CN106823821A - The complementing method of Carbon Molecular Sieve Membrane defect - Google Patents
The complementing method of Carbon Molecular Sieve Membrane defect Download PDFInfo
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- CN106823821A CN106823821A CN201510886176.6A CN201510886176A CN106823821A CN 106823821 A CN106823821 A CN 106823821A CN 201510886176 A CN201510886176 A CN 201510886176A CN 106823821 A CN106823821 A CN 106823821A
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- molecular sieve
- carbon molecular
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- silicon rubber
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Abstract
A kind of complementing method of Carbon Molecular Sieve Membrane defect, with silicon rubber as raw material, reaction is prepared into colloidal sol after mixing with catalyst, crosslinking agent and organic solvent, then colloidal sol is coated into film forming by the colloidal sol on Carbon Molecular Sieve Membrane surface, dries.Carbon Molecular Sieve Membrane complementing method of the invention is simple to operate, and repeatability is high, make use of the penetration property that silicon rubber is good, is applied to fill up Carbon Molecular Sieve Membrane defect, so as to substantially increase the permeance property of Carbon Molecular Sieve Membrane.The Carbon Molecular Sieve Membrane filled up after defect has excellent gas separating property, is had broad application prospects in gas separation field.
Description
Technical field
Carbon is carried out the present invention relates to gas separation membrane field, more particularly to a kind of colloidal sol prepared using silicon rubber
The complementing method of molecular screen membrane defect.
Background technology
Carbon Molecular Sieve Membrane is carbonized through high temperature pyrolysis under the protection of inert atmosphere by the presoma of carbonaceous material
A kind of new inorganic material film is prepared from, application (the CN201410713435.0 in applicant a few days ago
And CN201410719299.6) in be documented.There is homogeneous aperture and rich in itself due to carbon material
Rich microcellular structure, thus it is excellent with membrane material in combination with carbon material using the Carbon Molecular Sieve Membrane of its preparation
Gesture, the adsorptive selectivity not only having had very much with heat endurance higher but also for some micro-molecular gas,
Therefore it is considered as to be most hopeful to realize industrialization and the new inorganic material film of the class applied, therefore such
Membrane material has broad application prospects at the aspect that isolates and purifies of micro-molecular gas.
But due to Carbon Molecular Sieve Membrane, fragility is very big in itself, causes often to produce small lacking in preparation process
Fall into, the presence of these defects often leads to the very fast decline of gas separating property of Carbon Molecular Sieve Membrane, therefore at certain
Its further commercial Application is limited in a little degree.
The content of the invention
To solve Carbon Molecular Sieve Membrane in the prior art, fragility is very big in itself, is easily produced in preparation process small
Defect, so as to substantially reduce the gas separating property of itself, the present invention provides a kind of Carbon Molecular Sieve Membrane and lacks
Sunken complementing method, greatly improves the gas separating property of Carbon Molecular Sieve Membrane.
To realize above technical purpose, technical scheme is as follows：
A kind of complementing method of Carbon Molecular Sieve Membrane defect, comprises the following steps：
1. in mass ratio it is 3~4 by silicon rubber, catalyst, crosslinking agent and organic solvent：0.01~0.05：
0.05~0.08：10~20 mixing, stir 1~3 hour and stand prepared colloidal sol at room temperature；
2. the colloidal sol is coated into film forming on Carbon Molecular Sieve Membrane surface, is dried；
Wherein, the catalyst is selected from the one kind in organotin, titanate esters and amine；
The crosslinking agent is selected from tetraethyl orthosilicate, many alkoxy silanes, many butanone oximino silanes, many acetyl oxygen
One kind in base silane, many amino containing silanes, multiamide base silane, many iso-propenyloxysilanes and containing hydrogen silicone oil.
Compared with prior art, the present invention has advantages below：
The present invention may penetrate into the inside of Carbon Molecular Sieve Membrane, using silicon using the good penetration property of silicon rubber
Silicon rubber prepared by rubber cross in Carbon Molecular Sieve Membrane surface filming to fill up the defect of Carbon Molecular Sieve Membrane so that
Substantially increase the permeance property of Carbon Molecular Sieve Membrane.The present invention fills up the method operation letter of Carbon Molecular Sieve Membrane defect
Single, repeatability is high, and the Carbon Molecular Sieve Membrane filled up after defect has excellent gas separating property, in gas point
Had broad application prospects from field.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
The width of accompanying drawing of the present invention 1：
Fig. 1 fills up agent and fills up CO before and after Carbon Molecular Sieve Membrane for three kinds of films of the synthesis of embodiment 12/CH4Segregative line
Number is with CO2Permeability variation curve.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that described herein
Specific embodiment be merely to illustrate and explain the present invention, be not intended to limit the invention.
Present invention firstly provides a kind of complementing method of Carbon Molecular Sieve Membrane defect, comprise the following steps：
1. in mass ratio it is 3~4 by silicon rubber, catalyst, crosslinking agent and organic solvent：0.01~0.05：
0.05~0.08：10~20 mixing, stir 1~3 hour and stand prepared colloidal sol at room temperature；
2. the colloidal sol is coated into film forming on Carbon Molecular Sieve Membrane surface, is dried；
Wherein, the catalyst is selected from the one kind in organotin, titanate esters and amine；
The crosslinking agent is selected from tetraethyl orthosilicate, many alkoxy silanes, many butanone oximino silanes, many acetyl oxygen
One kind in base silane, many amino containing silanes, multiamide base silane, many iso-propenyloxysilanes and containing hydrogen silicone oil.
Further, the structure of the silicon rubber is as shown in formula I：
In formula I, R1And R2Methyl, vinyl, phenyl, methoxyl group and cyano group are each independently selected from,
The molecular weight of the silicon rubber is 50~800,000；As further preferred, R1And R2It is methyl.
Further, in all of above technical scheme, the catalyst is preferably organotin, used as more
The implementation method of body, the organotin is selected from least one in stannous methide, dioctyl tin and tetraphenyltin.
Further, in all of above technical scheme, the crosslinking agent is preferably tetraethyl orthosilicate.
Further, in all of above technical scheme, the organic solvent be selected from n-hexane, isooctane,
At least one of hexamethylene, acetone and tetrahydrofuran, wherein more preferably isooctane.
Further, in above-mentioned filling method, step 2. described in coating film forming mode be dip coating,
Dip-coating method, spin-coating method or spraying process, preferably dip-coating method；Further, dip-coating method
Concrete operations condition be：Immersion speed is 150~200mm/min, 20~30mm/min of the rate of pulling.
Further, in above-mentioned filling method, the drying is 12~48h of vacuum drying at 40~120 DEG C.
Further, the Carbon Molecular Sieve Membrane is passed through under the protection of inert atmosphere by the presoma of carbonaceous material
High temperature pyrolysis carbonization is prepared from a kind of new inorganic material film, more specifically, in applicant a few days ago
Application (CN201410713435.0 and CN201410719299.6) in be documented.As preferred
, heretofore described Carbon Molecular Sieve Membrane is the carbonized film as obtained by mixed substrate membrane containing nano-grade molecular sieve is carbonized, used as more entering one
What is walked is preferred, is the carbonized film as obtained by the mixed substrate membrane containing nano-grade molecular sieve carbonization containing metal-organic framework materials.
The present invention is further described below by specific embodiment, but does not therefore limit this
Invention.
Embodiment 1
(Carbon Molecular Sieve Membrane used is using in patent CN201410719299.6 for the filling up of Carbon Molecular Sieve Membrane defect
Prepared by the method for embodiment 2)：
1. 3.9085 grams of methyl silicone rubbers, 0.045 gram of stannous methide, 0.0738 gram of tetraethyl orthosilicate are weighed successively
Crosslinking agent, 10 grams of iso-octane solvents.2 hours formation colloidal sol is stood after being stirred at room temperature 3 hours stand-by.
2. colloidal sol is coated on defective Carbon Molecular Sieve Membrane surface, the Best-Effort request by dip-coating method
The immersion speed of method is 200mm/min, and the rate of pulling is 20mm/min.
3 Carbon Molecular Sieve Membranes that defect processing is filled up by above step are taken, is respectively placed in vacuum drying chamber
In 60 DEG C of dryings 4 hours, 80 DEG C of dryings 4 hours, 100 DEG C of dryings 24 hours.Products obtained therefrom number consecutively is A,
B, C.
Performance evaluation：
Permeability and selectivity are two important indicators of evaluated for film gas separating property, respectively with permeability (Pi)
With separation (αij) characterize.Permeability Pi=Ji/ A* Δ P, wherein JiIt is the seepage discharge of gas, it is single
Position molm-2·s-1, A is effective membrane area, unit m2, Δ P is the pressure differential of film both sides, unit Pa；
Gas selectivity αij=Pi/Pj, wherein PiIt is the permeability of gas i, PjIt is the permeability of gas j.Use
Wicke-Kallenbach (a kind of method of film test) method is with reference to online gas chromatographic technique to synthesizing
To silicon rubber fill up before and the gas permeability of Carbon Molecular Sieve Membrane after filling up carry out system testing.Test
Condition is：25 DEG C of temperature, the pressure difference of film both sides is 1bar.Shown in the table of test result as 1.
Table 1
Claims (10)
1. the complementing method of Carbon Molecular Sieve Membrane defect, comprises the following steps：
1. in mass ratio it is 3~4 by silicon rubber, catalyst, crosslinking agent and organic solvent：0.01~0.05：
0.05~0.08：10~20 mixing, stir 1~3 hour and stand prepared colloidal sol at room temperature；
2. the colloidal sol is coated into film forming on Carbon Molecular Sieve Membrane surface, is dried；
Wherein, the catalyst is selected from the one kind in organotin, titanate esters and amine；
The crosslinking agent is selected from tetraethyl orthosilicate, many alkoxy silanes, many butanone oximino silanes, many acetyl oxygen
One kind in base silane, many amino containing silanes, multiamide base silane, many iso-propenyloxysilanes and containing hydrogen silicone oil.
2. method according to claim 1, it is characterised in that the structure of the silicon rubber such as formula
Shown in I：
In formula I, R1And R2Methyl, vinyl, phenyl, methoxyl group and cyano group are each independently selected from,
The molecular weight of the silicon rubber is 50~800,000.
3. method according to claim 2, it is characterised in that in formula I, R1And R2It is first
Base.
4. method according to claim 1, it is characterised in that the catalyst is organotin, choosing
At least one from stannous methide, dioctyl tin and tetraphenyltin.
5. method according to claim 1, it is characterised in that the crosslinking agent is tetraethyl orthosilicate.
6. method according to claim 1, it is characterised in that the organic solvent be selected from n-hexane,
At least one of isooctane, hexamethylene, acetone and tetrahydrofuran.
7. method according to claim 1, it is characterised in that step 2. described in coating film forming
Mode is dip-coating method, and immersion speed is 150~200mm/min, and the rate of pulling is 20~30mm/min.
8. method according to claim 1, it is characterised in that step 2. described in dry be 40~120 DEG C
2~48h of lower vacuum drying.
9. method according to claim 1, it is characterised in that described Carbon Molecular Sieve Membrane is mixing
Carbonized film obtained by matrix membrane carbonization.
10. method according to claim 9, it is characterised in that described Carbon Molecular Sieve Membrane is by containing
Carbonized film obtained by the mixed substrate membrane containing nano-grade molecular sieve carbonization of metal-organic framework materials.
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| CN201510886176.6A CN106823821A (en) | 2015-12-04 | 2015-12-04 | The complementing method of Carbon Molecular Sieve Membrane defect |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110523292A (en) * | 2019-08-28 | 2019-12-03 | 李磊娜 | A kind of method for repairing and mending of the tubular type zeolite membrane applied to anti-penetration wastewater disposal |
| CN115052675A (en) * | 2019-12-11 | 2022-09-13 | 基金技术研究与创新公司 | Carbon molecular sieve membranes and their use in separation processes |
Citations (5)
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|---|---|---|---|---|
| JPH02307805A (en) * | 1989-05-22 | 1990-12-21 | Nippon Sanso Kk | Oxygen production apparatus |
| JPH04326930A (en) * | 1991-04-24 | 1992-11-16 | Agency Of Ind Science & Technol | Production of molecular sieve carbon membrane |
| CN101229487A (en) * | 2007-11-06 | 2008-07-30 | 清华大学 | PDMS/PVDF complex film for separating organic steam and preparation method thereof |
| CN102527259A (en) * | 2012-02-10 | 2012-07-04 | 南京工业大学 | Composite carbon molecular sieve membrane and preparation method and application thereof |
| CN104125855A (en) * | 2011-12-20 | 2014-10-29 | 佐治亚科技研究公司 | Stabilization of porous morphologies for high performance carbon molecular sieve hollow fiber membranes |
-
2015
- 2015-12-04 CN CN201510886176.6A patent/CN106823821A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02307805A (en) * | 1989-05-22 | 1990-12-21 | Nippon Sanso Kk | Oxygen production apparatus |
| JPH04326930A (en) * | 1991-04-24 | 1992-11-16 | Agency Of Ind Science & Technol | Production of molecular sieve carbon membrane |
| CN101229487A (en) * | 2007-11-06 | 2008-07-30 | 清华大学 | PDMS/PVDF complex film for separating organic steam and preparation method thereof |
| CN104125855A (en) * | 2011-12-20 | 2014-10-29 | 佐治亚科技研究公司 | Stabilization of porous morphologies for high performance carbon molecular sieve hollow fiber membranes |
| CN102527259A (en) * | 2012-02-10 | 2012-07-04 | 南京工业大学 | Composite carbon molecular sieve membrane and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| JOACHIM PETERSEN 等: "Capillary carbon molecular sieve membranes derived from Kapton for high temperature gas separation", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| LIU SAINAN等: "Ceramic Supported PDMS and PEGDA Composite Membranes for CO2 Separation", 《CHINESE JOURNAL OF CHEMICAL ENGINEERING》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110523292A (en) * | 2019-08-28 | 2019-12-03 | 李磊娜 | A kind of method for repairing and mending of the tubular type zeolite membrane applied to anti-penetration wastewater disposal |
| CN115052675A (en) * | 2019-12-11 | 2022-09-13 | 基金技术研究与创新公司 | Carbon molecular sieve membranes and their use in separation processes |
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