CN114768544A - UiO-66-NH2Preparation method of hollow fiber mixed matrix membrane - Google Patents

UiO-66-NH2Preparation method of hollow fiber mixed matrix membrane Download PDF

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CN114768544A
CN114768544A CN202210328309.8A CN202210328309A CN114768544A CN 114768544 A CN114768544 A CN 114768544A CN 202210328309 A CN202210328309 A CN 202210328309A CN 114768544 A CN114768544 A CN 114768544A
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uio
hollow fiber
membrane
mixed matrix
fiber mixed
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陈赞
何明
于海斌
臧毅华
袁标
段翠佳
严硕
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China National Offshore Oil Corp CNOOC
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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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
    • 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
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • 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
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • 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
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/104—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide

Abstract

The invention relates to a UiO-66-NH2A method for preparing the hollow fiber mixed matrix membrane. The method prepares UiO-66-NH with small particle size by a solvothermal method2As a filler, the filler is physically and uniformly blended with a polyimide film through ultrasonic dispersion to prepare a spinning solution, then a dry-wet spinning method is adopted to prepare an efficient gas separation hollow fiber mixed matrix film, and the efficient gas separation hollow fiber mixed matrix film is applied to CO2/N2、CO2/CH4、O2/N2And (4) separating. UiO-66-NH synthesized by the invention2The filler avoids stronger interface effect caused by overlarge property difference between the filler and the matrix membrane, and has small particle size and good hydrothermal stability, and the prepared UiO-66-NH2The hollow fiber mixed matrix membrane has high gas permeation flux and is suitable for gas separation.

Description

UiO-66-NH2Preparation method of hollow fiber mixed matrix membrane
Technical Field
The invention belongs to the technical field of high polymer material preparation, and particularly relates to UiO-66-NH2A method for preparing the hollow fiber mixed matrix membrane.
Background
Membrane separation technology has been around the beginning of the 20 th century for over 200 years. The gas separation membrane is a membrane with selective permeability for separating and purifying gases with different components. The membrane separation technology is known as one of the most promising "green technologies" in the future due to the advantages of simple operation, wide application range, simple separation process and equipment, and the like. In addition, the gas membrane separation technology has the advantages of no phase change in the process, low energy consumption, low cost and operation cost, high efficiency, less environmental pollution and the like. Therefore, the membrane separation technology has higher efficiency and economic benefit in the fields of flue gas separation, hydrogen recovery, natural gas purification, organic steam separation, gas dehumidification and the like. With the increasing exploitation of offshore natural gas, the membrane separation technology which is simple to operate and small in occupied area is flexibly applied to the offshore platform, so that the offshore platform has great advantages. Expanding the application of gas separation membranes requires further improvements in the permeation separation performance and stability of the membranes and reduction in the production cost of the membrane modules.
The gas separation membrane has various types, can be divided into different types according to different classification modes, can be divided into a tubular membrane, a flat membrane and a hollow fiber membrane according to different structural forms of the membrane component, and has the advantages of high filling density, low manufacturing cost and 1cm3The effective membrane area of the hollow fiber membrane of the membrane component can reach 10000m2The membrane is 10 times of the advantage of a flat membrane or a frame membrane, and the hollow fiber membrane is more suitable for industrial large-scale application.
The mixed matrix dense membrane prepared from the polymer matrix membrane and the filler is a common dense gas separation membrane at present, and can effectively improve the gas permeation flux and the separation selectivity of the matrix membrane. However, many fillers have large particle size and poor hydrothermal stability, and polymer matrix membranes and fillers are rarely used to prepare hollow fiber mixed matrix membranes.
Disclosure of Invention
Aiming at the phenomenon that the gas permeation flux is greatly improved and the separation selectivity is greatly reduced due to the serious interface effect of the current inorganic filler and the inherent 'balance effect' of a membrane material and the phenomenon that a hollow fiber mixed matrix membrane cannot be prepared by a plurality of porous fillers, the invention develops the UiO-66-NH for gas separation with high gas permeation flux2A method for producing a hollow fiber mixed matrix membrane.
In order to achieve the purpose of the invention, the design idea of the invention is as follows: UiO-66-NH with small grain size and good thermal stability is prepared by solvothermal reaction2. Using the UiO-66-NH2The filler is physically and uniformly blended with the polyimide film through ultrasonic dispersion, and the efficient gas separation hollow fiber mixed matrix film is prepared by adopting a dry-wet spinning method and applied to CO2/N2、CO2/CH4、O2/N2And (5) separating. UiO-66-NH synthesized by the invention2The packing avoids the blockage of the spinning nozzle caused by overlarge grain diameter of the packing. UiO-66-NH2The self-abundant pore structure can provide a rapid transmission channel for gas transmission. Furthermore, UiO-66-NH2The amino group of (2) can also promote CO2Interact with the hollow fiber mixed matrix membrane to promote CO2Solubility coefficient in hollow fiber mixed matrix membranes. Therefore, the gas permeation flux of the polyimide gas separation membrane is greatly improved under the condition of less separation selectivity loss.
The invention provides UiO-66-NH2The preparation method of the hollow fiber mixed matrix membrane comprises the following steps:
(1) zirconium (IV) oxide chloride octahydrate and 2-amino pairAdding phthalic acid into a reactor filled with N, N-dimethylformamide, uniformly stirring at room temperature, adding formic acid, refluxing and stirring for 1-10 hours in an oil bath at 80-200 ℃, centrifuging the product, washing for 2-4 times by using DMF (dimethyl formamide) and acetone respectively, and drying at 50-70 ℃ to obtain UiO-66-NH2；
Wherein the molar ratio of zirconium (IV) chloride octahydrate to 2-aminoterephthalic acid is 1-2, and the molar ratio of zirconium (IV) chloride octahydrate to formic acid is 1: 60-90, wherein the molar ratio of the zirconium (IV) oxide chloride octahydrate to the N, N-dimethylformamide is 1: 40-100;
(2) subjecting the UiO-66-NH obtained in the step 1)2Adding into strong polar solvent, ultrasonic processing for 0.5-6.0h to disperse uniformly, adding polyimide solid, and dissolving completely to obtain spinning solution; pouring the spinning solution into a spinning tank, standing for defoaming, preparing a membrane material by a dry-wet spinning method, carrying out solvent exchange treatment on the membrane material with low volatility, and carrying out heat treatment at 60-100 ℃ in a blast drying oven to obtain UiO-66-NH2A hollow fiber mixed matrix membrane;
wherein the mass fraction of the polyimide in the spinning solution is 20-40%, the loading capacity of the UiO-66-NH2 in the UiO-66-NH2 type hollow fiber mixed matrix membrane is 1-20%, and the strong polar solvent is any one or the mixture of any several of N, N-dimethylacetamide, N-dimethylformamide and N-methylpyrrolidone.
The invention provides UiO-66-NH2In the technical scheme of the preparation method of the hollow fiber mixed matrix membrane, the oil bath temperature in the step 1) is preferably 80-140 ℃.
The invention provides UiO-66-NH2In the technical scheme of the preparation method of the hollow fiber mixed matrix membrane, the polyimide is preferably one of polyetherimide, 6FDA/2,6-DAT and BDTA/2, 6-DAT.
The invention provides UiO-66-NH2In the technical scheme of the preparation method of the hollow fiber mixed matrix membrane, the spinning conditions of the dry-wet spinning method are preferably that the flow rate of a spinning solution is 1-10 ml/min, the flow rate of a core solution is 1-5 ml/min, a coagulation bath is water, the temperature of the coagulation bath is 20-50 ℃, and the hollow fiber mixed matrix membrane is obtainedA fibrous membrane.
The invention further provides UiO-66-NH prepared by the preparation method2The hollow fiber mixed matrix membrane.
Furthermore, the invention also provides the UiO-66-NH2The hollow fiber mixed matrix membrane is applied to carbon dioxide separation, air separation and natural gas decarburization.
The invention has the beneficial effects that: the method adopts filler UiO-66-NH with good hydrothermal stability2And dispersing UiO-66-NH by ultrasonic2The filler and the polymer are physically blended, so that a mixed matrix membrane with good compatibility is prepared, and the reduction of gas separation performance caused by a strong interface effect between the filler and the matrix membrane is avoided. UiO-66-NH2The porous structure of (a) provides a fast channel for gas transport in the mixed matrix membrane. Furthermore, UiO-66-NH2Has amino group to enhance CO2Solubility coefficient in mixed matrix membrane, therefore, the mixed matrix membrane prepared by the invention has high gas permeation flux and CO2/N2And the selectivity is improved.
Drawings
FIG. 1 shows UiO-66-NH in example 1 of the present invention2XRD pattern of (a).
FIG. 2 shows UiO-66-NH in example 1 of the present invention2(a) And a nitrogen adsorption-desorption isotherm and pore size profile of SNW-1 (b).
FIG. 3 shows that 20 wt% UiO-66-NH is loaded in example 2 of the present invention2Scanning Electron Microscope (SEM) images of the outer surface of the type hollow fiber mixed matrix membrane.
FIG. 4 shows that the load of example 3 of the present invention is 10 wt% UiO-66-NH2Scanning Electron Microscope (SEM) image of section of type hollow fiber mixed matrix membrane.
FIG. 5 shows that the load of example 3 of the present invention is 10 wt% UiO-66-NH2Scanning Electron Microscope (SEM) images of the outer surface of the type hollow fiber mixed matrix membrane.
FIG. 6 shows that the load of example 3 of the present invention is 10 wt% UiO-66-NH2Scanning Electron Microscope (SEM) image of the inner surface of type hollow fiber mixed matrix membrane.
Detailed Description
To further illustrate the technical solution of the present invention, the following specific examples are given. It should be understood that the present invention has been shown and described only by way of illustration and description, and it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention or exceeding the scope of the claims.
CO used in the following examples of the invention2、CH4、N2、O2All are high purity gases.
UiO-66-NH prepared by example2The gas separation and detection method of the hollow fiber mixed matrix membrane specifically comprises the following steps:
(1) reacting UiO-66-NH2The hollow fiber mixed matrix membrane is prepared into a small-sized membrane module and then placed in a membrane separation evaluation device.
(2) And after the gas is stably transmitted, testing the gas flow to obtain the permeation flux and the gas selection coefficient of the gas. Wherein the raw material gas is CO2、CH4、N2、O2Any two or more of them. The raw material gas used in the examples and comparative examples was CO2And N2。
Example 1
5mmol of ZrOCl2·8H2Dissolving O and 5mmol of 2-amino terephthalic acid in 389mmol of N, N-Dimethylformamide (DMF), stirring at room temperature for 5min, adding 397.5mmol of formic acid, refluxing and stirring at 140 ℃ for 5h, centrifuging after the reaction is finished, washing with DMF and acetone for 3 times respectively, and drying at 60 ℃ for 24h to obtain UiO-66-NH2(XRD as in FIG. 1), from UiO-66-NH2N of (A)2As can be seen from the adsorption/desorption curves (see FIG. 2), UiO-66-NH2Has very large specific surface area up to 810m2/g。
Preparation of a 5 wt% UiO-66-NH Loading2The hollow fiber mixed matrix membrane of (2): 4.95g of UiO-66-NH2Adding 172.29g of N-methyl pyrrolidone, carrying out ultrasonic treatment for 0.5h,so that it is uniformly dispersed. 94.05g of polyetherimide was added thereto and dissolved completely to obtain a uniform solution, and 28.71g of ethanol was added thereto. And pouring the spinning solution into a spinning tank, standing for defoaming for 2 days, spinning by a dry-wet spinning method by adopting a spinning head with the outer diameter of 0.6mm and the inner diameter of 0.4mm under the conditions that the flow rate of the spinning solution is 3ml/min, the flow rate of a core solution is 1ml/min, a coagulation bath is water, and the temperature of the coagulation bath is room temperature to obtain the hollow fiber membrane. Treating the hollow fiber membrane with water for 48h to remove a large amount of N-methylpyrrolidone, then performing solvent exchange with ethanol and N-hexane, and performing heat treatment at 70 ℃ in a forced air drying oven to obtain UiO-66-NH2The hollow fiber mixed matrix membrane.
Selecting hollow fibers with the length of about 15 cm, filling the hollow fibers into an aluminum film casting head, pouring and sealing the hollow fibers by using epoxy resin to prepare a small-sized membrane module, then putting the membrane module into a hollow fiber membrane gas evaluation device, and calculating the gas separation performance of a hollow fiber mixed matrix membrane by using a soap bubble flowmeter.
The results show that the polyetherimide hollow fiber membrane has CO2And N2Respectively 8.09GPU and 0.56GPU, CO2/N2The selectivity was 15.19. While the load is 5 wt% UiO-66-NH2Hollow fiber mixed matrix membrane CO2And N2Respectively, the permeation flux of (A) is 15.89GPU and 1.59GPU, CO2/N2The selectivity was 15.25.
Example 2
5mmol of ZrOCl2·8H2Dissolving O and 5mmol of 2-amino terephthalic acid in 30mL of N, N-Dimethylformamide (DMF), stirring for 5min at room temperature, adding 397.5mmol of formic acid, stirring at 140 ℃ under reflux for 5h, centrifuging the product after the reaction is finished, washing with DMF and acetone for 3 times respectively, and drying at 60 ℃ for 24h to obtain UiO-66-NH2。
Preparation of 20 wt% UiO-66-NH load2The hollow fiber mixed matrix membrane of (2): 19.8g of UiO-66-NH2172.29g of N-methylpyrrolidone was added and the mixture was subjected to ultrasonic treatment for 0.5 hour to disperse it uniformly. 79.2g of polyetherimide was added thereto and dissolved completely to form a uniform solutionThe solution was then supplemented with 28.71g of ethanol. And pouring the spinning solution into a spinning tank, standing for defoaming for 2 days, spinning by a dry-wet spinning method by adopting a spinning head with the outer diameter of 0.6mm and the inner diameter of 0.4mm under the conditions that the flow rate of the spinning solution is 3ml/min, the flow rate of a core solution is 1ml/min, a coagulation bath is water, and the temperature of the coagulation bath is room temperature to obtain the hollow fiber membrane. Treating the hollow fiber membrane with water for 48h to remove a large amount of N-methylpyrrolidone, then performing solvent exchange with ethanol and N-hexane, and performing heat treatment at 70 ℃ in a forced air drying oven to obtain UiO-66-NH2The hollow fiber mixed matrix membrane.
Selecting hollow fibers with the length of about 15 cm, filling the hollow fibers into an aluminum film casting head, pouring and sealing the hollow fibers by using epoxy resin to prepare a small-sized membrane module, then putting the membrane module into a hollow fiber membrane gas evaluation device, and calculating the gas separation performance of a hollow fiber mixed matrix membrane by using a soap bubble flowmeter.
Example 2 the procedure of example 1 was followed except that 20 wt% of UiO-66-NH was added2。
The results show that the load is 20 wt% UiO-66-NH2CO of polyetherimide mixed matrix hollow fiber membrane2And N2The permeation flux of (A) was 10.56GPU and 0.61GPU, respectively, CO2/N2The selectivity was 15.56.
In the examples, the loading was 20 wt% UiO-66-NH2The outer surface of the hollow fiber mixed matrix membrane (FIG. 3) can be seen to be UiO-66-NH2Agglomeration occurs, resulting in CO2The permeation flux of (a) is decreased.
Example 3
5mmol of ZrOCl2·8H2Dissolving O and 5mmol of 2-amino terephthalic acid in 30mL of N, N-Dimethylformamide (DMF), stirring at room temperature for 5min, adding 397.5mmol of formic acid, refluxing and stirring at 140 ℃ for 5h, centrifuging the product after the reaction is finished, washing with DMF and acetone for 3 times respectively, and drying at 60 ℃ for 24h to obtain UiO-66-NH2。
Preparation of 20 wt% UiO-66-NH load2The hollow fiber mixed matrix membrane of (2): 9.9g of UiO-66-NH2172.29g ofIn N-methyl pyrrolidone, the mixture is subjected to ultrasonic treatment for 0.5h to be uniformly dispersed. 89.1g of polyetherimide was further added and dissolved completely to obtain a uniform solution, and 28.71g of ethanol was added. And pouring the spinning solution into a spinning tank, standing for defoaming for 2 days, spinning by using a dry-wet spinning method by using a spinning head with the outer diameter of 0.6mm and the inner diameter of 0.4mm under the conditions that the flow rate of the spinning solution is 3ml/min, the flow rate of a core solution is 1ml/min, a coagulation bath is water and the temperature of the coagulation bath is room temperature, and thus obtaining the hollow fiber membrane. Treating the hollow fiber membrane with water for 48h to remove a large amount of N-methylpyrrolidone, then performing solvent exchange with ethanol and N-hexane, and performing heat treatment at 70 ℃ in a forced air drying oven to obtain UiO-66-NH2The hollow fiber mixed matrix membrane.
Selecting hollow fibers with the length of about 15 cm, filling the hollow fibers into an aluminum film casting head, pouring and sealing the hollow fibers by using epoxy resin to prepare a small-sized membrane module, then putting the membrane module into a hollow fiber membrane gas evaluation device, and calculating the gas separation performance of a hollow fiber mixed matrix membrane by using a soap bubble flowmeter.
Example 3 the procedure of example 1 is otherwise the same except that 10 wt% of UiO-66-NH is added2。
The results show that the load is 10 wt% UiO-66-NH2CO of polyetherimide mixed matrix hollow fiber membrane2And N2Respectively, the permeation flux of (A) is 32.09GPU and 2.17GPU, CO2/N2The selectivity was 15.63.
In the examples, the supported amount of 10 wt% was uniformly dispersed in the matrix membrane (cross-sectional SEM image shown in fig. 4, external surface SEM image shown in fig. 5, and internal surface SEM image shown in fig. 6), and the mixed matrix hollow fiber membrane was formed. Description of UiO-66-NH2Has better compatibility with a matrix membrane and does not generate agglomeration phenomenon.
Comparative example 1, the procedure of example 1 was otherwise the same except that UiO-66-NH was not added2The resulting product is referred to as a polyetherimide hollow fiber membrane.
The results show that the polyetherimide hollow fiber membrane has CO2And N2Respectively 8.09GPU and 0.56GPU, CO2/N2Selectivity is 15.19。
The above embodiments are only for illustrating the technical idea and features of the present invention, and the purpose of the embodiments is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The invention is not the best known technology.

Claims (6)

1. UiO-66-NH2The preparation method of the hollow fiber mixed matrix membrane is characterized by comprising the following steps:
1) adding zirconium (IV) chloride octahydrate and 2-amino terephthalic acid into a reactor filled with N, N-dimethylformamide, uniformly stirring at room temperature, adding formic acid, refluxing and stirring in an oil bath at the temperature of 80-200 ℃ for 1-10h, centrifuging the product, washing with DMF (dimethyl formamide) and acetone for 2-4 times respectively, and drying at the temperature of 50-70 ℃ to obtain UiO-66-NH2；
Wherein the molar ratio of zirconium (IV) chloride octahydrate to 2-aminoterephthalic acid is 1-2, and the molar ratio of zirconium (IV) chloride octahydrate to formic acid is 1: 60-90, wherein the molar ratio of the zirconium (IV) oxide chloride octahydrate to the N, N-dimethylformamide is 1: 40-100;
2) subjecting the UiO-66-NH obtained in the step 1)2Adding into strong polar solvent, ultrasonic treating for 0.5-6.0 hr to disperse uniformly, adding polyimide solid, and dissolving completely to obtain spinning solution; pouring the spinning solution into a spinning tank, standing for defoaming, preparing a membrane material by a dry-wet spinning method, performing solvent exchange treatment on the membrane material with low volatility, and performing heat treatment at 60-100 ℃ in a forced air drying oven to obtain UiO-66-NH2A hollow fiber mixed matrix membrane;
wherein the mass fraction of the polyimide in the spinning solution is 20-40 percent, and the mass fraction of the polyimide is UiO-66-NH2In UiO-66-NH2The load capacity of the hollow fiber mixed matrix membrane is 1-20%, and the strong polar solvent is any one or any one of N, N-dimethylacetamide, N-dimethylformamide and N-methylpyrrolidoneMeaning a mixture of several.
2. The method according to claim 1, wherein the oil bath temperature in the step 1) is 80 to 140 ℃.
3. The method of claim 1, wherein the polyimide is one of polyetherimide, 6FDA/2,6-DAT, BDTA/2, 6-DAT.
4. The method according to claim 1, wherein the dry-wet spinning method comprises a spinning solution flow rate of 1 to 10ml/min, a bore fluid flow rate of 1 to 5ml/min, a coagulation bath of water, and a coagulation bath temperature of 20 to 50 ℃ to obtain the hollow fiber membrane.
5. UiO-66-NH prepared by the preparation method according to claims 1 to 42The hollow fiber mixed matrix membrane.
6. The UiO-66-NH of claim 52The hollow fiber mixed matrix membrane is applied to carbon dioxide separation, air separation and natural gas decarburization.
CN202210328309.8A 2022-03-31 2022-03-31 UiO-66-NH2Preparation method of hollow fiber mixed matrix membrane Pending CN114768544A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115253611A (en) * 2022-07-23 2022-11-01 大连理工大学盘锦产业技术研究院 Mixed matrix membrane CO accurately regulated and controlled by using specific surface area of filler2Method for separating properties

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115253611A (en) * 2022-07-23 2022-11-01 大连理工大学盘锦产业技术研究院 Mixed matrix membrane CO accurately regulated and controlled by using specific surface area of filler2Method for separating properties
CN115253611B (en) * 2022-07-23 2023-05-26 大连理工大学盘锦产业技术研究院 Mixed matrix membrane CO accurately regulated and controlled by using specific surface area of filler 2 Method for separating properties

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