CN102247764A - Carbon/graphite/porous matrix composite membrane and preparation method and application thereof - Google Patents
Carbon/graphite/porous matrix composite membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN102247764A CN102247764A CN201110209457XA CN201110209457A CN102247764A CN 102247764 A CN102247764 A CN 102247764A CN 201110209457X A CN201110209457X A CN 201110209457XA CN 201110209457 A CN201110209457 A CN 201110209457A CN 102247764 A CN102247764 A CN 102247764A
- Authority
- CN
- China
- Prior art keywords
- graphite
- composite membrane
- carbon
- porous
- porous matrix
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention discloses a carbon composite membrane. The carbon composite membrane comprises a porous matrix, a transition layer mainly made of graphite on the surface of the porous matrix, and a porous carbon membrane on the surface of the transition layer. A method for preparing the carbon composite membrane comprises the following steps of: coating on the surface of the porous matrix to form the graphite transition layer, coating dopant-modified polymer solution, and carbonizing to obtain the carbon composite membrane. The graphite transition layer can improve the surface roughness of the porous matrix and eliminate surface defects, and can also prevent the carbon membrane from cracking in the process of polymer pyrolysis; meanwhile, the functional carbon composite membrane can be prepared and the separation performance of the membrane can be improved by changing the composition of a polymer. In the invention, the carbon composite membrane with high uniformity, few defects, and high permeability and selectivity can be prepared based on the low-cost macroporous matrix, the cost of the carbon membrane can be effectively reduced, the process is simple, and the carbon composite membrane can be widely applied to gas separation.
Description
Technical field
The present invention relates to a kind of compound carbon film, its preparation method and application, particularly a kind of high performance carbon/graphite/porous matrix composite membrane is the method that matrix prepares this composite membrane with large pore material cheaply, and the application of this composite membrane in gas separates.
Background technology
In today of energy scarcity, shortage of resources, the deterioration of the ecological environment, traditional isolation technics can't adapt to the requirement of era development, and membrane separation technique is efficient, energy-conservation with it, convenient easily advantages such as control, non-secondary pollution, become the new tool that solves the energy, resource and environmental problem, not only in the separation of liquid liquid, liquid-solid separation, obtained using widely, in the also growth rapidly of application of gas separation field.
Divide from membrane material, gas separation membrane can be divided into inoranic membrane and organic film.Except that the palladium alloy membrane that is used for purifying hydrogen, business-like gas separation membrane mostly is polymeric membrane, is widely used in that air separation, hydrogen reclaim, the removing of sour gas, steam gas separation etc. in the natural gas.Yet the variation of character such as swelling can take place in polymeric membrane under conditions such as high temperature, high pressure, strong acid-base, cause separating property to descend, thereby has limited the application of polymer film.Therefore, demanding people urgently develops and uses new material.
In recent years, carbon film is shown one's talent with its excellent performance.Carbon film is a kind of novel inorganic separating film, typically refers under inert gas or vacuum protection condition, and carbon matrix precursor is heated the microporous separation membrane that carbonization is made at higher temperature.It not only has the ability of high temperature resistant preferably, acid and alkali-resistance and organic solvent-resistant, also the close micro-molecular gas of molecular scale had higher permselective property, pore-size distribution homogeneous, the adjustable extent of carbon film are big simultaneously, be easy to the large tracts of land film forming, the high performance gas that is tool industrial prospect is separated inoranic membrane (Soria R. Overview on industrial membranes. Catal. Today, 1995,25 (3-4): 285-290).
According to the difference of membrane structure, carbon film is divided into non-support carbon film (homogeneous carbon film) and supports carbon film (compound carbon film).Non-support carbon film is because quality is more crisp, frangible, and practical application is inconvenience very.Studies show that and reduce separating property (the Hatori H that thickness can effectively improve carbon film, Yamada Y, Shiraishi M. Preparation of macroporous carbon films from polyimide by phase inversion method. Carbon, 1992,30 (2): 303-304).Matrix in the compound carbon film provides enough mechanical strengths for carbon film, can make thickness thin as much as possible, thereby reduces the resistance to mass tranfer of gas, improves the permeance property of carbon film.Therefore, main research at present mostly concentrates on and supports on the carbon film.
Matrix is the basis of compound carbon film, the quality of decision carbon film.Prepare even, continuous carbon film on matrix, the aperture and the roughness of matrix surface have tremendous influence: the surface is smooth more, the aperture is more little, then helps preparing flawless carbon film more.But the matrix of smooth surface, no big hole defect costs an arm and a leg, and has not only increased cost with its preparation carbon film, also is unfavorable for the heavy industrialization application.
Discover, by preparing roughness that transition zone can reduce the macropore matrix surface at matrix surface, filling up big hole defect, to reach the purpose of low-cost preparation carbon film.Sol-gal process is a kind of common method of preparation transition zone, also be a kind of effective ways (Brinker C J of preparation composite membrane, Sehgal R, Hietala S L, et al. Sol-gel strategies for controlled porosity inorganic materials. J. Membr. Sci., 1994,94 (1): 85-102, Deng Chao, Zhang Xiaoliang, Huang Yan. the gel modification of porous ceramic matrix surface and the preparation of palladium film. Nanjing University of Technology's journal, 2010,32 (1): 92-97).Concrete steps are at first raw material to be added in the solvent, form stable vitreosol by hydrolysis, condensation chemical reaction.Again it is coated on the matrix, dry back forms liquid film, gelation is after heat treatment is transformed into amorphous state (or polycrystalline attitude) film or coating (Kurz A, Brakecha K, Puetz J, et al. Strategies for novel transparent conducting sol-gel oxide coatings. J. Membr. Sci., 2006,501 (1-2): 212-218).But colloidal sol-gel process condition is extremely complicated, in the Drying of gels process because the volatilization of solvent, small molecular alcohol or water, can make the coating of formation occur crackle, obscission easily, sometimes also need repeat multi-pass operation, and on the bigger porous matrix in aperture, prepare the transition zone poor effect in this way.
Meanwhile, the pure carbon film still can't be broken away from the contradiction between the ubiquitous permeation flux and selectivity in the gas separation membrane.At this difficult problem, the researcher studies from membrane material and novel masking technique two aspects of exploration of seeking excellent performance, and obtained certain progress in the preparation and the application facet of carbon film, also developed some novel persursor materials, but only be that the carbon film that presoma prepares still can't reach high osmosis and high selectivity simultaneously with the single polymers.Therefore, the researcher begins from the chemical constitution that changes presoma and the angle of composition, in the hope of preparation high-performance carbon film.
Summary of the invention
The objective of the invention is problem at existence in carbon composite membrane and preparation method thereof, provide a kind of cost low, based on the high performance carbon composite membrane of macropore matrix, this carbon composite membrane good uniformity, defective are few, have higher mechanical strength, under the prerequisite that significantly improves the gas permeation flux, do not lose selectivity.
Another object of the present invention is to provide a kind of technology simple, and can on low-cost macropore matrix, prepare the method for carbon composite membrane.
Another object of the present invention also is to provide the application of described carbon composite membrane in gas separates.
The technical solution adopted in the present invention is:
A kind of carbon/graphite/porous matrix composite membrane comprises:
1) porous matrix;
2) the main transition zone of forming by graphite in porous matrix surface;
3) the porous carbon film on transition zone surface.
The present invention forms the transition zone of mainly being made up of graphite on the surface of porous matrix, to reduce matrix surface, the particularly roughness of macropore matrix surface, to fill up big hole defect.The applicant is unexpected to be found, graphite can satisfy the requirement that forms transition zone at defective macropore matrix surface, the carbon film and the matrix coefficient of expansion differ bigger simultaneously, rete meeting excess shrinkage even cracking when variations in temperature is too fast, and graphite linings can effectively prevent the generation of this situation, thereby prepares even, continuous carbon film on the macropore matrix.
The simplest mode of described transition zone (graphite transition zone) can adopt graphite or graphitiferous material to scrawle and form on the porous matrix surface, coating amount depends on the aperture and the roughness of matrix surface, the aperture and the roughness of matrix surface are bigger, can increase coating amount.Coating amount is preferably 2～50 g/m
2
The graphitiferous material is meant the material that mainly comprises graphite matter carbon, the preferred graphitiferous material of being made up of graphite and clay, for example commercially available pencil pen core, graphite carbon rod etc.
In the described graphitiferous material, common pencil pen core, graphite carbon rod etc. are made up of graphite and clay.Clay is the natural aluminosilicate hydrochlorate, fine size, good dispersion, plasticity height.It also is beneficial to the ventilative of graphite linings except the intensity that can increase graphite, obtain the better transition zone of performance.Employing is scrawled method and formed the graphite transition zone, and is with low cost, simple to operate.
Described porous carbon film is to form by the polymer precursor carbonization in inert atmosphere that is coated on the graphite transition zone.
Described carbon film presoma coating liquid comprises following two kinds of components:
A) polymer is selected from a kind of in polyimides, poly furfuryl alcohol, phenolic resins, polyethersulfone ketone, polyacrylonitrile or the PEI.
B) alloy is selected from inorganic particulate, metal or its salt, or a kind of in the organic additive.
Described carbon film presoma is introduced the inorganic particulate that gas is had translocation in the lattice chain segment structure of polymer, increase the porosity of carbon film by its " dimensional effect ", " interfacial effect " and " tunnel-effect ", resistance to mass tranfer when reducing the gas permeation carbon film, thereby the permeation flux of raising gas.Perhaps utilize some specific gas of metal pair that adsorbing character is arranged, in presoma, introduce metal or slaine to improve the separating property of carbon film.And introduce labile organic additive, its pore-creating effect meeting increases the specific area and the pore volume of carbon film, can increase substantially the performance of persursor material, realizes the complementation on polymer and the alloy performance.
Described inorganic particulate is zeolite molecular sieve, SiO
2Or carbon molecular sieve etc., metal or its salt are Pt, Pd, Ag, Cu, Au etc. and salt thereof, organic additive is polyvinyl alcohol, polyethylene glycol or polyvinylpyrrolidone etc.
Its quality optimization of described alloy is 3～50% of a coating liquid.
Described porous carbon film thickness is preferably 0.5～2.5 μ m, more preferably 1～2 μ m.
The present invention is applicable to various porous matrix, particularly has more advantage for the low-cost porous matrix that contains big hole defect.Described porous matrix is porous ceramics, porous stainless steel, porous ceramics/stainless steel composite material, cellular glass or porous silicon chip, and its average pore size is 0.1～10 μ m, preferred 1～5 μ m.
The invention still further relates to the preparation method of a kind of carbon/graphite/porous matrix composite membrane, may further comprise the steps:
1) scrawles on the porous matrix surface with graphite or graphitiferous material, form the graphite transition zone;
2) apply the alloy modified polymer solution on above-mentioned graphite transition zone, dry back forms polymeric layer;
3) polymeric layer carbonization in inert atmosphere makes described composite membrane.
Described method specifically may further comprise the steps:
A. the selection of porous matrix.
Choose a kind of as matrix in porous ceramics, porous stainless steel, porous ceramics/stainless steel composite material, cellular glass or the porous silicon chip, its average pore size is 0.1～10 μ m, preferred 1～5 μ m.
B. the preparation of graphite transition zone.
Material with graphite or graphitiferous is scrawled on the porous matrix surface, to form even, bright and clean graphite transition zone.Graphite or graphitiferous material shape are not limit.The graphitiferous material preferably comprises the composite of graphite and clay, as commercially available pencil pen core, graphite carbon rod etc.The coating amount of graphite transition zone is controlled at 2～50 g/m
2
C. the preparation of coating liquid.
The coating liquid that forms the carbon film presoma is the alloy modified polymer solution, its preparation method is by blend or sol-gel process alloy to be dispersed or dissolved in the solvent, mix, dropwise add again in the polymer solution, stir or ultrasonic mixing until evenly.In order to make alloy be easy to be dispersed in the polymer solution, should adopt suitable jitter time and process for dispersing, adopt ultrasonic usually or the high-speed stirred dispersion, ultrasonic dispersion or mixing time are at 1～10 h.
Described alloy is selected from inorganic particulate, metal or its salt, or a kind of in the organic additive.Wherein inorganic particulate is zeolite molecular sieve, SiO
2, carbon molecular sieve etc., metal or slaine are Pt, Pd, Ag, Cu, Au etc. and salt thereof, organic additive is polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone etc.
Described solvent is N, N-dimethylacetylamide, n-formyl sarcolysine base pyrrolidones, n-formyl sarcolysine yl acetamide, dimethyl sulfoxide (DMSO), chloroform etc.
Described polymer solution is polyimides, poly furfuryl alcohol, phenolic resins, polyethersulfone ketone, polyacrylonitrile or PEI.
In the coating liquid, the mass content of alloy is 3～50%.
D. the preparation of polymeric layer.
Adopt infusion process, spread coating, knife coating, spraying process or ultrasonic deposition method, coating liquid is coated on the graphite transition zone, dry back forms the homogeneous polymer layer.Baking temperature is 40～150 ℃, drying times 12～48 h, preferred 20～30 h.
E. carbonization.
Dried graphite/polymeric layer is put into the carbide furnace temperature programming, under inert gas shielding, prepare the carbon composite membrane by control carbonization condition.Usually the carbonization condition that adopts is: inert gas is selected nitrogen or argon gas usually for use, and gas flow rate is controlled at 10～200 mL/min; Heating rate is 0.5～10 ℃/min, preferred 1～5 ℃; The whole temperature of carbonization is 500～1000 ℃, preferred 600～800 ℃; Constant temperature time 0.5～5 h, preferred 2～4 h.
Promptly make carbon/graphite of the present invention/porous matrix composite membrane through above-mentioned steps.
Carbon composite membrane of the present invention carries out the mensuration of gas permeability, with H
2, N
2And O
2Be infiltration gas, adopt single gas method to measure.
The permeability of gas
Wherein, P
iBe the permeability of gas i through film, molm
-2S
-1Pa
-1N
iBe the seepage discharge of gas, mols
-1A is the effective area of film, m
2P is the pressure differential of film both sides, Pa.
Film is to the desired separated factor of two kinds of gases
Wherein, S
IjBe the ideal separation factor of film to gas i, j; P
iPermeability for gas i; P
jPermeability for gas j.
Further, the invention still further relates to the application of described carbon/graphite/porous matrix composite membrane on gas separates.
Described carbon composite membrane has the pore size suitable with the molecular diameter of separated gas, only has the gas with various of fine difference to have separating effect preferably to molecular size and shape, as gas separation membrane, can be used for N
2And O
2Separation and enrichment, C
2～C
3Hydrocarbon gas separates, H
2Enrichment and recovery, CO
2Fields such as separation.
Effect of the present invention and benefit:
(1) the invention provides a kind of based on carbon composite membrane that makes on the low-cost macropore matrix and preparation method thereof.
(2) carbon/graphite/porous matrix composite membrane good uniformity, the defective that make of the present invention is few, has higher mechanical strength, does not lose selectivity under the prerequisite that significantly improves the gas permeation flux, can be widely used in gas and separate.
(3) simple, the good reproducibility of preparation method of the present invention has been avoided problem in colloidal sol-gel process, the problem includes: three wastes problem belongs to environmentally friendly technology.
(4) the present invention can prepare " two high " function carbon film of high osmosis and high selectivity by component in the controlled doping thing and content.
(5) raw material of the present invention is easy to get, and many marketable material that directly adopt can shorten the process of carbon film production, and adopt macropore matrix cheaply, can significantly reduce the carbon film cost, are easy to commercially produce and use.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not exceeded with the specific embodiment, but is limited by claim.
Description of drawings
Fig. 1 graphite linings surface SEM shape appearance figure.
Fig. 2 carbon composite membrane surface SEM shape appearance figure.
Fig. 3 gas permeability determinator.
The specific embodiment
Embodiment 1
A kind of carbon/graphite/porous matrix composite membrane comprises:
(1) porous ceramic matrices suitable, average pore size are 2 μ m.
(2) transition zone of mainly being made up of graphite of matrix surface, coating amount is 20 g/m
2
(3) the porous carbon film on graphite transition zone surface forms thickness 1.5 μ m by the poly furfuryl alcohol coating liquid carbonization of adding ZSM-5.
Described carbon composite membrane prepares by the following method:
(1) choose porous ceramics as matrix, its average pore size is 2 μ m.
(2) scrawle to form the graphite transition zone at porous ceramic surface with pencil, measuring coating amount according to the weightening finish method is 20 g/m
2, its surface topography is seen Fig. 1.
(3) the ZSM-5 zeolite molecular sieve is added N, in N-dimethylacetylamide (DMAc) solution, stir 1 h ultrasonic 1 h afterwards, be designated as solution 1.
Furfuryl alcohol and oxalic acid adding are equipped with in the there-necked flask of condenser pipe, and the control reaction is 70 ℃ under slow stirring condition, heats 14 h, obtains poly furfuryl alcohol solution.Then solution 1 is dropwise added in the poly furfuryl alcohol, ultrasonic dispersion or stir 1h until evenly, the mass content of ZSM-5 is 10%, makes coating liquid.
(4) adopt infusion process that coating liquid is coated on the graphite linings, put into baking oven, dry 12 h form polymeric layer in the time of 80 ℃.
(5) the compound carbon film in the step (4) is put into carbide furnace, under argon gas (100 mL/min) atmosphere, rise to 700 ℃ with the heating rate of 2 ℃/min, and constant temperature 4 h, naturally cool to room temperature, make carbon composite membrane (surface topography is seen Fig. 2), its thickness is 1.5 μ m.
Adopt device mensuration gas permeability as shown in Figure 3.The permeance property data that record the carbon composite membrane under 20 ℃ are as shown in table 1.
Embodiment 2
A kind of carbon/graphite/porous matrix composite membrane comprises:
1) porous stainless steel base, average pore size are 4 μ m.
2) transition zone of mainly being made up of graphite of matrix surface, coating amount is 50 g/m
2
3) the porous carbon film on graphite transition zone surface is by adding AgNO
3Or the carbonization of the polyamic acid of AgAc (PAA) coating liquid forms thickness 1.5 μ m.
Described carbon composite membrane prepares by the following method:
(1) choose porous stainless steel as matrix, its average pore size is 4 μ m.
(2) scrawle on the porous stainless steel surface to form the graphite transition zone with pencil, measuring coating amount according to the weightening finish method is 50 g/m
2
(3) with pyromellitic dianhydride (PMDA) gradation, add in the DMAc solution of diamines yl diphenyl ether lentamente, the control reaction temperature is 25 ℃ under stirring condition, stirs 1 h.Behind reinforced the finishing, continue to stir 2～3 h, obtain the polyamic acid solution of yellow thickness.Then with AgNO
3Or AgAc solution dropwise adds among the PAA, stirs 1h until evenly making coating liquid, AgNO
3Or the mass content of AgAc is 15%.
(4) adopt spread coating that coating liquid is coated on the graphite linings, put into baking oven, dry 12 h form polymeric layer in the time of 80 ℃.
(5) the compound carbon film in the step (4) is put into carbide furnace, under nitrogen (50 mL/min) atmosphere, rise to 800 ℃ with the heating rate of 5 ℃/min, and constant temperature 4 h, naturally cooling to room temperature and promptly get the carbon composite membrane, its thickness is 2.1 μ m.
Adopt device mensuration gas permeability as shown in Figure 3.The permeance property data that record the carbon composite membrane under 20 ℃ are as shown in table 1.
Embodiment 3
A kind of carbon/graphite/porous matrix composite membrane comprises:
1) porous ceramics/stainless steel composite material matrix, average pore size are 3 μ m.
2) transition zone of mainly being made up of graphite of matrix surface, coating amount is 30 g/m
2
3) the porous carbon film on graphite transition zone surface forms thickness 1.7 μ m by the phenolic resins coating liquid carbonization of adding polyethylene glycol (PEG).
Described carbon composite membrane prepares by the following method:
(1) choose porous ceramics/stainless steel composite material as matrix, its average pore size is 3 μ m.
(2) scrawle on porous ceramics/stainless steel composite material surface to form the graphite transition zone with pencil, measuring coating amount according to the weightening finish method is 50 g/m
2
(3) thermosetting phenolic resin is mixed with PEG, fully stir ultrasonic 1 h in back, mix the formation coating liquid.
(4) coating liquid is packed in the reservoir of spray gun, under the gases at high pressure effect coating liquid is sprayed on graphite linings, put into baking oven, dry 12 h form polymeric layer in the time of 150 ℃.
(5) composite membrane that step (4) is made is put into carbide furnace, under nitrogen (80 mL/min) atmosphere, rises to 800 ℃ with the heating rate of 1 ℃/min, and constant temperature 2h, naturally cools to room temperature and makes the carbon composite membrane, and its thickness is 1.7 μ m.
Adopt device mensuration gas permeability as shown in Figure 3.The permeance property data that record the carbon composite membrane under 20 ℃ are as shown in table 1.
Embodiment 4
A kind of carbon/graphite/porous matrix composite membrane comprises:
1) cellular glass matrix, average pore size are 3 μ m.
2) transition zone of mainly being made up of graphite of matrix surface, coating amount is 35 g/m
2
3) the porous carbon film on graphite transition zone surface is by adding SiO
2The carbonization of polyacrylonitrile coating liquid form thickness 2 μ m.
Described carbon composite membrane prepares by the following method:
(1) choose cellular glass as matrix, its average pore size is 3 μ m.
(2) scrawling on the cellular glass surface to form the graphite transition zone with pencil, measuring coating amount according to the weightening finish method is 35 g/m
2
In the time of (3) 60 ℃ ethyl orthosilicate is dissolved in ethanol, stirs 1 h, be designated as solution 1.The solution that will contain ethanol, water and hydrochloric acid again adds in the solution 1, stir 1 h after ultrasonic 1h make Ludox.
It is 17% solution that polyacrylonitrile and dimethyl formamide (DMF) are mixed with mass concentration, after stirring, leaves standstill swelling 24 h under 70 ℃.After treating that polyacrylonitrile dissolves fully, sonic oscillation 10 min.Filter standing and defoaming 24 h then with layer of non-woven fabric.Ludox is added in the polyacrylonitrile solution, ultrasonic dispersion 1 h or stir 1.5 h and make coating liquid, the mass content of Ludox is 20%.
(4) adopt infusion process that coating liquid is coated on the graphite linings, put into baking oven, dry 20 h form polymeric layer in the time of 110 ℃.
(5) composite membrane that step (4) is made is put into carbide furnace, under nitrogen (80 mL/min) atmosphere, rises to 800 ℃ with the heating rate of 2 ℃/min, and constant temperature 4 h, naturally cools to room temperature and promptly gets the carbon composite membrane, and its thickness is 2 μ m.
Adopt device mensuration gas permeability as shown in Figure 3.The permeance property data that record the carbon composite membrane under 20 ℃ are as shown in table 1.
Embodiment 5
A kind of carbon/graphite/porous matrix composite membrane comprises:
1) porous silicon chip matrix, average pore size are 3 μ m.
2) transition zone of mainly being made up of graphite of matrix surface, coating amount is 30 g/m
2
3) the porous carbon film on graphite transition zone surface forms thickness 1.8 μ m by the polyethersulfone ketone coating liquid carbonization of adding the 4A molecular sieve.
Described carbon composite membrane prepares by the following method:
(1) choose porous silicon chip as matrix, its average pore size is 3 μ m.
(2) scrawle on the porous silicon chip surface to form the graphite transition zone with pencil, measuring coating amount according to the weightening finish method is 30 g/m
2
(3) the polyethersulfone ketone powder is put into vacuum drying chamber, in the time of 100 ℃ behind dry 24 h, be dissolved in N-methyl-2-pyrrole to be mixed with mass concentration in the alkane ketone (NMP) be 15% polyethersulfone ketone solution.To wherein adding the 4A molecular sieve, continuous stirring 10 h make coating liquid again, and the mass content of 4A molecular sieve is 20%.
(4) adopt infusion process that coating liquid is coated on the graphite linings, put into baking oven, dry 12 h form polymeric layer in the time of 80 ℃.
(5) composite membrane that step (4) is made is put into carbide furnace, under argon gas (200 mL/min) atmosphere, heating rate with 2 ℃/min rises to 400 ℃, heating rate with 1 ℃/min rises to 850 ℃ and constant temperature 2 h again, naturally cool to room temperature and promptly get the carbon composite membrane, its thickness is 1.8 μ m.
Adopt device mensuration gas permeability as shown in Figure 3.The permeance property data that record the carbon composite membrane under 20 ℃ are as shown in table 1.
Embodiment 6
A kind of carbon/graphite/porous matrix composite membrane comprises:
1) porous ceramic matrices suitable, average pore size are 2 μ m.
2) transition zone of mainly being made up of graphite of matrix surface, coating amount is 25 g/m
2
3) the porous carbon film on graphite transition zone surface forms thickness 2.1 μ m by the polyimide coating film liquid carbonization of adding carbon molecular sieve.
Described carbon composite membrane prepares by the following method:
(1) choose porous ceramics as matrix, its average pore size is 2 μ m.
(2) scrawling at porous ceramic surface to form the graphite transition zone with pencil, measuring coating amount according to the weightening finish method is 25 g/m
2
(3) with polyamic acid and N, it is 15% PEI coating liquid that N-dimethylacetylamide (DMAc) solution is hybridly prepared into mass concentration.Add carbon molecular sieve then, ultrasonic agitation 5 h make coating liquid, and the mass content of carbon molecular sieve is 20%.
(4) adopt spread coating that coating solution is coated on the graphite linings, put into vacuum drying chamber, dry 12 h in the time of 40 ℃, dry 12 h form polymeric layer in the time of 60 ℃.
(5) composite membrane that step (4) is made is put into carbide furnace, under argon gas (200 mL/min) atmosphere, heating rate with 2 ℃/min rises to 400 ℃, heating rate with 1 ℃/min rises to 850 ℃ and constant temperature 2 h again, naturally cool to room temperature and promptly get the carbon composite membrane, its thickness is 2.1 μ m.
Adopt device mensuration gas permeability as shown in Figure 3.The permeance property data that record the carbon composite membrane under 20 ℃ are as shown in table 1.
The permeance property of the carbon composite membrane that the different persursor materials of table 1 prepare on porous matrix
As above shown in the table, made function carbon film does not lose selectivity significantly improving under the prerequisite of gas permeability, have high osmosis and high selectivity.According to the permeance property of above-mentioned carbon film, can be applied to N respectively
2And O
2Separation and enrichment, H
2Enrichment and reclaim.
Claims (12)
1. carbon/graphite/porous matrix composite membrane comprises:
A) porous matrix;
B) the main transition zone of forming by graphite in porous matrix surface;
C) the porous carbon film on transition zone surface.
2. carbon/graphite according to claim 1/porous matrix composite membrane is characterized in that, described transition zone adopts graphite or graphitiferous material to scrawle and form on the porous matrix surface, and coating amount is 2～50 g/m
2
3. carbon/graphite according to claim 1/porous matrix composite membrane is characterized in that, described porous carbon film is to form by the polymer precursor carbonization in inert atmosphere that is coated on the transition zone.
4. carbon/graphite according to claim 3/porous matrix composite membrane is characterized in that, described polymer precursor coating liquid comprises following component:
A) polymer is selected from a kind of in polyimides, poly furfuryl alcohol, phenolic resins, polyethersulfone ketone, polyacrylonitrile or the PEI;
B) alloy is selected from inorganic particulate, metal or its salt, or organic additive.
5. carbon/graphite according to claim 4/porous matrix composite membrane is characterized in that, described inorganic particulate is zeolite molecular sieve, SiO
2Or carbon molecular sieve, metal or its salt are Pt, Pd, Ag, Cu, Au or its salt, organic additive is polyvinyl alcohol, polyethylene glycol or polyvinylpyrrolidone.
6. carbon/graphite according to claim 1/porous matrix composite membrane is characterized in that, described porous carbon film thickness is 0.5～2.5 μ m.
7. the preparation method of carbon/graphite/porous matrix composite membrane may further comprise the steps:
1) scrawles on the porous matrix surface to form the graphite transition zone with the composite of graphite or graphitiferous;
2) polymer solution of coating alloy modification on above-mentioned graphite transition zone, dry back forms polymeric layer;
3) polymeric layer carbonization in inert atmosphere makes compound carbon film.
8. the preparation method of composite membrane according to claim 7 is characterized in that, described porous matrix is porous ceramics, porous stainless steel, porous ceramics/stainless steel composite material, cellular glass or porous silicon chip, and its average pore size is 0.1～10 μ m.
9. the preparation method of composite membrane according to claim 7 is characterized in that, the coating amount of described graphite transition zone is 2～50 g/m
2
10. the preparation method of composite membrane according to claim 7 is characterized in that, described alloy is selected from inorganic particulate, metal or its salt, or a kind of in the organic additive; Described polymer is selected from a kind of in polyimides, poly furfuryl alcohol, phenolic resins, polyethersulfone ketone, polyacrylonitrile or the PEI.
11. the preparation method of composite membrane according to claim 10, it is characterized in that the method for modifying of described polymer solution is by blend, sol-gel processing alloy to be dispersed or dissolved in the solvent, dropwise join again in the polymer solution, stir or ultrasonic mixing until evenly; Wherein the mass content of alloy is 3～50%.
12. the application of the described carbon/graphite of claim 1/porous matrix composite membrane on gas separates.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110209457XA CN102247764A (en) | 2011-07-26 | 2011-07-26 | Carbon/graphite/porous matrix composite membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110209457XA CN102247764A (en) | 2011-07-26 | 2011-07-26 | Carbon/graphite/porous matrix composite membrane and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102247764A true CN102247764A (en) | 2011-11-23 |
Family
ID=44975544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110209457XA Pending CN102247764A (en) | 2011-07-26 | 2011-07-26 | Carbon/graphite/porous matrix composite membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102247764A (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527259A (en) * | 2012-02-10 | 2012-07-04 | 南京工业大学 | Compound carbon molecular sieve membrane as well as preparation method and application thereof |
| CN102600735A (en) * | 2012-03-29 | 2012-07-25 | 吉林大学 | Inorganic phase separation membrane and application of thereof to oil-water separation |
| CN102689870A (en) * | 2012-05-15 | 2012-09-26 | 清华大学 | Nano porous material capable of being perfomed direct photoetching imaging and preparation method thereof |
| CN103007775A (en) * | 2012-12-21 | 2013-04-03 | 武汉纺织大学 | Method for preparing polymer flat sheet microporous membrane |
| CN103846017A (en) * | 2012-11-29 | 2014-06-11 | 沈阳工业大学 | Magnetic field intervention film forming method used for regulating and controlling charcoal membrane gas separating performance |
| CN104785122A (en) * | 2015-04-10 | 2015-07-22 | 丽水学院 | Polyether sulfone-nanocarbon combined gas separation membrane and preparation method thereof |
| CN107020022A (en) * | 2017-04-26 | 2017-08-08 | 山东工业陶瓷研究设计院有限公司 | A kind of sewage disposal earthenware slab UF membrane film layer and its preparation technology |
| CN107847877A (en) * | 2015-07-28 | 2018-03-27 | 北川工业株式会社 | The manufacture method of reverse osmosis membrane |
| CN108837715A (en) * | 2018-05-24 | 2018-11-20 | 南京工业大学 | A kind of solvent-resistant polyimide film, preparation method and application |
| CN109678135A (en) * | 2019-02-01 | 2019-04-26 | 苏州大学 | A kind of preparation method of ultrathin carbon films |
| CN111285686A (en) * | 2018-12-07 | 2020-06-16 | 南京动量材料科技有限公司 | Preparation process of composite porous carbon film and capacitor |
| CN111389239A (en) * | 2020-03-20 | 2020-07-10 | 西安工程大学 | Pd/Ag/SiO2Method for preparing composite membrane |
| CN111644076A (en) * | 2020-06-15 | 2020-09-11 | 中化泉州能源科技有限责任公司 | Method for preparing carbonized organic layer on surface of porous ceramic matrix through negative-pressure coating |
| CN112619442A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Composite molecular sieve carbon film based on phenolic resin-based carbon tube as support body and preparation method and application thereof |
| CN112808029A (en) * | 2020-12-23 | 2021-05-18 | 华南理工大学 | Method for rapidly growing ZIF-8 film on ceramic substrate |
| CN113877444A (en) * | 2020-07-02 | 2022-01-04 | 中国石油化工股份有限公司 | Porous support body composite carbon film and preparation and application thereof |
| CN116514064A (en) * | 2023-07-04 | 2023-08-01 | 山东德仕化工有限公司 | Underground hydrogen production separation and purification system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040154A (en) * | 1988-08-08 | 1990-03-07 | 中国科学院兰州化学物理研究所 | Catalytic high molecular gas separation membrance |
| CN1837035A (en) * | 2005-12-28 | 2006-09-27 | 大连理工大学 | Process for preparing nano hybrid carbon film |
| CN101481263A (en) * | 2009-02-26 | 2009-07-15 | 南京工业大学 | Method for preparing supported palladium or palladium alloy membrane |
-
2011
- 2011-07-26 CN CN201110209457XA patent/CN102247764A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040154A (en) * | 1988-08-08 | 1990-03-07 | 中国科学院兰州化学物理研究所 | Catalytic high molecular gas separation membrance |
| CN1837035A (en) * | 2005-12-28 | 2006-09-27 | 大连理工大学 | Process for preparing nano hybrid carbon film |
| CN101481263A (en) * | 2009-02-26 | 2009-07-15 | 南京工业大学 | Method for preparing supported palladium or palladium alloy membrane |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527259A (en) * | 2012-02-10 | 2012-07-04 | 南京工业大学 | Compound carbon molecular sieve membrane as well as preparation method and application thereof |
| CN102600735A (en) * | 2012-03-29 | 2012-07-25 | 吉林大学 | Inorganic phase separation membrane and application of thereof to oil-water separation |
| WO2013143194A1 (en) * | 2012-03-29 | 2013-10-03 | 吉林大学 | Inorganic phase separation membrane and application thereof in oil-water separation |
| CN102600735B (en) * | 2012-03-29 | 2014-09-03 | 吉林大学 | Inorganic phase separation membrane and application of thereof to oil-water separation |
| CN102689870A (en) * | 2012-05-15 | 2012-09-26 | 清华大学 | Nano porous material capable of being perfomed direct photoetching imaging and preparation method thereof |
| WO2013170624A1 (en) * | 2012-05-15 | 2013-11-21 | 清华大学 | Nano porous material capable of being directly lithographically patterned and preparation method thereof |
| CN102689870B (en) * | 2012-05-15 | 2015-04-15 | 清华大学 | Nano porous material capable of being perfomed direct photoetching imaging and preparation method thereof |
| US9046784B2 (en) | 2012-05-15 | 2015-06-02 | Tsinghua University | Nanoporous film patterned by direct photolithography and method for preparing the same |
| CN103846017A (en) * | 2012-11-29 | 2014-06-11 | 沈阳工业大学 | Magnetic field intervention film forming method used for regulating and controlling charcoal membrane gas separating performance |
| CN103007775A (en) * | 2012-12-21 | 2013-04-03 | 武汉纺织大学 | Method for preparing polymer flat sheet microporous membrane |
| CN104785122A (en) * | 2015-04-10 | 2015-07-22 | 丽水学院 | Polyether sulfone-nanocarbon combined gas separation membrane and preparation method thereof |
| CN104785122B (en) * | 2015-04-10 | 2017-01-25 | 丽水学院 | Polyether sulfone-nanocarbon combined gas separation membrane and preparation method thereof |
| CN107847877B (en) * | 2015-07-28 | 2020-11-24 | 北川工业株式会社 | Method for producing reverse osmosis membrane |
| CN107847877A (en) * | 2015-07-28 | 2018-03-27 | 北川工业株式会社 | The manufacture method of reverse osmosis membrane |
| CN107020022A (en) * | 2017-04-26 | 2017-08-08 | 山东工业陶瓷研究设计院有限公司 | A kind of sewage disposal earthenware slab UF membrane film layer and its preparation technology |
| CN107020022B (en) * | 2017-04-26 | 2019-10-29 | 山东工业陶瓷研究设计院有限公司 | A kind of sewage treatment earthenware slab UF membrane film layer and its preparation process |
| CN108837715B (en) * | 2018-05-24 | 2020-10-16 | 南京工业大学 | Solvent-resistant polyimide film, preparation method and application |
| CN108837715A (en) * | 2018-05-24 | 2018-11-20 | 南京工业大学 | A kind of solvent-resistant polyimide film, preparation method and application |
| CN111285686A (en) * | 2018-12-07 | 2020-06-16 | 南京动量材料科技有限公司 | Preparation process of composite porous carbon film and capacitor |
| CN109678135A (en) * | 2019-02-01 | 2019-04-26 | 苏州大学 | A kind of preparation method of ultrathin carbon films |
| CN112619442A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Composite molecular sieve carbon film based on phenolic resin-based carbon tube as support body and preparation method and application thereof |
| CN112619442B (en) * | 2019-09-24 | 2022-11-04 | 中国石油化工股份有限公司 | Composite molecular sieve carbon film based on phenolic resin-based carbon tube as support body and preparation method and application thereof |
| CN111389239A (en) * | 2020-03-20 | 2020-07-10 | 西安工程大学 | Pd/Ag/SiO2Method for preparing composite membrane |
| CN111389239B (en) * | 2020-03-20 | 2022-04-22 | 西安工程大学 | Pd/Ag/SiO2Method for preparing composite membrane |
| CN111644076A (en) * | 2020-06-15 | 2020-09-11 | 中化泉州能源科技有限责任公司 | Method for preparing carbonized organic layer on surface of porous ceramic matrix through negative-pressure coating |
| CN111644076B (en) * | 2020-06-15 | 2023-11-14 | 中化泉州能源科技有限责任公司 | Method for preparing carbonized organic layer on surface of porous ceramic matrix through negative pressure coating |
| CN113877444A (en) * | 2020-07-02 | 2022-01-04 | 中国石油化工股份有限公司 | Porous support body composite carbon film and preparation and application thereof |
| CN112808029A (en) * | 2020-12-23 | 2021-05-18 | 华南理工大学 | Method for rapidly growing ZIF-8 film on ceramic substrate |
| CN116514064A (en) * | 2023-07-04 | 2023-08-01 | 山东德仕化工有限公司 | Underground hydrogen production separation and purification system |
| CN116514064B (en) * | 2023-07-04 | 2023-11-21 | 山东德仕化工有限公司 | Underground hydrogen production separation and purification system |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102247764A (en) | Carbon/graphite/porous matrix composite membrane and preparation method and application thereof | |
| CN102527259A (en) | Compound carbon molecular sieve membrane as well as preparation method and application thereof | |
| Rodrigues et al. | Preparation and characterization of carbon molecular sieve membranes based on resorcinol–formaldehyde resin | |
| CN102965848B (en) | A kind of nano-porous ceramic film and preparation method thereof | |
| CN104772043B (en) | Sodium alginate-graphite phase carbon nitride nano-sheet hybridized composite membrane as well as preparation and application of composite membrane | |
| CN100384722C (en) | Process for preparing nano hybrid carbon film | |
| CN104722215B (en) | Preparation method of carbon dioxide separation film based on graphene material | |
| Liu et al. | High-performance NaA zeolite membranes supported on four-channel ceramic hollow fibers for ethanol dehydration | |
| CN113105223B (en) | Preparation and application of whisker-shaped ceramic membrane with low cost and high permeability | |
| Shao et al. | Microstructure control of oxygen permeation membranes with templated microchannels | |
| CN102580567B (en) | Composite carbon diaphragm with mesoporous and microporous gradient structure and preparation method for diaphragm | |
| CN108246125B (en) | High-anti-pollution internal support polyvinylidene fluoride hollow fiber membrane and preparation method thereof | |
| Wang et al. | Decoration of porous ceramic substrate with pencil for enhanced gas separation performance of carbon membrane | |
| Li et al. | The preparation and gas separation properties of zeolite/carbon hybrid membranes | |
| CN113624048A (en) | Porous ceramic with straight-hole gradient structure, capillary core and preparation method of porous ceramic | |
| Ismail et al. | From polymeric precursors to hollow fiber carbon and ceramic membranes | |
| CN104128100A (en) | Nano attapulgite based hollow fiber microfiltration membrane and preparation method thereof | |
| CN103537206A (en) | Preparation and application of polyimide-imidazole micro-capsule hybrid membrane | |
| CN110479116B (en) | Preparation method of mesoporous hydrophobic silicon modified polyvinylidene fluoride flat microfiltration membrane | |
| CN102512987B (en) | Method for preparing high-flux polyvinylidene fluoride hollow fiber membrane | |
| CN107469640B (en) | A kind of preparation method of high gas permeability carbon membrane | |
| CN107983177B (en) | Preparation method of bi-component asymmetric hollow fiber ceramic membrane with petal-shaped cross section | |
| CN106823859B (en) | The preparation method of PVDF hollow-fibre membrane | |
| CN112755814B (en) | Black talc nanoparticle modified polyamide composite nanofiltration membrane | |
| CN113135567B (en) | Preparation method of activated carbon and product thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20111123 |