CN103073020A - Preparation method and application of hierarchical zeolite molecular sieve - Google Patents
Preparation method and application of hierarchical zeolite molecular sieve Download PDFInfo
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Abstract
The invention relates to a hierarchical zeolite molecular sieve and a preparation method and application thereof and belongs to the technical field of preparation and application of a catalyst, particularly the technical field of preparation and application of a zeolite molecular sieve catalyst. The invention provides a method for assembling silylation zeolite seed crystals under the hydrothermal condition to synthesize a hierarchical zeolite molecular sieve by using a cationic surfactant as a template. The method solves the difficult problem that a conventional cationic surfactant is unmatched with the zeolite template, so that hierarchical zeolite cannot be synthesized. The synthesized material realizes compounding of micropores and meso pores and is the hierarchical zeolite molecular sieve which is highly crystallized. Except for the advantages of micropore zeolite, the molecular sieve also has the advantages of meso pore material which has large aperture and is beneficial to macromolecule diffusion, and the like. The synthesized material has wide application prospect in the fields of petrochemical industry, coal chemical industry, fine chemical engineering and the like.
Description
Technical field
The present invention relates to a kind of hierarchical zeolite molecular sieve and its preparation method and application, belong to catalyzer preparation and applied technical field, specifically belong to preparation and the applied technical field of zeolite [molecular sieve.
Background technology
The hierarchical zeolite molecular sieve is owing to combine strongly-acid, highly selective and the high hydrothermal stability of micro-pore zeolite and the wide aperture of mesoporous material is conducive to the advantage of molecular diffusion, and receives investigator's concern always.
The method of synthetic hierarchical zeolite molecular sieve mainly contains: hard template method, soft template method and without template.Soft template method has simple to operate, structure and the acid characteristics such as controlled with respect to hard template method and has attracted many scholars' concern.Soft template method is template (tensio-active agent, silanized surface promoting agent and cation superpolymer) the Direct Hydrothermal crystallization that adds a certain amount of solubility in the synthetic zeolite precursor liquid, removes template through roasting and just can obtain hierarchical zeolite.Its structure can be come modulation by the add-on and the kind that change soft template.
Utilize the synthetic hierarchical zeolite molecular sieve of traditional cats product is world-famous puzzle always.Many scholar (Beck, J.S.et al, Chem.Mater.1994,6:1816-1821, Karlsson, A., Micropor.Mesopor.Mater.1999,27:181-192) attempt using the micro-pore zeolite directed agents, such as TPAOH (TPAOH) and mesoporous material template, add together in the synthetic liquid such as cetyl trimethylammonium bromide (CTAB), synthesize the hierarchical zeolite molecular sieve.But because TPAOH and CTAB are system rather than the synergy of a competition in building-up process, the material of last gained nearly all is the mixture of zeolite and unbodied mesoporous material.
Summary of the invention
The purpose of this invention is to provide and a kind ofly utilize conventional cats product to be the method for the synthetic hierarchical zeolite molecular sieve of template.
A kind of preparation method of hierarchical zeolite molecular sieve comprises the step of zeolite seed crystal solution preparation, the preparation of zeolite synthesis mother liquor, crystallization, also comprises the step of organosilane grafting to the zeolite seed crystal.
The technical solution adopted for the present invention to solve the technical problems is with the zeolite seed crystal silanization, can increase its hydrophobicity, thereby increase the reactive force of its Surfactant micella hydrophobic side, reduce to a certain extent the Competition of two kinds of directed agents, thereby better collaborative guiding is synthesized the hierarchical zeolite molecular sieve.
Preferred described with the step of organosilane grafting to the zeolite seed crystal in all technical schemes of the preparation method of hierarchical zeolite molecular sieve of the present invention, carry out as follows:
In zeolite seed crystal solution, add organosilane, stir 2～24h, 40～120 ℃ of silanization temperature, wherein the organosilane add-on is 0.005～0.5 times of silicon source amount, in molar content,
Wherein, described organosilane is vinyltriethoxysilane, vinyltrimethoxy silane, the 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, Union carbide A-162, ethyl triethoxysilane, propyl-triethoxysilicane, butyl triethoxyl silane, the propenyl triethoxyl silane, octyltri-ethoxysilane, phenyl ethoxy silane, hexadecyl triethoxyl silane, octadecyltriethoxy silane, the 3-chloropropyl triethoxysilane.
Among the preparation method of hierarchical zeolite molecular sieve of the present invention in the above-mentioned steps preferred organosilane add-on be 0.01～0.3 times of silicon source amount, more preferably 0.01～0.1 times of silicon source amount most preferably is 0.05 times of silicon source amount, in molar content.
The prior art of the preparation Si-Al zeolite molecular sieve that the preparation of zeolite seed crystal solution described in the preparation method of hierarchical zeolite molecular sieve of the present invention is known to those skilled in the art, the person skilled in the art can by silica alumina ratio, grain size etc. being required to determine selection and the consumption thereof of raw material, preferably prepare in all technical schemes of the present invention as follows:
Following raw material is got the raw materials ready in molar ratio silicon source: organic formwork agent: aluminium source or titanium source: water=1:0.01～1:0～0.2:5～200; Organic formwork agent, aluminium source or titanium source and water are mixed by proportioning, dropwise add the silicon source after stirring, in 40～120 ℃ of stirring 0～72h, get zeolite seed crystal solution,
Wherein, described silicon source is tetraethoxy, silicon sol, white carbon black or water glass; Described aluminium source is sodium metaaluminate, aluminum isopropylate, aluminum nitrate or Tai-Ace S 150; Described titanium source is tetrabutyl titanate or titanium tetrachloride; Described organic formwork agent is TPAOH.
Wherein, the known technology that is chosen as this area in silicon source, aluminium source and titanium source, the person skilled in the art can determine kind and the consumption thereof of raw material, preferred described silicon source is tetraethoxy (TEOS), silicon sol, white carbon black or water glass among the present invention; Described aluminium source is sodium metaaluminate, aluminum isopropylate (AIP), aluminum nitrate or Tai-Ace S 150; Described titanium source is tetrabutyl titanate or titanium tetrachloride.
Organic formwork agent is preferably conventional TPAOH (TPAOH) among the preparation method of hierarchical zeolite molecular sieve of the present invention.
The step of preferred described zeolite synthesis mother liquor preparation in all technical schemes of the preparation method of hierarchical zeolite molecular sieve of the present invention, carry out as follows:
The zeolite seed crystal of silanization joined in the cats product solution stir 0～24h, get the zeolite synthesis mother liquor, gained zeolite synthesis mother liquor proportioning is:
Silicon source: organic formwork agent: aluminium source or titanium source: Na
2O: organosilane: cats product: water=1:0.01～1:0～0.2:0～0.5:0.005～0.5:0～0.5:5～200.
Wherein, the amount of cats product be 0～0.5 times to silicon source amount, in molar content; Described cats product is chain alkyl trimethyl ammonium chloride or chain alkyl trimethylammonium bromide, and its chain alkyl carbon atom number is 12,14,16 or 18.
Preferred described crystallization steps in all technical schemes of the preparation method of hierarchical zeolite molecular sieve of the present invention, carry out as follows:
The zeolite synthesis mother liquor is carried out hydrothermal crystallizing, and crystallization temperature is 80～200 ℃, and crystallization time is 6～144h.
Those skilled in the art should know that the preparation method of hierarchical zeolite molecular sieve of the present invention further comprises the step of aftertreatment, comprises filtration washing, drying and roasting.Above-mentioned filtration washing, drying and roasting are the known technology of this area, the person skilled in the art can determine the processing condition of its operation steps and each step, preferred its carries out removing of template as follows among the present invention: maturing temperature is 300～800 ℃, roasting time 4～8h.
The further preferred following technical proposals of the preparation method of hierarchical zeolite molecular sieve of the present invention:
1. zeolite seed crystal solution preparation;
2. with the organosilane grafting to zeolite seed crystal, get the zeolite seed crystal of silanization;
3. the zeolite seed crystal with silanization joins in the cats product solution, gets the zeolite synthesis mother liquor;
4. the zeolite synthesis mother liquor is carried out hydrothermal crystallizing;
5. filtration washing, drying and roasting.
The preparation method of hierarchical zeolite molecular sieve of the present invention is preferred following technical proposals further:
1. following raw material is got the raw materials ready in molar ratio: silicon source: organic formwork agent: aluminium source or titanium source: water=1:0.01～1:0～0.2:5～200; Organic formwork agent, aluminium source or titanium source and water are mixed by proportioning, dropwise add the silicon source after stirring, in 40～120 ℃ of stirring 0～72h, get zeolite seed crystal solution;
2. in zeolite seed crystal solution, add organosilane, stir 2～24h, 40～120 ℃ of silanization temperature, wherein the organosilane add-on is 0.005～0.5 times of silicon source amount, in molar content;
3. the zeolite seed crystal of silanization is joined in the cats product solution and stir 0～24h, get the zeolite synthesis mother liquor;
4. the zeolite synthesis mother liquor is carried out hydrothermal crystallizing, crystallization temperature is 80～200 ℃, and crystallization time is 6～144h;
5. filtration washing, drying and roasting.
Another object of the present invention provides the hierarchical zeolite molecular sieve by the aforesaid method preparation, and is used for the synthetic of 2,6-dimethylnaphthalene take it as catalyzer.
With the hierarchical zeolite molecular sieve of gained of the present invention by with NH
4NO
3Solution carries out ammonium exchange system and gets Hydrogen ZSM-5 catalyzer, then makes beaded catalyst through shaping and roasting, fragmentation.
Among the present invention preferred its hierarchical zeolite molecular sieve by with NH
4NO
3Solution carries out the ammonium exchange at 80 ℃ and makes Hydrogen ZSM-5 catalyzer 3 times, is sieved to 20～40 order particles behind shaping and roasting.
A kind of 2, the preparation method of 6-dimethylnaphthalene is to prepare 2,6-dimethylnaphthalene catalyzed reaction take the 2-methylnaphthalene as raw material through methanol alkylation, and catalyst system therefor is above-mentioned Hydrogen ZSM-5 hierarchical zeolite molecular sieve.
The above-mentioned 2-of utilization methylnaphthalene prepares preferred its of 2,6-dimethylnaphthalene catalyzed reaction to carry out at continuous fixed-bed reactor, and catalytic reaction condition is: 300～500 ℃ of temperature, pressure 0.1～10MPa, 2-methylnaphthalene air speed: 0.2～2h
-1
The invention has the beneficial effects as follows: for overcoming the Competition between micropore directed agents and mesoporous directed agents, the present invention improves the hydrophobicity of crystal seed by the crystal seed liquid of preparation silanization, thereby increase the reactive force of its Surfactant micella hydrophobic side, reduce to a certain extent the Competition of two kinds of directed agents, thereby better collaborative guiding is synthesized the hierarchical zeolite molecular sieve, this molecular sieve also possesses the mesoporous material aperture and is conducive to greatly the advantages such as solid tumor except having the micro-pore zeolite advantage.Utilize traditional cats product to be the synthetic hierarchical zeolite of template, synthesize the characteristics that hierarchical zeolite has cheapness, is easy to get with respect to other soft template, this material is with a wide range of applications in fields such as petrochemical complex, Coal Chemical Industry and fine chemistry industries, especially in synthetic 2, the 6-dimethylnaphthalene process of 2-methylnaphthalene alkylation, have higher catalytic activity and long life-span.
Description of drawings
Accompanying drawing 6 width of cloth of the present invention,
Fig. 1 is embodiments of the invention 1 ZSM-5 zeolite with multilevel pore canals XRD figure.
Fig. 2 is embodiments of the invention 1 ZSM-5 zeolite with multilevel pore canals N
2The adsorption/desorption graphic representation.
Fig. 3 is the graph of pore diameter distribution of embodiments of the invention 1 ZSM-5 zeolite with multilevel pore canals.
Fig. 4 is embodiments of the invention 1 ZSM-5 zeolite with multilevel pore canals SEM figure.
Fig. 5 is that Comparative Examples 1 of the present invention is without the XRD figure of the directly synthetic prepared sample of pre-silanization.
Fig. 6 is that Comparative Examples 1 of the present invention is without the SEM figure of the directly synthetic prepared sample of pre-silanization.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Embodiment 1
According to proportioning SiO
2: Al
2O
3: TPAOH:H
2O:=1:0.02:0.25:25 disposes solution, and concrete steps are as follows: with 8.14g TPAOH, 11.90g H
2O and 0.33g aluminum isopropylate are configured to solution, stir, and dropwise add 8.57gTEOS, stir 18h in 80 ℃ of low temperature and prepare crystal seed, add 0.05 times to SiO again
2The vinyltriethoxysilane of molar content (VTES) continues at 80 ℃ of low temperature and stirs 6h so that the crystal seed silanization gets final product to get the silanization seed-solution.With 0.05 times to SiO
2The CTAB(cetyl trimethylammonium bromide of molar content) and 0.19g NaOH join in the 39.2g water.Then the silanization seed-solution is dropwise joined in the CTAB solution, final proportioning is SiO
2: Al
2O
3: TPAOH:Na
2O:H
2O:VTES:CTAB is 1:0.02:0.25:0.06:80:0.05:0.05, continue to stir in the teflon-lined Hydrothermal Synthesis still of packing into behind the 4h, in 150 ℃ of hydrothermal crystallizing 72h, obtain product after filtration, washing and 550 ℃ of roasting 4h remove template and can make multistage pore canal ZSM-5.XRD spectra can be found out the structure for MFI, the SEM photo can find out that institute's synthetic zeolite is particle and the surface irregularity about 500nm, and the nitrogen absorption result is indicated as IV type thermoisopleth, and pore size distribution is about 2.4nm, illustrate to have meso-hole structure, shown in Fig. 1～4.
Embodiment 2
The concentration that changes CTAB is about to 0.03 times to SiO
2The CTAB of molar content joins 39.2g water, and other synthesis step and raw material are analogous to embodiment 1 can make multistage pore canal ZSM-5.
Embodiment 3
Change synthetic liquid of hydrothermal crystallizing time in 150 ℃ of hydrothermal crystallizing 48h.Other synthesis step and raw material are analogous to embodiment 1 can make multistage pore canal ZSM-5.
Embodiment 4
The content that changes VTES namely adds 0.1 times to SiO
2The vinyltriethoxysilane of molar content.Other synthesis step and raw material are analogous to embodiment 1 can make multistage pore canal ZSM-5.
Change kinds of surfactants, namely dispose octadecyl trimethyl ammonium chloride (OTAC) solution: with 0.05 times to SiO
2The OTAC of molar content joins in the 39.2g water.Other synthesis step and raw material are analogous to embodiment 1 can make multistage pore canal ZSM-5.
Embodiment 6
Change the organosilane kind, namely add 0.05 times to SiO
2The 3-aminopropyl triethoxysilane of molar content, preparation silanization crystal seed.Other synthesis step is analogous to embodiment 1, makes multistage pore canal ZSM-5.
Embodiment 7
According to proportioning SiO
2: TPAOH:H
2O:=1:0.25:25 disposes seed-solution, and other synthesis step and raw material are analogous to embodiment 1 can make multistage pore canal Silicate-1.
Embodiment 8
Be the NH of 1M with the sample concentration of embodiment 1～3
4NO
3Solution carries out ammonium exchange three times in 80 ℃, drying and roasting gets Hydrogen ZSM-5 catalyzer, then after moulding, 500 ℃ of roastings were crushed to 20～40 orders in 4 hours, be used for 2-methylnaphthalene (2-MN) and synthetic 2, the 6-dimethylnaphthalene of methanol alkylation (2,6-DMN) in the reaction.The mass space velocity of 2-MN is 0.5h
-1, temperature of reaction is 400 ℃, pressure is normal pressure.Result such as table 1.The result shows that the reactive behavior of multistage pore canal ZSM-5 and stability all are better than conventional micropore ZSM-5.
Table 1 evaluating catalyst
Comparative Examples 1
According to proportioning SiO
2: Al
2O
3: TPAOH:Na
2O:H
2O:CTAB=1:0.02:0.25:0.06:80:0.05 disposes solution, does not namely add organosilane, omits low temperature and stirs preparation silanization seed crystal process.Synthesis step is as follows: with TPAOH, and NaOH, H
2O, AIP and CTAB are configured to solution, stir, dropwise add again TEOS, behind the stirring at room 28h, change over to again in the teflon-lined Hydrothermal Synthesis still, in 150 ℃ of hydrothermal crystallizing 72h, obtain product after filtration, washing and roasting remove template and get final product to get the sample of preparation.XRD spectra can be found out the structure for MFI, and as shown in Figure 5, but SEM can find out and be amorphous and mixture zeolite crystal, as shown in Figure 6.
Comparative Examples 2
Get with the commercial micropore ZSM-5 catalyzer (Tianjin Nankai university catalyst plant) of example 1～3 identical silica alumina ratio be used for 2-methylnaphthalene (2-MN) and synthetic 2, the 6-dimethylnaphthalene of methanol alkylation (2,6-DMN) in the reaction.Shaping of catalyst and reaction conditions are analogous to embodiment 8.
Claims (10)
1. the preparation method of a hierarchical zeolite molecular sieve comprises it is characterized in that the step of the preparation of zeolite seed crystal solution, the preparation of zeolite synthesis mother liquor, crystallization: also comprise the step of organosilane grafting to the zeolite seed crystal.
2. method according to claim 1 is characterized in that: described with the step of organosilane grafting to the zeolite seed crystal, carry out as follows:
In zeolite seed crystal solution, add organosilane, stir 2～24h, 40～120 ℃ of silanization temperature, wherein the organosilane add-on is 0.005～0.5 times of silicon source amount, in molar content,
Wherein, described organosilane is vinyltriethoxysilane, vinyltrimethoxy silane, the 3-aminopropyl triethoxysilane, 3-aminopropyl trimethoxysilane, Union carbide A-162, ethyl triethoxysilane, propyl-triethoxysilicane, butyl triethoxyl silane, the propenyl triethoxyl silane, octyltri-ethoxysilane, phenyl ethoxy silane, hexadecyl triethoxyl silane, octadecyltriethoxy silane, the 3-chloropropyl triethoxysilane.
3. method according to claim 1 is characterized in that: the step of described zeolite seed crystal solution preparation, carry out as follows:
Following raw material is got the raw materials ready in molar ratio silicon source: organic formwork agent: aluminium source or titanium source: water=1:0.01～1:0～0.2:5～200; Organic formwork agent, aluminium source or titanium source and water are mixed by proportioning, dropwise add the silicon source after stirring, in 40～120 ℃ of stirring 0～72h, get zeolite seed crystal solution,
Wherein, described silicon source is tetraethoxy, silicon sol, white carbon black or water glass; Described aluminium source is sodium metaaluminate, aluminum isopropylate, aluminum nitrate or Tai-Ace S 150; Described titanium source is tetrabutyl titanate or titanium tetrachloride; Described organic formwork agent is TPAOH.
4. method according to claim 1 is characterized in that: the step of described zeolite synthesis mother liquor preparation, carry out as follows:
The zeolite seed crystal of silanization joined in the cats product solution stir 0～24h, get the zeolite synthesis mother liquor, gained zeolite synthesis mother liquor proportioning is:
Silicon source: organic formwork agent: aluminium source or titanium source: Na
2O: organosilane: cats product: water=1:0.01～1:0～0.2:0～0.5:0.005～0.5:0～0.5:5～200.
Wherein, the amount of cats product be 0～0.5 times to silicon source amount, in molar content; Described cats product is chain alkyl trimethyl ammonium chloride or chain alkyl trimethylammonium bromide, and its chain alkyl carbon atom number is 12,14,16 or 18.
5. method according to claim 1, it is characterized in that: described crystallization steps, carry out as follows: the zeolite synthesis mother liquor is carried out hydrothermal crystallizing, and crystallization temperature is 80～200 ℃, and crystallization time is 6～144h.
6. the described method of arbitrary claim according to claim 1～5, it is characterized in that: the preparation method of described hierarchical zeolite molecular sieve comprises following processing step:
1. following raw material is got the raw materials ready in molar ratio: silicon source: organic formwork agent: aluminium source or titanium source: water=1:0.01～1:0～0.2:5～200; Organic formwork agent, aluminium source or titanium source and water are mixed by proportioning, dropwise add the silicon source after stirring, in 40～120 ℃ of stirring 0～72h, get zeolite seed crystal solution;
2. in zeolite seed crystal solution, add organosilane, stir 2～24h, 40～120 ℃ of silanization temperature, wherein the organosilane add-on is 0.005～0.5 times of silicon source amount, in molar content;
3. the zeolite seed crystal of silanization is joined in the cats product solution and stir 0～24h, get the zeolite synthesis mother liquor;
4. the zeolite synthesis mother liquor is carried out hydrothermal crystallizing, crystallization temperature is 80～200 ℃, and crystallization time is 6～144h;
5. filtration washing, drying and roasting.
7. hierarchical zeolite molecular sieve by the preparation of the described method of the arbitrary claim of claim 1～6.
8. Hydrogen ZSM-5 hierarchical zeolite molecular sieve, it is characterized in that: described Hydrogen ZSM-5 hierarchical zeolite molecular sieve prepares as follows: with hierarchical zeolite molecular sieve claimed in claim 7 by with NH
4NO
3Solution carries out ammonium exchange system and gets Hydrogen ZSM-5 catalyzer, then makes beaded catalyst through shaping and roasting, fragmentation.
9. one kind 2, the preparation method of 6-dimethylnaphthalene, it is characterized in that: described preparation method is for to prepare 2 take the 2-methylnaphthalene as raw material through methanol alkylation, 6-dimethylnaphthalene catalyzed reaction, and catalyst system therefor is Hydrogen ZSM-5 hierarchical zeolite molecular sieve as claimed in claim 8.
10. according to claim 92, the preparation method of 6-dimethylnaphthalene is characterized in that: described catalyzed reaction is carried out at continuous fixed-bed reactor, and catalytic reaction condition is: 300～500 ℃ of temperature, pressure 0.1～10MPa, 2-methylnaphthalene air speed: 0.2～2h
-1
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| EA034181B1 (en) * | 2013-08-05 | 2020-01-15 | Аркема Франс | Zeolites with hierarchical porosity |
| WO2015019013A3 (en) * | 2013-08-05 | 2015-04-09 | Ceca S.A. | Zeolites with hierarchical porosity |
| FR3009300A1 (en) * | 2013-08-05 | 2015-02-06 | Ceca Sa | ZEOLITHES HIERARCHISED POROSITY |
| US10106429B2 (en) | 2013-08-05 | 2018-10-23 | Arkema France | Method of making zeolites with hierarchical porosity |
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