CN103449474A - 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 crystalline growth on the porous support surface of some strength, forms fine and close, the continuous rete of one deck.Carrier used mainly contains Mierocrystalline cellulose, porous metal, porous ceramics, porous metal oxide etc.Supported molecular-sieve film has the good type of selecting usually to be separated and catalytic performance, has high temperature resistant, chemical resistance of concrete and reaches by force the physical strength high, has good application prospect in membrane sepn and film reaction.
ZSM-5 molecular sieve has two-dimentional ten-ring duct, is catalyzer or carrier important in petrochemical complex.The ZSM-5 molecular sieve film has the characteristics such as thermostability is high, resistance to acid good, catalytic performance is good, is one of zeolite membrane material had most potentiality to be exploited.
ZSM-5 molecular sieve film or to have the preparation method of molecular screen membrane of MFI structure more.Usually the molecular screen membrane crystallization method adopted comprises in-situ crystallization method and secondary crystallization method.The in-situ crystallization method is that carrier is put into to the synthesis mother liquid that contains ,Lv source, silicon source, alkali, water, template, makes molecular sieve crystal in the carrier surface nucleation under certain temperature and pressure and grows into continuous film.The secondary crystallization method refers on 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 report, be dissolved in nanometer MFI molecular sieve in ethanol and make molecular sieve colloidal solution, adopts afterwards centrifugal method, in solid support as silicon wafer, LiNbO
3the surface such as wafer, quartz plate above forms nano-zeolite membrane, can obtain 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 to obtain the MFI molecular screen membrane that continuous b-axle is orientated on the stainless steel supporter, and microwave heating can be shortened crystallization time.CN101643218A discloses a kind of method that adopts the synthetic MFI type molecular screen membrane of microwave heating, adopts microwave heating greatly to accelerate nucleation and the crystallization rate of molecular sieve, has reduced crystallization time.Although aforesaid method also can obtain the MFI molecular screen membrane, to the conditional request harshness of operation, and more difficultly realize scale operation.
J Mater Chem, 1998,8 (10), the 2217-2221 report, modified the quartz plate surface with the cation high molecular tensio-active agent, and the Silicate-1 molecular sieve of dispersion individual layer is as crystal seed, do not need the additional template agent, adopt hydrothermal method to prepare the ZSM-5 molecular sieve film.CN101653702A discloses take silicon sol and prepares high reactivity Silicate-1 molecular sieve crystal seed as synthesis material, first this crystal seed is loaded on supporting body surface, then prepare high-performance Silicate-1 molecular screen membrane in super rare synthetic liquid.In the super dilute solution that CN101837991A discloses to contain villiaumite, adopt the diauxic growth hydrothermal method, form one deck fluorine-containing MFI zeolite membrane of densification continuously on the perforated tubular supporter that applies fluorine-containing MFI zeolite molecular sieve crystal seed, significantly improved the penetrating quality of molecular screen membrane.CN101941716A discloses and adopts the directly fine and close molecular sieve crystal seed layer of preparation on macropore carrier of spin-coating method or low speed crystal pulling method, then be placed in the high pressure crystallizing kettle, add synthetic liquid, carrying out at least secondary synthesizes, be formed with the complete molecular screen membrane of orientation, further utilize heteroatomic autocatalysis performance, can obtain in molecular sieve pore passage forming Single Walled Carbon Nanotube, obtain a kind of high-performance hydrophobicity ZSM-5 molecular sieve film.Although the diauxic growth method can be reduced to nuclear process, improve synthetic repeatability and the orientation controllability of molecular screen membrane, at 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 anode porous oxide film, then has synthesized the method for ZSM-5 molecular sieve through hydrothermal crystallizing on its surface.
The Vacuum-assisted method method is widely used in the synthetic field of molecular screen membrane, and step is simple, but synthesis condition is had relatively high expectations, 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 phosphorous ZSM-5 molecular sieve film that the purpose of this invention is to provide a kind of even compact that adopts the preparation method of the standby phosphorous ZSM-5 molecular sieve film of Situ Hydrothermal crystallization legal system and prepared by the method.
The invention provides a kind of preparation method of phosphorous ZSM-5 molecular sieve film, wherein, the method comprises evenly mixes ,Gui source, aluminium source, template with phosphorous buffered soln, obtain uniform gel, then under the hydrothermal crystallizing condition, this gel is carried out on porous supporting body to hydrothermal crystallizing, form phosphorous ZSM-5 molecular sieve film, described phosphorous buffered soln is the pH ammonium phosphate salt that is 9.5-11.5 and the buffered soln of ammoniacal liquor.
The present invention also provides the phosphorous ZSM-5 molecular sieve film made by above-mentioned preparation method.
The even compact of molecular screen membrane has material impact to the application performance of molecular screen membrane.Usually, the molecular sieve rete is combined tightr with supporter, and molecular screen membrane is more even, more is conducive to the application of supported molecular-sieve film.The present inventor finds unexpectedly by great many of experiments, adopt Situ Hydrothermal crystallization method to introduce the buffered soln of ammonium phosphate salt and ammoniacal liquor in the process of synthetic ZSM-5 molecular sieve film, be conducive to form the film of the more even compact with certain thickness scope on the porous supporting body surface.This may be owing to introducing the buffered soln of ammonium phosphate salt with ammoniacal liquor, makes in building-up process gel more stable, is not easy to occur sedimentation, makes prolongation duration of contact of porous supporting body and gel, thus on porous supporting body the finer and close uniform molecular screen membrane of formation.And, due to phosphorous in buffered soln, phosphorus contributes to improve the hydrothermal stability of ZSM-5 molecular sieve, also can its acidity of modulation, so also can reach the purpose 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, can directly on the basis of synthetic phosphorous ZSM-5 molecular sieve film, carry out secondary crystal, and, after the without phosphorus system secondary crystal of prior art, still can obtain the phosphorous film of the ZSM-5 molecular sieve than even compact.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
The accompanying drawing explanation
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms the part of specification sheets, is used from explanation the present invention with following embodiment one, but is not construed as limiting the invention.In the accompanying drawings:
The SEM sectional view that Fig. 1 is the phosphorous ZSM-5 molecular sieve film that makes according to embodiment 1;
The EDS that Fig. 2 is the phosphorous ZSM-5 molecular sieve film that makes according to embodiment 1 can spectrogram;
Fig. 3 is the XRD spectra according to the phosphorous ZSM-5 molecular sieve of embodiment 1 acquisition;
The EDS that Fig. 4 is the phosphorous ZSM-5 molecular sieve film that makes according to embodiment 14 can spectrogram;
The SEM sectional view that Fig. 5 is the ZSM-5 molecular sieve film that makes according to Comparative Examples 1;
The SEM sectional view that Fig. 6 is the phosphorous ZSM-5 molecular sieve film that makes according to Comparative Examples 2.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation 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 evenly mixes ,Gui source, aluminium source, template with phosphorous buffered soln, obtain uniform gel, then under the hydrothermal crystallizing condition, this gel is carried out on porous supporting body to hydrothermal crystallizing, form phosphorous ZSM-5 molecular sieve film, described phosphorous buffered soln is the pH ammonium phosphate salt that is 9.5-11.5 and the buffered soln of ammoniacal liquor.
Preparation method according to 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 purpose of the present invention in above-mentioned scope, but in order better to realize purpose of the present invention, under preferable case, it is that 9.8-11 realizes that the effect of the object of the invention is better that the add-on of ammoniacal liquor makes the pH of the buffered soln of described ammonium phosphate salt and ammoniacal liquor.
Preparation method according to phosphorous ZSM-5 molecular sieve film of the present invention, wherein, in preparation method of the present invention, the consumption of the buffered soln of ,Gui source, aluminium source, template and ammonium phosphate salt and ammoniacal liquor can be selected in relative broad range, but in order better to realize purpose of the present invention, under preferable case, with Al
2o
3the meter the aluminium source, with SiO
2the silicon source, template of meter 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 further better to realize purpose of the present invention, under preferable case, with Al
2o
3the meter the aluminium source, with SiO
2the silicon source, template of meter 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.
Preparation method according to 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 better to realize purpose 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 further to realize purpose of the present invention, more preferably PO in the buffered soln of described ammonium phosphate salt and ammoniacal liquor
4 3-concentration be 0.15-0.3mol/L.Especially, in order further better to realize purpose of the present invention, PO in the buffered soln of preferred described ammonium phosphate salt and ammoniacal liquor
4 3-concentration be 0.2mol/L.In addition, if the pH of the mixture of the known synthetic ZSM-5 molecular sieve of those skilled in the art is less than at 9 o'clock, lower pH is unfavorable for the generation of ZSM-5 molecular sieve, can produce the stray crystal of more amount in system.Yet due to the pH that membership reduces described mixture that adds in some silicon source, and the buffered soln of the ammonium phosphate salt added in preparation method provided by the invention and ammoniacal liquor can effectively be controlled 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 better to realize purpose of the present invention, under preferable case, described ammonium phosphate salt is Secondary ammonium phosphate.The buffered soln that the buffered soln that is ammonium phosphate salt of the present invention and ammoniacal liquor is 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, preferably aluminum isopropylate.Described inorganic aluminium source can be Tai-Ace S 150 and/or aluminum nitrate.In order further to realize purpose of the present invention, 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 further to realize purpose of the present invention, more preferably described silicon source is tetraethyl orthosilicate.
Preparation method according to phosphorous ZSM-5 molecular sieve film of the present invention, wherein, the present invention without particular requirement, can all can realize purpose of the present invention to the kind of described template for the template that can be used in synthetic ZSM-5 molecular sieve well known by persons skilled in the art.In order better to realize purpose of the present invention, under preferable case, described template is TPAOH and/or 4-propyl bromide.When described template is TPAOH and 4-propyl bromide, the weight ratio of TPAOH and 4-propyl bromide is 1:0.1-10, is 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 be used, 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, it is that the porous supporting body that 50nm-15 μ m, porosity are 30-70% realizes that purpose of the present invention is better that the present invention preferably has aperture.In order further to realize purpose of the present invention, more preferably the aperture of described porous supporting body is 100nm-10 μ m, and porosity can be 40-60%.The present invention is not particularly limited the material of porous supporting body.But, in order better to realize purpose of the present invention, under preferable case, described porous supporting body is di-aluminium trioxide film pipe porous supporting body.In addition, in order better to realize purpose 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 further to realize purpose of the present invention, more preferably in situation, can adopt following step to carry out: to utilize sand paper to be polished to di-aluminium trioxide film pipe porous supporting body outside surface, then with deionized water, cleaned, ultra-sonic oscillation 5-10 minute to remove surface particles, after oven dry, then, at 500-600 ℃ of roasting 4-6 hour, obtain pretreated di-aluminium trioxide film pipe porous supporting body.
Preparation method according to phosphorous ZSM-5 molecular sieve film of the present invention, wherein, the present invention to described by ,Gui source, aluminium source, template and the mixed uniformly step of described phosphorous buffered soln without particular requirement, under preferable case, this step comprises: (1) is dissolved in aluminium source and template in described phosphorous buffered soln, fully stir, obtain translucent emulsion.Wherein, the sequencing that aluminium source and template is dissolved in to 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) the silicon source is dissolved in the mixture of step (1) gained, forms gel.The present invention does not have particular requirement to the mode that adds in silicon source, and can once add also can portion-wise addition.Under preferable case, slowly drip the silicon source and be conducive to obtain gel more uniformly under the mode stirred.
Preparation method according to 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 with reference to prior art in relative broad range, but in order better to realize purpose of the present invention, under preferable case, the condition of described hydrothermal crystallizing comprises: temperature is 110-180 ℃, and the time is 1-7 days.More preferably the condition of described hydrothermal crystallizing comprises: temperature is 120-160 ℃, and the time is within 3-5 days, to realize that the effect of the object of the invention is better.
The present invention also provides the phosphorous ZSM-5 molecular sieve film made by above-mentioned preparation method.
According to the preparation method of phosphorous ZSM-5 molecular sieve film of the present invention, usually also comprise by the phosphorous ZSM-5 molecular sieve film synthesized washed, the step of drying 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, in technical conceive scope 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 characterictic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not limited by these embodiment.
In following examples, the SEM of sample test is carried out on the launch environment scanning electronic microscope of the XL-30 of U.S. FEI Co. field, and the EDS test is carried out on the Vantage ESI of U.S. Thermo NORAN company energy spectrometer; The XRD test turns on the target X-ray diffractometer and carries out at the German Bruker AXS D8Advance of company superpower.
In following examples, di-aluminium trioxide film pipe porous supporting body and other reagent are all from being purchased, and the method for di-aluminium trioxide film pipe porous supporting body described in to specifications carried out pre-treatment.
Embodiment 1
Add 18 water Tai-Ace S 150 0.33 gram in there-necked flask, 4-propyl bromide 1.07 grams, the TPAOH aqueous solution 1.06 grams of 30 % by weight, the buffered soln (PO of Secondary ammonium phosphate and ammoniacal liquor
4 3-concentration be 0.20mol/L, buffered soln pH=10.2) 40.02 grams, fully stir 30 minutes, then slowly drip wherein tetraethyl orthosilicate 10.49 grams, continue to stir 2 hours, obtain even gel.Will be through pretreated di-aluminium trioxide film pipe porous supporting body (porosity 60%, aperture 100nm-10 μ m) be put in 100 milliliters of stainless steel reaction tanks, slowly inject gel obtained above, make the abundant submergence film of gel surface pipe porous supporting body top, sealing, in 130 ℃ of static crystallizations 72 hours.Film pipe porous supporting body is taken out, through washing, dry, 550 ℃ of roastings, within 6 hours, obtain phosphorous ZSM-5 molecular sieve film.Supernatant liquid pH=9.57 in reactor after crystallization.
As shown in Figure 1, the EDS spectrogram as shown in Figure 2 for the SEM figure of the phosphorous ZSM-5 molecular sieve film made.
SEM and EDS result show, phosphorous ZSM-5 molecular sieve thickness 40-50 μ m, and phosphorus content is 11.0mol%.
After film pipe porous supporting body is taken out, retort bottom crystallisate is filtered, washs, dries, roasting obtains phosphorous ZSM-5 molecular sieve.The XRD spectra of this sample as shown in Figure 3, consistent with standard ZSM-5 molecular sieve spectrogram.
Embodiment 2
Add 18 water Tai-Ace S 150 0.33 gram in there-necked flask, 4-propyl bromide 0.7 gram, the buffered soln (PO of Secondary ammonium phosphate and ammoniacal liquor
4 3-concentration be 0.15mol/L, buffered soln pH=10.6) 34 grams, fully stir 30 minutes, then slowly drip wherein tetraethyl orthosilicate 10.4 grams, continue to stir 2 hours, obtain even gel.Will be through pretreated di-aluminium trioxide film pipe porous supporting body (porosity 60%, aperture 100nm-10 μ m) be put in 100 milliliters of stainless steel reaction tanks, slowly inject gel obtained above, make the abundant submergence film of gel surface pipe porous supporting body top, sealing, in 130 ℃ of static crystallizations 72 hours.Film pipe porous supporting body is taken out, through washing, dry, 550 ℃ of roastings, within 6 hours, obtain phosphorous ZSM-5 molecular sieve film.Supernatant liquid pH=9.97 in reactor after crystallization.
The SEM figure of the phosphorous ZSM-5 molecular sieve film made is similar to Fig. 1, and the EDS spectrogram is similar to Fig. 2.SEM and EDS result show, phosphorous ZSM-5 molecular sieve thickness 35-45 μ m, and phosphorus content is 12.0mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained from the retort bottom is consistent with Fig. 3.
Embodiment 3
Add 18 water Tai-Ace S 150 0.33 gram in there-necked flask, the TPAOH aqueous solution 10 grams of 30 % by weight, the buffered soln (PO of Secondary ammonium phosphate and ammoniacal liquor
4 3-concentration be 0.30mol/L, buffered soln pH=9.8) 39.98 grams, fully stir 30 minutes, then slowly drip wherein tetraethyl orthosilicate 40.0 grams, continue to stir 2 hours, obtain even gel.Will be through pretreated di-aluminium trioxide film pipe porous supporting body (porosity 60%, aperture 100nm-10 μ m) be put in 100 milliliters of stainless steel reaction tanks, slowly inject gel obtained above, make the abundant submergence film of gel surface pipe porous supporting body top, sealing, in 130 ℃ of static crystallizations 72 hours.Film pipe porous supporting body is taken out, through washing, dry, 550 ℃ of roastings, within 6 hours, obtain phosphorous ZSM-5 molecular sieve film.Supernatant liquid pH=9.50 in reactor after crystallization.
The SEM figure of the phosphorous ZSM-5 molecular sieve film made is similar to Fig. 1, and the EDS spectrogram is similar to Fig. 2.SEM and EDS result show, phosphorous ZSM-5 molecular sieve thickness 40-50 μ m, and phosphorus content is 10.5mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained from the retort bottom is consistent with Fig. 3.
Embodiment 4
Adopt the method for embodiment 1 to synthesize phosphorous ZSM-5 molecular sieve film.Different, 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 the phosphorous ZSM-5 molecular sieve film made is similar to Fig. 1, and the EDS spectrogram is similar to Fig. 2.SEM and EDS result show, phosphorous ZSM-5 molecular sieve thickness 35-45 μ m, and phosphorus content is 14mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained from the retort bottom is consistent with Fig. 3.
Embodiment 5
Adopt the method for embodiment 1 to synthesize phosphorous ZSM-5 molecular sieve film.Different, add the buffered soln of 20 gram 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 the phosphorous ZSM-5 molecular sieve film made is similar to Fig. 1, and the EDS spectrogram is similar to Fig. 2.SEM and EDS result show, phosphorous ZSM-5 molecular sieve thickness 30-45 μ m, and phosphorus content is 10.1mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained from the retort bottom is consistent with Fig. 3.
Embodiment 6
Adopt the method for embodiment 1 to synthesize phosphorous ZSM-5 molecular sieve film.Different, 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 the phosphorous ZSM-5 molecular sieve film made is similar to Fig. 1, and the EDS spectrogram is similar to Fig. 2.SEM and EDS result show, phosphorous ZSM-5 molecular sieve thickness 30-36 μ m, and phosphorus content is 10.0mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained from the retort bottom is consistent with Fig. 3.
Embodiment 7
Adopt the method for embodiment 1 to synthesize phosphorous ZSM-5 molecular sieve film.Different, adopting 0.50 gram 4-propyl bromide is template.
Supernatant liquid pH=9.50 in reactor after crystallization.
The SEM figure of the phosphorous ZSM-5 molecular sieve film made is similar to Fig. 1, and the EDS spectrogram is similar to Fig. 2.SEM and EDS result show, phosphorous ZSM-5 molecular sieve thickness 30-40 μ m, and phosphorus content is 10.0mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained from the retort bottom is consistent with Fig. 3.
Embodiment 8
Adopt the method for embodiment 1 to synthesize phosphorous ZSM-5 molecular sieve film.Different, the TPAOH aqueous solution that adopts 1.25 gram 30 % by weight is template.
Supernatant liquid pH=9.63 in reactor after crystallization.
The SEM figure of the phosphorous ZSM-5 molecular sieve film made is similar to Fig. 1, and the EDS spectrogram is similar to Fig. 2.SEM and EDS result show, phosphorous ZSM-5 molecular sieve thickness 35-45 μ m, and phosphorus content is 11mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained from the retort bottom is consistent with Fig. 3.
Embodiment 9
Adopt the method for embodiment 1 to synthesize phosphorous ZSM-5 molecular sieve film.Different, adopt 2.5 gram tetraethyl orthosilicates.
Supernatant liquid pH=9.50 in reactor after crystallization.
The SEM figure of the phosphorous ZSM-5 molecular sieve film made is similar to Fig. 1, and the EDS spectrogram is similar to Fig. 2.SEM and EDS result show, phosphorous ZSM-5 molecular sieve thickness 30-40 μ m, and phosphorus content is 11.0mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained from the retort bottom is consistent with Fig. 3.
Adopt the method for embodiment 1 to synthesize phosphorous ZSM-5 molecular sieve film.Different, the crystallization temperature of employing is 120 ℃, and crystallization time is 24 hours.
Supernatant liquid pH=9.62 in reactor after crystallization.
The SEM figure of the phosphorous ZSM-5 molecular sieve film made is similar to Fig. 1, and the EDS spectrogram is similar to Fig. 2.SEM and EDS result show, phosphorous ZSM-5 molecular sieve thickness 8-15 μ m, and phosphorus content is 3mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained from the retort bottom is consistent with Fig. 3.
Embodiment 11
Adopt the method for embodiment 1 to synthesize phosphorous ZSM-5 molecular sieve film.Different, the crystallization temperature of employing is 160 ℃, and crystallization time is 24 hours.
Supernatant liquid pH=9.60 in reactor after crystallization.
The SEM figure of the phosphorous ZSM-5 molecular sieve film made is similar to Fig. 1, and the EDS spectrogram is similar to Fig. 2.SEM and EDS result show, phosphorous ZSM-5 molecular sieve thickness 15-25 μ m, and phosphorus content is 6mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained from the retort bottom is consistent with Fig. 3.
Embodiment 12
Adopt the method for embodiment 1 to synthesize phosphorous ZSM-5 molecular sieve film.Different, the crystallization temperature of employing is 180 ℃, and crystallization time is 24 hours.
Supernatant liquid pH=9.59 in reactor after crystallization.
The SEM figure of the phosphorous ZSM-5 molecular sieve film made is similar to Fig. 1, and the EDS spectrogram is similar to Fig. 2.SEM and EDS result show, phosphorous ZSM-5 molecular sieve thickness 35-40 μ m, and phosphorus content is 10.8mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained from the retort bottom is consistent with Fig. 3.
Embodiment 13
Adopt the method for embodiment 1 to synthesize phosphorous ZSM-5 molecular sieve film.Different, the crystallization temperature of employing is 150 ℃, and crystallization time is 120 hours.
Supernatant liquid pH=9.5 in reactor after crystallization.
The SEM figure of the phosphorous ZSM-5 molecular sieve film made is similar to Fig. 1, and the EDS spectrogram is similar to Fig. 2.SEM and EDS result show, phosphorous ZSM-5 molecular sieve thickness 35-45 μ m, and phosphorus content is 12mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained from the retort bottom is consistent with Fig. 3.
Embodiment 14
Add 18 water Tai-Ace S 150 0.33 gram in there-necked flask, sodium hydroxide 0.50 gram, deionized water 21.82 grams, the TPAOH aqueous solution 6.35 grams of 30 % by weight, fully stir 30 minutes, then slowly drips wherein tetraethyl orthosilicate 10.40 grams, continue to stir 2 hours, obtain even 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 μ m) be put in 100 milliliters of stainless steel reaction tanks, slowly inject gel obtained above, make the abundant submergence film of gel surface pipe porous supporting body top, sealing, in 110 ℃ of static crystallizations 72 hours.Film pipe porous supporting body is taken out, through washing, dry, 550 ℃ of roastings, within 6 hours, obtain phosphorous ZSM-5 molecular sieve film prepared by secondary crystallization.Supernatant liquid pH=10.60 in reactor after crystallization.
The SEM figure of the phosphorous ZSM-5 molecular sieve film made is similar to Fig. 1, and the EDS spectrogram as shown in Figure 4.SEM and EDS result show, phosphorous ZSM-5 molecular sieve thickness 35-45 μ m, and the top layer phosphorus content is 1.2mol%.
After film pipe porous supporting body is taken out, retort bottom crystallisate is filtered, washs, dries, roasting obtains phosphorous ZSM-5 molecular sieve.The XRD spectra of this sample is consistent with Fig. 3.
Adopt the method for embodiment 1 to synthesize phosphorous ZSM-5 molecular sieve film.Different, adopt the di-aluminium trioxide film pipe porous supporting body that porosity is 30%, aperture is 50nm-15 μ m to replace porosity 60%, the di-aluminium trioxide film pipe porous supporting body of aperture 100nm-10 μ m.
The SEM figure of the phosphorous ZSM-5 molecular sieve film made is similar to Fig. 1, and the EDS spectrogram is similar to Fig. 2.SEM and EDS result show, phosphorous ZSM-5 molecular sieve thickness 35-45 μ m, and phosphorus content is 10.5mol%.
The XRD spectra of the phosphorous ZSM-5 molecular sieve obtained from the retort bottom is consistent with Fig. 3.
Comparative Examples 1
Adopt the method for embodiment 1 to synthesize the ZSM-5 molecular sieve film.Different, do not add the buffered soln of Secondary ammonium phosphate and ammoniacal liquor in building-up process.The SEM figure on film pipe top layer as shown in Figure 5.
Comparative Examples 2
Adopt the method for embodiment 1 to synthesize phosphorous ZSM-5 molecular sieve film.Different, 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, preparation method according to 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 at synthetic ZSM-5 molecular sieve film, can on the porous supporting body surface, form the phosphorous ZSM-5 molecular sieve film with 40-50 μ m thickness range.And, in embodiment 1-15, according to method provided by the invention, the thickness difference of the phosphorous molecular screen membrane obtained all, in 10 μ m, illustrates according to method provided by the invention and can access the phosphorous molecular screen membrane than even compact.In addition, by regulating crystallization temperature and the crystallization time in building-up process, can obtain the different thickness scope than the phosphorous ZSM-5 molecular sieve film of even compact.In addition, due to phosphorous in buffered soln, can obtain the ZSM-5 molecular sieve film of phosphorus modification.Can find out from embodiment 14, on the basis of synthetic phosphorous ZSM-5 molecular sieve film, carry out secondary crystal, still can obtain the phosphorous film of the ZSM-5 molecular sieve than even compact.
By comparative example 1 and Comparative Examples 1, can find out, Comparative Examples 1 is not added the buffered soln of Secondary ammonium phosphate and ammoniacal liquor in the process of synthetic ZSM-5 molecular sieve film, under identical crystallization condition, although the film pipe top layer of Comparative Examples 1 has molecular sieve to form, but have obvious defect, subregion does not have molecular sieve, therefore can not obtain uniform ZSM-5 molecular sieve film.By comparative example 1 and Comparative Examples 2, can find out, even 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, can't obtain uniformly phosphorous ZSM-5 molecular sieve film.
Claims (12)
1. the preparation method of a phosphorous ZSM-5 molecular sieve film, it is characterized in that, the method comprises evenly mixes ,Gui source, aluminium source, template with phosphorous buffered soln, obtain uniform gel, then under the hydrothermal crystallizing condition, this gel is carried out on porous supporting body to hydrothermal crystallizing, form phosphorous ZSM-5 molecular sieve film, described phosphorous buffered soln is the pH ammonium phosphate salt that is 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
3the meter the aluminium source, with SiO
2the silicon source, template of meter 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, is preferably 1:25-400:5-30:10-25.
4. according to the described preparation method of any one in claim 1-3, wherein, PO in the buffered soln of described ammonium phosphate salt and ammoniacal liquor
4 3-concentration be 0.1-0.5mol/L, be preferably 0.15-0.3mol/L.
5. preparation method according to claim 4, wherein, described ammonium phosphate salt is one or more in primary ammonium phosphate, Secondary ammonium phosphate and ammonium phosphate.
6. according to the described preparation method of claim 1 or 3, wherein, described aluminium source is organoaluminum source and/or inorganic aluminium source, preferably, 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.
7. according to the described preparation method of claim 1 or 3, wherein, described silicon source is organosilicon source and/or inorganic silicon source, and preferably, described organosilicon source is tetraethyl orthosilicate and/or quanmethyl silicate; Described inorganic silicon source is water glass and/or silicon sol.
8. according to the described preparation method of claim 1 or 3, wherein, described template is TPAOH and/or 4-propyl bromide.
9. preparation method according to claim 1, wherein, the aperture of described porous supporting body is 50nm-15 μ m, is preferably 100nm-10 μ m; Porosity is 30-70%, is preferably 40-60%.
10. preparation method according to claim 1 wherein, describedly comprises ,Gui source, aluminium 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) the silicon source is dissolved in the mixture of step (1) gained, forms gel.
11. preparation method according to claim 1, wherein, the condition of described hydrothermal crystallizing comprises: temperature is 110-180 ℃, is preferably 120-160 ℃; Time is 1-7 days, is preferably 3-5 days.
12. the phosphorous ZSM-5 molecular sieve film that in claim 1-11, the described preparation method of any one makes.
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