CN109012244B - Separation membrane for sulfur dioxide gas separation - Google Patents
Separation membrane for sulfur dioxide gas separation Download PDFInfo
- Publication number
- CN109012244B CN109012244B CN201811063211.4A CN201811063211A CN109012244B CN 109012244 B CN109012244 B CN 109012244B CN 201811063211 A CN201811063211 A CN 201811063211A CN 109012244 B CN109012244 B CN 109012244B
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- membrane
- separation membrane
- layer
- sulfur dioxide
- polyvinylidene fluoride
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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
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- 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
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a separation membrane for separating sulfur dioxide gas. Specifically, the invention discloses a polyvinylidene fluoride-polyalcohol segmented copolymer gas separation membrane for sulfur dioxide separation. In the polyvinylidene fluoride-polyalcohol segmented copolymer gas separation membrane, the molecular weight of a polyvinylidene fluoride block accounts for at least 1000 percent of the total amount of the segmented copolymer, the molecular weight of polyalcohol accounts for at least 100 percent of the total amount of the segmented copolymer, and the molecular weight of the polyvinylidene fluoride block accounts for at least 1 percent of the total amount of the segmented copolymer. The prepared gas separation membrane can be used for separating mixed gas containing sulfur dioxide gas.
Description
Technical Field
The invention relates to a separation membrane for sulfur dioxide gas separation, and particularly discloses a polyvinylidene fluoride-polyalcohol block copolymer gas separation membrane for sulfur dioxide separation. In the polyvinylidene fluoride-polyalcohol segmented copolymer gas separation membrane, the molecular weight of a polyvinylidene fluoride block is at least 4900, the polyvinylidene fluoride block accounts for at least 50% of the total amount of the segmented copolymer, the molecular weight of polyalcohol is at least 100, and the polyvinylidene fluoride block accounts for at least 2% of the total amount of the segmented copolymer. The prepared separation membrane can be used for separating the mixed gas containing sulfur dioxide gas.
Background
The gas is separated by the polymer membrane due to different permeation speeds, and the separation performance is related to the gas molecules, the structural property of the membrane, the interaction between the gas separation and the membrane and other factors. The diffusion mechanism is the main separation mechanism of dense gas separation membranes. The dissolving and diffusing capacities of different gases in the separation membrane are different, so that the gas separation is realized. Sulfur dioxide, which is a condensed gas, has a high solubility in most polymer materials, and therefore, in the separation of sulfur dioxide from gases such as carbon dioxide, nitrogen, and oxygen, the solubility of sulfur dioxide in the membrane is improved as much as possible during the design of the membrane material, and the separation coefficient is further improved.
In the current commonly used membrane materials, the polyvinylidene fluoride material has the characteristics of excellent chemical stability, thermal stability, acid and alkali resistance and the like, so that the polyvinylidene fluoride material is prepared into a compact gas separation membrane, and has wide application space in the field of gas separation. However, the separation membrane prepared by only using polyvinylidene fluoride material has low solubility and permeability coefficient of sulfur dioxide, and is difficult to realize rapid separation.
Disclosure of Invention
The invention provides a separation membrane for separating sulfur dioxide gas, aiming at the technical problems in the prior art. The polyvinylidene fluoride-polyalcohol segmented copolymer is used as a membrane material to prepare a gas separation membrane, and the rapid separation of sulfur dioxide gas is realized by improving the osmotic diffusion coefficient of sulfur dioxide.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a separation membrane for separating sulfur dioxide gas is characterized in that,
(a) the multilayer structure has a support layer and an entrapment functional layer formed thereon, and the interface of the entrapment functional layer and the support layer is a continuous structure.
(b) The interception functional layer and the supporting layer are both of porous structures, the diameter of a surface membrane hole of the interception functional layer is 0.1-1 nanometer, and the diameter of a surface membrane hole of a bonding part of the supporting layer and the interception functional layer is 10-1000 nanometers. The diameter of the membrane pores on the surface of the interception function layer is smaller than that of the membrane pores on the surface of the support layer.
(c) The thickness of the gas separation film is 0.1-1 micron; wherein the thickness of the interception function layer is 0.01-0.5 micron and accounts for 1-50% of the thickness of the separation membrane; the thickness of the supporting layer is 0.5-0.99 microns and accounts for 50-99% of the thickness of the separation film.
(d) The gas separation membrane may be a flat sheet membrane or a hollow fiber separation membrane.
It is also characterized in that: the polyvinylidene fluoride block has a molecular weight of at least 4600, accounts for at least 50% of the total amount of the block copolymer, the polyalcohol has a molecular weight of at least 400, accounts for at least 2% of the total amount of the block copolymer, can be used for separating air and flue gas containing sulfur dioxide gas, and has a permeability coefficient for sulfur dioxide of not less than 4000 barrer.
Wherein the polyalcohol comprises hydrophilic material containing at least one hydroxyl group such as polyethylene glycol, polypropylene glycol, polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, polyethylene glycol methacrylate (PEGMA), polyoxypropylene, polyvinyl alcohol, polypropylene glycol, dextran, chitosan, etc.
The invention has the beneficial effects that:
the separation membrane for separating the sulfur dioxide gas has the characteristic of rapid separation of the mixed gas containing the sulfur dioxide.
Detailed Description
The invention will be further described and illustrated with reference to specific embodiments thereof for the purpose of promoting an understanding and appreciation of the invention.
Example 1
The polyvinylidene fluoride-polyethylene glycol gas separation membrane is prepared by a phase inversion method, and is a flat membrane which has a supporting layer and a retention layer structure and is a continuous structure. The observation of a scanning electron microscope shows that the interception functional layer and the supporting layer are both of porous structures, wherein the surface pore diameter of the interception layer is 1 nanometer, the surface membrane pore diameter of the bonding part of the supporting layer and the interception functional layer is 1000 nanometers, the thickness of the whole flat membrane is 0.1 micrometer, the thickness of the interception layer is 0.01 micrometer, and the thickness of the supporting layer is 0.09 micrometer. The molecular weight of the polyvinylidene fluoride block in the flat membrane is 20000, the molecular weight of the polyethylene glycol is 5000, and the permeability coefficient for sulfur dioxide is 6500 barrer.
Example 2
The polyvinylidene fluoride-polypropylene glycol gas separation membrane is prepared by a phase inversion method, and is a hollow fiber separation membrane which has a supporting layer and an interception layer structure and is a continuous structure. The observation of a scanning electron microscope shows that the interception functional layer and the supporting layer are both of porous structures, wherein the surface pore diameter of the interception layer is 0.1 nanometer, the surface membrane pore diameter of the bonding part of the supporting layer and the interception functional layer is 10 nanometers, the thickness of the hollow fiber separation membrane is 1 micrometer, the thickness of the interception layer is 0.01 micrometer, and the thickness of the supporting layer is 0.99 micrometer. The molecular weight of the polyvinylidene fluoride block in the hollow fiber separation membrane is 4600, the molecular weight of the polyethylene glycol is 400, and the permeability coefficient for sulfur dioxide is 4000 barrer.
Example 3
The polyvinylidene fluoride-polyalcohol gas separation membrane is prepared by a phase inversion method, and is a flat membrane which has a supporting layer and a retention layer structure and is of a continuous structure. The types of polyols in the flat sheet membrane and the membrane performance parameters are shown in table 1.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and equivalents and substitutions made on the above-mentioned technical solutions are included in the scope of the present invention, and the scope of the present invention is defined by the claims.
Claims (1)
1. A separation membrane for separating sulfur dioxide gas, which is characterized by being used for separating air and flue gas containing sulfur dioxide gas, and the permeability coefficient of the separation membrane for sulfur dioxide gas is not lower than 4000 barrer; wherein:
(a) the multilayer structure is provided with a supporting layer and an interception functional layer formed on the supporting layer, and the interface of the interception functional layer and the supporting layer is a continuous structure;
(b) the interception functional layer and the supporting layer are both of porous structures, wherein the diameter of a surface membrane pore of the interception functional layer is 0.1-1 nanometer, and the diameter of a surface membrane pore at the bonding part of the supporting layer and the interception functional layer is 10-1000 nanometers;
the diameter of the membrane hole on the surface of the interception function layer is smaller than that of the membrane hole on the surface of the support layer;
(c) the thickness of the gas separation film is 0.1-1 micron; wherein the thickness of the interception function layer is 0.01-0.5 micron and accounts for 1-50% of the thickness of the separation membrane; the thickness of the supporting layer is 0.5-0.99 micrometers, and accounts for 50-99% of the thickness of the separation film;
(d) the gas separation membrane can be a flat membrane or a hollow fiber separation membrane;
the gas separation membrane is a polyvinylidene fluoride-polyalcohol segmented copolymer, wherein polyalcohol is a hydrophilic material at least containing one hydroxyl group and comprises polyethylene glycol, polypropylene glycol, polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, polyethylene glycol methacrylate, polyoxypropylene, polyvinyl alcohol, polypropylene glycol, glucan and chitosan;
the molecular weight of the polyvinylidene fluoride block is at least 4900, the polyvinylidene fluoride block accounts for at least 50% of the total amount of the block copolymer, the molecular weight of the polyalcohol is at least 100, and the polyvinylidene fluoride block accounts for at least 2% of the total amount of the block copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811063211.4A CN109012244B (en) | 2018-09-12 | 2018-09-12 | Separation membrane for sulfur dioxide gas separation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811063211.4A CN109012244B (en) | 2018-09-12 | 2018-09-12 | Separation membrane for sulfur dioxide gas separation |
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| Publication Number | Publication Date |
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| CN109012244A CN109012244A (en) | 2018-12-18 |
| CN109012244B true CN109012244B (en) | 2021-05-28 |
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| CN115212736A (en) * | 2022-07-15 | 2022-10-21 | 中国科学院烟台海岸带研究所 | Separation membrane for seawater industrial aquaculture water treatment |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201643945U (en) * | 2010-02-09 | 2010-11-24 | 江苏工业学院 | Flue gas desulfurization device |
| US20150025293A1 (en) * | 2013-07-18 | 2015-01-22 | Cms Technologies Holdings, Inc. | Membrane separation of olefin and paraffin mixtures |
| US20150306549A1 (en) * | 2013-11-19 | 2015-10-29 | Applied Membrane Technology, Inc. | Organosiloxane Films for Gas Separations |
| CN106237867A (en) * | 2016-08-10 | 2016-12-21 | 长安大学 | A kind of blend film preparation method and application processing ammonium sulfate industrial waste gas |
| JP2018126729A (en) * | 2017-02-06 | 2018-08-16 | セントラル硝子株式会社 | Separation method of gas |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105435660B (en) * | 2015-12-24 | 2018-09-14 | 中国科学院烟台海岸带研究所 | A kind of antipollution composite multi-layer polymer separation film and preparation method thereof |
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- 2018-09-12 CN CN201811063211.4A patent/CN109012244B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201643945U (en) * | 2010-02-09 | 2010-11-24 | 江苏工业学院 | Flue gas desulfurization device |
| US20150025293A1 (en) * | 2013-07-18 | 2015-01-22 | Cms Technologies Holdings, Inc. | Membrane separation of olefin and paraffin mixtures |
| US20150306549A1 (en) * | 2013-11-19 | 2015-10-29 | Applied Membrane Technology, Inc. | Organosiloxane Films for Gas Separations |
| CN106237867A (en) * | 2016-08-10 | 2016-12-21 | 长安大学 | A kind of blend film preparation method and application processing ammonium sulfate industrial waste gas |
| JP2018126729A (en) * | 2017-02-06 | 2018-08-16 | セントラル硝子株式会社 | Separation method of gas |
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| CN109012244A (en) | 2018-12-18 |
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