CN104258746A - Preparation method of modified organosilicone dephenolized membrane - Google Patents
Preparation method of modified organosilicone dephenolized membrane Download PDFInfo
- Publication number
- CN104258746A CN104258746A CN201410447018.6A CN201410447018A CN104258746A CN 104258746 A CN104258746 A CN 104258746A CN 201410447018 A CN201410447018 A CN 201410447018A CN 104258746 A CN104258746 A CN 104258746A
- Authority
- CN
- China
- Prior art keywords
- membrane
- room temperature
- silicone rubber
- preparation
- liquid silicone
- 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.)
- Granted
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of pervaporation membrane separation and in particular relates to a preparation method of a modified organosilicone dephenolized membrane. The preparation method of the modified organosilicone dephenolized membrane comprises the following steps: firstly, mechanically stirring room temperature vulcanization liquid silicone rubber with a solvent until the room temperature vulcanization liquid silicone rubber is dissolved and a transparent solution is formed; then, adding a crosslinking agent and a catalyst, and mechanically stirring for 5-20 minutes, wherein the mass ratio of the room temperature vulcanization liquid silicone rubber to the solvent to the crosslinking agent to the catalyst is 33:60:5:2; then adding oleic alcohol the mass of which is 1%-5% of that of the room temperature vulcanization liquid silicone rubber, mechanically stirring for 2-10 minutes, and uniformly mixing; and finally, casting the obtained solution on a supporting basement membrane to form a membrane, standing at room temperature for 4-5 hours, and then drying the membrane in a vacuum drying oven at the temperature of 60-80 DEG C for 8-12 hours. A preparation process of the modified membrane is simple and easy, and the obtained membrane has good comprehensive performance of separating phenol from water when being used for separating a phenol/water mixture; permeation flux of the membrane can be 526g.m<-2>.h<-1>, and a separation factor of the membrane can be 8.63; great potential in industrialized application is shown.
Description
Technical field:
The present invention relates to a kind of preparation method that can be used for the modified organic silicon film of phenol in pervaporation method Separation of Water, belong to infiltration evaporation technical field of membrane separation
Background technology:
Infiltration evaporation (Pervaporation, PV) is under the steam pressure difference of liquid mixture component promotes, and utilizes the dissolving of component by film and the different processes realizing Component seperation of diffusion rate.Infiltration evaporation membrane separation technique has small investment, operating cost is low, separative efficiency is high, be easy to scale, expandability is good, be convenient to the remarkable advantage such as control, easy replacing is considered to substitute traditional separation method as distillation and liquid-liquid extraction.The main application of infiltration evaporation have in solvent dehydration, water remove organic matter (as alcohol, phenol), organic mixture be separated (as cyclohexane/benzene) three aspects.Wherein the film exploitation of solvent dehydration is than being easier to, and realize industrialization the earliest, and it is comparatively large to remove organic membrane material preparation and modification difficulty in water, but has good economic advantages, therefore, be the hot issue that those skilled in the art pay close attention to always.
Dimethyl silicone polymer is called for short PDMS, is a kind of the macromolecule organic silicon compound, is commonly called organosilicon.There is optical clear, and in the ordinary course of things, be considered to inertia, nontoxic, nonflammable.De-organic matter film in the most common water, the existing report being much used for separation of organic substances in water about PDMS film, but selective not good enough due to it, mechanical performance also has much room for improvement, and people design a lot of ways and carry out modification.Namely modification mode the most frequently used is at present added zeolite inorganic material and is carried out modification.
Hennepe (Hennepe H.J.C., Bargeman D, Mulder M.H.V., Smolders C.A., Zeolite-filled silicone rubber membranes:Part 1.Membrane preparation and pervaporation results.J.Mem.Sci., 35 (l): 39-55,1987) mechanism of this method of modifying is proposed already, namely based on the pore structure of total silicon zeolite.People develop various Zeolite modifying PDMS film always based on this subsequently, continue into the present always, as work (the Huang J of Huang etc., Meagher M.M, Pervaporative recovery of n-butanol from aqueous solutions and ABE fermentation broth using thin-film silicalite-filled silicone composite membranes) achieve certain effect.But the preparation flow more complicated of total silicon zeolite at present, need Hydrothermal Synthesis, zeolite only has facilitation to separation in certain content range in addition, exceed critical content then to there will be by particle aggregation, the separating property that the reasons such as boundary defect cause significantly declines, and the addition of general zeolite is comparatively large, has influence on the toughness of PDMS film.
Research work of the present invention, the organosilicon membrane modification thinking changed, no longer adopts inorganic Zeolite modifying, and transfer to adopt organic modifiers oleyl alcohol (being also called the positive oleyl alcohol of 9-) carry out modification, for the preferential separation of phenol in water.Utilize the phenyl ring of oleyl alcohol double bond structure Pyrogentisinic Acid to have good suction-operated, utilize the hydroxyl of oleyl alcohol and the crosslinking agent of PMDS to react simultaneously.Both improved selective, and avoided again the loss of oleyl alcohol in feed liquid, ensure that the operational stability of film.The preparation process of Modified Membrane is simple and easy to do, and the film obtained is when separating phenol/aqueous mixtures, shows good comprehensive separating property to the phenol in water.According to mark wait (mark, Chen Yinsheng, Li Qian. the research [J] of novel PDMS osmotic evaporation film Phenol-Containing Wastewater Treatment. water technology, 2010,1:74-77) report, the permeation flux of its organosilicon membrane is only 0.098gm
-2h
-1, separation factor is only 5.12, and the Modified Membrane reported in the present invention, far away higher than its reported values, permeation flux can reach 526gm
-2h
-1, and separation factor can reach 8.63.Especially permeation flux improves several thousand times, has embodied the great potential of industrial applications.
Summary of the invention:
The object of the invention is to prepare the oleyl alcohol modified organic silicon infiltrating and vaporizing membrane preferentially removing phenol from water, the modification diffusion barrier obtained has excellent tolerance, keeps enough toughness, mechanical strength in wide temperature range, segregational stability, has very large practical value in UF membrane field.In addition, separation membrane material component is simple, with low cost, and the preparation process of diffusion barrier easily operates, and has potentiality and the value of industrial applications.
The preparation method of modified organic silicon dephenolize film: first, forms clear solution by room temperature vulcanized liquid silicone rubber and solvent mechanical agitation to dissolving; Then, add crosslinking agent and catalytic mechanical stirring 5-20 minute, four mass ratioes are room temperature vulcanized liquid silicone rubber: solvent: crosslinking agent: catalyst=33:60:5:2; Next, add oleyl alcohol, oleyl alcohol quality is the 1%-5% of room temperature vulcanized liquid silicone rubber quality, within mechanical agitation 2-10 minute, mix, finally, gained solution is prolonged film forming at support counterdie upper reaches, after left at room temperature 4-5h, film is put into vacuum drying chamber in 60-80 DEG C of dry 8-12h.
Further, described room temperature vulcanized liquid silicone rubber is the one in hydroxyl-terminated injecting two methyl siloxane or terminal hydroxy group PSI; Solvent is normal heptane, normal octane, n-hexane, cyclohexane, toluene, the one in ethyl acetate; Crosslinking agent is ethyl orthosilicate, the one in phenyltrimethoxysila,e, octyl group trimethoxy silane.
Further, support counterdie is the one in milipore filter, NF membrane.
Preparation-obtained modified organic silicon film infiltrating and vaporizing membrane, under the operating condition of gentleness, can reach good separating effect.Permeation flux can reach 525gm
-2h
-1, and separation factor can reach 8.63, has embodied the great potential of industrial applications.The present invention also finds to increase with oleyl alcohol content and increase with feed temperature, the flux of film and separation factor realize increasing simultaneously, this modified effect is actually rare in diffusion barrier, because general diffusion barrier is modified, its permeation flux and separation factor all mutually disappear and rise, its temperature variant rule is also all generally that temperature raises, and flux raises and separation factor reduces, the situation that little appearance increases simultaneously.Also just because of this, the Modified Membrane preparation method of this research has very strong novelty and application prospect.
The modifier physics blending such as zeolite are entered the method for organosilicon membrane by the present invention's research different from the past, and oleyl alcohol is reacted as reactant and crosslinking agent, because oleyl alcohol is chemical bonding in film, so relative position is more fixing, ensure that the operational stability of film properties; And the molecular chain length of oleyl alcohol, there is thickening power can film swelling in control separation process; In the present invention, oleyl alcohol is monohydric alcohol, may carry out end-blocking to crosslinking agent, but due to oleyl alcohol addition in the present invention less, so the degree of cross linking can't have adverse effect, Modified Membrane still remains enough mechanical strengths.The more important thing is, oleyl alcohol Pyrogentisinic Acid has affinity interaction, and therefore the modification of oleyl alcohol has multiple advantageous effect.
Detailed description of the invention
Below by example, the present invention is specifically described.It is important to point out that embodiment is only for being further detailed the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the invention described above content to the present invention.
Embodiment 1
1) 1% oleyl alcohol modified organic silicon infiltration evaporation film preparation
First, hydroxyl-terminated injecting two methyl siloxane and normal octane mechanical agitation are formed clear solution to dissolving; Then, add ethyl orthosilicate and catalyst dibutyltin dilaurylate mechanical agitation 20 minutes, four mass ratioes are hydroxyl-terminated injecting two methyl siloxane: normal octane: ethyl orthosilicate: catalyst=33:60:5:2; Next, add oleyl alcohol, oleyl alcohol quality is 1% of hydroxyl-terminated injecting two methyl siloxane, mechanical agitation mixes for 10 minutes, finally, by gained solution casting film-forming on ultrafiltration counterdie, after left at room temperature 4h, film is put into vacuum drying chamber in 60 degree of dry 8h.
2) the 1% oleyl alcohol modified organic silicon infiltrating and vaporizing membrane adopting said method to prepare, test its phenol/water permeation vaporization separating property, charging adopts the mass content of phenol to be the phenol/water mixture of 0.5%, obtains membrane separating property under different temperatures as table 1:
Table 1 1% oleyl alcohol modified organic silicon infiltration evaporation membrane separating property
| Operating temperature (DEG C) | Permeation flux (gm -2·h -1) | Separation factor alpha |
| 60 | 351 | 4.39 |
| 70 | 388 | 5.16 |
| 80 | 407 | 5.68 |
Embodiment 2
1) 5% oleyl alcohol modified organic silicon infiltration evaporation film preparation
First, hydroxyl-terminated injecting two methyl siloxane and normal heptane mechanical agitation are formed clear solution to dissolving; Then, add ethyl orthosilicate and catalyst dibutyltin dilaurylate mechanical agitation 5 minutes, four mass ratioes are hydroxyl-terminated injecting two methyl siloxane: normal heptane: ethyl orthosilicate: catalyst=33:60:5:2; Next, add oleyl alcohol, oleyl alcohol quality is 5% of hydroxyl-terminated injecting two methyl siloxane quality, mechanical agitation mixes for 2 minutes, finally, by gained solution casting film-forming on nanofiltration counterdie, after left at room temperature 5h, film is put into vacuum drying chamber in 80 degree of dry 12h.
2) the 5% oleyl alcohol modified organic silicon infiltrating and vaporizing membrane adopting said method to prepare, test its phenol/water permeation vaporization separating property, charging adopts the mass content of phenol to be the phenol/water mixture of 0.5%, obtains membrane separating property under different temperatures as table 2:
Table 2 5% oleyl alcohol modified organic silicon infiltration evaporation membrane separating property
| Operating temperature (DEG C) | Permeation flux (gm -2·h -1) | Separation factor alpha |
| 60 | 425 | 5.17 |
| 70 | 465 | 6.75 |
| 80 | 526 | 8.63 |
Claims (3)
1. a preparation method for modified organic silicon dephenolize film, is characterized in that, comprises the following steps:
First, room temperature vulcanized liquid silicone rubber and solvent mechanical agitation are formed clear solution to dissolving; Then, add crosslinking agent and catalytic mechanical stirring 5-20 minute, four mass ratioes are room temperature vulcanized liquid silicone rubber: solvent: crosslinking agent: catalyst=33:60:5:2; Next, add oleyl alcohol, oleyl alcohol quality is the 1%-5% of room temperature vulcanized liquid silicone rubber quality, within mechanical agitation 2-10 minute, mix, finally, gained solution is prolonged film forming at support counterdie upper reaches, after left at room temperature 4-5h, film is put into vacuum drying chamber in 60-80 DEG C of dry 8-12h.
2. preparation method according to claim 1, is characterized in that: described room temperature vulcanized liquid silicone rubber is the one in hydroxyl-terminated injecting two methyl siloxane or terminal hydroxy group PSI; Solvent is normal heptane, normal octane, n-hexane, cyclohexane, toluene, the one in ethyl acetate; Crosslinking agent is ethyl orthosilicate, the one in phenyltrimethoxysila,e, octyl group trimethoxy silane.
3. preparation method according to claim 1, is characterized in that: support counterdie is the one in milipore filter, NF membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410447018.6A CN104258746B (en) | 2014-09-03 | 2014-09-03 | A kind of preparation method of modified organic silicon dephenolize film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410447018.6A CN104258746B (en) | 2014-09-03 | 2014-09-03 | A kind of preparation method of modified organic silicon dephenolize film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104258746A true CN104258746A (en) | 2015-01-07 |
| CN104258746B CN104258746B (en) | 2016-01-20 |
Family
ID=52150394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410447018.6A Expired - Fee Related CN104258746B (en) | 2014-09-03 | 2014-09-03 | A kind of preparation method of modified organic silicon dephenolize film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104258746B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106139925A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of composite nanometer filtering film and preparation method thereof and the application in water treatment field |
| CN106139924A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of composite nanometer filtering film and preparation method thereof and the application in water treatment field |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62171707A (en) * | 1986-01-22 | 1987-07-28 | Chiyoda Chem Eng & Constr Co Ltd | Method for separating and concentrating substance by osmotic vaporization method |
| CN103657456A (en) * | 2013-12-18 | 2014-03-26 | 北京工商大学 | Preparation method of ethanol-permselective POSS (polyhedral oligomeric silsesquioxanes)/silicone rubber composite membrane |
-
2014
- 2014-09-03 CN CN201410447018.6A patent/CN104258746B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62171707A (en) * | 1986-01-22 | 1987-07-28 | Chiyoda Chem Eng & Constr Co Ltd | Method for separating and concentrating substance by osmotic vaporization method |
| CN103657456A (en) * | 2013-12-18 | 2014-03-26 | 北京工商大学 | Preparation method of ethanol-permselective POSS (polyhedral oligomeric silsesquioxanes)/silicone rubber composite membrane |
Non-Patent Citations (2)
| Title |
|---|
| ERIC FAVRE: "Extraction of 1-Butanol from Aqueous Solutions by Pervaporation", 《J . CHEM. TECH. BIOTECHNOL.》 * |
| 杨树人: "PDMS/PVDF中空纤维复合膜渗透蒸发回收处理煤化工废水中酚", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106139925A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of composite nanometer filtering film and preparation method thereof and the application in water treatment field |
| CN106139924A (en) * | 2015-04-23 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of composite nanometer filtering film and preparation method thereof and the application in water treatment field |
| CN106139925B (en) * | 2015-04-23 | 2018-08-17 | 中国石油化工股份有限公司 | A kind of composite nanometer filtering film and preparation method thereof and the application in water treatment field |
| CN106139924B (en) * | 2015-04-23 | 2018-08-17 | 中国石油化工股份有限公司 | A kind of composite nanometer filtering film and preparation method thereof and the application in water treatment field |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104258746B (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106582317B (en) | A kind of preparation method of the metal organic framework modification graphene oxide layer structure composite film for organic solvent nanofiltration | |
| CN102000516B (en) | Method for preparing polydimethylsiloxane (PDMS)/polyvinylidene fluoride (PVDF) composite hollow fiber film | |
| CN105413412A (en) | Cross-linkable intrinsically-porous polymer gas separation membrane and preparation method thereof | |
| CN102050954A (en) | Preparation method of environment-friendly silicone rubber composite membrane | |
| CN104084059B (en) | A kind of preparation method of hydrophobically modified nanon calcium carbonatefilled composite silicone rubber membrane | |
| CN110559884B (en) | MIL-101@ PIM-1 composite pervaporation membrane and preparation method and application thereof | |
| CN102698621B (en) | High-flux hyperbranched polysiloxane pervaporation membrane and preparation method thereof | |
| CN104138717B (en) | A kind of preparation method of PDMS/PAN infiltration evaporation hollow-fibre membrane | |
| CN103521100B (en) | High-molecular-functional mesoporous silica hybrid membrane, preparation method and applications | |
| CN102743981A (en) | Preparation and application of sodium alginate pervaporation hybrid membrane | |
| CN103331108A (en) | Polymer pervaporation membrane prepared by dialysis method after membrane formation and preparation method of polymer pervaporation membrane | |
| CN102743982B (en) | Preparation method of modified polyurethane pervaporation phenol/water separation membrane | |
| Li et al. | Roll-coating of defect-free membranes with thin selective layer for alcohol permselective pervaporation: From laboratory scale to pilot scale | |
| CN104258746B (en) | A kind of preparation method of modified organic silicon dephenolize film | |
| CN102489178B (en) | Method for preparing molybdenum disulfide pervaporation membrane for separating alcohol-containing wastewater | |
| CN103691325B (en) | A kind of preparation method of preferential alcohol inorganic particulate/PVDF composite membrane thoroughly | |
| CN101077799A (en) | Infiltration vaporization blending composite film for removing phenols from waste water | |
| CN108201792B (en) | Preparation method of fluorine-containing silicone rubber composite separation membrane | |
| CN111036089A (en) | Preparation method of modified PDMS/ZIF pervaporation hybrid membrane | |
| CN101545213A (en) | Method for preparing PDMS/PVDF composite membrane | |
| CN109012232B (en) | Preparation method of anti-shrinkage polytetrafluoroethylene composite nanofiltration membrane | |
| CN101099924A (en) | Method for preparing chitosan/ZSM-5 molecular compound film | |
| Liu et al. | Performance of a pervaporation system for the separation of an ethanol-water mixture using fractional condensation | |
| CN102806023A (en) | Gas separation membrane and preparation method | |
| CN104147947B (en) | A kind of preparation method of PDMS/PAN composite hollow fiber membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Ye Hong Inventor after: Song Boyu Inventor after: Zhang Zhongguo Inventor after: Liao Yiping Inventor after: Zhang Xiang Inventor after: Zuo Siyuan Inventor after: Wang Yu Inventor before: Ye Hong Inventor before: Liao Yiping Inventor before: Wang Yu |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160120 Termination date: 20180903 |