CN102001681A - Method for synthesizing ZSM-5 zeolite - Google Patents
Method for synthesizing ZSM-5 zeolite Download PDFInfo
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- CN102001681A CN102001681A CN 201010546164 CN201010546164A CN102001681A CN 102001681 A CN102001681 A CN 102001681A CN 201010546164 CN201010546164 CN 201010546164 CN 201010546164 A CN201010546164 A CN 201010546164A CN 102001681 A CN102001681 A CN 102001681A
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- 239000010457 zeolite Substances 0.000 title claims abstract description 59
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 57
- 230000008025 crystallization Effects 0.000 claims abstract description 57
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 14
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000010189 synthetic method Methods 0.000 claims description 28
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 11
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- VJAXFMXUMKTBMO-UHFFFAOYSA-N trimethoxy-(2-methoxy-3-propyloxiran-2-yl)silane Chemical compound C(C)CC1C(O1)(OC)[Si](OC)(OC)OC VJAXFMXUMKTBMO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 229910004298 SiO 2 Inorganic materials 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 12
- 239000002808 molecular sieve Substances 0.000 description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- 241000275449 Diplectrum formosum Species 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- -1 phenylamino propyl Chemical group 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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Abstract
The invention relates to a method for synthesizing ZSM-5 zeolite with a multi-stage porous structure under the action of a silane coupling agent, and aims to provide the method for synthesizing the ZSM-5 zeolite, which has a simple crystallization process and low production cost, aiming at the defects of complex crystallization process and low production cost existing in the conventional process for synthesizing the ZSM-5 zeolite with multi-stage porous structure. The technical scheme of the invention is that: tetrapropyl ammonium bromide is used as a template agent, water glass is used as a silicon source and aluminum sulfate is used as an aluminum source; and a commercial silane coupling agent is directly added into the conventional ZSM-5 zeolite synthesis system. The method comprises the following steps of: (1) adding the silicon source into water and dissolving; (2) adding the silane coupling agent and stirring; (3) adding the template agent and the aluminum source; (4) adding an acid; (5) stirring the mixture obtained in the steps (1) to (4) and crystallizing; (6) filtering, washing and drying to obtain a template agent-containing product; and (7) drying the template agent-containing product and baking at the temperature of between 400 and 650 DEG C for 3 to 10 hours to obtain the zeolite product with multi-stage porous structure.
Description
Technical field
The present invention relates to a kind of synthetic method of ZSM-5 zeolite, particularly a kind of synthesizing under the silane coupling agent effect has the method for hierarchical porous structure ZSM-5 zeolite.
Background technology
Zeolite molecular sieve is the crystal aluminosilicate material that a class has regular microvoid structure, with its high-specific surface area, high absorption capacity, high hydrothermal stability and characteristics such as micropore canals with shape selective, all be widely used in fields such as petrochemical complex, refining of petroleum, fractionation by adsorption, the synthetic chemistry of zeolite molecular sieve and industrial application are subjected to the great attention of academia and industrial community all the time.
The catalytic active center of zeolite mainly is positioned at its micropore canals inside, and its duct size is generally between 0.3～1.0nm.The diffusion of molecule in micropore canals belongs to configuration diffusion (configurational diffusion), rate of diffusion is slower, the active centre of molecule from the zeolite crystal surface diffusion to crystals exists very strong restriction, and this just greatly reduces the effective rate of utilization of zeolite.The hierarchical porous structure zeolite generally refers to except that the zeolite micropore duct, also has the zeolite molecular sieve of mesopore orbit system.Mesoporous existence can improve the mass-transfer performance of zeolite greatly, and the catalyzed reaction that macromole is participated in can show good catalytic performance.
The ZSM-5 zeolite molecular sieve is the high-silica zeolite with two-dimentional ten-ring pore passage structure of the seventies in last century by the exploitation of U.S. Mobil company, be one of present of paramount importance molecular sieve catalytic material, be widely used in fields such as refining of petroleum, Coal Chemical Industry and fine chemistry industry.Synthetic ZSM-5 zeolite with hierarchical porous structure, the mass-transfer performance of raising molecular sieve, significant for the catalytic efficiency that improves the ZSM-5 zeolite.
Document (Nature Materials, 2006,5,718-723) reported a kind of synthetic method of hierarchical porous structure ZSM-5 zeolite, concrete is that the silane coupled cats product of employing is a template, directly synthesized hole wall by the mesoporous ZSM-5 zeolite that zeolite is formed, mesoporous aperture is adjustable by hydrothermal crystallizing, the silicone surfactant of employing partly is made up of long chain quaternary part and methoxy silane, and the centre is connected by the Si-C key.(Angewandte Chemie International Edition 2006,45 7603-7606) has reported that a kind of to adopt the polymkeric substance of silane coupledization be the method for the synthesising mesoporous ZSM-5 of mesoporous template to document.But the mesoporous template of silane coupledization that is adopted not is a commercially produced product, is that mesoporous zeolite of template preparation is faced with the preparation process complexity, production cost is crossed problems such as height with it.
Silane coupling agent is the silane that a class has organo-functional group, and it is widely used in the modification of macromolecular material.It of a great variety, available general formula Y (CH
2)
nSiX
3The expression (X is a methoxy or ethoxy, and Y is primary amine groups, quaternary ammonium group, chain alkyl etc.), in its molecule, have simultaneously can with the chemically combined reactive group of inorganic materials and with the chemically combined reactive group of organic materials.
U.S. Pat 5,194,410 have reported a kind of method of synthesizing the ZSM-5 zeolite molecular sieve under the organosilicon effect of quaternary ammonium salt functionalization.Organosilicon both as structure directing agent, provides part silicon source again in building-up process.Li Xiaotian etc. (SCI, 2000,21,683-685) also reported to be that structure directing agent has synthesized the ZSM-5 molecular sieve with the quaternary ammonium salt silane coupling agent.But this two portions work does not relate to the synthetic of hierarchical porous structure ZSM-5 zeolite.
People such as Serrano (Chemistry of Materials, 2006,18,2462-2464; 2009,21,641-654) the method for synthesis of nano ZSM-5 under a kind of silane coupling agent effect of report, this method is at first to make the pre-crystallization of synthetic system, and then adding silane coupling agent (as the phenylamino propyl trimethoxy silicane) continuation crystallization obtains the ZSM-5 molecular sieve with hierarchical porous structure of crystal grain less than 10nm.But the report that does not relate to pattern, to adopt expensive TPAOH (TPAOH) be template to this method in addition, adds silane coupling agent, crystallization process complexity in the middle of the crystallization process.
Summary of the invention
The objective of the invention is provides the synthetic method of the ZSM-5 zeolite that a kind of crystallization process is simple, production cost is low at having the existing crystallization process complexity of ZSM-5 zeolite of hierarchical porous structure, the weak point that production cost is high in existing synthesizing.
The technical scheme of the synthetic method of a kind of ZSM-5 zeolite of the present invention is: the synthetic method of ZSM-5 zeolite may further comprise the steps:
(1) the silicon source is added to the water dissolving;
(2) add silane coupling agent, stir;
(3) add template and aluminium source;
(4) add acid;
(5) after the mixture that step (1)-(4) obtain stirs, crystallization;
(6) obtain containing the product of template after filtration, washing, the drying;
(7) contain the product oven dry of template after, 400～650 ℃ of roastings promptly got in 3～10 hours has the hierarchical porous structure zeolite product.
In the synthetic method of above-mentioned ZSM-5 zeolite, the silicon source is a water glass.
In the synthetic method of above-mentioned ZSM-5 zeolite, template is 4-propyl bromide (TPABr).
In the synthetic method of above-mentioned ZSM-5 zeolite, the aluminium source is Tai-Ace S 150 (Al
2(SO
4)
318H
2O).
In the synthetic method of above-mentioned ZSM-5 zeolite, acid is sulfuric acid.
In the synthetic method of above-mentioned ZSM-5 zeolite, silane coupling agent is a kind of in aminopropyl triethoxysilane (APTES), aminopropyl trimethoxysilane (APTMS), (3-epoxy ethyl methoxy-propyl) Trimethoxy silane (GPTMS), the propyl-triethoxysilicane (PTES).
In the synthetic method of above-mentioned ZSM-5 zeolite, the reactant molar ratio scope of reaction system is: silane coupling agent: Si=0.025～0.1: 1, Na
2O: Si=0.05～0.1: 1, Al
2O
3: Si=0.01～0.025: 1, H
2O: Si=25: 1, TPABr: Si=0.2: 1.
In the synthetic method of above-mentioned ZSM-5 zeolite, in step (2), behind the adding silane coupling agent, stir more than 2 hours.
In the synthetic method of above-mentioned ZSM-5 zeolite, the time of stirring in step (5) is more than 2 hours.
In the synthetic method of above-mentioned ZSM-5 zeolite, carry out in autoclave in the crystallization described in the step (5), crystallization is finished at twice, directly carry out the crystallization second time after crystallization is finished for the first time, wherein, crystallization temperature is 100～150 ℃ for the first time, and crystallization time was less than 3 days; Crystallization temperature is 150～190 ℃ for the second time, and crystallization time is 1～10 day.
The ZSM-5 molecular sieve pattern that the present invention relates to is spherical, and has hierarchical porous structure.It is template that the present invention adopts 4-propyl bromide, be that silicon source, Tai-Ace S 150 are the aluminium source with water glass, the commercialization silane coupling agent directly joins in the synthetic system of ZSM-5 zeolite, synthesis material is simple and easy to, crystallization process is simple, and the ZSM-5 sample degree of crystallinity that obtains is higher, finds that simultaneously the adding of silane coupling agent can regulate the acidity of ZSM-5 zeolite.For the ZSM-5 zeolite molecular sieve for preparing hierarchical porous structure provides easy route of synthesis.
Description of drawings
Fig. 1 is embodiment 1 a sample powder X-ray diffractogram (XRD).
Fig. 2 is embodiment 1 sample scanning electron microscope microscope figure (SEM).
Fig. 3 is embodiment 1 sample-196 a ℃ following nitrogen adsorption isotherm.
Fig. 4 is embodiment 1 sample ammonia temperature programmed desorption(TPD) figure (NH
3-TPD).
Fig. 5 is embodiment 2 sample powder X-ray diffractograms (XRD).
Fig. 6 is embodiment 2 sample scanning electron microscope microscope figure (SEM).
Fig. 7 is embodiment 2 sample ammonia temperature programmed desorption(TPD) figure (NH
3-TPD).
Fig. 8 is embodiment 9 sample powder X-ray diffractograms (XRD).
Fig. 9 is embodiment 9 sample scanning electron microscope microscope figure (SEM).
Figure 10 is embodiment 9 samples-196 ℃ following nitrogen adsorption isotherm.
The specific examples mode
Below by some embodiment the synthetic method of a kind of ZSM-5 zeolite of the present invention is further described, but the present invention is not limited to these embodiment.
Embodiment 1
According to mole proportioning: 0.07Na
2O: SiO
2: 0.025Al
2O
3: 25H
2O: 0.2TPABr: 0.05APTES adds 9g water glass (Na successively in reactor
2O:10.6wt.%; SiO
2: 26.5wt.%), 6.4ml deionized water, 0.443g APTES, 2.1301g TPABr, 5.0g Al
2(SO
4)
318H
2O and 1.7g H
2SO
4(4.82mol/l), fully stir make gel mixture evenly after, 110 ℃ of following crystallization are 2 days earlier, again 180 ℃ of following crystallization 1 day, the crystallization product suction filtration, washing obtains white products after the drying.Sample was removed template in 6 hours 550 ℃ of following roastings.Fig. 1 is the x-ray diffractogram of powder (XRD) of embodiment 1 sample, and the XRD figure show sample has the MFI structure, and Fig. 2 is the SEM figure of embodiment 1 sample, and sample is spherical in shape, the about 5 μ m of diameter.Fig. 3 is the nitrogen adsorption isotherm under embodiment 1 sample-196 ℃, and it is at relative pressure P/P
0One hop is arranged, corresponding to N after being higher than 0.4
2The capillary condensation phenomenon of molecule in mesoporous, interpret sample has meso-hole structure.Fig. 4 is the NH of embodiment 1 sample
3-TPD figure has two peaks among the figure, correspond respectively to the desorption of weak acid and strong acidic site adsorb ammonia among the ZSM-5.
Embodiment 2
According to mole proportioning: 0.07Na
2O: SiO
2: 0.025Al
2O
3: 25H
2O: 0.2TPABr: 0.1APTES adds 9g water glass (Na successively in reactor
2O:10.6wt.%; SiO
2: 26.5wt.%), 6.4ml deionized water, 0.886g APTES, 2.130g TPABr, 5.0gAl
2(SO
4)
318H
2O and 1.9g H
2SO
4(4.82mol/l), fully stir make gel mixture evenly after, 110 ℃ of following crystallization are 2 days earlier, again 180 ℃ of following crystallization 7 days, the crystallization product suction filtration, washing obtains white products after the drying.Sample was removed template in 6 hours 550 ℃ of following roastings.Obtain XRD figure, SEM figure and the NH of product
3-TPD figure sees Fig. 5, Fig. 6 and Fig. 7 respectively.The synthetic sample has the MFI structure, and pattern is spherical, diameter between 16-20 μ m, NH
3Two peaks are arranged among-the TPD, correspond respectively to the desorption of weak acid and strong acidic site adsorb ammonia among the ZSM-5, obviously reduce with respect to strong acidic site quantity among the embodiment 1.
Embodiment 3
According to mole proportioning: 0.1Na
2O: SiO
2: 0.025Al
2O
3: 25H
2O: 0.2TPABr: 0.05APTES adds 9g water glass (Na successively in reactor
2O:10.6wt.%; SiO
2: 26.5wt.%), 6.4ml deionized water and 0.443g APTES stirred 3 hours, adds 2.1301g TPABr, 5.0g Al again
2(SO
4)
318H
2O and 1.5g H
2SO
4(4.82mol/l), treat that gel mixture stirs after, earlier 110 ℃ of following crystallization are 2 days, again 180 ℃ of following crystallization 1 day, the crystallization product suction filtration, washing obtains white products after the drying.Sample was removed template in 6 hours 550 ℃ of following roastings.Sample has the MFI structure, and spherical morphology, nitrogen adsorption characterize has meso-hole structure.
Embodiment 4
According to mole proportioning: 0.05Na
2O: SiO
2: 0.025Al
2O
3: 25H
2O: 0.2TPABr: 0.05APTES adds 9g water glass (Na successively in reactor
2O:10.6wt.%; SiO
2: 26.5wt.%), 6.4ml deionized water, 0.443g APTES, 2.1301g TPABr, 5.0g Al (SO
4)
318H
2O and 1.9gH
2SO
4(4.82mol/l), fully stir make gel mixture evenly after, 110 ℃ of following crystallization are 2 days earlier, again 180 ℃ of following crystallization 1 day, the crystallization product suction filtration, washing obtains white products after the drying.Sample was removed template in 6 hours 550 ℃ of following roastings.Sample has the MFI structure, and spherical morphology, nitrogen adsorption characterize has meso-hole structure.
Embodiment 5
According to mole proportioning: 0.07Na
2O: SiO
2: 0.025Al
2O
3: 25H
2O: 0.2TPABr: 0.025APTES adds 9g water glass (Na successively in reactor
2O:10.6wt.%; SiO
2: 26.5wt.%), 6.4ml deionized water, 0.221g APTES, 2.1301g TPABr, 5.0g Al
2(SO
4)
318H
2O and 1.9g H
2SO
4(4.82mol/l), fully stir make gel mixture evenly after, 110 ℃ of following crystallization are 2 days earlier, again 180 ℃ of following crystallization 1 day, the crystallization product suction filtration, washing obtains white products after the drying.Sample was removed template in 6 hours 550 ℃ of following roastings.Sample has the MFI structure, and spherical morphology, nitrogen adsorption characterize has meso-hole structure.
Embodiment 6
According to mole proportioning: 0.07Na
2O: SiO
2: 0.025Al
2O
3: 25H
2O: 0.2TPABr: 0.1APTES adds 9g water glass (Na successively in reactor
2O:10.6wt.%; SiO
2: 26.5wt.%), 6.4ml deionized water, 0.886g APTES, 2.1301g TPABr, 5.0g Al
2(SO
4)
318H
2O and 1.9g H
2SO
4(4.82mol/l), fully stir make gel mixture evenly after, 110 ℃ of following crystallization are 2 days earlier, again 180 ℃ of following crystallization 3 days, the crystallization product suction filtration, washing obtains white products after the drying.Sample was removed template in 6 hours 550 ℃ of following roastings.Sample has the MFI structure, and spherical morphology, nitrogen adsorption characterize has meso-hole structure.
Embodiment 7
According to mole proportioning: 0.07Na
2O: SiO
2: 0.025Al
2O
3: 25H
2O: 0.2TPABr: 0.1APTES adds 9g water glass (Na successively in reactor
2O:10.6wt.%; SiO
2: 26.5wt.%), 6.4ml deionized water, 0.886g APTES, 2.1301g TPABr, 5.0g Al
2(SO
4)
318H
2O and 1.9g H
2SO
4(4.82mol/l), fully stir make gel mixture evenly after, 110 ℃ of following crystallization are 2 days earlier, again 180 ℃ of following crystallization 4 days, the crystallization product suction filtration, washing obtains white products after the drying.Sample was removed template in 6 hours 550 ℃ of following roastings.Sample has the MFI structure, and spherical morphology, nitrogen adsorption characterize has meso-hole structure.
Embodiment 8
According to mole proportioning: 0.07Na
2O: SiO
2: 0.025Al
2O
3: 25H
2O: 0.2TPABr: 0.1APTMS adds 9g water glass (Na successively in reactor
2O:10.6wt.%; SiO
2: 26.5wt.%), 6.4ml deionized water, 0.718g APTMS, 2.1301g TPABr, 5.0g Al
2(SO
4)
318H
2O and 1.9g H
2SO
4(4.82mol/l), fully stir make gel mixture evenly after, 110 ℃ of following crystallization are 2 days earlier, again 180 ℃ of following crystallization 6 days, the crystallization product suction filtration, washing obtains white products after the drying.Sample was removed template in 6 hours 550 ℃ of following roastings.Sample has the MFI structure, and spherical morphology, nitrogen adsorption characterize has meso-hole structure.
Embodiment 9
According to mole proportioning: 0.07Na
2O: SiO
2: 0.025Al
2O
3: 25H
2O: 0.2TPABr: 0.05GPTMS adds 9g water glass (Na successively in reactor
2O:10.6wt.%; SiO
2: 26.5wt.%), 6.4ml deionized water, 0.473g GPTMS, 2.130g TPABr, 5.0gAl
2(SO
4)
318H
2O and 1.9gH
2SO
4(4.82mol/l), fully stir make gel mixture evenly after, 110 ℃ of following crystallization are 2 days earlier, again 180 ℃ of following crystallization 1 day, the crystallization product suction filtration, washing obtains white products after the drying.Sample was removed template in 6 hours 550 ℃ of following roastings.The XRD figure, SEM figure and the nitrogen adsorption desorption thermoisopleth that obtain product are seen Fig. 8, Fig. 9 and Figure 10 respectively.The XRD figure show sample has the MFI structure, and SEM figure show sample is spherical in shape, the about 1 μ m of diameter.One hop after being higher than 0.4, relative pressure P/P0 is arranged, corresponding to N among the nitrogen adsorption isotherm figure
2The capillary condensation phenomenon of molecule in mesoporous, interpret sample has meso-hole structure.
According to mole proportioning: 0.07Na
2O: SiO
2: 0.025Al
2O
3: 25H
2O: 0.2TPABr: 0.05PTES adds 9g water glass (Na successively in reactor
2O:10.6wt.%; SiO
2: 26.5wt.%), 6.4ml deionized water, 0.825g PTES, 2.130g TPABr, 5.0gAl
2(SO
4)
318H
2O and 1.9g H
2SO
4(4.82mol/l), fully stir make gel mixture evenly after, 110 ℃ of following crystallization are 2 days earlier, again 180 ℃ of following crystallization 4 days, the crystallization product suction filtration, washing obtains white products after the drying.Sample was removed template in 6 hours 550 ℃ of following roastings.Sample has the MFI structure, and spherical morphology, nitrogen adsorption characterize has meso-hole structure.
Claims (10)
1. the synthetic method of a ZSM-5 zeolite, it is characterized in that: the synthetic method of this ZSM-5 zeolite may further comprise the steps:
(1) the silicon source is added to the water dissolving;
(2) add silane coupling agent, stir;
(3) add template and aluminium source;
(4) add acid;
(5) after the mixture that step (1)-(4) obtain stirs, crystallization;
(6) obtain containing the product of template after filtration, washing, the drying;
(7) contain the product oven dry of template after, 400～650 ℃ of roastings promptly got in 3～10 hours has the hierarchical porous structure zeolite product.
2. according to the synthetic method of right 1 described ZSM-5 zeolite, it is characterized in that described silicon source is a water glass.
3. according to the synthetic method of right 1 or 2 described ZSM-5 zeolites, it is characterized in that described template is 4-propyl bromide (TPABr).
4. according to the synthetic method of right 1 or 2 described ZSM-5 zeolites, it is characterized in that described aluminium source is Tai-Ace S 150 (Al
2(SO
4)
318H
2O).
5. according to the synthetic method of right 1 or 2 described ZSM-5 zeolites, it is characterized in that described acid is sulfuric acid.
6. according to the synthetic method of right 1 or 2 described ZSM-5 zeolites, it is characterized in that described silane coupling agent is a kind of in aminopropyl triethoxysilane (APTES), aminopropyl trimethoxysilane (APTMS), (3-epoxy ethyl methoxy-propyl) Trimethoxy silane (GPTMS), the propyl-triethoxysilicane (PTES).
7. according to the synthetic method of right 1 or 2 described ZSM-5 zeolites, it is characterized in that in the synthetic method of this ZSM-5 zeolite that the reactant molar ratio scope of reaction system is: silane coupling agent: Si=0.025～0.1: 1, Na
2O: Si=0.05～0.1: 1, Al
2O
3: Si=0.01～0.025: 1, H
2O: Si=25: 1, TPABr: Si=0.2: 1.
8. according to the synthetic method of right 1 or 2 described ZSM-5 zeolites, after it is characterized in that in step (2), adding silane coupling agent, stir more than 2 hours.
9. according to the synthetic method of right 1 or 2 described ZSM-5 zeolites, it is characterized in that the time of stirring is more than 2 hours in step (5).
10. according to the synthetic method of right 1 or 2 described ZSM-5 zeolites, it is characterized in that in autoclave, carrying out in the crystallization described in the step (5), crystallization is finished at twice, directly carry out the crystallization second time after crystallization is finished for the first time, wherein, crystallization temperature is 100～150 ℃ for the first time, and crystallization time was less than 3 days; Crystallization temperature is 150～190 ℃ for the second time, and crystallization time is 1～10 day.
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