CN114011254B - Mixed matrix membrane with non-equilibrium olefin-alkane screening property - Google Patents
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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
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
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- 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
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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
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/144—Purification; Separation; Use of additives using membranes, e.g. selective permeation
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
- C08F299/028—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight photopolymerisable compositions
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
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- C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
Abstract
The invention provides a mixed matrix membrane with non-equilibrium olefin-alkane screening property, which is prepared by taking ZIF-8 (P-ZIF-8) modified by polyethylene glycol diacrylate as a filler and crosslinked PEGDA as a matrix through in-situ ultraviolet crosslinking polymerization. The invention has the following advantages and beneficial effects: the novel mixed matrix membrane has extremely high separation factor in a non-equilibrium stage, and is far higher than the mixed matrix membrane material reported at present. The non-equilibrium stage of the novel mixed matrix membrane can be quickly, simply and completely regenerated through vacuum and heating treatment, and necessary conditions are provided for the utilization of the non-equilibrium stage. The parallel separation system can lead the membrane material in each component to work in a high-efficiency screening interval through the alternate work of the components, thereby realizing the continuous high-efficiency separation of ethylene/ethane and propylene/propane.
Description
Technical Field
The invention belongs to the technical field of gas membrane separation, and particularly relates to a mixed matrix membrane with unbalanced olefin-alkane screening property.
Background
Ethylene and propylene are important chemical raw materials, are mainly separated from products of an ethylene cracking device by a low-temperature rectification method at present, and have extremely high energy consumption in the separation process. Compared with low-temperature rectification, membrane separation has great advantages in energy consumption, but at present, a high-performance and easily-prepared ethylene and propylene separation membrane material is still lacking. The key to efficient separation of ethylene/ethane and propylene/propane is precise control of the membrane channel dimensions. Due to the close molecular size of ethylene/ethane and propylene/propane (difference less than 0.2 nm), accurate screening of ethylene/ethane and propylene/propane is difficult to realize by de novo design of the structure of the material. In contrast, the pore size of the flexible material can be changed within a certain range due to the deformation of the structure or the rotation of the ligand, so that a more feasible new way is provided for obtaining the desired pore size.
ZIF-8 is assembled by Zn ions and 2-methylimidazole ligands through coordination bonds, is a typical metal-organic framework (MOF) material with flexible framework, and the angle of the ligands can be changed under the external condition or the stimulation of guest molecules, so that the effective pore size of the material is changed within the range of 0.34-0.60 nm. Based on this property, ZIF-8 materials have been intensively studied for propylene/propane separation. Most of propylene/propane separation membrane materials reported at present are polycrystal membranes made of ZIF-8 materials, and although the separation membranes have higher separation factors, the characteristics of high cost and difficult preparation of the polycrystal membranes limit the capacities of scale-up preparation and large-scale production of the polycrystal membranes. The mixed matrix membrane material is relatively easy to realize large-scale preparation and application, but the ethylene/ethane and propylene/propane separation factors of the currently reported mixed matrix membrane are low, and the application requirements are difficult to meet. Therefore, the development of high-performance and easily prepared ethylene and propylene separation membrane materials remains a difficulty in the field of membrane separation.
Disclosure of Invention
In view of the above problems, the present invention provides a mixed matrix membrane with non-equilibrium olefin-alkane sieving property, which has unique and reproducible non-equilibrium sieving property of ethylene/ethane and propylene propane, and can be used for continuous high-efficiency separation of ethylene/ethane and propylene/propane.
The technical scheme of the invention is as follows: a mixed matrix membrane having non-equilibrium alkene-alkane sieving properties, characterized by: the preparation method of the mixed matrix membrane comprises the following steps:
(1) Uniformly dispersing the filler in methanol through ultrasonic treatment to obtain a suspension A;
(2) Adding PEGDA oligomer into the suspension A, and uniformly mixing filler particles and the oligomer by stirring and ultrasonic treatment to obtain suspension B;
(3) Adding a photoinitiator into the suspension B, uniformly mixing the suspension B through stirring and ultrasonic treatment, dripping a proper amount of the obtained casting film liquid between two quartz glass plates with a certain gap, placing the quartz glass plates into an ultraviolet crosslinking instrument, and irradiating the quartz glass plates under ultraviolet light to crosslink and solidify the PEGDA oligomer into a film;
(4) Taking out the film after crosslinking and curing from between the quartz glass plates, and soaking the film in methanol for 3 days to fully dissolve out the oligomer which is not fully crosslinked; then taking out the film, slowly volatilizing the solvent at room temperature, and reducing the film curling and cracking caused by stress; and after the solvent is fully volatilized, carrying out vacuum treatment on the membrane, further volatilizing the residual solvent, and then storing the membrane in a vacuum environment for characterization and testing.
The mixed matrix membrane with the non-equilibrium olefin-alkane screening property is prepared by taking polyethylene glycol diacrylate modified ZIF-8 (P-ZIF-8) as a filler and crosslinked PEGDA as a matrix through in-situ ultraviolet crosslinking polymerization.
Wherein, the filler used in the step (1) is a ZIF-8 (P-ZIF-8) material modified by polyethylene glycol diacrylate (PEGDA).
The synthesis of the PEGDA modified ZIF-8 (P-ZIF-8) material comprises the following steps:
(i) Adding 1.0g of zinc hydroxide and 4.0g of 2-methylimidazole into a mortar, and grinding for 30min to uniformly mix the zinc hydroxide and the 2-methylimidazole;
(ii) The trituration was continued for 2 hours, during which 3.0mL of a 1mol/L solution of PEGDA in methanol was added dropwise in several portions. During the mechanical grinding process, zinc hydroxide and 2-methylimidazole are coordinated and combined and gradually converted into ZIF-8. Meanwhile, PEGDA molecules are modified in the structure of the ZIF-8 material in situ through the chelation between ester groups and Zn nodes;
(iii) The obtained powder was dispersed in 100mL of methanol and allowed to stand for 30min to separate the unreacted zinc hydroxide precipitate. Centrifuging the upper suspension to separate out a crude product of the P-ZIF-8, soaking in methanol, centrifuging and cleaning for several times, and removing unreacted 2-methylimidazole ligand to obtain the required P-ZIF-8 filler.
Wherein the PEGDA oligomer used in the step (3) is the same as the PEGDA used for synthesizing the P-ZIF-8, and the molecular weight of the PEGDA oligomer is 700g/mol. The mixed matrix membrane obtained by crosslinking the PEGDA based on the molecular weight has higher permeability.
Wherein, the total mass fraction of the P-ZIF-8 and the PEGDA in the suspension in the step (3) is 50 percent, so that the crosslinked membrane has enough mechanical strength.
Wherein the photoinitiator used in the step (4) is 2,2-dimethoxy-2-phenylacetophenone (DMPA), and the dosage of the photoinitiator is 0.1wt%.
Wherein the wavelength of the ultraviolet light used in the step (4) is 302nm, and the irradiation time is 60s.
Wherein, the rotation degree of the 2-methylimidazole ligand in the ZIF-8 structure is influenced by the degree of freedom of a PEGDA molecular chain: the smaller the degree of freedom of a PEGDA molecular chain, the stronger the constraint effect on the rotation of the ZIF-8 ligand is, and the smaller the effective pore size is; the larger the degree of freedom of a PEGDA molecular chain is, the weaker the binding effect of the rotation of the ZIF-8 ligand is, and the larger the effective pore size is; in the permeation process of the propylene/propane and ethylene/ethane mixed gas, the polymer matrix is gradually plasticized along with the dissolution of gas molecules, so that the degree of freedom of a PEGDA molecular chain is gradually increased, and the effective pore size of the ZIF-8 in the membrane is gradually expanded; therefore, there is a period of long duration of the non-equilibrium phase in the propylene/propane, ethylene/ethane mixed gas permeation curve of the mixed matrix membrane. During this stage, propylene (ethylene) molecules of relatively smaller molecular size permeate the membrane in preference to propane (ethane) molecules of relatively larger molecular size, exhibiting extremely high propylene/propane, ethylene/ethane separation factors.
Wherein, the non-equilibrium stage can be quickly, simply and repeatedly regenerated by vacuum and heating treatment, thereby providing necessary conditions for the application of the non-equilibrium stage in the separation of propylene/propane and ethylene/ethane; through the alternate work of a plurality of assemblies, the membrane material in each assembly can work in a high-efficiency screening interval, so that the continuous high-efficiency separation of ethylene/ethane and propylene/propane is realized.
The invention has the following advantages and beneficial effects:
(1) Provides a new method for accurately regulating and controlling the size of an intramembrane channel.
(2) Provides a novel mixed matrix membrane with extremely high separation factors (the separation factor of ethylene/ethane is more than 20, and the separation factor of propylene/propane is more than 200) in a non-equilibrium stage, which is far higher than the mixed matrix membrane material reported at present.
(3) The non-equilibrium stage of the novel mixed matrix membrane can be quickly, simply and completely regenerated through vacuum and heating treatment, and necessary conditions are provided for the utilization of the non-equilibrium stage.
(4) A plurality of membrane modules are connected in parallel, and membrane materials in each module can work in a high-efficiency screening interval through the alternate work of the modules, so that the continuous high-efficiency separation of ethylene/ethane and propylene/propane is realized.
(5) The membrane material belongs to a mixed matrix membrane, can combine the advantages of a polymer membrane in the aspects of cost and large-scale preparation, and has a good application prospect.
Drawings
FIG. 1 is a graph of propylene/propane permeability and separation factor over time for the novel mixed matrix membrane.
FIG. 2 is a graph of the ethylene/ethane permeability and separation factor of the novel mixed matrix membrane as a function of time.
FIG. 3 is a scanning electron microscope image of the cross section of the novel mixed matrix membrane.
FIG. 4 is a graph of the reproducibility test of the non-equilibrium phase of the novel mixed matrix membrane.
FIG. 5 is a schematic diagram of a membrane module parallel separation system and its use for continuous separation in a propylene/propane single stage membrane process.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific embodiments, but the invention is not limited thereto, and any modification or replacement within the basic spirit of the embodiments of the present invention will still fall within the scope of the present invention.
Example 1 preparation of a novel mixed matrix membrane comprising the steps of:
(1) Dispersing 0.12g P-ZIF-8 in 0.20g of methanol, and performing ultrasonic treatment and stirring treatment to form a P-ZIF-8 suspension;
(2) Adding 0.08g of PEGDA into the suspension, and uniformly mixing the suspension by sufficient ultrasonic and stirring treatment;
(3) To the above suspension was added 0.004g of DMPA, sonicated and stirred for 1 hour to dissolve the DMPA sufficiently and mix well. Approximately 0.5mL of the resulting cast film was dropped between two quartz glass plates with a gap, and then placed in an ultraviolet crosslinking apparatus (UVP CL-1000M) and irradiated for 60 seconds under ultraviolet light having a wavelength of 302nm to crosslink and cure the PEGDA oligomer into a film.
(4) The crosslinked and cured film was taken out from between the quartz glass plates and immersed in methanol for 3 days to sufficiently dissolve the oligomer which was not sufficiently crosslinked. The film was then removed and the solvent slowly evaporated at room temperature to reduce stress induced curling and cracking of the film. And after the solvent is fully volatilized, carrying out vacuum treatment on the membrane, further volatilizing the residual solvent, and then storing the membrane in a vacuum environment for characterization and testing.
FIG. 1 is a graph showing the permeation profile of an equimolar mixture of propylene and propane at 20 ℃ under a pressure drop of 0.3MPa for the novel mixed matrix membrane prepared in this example. FIG. 2 is a graph showing the permeation profile of the equimolar ethylene/ethane mixed gas at 0.3MPa pressure drop and 0 ℃ for the novel mixed matrix membrane prepared in this example. As can be seen from fig. 1 and fig. 2, the mixed matrix membrane prepared in this example has a non-equilibrium stage with a time length of about 8 hours in the process of permeation of equimolar propylene/propane mixed gas under a pressure drop of 0.3MPa and at 20 ℃, and the propylene/propane separation factor is always greater than 200 in this stage, i.e. the purity of propylene in the permeation gas is always higher than 99.5%. Under the conditions of 0.3MPa pressure drop and 0 ℃, a non-equilibrium stage with the length of a period of about 3 hours exists in the process of permeation of the equimolar ethylene/ethane mixed gas, and the ethylene/ethane separation factor is always greater than 20 in the non-equilibrium stage.
FIG. 3 is a scanning electron micrograph of a cross section of the novel mixed matrix membrane prepared according to this example, 60% ZIF-8/XLPOE. As can be seen from FIG. 3, the P-ZIF-8 particles are uniformly distributed within the mixed matrix film and there are no significant defects between the filler and the polymer.
Fig. 4 shows the results of the reproducibility test in the non-equilibrium stage of the novel mixed matrix membrane prepared in this example. The membrane regeneration treatment conditions after each permeation are shown as vacuum treatment at 60 ℃ for 2 hours. As can be seen from fig. 4, the non-equilibrium stage of the prepared novel mixed matrix membrane can be easily, rapidly and repeatedly regenerated, which provides the necessary conditions for the utilization of the non-equilibrium stage.
FIG. 5 is a schematic diagram of a membrane module parallel separation system and its use for continuous separation in a propylene/propane single stage membrane process (the straight through valve in the figure defaults to a closed state). Taking the novel mixed matrix membrane prepared in this example as an example, when the feed gas upstream of the membrane is an equimolar propylene/propane mixed gas, the pressure difference across the membrane is 0.3MPa, and the test temperature is 20 ℃, if the separation system is operated in the following manner, continuous separation of propylene with polymerization-grade purity (99.5%) can be achieved by a single-stage membrane process.
(1) Opening the air source valve and the valves (V-1U and V-1D) at the upstream and downstream of the component 1, and starting the component 1 to work;
(2) After the permeation lasts for 7 hours, closing the V-1U and the V-1D, carrying out vacuum and heating treatment on the component 1, and starting the regeneration of the membrane in the component 1; the valves (V-2U and V-2D) upstream and downstream of the module 2 are opened, and the module 2 starts to work;
(3) After the permeation lasts for 7 hours, closing the V-2U and the V-2D, carrying out vacuum and heating treatment on the component 2, and starting the regeneration of the membrane in the component 2; the valves (V-3U and V-3D) upstream and downstream of the module 3 are opened, and the module 3 starts to work;
(4) After the permeation lasts for 7 hours, closing the V-3U and the V-3D, performing vacuum and heating treatment on the component 3, and starting the regeneration of the membrane in the component 3; the valves (V-4U and V-4D) upstream and downstream of the module 4 are opened, and the module 4 starts to work;
(5) After the permeation lasts for 7 hours, closing V-4U and V-4D, carrying out vacuum and heating treatment on the component 4, and starting the regeneration of the membrane in the component 4; when the regeneration of the membrane in the component 1 is finished, the valves (V-1U and V-1D) at the upstream and downstream of the component 1 are opened, and the component 1 starts to work;
(6) The above steps are repeated.
Examples 2 to 7
The preparation method of the novel mixed matrix membrane in examples 2 to 7 was substantially the same as that in example 1, except that the mass ratio of P-ZIF-8 to PEGDA in the casting solution was different. The specific differences and results obtained are given in the following table:
Claims (1)
1. a mixed matrix membrane having non-equilibrium alkene-alkane sieving properties, characterized by: the preparation method of the mixed matrix membrane comprises the following steps:
(1) Uniformly dispersing the filler in methanol through ultrasonic treatment to obtain a suspension A;
(2) Adding PEGDA oligomer into the suspension A, and uniformly mixing filler particles and the oligomer by stirring and ultrasonic treatment to obtain suspension B;
(3) Adding a photoinitiator into the suspension B, uniformly mixing the suspension B through stirring and ultrasonic treatment, dripping a proper amount of the obtained casting film liquid between two quartz glass plates with a certain gap, placing the quartz glass plates into an ultraviolet crosslinking instrument, and irradiating the quartz glass plates under ultraviolet light to crosslink and solidify the PEGDA oligomer into a film;
(4) Taking out the film after crosslinking and curing from the space between the quartz glass plates, and soaking the film in methanol for 3 days to fully dissolve out the oligomer which is not fully crosslinked; then taking out the film, slowly volatilizing the solvent at room temperature, and reducing the film curling and cracking caused by stress; after the solvent is fully volatilized, carrying out vacuum treatment on the membrane, further volatilizing the residual solvent, and then storing the membrane in a vacuum environment for characterization and testing;
the filler used in the step (1) is PEGDA modified ZIF-8 (P-ZIF-8) material;
the synthesis of PEGDA modified ZIF-8 (P-ZIF-8) material comprises the following steps:
(i) Adding 1.0g of zinc hydroxide and 4.0g of 2-methylimidazole into a mortar, and grinding for 30min to uniformly mix the zinc hydroxide and the 2-methylimidazole;
(ii) Continuously grinding for 2 hours, and dripping 3.0mL of 1mol/L PEGDA/methanol solution for multiple times in the period; in the mechanical grinding process, zinc hydroxide and 2-methylimidazole are subjected to coordination combination and gradually converted into ZIF-8; meanwhile, PEGDA molecules are modified in the structure of the ZIF-8 material in situ through the chelation between ester groups and Zn nodes;
(iii) Dispersing the obtained powder in 100mL of methanol, standing for 30min to separate the unreacted zinc hydroxide precipitate; centrifuging the upper suspension to separate a P-ZIF-8 crude product, soaking in methanol, centrifuging, cleaning for several times, and removing unreacted 2-methylimidazole ligand to obtain the required P-ZIF-8 filler;
the PEGDA oligomer used in the step (3) is the same as the PEGDA used for synthesizing the P-ZIF-8, and the molecular weight of the PEGDA oligomer is 700 g/mol;
in the step (3), the total mass fraction of the P-ZIF-8 and the PEGDA in the suspension is 50%;
the photoinitiator used in the step (4) is 2,2-dimethoxy-2-phenylacetophenone (DMPA), and the dosage of the photoinitiator is 0.1 wt%;
the wavelength of the ultraviolet light used in the step (4) is 302nm, and the irradiation time is 60s;
the degree of rotation of the 2-methylimidazole ligand in the ZIF-8 structure is influenced by the degree of freedom of a PEGDA molecular chain: the smaller the degree of freedom of the PEGDA molecular chain is, the stronger the binding effect of the rotation of the ZIF-8 ligand is, and the smaller the effective pore size is; the larger the degree of freedom of a PEGDA molecular chain is, the weaker the binding effect of the rotation of the ZIF-8 ligand is, and the larger the effective pore size is; in the permeation process of the propylene/propane and ethylene/ethane mixed gas, the polymer matrix is gradually plasticized along with the dissolution of gas molecules, so that the degree of freedom of a PEGDA molecular chain is gradually increased, and the effective pore size of the ZIF-8 in the membrane is gradually expanded; therefore, in the propylene/propane, ethylene/ethane mixed gas permeation curve of the mixed matrix membrane, there is a non-equilibrium stage with a longer duration; during this stage, propylene or ethylene molecules with relatively smaller molecular size permeate the membrane in preference to propane or ethane molecules with relatively larger molecular size, showing extremely high separation factors of propylene/propane and ethylene/ethane;
the non-equilibrium stage can be regenerated rapidly, simply and repeatedly by vacuum and heat treatment, thereby providing necessary conditions for the application of the non-equilibrium stage in the separation of propylene/propane and ethylene/ethane; through the alternate work of a plurality of assemblies, the membrane material in each assembly can work in a high-efficiency screening interval, so that the continuous high-efficiency separation of ethylene/ethane and propylene/propane is realized.
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| 界面层极化诱导法制备低晶态MOF超薄膜;乔志华;《膜科学与技术》;第40卷(第04期);79 * |
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