CN113731184A - Helium separation membrane and preparation method and application thereof - Google Patents
Helium separation membrane and preparation method and application thereof Download PDFInfo
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- CN113731184A CN113731184A CN202010476482.3A CN202010476482A CN113731184A CN 113731184 A CN113731184 A CN 113731184A CN 202010476482 A CN202010476482 A CN 202010476482A CN 113731184 A CN113731184 A CN 113731184A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B23/00—Noble gases; Compounds thereof
- C01B23/001—Purification or separation processes of noble gases
- C01B23/0036—Physical processing only
- C01B23/0042—Physical processing only by making use of membranes
- C01B23/0047—Physical processing only by making use of membranes characterised by the membrane
Abstract
The invention provides a helium separation membrane, which comprises a base membrane and a functional layer positioned on the surface of the base membrane, wherein the functional layer comprises MOFs, dopamine or a reaction product of the MOFs and the dopamine; wherein, the selectivity of the helium separation membrane to helium/methane is 50-400, and the selectivity to helium/nitrogen is 60-300. The invention also provides a preparation method of the helium separation membrane, which comprises the following steps: (1) preparing a first mixture comprising a metal salt, an organic ligand, a solvent, and a base film; (2) heating the first mixture to react to prepare the MOFs separation membrane; (3) and immersing the MOFs separation membrane into a solution containing dopamine salt for reaction to prepare the helium gas separation membrane. The helium separation membrane has ultrahigh selectivity and higher permeation rate when used for separating helium, and the helium obtained by separation has high purity.
Description
Technical Field
The invention relates to a high-performance helium separation membrane, a preparation method and application thereof, and a membrane component containing the separation membrane and application thereof, and belongs to the field of gas separation.
Background
Helium is a rare strategic resource essential for national defense and military industry, semiconductor manufacturing, medical health and other high-tech industry development, and helium proposed from helium-rich natural gas is the only source of industrial helium so far. He is mainly distributed in a mantle, rock, air and natural gas, but the concentration of the He in the air is only 5ppm, so that the aim of resource utilization is difficult to achieve. Therefore, the extraction of He from natural gas is the only way for resource utilization of He at present. There is an imbalance in the distribution of He resource, the united states is the world where He is the most abundant, accounting for about 34% of the world's reserves, and our country has He only accounting for 0.1% of the world's He reserves, with He concentration also being substantially less than 0.2%. With the rapid increase of the demand of China for He resources, the development of an advanced natural gas helium stripping technology applied to a helium production process is urgently needed.
At present, the natural gas helium stripping technology mainly comprises a cryogenic process, a Pressure Swing Adsorption (PSA) process, an absorption process and a Membrane permeation separation process (Journal of Membrane Science,2016,520: 221-. The cryogenic process is the main method for extracting helium from natural gas, and has the basic principle that different components in natural gas have different boiling points, He is difficult to liquefy under low temperature, CH4, N2 and other alkanes can be liquefied, and He is separated out through low temperature rectification. Although the technology can extract high-purity He from natural gas, the operation flexibility is low, the equipment investment is large, the operation cost is high, and because the He concentration in the natural gas in China is low, the cost for extracting the He from the natural gas by a cryogenic method is high, and the large-scale construction of a natural gas helium extraction device in China is restricted. Adsorption Processes (PSA) separate the components of natural gas from He by their difference in their adsorption capacity on the surface of an adsorbent. Limited by the adsorption capacity of the adsorbent, and is generally suitable for a crude He refining process with an impurity content of less than 10%. In recent years, with the development of separation membrane technology, the membrane separation technology with the advantages of high separation efficiency, low operation energy consumption, large operation flexibility and the like is gradually applied to the experimental research process of extracting helium from natural gas, and shows great application potential. The organic polymer membrane has the advantages of corrosion resistance, easy processing and forming, high gas selectivity and the like, and is the most common and effective method in the field of gas separation. Because the existing helium separation membrane has the defects of poor selectivity, low separation efficiency and the like, the existing helium separation membrane is not used alone to realize the separation of helium, methane, nitrogen and the like, the industrial application needs to combine with pressure swing adsorption, cryogenic methods and the like to realize high-efficiency helium extraction, and the methods have high energy consumption and cannot economically and effectively realize the helium extraction from natural gas. Therefore, it is necessary to develop a helium separation membrane with high selectivity and high separation efficiency to realize low energy consumption and high efficiency of helium separation and concentration. Polyimide (PI) is a class of high performance polymer materials containing imine heterocycles. The catalyst has good thermal stability, chemical stability, excellent mechanical property and higher free volume, so that the catalyst has good gas selectivity and good permeability, and is expected to be widely applied to the field of gas separation. The metal organic framework material is a novel porous crystal material, has rich compositions, diversified pore channel structures and the characteristic of selective adsorption on specific gas, is expected to realize high-efficiency separation on the molecular scale, and provides wide space for the optimal selection of membrane materials. According to the invention, a layer of uniform metal organic framework material is constructed on the surface of the polyimide film, and then the metal organic framework material is anchored on the surface of the polyimide film by utilizing the universal adhesion effect of dopamine, so that the efficient separation of helium, nitrogen and methane can be better realized.
Disclosure of Invention
The invention aims to provide a high-performance helium separation membrane and a preparation method and application thereof, aiming at the technical problems of low separation efficiency, poor selectivity and the like of a helium separation membrane in the field of natural gas helium separation in the prior art. The helium separation membrane has ultrahigh selectivity and higher permeation rate when used for separating helium, and the helium obtained by separation has high purity.
According to one aspect of the present invention, there is provided a helium separation membrane comprising a base membrane and a functional layer on a surface of the base membrane, the functional layer comprising MOFs, dopamine or a cross-linked product of MOFs and dopamine; wherein, the selectivity of the helium separation membrane to helium/methane is 50-500, preferably 100-500, more preferably 200-500, and the selectivity to helium/nitrogen is 60-300, preferably 100-250, more preferably 150-250.
According to a preferred embodiment of the present invention, the base film comprises a polyimide film, preferably an aromatic polyimide film.
According to a preferred embodiment of the present invention, the MOFs are metal-containing organic framework materials.
In some embodiments, the MOFs are prepared by reacting a metal salt, an organic ligand, and a solvent.
According to a preferred embodiment of the invention, the metal salt comprises zirconium tetrachloride.
According to a preferred embodiment of the invention, the organic ligand comprises terephthalic acid.
According to a preferred embodiment of the present invention, the solvent comprises at least one of N, N-dimethylformamide, acetic acid, ethanol and water, preferably N, N-dimethylformamide and acetic acid.
According to a preferred embodiment of the invention, the molar ratio of N, N-dimethylformamide to acetic acid is (1-10): (1-100).
In some embodiments, the molar ratio of the metal salt, organic ligand, and solvent is (1-10): (1-10): (1-1000), preferably (1-5): (1-5): (300-600).
According to the separation membrane disclosed by the invention, dopamine is wrapped on the surfaces of MOFs particles through chemical crosslinking, so that a compact functional layer can be formed on the surface of a base membrane.
According to another aspect of the present invention, there is provided a method for preparing a helium separation membrane, comprising the steps of:
(1) providing a first mixture comprising a metal salt, an organic ligand, a solvent, and a base membrane;
(2) heating the first mixture to react to prepare the MOFs separation membrane;
(3) and (3) contacting the MOFs separation membrane with a solution containing dopamine salt to react to prepare the helium separation membrane.
According to some embodiments of the invention, step (1) comprises:
(1A) preparing a mixed solution comprising a metal salt, an organic ligand and a solvent;
(1B) and (2) adding the base film into the mixed solution obtained in the step (1A) to obtain a first mixture.
According to a preferred embodiment of the invention, the metal salt comprises zirconium tetrachloride.
According to a preferred embodiment of the invention, the organic ligand comprises terephthalic acid.
According to a preferred embodiment of the present invention, the solvent comprises one or more of N, N-dimethylformamide, acetic acid, ethanol and water, preferably N, N-dimethylformamide and acetic acid.
According to a preferred embodiment of the invention, the molar ratio of N, N-dimethylformamide to acetic acid is (1-10): (1-100).
According to a preferred embodiment of the present invention, the base film comprises a polyimide film, preferably an aromatic polyimide film.
According to a preferred embodiment of the present invention, the molar ratio of the metal salt, the organic ligand and the solvent is (1-10): (1-10): (1-1000), preferably (1-5): (1-5): (300-600).
According to some embodiments of the present invention, in step (1A), the metal salt, the organic ligand, and the solvent are mixed and sufficiently stirred to obtain a mixed solution.
According to a preferred embodiment of the present invention, in step (1B), the base film may be pretreated before being added to the solution obtained in step (1A). The pre-processing may include: washing the surface of the base film by sequentially adopting water and an organic solvent, and drying; the organic solvent is preferably ethanol, methanol or acetone; preferably, the base film is washed 2 times by water, 2 times by an organic solvent, and dried.
According to a preferred embodiment of the present invention, the ratio of the surface area of the base film to the volume of the mixed solution is (0.1 to 500) m2/L, preferably (0.5-200) m2L, more preferably (1-100) m2/L。
According to a preferred embodiment of the present invention, the step (2) comprises:
and heating the first mixture to react the organic ligand and the metal salt to generate the MOFs material on the surface of the base film.
According to a preferred embodiment of the present invention, in step (2), the reaction temperature is 50-300 deg.C, preferably 80-200 deg.C, more preferably 100-150 deg.C.
According to a preferred embodiment of the present invention, in step (2), the reaction pressure is from 0.01 to 0.5MPa (gauge), preferably from 0.05 to 0.1MPa (gauge).
According to a preferred embodiment of the present invention, in step (2), the reaction time is from 1 to 100h, preferably from 10 to 72h, more preferably from 24 to 48 h.
According to a preferred embodiment of the present invention, the step (2) may be performed under an inert gas atmosphere, preferably an inert gas is nitrogen.
According to some embodiments of the invention, in the step (3), the MOFs separation membrane is immersed in a solution containing dopamine salt for reaction, and the dopamine is coated on the MOFs surface through chemical crosslinking, so as to form a compact functional layer on the surface of the base membrane.
According to a preferred embodiment of the invention, the concentration of the dopamine hydrochloride in the dopamine salt-containing solution is 0.5 to 5g/L, preferably 1.5 to 2 g/L.
According to a preferred embodiment of the invention, the solution containing dopamine salt is a dopamine hydrochloride solution.
According to a preferred embodiment of the invention, the pH of the dopamine salt-containing solution is 7.0 to 9.5, preferably 7.5 to 9.0, more preferably 8.0 to 8.5.
According to a preferred embodiment of the invention, the ratio of the surface area of the basement membrane to the volume of the solution containing dopamine salt is (0.1-500) m2/L, preferably (0.5-200) m2L, more preferably (1-100) m2/L。
According to some embodiments of the invention, the method further comprises:
and (3) after the reaction in the step (3) is finished, taking out the separation membrane (or discharging the solution in the reaction system), and cleaning the separation membrane by using an organic solvent and/or water.
According to another aspect of the present invention, there is provided a helium separation membrane prepared according to the method of the above aspect of the present invention, wherein the helium separation membrane has a selectivity to helium/methane of 50-500, preferably 100-500, more preferably 200-500, and a selectivity to helium/nitrogen of 60-300, preferably 100-250, more preferably 150-250.
According to another aspect of the present invention there is provided a membrane assembly produced from a helium separation membrane according to the first aspect of the present invention or a helium separation membrane produced according to the method of the second aspect of the present invention or a helium separation membrane according to the third aspect of the present invention.
According to another aspect of the present invention there is provided the use of a helium separation membrane according to the first aspect of the present invention or a helium separation membrane prepared according to the method of the second aspect of the present invention or a helium separation membrane according to the third aspect of the present invention or a membrane module according to the fourth aspect of the present invention for the separation of helium, particularly in the separation of helium in natural gas.
According to a preferred embodiment of the invention, the main constituents of natural gas are nitrogen, helium and methane.
In some embodiments, the natural gas has a volume fraction of helium in the range of 1 to 60%, a volume fraction of methane in the range of 40 to 99%, and a volume fraction of nitrogen in the range of 0 to 30%. The helium separation membrane of the invention has a selectivity to helium/methane of 50-500, preferably 100-500, more preferably 200-500, and a selectivity to helium/nitrogen of 60-300, preferably 100-250, more preferably 150-250. The volume fraction of helium after separation is 80-99.9%.
Compared with the prior art, the invention has the following advantages:
(1) the preparation process is simple and convenient, easy to operate and low in cost;
(1) compared with the method for constructing the metal-containing organic framework membrane by an external current method, the method constructs a layer of uniform, compact and stable metal organic framework material on the surface of the base membrane by a hydrothermal method and the universal adhesion effect of dopamine, and the service life of the helium separation membrane is greatly prolonged due to the left and right universal adhesion effect of the dopamine.
(2) The helium separation membrane prepared by the invention has ultrahigh selectivity on helium, methane and nitrogen, and has higher permeation rate.
Drawings
FIG. 1 shows an SEM image of a MOFs separation membrane prepared in example 1 of the present invention;
FIG. 2 shows an SEM image of a helium separation membrane prepared in example 1 of the present invention;
FIG. 3 shows an SEM image of a helium separation membrane prepared in example 10 of the present invention;
FIG. 4 shows an SEM image of a polyimide film of comparative example 1;
FIG. 5 is a schematic view showing a process for separating helium by the helium separation membrane according to the present invention.
Detailed Description
The present invention will be further illustrated by the following examples, but is not limited to these examples.
The polyimide-based membranes used in the following examples were all polyimide-based hollow fiber membranes available from Prisen, USA, with a wall thickness of 50 μm and an outer diameter of 300 μm.
In the following examples, helium-rich natural gas was simulated by using a mixed gas of helium, nitrogen and methane, and the helium stripping process of the helium-rich natural gas was simulated by performing a gas separation performance test on the separation membrane.
(1) And (3) packaging the helium separation membrane prepared in the embodiment by using polyurethane glue to prepare a membrane component.
(2) When a helium separation membrane performance test is performed, a schematic diagram of a separation process is shown in fig. 5, raw material gas (simulated helium-rich natural gas) enters from one side of a membrane component, helium in the natural gas is concentrated by vacuumizing at a permeation side, then permeation gas is introduced into a gas chromatograph to detect the content of helium, nitrogen and methane, and the gas permeation rate and the separation selectivity of helium, nitrogen and methane are calculated through the following formulas.
Permeation rate:
selectivity coefficient:
j is the permeation rate of gas through the helium separation membrane, GPU;
p is the permeability coefficient, Barrer;
l is the separation layer (membrane) thickness, cm;
Qiis the flow rate of the intake air, cm3/min；
A is the test area, cm2；
Delta P is the pressure difference between the inside and the outside of the helium separation membrane, cmHg;
n is the number of the hollow fiber membranes;
d is the membrane outer diameter, cm;
l is the effective length of the membrane, cm;
i and j are different gases respectively;
alpha is the selectivity coefficient.
Example 1
(1) Adding zirconium tetrachloride powder and terephthalic acid powder into a beaker containing glacial acetic acid and N, N-dimethylformamide, and fully dissolving to obtain a mixed solution, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the glacial acetic acid to the N, N-dimethylformamide is 1:1:50: 450.
(2) After fully dissolving, pouring the mixed solution (1L) into a stainless steel reaction kettle with a tetrafluoroethylene lining, and adding the mixture with the specific surface area of 0.5m2Putting the polyimide basal membrane into an oven, and reacting for 36 hours at 120 ℃; and after the reaction is finished, taking out the polyimide film and washing the polyimide film by using deionized water after the reaction kettle is cooled to obtain the MOFs separation film. FIG. 1 is an SEM image of a MOFs separation membrane.
(3) And (3) putting the MOFs separation membrane obtained in the step (2) into 1L of Tris-HCl solution with the pH value of 8.5, adding 2g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 2g/L), reacting for 2h at 25 ℃, taking out and washing with deionized water to obtain the compact and stable helium separation membrane capable of being used for helium separation. FIG. 2 is an SEM image of a helium separation membrane.
(4) And (3) preparing a membrane component by using the helium separation membrane obtained in the step (3), and performing a gas separation performance test on a mixed gas with the helium volume fraction of 5%, the nitrogen volume fraction of 15% and the methane volume fraction of 80% by using the membrane component, wherein the results are shown in table 1.
Example 2
A film module was produced using the helium separation film produced in example 1, and a gas separation performance test was carried out using the film module on a mixed gas having a helium volume fraction of 15%, a nitrogen volume fraction of 25%, and a methane volume fraction of 60%, with a test pressure of 0.5MPa, with the results shown in table 1.
Example 3
The helium separation membrane prepared in example 1 was used to prepare a membrane module, and a gas separation performance test was performed using the membrane module on a mixed gas containing 30% by volume of helium, 45% by volume of nitrogen, and 25% by volume of methane at a test pressure of 0.5MPa, with the results shown in table 1.
Example 4
(1) Adding zirconium tetrachloride powder and terephthalic acid powder into a beaker containing glacial acetic acid and N, N-dimethylformamide, and fully dissolving to obtain a mixed solution, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the glacial acetic acid to the N, N-dimethylformamide is 1:1:150: 350.
(2) After fully dissolving, pouring the mixed solution (1L) into a stainless steel reaction kettle with a tetrafluoroethylene lining, and adding the mixture with the specific surface area of 0.5m2Putting the polyimide basal membrane into an oven, and reacting for 36 hours at 120 ℃; and after the reaction is finished, taking out the polyimide film and washing the polyimide film by using deionized water after the reaction kettle is cooled to obtain the MOFs separation film.
(3) And (3) putting the MOFs separation membrane obtained in the step (2) into 1L of Tris-HCl solution with the pH value of 8.5, adding 2g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 2g/L), reacting for 2h at 25 ℃, taking out and washing with deionized water to obtain the compact and stable helium separation membrane capable of being used for helium separation.
(4) And (3) preparing a membrane component by using the helium separation membrane obtained in the step (3), and performing a gas separation performance test on a mixed gas with the helium volume fraction of 5%, the nitrogen volume fraction of 15% and the methane volume fraction of 80% by using the membrane component, wherein the results are shown in table 1.
Example 5
(1) Adding zirconium tetrachloride powder and terephthalic acid powder into a beaker containing glacial acetic acid and N, N-dimethylformamide, and fully dissolving to obtain a mixed solution, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the glacial acetic acid to the N, N-dimethylformamide is 1:1:250: 250.
(2) After fully dissolving, pouring the mixed solution (1L) into a stainless steel reaction kettle with a tetrafluoroethylene lining, and adding the mixture with the specific surface area of 0.5m2Putting the polyimide basal membrane into an oven, and reacting for 36 hours at 120 ℃; and after the reaction is finished, taking out the polyimide film and washing the polyimide film by using deionized water after the reaction kettle is cooled to obtain the MOFs separation film.
(3) And (3) putting the MOFs separation membrane obtained in the step (2) into 1L of Tris-HCl solution with the pH value of 8.5, adding 2g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 2g/L), reacting for 2h at 25 ℃, taking out and washing with deionized water to obtain the compact and stable helium separation membrane capable of being used for helium separation.
(4) And (3) preparing a membrane component by using the helium separation membrane obtained in the step (3), and performing a gas separation performance test on a mixed gas with the helium volume fraction of 5%, the nitrogen volume fraction of 15% and the methane volume fraction of 80% by using the membrane component, wherein the results are shown in table 1.
Example 6
(1) Adding zirconium tetrachloride powder and terephthalic acid powder into a beaker containing glacial acetic acid and N, N-dimethylformamide, and fully dissolving to obtain a mixed solution, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the glacial acetic acid to the N, N-dimethylformamide is 1:1:350: 150.
(2) After fully dissolving, pouring the mixed solution (1L) into a stainless steel reaction kettle with a tetrafluoroethylene lining, and adding the mixture with the specific surface area of 0.5m2Putting the polyimide basal membrane into an oven, and reacting for 36 hours at 120 ℃; and after the reaction is finished, taking out the polyimide film and washing the polyimide film by using deionized water after the reaction kettle is cooled to obtain the MOFs separation film.
(3) And (3) putting the MOFs separation membrane obtained in the step (2) into 1L of Tris-HCl solution with the pH value of 8.5, adding 2g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 2g/L), reacting for 2h at 25 ℃, taking out and washing with deionized water to obtain the compact and stable helium separation membrane capable of being used for helium separation.
(4) And (3) preparing a membrane component by using the helium separation membrane obtained in the step (3), and performing a gas separation performance test on a mixed gas with the helium volume fraction of 5%, the nitrogen volume fraction of 15% and the methane volume fraction of 80% by using the membrane component, wherein the results are shown in table 1.
Example 7
(1) Adding zirconium tetrachloride powder and terephthalic acid powder into a beaker containing glacial acetic acid and N, N-dimethylformamide, and fully dissolving to obtain a mixed solution, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the glacial acetic acid to the N, N-dimethylformamide is 1:1:450: 50.
(2) After fully dissolving, pouring the mixed solution (1L) into a stainless steel reaction kettle with a tetrafluoroethylene lining, and adding the mixture with the specific surface area of 0.5m2Putting the polyimide basal membrane into an oven at 120 DEG CReacting for 36 h; and after the reaction is finished, taking out the polyimide film and washing the polyimide film by using deionized water after the reaction kettle is cooled to obtain the MOFs separation film.
(3) And (3) putting the MOFs separation membrane obtained in the step (2) into 1L of Tris-HCl solution with the pH value of 8.5, adding 2g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 2g/L), reacting for 2h at 25 ℃, taking out and washing with deionized water to obtain the compact and stable helium separation membrane capable of being used for helium separation.
(4) And (3) preparing a membrane component by using the helium separation membrane obtained in the step (3), and performing a gas separation performance test on a mixed gas with the helium volume fraction of 5%, the nitrogen volume fraction of 15% and the methane volume fraction of 80% by using the membrane component, wherein the results are shown in table 1.
Example 8
(1) Adding zirconium tetrachloride powder and terephthalic acid powder into a beaker containing glacial acetic acid and ethanol, and fully dissolving to obtain a mixed solution, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the glacial acetic acid to the ethanol is 1:1:50: 450.
(2) After fully dissolving, pouring the mixed solution (1L) into a stainless steel reaction kettle with a tetrafluoroethylene lining, and adding the mixture with the specific surface area of 0.5m2Putting the polyimide basal membrane into an oven, and reacting for 36 hours at 120 ℃; and after the reaction is finished, taking out the polyimide film and washing the polyimide film by using deionized water after the reaction kettle is cooled to obtain the MOFs separation film.
(3) And (3) putting the MOFs separation membrane obtained in the step (2) into 1L of Tris-HCl solution with the pH value of 8.5, adding 2g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 2g/L), reacting for 2h at 25 ℃, taking out and washing with deionized water to obtain the compact and stable helium separation membrane capable of being used for helium separation.
(4) And (3) preparing a membrane component by using the helium separation membrane obtained in the step (3), and performing a gas separation performance test on a mixed gas with the helium volume fraction of 5%, the nitrogen volume fraction of 15% and the methane volume fraction of 80% by using the membrane component, wherein the results are shown in table 1.
Example 9
(1) Adding zirconium tetrachloride powder and terephthalic acid powder into a beaker containing glacial acetic acid, and fully dissolving to obtain a mixed solution, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the glacial acetic acid is 1:1: 500.
(2) After fully dissolving, pouring the mixed solution (1L) into a stainless steel reaction kettle with a tetrafluoroethylene lining, and adding the mixture with the specific surface area of 0.5m2Putting the polyimide basal membrane into an oven, and reacting for 36 hours at 120 ℃; and after the reaction is finished, taking out the polyimide film and washing the polyimide film by using deionized water after the reaction kettle is cooled to obtain the MOFs separation film.
(3) And (3) putting the MOFs separation membrane obtained in the step (2) into 1L of Tris-HCl solution with the pH value of 8.5, adding 2g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 2g/L), reacting for 2h at 25 ℃, taking out and washing with deionized water to obtain the compact and stable helium separation membrane capable of being used for helium separation.
(4) And (3) preparing a membrane component by using the helium separation membrane obtained in the step (3), and performing a gas separation performance test on a mixed gas with the helium volume fraction of 5%, the nitrogen volume fraction of 15% and the methane volume fraction of 80% by using the membrane component, wherein the results are shown in table 1.
Example 10
(1) Adding zirconium tetrachloride powder and terephthalic acid powder into a beaker containing N, N-dimethylformamide, and fully dissolving to obtain a mixed solution, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the N, N-dimethylformamide is 1:1: 500.
(2) After fully dissolving, pouring the mixed solution (1L) into a stainless steel reaction kettle with a tetrafluoroethylene lining, and adding the mixture with the specific surface area of 0.5m2Putting the polyimide basal membrane into an oven, and reacting for 36 hours at 120 ℃; and after the reaction is finished, taking out the polyimide film and washing the polyimide film by using deionized water after the reaction kettle is cooled to obtain the MOFs separation film.
(3) And (3) putting the MOFs separation membrane obtained in the step (2) into 1L of Tris-HCl solution with the pH value of 8.5, adding 2g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 2g/L), reacting for 2h at 25 ℃, taking out and washing with deionized water to obtain the compact and stable helium separation membrane capable of being used for helium separation.
(4) And (3) preparing a membrane component by using the helium separation membrane obtained in the step (3), and performing a gas separation performance test on a mixed gas with the helium volume fraction of 5%, the nitrogen volume fraction of 15% and the methane volume fraction of 80% by using the membrane component, wherein the results are shown in table 1.
Example 11
(1) Adding zirconium tetrachloride powder and terephthalic acid powder into a beaker containing glacial acetic acid and N, N-dimethylformamide, and fully dissolving to obtain a mixed solution, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the glacial acetic acid to the N, N-dimethylformamide is 1:1:50: 450.
(2) After fully dissolving, pouring the mixed solution (0.5L) into a stainless steel reaction kettle with a tetrafluoroethylene lining, and adding the mixture into the stainless steel reaction kettle with a specific surface area of 0.5m2Putting the polyimide basal membrane into an oven, and reacting for 36 hours at 120 ℃; and after the reaction is finished, taking out the polyimide film and washing the polyimide film by using deionized water after the reaction kettle is cooled to obtain the MOFs separation film.
(3) And (3) putting the MOFs separation membrane obtained in the step (2) into 1L of Tris-HCl solution with the pH value of 8.5, adding 2g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 2g/L), reacting for 2h at 25 ℃, taking out and washing with deionized water to obtain the compact and stable helium separation membrane capable of being used for helium separation.
(4) And (3) preparing a membrane component by using the helium separation membrane obtained in the step (3), and performing a gas separation performance test on a mixed gas with the helium volume fraction of 5%, the nitrogen volume fraction of 15% and the methane volume fraction of 80% by using the membrane component, wherein the results are shown in table 1.
Example 12
(1) Adding zirconium tetrachloride powder and terephthalic acid powder into a beaker containing glacial acetic acid and N, N-dimethylformamide, and fully dissolving to obtain a mixed solution, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the glacial acetic acid to the N, N-dimethylformamide is 1:1:50: 450.
(2) After fully dissolving, pouring the mixed solution (1L) into a stainless steel reaction kettle with a tetrafluoroethylene lining, and addingThe specific surface area is 0.5m2Putting the polyimide basal membrane into an oven, and reacting for 36 hours at 120 ℃; and after the reaction is finished, taking out the polyimide film and washing the polyimide film by using deionized water after the reaction kettle is cooled to obtain the MOFs separation film.
(3) And (3) putting the MOFs separation membrane obtained in the step (2) into 1L of Tris-HCl solution with the pH value of 8.5, adding 1.5g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 1.5g/L), reacting for 2h at 25 ℃, taking out, and washing with deionized water to obtain the compact and stable helium separation membrane capable of being used for helium separation.
(4) And (3) preparing a membrane component by using the helium separation membrane obtained in the step (3), and performing a gas separation performance test on a mixed gas with the helium volume fraction of 5%, the nitrogen volume fraction of 15% and the methane volume fraction of 80% by using the membrane component, wherein the results are shown in table 1.
Example 13
(1) Adding zirconium tetrachloride powder and terephthalic acid powder into a beaker containing glacial acetic acid and N, N-dimethylformamide, and fully dissolving to obtain a mixed solution, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the glacial acetic acid to the N, N-dimethylformamide is 1:1:50: 450.
(2) After fully dissolving, pouring the mixed solution (1L) into a stainless steel reaction kettle with a tetrafluoroethylene lining, and adding the mixture with the specific surface area of 0.5m2Putting the polyimide basal membrane into an oven, and reacting for 36 hours at 120 ℃; and after the reaction is finished, taking out the polyimide film and washing the polyimide film by using deionized water after the reaction kettle is cooled to obtain the MOFs separation film.
(3) And (3) putting the MOFs separation membrane obtained in the step (2) into 1L of Tris-HCl solution with the pH value of 8.5, adding 5g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 5g/L), reacting for 2h at 25 ℃, taking out and washing with deionized water to obtain the compact and stable helium separation membrane capable of being used for helium separation.
(4) And (3) preparing a membrane component by using the helium separation membrane obtained in the step (3), and performing a gas separation performance test on a mixed gas with the helium volume fraction of 5%, the nitrogen volume fraction of 15% and the methane volume fraction of 80% by using the membrane component, wherein the results are shown in table 1.
Example 14
(1) Adding zirconium tetrachloride powder and terephthalic acid powder into a beaker containing glacial acetic acid and N, N-dimethylformamide, and fully dissolving to obtain a mixed solution, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the glacial acetic acid to the N, N-dimethylformamide is 1:1:50: 450.
(2) After fully dissolving, pouring the mixed solution (1L) into a stainless steel reaction kettle with a tetrafluoroethylene lining, and adding the mixture with the specific surface area of 0.5m2Putting the polyimide basal membrane into an oven, and reacting for 36 hours at 120 ℃; and after the reaction is finished, taking out the polyimide film and washing the polyimide film by using deionized water after the reaction kettle is cooled to obtain the MOFs separation film.
(3) And (3) putting the MOFs separation membrane obtained in the step (2) into 0.5L of Tris-HCl solution with the pH value of 8.5, adding 1g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 2g/L), reacting for 2h at 25 ℃, taking out, and washing with deionized water to obtain the compact and stable helium separation membrane capable of being used for helium separation.
(4) And (3) preparing a membrane component by using the helium separation membrane obtained in the step (3), and performing a gas separation performance test on a mixed gas with the helium volume fraction of 5%, the nitrogen volume fraction of 15% and the methane volume fraction of 80% by using the membrane component, wherein the results are shown in table 1.
Example 15
(1) Adding zirconium tetrachloride powder and terephthalic acid powder into a beaker containing glacial acetic acid and N, N-dimethylformamide, and fully dissolving to obtain a mixed solution, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the glacial acetic acid to the N, N-dimethylformamide is 1:1:50: 450.
(2) After fully dissolving, pouring the mixed solution (4L) into a stainless steel reaction kettle with a tetrafluoroethylene lining, and adding the mixture into the stainless steel reaction kettle with the specific surface area of 2m2Putting the polyimide basal membrane into an oven, and reacting for 36 hours at 120 ℃; and after the reaction is finished, taking out the polyimide film and washing the polyimide film by using deionized water after the reaction kettle is cooled to obtain the MOFs separation film.
(3) And (3) putting the MOFs separation membrane obtained in the step (2) into 1L of Tris-HCl solution with the pH value of 8.5, adding 2g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 2g/L), reacting for 2h at 25 ℃, taking out and washing with deionized water to obtain the compact and stable helium separation membrane capable of being used for helium separation.
(4) And (3) preparing a membrane component by using the helium separation membrane obtained in the step (3), and performing a gas separation performance test on a mixed gas with the helium volume fraction of 5%, the nitrogen volume fraction of 15% and the methane volume fraction of 80% by using the membrane component, wherein the results are shown in table 1.
Example 16
(1) Adding zirconium tetrachloride powder and terephthalic acid powder into a beaker containing glacial acetic acid and N, N-dimethylformamide, and fully dissolving to obtain a mixed solution, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the glacial acetic acid to the N, N-dimethylformamide is 1:1:50: 450.
(2) After fully dissolving, pouring the mixed solution (1L) into a stainless steel reaction kettle with a tetrafluoroethylene lining, and adding the mixture with the specific surface area of 0.5m2Putting the polyimide basal membrane into an oven, and reacting for 36 hours at 120 ℃; and after the reaction is finished, taking out the polyimide film and washing the polyimide film by using deionized water after the reaction kettle is cooled to obtain the MOFs separation film.
(3) And (3) putting the MOFs separation membrane obtained in the step (2) into 1L of Tris-HCl solution with the pH value of 8.0, adding 2g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 2g/L), reacting for 2h at 25 ℃, taking out and washing with deionized water to obtain the compact and stable helium separation membrane capable of being used for helium separation.
(4) And (3) preparing a membrane component by using the helium separation membrane obtained in the step (3), and performing a gas separation performance test on a mixed gas with the helium volume fraction of 5%, the nitrogen volume fraction of 15% and the methane volume fraction of 80% by using the membrane component, wherein the results are shown in table 1.
Example 17
(1) Adding zirconium tetrachloride powder and terephthalic acid powder into a beaker containing glacial acetic acid and N, N-dimethylformamide, and fully dissolving to obtain a mixed solution, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the glacial acetic acid to the N, N-dimethylformamide is 1:1:50: 450.
(2) After fully dissolving, pouring the mixed solution (1L) into a stainless steel reaction kettle with a tetrafluoroethylene lining, and adding the mixture with the specific surface area of 0.5m2Putting the polyimide basal membrane into an oven, and reacting for 36 hours at 120 ℃; and after the reaction is finished, taking out the polyimide film and washing the polyimide film by using deionized water after the reaction kettle is cooled to obtain the MOFs separation film.
(3) And (3) putting the MOFs separation membrane obtained in the step (2) into 1L of Tris-HCl solution with the pH value of 9.0, adding 2g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 2g/L), reacting for 2h at 25 ℃, taking out and washing with deionized water to obtain the compact and stable helium separation membrane capable of being used for helium separation.
(4) And (3) preparing a membrane component by using the helium separation membrane obtained in the step (3), and performing a gas separation performance test on a mixed gas with the helium volume fraction of 5%, the nitrogen volume fraction of 15% and the methane volume fraction of 80% by using the membrane component, wherein the results are shown in table 1.
Example 18
(1) Adding zirconium tetrachloride powder and terephthalic acid powder into a beaker containing glacial acetic acid and N, N-dimethylformamide, and fully dissolving to obtain a mixed solution, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the glacial acetic acid to the N, N-dimethylformamide is 1:1:30: 270.
(2) After fully dissolving, pouring the mixed solution (1L) into a stainless steel reaction kettle with a tetrafluoroethylene lining, and adding the mixture with the specific surface area of 0.5m2Putting the polyimide basal membrane into an oven, and reacting for 36 hours at 120 ℃; and after the reaction is finished, taking out the polyimide film and washing the polyimide film by using deionized water after the reaction kettle is cooled to obtain the MOFs separation film.
(3) And (3) putting the MOFs separation membrane obtained in the step (2) into 1L of Tris-HCl solution with the pH value of 8.5, adding 2g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 2g/L), reacting for 2h at 25 ℃, taking out and washing with deionized water to obtain the compact and stable helium separation membrane capable of being used for helium separation.
(4) And (3) preparing a membrane component by using the helium separation membrane obtained in the step (3), and performing a gas separation performance test on a mixed gas with the helium volume fraction of 5%, the nitrogen volume fraction of 15% and the methane volume fraction of 80% by using the membrane component, wherein the results are shown in table 1.
Example 19
(1) Adding zirconium tetrachloride powder and terephthalic acid powder into a beaker containing glacial acetic acid and N, N-dimethylformamide, and fully dissolving to obtain a mixed solution, wherein the molar ratio of the zirconium tetrachloride to the terephthalic acid to the glacial acetic acid to the N, N-dimethylformamide is 1:1:60: 540.
(2) After fully dissolving, pouring the mixed solution (1L) into a stainless steel reaction kettle with a tetrafluoroethylene lining, and adding the mixture with the specific surface area of 0.5m2Putting the polyimide basal membrane into an oven, and reacting for 36 hours at 120 ℃; and after the reaction is finished, taking out the polyimide film and washing the polyimide film by using deionized water after the reaction kettle is cooled to obtain the MOFs separation film.
(3) And (3) putting the MOFs separation membrane obtained in the step (2) into 1L of Tris-HCl solution with the pH value of 8.5, adding 2g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 2g/L), reacting for 2h at 25 ℃, taking out and washing with deionized water to obtain the compact and stable helium separation membrane capable of being used for helium separation.
(4) And (3) preparing a membrane component by using the helium separation membrane obtained in the step (3), and performing a gas separation performance test on a mixed gas with the helium volume fraction of 5%, the nitrogen volume fraction of 15% and the methane volume fraction of 80% by using the membrane component, wherein the results are shown in table 1.
Comparative example 1
With an unmodified specific surface area of 0.5m2A membrane module was prepared from polyimide-based membranes (shown in fig. 4 in SEM), and a gas separation performance test was performed on a mixed gas containing 5% by volume of helium, 15% by volume of nitrogen, and 80% by volume of methane at a test pressure of 0.5MPa, with the results shown in table 1.
Comparative example 2
(1) The unmodified specific surface area is 0.5m2Putting the polyimide base film into 1L Tr with pH value of 8.5Adding 2g of dopamine hydrochloride (the concentration of the dopamine hydrochloride solution is 2g/L) into the is-HCl solution, reacting for 2h at 25 ℃, taking out and washing with deionized water for later use.
(2) And (2) preparing a membrane module by using the separation membrane obtained in the step (1), and carrying out a gas separation performance test on a mixed gas with the volume fraction of helium being 5%, the volume fraction of nitrogen being 15% and the volume fraction of methane being 80%, wherein the test pressure is 0.5MPa, and the results are shown in Table 1.
Comparative example 3
A membrane module was prepared using the MOFs separation membrane prepared in step (2) of example 1, and a gas separation performance test was performed on a mixed gas having a helium volume fraction of 5%, a nitrogen volume fraction of 15%, and a methane volume fraction of 80%, with a test pressure of 0.5MPa, and the results are shown in table 1.
Table 1 example and comparative example helium separation membrane separation experimental results simulating helium-rich natural gas
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A helium separation membrane comprising a base membrane and a functional layer on a surface of the base membrane, the functional layer comprising MOFs, dopamine or a reaction product of MOFs and dopamine;
wherein, the selectivity of the helium separation membrane to helium/methane is 50-500, preferably 100-500, more preferably 200-500, and the selectivity to helium/nitrogen is 60-300, preferably 100-250, more preferably 150-250.
2. A method for preparing a helium separation membrane comprises the following steps:
(1) providing a first mixture comprising a metal salt, an organic ligand, a solvent, and a base membrane;
(2) heating the first mixture to react to prepare the MOFs separation membrane;
(3) and (3) contacting the MOFs separation membrane with a solution containing dopamine salt to react to prepare the helium separation membrane.
3. The production method according to claim 2, wherein the metal salt comprises zirconium tetrachloride; and/or, the organic ligand comprises terephthalic acid; and/or, the solvent comprises one or more of N, N-dimethylformamide, acetic acid, ethanol and water, preferably comprises N, N-dimethylformamide and acetic acid; and/or the base film comprises a polyimide film.
4. The production method according to claim 2 or 3, wherein the molar ratio of the metal salt, the organic ligand and the solvent is (1-10): (1-10): (1-1000), preferably (1-5): (1-5): (300-600).
5. The production method according to any one of claims 2 to 4, wherein the reaction temperature in the step (2) is 50 to 300 ℃ and the reaction time is 1 to 100 hours.
6. The preparation method according to any one of claims 2 to 5, wherein the concentration of dopamine hydrochloride in the dopamine salt-containing solution is 0.5 to 3g/L, and the pH value of the solution is 7.0 to 9.5.
7. The method according to any one of claims 2 to 6, wherein the volume ratio of the basement membrane to the dopamine salt-containing solution is (0.1 to 500) m2/L, preferably (0.3-300) m2L; and/or the reaction temperature in the step (3) is 100-160 ℃, and the reaction time is 2-48 h.
8. Helium separation membrane prepared according to the preparation method of any one of claims 2 to 7, having a selectivity to helium/methane of 50 to 500, preferably 100-500, more preferably 200-500, and a selectivity to helium/nitrogen of 60 to 300, preferably 100-250, more preferably 150-250.
9. A membrane module made from the helium separation membrane of claim 1 or 8.
10. Use of a helium separation membrane according to claim 1 or 8 or a membrane module according to claim 9 for the separation of helium, in particular in natural gas.
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