CN112915814A - Novel membrane material for gas separation and preparation method thereof - Google Patents

Novel membrane material for gas separation and preparation method thereof Download PDF

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CN112915814A
CN112915814A CN202110164833.1A CN202110164833A CN112915814A CN 112915814 A CN112915814 A CN 112915814A CN 202110164833 A CN202110164833 A CN 202110164833A CN 112915814 A CN112915814 A CN 112915814A
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membrane
maf
metal organic
organic framework
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CN112915814B (en
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陈祥树
张瑜平
张飞
何明亮
王兴钱
桂田
胡娜
吴婷
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Jiangxi Normal University
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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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • 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

Abstract

The invention relates to the technical field of membrane material preparation and application, and provides a novel membrane material for gas separation and a preparation method thereof. The preparation method comprises the following steps: s1, preparation of membrane synthesis mother liquor: mixing and stirring the triazole ligand solution and the zinc source solution uniformly to obtain a membrane synthesis mother solution; s2, preparation of a metal organic framework film: placing the support body in membrane synthesis mother liquor, and then carrying out a solvothermal reaction to obtain a MAF-66 metal organic framework membrane; s3, modification of the metal organic framework film: preparing a silane coupling agent solution, and putting the MAF-66 metal organic framework film into the silane coupling agent solution for modification. The invention grows a layer of MAF-66 film on a support under the condition of solvothermal synthesis; introducing a silane connector with amino on the surface of the membrane through covalent bonding reaction with a silane coupling agent to obtain the defect-free MAF-66 membrane layer with the surface modified by functionalization. The MAF-66 membrane prepared by the invention is suitable for separating small molecule gas.

Description

Novel membrane material for gas separation and preparation method thereof
Technical Field
The invention relates to the technical field of membrane material preparation and application, in particular to a novel membrane material for gas separation and a preparation method thereof.
Background
In relation to global climate change and increase of energy demand, large-scale development and utilization of renewable energy have become an important part of energy strategy of countries in the world. The hydrogen is a clean and efficient energy source, has rich sources, is environment-friendly and has high energy density, and is the most ideal energy source in the future. (International Journal of Hydrogen Energy,2012,37,11563-11578) most of the Hydrogen is produced by Steam Methane Reforming (SMR) and water-gas shift (WGS). The resulting gas mixture consists essentially of H2And CO2Compositions which are separated mainly by Pressure Swing Adsorption (PSA) (Journal of Membrane Science,2011,367, 233-. Membrane separation is considered to be the most promising separation method due to its low energy consumption, simple operation, and low cost, compared to conventional separation methods such as pressure swing adsorption and the like. Inorganic membranes are more promising under harsh separation conditions due to instability problems of organic polymer membranes in contact with solvents or at high temperatures.
To date, hydrogen permselective inorganic membranes, typically dense palladium-based metal membranes, microporous silica membranes, carbon membranes, and zeolite membranes have been developed for hydrogen separation. The Pd membrane shows higher H at high temperature2Selectivity and H2Transmittance, but in contact with CO or H2S is easily degraded. In addition, the high cost also restricts the wide application of Pd-based membranesAnother bottleneck. Microporous silica membranes have surprising H's compared to other small molecule gases2Selectivity, but suffers from instability in the presence of trace amounts of water vapor (International Journal of Hydrogen Energy,2020,45, 7488-. The carbon film is fragile, and the carbon film is difficult to be used in practical application. Due to intergranular defects and relatively large pore size (vs. H)2(0.29nm) and CO2(0.33nm) comparison), molecular sieve membranes generally exhibit lower H2/CO2Selectivity (Journal of Membrane Science,2016,511, 1-8. therefore, development of a catalyst having a high H content2Permselective microporous membranes are very important.
Chen et al used 3-amino-1, 2, 4-triazole (atz) to further increase the density of active centers-) Synthesis of novel zeolitic molecular sieves MAF-66[ Zn (atz) ] as imidazole ligands with interesting structures, high gas absorption and good gas adsorption selectivity2](Inorganic Chemistry,51(2012)9950-9955)。atz-As an imidazole acid salt type ligand, tetrahedron Zn (II) ions are connected to construct a three-dimensional zeolite metal polynitrogen azole framework to form a dia framework. MAF-66 vs. CO due to an increased content of non-coordinating N on the ligand2The adsorption performance of the composite material is obviously improved. Membranes made from MAF-66 materials in H2/CO2And CO2/CH4The system has a wide application prospect, but reports of introducing the MAF-66 material into membrane separation are not seen at present, the membrane prepared from the MAF-66 material is still a big problem, and the membrane layer is easy to have intercrystalline defects and pinholes.
Disclosure of Invention
The invention aims to overcome at least one of the defects of the prior art, and provides a method for preparing a novel material MAF-66 type metal organic framework film and finishing MAF-66 film modification under the condition of not influencing film quality, so that the gas selectivity of the MAF-66 film is greatly improved. The purpose of the invention is realized based on the following technical scheme:
in one aspect, the present invention provides a method for preparing a novel membrane material for gas separation, comprising the following steps:
s1, preparation of membrane synthesis mother liquor: mixing and stirring the 3-amino-1, 2, 4-triazole ligand solution and the zinc source solution uniformly to obtain a membrane synthesis mother solution;
s2, preparation of a metal organic framework film: placing the support body in membrane synthesis mother liquor, and then carrying out a solvothermal reaction to obtain a MAF-66 metal organic framework membrane;
s3, modification of the metal organic framework film: preparing a silane coupling agent solution, and putting the MAF-66 metal organic framework film into the silane coupling agent solution for modification.
Preferably, the solvent of the triazole ligand solution in step S1 is one or more of ethanol, isopropanol, methanol or N, N-dimethylformamide; the solvent of the zinc source solution is ammonia water, and the zinc source is Zn and ZnCO3、ZnCl2、(CH3COO)2Zn·2H2O、Zn(OH)2ZnO or Zn (NO)3)2·6H2O。
Preferably, the membrane synthesis mother liquor in step S1 includes the following substances in molar content ratio: 3-amino-1, 2, 4-triazole: zn2+: isopropyl alcohol: ethanol: ammonia water (3.5-9.5): (1-10): (500-750): (100-200): (10 to 100) and 0<Ammonia water: the membrane synthesis mother liquor is less than or equal to 0.095.
Preferably, the support is pretreated before reaction in step S2: and sequentially polishing the support body by using 800-mesh and 1200-mesh SiC abrasive paper, then ultrasonically cleaning for 30min, and drying at 60 ℃ for later use.
Preferably, the support in step S2 includes porous alumina, porous titania, porous zinc oxide, porous silica, mullite, a polytetrafluoroethylene substrate, or a glass substrate.
Preferably, the reaction temperature of the solvothermal reaction in the step S2 is 60-150 ℃, and the reaction time is 8-20 h.
Preferably, the solvent thermal reaction in step S2 further comprises: washing impurities in the obtained MAF-66 metal organic framework film by using ethanol, isopropanol, methanol or N, N-dimethylformamide, then washing the film to be neutral by using deionized water, and drying the film.
Preferably, the solvent of the silane coupling agent solution in step S3 is one or more of ethanol, isopropanol, methanol or N, N-dimethylformamide, and the silane coupling agent includes one or more of 3-aminopropyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, gamma- (methoxypropenoyloxy) propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 1, 2-ethylenediamine and diethylamine.
Preferably, the reaction temperature of the modification in the step S3 is 30-120 ℃, and the modification time is 0.5-3 h.
In another aspect, the present invention provides a novel membrane material for gas separation, prepared according to any one of the above-mentioned preparation methods.
In another aspect of the invention, a novel membrane material for gas separation is provided in H2、CO2、N2、CH4And the application in the separation of two or more gases in the low-carbon alkane gas.
The invention can obtain at least one of the following beneficial effects:
according to the invention, a MAF-66 metal organic framework film of a film layer is successfully prepared on the surface of a support body through a solvent thermal synthesis method; and modifying the film layer by using a silane coupling agent solution, introducing a silane connector with amino on the surface of the film through covalent bonding reaction with the silane coupling agent, and obtaining the defect-free MAF-66 film with the surface subjected to functional modification. The MAF-66 membrane material obtained by the invention has uniform and compact membrane layer, greatly reduces intercrystalline defects, pinholes and the like, improves the gas selectivity of the metal organic framework membrane and has good separation performance.
The invention successfully realizes the first synthesis of the MAF-66 type molecular sieve membrane, and has the advantages of simple method, quick operation, environmental protection and low cost.
Drawings
FIG. 1 is a photograph of a MAF-66 type metal organic framework film obtained in example 1, which is identified by SEM;
FIG. 2 is a photograph of a modified MAF-66 type metal organic framework film prepared in example 1, identified by SEM;
FIG. 3 is an X-ray diffraction pattern of example 1: (a) MAF-66 standard spectrum, (b) MAF-66 type metal organic framework film prepared on porous zinc oxide ceramic, (c) modified MAF-66 type metal organic framework film and (d) X-ray diffraction pattern (XRD) of porous zinc oxide support.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The chemicals and laboratory instruments used in the following examples are commercially available. The molar usage of the ammonia water is calculated as follows: the density of ammonia water is 0.91, and the molar amount of ammonia water is 2 × 0.91/17, wherein the relative molecular mass is 17, for example, 2 ml.
Example 1
A preparation method of a novel membrane material for gas separation comprises the following steps:
(1) and (3) treatment of the support: porous zinc oxide was used as a support for membrane synthesis, with a diameter of 23 mm, a thickness of 2.0 mm and a porosity of about 60%. The support body is sequentially polished by SiC sand paper of 800 meshes and 1200 meshes, then is ultrasonically cleaned for 30min, and is dried at 60 ℃;
(2) preparing a metal organic framework film: mixing ligand 3-amino-1, 2, 4-triazole, isopropanol and ethanol to obtain ligand solution, mixing zinc hydroxide with ammonia water to obtain zinc source solution, stirring thoroughly, pouring the ligand solution into the zinc source solution, and stirring continuously to obtain synthetic mother liquor with mole ratio of IPA/EtOH 4, Hatz/Zn (OH)2＝2，Hatz/EtOH＝0.03，NH3·H2O/EtOH ═ 0.3. Stirring the synthetic mother liquor at room temperature for 10 min, vertically placing the synthetic mother liquor into the support body treated in the step (1), placing the reaction kettle into an oven at 120 ℃ for reaction for 15 h to form a layer of MAF-66 film on a support body disc, washing off surface impurities with isopropanol, washing with deionized water to mediumDrying at 60 ℃ to obtain the ultrathin MAF-66 metal organic framework film;
(3) modification of the metal organic framework film: adding 3-aminopropyltriethoxysilane into ethanol, and stirring for 1 hour to obtain a mixture with a volume ratio of 4: the mixed solution of 1 is vertically placed into the MAF-66 membrane dried in the step (2), and is transferred into a 60 ℃ oven for reaction for 1 hour, and the membrane is taken out, cleaned and dried to obtain the successfully modified MAF-66 membrane.
FIG. 1 is an SEM image of the resulting MAF-66 type metal organic framework film. FIG. 2 is an SEM image of a modified MAF-66 membrane. As can be seen from the figure, the surface of the support was covered with a layer of MAF-66 crystals, the crystals grew tightly, and particularly, no defects were found on the surface of the modified membrane layer, and the thickness of the membrane layer was thin before and after modification.
Fig. 3 is an X-ray diffraction pattern (XRD) of the synthesized film. (a) MAF-66 standard spectrum, (b) MAF-66 type metal organic framework film prepared on porous zinc oxide ceramic in example 1, (c) modified MAF-66 type metal organic framework film, and (d) porous zinc oxide support. As can be seen from the figure, the standard spectrum of the metal organic framework in the MAF-66 is completely consistent, and is pure MAF-66 crystals.
The prepared membrane M-1 is characterized by small gas separation performance at 25 ℃ and 0.1MPa, and the results of gas separation experiments are shown in Table 1. The results show that the resulting MAF-66 film has H2/CO2The selectivity exceeds Knudsen diffusion, and the good separation performance is shown.
Example 2
The preparation method of this example is substantially the same as that of example 1 except that: the molar ratio of each component of the synthesis mother liquor is adjusted to IPA/EtOH-4, Hatz/Zn (OH)2＝1，Hatz/EtOH＝0.03，NH3·H2O/EtOH＝0.3。
The prepared membrane M-2 is characterized by small gas separation performance at 25 ℃ and 0.1MPa, and the results of gas separation experiments are shown in Table 1.
Example 3
The preparation method of this example is substantially the same as that of example 1 except that: the molar ratio of each component of the synthesis mother liquor is adjusted to IPA/EtOH-4, Hatz/Zn (OH)2＝3，Hatz/EtOH＝0.03，NH3·H2O/EtOH＝0.3。
The prepared membrane M-3 is characterized by small gas separation performance at 25 ℃ and 0.1MPa, and the results of the gas separation experiment are shown in Table 1.
Example 4
A preparation method of a novel membrane material for gas separation comprises the following steps:
(1) and (3) treatment of the support: the porous alumina support was treated in the same manner as in step (1) of example 1.
(2) Preparing a metal organic framework film: similar to example 1, step (2), except that: the zinc source is ZnO, the solvent is IPA and DMF, and the molar ratio of each component of the formed synthetic mother liquor is Hatz: zn2+：IPA：DMF：NH3·H2O ═ 3.5: 9: 750: 200: 100, the conditions of the solvothermal reaction are as follows: reacting for 20 hours in an oven at 60 ℃;
(3) modification of the metal organic framework film: adding 3-aminopropyltrimethoxysilane into isopropanol, and stirring for 1 hour to obtain a mixture with a volume ratio of 4: the mixed solution of 1 is vertically placed into the MAF-66 membrane dried in the step (2), and is transferred into a drying oven at 40 ℃ for reaction for 3 hours, and the membrane is taken out, cleaned and dried to obtain the successfully modified MAF-66 membrane.
The prepared membrane M-4 is characterized by small gas separation performance at 25 ℃ and 0.1MPa, and the results of the gas separation experiment are shown in Table 1.
Example 5
A preparation method of a novel membrane material for gas separation comprises the following steps:
(1) and (3) treatment of the support: the porous titania support was treated in the same manner as in step (1) of example 1.
(2) Preparing a metal organic framework film: similar to example 1, step (2), except that: the zinc source is Zn (NO)3)2·6H2O, solvent is CH3OH and EtOH, wherein the molar ratio of each component of the formed synthetic mother liquor is Hatz: zn2+：CH3OH：EtOH：NH3·H2O ═ 8: 1.5: 550: 100: 20, the solvothermal reaction conditions are 150 DEG CReacting for 8 hours in an oven;
(3) modification of the metal organic framework film: adding 3- (2, 3-epoxypropoxy) propyl trimethoxy silane into CH3In OH, stirring for 1 hour, giving a volume ratio of 3: the mixed solution of 1 is vertically placed into the MAF-66 membrane dried in the step (2), and is transferred into an oven with the temperature of 80 ℃ for reaction for 2 hours, and the membrane is taken out, cleaned and dried to obtain the successfully modified MAF-66 membrane.
The prepared membrane M-5 is characterized by small gas separation performance at 25 ℃ and 0.1MPa, and the results of the gas separation experiment are shown in Table 1.
Example 6
A preparation method of a novel membrane material for gas separation comprises the following steps:
(1) and (3) treatment of the support: the porous silica support was treated in the same manner as in step (1) of example 1.
(2) Preparing a metal organic framework film: similar to example 1, step (2), except that: the zinc source is (CH)3COO)2Zn·2H2O, solvent is CH3OH and IPA, wherein the molar ratio of each component of the formed synthetic mother liquor is Hatz: zn2+：IPA：CH3OH：NH3·H2O ═ 6: 5: 600: 150: 60, carrying out the solvothermal reaction for 12 hours in an oven at the temperature of 100 ℃;
(3) modification of the metal organic framework film: adding gamma- (methoxy acryloyl oxy) propyl trimethoxy silane into CH3In OH, stirring for 1 hour, giving a volume ratio of 5: 1, vertically putting the MAF-66 membrane dried in the step (2) into a drying oven at 100 ℃ for reaction for 0.5 hour, taking out, cleaning and drying to obtain the successfully modified MAF-66 membrane.
The prepared membrane M-6 is characterized by small gas separation performance at 25 ℃ and 0.1MPa, and the results of the gas separation experiment are shown in Table 1.
Example 7
A preparation method of a novel membrane material for gas separation comprises the following steps:
(1) and (3) treatment of the support: the mullite support was treated in the same manner as in step (1) of example 1.
(2) Preparing a metal organic framework film: similar to example 1, step (2), except that: the zinc source is Zn powder, and the solvent is CH3OH and DMF, wherein the molar ratio of each component of the formed synthetic mother liquor is Hatz: zn2+：CH3OH：DMF：NH3·H2O is 7: 3.5: 700: 180: 10, carrying out solvothermal reaction for 18 hours in an oven at the temperature of 80 ℃;
(3) modification of the metal organic framework film: adding gamma- (methoxyacryloyl oxy) propyl trimethoxy silane into ethanol, and stirring for 1 hour to obtain a mixture with a volume ratio of 5: 1, vertically putting the MAF-66 membrane dried in the step (2), transferring the membrane into a 50 ℃ oven for reacting for 1.5 hours, taking out, cleaning and drying to obtain the successfully modified MAF-66 membrane.
The prepared membrane M-7 is characterized by small gas separation performance at 25 ℃ and 0.1MPa, and the results of the gas separation experiment are shown in Table 1.
Example 8
A preparation method of a novel membrane material for gas separation comprises the following steps:
(1) and (3) treatment of the support: the procedure of treating the polytetrafluoroethylene-based sheet support was the same as in step (1) of example 1.
(2) Preparing a metal organic framework film: similar to example 1, step (2), except that: the zinc source is ZnCO3The solvent is DMF and EtOH, and the molar ratio of each component of the formed synthetic mother liquor is Hatz: zn2+：DMF：EtOH：NH3·H2O is 4: 2: 500: 160: 50, carrying out solvothermal reaction for 10 hours in an oven at the temperature of 130 ℃;
(3) modification of the metal organic framework film: adding gamma- (methoxyacryloyloxy) propyl trimethoxy silane into DMF, and stirring for 1 hour to obtain a mixture with a volume ratio of 5: 1, vertically putting the MAF-66 membrane dried in the step (2) into a drying oven at 100 ℃ for reaction for 0.5 hour, taking out, cleaning and drying to obtain the successfully modified MAF-66 membrane.
The prepared membrane M-8 is characterized by small gas separation performance at 25 ℃ and 0.1MPa, and the results of gas separation experiments are shown in Table 1.
Example 9
A preparation method of a novel membrane material for gas separation comprises the following steps:
(1) and (3) treatment of the support: the procedure of treating the polytetrafluoroethylene-based sheet support was the same as in step (1) of example 1.
(2) Preparing a metal organic framework film: similar to example 1, step (2), except that: the zinc source is ZnCl2And the molar ratio of each component of the formed synthetic mother liquor is Hatz: zn2+：IPA：EtOH：NH3·H2O is 4: 6: 650: 130: 40, carrying out solvothermal reaction for 15 hours in an oven at the temperature of 110 ℃;
(3) modification of the metal organic framework film: adding 1, 2-ethanediamine to CH3In OH, stirring for 1 hour, giving a volume ratio of 4: the mixed solution of 1 is vertically placed into the MAF-66 membrane dried in the step (2), and is transferred into an oven with the temperature of 70 ℃ for reaction for 1 hour, and the membrane is taken out, cleaned and dried to obtain the successfully modified MAF-66 membrane.
The prepared membrane M-9 is characterized by small gas separation performance at 25 ℃ and 0.1MPa, and the results of the gas separation experiment are shown in Table 1.
Comparative example 1
A preparation method of a novel membrane material for gas separation comprises the following steps:
(1) and (3) treatment of the support: the procedure was the same as in step (1) of example 1.
(2) Preparing a metal organic framework film: the procedure was as in step (1) of example 1, except that the molar ratio of each component of the synthesis mother liquor was adjusted to IPA/EtOH-4, Hatz/Zn (OH)2＝2，Hatz/EtOH＝0.03，NH3·H2O/EtOH＝1。
(3) Modification of the metal organic framework film: the preparation process was the same as in step (3) of example 1.
The prepared membrane M-10 has more membrane cracks, the small gas separation performance is characterized at 25 ℃ and 0.1MPa, and the results of the gas separation experiment are shown in Table 1.
Comparative example 2
A preparation method of a novel membrane material for gas separation comprises the following steps:
(1) and (3) treatment of the support: the procedure was the same as in step (1) of example 1.
(2) Preparing a metal organic framework film: the preparation process was the same as in step (1) of example 1.
(3) Modification of the metal organic framework film: 3-aminopropyltriethoxysilane was added to toluene, and the remaining procedure was the same as in step (3) of example 1.
The prepared membrane M-11 is characterized by small gas separation performance at 25 ℃ and 0.1MPa, and the results of the gas separation experiment are shown in Table 1.
Comparative example 3
A preparation method of a novel membrane material for gas separation comprises the following steps:
(1) and (3) treatment of the support: the procedure was the same as in step (1) of example 1.
(2) Preparing a metal organic framework film: the preparation process was the same as in step (1) of example 1.
(3) Modification of the metal organic framework film: 3-aminopropyltriethoxysilane was replaced with ethylenediamine and added to the ethanol solution, and the other procedure was the same as in step (3) of example 1.
The prepared membrane M-12 is characterized by small gas separation performance at 25 ℃ and 0.1MPa, and the results of the gas separation experiment are shown in Table 1.
Comparative example 4
The preparation method of this example is substantially the same as that of example 1 except that: the molar ratio of each component of the synthesis mother liquor is adjusted to IPA/EtOH-4, Hatz/Zn (OH)2＝2，Hatz/EtOH＝0.03，NH3·H2O/EtOH＝0.6。
The prepared membrane M-13 has more membrane cracks, the small gas separation performance is characterized at 25 ℃ and 0.1MPa, and the results of the gas separation experiment are shown in Table 1.
Comparative example 5
Step (3) was removed, i.e., the membrane was not modified, and the rest was the same as in example 1.
The prepared membrane M-14 is characterized by small gas separation performance at 25 ℃ and 0.1MPa, and the results of gas separation experiments are shown in Table 1.
Comparative example 6
The same procedure as in example 1 was repeated except that the zinc source was added directly to the synthesis mother liquor without adding ammonia water. As a result, MAF-66 material could not be made into a film.
The results of the gas separation performance test of the MAF-66 type metal organic framework films obtained in examples 1 to 9 and comparative examples 1 to 6 are shown in Table 1.
TABLE 1
Figure BDA0002937473450000111
Figure BDA0002937473450000121
As can be seen from the data in Table 1: compared with comparative examples 1, 4 and 6, the addition of ammonia water has a great influence on the gas selectivity of the prepared membrane, because the addition of ammonia water influences the pH value of the solution, the separation performance of the membrane is influenced by over-high and over-low pH values, and the MAF-66 material cannot be prepared into the membrane without adding ammonia water; compared with comparative examples 2 and 3, the modifying agent and the solvent added in the modification process can influence the modification effect, and the gas selectivity of the prepared membrane is greatly reduced; compared with comparative example 5, it was found that the gas selectivity effect of the prepared membrane was very poor, much lower than that of example 1, without modifying the membrane. The MAF-66 type metal organic framework film obtained in the embodiment of the invention is modified to H2/CO2、CO2/CH4The systems all show better separation performance, and all far exceed Knudsen diffusion; especially example 1, for H2/CO2、CO2/CH4Up to 9.90 and 5.63, H2Permeability of 15.80X 10-9mol/m2·S1·Pa1And has the most excellent separation performance.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.

Claims (10)

1. A preparation method of a novel membrane material for gas separation is characterized by comprising the following steps:
s1, preparation of membrane synthesis mother liquor: mixing and stirring the 3-amino-1, 2, 4-triazole ligand solution and the zinc source solution uniformly to obtain a membrane synthesis mother solution;
s2, preparation of a metal organic framework film: placing the support body in membrane synthesis mother liquor, and then carrying out a solvothermal reaction to obtain a MAF-66 metal organic framework membrane;
s3, modification of the metal organic framework film: preparing a silane coupling agent solution, and putting the MAF-66 metal organic framework film into the silane coupling agent solution for modification.
2. The method for preparing the novel membrane material for gas separation according to claim 1, wherein the solvent of the triazole ligand solution in step S1 is one or more of ethanol, isopropanol, methanol or N, N-dimethylformamide; the solvent of the zinc source solution is ammonia water, and the zinc source is Zn and ZnCO3、ZnCl2、(CH3COO)2Zn·2H2O、Zn(OH)2ZnO or Zn (NO)3)2·6H2O。
3. The method as claimed in claim 2, wherein the membrane synthesis mother liquor in step S1 comprises the following substances in molar ratio: 3-amino-1, 2, 4-triazole: zn2+: isopropyl alcohol: ethanol: ammonia water (3.5-9.5): (1-10): (500-750): (100-200): (10 to 100) and 0<Ammonia water: the membrane synthesis mother liquor is less than or equal to 0.095.
4. The method of claim 1, wherein the support is pretreated before reaction in step S2: and sequentially polishing the support body by using 800-mesh and 1200-mesh SiC abrasive paper, then ultrasonically cleaning, and drying for later use.
5. The method of claim 1, wherein the support in step S2 comprises porous alumina, porous titania, porous zinc oxide, porous silica, mullite, polytetrafluoroethylene substrate, or glass substrate.
6. The method for preparing a novel membrane material for gas separation according to claim 1, wherein the reaction temperature of the solvothermal reaction in the step S2 is 60-150 ℃, and the reaction time is 8-20 h.
7. The method of claim 1, wherein the solvent of the silane coupling agent solution in step S3 is one or more selected from ethanol, isopropanol, methanol and N, N-dimethylformamide, and the silane coupling agent comprises one or more selected from 3-aminopropyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltrimethoxysilane, γ - (methoxyacryloyloxy) propyltrimethoxysilane and 3-aminopropyltriethoxysilane.
8. The method for preparing a novel membrane material for gas separation according to claim 1, wherein the modification temperature in step S3 is 30-120 ℃ and the modification time is 0.5-3 h.
9. A novel membrane material for gas separation, characterized by being produced according to the production method of any one of claims 1 to 8.
10. A process for the production of a gas as claimed in claim 9Isolated novel membrane material, characterized in that2、CO2、N2、CH4And the application in the separation of two or more gases in the low-carbon alkane gas.
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