CN102049285A - Multistage pore-structure molecular sieve catalyst and preparation method thereof - Google Patents
Multistage pore-structure molecular sieve catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a multistage pore-structure molecular sieve, particularly discloses a ZSM-5 zeolite molecular sieve catalyst, relating to the field of inorganic materials and catalysts. The ZSM-5 type zeolite molecular sieve has grain size between 0.1 micrometer and 20 micrometers and comprises a microcellular structure and a mesoporous structure, wherein the microcellular structure has the aperture of 0.5-2 nanometers, and the mesoporous structure has the aperture of 2-15 nanometers; and the mole ratio of SiO2/Al2O3 is 30-500. A preparation method comprises the following steps of: directly adding a high molecular polymer polyaniline to a molecular sieve original solution by taking an organic template agent tetrapropylammonium bromide, silicic acids and aluminum salt as raw materials; synthesizing the ZSM-5 zeolite molecular sieve by adopting a hydro-thermal method; crystallizing, and then baking to remove the organic template agent and the polyaniline.
Description
Technical field
The present invention relates to inorganic material and catalyst field, be specially a kind of hierarchical porous structure nano molecular sieve catalyst and preparation method thereof.
Background technology
The scientist Argauer of U.S. Mobil company in 1972 and Landelt are with four propylamine (Pr
4NCl or Pr
4NOH) do the template agent at Na
2O:Al
2O
3: 24.2SiO
2: 14.4Pr
4OH:410H
2120 ℃ of following crystallization of O system obtain first important member ZSM-5 of " Pentasil " family.Because type ZSM 5 molecular sieve has unique microcellular structure, distinctive shape selective, high silica alumina ratio and and the characteristic of oleophilic drainage, have the high characteristics of thermostable type and catalytic activity simultaneously, so the ZSM-5 molecular sieve becomes one of present most important molecular sieve catalytic material, be widely used in catalytic fields such as PETROLEUM PROCESSING, Coal Chemical Industry and fine chemistry industry.But because the aperture of micro porous molecular sieve is less, the bulky molecular catalysis reaction is restricted, more and more can not satisfies the needs of fine chemistry industry reaction in recent years, thereby, limited the commercial Application of micro porous molecular sieve to a great extent.
The ZSM-5 molecular sieve of present industrial use mostly is to be of a size of several microns big crystal grain zeolite, is subjected to the restriction that its crystal grain is big, the duct is long and narrow, and big molecule is bigger at the intracrystalline diffusional resistance, more and more can not satisfy the needs of fine chemistry industry reaction in recent years.And the molecular sieve of preparation hierarchical porous structure can reduce the diffusional resistance of organic macromolecule, improve diffusion and ponder over, thus the catalytic performance of raising molecular sieve, so the molecular sieve of preparation hierarchical porous structure has very important significance.
In order to overcome the diffusion-restricted of reactant and product, the research for the molecular sieve of hierarchical porous structure has in recent years caused extensive concern.People mainly adopt following several method preparation to contain the ZSM-5 molecular sieve of hierarchical porous structure.
Patent CN 101723403A discloses the preparation method of the compound ZSM-5 zeolitic material in a kind of mesoporous and the multistage hole of micropore, it is characterized in that in the original mixed gel of molecular sieve, adding the polysaccharide compound or derivatives thereof as mesoporous pore creating material, in crystal growing process, can wrap up pore creating material, remove to make behind the pore creating material through roasting and contain little mesoporous molecular sieve that has, its mesoporous scope is at 5～100nm, mesoporous less, and mesoporous size is subjected to the restriction of pore creating material granular size.
Patent CN 101269819A with SBA-15 as the silicon source with sucrose clog mesoporous in, the hole wall with SBA-15 is converted into the ZSM-5 crystal structure of molecular sieve then.Contain order mesoporous molecular sieve though the method has made, still contain SBA-15 in the crystal, and operating procedure is more loaded down with trivial details.
Patent CN 1596150A has reported and a kind ofly will contain the molecular sieve carried on the inorganic oxide carrier that contains mesopore of micropore, thereby contained the material of mesopore and micropore simultaneously.The method can make the molecular sieve with perfect apertures size, and metal oxide can choose wantonly, enlarges the catalytic field of molecular sieve, but the method technology is also comparatively complicated.
Summary of the invention
The present invention aims to provide a kind of have mesoporous and hierarchical porous structure molecular sieve catalyst micropore.
Another object of the present invention provides above-mentioned Preparation of catalysts method.
Be realization the object of the invention,
(1) silicic acid, organic formwork agent, NaOH or potassium hydroxide is soluble in water, form B liquid; Aluminium salt, polyaniline and water are mixed, and the pH value is adjusted to 0～1, obtain A liquid;
Silicic acid and aluminium salt are converted into SiO respectively
2And Al
2O
3, SiO in the reaction system
2, Al
2O
3, NaOH or potassium hydroxide, organic formwork agent mol ratio be 1: 0.01～0.5: 0.1～2.5: 0.1～5; SiO
2With the amount ratio of polyaniline be 1mol: 0.1～50g;
Preferred, SiO in the reaction system
2, Al
2O
3, NaOH or potassium hydroxide, organic formwork agent mol ratio be 1: 0.01～0.05: 0.5～2.5: 0.1～5; SiO
2With the amount ratio of polyaniline be 1mol: 1～20g;
Described organic formwork agent is preferably n-butylamine, ethylenediamine, 4-propyl bromide or TPAOH, and described aluminium salt is preferably aluminum sulfate, aluminium chloride or sodium aluminate;
Preferred, the content of B liquid mesosilicic acid is 0.5～2mol/L; Al in the described A liquid
2O
3Content be 0.05～0.2mol/L; Available 60wt%～98wt% concentrated sulfuric acid is adjusted into 0～1 with A liquid pH value;
(2) under agitation the B drop is added in the A liquid, forms gel; The volume ratio of described A liquid and B liquid is preferably 1: 5～and 20;
Stirred 1～5 hour, and 20～100 ℃ of following ageings after 2～8 hours, 140～180 ℃ of following crystallization 1～100 hour;
More preferably, the ageing temperature is 50～70 ℃, and digestion time is 2～5 hours; Crystallization temperature is 150～180 ℃, and crystallization time is 10～80 hours;
(3) product after the crystallization is separated, get precipitation and wash to pH value be 9～10, dryly then removes organic formwork agent and high molecular polymer polyaniline, thereby obtains the hierarchical porous structure molecular sieve catalyst at 400～700 ℃ of following roasting 2～6h.
More preferably, dry temperature is 100～120 ℃, and sintering temperature is 500～700 ℃, and roasting time is 3～5 hours.
By the preparation-obtained hierarchical porous structure molecular sieve catalyst of said method, be ZSM-5 type zeolite molecular sieve catalyst, have micropore and mesoporous hierarchical porous structure simultaneously.Wherein the grain graininess of molecular sieve is between 0.1～20 μ m, SiO
2/ Al
2O
3Mol ratio is 30～500; The aperture of microcellular structure is 0.5～2nm on the hierarchical porous structure molecular sieve catalyst; The aperture of meso-hole structure is 2～15nm.
SiO
2/ Al
2O
3The mol ratio preferable range is 30～100, and grain graininess microballoon granularity is 1～10 μ m, and the aperture of meso-hole structure is 2～10nm.This catalyst can be used for benzene and ethene prepares in the cinnamic industrial production.
Hierarchical porous structure molecular sieve catalyst provided by the invention is a kind of catalyst that is used for macromolecular reaction of high stability, and molecular sieve is formed by the granule accumulation has mesoporous hierarchical porous structure.With organic formwork agent 4-propyl bromide, silicic acid and aluminium salt is raw material, and the high molecular polymer polyaniline is directly added in the original solution of molecular sieve, adopts the synthetic ZSM-5 molecular sieve of hydro-thermal method; By between Si-OH hydrogen bond action takes place in N-H and the gel on the polyaniline molecule chain, be connected with the molecular sieve surface thus, organic formwork agent and polyaniline are removed in roasting after the crystallization.
By the guide effect of high molecular polymer as the second template agent, can form the catalyst that not only has micropore but also have mesoporous hierarchical porous structure, overcome of the restriction of zeolite molecular sieve micropore to its catalytic performance; Simultaneously, the mesoporous specific area that increases catalyst obtains the catalytic reaction high conversion.
The specific embodiment
Embodiment 1
(1) silicic acid 7.80g (0.1mol), NaOH 2.50g (0.0625mol), 4-propyl bromide 2.66g (0.01mol) and water 100ml are mixed into B liquid; With aluminum sulfate (Al
2(SO
4)
318H
2O) 0.66g (1mmol), 90wt% concentrated sulfuric acid 1ml, polyaniline 0.4g and water 10ml are mixed into A liquid, and the pH value is 0～1;
(2) under agitation the B drop is added in the A liquid, stirs 3h at normal temperatures, make into even gel; Reactant mixture adds in the synthesis reaction vessel, at 50 ℃ of following ageing 4h, at 150 ℃ of following crystallization 48h, makes it crystallization under static state;
(3) crystallization fully after, with the product centrifugation, and spend deionised water to pH be 9～10,110 ℃ of dryings, and remove 4-propyl bromide and polyaniline, thereby obtain average crystal grain diameter 3 μ m, SiO at 500 ℃ of roasting 3h
2/ Al
2O
3Mol ratio is 100 ZSM-5 type hierarchical porous structure molecular sieve catalyst A.Wherein the meso-hole structure aperture is 2～10nm, and the aperture of microcellular structure is 0.5～2nm.
Embodiment 2
(1) silicic acid 7.80g (0.1mol), NaOH 2.50g (0.0625mol), 4-propyl bromide 2.66g (0.01mol) and water 100ml are mixed into A liquid, aluminum sulfate 1.32g (2mmol), 70wt% concentrated sulfuric acid 1.5ml, polyaniline 0.6g and water 10ml are mixed into A liquid, and the pH value is 0～1;
(2) under agitation the B drop is added in the A liquid, stirs 3h at normal temperatures, make into even gel; Reactant mixture adds in the synthesis reaction vessel, at 60 ℃ of following ageing 4h, at 160 ℃ of following crystallization 48h, makes it crystallization under static state;
(3) crystallization fully after, with the product centrifugation, and spend deionised water to pH be 9～10,110 ℃ of dryings, and remove 4-propyl bromide and polyaniline, thereby obtain average crystal grain diameter 2.5 μ m, SiO at 500 ℃ of roasting 3h
2/ Al
2O
3Mol ratio is 50 ZSM-5 type hierarchical porous structure molecular sieve catalyst B.Wherein the meso-hole structure aperture is 2～10nm, and the aperture of microcellular structure is 0.5～2nm.
Embodiment 3
(1) silicic acid 7.80g (0.1mol), NaOH 2.50g (0.0625mol), 4-propyl bromide 2.66g (0.01mol) and water 100ml are mixed into B liquid, aluminum sulfate 0.66g (1mmol), 95wt% concentrated sulfuric acid 1ml, polyaniline 0.5g and water 10ml are mixed into A liquid, and the pH value is 0～1;
(2) under agitation the B drop is added in the A liquid, stirs 3h at normal temperatures, make into even gel; Reactant mixture adds in the synthesis reaction vessel, at 60 ℃ of following ageing 3h, at 170 ℃ of following crystallization 24h, makes it crystallization under static state;
(3) crystallization fully after, with the product centrifugation, and spend deionised water to pH be 9～10,110 ℃ of dryings, and remove 4-propyl bromide and polyaniline, thereby obtain average crystal grain diameter 2.8 μ m, SiO at 500 ℃ of roasting 4h
2/ Al
2O
3Mol ratio is 100 ZSM-5 type hierarchical porous structure molecular sieve catalyst C.Wherein the meso-hole structure aperture is 2～10nm, and the aperture of microcellular structure is 0.5～2nm.
Embodiment 4
(1) silicic acid 4.68g (0.06mol), NaOH 2.50g (0.0625mol), 4-propyl bromide 2.66g (0.01mol) and water 100ml are mixed into B liquid, aluminum sulfate 0.66g (1mmol), 65wt% concentrated sulfuric acid 1.5ml, polyaniline 0.5g and water 10ml are mixed into A liquid, and the pH value is 0～1;
(2) under agitation the B drop is added in the A liquid, stirs 3h at normal temperatures, make into even gel; Reactant mixture adds in the synthesis reaction vessel, at 50 ℃ of following ageing 3h, at 170 ℃ of following crystallization 12h, makes it crystallization under static state;
(3) crystallization fully after, with the product centrifugation, and spend deionised water to pH be 9～10,110 ℃ of dryings, and remove 4-propyl bromide and polyaniline, thereby obtain average crystal grain diameter 2 μ m, SiO at 500 ℃ of roasting 3h
2/ Al
2O
3Mol ratio is 60 ZSM-5 type hierarchical porous structure molecular sieve catalyst D.Wherein the meso-hole structure aperture is 2～10nm, and the aperture of microcellular structure is 0.5～2nm.
Embodiment 5
(1) silicic acid 2.34g (0.03mol), NaOH 2.50g (0.0625mol), 4-propyl bromide 2.66g (0.01mol) and water 100ml are mixed into B liquid, aluminum sulfate 0.66g (1mmol), 80wt% concentrated sulfuric acid 1ml, polyaniline 0.5g and water 10ml are mixed into A liquid, and the pH value is 0～1;
(2) under agitation the B drop is added in the A liquid, stirs 3h at normal temperatures, make into even gel; Reactant mixture adds in the synthesis reaction vessel, at 60 ℃ of following ageing 3h, at 170 ℃ of following crystallization 24h, makes it crystallization under static state;
(3) crystallization fully after, with the product centrifugation, and spend deionised water to pH be 9～10,110 ℃ of dryings, and remove 4-propyl bromide and polyaniline, thereby obtain average crystal grain diameter 1.5 μ m, SiO at 500 ℃ of roasting 3h
2/ Al
2O
3Mol ratio is 30 ZSM-5 type hierarchical porous structure molecular sieve catalyst E.Wherein the meso-hole structure aperture is 2～10nm, and the aperture of microcellular structure is 0.5～2nm.
Embodiment 6
(1) silicic acid 7.8g (0.1mol), NaOH 2.50g (0.0625mol), 4-propyl bromide 2.66g (0.01mol) and water 100ml are mixed into B liquid; Aluminum sulfate 0.66g (1mmol), 75wt% concentrated sulfuric acid 1.5ml, polyaniline 0.5g and water 10ml are mixed into A liquid, and the pH value is 0～1;
(2) under agitation the B drop is added in the A liquid, stirs 3h at normal temperatures, make into even gel; Reactant mixture adds in the synthesis reaction vessel, at 60 ℃ of following ageing 3h, at 170 ℃ of following crystallization 72h, makes it crystallization under static state;
(3) crystallization fully after, with the product centrifugation, and spend deionised water to pH be 9-10,110 ℃ of dryings, and remove 4-propyl bromide and polyaniline, thereby obtain average crystal grain diameter 2 μ m, SiO at 500 ℃ of roasting 3h
2/ Al
2O
3Mol ratio is 100 type ZSM 5 molecular sieve catalyst F.Wherein the meso-hole structure aperture is 2～10nm, and the aperture of microcellular structure is 0.5～2nm.
Embodiment 7
With catalyst A～F, on fixed window reaction evaluating device, carry out catalysis benzene and ethylene reaction and prepare the active and selectivity investigation of ethylbenzene.The catalyst filling amount is 2.5g, and weight space velocity is 0.5 hour-1, and reaction temperature is 350 ℃, and reaction pressure is 1MPa, and benzene and ethylene molar ratio are 5.Reaction result is listed in table 1.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spiritual essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a hierarchical porous structure molecular sieve catalyst is characterized in that, comprises the steps:
(1) silicic acid, organic formwork agent, NaOH or potassium hydroxide is soluble in water, form B liquid; Aluminium salt, polyaniline and water are mixed, and the pH value is adjusted to 0～1, obtain A liquid;
Silicic acid and aluminium salt are converted into SiO respectively
2And Al
2O
3, SiO in the reaction system
2, Al
2O
3, NaOH or potassium hydroxide, organic formwork agent mol ratio be 1: 0.01～0.5: 0.1～2.5: 0.1～5; SiO
2With the amount ratio of polyaniline be 1mol: 0.1～50g;
(2) under agitation the B drop is added in the A liquid, forms gel; Stirred 1～5 hour, and 20～100 ℃ of following ageings after 2～8 hours, 140～180 ℃ of following crystallization 1～100 hour;
(3) product after the crystallization is separated, get precipitation and wash to pH value be 9～10, dryly then removes organic formwork agent and high molecular polymer polyaniline, thereby obtains the hierarchical porous structure molecular sieve catalyst at 400～700 ℃ of following roasting 2～6h.
2. the preparation method of the described hierarchical porous structure molecular sieve catalyst of claim 1 is characterized in that, the volume ratio of described A liquid and B liquid is 1: 5～20.
3. the preparation method of the described hierarchical porous structure molecular sieve catalyst of claim 1 is characterized in that, described organic formwork agent is selected from n-butylamine, ethylenediamine, 4-propyl bromide or TPAOH, and described aluminium salt is aluminum sulfate, aluminium chloride or sodium aluminate.
4. the preparation method of the described hierarchical porous structure molecular sieve catalyst of claim 1 is characterized in that, SiO in the reaction system
2, Al
2O
3, NaOH or potassium hydroxide, organic formwork agent mol ratio be 1: 0.01～0.05: 0.5～2.5: 0.1～5; SiO
2With the amount ratio of polyaniline be 1mol: 1～20g.
5. the preparation method of the described hierarchical porous structure molecular sieve catalyst of claim 1 is characterized in that, the described ageing temperature of step (2) is 50～70 ℃, and digestion time is 2～5 hours; Described crystallization temperature is 150～180 ℃, and crystallization time is 10～80 hours.
6. the preparation method of the described hierarchical porous structure molecular sieve catalyst of claim 1 is characterized in that, the temperature of the described drying of step (3) is 100～120 ℃, and described sintering temperature is 500～700 ℃, and roasting time is 3～5 hours.
7. the preparation method of the described hierarchical porous structure molecular sieve catalyst of claim 1 is characterized in that, the content of the described B liquid of step (1) mesosilicic acid is 0.5～2mol/L; Al in the described A liquid
2O
3Content be 0.05～0.2mol/L.
8. the preparation method of the described hierarchical porous structure molecular sieve catalyst of claim 1 is characterized in that, with 60wt%～98wt% concentrated sulfuric acid A liquid pH value is adjusted into 0～1 in the step (1).
9. a hierarchical porous structure molecular sieve catalyst is characterized in that, by each described method preparation of claim 1～8, is ZSM-5 type zeolite molecular sieve catalyst, and grain graininess is 0.1～20 μ m, SiO
2/ Al
2O
3Mol ratio is 30～500; Have microcellular structure and meso-hole structure on the hierarchical porous structure molecular sieve catalyst, the aperture of microcellular structure is 0.5～2nm; The aperture of meso-hole structure is 2～15nm.
10. the described hierarchical porous structure molecular sieve catalyst of claim 9 is characterized in that SiO
2/ Al
2O
3Mol ratio is 30～100, and grain graininess microballoon granularity is 1～10 μ m, and the aperture of meso-hole structure is 2～10nm.
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