CN102190314B - 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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- CN102190314B CN102190314B CN201110085433A CN201110085433A CN102190314B CN 102190314 B CN102190314 B CN 102190314B CN 201110085433 A CN201110085433 A CN 201110085433A CN 201110085433 A CN201110085433 A CN 201110085433A CN 102190314 B CN102190314 B CN 102190314B
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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, hydrogen cracking, unifining, 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 different but the polymorph A and the fault symbiotic structure of B along the accumulation of [001] direction that are closely related of two kinds of structures.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 each other, 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 is all possible 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 under same synthesis condition, is synthesized.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 confirm 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 characteristic of its A body.Chirality is and the closely-related a kind of characteristic 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 site 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 come to light at first to have the large pore molecular sieve of chirality characteristic.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 is contrasted with the mixed crystal simulation XRD spectra of polymorph A with different ratios and B, find 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 high (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 kinds of 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 following:
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 ir 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 of crystallization being accomplished is shifted out from the reaction kettle 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.
In reaction system, also can synthesize the excessive beta-zeolite molecular sieve of A type body during metal such as admixture Al, Ga, Sn, Zr, Ti, its step is following:
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 ir 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 of crystallization being accomplished is shifted out from the reaction kettle 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 volatile caustic 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 sem (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 confirmed 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 through diffax process simulation result has following corresponding relation:
Experiment XRD spectra and the chirality polymorph A content that Fig. 2 has provided the beta-molecular sieve of chirality polymorph A enrichment is the XRD spectra of the diffax process simulation of 50%, 60%, 70% beta-zeolite molecular sieve.Through contrast, the content that can find out chirality polymorph A is between 50～70%.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 confirmed to prepare is 70%.
The sample crystal grain that can find out preparation in the ESEM 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
Through embodiment the present invention is done further description below, but embodiment of the present invention is not limited thereto, can not be interpreted as restriction protection domain of the present 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 zero(ppm) 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 ir 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 accomplished with the product suction filtration, be washed with distilled water to neutrality, 100 ℃ of baking oven dried over night, retort furnace calcinations under 550 ℃ of temperature were removed template in 6 hours and are promptly prepared 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 is used anhydrous magnesium sulfate drying with chloroform extraction 2～3 times with the chloroformic solution of extraction.Rotary evaporation is removed chloroform and is obtained head product, and head product uses anhydrous methanol promptly to obtain quaternary ammonium salt as solvent recrystallization.Use the deuterochloroform dissolving to record H-NMR and be δ=3.5 (m, 1.99), δ=3.072 (s, 3.02), δ=1.7 (m, 6.22), δ=1.4 (d, 6.02), turn out to be title product through 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 uses hydrochloric acid to demarcate to such an extent that liquid quality fraction is 21.8% 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 zero(ppm) 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 accomplished 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 volatile caustic is template
With reference to N among the embodiment 2, N, 2, the compound method of 6-tetramethyl piperidine oxyhydroxide is a raw material synthesization of dimethyl di-isopropyl ammonium iodide with Diisopropylamine and methyl iodide.Use the deuterochloroform dissolving to record H-NMR and be δ=3.1 (s, 6.02), δ=3.9 (m, 2.00), δ=1.5 (d, 11.98), turn out to be title product through this hydrogen spectrum.With reference to instance 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 zero(ppm) 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 accomplished 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 the crystallization completion is carried 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 (4)
1. the preparation method of the excessive beta-zeolite molecular sieve of a chirality polymorph A, its step is following:
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; Template is tetraethyl ammonium hydroxide, N, N, 2,6-tetramethyl piperidine oxyhydroxide or dimethyl-di-isopropyl volatile caustic;
2) the step 1) mixture was stirred 0.5～2 hour at ambient temperature, add 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) with step 2) mixture stirred 3～4 hours at ambient temperature, or with ir lamp irradiation heating, or put into 60～90 ° of C baking oven for heating, H to the reaction system
2O and SiO
2Mol ratio be lower than 4:1;
4) in the step 3) reaction system, add the fluorine source, transferred in the hydrothermal reaction kettle of tetrafluoroethylene liner in the baking oven of 130～170 ° of C crystallization after stirring 10～30 days, wherein F and SiO
2Mol ratio be 0.2～0.55:1;
5) sample of crystallization being accomplished is shifted out from the reaction kettle transfer, and suction filtration also is washed with distilled water to neutrality; Then sample is put into 90～120 ° of C baking oven heating, dryings;
6) sample of oven dry is put into crucible, in the retort furnace of 550～600 ° of C, heat the template oxygenolysis is removed, promptly obtain the excessive beta-zeolite molecular sieve of chirality polymorph A.
2. the preparation method of the beta-zeolite molecular sieve that a kind of chirality polymorph A as claimed in claim 1 is excessive, it is characterized in that: the fluorine source is HF solution or NH
4F solution.
3. the preparation method of the beta-zeolite molecular sieve that a kind of chirality polymorph A as claimed in claim 1 is excessive, it is characterized in that: the silicon source is tetraethoxy, silicon sol or WHITE CARBON BLACK.
4. the preparation method of the beta-zeolite molecular sieve that a kind of chirality polymorph A as claimed in claim 1 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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| CN103601212B (en) * | 2013-11-11 | 2015-06-03 | 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 |
| CN104909382B (en) * | 2015-05-21 | 2017-01-11 | 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 |
| 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 |
| 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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| CN101279744A (en) * | 2007-04-05 | 2008-10-08 | Ifp公司 | Method for preparing a beta zeolite |
| CN101863490A (en) * | 2009-04-17 | 2010-10-20 | 和益化学工业股份有限公司 | Method for synthesizing full-silicon beta zeolite with small crystal grains |
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Patent Citations (2)
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|---|---|---|---|---|
| CN101279744A (en) * | 2007-04-05 | 2008-10-08 | Ifp公司 | Method for preparing a beta zeolite |
| CN101863490A (en) * | 2009-04-17 | 2010-10-20 | 和益化学工业股份有限公司 | Method for synthesizing full-silicon beta zeolite with small crystal grains |
Non-Patent Citations (2)
| Title |
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