CN102190314A - Method for preparing beta-zeolite molecular sieve containing excess chiral polymorph A - Google Patents
Method for preparing beta-zeolite molecular sieve containing excess chiral polymorph A Download PDFInfo
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Abstract
The invention belongs to the technical field of beta-zeolite molecular sieve preparation, particularly relates to a preparation method in which an organic template agent is used to synthesize a beta-zeolite molecular sieve doped with pure silicon or aluminum, gallium, titanium, tin, zirconium and other metals, wherein the beta-zeolite molecular sieve has more chiral polymorph A than common beta-zeolite. The template agent is tetraethyl ammonium hydroxide, N,N,2,6-tetramethyl piperidinyl hydrochloride, dimethyl diisopropyl ammonium hydroxide and other template agents capable of synthesizing the common beta-zeolite under a routine condition; a fluorine source can be a HF solution or a NH4F solution; a used silicon source can be ethyl orthosilicate, silicon sol, white carbon black and the like; an aluminum source can be aluminum isopropoxide, aluminum sulfate and the like; a gallium source can be gallium nitrate, gallium oxide and the like; a tin source can be tin tetrachloride and the like; a titanium source can be tetraisopropyl titanate, tetraethyl titanate and the like; and a zirconium source can be zirconium hydroxide.
Description
Technical field
The invention belongs to the beta-zeolite molecular sieve preparing technical field, be specifically related to a kind of employing organic formwork agent, synthesized pure silicon under given conditions or contained metal-doped beta-zeolite molecular sieves such as aluminium, gallium, titanium, tin, zirconium, this beta-zeolite molecular sieve and conventional β zeolite facies are than containing more chirality polymorph A.
Technical background
Beta-zeolite molecular sieve is a kind of molecular sieve that the Mobil oil company synthesized from the silica-alumina gel of tetraethyl ammonium hydroxide and sodium ion in 1967, is unique supersiliceous zeolite with three-dimensional twelve-ring intersection pore passage structure.Because its unique topological framework and good thermostability, hydrothermal stability, acidity and hydrophobicity, beta-zeolite molecular sieve has excellent catalytic performance at aspects such as hydrocarbon cracking, hydrocarbon isomerization, alkane aromatization, olefin alkylation, hydrocracking, hydrofining, Hydrodewaxing, diesel oil pour point depressions, be a kind of catalyzer in field widespread uses such as petrochemical complex, fine chemistry industries.
Although U.S. Mobil oil company has reported the synthetic and catalytic property of beta-zeolite molecular sieve very early, its structure was just accurately decided by means of X-ray diffraction analysis, high-resolution-ration transmission electric-lens, electron diffraction and theoretical modeling by people such as people such as J.Newsam and J.B.Higgins up to 1988.Structural analysis shows that beta-zeolite molecular sieve is that two kinds of structures are different but fault symbiotic structure that the polymorph A that is closely related and B pile up along [001] direction.Polymorph A forms a pair of enantiomorph, and crystallization is at spacer P4 respectively
122 and P4
322, thus have along structure cell c crystallization foraminous spiral tract axial or left hand shape or right hand shape.Polymorph B does not have chirality, and crystallization is at achirality spacer C2/c.
Practical fl zeolite crystal laminate secondary structure does not have rule fully along the accumulation of [001] direction, causes the β zeolite crystal to be mixed by chirality polymorph A and achirality polymorph B.Along the crystallography c direction of β zeolite crystal, chirality polymorph A and achirality polymorph B alternately pile up mutually, and the thickness of A body and B body do not have rule fully yet, so the accumulation situation of A body and B body all may be inequality in each β zeolite crystal.However, the ratio of A body and B body is roughly the same in the β zeolite crystal that is synthesized under same synthesis condition.By means of means such as X-ray diffraction analysis, high-resolution-ration transmission electric-lens, electron diffraction and theoretical modelings, people such as J.Newsman determine two kinds of polytypic ratios in the synthetic β zeolite crystal under the usual conditions, discovery ratio of A body and B body in common zeolite crystal is about 45: 55, and has obtained this area colleague's affirmation.
Zeolite has obtained important use in petrochemical complex and field of fine chemical, and its novel catalytic property has caused people's extensive studies interest, but the β zeolite the most attractive eyeball be the chirality feature of its A body.Chirality is and the closely-related a kind of feature of biological phenomena, is playing the part of crucial role in high and new technologies such as life science, pharmacy.Chiral inorganic microporous solids material is that people extremely crave for.Chirality microporous solids material is owing to the pore size distribution with chiral catalysis active centre uniform distribution, rule in material with than bigger serface, and higher advantages such as thermostability, they are synthetic in chirality, enantiomorph splits and the chiral catalysis field is with a wide range of applications.The A body of β zeolite is to be found the large pore molecular sieve with chirality feature at first.Davis and Lobo had once synthesized and had contained the beta-zeolite molecular sieve of volume chirality polymorph A slightly, and studied resulting beta-zeolite molecular sieve at anti-form-1, catalytic performance in the ring-opening reaction of 2-toluylene epoxide, the result shows that this zeolite has the asymmetry catalysis performance, the ee value of reaction very low (being about 5%).
Synthetic β zeolite crystal with single chiral polymorph A is people always and craves for.Although being arranged, some reports declared to obtain the chirality polymorph A β zeolite many than achirality polymorph B, but their experimental powder XRD spectra with the mixed crystal simulation XRD spectra contrast with the polymorph A of different ratios and B, is found that the relative content of chirality polymorph A in the β zeolite crystal of these reports all is no more than 50%.
If can take the crystal of high β zeolite of special methods synthesis of chiral polymorph A content and even single chiral polymorph A to have great pushing effect to chiral catalysis, chiral separation field.
Summary of the invention
The objective of the invention is to break through the restriction of aforesaid method, synthesized the beta-zeolite molecular sieve of A body content height (or be called excessive) with respect to achirality polymorph B.
The invention provides the preparation method of the excessive beta-zeolite molecular sieve of a kind of chirality polymorph A, this method has versatility to several agent with new template commonly used.Building-up process is a hydrothermal crystallization method, and the mole proportioning that synthesized gel rubber is formed meets the following conditions:
Method of the present invention, its concrete steps are as follows:
1) silicon source, template are joined in the beaker, add an amount of water again; Wherein template and SiO
2Mol ratio be 0.2～0.55: 1, H
2O and SiO
2Mol ratio be 15～20: 1;
2) said mixture was stirred 4～6 hours at ambient temperature, or with infrared lamp irradiation heating, or put into 60～90 ℃ of baking oven for heating, H to the reaction system
2O and SiO
2Mol ratio be lower than 4: 1;
3) in above-mentioned reaction system, add the fluorine source, transferred in the hydrothermal reaction kettle of tetrafluoroethylene liner in 130～170 ℃ baking oven crystallization after stirring 6～10 days, wherein F
-With SiO
2Mol ratio be 0.2～0.55: 1;
4) sample that crystallization is finished is shifted out from the reactor transfer, and suction filtration also is washed with distilled water to neutrality, then sample is put into 90～120 ℃ of baking oven heating, dryings;
5) sample of oven dry is put into crucible, in 550～600 ℃ retort furnace, heat the template oxygenolysis is removed, promptly obtain the excessive beta-zeolite molecular sieve of A body.
Also can synthesize the excessive beta-zeolite molecular sieve of A type body during metal such as admixture Al, Ga, Sn, Zr, Ti in reaction system, its step is as follows:
1) silicon source, template are joined in the beaker, add an amount of water again, wherein template and SiO
2Mol ratio be 0.2～0.55: 1, H
2O and SiO
2Mol ratio be 15～20: 1;
2) said mixture stirred 0.5～2 hour at ambient temperature, added aluminium source, gallium source, Xi Yuan, titanium source or zirconium source, wherein SiO again
2With the mol ratio of Al or Ga be 20～500: 1, SiO
2With the mol ratio of Sn, Zr or Ti be 100～500: 1;
3) said mixture was stirred 3～4 hours at ambient temperature, or with infrared lamp irradiation heating, or put into 60～90 ℃ of baking oven for heating, H to the reaction system
2O and SiO
2Mol ratio be lower than 4: 1;
4) in above-mentioned reaction system, add the fluorine source, transferred in the hydrothermal reaction kettle of tetrafluoroethylene liner in 130～170 ℃ baking oven crystallization after stirring 10～30 days, wherein F
-With SiO
2Mol ratio be 0.2～0.55: 1;
5) sample that crystallization is finished is shifted out from the reactor transfer, and suction filtration also is washed with distilled water to neutrality; Then sample is put into 90～120 ℃ of baking oven heating, dryings;
6) sample of oven dry is put into crucible, in 550～600 ℃ retort furnace, heat the template oxygenolysis is removed, promptly obtain the excessive beta-zeolite molecular sieve of A body.
Template described in the preceding step can be tetraethyl ammonium hydroxide, N, N, and 2,6-tetramethyl piperidine oxyhydroxide, dimethyl di-isopropyl ammonium hydroxide and other normal conditions can synthesize the template of conventional β zeolite; The fluorine source can be HF solution or NH
4F solution.
Used silicon source is tetraethoxy, silicon sol or white carbon black etc.; There are aluminum isopropylate, Tai-Ace S 150 etc. in the aluminium source; There are gallium nitrate, gallium oxide etc. in the gallium source; Xi Yuan is a tin tetrachloride etc.; The titanium source is metatitanic acid tetra isopropyl ester, metatitanic acid tetraethyl ester etc.; The zirconium source is a zirconium oxychloride.
Description of drawings
Fig. 1: be the powder X-ray RD figure of the excessive beta-zeolite molecular sieve sample of the A body of the embodiment of the invention 2 preparations;
Fig. 2: be the powder X-ray RD of the excessive beta-zeolite molecular sieve sample of the A body of the embodiment of the invention 2 preparations and the standard x RD comparison diagram of the different A body content beta-zeolite molecular sieves of diffax process simulation;
Fig. 3: be scanning electronic microscope (SEM) figure of the excessive beta-zeolite molecular sieve of the A body of the embodiment of the invention 2 preparations;
Fig. 4: be high resolution transmission electron microscopy (HRTEM) figure of the excessive beta-zeolite molecular sieve of the A body of the embodiment of the invention 2 preparations.
Shown in Figure 1 is the peak position of experiment XRD diffraction peak of the beta-zeolite molecular sieve of the chirality polymorph A enrichment determined by X ray powder crystal diffraction analysis JADE software commonly used, and 2 θ angles are 7.14,9.65,12.30,18.32,22.74 to be the characteristic diffraction peak of A body among the figure.Especially the diffraction peak of 2 θ angles about 12 degree is very responsive to A type body burden, and the content that gets its peak position and chirality polymorph A by diffax process simulation result has following corresponding relation:
Fig. 2 has provided the XRD spectra that the experiment XRD spectra of beta-molecular sieve of chirality polymorph A enrichment and chirality polymorph A content are the diffax process simulation of 50%, 60%, 70% beta-zeolite molecular sieve.By contrast, the content of chirality polymorph A is between 50～70% as can be seen.Content in conjunction with 2 θ angles chirality polymorph A in the sample that the peak position of the diffraction peak at 12.30 places can be determined to prepare is 70%.
The sample crystal grain for preparing as can be seen in the scanning electron microscope picture shown in Figure 3 is about 20um, and this sample has the pattern of common β zeolite, and a small amount of crystal grain symbiosis is arranged among the figure, does not have other dephasigns.
The brighter point of high-resolution electron microscopy shown in Figure 4 (HRTEM) is the duct of β zeolite [100] crystal face, and as can be seen from the figure the duct arrangement mode is ABAB....., is the arrangement mode of chirality polymorph A.
Embodiment
The present invention will be further described below by embodiment, but embodiments of the present invention are not limited thereto, and can not be interpreted as limiting the scope of the invention.
Embodiment 1: with tetraethyl ammonium hydroxide (TEAOH) is template
In plastic beaker, take by weighing the TEAOH of 6.34g massfraction 35%, add 6g distilled water, add the 6.00g tetraethoxy again, in stink cupboard, stirred 5 hours, make the tetraethoxy complete hydrolysis.Make ethanol and water in the system formation jelly that volatilizees fast with infrared lamp irradiation then, put into 85 ℃ of baking oven for heating again 3 days, in 12 hours no longer till the loss of weight, system is moisture hardly at this moment up to gel.Solid blob of viscose porphyrize is added 0.61g hydrogen fluoride solution (massfraction 40%) then stir, transferred in the teflon-lined stainless steel cauldron in 140 ℃ baking oven crystallization again 9 days.After crystallization is finished with the product suction filtration, be washed with distilled water to oven dry, the retort furnace calcination under 550 ℃ of temperature of spending the night of neutrality, 100 ℃ of baking ovens and removed template in 6 hours and promptly prepare beta-molecular sieve.
The A body relative content that is got institute's synthetic beta-zeolite molecular sieve sample by XRD analysis is approximately 60% (mol ratio).
Embodiment 2: with N, and N, 2,6-tetramethyl piperidine oxyhydroxide is template
N, N, 2,6-tetramethyl piperidine oxyhydroxide synthetic: with the anhydrous methanol is solvent, is at room temperature to react 5 days after mixing at 1: 2.2: 1 in molar ratio with lupetidine, methyl iodide, Anhydrous potassium carbonate, then the methyl alcohol rotary evaporation is gone out.Remaining solid chloroform extraction 2～3 times are with the chloroformic solution anhydrous magnesium sulfate drying of extraction.Rotary evaporation is removed chloroform and is obtained head product, and the head product anhydrous methanol is that solvent recrystallization promptly obtains quaternary ammonium salt.Recording H-NMR with the deuterochloroform dissolving is δ=3.5 (m, 1.99), δ=3.072 (s, 3.02), δ=1.7 (m, 6.22), δ=1.4 (d, 6.02), turns out to be target product by this hydrogen spectrum.Quaternary ammonium salt is handled with strong basic ion exchange resin, get final product N, N, 2,6-tetramethyl piperidine hydroxide solution is demarcated to such an extent that liquid quality fraction be 21.8% with hydrochloric acid solution concentration.
Take by weighing the N of 10.20g according to the synthesis step among the embodiment 1, N, 2,6-tetramethyl piperidine hydroxide solution adds 5g distilled water, adds the 6.00g tetraethoxy again, stirs to make the hydrolysis of silicon source and make ethanol and the water volatilization, and H is worked as in the calculating of weighing
2O/SiO
2Be approximately at 2 o'clock and add 0.61g hydrogen fluoride (massfraction 40%) and stir, gel was transferred in the teflon-lined stainless steel cauldron in 160 ℃ baking oven crystallization 8 days.The product that crystallization is finished carries out aftertreatment according to embodiment 1.
The A body relative content that is got institute's synthetic beta-zeolite molecular sieve sample by XRD analysis is approximately 70%.
Embodiment 3: with dimethyl di-isopropyl ammonium hydroxide is template
With reference to N among the embodiment 2, N, 2, the synthetic method of 6-tetramethyl piperidine oxyhydroxide is a raw material synthesization of dimethyl di-isopropyl ammonium iodide with Diisopropylamine and methyl iodide.Recording H-NMR with the deuterochloroform dissolving is δ=3.1 (s, 6.02), δ=3.9 (m, 2.00), δ=1.5 (d, 11.98), turns out to be target product by this hydrogen spectrum.With reference to example 2 by resins exchange, concentrate, demarcate that to obtain corresponding liquid quality fraction be 29.0%.
Take by weighing 8.28g dimethyl di-isopropyl solution of ammonium hydroxide according to the synthesis step among the embodiment 1, add 5g distilled water, add the 7.00g tetraethoxy again.Stirring makes the hydrolysis of silicon source, and makes ethanol and water volatilization, weighs to calculate and works as H
2O/SiO
2Be approximately at 3 o'clock and add 0.71g hydrogen fluoride (massfraction 40%) and stir, gel was transferred in the stainless steel cauldron of tetrafluoroethylene liner in 150 ℃ baking oven crystallization 8 days.The product that crystallization is finished carries out aftertreatment according to embodiment 1.
The A body relative content that is got institute's synthetic beta-zeolite molecular sieve sample by XRD analysis is approximately 60%.
Embodiment 4: the A body of synthesizing blender metal Ti is excessive
With N, N, 2,6-tetramethyl piperidine oxyhydroxide is that the template synthesis condition is with reference to embodiment 2.
The amount of mixing metal titanium satisfies following mol ratio: SiO
2: Ti=125: 1.
Take by weighing 10.20g N, N, 2,6-tetramethyl piperidine hydroxide solution (massfraction 21.8%) adds 5.6g silicon sol (massfraction 30%).Stir and mixed back adding 0.6mL hydrogen peroxide solution (massfraction 40%) and 0.075mL titanium isopropylate in 30 minutes.At room temperature stirred 4 hours, and made the hydrolysis of titanium source, and make Virahol and water volatilization, weigh to calculate and work as H
2O/SiO
2Be approximately at 2 o'clock and add 0.61g hydrogen fluoride (massfraction 40%) and stir, gel was transferred in the teflon-lined stainless steel cauldron in 160 ℃ baking oven crystallization 10 days.Product after crystallization finished carries out aftertreatment according to embodiment 1.
The A body relative content that is got institute's synthetic beta-zeolite molecular sieve sample by XRD analysis is approximately 70%.
Claims (6)
1. the preparation method of the excessive beta-zeolite molecular sieve of a chirality polymorph A, its step is as follows:
1) silicon source, template are joined in the beaker, add an amount of water again; Wherein template and SiO
2Mol ratio be 0.2～0.55: 1, H
2O and SiO
2Mol ratio be 15～20: 1;
2) said mixture was stirred 4～6 hours at ambient temperature, or with infrared lamp irradiation heating, or put into 60～90 ℃ of baking oven for heating, H to the reaction system
2O and SiO
2Mol ratio be lower than 4: 1;
3) in above-mentioned reaction system, add the fluorine source, transferred in the hydrothermal reaction kettle of tetrafluoroethylene liner in 130～170 ℃ baking oven crystallization after stirring 6～10 days, wherein F
-With SiO
2Mol ratio be 0.2～0.55: 1;
4) sample that crystallization is finished is shifted out from the reactor transfer, and suction filtration also is washed with distilled water to neutrality, then sample is put into 90～120 ℃ of baking oven heating, dryings;
5) sample of oven dry is put into crucible, in 550～600 ℃ retort furnace, heat the template oxygenolysis is removed, promptly obtain the excessive beta-zeolite molecular sieve of A body.
2. the preparation method of the excessive beta-zeolite molecular sieve of a chirality polymorph A, its step is as follows:
1) silicon source, template are joined in the beaker, add an amount of water again, wherein template and SiO
2Mol ratio be 0.2～0.55: 1, H
2O and SiO
2Mol ratio be 15～20: 1;
2) said mixture stirred 0.5～2 hour at ambient temperature, added aluminium source, gallium source, Xi Yuan, titanium source or zirconium source, wherein SiO again
2With the mol ratio of Al or Ga be 20～500: 1, SiO
2With the mol ratio of Sn, Zr or Ti be 100～500: 1;
3) said mixture was stirred 3～4 hours at ambient temperature, or with infrared lamp irradiation heating, or put into 60～90 ℃ of baking oven for heating, H to the reaction system
2O and SiO
2Mol ratio be lower than 4: 1;
4) in above-mentioned reaction system, add the fluorine source, transferred in the hydrothermal reaction kettle of tetrafluoroethylene liner in 130～170 ℃ baking oven crystallization after stirring 10～30 days, wherein F
-With SiO
2Mol ratio be 0.2～0.55: 1;
5) sample that crystallization is finished is shifted out from the reactor transfer, and suction filtration also is washed with distilled water to neutrality; Then sample is put into 90～120 ℃ of baking oven heating, dryings;
6) sample of oven dry is put into crucible, in 550～600 ℃ retort furnace, heat the template oxygenolysis is removed, promptly obtain the excessive beta-zeolite molecular sieve of A body.
3. the preparation method of the beta-zeolite molecular sieve that a kind of chirality polymorph A as claimed in claim 1 or 2 is excessive, it is characterized in that: template is tetraethyl ammonium hydroxide, N, N, 2,6-tetramethyl piperidine oxyhydroxide or dimethyl di-isopropyl ammonium hydroxide.
4. the preparation method of the beta-zeolite molecular sieve that a kind of chirality polymorph A as claimed in claim 1 or 2 is excessive, it is characterized in that: the fluorine source is HF solution or NH
4F solution.
5. the preparation method of the beta-zeolite molecular sieve that a kind of chirality polymorph A as claimed in claim 1 or 2 is excessive, it is characterized in that: the silicon source is tetraethoxy, silicon sol or white carbon black.
6. the preparation method of the beta-zeolite molecular sieve that a kind of chirality polymorph A as claimed in claim 1 or 2 is excessive, it is characterized in that: the aluminium source is aluminum isopropylate or Tai-Ace S 150; The gallium source is gallium nitrate or gallium oxide; Xi Yuan is a tin tetrachloride; The titanium source is metatitanic acid tetra isopropyl ester or metatitanic acid tetraethyl ester; The zirconium source is a zirconium oxychloride.
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Cited By (8)
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|---|---|---|---|---|
| CN103601212A (en) * | 2013-11-11 | 2014-02-26 | 吉林大学 | Method for preparing chiral polymorph A-shaped excessive Beta zeolite molecular sieve |
| CN104276581A (en) * | 2013-07-02 | 2015-01-14 | 天津海赛纳米材料有限公司 | Preparation method for chiral beta zeolite |
| 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 |
| CN105753009A (en) * | 2014-12-16 | 2016-07-13 | 中国科学院大连化学物理研究所 | Beta molecular sieve with adjustable relative content of polymorphs and synthetic method thereof |
| WO2017015423A1 (en) * | 2015-07-23 | 2017-01-26 | Chevron U.S.A. Inc. | Crystalline molecular sieves and synthesis thereof |
| CN106904635A (en) * | 2017-02-20 | 2017-06-30 | 吉林大学 | It is a kind of to be aided in by amino acid under dense gel rubber system and be segmented method of the crystallization coordinate system for nano molecular sieve |
| CN107954439A (en) * | 2016-10-17 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of preparation method of chirality A bodies enrichment Beta zeolite molecular sieve |
| CN115676849A (en) * | 2021-07-29 | 2023-02-03 | 中国石油化工股份有限公司 | SVR structure silicon-zirconium molecular sieve and preparation method thereof |
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| CN104276581A (en) * | 2013-07-02 | 2015-01-14 | 天津海赛纳米材料有限公司 | Preparation method for chiral beta zeolite |
| CN103601212B (en) * | 2013-11-11 | 2015-06-03 | 吉林大学 | Method for preparing chiral polymorph A-shaped excessive Beta zeolite molecular sieve |
| CN103601212A (en) * | 2013-11-11 | 2014-02-26 | 吉林大学 | Method for preparing chiral polymorph A-shaped excessive Beta zeolite molecular sieve |
| CN105753009B (en) * | 2014-12-16 | 2018-01-09 | 中国科学院大连化学物理研究所 | A kind of adjustable Beta molecular sieves of polymorph relative amount and its synthetic method |
| CN105753009A (en) * | 2014-12-16 | 2016-07-13 | 中国科学院大连化学物理研究所 | Beta molecular sieve with adjustable relative content of polymorphs and synthetic method thereof |
| 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 |
| WO2017015423A1 (en) * | 2015-07-23 | 2017-01-26 | Chevron U.S.A. Inc. | Crystalline molecular sieves and synthesis thereof |
| US9738537B2 (en) | 2015-07-23 | 2017-08-22 | Chevron U.S.A. Inc. | Crystalline molecular sieves and synthesis thereof |
| CN107954439A (en) * | 2016-10-17 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of preparation method of chirality A bodies enrichment Beta zeolite molecular sieve |
| CN107954439B (en) * | 2016-10-17 | 2019-09-24 | 中国石油化工股份有限公司 | A kind of preparation method of chirality A body enrichment Beta zeolite molecular sieve |
| CN106904635A (en) * | 2017-02-20 | 2017-06-30 | 吉林大学 | It is a kind of to be aided in by amino acid under dense gel rubber system and be segmented method of the crystallization coordinate system for nano molecular sieve |
| CN115676849A (en) * | 2021-07-29 | 2023-02-03 | 中国石油化工股份有限公司 | SVR structure silicon-zirconium molecular sieve and preparation method thereof |
| CN115676849B (en) * | 2021-07-29 | 2024-03-12 | 中国石油化工股份有限公司 | SVR structure silicon zirconium molecular sieve and preparation method thereof |
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