CN108975352A - A kind of preparation method of nano pure silicone ZSM-5 zeolite - Google Patents

A kind of preparation method of nano pure silicone ZSM-5 zeolite Download PDF

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CN108975352A
CN108975352A CN201811234589.6A CN201811234589A CN108975352A CN 108975352 A CN108975352 A CN 108975352A CN 201811234589 A CN201811234589 A CN 201811234589A CN 108975352 A CN108975352 A CN 108975352A
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zsm
zeolite
silicon source
hours
crystallization
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陈晓晖
罗玉莹
胡晖
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Fuzhou University
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Fuzhou University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38—Type ZSM-5
    • C01B39/40—Type ZSM-5 using at least one organic template directing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The present invention discloses a kind of preparation method of high-crystallinity nano pure silicone ZSM-5 zeolite.This method is by silicon source with SiO2Meter, according to silicon source: template: water molar ratio is that 1:0.05 ~ 0.5:2 ~ 12 are sufficiently mixed, aging 0.5 ~ 5 hour under conditions of temperature is 20 ~ 70 DEG C, it is 0.05 ~ 0.5 addition mineralizer according still further to mineralizer and silicon source molar ratio, continue stirring 0.2 ~ 2 hour, finally by obtained semisolid gel 110 ~ 170 DEG C crystallization 24 ~ 96 hours, and by the washing of crystallization obtained solid product it is dry after, it is calcined 8 ~ 24 hours at 500 ~ 600 DEG C, obtains high-crystallinity nano pure silicone ZSM-5 zeolite.This method goes out high-crystallinity nanoscale pure silicon ZSM-5 zeolite by " one kettle way " step hydrothermal synthesis, and step is simple, and generated time is short, synthesis process uses inorganic silicon source, and without using basic hydrolysis agent, template and water consumption are few, at low cost, environmental pollution is small, is conducive to industrial applications.

Description

A kind of preparation method of nano pure silicone ZSM-5 zeolite
Technical field
The present invention relates to a kind of preparation methods for the zeolite with MFI structure that element silicon is contained only in skeleton, specifically For be a kind of nanoscale pure silicon ZSM-5 zeolite with high-crystallinity preparation method.
Background technique
ZSM-5 zeolite has the function of significant shape selective catalysis, and unique three dimensional intersection pore canal system is not only reactant Abundant and unique disengaging duct is provided with the diffusion mass transfer of product, provides crystal to prepare high performance industrial catalyst Structure basis, and it is widely used in the preparation of industrial all kinds of adsorbents.And pure silicon ZSM-5 is because of its powerful hydrophobicity, extensively The general separating-purifying applied to water-insoluble organic matter, and with its flawless structural stability, it is widely used in other activity gold The doping of category and the synthesis of pure silicon molecular sieve film, as Sn element is once carried on pure silicon ZSM-5 molecular sieve and molecular sieve by Wang Xianwu In film, primary study absorption property of the pure silicon ZSM-5 in separating acetic acid-water；Meanwhile pure silicon ZSM-5 has as one kind The Zeolite support in unique three-dimensional duct, be widely used in it is compound with the zeolite of other topological structures, it is more superior multiple with processability Mould assembly zeolite catalyst has been prepared if Silicalite-1 is wrapped in ZSM-5 zeolite outer layer by Luo Lei and can be used for MTP reaction High-performance composite zeolite catalyst, that Jindan once synthesized ZSM-5/MCM-41 composite material and had studied its catalytic pyrolysis Energy.
1972, Mobile company of the U.S. prepared the ZSM-5 zeolite with MFI structure for the first time.It is public in US 4257885 Opened a kind of silica alumina ratio up to 100 ZSM-5 zeolite method.
Sandra L. Burkett et al. (Chem. Mater. 1995 (7), 920-928.) is in research structure directed agents A kind of method for synthesizing pure silicon ZSM-5 is reported when synthesis mechanism 1 in pure silicon molecular sieve.This method exists ethyl orthosilicate Heavy water (the D of tetraethyl ammonium hydroxide2O it) is dissolved in solution, ethyl alcohol is made to volatilize to form gel, then the static crystallization at 110 DEG C 360 hours, obtain pure silicon ZSM-5 zeolite.The template dosage of this method is big, and silicon source is organosilicon acid esters and solvent is heavy water, Synthesis cost is high；Crystallization time is very long, and the size of microcrystal synthesized is micron order, is unfavorable for the diffusion and biography of reactants and products Matter.
Sandra L. Burkett et al. (Chem. Mater. 1995 (7), 1453-1463.) further research structure A kind of method for synthesizing pure silicon ZSM-5 is reported when synthesis mechanism 2 of the directed agents in pure silicon molecular sieve again.This method is by positive silicon Acetoacetic ester is respectively in the heavy water (D of ethylenediamine2) or water (H O2O it) is dissolved in solution, makes ethyl alcohol volatilize to form gel, then exist respectively Static crystallization 1440 hours and 960 hours, obtain pure silicon ZSM-5 zeolite at 120 DEG C.This method silicon source is organosilicon acid esters, far Higher than the cost of inorganic silicon source；The size of microcrystal of synthesis is micron order, is unfavorable for diffusion and the mass transfer of reactants and products；Crystallization Time is extremely long, and step is complicated, is unfavorable for large-scale industrial production.
Yongrui Wang et al. (Micropor. Mesopor. Mat. 2008 (113), 286-295.) reports one The method that kind synthesizes hollow pure silicon ZSM-5.This method synthesizes nucleus Silicalite- in crystallization 96 hours first at 170 DEG C 1, then hydrolyzed by a certain percentage with ethyl orthosilicate and tetrapropylammonium hydroxide, make the silicon precursor of dissolution around nucleus 170 Secondary recrystallization at DEG C, crystallization obtain pure silicon ZSM-5 zeolite after 24 ~ 96 hours.The hollow pure silicon ZSM-5 zeolite of this method synthesis Process needs pre-synthesis nucleus Silliterate-1, then is recrystallized, and step is complicated, and long preparation period is equally unfavorable for Industrialized production.
Guan Hui et al. (the 5th National Chemical engineering in 2008 with biochemical industry annual meeting) reports a kind of two-step method and synthesizes The method of pure silicon ZSM-5 molecular sieve film.The molecular screen membrane of this method synthesis can realize a variety of difficult separation mixing on a molecular scale The screening of object, it may also be used for reaction-isolation integral technique exploitation.
CN102602959B discloses a kind of method for synthesizing nano pure silicone ZSM-5 in succession.This method utilizes secondary synthesis Organic silicic acid ester hydrolysis at silica solution, is further dried as silica gel particle, then it is mixed with template for method, first distintegrant It closes, crystallization 24 ~ 168 hours at 100 ~ 190 DEG C obtain pure silicon ZSM-5 zeolite after calcining.The ZSM-5 zeolite of this method synthesis Crystallinity it is lower；Using organosilicon acid esters as silicon source, template dosage is big, higher cost；Need to prepare silica gel particle intermediate, Step is more complex.
From the point of view of the technology for successfully synthesizing pure silicon ZSM-5 now: firstly, silicon source is mainly liquid phase organosilicon acid esters, Cost is much higher than inorganic silicon source, and organic silicic acid ester hydrolysis process needs a large amount of hydrolytic reagents, so that a large amount of alcohol gas are generated, In addition a large amount of uses of template, not only greatly increase synthesis cost, more exacerbate environmental pollution；Secondly, above-mentioned several sides Method synthesis pure silicon ZSM-5 crystallinity be not it is too high, this be unfavorable for very much later period heteroatomic doping vario-property with synthesize high activity, The catalyst of high stability, greatly limits industrial applications；Again, the process temperature of above-mentioned synthesis pure silicon ZSM-5 is higher, week Phase is longer, and partially synthetic process also needs secondary synthesis, and preparation process is more complicated；Finally, the pure silicon of above method synthesis ZSM-5 size of microcrystal is mostly micron order, is unfavorable for the diffusion mass transfer of reactants and products in reaction process.
Summary of the invention
The purpose of the present invention is being directed to the deficiency of the above pure silicon ZSM-5 zeolite synthetic method, provide that a kind of step is simple, consumption When it is short, at low cost, and the preparation method of the nanoscale pure silicon ZSM-5 zeolite of high-crystallinity can be synthesized.
Method includes the following steps:
1. basic step
1) silicon source is with SiO2Meter, according to silicon source: template: water molar ratio is 1:0.05 ~ 0.5:2 ~ 12, is sufficiently mixed, in temperature Aging 0.5 ~ 5 hour under conditions of being 20 ~ 70 DEG C, Templated hydrogel is obtained, is according to mineralizer and silicon source molar ratio 0.05 ~ 0.5 mineralizer is added into hydrogel, continues stirring 0.2 ~ 2 hour, obtains a kind of gel of semisolid；
2) by obtained semisolid gel 110 ~ 170 DEG C crystallization 24 ~ 96 hours, and crystallization obtained solid product washed dry It is dry, it is calcined 8 ~ 24 hours at 500 ~ 600 DEG C, obtains pure silicon ZSM-5 zeolite.
2. wherein, in step 1), silicon source: template: the molar ratio of water is 1:0.07 ~ 0.3:5 ~ 9.
3. wherein, in step 1), the aging temperature is 20 ~ 60 DEG C, the time is 1 ~ 5 hour.
4. wherein, in step 1), mineralizer is added into hydrogel for 0.1 ~ 0.5 according to mineralizer and silicon source molar ratio, Mixing time is 0.4 ~ 1 hour.
5. wherein, in step 2, the crystallization temperature is 120 ~ 150 DEG C, crystallization time is 24 ~ 72 hours, product Calcination temperature is 500 ~ 550 DEG C, and calcination time is 10 ~ 20 hours.
6. wherein, the silicon source is one or more of white carbon black, solid-state silica gel and silica solution.
7. wherein, the template is that tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide are molten One or more of liquid.
8. wherein, the mineralizer is one or more of sodium fluoride, potassium fluoride, ammonium fluoride.
Method provided by the invention is by will first have inorganic silicon source, template, water be sufficiently mixed adding mineralising Agent crystallization and the method for obtaining pure silicon ZSM-5.The pure silicon ZSM-5 zeolite of synthesis has nanoscale, and average grain diameter is less than 100 Nm has the significant advantages such as relative crystallinity is high, fault of construction is few, hydrophobicity is strong, and it is hydrophobic with other to can be widely used for separation water Property substance, secondary preparation answered mixed with heteroatomic modified ZSM-5 zeolite, with the compound preparation high-performance of zeolite of other topological structures Mould assembly zeolitic material etc..
This method has following remarkable advantage compared with existing synthesis pure silicon ZSM-5 technology:
(1) this method is by the method for " one kettle way " step hydrothermal synthesis pure silicon ZSM-5 zeolite, and the pure silicon ZSM-5 of synthesis boils Stone has very high crystallinity, and step is simple, and generated time is obviously shortened, and experiment condition is milder.
(2) in the method, silicon source used is inorganic silicon source, and it is (highly basic, organic not need to add additional hydrolytic reagent Amine etc.), it is only necessary to a small amount of saline and alkaline template of organic quaternary ammonium can successfully synthesize the high pure silicon ZSM-5 zeolite of crystallinity, have Effect, which avoids, catches up with alcohol process, substantially reduces synthesis cost and carrying capacity of environment, is conducive to industrial applications.
(3) hydrolytic reagents such as NaOH contain a large amount of alkaline kations, and according to the literature, this kind of alkaline kation may The activity of certain catalysis reactions is reduced, therefore needs preparatory removing sodium before to containing other zeolite-loaded active components of Na.And This method synthesizes in the synthesis process of pure silicon ZSM-5 zeolite, does not need to be added any containing Na+The substance of equal alkaline kations, because This pure silicon ZSM-5 zeolite synthesized can save the process of removing sodium, this considerably reduce the later periods when loading other active components The workload of load active component.
Detailed description of the invention
Fig. 1 is the X-ray powder diffraction figure of pure silicon ZSM-5 obtained in embodiment 1.
Specific embodiment
The present invention provides a kind of preparation method of high-crystallinity nano pure silicone ZSM-5 zeolite, which is characterized in that this method packet Include following steps:
1) silicon source is with SiO2Meter, with template and water according to silicon source: template: water=1:0.05 ~ 0.5:2 ~ 12 molar ratio is abundant Mixing obtains Templated hydrogel, into resulting hydrogel aging 0.5 ~ 5 hour under conditions of temperature is 20 ~ 70 DEG C Addition is equivalent to the mineralizer of silicon source mole 0.05 ~ 0.5, continues stirring 0.2 ~ 2 hour, obtains a kind of gel of semisolid, The template is organic quaternary ammonium alkaloids；
2) by obtained semisolid gel 110 ~ 170 DEG C crystallization 24 ~ 96 hours, and by crystallization obtained solid product wash, 500 ~ 600 DEG C are calcined 8 ~ 24 hours, and pure silicon ZSM-5 zeolite is obtained, and the mineralizer is fluorine-containing water soluble compound.
According to the method for the present invention, the preparation condition in step 1) is preferably according to silicon source: template: water=1:0.07 ~ The molar ratio of 0.3:5 ~ 9 is sufficiently mixed.
The temperature of the aging is preferably 20 ~ 60 DEG C, and the time is preferably 1.0 ~ 3.0 hours.
According to the method for the present invention, the preparation condition in step 1) is preferably to according to silicon source: template: water=1:0.07 ~ The molar ratio of 0.3:5 ~ 9 be sufficiently mixed after dilute colloidal sol in be added be equivalent to SiO2The mineralizer of mole 0.1 ~ 0.5.
According to the method for the present invention, the preparation condition in step 2 is preferably by the gel of semisolid at 120 ~ 150 DEG C Crystallization 24 ~ 72 hours, and crystallization obtained solid product is calcined 10 ~ 20 hours at 550 DEG C, obtain the nano pure silicone of high-crystallinity ZSM-5 zeolite product.
According to the method for the present invention, the side known to those skilled in the art of aging method described in the step 1) Method.
According to the method for the present invention, washing drying means described in the step 2) is known to those skilled in the art Method.
According to the method for the present invention, various height that can be well known in the art without silicon source compound described in step 1) The solid silicon source or liquid silicon source of quality purity.It specifically, can be one or more of white carbon black, silica gel, silica solution.It is excellent It is selected as white carbon black and/or silica solution.
According to the method for the present invention, the quaternary ammonium base that template described in step 1) can be well known in the art Class can be specifically one of tetramethylammonium hydroxide, tetraethyl ammonium hydroxide and tetrapropyl hydrogen-oxygen ammonium salt solution or several Kind.Preferably tetraethyl ammonium hydroxide solution.
According to the method for the present invention, the adding manner of mineralizer described in step 1) is known to those skilled in the art Method.
According to the method for the present invention, the fluorochemical that mineralizer described in step 1) can be well known in the art. It specifically, can be one or more of sodium fluoride, potassium fluoride and ammonium fluoride, preferably ammonium fluoride.
According to the method for the present invention, crystallization process in step 2) crystallization process well known in the art.The crystallization mistake Journey is also possible to static crystallization process either dynamic crystallization.Preferably dynamic crystallization.
According to the method for the present invention, this method further includes that will wash obtained product after crystallization, is dry, 500 ~ 600 DEG C calcining 8 ~ 24 hours, preferably 550 DEG C calcine 10 ~ 20 hours, obtain high-crystallinity crystallinity nano pure silicone ZSM-5 boiling Stone.
Above-mentioned washing, the method for drying are known to those skilled in the art.After being washed 3 times for example, by using deionized water, It is 2 ~ 10 hours dry at 110 DEG C.Under normal circumstances, the amount of washing water used is 8 ~ 10 times of crystallizing kettle volume.
Below by way of specific embodiment, the present invention will be described in detail, but the present invention is not restricted to following implementations Example.
In following embodiment, the mean grain size of zeolite uses Scherrer equation by x-ray powder diffraction (XRD) (being write see " catalyst characterization " Yuan Weikang etc., publishing house of East China University of Science, publish for 2008) measurement；The opposite crystallization of zeolite Degree is measured using the industrial ZSM-5 zeolite that Catalyst Factory, Nankai Univ produces as external sample.
Reagent in following example 1 ~ 5, silicon source are purchased from Shanghai Shan Bo Industrial Co., Ltd., remaining reagent is purchased from traditional Chinese medicines collection Chemical reagent Co., Ltd of group.
The mole of template in following embodiment is with TMA+And/or TEA+And/or TPA+Meter, silicon source is with SiO2Meter.
Embodiment 1
The present embodiment is used to illustrate the preparation method of nano pure silicone ZSM-5 zeolite.
According to white carbon black A200(with SiO2Meter): tetraethyl ammonium hydroxide: water=1:0.3:8 molar ratio is sufficiently mixed, Temperature is to obtain Templated dilute hydrogel aging 2 hours under conditions of 30 DEG C.It is added into resulting hydrogel and is equivalent to silicon The NH of source mole 0.24F continues stirring 0.5 hour, obtains a kind of gel of semisolid.The semisolid gel that will finally obtain 140 DEG C crystallization 72 hours, and by crystallization obtained solid product calcining 550 DEG C calcine 10 hours, obtain product S1.Measurement should The relative crystallinity and average grain diameter of product S1, the size of microcrystal acquired through Scherrer equation is less than 100 nm, specific value It is listed in table 1.The XRD spectra of S1 referring to Fig. 1, by Highscore Plus fitting matching (JCPDS 00-037-0361,2004 Year updates), S1 is the pure silicon ZSM-5 zeolite with MFI structure.Embodiment 2
The present embodiment is used to illustrate the preparation method of nano pure silicone ZSM-5 zeolite.
According to silica solution (with SiO2Meter): tetraethyl ammonium hydroxide: water=1:0.15:6 molar ratio is sufficiently mixed, in temperature Degree is to obtain Templated dilute gel aging 3 hours under conditions of 20 DEG C.Into resulting dilute gel, addition is equivalent to silicon source and rubs The KF of your amount 0.3 continues stirring 1 hour, obtains a kind of gel of semisolid.Finally by obtained semisolid gel at 140 DEG C Crystallization 48 hours, and the calcining of crystallization obtained solid product is calcined 10 hours at 550 DEG C, obtain product S2.Measure product S2 Relative crystallinity and average grain diameter, the size of microcrystal acquired through Scherrer equation be listed in table less than 100 nm, specific value 1.By the XRD spectra of S2, S2 is the pure silicon ZSM-5 zeolite with MFI structure.
Embodiment 3
The present embodiment is used to illustrate the preparation method of nano pure silicone ZSM-5 zeolite.
According to white carbon black A200(with SiO2Meter): tetrapropylammonium hydroxide: water=1:0.2:9 molar ratio is sufficiently mixed, Temperature is to obtain Templated dilute gel aging 2 hours under conditions of 30 DEG C.It is added into resulting dilute gel and is equivalent to silicon source The NH of 0.2 molar ratio4F continues stirring 0.5 hour, obtains a kind of gel of semisolid.Finally obtained semisolid gel is existed 140 DEG C crystallization 48 hours, and by crystallization obtained solid product calcining 550 DEG C calcine 10 hours, obtain product S3.Measure the production The relative crystallinity and average grain diameter of product S3, the size of microcrystal acquired through Scherrer equation is less than 100 nm, specific value column In table 1.By XRD spectra it is found that S3 is the pure silicon ZSM-5 zeolite with MFI structure.
Embodiment 4
The present embodiment is used to illustrate the preparation method of nano pure silicone ZSM-5 zeolite.
According to silica gel (with SiO2Meter): tetramethylammonium hydroxide: water=1:0.3:6 molar ratio is sufficiently mixed, and is in temperature Aging 3 hours under conditions of 20 DEG C obtain Templated dilute gel.Into resulting dilute gel, addition is equivalent to silicon source 0.15 and rubs The KF of your ratio continues stirring 1 hour, obtains a kind of gel of semisolid.Finally by obtained semisolid gel in 140 DEG C of crystallization 48 hours, and the calcining of crystallization obtained solid product is calcined 10 hours at 550 DEG C, obtain product S4.Measure the phase of product S4 To crystallinity and average grain diameter, for the size of microcrystal acquired through Scherrer equation less than 100 nm, specific value is listed in table 1.It is logical The XRD spectra of Fig. 1 is crossed it is found that S4 is the pure silicon ZSM-5 zeolite with MFI structure.
Embodiment 5
The present embodiment is used to illustrate the preparation method of nano pure silicone ZSM-5 zeolite.
According to silica solution (with SiO2Meter): tetraethyl ammonium hydroxide: water=1:0.20:8 molar ratio is sufficiently mixed, in temperature Degree is to obtain Templated dilute gel aging 2 hours under conditions of 30 DEG C.It is added into resulting dilute gel and is equivalent to silicon source The NH of 0.2 molar ratio4F continues stirring 2 hours, obtains a kind of gel of semisolid.Finally obtained semisolid gel is existed 140 DEG C crystallization 72 hours, and by crystallization obtained solid product calcining 550 DEG C calcine 10 hours, obtain product S5.Measure the production The relative crystallinity and average grain diameter of product S5, the size of microcrystal acquired through Scherrer equation is less than 100 nm, specific value column In table 1.By XRD spectra it is found that S5 is the pure silicon ZSM-5 zeolite with MFI structure.
Comparative example 1
According to the synthetic method of the patent CN102602959B nano pure silicone ZSM-5 announced a kind of, the specific steps are as follows:
According to silester (with SiO2Meter): ammonium fluoride: water=1:0.01:4 molar ratio, ammonium fluoride is successive with silester It being added to the water and is thoroughly mixed, the pH of gained mixture is 7, later by the mixture under conditions of temperature is 25 DEG C, Ageing obtains Silica hydrogel in 24 hours, by resulting Silica hydrogel after 60 DEG C and 100 DEG C are separately dried 24 hours, it is ground into 400 ~ The silica gel particle of 200 mesh；By resulting silica gel particle (with SiO2Meter), template TPAOH and water is according to SiO2: TPAOH: water=1 : 0.5: 35 molar ratio after mixing, the dynamic crystallization 72 hours at a temperature of 120 DEG C, take out washing, 100 DEG C drying 6 hours Afterwards, it roasts 6 hours for 550 DEG C, obtains product Z1.The relative crystallinity and average grain size for measuring the sample, are as a result listed in table 1.By the XRD spectra of Z1 it is found that Z1 is pure silicon ZSM-5 zeolite.
Table 1
Comparative example 1 Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Relative crystallinity (100%) 99% 210.5% 152.3% 170.6% 160.4% 161.0%
Average grain diameter (nm) 35.1 76 65 28 70 56
Ageing time (h) 24 2 1 2 3 2
Aging crystallization total time-consuming (h) 96 74 49 50 51 74
It is by table 1 it is found that lower using the pure silicon ZSM-5 zeolite relative crystallinity of prior art secondary synthesis method preparation, and The relative crystallinity of the pure silicon ZSM-5 zeolite prepared using method provided by the invention is 150% or more, therefore, compared to existing Technology, method provided by the invention can go out nanoscale height knot by " one kettle way " simple one-step synthesis in a relatively short period of time The pure silicon ZSM-5 zeolite of brilliant degree.In addition, required aging crystallization time of the invention shortens 22 ~ 47 hours than existing methods, make Manufacturing cycle greatly shortens, these are all more advantageous to the industrialization of pure silicon ZSM-5.

Claims (8)

1. a kind of preparation method of high-crystallinity nano pure silicone ZSM-5 zeolite, which is characterized in that method includes the following steps:
1) silicon source is with SiO2Meter, according to silicon source: template: water molar ratio is that 1:0.05 ~ 0.5:2 ~ 12 are sufficiently mixed, and is in temperature Aging 0.5 ~ 5 hour under conditions of 20 ~ 70 DEG C, obtains Templated hydrogel, according to mineralizer and silicon source molar ratio be 0.05 ~ 0.5 mineralizer is added into hydrogel, continues stirring 0.2 ~ 2 hour, obtains a kind of gel of semisolid；
2) by obtained semisolid gel 110 ~ 170 DEG C crystallization 24 ~ 96 hours, and crystallization obtained solid product washed dry It is dry, it is calcined 8 ~ 24 hours at 500 ~ 600 DEG C, obtains pure silicon ZSM-5 zeolite.
2. according to the method described in claim 1, wherein, in step 1), silicon source: template: the molar ratio of water be 1:0.07 ~ 0.3:5~9。
3. the time is 1 ~ 5 small according to the method described in claim 1, wherein, in step 1), the aging temperature is 20 ~ 60 DEG C When.
4. according to the method described in claim 1, wherein, in step 1), according to mineralizer and silicon source molar ratio be 0.1 ~ 0.5 to Mineralizer is added in hydrogel, mixing time is 0.4 ~ 1 hour.
5. in step 2, the crystallization temperature is 120 ~ 150 DEG C according to the method described in claim 1, wherein, when crystallization Between be 24 ~ 72 hours, the calcination temperature of product is 500 ~ 550 DEG C, and calcination time is 10 ~ 20 hours.
6. method according to claim 1 or 2, wherein the silicon source is in white carbon black, solid-state silica gel and silica solution It is one or more of.
7. method according to claim 1 or 2, wherein the template is tetramethylammonium hydroxide, tetraethyl hydrogen-oxygen Change one or more of ammonium, tetrapropylammonium hydroxide solution.
8. method according to claim 1 or 4, wherein the mineralizer is sodium fluoride, in potassium fluoride, ammonium fluoride It is one or more of.
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CN113184875A (en) * 2021-06-09 2021-07-30 南京信息工程大学 Preparation method of all-silicon type short b-axis ZSM-5 zeolite molecular sieve
CN113368891A (en) * 2021-05-19 2021-09-10 天津大学 Preparation method of hollow molecular sieve catalyst and application of hollow molecular sieve catalyst in preparation of high-density aviation fuel by hydrogenation of polycyclic aromatic hydrocarbon
CN113398985A (en) * 2021-06-08 2021-09-17 湖北大学 Synthesis method of central crossed zeolite flake solid acid catalyst

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Application publication date: 20181211