CN115501769A - Separation membrane for mixture of propylene and nitrogen and preparation method thereof - Google Patents

Separation membrane for mixture of propylene and nitrogen and preparation method thereof Download PDF

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CN115501769A
CN115501769A CN202211162351.3A CN202211162351A CN115501769A CN 115501769 A CN115501769 A CN 115501769A CN 202211162351 A CN202211162351 A CN 202211162351A CN 115501769 A CN115501769 A CN 115501769A
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mixture
separation membrane
propylene
nitrogen
membrane
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CN115501769B (en
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王晓东
张茜
杜翠花
陈风
黄伟
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Taiyuan University of Technology
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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
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • 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
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0011—Casting solutions therefor
    • 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
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0013—Casting processes
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Abstract

The invention discloses a separation membrane for a mixture of propylene and nitrogen and a preparation method thereof, belonging to the technical field of gas separation membranes. The separation membrane of the mixture of the propylene and the nitrogen is a mixed matrix membrane obtained by chemical reaction, the organic matrix of the separation membrane adopts a mixture of polyether block copolyamide and polyethylene glycol, and the additive is UiO-67-NH 2 Crystals, addition of UiO-67-NH using condensing agent and catalyst 2 The crystals chemically react with the organic matrix to form the separation membrane for the mixture of propylene and nitrogen.

Description

Separation membrane for mixture of propylene and nitrogen and preparation method thereof
Technical Field
The invention relates to the technical field of gas separation membranes, in particular to a separation membrane for a mixture of propylene and nitrogen and a preparation method thereof.
Background
Propylene is one of the most main raw materials in the petrochemical industry, and the propylene capacity in 2021 is 5000 ten thousand tons, which is increased by 11.68 percent on a par. The polypropylene produced by direct polymerization of propylene monomer accounts for 63% of the downstream product demand for propylene. The tail gas discharged in the production process of polypropylene mainly comprises 10-20% of propylene and 75-85% of nitrogen, and the waste of resources can be avoided by separating the propylene from the nitrogen and recycling the propylene.
The cryogenic separation process has high energy consumption, and in order to reduce the separation energy consumption, a cryogenic-membrane separation coupling process is industrially adopted to treat the tail gas for producing polypropylene. The performance of the membrane material is a key factor in determining the energy consumption of the process. At present, the membrane materials used in the process are mainly high polymer membranes such as PEBA2533, PEBA2533/PSF composite membranes, PDA/PDMS/PVDF composite membranes, PDMS/PSF composite membranes, PDMS/PTFE composite membranes and the like.
Polymer membranes often have a limiting relationship between gas permeability and selectivity, known as the "trade-off" effect, i.e., an increase in permeability comes at the expense of selectivity, and vice versa. In order to break through the Trade-off effect, researchers have developed Mixed Matrix Membranes (MMMs) that combine the advantages of inorganic additives and polymer matrices, while achieving both permeability and selectivity improvements.
However, in the process of preparing a mixed matrix membrane using conventional inorganic materials such as molecular sieves having a microporous structure, carbon nanotubes, and silica nanoparticles as additives, problems such as non-uniform distribution of inorganic particles, agglomeration, and interface defects between the inorganic additives and an organic matrix often occur, which may reduce the separation performance of the membrane.
Patent CN104689730A discloses the preparation of mixed matrix membrane for separating CO by using SAPO-34 molecular sieve as inorganic additive and polyether block copolyamide PEBA as polymer matrix 2 Light gas (N) 2 、CH 4 、H 2 、O 2 ) And (4) mixing the gases. The presence of an interface between the molecular sieve and the polymer was observedThe cavities and the molecular sieve show significant agglomeration in the polymer matrix.
The addition of metal-organic framework Materials (MOFs) containing organic ligands to the polymer matrix increased the additive loading and suppressed the defect generation, but significant interfacial defects were still observed. Patent CN112237852A discloses a mixed matrix membrane prepared by using a biomimetic material Bio-ZIF as an additive and polyether block copolyamide Pebax as a polymer matrix. When the Bio-ZIF content is more than 8wt%, poor compatibility of the additive with the organic matrix in the mixed matrix membrane is observed, and interfacial cavities appear, resulting in a decrease in the selectivity of the membrane for CO2/CH 4.
None of the above studies has fundamentally solved the problem of the drawbacks between additives and organic substrates.
Disclosure of Invention
In order to solve at least one aspect of the above problems and disadvantages of the related art, embodiments of the present invention provide a separation membrane for a mixture of propylene and nitrogen and a method for preparing the same. Wherein the organic matrix and the additive are chemically reacted, and the uniformity of the additive can be expected to be improved, the agglomeration of the additive can be prevented, the generation of defects of a two-phase interface can be inhibited, and the performance of the film can be improved.
According to one aspect of the present invention, a separation membrane for a mixture of propylene and nitrogen is provided. The separation membrane for the mixture of propylene and nitrogen is a mixed matrix membrane obtained by chemical reaction, the organic matrix in the separation membrane adopts a blend of polyether block copolyamide and polyethylene glycol, and the additive is UiO-67-NH 2 Crystals, addition of UiO-67-NH using condensing agent and catalyst 2 The crystals chemically react with the organic matrix to form the separation membrane for the mixture of propylene and nitrogen.
According to another aspect of the present invention, there is provided a method for preparing the separation membrane for a mixture of propylene and nitrogen.
The preparation method of the separation membrane for the mixture of propylene and nitrogen comprises the following steps:
(1) Dissolving polyether block copolyamide (PEBA) in a first solvent and adding polyethylene glycol (PEG) to obtain a PEBA/PEG blending solution;
(2) Adding additive UiO-67-NH 2 Adding the mixture into a second solvent, performing ultrasonic oscillation, adding the mixture into a PEBA/PEG blending solution, adding a condensing agent and a catalyst, reacting to obtain a first product, washing, drying, further dissolving to obtain a membrane casting solution, and defoaming;
(3) Pouring the membrane casting solution on a carrier to obtain a wet membrane; drying and removing the excess solvent to obtain the separation membrane with the carrier; or alternatively
The membrane casting solution is poured onto, for example, a flat support (a material such as glass or polytetrafluoroethylene) to obtain a wet membrane, and after drying, the membrane casting is peeled off to obtain the separation membrane.
Compared with the prior art, the technical scheme of the embodiment of the invention can at least realize at least one of the following technical advantages:
(1) According to the embodiment of the invention, the condensing agent and the catalyst are added, so that the MOFs additive and the organic matrix are subjected to chemical reaction, the compatibility between the additive and the organic matrix is greatly improved, the aggregation of the additive and the defect of a two-phase interface in a mixed matrix membrane are inhibited, and the high-quality gas separation membrane is obtained.
(2) Compared with the polymer blend membrane, the mixed matrix membrane prepared by the embodiment of the invention has the advantages that the permeability coefficient and ideal selectivity of gas are simultaneously improved, the membrane preparation process is simple, and the membrane preparation method has obvious industrial application prospect.
Drawings
These and/or other aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the preferred embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a process for producing a separation membrane for a propylene/nitrogen mixture according to the present invention;
FIG. 2 is a small particle size UiO-67-NH prepared in example 1 of the present invention 2 SEM pictures of the crystals;
FIG. 3 is UiO-67-NH prepared in example 1 of the present invention 2 A surface pattern of a mixed matrix film with a content of 5 wt%;
FIG. 4 is UiO-67-NH prepared in example 1 of the present invention 2 A cross-sectional view of the mixed matrix film in an amount of 5 wt%;
FIG. 5 is UiO-67-NH prepared in example 1 of the present invention 2 An infrared spectrum of a mixed matrix membrane with a content of 5 wt%.
Detailed Description
The technical scheme of the invention is further specifically described by the following embodiments and the accompanying drawings. In the specification, the same or similar reference numerals denote the same or similar components. The following description of the embodiments of the present invention with reference to the accompanying drawings is intended to explain the general inventive concept of the present invention and should not be construed as limiting the invention.
In order to obtain a separation membrane of a propylene/nitrogen mixture (or gas) with excellent performance and solve the problem of defects between an additive and an organic matrix in a mixed matrix membrane, the invention provides a method for leading the additive UiO-67-NH to react through a chemical reaction 2 A mixed matrix film with particles and polyether block copolyamide base forming a homogeneous phase and a corresponding preparation method.
First, the present invention provides a separation membrane for a mixture of propylene and nitrogen. The separation membrane for the mixture of propylene and nitrogen is a mixed matrix membrane obtained by chemical reaction, wherein the organic matrix adopts a blend of polyether block copolyamide and polyethylene glycol, and the additive is UiO-67-NH 2 Crystals, addition of UiO-67-NH using condensing agent and catalyst 2 The crystals chemically react with the organic matrix to form the separation membrane for the mixture of propylene and nitrogen.
Selecting a mixture of polyether block copolyamide and polyethylene glycol as an organic matrix film material, and selecting a functionalized metal framework material (UiO-67-NH) 2 ) Is used as an additive, and the novel membrane material is prepared under the action of a condensing agent and a catalyst. The novel membrane material is uniform, has no defects, and has excellent separation performance on propylene and nitrogen. The preparation process is simple and easy for industrial production.
In some embodiments, the polyether block copolyamides have different shore hardnesses and may be one or any combination of PEBA2533, PEBA3533, PEBA4033, PEBA6333, PEBA7033 and PEBA 1657.
In some embodiments, the condensing agent is any one of Dicyclohexylcarbodiimide (DCC), 1, 3-Diisopropylcarbodiimide (DIC), or 1- (3-dimethylaminopropyl) -3-Ethylcarbodiimide (EDCI), or any combination thereof.
In some embodiments, the catalyst is: any one of 4-Dimethylaminopyridine (DMAP) and 1-Hydroxybenzotriazole (HOBT), or any combination thereof.
Preferably, the polyether block co-polyamide is PEBA2533 and the polyethylene glycol is PEG600.
In some embodiments, the separation membrane does not include a support but is formed by drying directly from a support and then removing. Such a separation membrane is generally somewhat thicker because it is intended to provide a certain self-supporting force.
In some embodiments, the separation membrane comprises a carrier comprising carrier PSF or PES. In the case of a carrier, the separation membrane can be made thinner than in the case of no carrier, so that the separation membrane is more permeable to propylene and nitrogen, more efficient in separation, and less costly.
In another aspect, referring to fig. 1, the present invention also provides a method for preparing the above separation membrane for a mixture of propylene and nitrogen. The preparation method of the separation membrane for the mixture of the propylene and the nitrogen comprises the following steps:
(1) Dissolving polyether block copolyamide (PEBA) in a first solvent (after full dissolution) and adding polyethylene glycol (PEG) with required mass or predetermined mass to obtain PEBA/PEG blended solution,
(2) Adding (of a desired or predetermined mass) the additive UiO-67-NH 2 Adding the mixture into a second solvent, performing ultrasonic oscillation (for example, uniformly dispersing the mixture), adding the mixture into a PEBA/PEG (polyethylene glycol-ethylene glycol) blended solution, adding a condensing agent and a catalyst (with required or preset mass), reacting to obtain a (uniform) product, washing, drying, further dissolving to obtain a (uniform and stable) casting solution, and defoaming;
(3) Pouring the casting solution on a carrier to obtain a wet film (with a certain thickness or a preset thickness); after drying, excess solvent is removed to obtain a separation membrane with a carrier.
Alternatively, the casting solution may be poured onto a support having a flat surface (e.g., glass, teflon, etc.) to obtain a wet film, which is dried and then peeled off. The separation membrane thus formed is free of support.
In some embodiments, the first solvent is N, N-dimethylacetamide or N-butanol; the second solvent is N, N-dimethylacetamide or N-butanol. It is understood that the specific type of reagent for the first solvent or the second solvent, which may be the same or different, may be selected by one skilled in the art as desired.
In some embodiments, the vector comprises PSF or PES.
In some embodiments, the support comprises any suitable support material such as polytetrafluoroethylene or glass;
in the step (1), the mass concentration of PEBA is 3-20%, and the amount of added PEG accounts for 5-50% of the mass of PEBA;
in the step (2), the addition amount of the additive is 3-30% of the mass of PEBA.
In some embodiments, in step (2), the time of the sonication is 1 hour (h).
In some embodiments, the molecular weight of the polyethylene glycol may be selected as any one or more of PEG200, PEG400, PEG600, PEG1000, PEG2000, PEG10000, or any combination thereof.
The following detailed description will describe embodiments of the present invention and show the advantages of the technical solutions of the present invention through corresponding technical disclosures.
Under the operating conditions of-30-50 ℃ and 0.1-0.7 MPa, the invention adopts a constant volume variable pressure method and a constant pressure variable volume method to carry out the permeability test on the prepared mixed matrix membrane, and the test gases are propylene/nitrogen (20/80, v/v) mixed gas, pure propylene (99.9%) and pure nitrogen (99.9%).
Example 1
A preparation method of a separation membrane of a mixture of propylene and nitrogen comprises the following steps:
step 1: preparation of Small particle size UiO-67-NH 2 Crystal
(1) 67mg of ZrCl were weighed out 4 Then, the resulting solution was added to 7.5mL of DMF, and the mixture was dissolved with stirring to obtain solution A.
(2) 95.6mg of 2-amino-4, 4' -biphenyldicarboxylic acid was weighed out and added to 7.5mL of DMF, and the solution B was dissolved by stirring sufficiently.
(3) Adding 1.4mL of HAc into the solution A, and uniformly stirring; and adding 1mmol of triethylamine into the solution B, and stirring uniformly.
(4) And adding the two solutions into a polytetrafluoroethylene lining in a concurrent flow manner, sealing, placing in a crystallization kettle, and crystallizing for 24 hours in a drying oven at 120 ℃.
(5) After naturally cooling to room temperature, the mixture was washed 3 times with 30mL of DMF and then dried in a drying oven at 60 ℃ for 24 hours for use.
Step 2: preparation of Mixed matrix membranes
(1) 3.75g of PEBA2533 granulate was dissolved in 19.25g of N, N-dimethylacetamide solvent, sealed and stirred at 70 ℃ for 24h until complete dissolution to give a PEBA solution.
(2) 0.5625g of PEG600 was added to the PEBA solution and stirred at 70 ℃ for 12 hours to obtain a homogeneous PEBA/PEG blend.
(3) 0.075g, 0.1875g, 0.375g, 0.5625g, 0.25g UiO-67-NH were weighed respectively 2 And respectively dissolving the crystals in 2g of N, N-dimethylacetamide solvent, performing ultrasonic treatment for 1h at room temperature to obtain uniformly dispersed suspension, and adding the uniformly dispersed suspension into the PEBA/PEG blended solution. Then, 100. Mu.L of 1, 3-diisopropylcarbodiimide and 0.03g of 4-dimethylaminopyridine were added, and the mixture was sonicated at 60 ℃ for 1 hour, and finally stirred at 70 ℃ for 12 hours to allow complete reaction.
(4) The reaction product obtained is placed in a drying cabinet and dried for 24h at 60 ℃. And adding the dried product into 21.25g of N, N-dimethylacetamide solvent, and stirring at 70 ℃ for 12h to obtain uniform casting solution.
(5) Will getAnd standing the obtained casting solution at 70 ℃ for defoaming for 24h, scraping the film on a glass plate, drying in a vacuum oven at 40 ℃ for 24h, taking out, uncovering the film, and continuously drying in the vacuum oven at 60 ℃ for 24h to volatilize the residual solvent. To obtain a product containing UiO-67-NH 2 The mass fractions of (A) are respectively 2wt%, 5wt%, 10wt%, 15wt% and 20wt% of PEBA/PEG/UiO-67-NH 2 The mixed matrix membrane of (3), i.e., the separation membrane without a carrier according to the present invention.
See FIG. 2 for synthesized small particle size UiO-67-NH 2 The size of the synthesized crystal is uniform, about 200-300 nm, and the crystal has small grain size, which is favorable for the uniform dispersion in the organic matrix.
See FIG. 3, which is the additive UiO-67-NH 2 Surface map of mixed matrix membrane formed after reaction of the crystals with polymer matrix PEBA. The mixed matrix film has smooth and compact surface. The additive is covered by a polymer matrix.
See FIG. 4, which is the additive UiO-67-NH 2 Cross-sectional view of the mixed matrix membrane formed after the reaction of the crystals with the polymer matrix PEBA. It can be seen from the cross-sectional view of the mixed matrix film that the additive is not agglomerated after the chemical reaction, and is uniformly dispersed in the organic matrix, and the additive is well combined with the polymer matrix, and no interface defect occurs.
See FIG. 5, which is a PEBA/PEG blend membrane and additive UiO-67-NH 2 Attenuated total reflectance infrared (ATR-FTIR) profile of mixed matrix film formed after reaction of crystals with polymer matrix PEBA. As can be seen from the figure, the PEBA/PEG blend membrane and the chemically reacted PEBA/PEG/UiO-67-NH 2 The mixed matrix membrane has the characteristic peak of PEBA. Wherein, 3308cm -1 And 1734cm -1 The characteristic peak at (A) is ascribed to the stretching vibration of-O-H bond in the polyamide segment and-C = O bond in the carboxylic acid functional group, 1637cm -1 The absorption peak is attributed to the stretching vibration of H-N in amido bond, and 1369cm -1 The peak is the stretching vibration peak of the amide C-N bond. The peak (1637 cm) corresponding to the amide bond of the mixed matrix membrane obtained by the reaction -1 And 1369cm -1 ) The strength is increased, so to speakMing additive UiO-67-NH 2 -NH in the crystal 2 Successfully reacted with-COOH in the polymer matrix PEBA to form an amide bond.
UiO-67-NH with a thickness of 40 microns at 0.2MPa 2 5wt% of PEBA/PEG/UiO-67-NH 2 The permeability of the mixed matrix membrane (without carrier) is shown in table 1.
Table 1 permeability of separation membrane of example 1
Figure BDA0003860634570000071
Example 2
In another embodiment of the present invention, there is also provided a method for preparing a separation membrane of a mixture of propylene and nitrogen, including the steps of:
step 1: preparation of Small particle size UiO-67-NH 2 Crystal
(1) 67mg of ZrCl were weighed 4 Then, the resulting solution was added to 7.5mL of DMF, and the mixture was dissolved with stirring to obtain solution A.
(2) 95.6mg of 2-amino-4, 4' -biphenyldicarboxylic acid was weighed out and added to 7.5mL of DMF, and the solution B was dissolved by stirring sufficiently.
(3) Adding 1.4mL of HAc into the solution A, and uniformly stirring; and adding 1mmol of triethylamine into the solution B, and stirring uniformly.
(4) And adding the two solutions into a polytetrafluoroethylene lining in a concurrent flow manner, sealing, placing in a crystallization kettle, and crystallizing for 24 hours in a drying oven at 120 ℃.
(5) After naturally cooling to room temperature, the mixture was washed 3 times with 30mL of DMF and then dried in a drying oven at 60 ℃ for 24 hours for use.
Step 2: preparation of Mixed matrix membranes
(1) 3.75g of PEBA2533 granules were dissolved in 19.25g of N, N-dimethylacetamide solvent, sealed and stirred continuously at 70 ℃ for 24h until complete dissolution to give a PEBA solution.
(2) 0.5625g of PEG600 was added to the PEBA solution and stirred at 70 ℃ for 12 hours to obtain a homogeneous PEBA/PEG blend.
(3) Respectively weighing0.075g, 0.1875g, 0.375g, 0.5625g, 0.25g of UiO-67-NH 2 Respectively dissolving the crystals in 2g of N, N-dimethylacetamide solvent, performing ultrasonic treatment at room temperature for 1h to obtain uniformly dispersed suspension, and adding the uniformly dispersed suspension into the PEBA/PEG blended solution. Then, 100. Mu.L of 1, 3-diisopropylcarbodiimide and 0.03g of 4-dimethylaminopyridine were added, and the mixture was sonicated at 60 ℃ for 1 hour, and finally stirred at 70 ℃ for 12 hours to allow complete reaction.
(4) The reaction product obtained was dried in a drying oven at 60 ℃ for 24h. And adding the dried product into 21.25g of N, N-dimethylacetamide solvent, and stirring at 70 ℃ for 12h to obtain uniform casting solution.
(5) And standing the obtained casting solution at 70 ℃ for defoaming for 24h, pouring the casting solution onto a PSF carrier, drying the PSF carrier in a vacuum oven at 40 ℃ for 24h, taking out the PSF carrier, and continuously drying the PSF carrier in the vacuum oven at 60 ℃ for 24h to volatilize the residual solvent. To obtain a product containing UiO-67-NH 2 The mass fractions of (A) are respectively 2wt%, 5wt%, 10wt%, 15wt% and 20wt% of PEBA/PEG/UiO-67-NH 2 The mixed matrix membrane with the PSF carrier of the invention, i.e., the separation membrane of the invention.
UiO-67-NH at 0.2MPa and thickness of 20 microns 2 The mass fraction of the (B) is 5wt% of PEBA/PEG/UiO-67-NH 2 See table 2 for the permeability of the mixed matrix membrane (with PSF vector).
Table 2 permeability of separation membrane of example 2
Figure BDA0003860634570000091
By comparison, the thickness of the separation membrane can be made thinner under the condition of a carrier, so that the permeability of the separation membrane to nitrogen and propylene is improved by 10-30%, and the selection ratio of the gas is correspondingly improved.
As mentioned above, the novel membrane material for separating the mixture of propylene and nitrogen and the preparation method thereof provided by the embodiment of the invention select the blend of polyether block copolyamide and polyethylene glycol as the organic matrix membrane material, and select the functionalized metal framework material (UiO-67-NH) 2 ) Is added toAdding a reagent, and preparing the novel membrane material under the action of a condensing agent and a catalyst. The novel membrane material is uniform, has no defects, and has excellent separation performance on propylene and nitrogen. The preparation process is simple and easy for industrial amplification.
Compared with the prior art, the technical scheme of the embodiment of the invention can at least realize at least one of the following technical advantages:
(1) According to the embodiment of the invention, the condensing agent and the catalyst are added, so that the MOFs additive and the organic matrix are subjected to chemical reaction, the compatibility between the additive and the organic matrix is greatly improved, the agglomeration of the additive and the defect of a two-phase interface in a mixed matrix membrane are inhibited, and the high-quality gas separation membrane is obtained.
(2) Compared with a polymer blend membrane, the mixed matrix membrane prepared by the embodiment of the invention has the advantages that the gas permeability coefficient and ideal selectivity are simultaneously improved, the membrane preparation process is simple, and the industrial application prospect is obvious.
Although a few embodiments of the present general inventive concept have been shown and described, it will be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the general inventive concept, the scope of which is defined in the appended claims and their equivalents.

Claims (10)

1. The separation membrane for the mixture of the propylene and the nitrogen is a mixed matrix membrane obtained by chemical reaction, wherein an organic matrix in the separation membrane adopts a mixture of polyether block copolyamide and polyethylene glycol, and an additive is UiO-67-NH 2 Crystals, addition of UiO-67-NH using condensing agent and catalyst 2 The crystals chemically react with the organic matrix to form the separation membrane for the mixture of propylene and nitrogen.
2. The separation membrane for a mixture of propylene and nitrogen according to claim 1,
the polyether block copolyamide is one or any combination of PEBA2533, PEBA3533, PEBA4033, PEBA6333, PEBA7033 and PEBA 1657.
3. The separation membrane for a mixture of propylene and nitrogen according to claim 1,
the molecular weight of the polyethylene glycol is any one of PEG200, PEG400, PEG600, PEG1000, PEG2000 and PEG10000 or any combination thereof.
4. The separation membrane for a mixture of propylene and nitrogen according to claim 1,
the condensing agent is any one of Dicyclohexylcarbodiimide (DCC), 1, 3-Diisopropylcarbodiimide (DIC) or 1- (3-dimethylaminopropyl) -3-Ethylcarbodiimide (EDCI) or any combination thereof.
5. The separation membrane for a mixture of propylene and nitrogen according to claim 1,
the catalyst is as follows: any one of 4-Dimethylaminopyridine (DMAP) and 1-Hydroxybenzotriazole (HOBT), or any combination thereof.
6. The separation membrane for a mixture of propylene and nitrogen according to claim 1,
the separation membrane further comprises a carrier comprising PSF or PES.
7. A production method of the separation membrane for a propylene and nitrogen mixture according to any one of claims 1 to 6,
the preparation method of the separation membrane for the mixture of propylene and nitrogen comprises the following steps:
(1) Dissolving polyether block copolyamide (PEBA) in a first solvent and adding polyethylene glycol (PEG) to obtain a PEBA/PEG blend solution;
(2) Adding an additive UiO-67-NH 2 Adding the mixture into a second solvent, performing ultrasonic oscillation, adding the mixture into PEBA/PEG blended solution, and addingAdding a condensing agent and a catalyst, reacting to obtain a product, washing, drying, further dissolving to obtain a casting solution, and defoaming;
(3) Pouring the membrane casting solution on a carrier to obtain a wet membrane, and removing redundant solvent after drying to obtain a separation membrane with the carrier; or
And pouring the casting solution on a support to obtain a wet film, drying and then removing the wet film to obtain the separation film.
8. The method of claim 7,
the first solvent is N, N-dimethylacetamide or N-butanol;
the second solvent is N, N-dimethylacetamide or N-butanol.
9. The method of claim 7,
the vector comprises PSF or PES;
the support comprises polytetrafluoroethylene or glass, and the support has a flat surface.
10. The production method according to any one of claims 7 to 9,
in the step (1), the mass concentration of PEBA is 3-20%, and the amount of added PEG accounts for 5-50% of the mass of PEBA;
in the step (2), the additive is added in an amount of 3-30% by mass of PEBA.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2004287427A1 (en) * 2003-10-29 2005-05-19 Baxter International Inc. Process for production of essentially solvent-free small particles
US20080141863A1 (en) * 2006-12-18 2008-06-19 Chunqing Liu Method of Making High Performance Mixed Matrix Membranes Using Suspensions Containing Polymers and Polymer Stabilized Molecular Sieves
CN103100313A (en) * 2011-11-15 2013-05-15 中国科学院大连化学物理研究所 Polyether-b-polyamide (PEBA)/polyethyleneglycol (PEG) or polyoxyethylene (PEO) blend membrane, and preparation and application thereof
CN108097070A (en) * 2017-12-19 2018-06-01 太原理工大学 A kind of polyether block amide gas separation membrane for adulterating zeolite imidazole ester and its preparation method and application
CN109316978A (en) * 2018-10-25 2019-02-12 上海科技大学 A kind of MOFs material and its preparation method and application
CN112604507A (en) * 2020-12-07 2021-04-06 四川华造宏材科技有限公司 Preparation method of high-flux dye separation nanofiltration membrane
US20210236996A1 (en) * 2018-05-16 2021-08-05 Nissan Chemical Corporation Gas separation membrane manufacturing method
US20220002497A1 (en) * 2018-10-30 2022-01-06 University Of Notre Dame Du Lac Block polymer composite membranes

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2004287427A1 (en) * 2003-10-29 2005-05-19 Baxter International Inc. Process for production of essentially solvent-free small particles
US20080141863A1 (en) * 2006-12-18 2008-06-19 Chunqing Liu Method of Making High Performance Mixed Matrix Membranes Using Suspensions Containing Polymers and Polymer Stabilized Molecular Sieves
CN103100313A (en) * 2011-11-15 2013-05-15 中国科学院大连化学物理研究所 Polyether-b-polyamide (PEBA)/polyethyleneglycol (PEG) or polyoxyethylene (PEO) blend membrane, and preparation and application thereof
CN108097070A (en) * 2017-12-19 2018-06-01 太原理工大学 A kind of polyether block amide gas separation membrane for adulterating zeolite imidazole ester and its preparation method and application
US20210236996A1 (en) * 2018-05-16 2021-08-05 Nissan Chemical Corporation Gas separation membrane manufacturing method
CN109316978A (en) * 2018-10-25 2019-02-12 上海科技大学 A kind of MOFs material and its preparation method and application
US20220002497A1 (en) * 2018-10-30 2022-01-06 University Of Notre Dame Du Lac Block polymer composite membranes
CN112604507A (en) * 2020-12-07 2021-04-06 四川华造宏材科技有限公司 Preparation method of high-flux dye separation nanofiltration membrane

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
PUTU DODDY SUTRISNA, ET AL: "Surface functionalized UiO-66/Pebax-based ultrathin composite hollow fiber gas separation membranes", J. MATER. CHEM. A, pages 918 - 931 *
XI ZHANG,ET AL: "Separation of a C3H6/C2H4 mixture using Pebax 2533/PEG600 blend membranes", CHINESE JOURNAL OF CHEMICAL ENGINEERING, pages 192 - 198 *
冯世超;任吉中;任晓灵;李晖;花开胜;邓麦村;: "聚醚共聚酰胺/聚乙二醇共混膜的制备及其气体渗透性能的研究", 膜科学与技术, no. 05, pages 27 - 33 *
贾明民;冯艺;邱健豪;姚建峰;: "UiO-66的制备、功能化及膜分离研究进展", 化工进展, vol. 37, no. 09, pages 3471 - 3483 *

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