CN103449474B - Phosphorus-containing ZSM-5 molecular sieve membrane and preparation method thereof - Google Patents
Phosphorus-containing ZSM-5 molecular sieve membrane and preparation method thereof Download PDFInfo
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Abstract
The invention provides a phosphorus-containing ZSM-5 molecular sieve membrane and a preparation method thereof. The method comprises steps of uniformly mixing an aluminium source, a silicon source, a template and a phosphorus-containing buffer solution to obtain a uniform gel; and then carrying out hydrothermal crystallization on the gel on a porous support body under hydrothermal crystallization conditions to form the phosphorus-containing ZSM-5 molecular sieve membrane, wherein the phosphorus-containing buffer solution is a buffer solution with a pH value of 9.5-11.5 and containing ammonium phosphate salt and ammoniacal liquor. The invention also provides the phosphorus-containing ZSM-5 molecular sieve membrane prepared by the method. The preparation method of the phosphorus-containing ZSM-5 molecular sieve membrane provided by the invention can obtain uniform compact phosphorus-containing ZSM-5 molecular sieve membrane. The synthesized phosphorus-containing ZSM-5 molecular sieve membrane can be subjected to secondary crystallization to still obtain uniform compact phosphorus-containing ZSM-5 molecular sieve membrane.
Description
Technical field
The present invention relates to a kind of phosphorous ZSM-5 molecular sieve film and preparation method thereof.
Background technology
Supported molecular-sieve film is that molecular sieve has the porous support crystalline growth on the surface of some strength, forms one deck densification, continuous print rete.Carrier used mainly contains Mierocrystalline cellulose, porous metal, porous ceramics, porous metal oxide etc.Supported molecular-sieve film usually has good type of selecting and is separated and catalytic performance, have high temperature resistant, resistance to chemical attack strong and physical strength high, in membrane sepn and film reaction, have good application prospect.
ZSM-5 molecular sieve has two-dimentional ten-ring duct, is catalyzer important in petrochemical complex or carrier.ZSM-5 molecular sieve film has the features such as thermostability is high, resistance to acid good, catalytic performance is excellent, is one of zeolite membrane material most with potentiality to be exploited.
The preparation method of ZSM-5 molecular sieve film or the molecular screen membrane with MFI structure is more.The molecular screen membrane crystallization method of usual employing comprises in-situ crystallization method and secondary crystallization method.In-situ crystallization method carrier is put into the synthesis mother liquid containing silicon source, aluminium source, alkali, water, template, makes molecular sieve crystal in carrier surface nucleation and grow into continuous print film under certain temperature and pressure.Secondary crystallization method to refer in supporting body surface the uniform crystal seed layer of load one deck in advance, then is placed on hydrothermal crystallizing film forming in synthesis mother liquid.
Adv Mater, 2001,13 (24), 1880-1883 reports, are dissolved in nanometer MFI molecular sieve in ethanol and make molecular sieve colloidal solution, adopt centrifugal method afterwards, in solid support as silicon wafer, LiNbO
3wafer, quartz plate etc. form nano-zeolite membrane on the surface, can be obtained the molecular screen membrane of different thickness by the control of speed of rotation.Ind Eng Chem Res, 2010,49,5933-5938 report, adopt the method for microwave heating on stainless steel supporter, obtain the MFI molecular screen membrane of continuous print b-axle orientation, microwave heating can shorten crystallization time.CN101643218A discloses a kind of method adopting microwave heating to synthesize MFI-type molecular sieve film, adopts microwave heating greatly to accelerate nucleation and the crystallization rate of molecular sieve, decreases crystallization time.Although aforesaid method also can obtain MFI molecular screen membrane, harsh to the conditional request of operation, and more difficultly realize scale operation.
J Mater Chem, 1998,8 (10), 2217-2221 reports, modifies, and disperse the Silicate-1 molecular sieve of individual layer as crystal seed with cation high molecular tensio-active agent to quartz plate surface, do not need additional template agent, adopt hydrothermal method to prepare ZSM-5 molecular sieve film.It is that synthesis material prepares high reactivity Silicate-1 molecular sieve crystal seed with silicon sol that CN101653702A discloses, first by this crystal seed load in supporting body surface, then prepare high-performance Silicate-1 molecular screen membrane in super rare synthesis liquid.CN101837991A discloses with containing in the super dilute solution of villiaumite, adopt diauxic growth hydrothermal method, the perforated tubular supporter of the fluorine-containing MFI zeolite molecular sieve crystal seed of coating is formed one deck fluorine-containing MFI zeolite membrane fine and close continuously, significantly improves the penetrating quality of molecular screen membrane.CN101941716A discloses and adopts spin-coating method or low speed crystal pulling method on macropore carrier, directly prepare fine and close molecular sieve crystal seed layer, then be placed in high pressure crystallizing kettle, add synthesis liquid, carry out at least secondary synthesis, be formed with the complete molecular screen membrane of orientation, utilize heteroatomic autocatalysis performance further, can obtain forming Single Walled Carbon Nanotube in molecular sieve pore passage, obtain a kind of high-performance hydrophobicity ZSM-5 molecular sieve film.Although secondary growth method can be reduced to nuclear process, improve repeatability and the tropism control ability of the synthesis of molecular screen membrane, first need to obtain the uniform crystal seed of coating in supporting body surface, operational requirement is also harsher.
CN101934231A discloses a kind of Stainless Steel Cloth through acid treatment, anode electrochemical oxidizing process, forms Stainless Steel Cloth anodic porous oxide film, then has synthesized the method for ZSM-5 molecular sieve through hydrothermal crystallizing on its surface.
Vacuum-assisted method method is widely used in molecular screen membrane synthesis field, and step is simple, but requires higher to synthesis condition, and the microtexture of wayward molecular screen membrane, and the method film process depends on the performance of supporting body surface to a great extent.
Summary of the invention
The object of this invention is to provide a kind of Situ Hydrothermal crystallization legal system that adopts for the preparation method of phosphorous ZSM-5 molecular sieve film and the phosphorous ZSM-5 molecular sieve film of even compact prepared by the method thereof.
The invention provides a kind of preparation method of phosphorous ZSM-5 molecular sieve film, wherein, the method comprises aluminium source, silicon source, template and phosphorous buffered soln Homogeneous phase mixing, obtain uniform gel, then under hydrothermal crystallizing condition, this gel is carried out hydrothermal crystallizing on porous supporting body, forms phosphorous ZSM-5 molecular sieve film, described phosphorous buffered soln is pH is the ammonium phosphate salt of 9.5-11.5 and the buffered soln of ammoniacal liquor.
Present invention also offers the phosphorous ZSM-5 molecular sieve film obtained by above-mentioned preparation method.
The application performance of even compact to molecular screen membrane of molecular screen membrane has material impact.Usually, molecular sieve rete is combined tightr with supporter, molecular screen membrane is more even, is more conducive to the application of supported molecular-sieve film.The present inventor is found unexpectedly by great many of experiments, adopt Situ Hydrothermal crystallization method in the process of synthesis ZSM-5 molecular sieve film, introduce the buffered soln of ammonium phosphate salt and ammoniacal liquor, be conducive to porous supporting body formed on the surface have certain thickness scope evenly the film of densification.This owing to introducing the buffered soln of ammonium phosphate salt and ammoniacal liquor, may make gel in building-up process more stable, sedimentation is less likely to occur, the duration of contact of porous supporting body and gel is extended, thus on porous supporting body, forms the molecular screen membrane of more dense uniform.Further, due to phosphorous in buffered soln, phosphorus contributes to improving the hydrothermal stability of ZSM-5 molecular sieve, also can modulation it is acid, so also can reach the object of modified zsm-5 zeolite film.
In addition, the even compact of the phosphorous ZSM-5 molecular sieve film prepared due to method provided by the invention is better, therefore, directly can carry out secondary crystal on the basis of the phosphorous ZSM-5 molecular sieve film of synthesis, and after the without phosphorus system secondary crystal of prior art, still can obtain the phosphorous ZSM-5 molecular sieve film compared with even compact.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the SEM sectional view according to the obtained phosphorous ZSM-5 molecular sieve film of embodiment 1;
Fig. 2 is the EDS energy spectrogram according to the obtained phosphorous ZSM-5 molecular sieve film of embodiment 1;
Fig. 3 is the XRD spectra of the phosphorous ZSM-5 molecular sieve according to embodiment 1 acquisition;
Fig. 4 is the EDS energy spectrogram according to the obtained phosphorous ZSM-5 molecular sieve film of embodiment 14;
Fig. 5 is the SEM sectional view according to the obtained ZSM-5 molecular sieve film of comparative example 1;
Fig. 6 is the SEM sectional view according to the obtained phosphorous ZSM-5 molecular sieve film of comparative example 2.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of phosphorous ZSM-5 molecular sieve film, wherein, the method comprises aluminium source, silicon source, template and phosphorous buffered soln Homogeneous phase mixing, obtain uniform gel, then under hydrothermal crystallizing condition, this gel is carried out hydrothermal crystallizing on porous supporting body, forms phosphorous ZSM-5 molecular sieve film, described phosphorous buffered soln is pH is the ammonium phosphate salt of 9.5-11.5 and the buffered soln of ammoniacal liquor.
According to the preparation method of phosphorous ZSM-5 molecular sieve film of the present invention, wherein, the pH of the buffered soln of described ammonium phosphate salt and ammoniacal liquor can realize object of the present invention in above-mentioned scope, but in order to better realize object of the present invention, under preferable case, it is better that the add-on of ammoniacal liquor makes the pH of the buffered soln of described ammonium phosphate salt and ammoniacal liquor be that 9.8-11 realizes the effect of the object of the invention.
According to the preparation method of phosphorous ZSM-5 molecular sieve film of the present invention, wherein, the consumption of the buffered soln of aluminium source in preparation method of the present invention, silicon source, template and ammonium phosphate salt and ammoniacal liquor can be selected in relative broad range, but in order to better realize object of the present invention, under preferable case, with Al
2o
3meter aluminium source, with SiO
2the silicon source of meter, template and with PO
4 3-the mol ratio of the ammonium phosphate salt of meter and the buffered soln of ammoniacal liquor is 1:20-500:3-30:5-30.In order to better realize object of the present invention further, under preferable case, with Al
2o
3meter aluminium source, with SiO
2the silicon source of meter, template and with PO
4 3-the mol ratio of the ammonium phosphate salt of meter and the buffered soln of ammoniacal liquor is 1:25-400:5-30:10-25.
According to the preparation method of phosphorous ZSM-5 molecular sieve film of the present invention, wherein, in the buffered soln of described ammonium phosphate salt and ammoniacal liquor, the content of ammonium phosphate salt can be selected in relative broad range, but in order to better realize object of the present invention, under preferable case, PO in the buffered soln of described ammonium phosphate salt and ammoniacal liquor
4 3-concentration be 0.1-0.5mol/L.In order to realize object of the present invention further, PO in the buffered soln of more preferably described ammonium phosphate salt and ammoniacal liquor
4 3-concentration be 0.15-0.3mol/L.Especially, in order to better realize object of the present invention further, PO in the buffered soln of preferred described ammonium phosphate salt and ammoniacal liquor
4 3-concentration be 0.2mol/L.In addition, if when the pH of the mixture of those skilled in the art's known synthesis ZSM-5 molecular sieve is less than 9, lower pH is unfavorable for the generation of ZSM-5 molecular sieve, can produce the stray crystal of more amount in system.But, add due to some silicon source the pH that membership reduces described mixture, and the buffered soln of the ammonium phosphate salt added in preparation method provided by the invention and ammoniacal liquor effectively can control the pH of described mixture more than 9.
According to the preparation method of phosphorous ZSM-5 molecular sieve film of the present invention, wherein, ammonium phosphate salt described in the buffered soln of described ammonium phosphate salt and ammoniacal liquor can be one or more in primary ammonium phosphate, Secondary ammonium phosphate and ammonium phosphate.In order to better realize object of the present invention, under preferable case, described ammonium phosphate salt is Secondary ammonium phosphate.Namely the buffered soln of ammonium phosphate salt of the present invention and ammoniacal liquor is the buffered soln of Secondary ammonium phosphate and ammoniacal liquor.
According to the preparation method of phosphorous ZSM-5 molecular sieve film of the present invention, wherein, the present invention without particular requirement, can be organoaluminum source and/or inorganic aluminium source to the kind in described aluminium source.Under preferable case, described organoaluminum source can be one or more in aluminum methylate, aluminum ethylate, Tripropoxyaluminum, aluminum isopropylate and aluminium butoxide, preferred aluminum isopropylate.Described inorganic aluminium source can be Tai-Ace S 150 and/or aluminum nitrate.In order to realize object of the present invention further, more preferably described aluminium source is Tai-Ace S 150.
According to the preparation method of phosphorous ZSM-5 molecular sieve film of the present invention, wherein, the present invention without particular requirement, can be organosilicon source and/or inorganic silicon source to the kind in described silicon source.Under preferable case, described organosilicon source is tetraethyl orthosilicate and/or quanmethyl silicate; Described inorganic silicon source is water glass and/or silicon sol.In order to realize object of the present invention further, more preferably described silicon source is tetraethyl orthosilicate.
According to the preparation method of phosphorous ZSM-5 molecular sieve film of the present invention, wherein, the present invention without particular requirement, all can realize object of the present invention for the template that can be used in synthesizing ZSM-5 molecular sieve well known by persons skilled in the art to the kind of described template.In order to better realize object of the present invention, under preferable case, described template is TPAOH and/or 4-propyl bromide.When described template be TPAOH and 4-propyl bromide time, the weight ratio of TPAOH and 4-propyl bromide is 1:0.1-10, be preferably 1:0.2-5.
According to the preparation method of phosphorous ZSM-5 molecular sieve film of the present invention, wherein, all ingredients can directly use, and also can use with its aqueous solution form.
According to the preparation method of phosphorous ZSM-5 molecular sieve film of the present invention, wherein, the present invention preferably has aperture is 50nm-15 μm, porosity is 30-70% porous supporting body to realize object of the present invention better.In order to realize object of the present invention further, more preferably the aperture of described porous supporting body is 100nm-10 μm, and porosity can be 40-60%.The material of the present invention to porous supporting body is not particularly limited.But in order to better realize object of the present invention, under preferable case, described porous supporting body is di-aluminium trioxide film pipe porous supporting body.In addition, in order to better realize object of the present invention, need to carry out pre-treatment to described di-aluminium trioxide film pipe porous supporting body, described pre-treatment also can be carried out according to prior art.But in order to realize object of the present invention further, more preferably in situation, step below can be adopted to carry out: utilize sand paper to polish to di-aluminium trioxide film pipe open support external surface, then clean with deionized water, ultra-sonic oscillation 5-10 minute to remove surface particles, after oven dry, then at 500-600 DEG C of roasting 4-6 hour, obtain pretreated di-aluminium trioxide film pipe porous supporting body.
According to the preparation method of phosphorous ZSM-5 molecular sieve film of the present invention, wherein, the present invention to described by aluminium source, silicon source, template and the mixed uniformly step of described phosphorous buffered soln without particular requirement, under preferable case, this step comprises: aluminium source and template are dissolved in described phosphorous buffered soln by (1), abundant stirring, obtains translucent emulsion.Wherein, sequencing aluminium source and template being dissolved in described phosphorous buffered soln does not have particular requirement, aluminium source and template also can successively can be dissolved in described phosphorous buffered soln simultaneously in batches or separately.(2) silicon source is dissolved in the mixture of step (1) gained, forms gel.The feed postition of the present invention to silicon source does not have particular requirement, and can once add also can portion-wise addition.Under preferable case, under the mode stirred, slowly drip silicon source be conducive to obtaining more uniform gel.
According to the preparation method of phosphorous ZSM-5 molecular sieve film of the present invention, wherein, in preparation method of the present invention, the condition of hydrothermal crystallizing can be selected in relative broad range with reference to prior art, but in order to better realize object of the present invention, under preferable case, the condition of described hydrothermal crystallizing comprises: temperature is 110-180 DEG C, and the time is 1-7 days.More preferably the condition of described hydrothermal crystallizing comprises: temperature is 120-160 DEG C, and the time is that within 3-5 days, to realize the effect of the object of the invention better.
Present invention also offers the phosphorous ZSM-5 molecular sieve film obtained by above-mentioned preparation method.
According to the preparation method of phosphorous ZSM-5 molecular sieve film of the present invention, usually also comprise the phosphorous ZSM-5 molecular sieve film synthesized carried out wash, the step of dry and roasting, to remove template.The method of described washing, drying, roasting and condition can be carried out with reference to prior art.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
The present invention is further described below in conjunction with embodiment.Scope of the present invention does not limit by these embodiments.
In following examples, the SEM test of sample is carried out on FEI Co. of U.S. XL-30 Flied emission environmental scanning electron microscope, and EDS test is carried out on Thermo NORAN company of U.S. Vantage ESI energy spectrometer; XRD test turns on target X-ray diffractometer at German Bruker AXS company D8Advance superpower to be carried out.
In following examples, di-aluminium trioxide film pipe porous supporting body and other reagent all from being purchased, and di-aluminium trioxide film pipe porous supporting body to specifications described in method carry out pre-treatment.
Embodiment 1
Aluminum sulfate octadecahydrate 0.33 gram is added, 4-propyl bromide 1.07 grams, the TPAOH aqueous solution of 30 % by weight 1.06 grams, the buffered soln (PO of Secondary ammonium phosphate and ammoniacal liquor in there-necked flask
4 3-concentration be 0.20mol/L, buffered soln pH=10.2) 40.02 grams, fully stir 30 minutes, then slowly drip tetraethyl orthosilicate 10.49 grams wherein, continue stirring 2 hours, obtain homogeneous gel.Will through pretreated di-aluminium trioxide film pipe porous supporting body (porosity 60%, aperture 100nm-10 μm) be put in 100 milliliters of stainless steel reaction tanks, slow injection gel obtained above, make gel surface abundant submergence film pipe porous supporting body top, sealing, in 130 DEG C of static crystallizations 72 hours.Film pipe porous supporting body is taken out, through washing, dries, within 6 hours, obtain phosphorous ZSM-5 molecular sieve film 550 DEG C of roastings.Supernatant liquid pH=9.57 in reactor after crystallization.
As shown in Figure 1, EDS spectrogram as shown in Figure 2 for the SEM figure of obtained phosphorous ZSM-5 molecular sieve film.
SEM and EDS result shows, phosphorous ZSM-5 molecular sieve thickness 40-50 μm, phosphorus content is 11.0mol%.
After being taken out by film pipe porous supporting body, filter retort bottom crystal thing, wash, dry, roasting obtains phosphorous ZSM-5 molecular sieve.The XRD spectra of this sample is as shown in Figure 3, consistent with standard ZSM-5 molecular sieve spectrogram.
Embodiment 2
Aluminum sulfate octadecahydrate 0.33 gram is added, 4-propyl bromide 0.7 gram, the buffered soln (PO of Secondary ammonium phosphate and ammoniacal liquor in there-necked flask
4 3-concentration be 0.15mol/L, buffered soln pH=10.6) 34 grams, fully stir 30 minutes, then slowly drip tetraethyl orthosilicate 10.4 grams wherein, continue stirring 2 hours, obtain homogeneous gel.Will through pretreated di-aluminium trioxide film pipe porous supporting body (porosity 60%, aperture 100nm-10 μm) be put in 100 milliliters of stainless steel reaction tanks, slow injection gel obtained above, make gel surface abundant submergence film pipe porous supporting body top, sealing, in 130 DEG C of static crystallizations 72 hours.Film pipe porous supporting body is taken out, through washing, dries, within 6 hours, obtain phosphorous ZSM-5 molecular sieve film 550 DEG C of roastings.Supernatant liquid pH=9.97 in reactor after crystallization.
The SEM figure of obtained phosphorous ZSM-5 molecular sieve film is similar to Fig. 1, and EDS spectrogram is similar to Fig. 2.SEM and EDS result shows, phosphorous ZSM-5 molecular sieve thickness 35-45 μm, phosphorus content is 12.0mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained bottom retort is consistent with Fig. 3.
Embodiment 3
Aluminum sulfate octadecahydrate 0.33 gram is added, the TPAOH aqueous solution of 30 % by weight 10 grams, the buffered soln (PO of Secondary ammonium phosphate and ammoniacal liquor in there-necked flask
4 3-concentration be 0.30mol/L, buffered soln pH=9.8) 39.98 grams, fully stir 30 minutes, then slowly drip tetraethyl orthosilicate 40.0 grams wherein, continue stirring 2 hours, obtain homogeneous gel.Will through pretreated di-aluminium trioxide film pipe porous supporting body (porosity 60%, aperture 100nm-10 μm) be put in 100 milliliters of stainless steel reaction tanks, slow injection gel obtained above, make gel surface abundant submergence film pipe porous supporting body top, sealing, in 130 DEG C of static crystallizations 72 hours.Film pipe porous supporting body is taken out, through washing, dries, within 6 hours, obtain phosphorous ZSM-5 molecular sieve film 550 DEG C of roastings.Supernatant liquid pH=9.50 in reactor after crystallization.
The SEM figure of obtained phosphorous ZSM-5 molecular sieve film is similar to Fig. 1, and EDS spectrogram is similar to Fig. 2.SEM and EDS result shows, phosphorous ZSM-5 molecular sieve thickness 40-50 μm, phosphorus content is 10.5mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained bottom retort is consistent with Fig. 3.
Embodiment 4
The method of embodiment 1 is adopted to carry out synthesizing phosphorous ZSM-5 molecular sieve film.Unlike, PO in the buffered soln of Secondary ammonium phosphate and ammoniacal liquor
4 3-concentration be 0.30mol/L, buffered soln pH is 10.2.
Supernatant liquid pH=9.7 in reactor after crystallization.
The SEM figure of obtained phosphorous ZSM-5 molecular sieve film is similar to Fig. 1, and EDS spectrogram is similar to Fig. 2.SEM and EDS result shows, phosphorous ZSM-5 molecular sieve thickness 35-45 μm, phosphorus content is 14mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained bottom retort is consistent with Fig. 3.
Embodiment 5
The method of embodiment 1 is adopted to carry out synthesizing phosphorous ZSM-5 molecular sieve film.Unlike, add the buffered soln of 20 grams of Secondary ammonium phosphates and ammoniacal liquor, wherein PO
4 3-concentration be 0.50mol/L, buffered soln pH is 9.80.
Supernatant liquid pH=9.35 in reactor after crystallization.
The SEM figure of obtained phosphorous ZSM-5 molecular sieve film is similar to Fig. 1, and EDS spectrogram is similar to Fig. 2.SEM and EDS result shows, phosphorous ZSM-5 molecular sieve thickness 30-45 μm, phosphorus content is 10.1mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained bottom retort is consistent with Fig. 3.
Embodiment 6
The method of embodiment 1 is adopted to carry out synthesizing phosphorous ZSM-5 molecular sieve film.Unlike, PO in the buffered soln of Secondary ammonium phosphate and ammoniacal liquor
4 3-concentration be 0.10mol/L, buffered soln pH is 11.5.
Supernatant liquid pH=10.95 in reactor after crystallization.
The SEM figure of obtained phosphorous ZSM-5 molecular sieve film is similar to Fig. 1, and EDS spectrogram is similar to Fig. 2.SEM and EDS result shows, phosphorous ZSM-5 molecular sieve thickness 30-36 μm, phosphorus content is 10.0mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained bottom retort is consistent with Fig. 3.
Embodiment 7
The method of embodiment 1 is adopted to carry out synthesizing phosphorous ZSM-5 molecular sieve film.Unlike, adopt 0.50 gram of 4-propyl bromide to be template.
Supernatant liquid pH=9.50 in reactor after crystallization.
The SEM figure of obtained phosphorous ZSM-5 molecular sieve film is similar to Fig. 1, and EDS spectrogram is similar to Fig. 2.SEM and EDS result shows, phosphorous ZSM-5 molecular sieve thickness 30-40 μm, phosphorus content is 10.0mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained bottom retort is consistent with Fig. 3.
Embodiment 8
The method of embodiment 1 is adopted to carry out synthesizing phosphorous ZSM-5 molecular sieve film.Unlike, the TPAOH aqueous solution adopting 1.25 gram 30 % by weight is template.
Supernatant liquid pH=9.63 in reactor after crystallization.
The SEM figure of obtained phosphorous ZSM-5 molecular sieve film is similar to Fig. 1, and EDS spectrogram is similar to Fig. 2.SEM and EDS result shows, phosphorous ZSM-5 molecular sieve thickness 35-45 μm, phosphorus content is 11mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained bottom retort is consistent with Fig. 3.
Embodiment 9
The method of embodiment 1 is adopted to carry out synthesizing phosphorous ZSM-5 molecular sieve film.Unlike, adopt 2.5 grams of tetraethyl orthosilicates.
Supernatant liquid pH=9.50 in reactor after crystallization.
The SEM figure of obtained phosphorous ZSM-5 molecular sieve film is similar to Fig. 1, and EDS spectrogram is similar to Fig. 2.SEM and EDS result shows, phosphorous ZSM-5 molecular sieve thickness 30-40 μm, phosphorus content is 11.0mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained bottom retort is consistent with Fig. 3.
Embodiment 10
The method of embodiment 1 is adopted to carry out synthesizing phosphorous ZSM-5 molecular sieve film.Unlike, the crystallization temperature of employing is 120 DEG C, and crystallization time is 24 hours.
Supernatant liquid pH=9.62 in reactor after crystallization.
The SEM figure of obtained phosphorous ZSM-5 molecular sieve film is similar to Fig. 1, and EDS spectrogram is similar to Fig. 2.SEM and EDS result shows, phosphorous ZSM-5 molecular sieve thickness 8-15 μm, phosphorus content is 3mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained bottom retort is consistent with Fig. 3.
Embodiment 11
The method of embodiment 1 is adopted to carry out synthesizing phosphorous ZSM-5 molecular sieve film.Unlike, the crystallization temperature of employing is 160 DEG C, and crystallization time is 24 hours.
Supernatant liquid pH=9.60 in reactor after crystallization.
The SEM figure of obtained phosphorous ZSM-5 molecular sieve film is similar to Fig. 1, and EDS spectrogram is similar to Fig. 2.SEM and EDS result shows, phosphorous ZSM-5 molecular sieve thickness 15-25 μm, phosphorus content is 6mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained bottom retort is consistent with Fig. 3.
Embodiment 12
The method of embodiment 1 is adopted to carry out synthesizing phosphorous ZSM-5 molecular sieve film.Unlike, the crystallization temperature of employing is 180 DEG C, and crystallization time is 24 hours.
Supernatant liquid pH=9.59 in reactor after crystallization.
The SEM figure of obtained phosphorous ZSM-5 molecular sieve film is similar to Fig. 1, and EDS spectrogram is similar to Fig. 2.SEM and EDS result shows, phosphorous ZSM-5 molecular sieve thickness 35-40 μm, phosphorus content is 10.8mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained bottom retort is consistent with Fig. 3.
Embodiment 13
The method of embodiment 1 is adopted to carry out synthesizing phosphorous ZSM-5 molecular sieve film.Unlike, the crystallization temperature of employing is 150 DEG C, and crystallization time is 120 hours.
Supernatant liquid pH=9.5 in reactor after crystallization.
The SEM figure of obtained phosphorous ZSM-5 molecular sieve film is similar to Fig. 1, and EDS spectrogram is similar to Fig. 2.SEM and EDS result shows, phosphorous ZSM-5 molecular sieve thickness 35-45 μm, phosphorus content is 12mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained bottom retort is consistent with Fig. 3.
Embodiment 14
Aluminum sulfate octadecahydrate 0.33 gram is added, 0.50 gram, sodium hydroxide, deionized water 21.82 grams in there-necked flask, the TPAOH aqueous solution of 30 % by weight 6.35 grams, fully stirs 30 minutes, then slowly drips tetraethyl orthosilicate 10.40 grams wherein, continue stirring 2 hours, obtain homogeneous gel.
The di-aluminium trioxide film pipe porous supporting body (porosity 60% with phosphorous ZSM-5 molecular sieve film that embodiment 1 is synthesized, aperture 50nm-15 μm) be put in 100 milliliters of stainless steel reaction tanks, slow injection gel obtained above, make gel surface abundant submergence film pipe porous supporting body top, sealing, in 110 DEG C of static crystallizations 72 hours.Film pipe porous supporting body is taken out, through washing, dries, within 6 hours, obtain phosphorous ZSM-5 molecular sieve film prepared by secondary crystallization 550 DEG C of roastings.Supernatant liquid pH=10.60 in reactor after crystallization.
The SEM figure of obtained phosphorous ZSM-5 molecular sieve film is similar to Fig. 1, and EDS spectrogram as shown in Figure 4.SEM and EDS result shows, phosphorous ZSM-5 molecular sieve thickness 35-45 μm, top layer phosphorus content is 1.2mol%.
After being taken out by film pipe porous supporting body, filter retort bottom crystal thing, wash, dry, roasting obtains phosphorous ZSM-5 molecular sieve.The XRD spectra of this sample is consistent with Fig. 3.
Embodiment 15
The method of embodiment 1 is adopted to carry out synthesizing phosphorous ZSM-5 molecular sieve film.Unlike, adopt the di-aluminium trioxide film pipe porous supporting body that porosity is 30%, aperture is 50nm-15 μm to replace porosity 60%, the di-aluminium trioxide film pipe porous supporting body of aperture 100nm-10 μm.
The SEM figure of obtained phosphorous ZSM-5 molecular sieve film is similar to Fig. 1, and EDS spectrogram is similar to Fig. 2.SEM and EDS result shows, phosphorous ZSM-5 molecular sieve thickness 35-45 μm, phosphorus content is 10.5mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained bottom retort is consistent with Fig. 3.
Comparative example 1
The method of embodiment 1 is adopted to carry out synthesis ZSM-5 molecular sieve film.Unlike, in building-up process, do not add the buffered soln of Secondary ammonium phosphate and ammoniacal liquor.The SEM figure on film pipe top layer as shown in Figure 5.
Comparative example 2
The method of embodiment 1 is adopted to carry out synthesizing phosphorous ZSM-5 molecular sieve film.Unlike, PO in the buffered soln of Secondary ammonium phosphate and ammoniacal liquor
4 3-concentration be 0.05mol/L, buffered soln pH is 12.The SEM figure on film pipe top layer as shown in Figure 6.
As can be seen from Figure 1, according to the preparation method of phosphorous ZSM-5 molecular sieve film provided by the invention, by introducing the buffered soln of Secondary ammonium phosphate and ammoniacal liquor in the process of synthesis ZSM-5 molecular sieve film, the phosphorous ZSM-5 molecular sieve film with 40-50 μm of thickness range can be formed on the surface at porous supporting body.And in embodiment 1-15, according to method provided by the invention, the thickness difference of the phosphorous molecular screen membrane obtained, all within 10 μm, illustrates the phosphorous molecular screen membrane that can obtain compared with even compact according to method provided by the invention.In addition, by the crystallization temperature in adjustment building-up process and crystallization time, the phosphorous ZSM-5 molecular sieve film compared with even compact of different thickness scope can be obtained.In addition, due to phosphorous in buffered soln, the ZSM-5 molecular sieve film of P Modification can be obtained.As can be seen from embodiment 14, secondary crystal is carried out on the basis of the phosphorous ZSM-5 molecular sieve film of synthesis, still can obtain the phosphorous ZSM-5 molecular sieve film compared with even compact.
By comparative example 1 and comparative example 1, can find out, comparative example 1 does not add the buffered soln of Secondary ammonium phosphate and ammoniacal liquor in the process of synthesis ZSM-5 molecular sieve film, under identical crystallization condition, although the film pipe top layer of comparative example 1 has molecular sieve to be formed, but there is obvious defect, subregion does not have molecular sieve, uniform ZSM-5 molecular sieve film therefore can not be obtained.By comparative example 1 and comparative example 2, can find out, even if add the buffered soln of Secondary ammonium phosphate and ammoniacal liquor, if PO in the buffered soln of the Secondary ammonium phosphate added and ammoniacal liquor
4 3-concentration and the pH of buffered soln exceed the framework of the present definition, there is space on a large scale in the film pipe top layer obtained, cannot obtain ZSM-5 molecular sieve film phosphorous uniformly.
Claims (18)
1. the preparation method of a phosphorous ZSM-5 molecular sieve film, it is characterized in that, the method comprises aluminium source, silicon source, template and phosphorous buffered soln Homogeneous phase mixing, obtain uniform gel, then under hydrothermal crystallizing condition, this gel is carried out hydrothermal crystallizing on porous supporting body, forms phosphorous ZSM-5 molecular sieve film, described phosphorous buffered soln is pH is the ammonium phosphate salt of 9.5-11.5 and the buffered soln of ammoniacal liquor.
2. preparation method according to claim 1, wherein, the pH of the buffered soln of described ammonium phosphate salt and ammoniacal liquor is 9.8-11.
3. preparation method according to claim 1, wherein, with Al
2o
3meter aluminium source, with SiO
2the silicon source of meter, template and with PO
4 3-the mol ratio of the ammonium phosphate salt of meter and the buffered soln of ammoniacal liquor is 1:20-500:3-30:5-30.
4. preparation method according to claim 3, wherein, with Al
2o
3meter aluminium source, with SiO
2the silicon source of meter, template and with PO
4 3-the mol ratio of the ammonium phosphate salt of meter and the buffered soln of ammoniacal liquor is 1:25-400:5-30:10-25.
5. PO in the buffered soln of according to the preparation method in claim 1-4 described in any one, wherein, described ammonium phosphate salt and ammoniacal liquor
4 3-concentration be 0.1-0.5mol/L.
6. preparation method according to claim 5, wherein, PO in the buffered soln of described ammonium phosphate salt and ammoniacal liquor
4 3-concentration be 0.15-0.3mol/L.
7. preparation method according to claim 5, wherein, described ammonium phosphate salt is one or more in primary ammonium phosphate, Secondary ammonium phosphate and ammonium phosphate.
8. according to the preparation method in claim 1,3 and 4 described in any one, wherein, described aluminium source is organoaluminum source and/or inorganic aluminium source.
9. preparation method according to claim 8, wherein, described organoaluminum source is one or more in aluminum methylate, aluminum ethylate, Tripropoxyaluminum, aluminum isopropylate and aluminium butoxide, and described inorganic aluminium source is Tai-Ace S 150 and/or aluminum nitrate.
10. according to the preparation method in claim 1,3 and 4 described in any one, wherein, described silicon source is organosilicon source and/or inorganic silicon source.
11. preparation methods according to claim 10, wherein, described organosilicon source is tetraethyl orthosilicate and/or quanmethyl silicate, and described inorganic silicon source is water glass and/or silicon sol.
12. according to the preparation method in claim 1,3 and 4 described in any one, and wherein, described template is TPAOH and/or 4-propyl bromide.
13. preparation methods according to claim 1, wherein, the aperture of described porous supporting body is 50nm-15 μm, and porosity is 30-70%.
14. preparation methods according to claim 13, wherein, the aperture of described porous supporting body is 100nm-10 μm, and porosity is 40-60%.
15. preparation methods according to claim 1, wherein, describedly to comprise aluminium source, silicon source, template and the mixed uniformly step of described phosphorous buffered soln:
(1) aluminium source and template are dissolved in described phosphorous buffered soln;
(2) silicon source is dissolved in the mixture of step (1) gained, forms gel.
16. preparation methods according to claim 1, wherein, the condition of described hydrothermal crystallizing comprises: temperature is 110-180 DEG C, and the time is 1-7 days.
17. preparation methods according to claim 16, wherein, the condition of described hydrothermal crystallizing comprises: temperature is 120-160 DEG C, and the time is 3-5 days.
The phosphorous ZSM-5 molecular sieve film that preparation method in 18. claim 1-17 described in any one obtains.
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| CN106881147A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院大连化学物理研究所 | The preparation and catalyst film and application of ZSM-5 Type Zeolites agent film in metal passage |
| CN106981606B (en) * | 2016-01-19 | 2019-11-26 | 中国电力科学研究院 | A kind of preparation method of MFI type zeolite coating lithium ion battery separator |
| CN108264055B (en) * | 2018-01-27 | 2019-09-24 | 吴蓓蓓 | A kind of synthetic method of economy Silicalite-1 molecular screen membrane |
| CN114471674B (en) * | 2020-10-26 | 2024-05-07 | 中国石油化工股份有限公司 | Carbon nano tube/ZSM-5 molecular sieve compound and synthetic method and application thereof |
| CN112850740B (en) * | 2021-02-23 | 2022-03-08 | 浙江浙能技术研究院有限公司 | Synthesis method of sheet MFI topological structure molecular sieve |
| CN114713048B (en) * | 2022-04-14 | 2024-01-30 | 南京方膜高科技有限公司 | Method for preparing high-silicon CHA molecular sieve membrane in situ |
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