CN101239256B - Oil gas separation ceramic compound film tube and component and preparation thereof - Google Patents
Oil gas separation ceramic compound film tube and component and preparation thereof Download PDFInfo
- Publication number
- CN101239256B CN101239256B CN2007101902347A CN200710190234A CN101239256B CN 101239256 B CN101239256 B CN 101239256B CN 2007101902347 A CN2007101902347 A CN 2007101902347A CN 200710190234 A CN200710190234 A CN 200710190234A CN 101239256 B CN101239256 B CN 101239256B
- Authority
- CN
- China
- Prior art keywords
- oil
- ceramic
- film tube
- component
- gas separation
- 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.)
- Active
Links
Images
Abstract
The present invention provides a gas-oil dissociation ceramic composite film tube and its component and preparing method, the film and the component are mainly used for power equipment dielectric oil degassing online. The ceramic composite film tube use hyperfiltration, microfiltration or nanofiltration ceramic film tube as a support layer, a separating layer is a polymer having better oil resistance and ventilation property, a polymer film tube is formed on the surface of the ceramic tube by coating method. A degassing component is composed of a composite film tube, a case and an oil resistant rubber seal ring. The component may includes single ceramic composite film tube and also assembled by multiple film tubes. The component case is set with inlet and outler for gas and oil. The invention component combines the high strength of the ceramic film tube and the macromolecule better air permeability, has a rapid degassing speed, lower cost, convenient installation and use.
Description
Technical field
It is fast to the present invention relates to a kind of ventilative speed, installs, oil gas separation ceramic compound film tube and assembly and preparation method easy to use, is mainly used in online degassing purification process of power equipment insulating oil and oil dissolved gas monitoring oil and gas separating system.
Background technology
A lot of large-scale power equipments, for example transformer, power transformation switch etc. need in its running by insulating oil the heat that produces to be distributed, simultaneously to the isolation of insulating between each element of device interior.Transformer is one of most important equipment in the power system, and following narration is in the transformer being example, but the obvious scope of application of the present invention is not limited to transformer.The quality of transformer state directly influences the safe operation of electrical network.Hide or exist the transformer of fault, its insulating paper or insulating oil that H can take place to decompose and produce under the effect of heat and electricity
2(hydrogen), O
2(oxygen), CO (carbon monoxide), CO
2(carbon dioxide), CH
4(methane), C
2H
2(acetylene), C
2H
4(ethene), C
2H
6Failure gas such as (ethane) and aqueous vapor.These failure gas, the particularly existence of oxygen G﹠W can change the insulating properties of insulating paper/oil and quicken its decomposition.Can make early warning to transformer fault by monitoring these gases concentration in oil; In time with these foreign gases particularly oxygen and moisture removal, the further decomposition that can stop or slow down greatly dielectric.
Common insulating oil degas method is under the shutdown situation, and the insulating oil of heating is taken out with vavuum pump, and is so very inconvenient.The method that realizes the oil dissolved gas separation also can be dissolved by polymeric membrane-osmosis except above-mentioned vacuum method.Commonly used have flat sheet membrane, fluororesin doughnut body membrane, a doughnut and the high polymer compound film etc. of breathing freely.The effective contact area of the oil-film of flat sheet membrane is less, and degassing rate is slow, can not satisfy the requirement that the online degassing purifies and monitors in real time.Equally, no matter be with polytetrafluoroethylene (PTFE) or the capillary wall of high ventilative amorphous fluororesin preparation more than 100 μ m, degassing rate is also slow.
For further improve degassing rate and and reduce cost, U.S. Pat P5,902,747 and USP6,217,634 provide a kind of method of carrying out online Oil-gas Separation with the compound assembly of hollow fiber polymer membrane and amorphous fluororesin.Because the oil film contact area is than big many of flat sheet membrane, and fluororesin separating layer thickness has only 0.5-5 μ m, thereby shortened the gas and oil equilibration time greatly.When but transformer is in running status, the insulating oil temperature may reach more than 70 ℃, tens meters high oils column can produce certain static pressure, and be used for the gear pump of transferring oil and may produce pressurization, these factors all may make the distortion of polymeric hollow fiber compound film component, and then produce open defect and leakage of oil.
Summary of the invention
The objective of the invention is in order to improve the prior art degassing rate slow, the cost height, deficiency such as heatproof, withstand voltage difference and to have proposed a kind of ventilative speed fast, install, oil gas separation ceramic compound film easy to use, another object of the present invention provides the preparation method of above-mentioned oil gas separation ceramic compound film, the present invention also has a purpose to provide the assembly that contains above-mentioned composite membrane, is mainly used in the Oil-gas Separation in online degassing purification of power equipment insulating oil and the dissolved gas monitoring system.
Technical scheme of the present invention is: a kind of oil gas separation ceramic compound film tube is characterized in that being coated on the ceramic filter membrane pipe by polymeric material as separating layer forms.
Wherein said ceramic filter membrane pipe (13) is micro-filtration, ultrafiltration or nanofiltration ceramic-film tube, and pore size filter is 20-200nm.Ceramic-film tube is inner pressed or external-compression type.The polymeric material of separating layer (14) is the compound of unformed glassy state perfluorinated resin or unformed glassy state perfluorinated resin and full hydrophobic silica nano-powder, and silica content is the 0.1-5% of unformed glassy state perfluorinated resin weight.Separating layer is selected the polymeric material that permeability is good, be suitable for applying for use, preferably as Du-pont company's T eflonAF series or the Solvay Solexis HyflonAD of company series of products.Wherein separating layer thickness can be controlled by the concentration and the coating number of times of coating liquid, and thickness generally is controlled at 0.1-10 μ m (as shown in Figure 2).
The present invention also provides the preparation method of above-mentioned oil gas separation ceramic compound film, and its concrete steps are: with solution ceramic supporting body is cleaned up; Polymer material solution is poured in the film pipe that an end seals temporarily, kept 0.5-20min to pour out, applies 1-10 time, the drying that heats up processing removes solvent, makes oil gas separation ceramic compound film.
The concentration expressed in percentage by weight of above-mentioned polymer material solution is 0.1-10%.The coating number of times changes according to the concentration of polymer material solution.
In preparation process, in order to improve the adhesion of ceramic supporting body and high polymer separating layer, the preferably ceramic supporter cleans the back and with silane or silicon fluoride material ceramic surface is handled; Also, preferably the separating layer of ceramic composite membrane is carried out surface treatment by high energy particle, plasma for to improve oil gas separation ceramic compound film oil resistivity and gas permeability.
The present invention also provides a kind of Oil-gas Separation assembly, it is characterized in that being made up of the above-mentioned compound film tube that makes (2), package shell (8), oil resistant rubber sealing ring (3); The film pipe places in the shell, with sealing ring sealing (as shown in Figure 1).
Package shell is a tubulose, and sidewall is provided with the import and export of gas, and two ends are provided with the import and export of oil, and oily gentle import and export position can be that inner pressed or external-compression type change according to ceramic membrane.In the linkloop of assembly and transformer, be provided with an oil pump and an air pump.Oil pump (10) makes power equipment insulation fuel tank (9) and assembly (1) constitute a loop, and insulating oil flows by component loops, reaches the continuous degassing purpose; Air pump (11) makes the probe tube (12) of assembly (1) air chamber and air extractor (12) or gas-detecting device constitute the loop, reaches the purpose (as shown in Figure 3) of exhaust or conveying sample gas.
An oil gas separation ceramic compound film assembly can only comprise single ceramic compound film tube and also can be assembled by many film pipes.Also a plurality of assembly serial or parallel connections can be used in the practical application.
Beneficial effect:
Advantage of the present invention is: 1) the present invention adopts the backing material of ceramic filter membrane pipe as the Oil-gas Separation composite membrane, formed separation assembly heatproof, good pressure-resistant performance, the harsh conditions of the online degassing of adaptation power equipment insulating oil; 2) the Oil-gas Separation assembly that utilizes the inventive method to obtain is a tubulose, compares with flat sheet membrane, and is not only simple in structure, and the oil film contact area increases greatly, helps improving the permeability of gas; 3) separating layer is used high breathable polymer, and for example TeflonAF or HyflonAD apply, and owing to be composite membrane, separating layer thickness can be very thin, further improved the permeability of gas; 4) because the ventilative speed of the formed assembly of the present invention is very fast, can carry out the online degassing to the power equipment insulating oil under in running order purifies, and assembly can shorten analytical cycle when being used for the Oil-gas Separation of dissolved gas monitoring system greatly, realizes monitoring in real time; 5) thickness owing to separating layer in the composite membrane is thin more a lot of than body membrane, has significantly reduced the consumption of expensive high polymers such as TeflonAF or HyflonAD, has reduced cost.
Description of drawings
Fig. 1 Ceramic Composite membrane module organigram, 1-Oil-gas Separation assembly wherein, 2-ceramic compound film tube, 3-sealing gasket, 4, the 5-insulating oil imports and exports, 6, the 7-gas inlet and outlet, 8-package shell.
The cutaway view of Fig. 2 ceramic compound film tube, wherein, 13-ceramic filter membrane pipe, 14-separating layer.
Fig. 3 Ceramic Composite membrane module and relevant portion connection diagram, 1-Oil-gas Separation assembly wherein, 9-power equipment fuel tank, 10-gear pump, 11-vavuum pump or micro air pump, 12-chromatogram quantification pipe.
The specific embodiment
The following examples are that example illustrates superiority of the present invention with ceramic composite membrane at insulating oil dissolved gas on-line monitoring, but the application and the preparation method of ceramic composite membrane of the present invention are not limited to this.
Selecting the aperture for use is the inner pressed ceramic-film tube of 50nm, earthenware internal diameter 10mm, and external diameter 12.5mm, length 100mm cleans up it with ethanolic solution.The TeflonAF2400 solution that separating layer selects for use du pont company to produce, this solution weight percentage concentration is 1.0%.Polymer solution is poured in the film pipe that an end seals temporarily, kept 0.5min to pour out, be coated with repeatedly 7 times, be warming up to 200 ℃ of dry processing, remove solvent.The thickness that can be told separating layer by profile scanning Electronic Speculum figure is about 5 μ m.The assembly that is formed by this film and stainless steel casing is connected with the small-sized analogue transformer in laboratory, with online oil chromatography system testing, can reach gas and oil equilibration in 2hr.This assembly oiling, under 500kPa pressure, keep not seeing in 48 hours break, oil impregnate.
Selecting the aperture for use is the inner pressed ceramic-film tube of 100nm, earthenware internal diameter 10mm, and external diameter 12.5mm, length 100mm cleans up it with ethanolic solution.The Hyflon AD80 that separating layer selects for use Solvay Solexis company to produce, solvent is that Galden HT90 solution weight percentage concentration is 8.0%.Polymer solution is poured in the film pipe that an end seals temporarily, kept 1min to pour out, applies 1 time, be warming up to 250 ℃ of dry processing, remove solvent.The assembly that is formed by this film and stainless steel casing is connected with the small-sized analogue transformer in laboratory, with online oil chromatography system testing, can reach gas and oil equilibration in 4hr.This assembly oiling, under 500kPa pressure, keep not seeing in 48 hours break, oil impregnate.
Embodiment 3
Selecting the aperture for use is the external-compression type earthenware of 100nm, earthenware internal diameter 10mm, and external diameter 13.0mm, length 100mm cleans up it with ethanolic solution.The Hyflon AD80 that separating layer selects for use Solvay Solexis company to produce, solvent is Galden HT90.After polymer dissolution, add the full hydrophobic nano SiO that is equivalent to its weight 5%
2, ultrasonic dispersion.The average grain diameter of nano-powder is 20nm, and the total weight of solids percentage concentration is 1.0% in the solution.Polymer solution is poured in the film pipe that an end seals temporarily, kept 8min to pour out, applies 6 times, be warming up to 200 ℃ of dry processing, remove solvent.The assembly that is formed by this film and stainless steel casing is connected with the small-sized analogue transformer in laboratory, with online oil chromatography system testing, can reach gas and oil equilibration in 2.8hr.This assembly oiling, under 500kPa pressure, keep not seeing in 48 hours break, oil impregnate.
Claims (8)
1. an oil gas separation ceramic compound film tube is characterized in that being coated on ceramic filter membrane pipe (13) by polymeric material as separating layer (14) forms; Wherein said ceramic filter membrane pipe (13) is micro-filtration, ultrafiltration or NF membrane pipe, and membrane aperture is 20-200nm; The polymeric material of separating layer (14) is the compound of unformed glassy state perfluorinated resin or unformed glassy state perfluorinated resin and full hydrophobic silica nano-powder, and wherein silica content is the 0.1-5% of unformed glassy state perfluorinated resin weight; The THICKNESS CONTROL of separating layer is at 0.1-10 μ m.
2. compound film tube as claimed in claim 1 is characterized in that ceramic-film tube is inner pressed or external-compression type.
3. method for preparing oil gas separation ceramic compound film as claimed in claim 1, its concrete steps are: ceramic supporting body is cleaned up; Polymer material solution is poured in the film pipe that an end seals temporarily, kept pouring out behind the 0.5-20min, the dry processing of heating up removes solvent, makes oil gas separation ceramic compound film; Wherein said polymeric material is the compound of unformed glassy state perfluorinated resin or unformed glassy state perfluorinated resin and full hydrophobic silica nano-powder, and wherein silica content is the 0.1-5% of unformed glassy state perfluorinated resin weight.
4. preparation method as claimed in claim 3, the concentration expressed in percentage by weight that it is characterized in that described polymer material solution is 0.1-10%.
5. preparation method as claimed in claim 3 is characterized in that described ceramic supporting body cleans the back and with silane or silicon fluoride material ceramic surface handled, and improves the adhesion of ceramic supporting body and high polymer separating layer.
6. preparation method as claimed in claim 3 is characterized in that the separating layer that makes composite membrane carries out surface treatment to improve its oil resistivity and gas permeability by high energy particle or plasma.
7. an Oil-gas Separation assembly is characterized in that being made up of the described compound film tube of claim 1 (2), package shell (8) and oil resistant rubber sealing ring (3); The film pipe places in the shell, seals with sealing ring.
8. Oil-gas Separation assembly as claimed in claim 7 is characterized in that package shell is a tubulose, and sidewall is provided with the import and export of gas, and two ends are provided with the import and export of oil, and oily gentle import and export position can be that inner pressed or external-compression type change according to ceramic membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101902347A CN101239256B (en) | 2007-11-22 | 2007-11-22 | Oil gas separation ceramic compound film tube and component and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101902347A CN101239256B (en) | 2007-11-22 | 2007-11-22 | Oil gas separation ceramic compound film tube and component and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101239256A CN101239256A (en) | 2008-08-13 |
| CN101239256B true CN101239256B (en) | 2011-01-12 |
Family
ID=39931252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101902347A Active CN101239256B (en) | 2007-11-22 | 2007-11-22 | Oil gas separation ceramic compound film tube and component and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101239256B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101791494B (en) * | 2010-04-22 | 2013-05-22 | 大连理工大学 | Defoaming method adopting porous ceramics |
| CN103752045A (en) * | 2013-12-31 | 2014-04-30 | 江苏有能电力自动化有限公司 | Composite membrane tube |
| CN103752046A (en) * | 2013-12-31 | 2014-04-30 | 江苏有能电力自动化有限公司 | Preparation method for composite membrane pipe |
| CN105251244B (en) * | 2014-07-15 | 2017-06-30 | 东华大学 | The defoaming device and its application method of a kind of high viscosity slurry |
| CN105148686B (en) * | 2015-07-16 | 2017-09-22 | 西安理工大学 | A kind of paraxylene production membrane separation reactor |
| CN105344253A (en) * | 2015-11-26 | 2016-02-24 | 江苏有能电力自动化有限公司 | Preparation method for transformer oil chromatographic composite membrane tube |
| CN109647220B (en) * | 2018-09-11 | 2021-09-14 | 全球能源互联网研究院有限公司 | Composite film with high durability and high gas permeability and preparation method thereof |
| CN112093303B (en) * | 2020-08-19 | 2022-07-19 | 江苏全卓软件科技有限公司 | Membrane type water sealer and storage tank waste gas collecting system and method using same |
| CN112439226A (en) * | 2020-11-20 | 2021-03-05 | 安徽盛世开元装备科技有限公司 | Stirring degassing tank of high-efficiency thickener |
| CN114428129B (en) * | 2021-12-17 | 2023-11-28 | 国网湖北省电力有限公司电力科学研究院 | Degassing membrane tube assembly and on-line monitoring device for gas in vacuum on-load tap-changer oil |
| CN114984773B (en) * | 2022-06-29 | 2023-09-01 | 江苏久膜高科技股份有限公司 | Oil gas recovery composite membrane and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5902747A (en) * | 1996-10-24 | 1999-05-11 | Compact Membrane Systems, Inc. | Method of gasifying or degasifying a liquid containing cells |
| US6217634B1 (en) * | 1999-08-27 | 2001-04-17 | Electric Power Research Institute, Inc. | Apparatus and method for monitoring and purifying dielectric fluids |
| CN1579604A (en) * | 2003-08-05 | 2005-02-16 | 中国科学技术大学 | Positive charged organic-inorganic hybrid membrane preparing method |
| CN1724127A (en) * | 2005-06-16 | 2006-01-25 | 南京工业大学 | Organic and inorganic composite hydrophobic film and its preparing process |
| CN1768912A (en) * | 2005-10-13 | 2006-05-10 | 中材科技股份有限公司 | High temperature resistant P.T.F.E. coated filter material |
-
2007
- 2007-11-22 CN CN2007101902347A patent/CN101239256B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5902747A (en) * | 1996-10-24 | 1999-05-11 | Compact Membrane Systems, Inc. | Method of gasifying or degasifying a liquid containing cells |
| US6217634B1 (en) * | 1999-08-27 | 2001-04-17 | Electric Power Research Institute, Inc. | Apparatus and method for monitoring and purifying dielectric fluids |
| CN1579604A (en) * | 2003-08-05 | 2005-02-16 | 中国科学技术大学 | Positive charged organic-inorganic hybrid membrane preparing method |
| CN1724127A (en) * | 2005-06-16 | 2006-01-25 | 南京工业大学 | Organic and inorganic composite hydrophobic film and its preparing process |
| CN1768912A (en) * | 2005-10-13 | 2006-05-10 | 中材科技股份有限公司 | High temperature resistant P.T.F.E. coated filter material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101239256A (en) | 2008-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101239256B (en) | Oil gas separation ceramic compound film tube and component and preparation thereof | |
| Shu et al. | High-flux MFI zeolite membrane supported on YSZ hollow fiber for separation of ethanol/water | |
| Ma et al. | Gamma-alumina supported carbon molecular sieve membrane for propylene/propane separation | |
| Yousef et al. | CO2/CH4, CO2/N2 and CO2/H2 selectivity performance of PES membranes under high pressure and temperature for biogas upgrading systems | |
| Li et al. | Recycling of phenol from aqueous solutions by pervaporation with ZSM-5/PDMS/PVDF hollow fiber composite membrane | |
| Choi et al. | In-line formation of chemically cross-linked P84® co-polyimide hollow fibre membranes for H2/CO2 separation | |
| CN104722215B (en) | Preparation method of carbon dioxide separation film based on graphene material | |
| US20160263531A1 (en) | Plasma-treated polymeric membranes | |
| EP1559902B1 (en) | Method for preventing fuel infiltration into microporous polymer membranes | |
| US20160263532A1 (en) | Ultraviolet and plasma-treated polymeric membranes | |
| JP2018047463A (en) | Carbon dioxide separation apparatus utilizing silicone separation membrane, and manufacturing method thereof | |
| KR20120100920A (en) | Method to improve the selectivity of polybenzoxazole membranes | |
| US8343348B2 (en) | Method for producing carbon film, carbon film and separator | |
| JP2018536531A (en) | Double layer coated membrane for gas separation | |
| CN105311972A (en) | Method for synthesizing hydrophilic ZSM-5 zeolite molecular sieve membrane | |
| Zhu et al. | Recycle of ceramic substrate of PDMS/ceramic composite membranes towards alcohol-permselective pervaporation | |
| WO2010070992A1 (en) | Method for separating liquid mixture, and device for separating liquid mixture | |
| CN103752045A (en) | Composite membrane tube | |
| WO2010125898A1 (en) | Separation membrane for concentration of hydrochloric acid, method for concentration of hydrochloric acid, and apparatus for concentration of hydrochloric acid | |
| CN113750821B (en) | g-C based on embedded porous few layers 3 N 4 Preparation method and application of/ZIF-8 mixed matrix membrane | |
| EP1993711B1 (en) | Method and apparatus for removing metal sulphide particles from a liquid stream | |
| CN107456881B (en) | Flat multilayer composite film and preparation method thereof | |
| CN113457467B (en) | High-stability GO-confinement ionic liquid supported liquid membrane and preparation method and application thereof | |
| Ren et al. | Long alkyl chain-containing organosilica/silicalite-1 composite membranes for alcohol recovery | |
| CN108295669A (en) | A kind of composite membrane and preparation method thereof of separation VOCs |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160217 Address after: 211505 Jiangsu Province, Nanjing Yangtze River Development Zone geguan Road No. 889 room 105 Patentee after: Nanjing no Book Chemical Co., Ltd. Address before: 210009 Zhongshan North Road, Jiangsu, No. 200, Patentee before: Nanjing University of Technology |