CN113262650A - Two-dimensional MOF (Metal organic framework) membrane for hydrogen isotope purification and preparation method and application thereof - Google Patents

Two-dimensional MOF (Metal organic framework) membrane for hydrogen isotope purification and preparation method and application thereof Download PDF

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CN113262650A
CN113262650A CN202110441346.5A CN202110441346A CN113262650A CN 113262650 A CN113262650 A CN 113262650A CN 202110441346 A CN202110441346 A CN 202110441346A CN 113262650 A CN113262650 A CN 113262650A
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membrane
dimensional mof
support body
hydrogen isotope
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CN113262650B (en
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冯兴文
王祥霖
姚伟志
罗军洪
杨莞
姚勇
陈克琳
宋江锋
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • 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
    • 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
    • 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
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness

Abstract

The invention discloses a two-dimensional MOF (metal organic framework) membrane for hydrogen isotope purification, which is prepared from M2+As metal centre, benzimidazole as organic ligand, forming a compound of formula M2(Bim)4The film of (a); wherein M is one or more of Zn, Co and Ni. Also included is a method of making a two-dimensional MOF film. By adopting the two-dimensional MOF membrane for hydrogen isotope purification and the preparation method thereof, the membrane separation performance is excellent, the permeation rate is high, and the selectivity is high in the application of purifying the mixed gas of hydrogen isotopes and impurity gases.

Description

Two-dimensional MOF (Metal organic framework) membrane for hydrogen isotope purification and preparation method and application thereof
Technical Field
The invention relates to a two-dimensional MOF (metal organic framework) membrane for hydrogen isotope purification and a preparation method and application thereof, belonging to the technical field of membrane materials.
Background
Due to the special properties, hydrogen isotopes have very important applications in research and industry. Deuterium tritium is an important fuel for fusion reactors. Different from non-renewable energy sources and conventional clean energy sources, the accumulation energy has the advantages of unlimited resources, no environmental pollution, no generation of high-radioactivity waste and the like, and is one of the leading forms of human future energy sources.
The fusion reactor provides energy through the nuclear reaction of deuterium and tritium, and as the reaction progresses, the temperature of plasma is reduced due to the gradual accumulation of helium which is a nuclear reaction product, and burnt gas must be continuously pumped out. Because the content of deuterium and tritium in the ash discharge gas is extremely high, the ash discharge gas needs to be treated by a fusion reactor tritium factory, and the treated ash discharge gas is put into a vacuum chamber to participate in reaction again after being purified and separated by hydrogen isotopes. Besides a large amount of deuterium-tritium-hydrogen isotopes in the ash discharge gas, main impurities are fusion products of helium and plasma enhanced gas of argon and neon. Therefore, the deuterium-tritium hydrogen isotope and the impurities such as argon gas, helium gas and the like are purified, the deuterium-tritium fuel in the deuterium-tritium hydrogen isotope is recovered, and the deuterium-tritium fuel participates in the fusion reaction again.
For the separation of hydrogen isotopes and impurity gases, absorption methods, palladium membrane separation methods and molecular sieve membrane separation methods are mainly adopted at present. The adsorption method mainly uses active metal hydrogen absorption materials to selectively absorb hydrogen isotopes, and has the defects that the hydrogen absorption materials need to be repeatedly regenerated, the energy consumption is high, the separation process is discontinuous, and the like. The palladium membrane separation method is a method for separating deuterium and tritium from impurity gases by using a palladium and palladium alloy membrane having high hydrogen permeation selectivity, but palladium is expensive and has a high operation temperature, and the palladium membrane is easily poisoned by hydrocarbons or sulfur-containing gases, thereby greatly reducing the separation performance. The molecular sieve membrane method has a low permeation rate due to the large thickness of the membrane layer, which is generally on the level of several to tens of microns. In addition, the pore size of molecular sieve materials is generally large such that selectivity is poor.
Disclosure of Invention
The invention aims to: in the application of the invention in purifying the mixed gas of hydrogen isotopes and inert gases, the membrane separation performance is excellent, the permeation rate is high, and the selectivity is high.
The technical scheme adopted by the invention is as follows:
a two-dimensional MOF for hydrogen isotope purification, M2+As metal centre, benzimidazole as organic ligand, forming a compound of formula M2(Bim)4The film of (a); wherein M is one or more of Zn, Co and Ni.
In the present invention, Zn is selected2+、Co2+And Ni2+One or more of them as metal centre and benzimidazole as organic ligand to form a compound of general formula M2(Bim)4The membrane has small aperture, which is equivalent to the hydrogen isotope kinetic diameter, and has the advantages of excellent membrane separation performance, high permeation rate and high selectivity when being applied to purifying the mixed gas of hydrogen isotopes and impurity gases.
In the present invention, M is one or more of Zn, Co and Ni, and in the case of plural kinds, M may be a combination of Zn, Co and Ni in any ratio.
Preferably, the two-dimensional MOF film is a highly oriented two-dimensional MOF film, and the thickness of the film layer is 100-300 nm.
In the scheme, the graphene oxide is used for processing during the preparation of the MOF film, so that the effects of limiting the domain and inducing can be achieved, the MOF material forms a highly-oriented two-dimensional MOF film, the film is continuous and free of defects, and the functional stability of the two-dimensional MOF film is ensured.
A method of making a two-dimensional MOF membrane for hydrogen isotope purification comprising the steps of:
step a: treating a support body by using porous alumina as the support body;
step b: preparing an MO nanoparticle layer on the surface of a support, wherein M is one or more of Zn, Co and Ni;
step c: treating the MO nanoparticle layer with graphene oxide;
step d: and c, immersing the support in the step c into a reaction solution containing benzimidazole and ammonia water for reaction, and cleaning and drying to obtain the two-dimensional MOF membrane.
In the invention, the support body is treated through the step a, so that oil contamination impurities on the support body are removed, and the performance of the prepared two-dimensional MOF membrane is ensured; b, preparing a uniform MO nanoparticle layer on the surface of the support body through the step b, so that the surface flatness of the support body is improved, the aperture is reduced, and a metal source of MOFs is provided; in the step c, the MO nanoparticle layer is treated by graphene oxide, so that the domain limitation and the growth induction of the MOF film are realized, and the highly-oriented two-dimensional MOF film is formed; by reacting benzimidazole, ammonia and MO in step d, thereby generating two-dimensional M2(Bim)4And (3) a membrane.
The preparation method for preparing the two-dimensional MOF membrane is simple to operate, and the membrane layer is uniform, continuous and free of defects, so that the two-dimensional MOF membrane is stable in performance, excellent in membrane separation performance, high in permeation rate and high in selectivity.
Preferably, in the step a, the support body is ultrasonically cleaned by acetone and deionized water respectively, then dried at 80-120 ℃ for 40-80min, roasted at 350-450 ℃ for 4-6h, and one surface of the alumina support body is wrapped by a polytetrafluoroethylene adhesive tape for later use.
In the scheme, impurities and stains on the surface of the support body are removed through ultrasonic cleaning and roasting, and one surface of the support body is wrapped to form a film.
Preferably, in the step b, Zn salt and/or Co salt and/or Ni salt is dissolved in ethylene glycol monomethyl ether, then ethanolamine is slowly added, and the mixture is aged for 8 to 12 hours at room temperature; immersing the treated support body into the solution, keeping the solution for 15-25s, taking out the support body, drying the support body in an oven at 80-120 ℃ for 40-80min, and then roasting the support body at 350-450 ℃ for 4-6 h.
In the above scheme, the ZnO and/or CoO and/or NiO nanoparticle layer was obtained by a sol-gel method.
Preferably, the Zn salt, Co salt, and Ni salt are soluble salts such as nitrate, acetate, hydrochloride, and sulfate.
Preferably, in the step c, the support body in the step b is immersed in the graphene oxide ethanol water solution, kept for 15-25s, taken out and put into an oven to be dried for 40-80min at the temperature of 80-120 ℃.
Preferably, in the embodiment, the concentration of the graphene oxide is 0.1-0.3 mg/mL.
In the scheme, the proper concentration of the graphene oxide avoids the formed GO layer from being too thick, and the thickness is 10-20 nm.
Preferably, in step d, the reaction solution contains benzimidazole, ammonia, methanol, toluene, 1:1-2:40-50: 40-50.
Preferably, in step d, the support is immersed in the reaction solution, reacted at 80-100 ℃ for 8-12h, washed and dried to obtain the two-dimensional MOF membrane.
Preferably, in step d, the support is washed with ethanol.
In the above scheme, methanol and toluene act as a solution and benzimidazole reacts with ZnO and/or CoO and/or NiO to produce MOF films.
Preferably, the pore size of the support is 50 to 150 nm.
Preferably, the support is a sheet-like or tubular support.
The application of the two-dimensional MOF membrane is used for purifying hydrogen isotopes, particularly for purifying a mixed gas of the hydrogen isotopes and an impurity gas to remove the impurity gas in the hydrogen isotopes.
Preferably, the MOF membrane pressure differential is from 0.1 to 0.5 MPa.
In the scheme, the selectivity of the MOF membrane to helium is more than 1.8, and the selectivity to argon is more than 70; the permeation rate of the hydrogen isotope is greater than 500 GPU.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the membrane separation performance is excellent, the permeation rate is high, and the selectivity is high;
2. the preparation method is simple, and the film layer is uniform and continuous without defects;
drawings
The invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a graph of hydrogen isotope purification performance of two-dimensional MOF membranes.
Detailed Description
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
Example 1
The preparation method of the two-dimensional MOF membrane comprises the following steps:
step a: taking a porous alumina wafer with the average pore diameter of 50nm as a support body, ultrasonically cleaning the support body for 2 times by using acetone and deionized water respectively, then drying at 80 ℃ for 80min, roasting at 350 ℃ for 6h, and wrapping one surface of the support body by using a polytetrafluoroethylene adhesive tape for later use;
step b: dissolving 5.7g of cobalt acetate in 30ml of ethylene glycol monomethyl ether, slowly adding 1.3ml of ethanolamine, and aging at room temperature for 8 h; immersing the treated support body into the solution, keeping the solution for 15s, taking out the support body, drying the support body in an oven at 80 ℃ for 80min, and then roasting the support body at 350 ℃ for 6h to form a uniform CoO nanoparticle layer on the surface of the support body;
step c: immersing the support body into 0.1mg/mL graphene oxide ethanol water solution, keeping for 15s, taking out, and drying in an oven at 80 ℃ for 80 min;
step d: placing the support on a polytetrafluoroethylene supportPutting the mixture on a rack, vertically putting the mixture into an alumina reaction kettle with a polytetrafluoroethylene lining, and pouring benzimidazole: ammonia water: methanol: reacting the reaction solution with the toluene molar ratio of 1:2:40:40 at 80 ℃ for 12h, cooling, taking out the support, washing with ethanol, and drying at room temperature to obtain two-dimensional Co2(Bim)4And (3) a membrane.
This example gives a two-dimensional Co thickness of 100nm2(Bim)4And (5) film layer.
Example 2
The preparation method of the two-dimensional MOF membrane comprises the following steps:
step a: taking a porous alumina tube with the average pore diameter of 150nm as a support body, respectively ultrasonically cleaning the support body for 2 times by using acetone and deionized water, then drying at 120 ℃ for 40min, roasting at 450 ℃ for 4h, and wrapping the outer surface of the alumina tube-shaped support body by using a polytetrafluoroethylene adhesive tape for later use;
step b: dissolving 4.3g of nickel chloride in 30ml of ethylene glycol monomethyl ether, slowly adding 2.1ml of diethylamine, and aging at room temperature for 12 h; immersing the treated support body into the solution, keeping the solution for 20s, taking out the support body, putting the support body into an oven, drying the support body for 40min at 120 ℃, repeating the drying for 2 times, and then roasting the support body for 4h at 450 ℃ to form a uniform NiO nano particle layer on the surface of the support body;
step c: soaking the support in 0.2mg/mL graphene oxide ethanol water solution, keeping for 15s, taking out, drying in an oven at 80 deg.C for 80min, and repeating for 2 times;
step d: putting the support body on a polytetrafluoroethylene support, vertically putting the support body into an alumina reaction kettle with a polytetrafluoroethylene lining, and pouring benzimidazole: ammonia water: methanol: reacting the reaction solution with the toluene molar ratio of 1:1.5:50:50 at 80 ℃ for 12h, cooling the support taken out, washing the support with ethanol, and drying at room temperature to obtain two-dimensional Ni2(Bim)4And (3) a membrane.
This example gives two-dimensional Ni of 200nm thickness2(Bim)4And (5) film layer.
Example 3
The preparation method of the two-dimensional MOF membrane comprises the following steps:
step a: taking a porous alumina wafer with the average pore diameter of 100nm as a support body, ultrasonically cleaning the support body for 2 times by using acetone and deionized water respectively, then drying at 100 ℃ for 60min, roasting at 400 ℃ for 5h, and wrapping one surface of the support body by using a polytetrafluoroethylene adhesive tape for later use;
step b: dissolving 2.1g of nickel chloride and 3.2g of zinc nitrate in 30ml of ethylene glycol monomethyl ether, slowly adding 2.1ml of diethylamine, and aging at room temperature for 10 hours; immersing the treated support body into the solution, keeping the solution for 20s, taking out the support body, drying the support body in an oven at 100 ℃ for 60min, repeating the drying for 3 times, and then roasting the support body at 400 ℃ for 5h to form a uniform ZnO/NiO nanoparticle layer on the surface of the support body;
step c: soaking the support body into 0.3mg/mL graphene oxide ethanol water solution, keeping for 20s, taking out, drying in an oven at 60 ℃ for 60min, and repeating for 2 times;
step d: putting the support body on a polytetrafluoroethylene support, vertically putting the support body into an alumina reaction kettle with a polytetrafluoroethylene lining, and pouring benzimidazole: ammonia water: methanol: reacting the reaction solution with the toluene molar ratio of 1:1:45:45 at 80 ℃ for 12h, cooling the support taken out, washing the support with ethanol, and drying at room temperature to obtain two-dimensional ZnNi (bim)4And (3) a membrane.
This example gives a two-dimensional ZnNi (bim) thickness of 300nm4And (5) film layer.
The two-dimensional MOF membranes obtained in the above examples were used for mixed gas permeation testing. The results obtained were as follows:
example 1 Example 2 Example 3
Deuterium penetration rate/GPU 588 574 567
Deuterium/helium permselectivity 1.8 1.9 2.1
Deuterium/argon permselectivity 70 74 76
In the test, the mixed gas of the hydrogen isotope and 50 percent of helium and argon is used for testing, and the test conditions are that the feeding temperature is 25 ℃ and the pressure difference between two sides of the membrane is 0.1 MPa; from the above table, we can see that the MOF film in the examples has a large deuterium permeation rate, so that the MOF film can purify hydrogen isotopes and impurity gases efficiently; has better separation effect, especially the osmotic selectivity of argon can reach more than 70; the effect of separation of helium is general, but a permselectivity of 1.8 or more can be achieved as well.
In other embodiments, M is a combination of other different proportions of Zn, Co and Ni, and the obtained two-dimensional MOF film has good permselectivity and permeation rate, and does not affect the performance of the two-dimensional MOF film.
The lower curve in FIG. 1 is a graph of the change in permselectivity and the upper curve is a graph of the change in permeation rate for the MOF membrane of example 3.
Meanwhile, the influence of different pressure differences on the permeability of the same two-dimensional MOF membrane is tested, and the attached figure 1 shows that the MOF membrane still keeps good permeation selectivity and permeation speed along with the rise of the pressure difference.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.

Claims (10)

1. A two-dimensional MOF membrane for hydrogen isotope purification, comprising: with M2+As metal centre, benzimidazole as organic ligand, forming a compound of formula M2(Bim)4The film of (a); wherein M is one or more of Zn, Co and Ni.
2. The two-dimensional MOF membrane for hydrogen isotope purification of claim 1, wherein: the two-dimensional MOF film is a highly oriented two-dimensional MOF film, and the thickness of the film layer is 100-300 nm.
3. A preparation method of a two-dimensional MOF membrane for hydrogen isotope purification is characterized by comprising the following steps: the method comprises the following steps:
step a: treating a support body by using porous alumina as the support body;
step b: preparing an MO nanoparticle layer on the surface of a support, wherein M is one or more of Zn, Co and Ni;
step c: treating the MO nanoparticle layer with graphene oxide;
step d: and c, immersing the support in the step c into a reaction solution containing benzimidazole and ammonia water for reaction, and cleaning and drying to obtain the two-dimensional MOF membrane.
4. A method of making a two-dimensional MOF membrane for hydrogen isotope purification according to claim 3, wherein: in the step a, the support body is ultrasonically cleaned by acetone and deionized water respectively, then dried at 80-120 ℃ for 40-80min, roasted at 350-450 ℃ for 4-6h, and one surface of the alumina support body is wrapped by an adhesive tape for later use.
5. A method of making a two-dimensional MOF membrane for hydrogen isotope purification according to claim 3, wherein: in the step b, Zn salt and/or Co salt and/or Ni salt is dissolved in ethylene glycol monomethyl ether, and then ethanolamine or diethylamine is slowly added, and the mixture is aged for 8 to 12 hours at room temperature; immersing the treated support body into the solution, taking out and placing the support body into an oven to be dried for 40-80min at the temperature of 80-120 ℃, and then roasting for 4-6h at the temperature of 350-450 ℃.
6. A method of making a two-dimensional MOF membrane for hydrogen isotope purification according to claim 3, wherein: and c, immersing the support body in the step b into an ethanol water solution of graphene oxide, taking out, and drying in an oven at 80-120 ℃ for 40-80 min.
7. A method of making a two-dimensional MOF membrane for hydrogen isotope purification according to claim 6, wherein: in the step c, the concentration of the graphene oxide ethanol aqueous solution is 0.1-0.3 mg/mL.
8. A method of making a two-dimensional MOF membrane for hydrogen isotope purification according to claim 3, wherein: in the step d, the reaction solution contains benzimidazole, ammonia water, methanol and toluene in a ratio of 1:1-2:40-50: 40-50.
9. A method of making a two-dimensional MOF membrane for hydrogen isotope purification according to claim 3, wherein: and d, immersing the support into the reaction solution, reacting for 8-12h at 80-100 ℃, and cleaning and drying to obtain the two-dimensional MOF membrane.
10. Use of a two-dimensional MOF film according to claim 1 wherein: the device is used for purifying the hydrogen isotopes and removing impurity gases in the hydrogen isotopes.
CN202110441346.5A 2021-04-23 2021-04-23 Two-dimensional MOF (Metal organic framework) membrane for hydrogen isotope purification and preparation method and application thereof Active CN113262650B (en)

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