CN101693167A - Novel loaded transition metal composite membrane and preparation method thereof - Google Patents
Novel loaded transition metal composite membrane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a separation membrane, in particular to a novel loaded transition metal composite membrane. A separation layer is compounded on a support layer which adopts a porous membrane or a microporous membrane; the separation layer adopts a polymeric material coating containing ether-oxygen bonds or ketonic oxygen; the upper surface of the separation layer is a transition metal infiltration layer which is contacted with the separation layer through transition metal soluble salt solution; the transition metal infiltration layer is formed by the matching of transition metal ions and functional groups of the ether-oxygen bonds or ketonic oxygen in the separation layer material; the separation layer material contains the functional groups which can be matched with transition metal ion carriers; and through detection, in the novel loaded transition metal composite membrane, the transition metal ions are only introduced into the surface layer of the dense separation layer at the thickness of 1-300nm, and olefin is promoted and transferred due to complexation of carrier ions to the olefin, thus improving the separation effect of the olefin/alkane.
Description
One, technical field:
The present invention relates to a kind of composite gas separation, also relate to the preparation method of composite membrane in addition.
Two, background technology:
Alkene and alkane are the important raw and processed materials of chemical industry.All produce a large amount of olefin/paraffin admixture of gas at petrochemical process such as thermal cracking, catalytic cracking, need to select the method for economical and energy saving to make it to separate.Because separation method energy consumption height such as tradition distillation, absorption and efficient are low.The separation method of exploring energy-efficient olefin/paraffin just becomes one of important topic of petrochemical industry.
Along with the continuous development of gas separation membrane technology, the membrane separating hydro carbons receives scientific research personnel's very big concern.Yet the gas permeation rate and the olefin/paraffin that generally are used for the polymer film of gas separation select performance not high, and the ethylene/ethane separation factor only is 4-5.Reversible complexing can take place with alkene in transition metal ions, and the promotion transport membranes of utilizing this principle preparation is hopeful fundamentally to break away from the restriction of " the Robeson upper limit " because simple dissolving-diffusion mechanism is no longer followed in the introducing of complex reaction.
The solid polyelectrolyte of transition metal salt and macromolecular material blend preparation promotes transport membranes, under the condition that does not have water vapour to exist, the ideal separation factor of alkene/alkane is reached thousands of, and the work of this respect is with U.S. Membrane Technology ﹠amp at present; The research of Research company is the most outstanding.The U.S. patent of invention US005670051 play-by-play preparation of multiple solid polyelectrolyte film, with and to the separating property of alkene/alkane, but owing to the chemical instability and the so-called alkene restriction phenomenon of the transition metal ions carrier in its film is difficult to industrialization.
Summary of the invention:
The object of the invention is to overcome existing not enough problem, and a kind of novel loaded transition metal composite membrane is provided, and is used for alkene/alkane separation field, the excellent the present invention in addition of separating effect also provides the preparation method of novel loaded transition metal composite membrane, preparation technology's uniqueness, easy to operate, noble metal carrier consumption is little.
The present invention is that the technical scheme that is adopted that achieves the above object is: a kind of novel loaded transition metal composite membrane, compound separating layer on the supporting layer, supporting layer adopts perforated membrane or microporous barrier, separating layer adopts the macromolecule material coating that contains ether-oxygen bond or ketonic oxygen, the separating layer upper surface is the transition metal penetrating layer, the transition metal penetrating layer contacts with separating layer by transition metal soluble-salt solution, and the cooperation of the ether-oxygen bond in transition metal ions and the separating layer material/ketonic oxygen functional group forms the transition metal penetrating layer.
Described supporting layer perforated membrane or microporous barrier adopt one or more or the modification in the following membrane material to make: cellulose acetate (cellulose acetates), cellulose derivative (cellulosicderivatives), celluloid (cellulose nitrates), ethyl cellulose (ethylcellulose), polyamide (polyamides), polyimides (polyimides), polyester (polyester), Merlon (polycarbonates), Copolycarbonate (copolycarbonate ester), poly-(many) ether (polyether), polyether-ketone (polyetherketones), PEI (polyetherimides), polyether sulfone (polyethersulfones), polysulfones (polysulfones), Kynoar (polyvinylidene fluoride), polybenzimidazoles (polybenzimidazoles), polyacrylonitrile (polyacrylonitrile), polypropylene (PP), polyvinyl alcohol (polyvinylalcohol), polyvinyl chloride (polyvinylchloride), poly-azo aromatic hydrocarbons (polyazoaromatics), polyphenylene oxide/polyphenylene oxygen/poly-2,6-dimethyl-1,4-phenylate (polyphenylene oxide)/poly (2,6-dimethylphenylene oxide), polyureas (polyureas), polyurethane (polyurethanes), polyhydrazide (polyhydrazides), poly-azomethine/poly methylene imine (polyazomethines), the rare lonitrile copolymer of styrene-third (styrene-acrylonitrile copolymers), bromo polyxylene ether (brominated poly (xylene oxide)), sulfonation polyxylene ether (sulfonated poly (xylene oxide)), four halogenated polycarbonates (tetrahalogen-substituted polycarbonates), four halo polyester (tetrahalogen-substituted polyesters), polyamide-imide (polyamideimides), polyester-imides (polyimide esters), polyethersulfone ketone (PPESK)/diazanaphthalene biphenyl type poly (aryl ether sulfone ketone) (poly (phthalazine ether sulfoneketone)) and sulfonated polyether sulfone ketone (PPESK)/sulfonation diazanaphthalene biphenyl type poly (aryl ether sulfone ketone) (sulfonated poly (phthalazine ether sulfone ketone)) etc.
The polymeric coating layer that contains ether-oxygen bond or ketonic oxygen that described separating layer adopts is selected from one or more in the following material: polyethers copolyamide (PEBA), polyphenylene oxide (PPO), polyethylene glycol oxide (PEO) and polyvinylpyrrolidone (PVP) etc.
Described separating layer coating layer thickness is 0.1-50 μ m, and optimum is 0.1-10 μ m.
The transition metal soluble-salt solution that described transition metal penetrating layer adopts is selected from a kind of in following: the soluble-salt solution of Transition Metal Ag, Cu, Co, Ru, Rh, Ir, Au etc.
The anion of described transition metal soluble-salt solution is selected from a kind of in the following anionic radical: SCN
-, NO
3 -, BF
4 -, ClO
4 -, SbF
6 -, thioether anion, mercaptan anion, Cl
-, CF
3SO
3 -Deng.
Composite membrane behind the described carrying transition metal ion is at transition metal penetrating layer one side silicone rubber coating, and coating concentration is 0.01-3wt%.
The preparation method of novel load filtering metal composite membrane of the present invention, its preparation process is as follows: coated separating layer on supporting layer at first, adopt one-sided ligand exchange method composite transition metal penetrating layer then on separating layer, the method for introducing transition metal ions is one-sided solution ligand exchange method; Transition metal soluble-salt solution concentration is 0.01M-12M; Be 30 seconds-60 hours swap time, was preferably 5 minutes-2 hours.
The H that adds 0.01-3wt% in the described transition metal soluble-salt solution
2O
2/ HBF
4Mixture is used to prevent the reduction of transition metal ions carrier.
At separating layer one side coating silicon rubber, silicone rubber coating concentration is 0.01-3wt% to composite membrane behind the described carrying transition metal ion again.
It is supporting layer that the present invention adopts perforated membrane or microporous barrier, by coating on the support counterdie the higher macromolecular material of gas permeability is formed fine and close separating layer, makes composite membrane that the good penetration performance be arranged.Contain the functional group that can cooperate with the transition metal ions carrier in the separating layer material, by the ligand exchange method, the feed side of fine and close separating layer simultaneously the thickness of about 1-300nm introduce transition metal ions, thereby obtain a kind of novel loaded transition metal composite membrane.Technology of the present invention is simple, operation easily, adopt one-sided solution ligand exchange method, composite membrane with fine and close separating layer is contacted with transition metal soluble-salt solution, cooperation by the ether-oxygen bond in transition metal ions and the separating layer material/ketonic oxygen functional group, the about 1-300nm in surface introduces metal ion in fine and close separating layer, forms the transition metal penetrating layer.By the concentration of control transition metal soluble-salt solution, the infiltration thickness and the dispersity of control metal ion; Control by swap time prepares the composite membrane that the different metal ion infiltrates thickness.
After testing, the present invention only thickness about fine and close separating layer top layer 1-300nm introduces transition metal ions, and owing to the complexing of carrier ion to alkene, alkene obtains promoting to transmit, and has improved the separating effect of olefin/paraffin.
Four, description of drawings:
Fig. 1 is a structure of composite membrane schematic diagram of the present invention.
Fig. 2 is the TEM figure of composite membrane section of the present invention.Be the thickness of examination metal infiltration separating layer, carry out TEM after transition metal ions is reduced fully and characterize.There is the metal level of nanometer grade thickness on the composite membrane surface, and this layer thickness is the thickness that transition metal infiltrates separating layer.
Five, the specific embodiment:
Below in conjunction with specific embodiment the present invention is described in further detail, but the invention is not restricted to specific embodiment.
Embodiment 1:
On support membrane 1 porous PEI milipore filter, use dip coating method coating quality concentration 6%PEBA2533, its solvent is a butanols, the coating temperature is 50 ℃, drying time 4h, the composite membrane of preparation 30 ℃ of dry 24h in vacuum drying oven remove residual solvent and form separating layer 2.Adopt one-sided ligand solution exchange process then, with the AgNO of 1.0M
3Solution single face in the composite membrane separating layer is introduced transition metal ions, behind the 2h transition metal soluble-salt solution is poured out, used the deionized water rinsing surface, place dry 24h under the lucifuge condition, the separating layer surface has transition metal penetrating layer 3, carries out gas permeation test then.
Embodiment 2:
On support membrane porous PEI milipore filter, use dip coating method coating quality concentration 6%PEBA2533, its solvent is a butanols, the coating temperature is 50 ℃, drying time 4h, the composite membrane of preparation 30 ℃ of dry 24h in vacuum drying oven remove residual solvent and form separating layer 2.Adopt one-sided ligand solution exchange process, with the AgNO of 5.0M
3Solution single face in the composite membrane separating layer is introduced transition metal ions, behind the 2h transition metal soluble-salt solution is poured out, used the deionized water rinsing surface, place dry 24h under the lucifuge condition, the separating layer surface has transition metal penetrating layer 3, carries out gas permeation test then.
Embodiment 3:
With dip coating method coating 6%PEBA2533, its solvent is a butanols on support membrane porous PEI milipore filter, and the coating temperature is 50 ℃, drying time 4h.The composite membrane of preparation 30 ℃ of dry 24h in vacuum drying oven remove residual solvent and form separating layer 2.Adopt one-sided ligand solution exchange process, with the AgBF of 1.0M
4Solution single face in the composite membrane separating layer is introduced transition metal ions, behind the 2h transition metal soluble-salt solution is poured out, used the deionized water rinsing surface, place dry 24h under the lucifuge condition, the separating layer surface has transition metal penetrating layer 3, carries out gas permeation test then.
Embodiment 4:
With dip coating method coating 6%PEBA2533, its solvent is a butanols on support membrane porous PEI milipore filter, and the coating temperature is 50 ℃, drying time 4h.The composite membrane of preparation 30 ℃ of dry 24h in vacuum drying oven remove residual solvent and form separating layer 2.Adopt one-sided ligand solution exchange process, with the AgBF of 5.0M
4Solution single face in the composite membrane separating layer is introduced transition metal ions, behind the 2h transition metal soluble-salt solution is poured out, used the deionized water rinsing surface, place dry 24h under the lucifuge condition, the separating layer surface has transition metal penetrating layer 3, carries out gas permeation test then.
The performance of the made film of embodiment 1-4 sees the following form:
Embodiment 5:
With dip coating method coating 6%PEBA2533, its solvent is a butanols on support membrane porous PEI milipore filter, and the coating temperature is 50 ℃, drying time 4h.The composite membrane of preparation 30 ℃ of dry 24h in vacuum drying oven remove residual solvent and form separating layer 2.Adopt one-sided ligand solution exchange process, with the AgBF of 6.0M
4Solution single face in the composite membrane separating layer is introduced transition metal ions, behind the 2h transition metal soluble-salt solution is poured out, used the deionized water rinsing surface, place dry 24h under the lucifuge condition, the separating layer surface has transition metal penetrating layer 3, carries out gas permeation test then.
Embodiment 6
With dip coating method coating 6%PEBA2533, its solvent is a butanols on support membrane porous PEI milipore filter, and the coating temperature is 50 ℃, drying time 4h.The composite membrane of preparation 30 ℃ of dry 24h in vacuum drying oven remove residual solvent and form separating layer 2.Adopt one-sided ligand solution exchange process, with the AgBF of 8.0M
4Solution single face in the composite membrane separating layer is introduced transition metal ions, behind the 2h transition metal soluble-salt solution is poured out, used the deionized water rinsing surface, place dry 24h under the lucifuge condition, the separating layer surface has transition metal penetrating layer 3, carries out gas permeation test then.
The performance of embodiment 5,6 made films sees the following form:
Embodiment 7-10
Prepare novel loaded transition metal composite membrane by embodiment 1 described method, concrete raw material and technological parameter such as following table.
Claims (10)
1. novel loaded transition metal composite membrane, compound separating layer on the supporting layer, supporting layer adopts perforated membrane or microporous barrier, it is characterized in that: separating layer adopts the macromolecule material coating that contains ether-oxygen bond or ketonic oxygen, the separating layer upper surface is the transition metal penetrating layer, the transition metal penetrating layer contacts with separating layer by transition metal soluble-salt solution, and the cooperation of the ether-oxygen bond in transition metal ions and the separating layer material/ketonic oxygen functional group forms the transition metal penetrating layer.
2. a kind of novel loaded transition metal composite membrane according to claim 1 is characterized in that: supporting layer perforated membrane or microporous barrier adopt one or more or the modification in the following membrane material to make: cellulose acetate, cellulose derivative, celluloid, ethyl cellulose, polyamide, polyimides, polyester, Merlon, Copolycarbonate, poly-(many) ether, polyether-ketone, PEI, polyether sulfone, polysulfones, Kynoar, polybenzimidazoles, polyacrylonitrile, polypropylene, polyvinyl alcohol, polyvinyl chloride, poly-azo aromatic hydrocarbons, polyphenylene oxide/polyphenylene oxygen/gather 2,6-dimethyl-1, the 4-phenylate, polyureas, polyurethane, polyhydrazide, poly-azomethine/poly methylene imine, the rare lonitrile copolymer of styrene-third, the bromo polyxylene ether, the sulfonation polyxylene ether, four halogenated polycarbonates, four halo polyester, polyamide-imide, polyester-imides, polyethersulfone ketone/diazanaphthalene biphenyl type poly (aryl ether sulfone ketone) and sulfonated polyether sulfone ketone (PPESK)/sulfonation diazanaphthalene biphenyl type poly (aryl ether sulfone ketone) etc.
3. a kind of novel loaded transition metal composite membrane according to claim 1 is characterized in that: the polymeric coating layer that contains ether-oxygen bond or ketonic oxygen that separating layer adopts is selected from one or more in the following material: polyethers copolyamide, polyphenylene oxide, polyethylene glycol oxide and polyvinylpyrrolidone etc.
4. a kind of novel loaded transition metal composite membrane according to claim 1 is characterized in that: the separating layer coating layer thickness is 0.1-50 μ m, and optimum is 0.1-10 μ m.
5. a kind of novel loaded transition metal composite membrane according to claim 1 is characterized in that: the transition metal soluble-salt solution that the transition metal penetrating layer adopts is selected from a kind of in following: the soluble-salt solution of Transition Metal Ag, Cu, Co, Ru, Rh, Ir, Au etc.
6. a kind of novel loaded transition metal composite membrane according to claim 5 is characterized in that: the anion of transition metal soluble-salt solution is selected from a kind of in the following anionic radical: SCN
-, NO
3 -, BF
4 -, ClO
4 -, SbF
6 -, thioether anion, mercaptan anion, Cl
-, CF
3SO
3 -Deng.
7. a kind of novel loaded transition metal composite membrane according to claim 1 is characterized in that: the composite membrane behind the carrying transition metal ion is at separating layer one side silicone rubber coating, and coating silicon rubber concentration is 0.01-3wt%.
8. the preparation method of novel load filtering metal composite membrane, it is characterized in that: its preparation process is as follows: coated separating layer on supporting layer at first, adopt one-sided ligand exchange method composite transition metal penetrating layer then on separating layer, the method for introducing transition metal ions is one-sided solution ligand exchange method; Transition metal soluble-salt solution concentration is 0.01M-12M; Be 30 seconds-60 hours swap time, was preferably 5 minutes-2 hours.
9. a kind of novel loaded transition metal composite membrane according to claim 8 is characterized in that: add peroxide and acid in the transition metal soluble-salt solution, (be generally H
2O
2/ HBF
4Mixture) is used to prevent the reduction of transition metal ions carrier.
10. a kind of novel loaded transition metal composite membrane according to claim 9 is characterized in that: add H in the transition metal soluble-salt solution
2O
2And HBF
4Mixture.
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| CN102302900A (en) * | 2011-08-26 | 2012-01-04 | 国家海洋局天津海水淡化与综合利用研究所 | Method for detecting microstructure of reverse osmosis membrane separating layer |
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| CN105536566A (en) * | 2016-01-19 | 2016-05-04 | 长安大学 | Composite membrane with function of separating lithium ions and cobalt ions and preparation method thereof |
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| CN108404680A (en) * | 2018-03-09 | 2018-08-17 | 西部宝德科技股份有限公司 | A kind of inorganic-organic composite membrane and preparation method thereof |
| CN111111477B (en) * | 2018-11-01 | 2021-04-13 | 中国科学院过程工程研究所 | Olefin/alkane separation membrane and preparation method thereof |
| CN111111477A (en) * | 2018-11-01 | 2020-05-08 | 中国科学院过程工程研究所 | Olefin/alkane separation membrane and preparation method thereof |
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| CN110508166B (en) * | 2019-07-23 | 2021-10-12 | 西北大学 | Surface metal ion modified silicon rubber desulfurization film and preparation method and application thereof |
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| CN114432910A (en) * | 2022-01-29 | 2022-05-06 | 中国科学院过程工程研究所 | Separation membrane and preparation method and application thereof |
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