CN103170251B - A kind of for the preparation of CO 2the coating liquid of composite membrane for separation and CO 2composite membrane for separation - Google Patents
A kind of for the preparation of CO 2the coating liquid of composite membrane for separation and CO 2composite membrane for separation Download PDFInfo
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- CN103170251B CN103170251B CN201110428653.6A CN201110428653A CN103170251B CN 103170251 B CN103170251 B CN 103170251B CN 201110428653 A CN201110428653 A CN 201110428653A CN 103170251 B CN103170251 B CN 103170251B
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Abstract
The invention provides a kind of for the preparation of CO
2the formula of the coating liquid of composite membrane for separation and CO
2composite membrane for separation.Described coating liquid is by by following every blended and obtain: the Aqueous polyvinylamine solutions of 2 ~ 5 quality %, the polyacrylamide solution of 0.1 ~ 5 quality % and the polyvinyl alcohol water solution of 0.1 ~ 3 quality %, and the volume ratio of described Aqueous polyvinylamine solutions, polyacrylamide solution and polyvinyl alcohol water solution is (95 ~ 30): (4 ~ 50): (1 ~ 20).Described diffusion barrier comprises hollow-fibre membrane and the film formed by coating liquid of the present invention in described hollow-fibre membrane inner chamber.Coating liquid of the present invention is simple, be easy to operation, cost is low, and produces the composite membrane that in enormous quantities to CO
2/ CH
4gaseous mixture has more excellent separation factor and infiltration rate, thus promotes that carrier compound membrane realization of industrialization is laid a good foundation for doughnut.
Description
Technical field
The present invention relates to the technology of preparing of composite gas separation, specifically the present invention relates to for the preparation of CO
2the formula of the coating liquid of composite membrane for separation and CO
2composite membrane for separation.
Background technology
Fixed carrier composite membrane is a kind of novel gas separation membrane, has high osmosis and high selectivity.Amido can be used as the Faciliated diffusion carrier in composite membrane, polyvinylamine, PAH and polyacrylamide etc. because containing a large amount of high activity amido can with CO
2reversible reaction occurs, and is therefore desirable separation of C O
2immobilization carrier membrane material.
At present, the research of domestic and international immobilization carrier film mainly concentrates on the preparation of flat composite membrane, and is only confined in laboratory scope.As [Wang Zhi, Lv Qiang, Li Baoan such as Wang Zhi.Novel C O
2the stuctures and properties of diffusion barrier.Polymer material science and engineering, 2000,16 (5): 5-8] utilize polyvinylamine (PVAm)/polysulfones (PS) basement membrane to prepare CO
2faciliated diffusion composite membrane, wherein primary amine groups is as transport CO
2carrier, by covalently immobolization on macromolecular scaffold.This film is at elevated pressures to CO
2gas carries out high-selectivity adsorption, and the separation of long-play caudacoria still can maintain very high level.
Hollow-fibre membrane CO
2faciliated diffusion composite membrane for separation is because its specific area is large, treatment effeciency is high and the large tunicle worker always of packed density paid attention to, but the coating of hollow-fibre membrane can operate unlike Flat Membrane under the effect of mechanical external force, the thickness of its coating and film forming are easily controlled.Therefore seldom use doughnut to be used as the carrier of carrier film in prior art, and active amine be it is not yet seen report as producing doughnut fixed carrier composite membrane in enormous quantities.
Therefore, exploitation is conducive to forming CO on doughnut base material further
2the coating liquid of composite membrane for separation, and the method that can realize large batch of production when the hollow-fibre membrane excellent release energy prepared by keeping is very necessary.
Summary of the invention
The object of the present invention is to provide a kind of formula being suitable for the coating liquid producing internal air pressure type hollow fiber compound film in enormous quantities.Coating liquid of the present invention is simple, be easy to operation, cost is low, and produces the composite membrane that in enormous quantities to CO
2/ CH
4gaseous mixture has more excellent separation factor and infiltration rate, thus promotes that carrier compound membrane realization of industrialization is laid a good foundation for doughnut.
For this reason, the invention provides following aspect:
<1> coating liquid, described coating liquid is by by following every blended and obtain:
The Aqueous polyvinylamine solutions of 2 ~ 5 quality %, the polyacrylamide solution of 0.1 ~ 5 quality % and the polyvinyl alcohol water solution of 0.1 ~ 3 quality %, and the volume ratio of described Aqueous polyvinylamine solutions, polyacrylamide solution and polyvinyl alcohol water solution is (95 ~ 30): (4 ~ 50): (1 ~ 20).
<2>. the coating liquid according to <1>, Aqueous polyvinylamine solutions uses with 2 ~ 4.5 quality %, polyacrylamide uses with 0.1 ~ 3 quality % and polyvinyl alcohol water solution uses with 0.1 ~ 2 quality %, and the blended volume ratio (92 ~ 40) of Aqueous polyvinylamine solutions, polyacrylamide solution and polyvinyl alcohol water solution: (5 ~ 40): (3 ~ 20).
<3>. the coating liquid according to <1>, Aqueous polyvinylamine solutions uses with 2 ~ 4.0 quality %, polyacrylamide uses with 0.5 ~ 2.5 quality % and polyvinyl alcohol water solution uses with 0.5 ~ 1 quality %, and the blended volume ratio (90 ~ 45) of Aqueous polyvinylamine solutions, polyacrylamide solution and polyvinyl alcohol water solution: (7 ~ 40): (3 ~ 15).
<4>. a CO
2composite membrane for separation, described diffusion barrier comprises hollow-fibre membrane and the film formed by the coating liquid according to any one of <1> to <3> in described hollow-fibre membrane surface of internal cavity.
<5>. the CO according to <4>
2composite membrane for separation, described doughnut is the doughnut formed by polyvinyl chloride, polyethylene, polysulfones, Kynoar or polytetrafluoroethylene (PTFE).
<6>. the CO according to <5>
2composite membrane for separation, wherein said hollow-fibre membrane to be molecular cut off be 5000 ~ 50,000 PVC hollow fiber membrane.
<7>. the CO according to <6>
2composite membrane for separation, wherein said hollow-fibre membrane is the fiber film component that the PVC hollow fiber membrane being 5000 ~ 50,000 by molecular cut off is formed.
<8>. the CO according to <7>
2composite membrane for separation, wherein said fiber film component is prepared by following process: by least 2 hollow fiber film threads as a branch of, often restraints film silk two ends silicone rubber seal, is then loaded in pvc pipe, pvc pipe two ends epoxy resin seals, and namely obtains membrane module after solidification.
<9>. the CO according to <4>
2composite membrane for separation, described film is pressed in hollow-fibre membrane inner chamber by membrane pump by described coating liquid, surface of internal cavity is applied under the flow of 350 ~ 550ml/min, then coating liquid is released, last temperature 25 DEG C ~ 35 DEG C, relative humidity 35% ~ 45% time dry 10h ~ 15h obtains.
Accompanying drawing explanation
Fig. 1 is the CO that the present invention obtains
2the CO of composite membrane for separation
2/ CH
4separation factor and CO
2infiltration rate test flow chart, wherein the implication of Reference numeral is as follows:
1: unstripped gas;
2: humidifier;
3: sweep gas;
4,7,8,11: pressure-regulating valve;
5: Pressure gauge;
6: film separation unit;
9: gas-chromatography;
10: gas flowmeter.
Detailed description of the invention
In this article, term " infiltration rate " and refer to per membrane area under unit interval unit pressure reduction through the amount of gas.
In this article, term " inner pressed " refers to the surface of internal cavity of separating layer at hollow-fibre membrane.
In this article, term " separation factor " has implication well-known to those skilled in the art.
In this article, term " interior painting technique " refers to the technique that coating liquid can be coated on the surface of internal cavity of doughnut.Such as, coating liquid is pressed into hollow-fibre membrane inner chamber by membrane pump and applies the method for surface of internal cavity.
In this article, term " solidification " has implication well-known to those skilled in the art, and namely epoxy resin adds certain proportion common curatives at a certain temperature, leaves standstill epoxy resin and unclassified stores are formed holistic technical process through after a while.
Active amine in the present invention mainly refers to those energy and CO
2there is the group that reversible reaction forms complex compound, CO
2carry out transmitting and being separated between these groups.
A first aspect of the present invention is to provide a kind of coating liquid, described coating liquid passes through following every blended obtained coating liquid: the Aqueous polyvinylamine solutions of 2 ~ 5 quality %, the polyacrylamide solution of 0.1 ~ 5 quality % and 0.1 ~ 3 quality % polyvinyl alcohol water solution, wherein Aqueous polyvinylamine solutions, polyacrylamide solution and polyvinyl alcohol water solution volume ratio (95 ~ 30): (4 ~ 50): (1 ~ 20).
In the preparation of coating liquid of the present invention, Aqueous polyvinylamine solutions uses with preferred mass concentration in the scope of 2 ~ 4.5 quality %, more preferably 2.5 ~ 4.0 quality %.When used Aqueous polyvinylamine solutions mass concentration lower than 2% time the mechanical strength of film that formed decline, easily impaired in the course of the work, coating liquid viscosity can be made excessive when this mass concentration is greater than 5%, easily cause tunica fibrosa silk inner chamber to block and lose separating property.
In the preparation process of coating liquid of the present invention, polyacrylamide uses with preferred mass concentration in the scope of 0.1 ~ 3 quality %, more preferably 0.5 ~ 2.5 quality %.When used polyacrylamide mass concentration lower than 0.1% time can decline because of the too little filming performance that makes of viscosity, can coating be made because viscosity is excessive when this mass concentration is more than 5% too thick and gas flux be reduced greatly.
In the preparation process of coating liquid of the present invention, polyvinyl alcohol water solution uses with preferred mass concentration in the scope of 0.1 ~ 2 quality %, more preferably 0.5 ~ 1 quality %.When mass concentration is lower than 0.1 quality %, the ductility of coating liquid reduces, and the filming performance of film declines, when this mass concentration is unfavorable for film higher than during 3 quality % because the surface-active of polyvinyl alcohol can make coating liquid produce a large amount of bubble.
Therefore, in the preparation process of coating liquid of the present invention, using the Aqueous polyvinylamine solutions meeting above-mentioned preferred mass concentration requirement respectively, when polyacrylamide solution and polyvinyl alcohol water solution, the preferred volume scope of these three kinds of solution blendings is (92 ~ 40): (5 ~ 40): (3 ~ 20), and meeting the Aqueous polyvinylamine solutions of above-mentioned more preferably mass concentration requirement respectively, when polyacrylamide solution and polyvinyl alcohol water solution, more preferably the scope (90 ~ 45) of these three kinds of solution blendings: (7 ~ 40): (3 ~ 15).
Coating liquid of the present invention is a kind of for the formation of CO
2the coating liquid of composite membrane for separation.Coating liquid of the present invention be suitable for this area in prepare CO
2any base material that composite membrane for separation uses combines the flat board of use, such as polysulfones or polyether sulfone, is especially applicable to and doughnut base material compound and form CO
2composite membrane for separation, but also be applicable to the assembly compound that formed with many doughnut base materials and form CO
2composite membrane for separation.And the diffusion barrier obtained by base material compound normally used in coating liquid of the present invention and the present invention all can obtain good CO
2separating property.
Therefore, on the other hand, the present invention also provides a kind of CO
2composite membrane for separation, described diffusion barrier comprises hollow-fibre membrane and the film formed by coating liquid of the present invention in described hollow-fibre membrane inner chamber.
The present inventor thinks, CO of the present invention
2the separating mechanism mainly CO of composite membrane for separation
2amido in composite membrane for separation and CO
2there is reversible reaction and form complex compound, and CO
2carry out transmitting between amido and form new complex compound, transmit until CO so according to this
2be separated at the opposite side of film.
In the present invention, described doughnut refers to the fiber of any hollow shape, normally, can be the doughnut of the materials such as polyvinyl chloride, polyethylene, polysulfones, Kynoar or polytetrafluoroethylene (PTFE).
Preferably, described hollow-fibre membrane is molecular cut off 5000 ~ 50, the PVC hollow fiber membrane of 000.
The method that coating liquid of the present invention is coated on the surface of internal cavity of hollow-fibre membrane be not particularly limited, in the art the normally used method for completing interior painting technique, such as, coating liquid is pressed into the method for hollow-fibre membrane inner chamber by membrane pump.
Coating liquid of the present invention by interior be coated onto doughnut inner surface after, as required, can also the techniques such as drying be carried out.
Therefore, in one embodiment of the invention, CO of the present invention is obtained as follows
2composite membrane for separation:
1, with molecular cut off 5000 ~ 50, the PVC hollow fiber membrane of 000 is basement membrane, is dipped in by basement membrane in pure water, at room temperature soaks 20 ~ 24h, afterwards temperature 25 DEG C ~ 35 DEG C, and the dry 10h ~ 15h of relative humidity 35% ~ 45%, for subsequent use.
2, the length of tunica fibrosa silk in step 1 is cut into 1200mm and 400mm two kinds respectively.Every 400 of the film silk of long 1200mm is a branch of, often restraint film silk two ends silicon rubber as 705 silicon rubber (production of pilot plant of Nanjing University) sealing, then by often restrainting film silk, to be loaded into diameter be 180mm, in the pvc pipe of long 1200mm, two ends epoxy resin seals, and namely obtains membrane module after solidification.Or, when investigating laboratory scale separating property, be a branch of by every for the film silk of long 400mm 4, often restraint film silk two ends silicon rubber as 705 silicon rubber (production of pilot plant of Nanjing University) sealing, then by often restrainting film silk, to be loaded into diameter be 75mm, in the pvc pipe of long 400mm, two ends epoxy resin seals, and namely obtains membrane module after solidification.
3. by coating liquid of the present invention by membrane pump (such as, the WT600-1F that Baoding LanGe constant flow pump Co., Ltd produces) be pressed in hollow-fibre membrane inner chamber, apply under the flow of 350 ~ 550ml/min, then coating liquid is released, last temperature 25 DEG C ~ 35 DEG C, relative humidity 35% ~ 45% time dry 10h ~ 15h, can obtain the CO for testing
2composite membrane for separation.Test finds, is optimum at the flow of 350 ~ 550ml/min because flow lower and higher all can cause coating liquid infilter in basement membrane the decline causing infiltration rate.
In research process of the present invention, the CO that inventor obtains coating liquid of the present invention
2composite membrane for separation passes through its CO for 60 volume %/40 volume % of gas-chromatography (such as, the gas-chromatography of the model 7820A of Agilent production) high spot reviews
2/ CH
4mist, when feed gas pressure is 0.1MPa ~ 5.0MPa, CO
2/ CH
4separation factor and CO
2infiltration rate.Described separation factor and ml/min infiltration rate be have employed when gas humidification gas purging add chromatogram detect method test.As Fig. 1, first temperature control is regulated to make film separation unit remain on uniform temperature (being generally 35 DEG C), then open sample introduction gas and valve 4,7 to purge osmotic cell surface and make tested gas be full of osmotic cell to remove air, then valve-off 7, control valve 4 makes unstripped gas control at certain pressure.Sweep gas uses H
2, open sweep gas, control valve 11, sweep gas flow kept in certain limit (0.4 ~ 1.0ml/min).Then determine the content of infiltration gas in implication (comprising infiltration gas and sweep gas) and total flow of working off one's feeling vent one's spleen respectively by gas-chromatography (GC) and soap bubble flowmeter, and then calculate infiltration rate and the separation factor of infiltration gas.
In formula:
P
a---infiltration rate cm
3(STP)/(cm
2scmHg)
Δ
p---permeable pressure head, cmHg
V
a---in the Δ t time, infiltration gas amasss, cm
3(STP)
X
a---the content of tested gas in infiltration gas, cm
3/ cm
3
The test area of A---film, cm
2
α
a/B---separation
The result of test confirms, the CO obtained by coating liquid of the present invention
2composite membrane for separation has good CO
2no matter separating property is the CO formed on laboratory scale doughnut or on plant-scale doughnut
2composite membrane for separation all shows and possesses good CO
2separating property.
CO is prepared from above-mentioned use coating liquid of the present invention
2the process of composite membrane for separation can be found out, this inventive method is simple, be easy to operation, cost is low.Particularly, be a branch of membrane module made owing to such as can use by every 400 doughnuts, and the composite membrane produced by such assembly is to CO
2/ CH
4gaseous mixture still has more excellent separation factor and infiltration rate, thus promotes that carrier compound membrane realization of industrialization is laid a good foundation for doughnut.
In addition, it should be noted that, although the membrane module laboratory scale used in example of the present invention is employing, 4 doughnuts are a branch of, extensive preparation adopt 400 doughnuts be a branch of only as an example, but in fact adopt how many doughnuts to carry out the not strict restriction of test as a branch of, those skilled in the art can experimentally suitably choose by condition such as membrane pump power, film pipe fitting internal diameter etc.
To be described in more detail the present invention by embodiment below, but these embodiments are not limitation of the scope of the invention, scope of the present invention should be defined by the claims.
Embodiment
Embodiment 1 (laboratory scale preparation)
Preparation mass concentration is the Aqueous polyvinylamine solutions of 5%, preparation mass concentration is 5% polyacrylamide solution and 3% polyvinyl alcohol water solution, according to polyvinylamine, polyacrylamide and polyvinyl alcohol water solution volume ratio 85: 10: 5 preparation 500ml coating liquid, by 4 × 400mm hollow fiber film assembly (molecular cut off 20,000) be dipped in pure water, at room temperature soak 20h, afterwards temperature 30 DEG C, the dry 12h of relative humidity 40%, for subsequent use.Be pressed into by membrane pump by the 500ml coating liquid of above-mentioned preparation and be coated in the inner surface of tunica fibrosa, be 30 DEG C in temperature, relative humidity 40% time dry 10h ~ 15h, obtains separation of C O
2the doughnut Faciliated diffusion composite membrane of gas.With the CO of 60 volume %/40 volume %
2/ CH
4mist is tested its performance.Test result, when feed gas pressure is 0.1MPa ~ 5.0MPa, CO
2/ CH
4separation factor 55 ~ 30, CO
2infiltration rate (40 ~ 70) × 10
-6cm
3(STP) cm
-2s
-1cmHg
-1.
Comparative example (laboratory scale preparation)
Coating liquid (by method described in application for a patent for invention 02158530.x configuration) 500ml will be contrasted, by 4 × 400mm hollow fiber film assembly (molecular cut off 20,000) be dipped in pure water, at room temperature soak 20h, afterwards temperature 30 DEG C, the dry 12h of relative humidity 40%, for subsequent use.Be pressed into by membrane pump by the 500ml coating liquid of above-mentioned preparation and be coated in the inner surface of tunica fibrosa, be 30 DEG C in temperature, relative humidity 40% time dry 10h ~ 15h, obtains separation of C O
2the doughnut Faciliated diffusion composite membrane of gas.With the CO of 60 volume %/40 volume %
2/ CH
4mist is tested its performance.Test result, when feed gas pressure is 0.1MPa ~ 5.0MPa, CO
2/ CH
4separation factor 6 ~ 2, CO
2infiltration rate (30 ~ 60) × 10
-6cm
3(STP) cm
-2s
-1cmHg
-1.
Therefore the comparison of embodiment 1 and comparative example 1 is passed through, under identical feed gas pressure, the CO of embodiment 1
2/ CH
4separation factor, far away higher than comparative example 1, describes the separating property adopting formula of the present invention can improve composite membrane, also illustrate that the CO adopting coating liquid of the present invention to prepare
2composite membrane for separation a kind ofly has good separation of C O
2/ CH
4the film of ability.
The following examples 2-6, even if further demonstrate that in the carrier film of extensive preparation, also can obtain desirable result of the test.
Embodiment 2
Preparation mass concentration is the Aqueous polyvinylamine solutions of 5%, preparation mass concentration is 5% polyacrylamide solution and 3% polyvinyl alcohol water solution, according to polyvinylamine, polyacrylamide and polyvinyl alcohol water solution volume ratio 85: 10: 5 preparation 5000ml coating liquid, 400 × 1200mm hollow fiber film assembly (molecular cut off 20000) is dipped in pure water, at room temperature soak 20h, afterwards temperature 30 DEG C, the dry 12h of relative humidity 40%, for subsequent use.The 5000ml coating liquid of above-mentioned preparation being coated in the inner surface of tunica fibrosa by interior painting technique, is 30 DEG C in temperature, and relative humidity 40% time dry 10h ~ 15h, obtains separation of C O
2the doughnut Faciliated diffusion composite membrane of gas.With the CO of 60 volume %/40 volume %
2/ CH
4mist is tested its performance.Test result, when feed gas pressure is 0.1MPa ~ 5.0MPa, CO
2/ CH
4separation factor 40 ~ 18, CO
2infiltration rate (60 ~ 180) × 10
-6cm
3(STP) cm
-2s
-1cmHg
-1.
Embodiment 3
Adopt mass concentration prepared in example 2 be 5% Aqueous polyvinylamine solutions, mass concentration be 5% polyacrylamide solution and 3% polyvinyl alcohol water solution, according to polyvinylamine, polyacrylamide and polyvinyl alcohol water solution volume ratio 80: 13: 7 preparation 5000ml coating liquid, 400 × 1200mm hollow fiber film assembly (molecular cut off 20000) is dipped in pure water, at room temperature soak 20h, afterwards temperature 30 DEG C, the dry 12h of relative humidity 40%, for subsequent use.The 5000ml coating liquid of above-mentioned preparation being coated in the inner surface of tunica fibrosa by interior painting technique, is 30 DEG C in temperature, and relative humidity 40% time drying, obtains separation of C O
2the doughnut Faciliated diffusion composite membrane of gas.With the CO of 60 volume %/40 volume %
2/ CH
4mist is tested its performance.Test result, when feed gas pressure is 0.1MPa ~ 5.0MPa, CO
2/ CH
4separation factor 40 ~ 25, CO
2infiltration rate (45 ~ 120) × 10
-6cm
3(STP) cm
-2s
-2cmHg
-1.
Embodiment 4
Adopt mass concentration prepared in example 2 be 5% polyacrylamide solution, 3% polyvinyl alcohol water solution and 5% Aqueous polyvinylamine solutions, according to polyvinylamine, polyacrylamide and polyvinyl alcohol water solution volume ratio 88: 10: 2 preparation 5000ml coating liquid, 400 × 1200mm hollow fiber film assembly (molecular cut off 20000) is dipped in pure water, at room temperature soak 20h, afterwards temperature 30 DEG C, the dry 12h of relative humidity 40%, for subsequent use.The 5000ml coating liquid of above-mentioned preparation being coated in the inner surface of tunica fibrosa by interior painting technique, is 30 DEG C in temperature, and relative humidity 40% time drying, obtains separation of C O
2the doughnut Faciliated diffusion composite membrane of gas.With the CO of 60 volume %/40 volume %
2/ CH
4mist is tested its performance.Test result, when feed gas pressure is 0.1MPa ~ 5.0MPa, CO
2/ CH
4separation factor 30 ~ 20, CO
2infiltration rate (55 ~ 135) × 10
-6cm
3(STP) cm
-2s
-2cmHg
-1.
Embodiment 5
Adopt mass concentration prepared in example 2 be 5% polyacrylamide solution, 3% polyvinyl alcohol water solution and 5% Aqueous polyvinylamine solutions, according to polyvinylamine, polyacrylamide and polyvinyl alcohol water solution volume ratio 85: 13: 2 preparation 5000ml coating liquid, 400 × 1200mm hollow fiber film assembly (molecular cut off 20000) is dipped in pure water, at room temperature soak 20h, afterwards temperature 30 DEG C, the dry 12h of relative humidity 40%, for subsequent use.The 5000ml coating liquid of above-mentioned preparation being coated in the inner surface of tunica fibrosa by interior painting technique, is 30 DEG C in temperature, and relative humidity 40% time drying, obtains separation of C O
2the doughnut Faciliated diffusion composite membrane of gas.With the CO of 60 volume %/40 volume %
2/ CH
4mist is tested its performance.Test result, when feed gas pressure is 0.1MPa ~ 5.0MPa, CO
2/ CH
4separation factor 35 ~ 20, CO
2infiltration rate (50 ~ 110) × 10
-6cm
3(STP) cm
-2s
-2cmHg
-1.
Embodiment 6
Adopt mass concentration prepared in example 2 be 5% polyacrylamide solution, 3% polyvinyl alcohol water solution and 5% Aqueous polyvinylamine solutions, according to polyvinylamine, polyacrylamide and polyvinyl alcohol water solution volume ratio 82: 15: 3 preparation 5000ml coating liquid, 400 × 1200mm hollow fiber film assembly (molecular cut off 20000) is dipped in pure water, at room temperature soak 20h, afterwards temperature 30 DEG C, the dry 12h of relative humidity 40%, for subsequent use.The 5000ml coating liquid of above-mentioned preparation being coated in the inner surface of tunica fibrosa by interior painting technique, is 30 DEG C in temperature, and relative humidity 40% time drying, obtains separation of C O
2the doughnut Faciliated diffusion composite membrane of gas.With the CO of 60 volume %/40 volume %
2/ CH
4mist is tested its performance.Test result, when feed gas pressure is 0.1MPa ~ 5.0MPa, CO
2/ CH
4separation factor 42 ~ 25, CO
2infiltration rate (50 ~ 75) × 10
-6cm
3(STP) cm
-2s
-2cmHg
-1.
The test of embodiment 2-6 describes, although by coating liquid of the present invention from laboratory (adopting 4 doughnuts) application extension to the application of commercial scale (adopting 400 doughnuts) time, although make CO due to enlarge-effect
2/ CH
4separating property reduce a little, but to CO
2/ CH
4separating property be still good.
Industrial applicability
The complex carrier film of the hollow-fibre membrane prepared by coating liquid of the present invention is to CO
2/ CH
4there is excellent separating property, and be particularly suitable for the production in enormous quantities of complex carrier film.
Claims (7)
1. a coating liquid, described coating liquid is by by following every blended and obtain:
The Aqueous polyvinylamine solutions of 2 ~ 5 quality %, the polyacrylamide solution of 0.1 ~ 5 quality % and the polyvinyl alcohol water solution of 0.1 ~ 3 quality %, and the volume ratio of described Aqueous polyvinylamine solutions, described polyacrylamide solution and described polyvinyl alcohol water solution is (95 ~ 30): (4 ~ 50): (1 ~ 20).
2. coating liquid according to claim 1, Aqueous polyvinylamine solutions uses with 2 ~ 4.5 quality %, polyacrylamide uses with 0.1 ~ 3 quality % and polyvinyl alcohol water solution uses with 0.1 ~ 2 quality %, and the blended volume ratio (92 ~ 40) of described Aqueous polyvinylamine solutions, described polyacrylamide solution and described polyvinyl alcohol water solution: (5 ~ 40): (3 ~ 20).
3. coating liquid according to claim 1, Aqueous polyvinylamine solutions uses with 2 ~ 4.0 quality %, polyacrylamide uses with 0.5 ~ 2.5 quality % and polyvinyl alcohol water solution uses with 0.5 ~ 1 quality %, and the blended volume ratio (90 ~ 45) of described Aqueous polyvinylamine solutions, described polyacrylamide solution and described polyvinyl alcohol water solution: (7 ~ 40): (3 ~ 15).
4. a CO
2composite membrane for separation, described diffusion barrier comprises hollow-fibre membrane and the film formed by coating liquid according to any one of claim 1 to 3 in described hollow-fibre membrane surface of internal cavity.
5. CO according to claim 4
2composite membrane for separation, described hollow-fibre membrane is the hollow-fibre membrane formed by polyvinyl chloride, polyethylene, polysulfones, Kynoar or polytetrafluoroethylene (PTFE).
6. CO according to claim 5
2composite membrane for separation, wherein said hollow-fibre membrane to be molecular cut off be 5000 ~ 50,000 PVC hollow fiber membrane.
7. CO according to claim 4
2composite membrane for separation, described film is pressed in hollow-fibre membrane inner chamber by membrane pump by described coating liquid, applies, then released by coating liquid under the flow of 350 ~ 550mL/min, last temperature 25 DEG C ~ 35 DEG C, relative humidity 35% ~ 45% time dry 10h ~ 15h obtains.
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| CN105561811B (en) * | 2014-11-05 | 2018-05-01 | 上海交通大学 | Environment-friendly liquid supports carbon dioxide separation film |
| CN113594524B (en) * | 2021-07-15 | 2023-12-12 | 天津工业大学 | Microbial electrosynthesis reactor for supplying carbon dioxide by using hollow fiber membrane and using method thereof |
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| CN103170251A (en) | 2013-06-26 |
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