CN111744375B - Mixed matrix membrane with high-selectivity gas channel and preparation method thereof - Google Patents
Mixed matrix membrane with high-selectivity gas channel and preparation method thereof Download PDFInfo
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Abstract
The application discloses a mixed matrix membrane with a high-selectivity gas channel and a preparation method thereof, belonging to the technical field of membrane separation. The preparation process comprises the steps of firstly coating polydimethylsiloxane and polyvinyl alcohol on the surface of polysulfone to prepare a hydrophilic modified polysulfone membrane, then adopting a low-temperature solid-phase synthesis method to synthesize metal compound hydrophobic filler particles on the surface of the hydrophilic modified polysulfone membrane in situ by using metal salt and a ligand to obtain a hydrophobic HMP/MPSf membrane, finally coating hydrophilic polymer polyvinylamine on the surface of the hydrophobic HMP/MPSf membrane to perform interface self-assembly, and drying to obtain a mixed matrix membrane with a high-selectivity gas channel, wherein CO of the mixed matrix membrane is CO2The permeation rate of (A) is 1800-3400GPU and CO2Has a permeability coefficient of 490-995Barrer, CO2/N2The selectivity of (A) is preferably 65-70, and the method is particularly suitable for separating mixed gas containing carbon dioxide.
Description
Technical Field
The application discloses a mixed matrix membrane with a high-selectivity gas channel and a preparation method thereof, belonging to the technical field of membrane separation.
Background
The membrane separation technology has the advantages of high efficiency, greenness, energy conservation, easy processing and the like, and is considered to be a gas separation technology with great potential. Mixed Matrix Membranes (MMMs) are mainly composed of polymers and fillers, with the potential to obtain very high permeability and high selectivity. However, the presence of interfacial compatibility defects between the polymer matrix and the filler has a significant impact on the gas permeation selectivity properties of MMMs. To date, while some progress has been made, the drawbacks of MMMs have not been completely avoided.
The novel mixed matrix membrane for gas separation reported in the related art consists of a polymer matrix and an organic filler containing benzene rings, but there is also a problem of interfacial compatibility between the polymer matrix and the filler, and the resulting mixed matrix membrane such as CO2The permeability coefficient of (A) is only 2.69Barrer-397.07Barrer, CO2/N2The selectivity of (A) is only 26-39, and the permeability and the selectivity of the obtained gas separation membrane are low.
Disclosure of Invention
In order to solve the technical problems of low permeability and selectivity of the gas separation membrane, the application provides a mixed matrix membrane with a high-selectivity gas channel, and the gap size of the gas channel is adjusted by adjusting the electronegativity difference between a hydrophilic polymer and a hydrophobic filler to realize the efficient separation of the gas by the gap between the hydrophilic polymer and the hydrophobic filler in the mixed matrix membrane, so that the mixed matrix membrane has good permeability and selectivity and good application prospects.
In a second aspect, the present application provides a method for preparing the mixed matrix membrane with a high-selectivity gas channel, the method for preparing the mixed matrix membrane with the high-selectivity gas channel adopts a novel method for constructing a gas separation high-speed transfer channel by regulating and controlling the gap size of a polymer and a filler through interface self-assembly, and the method has the advantages of simple preparation process, convenient operation, mild preparation conditions and suitability for industrial production.
Technical principle of the present application
The defect gap size between the polymer matrix and the filler is used as a high-speed gas conveying channel, and then a strategy of forming a mixed matrix membrane by self-assembly of an interface between the hydrophilic polymer and the hydrophobic filler is provided, so that efficient separation of gas by the gap between the polymer and the filler in the mixed matrix membrane is realized. On the hydrophilic polysulfone support layer, the hydrophilic polymer tends to be bonded with the surface of the hydrophilic polysulfone support layer and away from the hydrophobic filler, resulting in the in-situ formation of a gap between the hydrophilic polymer and the hydrophobic filler, the formed gap penetrating the mixed matrix membrane, and the size of the gap being adjusted by adjusting the electronegativity difference between the hydrophilic polymer and the hydrophobic filler.
Technical scheme of the application
A mixed matrix membrane with high-selectivity gas channels is composed of a hydrophilic modified polysulfone membrane (hereinafter referred to as MPSf membrane), a hydrophilic polymer membrane (hereinafter referred to as PVAm membrane) and metal composite hydrophobic filler particles (hereinafter referred to as HMP), wherein the PVAm membrane is combined with the MPSf membrane through hydrogen bond action, the HMP is uniformly and vertically distributed on the MPSf membrane and mutually penetrates through the PVAm membrane, and the PVAm membrane and the HMP are mutually far away due to electronegativity difference to form gas channel gaps;
the gas channel gap is 0.73-1.25nm, preferably 0.73-0.78 nm; the thickness of the MPSf membrane is 50-100nm, the thickness of the HMP is 480-740nm, and the thickness of the PVAm membrane is 270-300nm, in the embodiment of the application, the thickness of the MPSf membrane is only 50nm for illustration, but the MPSf membrane with other thickness is not limited, and the specific thickness of the MPSf membrane is determined by the thickness of the selected polysulfone commercial ultrafiltration membrane.
The mixed matrix membrane with the high-selectivity gas channel is prepared by the method comprising the following steps of:
(1) coating polydimethylsiloxane (hereinafter abbreviated as PDMS) and polyvinyl alcohol (hereinafter abbreviated as PVA) on the surface of polysulfone (hereinafter abbreviated as PSf membrane) to prepare a hydrophilic modified polysulfone membrane (hereinafter abbreviated as MPSf membrane);
the structural formula of the PDMS is
Wherein n is 300-500;
the polymerization degree of PVA is 1700, and the alcoholysis degree is 87-89%;
the polysulfone is a commercial ultrafiltration membrane, and the average pore diameter is 20-50 nm;
(2) in-situ synthesizing metal compound hydrophobic filler particles (HMP for short) on the surface of the MPSf membrane obtained in the step (1) by using a low-temperature solid-phase synthesis method and a metal salt and a ligand to obtain a hydrophobic HMP/MPSf membrane;
the metal salt is anhydrous copper acetate;
the ligand is 4-fluorobenzoic acid, 4-chlorobenzoic acid, 4-bromobenzoic acid or 4-iodobenzoic acid, and is preferably 4-fluorobenzoic acid;
(3) coating hydrophilic polymer polyvinylamine (PVAm) on the surface of the hydrophobic HMP/MPSf membrane obtained in the step (2) for interface self-assembly to form a hydrophilic polymer membrane (PVAm membrane for short), and finally obtaining a mixed matrix membrane with a high-selectivity gas channel (PVAm-HMP/MPSf membrane for short);
the weight average molecular weight Mw of the hydrophilic polymer polyvinylamine is 10-50 ten thousand.
The step (1) is realized by the following operation steps:
firstly, preparing PDMS into a PDMS (polydimethylsiloxane) n-heptane solution with the concentration of 0.1wt% -1.0wt% by using n-heptane, then coating the n-heptane PDMS solution with the concentration of 0.1wt% -1.0wt% on the surface of the PSf film by using a scraper, wherein the coating thickness is 0.05 mu m-1.00 mu m, and then drying for 16-24h under the conditions of controlling the temperature to be 60 ℃ and 40% RH to obtain the PSf film coated with PDMS; then soaking the PSf film coated with PDMS in an aqueous solution of PVA with the concentration of 0.01-0.5 wt% for 1h, and then continuously drying for 4-12h under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain an MPSf film; the PDMS is used for making the surface of the polysulfone more uniform, and the PVA is used for carrying out hydrophilic modification on the polysulfone membrane; the step (2) is realized by the following operation steps:
firstly, uniformly coating a ligand-methanol solution with the concentration of 60mmol/L on the surface of an MPSf membrane by using a scraper, wherein the coating thickness is 20nm-80nm, then drying for 4-8h under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain the MPSf membrane coated with the ligand, then soaking the MPSf membrane coated with the ligand in a metal salt aqueous solution with the concentration of 0.25wt% for 0.5h-2h, and synthesizing metal composite hydrophobic filler particles (hereinafter referred to as HMP in situ on the surface of the MPSf membrane, in each embodiment of the application, the HMP of the metal composite hydrophobic filler particles is different according to the halogen contained in the ligand, such as 4-fluorobenzoic acid in embodiment 1 and embodiment 5-7, the HMP (F) is abbreviated as the metal composite hydrophobic filler particles, such as 4-chlorobenzoic acid in embodiment 2, the metal composite hydrophobic filler particles are abbreviated as HMP (Cl); if the ligand in example 3 is 4-bromobenzoic acid, the metal composite hydrophobic filler particles are abbreviated as HMP (Br); if the ligand in example 4 is 4-iodobenzoic acid, the hydrophobic filler particles of the metal composite are abbreviated as HMP (i)), and then the hydrophobic filler particles are dried for 24 hours at a controlled temperature of 30 ℃ and 40% RH to obtain a hydrophobic HMP/MPSf membrane (in each example of the present application, the name of the obtained hydrophobic HMP/MPSf membrane is different depending on the halogen contained in the ligand, and if the ligand in example 1 and examples 5 to 7 is 4-fluorobenzoic acid, the HMP (f)/MPSf membrane is obtained; if the ligand is 4-chlorobenzoic acid in example 2, an HMP (Cl)/MPSf membrane is obtained; if the ligand in example 3 is 4-bromobenzoic acid, an HMP (Br)/MPSf membrane is obtained; if the ligand in example 4 is 4-iodobenzoic acid, HMP (I)/MPSf membrane is obtained; the contact angle of the surface of the obtained hydrophobic HMP/MPSf membrane is 125-160 degrees, preferably 125-135 degrees;
the step (3) is realized by the following operation steps:
firstly, uniformly coating 0.1-3.0 wt% of PVAm aqueous solution on the surface of the hydrophobic HMP/MPSf membrane obtained in the step (2) by using a scraper, wherein the coating thickness is 0.05-2.00 μm, and then drying the membrane for 24h under the conditions of controlling the temperature to be 30 ℃ and 40% RH, so as to obtain a mixed matrix membrane with high-selectivity gas channels, namely a PVAm-HMP/MPSf membrane (in each embodiment of the application, the PVAm-HMP/MPSf membrane is different according to the difference of halogen contained in the ligand used in the step (2), such as 4-fluorobenzoic acid serving as the ligand in embodiment 1 and 5-7, PVAm-HMP (F)/MPSf membrane, such as 4-chlorobenzoic acid serving as the ligand in embodiment 2, such as PVAm-HMP (MPCl)/MPSf membrane, and 4-bromobenzoic acid serving as the ligand in embodiment 3, PVAm-HMP (Br)/MPSf membrane for short; if the ligand in the embodiment 4 is 4-iodobenzoic acid, PVAm-HMP (I)/MPSf membrane for short);
the coating or the soaking in any one of the steps (1), (2) and (3) is carried out at room temperature.
The mixed matrix membrane with high-selectivity gas channel is characterized in that the hydrophilic polymer contains hydrophilic CO2The groups, and the gap between the hydrophilic polymer and the hydrophobic filler can be controlled according to the ligand used in the preparation process, so that it can be used for the separation of mixed gas containing carbon dioxide, especially for CO2/N2Separation, can also be applied to CO2/H2Or CO2/CH4Separation of (4).
Advantageous technical effects of the present application
According to the mixed matrix membrane with the high-selectivity gas channel, in the preparation process, the gas channel with the proper size is adjusted by adjusting the electronegativity difference between the hydrophilic polymer and the metal composite hydrophobic filler particles, so that the influence of the defects between the polymer matrix and the filler in the related technology on the gas separation performance of MMMs is solved, and good CO is obtained2The mixed gas separation membrane has universality prospect.
Furthermore, according to the mixed matrix membrane with the high-selectivity gas channel, as the ligand adopted for preparing the metal composite hydrophobic filler particles contains halogen, the surface energy of the obtained metal composite hydrophobic filler particles is relatively low, the hydrophobic property is good, and the difference of electronegativity is easily formed between the metal composite hydrophobic filler particles and a hydrophilic polymer, so that the gas channel gap is adjusted, and good CO is obtained2The permeability and selectivity of the membrane.
Further, the mixed matrix membrane with a highly selective gas channel of the present application uses common high molecular polymers such as Polydimethylsiloxane (PDMS), polyvinyl alcohol (PVA), polyvinyl amine (PVAm), and the like. In particular, PVAm is a hydrophilic polymer with a high number of amino functions, which can react with CO2A reversible reaction occurs to increase the CO of the finally obtained mixed matrix membrane with high selectivity gas channel2Permeability andand (4) selectivity.
Further, a mixed matrix membrane with highly selective gas channels for the separation of carbon dioxide containing mixed gases, in particular for CO, is claimed2/N2When separated, its CO2The permeation rate of (A) is 1800-3400GPU, CO2Has a permeability coefficient of 490-995Barrer, CO2/N2Has selectivity of 3.2-70, and is preferably CO of mixed matrix membrane with high selectivity gas channel obtained under the condition of using 4-fluorobenzoic acid as ligand2Has a permeation rate of 1800-1900GPU, CO2Has a permeability coefficient of 490-520Barrer, CO2/N2The selectivity of (A) is 65-70.
Furthermore, according to the preparation method of the mixed matrix membrane with the high-selectivity gas channel, the metal compound hydrophobic filler particles are synthesized by using a low-temperature solid-phase synthesis method in the preparation process, so that the preparation method has the advantages of low reaction temperature, simple process, high selectivity, high yield, energy conservation and the like.
Further, according to the preparation method of the mixed matrix membrane with the high-selectivity gas channel, the preparation process basically adopts the operations of coating, soaking, drying at 30 ℃ and 40% RH and the like, so that the preparation method has the advantages of simple preparation process, mild preparation conditions, convenience in operation and the like, and is suitable for industrial mass production.
In summary, a mixed matrix membrane with highly selective gas channels of the present application has good CO2The method has the advantages of simple preparation process, convenient operation and suitability for industrial mass production, and is suitable for separation of mixed gas containing carbon dioxide.
Drawings
FIG. 1, wherein A is a surface SEM picture of the hydrophobic HMP (F)/MPSf membrane obtained in example 1, B is a cross-sectional SEM picture of the PVAm-HMP (F)/MPSf membrane obtained in example 1, and C is the EDX elemental analysis result of N element in the PVAm-HMP (F)/MPSf membrane obtained in example 1;
FIG. 2, wherein A is a surface SEM picture of the hydrophobic HMP (Cl)/MPSf membrane obtained in example 2, B is a cross-sectional SEM picture of the PVAm-HMP (Cl)/MPSf membrane obtained in example 2, and C is an EDX elemental analysis result of N element in the PVAm-HMP (Cl)/MPSf membrane obtained in example 2;
FIG. 3, wherein A is the surface SEM picture of the hydrophobic HMP (Br)/MPSf membrane obtained in example 3, B is the cross-sectional SEM picture of the PVAm-HMP (Br)/MPSf membrane obtained in example 3, and C is the EDX elemental analysis result of the N element in the PVAm-HMP (Br)/MPSf membrane obtained in example 3;
FIG. 4, wherein A is a surface SEM picture of the hydrophobic HMP (I)/MPSf membrane obtained in example 4, B is a cross-sectional SEM picture of the PVAm-HMP (I)/MPSf membrane obtained in example 4, and C is the EDX elemental analysis result of N element in the PVAm-HMP (I)/MPSf membrane obtained in example 4;
FIG. 5 is a graph showing gas permeation separation performance of the mixed matrix membranes having highly selective gas channels obtained in examples 1 to 4.
Detailed Description
The technical solution of the present application is further illustrated by the following specific examples in combination with the accompanying drawings, but the present application is not limited thereto.
The model and manufacturer information of the instrument used in the measurements in the examples of the present application are as follows:
scanning electron microscope (model Drop Shape Analyzer 100, produced by Bruker, Germany);
an electron spectrometer model EDAX APOLLO XL, manufactured by EDAX corporation, USA;
the permeation rate measuring instrument is a gas chromatograph with the model number of (HP7890, Porapak N) manufactured by Agilent company in America;
the gas channel gap determinator is a conventional positron annihilation lifetime spectrometer, LT9.0 software is used as a spectrum resolving program, the time resolution of the spectrometer is about 210ps, and a measurement system electronics plug-in is produced by standard NIM plug-in company of EG & G company in America; the measurement methods used in the examples of the present application are specifically as follows:
methods for measuring contact angles of hydrophobic membrane surfaces, see literature: ning, Yang, Xuemeing Jia, Dandan Wang, Chenjie Wei, Yang He, Li Chen, Yiping Zha.Silibinin as a natural antioxidant for modifying polysulfones membranes to coatings of fibrous-induced oxidative stress. journal of Membrane Science,2019, 574,86-99.
CO2See literature: yu, Z.Wang, Z.Wei, S.Yuan, J.ZHao, J.Wang, and S.Wang.novel derivative amino relating in film composite membranes prepared by interfacial polymerization for CO2Journal of Membrane Science,2010,362, 265-278; the instrument used for the measurement is a gas chromatograph, and the model number of the gas chromatograph is (HP7890, Porapak N) produced by Agilent company in America;
CO2see in particular references, the formula for calculating the permeability coefficient of (c): S.A.Stern.the "Barrer" fitness unit. journal of polymer science part B-polymer physics,1968,6, 1933-: the calculation formula is as follows:
wherein, PpermThe permeation flux of a gas is given in Barrer (1Barrer ═ 10)-10×cm3(STP)cm.sec-1.cm-2.cm.Hg-1) (ii) a l thickness of the film in cm; a is the effective test area of the sample to be tested, and the unit is cm2(ii) a Δ p and dV/dt represent the partial pressure drop and volumetric flow rate of gas through the membrane, in cmHg and cm, respectively3(ii)/s (standard case);
CO2/N2see the literature Koros W J, Ma Y H, Shimidzu.T. Terminologus for membranes and membrane processes (IUPAC Recommendations 1996) [ J]Pure appl. chem., 1996, 68 (7): 1479-1489), according to the IUPAC description of membranes and membrane separation processes, the two-component mixed gas separation factor is defined as the ratio of the gas composition on the permeate side to the gas composition in the retentate gas, i.e.:
the method for measuring the gas channel gap in the PVAm-HMP/MPSf membrane is positron interference (PALS) experiments, and is specifically shown in the literature: R.Xia, X.Cao, M.Gao, P.Zhang, M.Zeng, B.Wang, and L.Wei, Phys.chem.chem.Phys.,2017,19, 3616-containing 3626 and S.J.Tao, J.chem.Phys.,1972,56, 5499-containing 5510.
The specifications of the various raw materials used in the examples of the present application and the information of the manufacturers are as follows:
polysulfone is a commercial ultrafiltration membrane with an average pore diameter of 20nm-50nm, produced by membrane technologies, Inc., Jiuzhong Shandong;
polydimethylsiloxane (PDMS), available from Shanghai Aladdin Biotechnology Ltd;
polyvinyl alcohol (PVA), with a polymerization degree of 1700 and an alcoholysis degree of 87-89%, produced by Shanghai Allan Biotech Co., Ltd;
polyvinylamine having a weight average molecular weight Mw of 10 to 50 ten thousand, manufactured by DOW CORNING corporation, USA;
4-fluorobenzoic acid, 4-chlorobenzoic acid, 4-bromobenzoic acid and 4-iodobenzoic acid, produced by Shanghai' an naiji Co., Ltd;
anhydrous copper acetate, manufactured by Shanghai' an naiji Co., Ltd;
n-heptane, national pharmaceutical group chemical agents ltd.
Example 1
A mixed matrix membrane having a highly selective gas channel, prepared by a method comprising the steps of:
(1) coating Polydimethylsiloxane (PDMS) and polyvinyl alcohol (PVA) on the surface of polysulfone to prepare a hydrophilic modified polysulfone membrane, wherein the specific operation steps are as follows:
firstly, preparing PDMS into a PDMS n-heptane solution with the concentration of 0.4 wt% by using n-heptane, then coating the PDMS n-heptane solution with the concentration of 0.4 wt% on the surface of the PSf film by using a scraper, wherein the coating thickness is 0.08 mu m, and then drying for 18h under the conditions of controlling the temperature to be 60 ℃ and 40% RH to obtain the PSf film coated with PDMS; then soaking the PSf membrane coated with PDMS in an aqueous solution of PVA with the concentration of 0.25wt% for 1h, and then continuously drying for 8h under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain a hydrophilic modified polysulfone membrane, which is hereinafter referred to as MPSf membrane;
(2) in-situ synthesizing metal composite hydrophobic filler particles on the surface of the MPSf membrane obtained in the step (1) by using a low-temperature solid-phase synthesis method and a metal salt and a ligand, wherein the metal salt is anhydrous copper acetate, the ligand is 4-fluorobenzoic acid, and the hydrophobic HMP (F)/MPSf membrane is obtained, and the specific operation steps are as follows;
uniformly coating a ligand-methanol solution with the concentration of 60mmol/L on the surface of the MPSf membrane obtained in the step (1) by using a scraper, wherein the coating thickness is 60nm, drying for 4h under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain the MPSf membrane coated with the ligand, soaking the MPSf membrane coated with the ligand 4-fluorobenzoic acid in a copper acetate aqueous solution with the concentration of 0.25wt% for 2h, synthesizing metal compound hydrophobic filler particles (hereinafter referred to as HMP (F)) on the surface of the MPSf membrane in situ, and drying for 24h under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain a hydrophobic HMP (F)/MPSf membrane;
the contact angle of the surface of the hydrophobic HMP (F)/MPSf membrane obtained above was determined to be 125 ° -135 °;
scanning the surface of the obtained hydrophobic HMP (F)/MPSf membrane by using a scanning electron microscope, wherein the obtained SEM image is shown as A in figure 1, and the successful in-situ synthesis of metal composite hydrophobic filler particles, namely HMP (F), on the surface of the MPSf membrane can be seen from A in figure 1;
(3) coating polyvinyl amine (PVAm) on the surface of the hydrophobic HMP (F)/MPSf membrane obtained in the step (2) for interface self-assembly to form a hydrophilic polymer membrane (hereinafter referred to as PVAm membrane), and finally obtaining a mixed matrix membrane with a high-selectivity gas channel, which is referred to as PVAm-HMP (F)/MPSf membrane for short, wherein the specific operation steps are as follows:
uniformly coating the surface of the hydrophobic HMP (F)/MPSf membrane obtained in the step (2) with an aqueous solution of 0.3 wt% of PVAm by using a scraper, wherein the coating thickness is 0.3 mu m, and then drying for 24h under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain a mixed matrix membrane with a high-selectivity gas channel, namely a PVAm-HMP (F)/MPSf membrane;
the coating or the soaking in any one of the steps (1), (2) and (3) is carried out at room temperature.
Scanning the section of the obtained PVAm-HMP (F)/MPSf membrane by using a scanning electron microscope, wherein the obtained SEM image is shown as B in figure 1, B in figure 1 shows that HMP (F) is uniformly and vertically distributed on the MPSf membrane, the PVAm membrane is combined with the MPSf membrane through hydrogen bonding, the PVAm membrane and the HMP (F) mutually penetrate, the thickness of the MPSf membrane is 50nm, the thickness of the HMP (F) is about 740nm, and the thickness of the PVAm membrane is about 270 nm.
EDX elemental analysis of N element in the obtained PVAm-hmp (f)/MPSf film by using an electron spectrometer, the result is shown as C in fig. 1, it can be seen from C in fig. 1 that N element is mainly uniformly distributed in hmp (f) with a thickness of about 740nm, and since PVAm is a characterization of N element, that is, only PVAm film should normally contain N element, the uniform distribution of N element in hmp (f) film further proves interpenetration between PVAm film and hmp (f).
The gas channel gap of the PVAm-HMP (F)/MPSf membrane obtained in the way is detected to be 0.73-0.78 nm.
Example 2
A mixed matrix membrane having a highly selective gas channel, prepared by a method comprising the steps of:
(1) coating Polydimethylsiloxane (PDMS) and polyvinyl alcohol (PVA) on the surface of polysulfone to prepare a hydrophilic modified polysulfone membrane, which is the MPSf membrane, by the specific steps of the step (1) in the embodiment 1;
(2) in-situ synthesizing metal composite hydrophobic filler particles on the surface of the MPSf membrane obtained in the step (1) by using a metal salt and a ligand by adopting a low-temperature solid-phase synthesis method, wherein the metal salt is anhydrous copper acetate, the ligand is 4-chlorobenzoic acid, and the rest is the same as the step (2) of the example 1 to obtain a hydrophobic HMP (sodium chloride)/MPSf membrane;
the contact angle of the surface of the hydrophobic HMP (Cl)/MPSf membrane obtained above was determined to be 140-145 °;
scanning the surface of the obtained hydrophobic HMP (Cl)/MPSf membrane by using a scanning electron microscope, wherein the obtained SEM image is shown as A in figure 2, and the successful in-situ synthesis of metal compound hydrophobic filler particles, namely HMP (Cl), on the surface of the MPSf membrane can be seen from A in figure 2;
(3) and (3) coating hydrophilic polymer polyvinylamine (PVAm) on the surface of the hydrophobic HMP (Cl)/MPSf membrane obtained in the step (2) for interface self-assembly to form a hydrophilic polymer membrane (hereinafter referred to as PVAm membrane), and performing the specific operation steps in the step (3) of the embodiment 1 to finally obtain the mixed matrix membrane with the high-selectivity gas channel, which is referred to as PVAm-HMP (Cl)/MPSf membrane.
Scanning the section of the obtained PVAm-HMP (Cl)/MPSf membrane by using a scanning electron microscope, wherein the obtained SEM image is shown as B in figure 2, B in figure 2 shows that HMP (Cl) is uniformly and vertically distributed on the MPSf membrane, the PVAm membrane is combined with the MPSf membrane through hydrogen bonding, the PVAm membrane and the HMP (Cl) mutually penetrate, the thickness of the MPSf membrane is 50nm, the thickness of the HMP (Cl) is about 640nm, and the thickness of the PVAm membrane is about 300 nm.
The results of EDX elemental analysis of N element in the obtained PVAm-hmp (cl)/MPSf membrane by using an electron spectrometer are shown as C in fig. 2, and it can be seen from C in fig. 2 that N element is mainly uniformly distributed in hmp (cl) with a thickness of about 640nm, and the uniform distribution of N element in hmp (cl) further proves interpenetration between the PVAm membrane and hmp (cl) because PVAm is a characterization of N element, i.e. only PVAm membrane should normally contain N element.
The gas channel gap of the PVAm-HMP (Cl)/MPSf membrane obtained in the above way is detected to be 0.83-0.86 nm.
Example 3
A mixed matrix membrane having a highly selective gas channel, prepared by a method comprising the steps of:
(1) coating Polydimethylsiloxane (PDMS) and polyvinyl alcohol (PVA) on the surface of polysulfone to prepare a hydrophilic modified polysulfone membrane, which is the MPSf membrane, by the specific steps of the step (1) in the embodiment 1;
(2) in-situ synthesizing metal composite hydrophobic filler particles on the surface of the MPSf membrane obtained in the step (1) by using a low-temperature solid-phase synthesis method and a metal salt and a ligand, wherein the metal salt is anhydrous copper acetate, the ligand is 4-bromobenzoic acid, and the rest is the same as the step (2) of the example 1 to obtain a hydrophobic HMP (Br)/MPSf membrane;
the contact angle of the surface of the obtained hydrophobic HMP (Br)/MPSf membrane is determined to be 143-147 degrees;
scanning the surface of the obtained hydrophobic HMP (Br)/MPSf membrane by using a scanning electron microscope, wherein the obtained SEM image is shown as A in figure 3, and the successful in-situ synthesis of metal composite hydrophobic filler particles, namely HMP (Br), on the surface of the MPSf membrane can be seen from A in figure 3;
(3) and (3) coating hydrophilic polymer polyvinylamine (PVAm) on the surface of the hydrophobic HMP (Br)/MPSf membrane obtained in the step (2) for interface self-assembly to form a hydrophilic polymer membrane (hereinafter referred to as PVAm membrane), and performing the specific operation steps in the step (3) of the embodiment 1 to finally obtain a mixed matrix membrane with a high-selectivity gas channel, which is referred to as PVAm-HMP (Br)/MPSf membrane.
Scanning the section of the obtained PVAm-HMP (Br)/MPSf membrane by using a scanning electron microscope, wherein the obtained SEM image is shown as B in figure 3, B in figure 3 shows that HMP (Br) is uniformly and vertically distributed on the MPSf membrane, the PVAm membrane is combined with the MPSf membrane through hydrogen bonding, the PVAm membrane and the HMP (Br) mutually penetrate, the thickness of the MPSf membrane is 50nm, the thickness of the HMP (Br) is about 650nm, and the thickness of the PVAm membrane is about 270 nm.
EDX elemental analysis of N element in the obtained PVAm-hmp (br)/MPSf membrane by using an electron spectrometer, the result is shown as C in fig. 3, it can be seen from C in fig. 3 that N element is mainly uniformly distributed in hmp (br) with a thickness of about 650nm, and since PVAm is a characterization of N element, that is, only PVAm membrane should normally contain N element, the uniform distribution of N element in hmp (br) further proves interpenetration between PVAm membrane and hmp (br).
The gas channel gap of the PVAm-HMP (Br)/MPSf membrane obtained by the method is detected to be 0.90-0.94 nm.
Example 4
A mixed matrix membrane having a highly selective gas channel, prepared by a method comprising the steps of:
(1) coating Polydimethylsiloxane (PDMS) and polyvinyl alcohol (PVA) on the surface of polysulfone to prepare a hydrophilic modified polysulfone membrane, which is the MPSf membrane, by the specific steps of the step (1) in the embodiment 1;
(2) in-situ synthesizing metal composite hydrophobic filler particles on the surface of the MPSf membrane obtained in the step (1) by using a metal salt and a ligand by adopting a low-temperature solid-phase synthesis method, wherein the metal salt is anhydrous copper acetate, the ligand is 4-iodobenzoic acid, and the steps are the same as the step (2) of the example 1 to obtain a hydrophobic HMP (I)/MPSf membrane;
the contact angle of the surface of the hydrophobic HMP (I)/MPSf membrane obtained above was determined to be 151-160 °;
scanning the surface of the obtained hydrophobic HMP (I)/MPSf membrane by using a scanning electron microscope, wherein the obtained SEM image is shown as A in fig. 4, and the successful in-situ synthesis of metal composite hydrophobic filler particles, namely HMP (I), on the surface of the MPSf membrane can be seen from A in fig. 4;
(3) and (3) coating hydrophilic polymer polyvinylamine (PVAm) on the surface of the hydrophobic HMP (I)/MPSf membrane obtained in the step (2) for interface self-assembly to form a hydrophilic polymer membrane (hereinafter referred to as PVAm membrane), and performing the specific operation steps in the step (3) of the embodiment 1 to finally obtain the mixed matrix membrane with the high-selectivity gas channel, which is referred to as PVAm-HMP (I)/MPSf membrane.
Scanning the section of the obtained PVAm-HMP (I)/MPSf membrane by using a scanning electron microscope, wherein the obtained SEM image is shown as B in figure 4, B in figure 4 shows that HMP (I) is uniformly and vertically distributed on the MPSf membrane, the PVAm membrane is combined with the MPSf membrane through hydrogen bonding, the PVAm membrane and the HMP (I) mutually penetrate, the thickness of the MPSf membrane is 50nm, the thickness of the HMP (I) is about 480nm, and the thickness of the PVAm membrane is about 290 nm.
The results of EDX elemental analysis of N element in the obtained PVAm-hmp (i)/MPSf film by using an electron spectrometer are shown in fig. 4C, and it can be seen from C in fig. 4 that N element is mainly uniformly distributed in hmp (i) with a thickness of about 480nm, and since PVAm is a characterization of N element, that is, only PVAm film should normally contain N element, the uniform distribution of N element in hmp (i) further proves interpenetration between PVAm film and hmp (i).
The gas channel gap of the PVAm-HMP (I)/MPSf membrane obtained in the above way is detected to be 1.15-1.23 nm.
It can be seen from the above examples 1-4 that, the HMP is uniformly and vertically distributed on the MPSf membrane, the PVAm membrane is bonded to the MPSf membrane through hydrogen bonding, the PVAm membrane and the HMP penetrate each other, and the PVAm membrane and the HMP are far away from each other due to electronegativity difference, so as to form a gas channel gap. The thickness of the MPSf film is 50-100nm, the thickness of the HMP film is about 480-740nm, and the thickness of the PVAm film is about 270-300 nm. The gas channel gap formed is 0.73-1.23nm, preferably 0.73-0.78 nm.
At 25 deg.C and 1.1-3.0bar pressure, pure CO is used2/N2CO gas treatment of the PVAm-HMP/MPSf membranes obtained in example 1, example 2, example 3, and example 42Permeation rate, CO2Permeability coefficient, CO2/N2The selectivity of (b) and the like, and the results of the measurements are shown in the following table:
as can be seen from the above table, the PVAm-HMP/MPSf membranes of the present application have CO with increasing gas channel gap2Gradually increase the permeation rate of, but CO2/N2The selectivity of (a) is gradually reduced, and various factors such as gas permeation flux, gas selectivity and the like are comprehensively considered, so that the PVAm-HMP (F)/MPSf membrane pair CO finally obtained by taking 4-fluorobenzoic acid as a ligand in example 1 is preferably adopted in the application2/N2Performing gas separation with gas channel gap of 0.73-0.78nm, and obtaining CO of PVAm-HMP (F)/MPSf membrane2Has a permeation rate of 1800-1900GPU, CO2Has a permeability coefficient of 490-520Barrer, CO2/N2The selectivity of (A) is 65-70.
CO of PVAm-HMP/MPSf membranes obtained according to the above-mentioned examples 1, 2, 3 and 42Permeation rate, CO2/N2The resulting gas permeation separation performance graph is shown in FIG. 5, and it can be further seen from FIG. 5 that the PVAm-HMP (F)/MPSf membrane obtained by using 4-fluorobenzoic acid as ligand in example 1 is used for CO2/N2The effect of gas separation is better. The reason for this is analyzed to be that a mixed matrix membrane having a highly selective gas channel is formed due to the difference in electronegativity of the ligands of the metal composite hydrophobic filler particles formed during the preparation of the mixed matrix membrane having a highly selective gas channel of the present application, i.e., the size of the gas channel gap of the gas separation membrane is adjusted by adjusting the difference in electronegativity between the hydrophilic polymer and the metal composite hydrophobic filler particles.
Example 5
A mixed matrix membrane having a highly selective gas channel, prepared by a method comprising the steps of:
(1) coating Polydimethylsiloxane (PDMS) and polyvinyl alcohol (PVA) on the surface of polysulfone to prepare a hydrophilic modified polysulfone membrane, wherein the specific operation steps are as follows:
firstly, preparing PDMS into a PDMS n-heptane solution with the concentration of 0.1wt% by using n-heptane, then coating the PDMS n-heptane solution with the concentration of 0.1wt% on the surface of the PSf film by using a scraper, wherein the coating thickness is 0.05 mu m, and then drying for 16h under the conditions of controlling the temperature to be 60 ℃ and 40% RH to obtain the PSf film coated with PDMS; then soaking the PSf membrane coated with PDMS in an aqueous solution of PVA with the concentration of 0.01wt% for 1h, and then continuously drying for 4h under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain a hydrophilic modified polysulfone membrane, namely an MPSf membrane;
(2) the method comprises the following steps of adopting a low-temperature solid-phase synthesis method, utilizing metal salt and a ligand to synthesize metal compound hydrophobic filler particles on the surface of the MPSf membrane in situ, wherein the metal salt is anhydrous copper acetate, and the ligand is 4-fluorobenzoic acid to obtain the hydrophobic HMP (F)/MPSf membrane, and the specific operation steps are as follows;
uniformly coating a ligand-methanol solution with the concentration of 60mmol/L on the surface of the MPSf membrane obtained in the step (1) by using a scraper, wherein the coating thickness is 20nm, drying for 6h under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain the MPSf membrane coated with the ligand, soaking the MPSf membrane coated with the ligand in a copper acetate aqueous solution with the concentration of 0.25wt% for 0.5h, synthesizing metal compound hydrophobic filler particles (hereinafter referred to as HMP (F)) on the surface of the MPSf membrane in situ, and drying for 24h under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain a hydrophobic HMP (F)/MPSf membrane;
(3) coating hydrophilic polymer polyvinylamine (PVAm) on the surface of a hydrophobic HMP (F)/MPSf membrane for interface self-assembly to form a hydrophilic polymer membrane (hereinafter referred to as PVAm membrane), and finally obtaining a mixed matrix membrane with a high-selectivity gas channel, which is referred to as PVAm-HMP (F)/MPSf membrane for short, wherein the specific operation steps are as follows:
uniformly coating the surface of the hydrophobic HMP (F)/MPSf membrane obtained in the step (2) with an aqueous solution of 0.1wt% of PVAm by using a scraper, wherein the coating thickness is 0.05 mu m, and then drying for 24 hours under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain the PVAm-HMP (F)/MPSf membrane;
the coating or the soaking in any one of the steps (1), (2) and (3) is carried out at room temperature.
Example 6
A mixed matrix membrane having a highly selective gas channel, prepared by a method comprising the steps of:
(1) coating Polydimethylsiloxane (PDMS) and polyvinyl alcohol (PVA) on the surface of polysulfone to prepare a hydrophilic modified polysulfone membrane, wherein the specific operation steps are as follows:
firstly, preparing PDMS into a PDMS (polydimethylsiloxane) n-heptane solution with the concentration of 0.8 wt% by using n-heptane, then coating the PDMS n-heptane solution with the concentration of 0.8 wt% on the surface of the PSf film by using a scraper, wherein the coating thickness is 0.6 mu m, and then drying for 20h under the conditions of controlling the temperature to be 60 ℃ and 40% RH to obtain the PSf film coated with PDMS; then soaking the PSf membrane coated with PDMS in an aqueous solution of PVA with the concentration of 0.15 wt% for 1h, and then continuously drying for 8h under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain a hydrophilic modified polysulfone membrane, namely an MPSf membrane;
(2) the method comprises the following steps of adopting a low-temperature solid-phase synthesis method, utilizing metal salt and a ligand to synthesize metal compound hydrophobic filler particles on the surface of the MPSf membrane in situ, wherein the metal salt is anhydrous copper acetate, and the ligand is 4-fluorobenzoic acid to obtain the hydrophobic HMP (F)/MPSf membrane, and the specific operation steps are as follows;
uniformly coating a ligand-methanol solution with the concentration of 60mmol/L on the surface of the MPSf membrane obtained in the step (1) by using a scraper, wherein the coating thickness is 40nm, drying for 6h under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain the MPSf membrane coated with the ligand, soaking the MPSf membrane coated with the ligand 4-fluorobenzoic acid in a copper acetate aqueous solution with the concentration of 0.25wt% for 1h, synthesizing metal compound hydrophobic filler particles (hereinafter referred to as HMP (F)) on the surface of the MPSf membrane in situ, and drying for 24h under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain a hydrophobic HMP (F)/MPSf membrane;
(3) coating hydrophilic polymer polyvinylamine (PVAm) on the surface of a hydrophobic HMP (F)/MPSf membrane for interface self-assembly to form a hydrophilic polymer membrane (hereinafter referred to as PVAm membrane), and finally obtaining a mixed matrix membrane with a high-selectivity gas channel, which is referred to as PVAm-HMP (F)/MPSf membrane for short, wherein the specific operation steps are as follows:
uniformly coating the surface of the hydrophobic HMP (F)/MPSf membrane obtained in the step (2) with an aqueous solution of 1.5 wt% of PVAm by using a scraper, wherein the coating thickness is 1.0 mu m, and then drying for 24 hours under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain the PVAm-HMP (F)/MPSf membrane;
the coating or the soaking in any one of the steps (1), (2) and (3) is carried out at room temperature.
Example 7
A mixed matrix membrane having a highly selective gas channel, prepared by a method comprising the steps of:
(1) coating Polydimethylsiloxane (PDMS) and polyvinyl alcohol (PVA) on the surface of polysulfone to prepare a hydrophilic modified polysulfone membrane, wherein the specific operation steps are as follows:
firstly, preparing PDMS into a PDMS (polydimethylsiloxane) n-heptane solution with the concentration of 1.0wt% by using n-heptane, then coating the PDMS n-heptane solution with the concentration of 1.0wt% on the surface of the PSf film by using a scraper, wherein the coating thickness is 1 mu m, and then drying for 24h under the conditions of controlling the temperature to be 60 ℃ and 40% RH to obtain the PSf film coated with PDMS; then soaking the PSf membrane coated with PDMS in an aqueous solution of PVA with the concentration of 0.50 wt% for 1h, and then continuously drying for 12h under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain a hydrophilic modified polysulfone membrane, namely an MPSf membrane;
(2) the method comprises the following steps of adopting a low-temperature solid-phase synthesis method, utilizing metal salt and a ligand to synthesize metal compound hydrophobic filler particles on the surface of the MPSf membrane in situ, wherein the metal salt is anhydrous copper acetate, and the ligand is 4-fluorobenzoic acid to obtain the hydrophobic HMP (F)/MPSf membrane, and the specific operation steps are as follows;
uniformly coating a ligand-methanol solution with the concentration of 60mmol/L on the surface of the MPSf membrane obtained in the step (1) by using a scraper, coating the MPSf membrane with the thickness of 80nm, drying for 8 hours under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain the MPSf membrane coated with the ligand, soaking the MPSf membrane coated with the ligand 4-fluorobenzoic acid in a copper acetate aqueous solution with the concentration of 0.25wt% for 2 hours, synthesizing metal compound hydrophobic filler particles (hereinafter referred to as HMP (F)) on the surface of the MPSf membrane in situ, and drying for 24 hours under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain a hydrophobic HMP (F)/MPSf membrane;
(3) coating hydrophilic polymer polyvinylamine (PVAm) on the surface of a hydrophobic HMP (F)/MPSf membrane for interface self-assembly to form a hydrophilic polymer membrane (hereinafter referred to as PVAm membrane), and finally obtaining a mixed matrix membrane with a high-selectivity gas channel, which is referred to as PVAm-HMP (F)/MPSf membrane for short, and the specific steps are as follows:
uniformly coating the surface of the hydrophobic HMP (F)/MPSf membrane obtained in the step (2) with an aqueous solution with the concentration of 3 wt% by using a scraper, wherein the coating thickness is 2.0 mu m, and then drying for 24h under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain the PVAm-HMP (F)/MPSf membrane;
the coating or the soaking in any one of the steps (1), (2) and (3) is carried out at room temperature.
The foregoing detailed description is only for the purpose of explaining the technical solutions of the present application in detail, and the present application is not limited to the foregoing embodiments, and it should be understood by those skilled in the art that all modifications, substitutions and alterations based on the above principles and spirit should be within the scope of the present application.
Claims (7)
1. A preparation method of a mixed matrix membrane with a high-selectivity gas channel is characterized in that the mixed matrix membrane with the high-selectivity gas channel consists of a hydrophilic modified polysulfone membrane, a hydrophilic polymer membrane and metal composite hydrophobic filler particles, wherein the hydrophilic polymer membrane is combined with the hydrophilic modified polysulfone membrane through hydrogen bond action, the metal composite hydrophobic filler particles are uniformly and vertically distributed on the hydrophilic modified polysulfone membrane and mutually penetrate through the hydrophilic polymer membrane, and the hydrophilic polymer membrane and the metal composite hydrophobic filler particles are mutually far away due to electronegativity difference to form a gas channel gap;
the hydrophilic modified polysulfone membrane is prepared by coating polydimethylsiloxane and polyvinyl alcohol on the surface of polysulfone;
the polysulfone is a commercial ultrafiltration membrane, the average pore diameter is 20-50nm, and the structural formula of the polydimethylsiloxane is shown in the specification
Wherein n is 300-500;
the polyvinyl alcohol has a polymerization degree =1700 and an alcoholysis degree = 87-89%;
the metal compound hydrophobic filler particles are synthesized in situ on the surface of the hydrophilic modified polysulfone membrane by using a metal salt and a ligand by adopting a low-temperature solid-phase synthesis method;
the hydrophilic polymer membrane is formed by coating polyvinylamine on the surface of metal composite hydrophobic filler particles for interfacial self-assembly;
the weight average molecular weight Mw of the polyvinylamine is 10-50 ten thousand;
the preparation method of the mixed matrix membrane with the high-selectivity gas channel comprises the following steps:
(1) coating polydimethylsiloxane and polyvinyl alcohol on the surface of polysulfone to prepare a hydrophilic modified polysulfone membrane;
(2) and (2) adopting a low-temperature solid-phase synthesis method, and utilizing metal salt and a ligand to synthesize metal compound hydrophobic filler particles in situ on the surface of the hydrophilic modified polysulfone membrane obtained in the step (1) to obtain the hydrophobic HMP/MPSf membrane, wherein the method specifically comprises the following steps:
firstly, respectively and uniformly coating a ligand-methanol solution with the concentration of 60mmol/L on the surface of a hydrophilic modified polysulfone membrane by using a scraper, wherein the coating thickness is 20nm-80nm, then drying for 4-8h under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain the hydrophilic modified polysulfone membrane coated with the ligand, then soaking the hydrophilic modified polysulfone membrane coated with the ligand in a metal salt aqueous solution with the concentration of 0.25wt% for 0.5-2 h, in-situ synthesizing metal compound hydrophobic filler particles on the surface of the hydrophilic modified polysulfone membrane, and then drying for 24h under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain a hydrophobic HMP/MPSf membrane;
(3) and (3) coating polyvinylamine on the surface of the hydrophobic HMP/MPSf membrane obtained in the step (2) for interfacial self-assembly to form a hydrophilic polymer membrane, and finally obtaining the mixed matrix membrane with high-selectivity gas channels.
2. The method for preparing a mixed matrix membrane having a high selectivity gas channel as claimed in claim 1, wherein the metal salt is anhydrous cupric acetate; the ligand is 4-fluorobenzoic acid, 4-chlorobenzoic acid, 4-bromobenzoic acid or 4-iodobenzoic acid.
3. The method for preparing a mixed matrix membrane with a highly selective gas channel as claimed in claim 2, wherein the gas channel gap of the mixed matrix membrane with a highly selective gas channel is 0.73 to 1.23 nm.
4. The method of preparing a mixed matrix membrane having a high-selectivity gas channel according to claim 3, wherein the gas channel gap of the mixed matrix membrane having a high-selectivity gas channel is 0.73 to 0.78 nm.
5. The method as claimed in claim 4, wherein the thickness of the hydrophilic modified polysulfone membrane is 50-100nm, the thickness of the metal composite hydrophobic filler particles is 480-740nm, and the thickness of the hydrophilic polymer membrane is 270-300 nm.
6. The method for preparing a mixed matrix membrane having a highly selective gas channel according to claim 1, wherein the step (1) is carried out by the following steps:
firstly, preparing polydimethylsiloxane into a polydimethylsiloxane-n-heptane solution with the concentration of 0.1-1.0 wt% by using n-heptane, coating the n-heptane polydimethylsiloxane solution with the concentration of 0.1-1.0 wt% on the surface of polysulfone by using a scraper, wherein the coating thickness is 0.05 mu m-1.00 mu m, and then drying for 16-24 hours under the conditions of controlling the temperature to be 60 ℃ and 40% RH to obtain the polysulfone coated with the polydimethylsiloxane; and then soaking the polysulfone coated with the polydimethylsiloxane in an aqueous solution of polyvinyl alcohol with the concentration of 0.01-0.5 wt% for 1h, and then continuously drying for 4-12h under the conditions of controlling the temperature to be 30 ℃ and 40% RH to obtain the hydrophilic modified polysulfone membrane.
7. The method for preparing a mixed matrix membrane having a highly selective gas channel as claimed in claim 1, wherein said step (3) is carried out by the following steps:
firstly, uniformly coating a 0.1-3.0 wt% aqueous solution of polyvinylamine on the surface of a hydrophobic HMP/MPSf membrane by using a scraper, wherein the coating thickness is 0.05-2.00 mu m, and then drying for 24h under the conditions of controlling the temperature to be 30 ℃ and 40% RH, thus obtaining the mixed matrix membrane with the high-selectivity gas channel.
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