CN114307689A - Preparation method for synthesizing A-type zeolite membrane by wet gel conversion - Google Patents
Preparation method for synthesizing A-type zeolite membrane by wet gel conversion Download PDFInfo
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Abstract
The invention provides a preparation method for synthesizing an A-type zeolite membrane by wet gel conversion, belonging to the field of zeolite membrane materials and the technical field of organic matter dehydration. The invention adopts a wet gel conversion method to prepare the A-type zeolite membrane, coats a certain proportion of gel synthetic liquid on the surface of the coated crystal carrier, crystallizes at high temperature, has uniform and continuous surface growth and a membrane thickness of about 4 mu m, has higher water permeation flux and separation factors when being used for pervaporation, has better water permeation flux compared with the zeolite membrane with high silica-alumina ratio, can solve the problem of industrial amplification of a flat-plate carrier by adopting the method, and reduces the preparation cost of the membrane.
Description
Technical Field
The invention belongs to the field of zeolite membrane materials and the technical field of organic matter dehydration, and particularly relates to a preparation method for synthesizing an A-type zeolite membrane by wet gel conversion.
Background
With the development of chemical fields in China, the refining of organic matters in the fields of petrochemical industry, fine chemical industry, organic chemical industry, pharmaceutical chemical industry and the like becomes more and more important, and the biggest problem in the refining process of the organic matters is the dehydration of the organic matters. In chemical synthesis and wastewater treatment, the existence of moisture is a gap which is difficult for organic matters to exceed. Organic materials often form azeotropes with water, which increases the difficulty of dehydration, and therefore, the search for practical and effective methods for dehydrating organic materials is urgent. Organic dehydration has received global attention from researchers and governments and is a research hotspot in the engineering field.
The major problem facing the current ethanol dehydration industry is that ethanol and water can form an azeotrope. The ethanol water solution with the mass fraction or volume fraction of 97.2 percent forms azeotrope which can not be separated by the traditional rectification mode at the temperature of 78.15 ℃. The traditional rectification mode can realize effective separation only for 10-85 wt% ethanol solution, and if the proportion of ethanol and water is close to the composition of an azeotrope, the ethanol content exceeds 86%, and the energy consumption required by the traditional rectification is higher. Especially when the target product is absolute ethyl alcohol, the reflux ratio of the equipment is higher. The dehydration and separation of ethanol solution and most of organic solvent are generally divided into two stages, the solution is concentrated to about 92 percent in a general conventional distillation method, and then the concentrated solution is specially treated to obtain absolute ethanol and other high-purity organic matters. Common dehydration refining methods include rectification, liquid-liquid extraction and adsorption. For rectification, the process is mature, but the energy consumption is too high, the introduction of components is liable to cause pollution [ Jaime J A, Rodri I guez G, Gil I D. Industrial & Engineering Chemistry Research, 2018, 57(29): 9615-.
Compared with organic membrane materials, the inorganic zeolite membrane materials not only have high mechanical stability and biological pollution resistance, but also have the characteristics of regular crystallization pore channels, adjustable framework silica-alumina ratio (hydrophilic-hydrophobic property) and the like, so that the inorganic zeolite membrane has good stability, excellent separation factors and higher water permeation flux when being used for dehydrating organic matters.
The conventional hydrothermal synthesis method is widely used due to mature process, convenience and simplicity, but the membrane formation requires multiple crystallization, and Masuda et al prepare zeolite membrane by multiple in-situ synthesis methods, and attempt to compensate for the increase in thickness of the membrane layer by increasing the synthesis times [ Masuda T, Hara H. Microporous Mater,1995,3(4-5):565-571 ]. At present, NaA type zeolite molecular sieve membranes are mostly prepared by adopting a secondary growth method, and the method can greatly reduce crystallization times [ Liuguanrui, Yang Jianhua, Wang Lei, and the like. The wet gel conversion method effectively reduces the self pressure due to the lack of the solvent in the zeolite crystallization process, eliminates a plurality of potential safety hazards, can be quickly synthesized at a higher temperature, improves the mechanical strength of the membrane to a certain extent, is more beneficial to the research of a reaction mechanism, and promotes the improvement of the crystallinity. The wet gel conversion method saves more raw materials, can crystallize by coating a gel layer once, and has important significance for environmental pollution and industrial amplification.
Disclosure of Invention
The invention provides a preparation method for synthesizing an A-type zeolite membrane by adopting a wet gel conversion method, aiming at the problems of high cost, large damage to the mechanical strength of the membrane and the like of the traditional synthesis method in the organic matter dehydration process.
The technical scheme of the invention is as follows:
a preparation method for synthesizing an A-type zeolite membrane by wet gel conversion comprises the steps of modifying the surface of a porous carrier, coating seed crystal liquid to obtain a seed crystal layer, and coating membrane liquid to obtain a gel layer; then crystallizing the carrier to obtain the A-type zeolite molecular sieve membrane; the porous carrier is modified, then seed crystals are introduced, gel liquid is directly coated on the seed crystals to prepare gel, the gel is directly converted into a molecular sieve membrane in a steam environment, and the membrane forming quality is controlled by adjusting synthesis pressure in the synthesis process. The method is characterized in that a seed crystal layer is pre-coated on a cheap macroporous carrier, and the A-type zeolite molecular sieve membrane prepared by a gel method has excellent separation performance and certain stability. The method has high repeatability, effective solvent saving and high film performance.
The method comprises the following specific steps:
(1) modifying the carrier: wetting the porous carrier with deionized water, wiping the alumina powder with uniform particle size on the surface of the porous carrier, drying and wiping with absorbent cotton;
(2) coating a seed layer: dispersing A-type zeolite molecular sieve seed crystals in deionized water to obtain A-type zeolite molecular sieve seed crystal liquid, coating the seed crystal liquid on the surface of a porous carrier, and wiping the porous carrier with absorbent cotton to obtain a uniform, compact and defect-free seed crystal layer;
(3) preparing a gel liquid: taking silica sol as a silicon source, sodium metaaluminate as an aluminum source and sodium hydroxide as an alkali source, mixing the aluminum source, the alkali source and the silicon source, and continuously stirring and aging for 4-6 hours to form stable SiO2-Na2O-Al2O3-H2An O system; wherein the molar ratio of each component is as follows: SiO 22/Al2O3＝1～5，H2O/SiO2＝50～60，Na2O/SiO2＝1～2；
(4) Coating a gel layer: uniformly coating the surface of the porous carrier obtained in the step (2) with the gel liquid obtained in the step (3) as a coating liquid;
(5) and (3) crystallization: before crystallization, adding water accounting for 0.1-2% of the volume of the kettle body into the kettle for adjusting the steam pressure in the kettle; and (4) crystallizing the porous carrier obtained in the step (4) in an autoclave at the temperature of 80-120 ℃ for 3-5.5 hours.
The crystallization reaction condition is that the reaction is carried out for 3 to 5.5 hours at the temperature of 80 to 120 ℃, the crystallization time is reduced along with the increase of the crystallization temperature, and the crystallization reaction condition is preferably that the reaction is carried out for 4 hours at the temperature of 100 ℃.
In the step (2), the content of the A-type zeolite molecular sieve in the A-type zeolite molecular sieve liquid crystal is 0.5-2%, the crystal particle size of the A-type zeolite molecular sieve is 0.2-3 μm, and the size of the A-type zeolite molecular sieve is preferably 0.5-1 time of the aperture of the carrier.
In the step (2), the method for introducing the seed crystal layer into the A-type zeolite molecular sieve liquid crystal on the surface of the porous carrier is a dipping method, a hot dipping method, a variable temperature hot dipping method, a vacuum crystal coating method, a spraying method, a wiping method or a spin coating method.
In the step (3), the preparation conditions of the gel liquid are as follows: stirring for 4-6h at 20-50 ℃.
The preparation process of the A-type zeolite membrane synthetic solution comprises the steps of stirring and dissolving sodium hydroxide and sodium aluminate in water, adding silica sol after the solution is clarified, and stirring and aging for 4-6 hours.
In the step (4), the method for preparing the gel layer is a dipping method, a spin coating method, a flowing method, a vacuum method, a spraying method or a spin coating method; the single-channel tubular and hollow fiber carrier is preferably subjected to an impregnation method; the multi-channel tubular and plate carriers are preferably flow processes.
In the step (5), the crystallization temperature is 80-120 ℃, and the crystallization time is 3-5.5 h.
The porous carrier is made of alumina, zirconia, mullite and porous metal; the porous carrier is in the form of single-channel and multi-channel tubular, plate-type and hollow fibers; the pore diameter of the porous carrier is 0.02-40 mu m.
The crystallization heating mode adopts conventional heating and microwave.
The porous carrier is alpha-Al2O3Tubes, hollow fibres or stainless steel tubes, preferably alpha-Al2O3A tube.
The pore diameter of the porous carrier is 0.5-5 μm, and the pore diameter of the carrier is preferably 2-3 μm.
The method for modifying the alumina particles is a wiping method, a hot dipping method or a spraying method, and preferably the wiping method.
After the carrier is formed into a film, the surface impurities are quickly cleaned by clear water and soaked in deionized water for 12 hours.
The A-type zeolite molecular sieve membrane has a flux of 2.62 kg-m for 90 wt.% ethanol/water at a temperature of 75 DEG C-2·h-1The separation factor is greater than 10000.
The invention has the beneficial effects that: the A-type zeolite membrane is used for pervaporation alcohol dehydration, has a higher separation factor, has larger permeation flux compared with a zeolite membrane with a high silica-alumina ratio, and is lower in operation cost of a wet gel conversion method and easier than a traditional hydrothermal method.
Drawings
FIG. 1 is a schematic diagram of a Pervaporation (PV) apparatus, wherein a is a magnetic stirrer, b is a water bath, c is a membrane tube, d is a membrane module, e is a raw material storage tank, f is a cold trap, g is liquid nitrogen, h is a buffer bottle, i is a vacuum meter, and j is a vacuum pump;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the surface of a type A zeolite membrane;
FIG. 3 is a Scanning Electron Microscope (SEM) cross-section of a type A zeolite membrane;
FIG. 4 is a diagram of the hydrothermal stability of pervaporation of a type A zeolite membrane;
figure 5 is an x-ray diffraction pattern (XRD) pattern of the type a zeolite membrane, where a is the membrane and b is the crystal.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
(1) Modifying the carrier: wetting a porous carrier with deionized water, wiping 3 mu m of aluminum oxide powder on the surface of the porous carrier, and then putting the porous carrier into a 100 ℃ oven for drying;
(2) treating the carrier: after drying the modified carrier, the carrier was wiped dry with absorbent cotton.
(3) Coating a seed layer: dispersing A-type zeolite molecular sieve seed crystals in deionized water to obtain A-type zeolite molecular sieve seed crystal liquid, and coating the seed crystal liquid on the surface of a porous carrier to obtain a uniform, compact and defect-free seed crystal layer;
(4) preparing a gel liquid: the invention takes the synthetic fluid as the gel coating fluid, and the water content is less; the synthetic solution takes silica sol as a silicon source, sodium metaaluminate as an aluminum source and sodium hydroxide as an alkali source, the aluminum source, the alkali source and the silicon source are added and mixed, and the mixture is continuously stirred and aged for 4-6 hours to form stable SiO2-Na2O-Al2O3-H2And (4) an O system. Wherein the molar ratio of each component is as follows: SiO 22/Al2O3＝1～5，H2O/SiO2＝50～60，Na2O/SiO2＝1～2；
(5) Treating the carrier: after the crystal coated carrier is solidified, the carrier is wiped dry by absorbent cotton.
(6) Coating a gel layer: uniformly coating the gel liquid obtained in the step (4) on the surface of a carrier by using the gel liquid as a coating liquid;
(7) and (3) crystallization: and (3) crystallizing the carrier in an autoclave at the temperature of 80-120 ℃ for 3-5.5 h.
In the step (3), the content of the A-type zeolite molecular sieve in the A-type zeolite molecular sieve liquid crystal is 0.5-2%, and the particle size of the A-type zeolite molecular sieve crystal in the liquid crystal is 0.2-3 μm.
In the step (3), the method for introducing the seed crystal layer on the surface of the porous carrier by the type a zeolite molecular sieve liquid crystal is a dipping method, a hot dipping method, a variable temperature hot dipping method, a vacuum crystal coating method, a spray coating method, a wiping method or a spin coating method, and preferably the variable temperature hot dipping method.
In the step (4), the preparation conditions of the gel liquid are as follows: stirring for 4-6h at 20-50 ℃, preferably for 4h at 30 ℃.
In the step (6), the method of applying the gel layer is a dipping method, a hot dipping method, a vacuum method, a spray method, a rubbing method or a spin coating method, and preferably a dipping method.
In the step (7), the crystallization temperature is 80-120 ℃, the crystallization time is 3-5.5 hours, preferably the crystallization temperature is 100 ℃, and the crystallization time is 4 hours.
In order to further describe the invention, several embodiments are given below, but the patent claims are not limited to the following examples.
Example 1
(1) Pretreatment of alpha-Al2O3A carrier tube: the outer diameter of the pipe is 12mm, the inner diameter of the pipe is 8mm, the average pore diameter is 2-3 mu m, and the porosity is about 30-40%; sequentially polishing the outer surface of the carrier tube once by using 800-mesh and 1500-mesh sand paper; removing residual sand particles on the carrier tube by ultrasonic oscillation of deionized water, repeating the steps for several times until the water for washing the tube does not become turbid any more, then removing residues in carrier holes by ultrasonic oscillation of acid and alkali in sequence, and washing the carrier holes to be neutral by the deionized water; finally, placing the tube in a drying oven for drying, placing the tube in a muffle furnace for calcining at 550 ℃ for 6 hours, and sealing two ends for later use;
(2) wetting the carrier tube obtained in the step (1) in deionized water for 10-15 s, and then performing wiping and coating modification by using spherical alumina powder of 3 microns to obtain a modified carrier;
(3) preheating the carrier tube obtained in the step (2) at 175 ℃ for 3-4 h, then quickly soaking the carrier tube into a large seed crystal (3 mu m) suspension I with the mass concentration of 2 wt.%, drying the carrier tube at 80 ℃ overnight, and curing the carrier tube at 175 ℃ for 3-4 h to obtain a seed crystal layer loaded carrier I;
(4) wiping off seed crystals on the surface of the carrier by using absorbent cotton, preheating the seed crystal layer loading carrier I at 80 ℃ for 3-4 h, then soaking the seed crystal layer loading carrier I into a small seed crystal (200nm) suspension II with the mass concentration of 0.5 wt.%, drying the seed crystal layer loading carrier I at 80 ℃ overnight, and curing the seed crystal layer loading carrier I at 175 ℃ for 3-4 h to obtain a seed crystal layer loading carrier II;
(5) at a molar ratio of 1Al2O3：2SiO2：2Na2O：100H2O is prepared into a synthetic liquid, and the synthetic liquid is stirred and aged for 4-6 hours at room temperature;
(6) soaking the carrier tube II in the synthetic solution for about 15-20 s to obtain a load carrier III with a gel layer
(7) Loading the load carrier III obtained in the step (6) into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, and placing the stainless steel crystallization kettle in a drying oven at 100 ℃ for crystallization for 4 hours;
(8) and washing the synthesized A-type molecular sieve zeolite membrane to be neutral by using deionized water, and drying in an oven at 50 ℃.
Example 2
The procedure was the same as in example 1 except for (7);
changing synthesis conditions, adding 1mL of water at the bottom of the kettle to synthesize the A-type zeolite molecular sieve membrane, and performing a 90 wt.% ethanol/water pervaporation test at 75 ℃ to obtain a membrane with flux and separation factor of 1.30kg m-2·h-1，1491。
Example 3
The zeolite a type molecular sieve membrane prepared in example 1 was subjected to a time dependency test on a 90 wt.% ethanol/water system, and the test results are shown in fig. 4. After 10h of test, the total flux is reduced from the initial 2.62 kg.m-2. h-1 to about 2.32 kg.m-2. h-1, and the water content on the permeation side is basically kept unchanged.
Comparative example 1
A type zeolite molecular sieve membrane is synthesized by adopting a conventional in-situ hydrothermal synthesis method, the steps (1), (2) and (5) in the example 1 are unchanged, the steps (3) and (4) are removed, and the aged synthetic solution is slowly introduced into a reaction kettle along the inner lining wall of the kettle in the step (6) and crystallized at high temperature. As can be seen from Table 1, the separation factor of the in situ synthesis directly on the macroporous carrier is only 1.45, and the flux reaches 23.53 kg.m2·h-1And the discontinuous densification of the NaA molecular sieve membrane grown in situ is demonstrated.
Table 1 flux and separation factor for example 1 and comparative example 1
Claims (8)
1. A preparation method for synthesizing an A-type zeolite membrane by wet gel conversion comprises the steps of modifying the surface of a porous carrier, coating seed crystal liquid to obtain a seed crystal layer, and coating membrane liquid to obtain a gel layer; then crystallizing the carrier to obtain the A-type zeolite molecular sieve membrane; the method is characterized in that the porous carrier is modified, then seed crystals are introduced and gel liquid is directly coated on the seed crystals to prepare gel, the gel is directly converted into a molecular sieve membrane in a steam environment, and the membrane forming quality is controlled by adjusting synthesis pressure in the synthesis process; the method comprises the following specific steps:
(1) modifying the carrier: wetting the porous carrier with deionized water, wiping the alumina powder with uniform particle size on the surface of the porous carrier, drying and wiping with absorbent cotton;
(2) coating a seed layer: dispersing A-type zeolite molecular sieve seed crystals in deionized water to obtain A-type zeolite molecular sieve seed crystal liquid, coating the seed crystal liquid on the surface of a porous carrier, and wiping the porous carrier with absorbent cotton to obtain a uniform, compact and defect-free seed crystal layer;
(3) preparing a gel liquid: taking silica sol as a silicon source, sodium metaaluminate as an aluminum source and sodium hydroxide as an alkali source, mixing the aluminum source, the alkali source and the silicon source, and continuously stirring and aging for 4-6 hours to obtain the catalystStabilized SiO2-Na2O-Al2O3-H2An O system; wherein the molar ratio of each component is as follows: SiO 22/Al2O3＝1～5，H2O/SiO2＝50～60，Na2O/SiO2＝1～2；
(4) Coating a gel layer: uniformly coating the surface of the porous carrier obtained in the step (2) with the gel liquid obtained in the step (3) as a coating liquid;
(5) and (3) crystallization: before crystallization, adding water accounting for 0.1-2% of the volume of the kettle body into the kettle for adjusting the steam pressure in the kettle; and (4) crystallizing the porous carrier obtained in the step (4) in an autoclave at the temperature of 80-120 ℃ for 3-5.5 hours.
2. The preparation method of claim 1, wherein in the step (2), the content of the type A zeolite molecular sieve in the type A zeolite molecular sieve crystal liquid is 0.5-2%, and the crystal particle size of the type A zeolite molecular sieve is 0.2-3 μm.
3. The preparation method according to claim 1, wherein in the step (2), the method for introducing the type A zeolite molecular sieve liquid crystal into the seed layer on the surface of the porous carrier is dipping method, hot dipping method, variable temperature hot dipping method, vacuum crystal coating method, spraying method, wiping method or spin coating method.
4. The method according to claim 1, wherein in the step (3), the gel liquid is prepared under the conditions of: stirring for 4-6h at 20-50 ℃.
5. The preparation method according to claim 1, wherein the material of the porous carrier is alumina, zirconia, mullite or porous metal; the porous carrier is in the form of single-channel tube type, multi-channel tube type, plate type or hollow fiber; the pore diameter of the porous carrier is 0.02-40 mu m.
6. The production method according to claim 1, wherein in the step (4), the method for producing the gel layer is a dipping method, a spin coating method, a flow method, a vacuum method, a spray method or a spin coating method; selecting a single-channel tubular hollow fiber carrier impregnation method; multi-channel tubular and plate carrier selective flow method.
7. The method according to claim 1, wherein in the step (5), the crystallization temperature is 80-120 ℃ and the crystallization time is 3-5.5 h.
8. The method according to claim 1, wherein the crystallization heating is performed by conventional heating and microwave heating.
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Application publication date: 20220412 |