CN101342496B - Preparation method for zirconium-silicon molecular sieve catalytic active membrane - Google Patents
Preparation method for zirconium-silicon molecular sieve catalytic active membrane Download PDFInfo
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- CN101342496B CN101342496B CN2008101507164A CN200810150716A CN101342496B CN 101342496 B CN101342496 B CN 101342496B CN 2008101507164 A CN2008101507164 A CN 2008101507164A CN 200810150716 A CN200810150716 A CN 200810150716A CN 101342496 B CN101342496 B CN 101342496B
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Abstract
The invention provides a method for preparing zirconium molecular sieve catalytic active film, including the procedures of carrier treatment, preparation of molecular-sieve precursor collosol, hydrothermal crystallization and preparation of zirconium molecular sieve catalytic active film. The zirconium molecular sieve catalytic active film prepared by the method is used to catalyze the selective oxidation of isopropanol and the epoxidation reaction of micromolecule olefin; the experiment result shows that the flux is 0.16kg/m2 per h when the mass concentration of isopropyl at the feed side is10 percent, the conversion rate of catalytic reaction is 63 percent; with regard to vinyl chloride reaction system, the conversion can be as high as 62 percent. The zirconium molecular sieve catalytic active film prepared by such method has relatively high catalytic activity. The invention has the advantages of that the method is simple, the product cost is low, the conversion rate is high, etc.,and the zirconium molecular sieve catalytic active film prepared by such method can be applied to the selective catalytic oxidation reaction of alcohol and low-carbon olefin.
Description
Technical field
The invention belongs to the inorganic material film technical field, be specifically related to zirconium-silicon molecular sieve film.
Background technology
Molecular sieve has regular pore passage structure, bigger specific area and pore volume, has been used as catalysis material, gas separation and adsorbent, ion-exchanger etc., is widely used in fields such as oil and natural gas processing, fine chemistry industry, environmental protection and nuclear waste disposal.Compare with homogeneous catalyst, molecular sieve solid is made catalyst, catalytic efficiency height, good hydrothermal stability, recyclable recycling.But, because molecular sieve catalyst is small-sized, mostly be nanometer grade powder, there are shortcomings such as difficult recovery, easy inactivation and gathering, in actual applications because too high pressure drop, the zeolite molecular sieve powder is not suitable for fixed bed reactors when using in catalytic reaction, need to add the binding agent moulding make have certain mechanical strength and shape particle to adapt to various application.In addition,, obtain intermediate product, react difficult with control for some chain reaction.Make fine and close crystal film on perforated tubular or the porous flat plate and the nanoscale molecular sieve catalyst is fixed on, not only can solve the problem of catalyst recovery, can also avoid deep reaction, but and the binding film characteristics of separating, product is separated with reactant.Thereby greatly reduced production cost, simplified production technology.At present, membrane reactor has product yield height, selectivity is good and accessory substance lacks characteristics than traditional packed bed reactor.
The kind of molecular film reactor is a lot, divides by molecular screen membrane role in reaction, can be divided into catalytically inactive membrane reactor and catalytic activity membrane reactor.What at present, research was more is the catalytically inactive membrane reactor.In this reactor, catalyst is what to separate with molecular screen membrane, and molecular screen membrane has only separation function.This type of membrane reactor is used for esterification and dehydrogenation reaction more.As, utilize the high-hydrophilic of film that the water selectivity that esterification produces is removed, thereby this balanced reaction is carried out to the right, improve the conversion ratio of reactant.The NaA molecular screen membrane just can effectively be removed ethanol and oleic acid, methyl alcohol and oleic acid, the water that generates in the esterification of lactic acid and ethanol.Inert molecule sieve membrane reactor also is usually used in the partial oxidation reaction, and it mainly acts on is the amount of control reactant.For example, the MFI molecular film reactor is used for the normal butane partial oxygen and changes into the maleic anhydride reaction, (VO)
2P
2O
7Make catalyst, control the sample size of oxygen and normal butane, significantly improved the conversion ratio and the selectivity of reaction by the MFI molecular screen membrane.
Because some molecular sieve itself has catalytic activity, prepared molecular screen membrane can be used as the molecular sieve catalytic active membrane reactor and is used for all kinds of catalytic reactions.In recent years, the ZSM-5 molecular sieve catalytic active membrane is successfully applied to the reaction that methyl alcohol prepares alkene as membrane reactor.Because methyl alcohol is under the catalysis of ZSM-5 molecular sieve catalyst, generation be chain reaction, methyl alcohol → dimethyl ether → alkene → paraffin+aromatic hydrocarbon.If with traditional ZSM-5 molecular sieve catalyst packed bed reactor, because molecule can diffuse into catalyst granules repeatedly and contact with the activated centre, impel reaction to go on always, the productive rate of intermediate product alkene is low, poor selectivity.And with ZSM-5 molecular sieve catalytic active membrane reactor, under the driving of film pressure at both sides difference, methyl alcohol reacts in rete, and along with the difference of the rete degree of depth, it is also different to generate product.By the diffusion rate of effective adjusting molecule in rete, can obtain alkene by highly selective.In the side that sees through of film, the selectivity of alkene is up to 80%～90%, and conversion of methanol is also up to 60%～98% simultaneously.The example that another successful Application molecular sieve catalytic active membrane is made membrane reactor is the H-ZSM-5 molecular sieve catalytic active membrane.The H-ZSM-5 molecular sieve catalytic active membrane is applied to the esterification of ethanol and acetate.When ethanol and molecular acid pass rete, the H-ZSM-5 molecular sieve as catalyst this reaction carry out fast, because the H-ZSM-5 molecular screen membrane has very strong hydrophily, can optionally the water that generates in the reaction be removed simultaneously, thereby greatly improve the conversion ratio of reaction.Compare with H-ZSM-5 molecular sieve powder catalyst with the molecular sieve filled bed bioreactor of traditional H-ZSM-5, the conversion ratio of ethanol and acetate is much higher in the H-ZSM-5 molecular film reactor.
The zirconium-silicon molecular sieve powder is a kind of good catalyst, can be used in the selective catalytic oxidation reaction, yet zirconium-silicon molecular sieve catalytic active membrane does not but appear in the newspapers as the application of membrane reactor.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of the zirconium-silicon molecular sieve catalytic active membrane that a kind of method is easy, product cost is low, conversion ratio is high.
Solving the problems of the technologies described above the technical scheme that is adopted is that it comprises the steps:
A kind of preparation method of zirconium-silicon molecular sieve catalytic active membrane is characterized in that it comprises the steps:
(1) vehicle treated
With mullite pipe or α-Al
2O
3The pipe carrier is through sand papering, with power is that the ultrasonic frequency of 200W is that the ultrasonic wave of 40Hz cleaned 10 minutes, place 100 ℃ of dryings of electric heating constant temperature air dry oven 4 hours of 1800W, reduce to room temperature, from the electric heating constant temperature air dry oven, take out, be fixed in the water under high pressure thermal synthesis reactor that contains teflon lined mullite pipe or α-Al
2O
3The two ends of pipe carrier seal with teflin tape;
Above-mentioned mullite pipe or α-Al
2O
3The average pore size of pipe is that 7 μ m, porosity are 50%, external diameter is 12.5mm, and wall thickness is 2mm;
(2) preparation molecular sieve precursor colloidal sol
Under 700 rev/mins rotating speeds stir with tetraethyl orthosilicate ester, tetrabutyl zirconate, TPAOH, hydromassage you than being 1: 0.01～0.02: 0.20～0.35: 25～55 fully mixing, make the precursor colloidal sol of zirconium-silicon molecular sieve;
(3) hydrothermal crystallizing
Precursor colloidal sol poured into mullite pipe or α-Al are housed
2O
3Seal behind the water under high pressure thermal synthesis reactor of pipe carrier, place the electric heating constant temperature air dry oven static hydrothermal crystallization that presets temperature, the temperature of static hydrothermal crystallization is 150 ℃ of degree, and crystallization time is 80 hours;
(4) preparation zirconium-silicon molecular sieve catalytic active membrane
Take out water under high pressure thermal synthesis reactor, naturally the cooling or with being water-cooled to room temperature, taking-up contains the molecular screen membrane of template agent, with 100 ℃ in secondary water washing 1 hour, put into 100 ℃ of dryings of electric heating constant temperature air dry oven 12 hours of 1800W, place the Muffle furnace of 5000W, be warming up to 550 ℃ with 0.5 ℃/minute, the template agent was removed in roasting in 5～6 hours, was cooled to room temperature with 0.5 ℃/minute, was prepared into zirconium-silicon molecular sieve film.
2, according to the preparation method of the said zirconium-silicon molecular sieve catalytic active membrane of claim 1, it is characterized in that: in preparation molecular sieve precursor collosol craft step (2), the mol ratio of said tetraethyl orthosilicate ester and tetrabutyl zirconate, TPAOH, water is 1: 0.012～0.017: 0.27～0.32: 30～50.
3, according to the preparation method of the said zirconium-silicon molecular sieve catalytic active membrane of claim 1, it is characterized in that: in preparation molecular sieve precursor collosol craft step (2), the mol ratio of said tetraethyl orthosilicate ester and tetrabutyl zirconate, TPAOH, water is 1: 0.015: 0.30: 40.
4,, it is characterized in that said vehicle treated processing step (1) is: with mullite pipe or α-Al according to the preparation method of the described zirconium-silicon molecular sieve catalytic active membrane of claim 1
2O
3The pipe carrier is through sand papering, is that the ultrasonic wave of 40Hz cleaned 10 minutes with power for the 200W frequency, place 100 ℃ of dryings of electric heating constant temperature air dry oven 4 hours of 1800W, reduce to room temperature, take out, be coated with method or dip coating carries out kind of a crystallization treatment with hand, be fixed in the water under high pressure thermal synthesis reactor that contains teflon lined mullite pipe or α-Al
2O
3The two ends of pipe carrier seal with teflin tape.
5, packing
Wrap with toilet paper, be placed in the drier.
In preparation molecular sieve precursor collosol craft step 2 of the present invention, the preferred molar ratio of tetraethyl orthosilicate ester and tetrabutyl zirconate, TPAOH, water is 1: 0.012～0.017: 0.27～0.32: 30～50.
In preparation molecular sieve precursor collosol craft step 2 of the present invention, the optimum mole ratio of tetraethyl orthosilicate ester and tetrabutyl zirconate, TPAOH, water is 1: 0.015: 0.30: 40.
The zirconium-silicon molecular sieve catalytic active membrane that adopts the present invention to prepare carries out the epoxidation reaction of the selective oxidation and the small-numerator olefin of catalysis isopropyl alcohol, and experimental result shows that feed side isopropyl alcohol mass concentration is at 10% o'clock, and flux is 0.16kg/m
2H, catalytic oxidation conversion ratio are 63%, and for the vinyl chloride reaction system, the conversion ratio of vinyl chloride also can reach 62%.The catalytic activity zirconium-silicon molecular sieve film of the present invention's preparation has good catalytic activity, can be used for the selective catalytic oxidation reaction of pure and mild low-carbon alkene.
Description of drawings
Fig. 1 is the X-ray diffraction curve that adopts the zirconium-silicon molecular sieve catalytic active membrane of the embodiment of the invention 1 preparation.
Fig. 2 is the infrared spectrum curve that adopts the zirconium-silicon molecular sieve catalytic active membrane of the embodiment of the invention 1 preparation.
Fig. 3 is the electron scanning micrograph that adopts the zirconium-silicon molecular sieve catalytic active membrane surface of the embodiment of the invention 1 preparation.
Fig. 4 is the electron scanning micrograph that adopts the zirconium-silicon molecular sieve catalytic active membrane section of the embodiment of the invention 1 preparation.
Fig. 5 is the structural representation of zirconium-silicon molecular sieve catalytic active membrane catalytic reaction experimental provision.
The specific embodiment
The present invention is described in more detail below in conjunction with drawings and Examples, but the invention is not restricted to these embodiment.
Raw materials used total amount 320g is an example with the preparation zirconium-silicon molecular sieve catalytic active membrane, and its preparation method is as follows:
1, vehicle treated
It is carrier that the porous ceramic pipe of present embodiment adopts the mullite pipe, and the average pore size of mullite pipe is 7 μ m, and porosity is 50%, and external diameter is 12.5mm, and wall thickness is 2mm.With the mullite pipe through 600 purpose sand paperings, is that the ultrasonic wave of 40Hz cleaned 10 minutes with power for the 200W frequency, place 100 ℃ of dryings of electric heating constant temperature air dry oven 4 hours of 1800W, reduce to room temperature, from the electric heating constant temperature air dry oven, take out, be fixed in the water under high pressure thermal synthesis reactor that contains teflon lined, the two ends of porous ceramic pipe carrier seal with teflin tape.
2, preparation molecular sieve precursor colloidal sol
Getting mass concentration and be 98% tetraethyl orthosilicate ester 68.381g, mass concentration and be 80% tetrabutyl zirconate 2.31g, mass concentration and be 20.9% TPAOH 93.838g, water 155.471g adds in the flask, the mol ratio of tetrabutyl zirconate and tetraethyl orthosilicate ester, TPAOH, water is 1: 0.015: 0.30: 40, under 700 rev/mins rotating speeds stir, will fully mix, make the precursor colloidal sol of zirconium-silicon molecular sieve.
3, hydrothermal crystallizing
Seal after pouring precursor colloidal sol into water under high pressure thermal synthesis reactor that the porous ceramic pipe carrier is housed, place the electric heating constant temperature air dry oven static hydrothermal crystallization that presets temperature, the temperature of static hydrothermal crystallization is 150 ℃, and crystallization time is 80 hours.
4, preparation zirconium-silicon molecular sieve catalytic active membrane
Take out water under high pressure thermal synthesis reactor, naturally the cooling or with being water-cooled to room temperature, taking-up contains the molecular screen membrane of template agent, with 100 ℃ in secondary water washing 1 hour, put into 100 ℃ of dryings of electric heating constant temperature air dry oven 12 hours of 1800W, place the Muffle furnace of 5000W, be warming up to 550 ℃ with 0.5 ℃/minute, the template agent was removed in roasting in 5.5 hours, was cooled to room temperature with 0.5 ℃/minute, was prepared into zirconium-silicon molecular sieve catalytic active membrane
5, packing
Wrap with toilet paper, be placed in the drier.
Raw materials used total amount 320g is an example with the preparation zirconium-silicon molecular sieve catalytic active membrane, and its preparation method is as follows:
In vehicle treated processing step 1, it is carrier that the porous ceramic pipe of present embodiment adopts the mullite pipe, and the average pore size of mullite pipe is 0.1 μ m, and porosity is 30%, and external diameter is 10mm, and wall thickness is 1mm.Other step in this processing step is identical with embodiment 1.In preparation zirconium-silicon molecular sieve precursor collosol craft step 2, getting mass concentration and be 98% tetraethyl orthosilicate ester 96.813g, mass concentration and be 80% tetrabutyl zirconate 2.181g, mass concentration and be 20.9% TPAOH 88.569g, water 132.437g adds in the flask, 700 rev/mins rotating speed stirs down and fully mixes, the mol ratio of tetraethyl orthosilicate ester and tetrabutyl zirconate, TPAOH, water is 1: 0.01: 0.2: 25, be prepared into zirconium-silicon molecular sieve precursor colloidal sol.In crystallization process step 3, zirconium-silicon molecular sieve precursor colloidal sol is poured in the water under high pressure thermal synthesis reactor that mullite pipe carrier is housed, sealed high pressure hydrothermal synthesis reaction still, place the electric heating constant temperature air dry oven static hydrothermal crystallization of 1800W, 140 ℃ of crystallization 100 hours are prepared into the molecular screen membrane that contains the template agent.In preparation zirconium-silicon molecular sieve catalytic active membrane processing step 4, contain the molecular screen membrane of template agent, place the Muffle furnace of 5000W, be warming up to 550 ℃ with 0.5 ℃/minute, the template agent was removed in roasting in 5 hours, and other step in this processing step is identical with embodiment 1.Other processing step is identical with embodiment 1, is prepared into zirconium-silicon molecular sieve catalytic active membrane.
Raw materials used total amount 320g is an example with preparation zirconium silicon catalytic activity molecular screen membrane, and its preparation method is as follows:
In vehicle treated processing step 1, it is carrier that the porous ceramic pipe of present embodiment adopts the mullite pipe, and the average pore size of mullite pipe is 10 μ m, and porosity is 60%, and external diameter is 13mm, and wall thickness is 3mm.Other step in this processing step is identical with embodiment 1.In preparation zirconium-silicon molecular sieve precursor collosol craft step 2, getting mass concentration and be 98% tetraethyl orthosilicate ester 53.279g, mass concentration and be 80% tetrabutyl zirconate 2.400g, mass concentration and be 20.9% TPAOH 48.742g, water 215.579g adds in the flask, 700 rev/mins rotating speed stirs down and fully mixes, tetraethyl orthosilicate ester and tetrabutyl zirconate, TPAOH, hydromassage you than being 1: 0.02: 0.35: 55, be prepared into zirconium-silicon molecular sieve precursor colloidal sol.In hydrothermal crystallizing processing step 3, zirconium-silicon molecular sieve precursor colloidal sol is poured in the water under high pressure thermal synthesis reactor that mullite pipe carrier is housed, sealed high pressure hydrothermal synthesis reaction still, place the electric heating constant temperature air dry oven static hydrothermal crystallization of 1800W, 160 ℃ of crystallization 72 hours are prepared into the molecular screen membrane that contains the template agent.In preparation catalytic activity zirconium-silicon molecular sieve film 4, contain the molecular screen membrane of template agent, place the Muffle furnace of 5000W, be warming up to 550 ℃ with 0.5 ℃/minute, the template agent was removed in roasting in 6 hours, and other step in this processing step is identical with embodiment 1.Other processing step is identical with embodiment 1, is prepared into zirconium-silicon molecular sieve catalytic active membrane.
Raw materials used total amount 320g is an example with the preparation zirconium-silicon molecular sieve catalytic active membrane, and its preparation method is as follows:
In the vehicle treated processing step 1 of above embodiment 1～3, used porous ceramic pipe adopts α-Al
2O
3Pipe, α-Al
2O
3The geometry of pipe is identical with mullite pipe in the respective embodiments, and other step in this processing step is identical with respective embodiments.Other processing step is identical with respective embodiments, is prepared into the catalytic activity zirconium-silicon molecular sieve film.
Raw materials used total amount 320g is an example with the preparation zirconium-silicon molecular sieve catalytic active membrane, and its preparation method is as follows:
In the vehicle treated processing step 1 of above embodiment 1～4, with the porous ceramic pipe carrier through sand papering, is that the ultrasonic wave of 40Hz cleaned 10 minutes with power for the 200W frequency, place 100 ℃ of dryings of electric heating constant temperature air dry oven 4 hours of 1800W, reduce to room temperature, take out, be coated with method or dip coating carries out kind of a crystallization treatment with hand, be fixed in the water under high pressure thermal synthesis reactor that contains teflon lined, the two ends of porous ceramic pipe carrier seal with teflin tape.Other processing step is identical with respective embodiments, is prepared into zirconium-silicon molecular sieve catalytic active membrane.
In order to verify beneficial effect of the present invention, the inventor adopts the zirconium-silicon molecular sieve catalytic active membrane of the embodiment of the invention 1 preparation to test, and various tests are as follows:
Test apparatus: X-ray diffractometer, model are Rigaku D/Max2550VB+/PC, and produced by Japanese Rigalcu: Fourier transformation infrared spectrometer, model are EQUINX, are produced by German Brucher company; SEM, model are Quanta 200, are produced by FEI Co..
1, the sign of zirconium-silicon molecular sieve catalytic active membrane
Adopt the X-ray diffraction curve of the zirconium-silicon molecular sieve catalytic active membrane of the embodiment of the invention 1 preparation to see Fig. 1, the infrared spectrum curve is seen Fig. 2, and electron scanning micrograph is seen Fig. 3, Fig. 4.
In Fig. 1, curve a is the X-ray diffraction spectrogram of zirconium-silicon molecular sieve catalytic active membrane, and curve b is the X-ray diffraction spectrogram of the molecular sieve crystal of association, and curve c is the X-ray diffraction spectrogram of mullite pipe carrier.As seen from Figure 1, the characteristic peak 8.5 ° and 24.4 ° proves that obviously the zirconium-silicon molecular sieve film of gained and the powder of association thereof all have the MFI structure.As seen from Figure 2, at 960cm
-1The acromion explanation zirconium atom at place enters into the MFI structural framework, has formed the Zr-O-Si structure.As seen from Figure 3, mullite pipe carrier surface is covered by the zirconium-silicon molecular sieve crystal of catalytic activity, and the size of crystal is less, and average grain diameter is 1～2 μ m.As seen from Figure 4, the thickness of zirconium-silicon molecular sieve catalytic active membrane is extremely thin, almost can't measure, and most of crystal growth is in the hole of carrier.
2, with the selective oxidation of zirconium-silicon molecular sieve catalytic active membrane catalysis isopropyl alcohol and the epoxidation reaction of small-numerator olefin
Reaction system solution is contained in the glass container 5 that has reflux condensing tube 1, is placed on then in the water bath 4 that is fixed on the magnetic stirring apparatus 6.One end of zirconium-silicon molecular sieve catalytic active membrane 8 and external diameter are 12mm, longly block up for the teflon rod 7 of 2cm is connected, and the other end of zirconium-silicon molecular sieve catalytic active membrane 8 is that 12mm, length are that glass tube and the vacuum system 3 of 3～4cm links by an external diameter.The outside of zirconium-silicon molecular sieve catalytic active membrane 8 contacts with reaction system solution, the inboard vacuumizes is 25～45Pa.When catalytic oxidation takes place when reaction system solution passes zirconium-silicon molecular sieve catalytic active membrane 8 reactant molecule, product and unreacted reactant pass carrier layer by the infiltration steam course, be collected in the cold-trap 2 with cooled with liquid nitrogen, also can adopt alternately follow-on test of two cold-traps 2.Each component concentrations is determined by gas chromatographic analysis in reaction system solution and the collection liquid.Total flux is calculated as follows:
Q (kg/m
2H)=collect gross mass/(area of acquisition time * film) of liquid
Q is a total flux in the formula, in the unit interval unit are, is seeing through the collected quality of side by the infiltration evaporation process; The gross mass of collecting obtains by the quality of collecting liquid in the balance weighing cold-trap 2.Acquisition time begins to collected specimens institute elapsed time from cold-trap 2 for the infiltration evaporation process; The area of zirconium-silicon molecular sieve catalytic active membrane 8 is the area of the film that contacted with reaction system solution in the infiltration evaporation process.The area of used zirconium-silicon molecular sieve catalytic active membrane 8 is 22.6cm in this experiment
2The conversion ratio of reaction is calculated as follows
C=M
Product/ (M
Product+ M
Unreacted reactant) * 100%,
C is a conversion ratio in the formula, M
ProductThe molal quantity of the product that generates for the reaction of collecting in the cold-trap 2, M
Unreacted reactantBe the molal quantity of the unreacted reactant of collection in the cold-trap 2, the size of conversion ratio is to estimate the major parameter of zirconium-silicon molecular sieve catalytic active membrane 8 catalytic performance quality.
For the oxidation reaction of isopropyl alcohol, the molar concentration of reactant isopropyl alcohol is 1.667mol/L in the reaction system solution, and the molar concentration of oxidant hydrogen peroxide is 1.667mol/L, and water is as reaction dissolvent, and reaction temperature is 60 ℃.When each component of this system was passed through zirconium-silicon molecular sieve catalytic active membrane 8 under the infiltration evaporation condition, following reaction took place:
CH
3CH(OH)CH
3+H
2O
2→CH
3COCH
3+2H
2O
Result of the test sees Table 1.
Table 1 zirconium-silicon molecular sieve catalytic active membrane 8 is used for isopropyl alcohol catalytic oxidation result
For the epoxidation reaction of vinyl chloride, the molar concentration of reactant vinyl chloride is 0.667mol/L in the reaction system solution, and the molar concentration of oxidant hydrogen peroxide is 0.667mol/L, and methyl alcohol is as reaction dissolvent, and reaction temperature is 50 ℃.When each component of this system was passed through zirconium-silicon molecular sieve catalytic active membrane 5 under the infiltration evaporation condition, following reaction took place:
ClCHCH
2+H
2O
2→ClCHOCH+2H
2O
Result of the test sees Table 2.
Table 2 zirconium-silicon molecular sieve catalytic active membrane 8 is used for vinyl chloride epoxidation reaction result
By table 1 and table 2 as seen, feed side isopropyl alcohol mass concentration is 10% o'clock, and flux is 0.16kg/m
2H, catalytic oxidation conversion ratio are 63%, and for the vinyl chloride reaction system, the conversion ratio of vinyl chloride also can reach 62%.The zirconium-silicon molecular sieve catalytic active membrane of the present invention's preparation has good catalytic activity, can be used for the selective catalytic oxidation reaction of pure and mild low-carbon alkene.
Claims (4)
1. the preparation method of a zirconium-silicon molecular sieve catalytic active membrane is characterized in that it comprises the steps:
(1) vehicle treated
With mullite pipe or α-Al
2O
3The pipe carrier is through sand papering, with power is that the ultrasonic frequency of 200W is that the ultrasonic wave of 40Hz cleaned 10 minutes, place 100 ℃ of dryings of electric heating constant temperature air dry oven 4 hours of 1800W, reduce to room temperature, from the electric heating constant temperature air dry oven, take out, be fixed in the water under high pressure thermal synthesis reactor that contains teflon lined mullite pipe or α-Al
2O
3The two ends of pipe carrier seal with teflin tape;
Above-mentioned mullite pipe or α-Al
2O
3The average pore size of pipe is that 7 μ m, porosity are 50%, external diameter is 12.5mm, and wall thickness is 2mm;
(2) preparation molecular sieve precursor colloidal sol
Under 700 rev/mins rotating speeds stir with tetraethyl orthosilicate ester, tetrabutyl zirconate, TPAOH, hydromassage you than being 1: 0.01～0.02: 0.20～0.35: 25～55 fully mixing, make the precursor colloidal sol of zirconium-silicon molecular sieve;
(3) hydrothermal crystallizing
Precursor colloidal sol poured into mullite pipe or α-Al are housed
2O
3Seal behind the water under high pressure thermal synthesis reactor of pipe carrier, place the electric heating constant temperature air dry oven static hydrothermal crystallization that presets temperature, the temperature of static hydrothermal crystallization is 150 ℃, and crystallization time is 80 hours;
(4) preparation zirconium-silicon molecular sieve catalytic active membrane
Take out water under high pressure thermal synthesis reactor, naturally the cooling or with being water-cooled to room temperature, taking-up contains the molecular screen membrane of template agent, with 100 ℃ in secondary water washing 1 hour, put into 100 ℃ of dryings of electric heating constant temperature air dry oven 12 hours of 1800W, place the Muffle furnace of 5000W, be warming up to 550 ℃ with 0.5 ℃/minute, the template agent was removed in roasting in 5～6 hours, was cooled to room temperature with 0.5 ℃/minute, was prepared into zirconium-silicon molecular sieve film.
2. according to the preparation method of the said zirconium-silicon molecular sieve catalytic active membrane of claim 1, it is characterized in that: in preparation molecular sieve precursor collosol craft step (2), the mol ratio of said tetraethyl orthosilicate ester and tetrabutyl zirconate, TPAOH, water is 1: 0.012～0.017: 0.27～0.32: 30～50.
3. according to the preparation method of the said zirconium-silicon molecular sieve catalytic active membrane of claim 1, it is characterized in that: in preparation molecular sieve precursor collosol craft step (2), the mol ratio of said tetraethyl orthosilicate ester and tetrabutyl zirconate, TPAOH, water is 1: 0.015: 0.30: 40.
4. according to the preparation method of the described zirconium-silicon molecular sieve catalytic active membrane of claim 1, it is characterized in that said vehicle treated processing step (1) is: with mullite pipe or α-Al
2O
3The pipe carrier is through sand papering, is that the ultrasonic wave of 40Hz cleaned 10 minutes with power for the 200W frequency, place 100 ℃ of dryings of electric heating constant temperature air dry oven 4 hours of 1800W, reduce to room temperature, take out, be coated with method or dip coating carries out kind of a crystallization treatment with hand, be fixed in the water under high pressure thermal synthesis reactor that contains teflon lined mullite pipe or α-Al
2O
3The two ends of pipe carrier seal with teflin tape.
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| CN102274705B (en) * | 2011-04-29 | 2013-06-12 | 浙江大学 | Method for preparing molecular sieve membrane catalytic reactor taking active carbon as carrier |
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