CN101830480B - Preparation method of zeolite molecular sieve monolith with composite pore structure - Google Patents
Preparation method of zeolite molecular sieve monolith with composite pore structure Download PDFInfo
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Abstract
The invention relates to a preparation method of a zeolite molecular sieve monolith with a composite pore structure, which mainly solves the problem that a composite-pore molecular sieve which has both mesopores (or macropores) and a zeolite pore wall is difficult to obtain in the prior art. The zeolite molecular sieve monolith with bicontinuous macropores and three-dimensional communicated mesoporous paths is prepared from a macroporous silicagel monolith used as a substrate by using a method of in-situ carbonizing protection or secondary carbon addition by using carbon sources and then vapor-phase crystallization. The molecular sieve with excellent diffusivity has important application prospect in fields of catalysis, absorption, separation and the like.
Description
Technical field
The present invention relates to a kind of preparation method with zeolite molecular sieve monolith with composite pore structure.
Background technology
Zeolite molecular sieve material has regular microvoid structure, higher hydrothermal stability, suitable advantages such as surface acid alkalescence, thereby becomes one of catalyzer that the most often uses in the petrochemical process.But along with improving constantly of requiring " eaten to do and press only " to the growing and petroleum industry of science and technology to raw material, traditional zeolite molecular sieve shows deficiency gradually.This mainly is that this has greatly limited mass transfer and the diffusion of macromole such as heavy oil component in catalyzer, thereby has suppressed reactive behavior, selectivity and the life-span of catalyzer because zeolite molecular sieve only has microvoid structure.
For addressing these problems; The researchist has proposed the notion of " classification composite holes material "; I.e. preparation has the new catalytic material of micropore and mesoporous or macropore simultaneously; Make it have pore passage structure mesoporous or that large pore material is open simultaneously, and characteristics such as the strongly-acid of zeolitic material and high reactivity, the advantage that real performance " is taken what one needs, maximized favourable factors and minimized unfavourable ones ".At present, the compound method to the composite pore structural molecular screen material mainly can be divided three classes:
One, in zeolite, make mesoporous.A kind of method is methods such as acid, alkali, steam or chemical after-treatment reason that molecular screen material is adopted, and makes its skeleton remove part aluminium or silicon, thereby produces bigger duct in the part; Another kind of research thinking is in the building-up process of zeolite, to add the occupy-place agent, for example raw material of wood-charcoal material, lime carbonate, starch, ion exchange resin etc., thus in product, introduce the bigger hole of part.But this method receives the restriction of zeolite grain size, produces mesoporous limitedly, and is clearance hole mostly, and is connective poor, therefore limited to the contribution of raising product mass transfer and diffusion.(J.C.Groen，J.A.Moulijin，J.Perez-Ramirez.J.Mater.Chem.2006，16：2121)
Two, the commentaries on classics of the amorphous hole wall of mesoporous material is brilliant.Promptly through the method for in-situ crystallization, the hole wall that makes mesoporous material is by the amorphous zeolite grain that changes into.But because Nano grade order mesoporous has quite high curvature, the inflexible zeolite grain can't be kept; In the crystallization process of amorphous hole wall, can produce higher local stress in addition, and the effect that the thin hole wall of mesoporous material is difficult to bear this stress very easily causes caving in fully of meso-hole structure.(W.Li，F.Schuth，et?al.J.Am.Chem.Soc.2005，127：12595)
Three, the template of zeolite grain assembling.Through the control to building-up process, making the self-assembly of zeolite nanocrystal is specific morphology, thereby obtains mesopore orbit.But since nanocrystal and mesoporous template dimensionally with reactive force on couplings not really all, and assembly is unstable, in removing the process of template, is prone to cave in, what therefore often obtain is the mixture of two kinds of structures.(appoint nanmu, Tang's chin or cheek. petrochemical complex, 2005,34:405)
By above visible, although the various countries researchist develops numerous compound methods, the preparation of composite pore structural zeolitic material at present is still one of difficult point in the synthetic field.
Summary of the invention
Technical problem to be solved by this invention is the problem that in the past was difficult to obtain have simultaneously the composite holes molecular sieve of mesoporous (or macropore) and zeolite hole wall in the technology, and a kind of preparation method of new zeolite molecular sieve monolith with composite pore structure is provided.This method can obtain to have simultaneously the zeolite molecular sieve material of co-continuous macropore and three-dimensional communication mesopore orbit, and product has only stone shape characteristic.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of preparation method of zeolite molecular sieve monolith with composite pore structure may further comprise the steps:
The mixture that a) will comprise template R1, acid catalyst, water, silicon source and aluminium source changes in the mould 0～40 ℃ of hydrolysis then, and 40～80 ℃ are reacted to gel, the aging back demoulding, and drying obtains sample A;
Wherein template R1 is selected from least a in polyoxyethylene glycol, T 46155, polyethylene oxide, polyoxyethylene-poly-oxypropylene polyoxyethylene, chain alkyl trimethylammonium halogenation ammonia, Hydrocerol A, tartrate, oxysuccinic acid or the lactic acid;
Acid catalyst is selected from least a in nitric acid, hydrochloric acid, sulfuric acid or the acetic acid;
The silicon source is selected from least a in positive quanmethyl silicate, positive tetraethyl orthosilicate, positive silicic acid orthocarbonate or positive silicic acid four butyl esters;
The aluminium source is selected from least a in aluminum nitrate, aluminum chloride, Tai-Ace S 150, aluminum isopropylate, isobutanol aluminum or the pseudo-boehmite;
The reaction mixture mass ratio consists of: R1/SiO
2=0.3～2.0, H
+/ SiO
2=0.1～0.5, H
2O/SiO
2=1～10, Al
2O
3/ SiO
2=0.001～0.85;
B) sample A is added the sulphuric acid soln of 0.27～18.4 mol or contain in the mixed solution I of sucrose, sulfuric acid and water and flood,, change that 700～900 ℃ of roastings obtain sample B under the inert atmosphere over to then at 30～150 ℃ and 150～200 ℃ of stage dryings;
Wherein in the mixed solution I each component based on SiO
2Mass ratio be: sucrose/SiO
2=0.5～5, sulfuric acid/SiO
2=0.1～0.5, water/SiO
2=1～10;
C) sample B is placed the reaction kettle upper strata, underlying template R2,120～200 ℃ of crystallization under autogenous pressure make the only stone material of composite pore structural zeolite after washing, drying, roasting;
Wherein template R2 is selected from least a in tetraethyl ammonium hydroxide, TPAOH, triethylamine or the diethylamine, and the volume ratio of add-on and sample B is 5～20 times.
In the technique scheme, it is complete that the mixture that comprises template R1, acid catalyst, water, silicon source and aluminium source in the step a) is hydrolyzed into hydrolysis at 0～40 ℃, and the reaction times is preferably 0.1～24 hour, and digestion time is preferably 12～72 hours; The time of immersion of sample A is preferably 1～48 hour in the step b), and 30～150 ℃ and 150～200 ℃ of stage drying times all are preferably 2～10 hours, and 700～900 ℃ of roasting time are preferably 1～10 hour; 120～200 ℃ of crystallization times of step c) are preferably 1～7 day.The reaction mixture quality than preferable range is in the step a): R1/SiO
2=0.35～1.5, H
+/ SiO
2=0.15～0.4, H
2O/SiO
2=2～7, Al
2O
3/ SiO
2=0.004～0.5; Each component is based on SiO in the step b) mixed solution I
2Quality than preferable range be: sucrose/SiO
2=1～3, sulfuric acid/SiO
2=0.1～0.3, water/SiO
2=1.5～5; Step c) template R2 and sample B volume ratio preferable range are 8～15.A) preferred version is for also adding the nanometer crystal seed that contains MFI or the basic cell configuration of BEA in the step, and add-on is crystal seed/SiO
2Mass ratio be 0～1.0.C) step can also for: sample B is immersed among the mixed solution I I that contains alkali, organic amine and aluminium source 1～48 hour, drying in the shade is placed on the reaction kettle upper strata, underlying water, 90～200 ℃ of crystallization make said zeolite molecular sieve monolith with composite pore structure after 1～7 day; Wherein said alkali is selected from least a in sodium hydroxide or the ammoniacal liquor; Said organic amine is selected from least a in tetraethyl ammonium hydroxide, TPAOH, triethylamine, diethylamine, 4-propyl bromide or the tetraethylammonium bromide; Each component is based on SiO among the said mixed solution I I
2Mass ratio be organic amine/SiO
2=0.05～3.0, alkali/SiO
2=0.02～2.5, Al
2O
3/ SiO
2=0.004～0.85; The volume ratio of the add-on of water and sample B is 0.5～20 times.Each component is based on SiO among the mixed solution I I
2Quality be organic amine/SiO than preferable range
2=0.1～2.0, alkali/SiO
2=0.05～1.5, Al
2O
3/ SiO
2=0.005～0.5.
The present invention organically combines the preparation of the only stone of macroporous silica gel and the zeolitization of amorphous silica gel hole wall; Make organic formwork agent original position carbonization after vitriolization and inert atmosphere roasting abundant in the macroporous silica gel synthetic system, form carbon protective layer; Perhaps add sucrose and mend the stability that carbon further improves skeleton structure as the secondary carbon source; Make the co-continuous macroporous structure of material in follow-up vapour phase crystallization process, obtain protection effectively, obtained to have the zeolite molecular sieve monolith of co-continuous macroporous structure.In addition, the present invention comes effectively to reduce temperature of reaction, minimizing induction time in the crystallization steps through in reaction mixture, mixing the nanometer crystal seed.The product that adopts this method to obtain has the macropore duct of co-continuous, the three-dimensional mesopore orbit that connects and controlled crystal phase structure simultaneously, and specific surface area is up to 1000 meters
2/ gram is distributed in to mesoporous high concentration 2～8 nanometers, and macropore is adjustable continuously between 0.1～10 micron, has obtained better technical effect.
Description of drawings
The XRD spectra of the only stone of composite pore structural beta-molecular sieve that Fig. 1 obtains for embodiment 1.
The SEM photo of the only stone of composite pore structural beta-molecular sieve that Fig. 2 obtains for embodiment 1.
The XRD spectra of the composite pore structural ZSM-5 molecular sieve monolith that Fig. 3 obtains for embodiment 2.
The SEM photo of the composite pore structural ZSM-5 molecular sieve monolith that Fig. 4 obtains for embodiment 2.
Embodiment
[embodiment 1]
A) polyoxyethylene glycol, 0.4 mol salpeter solution and aluminum nitrate are mixed, change frozen water after the dissolving over to and mix in the bath, add positive tetraethyl orthosilicate, stir and change die sealing over to after 2 hours, 60 ℃ were reacted 24 hours down.Obtain sample A after taking out the back demoulding, drying.Wherein quality is than polyoxyethylene glycol/SiO
2=0.35, H
+/ SiO
2=0.16, H
2O/SiO
2=2.25, Al
2O
3/ SiO
2=0.004.
B) sample A is dripped the sulphuric acid soln dipping overnight of 0.84 mol, behind 60 ℃ and 170 ℃ of stage dryings, the following 800 ℃ of roastings of nitrogen protection obtain sample B.Wherein quality is than sulfuric acid/SiO
2=0.1.
C) sample B is placed the porous support on reaction kettle upper strata, underlying and sample B volume ratio are 8 tetraethyl-oxyammonia solution, 160 ℃ of crystallization 6 days.
Go out the still after product and obtain the only stone of composite hole zeolite that hole wall is the Beta crystal formation after XRD spectra proves through washing, drying, roasting.The XRD spectra of product is seen Fig. 1, and the SEM photo is seen Fig. 2.The specific surface area of product is 820 meters
2/ gram, mesoporous aperture is 6.2 nanometers, macropore diameter is 5 microns.
[embodiment 2]
A) acetum with Hydrocerol A, polyoxyethylene-poly-oxypropylene polyoxyethylene, 1 mol mixes, and changes frozen water after the dissolving over to and mixes in the bath, adds positive quanmethyl silicate, and vigorous stirring changes in the mould after 0.1 hour and seals, and 40 ℃ were reacted 48 hours down.The demoulding after taking out, drying obtain sample A.Wherein quality is than Hydrocerol A/SiO
2=0.5, polyoxyethylene-poly-oxypropylene polyoxyethylene/SiO
2=0.3, H
+/ SiO
2=0.25, H
2O/SiO
2=2.5.
B) sample A is added the sulphuric acid soln dipping overnight of 18.4 mol, behind 120 ℃ and 200 ℃ of stage dryings, the following 700 ℃ of roastings of nitrogen protection obtain sample B.Wherein quality is than sulfuric acid/SiO
2=0.15.
C) sample B is added the mixing solutions of sodium hydroxide, tetrapropyl amine bromide, aluminum isopropylate and water, change over to behind the dipping overnight in the porous support on reaction kettle upper strata, underlying 10 ml waters, 150 ℃ of crystallizations 3 days.Wherein quality is than tetrapropyl amine bromide/SiO
2=0.3, alkali/SiO
2=0.05, Al
2O
3/ SiO
2=0.1.
Go out the still after product and obtain the only stone of composite hole zeolite that hole wall is the ZSM-5 crystal formation after XRD spectra proves through washing, drying, roasting.The XRD spectra of product is seen Fig. 3, and the SEM photo is seen Fig. 4.The specific surface area of product is 1014 meters
2/ gram, mesoporous aperture is 3.3 nanometers, macropore diameter is 0.3 micron.
[embodiment 3]
A) hydrochloric acid soln of polyoxyethylene-poly-oxypropylene polyoxyethylene, 1 mol and aluminum chloride are mixed, the dissolving back adds positive silicic acid orthocarbonate, and 40 ℃ are stirred to change in the mould after 5 hours and seal, 80 ℃ down reaction obtained sample A in 24 hours.Wherein quality is than polyoxyethylene-poly-oxypropylene polyoxyethylene/SiO
2=1.0, H
+/ SiO
2=0.2, H
2O/SiO
2=4, Al
2O
3/ SiO
2=0.4.
B) sample A is taken out the back demoulding, drying.Add the mixing solutions of sucrose, the vitriol oil and deionized water, at 100 ℃ and 180 ℃ of stage dryings, the following 900 ℃ of roastings of nitrogen protection obtain sample B behind the dipping overnight.Wherein quality is than sucrose/SiO
2=1, sulfuric acid/SiO
2=0.1, water/SiO
2=2.
C) sample B is placed the porous support on reaction kettle upper strata, the tetraethyl ammonium hydroxide solution of underlying and sample B volume ratio 10,180 ℃ of crystallization 3 days.
Go out the still after product and obtain the only stone of composite hole zeolite that hole wall is the Beta crystal formation after XRD spectra proves through washing, drying, roasting.The specific surface area of product is 897 meters
2/ gram, mesoporous aperture is 7.0 nanometers, macropore diameter is 2.1 microns.
[embodiment 4]
A) sulphuric acid soln with cetyltrimethylammonium hydroxide, polyoxyethylene glycol and 1 mol mixes, and adds positive quanmethyl silicate, and 40 ℃ of stirrings are poured in the mould after 0.1 hour and sealed, and 60 ℃ were reacted 48 hours down.The demoulding after taking out, drying obtain sample A.Wherein quality is than cetyltrimethylammonium hydroxide/SiO
2=0.4, polyoxyethylene glycol/SiO
2=1, H
+/ SiO
2=0.4, H
2O/SiO
2=7.
B) sample A and sucrose, vitriolic mixing solutions are flooded, at 100 ℃ and 170 ℃ of stage dryings, the following 800 ℃ of roastings of nitrogen protection obtain sample B.Wherein quality is than sucrose/SiO
2=3, sulfuric acid/SiO
2=0.3, water/SiO
2=5.
C) sample B is added the mixing solutions dipping of ammoniacal liquor, tetrapropyl amine bromide, aluminum nitrate, change in the porous support on reaction kettle upper strata, underlying 10 ml waters, 170 ℃ of crystallizations 2 days.Wherein quality is than tetrapropyl amine bromide/SiO
2=2.0, ammoniacal liquor/SiO
2=1.4, Al
2O
3/ SiO
2=0.5.
Go out the still after product and obtain the only stone of composite hole zeolite that hole wall is the ZSM-5 crystal formation after XRD spectra proves through washing, drying, roasting.The specific surface area of product is 960 meters
2/ gram, mesoporous aperture is 4.2 nanometers, macropore diameter is 6.6 microns.
[embodiment 5]
A) polyoxyethylene glycol, ZSM-5 crystal seed, 0.4 mol salpeter solution are mixed, add positive tetraethyl orthosilicate, 30 ℃ of following vigorous stirring are poured in the mould after 1 hour and are sealed, and put into 60 ℃ of water-bath oscillatory reactions 48 hours.The demoulding after taking out, drying obtain sample A.Wherein quality is than polyoxyethylene glycol/SiO
2=1.0, H
+/ SiO
2=0.3, H
2O/SiO
2=5, crystal seed/SiO
2Be 0.5.
B) sample B is dripped the sulfuric acid dipping overnight of 18.4 mol, at 110 ℃ and 180 ℃ of stage dryings, the following 800 ℃ of roastings of nitrogen protection obtain sample B.Wherein quality is than sulfuric acid/SiO
2=0.1.
C) sample B is placed the porous support on reaction kettle upper strata, the mixing solutions of underlying triethylamine, quadrol and water, 100 ℃ of crystallizations 1 day.Wherein quality is than triethylamine/SiO
2=0.3; Quadrol/SiO
2=0.5.
Go out the still after product and obtain the only stone of composite hole zeolite that hole wall is the ZSM-5 crystal formation after XRD spectra proves through washing, drying, roasting.The specific surface area of product is 987 meters
2/ gram, mesoporous aperture is 2.8 nanometers, macropore diameter is 9.9 microns.
[embodiment 6]
A) hydrochloric acid soln with polyoxyethylene-poly-oxypropylene polyoxyethylene, Beta crystal seed and 1 mol mixes, and changes frozen water over to and mixes in the bath, adds positive quanmethyl silicate, and vigorous stirring is poured in the mould after 5 minutes and sealed, and puts into 60 ℃ of baking oven standing and reacting 24 hours.The demoulding after taking out, drying obtain sample A.Wherein quality is than polyoxyethylene-poly-oxypropylene polyoxyethylene/SiO
2=0.8, H
+/ SiO
2=0.35, H
2O/SiO
2=5, crystal seed/SiO
2Mass ratio be 0.25.
B) sample A is dripped the sulphuric acid soln dipping overnight of 0.84 mol, respectively 100 ℃ and 170 ℃ of dryings, the following 900 ℃ of roastings of nitrogen protection obtain sample B.Wherein quality is than sulfuric acid/SiO
2=0.15.
C) sample B is added the mixing solutions of sodium hydroxide, tetraethyl-amine bromide, aluminum isopropylate, change over to behind the dipping overnight in the porous support on reaction kettle upper strata, underlying 10 ml waters, 150 ℃ of crystallizations 2 days.Wherein quality is than tetraethyl-amine bromide/SiO
2=1.8, sodium hydroxide/SiO
2=1.5, Al
2O
3/ SiO
2=0.2.
Go out the still after product and obtain the only stone of composite hole zeolite that hole wall is the Beta crystal formation after XRD spectra proves through washing, drying, roasting.The specific surface area of product is 863 meters
2/ gram, mesoporous aperture is 7.1 nanometers, macropore diameter is 4.0 microns.
[embodiment 7]
A) tartrate, polyethylene oxide and 1 mol sulphuric acid soln are mixed, change frozen water after the dissolving over to and mix in the bath, add positive quanmethyl silicate, vigorous stirring changes in the mould after 0.2 hour and seals, and 50 ℃ were reacted 24 hours down.The demoulding after taking out, drying obtain sample A.Wherein quality is than tartrate/SiO
2=0.4, polyethylene oxide/SiO
2=0.9, H
+/ SiO
2=0.4, H
2O/SiO
2=3.
B) sample A is added the sulphuric acid soln dipping overnight of 1 mol, behind 150 ℃ and 180 ℃ of stage dryings, the following 700 ℃ of roastings of nitrogen protection obtain sample B.Wherein quality is than sulfuric acid/SiO
2=0.18.
C) sample B is added the mixing solutions of ammoniacal liquor, tetrapropyl amine bromide, isobutanol aluminum and water, change over to behind the dipping overnight in the porous support on reaction kettle upper strata, underlying 15 ml waters, 150 ℃ of crystallizations 3 days.Wherein quality is than tetrapropyl amine bromide/SiO
2=1.6, ammoniacal liquor/SiO
2=1.5, Al
2O
3/ SiO
2=0.08.
Go out the still after product and obtain the only stone of composite hole zeolite that hole wall is the ZSM-5 crystal formation after XRD spectra proves through washing, drying, roasting.The specific surface area of product is 1006 meters
2/ gram, mesoporous aperture is 4.5 nanometers, macropore diameter is 4.9 microns.
[embodiment 8]
A) acetum with T 46155, pseudo-boehmite and 1 mol mixes, and dissolves the back and adds positive silicic acid orthocarbonate, and 40 ℃ of stirrings change in the mould after 8 hours and seal, and 80 ℃ were reacted 24 hours down.The demoulding after taking out, drying obtain sample A.Wherein quality is than T 46155/SiO
2=1.1, H
+/ SiO
2=0.37, H
2O/SiO
2=4, Al
2O
3/ SiO
2=0.008.
B) with the mixing solutions of sample A adding sucrose, the vitriol oil and water, at 100 ℃ and 190 ℃ of stage dryings, the following 900 ℃ of roastings of nitrogen protection obtain sample B behind the dipping overnight.Sucrose/SiO wherein
2=2.25, sulfuric acid/SiO
2=0.28, water/SiO
2=4.5.
C) sample B is placed the porous support on reaction kettle upper strata, the tetraethyl ammonium hydroxide solution of underlying and sample B volume ratio 15,160 ℃ of crystallization 3 days.
Go out the still after product and obtain the only stone of composite hole zeolite that hole wall is the Beta crystal formation after XRD spectra proves through washing, drying, roasting.The specific surface area of product is 876 meters
2/ gram, mesoporous aperture is 5.7 nanometers, macropore diameter is 0.8 micron.
Claims (6)
1. the preparation method of a zeolite molecular sieve monolith with composite pore structure may further comprise the steps:
The mixture that a) will comprise template R1, acid catalyst, water, silicon source and aluminium source changes in the mould 0～40 ℃ of hydrolysis then, and 40～80 ℃ are reacted to gel, the aging back demoulding, and drying obtains sample A;
Wherein template R1 is selected from least a in polyoxyethylene glycol, T 46155, polyethylene oxide, polyoxyethylene-poly-oxypropylene polyoxyethylene, Hydrocerol A, tartrate, oxysuccinic acid or the lactic acid;
Acid catalyst is selected from least a in nitric acid, hydrochloric acid, sulfuric acid or the acetic acid;
The silicon source is selected from least a in positive quanmethyl silicate, positive tetraethyl orthosilicate, positive silicic acid orthocarbonate or positive silicic acid four butyl esters;
The aluminium source is selected from least a in aluminum nitrate, aluminum chloride, Tai-Ace S 150, aluminum isopropylate, isobutanol aluminum or the pseudo-boehmite;
The reaction mixture mass ratio consists of: R1/SiO
2=0.3～2.0, H
+/ SiO
2=0.1～0.5, H
2O/SiO
2=1～10, Al
2O
3/ SiO
2=0.001～0.85;
B) sample A is added the sulphuric acid soln of 0.27～18.4 mol or contain in the mixed solution I of sucrose, sulfuric acid and water and flood,, change that 700～900 ℃ of roastings obtain sample B under the inert atmosphere over to then at 30～150 ℃ and 150～200 ℃ of stage dryings;
Wherein in the mixed solution I each component based on SiO
2Mass ratio be: sucrose/SiO
2=0.5～5, sulfuric acid/SiO
2=0.1～0.5, water/SiO
2=1～10;
C) sample B is placed the reaction kettle upper strata, underlying template R2,120～200 ℃ of crystallization under autogenous pressure make the only stone material of composite pore structural zeolite after washing, drying, roasting;
Wherein template R2 is selected from least a in tetraethyl ammonium hydroxide, TPAOH, triethylamine or the diethylamine, and the volume ratio of add-on and sample B is 5～20 times.
2. according to the preparation method of the said zeolite molecular sieve monolith with composite pore structure of claim 1; The mixture that it is characterized in that comprising in the step a) template R1, acid catalyst, water, silicon source and aluminium source is 0.1～24 hour at 0～40 ℃ of hydrolysis time, and digestion time is 12～72 hours; The time of immersion of sample A is 1～48 hour in the step b), and 30～150 ℃ and 150～200 ℃ of stage drying times all are 2～10 hours, and 700～900 ℃ of roasting time are 1～10 hour; 120～200 ℃ of crystallization times of step c) are 1～7 day.
3. according to the preparation method of the said zeolite molecular sieve monolith with composite pore structure of claim 1, it is characterized in that the reaction mixture mass ratio is in the step a): R1/SiO
2=0.35～1.5, H
+/ SiO
2=0.15～0.4, H
2O/SiO
2=2～7, Al
2O
3/ SiO
2=0.004～0.5; Each component is based on SiO in the step b) mixed solution I
2Mass ratio be: sucrose/SiO
2=1～3, sulfuric acid/SiO
2=0.1～0.3, water/SiO
2=1.5～5; Step c) template R2 and sample B volume ratio are 8～15.
4. according to the preparation method of the said zeolite molecular sieve monolith with composite pore structure of claim 1, it is characterized in that a) also adding the nanometer crystal seed that contains MFI or the basic cell configuration of BEA in the step, add-on is crystal seed/SiO
2Mass ratio be 0～1.0.
5. the preparation method of a zeolite molecular sieve monolith with composite pore structure may further comprise the steps:
The mixture that a) will comprise template R1, acid catalyst, water, silicon source and aluminium source changes in the mould 0～40 ℃ of hydrolysis then, and 40～80 ℃ are reacted to gel, the aging back demoulding, and drying obtains sample A;
Wherein template R1 is selected from least a in polyoxyethylene glycol, T 46155, polyethylene oxide, polyoxyethylene-poly-oxypropylene polyoxyethylene, Hydrocerol A, tartrate, oxysuccinic acid or the lactic acid;
Acid catalyst is selected from least a in nitric acid, hydrochloric acid, sulfuric acid or the acetic acid;
The silicon source is selected from least a in positive quanmethyl silicate, positive tetraethyl orthosilicate, positive silicic acid orthocarbonate or positive silicic acid four butyl esters;
The aluminium source is selected from least a in aluminum nitrate, aluminum chloride, Tai-Ace S 150, aluminum isopropylate, isobutanol aluminum or the pseudo-boehmite;
The reaction mixture mass ratio consists of: R1/SiO
2=0.3～2.0, H
+/ SiO
2=0.1～0.5, H
2O/SiO
2=1～10, Al
2O
3/ SiO
2=0.001～0.85;
B) sample A is added the sulphuric acid soln of 0.27～18.4 mol or contain in the mixed solution I of sucrose, sulfuric acid and water and flood,, change that 700～900 ℃ of roastings obtain sample B under the inert atmosphere over to then at 30～150 ℃ and 150～200 ℃ of stage dryings;
Wherein in the mixed solution I each component based on SiO
2Mass ratio be: sucrose/SiO
2=0.5～5, sulfuric acid/SiO
2=0.1～0.5, water/SiO
2=1～10;
C) sample B is immersed among the mixed solution I I that contains alkali, organic amine and aluminium source 1～48 hour, drying in the shade is placed on the reaction kettle upper strata, underlying water, and 90～200 ℃ of crystallization make said zeolite molecular sieve monolith with composite pore structure after 1～7 day;
Wherein said alkali is selected from least a in sodium hydroxide or the ammoniacal liquor; Said organic amine is selected from least a in tetraethyl ammonium hydroxide, TPAOH, triethylamine, diethylamine, 4-propyl bromide or the tetraethylammonium bromide; Each component is based on SiO among the said mixed solution I I
2Mass ratio be organic amine/SiO
2=0.05～3.0, alkali/SiO
2=0.02～2.5, Al
2O
3/ SiO
2=0.004～0.85; The volume ratio of the add-on of water and sample B is 0.5～20 times.
6. according to the preparation method of the said zeolite molecular sieve monolith with composite pore structure of claim 5, it is characterized in that each component is based on SiO among the mixed solution I I
2Mass ratio be organic amine/SiO
2=0.1～2.0, alkali/SiO
2=0.05～1.5, Al
2O
3/ SiO
2=0.005～0.5.
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| CN102660766B (en) * | 2012-05-08 | 2015-02-25 | 陕西科技大学 | Preparation method of Y2Si2O7 whisker |
| CN103864092A (en) * | 2012-12-10 | 2014-06-18 | 国际壳牌研究有限公司 | Synthesis method and application of composite pore zeolite beta |
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| CN103979570B (en) * | 2014-05-14 | 2016-01-06 | 武汉理工大学 | The synthetic method of a kind of novel ordered big hole-mesoporous-micropore multi-stage porous Si-Al molecular sieve |
| CN107188195A (en) * | 2017-05-18 | 2017-09-22 | 浙江大学 | A kind of preparation method and application of the molecular sieves of multi-stage porous HZSM 5 |
| CN107311203A (en) * | 2017-08-11 | 2017-11-03 | 武汉理工大学 | A kind of multi-stage pore canal molecular sieve and preparation method thereof |
| CN110498424B (en) * | 2018-05-16 | 2021-10-08 | 中国石油化工股份有限公司 | Method for modifying Y molecular sieve |
| CN110240177B (en) * | 2019-07-02 | 2022-11-11 | 华东理工大学 | MFI type zeolite molecular sieve with sheet structure and preparation method thereof |
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