CN109701399A - A kind of plasma treatment multilayer gas composite film and its preparation method and application - Google Patents
A kind of plasma treatment multilayer gas composite film and its preparation method and application Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000009832 plasma treatment Methods 0.000 title abstract description 4
- 239000010410 layer Substances 0.000 claims abstract description 95
- 239000012528 membrane Substances 0.000 claims abstract description 50
- 238000000926 separation method Methods 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000003851 corona treatment Methods 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 229920001400 block copolymer Polymers 0.000 claims description 16
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- 239000004642 Polyimide Substances 0.000 claims description 10
- 229920001721 polyimide Polymers 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000002608 ionic liquid Substances 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 6
- 239000004697 Polyetherimide Substances 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229920002492 poly(sulfone) Polymers 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 6
- 229920001601 polyetherimide Polymers 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 125000004185 ester group Chemical group 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- -1 poly (aryl ether sulfone ketone Chemical class 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004941 mixed matrix membrane Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 4
- 229920005649 polyetherethersulfone Polymers 0.000 claims description 4
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 4
- 229920002379 silicone rubber Polymers 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 3
- 239000011229 interlayer Substances 0.000 claims description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 3
- 229940044613 1-propanol Drugs 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000011877 solvent mixture Substances 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 238000012661 block copolymerization Methods 0.000 claims 1
- 238000003618 dip coating Methods 0.000 claims 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 150000003951 lactams Chemical class 0.000 claims 1
- 229920002239 polyacrylonitrile Polymers 0.000 claims 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims 1
- 239000011241 protective layer Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000003204 osmotic effect Effects 0.000 abstract 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 23
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 23
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 23
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 23
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 23
- 229920002614 Polyether block amide Polymers 0.000 description 16
- 230000004907 flux Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000007547 defect Effects 0.000 description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 229920005573 silicon-containing polymer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明公开了一种等离子体处理多层气体复合膜及其制备方法和应用，属于气体分离膜领域。对复合膜中间层进行常压低温等离子处理，可方便快捷地提高其表面能及与分离层的亲和性。通过等离子处理的中间层与分离层具有良好的亲和性，可涂覆低浓度涂层溶液，并获得超薄无缺陷分离层及优异的渗透分离性能，可避免常规制膜方法中必不可少的保护层的使用，减少了涂层次数，可有效提高复合膜的制备效率。The invention discloses a plasma-treated multilayer gas composite membrane, a preparation method and application thereof, and belongs to the field of gas separation membranes. The normal pressure and low temperature plasma treatment of the intermediate layer of the composite membrane can easily and quickly improve its surface energy and affinity with the separation layer. The plasma-treated intermediate layer and the separation layer have good affinity, and can be coated with low-concentration coating solution, and obtain an ultra-thin defect-free separation layer and excellent osmotic separation performance, which can avoid the necessity of conventional membrane production methods. The use of the protective layer reduces the number of coatings and can effectively improve the preparation efficiency of the composite film.
Description
Technical field
The invention belongs to gas separation membrane technical fields, and in particular to a kind of corona treatment multi-layer gas composite membrane and
Preparation method and application.
Background technique
In the energy resource structure in the whole world, there is no in the case where basic variation, the development of social economy is big there is still a need for consuming
The fossil energy of amount, and the use of fossil energy can bring a large amount of pollutants and CO2、SO2、H2The discharge of the acidity such as S, leads to one
Serial environmental problem, such as CO2A large amount of excess emissions will lead to greenhouse effects.For CO2The separation of equal sour gas, UF membrane
Technology has that low energy consumption, and occupied area is few, easy to operate, and easily amplification and control is easy to the combination of other processes, invests less, item
The advantages that part is mild is a kind of very with application prospect separation method.
In CO2Separation in, ether oxygen (EO) group is with it to CO2Wide pass is obtained with excellent permeability and separation performance
Therefore note, the material of the group containing EO also become UF membrane field focus of attention.Polyether block amide (Pebax), polyoxyethylene
Alkene-polybutylene terephthalate (PBT) (Polyactive), polyethylene glycol oxide-polyimide block copolymer, polyethylene glycol oxide-
Polyetherimide blocks' copolymer etc. is all the copolymer containing polyethylene glycol oxide (PEO) block.In addition to EO group, ester group, itrile group,
Amino groups are also to CO2With biggish dissolubility, it can be used to improve membrane material to CO2Solubility.Currently, gas separates
One important development direction of film is the structure optimization of composite membrane.In composite membrane, in order to obtain bigger permeation flux, often
It is required that gas separation membrane has relatively thin separating layer, most of materials cannot keep enough mechanical strengths at this time, therefore, usually
It needs to support counterdie.But be directly coated on separation layer materials on support counterdie, it is easy to the generation of bleed hole infiltration in this way,
Cause film properties poor.The polyether sulfone PES/Pebax-MWNTs composite membrane of the preparations such as Murali, selective separating > 10 μm, CO2
Permeation flux is less than 25GPU (Ind.Eng.Chem.Res., 49 (2010) 6530-6538).Although by counterdie and separating layer
Between introduce dimethyl silicone polymer (PDMS) middle layer can prevent hole seep generation, but due to the surface PDMS can it is lower,
Interfacial effect to hardly result in relatively thin zero defect separating layer on its surface.Currently, most of researchs are by repeatedly coating
PDMS is repaired, i.e., coats one layer of PDMS again in separating layer as protective layer, film-forming process is relatively complicated.
The present invention carries out processing modification to composite membrane middle layer by plasma technique, easily and effectively improves its surface
Can, be conducive to the coating for eliminating interfacial effect and ultra-thin zero defect separating layer, reduction applies hierachy number less, improves the preparation of composite membrane
Efficiency and its separating property.
Summary of the invention
The purpose of the present invention is to provide a kind of composite membrane middle layer method of modifying, reduce and apply hierachy number, improve composite membrane
Preparation efficiency and its separating property.
A kind of corona treatment multi-layer gas composite membrane, the composite membrane are bottom/middle layer/separating layer structure multilayer
Composite membrane；Bottom is porous support layer, 50-200 μm of thickness；Middle layer be high osmosis material, 0.1-10 μm of thickness；Separation
Layer is has the membrane material of good intrinsic separating property to specific gas component, and 10nm-5 μm of thickness.
The primer includes but is not limited to poly (aryl ether sulfone ketone), polyimides, polyetherimide, polysulfones, polyether sulfone, gathers
Acrylonitrile or Kynoar.
The middle layer is silicon rubber or derivatives thereof.
The separation layer materials include but is not limited to the block copolymer containing polyether segment, polyurethane, polyphenylene oxide, polyamides
Amine, polyimides, polyether sulfone, polyether ethersulfone；
Or above-mentioned material and contain ether oxygen, ester group, itrile group, the small organic molecule of amino group or ionic liquid；
Or the blending that constitutes of above-mentioned radical functino ionic liquid, metal organic frame, molecular sieve or carbon nanotube and mixed-matrix
Membrane material；
The block copolymer containing polyether segment includes but is not limited to polyethers-b- amide, polyethers-poly terephthalic acid
Butanediol ester block copolymer, polyethers-polyimide block copolymer, polyethers-polyetherimide blocks' copolymer, polyethers-are poly-
Urethane, polyethers-polylauryllactam, thermoplastic polyurethane and other polyether block copolymers.
A kind of preparation method of corona treatment multi-layer gas composite membrane, multilayer complex films use immersion coating legal system
It is standby, the specific steps are as follows:
(1) bottom is immersed into intermediate layer solution, prepares bottom/interlayer film；
(2) corona treatment is carried out to bottom/middle layer composite membrane；Corona treatment voltage is 0-200V, electric current
For 0-3A, processing speed 1-50cm/s；
(3) by treated, bottom/middle layer composite membrane is impregnated in concentration as in 0.1-10% separating layer solution, dipping is applied
The pull rate covered is 0.1-40cm/s, then by evaporation of solvent, forms bottom/middle layer/separating layer MULTILAYER COMPOSITE
Film.
The intermediate layer solution is the solution of described silicon rubber or derivatives thereof, and wherein solvent includes but is not limited to positive penta
Alkane, hexamethylene, normal heptane, chloroform, methylene chloride, toluene, benzene.
The separating layer Solutions Solution is the solution of separation layer materials, and wherein solvent includes but is not limited to N, N- dimethyl methyl
Amide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, 1-1-2- trichloroethanes, formic acid, acetic acid, n-butyl alcohol, n-butyl alcohol and
1- propanol solvent mixture, ethyl alcohol and water mixed solvent, chloroform, tetrafluoroacetate.
The separation layer materials include but is not limited to the block copolymer containing polyether segment, polyurethane, polyphenylene oxide, polyamides
Amine, polyimides, polyether sulfone, polyether ethersulfone；
Or above-mentioned material and contain ether oxygen, ester group, itrile group, the small organic molecule of amino group or ionic liquid；
Or the blending that constitutes of above-mentioned radical functino ionic liquid, metal organic frame, molecular sieve or carbon nanotube and mixed-matrix
Membrane material；
The block copolymer containing polyether segment includes but is not limited to polyethers-b- amide, polyethers-poly terephthalic acid
Butanediol ester block copolymer, polyethers-polyimide block copolymer, polyethers-polyetherimide blocks' copolymer, polyethers-are poly-
Urethane, polyethers-polylauryllactam, thermoplastic polyurethane and other polyether block copolymers.
The corona treatment is atmospheric low-temperature plasma processing；Low-temperature plasma is generated by glow discharge, is put
Dielectric is air, Ar, He, Ne, Kr, Xe, H2、N2Or O2One of.
A kind of application of corona treatment multi-layer gas composite membrane, it is characterised in that the multilayer complex films are applied to
Gas separation.
The multilayer complex films are applied to sour gas CO2、SO2And H2The separation of S.
Corona treatment acts on middle layer, can effectively improve its surface energy, and decrease even is eliminated interfacial effect, avoids
The use of essential protective layer in conventional film-forming method reduces and applies hierachy number, improves production efficiency.
It is plasma-treated, the compatibility of middle layer and separating layer be improved significantly, can be without using protective layer
In the case of and obtain close to intrinsic selective separating property, that is, obtain ultra-thin zero defect separating layer.
The present invention has the advantages that using plasma processing middle layer is modified have the advantages that it is convenient and efficient,
The modified surface energy that middle layer can be improved, is conducive to the coating of zero defect separating layer.It is separated with traditional bottom/middle layer/
Layer/protective layer structure compares the use for eliminating protective layer, reduces painting hierachy number, can effectively improve production efficiency.
Specific embodiment
Comparative example 1
Polyethers-b- amide (Pebax1657) is dissolved in ethanol/water and obtains 5wt% casting solution, is obtained through casting filming therapy
Pebax homogeneous membrane, 35 DEG C, the film is to CO when 0.5MPa2Selectivity be shown in Table 1.
Table 1.
| CO2Infiltration coefficient (Barrer) | CO2/N2 | |
| Pure Pebax | 129 | 51 |
Comparative example 2
Polysulfones (Psf) counterdie is impregnated in the pentane solution of middle layer dimethyl silicone polymer (PDMS), will be dried
After wait until Psf/PDMS film.Not plasma treated Psf/PDMS is impregnated in the Pebax1657 ethanol/water separation of 1wt%
In layer solution, composite membrane is taken out from coating solution with the pull rate of 0.5cm/s, then in 40 DEG C of solvent flashing 1d, is obtained
Psf/PDMS/Pebax composite membrane.Room temperature, the performance of the film is shown in Table 3 when 0.5MPa.
Comparative example 3
Polysulfones (Psf) counterdie is impregnated in the pentane solution of middle layer dimethyl silicone polymer (PDMS), will be dried
After wait until Psf/PDMS film.Not plasma treated Psf/PDMS is impregnated in the Pebax1657 ethanol/water separation of 5wt%
In layer solution, composite membrane is taken out from coating solution with the pull rate of 2cm/s, then in 40 DEG C of solvent flashing 1d, is obtained
Psf/PDMS/Pebax composite membrane.Room temperature, the performance of the film is shown in Table 3 when 0.5MPa.
Embodiment 1
Polysulfones (Psf) counterdie is impregnated in the pentane solution of middle layer dimethyl silicone polymer (PDMS), will be dried
After wait until Psf/PDMS film.The Psf/PDMS of (voltage 50V, electric current 1.8A, processing speed 20cm/s) is denoted as after plasma treatment
Psf/PDMS-plasme is impregnated in the Pebax1657 ethanol/water separating layer solution of 1wt%, with the lifting of 20cm/s
Speed takes out composite membrane from coating solution, and then in 40 DEG C of solvent flashing 1d, it is compound to obtain Psf/PDMS-plasme/Pebax
Film, the performance of the film is shown in Table 2 when 0.5MPa.
Table 2.
Embodiment 2
Polysulfones (Psf) counterdie is impregnated in the pentane solution of middle layer dimethyl silicone polymer (PDMS), will be dried
After wait until Psf/PDMS film.Psf/PDMS after plasma treatment (voltage 100V, electric current 2A, processing speed 50cm/s) is denoted as
Psf/PDMS-plasme is impregnated in the Pebax1657 ethanol/water separating layer solution of 1wt%, with the lifting of 40cm/s
Speed takes out composite membrane from coating solution, and then in 40 DEG C of solvent flashing 1d, it is compound to obtain Psf/PDMS-plasme/Pebax
Film, CO2 flux are higher than 150GPU, and CO2/N2 is selectively greater than 35, function admirable.
Embodiment is analyzed as follows with comparative example data:
Table 3.
| CO2Permeation flux (GPU) | CO2/N2 | |
| Pure Pebax | 129Barrer | 51 |
| Psf/PDMS/Pebax (1wt%) | 1536 | 10 |
| Psf/PDMS/Pebax (5wt%) | 8 | 50 |
The intrinsic CO of PDMS and Pebax2/N2Selectivity is respectively 10 and 51.It can by the comparison of 3 comparative example 1,2,3 of table
Know, misaligns interbed and carry out corona treatment, when separating layer solution concentration is lower, since interlayer surfaces can be larger, with
Separating layer compatibility is poor, can not obtain complete separating layer, causes prepared multilayer complex films without separating property.Work as separating layer
Solution concentration increases, and viscosity increases, and the bonding force between middle layer also increases with it, and can obtain complete separation at this time
Layer, acquisition and the comparable selectivity of intrinsic separation property, but separating layer is thicker at this time, the CO of acquisition2Permeation flux is extremely low.
Table 4.
| CO2Permeation flux (GPU) | CO2/N2 | |
| Psf/PDMS/Pebax (1wt%) | 1536 | 10 |
| Psf/PDMS-plasme/Pebax (1wt%) | 152 | 50 |
| Psf/PDMS/Pebax (5wt%) | 8 | 50 |
Table 4 is comparative example 2,3, the comparison of embodiment 1, it can be seen that after corona treatment, composite membrane be can get and this
The comparable selectivity of separation property is levied, shows that separating layer is complete, while separating layer is again relatively thin, so that permeation flux is larger.
Table 5.
| CO2Permeability | CO2/N2 | |
| Pure Pebax | 129Barrer | 51 |
| Psf/PDMS-plasme/Pebax (1wt%) | 218GPU | 38 |
Table 5 is the comparison of comparative example 1, embodiment 1, under the same test conditions, after corona treatment, composite membrane
The available and comparable selectivity of intrinsic separation property, and permeation flux is larger, shows there is ultra-thin complete separating layer, separating layer
Know that separating layer is at this time with a thickness of 0.6 μm by calculating.
It is modified to composite membrane middle layer by plasma, ultra-thin zero defect can be obtained in unprotected situation
Separating layer reduces painting hierachy number, can effectively improve production efficiency.
Claims (10)
1. a kind of corona treatment multi-layer gas composite membrane, it is characterised in that: the composite membrane is bottom/middle layer/separating layer
The multilayer complex films of structure；Bottom is porous support layer, 50-200 μm of thickness；Middle layer is the material of high osmosis, thickness
0.1-10μm；Separating layer is the membrane material for having good intrinsic separating property to specific gas component, 10nm-5 μm of thickness.
2. a kind of corona treatment multi-layer gas composite membrane according to claim 1, it is characterised in that: the backsheet
Material includes but is not limited to poly (aryl ether sulfone ketone), polyimides, polyetherimide, polysulfones, polyether sulfone, polyacrylonitrile or polyvinylidene fluoride
Alkene.
3. a kind of corona treatment multi-layer gas composite membrane according to claim 1, it is characterised in that: the middle layer
For silicon rubber or derivatives thereof.
4. a kind of corona treatment multi-layer gas composite membrane according to claim 1, it is characterised in that: the separating layer
Material includes but is not limited to the block copolymer containing polyether segment, polyurethane, polyphenylene oxide, polyamide, polyimides, polyether sulfone
Or polyether ethersulfone；
Or above-mentioned material and contain ether oxygen, ester group, itrile group, the small organic molecule of amino group or ionic liquid；Or
The blending and mixed-matrix membrane material that above-mentioned radical functino ionic liquid, metal organic frame, molecular sieve or carbon nanotube are constituted
Material.
5. a kind of corona treatment multi-layer gas composite membrane according to claim 4, it is characterised in that: described containing poly-
The block copolymer of ether segment includes but is not limited to polyethers-b- amide, polyethers-polybutylene terephthalate (PBT) block copolymerization
Object, polyethers-polyimide block copolymer, polyethers-polyetherimide blocks' copolymer, polyether-polyurethane, polyethers-polyoxyethylene lauryl
Base lactams, thermoplastic polyurethane and other polyether block copolymers.
6. a kind of preparation of corona treatment multi-layer gas composite membrane described in any claim in -5 according to claim 1
Method, it is characterised in that: multilayer complex films are prepared using dip-coating method, the specific steps are as follows:
(1) bottom is immersed into intermediate layer solution, prepares bottom/interlayer film；
(2) corona treatment is carried out to bottom/middle layer composite membrane；Corona treatment voltage is 0-200V, electric current 0-
3A, processing speed 1-50cm/s；
(3) will treated that bottom/middle layer composite membrane is impregnated in that concentration is in 0.1-10% separating layer solution, immersion coating
Pull rate is 0.1-40cm/s, then by evaporation of solvent, forms bottom/middle layer/separating layer multilayer complex films.
7. a kind of preparation method of corona treatment multi-layer gas composite membrane according to claim 6, it is characterised in that:
The intermediate layer solution is the solution of silicon rubber or derivatives thereof, and wherein solvent includes but is not limited to pentane, hexamethylene, positive heptan
Alkane, chloroform, methylene chloride, toluene or benzene；
The separating layer Solutions Solution is the solution of separation layer materials, and wherein solvent includes but is not limited to N, N- dimethyl formyl
Amine, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, 1-1-2- trichloroethanes, formic acid, acetic acid, n-butyl alcohol, n-butyl alcohol and 1-
Propanol solvent mixture, ethyl alcohol and water mixed solvent, chloroform or tetrafluoroacetate；
The separation layer materials include but is not limited to the block copolymer containing polyether segment, polyurethane, polyphenylene oxide, polyamide,
Polyimides, polyether sulfone or polyether ethersulfone；
Or above-mentioned material and contain ether oxygen, ester group, itrile group, the small organic molecule of amino group or ionic liquid；Or
The blending and mixed-matrix membrane material that above-mentioned radical functino ionic liquid, metal organic frame, molecular sieve or carbon nanotube are constituted
Material.
8. a kind of preparation method of corona treatment multi-layer gas composite membrane according to claim 6, it is characterised in that
The corona treatment is atmospheric low-temperature plasma processing；Low-temperature plasma is generated by glow discharge, and discharge medium is
Air, Ar, He, Ne, Kr, Xe, H2、N2Or O2One of.
9. a kind of application of corona treatment multi-layer gas composite membrane described in -5 any claims according to claim 1,
It is characterized in that the multilayer complex films are separated applied to gas.
10. a kind of application of corona treatment multi-layer gas composite membrane according to any claim of claim 9,
It is characterized in that the multilayer complex films are applied to sour gas CO2、SO2And H2The separation of S.
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