CN105879707B - A kind of redox graphene modified ceramic membrane with ion rejection performance - Google Patents
A kind of redox graphene modified ceramic membrane with ion rejection performance Download PDFInfo
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- CN105879707B CN105879707B CN201610509329.XA CN201610509329A CN105879707B CN 105879707 B CN105879707 B CN 105879707B CN 201610509329 A CN201610509329 A CN 201610509329A CN 105879707 B CN105879707 B CN 105879707B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/35—Use of magnetic or electrical fields
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Abstract
The invention discloses a kind of, and the nanometer redox graphene coating with high-effect ionic cutoff performance modifies ceramic membrane, and this method prepares graphene oxide using improved Hummer methods using micro crystal graphite as primary raw material；Thermal reduction technique is used again, obtains redox graphene；The dispersion liquid formed after above-mentioned nanometer redox graphene is ultrasonically treated modifies raw material as coating, using negative pressure leaching coating and heat treatment process, modifies ceramic membrane, to be firmly combined with, conductive redox graphene modification ceramic membrane；Top/the bottom surface for finally modifying above-mentioned redox graphene ceramic membrane carries out, by silver net and connecting wire, membrane component being made.The film is under the booster action of external electric field, there are the good characteristics such as higher ion rejection rate and permeation flux to the ion in solution, to widen the application field of ceramic membrane, meanwhile, the present invention has many advantages, such as that simple for process, of low cost, operating condition is easily-controllable.
Description
Technical field
The invention belongs to ceramic membrane materials technical field more particularly to a kind of reduction-with high-effect ionic cutoff performance
Graphene oxide modifies ceramic membrane.
Background technology
Water is Source of life, and the production and life of the mankind all be unable to do without water, the wretched insufficiency and water pollution of freshwater resources
The aggravation seriously development of restriction human social economy, water technology has been a concern.Seawater and brackish water desalination are all
Be unable to do without effective ion isolation removal technology, compared with traditional isolation technics, membrane separation technique have process it is simple, without two
Secondary pollution, the advantages that separation is big, efficient, energy saving, it is critical process to have become in numerous commercial Applications, especially in height
Effect is great in terms of pure water preparation and sewage disposal.
Currently, the most ion isolation removal technology of commercial Application mainly has electrodialysis embrane method and reverse osmosis membrane.Electric osmose
Analysis method needs higher DC electric field（100~300 V）, salt rejection rate and the water rate of recovery are relatively low, and easily structure cleaning dismounting trouble, if
It is standby easily to damage；Reverse osmosis deaslination rate is high, but its operating pressure is high（1.5~20 MPa）, energy consumption is big, efficiency is low；Current research
Hot spot is organic charged nanofiltration membrane（Aperture is 1 ~ 2 nm）, with preferable ion rejection performance, but its required operating pressure
Also higher（1.0~10 MPa）, exist simultaneously the bottleneck problems such as energy consumption is big, efficiency is low.Therefore, Nanofiltration-membrane technique is in waste water and sea
Commercial Application in terms of water desalination processing is also restricted.Ceramic membrane of the current common aperture between 0.05 ~ 0.35 μm,
Its operating pressure is generally 0.01 ~ 0.2 MPa, and permeation flux is high, but it does not have cutoff performance to ion, can not be used directly to
Detach effects of ion.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of simple for process, of low cost, operating conditions
The easily-controllable redox graphene modified ceramic membrane with high-effect ionic cutoff performance.
In order to solve the above technical problems, the technical scheme is that：A kind of nanometer with high-effect ionic cutoff performance
Redox graphene modified ceramic membrane, it is characterised in that：Include the following steps：
Step 1：Graphene oxide is prepared using micro crystal graphite as raw material using improved Hummer methods；
Step 2：Using thermal reduction technique, reductase 12 is carried out to graphene oxide prepared by step 1 at 200~300 DEG C
~4 hours, obtain the redox graphene that conductivity is 100~150 s/m；Step 3：The reduction-that step 2 is obtained
Graphene oxide forms the dispersion liquid of about 0.1~0.5 wt% of concentration, with this after 300~600 W are ultrasonically treated 2~4 hours
Dispersion liquid is modification raw material, and coating modification is carried out to ceramic membrane hole surface using negative pressure leaching coating processes, then 200~
It dries 2~4 hours, is firmly combined with, conductive nanometer redox graphene modified ceramic membrane at 300 DEG C；
Step 4：The top of ceramic membrane after modifying step 3/bottom surface is carried out by silver net and connecting wire, and by conducting wire
Connect external power.
The grain size of the redox graphene obtained in the step 2 is 8~20 nanometers.
The material of ceramic membrane is non-conductive material in the step 3, and aperture is 50~100 nanometers.
The non-conductive material is one in aluminium oxide, cordierite, zirconium oxide, clayey, quartz, mullite, titanium oxide
Kind.
The conductivity that the step 3 obtains nanometer redox graphene modified ceramic membrane is 2.5~3.5 × 10-8
s/m。
External power is DC power supply in the step 4, and voltage is 6~10V.
The negative pressure value of negative pressure leaching coating processes is -0.8 bar in the step 3, and it is 5 minutes to filter the time.
The number that negative pressure leaching coating processes carry out ceramic membrane hole surface coating modification in the step 3 is 3 times.
A kind of nanometer redox graphene modified ceramic membrane with high-effect ionic cutoff performance of the present invention, for mesh
The problem of preceding existing ceramic membrane ion rejection poor performance, is assisted by nanometer redox graphene modified and external electric field,
Film, which can be assigned, has higher ion rejection rate and permeation flux, to widen the application field of ceramic membrane.Meanwhile the present invention
Have many advantages, such as that simple for process, of low cost, operating condition is easily-controllable, therefore has a vast market space.
Description of the drawings
Fig. 1 is nanometer redox graphene modified ceramic membrane preparation technology flow chart；
Fig. 2 is nanometer redox graphene modified ceramic membrane micro-structure figure；
Fig. 3 is nanometer redox graphene modified ceramic membrane element schematic diagram.
Specific implementation mode
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Embodiment 1
To improve the graphene oxide of Hummer methods preparation, heat treatment time is 4 hours at 200 DEG C, obtains conductivity
The redox graphene for being 15 nanometers for 100 s/m, grain size.The redox graphene is ultrasonically treated 2 in 300 W afterwards
Hour, form the dispersion liquid of a concentration of 0.1 wt%.Negative pressure leaching coating processes are used again, by about 80 nanometers of oxygen of average pore size
Change aluminium ceramic membrane upper surface and completely attach to above-mentioned redox graphene dispersing solution, lower surface is vacuum-treated 5 at -0.8 bar
After minute, make modification raw material completely into and by fenestra road, and then redox graphene is made to be adsorbed on film channel surfaces.
After take out ceramic membrane, then heat treatment time is 4 hours at 200 DEG C.Such negative pressure leaching be repeated 3 times to get to be firmly combined with,
Conductivity is 2.5 × 10-8The ceramic membrane of the nanometer redox graphene modified of s/m.
Ceramic membrane top/bottom surface of above-mentioned nanometer redox graphene modified by silver and connecting wire, constitute
Membrane component.The external voltage that the membrane component is connected to 9 V, when transmembrane pressure is 0.15 MPa, to 0.8 × 10-3Mol/l's
MgCl2、NaCl、CaCl2Solution carries out ion remaval, and film is to Mg2+、Ca2+、Na+Rejection reaches 87.7%, 58.5%, 66.8%.
Meanwhile film permeation flux reaches 1870 l/ (m2·h·bar)。
Embodiment 2
To improve the graphene oxide of Hummer methods preparation, heat treatment time is 2 hours at 300 DEG C, obtains conductivity
It is 20 nanometers of redox graphenes for 120 s/m, grain size.It is small that the redox graphene is ultrasonically treated 3 in 600 W afterwards
When, form the dispersion liquid of a concentration of 0.2 wt%.Negative pressure leaching coating processes are used again, by about 50 nanometers of oxidation of average pore size
Zircon ceramic film upper surface completely attaches to above-mentioned redox graphene dispersing solution, and lower surface is vacuum-treated 5 points at -0.8 bar
Zhong Hou makes modification raw material completely into and by fenestra road, and then redox graphene is made to be adsorbed on film channel surfaces.Afterwards
Ceramic membrane is taken out, then heat treatment time is 3 hours at 250 DEG C.Such negative pressure leaching be repeated 3 times to get to be firmly combined with, electricity
Conductance is 3.1 × 10-8The ceramic membrane of s/m nanometers of redox graphene modifieds.
Ceramic membrane top/bottom surface of above-mentioned nanometer redox graphene modified by silver and connecting wire, constitute
Membrane component.The external voltage that the membrane component is connected to 6V, when transmembrane pressure is 0.15 MPa, to 0.8 × 10-3Mol/l's
MgCl2、NaCl、CaCl2Solution carries out ion remaval, and film is to Mg2+、Ca2+、Na+Rejection reaches 89.2%, 67.5%, 73.3%.
Meanwhile film permeation flux reaches 1056 l/ (m2·h·bar)。
Embodiment 3：
To improve the graphene oxide of Hummer methods preparation, heat treatment time is 3 hours at 250 DEG C, obtains conductivity
It is 8 nanometers of redox graphenes for 150 s/m, grain size.It is small that the redox graphene is ultrasonically treated 4 in 450 W afterwards
When, form the dispersion liquid of a concentration of 0.5 wt%.Negative pressure leaching coating processes are used again, by about 100 nanometers of oxidation of average pore size
Titanium ceramic membrane upper surface completely attaches to above-mentioned redox graphene dispersing solution, and lower surface is vacuum-treated 5 points at -0.8 bar
Zhong Hou makes modification raw material completely into and by fenestra road, and then redox graphene is made to be adsorbed on film channel surfaces.Afterwards
Ceramic membrane is taken out, then heat treatment time is 4 hours at 300 DEG C.Such negative pressure leaching be repeated 3 times to get to be firmly combined with, electricity
Conductance is 3.5 × 10-8The ceramic membrane of s/m nanometers of redox graphene modifieds.
Ceramic membrane top/bottom surface of above-mentioned nanometer redox graphene modified by silver and connecting wire, constitute
Membrane component.The external voltage that the membrane component is connected to 10V, when transmembrane pressure is 0.15 MPa, to 1 × 10-3Mol/l's
MgCl2、NaCl、CaCl2Solution carries out ion remaval, and film is to Mg2+、Ca2+、Na+Rejection reaches 80.8%, 54.7%, 57.9%.
Meanwhile film permeation flux reaches 2390 l/ (m2·h·bar)。
A kind of redox graphene modified ceramic membrane with high-effect ionic cutoff performance of the present invention, technological parameter
It is not limited to the above-mentioned embodiment enumerated.
Claims (8)
1. a kind of nanometer redox graphene modified ceramic membrane with ion rejection performance, it is characterised in that：Including following
Step：
Step 1：Graphene oxide is prepared using micro crystal graphite as raw material using improved Hummer methods；
Step 2：Using thermal reduction technique, reductase 12~4 are carried out to graphene oxide prepared by step 1 at 200~300 DEG C
Hour, obtain the redox graphene that conductivity is 100~150 s/m；
Step 3：The redox graphene that step 2 is obtained is formed dense after 300~600 W are ultrasonically treated 2~4 hours
Degree is the dispersion liquid of 0.1~0.5 wt%, is modification raw material with the dispersion liquid, using negative pressure leaching coating processes to ceramic fenestra
Surface carries out coating modification, is then dried 2~4 hours at 200~300 DEG C, is firmly combined with, conductive redox
Graphene modified ceramic membrane；
Step 4：The top of ceramic membrane after modifying step 3/bottom surface is carried out by silver net and connecting wire, and conducting wire is connected
External power.
2. according to claim 1 nanometer of redox graphene modified ceramic membrane, it is characterised in that：The step 2
The grain size of the redox graphene of middle acquisition is 8~20 nanometers.
3. according to claim 1 nanometer of redox graphene modified ceramic membrane, it is characterised in that：The step 3
The material of middle ceramic membrane is non-conductive material, and aperture is 50~100 nanometers.
4. according to claim 3 nanometer of redox graphene modified ceramic membrane, it is characterised in that：It is described non-conductive
Material is one kind in aluminium oxide, cordierite, zirconium oxide, clayey, quartz, mullite, titanium oxide.
5. according to claim 1 nanometer of redox graphene modified ceramic membrane, it is characterised in that：The step 3
The conductivity for obtaining nanometer redox graphene modified ceramic membrane is 2.5~3.5 × 10-8 s/m。
6. according to claim 1 nanometer of redox graphene modified ceramic membrane, it is characterised in that：The step 4
Middle external power is DC power supply, and voltage is 6~10V.
7. according to claim 1 nanometer of redox graphene modified ceramic membrane, it is characterised in that：The step 3
The negative pressure value of middle negative pressure leaching coating processes is -0.8 bar, and it is 5 minutes to filter the time.
8. according to claim 1 nanometer of redox graphene modified ceramic membrane, it is characterised in that：The step 3
The number that middle negative pressure leaching coating processes carry out ceramic membrane hole surface coating modification is 3 times.
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| CN106861453A (en) * | 2017-03-31 | 2017-06-20 | 华南理工大学 | Composite membrane prepared by the controllable modification in microporous ceramic substrates surface and preparation method thereof and the application in pulping wastewater treatment |
| CN107537322B (en) * | 2017-08-17 | 2021-05-25 | 中国科学院生态环境研究中心 | rGO/CNT three-dimensional composite conductive film for salt interception, and preparation method and use method thereof |
| CN112158923B (en) * | 2020-09-16 | 2022-10-25 | 景德镇陶瓷大学 | Preparation method of graphene-alumina porous composite material capable of being used as capacitive deionization electrode |
| JP2024500108A (en) * | 2020-12-16 | 2024-01-04 | ナショナル ユニバーシティ オブ シンガポール | Separation equipment and composite membranes |
| CN112808029A (en) * | 2020-12-23 | 2021-05-18 | 华南理工大学 | Method for rapidly growing ZIF-8 film on ceramic substrate |
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| CN102908908B (en) * | 2012-11-12 | 2014-10-22 | 景德镇陶瓷学院 | Method for modifying modified ceramic microfiltration membrane by adopting graphite oxide |
| CN103346024B (en) * | 2013-06-18 | 2016-10-19 | 常州大学 | The preparation method of high-conductivity flexible graphene membrane electrode |
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