CN111603950B - Solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane and preparation method thereof - Google Patents
Solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane. The preparation method comprises the following steps: (1) dissolving the bridged polysilsesquioxane precursor in ethanol, and sequentially adding hydrochloric acid, ammonia water and hydrochloric acid to perform acid-base-acid alternative catalytic reaction to prepare the bridged polysilsesquioxane polymer sol. (2) Coating SiO on ceramic support2‑ZrO2And preparing the solvent-resistant nano transition layer by using the sol. (3) And coating the prepared bridged polysilsesquioxane polymeric sol on the surface of the transition layer to be used as a separation layer, and performing heat treatment to prepare the solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane with the nano transition layer structure. The bridged polysilsesquioxane composite membrane provided by the invention has good solvent resistance and separability, and has wide application prospect in the field of nanofiltration recovery of organic solvents.
Description
Technical Field
The invention belongs to the field of nanofiltration membrane preparation, and particularly relates to a solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane and a preparation method thereof.
Background
The usage amount of organic solvents in industrial production is increased year by year, and at present, more than 3000 organic solvents are widely applied to the fields of petroleum and petrochemical industry, medicine, printing, textile and the like. Common organic solvents include alcohols, esters, ketones, amides, aromatic hydrocarbons, halogenated hydrocarbons and the like, most of which have certain toxicity, and how to safely and effectively recycle the organic solvents is particularly important.
Nanofiltration of organic solvents is a pressure-driven membrane separation technique, which is widely applied to processes such as product purification and solvent recovery in non-aqueous media. Compared with the traditional separation technologies such as distillation and the like, the nanofiltration of the organic solvent has the advantages of energy conservation, environmental protection, small occupied area, mild operation conditions and the like. The core of the nanofiltration recovery of the organic solvent is the development of a solvent-resistant nanofiltration membrane.
In the prior art, organic polymer membrane materials are widely applied in the field of organic solvent separation and recovery due to good membrane forming property and lower preparation cost. Chinese patent CN 105435655A proposes a solvent-resistant separation membrane material and a preparation method thereof, wherein a composite material obtained by entanglement of two different high molecular polymers at molecular chain level is prepared into a membrane, and the solvent resistance of the membrane material is changed by post-treatment, so that the membrane material is applied to alkane, ester and alcohol solvents. Chinese patent CN 106215726A proposes a silicon-containing solvent-resistant nanofiltration membrane and a preparation method thereof, wherein silicon or a silicon compound is introduced into a functional layer of a polymer nanofiltration membrane, so that the permeation flux and the rejection rate of an organic solvent are improved, but the membrane still has swelling to a certain degree. In the separation and recovery of organic solvent, the polymer high molecular membrane is easy to swell and dissolve, which destroys the structural form of the original membrane, resulting in the reduction of membrane separation performance and the reduction of service life. Although the membrane structure and performance can be adjusted by various modification methods, the characteristic of similar solubility of the polymer material and an organic solvent, especially a strong polar solvent such as Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and the like cannot be eliminated, so that the wide application of the polymer material as a nanofiltration membrane in polar organic solvent recovery is greatly limited.
Disclosure of Invention
The invention provides a solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane and a preparation method thereof, aiming at solving the problem that a polymer polymeric membrane is easy to swell and dissolve in the prior art2O3Preparation of SiO with good solvent resistance in advance for ceramic support2-ZrO2And (3) selecting a bridged polysilsesquioxane organic-inorganic material with excellent solvent resistance from the nano transition layer, and preparing the solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane with excellent separation performance by acid-base-acid alternative catalysis and low-temperature heat treatment processes.
In order to solve the problems, the technical scheme adopted by the invention is as follows: a preparation method of a solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane comprises the following steps
a coating of SiO on a ceramic support2-ZrO2Sol is carried out to generate a solvent-resistant nano transition layer;
b, coating bridged polysilsesquioxane polymer sol on the nano transition layer to serve as a separation layer, and performing heat treatment to obtain a solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane with a nano transition layer structure;
the bridged polysilsesquioxane polymeric sol is prepared by the following method:
dissolving a bridged polysilsesquioxane precursor in ethanol, and sequentially adding hydrochloric acid I, ammonia water and hydrochloric acid II to perform acid-base-acid alternative catalytic reaction to obtain the bridged polysilsesquioxane polymer sol.
Further, the bridged polysilsesquioxane precursor is one or more of bis (triethoxysilyl) octane, bis (trimethoxysilylhexyl) hexane and bis (triethoxysilyl) ethane.
Further, in the acid-base-acid alternative catalytic reaction process, the concentrations of the hydrochloric acid I and the hydrochloric acid II are both 1-10 wt% by mass, and the concentration of the ammonia water is 1-10 wt% by mass.
Further, in the acid-base-acid alternative catalytic reaction process, in the first step of acid catalysis, the mol ratio of the bridged polysilsesquioxane precursor to water to hydrochloric acid is 1: 30-240: 0.05-0.30, the reaction time is 20-60 min, and the reaction temperature is 25-60 ℃.
Further, in the acid-base-acid alternative catalytic reaction process, the molar ratio of ammonia in the second-step base catalysis to hydrochloric acid used in the first-step acid catalysis is 2-10: 1, adjusting the pH value of the alkali-catalyzed sol to 10-12, reacting for 10-90 min, and controlling the reaction temperature to 25-60 ℃.
Further, in the acid-base-acid alternative catalytic reaction process, the molar ratio of the ammonia water in the second step of acid catalysis to the ammonia water in the second step of base catalysis is 1-2: 1, adjusting the pH value of the final sol to 3-4, reacting for 20-60 min, and controlling the reaction temperature to 25-60 ℃.
Further, the membrane support comprises tubular or sheet alpha-Al2O3The support body has a porosity of 40-50% and a pore size of 100-200 nm.
Further, preparing SiO in the solvent-resistant nano transition layer sol2-ZrO2The raw material of the solvent-resistant nano transition layer sol adopts one or more of zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide and zirconium tert-butoxide, and SiO in the solvent-resistant nano transition layer sol2-ZrO2The concentration is 0.5-5 wt%, and the particle size is 50-100 nm.
Further, the solvent-resistant nano transition layer is formed by coating alpha-Al on the surface of the nano transition layer2O3Fast wiping SiO on support2-ZrO2Sol and then SiO coating2-ZrO2alpha-Al of sol2O3And calcining the support body for 10-20 min at the calcining temperature of 600-800 ℃ in air atmosphere, and repeatedly coating the support body until a solvent-resistant nano transition layer with the aperture of 2-3 nm is generated.
Further, the separating layer is formed by quickly wiping bridging polysilsesquioxane polymer sol on the nanometer transition layer, then carrying out heat treatment in a drying box, and carrying out heat treatment for 30min at the temperature of 80-200 ℃ in a nitrogen atmosphere. The process is repeated until a separation layer with a pore diameter of 0.8-1.5 nm is formed.
The invention also provides a solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane prepared according to the preparation method.
The preparation method comprises the following steps:
(1) dissolving a bridged polysilsesquioxane precursor with the mass fraction of 5 wt% in ethanol, and adding hydrochloric acid and water to perform hydrolysis reaction, wherein the molar ratio of the bridged polysilsesquioxane precursor to the water to the hydrochloric acid is 1: 30-240: 0.1, and the reaction time is 20-60 min. Then, adding ammonia water for carrying out alkali catalytic reaction, wherein the molar ratio of the ammonia water to hydrochloric acid is 2-10: 1, the reaction time is 10-90 min, and the reaction temperature is 25-60 ℃. And finally adding hydrochloric acid to stop the alkali catalytic reaction and continuing to react for 20-60 min, wherein the molar ratio of the hydrochloric acid to the ammonia water is 1-2: 1, the whole reaction temperature is 25-60 ℃, and finally the bridged polysilsesquioxane polymeric sol is prepared.
(2) And sequentially coating the ceramic support body and generating a particle layer and a nanometer transition layer. alpha-Al with particle layers of 1um and 0.2um2O3The nano transition layer is 0.5-5 wt% of SiO2-ZrO2And (3) sol. And sequentially wiping the particle layer and the nanometer transition layer on the ceramic support body, and then calcining for 10-20 min at the temperature of 600-800 ℃ in air atmosphere. The process is repeated until a solvent-resistant nano transition layer with the aperture of 2-3 nm is generated. Wherein the ceramic support comprises a tubular ceramic support and a sheet ceramic support. GranuleThe sub-layer and the nanometer transition layer can reduce the pore diameter of the surface of the membrane layer, increase the thermal stability of the membrane and prevent the occurrence of the pore permeation phenomenon.
(3) And (3) coating the bridged polysilsesquioxane polymer sol prepared in the step (1) on the surface of the nanometer transition layer in the step (2), carrying out heat treatment in a drying oven, carrying out heat treatment for 30min at the temperature of 80-200 ℃ in a nitrogen atmosphere, repeatedly wiping the separation layer until the aperture of the separation layer is 0.8-1.5 nm, and preparing the solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane.
Has the advantages that:
(1) the acid-alkali-acid alternative catalysis is adopted to control the hydrolysis polymerization reaction process of the sol, after small-particle sol is generated through acid-catalyzed hydrolysis polymerization in the first step, the sol network is extended and densified again through alkali-catalyzed secondary growth, the particle size is increased, the particle growth process is stopped through final acid catalysis, the particle size is regulated and controlled, the sol stability is maintained, the pore diameter and the pore diameter distribution of the membrane are effectively regulated, the bridged polysilsesquioxane membrane with the average pore diameter of 1nm and narrow pore diameter distribution is successfully prepared, and the bridged polysilsesquioxane membrane can be widely applied to the nanofiltration process.
(2) The overall solvent resistance of the composite membrane is not only dependent on the separating layer, but is also closely related to the transition layer and the support layer. Compared with polysulfone or polyether sulfone transition layer of organic polymer membrane, inorganic SiO2-ZrO2The preparation of the nanometer transition layer greatly improves the integral solvent resistance of the composite film.
(3) The solvent-resistant nanofiltration composite membrane with high separation performance is prepared by selecting polysilsesquioxane materials bridged by covalent bonds such as bis (triethoxysilyl) octane, bis (trimethoxysilylhexane) hexane and the like, combining the excellent performances of organic and inorganic components of the materials, and having good hydrothermal stability and excellent chemical stability.
Drawings
FIG. 1: bis (triethoxysilyl) octane bridged polysilsesquioxane membranes for DMF/reactive Black 5 isolation 50h stability test.
FIG. 2: bis (trimethoxysilyl) hexane bridged polysilsesquioxane membranes to isolate DMF/reactive Black 5 for 50h stability test.
FIG. 3: bis (trimethoxysilyl) ethane-bridged polysilsesquioxane membranes for DMF/reactive Black 5 isolation 50h stability test.
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) Dissolving bis (triethoxysilyl) octane into ethanol to form a solution with the mass fraction of 5 wt%, adding deionized water and 2 wt% hydrochloric acid, and continuously stirring for 30min in a water bath at 50 ℃, wherein the molar ratio of the bis (triethoxysilyl) octane to the water to the hydrochloric acid is 1:60: 0.1.
(2) Ammonia water according to molar ratio: adding ammonia water with the mass fraction of 5 wt% into hydrochloric acid with the proportion of 10:1, and continuously stirring for 30min at 50 ℃ in a water bath to perform alkali catalytic reaction so as to increase the particle size of the sol.
(3) According to molar ratio, hydrochloric acid: and (3) adding 2 wt% hydrochloric acid into ammonia water in a ratio of 1.5:1 to stop the base catalytic reaction in the step (2), and generating stable bridged polysilsesquioxane sol in an acidic environment.
(4) Coating two alpha-Al with different grain sizes on a sheet type ceramic support body2O3(1 μm, 0.2 μm) were fired 3 times as a particle layer. Each time baking in a 600 ℃ tube furnace for 15min to generate a particle layer, and then coating SiO on the surface of the particle layer2-ZrO2The sol is moved into a 600 ℃ tube furnace to be roasted for 8 times, and a nano transition layer is generated after 20min each time; and (3) coating the bridged polysilsesquioxane sol prepared in the step (3) on the surface of the nano transition layer, carrying out heat treatment in a drying oven, carrying out heat treatment for 30min at the temperature of 120 ℃ in a nitrogen atmosphere, and repeating the process for 3 times to obtain the bridged polysilsesquioxane film.
(5) The prepared bridged polysilsesquioxane composite membrane was tested for solvent recovery from DMF/active black 5 at 25 ℃ and 1.5MPa, and the experimental results are shown in Table 1.
Example 2
(1) Dissolving bis (trimethoxysilyl) hexane in ethanol to form a solution with the mass fraction of 5 wt%, adding deionized water and 2 wt% hydrochloric acid, and continuously stirring for 30min in a water bath at 40 ℃, wherein the molar ratio of the bis (trimethoxysilyl) hexane to the water to the hydrochloric acid is 1:30: 0.1.
(2) Ammonia water according to molar ratio: adding 5 wt% ammonia water into hydrochloric acid at a ratio of 5:1, and continuously stirring for 30min in water bath at 50 ℃ to perform alkali catalysis reaction.
(3) According to molar ratio, hydrochloric acid: and (3) adding 2 wt% hydrochloric acid into ammonia water in a ratio of 1.5:1 to stop the base catalytic reaction in the step (2), and generating stable bridged polysilsesquioxane sol in an acidic environment.
(4) Coating two alpha-Al with different grain diameters on a tubular ceramic support body2O3(1 μm, 0.2 μm) were fired 2 times as a particle layer. Each time baking in a tube furnace at 550 ℃ for 15min to generate a particle layer, and then coating SiO on the surface of the particle layer2-ZrO2The sol is moved into a 700 ℃ tube furnace to be roasted for 6 times, and a nano transition layer is generated after 20min each time; and (3) coating the surface of the nano transition layer with the bridged polysilsesquioxane sol prepared in the step (3), carrying out heat treatment in a drying oven, carrying out heat treatment for 30min at the temperature of 150 ℃ in a nitrogen atmosphere, and repeating the process for 2 times to obtain the bridged polysilsesquioxane film.
(5) The prepared bridged polysilsesquioxane composite membrane was tested for solvent recovery from DMF/active black 5 at 25 ℃ and 1.5MPa, and the experimental results are shown in Table 1.
Example 3
(1) Dissolving bis (triethoxysilyl) ethane in ethanol to form a solution with the mass fraction of 5 wt%, adding deionized water and 2 wt% hydrochloric acid, and continuously stirring for 30min in a water bath at 50 ℃, wherein the molar ratio of the bis (triethoxysilyl) ethane to the water to the hydrochloric acid is 1:120: 0.1.
(2) Ammonia water according to molar ratio: adding ammonia water with the mass fraction of 5 wt% into hydrochloric acid with the proportion of 2:1, and continuously stirring for 60min at the temperature of 50 ℃ in a water bath to perform alkali catalytic reaction.
(3) According to molar ratio, hydrochloric acid: and (3) adding 2 wt% hydrochloric acid into the ammonia water in a ratio of 2:1 to stop the base catalytic reaction in the step (2), and generating the stable bridged polysilsesquioxane sol in an acidic environment.
(4) Coating two kinds of ceramic support bodies on a sheet type ceramic support bodyalpha-Al with same grain size2O3(1 μm, 0.2 μm) were fired 2 times as a particle layer. Each layer was fired in a 550 ℃ tube furnace for 20min to produce a particle layer, and then the surface of the particle layer was coated with SiO2-ZrO2Transferring the sol into a 800 ℃ tube furnace to be roasted for 5 times, and generating a nano transition layer each time for 20 min; and (3) coating the surface of the nano transition layer with the bridged polysilsesquioxane sol prepared in the step (3), carrying out heat treatment in a drying oven, carrying out heat treatment for 30min at 200 ℃ in a nitrogen atmosphere, and repeating the process for 2 times to obtain the bridged polysilsesquioxane film.
(5) The prepared bridged polysilsesquioxane composite membrane was tested for solvent recovery from DMF/active black 5 at 25 ℃ and 1.5MPa, and the experimental results are shown in Table 1.
As can be seen from the table, the retention rate of all the prepared bridged polysilsesquioxane membranes to the active black 5 is more than 97 percent, and the DMF flux is more than 20L/(m)2H). And in a long-time solvent-resistant stability test of 50h, the bridged polysilsesquioxane membrane is found to be stable in various performances of DMF, and the flux and the rejection rate are not greatly changed, so that the bridged polysilsesquioxane membrane is proved to be an excellent polar solvent-resistant membrane material.
TABLE 1
The above description is only a preferred embodiment of the present invention, and the present invention is not limited to the content of the embodiment. It will be apparent to those skilled in the art that various changes and modifications can be made within the technical scope of the present invention, and any changes and modifications made are within the protective scope of the present invention.
Claims (6)
1. The preparation method of the solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane is characterized by comprising the following steps
a coating of SiO on a ceramic support2-ZrO2Sol is carried out to generate a solvent-resistant nano transition layer;
b, coating bridged polysilsesquioxane polymer sol on the nano transition layer to serve as a separation layer, and performing heat treatment to obtain a solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane with a nano transition layer structure;
the bridged polysilsesquioxane polymeric sol is prepared by the following method:
dissolving a bridged polysilsesquioxane precursor in ethanol, and sequentially adding hydrochloric acid I, ammonia water and hydrochloric acid II to perform acid-base-acid alternative catalytic reaction to prepare the bridged polysilsesquioxane polymer sol; in the acid-alkali-acid alternative catalytic reaction process, the concentrations of the hydrochloric acid I and the hydrochloric acid II are both 1-10 wt% by mass, and the concentration of the ammonia water is 1-10 wt% by mass;
in the acid-base-acid alternative catalytic reaction process, in the first step of acid catalysis, the mol ratio of the bridged polysilsesquioxane precursor to water to hydrochloric acid is 1: 30-240: 0.05-0.30, the reaction time is 20-60 min, and the reaction temperature is 25-60 ℃; the molar ratio of ammonia in the second-step base catalysis to hydrochloric acid used in the first-step acid catalysis is 2-10: 1, adjusting the pH value of the alkali-catalyzed sol to 10-12, reacting for 10-90 min, and controlling the reaction temperature to 25-60 ℃; the molar ratio of the hydrochloric acid in the acid catalysis in the third step to the ammonia water in the alkali catalysis in the second step is 1-2: 1, adjusting the pH value of the final sol to 3-4, reacting for 20-60 min, and controlling the reaction temperature to 25-60 ℃.
2. The method for preparing the solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane of claim 1, wherein: the bridged polysilsesquioxane precursor is one or more of bis (triethoxysilyl) octane, bis (trimethoxysilyl) hexane and bis (triethoxysilyl) ethane.
3. The method for preparing the solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane of claim 1, wherein: the ceramic support comprises tubular or sheet alpha-Al2O3The support body has a porosity of 40-50% and a pore size of 100-200 nm.
4. A fabric as claimed in claim 1The preparation method of the solvent-bridged polysilsesquioxane nanofiltration composite membrane is characterized by comprising the following steps of: preparing SiO in the solvent-resistant nano transition layer sol2-ZrO2The raw material of the solvent-resistant nano transition layer sol adopts one or more of zirconium ethoxide, zirconium n-propoxide, zirconium isopropoxide, zirconium n-butoxide and zirconium tert-butoxide, and SiO in the solvent-resistant nano transition layer sol2-ZrO2The concentration is 0.5-5 wt%, and the particle size is 50-100 nm.
5. The method for preparing the solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane of claim 1, wherein: the solvent-resistant nano transition layer is formed by coating alpha-Al on the surface of a substrate2O3Fast wiping SiO on support2-ZrO2Sol and then SiO coating2-ZrO2alpha-Al of sol2O3Calcining the support body for 10-20 min at the calcining temperature of 600-800 ℃ in air atmosphere, and repeatedly coating the support body until a solvent-resistant nano transition layer with the aperture of 2-3 nm is generated;
the separation layer is formed by quickly wiping bridging polysilsesquioxane polymer sol on the nanometer transition layer, then carrying out heat treatment in a drying box, carrying out heat treatment for 30min at the temperature of 80-200 ℃ in a nitrogen atmosphere, and repeatedly wiping until the separation layer with the aperture of 0.8-1.5 nm is generated.
6. A solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane prepared by the method of claim 1.
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