CN107902668B - A kind of self-supporting film shape MFI molecular sieve and preparation method - Google Patents
A kind of self-supporting film shape MFI molecular sieve and preparation method Download PDFInfo
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- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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Abstract
The present invention provides a kind of self-supporting film shape MFI molecular sieve and preparation method, includes the following steps: to mix silicon source, template, water and silicon source, obtain starting sol；The starting sol is mixed with aldehydes solvent, obtains molecular sieve mother liquor；The molecular sieve mother liquor is successively subjected to hydrothermal crystallizing, drying and roasting, obtains self-supporting film shape MFI molecular sieve.Preparation method provided by the invention is not necessarily to supporter, get rid of limitation of the backing material to molecular screen membrane, the film-form molecular sieve structure of synthesis is regular, particle diameter distribution is uniform, crystallinity is high, thermal stability is good, and by changing synthesis condition, can control the thickness and size of molecular screen membrane.
Description
Technical field
The present invention relates to molecular sieve and its preparation technical fields, and in particular to a kind of self-supporting film shape MFI molecular sieve and
Preparation method.
Background technique
Zeolite-type molecular sieve has unique cellular structure and catalytic performance, is widely used in catalysis, adsorbing separation, sensing
Device, microelectrode, electron microprobe etc..Sieve particle itself can only be used as a kind of catalyst or adsorbent, if energy
It is prepared into continuous molecular sieve film, so that it may easily carry out UF membrane and film reaction operation, both can greatly mention
High separating effect, and integrated reaction and separation may be implemented.Mainly there are MFI type, LTA type, FAU currently as membrane material research
Type, CHA type, MOR type and FER type molecular sieve, in the study on the synthesis of zeolite molecular sieve film, MFI molecular sieve is to grind so far
Study carefully most one kind.
Molecular sieve with MFI type skeleton structure is intersected by two different ten-ring ducts, and one kind is in straight
Line style and the ten-ring straight hole road for being parallel to b axis directionAnother kind is that S-type (zig-zag) bending is parallel to
The ten-ring duct of a axis directionDue to its special cellular structure, MFI molecular sieve is suitble to separate many important
The raw material of industry, it is considered to be the most molecular screen membrane of potentiality to be exploited.
It is prepared currently, molecular screen membrane mainly passes through Vacuum-assisted method method.Vacuum-assisted method method be by silicon source, silicon source,
Template and alkali are configured to Synthesis liquid according to a certain percentage, are put into togerther in hydrothermal reaction kettle and are reacted with supporter, finally
It is cleaned with deionized water to neutral and drying and roasting.This synthetic method Synthesis liquid is ultimately formed in supporting body surface random nucleation
Molecular screen membrane.Jansen J etc. has synthesized the MFI type zeolite molecular screen membrane of oriented growth on silicon with this method
(Journal ofCrystal Growth 128(1993)1150-1156).But this synthesizing molecular sieve film on supporter
The material selection of method its supporter have a very big limitation, it is most can only be in more smooth non-porous support or mesoporous load
Synthesize the molecular screen membrane for having orientation on body, this is restricted the preparation of molecular screen membrane and application all.
Summary of the invention
In consideration of it, the purpose of the present invention is to provide a kind of preparation method of self-supporting film shape MFI molecular sieve, in view of
This, the purpose of the present invention is to provide a kind of preparation method of self-supporting film shape MFI molecular sieve, preparation sides provided by the invention
Method is not necessarily to supporter, and the uniform, crystallinity using film-form molecular sieve structure rule, the particle diameter distribution of the method for the present invention synthesis
It is high, thermal stability is good, molecular screen membrane thickness and size are controllable.
To achieve the goals above, the present invention provides following technical proposals:
A kind of preparation method of self-supporting film shape MFI molecular sieve includes the following:
The Si-MFI molecular sieve of synthesis is to be intersected with MFI topological structure by two different ten-ring ducts, than
Surface area reaches 250-450m2/ g, about 0.1-2 μm of the thickness of film, size is about in 0.1-5 μ m 0.1-15 μ m.
Silicon source, template, water and silicon source are mixed, starting sol is obtained；
The starting sol is mixed with aldehydes solvent, obtains molecular sieve mother liquor；
The molecular sieve mother liquor is successively subjected to hydrothermal crystallizing, drying and roasting, obtains self-supporting film shape MFI molecule
Sieve；
The molar ratio of element silicon is 0~0.05:0.1~0.8 in aluminium element, template, water and silicon source in source of aluminium:
10~80:1.
Preferably, source of aluminium be aluminum nitrate, aluminium isopropoxide, aluminum sulfate, aluminium chloride, aluminium hydroxide, boehmite and
One or more of sodium metaaluminate.
Preferably, the template is tetrapropylammonium hydroxide, 4-propyl bromide, n-butylamine, ethylenediamine and hexamethylene diamine
One or more of.
Preferably, the silicon source is positive esters of silicon acis, silicic acid, white carbon black and silica solution.
Preferably, the aldehydes solvent is formaldehyde, acetaldehyde, propionic aldehyde, benzaldehyde, p-tolyl aldehyde, naphthaldehyde, adjacent benzene two
One or more of formaldehyde, m-terephthal aldehyde, terephthalaldehyde, phenylacetaldehyde and benzenpropanal.
Preferably, the molar ratio of the aldehydes solvent and element silicon in silicon source is 0.3~10:1.
Preferably, the temperature of the hydrothermal crystallizing is 120~220 DEG C, and the time of the hydrothermal crystallizing is 24~220h.
Preferably, the temperature of the drying is 40~150 DEG C, time of the drying is 1~for 24 hours.
Preferably, the temperature of the roasting is 500~560 DEG C, time of the roasting is 1~for 24 hours.
The present invention also provides self-supporting film shape MFI molecular sieve prepared by the above method, the MFI molecular sieves
It is with MFI topological structure, specific surface area is 250~450m2/ g, micro pore volume are 0.09~0.30cm3/g；Film with a thickness of
0.1~2 μm, size is in the range of 0.1~15 μm of 0.1~5 μ m.Advantageous effects:
The present invention is adsorbed on surface by the way that aldehydes solvent, the aldehydes in preparation solution is added, and makes crystal face-selective exposure, passes through
Hydro-thermal method promotes the silicone hydroxyl condensation between crystal to form self-supporting film shape MFI molecular sieve, preparation method provided by the invention
Without supporter, limitation of the backing material to molecular screen membrane is got rid of.
The film-form molecular sieve structure of method synthesis provided by the invention is regular, particle diameter distribution is uniform, and crystallinity is high, and heat is steady
It is qualitative good；By changing synthesis condition, the thickness and size of molecular screen membrane can control.
Detailed description of the invention
Fig. 1 is the SEM figure of MFI molecular sieve obtained in the embodiment of the present invention 1；
Fig. 2 is the XRD diagram of MFI molecular sieve obtained in the embodiment of the present invention 1；
Fig. 3 is that MFI molecular sieve obtained in the embodiment of the present invention 1 roasts the SEM figure after 8h；
Fig. 4 is the SEM figure of MFI molecular sieve obtained in the embodiment of the present invention 2；
Fig. 5 is the SEM figure of MFI molecular sieve obtained in the embodiment of the present invention 3；
Fig. 6 is the SEM figure of MFI molecular sieve obtained in the embodiment of the present invention 4；
Fig. 7 is the SEM figure of MFI molecular sieve obtained in the embodiment of the present invention 5,13；
Fig. 8 is the SEM figure of MFI molecular sieve obtained in the embodiment of the present invention 6；
Fig. 9 is the SEM figure of MFI molecular sieve obtained in the embodiment of the present invention 7,12；
Figure 10 is the SEM figure of MFI molecular sieve obtained in the embodiment of the present invention 8；
Figure 11 is the SEM figure of MFI molecular sieve obtained in the embodiment of the present invention 9,11；
Figure 12 is the SEM figure of MFI molecular sieve obtained in the embodiment of the present invention 10.
Specific embodiment
The present invention provides a kind of preparation methods of self-supporting film shape MFI molecular sieve, include the following:
Silicon source, template, water and silicon source are mixed, starting sol is obtained；
The starting sol is mixed with aldehydes solvent, obtains molecular sieve mother liquor；
The molecular sieve mother liquor is successively subjected to hydrothermal crystallizing, drying and roasting, obtains self-supporting film shape MFI molecule
Sieve.
The present invention mixes silicon source, template, water and silicon source, obtains starting sol.In the present invention, source of aluminium is preferred
For one or more of aluminum nitrate, aluminium isopropoxide, aluminum sulfate, aluminium chloride, aluminium hydroxide, boehmite and sodium metaaluminate,
More preferably aluminum nitrate, aluminum sulfate, boehmite and/or aluminium isopropoxide；When source of aluminium be aluminum nitrate, aluminum sulfate, intend it is thin
Diaspore or aluminium isopropoxide wherein any two kinds when, the present invention is not particularly limited its mass ratio, is with arbitrary proportion mixing
It can.
In the present invention, the template is preferably tetrapropylammonium hydroxide, 4-propyl bromide, n-butylamine, ethylenediamine
One or more of with hexamethylene diamine, more preferably tetrapropylammonium hydroxide, n-butylamine or 4-propyl bromide.
In the present invention, the silicon source is preferably positive esters of silicon acis, silicic acid, white carbon black and silica solution, the esters of silicon acis that is preferably positive,
White carbon black and silica solution, the quanmethyl silicate that is more preferably positive, tetraethyl orthosilicate and positive silicic acid orthocarbonate.
The present invention does not have special limitation to the type of the water, is with water using dissolution well known to those skilled in the art
Can, in an embodiment of the present invention, it can specifically use deionized water.
In the present invention, the molar ratio of element silicon is preferably 0 in the aluminium element in source of aluminium, template, water and silicon source
~0.05:0.1~0.8:10~80:1, more preferably 0.005~0.04:0.2~0.6:20~70:1.
In the present invention, the molecular sieve obtained when aluminium element is zero be it is a kind of without aluminium have MFI topology framework knot
The molecular sieve of structure, i.e. silicalite-1 molecular sieve.When aluminium element is zero, the present invention by adjusting aldehyde type, such as by benzene
The acetaldehyde of formaldehyde same amount replaces, and the thickness of film reduces, or increases the amount of aldehyde to increase the thickness of film.
In the present invention, the molecular sieve obtained when aluminium element is not zero has MFI topology framework knot containing aluminium to be a kind of
The molecular sieve of structure, i.e. ZSM-5 molecular sieve.When aluminium element is not zero, the present invention controls single crystal grain by adjusting silica alumina ratio
Prolong the length of c-axis and then control the thickness of film, in the amount ranges (0~0.05) of aluminium element of the present invention and element silicon: 1
Interior, when aluminium content increases, the thickness of film increases.
The present invention does not have particular/special requirement to the hybrid mode of source of aluminium, template, water and silicon source, selects art technology
Hybrid mode known to personnel.Silicon source and template are preferably added sequentially to carry out the first stirring in water by the present invention, obtain
To mixture；Silicon source is added in the mixture again and carries out the second stirring, obtains starting sol.In the present invention, described
One stirring rate is preferably 100~600rpm, more preferably 150-400rpm, and first mixing time is preferably 1~10h,
More preferably 2-8h；Second stirring rate is preferably 100~600rpm, more preferably 150-300rpm, and described second stirs
Mixing the time is preferably 2~48h, more preferably 4~40h.The present invention is not particularly limited stirring means, selects art technology
Stirring means known to personnel.
After obtaining starting sol, the present invention mixes the starting sol with aldehydes solvent, obtains molecular sieve mother liquor.At this
In invention, the aldehydes solvent is preferably formaldehyde, acetaldehyde, propionic aldehyde, benzaldehyde, p-tolyl aldehyde, naphthaldehyde, O-phthalic
One or more of aldehyde, m-terephthal aldehyde, terephthalaldehyde, phenylacetaldehyde and benzenpropanal, more preferably formaldehyde, acetaldehyde, benzene first
One or more of aldehyde and p-tolyl aldehyde.
In the present invention, the molar ratio of the aldehydes solvent and element silicon in silicon source is preferably 0.3~10:1, more preferably
1~8:1.
The present invention controls the size of film size by adjusting the ratio of aldehydes solvent and element silicon, of the present invention
Aldehydes solvent and element silicon amount ranges in, when the ratio of aldehydes solvent and element silicon increase when, the area of film increases therewith
Greatly.
The present invention is not particularly limited the hybrid mode of the starting sol and aldehydes solvent, selects this field routine
Starting sol and aldehydes solvent can be uniformly mixed by hybrid mode.
After obtaining molecular sieve mother liquor, the molecular sieve mother liquor is successively carried out hydrothermal crystallizing, drying and roasting by the present invention, is obtained
To self-supporting film shape MFI molecular sieve.In the present invention, the temperature of the hydrothermal crystallizing is preferably 120~220 DEG C, more preferably
It is 150-210 DEG C；The time of the hydrothermal crystallizing is preferably 24~200h, more preferably 48-160h；The present invention is to the water
The device of thermal crystallisation reaction is not particularly limited, and selects hydro-thermal reaction device conventional in the art, the present invention preferably exists
It is carried out in high-pressure hydrothermal reaction kettle.
After the reaction was completed, hydrothermal crystallizing reaction solution is preferably successively filtered, washs hydrothermal crystallizing by the present invention, obtains water
Thermal crystallisation product.The present invention is not particularly limited the method for filtering, selects filter method well known to those skilled in the art i.e.
It can；The present invention preferably washs hydrothermal crystallizing product to neutrality, and the washing preferably uses deionized water or alcohol in the present invention
It is washed, the present invention is not particularly limited washing methods, selects washing methods well known to those skilled in the art.
After obtaining hydrothermal crystallizing product, the present invention is dry by the hydrothermal crystallizing product, the hydrothermal crystallizing after being dried
Product.In the present invention, the drying temperature is preferably 40~150 DEG C, and the drying time is preferably 1~for 24 hours.
After hydrothermal crystallizing product after being dried, the present invention roasts the hydrothermal crystallizing product after the drying, obtains
Self-supporting film shape MFI molecular sieve.In the present invention, the temperature of the roasting is preferably 500~560 DEG C；The roasting when
Between preferably 1~for 24 hours.
The present invention utilizes traditional hydro-thermal method, by the way that aldehydes solvent is added, forms self-supporting film shape molecule in an orderly manner
Sieve, and in the case where no supporter, the thickness and area of molecular screen membrane can be controlled, by changing preparation condition with satisfaction pair
Different size, requirement when variety classes molecule is sieved；And the film-form MFI molecule synthesized using method of the invention
Sieve structure is regular, particle diameter distribution is uniform, thermal stability is good, there is extensive prospect in molecular sieve separation field.
The present invention also provides closing self-supporting film shape MFI molecular sieve prepared by the above method,
The MFI molecular sieve has MFI topological structure in the present invention, and specific surface area is preferably 250~450m2/ g, it is micro-
Pore volume is preferably 0.09~0.30cm3/g；The thickness of film is preferably 0.1~2 μm, size preferably 0.1~5 μ m 0.1~
In the range of 15 μm.
It is carried out below with reference to preparation method of the embodiment to self-supporting film shape MFI molecular sieve provided by the invention detailed
Illustrate, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Tetrapropylammonium hydroxide 6.25g is added dropwise in 32.74g deionized water to be slowly dropped into after stirring 1 hour
10.4g tetraethyl orthosilicate.It stirs after mixing for 24 hours, 21.19g benzaldehyde is then added into system.Then by molecular sieve
Synthesis mother liquid moves into high pressure hydrothermal synthesis kettle, and crystallization is taken out after 160 hours at 190 DEG C, washs to neutrality, in 80 DEG C of baking ovens
12 hours dry, taking-up roasts 8 hours at 550 DEG C, obtains film-form MFI sieve sample.
Original powder is roasted into 8h at 550 DEG C, the structure of molecular sieve after then being roasted with scanning electron microscopic observation, as shown in Figure 3.
Fig. 1 is the SEM figure of film-form MFI sieve sample obtained in embodiment 1, and wherein Fig. 1 (a) is film-form molecule
Sieve amplifies 10000 times of SEM figure, and Fig. 1 (b) is the SEM figure that film-form molecular sieve amplifies 20000 times.As shown in Figure 1, embodiment 1
Obtained in film-form MFI sieve sample particle size distribution it is uniform, and the size of film be 3.5 μm of 2.5 μ m, with a thickness of
0.4μm。
Fig. 2 is the XRD diagram of film-form MFI molecular sieve obtained in embodiment 1.As shown in Figure 2, obtained in embodiment 1
Film-form MFI sieve sample has apparent MFI topological structure, and crystallinity is high.
Fig. 3 is that film-form MFI sieve sample obtained in embodiment 1 roasts the film-form MFI sieve sample after 8h
SEM figure, from the figure 3, it may be seen that this stable structure, high temperature resistant can expand its use scope.
Embodiment 2
0.07g aluminium isopropoxide is dissolved in 15.95g water, tetrapropylammonium hydroxide 13.64g is added dropwise, is stirred 10 hours
Afterwards, it is slowly dropped into 7g tetraethyl orthosilicate.48h is stirred after mixing, and 35.66g benzaldehyde is then added into system.Then
Molecular sieve synthesis mother liquid is moved into high pressure hydrothermal synthesis kettle, crystallization is taken out after 96 hours at 180 DEG C, washs to neutrality, 100
12 hours dry in DEG C baking oven, taking-up roasts 20 hours at 550 DEG C, obtains film-form MFI sieve sample.
Fig. 4 is the SEM figure of film-form MFI sieve sample obtained in embodiment 2.As shown in Figure 4, in embodiment 2
The film-form MFI sieve sample particle size distribution arrived is uniform, and the size of film is 3.6 μm of 1.4 μ m, with a thickness of 0.3 μ
m。
Embodiment 3
0.13g aluminum nitrate is dissolved in 4.97g water, tetrapropylammonium hydroxide 1.71g is added dropwise, after stirring 10 hours,
It is slowly dropped into 7g tetraethyl orthosilicate.2h is stirred after mixing, and 1.35 pairs// neighbour, two benzaldehyde is then added into system.
Then molecular sieve synthesis mother liquid moving into high pressure hydrothermal synthesis kettle, crystallization is taken out after 24 hours at 220 DEG C, washing to neutrality,
24 hours dry in 40 DEG C of baking ovens, taking-up roasts 24 hours at 520 DEG C, obtains film-form MFI sieve sample.
Fig. 5 is the SEM figure of sieve sample obtained in embodiment 3.As shown in Figure 5, the film-form MFI molecular sieve obtained
Sample particle size distribution is uniform, and the size of film is 3.2 μm of 1.2 μ m, with a thickness of 0.25 μm.
Embodiment 4
0.10g aluminum sulfate is dissolved in 37.74g deionized water, 4-propyl bromide 6.13g is added dropwise, stirring 10 is small
Shi Hou is slowly dropped into 6g tetraethyl orthosilicate.It stirs after mixing for 24 hours, 17.30g phenylacetaldehyde is then added into system.So
Molecular sieve synthesis mother liquid is moved into high pressure hydrothermal synthesis kettle afterwards, crystallization is taken out after 220 hours at 120 DEG C, washing to neutrality,
12 hours dry in 80 DEG C of baking ovens, taking-up roasts 4 hours at 560 DEG C, obtains sieve sample.
Fig. 6 is the SEM figure of film-form MFI molecular sieve molecular sieve obtained in embodiment 4.As shown in Figure 6 in embodiment 4
The film-form MFI sieve sample particle size distribution arrived is uniformly and the size of film is 5.5 μm of 3.5 μ m, with a thickness of 0.4 μ
m。
Embodiment 5
0.02g sodium metaaluminate is dissolved in 31.06g water, n-butylamine 1.68g is added dropwise and is slowly dripped after stirring 4 hours
Enter 6g tetraethyl orthosilicate.12h is stirred after mixing, and 15.46g benzenpropanal is then added into system.Then by molecular sieve
Synthesis mother liquid moves into high pressure hydrothermal synthesis kettle, and crystallization is taken out after 96 hours at 200 DEG C, washs to neutrality, in 150 DEG C of baking ovens
1 hour dry, taking-up roasts 24 hours at 500 DEG C, obtains film-form MFI sieve sample.
Fig. 7 is the SEM figure of film-form MFI sieve sample obtained in embodiment 5.As shown in Figure 7, in embodiment 5
The ZSM-5 molecular sieve sample particle size distribution arrived is uniformly and the size of film is 6~15 μm of 2.8-5 μ m, with a thickness of 0.5 μ
m。
Embodiment 6
Ethylenediamine 2.43g is added dropwise in 54.63g deionized water and is slowly dropped into the positive silicic acid of 7.7g after stirring 4 hours
Four methyl esters.It stirs after mixing for 24 hours, 6.08g p-tolyl aldehyde is then added into system.Then by Zeolite synthesis mother
Liquid moves into high pressure hydrothermal synthesis kettle, and crystallization is taken out after 96 hours at 200 DEG C, washing to neutrality, dry 12 in 105 DEG C of baking ovens
Hour, taking-up roasts 10 hours at 550 DEG C, obtains film-form MFI sieve sample.
Fig. 8 is the SEM figure of film-form MFI sieve sample obtained in embodiment 6.As shown in Figure 8, in embodiment 6
The film-form MFI sieve sample particle size distribution arrived is uniformly and the size of film is 1.3 μm of 1.3 μ m, with a thickness of 0.2 μ
m。
Embodiment 7
Hexamethylene diamine 3.77g is added dropwise in 50.08g deionized water and is slowly dropped into the positive silicic acid of 11.5g after stirring 4 hours
Orthocarbonate.12h is stirred after mixing, and 4.09g acetaldehyde is then added into system.Then molecular sieve synthesis mother liquid is moved into high
It presses in hydrothermal synthesis kettle, crystallization is taken out after 120 hours at 200 DEG C, washing to neutrality, and it is 8 hours dry in 110 DEG C of baking ovens, it takes
It is roasted 10 hours at 550 DEG C out, obtains film-form MFI sieve sample.
Fig. 9 is the SEM figure of film-form MFI sieve sample obtained in embodiment 7.As shown in Figure 9, in embodiment 7
The film-form MFI sieve sample particle size distribution arrived is uniformly and the size of film is 8 μm of 2 μ m, with a thickness of 1-2 μm.
Embodiment 8
4-propyl bromide 7.79g is added dropwise in 31.62g deionized water and is slowly dropped into 12.2g after stirring 6 hours
Tetraethyl orthosilicate.36h is stirred after mixing, and 18.29g naphthaldehyde is then added into system.Then by Zeolite synthesis
Mother liquor moves into high pressure hydrothermal synthesis kettle, and crystallization is taken out after 100 hours at 160 DEG C, and washing to neutrality is done in 120 DEG C of baking ovens
Dry 12 hours, taking-up roasted 3 hours at 560 DEG C, obtained film-form MFI sieve sample.
Figure 10 is the SEM figure of film-form MFI sieve sample obtained in embodiment 8.As shown in Figure 9, in embodiment 8
The film-form MFI sieve sample particle size distribution arrived is uniformly and the size of film is 0.1-1.5 μm of 0.1-1.2 μ m, thick
Degree is 0.1-0.25 μm.
Embodiment 9
0.10g aluminum nitrate is dissolved in 46.61g deionized water, 4-propyl bromide 6.90g is added dropwise, is stirred 8 hours
Afterwards, it is slowly dropped into 10.8g tetraethyl orthosilicate.48h is stirred after mixing, and 6.23g formaldehyde is then added into system.Then
Molecular sieve synthesis mother liquid is moved into high pressure hydrothermal synthesis kettle, crystallization is taken out after 180 hours at 180 DEG C, washs to neutrality, 40
24 hours dry in DEG C baking oven, taking-up roasts 1 hour at 560 DEG C, obtains film-form MFI sieve sample.
Figure 11 is the SEM figure of film-form MFI sieve sample obtained in embodiment 9.As shown in Figure 11, in embodiment 9
Obtained film-form MFI sieve sample particle size distribution is uniformly and the size of film is 2 μm of 0.8 μ m, with a thickness of 0.4 μ
m。
Embodiment 10
Tetrapropylammonium hydroxide 14.01g is added dropwise in 31.34g deionized water to be slowly dropped into after stirring 2 hours
11.5g tetraethyl orthosilicate.20h is stirred after mixing, and 12.82g propionic aldehyde is then added into system.Then molecular sieve is closed
It is moved into high pressure hydrothermal synthesis kettle at mother liquor, crystallization is taken out after 120 hours at 220 DEG C, washs to neutrality, in 100 DEG C of baking ovens
10 hours dry, taking-up roasts 12 hours at 550 DEG C, obtains film-form MFI sieve sample.
Figure 12 is the SEM figure of film-form MFI sieve sample obtained in embodiment 10.As shown in Figure 9, in embodiment 10
Obtained film-form MFI sieve sample particle size distribution is uniformly and the size of film is 1.2 μm of 1 μ m, with a thickness of 0.25 μ
m。
Embodiment 11
0.05g aluminium chloride is dissolved in 48.06g deionized water, 4-propyl bromide 5.93g is added dropwise, is stirred 4 hours
Afterwards, it is slowly dropped into 10.7g silica solution.26h is stirred after mixing, and 5.35g formaldehyde is then added into system.Then by molecule
It sieves synthesis mother liquid to move into high pressure hydrothermal synthesis kettle, crystallization is taken out after 160 hours at 175 DEG C, washs to neutrality, in 80 DEG C of baking ovens
Middle drying 8 hours, taking-up roast 3 hours at 560 DEG C, obtain film-form MFI sieve sample.
Figure 11 is the SEM figure of film-form MFI sieve sample obtained in embodiment 11.As shown in Figure 11, embodiment 11
Obtained in film-form MFI sieve sample particle size distribution uniformly and film size be 2 μm of 0.8 μ m, with a thickness of 0.4
μm。
Embodiment 12
0.04g aluminium hydroxide is dissolved in 44.00g water, n-butylamine 2.39g is added dropwise and is slowly dripped after stirring 2 hours
Enter 2.45g white carbon black.18h is stirred after mixing, and 21.92g benzenpropanal is then added into system.Then by Zeolite synthesis
Mother liquor moves into high pressure hydrothermal synthesis kettle, and crystallization is taken out after 96 hours at 190 DEG C, washing to neutrality, dry in 120 DEG C of baking ovens
6 hours, taking-up roasted 20 hours at 500 DEG C, obtained film-form MFI sieve sample.
Fig. 9 is the SEM figure of film-form MFI sieve sample obtained in embodiment 12.As shown in Figure 9, in embodiment 12
Obtained film-form MFI sieve sample particle size distribution is uniformly and the size of film is 8 μm of 2 μ m, with a thickness of 1-2 μm.
Embodiment 13
0.06g boehmite is dissolved in 56.68g water, hexamethylene diamine 4.27g is added dropwise, after stirring 3 hours, slowly
Instill 4.1g silicic acid.16h is stirred after mixing, and 4.62g acetaldehyde is then added into system.Then by molecular sieve synthesis mother liquid
It moves into high pressure hydrothermal synthesis kettle, crystallization is taken out after 120 hours at 205 DEG C, washing to neutrality, and dry 5 is small in 110 DEG C of baking ovens
When, taking-up roasts 24 hours at 500 DEG C, obtains film-form MFI sieve sample.
Fig. 7 is the SEM figure of film-form MFI sieve sample obtained in embodiment 13.As shown in Figure 7, in embodiment 13
Obtained ZSM-5 molecular sieve sample particle size distribution is uniformly and the size of film is 6-15 μm of 2.8-5 μ m, with a thickness of 0.5 μ
m。
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of self-supporting film shape MFI molecular sieve, includes the following:
Silicon source, template, water and silicon source are mixed, starting sol is obtained；
The starting sol is mixed with aldehydes solvent, obtains molecular sieve mother liquor；
The molecular sieve mother liquor is successively subjected to hydrothermal crystallizing, drying and roasting, obtains self-supporting film shape MFI molecular sieve；
In aluminium element, template, water and silicon source in source of aluminium the molar ratio of element silicon be 0~0.05:0.1~0.8:10~
80:1；
The molar ratio of element silicon is 0.3~10:1 in the aldehydes solvent and silicon source.
2. preparation method according to claim 1, which is characterized in that source of aluminium is aluminum nitrate, aluminium isopropoxide, sulfuric acid
One or more of aluminium, aluminium chloride, aluminium hydroxide, boehmite and sodium metaaluminate.
3. preparation method according to claim 1, which is characterized in that the template is tetrapropylammonium hydroxide, 4 third
One or more of base ammonium bromide, n-butylamine, ethylenediamine and hexamethylene diamine.
4. preparation method according to claim 1, which is characterized in that the silicon source be positive esters of silicon acis, silicic acid, white carbon black and
Silica solution.
5. preparation method according to claim 1, which is characterized in that the aldehydes solvent is formaldehyde, acetaldehyde, propionic aldehyde, benzene
In formaldehyde, p-tolyl aldehyde, naphthaldehyde, o-phthalaldehyde, m-terephthal aldehyde, terephthalaldehyde, phenylacetaldehyde and benzenpropanal
It is one or more of.
6. preparation method according to claim 1, which is characterized in that the temperature of the hydrothermal crystallizing is 120~220 DEG C,
The time of the hydrothermal crystallizing is 24~220h.
7. preparation method according to claim 1, which is characterized in that the temperature of the drying is 40~150 DEG C, described dry
The dry time be 1~for 24 hours.
8. preparation method according to claim 1, which is characterized in that the temperature of the roasting is 500~560 DEG C, described
The time of roasting be 1~for 24 hours.
9. the self-supporting film shape MFI molecular sieve that preparation method described in claim 1~8 any one is prepared, special
Sign is that the self-supporting film shape MFI molecular sieve has MFI topological structure, by two different ten-ring ducts intersection
At specific surface area is 250~450m2/ g, micro pore volume are 0.09~0.30cm3/g；Film with a thickness of 0.1~2 μm, size exists
In the range of 0.1~5 0.1~15 μm of μ m.
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| CN101284672A (en) * | 2008-04-24 | 2008-10-15 | 中国石油化工股份有限公司 | Process for preparing SAPO molecular sieve |
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| CN101284672A (en) * | 2008-04-24 | 2008-10-15 | 中国石油化工股份有限公司 | Process for preparing SAPO molecular sieve |
| CN101585545A (en) * | 2008-05-21 | 2009-11-25 | 西江大学校产学协力团 | Uniformly b-oriented mfi zeolite membrane with variable thickness supported on substrate and preparation method thereof |
| CN106809859A (en) * | 2015-11-30 | 2017-06-09 | 中国科学院大连化学物理研究所 | The synthetic method and ZSM-5 molecular sieve of a kind of ZSM-5 molecular sieve |
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