CN116078174A - Method for preparing gas separation membrane by interfacial polymerization and application thereof - Google Patents

Method for preparing gas separation membrane by interfacial polymerization and application thereof Download PDF

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CN116078174A
CN116078174A CN202310141030.3A CN202310141030A CN116078174A CN 116078174 A CN116078174 A CN 116078174A CN 202310141030 A CN202310141030 A CN 202310141030A CN 116078174 A CN116078174 A CN 116078174A
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phase solution
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organic phase
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王志
原野
时飞
生梦龙
王纪孝
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Tianjin University
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Abstract

The invention relates to a method for preparing a gas separation membrane by interfacial polymerization and application thereof. According to the invention, the 'oil before water' interfacial polymerization preparation method of firstly contacting an organic phase solution and then contacting an aqueous phase solution is developed by introducing a hydrophobic intermediate layer with high gas permeation flux on the surface of a traditional ultrafiltration membrane. Further adopting polybasic organic amine as water phase monomer, simultaneously introducing surface into water phaseThe active agent and the film forming reaction regulator are coated on the surface of the catalyst to realize the CO production 2 The comprehensive performance of the separation membrane is greatly improved. CO with 25 ℃, 0.50MPa and saturated humidity 2 /N 2 (15/85 vol%) gas mixture test of CO of the films produced 2 Separation performance, CO 2 The permeability can reach 491GPU, CO 2 /N 2 The separation factor can reach 42, and the method has wide application prospect. The invention is high-performance CO 2 The separation membrane interfacial polymerization lays a foundation for large-scale preparation and application.

Description

Method for preparing gas separation membrane by interfacial polymerization and application thereof
Technical Field
The invention belongs to the field of polymer film preparation, and particularly relates to a method for preparing high CO by an improved interfacial polymerization method 2 Permeation selectivity CO 2 The method for separating the composite membrane and the application thereof are suitable for the field of gas separation membranes.
Background
Membrane separation is an emerging technology that utilizes the difference in rate of permeation of gas molecules through a membrane under the action of a driving force (typically, a partial pressure difference). Compared with other carbon trapping methods, the membrane separation method has the advantages of simple process, high operation elasticity and insignificant amplification effect, and has wide application prospect. The membrane may be classified into a symmetrical membrane and an asymmetrical membrane according to differences in structural characteristics. The symmetrical membrane has high mechanical property, but has larger transfer resistance, and the membrane separation process has poor economy; the asymmetric membrane with the ultrathin surface layer structure can independently regulate and control each layer structure, generally has high selectivity and high permeability, and is the future development direction of the separation membrane.
Interfacial polymerization is a process in which a dense, continuous polymer separation layer is formed by chemical reaction at the interface of mutually incompatible two-phase solutions. Compared with the traditional doctor blade method, the interfacial polymerization method involves reaction and diffusion coupling, has complex and difficult regulation and control process, but is easier to obtain a thin and flawless separation layer, has weak dependence on the precision of film-making equipment and has wide application prospect.
The traditional interfacial polymerization method for preparing the membrane is to directly use an ultrafiltration membrane as a base membrane, small-molecule binary organic amine monomers such as piperazine, m-phenylenediamine and the like as water phase monomers, trimesoyl chloride as an organic phase monomer, firstly soak a water phase solution through the base membrane, and then react at a two-phase interface in the organic phase solution, namelyThe separation membrane is prepared by the method of oil after water. The membrane preparation method is widely used for preparing industrial nanofiltration membranes and reverse osmosis membranes, but is difficult to be used in the field of gas separation. This is because the primary layer of the membrane produced by the conventional interfacial polymerization method grows from the pores of the base membrane, and finally a thin and dense rigid separation layer is formed. According to the gas separation membrane "resistance series model", even if there is a small pore penetration depth in the membrane pores, the resistance to gas permeation through the membrane increases significantly, resulting in a drastic decrease in membrane penetration selectivity. Meanwhile, the cross-linked network formed by the two-phase monomer interface reaction used in the traditional interfacial polymerization reaction has extremely strong rigidity, the free volume of the separation layer is smaller, active groups are absent, and CO 2 The permeation selectivity performance is extremely poor. For example, a film produced by a conventional interfacial polymerization method (see comparative example) using piperazine as an aqueous monomer and trimesoyl chloride as an organic monomer has a saturation humidity CO of 0.50MPa at 25 DEG C 2 /N 2 (15/85 vol%) CO under mixed gas conditions 2 The permeability is only 3.7GPU (1gpu=10 -6 cm 3 (STP)cm -2 s -1 cmHg -1 )，CO 2 /N 2 The separation factor was 31.
The membrane element is a basic operation unit for membrane separation, and any separation membrane can be applied only by preparing the membrane element. To reduce concentration polarization, ensure uniform and stable flow of gas and adequate mass transfer within the membrane elements, it is often necessary to fill diamond-shaped webs of intersecting double-layered filaments between the membrane bags. However, high performance thin layer separation layers tend to separate the web from compression and scoring during the rolling of the membrane elements, resulting in an irreversible decrease in membrane performance and even loss of separation selectivity.
Disclosure of Invention
The invention aims to introduce a hydrophobic intermediate layer with high gas permeation flux on the surface of a traditional ultrafiltration membrane, and change the preparation flow of the traditional interfacial polymerization method into a membrane preparation flow of 'the intermediate layer is firstly contacted with an organic phase solution and then reacts at a two-phase interface of an aqueous phase solution', namely 'oil before water', so as to solve the membrane CO caused by pore permeation phenomenon 2 The problem of low permeation selectivity. Simultaneously selects the multi-element organic amine containing tertiary amino as the water phase monomer, simultaneouslyThe water phase is introduced with a surfactant and a film forming reaction regulator, and the film structure is comprehensively regulated and controlled in terms of groups, molecules, aggregation state and the like, so that the prepared film is suitable for high-efficiency CO 2 And (5) separating. Further, the protection of the thin-layer separation layer is realized by coating high-flux flexible polymer on the surface of the prepared multi-layer composite membrane of the high-performance separation layer.
The technical scheme adopted by the invention for achieving the purpose is as follows:
the invention provides a novel high-performance CO 2 The interfacial polymerization preparation method of the separation membrane comprises the following steps:
(1) The hydrophobic flexible polymer with the concentration of 0.025 to 0.1 weight percent is coated on the surface of the ultrafiltration membrane to form the hydrophobic middle layer with high gas permeation flux so as to lead CO thereof to be 2 The permeability is more than or equal to 6000GPU;
(2) Preparing a water phase solution of a polybasic organic amine, an acid absorbent, a surfactant, a film forming reaction regulator and water; or no surfactant is added into the solution;
(3) Preparing binary or polybasic acyl chloride and an organic solvent into an organic phase solution;
(4) Uniformly distributing the organic phase solution monolayer prepared in the step (3) on the surface of the hydrophobic intermediate layer with high gas permeation flux in the step (1), drying, uniformly distributing the aqueous phase solution monolayer prepared in the step (2) on the surface of the intermediate layer treated by the organic phase solution for reaction, and performing heat treatment after blowing off residual liquid on the surface to obtain a separation layer;
(5) And coating a high-flux flexible polymer on the surface of the separation layer to obtain the gas separation membrane.
Wherein the hydrophobic flexible polymer in the step (1) is polydimethylsiloxane or poly (1 (trimethylsilyl) -1-propyne); the ultrafiltration membrane material is polysulfone, polyethersulfone, polyacrylonitrile and the mixture containing the above substances;
preferably, the hydrophobic flexible polymer is polydimethylsiloxane;
preferably, the coating concentration of the polymer is 0.035-0.05 wt%;
preferably, the ultrafiltration membrane material is polysulfone.
Wherein the aqueous phase solution in the step (2) comprises 0.05 to 1.0 weight percent of polybasic organic amine, 0.2 to 1.0 weight percent of acid absorbent, 0 to 0.2 weight percent of surfactant and 0.01 to 0.5 weight percent of film forming reaction regulator;
the polybasic organic amine in the step (2) is one or more of N 'N-bis (3-aminopropyl) methylamine, N-aminoethylpiperazine, N-bis (3-aminopropyl) piperazine, N-bis [3- (methylamino) propyl ] methylamine and 3,3' -diaminodipropylamine;
the acid absorbent is sodium carbonate, sodium bicarbonate and sodium hydroxide;
the surfactant is anionic surfactant such as sodium dodecyl benzene sulfonate, sodium dodecyl benzene sulfate, sodium dodecyl sulfate, etc.;
the film forming reaction regulator is an ether oxygen polymer such as polyvinyl alcohol, polyoxyethylene, polyethylene glycol and the like; or an amino polymer such as polyvinyl amine, polyallylamine, or polyethyleneimine;
preferably, the polybasic organic amine is a mixture of N 'N-bis (3-aminopropyl) methylamine and 3,3' -diaminodipropylamine in a mass ratio of 1:1;
preferably, the acid absorbent is sodium carbonate;
preferably, the surfactant is sodium dodecyl sulfonate;
preferably, the film forming reaction modifier is polyoxyethylene.
Wherein the organic phase solution in the step (3) comprises 0.05 to 1.0 weight percent of binary or polybasic acyl chloride;
the binary or polybasic acyl chloride in the step (3) is one or more of isophthaloyl chloride, terephthaloyl chloride, 1, 4-cyclohexanediyl chloride and trimesoyl chloride; the organic solvent is n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, cycloheptane, n-octane, isoparaar G, etc.;
preferably, the binary or multi-membered acyl chloride is trimesoyl chloride;
preferably, the organic solvent is cyclohexane.
Wherein the organic phase solution in the step (4) is uniformly distributed on the surface of the hydrophobic intermediate layer with high gas permeation flux for 0.5-2 min at the distribution temperature of 10-30 ℃;
preferably, the contact time with the organic phase solution is 0.8-1.2 min;
preferably, the temperature of the contact with the organic phase solution is 15-22 ℃.
Wherein the reaction time of the aqueous phase solution in the step (4) on the surface of the intermediate layer treated by the organic phase solution is 0.4-2 min, and the reaction temperature is 20-70 ℃; the heat treatment temperature is 50-90 ℃; the heat treatment time is 10-25 min;
preferably, the reaction time with the aqueous phase solution is 0.5-0.7 min;
preferably, the reaction temperature with the aqueous phase solution is 40-60 ℃;
preferably, the heat treatment temperature is 70-80 ℃;
preferably, the heat treatment time is 12-17 min.
Wherein the high-flux flexible polymer material in the step (5) is polydimethylsiloxane or poly (1 (trimethylsilyl) -1-propyne), and the coating concentration of the polymer is 0.02-0.06 wt%;
preferably, the high throughput flexible polymeric material is polydimethylsiloxane;
preferably, the high throughput flexible polymeric material is coated at a concentration of 0.03 to 0.04wt%.
Compared with the prior art, the invention has the following beneficial effects:
the invention improves the traditional interfacial polymerization film-making method, takes the tertiary amino group-containing multi-element organic amine as a water phase monomer, takes the ether oxygen polymer or the amino polymer as a film-forming reaction regulator, and uses an anionic surfactant to accelerate the migration rate of the multi-element organic amine and the film-forming reaction regulator to the two-phase interface. Meanwhile, a protective layer is introduced on the surface of the separation layer to realize the CO of the prepared membrane 2 The separation performance is greatly improved. CO using saturated humidity 2 /N 2 (15/85 vol%) CO of the gas separation membrane produced by the gas mixture test 2 Separation performance. CO at 25℃and 0.50MPa 2 The permeability reaches 491GPU, CO 2 /N 2 The separation factor reaches 42; the CO of the membrane is pressed for 15min by using a diamond-shaped separation net made of PP material with the thickness of 28mil and the warp and weft being woven at 90 DEG on the surface of the membrane with a weight of 5kg 2 Permeability is 53 GPU, CO 2 /N 2 The separation factor is up to 38. The invention is high-performance CO 2 The separation membrane interfacial polymerization lays a foundation for large-scale preparation and application.
The invention has the advantages that:
firstly, the novel interfacial polymerization membrane preparation method of 'oil before water' is adopted, and the organic phase solution is firstly used for swelling the hydrophobic intermediate layer with high gas permeation flux, so that the acyl chloride monomer is embedded into the intermediate layer. When contacting with aqueous phase solution, the organic amine monomer accelerates diffusion to the hydrophobic middle layer with high gas permeation flux under the amphiphilic action of the surfactant, so that the separation membrane grows from the surface of the middle layer to the inner layer, thereby enhancing the interlayer binding force of the multilayer composite membrane. Meanwhile, the existence of the middle layer thoroughly solves the problem of pore permeation in the traditional interfacial polymerization film forming process, and ensures that permeation air is uniformly distributed in the transverse direction so as to quickly pass through the through pore canal of the supporting layer.
Secondly, the invention comprehensively regulates and controls the membrane structure in the aspects of groups, molecules, aggregation state and the like. The method successfully introduces the organic amine and CO into the membrane by taking the tertiary amino group-containing polybasic organic amine as an aqueous phase monomer, the ether oxygen polymer or amino polymer as a membrane forming reaction regulator and the anionic surfactant as a monomer diffusion auxiliary agent 2 Ether oxygen groups with strong affinity and CO promotion in aqueous environments 2 Tertiary amine group with transfer function, further reduces the film forming rigidity of the cross-linked network, improves the free volume of the separating layer, thereby greatly improving the CO of the prepared film 2 Is used for the permeation selectivity of (a).
Finally, on the basis of interfacial polymerization film formation, the invention reduces the influence of screen pressing and scratch on the performance of the thin-layer separation film in the film element rolling process by introducing the high-flux flexible polymer as the protective layer, and ensures the structural integrity of the separation film in the film element.
Drawings
FIG. 1 is a novel high performance CO 2 Schematic diagram of interfacial polymerization preparation method of separation membrane;
FIG. 2 is a SEM image of the surfaces of a polysulfone ultrafiltration membrane, a high gas permeation flux hydrophobic intermediate layer, and a high performance separation layer;
FIG. 3 is a surface and cross-sectional SEM image of the gas separation membrane produced;
fig. 4 is a photograph of the object of example 1 after being pressed by a spacer.
Detailed Description
In order to fully show the function of the protective layer in the film element rolling process, the invention refers to the industrial film element rolling process, the film is placed under a diamond-shaped separation net made of PP material, the thickness of which is 28mil, and the warp and weft of which are woven at 90 degrees, and a weight of 5kg is placed on the separation net for 15 minutes for pressing, and the performance change of the film before and after pressing treatment is examined.
According to the invention, the 'oil before water' interfacial polymerization preparation method of firstly contacting an organic phase solution and then contacting an aqueous phase solution is developed by introducing a hydrophobic intermediate layer with high gas permeation flux on the surface of a traditional ultrafiltration membrane. Furthermore, by introducing a surfactant and a film forming reaction regulator into the water phase and coating a high-flux flexible polymer on the surface of the prepared multi-layer composite film with a high-performance separation layer, CO is realized 2 The comprehensive performance of the separation membrane is greatly improved. CO with 25 ℃, 0.50MPa and saturated humidity 2 /N 2 (15/85 vol%) gas mixture test of CO of the films produced 2 Separation performance, CO 2 The permeability can reach 491GPU, CO 2 /N 2 The separation factor can reach 42, and the method has wide application prospect. The invention is high-performance CO 2 The separation membrane interfacial polymerization lays a foundation for large-scale preparation and application. The invention is further described below with reference to examples:
example 1
(1) Polydimethylsiloxane with the concentration of 0.035 weight percent is coated on a polysulfone ultrafiltration membrane to form a hydrophobic middle layer with high gas permeation flux, and CO thereof 2 The permeability is about 9800GPU;
(2) Preparing an aqueous solution containing 0.05wt% of N 'N-bis (3-aminopropyl) methylamine, 0.05wt% of 3,3' -diaminodipropylamine, 0.4wt% of sodium carbonate, 0.05wt% of sodium dodecyl sulfate and 0.05wt% of polyoxyethylene using deionized water;
(3) Preparing an organic phase solution containing 0.1wt% trimesic chloride by using cyclohexane;
(4) Uniformly distributing the organic phase solution prepared in the step (3) on the surface of the high gas permeation flux hydrophobic interlayer in the step (1) for 1.0min at the constant temperature of 20 ℃; after the residual organic solvent is dried, uniformly distributing the aqueous phase solution monolayer prepared in the step (2) on the surface of the intermediate layer treated by the organic phase solution, and after reacting for 0.6min at the constant temperature of 50 ℃, blowing off the surface residual liquid; treating the primary membrane in an oven with constant temperature of 75 ℃ for 15min to obtain a separation layer;
(5) And (3) coating polydimethylsiloxane with the concentration of 0.03 weight percent on the surface of the separation layer prepared in the step (4) to obtain the gas separation membrane.
CO using saturated humidity 2 /N 2 (15/85 vol%) CO of the gas separation membrane produced by the gas mixture test 2 Separation performance: CO at 25℃and 0.50MPa 2 The permeability reaches 491GPU, CO 2 /N 2 The separation factor reaches 42; the CO of the membrane is pressed for 15min by using a diamond-shaped separation net made of PP material with the thickness of 28mil and the warp and weft being woven at 90 DEG on the surface of the membrane with a weight of 5kg 2 Permeability is 53 GPU, CO 2 /N 2 The separation factor is up to 38.
Example 2
(1) Polydimethylsiloxane with the concentration of 0.075 weight percent is coated on a polyacrylonitrile ultrafiltration membrane to form a hydrophobic middle layer with high gas permeation flux, and CO thereof 2 The permeability is about 6100GPU;
(2) Preparing an aqueous solution containing 1.0wt% of N-aminoethylpiperazine, 1.0wt% of sodium bicarbonate, 0.01wt% of sodium dodecylbenzenesulfonate and 0.5wt% of polyvinyl alcohol using deionized water;
(3) Preparing an organic phase solution containing 1.0wt% terephthaloyl chloride using n-heptane;
(4) Uniformly distributing the organic phase solution prepared in the step (3) on the surface of the high gas permeation flux hydrophobic interlayer in the step (1) for 0.5min at the constant temperature of 30 ℃; after the residual organic solvent is dried, uniformly distributing the aqueous phase solution monolayer prepared in the step (2) on the surface of the intermediate layer treated by the organic phase solution, and after the intermediate layer is reacted for 1.0min at the constant temperature of 20 ℃, blowing off the surface residual liquid; treating the primary membrane in an oven with a constant temperature of 90 ℃ for 10min to obtain a separation layer;
(5) Coating the surface of the separation layer prepared in the step (4) with poly (1 (trimethylsilyl) -1-propyne) with the concentration of 0.06 weight percent to obtain the gas separation membrane.
CO using saturated humidity 2 /N 2 (15/85 vol%) CO of the gas separation membrane produced by the gas mixture test 2 Separation performance: CO at 25℃and 0.50MPa 2 Permeation rate reaches 309GPU, CO 2 /N 2 The separation factor reaches 50; the CO of the membrane is pressed for 15min by using a diamond-shaped separation net made of PP material with the thickness of 28mil and the warp and weft being woven at 90 DEG on the surface of the membrane with a weight of 5kg 2 Permeability of 364GPU, CO 2 /N 2 The separation factor was 45.
Example 3
(1) Poly (1 (trimethylsilyl) -1-propyne) at a concentration of 0.025wt% was coated on a polysulfone-polyethersulfone ultrafiltration membrane to form a high gas permeation flux hydrophobic interlayer with CO 2 The permeability is about 11700GPU;
(2) An aqueous solution containing 0.05wt% N, N-bis (3-aminopropyl) piperazine, 0.2wt% sodium hydroxide, 0.2wt% sodium lauryl sulfate, and 0.25wt% polyvinyl amine was prepared using deionized water;
(3) An organic phase solution containing 0.025wt%1, 4-cyclohexanedicarboxylic acid chloride and 0.025wt% trimesoyl chloride was prepared using n-pentane; (4) Uniformly distributing a monolayer of the organic phase solution prepared in the step (3) on the surface of the hydrophobic intermediate layer with high gas permeation flux in the step (1) for 2.0min at the constant temperature of 10 ℃; after the residual organic solvent is dried, uniformly distributing the aqueous phase solution monolayer prepared in the step (2) on the surface of the intermediate layer treated by the organic phase solution, and after the intermediate layer is reacted for 1.5min at the constant temperature of 60 ℃, blowing off the surface residual liquid; treating the primary membrane in an oven with constant temperature of 65 ℃ for 20min to obtain a separation layer;
(5) And (3) coating polydimethylsiloxane with the concentration of 0.02wt% on the surface of the separation layer prepared in the step (4) to obtain the gas separation membrane.
By means of saturated humidityCO 2 /N 2 (15/85 vol%) CO of the gas separation membrane produced by the gas mixture test 2 Separation performance. CO at 25℃and 0.50MPa 2 Permeation rate reaches to 53 GPU, CO 2 /N 2 The separation factor reaches 26; the CO of the membrane is pressed for 15min by using a diamond-shaped separation net made of PP material with the thickness of 28mil and the warp and weft being woven at 90 DEG on the surface of the membrane with a weight of 5kg 2 GPU, CO with permeability of 560 2 /N 2 The separation factor was 23.
Example 4
(1) Poly (1 (trimethylsilyl) -1-propyne) with concentration of 0.05wt% is coated on polysulfone ultrafiltration membrane to form a high gas permeation flux hydrophobic interlayer, CO thereof 2 The permeability is about 8500GPU; the method comprises the steps of carrying out a first treatment on the surface of the
(2) An aqueous solution containing 0.25wt% N' N-bis (3-aminopropyl) methylamine, 0.25wt% N, N-bis [3- (methylamino) propyl ] methylamine, 0.75wt% sodium bicarbonate, 0.15wt% sodium dodecylbenzene sulfate, and 0.35wt% polyallylamine was prepared using deionized water; (3) Preparing an organic phase solution containing 0.5wt% trimesic chloride by using cyclopentane;
(4) Uniformly distributing a monolayer of the organic phase solution prepared in the step (3) on the surface of the hydrophobic intermediate layer with high gas permeation flux in the step (1) for 0.8min at the constant temperature of 25 ℃; after the residual organic solvent is dried, uniformly distributing the aqueous phase solution monolayer prepared in the step (2) on the surface of the intermediate layer treated by the organic phase solution, and after the intermediate layer is reacted for 0.4min at the constant temperature of 30 ℃, blowing off the surface residual liquid; treating the primary membrane in an oven with constant temperature of 50 ℃ for 25min to obtain a separation layer;
(5) Coating the surface of the separation layer prepared in the step (4) with poly (1 (trimethylsilyl) -1-propyne) with the concentration of 0.04 weight percent to obtain the gas separation membrane.
CO using saturated humidity 2 /N 2 (15/85 vol%) CO of the gas separation membrane produced by the gas mixture test 2 Separation performance. CO at 25℃and 0.50MPa 2 Permeation rate reaches 390GPU, CO 2 /N 2 The separation factor reaches 33; the CO of the membrane is pressed for 15min by using a diamond-shaped separation net made of PP material with the thickness of 28mil and the warp and weft being woven at 90 DEG on the surface of the membrane with a weight of 5kg 2 Permeability of 460 GPU, CO 2 /N 2 The separation factor was 29.
Example 5
(1) Poly (1 (trimethylsilyl) -1-propyne) at a concentration of 0.055wt% was coated onto polysulfone ultrafiltration membrane to form a high gas permeation flux hydrophobic interlayer with CO 2 The permeability is about 8000GPU;
(2) An aqueous solution containing 0.05wt% N 'N-bis (3-aminopropyl) methylamine, 0.15wt%3,3' -diaminodipropylamine, 0.6wt% sodium bicarbonate, 0.02wt% sodium dodecyl sulfate, and 0.1wt% polyethylenimine was prepared using deionized water;
(3) Using n-octane to prepare an organic phase solution containing 0.1wt% terephthaloyl chloride and 0.1wt% trimesoyl chloride;
(4) Uniformly distributing the organic phase solution prepared in the step (3) on the surface of the high gas permeation flux hydrophobic interlayer in the step (1) for 1.0min at the constant temperature of 22 ℃; after the residual organic solvent is dried, uniformly distributing the aqueous phase solution monolayer prepared in the step (2) on the surface of the intermediate layer treated by the organic phase solution, and after the intermediate layer is reacted for 1.2min at the constant temperature of 40 ℃, blowing off the surface residual liquid; treating the primary membrane in an oven with a constant temperature of 80 ℃ for 12min to obtain a separation layer;
(5) And (3) preparing the polydimethylsiloxane with the separation layer surface coating concentration of 0.035wt% in the step (4) to obtain the gas separation membrane.
CO using saturated humidity 2 /N 2 (15/85 vol%) CO of the gas separation membrane produced by the gas mixture test 2 Separation performance: CO at 25℃and 0.50MPa 2 Permeability up to 4984GPU, CO 2 /N 2 The separation factor is up to 30; the CO of the membrane is pressed for 15min by using a diamond-shaped separation net made of PP material with the thickness of 28mil and the warp and weft being woven at 90 DEG on the surface of the membrane with a weight of 5kg 2 Permeability is 541GPU, CO 2 /N 2 The separation factor was 26.
Example 6
(1) Polydimethylsiloxane with the concentration of 0.065 weight percent is coated on the polyacrylonitrile ultrafiltration membrane to form the hydrophobic middle layer with high gas permeation flux, and CO thereof 2 The permeability is about 7200GPU;
(2) Preparing an aqueous solution containing 0.8wt%3,3' -diaminodipropylamine, 0.5wt% sodium bicarbonate, and 0.15wt% polyethylene glycol using deionized water;
(3) Using cyclopentane to prepare an organic phase solution containing 0.4wt% isophthaloyl chloride and 0.4wt% terephthaloyl chloride;
(4) Uniformly distributing a monolayer of the organic phase solution prepared in the step (3) on the surface of the hydrophobic intermediate layer with high gas permeation flux in the step (1) for 1.5min at the constant temperature of 15 ℃; after the residual organic solvent is dried, uniformly distributing the aqueous phase solution monolayer prepared in the step (2) on the surface of the intermediate layer treated by the organic phase solution, and after the intermediate layer is reacted for 2.0min at the constant temperature of 70 ℃, blowing off the surface residual liquid; treating the primary membrane in an oven with constant temperature of 55 ℃ for 22min to obtain a separation layer;
(5) And (3) coating polydimethylsiloxane with the concentration of 0.06wt% on the surface of the separation layer prepared in the step (4) to obtain the gas separation membrane.
CO using saturated humidity 2 /N 2 (15/85 vol%) CO of the gas separation membrane produced by the gas mixture test 2 Separation performance. CO at 25℃and 0.50MPa 2 Permeability up to 349GPU, CO 2 /N 2 The separation factor reaches 27; the CO of the membrane is pressed for 15min by using a diamond-shaped separation net made of PP material with the thickness of 28mil and the warp and weft being woven at 90 DEG on the surface of the membrane with a weight of 5kg 2 Permeability of 41X1pu, co 2 /N 2 The separation factor was 22.
Comparative example
Comparative examples are cited in journal Journal of Membrane Science,2021,618,118572 and Journal of Materials Chemistry A,2018,6,30-35, which are prepared by the process of:
(1) Soaking the porous polysulfone support layer in water for 24 hours;
(2) Immersing the support layer in 2wt% m-phenylenediamine aqueous solution for 5 minutes, and removing surface liquid drops;
(3) By means of
Figure BDA0004087485340000081
Preparing 0.1wt% of trimesic acid chloride solution, pouring the trimesic acid chloride solution on the support layer obtained in the step (2), and reacting for 300s at 20 ℃;
(4) By using
Figure BDA0004087485340000082
And isopropanol was continuously washed three times and dried at room temperature for 48 hours.
The film was tested under pure gas, CO 2 Permeability is only 3.7GPU, CO 2 /N 2 The separation factor was 31.
Test data and conclusions
CO with 25 ℃, 0.50MPa and saturated humidity 2 /N 2 (15/85 vol%) gas mixture test the CO before and after pressing of the gas separation membrane produced 2 The separation properties are shown in table 2.
Table 2 different examples and comparative examples CO before and after the screen compression experiment 2 Separation performance
Figure BDA0004087485340000091
Compared with the comparative example, the invention introduces a high flux hydrophobic intermediate layer on the surface of the ultrafiltration membrane, adopts a novel interfacial polymerization method of 'oil before water', takes tertiary amino group-containing polybasic organic amine as a water phase monomer, takes an anionic surfactant as a monomer diffusion auxiliary agent, and takes an ether oxygen polymer or an amino polymer as a film forming reaction regulator, thereby successfully realizing high performance CO 2 Preparation of a separation membrane. The performance of the prepared film is compared with that of the film prepared by the comparative example 2 The permeability is improved by approximately 132 times, and CO 2 /N 2 The separation factor is improved by 35%.
This is due to: the high-flux hydrophobic middle layer can prevent pore permeation phenomenon in the film forming process, and uniformly distribute permeation air in the transverse direction so as to quickly pass through the through pore canal of the supporting layer; the incorporation of the polybasic organic amine in the membrane promotes CO 2 Tertiary amine group for transferring function, so that the film can be combined with CO under saturated humidity 2 The molecules undergo specific reversible reaction, thereby greatly promoting CO 2 Specific dissolution and diffusion in the membrane; the film forming reaction regulator can regulate and control the crosslinking degree of the polymer separating layer produced by the interfacial polymerization reaction and improve the crosslinking degreeFree volume of film formation, simultaneously introducing CO 2 Ether oxygen radical and primary amino radical with strong affinity function, and improve CO 2 Solubility in the film; the hydrophilic part of the anionic surfactant can be combined with positively charged multi-element organic amine and ether oxygen/amine polymer, and the lipophilic part is adsorbed on the surface of the organic layer, so that the diffusion of the water phase monomer and the film forming reaction regulator to the two-phase interface is promoted, the growth rate and the film forming efficiency of the primary layer are improved, and the compactness of the polymer of the prepared film is regulated.
As described above, the anionic surfactant plays a role in accelerating diffusion of the aqueous monomer and the film formation reaction modifier into the organic layer during the film formation. The addition or non-addition of the reagent only affects the CO of the film 2 Permeability and interfacial polymerization reaction conditions. Example 6 demonstrates that if no surfactant is added to the aqueous solution, a higher reaction temperature and longer reaction time are required during the reaction to grow a dense, defect free separation layer.
The high-flux flexible polymer is coated on the surface of the multi-layer composite membrane of the high-performance separation layer, so that the complete membrane structure of the thin-layer separation layer can be protected to the greatest extent. After being pressed by a screen, the prepared film is CO 2 The selectivity was only slightly reduced (the film produced in example 1 after screen pressing, CO 2 /N 2 The separation factor is reduced by only 9.5 percent), which proves that the high-flux flexible polymer has obvious protective effect on separation, reduces the influence on the performance of the thin-layer separation membrane caused by rubbing, scratching and pressing in the process of processing and manufacturing the membrane element, and is high-performance CO 2 And the separation membrane interfacial polymerization lays a foundation for large-scale preparation and application.
The technical scheme disclosed and proposed by the invention can be realized by a person skilled in the art by appropriately changing the condition route and other links in consideration of the content of the present invention, although the method and the preparation technology of the invention have been described by the preferred embodiment examples, the related person can obviously modify or recombine the method and the technical route described herein to realize the final preparation technology without departing from the content, spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be included within the spirit, scope and content of the invention.

Claims (10)

1. The preparation method of the interfacial polymerization gas separation membrane is characterized by comprising the following steps:
(1) The hydrophobic flexible polymer with the concentration of 0.025 to 0.1 weight percent is coated on the surface of the ultrafiltration membrane to form the hydrophobic middle layer with high gas permeation flux so as to lead CO thereof to be 2 The permeability is more than or equal to 6000GPU;
(2) Preparing a water phase solution of a polybasic organic amine, an acid absorbent, a surfactant, a film forming reaction regulator and water; or no surfactant is added into the solution;
(3) Preparing binary or polybasic acyl chloride and an organic solvent into an organic phase solution;
(4) Uniformly distributing the organic phase solution monolayer prepared in the step (3) on the surface of the hydrophobic intermediate layer with high gas permeation flux in the step (1), drying, uniformly distributing the aqueous phase solution monolayer prepared in the step (2) on the surface of the intermediate layer treated by the organic phase solution for reaction, and performing heat treatment after blowing off residual liquid on the surface to obtain a separation layer;
(5) And coating a high-flux flexible polymer on the surface of the separation layer to obtain the gas separation membrane.
2. The method of claim 1, wherein the hydrophobic flexible polymer is polydimethylsiloxane or poly (1 (trimethylsilyl) -1-propyne); the ultrafiltration membrane material is polysulfone, polyethersulfone, polyacrylonitrile or a mixture containing the above substances.
3. The method of claim 1, wherein the aqueous solution comprises 0.05 to 1.0wt% of the multi-component organic amine, 0.2 to 1.0wt% of the acid absorber, 0 to 0.2wt% of the surfactant, and 0.01 to 0.5wt% of the film forming reaction modifier.
4. The method of claim 1, wherein the polybasic organic amine is one or more of N 'N-bis (3-aminopropyl) methylamine, N-aminoethylpiperazine, N-bis (3-aminopropyl) piperazine, N-bis [3- (methylamino) propyl ] methylamine, 3' -diaminodipropylamine; the acid absorbent is sodium carbonate, sodium bicarbonate and sodium hydroxide; the surfactant is anionic surfactant such as sodium dodecyl benzene sulfonate, sodium dodecyl benzene sulfate, sodium dodecyl sulfate, etc.; the film forming reaction regulator is polymer of ether oxygen such as polyvinyl alcohol, polyoxyethylene, polyethylene glycol, etc., or amino polymer such as polyvinyl amine, polyallylamine, polyethylene imine, etc.
5. The method of claim 1, wherein the organic phase solution comprises 0.05 to 1.0wt% of the di-or poly-acid chloride.
6. The method of claim 1, wherein the binary or multi-membered acyl chloride is one or more of isophthaloyl chloride, terephthaloyl chloride, 1, 4-cyclohexanedicarbonyl chloride, trimesoyl chloride; the organic solvent is n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, cycloheptane, n-octane, isoparaar G, etc.
7. The method according to claim 1, wherein the organic phase solution is uniformly distributed on the surface of the hydrophobic intermediate layer with high gas permeation flux for 0.5 to 2 minutes at a distribution temperature of 10 to 30 ℃.
8. The method according to claim 1, wherein the reaction time of the aqueous phase solution on the surface of the intermediate layer treated by the organic phase solution is 0.4-2 min, and the reaction temperature is 20-70 ℃; the heat treatment temperature is 50-90 ℃; the heat treatment time is 10-25 min.
9. The method of claim 1, wherein the high-throughput flexible polymeric material is polydimethylsiloxane or poly (1 (trimethylsilyl) -1-propyne) and the polymer is applied at a concentration of 0.02 to 0.06wt%.
10. As claimed in claim 1The interfacial polymerization gas separation membrane is applied to CO-containing gas separation 2 Is a gas separation of (a).
CN202310141030.3A 2023-02-21 2023-02-21 Method for preparing gas separation membrane by interfacial polymerization and application thereof Pending CN116078174A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117861456A (en) * 2024-03-12 2024-04-12 中恒新材料科技(山东)有限责任公司 Process for preparing carbon dioxide gas separation membrane by interfacial polymerization method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117861456A (en) * 2024-03-12 2024-04-12 中恒新材料科技(山东)有限责任公司 Process for preparing carbon dioxide gas separation membrane by interfacial polymerization method

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