CN100368294C - Method for preparing ZSM-5 zeolite in small crystal grain - Google Patents
Method for preparing ZSM-5 zeolite in small crystal grain Download PDFInfo
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- CN100368294C CN100368294C CNB2005100287816A CN200510028781A CN100368294C CN 100368294 C CN100368294 C CN 100368294C CN B2005100287816 A CNB2005100287816 A CN B2005100287816A CN 200510028781 A CN200510028781 A CN 200510028781A CN 100368294 C CN100368294 C CN 100368294C
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Abstract
This invention relates to a method for preparing ZSM-5 zeolite with fine grains. The method comprises: (1) adopting water glass, silica sol or white carbon black as the Si source, and Al salt or aluminate as the Al source with Na2O : Al2O3 : SiO2 : H2O = (4-36) : (0-3) : 100 : (1400-6000); (2) adding a small amount of crystal seed directing-agent into the crystallization mother liquid; (3) crystallizing to obtain ZSM-5 zeolite with fine grains. The method solves the problems of large amounts of templating agent, long crystallization time, and serious environmental pollution, and can be used in industrial manufacture of ZSM-5 zeolite.
Description
Technical field
The present invention relates to a kind of method for preparing the small-grain ZSM-5 zeolite.
Background technology
Zeolite molecular sieve is a most important class crystalline microporous body, it has uniform sequential micropore, big specific surface, high hydrothermal stability, good ion-exchange performance and enriches adjustable surperficial physico-chemical property, is widely used in fields such as catalysis, absorption, ion-exchange and functional materials.But along with the development of fine chemistry industry, big crystal grain zeolitic material is owing to its arctation, and diffusional resistance is bigger, in relating to macromole or liquid phase reaction, can not reach the catalytic effect of expection.And the zeolite molecular sieve of little crystal grain is owing to have bigger external surface area and higher intracrystalline rate of diffusion, more active sites can be provided, reactant molecule is easy to arrive catalytic active site, and the product that generates can spread out from the duct very soon, in the utilization ratio that improves catalyzer, strengthen macromolecular conversion capability, reduce the deep reaction of product, and reduce aspect such as catalyzer coking deactivation rate and all have more superior performance.Therefore little crystal grain particularly has the zeolite synthesis of nano level (particle diameter is generally below 100 nanometers) size and property research thereof becomes one of focus of zeolite molecular sieve research field in recent years.
The ZSM-5 molecular sieve becomes a kind of very important shape selective catalysis material with its unique pore passage structure and good catalytic performance, is used widely in the organic catalysis conversion reaction.Since 1976, Mobil company repeatedly delivers patent utilization small-grain ZSM-5 zeolite molecular sieve can obviously improve catalytic activity, and the ZSM-5 zeolite molecular sieve that therefore prepares little crystal grain becomes needs.Tetrapropyl quaternary ammonium hydroxide or quaternary ammonium salt are the directed agents of synthetic ZSM-5 zeolite molecular sieve relatively commonly used.In the nano-ZSM-5 zeolite molecular sieve is synthetic, in order to obtain the colloidal sol of transparent and homogeneous, be alkali source mostly with TPAOH (TPAOH), tetraethoxy is the silicon source, the existence of alkalimetal ion will make the silicon-aluminum sol instability and assemble in this system, therefore need under the alkali free metal ion condition synthetic.Schoeman etc. synthesize dispersive ZSM-5 zeolite molecular sieve colloid under 373K and alkali free metal ion condition, but because lower sodium content and lower crystallization temperature are unfavorable for that all aluminium enters zeolite framework, the zeolite silica alumina ratio that this method synthesizes is higher.To be aluminium source, long digestion time, higher basicity and lower sodium content with the aluminum isopropylate become hydro-thermal under the glue conditions of mixture ratios to synthesize the ZSM-5 zeolite molecular sieve of 10～100 nanometers in supersaturation to Van Grieken etc., find that the existence of sodium ion has reduced the crystallization velocity of ZSM-5 zeolite molecular sieve, causes crystal grain obviously to increase.In addition, Yamamura etc. are that silicon source, 4-propyl bromide are that template, sodium hydroxide are that alkali source, aluminum nitrate are the aluminium source with silicon sol or the silicon that obtains from GEOTHERMAL WATER also, dynamic crystallization under 433K obtains the ZSM-5 zeolite molecular sieve aggregate of 30～50 nanometers.A lot of organic amines also can be used as the directed agents of synthetic ZSM-5 zeolite molecular sieve.Zhang etc. are template with the n-Butyl Amine 99, water glass is the silicon source, and Tai-Ace S 150 is the aluminium source, and sodium hydroxide is that alkali source is prepared the nano-ZSM-5 zeolite molecular sieve, and, find that the content that increases NaCl can make its crystal grain be decreased to about 70 nanometers by adding inorganic salt modulation zeolite particle diameter.Hu Jinxian etc. are then with organic amine n-Butyl Amine 99, quadrol, ethamine or 1, the 6-hexanediamine is that template prepares directed agents in advance, join then in the middle of the mixed system of molecular sieve in synthetic, prepare the ZSM-5 zeolite (method of directing agent method quickly synthesizing small crystal grain ZSM-5-5 molecular sieve about 100 nanometers, Chinese patent CN1303816, CN1417121).Kacirek, et al. is by adding in the reaction system that still contains a large amount of template with tetrapropyl quaternary ammonium salt or the previously prepared amorphous silicon alumina gel of quaternary ammonium hydroxide crystallization accelerator, crystallization rate can be accelerated on the one hand, degree of crystallinity (US Patent:4606900) can be improved on the other hand.Wang Zhongnan etc. also find to add an amount of NaCl in synthetic system, the particle diameter of ZSM-5 zeolite molecular sieve can drop to about 60 nanometers, further the result shows, crystallization temperature can obtain the nano zeolite below 100 nanometers in 373～393K: when crystallization temperature was higher than 403K, the ZSM-5 zeolite molecular sieve crystal grain that obtains was greater than 700 nanometers.In these small-grain ZSM-5 prepare zeolite methods, need in becoming colloid system, add a large amount of template, production cost is higher on the one hand, and crystallization time is long, and extensive the use caused restriction; The aftertreatment removed template method can cause environmental pollution on the other hand.
Summary of the invention
Technical problem to be solved by this invention is to have problems such as the template consumption is big, crystallization time length, cost height in the conventional art, and a kind of new method for preparing the small-grain ZSM-5 zeolite is provided.The usage quantity that this small-grain ZSM-5 prepare zeolite method has template is low, and crystallization time is short, output capacity height, the advantage that three waste discharge is few.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for preparing the small-grain ZSM-5 zeolite is the silicon source with water glass, silicon sol or white carbon black, and aluminium salt or aluminate are the aluminium source, and the mole proportioning of crystallization mother liquor is XNa
2O: YAl
2O
3: 100SiO
2: ZH
2O, wherein, X=4～36, Y=0～3, Z=1400～6000, at crystallization temperature is 100～240 ℃, crystallization time is 8～100 hours down synthetic ZSM-5 zeolites, be the silicon source with tetraethoxy, silicon sol or white carbon black in advance wherein in the crystallization mother liquor, adding before the crystallization, TPAOH or 4-propyl bromide are the crystal seed directed agents of template preparation, crystal seed directed agents add-on is 1～15% of a crystallization mother liquor weight, and the crystal seed directed agents is (TPA) by the feed molar proportioning
2O: 2～10SiO
2: 60～150H
2The mixture of O wore out under 50～100 ℃ 12～240 hours and gets, and TPA is a tetrapropyl ammonium.
In the technique scheme, the crystal seed of adding guiding dosage preferable range is 1.0～10% of a crystallization mother liquor weight.The preferred span of X is 6～28 in the mole proportioning of reaction mother liquor, and the preferred span of Z is 1500～4500; Reaction crystallization temperature preferable range is 140～180 ℃, and reaction crystallization time preferable range is 10～24 hours.
The present invention is owing to added the crystal seed directed agents in the crystallization mother liquor, directed agents has produced a large amount of ZSM-5 primary structure and secondary structure unit in its preparation weathering process, the nucleus of in the synthetic crystallization process of back, growing as the ZSM-5 zeolite crystallization, significantly reduced template agent on the one hand, accelerated crystallization rate on the other hand, shorten crystallization time, obtained better technical effect.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment 1 product.
Fig. 2 is the SEM figure of embodiment 1 product.
Fig. 3 is the SEM figure of embodiment 4 products.
Fig. 4 is the SEM figure of embodiment 25 products.
Higher XRD diffraction peak has shown that embodiment 1 products obtained therefrom is the ZSM-5 zeolite of high-crystallinity among Fig. 1.
Show among Fig. 2 that embodiment 1 product is the particle about 100～150 nanometers, epigranular.
Fig. 3 shows that product embodiment 4 is the particle about 100～200 nanometers, epigranular.
Fig. 4 shows that embodiment 25 products are the agglomerating particles less than 500 nanometers.
The invention will be further elaborated below by embodiment.
Embodiment
Following example is to further specifying that the method that the present invention adopts commercial general reagent to prepare the small-grain ZSM-5 zeolite under the situation of adding a small amount of previously prepared crystal seed directed agents is done.The preparation process of small-grain ZSM-5 zeolite molecular sieve is: the previously prepared crystal seed directed agents that takes a morsel adds in the reaction mixture that (with the raw material mixing and stirring, becoming the glue proportioning is X Na to
2O: YAl
2O
3: 100SiO
2: ZH
2O), be 100～240 ℃ at crystallization temperature, crystallization time is to be synthesized under 8～100 hours.Reaction product is repeatedly washed drying then through separating.
[embodiment 1～3]
The crystal seed directed agents: is raw material with TPAOH (TPAOH) solution with positive tetraethyl orthosilicate (TEOS), is (TPA) according to the mole proportioning
2O: 5.5TEOS: 90H
2The mixture of O at room temperature stirs to spend the night and mixes, and wears out 72 hours down at 80 ℃ then, makes the crystal seed directed agents.
With silicon sol and Tai-Ace S 150 is raw material, and the mole proportioning that is made into the crystallization mother liquor is 28Na
2O: 1.5Al
2O
3: 100SiO
2: 4000H
2O, in the crystallization mother liquor, add the crystal seed directed agents of its weight 10%, reaction system was reacted 10 hours in 180 ℃ of following 300 milliliters of crystallizing kettles, 12 hours and 14 hours, the bright product of product XRD figure stave is the ZSM-5 zeolite of high-crystallinity, the SEM characterization result shows that zeolite granular is of a size of about 100 nanometers, and physical adsorption is measured its BET specific surface area all greater than 360 meters squared per gram.
[embodiment 4～6]
With silicon sol and Tai-Ace S 150 is raw material.The mole proportioning that is made into the crystallization mother liquor is 28Na
2O: 1.5Al
2O
3: 100SiO
2: 4000H
2O, in the crystallization mother liquor, add the embodiment 1 described crystal seed directed agents of its weight 2.7%, reaction system was reacted 10 hours in 180 ℃ of following 300 milliliters of crystallizing kettles, 12 hours and 14 hours, the bright product of product XRD figure stave is the ZSM-5 zeolite of high-crystallinity, and the SEM characterization result shows that zeolite granular is of a size of 100～200 nanometers.
[embodiment 7～9]
With silicon sol and Tai-Ace S 150 is raw material, and the mole proportioning that is made into the crystallization mother liquor is 28Na
2O: 1.5Al
2O
3: 100
SiO
2: 4000H
2O, in the crystallization mother liquor, add the embodiment 1 described crystal seed directed agents of its weight 1.0%, reaction system was reacted 10 hours, 12 hours and 14 hours in 180 ℃ of following 300 milliliters of crystallizing kettles, the bright product of product XRD figure stave is the ZSM-5 zeolite of high-crystallinity, and the SEM characterization result shows that zeolite granular is of a size of 100～250 nanometers.
[embodiment 10～11]
The crystal seed directed agents: with 4-propyl bromide (TPABr) solution and silicon sol is raw material, according to mole proportioning (TPA)
2O: 4SiO
2: 100H
2Mix under the O room temperature and stirred 24 hours, adjusting pH with ammoniacal liquor is 12, wears out 140 hours down at 60 ℃ then, makes the crystal seed directed agents.
With silicon sol and Tai-Ace S 150 is raw material, and the mole proportioning that is made into the crystallization mother liquor is 6Na
2O: 0.83Al
2O
3: 100SiO
2: 1500H
2O, add the above-mentioned crystal seed directed agents of its weight 1.0% in the crystallization mother liquor, reaction system is reacted 12 hours and 20 hours in 180 ℃ of following 300 milliliters of crystallizing kettles, the bright product of product XRD figure stave is the ZSM-5 zeolite, and the SEM characterization result shows that zeolite granular is of a size of 200～400 nanometers.
[embodiment 12～16]
With white carbon black and Tai-Ace S 150 is raw material, and the mole proportioning that is made into the crystallization mother liquor is 6Na
2O: 0.83Al
2O
3: 100SiO
2: 1500H
2O, in the crystallization mother liquor, add the embodiment 10 described crystal seed directed agents of its weight 10%, reaction system was reacted 24,36 and 48 hours in 140 ℃ of following 300 milliliters of crystallizing kettles, the bright product of product XRD figure stave is the ZSM-5 zeolite, and the SEM characterization result shows that zeolite granular is of a size of 200～500 nanometers.
[embodiment 17～21]
With white carbon black and Tai-Ace S 150 is raw material, and the mole proportioning that is made into the crystallization mother liquor is 6Na
2O: 0.83Al
2O
3: 100
SiO
2: 1500H
2O, in the crystallization mother liquor, add the embodiment 1 described crystal seed directed agents of its weight 5.0%, reaction system was reacted 12,14 and 16 hours in 140 ℃ of following 300 milliliters of crystallizing kettles, the bright product of product XRD figure stave is the ZSM-5 zeolite, and the SEM characterization result shows that zeolite granular is of a size of 100～200 nanometers.
[embodiment 22～23]
With silicon sol and Tai-Ace S 150 is raw material, and the mole proportioning that is made into the crystallization mother liquor is 6Na
2O: 0.83Al
2O
3: 100SiO
2: 1500H
2O, in the crystallization mother liquor, add the embodiment 1 described crystal seed directed agents of its weight 5.0%, the hexanediamine that adds crystallization mother liquor weight 0.25 weight % and 0.75 weight % in addition in reaction system respectively improves the degree of crystallinity of product, reaction system was reacted 12 and 16 hours in 140 ℃ of following 300 milliliters of crystallizing kettles, the bright product of product XRD figure stave is the ZSM-5 zeolite of high-crystallinity, and the SEM characterization result shows that zeolite granular is of a size of 100～200 nanometers.
[embodiment 24]
With water glass, white carbon black and Tai-Ace S 150 is raw material, is raw material with silicon sol and Tai-Ace S 150, and the mole proportioning that is made into the crystallization mother liquor is 18Na
2O: 0.83Al
2O
3: 100SiO
2: 3000H
2O, in the crystallization mother liquor, add the embodiment 1 described crystal seed directed agents of its weight 2.0%, reaction system was reacted 16 hours in 140 ℃ of following 2 liters of crystallizing kettles, the bright product of product XRD figure stave contains the ZSM-5 zeolite of a small amount of stray crystal, and the SEM characterization result shows that zeolite granular is of a size of 100～200 nanometers.
[embodiment 25]
With silicon sol and Tai-Ace S 150 is raw material, and the mole proportioning that is made into the crystallization mother liquor is 6Na
2O: 0.83Al
2O
3: 100SiO
2: 1500H
2O, in the crystallization mother liquor, add the embodiment 1 described crystal seed directed agents of its weight 5.0%, the hexanediamine that in reaction system, adds 0.80 weight % in addition respectively, reaction is 12 hours in 140 ℃ of following 2 liters of crystallizing kettles, the bright product of product XRD figure stave is the ZSM-5 zeolite, and the SEM characterization result shows that the zeolite granular size is less than 500 nanometers.
[embodiment 26～28]
The crystal seed directed agents: is raw material with TPAOH (TPAOH) solution with white carbon black, according to mole proportioning (TPA)
2O: 3SiO
2: 100H
2Mix under the O room temperature, adjusting pH with ammoniacal liquor is 13, wears out 36 hours down at 100 ℃ then, makes the crystal seed directed agents.
With silicon sol and Tai-Ace S 150 is raw material, and the mole proportioning that is made into the crystallization mother liquor is 24NaO: 1.5Al
2O
3: 100SiO
2: 3500H
2O, in the crystallization mother liquor, add the above-mentioned crystal seed directed agents of its weight 5%, reaction system was reacted 12,16 and 20 hours in 160 ℃ of following 300 milliliters of crystallizing kettles, the bright product ZSM-5 of product XRD figure stave zeolite, and the SEM characterization result shows that zeolite granular is of a size of 200～400 nanometers.
[embodiment 29～30]
The crystal seed directed agents: is raw material with 4-propyl bromide (TPABr) solution with positive tetraethyl orthosilicate (TEEOS), according to mole proportioning (TPA)
2O: 5.5TEOS: 90H
2Stirring under the O room temperature and adjusting pH with ammoniacal liquor promotion TEOS hydrolysis is 12, wears out 100 hours down at 90 ℃ then, makes the crystal seed directed agents.
With silicon sol and Tai-Ace S 150 is raw material, and the mole proportioning that is made into the crystallization mother liquor is 6Na
2O: 0.83Al
2O
3: 100SiO
2: 1500H
2O, in the crystallization mother liquor, add the above-mentioned crystal seed directed agents of its weight 10%, the hexanediamine that in reaction system, adds crystallization mother liquor 1.0 weight % in addition respectively, reaction is 12 hours and 20 hours in 150 ℃ of following 300 milliliters of crystallizing kettles, the bright product of product XRD figure stave contains the ZSM-5 zeolite of a small amount of stray crystal, and the SEM characterization result shows that the zeolite granular size is less than 500 nanometers.
Claims (5)
1. a method for preparing the small-grain ZSM-5 zeolite is the silicon source with water glass, silicon sol or white carbon black, and aluminium salt or aluminate are the aluminium source, and the mole proportioning of crystallization mother liquor is XNa
2O: YAl
2O
3: 100SiO
2: ZH
2O, wherein, X=4～36, Y=0～3, Z=1400～6000, at crystallization temperature is 100～240 ℃, crystallization time is 8～100 hours down synthetic ZSM-5 zeolites, it is characterized in that adding before the crystallization be the silicon source with tetraethoxy, silicon sol or white carbon black in advance in the crystallization mother liquor, TPAOH or 4-propyl bromide are the crystal seed directed agents of template preparation, crystal seed directed agents add-on is 1～15% of a crystallization mother liquor weight, and the crystal seed directed agents is (TPA) by the feed molar proportioning
2O: 2～10SiO
2: the mixture of 60～150 H2O, under 50～100 ℃, wore out 12～240 hours and get, TPA is a tetrapropyl ammonium.
2. according to the described method for preparing the small-grain ZSM-5 zeolite of claim 1, it is characterized in that the crystal seed guiding dosage that adds is 1.0～10% of crystallization mother liquor weight.
3. according to the described method for preparing the small-grain ZSM-5 zeolite of claim 1, it is characterized in that X=6～28 in the mole proportioning of reaction mother liquor, Z=1500～4500.
4. according to the described method for preparing the small-grain ZSM-5 zeolite of claim 1, it is characterized in that reacting crystallization temperature is 140～180 ℃.
5. according to the described method for preparing the small-grain ZSM-5 zeolite of claim 1, it is characterized in that reacting crystallization time is 10～24 hours.
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Families Citing this family (18)
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| CN101348262B (en) * | 2007-07-18 | 2010-12-22 | 中国石油化工股份有限公司 | Preparation of zeolite binderless ZSM-5 |
| CN101348261B (en) * | 2007-07-18 | 2010-12-01 | 中国石油化工股份有限公司 | Preparation of binderless ZSM-11 zeolite |
| CN101538051B (en) * | 2009-05-06 | 2011-01-05 | 北京化工大学 | Method for preparing ZSM-5 zeolite catalyst |
| CN101898767B (en) * | 2010-07-20 | 2011-12-28 | 华东师范大学 | Synthetic method of high silica ZSM-5 zeolite |
| CN102372285B (en) * | 2010-08-23 | 2013-01-09 | 中国石油化工股份有限公司 | Preparation method of ZSM-5 zeolite |
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| CN102372286B (en) * | 2010-08-23 | 2013-05-08 | 中国石油化工股份有限公司 | Method for synthesizing small crystal grain ZSM-5 zeolite |
| CN102371172B (en) * | 2010-08-23 | 2013-08-21 | 中国石油化工股份有限公司 | Fluidized bed catalyst for preparing alkene through catalytic cracking |
| CN101983921A (en) * | 2010-12-01 | 2011-03-09 | 复旦大学 | Method for synthesizing ZSM-5 zeolite orderly accumulated by nanometer crystallite |
| CN103086399B (en) * | 2011-10-31 | 2014-12-10 | 华东师范大学 | Small-grain NH4-ZSM-5 zeolite and its one-step synthetic method |
| CN102502696B (en) * | 2011-11-16 | 2014-04-23 | 大连理工大学 | Synthetic method of ZSM-5 zeolites |
| CN104418357B (en) * | 2013-08-22 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of preparation method of ZSM-35 molecular sieve |
| CN104512908B (en) * | 2013-09-26 | 2017-02-08 | 天津神能科技有限公司 | Synthesis method of ZSM-5 zeolite molecular sieve in small crystal grains |
| CN105460952B (en) * | 2014-08-19 | 2018-05-11 | 神华集团有限责任公司 | The ZSM-5 molecular sieve material that the preparation method and this method of a kind of ZSM-5 molecular sieve material are prepared |
| CN104475151A (en) * | 2014-12-11 | 2015-04-01 | 郭帅 | Novel efficient environment-friendly catalyst for regeneration of used oil |
| CN106145155B (en) * | 2015-04-23 | 2019-02-15 | 中国科学院大连化学物理研究所 | A kind of method preparing high silica alumina ratio Y type molecular sieve, product and its application |
| CN106745052B (en) * | 2016-12-06 | 2021-03-30 | 神华集团有限责任公司 | Method for synthesizing HZSM-5 molecular sieve by using double templates |
| CN109694087B (en) * | 2017-10-20 | 2020-11-06 | 惠生工程（中国）有限公司 | Synthesis method of nano ZSM-5 molecular sieve aggregate |
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