CN111111465A - CO (carbon monoxide)2/N2Gas separation membrane, preparation method and application thereof - Google Patents
CO (carbon monoxide)2/N2Gas separation membrane, preparation method and application thereof Download PDFInfo
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- 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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Abstract
The invention discloses CO2/N2A gas separation membrane, a method for its preparation and use. The preparation method comprises the following steps: carbonizing the polyvinyl chloride film or the polyvinyl chloride powder in an oxygen-free atmosphere to obtain CO2/N2A gas separation membrane. The invention also discloses a gas separation method, which comprises: CO prepared by the aforementioned method2/N2The gas separation membrane will contain CO2And N2CO in the mixed gas2And N2Are separated from each other. The matrix adopted by the invention is polyvinyl chloride with poorer thermal stability, the raw materials are wide, and the price is low; the preparation method of the separation membrane is simple and easy to operate, and the separation membrane is used for N2Low adsorption amount or even no adsorption, and can effectively adsorb and separate CO2/N2To CO2/N2Has high selectivity.
Description
Technical Field
The invention relates to a gas separation membrane, in particular to CO2/N2A gas separation membrane and a preparation method and application thereof belong to the technical field of gas separation.
Background
Today, greenhouse effects have a serious impact on the survival and development of human society, and the sources of greenhouse gases are diverse, mainly comprising CO2、CH4Nitrogen oxides and fluorides, etc., wherein CO2Is the most important greenhouse gas. The amount of carbon emitted into the atmosphere by humans has become greater and greater, and 85% of all carbon emissions are in the form of carbon dioxide. Artificially produced CO2Mainly through the burning of chemical industry fuel, for example thermal power factory, steel plant, cement factory etc. wherein mainly with the emission of thermal power factory. Thermal power plants emit a large amount of flue gas, and the emission of carbon dioxide from the gas composition aggravates the greenhouse effect and causes harm to the environment.
In recent years, the part of environmental protection has been paid more and more attention by people, and the emission management of waste gas is stronger and stronger. However, in future development, human society still depends highly on fossil fuel, which inevitably produces a large amount of carbon dioxide, which is an important raw material for chemical production in addition to ecological problems such as greenhouse effect and global warming, and has wide application, such as alkali production industry and sugar production industry. Therefore, much attention has been paid to the separation and recovery of carbon dioxide.
Removing CO from waste gas discharged by chemical fuel combustion2In addition, nitrogen is also present as a main component in the exhaust gas. For example, in flue gas, the content of nitrogen and carbon dioxide exceeds 90%, wherein the content of nitrogen is about 85% and the content of carbon dioxide is about 12%. Thus, as a first step in carbon separation, CO is removed from the exhaust stream of fossil fuel combustion2Especially CO2And N2For reducing greenhouse gases in the atmosphere, recovery of CO2Has important significance.
At present, the following methods are mainly used for separating the carbon dioxide: 1) an absorption separation method, 2) a pressure swing adsorption separation method, 3) a membrane separation method, and 4) a cryogenic separation method. The adsorption method for removing carbon dioxide is based on the principle that carbon dioxide is adsorbed on the surface of an adsorbent or reacts with the adsorbent. The main adsorbents at present are active carbon, zeolite molecular sieves, carbon molecular sieves, silica gel, metal organic framework materials and the like. Table 1 shows the existing pairs of CO2/N2Adsorption results of the adsorption separation material.
Table 1 section already for CO2/N2Separation results of adsorptive separation materials
However, these have been used for CO2/N2Adsorption of separated material pair N2Large adsorption amount of CO2/N2The separation coefficient is low, so that a pair of N is sought2Small adsorption amount of CO2/N2The gas separation membrane material with good separation effect has been the direction of research personnel in the industry for a long time.
Disclosure of Invention
The invention mainly aims at providing CO2/N2CO with good separation effect2/N2A gas separation membrane and a preparation method thereof, thereby overcoming the defects in the prior art.
It is also an object of the present invention to provide said CO2/N2Use of a gas separation membrane.
In order to achieve the purpose, the invention adopts the following technical scheme:
the embodiment of the invention provides CO2/N2A method of making a gas separation membrane, comprising: carbonizing the polyvinyl chloride film or the polyvinyl chloride powder in an oxygen-free atmosphere to obtain CO2/N2A gas separation membrane.
The embodiment of the invention also provides CO prepared by the method2/N2A gas separation membrane.
Preferably, the CO is2/N2Gas separation membrane pair CO2The adsorption amount of (A) is 0.00409-0.414 mmol/g, CO2/N2The separation factor is greater than 101.22.
The embodiment of the invention also provides a gas separation method, which comprises the following steps: with the aforementioned CO2/N2The gas separation membrane will contain CO2And N2CO in the mixed gas2And N2Are separated from each other.
The embodiment of the invention also provides a gas separation device which comprises the CO2/N2A gas separation membrane.
Compared with common polyimide-based carbon films and phenolic resin-based carbon films, the matrix adopted by the invention is polyvinyl chloride with poorer thermal stability, and the carbon film has the advantages of wide raw materials and low price; the preparation method of the separation membrane is simple and easy to operate, and the separation membrane is used for N2Low adsorption amount or even no adsorption, and can effectively adsorb and separate CO2/N2To CO2/N2Has high selectivity and good separation effect.
Drawings
FIG. 1 is a scanning electron micrograph of a polyvinyl chloride carbonized film in example 1 of the present invention.
FIG. 2 is an infrared spectrum of a polyvinyl chloride carbonized film in example 1 of the present invention.
FIG. 3 shows the comparison of the carbonized polyvinyl chloride film against CO at room temperature in example 1 of the present invention2、N2Adsorption isotherm plot for pure component gas adsorption.
FIGS. 4a and 4b are SEM images of the cross section and surface of the carbonized PVC powder at 300 deg.C in example 6 of the present invention.
FIG. 5 is a scanning electron microscope image of polyvinyl chloride powder carbonized at 600 ℃ in example 7 of the present invention.
FIG. 6 is a schematic diagram of a gas adsorber test system.
Description of reference numerals: 1-CO2Gas cylinder, 2-N2The gas cylinder, the 3-He gas cylinder, the 4-vacuum pump, the 5-high pressure sensor, the 6-gas storage device, the 7-pressure regulator, the 8-temperature sensor, the 9-low pressure sensor, the 10-filter, the 11-sample chamber and the 12-temperature controller.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention provides a technical scheme of the present invention through long-term research and a great deal of practice, wherein polyvinyl chloride (PVC) powder is dissolved in an organic solvent to prepare a solution, and the solution is heated, stirred, fully dissolved and dried to obtain a transparent polyvinyl chloride film; carbonizing the polyvinyl chloride film or polyvinyl chloride powder in a tube furnace filled with oxygen-free inert gas to obtain CO2/N2A gas separation membrane. The technical solution, its implementation and principles, etc. will be further explained as follows.
As one aspect of the technical scheme of the invention, the invention relates to CO2/N2A method of making a gas separation membrane, comprising: carbonizing the polyvinyl chloride film or the polyvinyl chloride powder in an oxygen-free atmosphere to obtain CO2/N2A gas separation membrane.
In some embodiments, the temperature of the carbonization treatment is 300-800 ℃ and the time is 60-180 min.
In some embodiments, the preparation method specifically comprises: in an oxygen-free atmosphere, the temperature rise speed is 1-5 ℃/minHeating a polyvinyl chloride film or polyvinyl chloride powder to 300-800 ℃ for carbonization treatment, preserving heat for 60-180 min, and then cooling to room temperature at a cooling rate of 1-5 ℃/min to obtain CO2/N2A gas separation membrane.
In the invention, the polyvinyl chloride film is carbonized at different rates and different temperatures, and CO with different apertures is obtained by controlling2/N2A gas separation membrane.
Further, the oxygen-free atmosphere includes, but is not limited to, a nitrogen atmosphere and/or an inert gas atmosphere such as helium.
In some embodiments, the polyvinyl chloride has a degree of polymerization of 850 to 1200.
Further, the polyvinyl chloride includes any one or a combination of two or more of polyvinyl chloride SG-4, polyvinyl chloride SG-5, polyvinyl chloride SG-6 and the like, but is not limited thereto.
In some embodiments, the preparation method specifically comprises: polyvinyl chloride (PVC) powder is dissolved in an organic solvent and heated to form a polyvinyl chloride solution, which is then applied to a substrate, and the organic solvent is removed to obtain a transparent flat polyvinyl chloride film.
Further, the organic solvent includes any one or a combination of two or more of N, N-dimethylformamide, cyclohexanone, dichloroethane, tetrachloroethane, tetrahydrofuran, and the like, but is not limited thereto.
Further, the concentration of the polyvinyl chloride solution is 10-15 wt%.
Further, the heating temperature is 60-80 ℃.
In some embodiments, the preparation method specifically comprises: and casting the polyvinyl chloride solution on the substrate, drying for 24-48h at the temperature of 60-80 ℃, and volatilizing the organic solvent to obtain the transparent and flat polyvinyl chloride film.
Further, the substrate includes a glass dish, but is not limited thereto.
Wherein, in some more specific embodiments, the CO2/N2Preparation of gas separation MembraneThe method specifically comprises the following steps:
(1) preparing a PVC film: pouring polyvinyl chloride (PVC) powder into a beaker filled with an organic solvent, stirring while pouring to fully dissolve the PVC powder, putting the PVC powder into an oil bath pot at 60-80 ℃ after the PVC powder is uniformly dispersed in the organic solvent to fully dissolve the PVC powder to prepare a solution with the PVC content of 10-15 wt%, cooling to room temperature, casting the solution into a glass culture dish, drying in an oven at 60-80 ℃ for 24-48h, and volatilizing the solvent to finally obtain the transparent and flat PVC film.
(2) Preparation of gas separation membrane: carbonizing the obtained PVC film or directly using PVC powder under the condition of nitrogen, wherein the carbonization temperature is 300-800 ℃, the temperature is kept for 60-180 min, and the heating rate and the cooling rate are both controlled to be 1-5 ℃/min, and finally, CO is obtained2/N2Gas separation membrane for CO2、N2And (5) adsorbing and separating gas.
As another aspect of the present invention, it relates to CO produced by the aforementioned method2/N2A gas separation membrane.
Further, the CO is2/N2Gas separation membrane pair CO2The adsorption amount of (A) is 0.00409-0.414 mmol/g, CO2/N2The separation factor is greater than 101.22.
Further, the CO is2/N2The gas separation membrane is a high-temperature-resistant and chemical-corrosion-resistant carbon membrane.
As another aspect of the present invention, there is provided CO as described above2/N2Gas separation membrane for CO in mixed gas2、N2The method is applied to adsorption separation.
In another aspect of the present invention, a gas separation method includes: with the aforementioned CO2/N2The gas separation membrane will contain CO2And N2CO in the mixed gas2And N2Are separated from each other. Wherein, CO2Is covered with the CO2/N2Gas separation membrane adsorption, and N2Is not adsorbed and realizesCO2And N2Separation of (4).
As another aspect of the present invention, it relates to a gas separation apparatus comprising the aforementioned CO2/N2A gas separation membrane.
In conclusion, by the technical scheme, the adopted matrix is polyvinyl chloride with poorer thermal stability, the raw materials are wide, and the price is low; the preparation method of the separation membrane is simple and easy to operate, and the separation membrane is used for N2Low adsorption amount or even no adsorption, and can effectively adsorb and separate CO2/N2To CO2/N2Has high selectivity and good separation effect.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The test methods in the following examples, which are not specified under specific conditions, are generally carried out under conventional conditions.
The separation factor was calculated in the following examples:
0.1g of a polyvinyl chloride carbide film was mounted in a gas adsorption apparatus as shown in FIG. 5, evacuated at 110 ℃ for 12 hours, and then tested for CO at normal temperature under a certain pressure2、N2The single-component gas adsorption isotherm, the separation coefficient was calculated according to the following formula:
wherein q isiIs the adsorption capacity of the i component, piIs the partial pressure of the i component.
Example 1
Pouring 5g SG-5PVC into a beaker filled with 30ml of N, N-dimethylformamide solvent, stirring while pouring, putting the PVC powder into a 70 ℃ water bath kettle after the PVC powder is uniformly dispersed in the organic solvent, fully dissolving the PVC powder, and then cooling to room temperature. After cooling to room temperature, casting the 14 wt% PVC solution in a glass dish, and placing the glass dish in an oven at 60 ℃ for drying for 24 hours to obtain the flat PVC film. 3g of PVC film is put into a crucible, and is put into a 300 ℃ tube furnace to be carbonized for 3h under the condition of nitrogen, the heating rate is 1 ℃/min, the temperature of the tube furnace is reduced to room temperature, and then the tube furnace is taken out to obtain the carbonized film, wherein, FIG. 1 is a scanning electron microscope picture of the carbonized PVC film in the embodiment, and FIG. 2 is an infrared spectrogram of the carbonized polyvinyl chloride film in the embodiment.
The carbonized film prepared by the method is used for CO2、N2The one-component gas adsorption test was performed and installed in the gas adsorption apparatus shown in fig. 6, and the sample was subjected to degassing treatment before the test. As shown in FIG. 3, the film was carbonized at room temperature against CO2The maximum adsorption capacity of the gas can reach 0.414mmol/g, and the adsorption capacity to N can reach2The adsorption capacity is only 0.00409mmol/g, namely to CO2/N2Has good separation effect.
Example 2
Pouring 10g of SG-6PVC into a beaker filled with 65ml of tetrahydrofuran solvent, stirring while pouring, putting the PVC powder into a water bath kettle at 60 ℃ after the PVC powder is uniformly dispersed in the organic solvent, fully dissolving the PVC powder, and then cooling to room temperature. And after cooling to room temperature, casting the 15 wt% PVC solution in a glass dish, and placing the glass dish in an oven at 70 ℃ for drying for 24 hours to obtain the flat PVC film. And 3g of PVC film is taken and put into a crucible, and is put into a 300 ℃ tubular furnace for carbonization for 3h under the condition of nitrogen, the heating rate is 3 ℃/min, and the tubular furnace is taken out after the temperature is reduced to the room temperature, so that the carbonized film is obtained.
The carbonized film prepared by the method is used for CO2、N2The one-component gas adsorption test was performed and installed in the gas adsorption apparatus shown in fig. 6, and the sample was subjected to degassing treatment before the test. Carbonization of film pair CO at room temperature2The maximum adsorption capacity of the gas can reach 0.40mmol/g, and the adsorption capacity of the gas on CO can reach 0.40mmol/g2/N2Has good separation effect.
Example 3
Pouring 10g SG-5PVC into a beaker filled with 95ml of N, N-dimethylformamide solvent, stirring while pouring, putting the PVC powder into a 70 ℃ water bath kettle after the PVC powder is uniformly dispersed in the organic solvent, fully dissolving the PVC powder, and then cooling to room temperature. And after cooling to room temperature, casting the 10 wt% PVC solution in a glass dish, and placing the glass dish in an oven at 60 ℃ for drying for 24 hours to obtain the flat PVC film. And 3g of PVC film is taken and put into a crucible, and is put into a 300 ℃ tubular furnace for carbonization for 3h under the condition of nitrogen, the heating rate is 1 ℃/min, and the tubular furnace is taken out after the temperature is reduced to the room temperature, so that the carbonized film is obtained.
The carbonized film prepared by the above method was used for CO2, N2 single component gas adsorption test and mounted in a gas adsorption apparatus as shown in fig. 6, and the sample was subjected to degassing treatment before the test. Carbonization of film pair CO at room temperature2The maximum adsorption capacity of the gas can reach 0.42mmol/g, and the adsorption capacity of the gas on CO can reach 0.42mmol/g2/N2Has good separation effect.
Example 4
Pouring 10g of SG-6PVC into a beaker filled with 65ml of tetrahydrofuran solvent, stirring while pouring, putting the PVC powder into a water bath kettle at 60 ℃ after the PVC powder is uniformly dispersed in the organic solvent, fully dissolving the PVC powder, and then cooling to room temperature. And after cooling to room temperature, casting the 15 wt% PVC solution in a glass dish, and placing the glass dish in an oven at 70 ℃ for drying for 24 hours to obtain the flat PVC film. And 3g of PVC film is taken and put into a crucible, and is put into a 300 ℃ tubular furnace for carbonization for 3h under the condition of nitrogen, the heating rate is 5 ℃/min, and the tubular furnace is taken out after the temperature is reduced to the room temperature, so that the carbonized film is obtained.
The carbonized film prepared by the above method was used for CO2, N2 single component gas adsorption test and mounted in a gas adsorption apparatus as shown in fig. 6, and the sample was subjected to degassing treatment before the test. Carbonization of film pair CO at room temperature2The maximum adsorption capacity of the gas can reach 0.45mmol/g, and the adsorption capacity of the gas on CO can reach 0.45mmol/g2/N2Has good separation effect.
Example 5
Pouring 10g of SG-6PVC into a beaker filled with 65ml of tetrahydrofuran solvent, stirring while pouring, putting the PVC powder into a water bath kettle at 60 ℃ after the PVC powder is uniformly dispersed in the organic solvent, fully dissolving the PVC powder, and then cooling to room temperature. And after cooling to room temperature, casting the 15 wt% PVC solution in a glass dish, and placing the glass dish in an oven at 70 ℃ for drying for 24 hours to obtain the flat PVC film. And 3g of PVC film is taken and put into a crucible, and is put into a 800 ℃ tubular furnace for carbonization for 3h under the condition of nitrogen, the heating rate is 3 ℃/min, and the tubular furnace is taken out after the temperature is reduced to the room temperature, so that the carbonized film is obtained.
The carbonized film prepared by the method is used for CO2、N2The one-component gas adsorption test was performed and installed in the gas adsorption apparatus shown in fig. 6, and the sample was subjected to degassing treatment before the test. Carbonization of film pair CO at room temperature2The maximum adsorption capacity of the gas can reach 0.54mmol/g, and the adsorption capacity of the gas to CO can reach2/N2Has good separation effect.
Example 6
Directly weighing 5g of SG-4PVC powder, putting the powder into a crucible, putting the crucible into a 300 ℃ tube furnace under the condition of nitrogen for carbonization for 3h, wherein the heating rate is 3 ℃/min, taking out the tube furnace after the temperature is reduced to the room temperature to obtain a carbonized film, and the images in the figure 4a and the figure 4b are scanning electron microscope images of the carbonized PVC powder at the temperature of 300 ℃.
The carbonized film prepared by the method is used for CO2、N2The one-component gas adsorption test was performed and installed in the gas adsorption apparatus shown in fig. 6, and the sample was subjected to degassing treatment before the test. Carbonization of film pair CO at room temperature2The maximum adsorption capacity of the gas can reach 0.41mmol/g, and the adsorption capacity to N can reach2The maximum adsorption capacity of the gas can reach 0.029mmol/g, namely SCO2/N2Greater than 14 to CO2/N2Has good separation effect.
Example 7
10g of SG-5PVC powder is directly weighed and put into a crucible, and is put into a 600 ℃ tube furnace for carbonization for 3h under the condition of nitrogen, the heating rate is 3 ℃/min, the temperature of the tube furnace is reduced to room temperature, and then the tube furnace is taken out to obtain a carbonized film, and a scanning electron microscope picture of the carbonized PVC powder at 600 ℃ in the embodiment is shown in figure 5.
The carbonized film prepared by the method is used for CO2、N2The one-component gas adsorption test was performed and installed in the gas adsorption apparatus shown in fig. 6, and the sample was subjected to degassing treatment before the test. Carbonization film pair CO at the temperature of 0 DEG C2The maximum adsorption capacity of the gas can reach 0.69mmol/g, and the adsorption capacity to N can reach2The maximum adsorption capacity of the gas can reach 0.00058mmol/g, namely SCO2/N2To 1189, to CO2/N2Has good separation effect.
Comparative example 1
The comparative example differs from example 1 in the lack of a carbonization step. PVC film obtained in this comparative example was paired with CO2The adsorption amount of gas is large, and CO2/N2The separation coefficient is low.
In conclusion, by the technical scheme, the adopted matrix is polyvinyl chloride with poorer thermal stability, the raw materials are wide, and the price is low; the preparation method of the separation membrane is simple and easy to operate, and the separation membrane is used for N2Low adsorption amount or even no adsorption, and can effectively adsorb and separate CO2/N2To CO2/N2Has high selectivity and good separation effect.
Furthermore, the present inventors have also made experiments with other raw materials and conditions and the like listed in the present specification in the manner of examples 1 to 7 and also succeeded in obtaining CO2/N2CO with high selectivity and good separation effect2/N2A gas separation membrane.
It should be noted that, in the present context, an element defined by the phrase "comprising … …" does not exclude the presence of other identical elements in steps, processes, methods or experimental facilities including the element.
It should be understood that the above preferred embodiments are only for illustrating the present invention, and other embodiments of the present invention are also possible, but those skilled in the art will be able to adopt the technical teaching of the present invention and equivalent alternatives or modifications thereof without departing from the scope of the present invention.
Claims (10)
1. CO (carbon monoxide)2/N2A method for producing a gas separation membrane, characterized by comprising: carbonizing the polyvinyl chloride film or the polyvinyl chloride powder in an oxygen-free atmosphere to obtain CO2/N2A gas separation membrane.
2. The method of claim 1, wherein: the temperature of the carbonization treatment is 300-800 ℃, and the time is 60-180 min.
3. The method according to claim 1, comprising: heating a polyvinyl chloride film or polyvinyl chloride powder to 300-800 ℃ at a heating rate of 1-5 ℃/min in an oxygen-free atmosphere for carbonization treatment, preserving heat for 60-180 min, and then cooling to room temperature at a cooling rate of 1-5 ℃/min to obtain CO2/N2A gas separation membrane.
4. The production method according to claim 1, 2 or 3, characterized in that: the oxygen-free atmosphere comprises a nitrogen atmosphere and/or an inert gas atmosphere; and/or the polymerization degree of the polyvinyl chloride is 850-1200; and/or the polyvinyl chloride comprises any one or the combination of more than two of polyvinyl chloride SG-4, polyvinyl chloride SG-5 and polyvinyl chloride SG-6.
5. The method according to claim 1, comprising: the polyvinyl chloride powder is dissolved in an organic solvent and heated to form a polyvinyl chloride solution, then the polyvinyl chloride solution is applied on a substrate, and the organic solvent is removed to obtain a transparent and flat polyvinyl chloride film.
6. The method of claim 5, wherein: the concentration of the polyvinyl chloride solution is 10-15 wt%; and/or the heating temperature is 60-80 ℃; and/or the organic solvent comprises any one or the combination of more than two of N, N-dimethylformamide, cyclohexanone, dichloroethane, tetrachloroethane and tetrahydrofuran.
7. The preparation method according to claim 5, characterized by specifically comprising: and casting the polyvinyl chloride solution on the substrate, and drying at 60-80 ℃ to volatilize the organic solvent to obtain the transparent and flat polyvinyl chloride film.
8. CO produced by the process of any one of claims 1 to 72/N2A gas separation membrane; preferably, the CO is2/N2Gas separation membrane pair CO2The adsorption amount of (A) is 0.00409-0.414 mmol/g, CO2/N2The separation factor is greater than 101.22.
9. A gas separation method, characterized by comprising: CO as claimed in claim 82/N2The gas separation membrane will contain CO2And N2CO in the mixed gas2And N2Are separated from each other.
10. A gas separation apparatus comprising the CO according to claim 82/N2A gas separation membrane.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5104425A (en) * | 1989-11-14 | 1992-04-14 | Air Products And Chemicals, Inc. | Gas separation by adsorbent membranes |
| US20040050249A1 (en) * | 2000-06-22 | 2004-03-18 | Corbin David Richard | Mixed matrix nanoporous carbon membranes |
| CN1830533A (en) * | 2005-12-13 | 2006-09-13 | 大连理工大学 | Preparation method of polyether sulphone ketone base gas separation carbon membrane |
| US20080141858A1 (en) * | 2006-12-18 | 2008-06-19 | Chunqing Liu | Gas Separations Using High Performance Mixed Matrix Membranes |
| US20120079944A1 (en) * | 2010-10-01 | 2012-04-05 | Basf Se | Process for producing carbon membranes |
| CN102824857A (en) * | 2011-06-14 | 2012-12-19 | 北京航空航天大学 | Preparation method of gas separation carbon membrane |
| CN103237588A (en) * | 2010-10-01 | 2013-08-07 | 巴斯夫欧洲公司 | Method for producing carbon membranes |
| CN107635646A (en) * | 2015-06-01 | 2018-01-26 | 佐治亚科技研究公司 | Super-selective Carbon Molecular Sieve Membrane and manufacture method |
-
2018
- 2018-11-01 CN CN201811295580.6A patent/CN111111465A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5104425A (en) * | 1989-11-14 | 1992-04-14 | Air Products And Chemicals, Inc. | Gas separation by adsorbent membranes |
| US20040050249A1 (en) * | 2000-06-22 | 2004-03-18 | Corbin David Richard | Mixed matrix nanoporous carbon membranes |
| CN1830533A (en) * | 2005-12-13 | 2006-09-13 | 大连理工大学 | Preparation method of polyether sulphone ketone base gas separation carbon membrane |
| US20080141858A1 (en) * | 2006-12-18 | 2008-06-19 | Chunqing Liu | Gas Separations Using High Performance Mixed Matrix Membranes |
| US20120079944A1 (en) * | 2010-10-01 | 2012-04-05 | Basf Se | Process for producing carbon membranes |
| CN103237588A (en) * | 2010-10-01 | 2013-08-07 | 巴斯夫欧洲公司 | Method for producing carbon membranes |
| CN102824857A (en) * | 2011-06-14 | 2012-12-19 | 北京航空航天大学 | Preparation method of gas separation carbon membrane |
| CN107635646A (en) * | 2015-06-01 | 2018-01-26 | 佐治亚科技研究公司 | Super-selective Carbon Molecular Sieve Membrane and manufacture method |
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