CN113289497A - Hydrophilic modification method of ceramic membrane - Google Patents
Hydrophilic modification method of ceramic membrane Download PDFInfo
- Publication number
- CN113289497A CN113289497A CN202110611479.2A CN202110611479A CN113289497A CN 113289497 A CN113289497 A CN 113289497A CN 202110611479 A CN202110611479 A CN 202110611479A CN 113289497 A CN113289497 A CN 113289497A
- Authority
- CN
- China
- Prior art keywords
- ceramic membrane
- ammonium chloride
- hydrophilic
- hydrophilic modification
- chloro
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a hydrophilic modification method of a ceramic membrane, which is characterized in that the ceramic membrane is used as a raw material, surface activation treatment is carried out through an alkaline treating agent, and then the ceramic membrane is immersed into a cationic etherifying agent for surface hydrophilic modification, so that the pollution-resistant ceramic membrane with super-hydrophilic performance is obtained. The invention is helpful to greatly simplify the hydrophilic modification treatment process of the ceramic membrane, the cationic etherifying agent and the ceramic membrane material belong to chemical bonding action, and the chemical stability and the long-term use performance of the hydrophilic material are effectively enhanced; in addition, the cationic etherifying agent belongs to a small molecular compound, and mass transfer resistance is not increased after hydrophilic modification. Therefore, the obtained ceramic membrane has good hydrophilicity, does not increase the mass transfer resistance and effectively improves the flux by modifying the ceramic membrane by the cationic etherifying agent.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a ceramic membrane hydrophilic modification method suitable for treating organic pollutants and municipal wastewater.
Background
The ceramic membrane is a separation membrane prepared from an inorganic ceramic material, and is commonly a tubular ceramic membrane and a flat ceramic membrane. Compared with a polymer membrane, the ceramic membrane has better chemical stability, acid resistance, high temperature resistance and solvent resistance, and is widely applied to some complex wastewater treatment. Has been successfully applied to a plurality of fields such as food, beverage, plant (medicine) deep processing, biological medicine, fermentation, fine chemical engineering and the like, and can be used for separation, clarification, purification, concentration, sterilization, desalination and the like in the technical process. However, the flux of the ceramic membrane is attenuated quickly due to surface pollution and the like in the use process, and the separation efficiency is reduced. The hydrophilic modification is carried out on the surface of the ceramic membrane by a learner, and the pollution resistance of the membrane is improved by introducing the hydrophilic ultrathin skin layer, but the process of the membrane modification process is complex, and uniform control is difficult to realize or the permeation flux of the membrane is obviously reduced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a ceramic separation membrane with super-hydrophilic performance. The method comprises the steps of taking a ceramic membrane as a raw material, carrying out surface activation treatment through an alkaline treatment agent, and then immersing the ceramic membrane into a cationic etherifying agent for carrying out surface hydrophilic modification to obtain the pollution-resistant ceramic membrane with super-hydrophilic performance. The invention is helpful to greatly simplify the hydrophilic modification treatment process of the ceramic membrane, the hydrophilic reagent and the ceramic membrane material belong to chemical bonding action, the chemical stability and the long-term service performance of the hydrophilic material are effectively enhanced, and in addition, the flux of the ceramic membrane is improved.
The technical scheme of the invention is as follows:
a hydrophilic modification method of a ceramic membrane comprises the steps of firstly immersing the ceramic membrane into an alkaline treatment agent for surface activation treatment, and then immersing the ceramic membrane subjected to the surface activation treatment into a cationic etherifying agent for surface hydrophilic modification to obtain a hydrophilic ceramic membrane (an anti-pollution ceramic membrane with super-hydrophilic performance).
The surface activation treatment specifically comprises the following steps: immersing the ceramic membrane into an alkaline treating agent aqueous solution, taking out after 1-5 hours, and drying to obtain a ceramic membrane subjected to surface activation treatment; wherein the mass percentage concentration of the aqueous solution of the alkali treatment agent is 2-10 wt%.
The surface hydrophilic modification specifically comprises the following steps: immersing the ceramic membrane subjected to activation treatment into 0.5-5% cationic etherifying agent water solution for 2-10 minutes, taking out, and then placing in drying equipment or microwave heating equipment for treatment for 10-30 minutes to obtain the hydrophilic ceramic membrane.
The cation etherifying agent is one or more of 3-chloro-2 hydroxypropyl trimethyl ammonium chloride, 3-chloro-2 hydroxypropyl triethyl ammonium chloride, 3-chloro-2 hydroxypropyl dimethyl butyl ammonium chloride, 3-chloro-2 hydroxypropyl dimethyl benzyl ammonium chloride, 3-chloro-2 hydroxypropyl dimethyl dodecyl ammonium chloride, epoxypropyl trimethyl ammonium chloride, epoxypropyl triethyl ammonium chloride, epoxypropyl dimethyl butyl ammonium chloride, epoxypropyl dimethyl benzyl ammonium chloride and epoxypropyl dimethyl dodecyl ammonium chloride.
The ceramic membrane is a tubular membrane or a flat membrane and comprises a supporting layer and a separating layer. The support layer is located below the separation function layer.
The ceramic membrane material is silicon oxide, aluminum oxide, silicon carbide or zirconium oxide.
The alkaline treating agent is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and barium hydroxide.
The invention has the beneficial effects that: the invention provides a hydrophilic modification method for a commercial ceramic membrane with high stability. The ceramic membrane may be of a tubular structure or a flat plate structure. The functional layer (separation layer) is modified by the cationic etherifying agent containing quaternary amino, so that the hydrophilicity of the ceramic membrane is greatly improved, the cationic etherifying agent and the surface hydroxyl of the ceramic membrane belong to a chemical bonding effect, uniform control can be realized, small molecules are not easy to fall off, the obtained hydrophilic ceramic membrane has good stability and strong antibacterial property, the preparation process is simple, the pollution resistance of the ceramic membrane can be obviously improved, the use range of the ceramic membrane is widened, and the cleaning cost is reduced. In addition, the cation etherifying agent belongs to a small molecular compound, and mass transfer resistance is not increased after hydrophilic modification, so that the flux is obviously increased compared with an unmodified ceramic membrane; when the hydrophilicity of the ceramic membrane is improved by introducing the hydrophilic ultrathin skin layer, the mass transfer resistance is obviously improved, and the flux is reduced. Therefore, the obtained ceramic membrane has good hydrophilicity, does not increase the mass transfer resistance and effectively improves the flux by modifying the ceramic membrane by the cationic etherifying agent.
Detailed Description
The following further describes the specific embodiments of the present invention in combination with the technical solutions.
The first embodiment is as follows:
(1) ceramic membrane surface activation treatment
Immersing a commercial alumina ceramic membrane into a sodium hydroxide aqueous solution, taking out and drying after 1 hour to obtain an alumina ceramic membrane with activated surface; wherein the mass percent concentration of the sodium hydroxide aqueous solution is 10 wt%;
(2) preparation of hydrophilic ceramic membranes
And (3) immersing the ceramic membrane subjected to surface activation treatment into a 1% cationic etherifying agent epoxypropyl trimethyl ammonium chloride aqueous solution for 10 minutes, taking out the ceramic membrane, and then placing the ceramic membrane into microwave heating equipment for treatment for 10 minutes to obtain the hydrophilic ceramic membrane. Before membrane modification, the retention rate of bovine serum albumin at room temperature and 0.1MPa is 90%, and the stable flux is 290L/m2h. After hydrophilic modification, the retention rate is unchanged, and the stable flux reaches 350L/m2h。
Example two:
(1) ceramic membrane surface activation treatment
Immersing a commercial alumina ceramic membrane into a sodium hydroxide aqueous solution, taking out and drying after 1 hour to obtain an alumina ceramic membrane with activated surface; wherein the mass percent concentration of the sodium hydroxide aqueous solution is 10 wt%;
(2) preparation of hydrophilic ceramic membranes
And (3) immersing the ceramic membrane subjected to the activation treatment into a 5% cationic etherifying agent 3-chloro-2 hydroxypropyl trimethyl ammonium chloride aqueous solution for 10 minutes, taking out the ceramic membrane, and then placing the ceramic membrane into microwave heating equipment for treatment for 10 minutes to obtain the hydrophilic ceramic membrane. Before membrane modification, the retention rate of bovine serum albumin at room temperature and 0.1MPa is 90%, and the stable flux is 290L/m2h. After hydrophilic modification, the retention rate is 94 percent, and the stable flux reaches 360L/m2h。
Example three:
(1) ceramic membrane surface activation treatment
Soaking a commercial alumina ceramic membrane into a lithium hydroxide aqueous solution, taking out and drying the alumina ceramic membrane after 2 hours to obtain an alumina ceramic membrane with activated surface; wherein the mass percent concentration of the lithium hydroxide aqueous solution is 3 wt%;
(2) preparation of hydrophilic ceramic membranes
Immersing the ceramic membrane after activation treatment into 2% cationic etherifying agent 3-chloro-2 hydroxypropyl triethyl ammonium chloride water solution for 10 minutes, taking outAnd (5) treating the mixture in an oven device for 10 minutes to obtain the hydrophilic ceramic membrane. Before membrane modification, the retention rate of bovine serum albumin at room temperature and 0.1MPa is 90%, and the stable flux is 290L/m2h. After hydrophilic modification, the retention rate is 92 percent, and the stable flux reaches 320L/m2h。
Claims (5)
1. A hydrophilic modification method of a ceramic membrane is characterized by comprising the following steps: the method comprises the following steps: firstly, immersing a ceramic membrane into an alkaline treating agent for surface activation treatment, and then immersing the ceramic membrane subjected to the surface activation treatment into a cationic etherifying agent for surface hydrophilic modification to obtain the hydrophilic ceramic membrane.
2. A method of hydrophilically modifying a ceramic membrane according to claim 1, wherein: the surface activation treatment specifically comprises the following steps: immersing the ceramic membrane into an alkaline treating agent aqueous solution, taking out after 1-5 hours, and drying to obtain a ceramic membrane subjected to surface activation treatment; wherein the mass percentage concentration of the aqueous solution of the alkali treatment agent is 2-10 wt%.
3. A method of hydrophilically modifying a ceramic membrane according to claim 1, wherein: the surface hydrophilic modification specifically comprises the following steps: immersing the ceramic membrane subjected to surface activation treatment into 0.5-5% cationic etherifying agent aqueous solution for 2-10 minutes, taking out, and then placing in drying equipment or microwave heating equipment for treatment for 10-30 minutes.
4. A method of hydrophilically modifying a ceramic membrane according to claim 1, wherein: the cation etherifying agent is one or more of 3-chloro-2 hydroxypropyl trimethyl ammonium chloride, 3-chloro-2 hydroxypropyl triethyl ammonium chloride, 3-chloro-2 hydroxypropyl dimethyl butyl ammonium chloride, 3-chloro-2 hydroxypropyl dimethyl benzyl ammonium chloride, 3-chloro-2 hydroxypropyl dimethyl dodecyl ammonium chloride, epoxypropyl trimethyl ammonium chloride, epoxypropyl triethyl ammonium chloride, epoxypropyl dimethyl butyl ammonium chloride, epoxypropyl dimethyl benzyl ammonium chloride and epoxypropyl dimethyl dodecyl ammonium chloride.
5. A method of hydrophilically modifying a ceramic membrane according to claim 1, wherein: the alkaline treating agent is one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide and barium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110611479.2A CN113289497A (en) | 2021-06-02 | 2021-06-02 | Hydrophilic modification method of ceramic membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110611479.2A CN113289497A (en) | 2021-06-02 | 2021-06-02 | Hydrophilic modification method of ceramic membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113289497A true CN113289497A (en) | 2021-08-24 |
Family
ID=77326749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110611479.2A Pending CN113289497A (en) | 2021-06-02 | 2021-06-02 | Hydrophilic modification method of ceramic membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113289497A (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5645891A (en) * | 1994-11-23 | 1997-07-08 | Battelle Memorial Institute | Ceramic porous material and method of making same |
| CN1270079A (en) * | 2000-06-09 | 2000-10-18 | 清华大学 | Polyelectrolyte membrane for osmotic vaporization and process for preparing compound polyelectrolyte membrane |
| CN102355936A (en) * | 2009-03-20 | 2012-02-15 | 威拓股份有限公司 | Surface-modified inorganic matrix and method for preparation thereof |
| CN102423641A (en) * | 2011-11-23 | 2012-04-25 | 华东理工大学 | Method for modifying hydrophobicity of ceramic membrane, its application and its apparatus |
| US20130048563A1 (en) * | 2011-08-30 | 2013-02-28 | General Electric Company | Tannin polymers as aids for reducing fouling of ceramic membranes |
| CN103846019A (en) * | 2014-03-02 | 2014-06-11 | 惠州市银嘉环保科技有限公司 | Bacteriostatic composite kieselguhr ceramic membrane and preparation method thereof |
| CN104759214A (en) * | 2015-03-27 | 2015-07-08 | 北京工业大学 | Preparation method of superhydrophilic/superhydrophobic composite nanofiltration membrane |
| CN104785124A (en) * | 2015-03-30 | 2015-07-22 | 北京工业大学 | Charged TiO2/polyelectrolyte composite nanofiltration membrane as well as preparation method and application thereof |
| CN107138050A (en) * | 2017-05-27 | 2017-09-08 | 天津工业大学 | The preparation method of quaternary ammonium salt graft modification cellulose acetate reverse osmosis film |
| CN108774316A (en) * | 2018-05-08 | 2018-11-09 | 四川大学 | Cationic polyarylether resin, seperation film and preparation method thereof |
| CN110124526A (en) * | 2019-04-30 | 2019-08-16 | 湖北工业大学 | A kind of production method of silicon carbide inorganic ceramic membrane |
| CN110585930A (en) * | 2019-10-05 | 2019-12-20 | 武建云 | Preparation method of ceramic membrane for oil-water separation |
| WO2020200289A1 (en) * | 2019-04-04 | 2020-10-08 | 三达膜科技（厦门）有限公司 | Preparation method for organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane |
-
2021
- 2021-06-02 CN CN202110611479.2A patent/CN113289497A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5645891A (en) * | 1994-11-23 | 1997-07-08 | Battelle Memorial Institute | Ceramic porous material and method of making same |
| CN1270079A (en) * | 2000-06-09 | 2000-10-18 | 清华大学 | Polyelectrolyte membrane for osmotic vaporization and process for preparing compound polyelectrolyte membrane |
| CN102355936A (en) * | 2009-03-20 | 2012-02-15 | 威拓股份有限公司 | Surface-modified inorganic matrix and method for preparation thereof |
| US20130048563A1 (en) * | 2011-08-30 | 2013-02-28 | General Electric Company | Tannin polymers as aids for reducing fouling of ceramic membranes |
| CN102423641A (en) * | 2011-11-23 | 2012-04-25 | 华东理工大学 | Method for modifying hydrophobicity of ceramic membrane, its application and its apparatus |
| CN103846019A (en) * | 2014-03-02 | 2014-06-11 | 惠州市银嘉环保科技有限公司 | Bacteriostatic composite kieselguhr ceramic membrane and preparation method thereof |
| CN104759214A (en) * | 2015-03-27 | 2015-07-08 | 北京工业大学 | Preparation method of superhydrophilic/superhydrophobic composite nanofiltration membrane |
| CN104785124A (en) * | 2015-03-30 | 2015-07-22 | 北京工业大学 | Charged TiO2/polyelectrolyte composite nanofiltration membrane as well as preparation method and application thereof |
| CN107138050A (en) * | 2017-05-27 | 2017-09-08 | 天津工业大学 | The preparation method of quaternary ammonium salt graft modification cellulose acetate reverse osmosis film |
| CN108774316A (en) * | 2018-05-08 | 2018-11-09 | 四川大学 | Cationic polyarylether resin, seperation film and preparation method thereof |
| WO2020200289A1 (en) * | 2019-04-04 | 2020-10-08 | 三达膜科技（厦门）有限公司 | Preparation method for organic-inorganic piperazine polyamide composite ceramic nanofiltration membrane |
| CN110124526A (en) * | 2019-04-30 | 2019-08-16 | 湖北工业大学 | A kind of production method of silicon carbide inorganic ceramic membrane |
| CN110585930A (en) * | 2019-10-05 | 2019-12-20 | 武建云 | Preparation method of ceramic membrane for oil-water separation |
Non-Patent Citations (5)
| Title |
|---|
| PENGFEI FEI: "Non-leaching antibacterial cellulose triacetate reverse osmosis membrane via covalent immobilization of quaternary ammonium cations", 《CARBOHYDRATE POLYMERS》 * |
| ZHAO, YANG-YING: "Effects of organic fouling and cleaning on the retention of pharmaceutically active compounds by ceramic nanofiltration membranes", 《JOURNAL OF MEMBRANE SCIENCE》 * |
| 曲远方: "《现代陶瓷材料及技术》", 1 May 2008 * |
| 章婧: "油水乳液污染纳米TiO2改性AL2O3陶瓷膜的化学清洗", 《膜科学与技术》 * |
| 郭子涵等: "热处理温度对氧化石墨烯改性陶瓷膜油水分离性能的影响", 《陶瓷学报》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102921315B (en) | Anti-pollution reverse osmosis membrane and preparation method thereof | |
| CN1817427A (en) | Polymer microporous modification by corona induced grafting technology | |
| CN107744727B (en) | Surface hydrophilic modification method of chloromethylated polyether sulfone ultrafiltration membrane | |
| CN105148750A (en) | Method for modifying surface of polyamide composite film | |
| CN109499391B (en) | Preparation method and application of cross-linked modified regenerated cellulose nanofiltration membrane | |
| CN114917764B (en) | Method for preparing high-selectivity high-flux PES (polyether sulfone) ultrafiltration membrane by using monomer self-crosslinking | |
| CN110813103A (en) | Preparation method of antibacterial and anti-pollution hollow fiber membrane | |
| CN102512997B (en) | Hydrophilic polyethersulfone with cardo alloy ultrafiltration membrane and preparation method thereof | |
| CN109081430A (en) | It can accelerate the preparation method of the reproducibility graphene oxide Modified Membrane of water treatment procedure | |
| CN113289497A (en) | Hydrophilic modification method of ceramic membrane | |
| CN114797473A (en) | Preparation method of hydrophilic multifunctional organic ultrafiltration membrane | |
| CN111408277B (en) | Rapid crosslinking preparation method of super-hydrophilic polyvinylidene fluoride microporous membrane | |
| CN115569539B (en) | Ultrafiltration membrane for acrylic resin wastewater treatment | |
| CN112569811A (en) | Poly (m-phenylene isophthalamide) mixed matrix membrane with white spirit catalytic filtration performance and preparation and application thereof | |
| CN112569808A (en) | Polyvinylidene fluoride mixed matrix membrane with white spirit catalytic filtration performance and preparation and application thereof | |
| CN101850217A (en) | Method for preparing skin-free homogeneous structural polyvinylidene fluoride transfer film | |
| CN114471197B (en) | Mixed charged nanofiltration membrane and preparation method and application thereof | |
| CN113274890B (en) | Porous high-permeability polyethylene sewage treatment membrane and preparation method thereof | |
| CN113797774B (en) | Antibacterial reverse osmosis composite membrane and preparation method thereof | |
| CN113908705B (en) | High-flux inorganic-scaling-resistant medium-desalination nanofiltration membrane and preparation method thereof | |
| CN110975637B (en) | Preparation method of gallic acid-chitosan/polysulfone composite nanofiltration membrane | |
| CN110624276A (en) | Preparation method of flat composite ceramic membrane for treating oily wastewater | |
| CN112604508A (en) | Method for preparing high-flux polyimide solvent-resistant nanofiltration membrane | |
| CN112044288A (en) | Based on F-TiO2/Fe-g-C3N4Self-cleaning PVDF hollow fiber ultrafiltration membrane and preparation method thereof | |
| CN112058096A (en) | Nanofiltration membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210824 |
|
| RJ01 | Rejection of invention patent application after publication |