CN109607560A - A kind of flake hetero-atom molecular-sieve and its green synthesis method - Google Patents
A kind of flake hetero-atom molecular-sieve and its green synthesis method Download PDFInfo
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- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
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Abstract
The present invention relates to catalyst synthesis technology field, in particular to a kind of method of green syt flake hetero-atom molecular-sieve.The method of the present invention is b axis orientation nano piece hetero-atom molecular-sieve by the way that the structure regulators such as amino acid, fatty acid and amine, obtained molecular sieve is added.The maximum surface of the hetero-atom molecular-sieve nanometer sheet is parallel with (0 2 0) crystal face, i.e., perpendicular to straight hole road direction, keeps the diffusion path of reactant and product in duct shorter, diffusional resistance is smaller；And b axis direction length can regulate and control between 30~200nm, so that molecular sieve is catalyzed the reaction of a variety of different sized molecules, reduce carbon distribution, improve catalyst life.The structure regulator that the present invention is added is from a wealth of sources, cheap, is a kind of environmentally protective additive.It is generated in synthesis process without mother liquor, without handling waste water, product is energy-saving without separating, and shortens the manufacturing cycle of molecular sieve, reduces production cost.
Description
Technical field
The present invention relates to catalyst synthesis technology field, in particular to a kind of green syt flake hetero-atom molecular-sieve
Method.
Background technique
Zeolite is microporous silicate crystal, is widely used in absorption, separation and catalytic field, zeolite and is found in earliest
The mineral of nature have more than 260 years history so far.From the fifties in 18th century, it has been found that since zeolite group mineral, great Pi Ke
It grinds worker and lasting further investigation has been carried out to the properity of zeolitic material, synthesis and application etc..
1756, Sweden mineralogist had found foresite for the first time in basalt.McBain is proposed earliest within 1932
The concept of molecular sieve, Lai Dingyi serve as the cellular solid of sieve on molecular scale.Mobil Corporation is in 1962 with synthesis
X zeolite carried out catalytic cracking, the zeolite and ZSM-5 zeolite conduct of first high silica alumina ratio were prepared in 1967~1972 years
Important inorganic microporous crystalline material is mainly used in the three big fields such as absorption, ion exchange and catalysis.
In the synthesis process of molecular sieve, mother liquor can be generated after high temperature crystallization, it is one that product is separated from mother liquor
Highly energy-consuming process, the substances such as organic formwork agent containing a large amount of unreacted raw materials and pyrolytic in the mother liquor after separation,
Complicated composition, content are difficult to measure, and make it difficult to recycle, cause damages if direct emission to environment.In addition, molecular sieve
Washing process can also consume a large amount of water, and generate a large amount of waste water, it is equally unfavorable to environment and control production cost.
A kind of Solid raw materials grinding synthesis point under solvent-free conditions is reported in Chinese patent CN201210118788.7
The method of son sieve, this method can obtain ZSM-5 molecular sieve, Beta molecular sieve, ZSM-39 molecular sieve etc., not make in synthesis process
With any solvent, synthesis step simplifies, reduces costs, also more friendly to environment.
Simultaneously as microporous molecular mesh size is smaller, macromolecular is limited in duct by serious diffusion, limits it
Application range.It is influenced to reduce diffusion bring, researcher is by the method for fabricated in situ either post-processing in micropore point
Meso-hole structure or preparation nanometer aggregate are introduced in son sieve to introduce intracrystalline pore, to reduce diffusional resistance, are improved catalysis and are lived
Property.
Mesoporous introducing reduces diffusion limitation, but extends manufacturing cycle, according to document (Nature, 2009,40
(47): it 246) reports, by addition quaternary ammonium salt surface active agent, obtains the ZSM-5 molecular sieve with nano-lamellar structure,
Single crystal thickness is 2nm.Studies have shown that the nano flake molecular sieve that this kind of quaternary ammonium salt surface active agent is prepared is in methanol
Good anticoking capability is shown in the macromolecular reactions such as gasoline (MTG) processed, improves the service life of catalyst.Currently, synthesis
The preparation process of various quaternary ammonium salt surface active agents is complicated, and yield is lower, expensive raw material price, significantly limits it and is dividing
Application in son sieve synthesis.
Summary of the invention
It is an object of the invention to solve the problems, such as the existing synthetic technology of molecular sieve, if diffusional resistance is big, waste water
Amount is big, separates the problems such as difficult yield is low.
To solve the above problems, the present invention provides a kind of methods of green syt flake hetero-atom molecular-sieve, specifically
Step are as follows:
S1, silicon source, the tetrapropylammonium hydroxide solution of 20~40wt%, water and structure regulator are mixed, stirring is equal
It is even, obtain mixed liquor A；By mixed liquor A in 0~60 DEG C of 0~6h of hydrolysis；
The molar ratio of each substance in the mixed liquor A are as follows:
SiO2:TPAOH:H2O=1:(0.0101~0.3499): (10.01~34.99)；
Structure regulator and SiO in the mixed liquor2Mass ratio be 0.010~2.449；
The structure regulator is the mixture or amino acid, fatty acid of two substance of amino acid, fatty acid and amine
The mixture of three substance of class and amine；These structure regulators change solution acid by the amino or carboxylic group of itself institute's band
Basicity, to influence the hydrolysis and polymerization process of silicon source, such as hydrolysis rate and the degree of polymerization.
The amino acid includes glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, color
Propylhomoserin, tyrosine, cysteine, methionine, glutamic acid, threonine, arginine, histidine, aspartic acid, lysine and silk ammonia
At least one of acid；
S2, by metal component, 20%~40% tetrapropylammonium hydroxide solution and water mix, stir evenly, obtain
Mixed liquid B；By mixed liquid B in 0~60 DEG C of 0~6h of hydrolysis；
The molar ratio of each substance in the mixed liquid B are as follows:
MOx:TPAOH:H2O=1:(0~9.99): (50.01~999.99)；
Wherein MOxMetal component is referred to calculate in the form of the oxide；
S3, mixed liquor A and mixed liquid B are mixed, is stirred evenly, remove 0~3h of alcohol at 60~90 DEG C；Structure is added to adjust
Agent obtains mixed liquor C；By mixed liquor C in 40~80 DEG C of 10~60min of stirring；
The molar ratio of each substance in the mixed liquor C are as follows:
SiO2:MOx:TPAOH:H2O=1:(0.0201~0.1000): (0.0501~0.4999): (20.01~
54.99)；
The structure regulator is the mixture or amino acid, fatty acid of two substance of amino acid, fatty acid and amine
The mixture of three substance of class and amine；Contain a large amount of amino and carboxyl in these structure regulators, the addition of functional group makes to close
It changes at the pH value of colloidal sol, synthesis colloidal sol is caused to be converted into gel, using solid phase transformation mechanism, generate molecular sieve,
After the completion of crystallization, the substance in crystallizing kettle is still solid state, rather than suspension, because of the process without separation of solid and liquid.
The amino acid includes glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, color
Propylhomoserin, tyrosine, cysteine, methionine, glutamic acid, threonine, arginine, histidine, aspartic acid, lysine and silk ammonia
At least one of acid；
The structure regulator and SiO2Mass ratio be 0~6.3499；
S4, the product for obtaining step S3 are packed into crystallizing kettle, and 100~250 DEG C of 6~72h of crystallization obtain crystallization product；
S5, the crystallization product for obtaining step S4 in 80~120 DEG C of dry 2~12h, 400~600 DEG C of 3~12h of roasting,
Obtain laminar hetero-atom molecular-sieve.
Under preferred embodiment, the metallic element of metal component described in step S1 include magnesium, aluminium, titanium, zinc, silver, gallium, molybdenum, tungsten,
In copper, manganese, nickel, iron, zirconium, platinum, chromium, billows, cerium, praseodymium, rubidium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium or yttrium
It is at least one；
The metal component is the chloride of metal oxide or corresponding metallic element, in sulfate, nitrate, esters
It is at least one.
Under preferred embodiment, silicon source described in step S1 is in silica solution, methyl orthosilicate, ethyl orthosilicate or white carbon black
It is at least one.
Under preferred embodiment, when the silicon source described in the step S1 uses non-Ester, hydrolysis time is 0h in the step.Work as step
When metal component described in rapid S2 uses non-Ester, hydrolysis time is 0h in the step.The silicon source described in step S1, the step S2
When using non-Ester simultaneously with metal component, the alcohol time of removing of mixed liquor C described in step S3 is 0h.
The present invention also provides the laminar hetero-atom molecular-sieve of above-mentioned green synthesis method preparation, the molecular sieve nanometer sheets
Maximum surface it is parallel with (0 2 0) crystal face, i.e., perpendicular to straight hole road direction, and straight orifice throat length is controllable, length-adjusting model
It encloses for 30~200nm.
The synthetic method of hetero-atom molecular-sieve provided in the present invention has the advantage that compared with prior art
1, preparation method provided by the invention is using substances conducts such as cheap, from a wealth of sources and edible amino acid
Structure regulator is generated without mother liquor after crystallization, does not need processing waste water, environmentally friendly.It does not need to carry out product and mother liquor
Separation is not necessarily to separation equipment, shortens the production cycle, reduces production cost.
2, the hetero-atom molecular-sieve straight hole road direction of the method for the present invention preparation makes reactant and product perpendicular to maximum crystal face
Diffusion path in duct is shorter, and diffusional resistance is smaller；And b axis direction length can regulate and control between 30~200nm, make
Molecular sieve can be catalyzed the reaction of a variety of different sized molecules.
3, synthetic method provided by the present invention can regulate and control metal component in molecule while modulation Molecular Sieve Morphology
Existence form in sieve promotes more metal components to enter framework of molecular sieve, forms activated centre, improves catalyst activity.
In conclusion generating after the method for the present invention crystallization without mother liquor, product is not necessarily to separate from mother liquor, does not generate waste water,
Environmental-friendly without separation equipment, step is simple, and cost reduces.This method can control individual particle size, reduce single
Grain thickness keeps straight hole road vertical with maximum surface, obtains shorter diffusion path, to improve reaction rate, carbon distribution inhibited to lose
It is living, the content of non-skeleton metal species is reduced, catalytic activity is improved.
Detailed description of the invention
Fig. 1 is the electron scanning micrograph of ZSM-5-A made from comparative example 2；
Fig. 2 is the electron scanning micrograph of titanium-silicon molecular sieve TS-1-C made from embodiment 2；
Fig. 3 is the electron scanning micrograph of the tiling of TS-1-E made from embodiment 4 on the glass sheet；
Fig. 4 is the XRD spectra of the tiling of TS-1-E made from embodiment 4 on the glass sheet.
Specific embodiment
Comparative example 1
It is according to the method that document " catalysis journal " (2001,22 (6): 513-514) provides, tetrapropylammonium hydroxide is water-soluble
Liquid is added in ethyl orthosilicate, heats at 60-85 DEG C；Titanium esters are added isopropanol and tetrapropylammonium hydroxide solution are added, by two
5-6h is stirred after kind solution mixing, the molar ratio of mixture is 1SiO2: (0.02~0.03) TiO2: (0.25~0.35) TPAOH:
(1.0~1.1) IPA:(25~40) H2O. mixture is transferred in crystallizing kettle, in 170 DEG C of standing crystallization 12h, separation is washed
It washs, dry 550 DEG C of roasting 5-8h at 100 DEG C.Obtained TS-1, being numbered is TS-1-A.
Comparative example 2
According to the method that patent CN201210118788.7 is provided, first by solid material: the amorphous titanium dioxide of 0.285g
Silicon, nine water sodium metasilicate of 1.319g, 0.72g 4-propyl bromide, 0.013g boehmite and the 0.69g ammonium nitrate amount of weighing up are poured into well
Mortar, then ground and mixed is carried out, after grinding 15min, reaction mixture is fitted into the steel bomb of polytetrafluoroethyllining lining,
2d is reacted under the conditions of 180 DEG C, reaction product is sufficiently washed with water, and in 80 DEG C of dry 12h or more, obtains final products.
The stoicheiometry of the system is as follows: Na2O:Al2O3:SiO2:H2O:R is 0.5:0.0125:1:4.5:0.3.Obtained ZSM-5, will
Its number is ZSM-5-A.
In comparative example 1 after crystallization, a large amount of mother liquors are generated.
Fig. 1 is the electron scanning micrograph of ZSM-5-A obtained in comparative example 2, it can be seen that since raw material mixes
Unevenly, the crystallite dimension that obtains is simultaneously uneven.
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Embodiment 1
12.1g methyl orthosilicate, the tetrapropylammonium hydroxide solution of 20g25wt%, 15g water, 3g glycine are added
It in the three-necked flask of jacketed, stirs evenly, obtains mixed liquor A；Mixed liquor A is hydrolyzed into 1.5h at 50 DEG C.By 0.48g metatitanic acid
The tetrapropylammonium hydroxide solution of tetra-ethyl ester and 8.1g 25wt%, the mixing of 15g water, are uniformly mixing to obtain mixed liquid B；It will mix
Liquid B is closed in 50 DEG C of hydrolysis 1.5h；Mixed liquor A and mixed liquid B are mixed, stirred evenly, alcohol 1h is removed at 90 DEG C, glycine is added
1.2g obtains mixed liquor C, by mixed liquor C in 40 DEG C of stirring 20min, mixed liquor is fitted into crystallizing kettle, in 160 DEG C of crystallization
72h, crystallization product is through drying, and in 500 DEG C of roasting 4h, obtained TS-1, being numbered is TS-1-B.
Embodiment 2
16.5g ethyl orthosilicate, the tetrapropylammonium hydroxide solution of 20g25wt%, 15g water, 6g aspartic acid are added
Enter in the three-necked flask of jacketed, stir evenly, obtains mixed liquor A；Mixed liquor A is hydrolyzed into 3h at 50 DEG C.By 0.68g metatitanic acid
The tetrapropylammonium hydroxide solution of four butyl esters and 8.1g 25wt%, the mixing of 15g water, are uniformly mixing to obtain mixed solution B；It will
Mixed liquid B hydrolyzes 0.5h at 50 DEG C；Mixed liquor A and mixed liquid B are mixed, stirred evenly, alcohol 1h is removed at 90 DEG C, asparagus fern is added
Propylhomoserin 2.4g obtains mixed liquor C, by mixed liquor C in 50 DEG C of stirring 15min, mixed liquor is fitted into crystallizing kettle, in 170 DEG C of crystalline substances
Change 48h, crystallization product is through drying, and in 540 DEG C of roasting 5h, obtained TS-1, being numbered is TS-1-C.
Fig. 2 is the electron scanning micrograph of titanium-silicon molecular sieve TS-1-C made from embodiment 2, can from figure
Out, sample made from the present embodiment is nano flake, and thickness is about 40nm.And sample is the generation of no mother liquor after crystallization, is not required to
It is separated by solid-liquid separation.
Embodiment 3
16.5g ethyl orthosilicate, the tetrapropylammonium hydroxide solution of 15g25wt%, 15g water, alanine 4g are added
It in the three-necked flask of jacketed, stirs evenly, obtains mixed liquor A；Mixed liquor A is hydrolyzed into 3h at 50 DEG C.By 0.68g metatitanic acid four
The tetrapropylammonium hydroxide solution of butyl ester and 5.5g 25wt%, the mixing of 15g water, are uniformly mixing to obtain mixed solution B；It will mix
It closes liquid B and hydrolyzes 0.5h at 50 DEG C；Mixed liquor A and mixed liquid B are mixed, stirred evenly, alcohol 1h is removed at 90 DEG C, alanine is added
0.2g obtains mixed liquor C, by mixed liquor C in 50 DEG C of stirring 15min, mixed liquor is fitted into crystallizing kettle, in 170 DEG C of crystallization
48h, crystallization product is through drying, and in 500 DEG C of roasting 5h, obtained TS-1, being numbered is TS-1-D.
Embodiment 4
16.5g ethyl orthosilicate, the tetrapropylammonium hydroxide solution of 15g25wt%, 15g water, arginine 3.5g are added
Enter in the three-necked flask of jacketed, stir evenly, obtains mixed liquor A；Mixed liquor A is hydrolyzed into 2h at 40 DEG C.By 0.68g metatitanic acid
The tetrapropylammonium hydroxide solution of four butyl esters and 5.5g 25wt%, the mixing of 15g water, are uniformly mixing to obtain mixed solution B；It will
Mixed liquid B hydrolyzes 1h at 45 DEG C；Mixed liquor A and mixed liquid B are mixed, stirred evenly, alcohol 2h is removed at 80 DEG C, arginine is added
2.5g obtains mixed liquor C, by mixed liquor C in 50 DEG C of stirring 20min, mixed liquor is fitted into crystallizing kettle, the crystallization at 150 DEG C
72h, crystallization product passes through drying, in 540 DEG C of roastings 4h, obtained TS-1, TS-1-E.
Fig. 3 is the electron scanning micrograph of the tiling of TS-1-E made from embodiment 4 on the glass sheet；Fig. 4 is to implement
The XRD spectra of the tiling of TS-1-E made from example 4 on the glass sheet.Sample is laid in sheet glass, it, can by SEM in Fig. 3
To see that sample exposes its maximum planes, the test of XRD is carried out to sample, as a result as shown in fig. 4, it can be seen that molecular sieve
TS-1-E only waits crystal faces to have diffraction maximum 010, and the molecular sieve for caning be found that prepared by the method for the present invention in conjunction with XRD and SEM spectrum is straight
Duct direction keeps the diffusion path of reactant and product in duct shorter, diffusional resistance is smaller perpendicular to maximum crystal face.
Embodiment 5
By the tetrapropylammonium hydroxide solution of 15.8g 30wt% silica solution, 15g 25wt%, 20g water, 3g lysine
It is added in the three-necked flask of jacketed, stirs evenly, obtain mixed liquor A；By 0.68g butyl titanate and 5.3g 25wt%
Tetrapropylammonium hydroxide solution, 10g water mixing, mixed liquid B is uniformly mixing to obtain, by mixed liquid B in 40 DEG C of hydrolysis 3h；It will
Mixed liquor A and mixed liquid B mixing, stir evenly, and remove alcohol 1h at 90 DEG C, lysine 0.6g is added, obtains mixed liquor C, will mix
Mixed liquor is fitted into crystallizing kettle by liquid C in 40 DEG C of stirring 20min, and in 140 DEG C of crystallization 60h, crystallization product is through drying, at 540 DEG C
8h is roasted, obtained TS-1, being numbered is TS-1-F.
Embodiment 6
By the tetrapropylammonium hydroxide solution of 16.5g ethyl orthosilicate, 20g 25wt%, 20g water, 6.5g aspartic acid
It is added in the three-necked flask of jacketed, stirs evenly, obtain mixed liquor A；By mixed liquor A in 40 DEG C of hydrolysis 2.5h；By 0.47g titanium
The tetrapropylammonium hydroxide solution of sour tetra-ethyl ester and 9.3g 25wt%, the mixing of 10g water, are uniformly mixing to obtain mixed liquid B, will
Mixed liquid B is in 50 DEG C of hydrolysis 30min；Mixed liquor A and mixed liquid B are mixed, stirred evenly, alcohol 1h is removed at 90 DEG C, asparagus fern is added
Propylhomoserin 1.9g obtains mixed liquor C, mixed solution is fitted into crystallizing kettle, the crystallization 48h at 170 DEG C, crystallization product through drying,
In 540 DEG C of roasting 5h, obtained TS-1, being numbered is TS-1-G.
Embodiment 7
By the tetrapropylammonium hydroxide solution of 16.5g ethyl orthosilicate, 20g 25wt%, 20g water, 6.5g aspartic acid
It is added in the three-necked flask of jacketed, stirs evenly, obtain mixed liquor A；By mixed liquor A in 40 DEG C of hydrolysis 2.5h；By 1.45g titanium
The tetrapropylammonium hydroxide solution of sour four butyl esters and 9.3g 25wt%, the mixing of 10g water, are uniformly mixing to obtain mixed liquid B, will
Mixed liquid B is in 50 DEG C of hydrolysis 30min；Mixed liquor A and mixed liquid B are mixed, stirred evenly, alcohol 1h is removed at 90 DEG C, asparagus fern is added
Propylhomoserin 1.9g obtains mixed liquor C, mixed solution is fitted into crystallizing kettle, the crystallization 48h at 170 DEG C, crystallization product through drying,
In 540 DEG C of roasting 5h, obtained TS-1, being numbered is TS-1-H.
Embodiment 8
By the tetrapropylammonium hydroxide solution of 16.5g ethyl orthosilicate, 20g 25wt%, 20g water, 8.4g aspartic acid
It is added in the three-necked flask of jacketed, stirs evenly, obtain mixed liquor A；By mixed liquor A in 40 DEG C of hydrolysis 2.5h；By 1.45g titanium
The tetrapropylammonium hydroxide solution of sour four butyl esters and 8.1g 25wt%, the mixing of 10g water, are uniformly mixing to obtain mixed liquid B, will
Mixed liquid B is in 50 DEG C of hydrolysis 30min；Mixed liquor A and mixed liquid B are mixed, stirred evenly, alcohol 1h is removed at 80 DEG C, is mixed
Liquid C, mixed solution is fitted into crystallizing kettle, the crystallization 48h at 180 DEG C, and crystallization product is obtained through drying in 500 DEG C of roasting 4h
TS-1, being numbered is TS-1-I.
Embodiment 9
By the tetrapropylammonium hydroxide solution of 16g ethyl orthosilicate, 20g 25wt%, 20g water, 1.6g glycine are added
It in the three-necked flask of jacketed, stirs evenly, obtains mixed liquor A；By mixed liquor A in 40 DEG C of hydrolysis 2.5h；By 0.62g metatitanic acid four
The tetrapropylammonium hydroxide solution of butyl ester and 8.3g 25wt%, the mixing of 10g water, are uniformly mixing to obtain mixed liquid B, will mix
Liquid B is in 50 DEG C of hydrolysis 30min；Mixed liquor A and mixed liquid B are mixed, stirred evenly, alcohol 2h is removed at 90 DEG C, obtains mixed liquor C,
Arginine 5.9g is added, obtains mixed liquor C, mixed solution is fitted into crystallizing kettle, the crystallization 60h at 180 DEG C, crystallization product warp
Dry, in 540 DEG C of roasting 5h, obtained TS-1, being numbered is TS-1-J.
Embodiment 10
By the tetrapropylammonium hydroxide solution of 15.8g 30wt% silica solution, 13g 40wt%, 20g water, 6g glycine
It is added in the three-necked flask of jacketed, stirs evenly, obtain mixed liquor A；By the four of 0.38g titanium tetrachloride and 5.3g 40wt%
Propyl ammonium hydroxide aqueous solution, the mixing of 10g water, be uniformly mixing to obtain mixed liquid B, mixed liquor A and mixed liquid B mixed, stirring
Uniformly, arginine 0.42g is added, obtains mixed liquor C, by mixed liquor C in 40 DEG C of stirring 20min, mixed liquor is packed into crystallizing kettle
In, in 160 DEG C of crystallization 48h, crystallization product is through drying, and in 540 DEG C of roasting 3h, obtained TS-1, being numbered is TS-1-K.
Embodiment 11
16g ethyl orthosilicate, the tetrapropylammonium hydroxide solution of 20g 25wt%, concentration is molten for the ethamine of 30wt%
Liquid 15mL, the acetic acid solution 15mL that concentration is 30wt% are added in the three-necked flask of jacketed, stir evenly, obtain mixed liquor A；
By mixed liquor A in 50 DEG C of hydrolysis 3h；By the tetrapropylammonium hydroxide solution of 0.62g butyl titanate 8.3g25wt%, 10g water
Mixing, is uniformly mixing to obtain mixed liquid B；By mixed liquid B in 50 DEG C of hydrolysis 1h；Mixed liquor A and mixed liquid B are mixed, stirred
It mixes uniformly, removes alcohol 1h at 90 DEG C, obtain mixed liquor C, mixed liquor is fitted into crystallizing kettle, in 170 DEG C of crystallization 48h, crystallization product
Through drying, in 540 DEG C of roasting 3h, obtained obtained TS-1, being numbered is TS-1-L.
Embodiment 12
16g ethyl orthosilicate, the tetrapropylammonium hydroxide solution of 20g 25wt%, concentration is molten for the hexylamine of 30wt%
Liquid 10mL, the caproic acid solution 10mL that concentration is 30wt% are added in the three-necked flask of jacketed, stir evenly, obtain mixed liquor A；
By mixed liquor A in 50 DEG C of hydrolysis 3h；By the tetrapropylammonium hydroxide solution of 0.62g butyl titanate 8.3g25wt%, 10g water
Mixing, is uniformly mixing to obtain mixed liquid B；By mixed liquid B in 50 DEG C of hydrolysis 1h；Mixed liquor A and mixed liquid B are mixed, stirred
It mixes uniformly, removes alcohol 1h at 90 DEG C, the hexylamine solution 5mL that concentration is 30wt% is added, concentration is the caproic acid solution 5mL of 30wt%,
Mixed liquor C is obtained, by mixed liquor C in 50 DEG C of stirring 30min, mixed liquor is fitted into crystallizing kettle, in 170 DEG C of crystallization 48h, crystallization
Product is through drying, and in 540 DEG C of roasting 3h, obtained obtained TS-1, being numbered is TS-1-M.
Embodiment 13
16g ethyl orthosilicate, the tetrapropylammonium hydroxide solution of 20g 25wt%, concentration is molten for the ethamine of 30wt%
Liquid 10mL, the acetic acid solution 10mL that concentration is 30wt% are added in the three-necked flask of jacketed, stir evenly, obtain mixed liquor A；
By mixed liquor A in 50 DEG C of hydrolysis 3h；By the tetrapropylammonium hydroxide solution of 0.62g butyl titanate 8.3g25wt%, 10g water
Mixing, is uniformly mixing to obtain mixed liquid B；By mixed liquid B in 50 DEG C of hydrolysis 1h；Mixed liquor A and mixed liquid B are mixed, stirred
It mixes uniformly, removes alcohol 1h at 90 DEG C, the hexylamine solution 5mL that concentration is 30wt% is added, concentration is the caproic acid solution 5mL of 30wt%,
Mixed liquor C is obtained, by mixed liquor C in 50 DEG C of stirring 30min, mixed liquor is fitted into crystallizing kettle, in 170 DEG C of crystallization 48h, crystallization
Product is through drying, and in 540 DEG C of roasting 3h, obtained TS-1, being numbered is TS-1-N.
Embodiment 14
16g ethyl orthosilicate, the tetrapropylammonium hydroxide solution of 20g 25wt%, concentration is molten for the ethamine of 30wt%
Liquid 10mL, the acetic acid solution 10mL that concentration is 30wt% are added in the three-necked flask of jacketed, stir evenly, obtain mixed liquor A；
By mixed liquor A in 50 DEG C of hydrolysis 3h；By the tetrapropylammonium hydroxide solution of 0.62g butyl titanate 8.3g25wt%, 10g water
Mixing, is uniformly mixing to obtain mixed liquid B；By mixed liquid B in 50 DEG C of hydrolysis 1h；Mixed liquor A and mixed liquid B are mixed, stirred
It mixes uniformly, removes alcohol 1h at 90 DEG C, the hexylamine solution 5mL that concentration is 30wt% is added, concentration is the caproic acid solution 5mL of 30wt%,
Mixed liquor C is obtained, by mixed liquor C in 50 DEG C of stirring 30min, mixed liquor is fitted into crystallizing kettle, in 170 DEG C of crystallization 58h, crystallization
Product is through drying, and in 540 DEG C of roasting 3h, obtained TS-1, being numbered is TS-1-O.
Embodiment 15
16g ethyl orthosilicate, the tetrapropylammonium hydroxide solution of 20g 25wt%, concentration is molten for the ethamine of 26wt%
Liquid 10mL, the acetic acid solution 10mL that concentration is 30wt% are added in the three-necked flask of jacketed, stir evenly, obtain mixed liquor A；
By mixed liquor A in 50 DEG C of hydrolysis 4h；By the tetrapropylammonium hydroxide solution of 0.62g butyl titanate 8.3g25wt%, 10g water
Mixing, is uniformly mixing to obtain mixed liquid B；By mixed liquid B in 50 DEG C of hydrolysis 1h；Mixed liquor A and mixed liquid B are mixed, stirred
It mixes uniformly, removes alcohol 1h at 85 DEG C, alanine 1.9g is added, obtains mixed liquor C, by mixed liquor C in 50 DEG C of stirring 30min, will mix
It closes liquid to be fitted into crystallizing kettle, in 170 DEG C of crystallization 58h, crystallization product is through drying, in 540 DEG C of roastings 3h, obtained TS-1, by it
Number is TS-1-P.
Embodiment 16
16g ethyl orthosilicate, the tetrapropylammonium hydroxide solution of 20g 25wt%, 10ml water, alanine 1.9g are added
Enter in the three-necked flask of jacketed, stir evenly, obtains mixed liquor A；By mixed liquor A in 50 DEG C of hydrolysis 4h；By 0.62g metatitanic acid four
The tetrapropylammonium hydroxide solution of butyl ester 8.1g 25wt%, the mixing of 10g water, are uniformly mixing to obtain mixed liquid B；It will mix
Liquid B is closed in 50 DEG C of hydrolysis 1h；Mixed liquor A and mixed liquid B are mixed, stirred evenly, removes alcohol 1.5h at 85 DEG C, concentration, which is added, is
The ethylamine solution 10mL of 26wt%, concentration are that the acetic acid solution 10mL of 30wt% obtains mixed liquor C, and mixed liquor C is stirred at 50 DEG C
30min is mixed, mixed liquor is fitted into crystallizing kettle, in 170 DEG C of crystallization 58h, crystallization product is obtained through drying in 540 DEG C of roasting 3h
TS-1, being numbered is TS-1-Q.
Embodiment 17
By the tetrapropylammonium hydroxide solution of 16.5g ethyl orthosilicate, 15g 25wt%, 20g water, 5g aspartic acid add
Enter in the three-necked flask of jacketed, stir evenly, obtain mixed liquor A, by mixed liquor A in 40 DEG C of hydrolysis 2.5h.0.27g is anhydrous
The tetrapropylammonium hydroxide solution of aluminium chloride and 5.3g 25wt%, the mixing of 10g water, are uniformly mixing to obtain mixed liquid B, will mix
Liquid A and mixed liquid B mixing are closed, is stirred evenly, alcohol 1h is removed at 90 DEG C, aspartic acid 1g is added, mixed liquor C is obtained, by mixed liquor C
In 170 DEG C of crystallization 48h, crystallization product is through drying, and in 540 DEG C of roasting 6h, obtained ZSM-5, being numbered is ZSM-5-B.
Application examples 1
0.1g Titanium Sieve Molecular Sieve is added in 200mL stainless steel intermittent kettle reactor, 34mL1.0mol/L H is added2O2
Methanol solution is passed through 0.15MPa butylene, is heated to 50 DEG C, reacts 1h, and taking-up product, which is centrifugated out, after being cooled to room temperature is catalyzed
Agent takes supernatant liquid to carry out iodometric titrationiodimetry titration H2O2Concentration and chromatography product assay, the results are shown in Table 1.
It can be seen that, under the same reaction time, it is added without in the TS-1-A of any structure regulator, due to butylene from table
Molecule takes a long time in the active site being diffused into duct, and conversion ratio is lower, and knot is added in the synthesis process
The catalyst such as sample TS-1-B, TS-1-C of structure regulator are due to relatively thin in straight hole road direction, and straight hole road is perpendicular to maximum sudden and violent
Reveal plane, reactant molecule can be diffused into duct interior contact to active site faster, and conversion ratio is higher.
Table 1
Note: X (H2O2) indicate H2O2Conversion ratio, S (BO) indicate epoxy butane (BO) selectivity, respectively by following formula meter
It calculates:
X(H2O2- n (the H of)=12O2)/n0(H2O2) (1)
S (BO)=n (BO)/(n (BO)+n (MME)+n (BG)) (2)
In formula, n0(H2O2) and n (H2O2) respectively indicate reaction front and back H2O2Substance withdrawl syndrome, n (BO), n (MME) and
N (BG) respectively indicates the substance withdrawl syndrome of BO, butanediol monomethyl ether (MME) and butanediol (BG).
To sum up, the present invention relates to a kind of synthesis sides of the MFI type nano flake hetero-atom molecular-sieve of green syt b axis orientation
Method.After crystallization, no mother liquor is generated, and without separation, is not necessarily to separation equipment, is not generated waste water, environmental-friendly, shortens production week
Phase reduces production cost.The molecular sieve of provided method preparation is that b axis is orientated according to the present invention, biggish straight in MFI structure
Perpendicular to maximum exposure crystal face, the straight hole road of MFI structure is shorter in duct, shortens diffusion path of the molecule in duct, reduces
Diffusional resistance reduces carbon distribution, extends catalyst life.The addition of structure regulator exists in the synthesis of titanium-silicon molecular sieve TS-1
Regulate and control titanium species while adjusted and controlled and pattern, reduces the content of extra-framework titanium.For alkene epoxidation, aromatic hydrocarbons hydroxyl
Change, the Selective Oxidations such as ketone ammoxidation show excellent catalytic activity.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art within the technical scope of the present disclosure, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (5)
1. a kind of green synthesis method of flake hetero-atom molecular-sieve, which is characterized in that specific steps are as follows:
S1, silicon source, the tetrapropylammonium hydroxide solution of 20~40wt%, water and structure regulator are mixed, stirs evenly, obtains
To mixed liquor A；By mixed liquor A in 0~60 DEG C of 0~6h of hydrolysis；
The molar ratio of each substance in the mixed liquor A are as follows:
SiO2:TPAOH:H2O=1:(0.0101~0.3499): (10.01~34.99)；
Structure regulator and SiO in the mixed liquor2Mass ratio be 0.010~2.449；
The structure regulator be two substance of amino acid, fatty acid and amine mixture or amino acid, fatty acid and
The mixture of three substance of amine；
The amino acid includes glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, color ammonia
Acid, tyrosine, cysteine, methionine, glutamic acid, threonine, arginine, histidine, aspartic acid, lysine and serine
At least one of；
S2, by metal component, 20%~40% tetrapropylammonium hydroxide solution and water mix, stir evenly, mixed
Liquid B；By mixed liquid B in 0~60 DEG C of 0~6h of hydrolysis；
The molar ratio of each substance in the mixed liquid B are as follows:
MOx:TPAOH:H2O=1:(0~9.99): (50.01~999.99)；
Wherein MOxMetal component is referred to calculate in the form of the oxide；
S3, mixed liquor A and mixed liquid B are mixed, is stirred evenly, remove 0~3h of alcohol at 60~90 DEG C；Structure regulator is added, obtains
To mixed liquor C；By mixed liquor C in 40~80 DEG C of 10~60min of stirring；
The molar ratio of each substance in the mixed liquor C are as follows:
SiO2:MOx:TPAOH:H2O=1:(0.0201~0.1000): (0.0501~0.4999): (20.01~54.99)；
The structure regulator be two substance of amino acid, fatty acid and amine mixture or amino acid, fatty acid and
The mixture of three substance of amine；
The amino acid includes glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, color ammonia
Acid, tyrosine, cysteine, methionine, glutamic acid, threonine, arginine, histidine, aspartic acid, lysine and serine
At least one of；
The structure regulator and SiO2Mass ratio be 0~5.002；
S4, the product for obtaining step S3 are packed into crystallizing kettle, and 100~250 DEG C of 6~72h of crystallization obtain crystallization product；
S5, the crystallization product for obtaining step S4 in 80~120 DEG C of dry 2~12h, 400~600 DEG C of 3~12h of roasting to get
To laminar hetero-atom molecular-sieve.
S3, when step S2 is hydrolyzed and except alcohol process is 0h, structure is added directly in the mixed liquor made from step S1 and adjusts
Agent simultaneously stirs evenly；
When the hydrolysis of step S2 or except alcohol process be not 0h when, step S2 obtain except structure regulator is added in alcohol product,
It stirs evenly；
The structure regulator and SiO2Mass ratio be 0.001~6.3499；
The structure regulator be two substance of amino acid, fatty acid and amine mixture or amino acid, fatty acid and
The mixture of three substance of amine；
The amino acid includes glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, color ammonia
Acid, tyrosine, cysteine, methionine, glutamic acid, threonine, arginine, histidine, aspartic acid, lysine and serine
At least one of；
S4, the product for obtaining step S3 are packed into crystallizing kettle, and 90~250 DEG C of 6~72h of crystallization obtain crystallization product；
S5, the crystallization product for obtaining step S4 dry 2~12h at 80~120 DEG C, roast 3~12h at 400~600 DEG C,
Obtain laminar hetero-atom molecular-sieve.
2. the green synthesis method of laminar hetero-atom molecular-sieve according to claim 1, which is characterized in that institute in step S1
The metallic element for the metal component stated include magnesium, aluminium, titanium, zinc, silver, gallium, molybdenum, tungsten, copper, manganese, nickel, iron, zirconium, platinum, chromium, billows, cerium,
At least one of praseodymium, rubidium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, yttrium；
The metal component be the chloride of metal oxide or corresponding metallic element, sulfate, nitrate, in esters at least
It is a kind of.
3. the green synthesis method of laminar hetero-atom molecular-sieve according to claim 1, which is characterized in that described in step S1
Silicon source be at least one of silica solution, methyl orthosilicate, ethyl orthosilicate, white carbon black.
4. the green synthesis method of laminar hetero-atom molecular-sieve according to claim 1, which is characterized in that when step S1 institute
It states silicon source and when metal component uses non-Ester simultaneously, step S1 hydrolysis time is 0h；
When the metal component described in the step S2 uses non-Ester, step S2 hydrolysis time is 0h；
When silicon source and metal component described in step S1, the step S2 use non-Ester simultaneously, mixed liquor C's described in step S3
Except the alcohol time is 0h.
5. the laminar hetero-atom molecular-sieve of the preparation of green synthesis method described in claim 1, which is characterized in that nanometer sheet is most
Large surface is parallel with (0 2 0) crystal face, and straight orifice throat length is controllable, and modification scope is 30~200nm.
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