CN102580567A - Composite carbon diaphragm with mesoporous and microporous gradient structure and preparation method for diaphragm - Google Patents
Composite carbon diaphragm with mesoporous and microporous gradient structure and preparation method for diaphragm Download PDFInfo
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Abstract
The invention relates to a composite carbon diaphragm with a mesoporous and microporous gradient structure and a preparation method for the diaphragm. The composite carbon diaphragm with the mesoporous and microporous gradient structure consists of a porous support body, a mesoporous intermediate layer and a surface separation layer, and is characterized in that the pore diameter of the porous support body is 100 to 500 nanometers, the breaking strength is 2 to 15MPa, and the anti-explosion strength is 3 to 10MPa; the pore diameter of the mesoporous intermediate layer is 2 to 10 nanometers, the specific surface area is 400 to 1,000 m<2>/g, the porosity is 30 to 50 percent, and the thickness is 1 to 10 micrometers; and the pore diameter of the surface separation layer is 0.3 to 0.5 nanometer, the specific surface area is 300 to 600 m<2>/g, the porosity is 20 to 40 percent, and the thickness is 0.1 to 5 micrometers. By the composite carbon diaphragm with the mesoporous and microporous gradient structure, the phenomenon that the gas separation performance of the composite carbon diaphragm is greatly reduced due to the defect of the surface of the support body is avoided, and the permeability of the prepared composite carbon diaphragm is improved obviously on the basis of keeping high gas separation selectivity.
Description
Technical field
The invention belongs to new material technology field, relate to a kind of carbon membrane and preparation method thereof, particularly relate to compound carbon membrane of a kind of Jie's of having microinverse pore passage structure and preparation method thereof
Background technology
Membrane separation technique is an emerging new and high technology, also is the science and technology of a multiple subject crossing.The gas separation membrane technology is as new separation technology; Compare with traditional gas separation; Have the technical characterstic of " efficient, economic, convenient, cleaning ", the aspects such as recovery of hydrogen and organic hydrocarbon gas are with a wide range of applications in enrichment, acid gas removal, petrochemical industry and the synthetic ammonia tailgas of air separation, carbon dioxide recovery, low concentration natural gas and coal bed gas.
Carbon membrane is a kind of novel charcoal basal lamina material that is prepared from through the high temperature pyrolysis charing precursor polymer.Because of it has nano level superfine microcellular structure flourishing, that can distinguish the gas molecule size, gas meter is revealed high separation selectivity and penetrating power, to compare with polymer film in addition, carbon membrane also has excellent mechanical intensity, heat and chemical stability.Therefore carbon membrane is considered to be hopeful most to realize the new gas diffusion barrier of extensive commercial application.
Yet, because the matter of carbon membrane own is crisp frangible, realize the practical application of carbon membrane, must be prepared into compound carbon membrane, be about to precursor polymer and be compounded on the porous supporting body, carry out charing again and prepare composite membrane.Supporter is that carbon membrane provides mechanical strength, makes compound carbon membrane show good prospects for application.But prepare flawless compound carbon membrane, must adopt the aperture less, surperficial flawless supporter makes that resulting compound carbon membrane gas permeation flux is less; And the bigger supporter in employing aperture; Because of having pinprick or defective; Be difficult to the disposable flawless compound carbon membrane continuously of preparing, must employing repeatedly film-the cycles prepare technology of charing, this has not only increased the manufacture difficulty and the complexity of compound carbon membrane; The manufacturing cost that increases, the while has also obviously been reduced the gas permeation flux of compound carbon membrane.Therefore, how preparing high permeating flux, high score from compound carbon membrane optionally, is the key that realizes the extensive commercial application of carbon membrane.
Ordered mesoporous carbon material (Ordered Mesoporous Carbon, be called for short OMC) is one type and has the regular pore canal structure, channel diameter at 2nm between the 50nm, the material of aperture size homogeneous.In numerous nano structural materials, ordered mesoporous carbon material has high specific area because of it, bigger pore volume and narrower pore-size distribution; And has a fabulous hydrophobicity, acidproof, alkaline-resisting, heat resistance and chemical stability, high mechanical strength and electric conductivity; Therefore separating, adsorbing organic macromolecule; Catalyst carrier, energy store and transform, and fields such as sensor and conducting material and biomedicine have potential using value.
At present, preparing the most frequently used method of ordered mesoporous carbon material is template.Template is divided into hard template method and soft template method again, and soft template method is directly to utilize organic macromolecule as template, through non-covalent organic-effect of organic self assembly, the method for synthesizing ordered mesoporous charcoal.Compare with hard template method, soft template method preparation technology is simple, does not need removed template method, and pore structure is had bigger regulation and control space.More existing at present employing acid or base catalysis prepare the document of ordered mesoporous carbon material.(Chem.Commun.2005 such as Tanaka; 2125) be template with triblock copolymer F127; Resorcin/formaldehyde colloidal sol and triethly orthoacetate (EOA) are carbon source; Concentrated hydrochloric acid is made catalyst, has prepared the RF/EOA-F127 nano composite material, handles just can obtain the highly ordered mesosize pores charcoal through direct charing.Though the method technology is simple, in building-up process, must adds a kind of material triethly orthoacetate and strengthen order mesoporous stability of structure.(Angew.Chem.Int.Ed.2005 such as Zhao; 44) with PEO-PPO-PEO as template; The polymer of low-molecular-weight (in the Mw=500-5000) phenol of solubility and formaldehyde is as presoma, induces the method for self assembly through solvent evaporates, prepared ordered mesoporous polymer FDU-15 and FDU-16 and corresponding charcoal skeleton C-FDU-15 and C-FDU-16; And through adjusting the quality ratio of polymer precursor and amphiphilic surfactant, the pore structure of coming the modulation ordered mesoporous carbon material.
Summary of the invention
The objective of the invention is to: utilize the architectural characteristic of ordered mesoporous carbon, prepare order mesoporous carbon membrane, between supporter and separating layer, set up a bridge; Reduce the defective of supporting body surface; The production of coatings separating layer is gone up on its surface then, forms the compound carbon membrane with Jie's microinverse pore passage structure, on the basis that does not reduce the carbon membrane separation selectivity; Improve the raising permeance property of carbon membrane, prepare and a kind ofly have high permeating flux, high score from selectivity composite gas separation carbon membrane.Simplify the preparation technology of compound carbon membrane with it,, accelerate the commercial application paces of carbon membrane for the preparation of carbon membrane provides a new approach.
The compound carbon membrane of Jie's of having microinverse pore passage structure provided by the invention is made up of three parts: porous supporting body, mesoporous intermediate layer, surface isolation layer; Described porous supporting body aperture is 100-500nm, and rupture strength is 2-15MPa, and uprising intensity is 3-10MPa; Aperture, described mesoporous intermediate layer is 2-10nm, and specific area is 400-1000m
2/ g, porosity is 30-50%, thickness is 1-10 μ m.Described surface isolation layer aperture is 0.3-0.5nm, and specific area is 300-600m
2/ g, porosity is 20-40%, thickness is 0.1-5 μ m.The pore passage structure of described mesoporous intermediate layer or surface isolation layer is orderly pore passage structure or unordered pore passage structure;
Described a kind of preparation method with compound carbon membrane of Jie's microinverse pore passage structure, its preparation method comprises the steps:
1. the preparation in mesoporous intermediate layer
The configuration of a preparation liquid: it is 10～75% preparation liquid that the ordered mesoporous polymer presoma is configured to mass percentage concentration, and solvent is N, N-dimethylacetylamide or N-methyl pyrrolidone;
The b composite membrane applies: adopt rotation to apply, and blade coating, the mode of spraying or serigraphy is coated in preparation liquid on the supporting body surface, and dry 15-36h processes composite polymeric film under 30-100 ℃ temperature;
The charing of c composite polymeric film: put into retort to composite polymeric film, under inert gas shielding, carry out high temperature carbonization and process composite mesopore intermediate layer carbon membrane; Carbonization condition is: carbonization temperature 500-850 ℃, and heating rate 1-3 ℃/min, constant temperature time 1-2h, protection throughput 100-200ml/min;
2. the preparation of surface isolation layer
The configuration of a preparation liquid: it is 3～20% preparation liquid that polymer precursor is configured to mass percentage concentration, and solvent is N, N-dimethylacetylamide or N-methyl pyrrolidone;
The coating of b surface isolation layer: adopt the mode of rotation coating or ultrasonic spray that preparation liquid is coated in formation surface isolation layer on composite polymeric film or the carbon membrane surface, composite mesopore intermediate layer;
The drying of c surface isolation layer: the dry 15-24h under 30-50 ℃ temperature of elder generation, dry 20-30h under 70-80 ℃ temperature processes Jie's micropore composite polymeric film then;
The charing of Jie's d micropore composite polymeric film: put into retort to Jie's micropore composite polymeric film, under inert gas shielding, carry out high temperature carbonization and process compound carbon membrane with Jie's micropore gradient-structure.Carbonization condition is: carbonization temperature 500-750 ℃, and heating rate 0.5-3 ℃/min, constant temperature time 1-2h, protection throughput 100-200ml/min.
Among the above-mentioned preparation method, described step 1. in the ordered mesoporous polymer presoma of a be a kind of in mesoporous phenolic resin, mesoporous polyimides, benzoxazine colophony or the cyanate ester resin.
Described step 1. in the porous supporting body of b be a kind of in porous charcoal pipe, porous carbon slab, porous ceramic pipe, porous ceramic plate, porous stainless steel sintered pipes or the porous stainless steel sintered plate.
Described step 2. in the polymer precursor of a be a kind of in micropore polyimides, micropore cyanate ester resin, benzoxazine colophony, PAEK, poly (aryl ether sulfone ketone), the polyarylether acid amides.
The described step 2. inert gas of middle d is a kind of of nitrogen or argon gas.
Above-mentioned mesoporous polyimides, mesoporous phenolic resin are meant and in the polymer building-up process, add template such as organic block copolymer or additives such as pore creating material such as polyethylene glycol; Obtain polymeric articles after the heat of solidification is handled; Additives such as these template or pore creating material can be separated out and formed some apertures is that the hole of 20-50nm is promptly mesoporous; Therefore, these polymer are referred to as mesoporous polymer such as above-mentioned several kinds of polymer.
Effect of the present invention and benefit are:
1. the preparation method that proposes of the present invention with the compound carbon membrane of Jie's microinverse pore passage structure; Avoided causing the decline significantly of the gas separating property of prepared composite carbon membrane because of the defective of supporting body surface; The filming technology of simplifying; And make the prepared composite carbon membrane on the basis of the higher gas separation selectivity of maintenance, improve the raising permeance property of carbon membrane significantly.
2. the preparation method that proposes of the present invention, preparation process is simple, and can go out to have higher mechanical strength from the feedstock production of cheapness, high gas permeation flux separates carbon membrane with separation selectivity gas.
The specific embodiment
Embodiment 1
The 10g mesoporous phenolic resin is dissolved in to be configured to mass percentage concentration among the DMAc be 58% preparation liquid; It is that dry 30h processes composite polymeric film under 80 ℃ temperature on 360nm porous carbon slab or the charcoal pipe support body supports surface that the mode that adopts rotation to apply is coated in the aperture respectively; Putting into retort, is under the nitrogen protection of 200ml/min at flow, is heated to 750 ℃ with the heating rate of 1 ℃/min and carries out high temperature carbonization, behind the constant temperature time 1h, naturally cools to normal temperature, obtains having the composite interlayer carbon membrane of meso-hole structure; Adopting the mode of ultrasonic spraying then is 8% with mass percentage concentration; Solvent is N; The micropore polyimides preparation liquid of N-dimethylacetylamide is sprayed on their surface and forms separating layer; The dry 20h under 30 ℃ temperature of elder generation, dry 25h under 80 ℃ temperature processes Jie's micropore composite polymeric film then.Put into retort again; At flow is under the nitrogen protection of 200ml/min; Be heated to 700 ℃ with the heating rate of 0.5 ℃/min and carry out high temperature carbonization, behind the constant temperature time 1h, naturally cool to normal temperature; Obtain having the compound carbon membrane of Jie's microinverse pore passage structure, the gas separating property of carbon membrane is as shown in table 1.
Embodiment 2～4
The supporter of pressing appointment in the following table 1 repeats the method for embodiment 1, in table 1, has listed test result.
Table 1
Embodiment 5
In DMAc, being configured to mass percentage concentration by the 10g mesoporous polymer of appointment in the table 1 is 20% preparation liquid; Adopt the mode of blade coating to be coated on the porous carbon slab supporting body surface that the aperture is 230nm, dry 28h processes composite polymeric film under 40 ℃ temperature; Putting into retort respectively, is under the nitrogen protection of 200ml/min at flow, is heated to 800 ℃ with the heating rate of 2 ℃/min and carries out high temperature carbonization, behind the constant temperature time 2h, naturally cools to normal temperature, obtains having the composite interlayer carbon membrane of meso-hole structure.The mode that adopts rotation to apply then is mass percentage concentration 13%; Solvent is that the micropore cyanate ester resin preparation liquid spraying of N-methyl pyrrolidone forms separating layer in its surface; The dry 15h under 40 ℃ temperature of elder generation; Dry 20h under 80 ℃ temperature processes Jie's micropore composite polymeric film then.Put into retort again; At flow is under the nitrogen protection of 200ml/min; Be heated to 750 ℃ with the heating rate of 1 ℃/min and carry out high temperature carbonization, behind the constant temperature time 1h, naturally cool to normal temperature; Obtain having the compound carbon membrane of Jie's microinverse pore passage structure, the gas separating property of carbon membrane is as shown in table 2.
Embodiment 6～7
The mesoporous polymer of pressing appointment in the following table 2 repeats the method for embodiment 5, in table 2, has listed test result.
Table 2
Embodiment 8
The 10g mesoporous phenolic resin is dissolved in to be configured to mass percentage concentration among the DMAc be 58% preparation liquid; It is that dry 30h processes composite polymeric film under 80 ℃ temperature on the 180nm stainless steel sintered plate supporting body surface that the mode of employing serigraphy is coated in the aperture; Putting into retort, is under the nitrogen protection of 200ml/min at flow, is heated to 750 ℃ with the heating rate of 1 ℃/min and carries out high temperature carbonization, behind the constant temperature time 1h, naturally cools to normal temperature, obtains having the composite interlayer carbon membrane of meso-hole structure.The mode that adopts rotation to apply then; With the mass percentage concentration of appointment in the table 3 is 6%; Solvent is N, and the polymer solution of N-dimethylacetylamide is coated on the surface of composite interlayer and forms separating layer, earlier dry 20h under 30 ℃ temperature; Dry 25h under 80 ℃ temperature processes Jie's micropore composite polymeric film then.Put into retort again; At flow is under the nitrogen protection of 200ml/min; Be heated to 700 ℃ with the heating rate of 0.5 ℃/min and carry out high temperature carbonization, behind the constant temperature time 1h, naturally cool to normal temperature; Obtain having the compound carbon membrane of Jie's microinverse pore passage structure, the gas separating property of carbon membrane is as shown in table 3.
Embodiment 9～11
The polymer precursor of pressing appointment in the following table 3 repeats the method for embodiment 8, in table 3, has listed test result.
Table 3
Embodiment 12
The 10g mesoporous phenolic resin is dissolved in to be configured to mass percentage concentration among the DMAc be 58% preparation liquid, adopting the mode of spraying to be coated in the aperture is that dry 30h processes composite polymeric film under 80 ℃ temperature on the 150nm stainless steel sintered pipes surface; Directly adopting the mode of ultrasonic spraying then is 8% with mass percentage concentration; Solvent is N; Form separating layer on the PAEK solution spraying polymerizable compound within thing film surface of N-dimethylacetylamide; The dry 20h under 30 ℃ temperature of elder generation, dry 25h under 80 ℃ temperature processes Jie's micropore composite polymeric film then.Putting into retort again, is under the nitrogen protection of 200ml/min at flow, is heated to 700 ℃ with the heating rate of 0.5 ℃/min and carries out high temperature carbonization, behind the constant temperature time 1h, naturally cools to normal temperature, obtains having the compound carbon membrane of Jie's microinverse pore passage structure.The H of carbon membrane
2, CO
2, O
2, N
2, CH
4Infiltration capacity be respectively 1236,1102,294,21,7; CO
2/ N
2, CO
2/ CH
4, O
2/ N
2Separation selectivity be respectively 52,157,14.
Claims (7)
1. the compound carbon membrane with Jie's microinverse pore passage structure is made up of porous supporting body, mesoporous intermediate layer and surface isolation layer; It is characterized in that: the aperture of porous supporting body is 100-500nm, and rupture strength is 2-15MPa, and uprising intensity is 3-10MPa; The aperture in mesoporous intermediate layer is 2-10nm, and specific area is 400-1000m
2/ g, porosity is 30-50%, thickness is 1-10 μ m; The aperture of surface isolation layer is 0.3-0.5nm, and specific area is 300-600m
2/ g, porosity is 20-40%, thickness is 0.1-5 μ m.
2. a kind of compound carbon membrane with Jie's microinverse pore passage structure according to claim 1 is characterized in that: the pore passage structure of said mesoporous intermediate layer or surface isolation layer is orderly pore passage structure or unordered pore passage structure.
3. a kind of preparation method with compound carbon membrane of Jie's microinverse pore passage structure according to claim 1, it is characterized in that: described method comprises the steps:
1. the preparation in mesoporous intermediate layer
The configuration of a preparation liquid: it is 10～75% preparation liquid that the ordered mesoporous polymer presoma is configured to mass percentage concentration, and solvent is N, N-dimethylacetylamide or N-methyl pyrrolidone;
The b composite membrane applies: adopt rotation to apply, and blade coating, the mode of spraying or serigraphy is coated in preparation liquid on the supporting body surface, and dry 15-36h processes composite polymeric film under 30-100 ℃ temperature;
The charing of c composite polymeric film: put into retort to composite polymeric film, under inert gas shielding, carry out high temperature carbonization and process composite mesopore intermediate layer carbon membrane; Carbonization condition is: carbonization temperature 500-850 ℃, and heating rate 1-3 ℃/min, constant temperature time 1-2h, protection throughput 100-200ml/min;
2. the preparation of surface isolation layer
The configuration of a preparation liquid: it is 3～20% preparation liquid that polymer precursor is configured to mass percentage concentration, and solvent is N, N-dimethylacetylamide or N-methyl pyrrolidone;
The coating of b surface isolation layer: adopt the mode of rotation coating or ultrasonic spray that preparation liquid is coated in formation surface isolation layer on composite polymeric film or the carbon membrane surface, composite mesopore intermediate layer;
The drying of c surface isolation layer: the dry 15-24h under 30-50 ℃ temperature of elder generation, dry 20-30h under 70-80 ℃ temperature processes Jie's micropore composite polymeric film then;
The charing of Jie's d micropore composite polymeric film: put into retort to Jie's micropore composite polymeric film, under inert gas shielding, carry out high temperature carbonization and process compound carbon membrane with Jie's micropore gradient-structure; Carbonization condition is: carbonization temperature 500-750 ℃, and heating rate 0.5-3 ℃/min, constant temperature time 1-2h, protection throughput 100-200ml/min.
4. a kind of preparation method with compound carbon membrane of Jie's microinverse pore passage structure according to claim 3 is characterized in that: described step 1. in the ordered mesoporous polymer presoma of a be a kind of in mesoporous phenolic resin, mesoporous polyimides, benzoxazine colophony or the cyanate ester resin.
5. a kind of preparation method with compound carbon membrane of Jie's microinverse pore passage structure according to claim 3 is characterized in that: described step 1. in the porous supporting body of b be a kind of in porous charcoal pipe, porous carbon slab, porous ceramic pipe, porous ceramic plate, porous stainless steel sintered pipes or the porous stainless steel sintered plate.
6. a kind of preparation method with compound carbon membrane of Jie's microinverse pore passage structure according to claim 3 is characterized in that: described step 2. in the polymer precursor of a be a kind of in micropore polyimides, micropore cyanate ester resin, benzoxazine colophony, PAEK, poly (aryl ether sulfone ketone), the polyarylether acid amides.
7. a kind of preparation method with compound carbon membrane of Jie's microinverse pore passage structure according to claim 3 is characterized in that: the described step 2. inert gas of middle d is a kind of of nitrogen or argon gas.
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| 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 |
| CN103933869A (en) * | 2013-01-23 | 2014-07-23 | 同济大学 | Preparing method of ordered mesoporous carbon-stainless steel wire mesh composite separating membrane |
| CN108883377A (en) * | 2016-03-31 | 2018-11-23 | 日本碍子株式会社 | Porous supporter, the manufacturing method of Porous supporter, separation film structure and the manufacturing method for separating film structure |
| CN111326349A (en) * | 2020-03-03 | 2020-06-23 | 华东师范大学 | PIM-1 loaded polypyrrole composite material, and preparation method and application thereof |
| CN112028662A (en) * | 2020-07-28 | 2020-12-04 | 盐城工学院 | Composite hierarchical pore structure ceramic and preparation method thereof |
| CN113083040A (en) * | 2021-04-23 | 2021-07-09 | 兰州理工大学 | Preparation method of soot carbon-based composite membrane material |
| CN114870647A (en) * | 2022-03-28 | 2022-08-09 | 南京工业大学 | Hollow fiber composite carbon membrane and preparation method thereof |
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| 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 |
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| CN108883377A (en) * | 2016-03-31 | 2018-11-23 | 日本碍子株式会社 | Porous supporter, the manufacturing method of Porous supporter, separation film structure and the manufacturing method for separating film structure |
| CN108883377B (en) * | 2016-03-31 | 2021-05-07 | 日本碍子株式会社 | Porous support, method for producing porous support, separation membrane structure, and method for producing separation membrane structure |
| CN111326349A (en) * | 2020-03-03 | 2020-06-23 | 华东师范大学 | PIM-1 loaded polypyrrole composite material, and preparation method and application thereof |
| CN112028662A (en) * | 2020-07-28 | 2020-12-04 | 盐城工学院 | Composite hierarchical pore structure ceramic and preparation method thereof |
| CN113083040A (en) * | 2021-04-23 | 2021-07-09 | 兰州理工大学 | Preparation method of soot carbon-based composite membrane material |
| CN114870647A (en) * | 2022-03-28 | 2022-08-09 | 南京工业大学 | Hollow fiber composite carbon membrane and preparation method thereof |
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