CN109433018B - Preparation method of ultrathin silicon-based alcohol-water separation membrane with thickness less than 50nm - Google Patents
Preparation method of ultrathin silicon-based alcohol-water separation membrane with thickness less than 50nm Download PDFInfo
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Abstract
The invention belongs to the field of membrane material preparation, and particularly relates to a preparation method of an ultrathin silicon-based alcohol-water separation membrane with the thickness of less than 50 nm. The dip-coating method commonly used in the current film preparation process has the problems of large thickness (>300nm) of a separation layer, small flux, incapability of accurately regulating and controlling the preparation process and the like, and the thickness of the separation layer prepared by adopting methods such as a spin coating method, a wiping coating method and the like is difficult to reach below 200 nm. Aiming at the problems, the invention uses ultrasonic waves to atomize low-concentration organic silicon sol so that the sol is dispersed into countless tiny droplets, then uses carrier gas to blow and deposit the atomized sol on a porous polymer support, and finally dries the porous polymer support to prepare the ultrathin silicon-based alcohol-water separation membrane with the separation layer thickness of less than 50 nm.
Description
Technical Field
The invention belongs to the field of preparation of separation membranes, and particularly relates to a preparation method of an ultrathin silicon-based alcohol-water separation membrane with the thickness of less than 50 nm.
Background
The sol-gel method can accurately control the aperture and the pore structure, and can directly prepare the microporous inorganic membrane on a support body (or a transition layer). Like the conventional inorganic silicon film, the organic silicon film is generally prepared by a sol-gel method, and the coating method generally includes a dip-coating method, a spin-coating method, a wiping method, and the like.
The commonly used dipping and pulling method is to dip one surface of a support body into a sol prepared in advance, after dipping for a period of time, the support body is stably pulled out of the sol at a certain speed, and then the support body is calcined to remove the solvent and is subjected to dehydration condensation reaction to form a porous separation layer. The spin coating method is to fix the support on a turntable, to drop the sol on the support during the rotation of the support, to perform spin coating operation and drying, to repeat the process several times, and to finally perform calcination to obtain the film. The wiping method is to dip absorbent cotton into the sol, quickly wipe the sol on the support body in one direction, and obtain the organic silicon film after calcination.
The dip-coating method has the problems of large thickness (>300nm) of the separation layer, small flux, incapability of accurately regulating and controlling the preparation process and the like, and the thickness of the separation layer prepared by adopting methods such as a spin coating method, a wiping method and the like is difficult to reach below 200 nm. How to reduce the thickness of the film on the premise of ensuring the integrity, compactness and no defect of the film is a difficult point of the current film making technology.
Disclosure of Invention
Aiming at the technical problems, the invention adopts an ultrasonic atomization physical deposition method to prepare the separation membrane, uses ultrasonic waves to atomize the low-concentration organic silica sol, then deposits the low-concentration organic silica sol on the porous polymer support body, and finally dries the porous polymer support body to prepare the ultrathin silicon-based alcohol-water separation membrane with the thickness of the separation layer being less than 50 nm.
The preparation method comprises the following steps:
adding Isopropanol (IPA) into a beaker, adding the composite silicon source precursor, stirring until the composite silicon source precursor is fully dissolved, and dripping water (H) while stirring2O), continuously stirring for 1-2 min, and then dropwise adding nitric acid (HNO)3) Immediately transferring the beaker into a constant-temperature water bath, continuously stirring for 1-3 hours to obtain silica sol, and diluting the silica sol to 0.1-0.5 wt% by using IPA; pouring the diluted sol into an ultrasonic atomizer, dispersing the sol into tiny liquid drops by ultrasonic waves, then enabling the liquid drops to enter a deposition chamber along with argon, enabling the liquid drops to be vertically and upwards sprayed from a spray nozzle and then deposited on a PA/PS composite film support body, horizontally placing the support body right above the spray nozzle and fixing the support body on a flat glass plate, enabling the temperature of the polymer support body to be kept at 80-100 ℃ through a heating device, evaporating a solvent for 2-3 min after primary deposition is completed, then performing next deposition, and drying for 15-20 min at 80-200 ℃ after 3-5 times of deposition to obtain the separation film.
Wherein the molar ratio of each component is H as the precursor of the composite silicon source2O:HNO3The ratio of the argon to the water is 1:120:0.1, the water bath temperature is 50-60 ℃, the flow rate of the argon is 150-400 mL/min, and once deposition is completed after argon is introduced for 30-60 s each time.
The composite silicon source precursor is BTESM and AEAPS, and the molar ratio of the BTESM to the AEAPS is 1: 0.1-0.4. The structure of bridging silicon source precursors BTESM or BTESE (1, 2-di (triethoxysilyl) ethane), BTESEthyl (1, 2-di (triethoxysilyl) ethylene) and the like has strong rigidity, silica sol prepared by the bridging silicon source precursors is deposited on a polymer support, and uneven stress is generated at the joint interface of a separation layer and the support in the process of evaporating a solvent (the solvent is isopropanol and water), so that the defects of cracks and the like are easily generated on the surface of a membrane. The number of depositions is greatly increased to ensure the integrity of the film, so that the thickness of the separation layer cannot be further reduced. Through copolymerization of AEAPS and BTESM with a flexible structure, long-side chain groups of AEAPS are introduced into a silicon network structure of BTESM, so that the flexibility of a separation layer structure is enhanced, defects such as cracks can be effectively avoided, and a complete and defect-free separation layer can be formed only by depositing for 3-5 times. On the contrary, if a flexible precursor of a long carbon chain side-end silicon source, such as AEAPS, is used as a material of the separation layer, the long side chain flexible structure is easy to collapse due to lack of rigid support during drying to form dead pores and closed pores, which is not favorable for constructing a microporous structure suitable for separation of small molecules, such as alcohol, water and the like.
The polymer support is horizontally placed right above the spray opening, the distance between the polymer support and the spray opening is 4-6 cm, if the distance between the spray opening and the support is too close, local liquid drops can be gathered, and uniform deposition on the surface of the support cannot be achieved. The temperature of the polymer support is controlled to be 80-100 ℃, and the solvent is rapidly evaporated by utilizing the high temperature on the surface of the support, so that a gel layer is rapidly formed. And drying at 80-200 ℃ after deposition is finished so as to further evaporate the residual solvent, and further performing dehydration condensation reaction on silanol groups in the silicon network to form a more compact silicon network structure. The invention adopts a vertical upward spray deposition mode, eliminates large-particle fog drops through gravity factors, narrows the particle size of the liquid drops, simultaneously avoids the phenomenon that convection in thermal mass conduction is caused by upward cooling and downward heating during vertical downward spray deposition, reduces the quantity of the fog drops reaching the surface of the support body, and is favorable for improving the uniformity and the deposition rate of the film.
Drawings
FIG. 1 is a diagram of the mechanism of the copolymerization, hydrolysis and condensation reaction of BTESM and AEAPS as precursors of composite silicon source.
Fig. 2 is SEM images of the surface (a) and the cross section (b) of the separation membrane prepared in example 1.
Fig. 3 is a surface SEM image of the film prepared in comparative example 1.
Fig. 4 is a cross-sectional SEM image of the separation membrane prepared in comparative example 2.
Fig. 5 is a cross-sectional SEM image of the separation membrane prepared in comparative example 3.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
(1) Preparing BTESM/AEAPS sol: adding 24.494g IPA into a 100mL beaker, then adding 0.500g BTESM and 0.078g AEAPS, stirring for 2min, dropwise adding 3.808g water while stirring, continuously stirring for 2min, dropwise adding 1-2 drops of 68 wt% concentrated nitric acid, transferring the beaker into a constant-temperature water bath at 50 ℃, continuously stirring for 2 hours to obtain silica sol, and diluting the silica sol to 0.2 wt% by using IPA;
(2) and (2) pouring the sol prepared in the step (1) into an ultrasonic atomizer, dispersing the sol into droplets with the diameter of 1-2 microns by 2.4MHz ultrasonic waves, then feeding the droplets into a deposition chamber along with argon with the flow rate of 300mL/min, vertically and upwards spraying the droplets from a spray nozzle, depositing the droplets on a PA/PS composite membrane support, horizontally placing the support right above the spray nozzle and fixing the support on a flat glass plate, keeping the temperature of the support at 80 ℃ by a heating device, evaporating the solvent for 2min, then performing next deposition, introducing argon for 45s each time, depositing for 5 times, and drying at 120 ℃ for 15min to obtain the separation membrane.
(3) The 90 wt% isopropanol/water solution was separated using a separation membrane at a flux of 3.1 kg/(m)2h) The separation factor is 400.
Fig. 2 is SEM images of the surface (a) and the cross-section (b) of the separation membrane prepared in example 1, and it can be seen that the thickness of the separation layer is about 50nm, and the surface of the membrane is intact and defect-free.
Comparative example 1
(1) Preparing BTESM sol: adding 21.309g IPA into a 100mL beaker, adding 0.500g BTESM, stirring for 2min, dropwise adding 3.171g water while stirring, continuously stirring for 2min, dropwise adding 1-2 drops of 68 wt% concentrated nitric acid, transferring the beaker into a 50 ℃ constant-temperature water bath, continuously stirring for 2 h to obtain silica sol, and diluting the silica sol to 0.2 wt% by using IPA;
(2) and (2) pouring the sol prepared in the step (1) into an ultrasonic atomizer, dispersing the sol into droplets with the diameter of 1-2 microns by 2.4MHz ultrasonic waves, then feeding the droplets into a deposition chamber along with argon with the flow rate of 300mL/min, vertically and upwards spraying the droplets from a spray nozzle, depositing the droplets on a PA/PS composite membrane support, horizontally placing the support right above the spray nozzle and fixing the support on a flat glass plate, keeping the temperature of the support at 80 ℃ by a heating device, evaporating the solvent for 2min, then performing next deposition, introducing argon for 45s each time, depositing for 5 times, and drying at 120 ℃ for 15min to obtain the membrane.
(3) The membrane was used to separate a 90 wt% isopropyl alcohol/water solution, as shown in fig. 3, and there was no separation performance because there was a crack on the membrane surface.
Comparative example 2
(1) Preparing BTESM/AEAPS sol: adding 24.494g IPA into a 100mL beaker, then adding 0.500g BTESM and 0.078g AEAPS, stirring for 2min, dropwise adding 3.808g water while stirring, continuously stirring for 2min, dropwise adding 1-2 drops of 68 wt% concentrated nitric acid, transferring the beaker into a constant-temperature water bath at 50 ℃, continuously stirring for 2 hours to obtain silica sol, and diluting the silica sol to 0.2 wt% by using IPA;
(2) and (2) pouring the sol prepared in the step (1) into an ultrasonic atomizer, dispersing the sol into droplets with the diameter of 1-2 microns by 2.4MHz ultrasonic waves, then feeding the droplets into a deposition chamber along with argon with the flow rate of 300mL/min, vertically and upwards spraying the droplets from a spray nozzle, depositing the droplets on a PA/PS composite membrane support, horizontally placing the support right above the spray nozzle and fixing the support on a flat glass plate, evaporating the solvent for 2min at normal temperature, then performing next deposition, introducing argon for 45s every time, depositing for 5 times, and drying for 15min at 120 ℃ to obtain the separation membrane.
(3) The 90 wt% isopropanol/water solution was separated using a separation membrane at a flux of 2.5 kg/(m)2h) The separation factor is 380.
Fig. 4 is a cross-sectional SEM image of the separation membrane prepared in comparative example 2, from which it can be seen that the thickness of the separation layer is about 100 nm.
Comparative example 3
(1) Preparing BTESM/AEAPS sol: adding 24.494g IPA into a 100mL beaker, then adding 0.500g BTESM and 0.078g AEAPS, stirring for 2min, dropwise adding 3.808g water while stirring, continuously stirring for 2min, dropwise adding 1-2 drops of 68 wt% concentrated nitric acid, transferring the beaker into a constant-temperature water bath at 50 ℃, continuously stirring for 2 hours to obtain silica sol, and diluting the silica sol to 0.2 wt% by using IPA;
(2) and (2) pouring the sol prepared in the step (1) into an ultrasonic atomizer, dispersing the sol into droplets with the diameter of 1-2 microns by 2.4MHz ultrasonic waves, then feeding the droplets into a deposition chamber along with argon with the flow rate of 300mL/min, vertically and downwards spraying the droplets from a spray nozzle, depositing the droplets on a PA/PS composite membrane support, horizontally placing the support under the spray nozzle and fixing the support on a flat glass plate, keeping the temperature of the support at 80 ℃ by a heating device, evaporating the solvent for 2min, then performing next deposition, introducing argon for 45s each time, depositing for 5 times, and drying at 120 ℃ for 15min to obtain the separation membrane.
(3) The 90 wt% isopropanol/water solution was separated using a separation membrane at a flux of 2.0 kg/(m)2h) The separation factor is 405.
Fig. 5 is a cross-sectional SEM image of the separation membrane prepared in comparative example 3, from which it can be seen that the thickness of the separation layer is about 150 nm.
Claims (5)
1. A preparation method of an ultrathin silicon-based alcohol-water separation membrane with the thickness of less than 50nm is characterized by comprising the following steps:
(1) adding Isopropanol (IPA) into a beaker, adding the composite silicon source precursor, stirring, and dripping water (H) while stirring2O), continuously stirring, and dropwise adding nitric acid (HNO)3) Then immediately transferring the beaker into a constant-temperature water bath, continuously stirring to obtain silica sol, and diluting the silica sol with IPA (isopropyl alcohol); wherein, the composite silicon source precursor adopts bis (triethoxysilyl) methane (BTESM) and N- (2-aminoethyl) -3-aminopropyltriethoxysilane (AEAPS) for copolymerization;
composite silicon source precursor H2O: HNO3At a molar ratio of =1:120: 0.1;
the molar ratio of bis (triethoxysilyl) methane (BTESM) to N- (2-aminoethyl) -3-aminopropyltriethoxysilane (AEAPS) is 1: 0.1-0.4, and the concentration of the diluted silica sol is 0.1-0.5 wt%;
(2) pouring the diluted sol into an ultrasonic atomizer, dispersing the sol into tiny liquid drops by ultrasonic waves, then feeding the liquid drops into a deposition chamber along with argon gas at the flow rate of 150-400 mL/min, vertically and upwards spraying the liquid drops from a spray nozzle, depositing the liquid drops on a polymer support, horizontally placing the polymer support right above the spray nozzle and fixing the polymer support on a flat glass plate, keeping the distance between the polymer support and the spray nozzle at 4-6 cm, keeping the temperature of the polymer support at 80-100 ℃ through a heating device, evaporating the solvent after completing one-time deposition, then performing next-time deposition, completing one-time deposition after introducing 30-60 s of argon gas each time, and drying at 80-200 ℃ after 3-5-time deposition to obtain the separation membrane.
2. The method for preparing the ultra-thin silicon-based alcohol-water separation membrane with the thickness of less than 50nm according to claim 1, wherein the method comprises the following steps: the temperature of the water bath is 50-60 ℃, and the stirring is continuously carried out for 1-3 hours at the temperature of the water bath.
3. The method for preparing the ultrathin silicon-based alcohol-water separation membrane with the thickness of less than 50nm according to claim 1, wherein the ultrasonic frequency used by the ultrasonic atomizer is 1.5-3 MHz.
4. The method for preparing the ultra-thin silicon-based alcohol-water separation membrane with the thickness of less than 50nm according to claim 1, wherein the method comprises the following steps: the drying time is 15-20 min.
5. The method for preparing the ultra-thin silicon-based alcohol-water separation membrane with the thickness of less than 50nm according to claim 1, wherein the method comprises the following steps: the polymer support is a composite film of Polyamide (PA) and Polystyrene (PS), the aperture of the film is 1-2 nm, and the molecular weight cut-off is 600-1000.
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| CN115025635B (en) * | 2022-06-30 | 2023-08-18 | 常州大学 | Preparation method of bridge organic silicon/GO composite nanofiltration membrane |
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