CN111346516B - Modification method of T-shaped molecular sieve membrane, modified T-shaped molecular sieve membrane and application thereof - Google Patents
Modification method of T-shaped molecular sieve membrane, modified T-shaped molecular sieve membrane and application thereof Download PDFInfo
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Abstract
The invention provides a method for modifying a T-shaped molecular sieve membrane, which is used for modifying the surface of the T-shaped molecular sieve membrane by using a silane coupling agent, wherein the silane coupling agent plays a dual-function role, so that the hydrophilicity of the surface of the membrane layer can be improved, the defects of the membrane layer can be modified, and the method can be used for obtaining a high-quality modified T-shaped molecular sieve membrane. The modification method has simple process and high repeatability, and has effective effect on improving the defects of the polycrystalline film. The modified T-shaped molecular sieve membrane has stable structure and uniform and compact surface. When the modified T-shaped molecular sieve membrane is used for dehydrating and separating organic matters, the modified T-shaped molecular sieve membrane has good separation performance and good stability.
Description
Technical Field
The invention relates to the technical field of membrane preparation and application, in particular to a modification method of a T-shaped molecular sieve membrane, the modified T-shaped molecular sieve membrane and application thereof.
Background
Compared with the traditional Separation Technology in the industry, the membrane Separation Technology has the advantages of low energy consumption, less pollution, easy realization of continuous Separation, easy coupling with other Separation processes, mild use conditions, easy amplification and the like, and is more and more widely applied in the industrial fields of chemical industry, food industry, medicine industry, Environmental protection industry, metallurgy and the like (Separation & Purification Technology,25(2001) 251-260; Environmental Progress,22(2003) 46-56.). The membrane separation process mainly comprises microfiltration, ultrafiltration, reverse osmosis, nanofiltration, electrophoresis, gas separation, pervaporation and the like.
Various types of membranes have been used in membrane separation technologies, such as polymer membranes and polycrystalline membranes (molecular sieve membranes and metal organic framework membranes, etc.) (Chem Soc Rev,43(2014) 6116-. Compared with a polymer membrane with flexibility, the polycrystalline membrane loaded on a ceramic support is easy to damage, and defects are inevitably generated in the preparation process of the polycrystalline membrane, and the defects directly influence the separation performance of the membrane. There are some reports in the literature that the film is repaired by post-treatment to improve the film performance. Such as Lin et al, which adopts a steam diffusion method (AICheJ, 54(2008)1478-1486), repairs defects formed in the preparation process and improves the performance of the membrane by modifying a DDR type molecular sieve membrane. Nomura et al modify the all-silicon type molecular sieve membranes by diffusion chemical vapor deposition with less intergranular defects and greater selectivity enhancement of the membranes (Ind Eng Chem Res,36(1997) 4217-4223).
The T-type molecular sieve is a symbiotic crystal formed by the interactive growth of erionite and offretite, the skeletal structures of the erionite and the offretite are different but closely related, and the effective aperture of the T-type zeolite is 0.36nm multiplied by 0.51nm due to the eutectic growth of the two zeolites. The pore size is between that of most organic molecules and water, because the T-type molecular sieve membrane is considered to be one of the ideal membrane materials for separating alcohol-water mixtures. However, as a polycrystalline membrane material, the T-type molecular sieve membrane has inevitable defects in the preparation process, resulting in poor separation performance.
Disclosure of Invention
The invention aims to solve the problems, provides a method for modifying the surface defects of a T-shaped molecular sieve membrane, increasing the hydrophilicity of a membrane layer and improving the separation selectivity of the T-shaped molecular sieve membrane, and provides a modified T-shaped molecular sieve membrane with a stable structure and a uniform and compact surface and application thereof.
The invention provides the following technical scheme:
a method for modifying a T-shaped molecular sieve membrane comprises the following steps:
s1, preparing a silane coupling agent solution, and putting the T-shaped molecular sieve membrane into the silane coupling agent solution for modification;
and S2, placing the modified T-shaped molecular sieve membrane into an inert gas atmosphere for heat treatment.
Preferably, the preparing of the silane coupling agent solution in step S1 is specifically: mixing a silane coupling agent and an organic solvent according to the proportion of (1-40) mmol/60 mL.
Preferably, the silane coupling agent is one or more of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.
Preferably, the organic solvent is one or more of benzene, toluene, xylene, and n-heptane.
Preferably, the modification in step S1 is specifically: reacting for 0.5-3 h at 80-150 ℃.
Preferably, the inert gas in step S2 is helium, nitrogen or argon.
Preferably, the heat treatment in step S2 is specifically: drying at 80-150 deg.C.
The invention also provides a modified T-shaped molecular sieve membrane which is prepared by adopting any one of the modification methods of the T-shaped molecular sieve membrane.
The invention also provides application of the modified T-shaped molecular sieve membrane in organic matter dehydration.
Preferably, the organic matter dehydration system is an alcohol-water mixture.
The invention can obtain the following beneficial effects:
1. according to the modification method of the T-shaped molecular sieve membrane, the silane coupling agent is used for modifying the surface of the T-shaped molecular sieve membrane with more defects and poor separation selectivity, the silane coupling agent plays a dual-function role, the hydrophilicity of the surface of the membrane layer can be improved, the defects of the membrane layer can be modified, and the method can obtain the high-quality T-shaped molecular sieve membrane.
2. The modification method of the invention has simple process and high repeatability, and has effective effect on improving the defects of the polycrystalline film.
3. The modified T-shaped molecular sieve membrane has a stable structure, and the surface of the modified T-shaped molecular sieve membrane is uniform and compact.
4. The modified T-type molecular sieve membrane has good separation performance, and compared with the T-type molecular sieve membrane before modification, the separation selectivity reaches more than 5 times, and the modified T-type molecular sieve membrane has good stability; the modified T-shaped molecular sieve membrane has wide application prospect in organic matter dehydration.
Drawings
FIG. 1 is an SEM image of the surface of a T-type molecular sieve membrane before modification;
FIG. 2 is an SEM image of the modified T-shaped molecular sieve membrane surface after modification;
figure 3 is an XRD spectrum: (a) a standard T-shaped molecular sieve, (b) a mullite supporter, (c) a T-shaped molecular sieve membrane before modification and (d) a modified T-shaped molecular sieve membrane after modification.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1:
1. synthesizing T-type molecular sieve membrane and applying the same to separation of water/isopropanol
Coating a layer of uniform micron-sized seed crystal on the surface of a tubular mullite support body by a rub-coating method, and naturally airing at room temperature to obtain a seed crystal support body;
in a molar ratio n (SiO)2):n(Al2O3):n(Na2O):n(K2O):n(H2Preparing a synthetic gel from O) 1:0.015:0.25:0.08:25, and stirring and aging for 24 hours at room temperature;
vertically placing the dried support body pre-coated with the seed crystals into a stainless steel reaction kettle filled with the sol, placing the reaction kettle into a drying oven preheated to a specified temperature to start crystallization, wherein the crystallization condition is that the support body is crystallized at 150 ℃ for 2 hours and then is crystallized at 100 ℃ for 10 hours;
and taking out the reaction kettle after the reaction is finished, taking out the crystallized film after cooling, repeatedly washing the surface of the film to be neutral by using deionized water, and drying at 100 ℃ for later use.
The T-shaped molecular sieve membrane obtained above has an operating temperature of 75 ℃ and a separation performance on 90 wt.% water/isopropanol of about 3.66kg m-2h-1The separation factor is only 360.
The surface morphology of the T-type molecular sieve membrane is shown in figure 1, and the selectivity of the T-type molecular sieve membrane is combined, so that the existence of intercrystalline defects in the membrane layer is shown.
The synthesized T-type molecular sieve membrane was subjected to XRD characterization, and the result is shown in fig. 3 (c). As can be seen from FIG. 3(c), the prepared T-type zeolite membrane is a pure phase.
2. Modification of T-type molecular sieve membrane, and application of the modified T-type molecular sieve membrane in water/isopropanol separation
And (3) carrying out modification treatment on the synthesized T-shaped molecular sieve membrane: preparing 3-aminopropyltriethoxysilane and toluene into a silane coupling agent solution according to the proportion of 8mmol/60mL, then placing the pretreated T-shaped molecular sieve membrane into the silane coupling agent solution, then placing the T-shaped molecular sieve membrane into a drying oven to react for 1.5h at 110 ℃, removing the weakly-combined silane coupling agent by soaking the T-shaped molecular sieve membrane in the toluene solvent, and finally drying the T-shaped molecular sieve membrane at 120 ℃ under the protection of argon to obtain the modified T-shaped molecular sieve membrane.
Testing the separation performance of the modified T-shaped molecular sieve membrane: the operating temperature was 75 ℃, and 90 wt.% isopropanol/water was subjected to pervaporation separation. The flux is measured from the original 3.85kg m-2h-1Reduced to 3.06kg m-2h-1The separation factor is increased from the original 360 to 2800, and the selectivity is greatly improved.
Example 2:
1. synthesis of T-type molecular sieve membrane and its application in water/isopropanol separation
The operation method and reaction parameters were the same as in example 1.
2. Modification of T-type molecular sieve membrane, and application of the modified T-type molecular sieve membrane in water/isopropanol separation
And (3) carrying out modification treatment on the synthesized T-type molecular sieve membrane: preparing 3-aminopropyltrimethoxysilane and toluene into a silane coupling agent solution according to the proportion of 5mmol/60mL, then putting the pretreated T-shaped molecular sieve membrane into the silane coupling agent solution, then putting the T-shaped molecular sieve membrane into a drying oven to react for 1.5h at 110 ℃, removing the weakly-combined silane coupling agent by soaking the T-shaped molecular sieve membrane in the toluene solvent, and finally drying the T-shaped molecular sieve membrane at 120 ℃ under the protection of argon to obtain the modified T-shaped molecular sieve membrane.
XRD (X-ray diffraction) characterization and SEM (scanning Electron microscope) characterization are carried out on the obtained modified T-shaped molecular sieve membrane, and the results show that the T-shaped molecular sieve membrane is stable in structure and uniform and compact in surface change after being modified.
Testing the separation performance of the modified T-shaped molecular sieve membrane: the operating temperature was 75 ℃, and 90 wt.% isopropanol/water was subjected to pervaporation separation. The flux is measured from the original 3.33kg m-2h-1Reduced to 3.06kg m-2h-1The separation factor increased from the original 600 to 3000.
Example 3:
1. synthesis of T-type molecular sieve membrane and its application in water/isopropanol separation
The operation method and reaction parameters were the same as in example 1.
2. Modification of T-type molecular sieve membrane, and application of the modified T-type molecular sieve membrane in water/isopropanol separation
And (3) carrying out modification treatment on the synthesized T-shaped molecular sieve membrane: preparing 3-aminopropyltriethoxysilane and toluene according to the proportion of 8mmol/60mL to obtain a silane coupling agent solution, then placing the pretreated T-type molecular sieve membrane into the silane coupling agent solution, then placing the pretreated T-type molecular sieve membrane into a drying oven to react for 1h at 110 ℃, removing the weakly-combined silane coupling agent by soaking the T-type molecular sieve membrane in the toluene solvent, and finally drying the T-type molecular sieve membrane at 120 ℃ under the protection of argon to obtain the modified T-type molecular sieve membrane.
Testing the separation performance of the modified T-shaped molecular sieve membrane: the operating temperature was 75 ℃, and 90 wt.% isopropyl alcohol/water was subjected to pervaporation separation. The flux is increased from the original 3.66kg m-2h-1Reduced to 2.95kg m-2h-1The separation factor increased from original 360 to 3000.
The obtained modified T-type molecular sieve membrane was subjected to XRD and SEM characterization, and the results are shown in fig. 2 and fig. 3(d), respectively. From the characterization result of XRD, the T-type molecular sieve membrane has a stable structure after being modified, and from the SEM image, the surface of the T-type molecular sieve membrane becomes more uniform and compact under the modification condition.
Example 4:
1. synthesis of T-type molecular sieve membrane and its application in water/isopropanol separation
The operation method and reaction parameters were the same as in example 1. The flux of the T-shaped molecular sieve membrane is 3.45kg m-2h-1The separation factor is 480.
2. Modification of T-type molecular sieve membrane, and application of the modified T-type molecular sieve membrane in water/isopropanol separation
And (3) carrying out modification treatment on the synthesized T-shaped molecular sieve membrane: preparing 3- (2, 3-epoxypropoxy) propyl trimethoxy silane and benzene into silane coupling agent solution according to the proportion of 15mmol/60mL, then putting the pretreated T-shaped molecular sieve membrane into the silane coupling agent solution, then putting the T-shaped molecular sieve membrane into an oven to react for 2.5 hours at 100 ℃, removing the weakly-combined silane coupling agent by soaking the T-shaped molecular sieve membrane in benzene solvent, and finally drying the T-shaped molecular sieve membrane under the protection of helium at 110 ℃ to obtain the modified T-shaped molecular sieve membrane.
XRD (X-ray diffraction) characterization and SEM (scanning Electron microscope) characterization are carried out on the obtained modified T-shaped molecular sieve membrane, and the results show that the T-shaped molecular sieve membrane is stable in structure and uniform and compact in surface change after being modified.
Testing the separation performance of the modified T-shaped molecular sieve membrane: the operating temperature was 75 ℃, and 90 wt.% isopropanol/water was subjected to pervaporation separation. The flux is measured from the original 3.45kg m-2h-1Reduced to 3.06kg m-2h-1The separation factor is increased from original 480 to 2800, and the selectivity is greatly improved.
Example 5:
1. synthesis of T-type molecular sieve membrane and its application in water/isopropanol separation
The operation method and reaction parameters were the same as in example 1. The flux of the T-shaped molecular sieve membrane is 3.73kg m-2h-1The separation factor is 340.
2. Modification of T-type molecular sieve membrane, and application of the modified T-type molecular sieve membrane in water/isopropanol separation
And (3) carrying out modification treatment on the synthesized T-shaped molecular sieve membrane: preparing aminopropyl trimethoxysilane, gamma- (methoxyacryloyloxy) propyl trimethoxysilane and xylene into a silane coupling agent solution according to the proportion of 10mmol/10mmol/60mL, then putting the pretreated T-shaped molecular sieve membrane into the silane coupling agent solution, then putting the T-shaped molecular sieve membrane into a drying oven to react for 2 hours at 120 ℃, removing the weakly-combined silane coupling agent by soaking the T-shaped molecular sieve membrane in a xylene solvent, and finally putting the T-shaped molecular sieve membrane into a tubular furnace to dry under the protection of nitrogen at 130 ℃ to obtain the modified T-shaped molecular sieve membrane.
XRD (X-ray diffraction) characterization and SEM (scanning Electron microscope) characterization are carried out on the obtained modified T-shaped molecular sieve membrane, and the results show that the T-shaped molecular sieve membrane is stable in structure and uniform and compact in surface change after being modified.
Testing the separation performance of the modified T-shaped molecular sieve membrane: the operating temperature was 75 ℃, and 90 wt.% isopropanol/water was subjected to pervaporation separation. The flux is measured from the original 3.73kg m-2h-1Reduced to 3.10kg m-2h-1The separation factor is increased from the original 340 to 2100, and the selectivity is greatly improved.
Example 6:
1. synthesis of T-type molecular sieve membrane and its application in water/isopropanol separation
The operation method and reaction parameters were the same as in example 1. The flux of the T-shaped molecular sieve membrane is 3.88kg m-2h-1The separation factor is 390.
2. Modification of T-type molecular sieve membrane, and application of the modified T-type molecular sieve membrane in water/isopropanol separation
And (3) carrying out modification treatment on the synthesized T-type molecular sieve membrane: preparing aminopropyltrimethoxysilane, aminopropyltriethoxysilane and n-heptane into a silane coupling agent solution according to the proportion of 15mmol/15mmol/60mL, then putting the pretreated T-shaped molecular sieve membrane into the silane coupling agent solution, then placing the T-shaped molecular sieve membrane into a drying oven to react for 0.5h at 130 ℃, removing the weakly-combined silane coupling agent by soaking the T-shaped molecular sieve membrane in the n-heptane solvent, and finally placing the T-shaped molecular sieve membrane into a tubular furnace to dry under the protection of nitrogen at 90 ℃ to obtain the modified T-shaped molecular sieve membrane.
XRD (X-ray diffraction) characterization and SEM (scanning Electron microscope) characterization are carried out on the obtained modified T-shaped molecular sieve membrane, and the results show that the T-shaped molecular sieve membrane is stable in structure and uniform and compact in surface change after being modified.
Testing the separation performance of the modified T-shaped molecular sieve membrane: the operating temperature was 75 ℃, and 90 wt.% isopropanol/water was subjected to pervaporation separation. The flux is measured from the original 3.85kg m-2h-1Reduced to 3.01kg m-2h-1The separation factor is increased from original 390 to 3010, and the selectivity is greatly improved.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (5)
1. A method for modifying a T-shaped molecular sieve membrane is characterized by comprising the following steps:
s1, mixing a silane coupling agent and an organic solvent according to the proportion of (1-40) mmol/60mL to prepare a silane coupling agent solution, wherein the silane coupling agent is one or more of aminopropyltrimethoxysilane, aminopropyltriethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane and gamma- (methoxyacryloyloxy) propyltrimethoxysilane, and the organic solvent is one or more of benzene, toluene, xylene and n-heptane; putting the T-shaped molecular sieve membrane into the silane coupling agent solution, and reacting at 80-150 ℃ for 0.5-3 h to modify the T-shaped molecular sieve membrane;
s2, soaking the modified T-shaped molecular sieve membrane in a benzene, toluene, xylene or n-heptane solvent, removing the weakly bonded silane coupling agent, and then placing the membrane in an inert gas atmosphere for heat treatment, wherein the heat treatment is drying at the temperature of 80-150 ℃.
2. The method for modifying a T-type molecular sieve membrane according to claim 1, wherein the inert gas in step S2 is helium, nitrogen or argon.
3. A modified T-type molecular sieve membrane, which is prepared by the modification method of the T-type molecular sieve membrane in claim 1 or 2.
4. The use of a modified T-shaped molecular sieve membrane according to claim 3 in organic dehydration.
5. The use of the modified T-shaped molecular sieve membrane in organic matter dehydration according to claim 4, characterized in that the system for organic matter dehydration is an alcohol-water mixture.
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