite molecular sieves preferably uses reactive gel rR 1 OH:aHF:xX2O3:yYO2:SiO2:zR 2 Si(OR 3 )3:wH2O; r=0.1-1, a=0-1, x=0-0.2, y=0-0.1, z=0.01-0.3, w=2-20, preferably 160-180℃, reaction time 7-20 days.

[0007] In the preparation method of the above-mentioned chiral enantiomers of Beta zeolite molecular sieves, the preferred silicon source is one or more of water glass, silica sol, silica, tetraethyl orthosilicate, or tetrabutyl orthosilicate. The preferred fluorine source is hydrofluoric acid and / or ammonium fluoride. The preferred aluminum source is one or more of sodium aluminate, aluminum isopropoxide, aluminum sulfate hexadecahydrate, or aluminum hydroxide. The preferred boron group element compound is one or more of sodium aluminate, aluminum isopropoxide, aluminum sulfate hexadecahydrate, aluminum hydroxide, or boric acid. The preferred fluorine source is hydrofluoric acid or ammonium fluoride. The preferred tetravalent element compound other than silicon is germanium dioxide, tetrabutyl titanate, or tin dioxide.

[0008] The above method for preparing chiral enantiomers of Beta zeolite molecular sieves, wherein the organic template agent has a positively charged group R 1 The preferred options are those listed in Table 1.

[0009] Table 1

[0010] The above method for preparing chiral enantiomers of Beta zeolite molecular sieves involves exchanging the organic template agent with a hydroxide base (R) via an ion exchange resin before preparing the reaction gel. 1 The concentration of the OH group is determined by standardizing it with 0.1M hydrochloric acid solution before use.

[0011] The above method for preparing chiral enantiomers of Beta zeolite molecular sieves, wherein the chiral silicon source material R 2 Si(OR3 )3 contains a chiral organic group R 2 Silicon ester, R 3 It is a C1-C6 alkyl group (preferably methyl or ethyl), R 2 Selected from the following structures: n represents an integer from 1 to 6, preferably the structure listed in Table 2.

[0012] Table 2

[0013] The preparation method of the above-mentioned chiral enantiomers of Beta zeolite molecular sieves generally involves first adding tetravalent elements other than silicon and boron group element compounds to the obtained basic template agent solution, stirring to dissolve, then adding a silicon source and continuing to stir. After stirring evenly, a fluorine source or a non-fluorine source (fluorine-free system) is added, and the system is heated under an infrared lamp or in an oven to remove excess solvent, thereby obtaining the target gel.

[0014] The method described in this invention can prepare chiral enantiomers of Beta zeolite molecular sieves in the pores of a porous support to obtain chiral enantiomer membrane materials of Beta zeolite molecular sieves.

[0015] The chiral enantiomers of Beta zeolite molecular sieves prepared by the method described in this invention exhibit optical activity and a specific chemical composition, which, after calcination, is p(M... 1 / n XO2)·qYO2·SiO2, where M represents a proton or +n valence inorganic cation, derived from silicon-based materials or boron group element compounds, such as sodium ions in water glass or sodium aluminate; X represents a trivalent element; Y represents a tetravalent element other than Si; n represents 1 or 2; p = 0–0.4; q = 0–0.2. M is preferably proton or sodium, X is preferably Al, and Y is preferably titanium. Preferred p = 0–0.1; preferred q = 0–0.1.

[0016] Another object of the present invention is to provide the application of the chiral enantiomeric Beta zeolite molecular sieve prepared by the method described herein as a separation material in the chemical and chemical engineering fields. A specific example is the separation of R / S-1-phenylethanol (or R / S-1-phenylethylamine) at a molar ratio of 1 SiO2:1 R... 1 OH:0.3R 2 Si(OR 3A gel synthesized from molecular sieves was prepared using a ratio of 3:1HF:10H2O, and the resulting molecular sieve was further prepared. After calcination in air at 500-650℃ for 2-5 hours, chiral enantiomers of Beta zeolite molecular sieves with removed organic matter were obtained. The separation conditions were: room temperature, 200 mg of the organic-removed Beta zeolite molecular sieve chiral enantiomers as the packing material, ethanol as the eluent, and chiral separation of 100 mg of R / S-1-phenylethanol or R / S-1-phenylethylamine. Advantages of this invention:

[0017] This invention utilizes a low-cost template agent, combined with a chiral silicon source, to obtain chiral enantiomers of Beta zeolite molecular sieves via a conventional hydrothermal synthesis method. Furthermore, the prepared chiral enantiomers of Beta zeolite molecular sieves exhibit excellent chiral resolution properties. Attached Figure Description

[0018] Figure 1 The image shows the X-ray powder diffraction pattern of the Beta zeolite molecular sieve prepared according to an embodiment of the present invention.

[0019] Figure 2 This is a solid circular dichroism chromatogram of the Beta zeolite molecular sieve prepared in an embodiment of the present invention.

[0020] Figure 3 The diagram shows the chiral separation performance of Beta zeolite molecular sieve prepared in the embodiments of the present invention for (a) R / S-1-phenylethanol, (b) R / S-1-phenylethylamine, and (c) R / S-p-hydroxyphenylglycine sodium. Detailed Implementation

[0021] The specific steps of the present invention are illustrated below through examples, but are not limited to these examples.

[0022] Unless otherwise stated, the terms used in this invention generally have the meanings commonly understood by those skilled in the art.

[0023] The present invention will now be described in further detail with reference to specific examples and data. It should be understood that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention in any way.

[0024] In the following embodiments, various processes and methods not described in detail are conventional methods known in the art.

[0025] Example 1: Taking the template agent cation 1-1 in Table 1 as an example, the template agent R is explained. 1Synthesis of OH: First, piperidine (100 mmol, 9.9 mL), 1,5-dibromopentane (100 mmol, 13.6 mL), and K₂CO₃ (100 mmol, 13.82 g) were added to acetonitrile (150 mL). The mixture was heated at 80 °C for 12 hours. The filtrate was then filtered, recrystallized in diethyl ether to give a solid, which was dried overnight at 80 °C to give a white product in 94% yield. The product was analyzed by liquid NMR (hydrochloric acid). 1 H NMR (400MHz, D2O) δ3.41 (d, J = 4.8Hz, 8H), 1.88 (s, 8H), 1.71 (d, J = 5.3Hz, 4H); 13 C NMR (101 MHz, D2O) δ 59.51, 21.16, 18.91 and electrospray mass spectrometry (m / z: 154.1591) confirmed it as the bromide salt of the target cation.

[0026] The obtained product was dissolved in 200 mL of deionized water and subjected to ion exchange using a 717 strong-base anion exchange resin. The exchange yielded a template agent alkaline aqueous solution in the form of hydroxide ions. An appropriate amount of this solution was weighed and standardized with 0.1 mol / L hydrochloric acid solution, using phenolphthalein as an indicator. The standardization results confirmed that the exchange efficiency from the template agent bromide salt to the hydroxide base reached 95%.

[0027] Example 2: Taking organosilicon ester 2-1 in Table 2 as an example, the synthesis process of chiral organosilicon ester is explained. First, R-(+)-1-phenylethylamine (100 mmol, 12.12 g), 3-chloropropyltriethoxysilane (100 mmol, 24.08 g), and triethylamine (100 mmol, 13.9 mL) were added to toluene (150 mL). The mixture was heated at 120 °C for 6 hours. After the reaction was completed, the solvent toluene and most of the triethylamine were removed by rotary evaporation under reduced pressure. Further toluene-water extraction was performed, and the organic phase was evaporated under reduced pressure to give a yellow liquid with a yield of 98%. The product was characterized by electrospray ionization mass spectrometry (m / z: 326.2107) and confirmed to be the target product, chiral organosilicon 2-1.

[0028] Example 3: According to the molar ratio 1SiO2:1R 1 OH:0.3RR 2 The gel for molecular sieve synthesis was prepared by the following steps: 1 mmol of template agent (template agent 1-1) alkaline solution was weighed, and 0.3 mmol of RR was added. 2Si(OEt)3 (organosilicon 2-1) and 1 mmol of tetraethyl orthosilicate were stirred at room temperature for about two hours until completely dissolved. Then, 1 mmol of hydrofluoric acid solution was added and stirred until homogeneous. The mixed gel was placed under an infrared lamp or in an 80°C oven to remove excess solvent to the theoretical weight. The final reaction gel was transferred to a 15 mL stainless steel reactor with a polytetrafluoroethylene liner and reacted at 160°C for 8 days under sealed conditions. The product was washed twice with water and twice with ethanol, and then dried for later use. Calcination at 550°C in air for 5 hours yielded a product with organic matter removed. X-ray powder diffraction phase identification showed that the product was a Beta-type silicate molecular sieve (…). Figure 1 ). Solid circular dichroism chromatogram ( Figure 2 This indicates that the product is optically active and is a chiral enantiomer of R-type Beta zeolite molecular sieve.

[0029] Example 4: According to the molar ratio 1SiO2:1R 1 OH:0.3SR 2 The gel for molecular sieve synthesis was prepared by the following steps: 1 mmol of template agent (template agent 1-1) alkaline solution was weighed, and 0.3 mmol of SR was added. 2 Si(OEt)3 (organosilicon 2-2) and 1 mmol of tetraethyl orthosilicate were stirred at room temperature for about two hours until completely dissolved. Then, 1 mmol of hydrofluoric acid solution was added and stirred until homogeneous. The mixed gel was placed under an infrared lamp or in an 80°C oven to remove excess solvent to the theoretical weight. The final reaction gel was transferred to a 15 mL stainless steel reactor with a polytetrafluoroethylene liner and reacted at 160°C for 8 days under sealed conditions. The product was washed twice with water and twice with ethanol, and then dried for later use. Calcination at 550°C in air for 5 hours yielded a product with organic matter removed. X-ray powder diffraction phase identification showed that the product was a Beta-type silicate molecular sieve (…). Figure 1 ). Solid circular dichroism chromatogram ( Figure 2 This indicates that the product is optically active and is a chiral enantiomer of the S-type Beta zeolite molecular sieve.

[0030] Example 5: According to the molar ratio 1SiO2:1R 1The gel for molecular sieve synthesis was prepared using the following steps: 1 mmol of template agent (template agent 1-1) alkaline solution was weighed and 1 mmol of tetraethyl orthosilicate was added. The mixture was stirred at room temperature for approximately two hours until completely dissolved. Then, 1 mmol of hydrofluoric acid solution was added and stirred until homogeneous. The mixed gel was placed under an infrared lamp or in an 80°C oven to remove excess solvent down to the theoretical weight. The resulting reaction gel was transferred to a 15 mL stainless steel reactor with a polytetrafluoroethylene liner and reacted at 160°C for 15 days under sealed conditions. The product was washed twice with water and twice with ethanol, and then dried for later use. The product was calcined at 550°C in air for 5 hours to obtain a product with organic matter removed. X-ray powder diffraction phase identification showed that the product was a Beta-type silicate molecular sieve (…). Figure 1 ). Solid circular dichroism chromatogram ( Figure 2 This indicates that the product is not optically active and is a racemic mixture.

[0031] Example 6: According to the molar ratio 1SiO2:0.5R 1 OH:0.125RR 2 The gel for molecular sieve synthesis was prepared using the following steps: 0.5 mmol of template agent (template agent 1-3) alkaline solution was weighed, and 0.125 mmol of RR was added. 2 Si(OEt)3 (organosilicon 2-3) and 1 mmol of tetraethyl orthosilicate and 0.02 mmol of aluminum isopropoxide were stirred at room temperature for about two hours until completely dissolved. Then, 0.5 mmol of hydrofluoric acid solution was added and stirred until homogeneous. The mixed gel was placed under an infrared lamp or in an 80°C oven to remove excess solvent to the theoretical weight. The final reaction gel was transferred to a 15 mL stainless steel reactor with a polytetrafluoroethylene liner and reacted at 160°C for 15 days under sealed conditions. The product was washed twice with water and twice with ethanol, and then dried for later use. Calcination at 550°C in air for 5 hours yielded a product with organic matter removed. X-ray powder diffraction phase identification showed that the product was a Beta-type aluminosilicate molecular sieve (…). Figure 1 The solid circular dichroism chromatogram is similar to that of Example 3. The product is optically active and is a chiral enantiomer of R-type Beta zeolite molecular sieve.

[0032] Example 7: According to the molar ratio 1SiO2:0.2R 1 OH:0.125SR 2 The gel for molecular sieve synthesis was prepared using a Si(OEt)3:0.01Al2O3:5H2O ratio as follows: 0.2 mmol of template agent (template agent 1-4) alkaline solution was weighed, and 0.125 mmol of SR was added. 2Si(OEt)3 (organosilicon 2-4), 1 mmol of tetraethyl orthosilicate, and 0.02 mmol of aluminum isopropoxide were stirred at room temperature for about two hours until completely dissolved and homogeneous. The mixed gel was placed under an infrared lamp or in an 80°C oven to remove excess solvent to the theoretical weight. The resulting reaction gel was transferred to a 15 mL stainless steel reactor with a polytetrafluoroethylene liner and reacted at 160°C for 15 days under sealed conditions. The product was washed twice with water and twice with ethanol, and then dried for later use. The product was calcined at 550°C in air for 5 hours to obtain a product with organic matter removed. X-ray powder diffraction phase identification showed that the product was a Beta-type aluminosilicate molecular sieve. The solid circular dichroism chromatogram was similar to that of Example 4, and the product was optically active, indicating it was a chiral enantiomer of an S-type Beta zeolite molecular sieve.

[0033] Example 8: According to the molar ratio 1SiO2:0.2R 1 OH:0.125RR 2 The gel for molecular sieve synthesis was prepared using the following steps: 0.2 mmol of template agent (template agent 1-2) alkaline solution was weighed, and 0.02 mmol of aluminum isopropoxide was added. The mixture was stirred until completely dissolved, and then 0.125 mmol of RR was added. 2 Si(OEt)3 (organosilicon ester 2-7) and 1 mmol of tetraethyl orthosilicate were stirred at room temperature for about two hours until completely dissolved and homogeneous. The mixed gel was placed under an infrared lamp or in an 80°C oven to remove excess solvent to the theoretical weight. The resulting reaction gel was transferred to a 15 mL stainless steel reactor with a polytetrafluoroethylene liner and reacted at 160°C for 15 days under sealed conditions. The product was washed twice with water and twice with ethanol, and then dried for later use. The product was calcined at 550°C in air for 5 hours to obtain a product with organic matter removed. X-ray powder diffraction phase identification showed that the product was a Beta-type aluminosilicate molecular sieve. The solid circular dichroism chromatogram was similar to that of Example 3, and the product was optically active, indicating it was a chiral enantiomer of an R-type Beta zeolite molecular sieve.

[0034] Example 9: According to the molar ratio 1SiO2:0.2R 1 OH:0.125SR 2 The gel for molecular sieve synthesis was prepared using the following steps: 0.2 mmol of template agent (template agent 1-1) alkaline solution was weighed, and 0.02 mmol of aluminum isopropoxide was added. The solution was stirred until completely dissolved, and then 0.125 mmol of SR was added. 2Si(OEt)3 (organosilicon 2-8) and 1 mmol of tetraethyl orthosilicate were stirred at room temperature for about two hours until completely dissolved and homogeneous. The mixed gel was placed under an infrared lamp or in an 80°C oven to remove excess solvent to the theoretical weight. The resulting reaction gel was transferred to a 15 mL stainless steel reactor with a polytetrafluoroethylene liner and reacted at 160°C for 15 days under sealed conditions. The product was washed twice with water and twice with ethanol, and then dried for later use. The product was calcined at 550°C in air for 5 hours to obtain a product with organic matter removed. X-ray powder diffraction phase identification showed that the product was a Beta-type aluminosilicate molecular sieve. The solid circular dichroism chromatogram was similar to that of Example 4, and the product was optically active, indicating it was a chiral enantiomer of an S-type Beta zeolite molecular sieve.

[0035] Example 10: According to the molar ratio 1SiO2:0.5R 1 OH:0.125RR 2 The gel for molecular sieve synthesis was prepared using the following steps: 0.5 mmol of template agent (template agent 1-1) alkaline solution was weighed, and 0.1 mmol of tetrabutyl titanate was added. The mixture was stirred until completely dissolved, and then 0.125 mmol of RR was added. 2 Si(OEt)3 (organosilicon ester 2-5) and 1 mmol of tetraethyl orthosilicate were stirred at room temperature for about two hours until completely dissolved and homogeneous. The mixed gel was placed under an infrared lamp or in an 80°C oven to remove excess solvent down to the theoretical weight. The resulting reaction gel was transferred to a 15 mL stainless steel reactor with a polytetrafluoroethylene liner and reacted at 160°C for 15 days under sealed conditions. The product was washed twice with water and twice with ethanol, and then dried for later use. The product was calcined at 550°C in air for 5 hours to obtain a product with organic matter removed. X-ray powder diffraction phase identification showed that the product was a Beta titanate molecular sieve. The solid circular dichroism chromatogram was similar to that of Example 3, and the product was optically active, indicating it was a chiral enantiomer of the R-type Beta zeolite molecular sieve.

[0036] Example 11: According to the molar ratio 1SiO2:0.5R 1 OH:0.125RR 2 The gel for molecular sieve synthesis was prepared using the following steps: 0.5 mmol of template agent (template agent 1-1) alkaline solution was weighed, and 0.05 mmol of tin dioxide was added. The mixture was stirred until completely dissolved, and then 0.125 mmol of RR was added. 2Si(OEt)3 (organosilicon ester 2-6) and 1 mmol of tetraethyl orthosilicate were stirred at room temperature for about two hours until completely dissolved and homogeneous. The mixed gel was placed under an infrared lamp or in an 80°C oven to remove excess solvent to the theoretical weight. The resulting reaction gel was transferred to a 15 mL stainless steel reactor with a polytetrafluoroethylene liner and reacted at 160°C for 15 days under sealed conditions. The product was washed twice with water and twice with ethanol, and then dried for later use. The product was calcined at 550°C in air for 5 hours to obtain a product with organic matter removed. X-ray powder diffraction phase identification showed that the product was a Beta stanzite molecular sieve. The solid circular dichroism chromatogram was similar to that of Example 3, and the product was optically active, indicating it was a chiral enantiomer of the R-type Beta zeolite molecular sieve.

[0037] Example 12: According to the molar ratio 1SiO2:1R 1 OH:0.3RR 2 The gel for molecular sieve synthesis was prepared by the following steps: Weigh 1 mmol of template agent (template agent 1-1) alkaline solution and add 0.3 mmol of RR. 2 Si(OEt)3 (organosilicon 2-1) and 1 mmol of tetraethyl orthosilicate were stirred at room temperature for about two hours until completely dissolved. Then, 1 mmol of hydrofluoric acid solution was added and stirred until homogeneous. The mixed gel was placed under an infrared lamp or in an 80°C oven to remove excess solvent to the theoretical weight, yielding a reactive gel. A porous alumina ceramic tube with an outer diameter of 12 mm and an inner diameter of 9 mm (50 nm pore size) was cut into 1 cm pieces, and the reactive gel was then uniformly coated onto the outer surface of the tubes. Finally, the reactive gel and the coated alumina ceramic tubes were transferred to a 15 mL stainless steel reactor with a polytetrafluoroethylene liner and reacted at 160°C for 15 days under sealed conditions. The alumina ceramic tubes and the powdered product were washed twice with water and twice with ethanol, respectively, and dried for later use. The mixture was calcined at 550°C in air for 5 hours to obtain an alumina-supported zeolite membrane and a powdered product with organic matter removed. X-ray powder diffraction phase identification showed that the powdered product was a Beta zeolite molecular sieve, and the alumina-supported zeolite membrane contained Beta zeolite molecular sieves. The solid circular dichroism chromatogram of the powdered product was similar to that of Example 3, and the product was optically active, indicating it was a chiral enantiomer of the R-type Beta zeolite molecular sieve.

[0038] Example 13: According to the molar ratio 1SiO2:0.5R 1 OH:0.125SR 2 The gel for molecular sieve synthesis was prepared using the following steps: 0.5 mmol of template agent (template agent 1-3) alkaline solution was weighed, and 0.125 mmol of SR was added. 2Si(OEt)3 (organosilicon 2-4) and 1 mmol of tetraethyl orthosilicate and 0.02 mmol of aluminum isopropoxide were stirred at room temperature for about two hours until completely dissolved. Then, 0.5 mmol of hydrofluoric acid solution was added and stirred until homogeneous. The mixed gel was placed under an infrared lamp or in an 80°C oven to remove excess solvent to the theoretical weight, yielding the reaction gel. A porous alumina ceramic tube with an outer diameter of 12 mm and an inner diameter of 9 mm (50 nm pore size) was cut into 1 cm pieces, and the above reaction gel was then uniformly coated onto the outer surface of the tubes to form a film. Finally, the reaction gel and the coated alumina ceramic tubes were transferred to a 15 mL stainless steel reactor with a polytetrafluoroethylene liner and reacted at 160°C for 15 days under sealed conditions. The alumina ceramic tubes and the powdered product were washed twice with water and twice with ethanol, and then dried for later use. Calcination was carried out at 550°C in air for 5 hours to obtain an alumina-supported zeolite film and a powdered product with organic matter removed. X-ray powder diffraction phase identification showed that the powdered product was a Beta zeolite molecular sieve, and the alumina-supported zeolite membrane contained Beta zeolite molecular sieves. The solid circular dichroism chromatogram of the powdered product was similar to that of Example 3, and the product was optically active, indicating it was a chiral enantiomer of the S-type Beta zeolite molecular sieve.

[0039] Example 14: Performance of chiral Beta zeolite molecular sieve enantiomers as chiral resolving materials in the separation of R / S-1-phenylethanol. Beta zeolite molecular sieves were prepared according to the method described in this invention and calcined in air at 500-650°C for 2-5 hours to obtain Beta zeolite molecular sieves with removed organic matter. The separation conditions were: room temperature, 200 mg of the organic-removed Beta molecular sieve as the packing material, ethanol as the eluent, and chiral separation of 100 mg of R / S-phenylethanol. The circular dichroism chromatogram results of the first drop of the separated solution are shown below. Figure 3 As shown in (a), the results indicate that the chiral enantiomers of Beta zeolite molecular sieves prepared by the method of the present invention have a good chiral resolution effect on R / S-1-phenylethanol: the R-type enantiomer of Beta zeolite molecular sieve obtained in Example 3 was resolved to obtain pure R-(+)-1-phenylethanol, the S-type enantiomer of Beta zeolite molecular sieve obtained in Example 4 was resolved to obtain pure S-(-)-1-phenylethanol, while the racemic Beta molecular sieve obtained in Example 5 did not have a selective adsorption and resolution effect on R / S-1-phenylethanol.

[0040] Example 15: Performance of chiral Beta zeolite molecular sieve enantiomers as chiral resolving materials in the separation of R / S-1-phenylethylamine. Beta zeolite molecular sieves were prepared according to the method described in this invention, and calcined in air at 500-650°C for 2-5 hours to obtain Beta zeolite molecular sieves with removed organic matter. Separation conditions were: room temperature, 200 mg of organic-removed Beta molecular sieve as the packing material, ethanol as the eluent, and chiral resolution of 100 mg of R / S-1-phenylethylamine. The circular dichroism chromatographic separation results of the first drop of the separated solution are shown below. Figure 3 As shown in (b), the results indicate that the chiral enantiomers of the Beta molecular sieve prepared by the method of the present invention have a good chiral resolution effect on R / S-1-phenylethylamine: the R-type enantiomer of the Beta zeolite molecular sieve obtained in Example 8 was resolved to obtain pure R-(+)-1-phenylethylamine, the S-type enantiomer of the Beta zeolite molecular sieve obtained in Example 9 was resolved to obtain pure S-(-)-1-phenylethylamine, while the racemic Beta molecular sieve obtained in Example 5 did not have a selective adsorption and resolution effect on R / S-1-phenylethylamine.

[0041] Example 16: Performance of chiral Beta zeolite molecular sieve enantiomers as chiral resolving materials in the separation of R / S-p-hydroxyphenylglycine sodium. Beta zeolite molecular sieves were prepared according to the method described in this invention and calcined in air at 500-650°C for 2-5 hours to obtain Beta zeolite molecular sieves with removed organic matter. Separation conditions were: room temperature, 200 mg of organic-removed Beta molecular sieve as the packing material, water as the eluent, and chiral separation of 100 mg of R / S-p-hydroxyphenylglycine sodium. The circular dichroism chromatographic separation results of the first drop of the separated solution are shown below. Figure 3 As shown in (c), the results indicate that the chiral enantiomers of the Beta molecular sieve prepared by the method of the present invention have a good chiral resolution effect on R / S-p-hydroxyphenylglycine sodium: the R-type enantiomer of the Beta zeolite molecular sieve obtained in Example 6 was resolved to obtain pure R-(+)-p-hydroxyphenylglycine sodium, the S-type enantiomer of the Beta zeolite molecular sieve obtained in Example 7 was resolved to obtain pure S-(-)-p-hydroxyphenylglycine sodium, while the racemic Beta molecular sieve obtained in Example 5 did not have a selective adsorption and resolution effect on R / S-p-hydroxyphenylglycine sodium.

Claims

1. A process for the preparation of a chiral enantiomer of a Beta zeolite molecular sieve characterized by Comprising the following steps: (1) mixing uniformly the silicon source material, boron group element compound, tetravalent element compound except silicon and germanium, organic template agent, fluorine source material, chiral silicon source material and water in proportion under stirring to obtain a reaction gel, the chemical composition of the reaction gel is: rR 1 OH : aHF : xX2O3 : yYO2 : SiO2 : zR 2 Si(OR 3 )3 : wH2O, wherein R 1 represents the positive charge group of the organic template agent, which is a nitrogen-containing organic cation; X represents one or several of the trivalent boron group elements; Y represents one or several of the tetravalent elements except silicon; R 2 Si(OR 3 )3 is the chiral silicon source material, which represents the silicon ester containing the chiral organic group R 2 , R 3 is an organic hydrocarbon group; r = 0.1-1, a = 0-1, x = 0-0.2, y = 0-0.2, z = 0.01-0.3, w = 1-50; (2) heating the reaction gel to a temperature of 100-200°C under a pressure of 0.1-10 MPa for 1-100 hours to obtain a chiral zeolite; (3) washing the chiral zeolite obtained in step (2) with water, and drying the chiral zeolite at a temperature of 50-150°C for 1-100 hours to obtain a chiral zeolite powder. (4) mixing the chiral zeolite powder obtained in step (3) with a binder to obtain a chiral zeolite catalyst. (2) transferring the reaction gel to a hydrothermal reactor, reacting at 120-200℃ for 1-30 days under sealed conditions; (3) washing and drying the product after crystallization in step (2), and calcining at 500-650℃ in air for 2-5 hours to obtain the Beta zeolite molecular sieve chiral enantiomer with organic matter removed, The silicon source material is selected from one or more of white carbon black, water glass, silica sol, tetraethyl orthosilicate or tetra-n-butyl orthosilicate; the fluorine source material is hydrofluoric acid and / or ammonium fluoride; the boron family element compound is selected from one or more of sodium metaaluminate, aluminum isopropylate, aluminum sulfate hexadecahydrate, aluminum hydroxide or boric acid; the fluorine source material is hydrofluoric acid or ammonium fluoride; and the tetravalent element compound other than silicon is an oxide or ester of germanium, titanium and / or tin.

2. The process of claim 1 for the preparation of a chiral enantiomer of a Beta zeolite molecular sieve, characterized in that r, a, x, y, z and w are respectively: r = 0.1-1, a = 0-1, x = 0-0.2, y = 0-0.1, z = 0.01-0.3, w = 2-20.

3. The process of claim 1 for the preparation of a chiral enantiomer of a Beta zeolite molecular sieve, characterized by R 1 selected from the group consisting of:

4. The process of claim 1 for the preparation of a chiral enantiomer of a Beta zeolite molecular sieve, characterized by said silylester R 2 Si(OR 3 )3, R 2 is selected from the following structures: n represents an integer from 1 to 6, R 3 is an alkyl group of C1-C6.

5. The process of claim 4 for the preparation of a chiral enantiomer of a Beta zeolite molecular sieve, characterized by The R 2 Si(OR 3 )3 is selected from the following structures:

6. The process of making a chiral enantiomer of a Beta zeolite molecular sieve of claim 1, characterized in that Step (2) is reacted at 140-180℃ for 3-20 days under sealed conditions.

7. A chiral enantiomer of a Beta zeolite molecular sieve characterized by prepared by the method of any one of claims 1-6, having a chemical composition of p(M 1 / n XO2) • qYO2 • SiO2, wherein M represents a proton or a +n-valent inorganic cation; X represents one or more trivalent elements other than aluminum; Y represents one or more tetravalent elements other than silicon; p = 0 - 0.4, q = 0 - 0.

2.

8. A Beta zeolite molecular sieve chiral enantiomeric membrane material characterized by Prepared by the method of any one of claims 1-6 in the pores of a porous support.

9. The Beta zeolite molecular sieve chiral enantiomer of claim 7 or the chiral enantiomer membrane material of claim 8 for use as a chiral adsorption separation material, a chiral catalyst in the field of chemical engineering and medicine.

10. The use according to claim 9, wherein The chiral Beta zeolite molecular sieve chiral enantiomer or chiral enantiomer membrane material is used in the preparation of chiral enantiomers of organic molecules. The chiral Beta zeolite molecular sieve chiral enantiomer or chiral enantiomer membrane material is used in the preparation of chiral enantiomers of organic molecules.

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