CN110559873B - Preparation method of graphene oxide separation membrane with adsorption function and product prepared by preparation method - Google Patents
Preparation method of graphene oxide separation membrane with adsorption function and product prepared by preparation method Download PDFInfo
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- CN110559873B CN110559873B CN201910896429.6A CN201910896429A CN110559873B CN 110559873 B CN110559873 B CN 110559873B CN 201910896429 A CN201910896429 A CN 201910896429A CN 110559873 B CN110559873 B CN 110559873B
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- 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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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
The invention discloses a preparation method of a graphene oxide separation membrane with an adsorption function and a product prepared by the graphene oxide separation membrane, wherein the method comprises the steps of taking reaction generation liquid for preparing graphene oxide by a Hummers method as a synthesis precursor, carrying out centrifugal treatment on the reaction generation liquid, adjusting the pH value of the solution to obtain a precipitate, and then carrying out filtration separation, cleaning and drying processes to obtain a mixed precipitate of nano manganese oxide hydrate and graphene oxide; and then the mixture is precipitated in water for ultrasonic dispersion, and the membrane preparation slurry can be obtained. By adopting the slurry and combining a certain membrane preparation method, a graphene oxide separation membrane product with an adsorption function can be prepared on a porous inorganic or organic carrier. The invention has the advantages of environmental protection, low cost, simple and convenient process, excellent product performance and the like, and has wide market prospect.
Description
Technical Field
The invention belongs to the technical field of separation membrane material preparation, and particularly relates to a preparation method of a graphene oxide separation membrane with an adsorption function and a product prepared by the graphene oxide separation membrane.
Background
At present, the membrane method water treatment technology has the advantages of simple device, easy operation and control, high separation efficiency, no secondary pollution and the like, and is widely popularized and applied in the separation and purification field, in particular to the fields of recovery treatment of various polluted wastewater and the like. At the present stage, with the increasing importance of the country on water environment protection, the requirements of various industries on wastewater treatment precision are higher and higher, and the efficient removal of pollutants such as various ions or small molecular organic matters in water becomes an increasingly urgent technical task. At present, as for the removal of various pollutants, as for a membrane water treatment technology, nanofiltration, reverse osmosis, electrodialysis and the like are mainly used, and although the technologies have certain technical advantages in the treatment of various ions or small-molecule organic pollutants, the technologies still have the defects of low treatment precision, high treatment cost, high energy consumption, high technical requirements and the like. Meanwhile, the adsorption method is a separation technology with low energy consumption, simple process and high selectivity, and is widely applied to removing various pollutants in water. However, in the present stage, the commonly used adsorbent generally has various defects of difficult recovery, easy secondary pollution, unstable adsorption performance and the like due to the fact that the commonly used adsorbent is generally in a powder dispersion state.
Therefore, in order to solve the key technical problems that the separation membrane does not have adsorbability and the adsorbent does not have membrane separation performance, the separation membrane is mixed with the efficient adsorbent, and on the basis of fully utilizing the technical advantages of the two materials, the technical defects of the two materials are properly avoided, so that the aim of synchronously realizing the separation and adsorption functions can be fulfilled, and the high-precision purification of the water body is realized. On the basis, a novel separation membrane material preparation technology with the adsorption function and the related products, which are green and environment-friendly, low in cost, simple and convenient in process and excellent in performance, are developed in time, and have important values and meanings for protecting water environment and promoting the development of the membrane industry.
Disclosure of Invention
The invention aims to provide a preparation method of a graphene oxide separation membrane with an adsorption function, which is green and environment-friendly, low in cost, simple and convenient in process and excellent in performance, and a product prepared by the preparation method.
In order to solve the key technical problems that the separation membrane usually does not have adsorptivity and the adsorbent does not have membrane separation performance, the technical scheme of the invention is as follows: a preparation method of a graphene oxide separation membrane with an adsorption function is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: preparing graphene oxide by using a Hummers method, and centrifuging a reaction product liquid;
step two: adjusting the pH value of the reaction product liquid after centrifugation in the step one to promote the formation of a precipitate;
step three: filtering and separating the precipitate obtained in the step two, and then cleaning and drying to obtain a mixed precipitate of nano manganese oxide hydrate and graphene oxide;
step four: ultrasonically dispersing the mixture precipitate obtained in the step three into water to obtain membrane preparation slurry;
step five: and D, preparing the membrane preparation slurry obtained in the step four into the graphene oxide separation membrane with the adsorption function on the porous carrier by adopting a proper membrane preparation method and a proper heat treatment process.
The centrifugal treatment process in the first step comprises the following steps of; the centrifugal speed is 5000-8000 rpm, and the centrifugal time is 10-20 minutes.
The pH value regulator of the reaction product liquid in the second step is ammonia water solution; when the precipitate is formed, the pH value of the mixed solution is 6-8.
In the fourth step, the solid content of the film preparation slurry is 2-5 wt%.
And the film preparation method in the fifth step is a spin coating method, a dipping method or a suction filtration method.
The heat treatment process in the fifth step comprises the following steps: the heat treatment temperature is 100-150 ℃, and the heat treatment time is 1-2 hours.
In the fifth step, the matrix comprises an organic or inorganic porous carrier, and the average pore diameter of the carrier is 100-200 nanometers.
The product prepared by the method is characterized in that: and fifthly, the thickness of the graphene oxide separation membrane in the step five is 200-500 micrometers.
The graphene oxide separation membrane has high separation performance and high adsorption performance.
Aiming at the key technical problems that a separation membrane does not usually have adsorbability and an adsorbent does not have membrane separation performance, the reaction product liquid of graphene oxide prepared by a Hummers method is taken as a synthesis precursor, after the reaction product liquid is subjected to centrifugal treatment, the pH value of the solution is adjusted to obtain a precipitate, and then the mixed precipitate of nano manganese oxide hydrate and graphene oxide is obtained by adopting the processes of filtering separation, cleaning and drying; the graphene oxide separation membrane product with the adsorption function can be prepared on a porous inorganic or organic carrier by adopting the mixture precipitation and combining a certain membrane preparation method. The invention has the advantages of environmental protection, low cost, simple and convenient process, excellent product performance and the like, and has wide market prospect.
Drawings
FIG. 1 is a flow chart of the manufacturing process of the present invention;
FIG. 2 is a phase analysis diagram of hydrated manganese oxide;
fig. 3 is a phase analysis diagram of the graphene oxide separation membrane.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Example 1
Graphene oxide was prepared by the Hummers method, the reaction product was centrifuged at 5000 rpm for 20 minutes, 200 ml of the reaction product was measured, and an aqueous ammonia solution was added dropwise until a precipitate was formed, at which time the pH of the mixture was 8. Filtering, separating, cleaning and drying the precipitate to obtain a mixed precipitate of nano manganese oxide hydrate and graphene oxide; weighing a proper amount of the mixture, precipitating and ultrasonically dispersing the mixture into water to obtain membrane preparation slurry with the solid content of 5 wt%; preparing a graphene oxide separation membrane containing nano hydrated manganese oxide on an alumina porous ceramic support body with the average pore diameter of 150 nm by adopting the membrane preparation slurry and combining a spin coating method; the film was treated at 100 ℃ for 2 hours to produce a corresponding film product having a thickness of 500 microns.
The adsorption separation experiment is carried out on the graphene oxide separation membrane containing the nano manganese oxide hydrate, the water solution containing zinc ions is taken as a treatment object, the adsorption capacity of the membrane to the zinc ions reaches 120 mg/g under normal temperature and neutral conditions, and the membrane permeation flux is 115 L.m-2·h-1·bar-1。
Example 2
Preparing graphene oxide by adopting a Hummers method, centrifuging the reaction product liquid at a centrifugation speed of 8000 rpm for 10 minutes, measuring 200 ml of the reaction product liquid, and dropwise adding an ammonia water solution into the reaction product liquid until a precipitate is formed, wherein the pH value of the mixed liquid is 7; filtering, separating, cleaning and drying the precipitate to obtain a mixed precipitate of nano manganese oxide hydrate and graphene oxide; weighing a proper amount of the mixture, precipitating and ultrasonically dispersing the mixture into water to obtain membrane preparation slurry with the solid content of 2 wt%; preparing a graphene oxide separation membrane containing nano hydrated manganese oxide on a zirconia porous ceramic support body with the average pore diameter of 100 nm by adopting the membrane preparation slurry and combining a spin coating method; the film was treated at 150 ℃ for 1 hour to produce a corresponding film product having a thickness of 200 microns.
The adsorption separation experiment is carried out on the graphene oxide separation membrane containing the nano manganese oxide hydrate, the phenol-containing aqueous solution is taken as a treatment object, the adsorption capacity of the membrane on phenol reaches 260 mg/g under normal temperature and neutral conditions, and the membrane permeation flux is 253 L.m-2·h-1·bar-1。
Example 3:
graphene oxide is prepared by a Hummers method, the reaction product liquid is centrifuged at a centrifugation speed of 6000 rpm for 15 minutes, 200 ml of the reaction product liquid is measured, an ammonia solution is added dropwise until a precipitate is formed, and the pH value of the mixed solution is 6. Filtering, separating, cleaning and drying the precipitate to obtain a mixed precipitate of nano manganese oxide hydrate and graphene oxide; weighing a proper amount of the mixture, precipitating and ultrasonically dispersing the mixture into water to obtain membrane preparation slurry with the solid content of 3 wt%; preparing a graphene oxide separation membrane containing nano hydrated manganese oxide on a polytetrafluoroethylene filter membrane support body with the average pore diameter of 200 nm by adopting the membrane preparation slurry and combining a spin coating method; the film is processed for 2 hours at 100 ℃ to obtain a corresponding film product with the thickness of 300 microns.
The adsorption separation experiment is carried out on the graphene oxide separation membrane containing the nano manganese oxide hydrate, the zirconium ion adsorption amount of the membrane reaches 290 mg/g under normal temperature and neutral conditions by taking the aqueous solution containing zirconium ions as a treatment object, and the membrane permeation flux is 186 L.m-2·h-1·bar-1。
The process parameters of the present invention are not limited to the examples listed above.
Claims (4)
1. A preparation method of a graphene oxide separation membrane with an adsorption function is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: preparing graphene oxide by using a Hummers method, and centrifuging a reaction product liquid;
step two: adjusting the pH value of the reaction product liquid after centrifugation in the step one to promote the formation of a precipitate;
step three: filtering and separating the precipitate obtained in the step two, and then cleaning and drying to obtain a mixed precipitate of nano manganese oxide hydrate and graphene oxide;
step four: ultrasonically dispersing the mixture precipitate obtained in the step three into water to obtain membrane preparation slurry;
step five: preparing the membrane preparation slurry obtained in the step four into a graphene oxide separation membrane with an adsorption function on a porous carrier by adopting a proper membrane preparation method and a proper heat treatment process;
the film preparation method in the fifth step is a spin coating method, a dipping method or a suction filtration method;
the heat treatment process in the fifth step comprises the following steps: the heat treatment temperature is 100-150 ℃, and the heat treatment time is 1-2 hours;
the carrier in the fifth step comprises an organic or inorganic porous carrier, and the average pore diameter of the carrier is 100-200 nanometers;
and fifthly, the thickness of the graphene oxide separation membrane in the step five is 200-500 micrometers.
2. The method of claim 1, wherein: the centrifugal treatment process in the first step comprises the following steps of; the centrifugal speed is 5000-8000 rpm, and the centrifugal time is 10-20 minutes.
3. The method of claim 1, wherein: the pH value regulator of the reaction product liquid in the second step is ammonia water solution; when the precipitate is formed, the pH value of the mixed solution is 6-8.
4. The method of claim 1, wherein: in the fourth step, the solid content of the film preparation slurry is 2-5 wt%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103334096A (en) * | 2013-07-02 | 2013-10-02 | 江苏大学 | Method for preparing nano-silver-graphene composite film |
| CN106006609A (en) * | 2016-05-17 | 2016-10-12 | 西南民族大学 | Method for preparing graphene with step-by-step purification method |
| CN107626218A (en) * | 2017-10-24 | 2018-01-26 | 陕西省石油化工研究设计院 | A kind of preparation method of graphene oxide/nonwoven fabrics composite film |
| CN109012598A (en) * | 2018-09-12 | 2018-12-18 | 南昌航空大学 | A kind of preparation method based on manganese dioxide/stannic oxide/graphene nano composite material Ciprofloxacin absorption purifier |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US8925736B2 (en) * | 2011-09-12 | 2015-01-06 | University Of Houston | Nanocomposite polymer-carbon based nanomaterial filters for the simultaneous removal of bacteria and heavy metals |
| KR20160123190A (en) * | 2015-04-15 | 2016-10-25 | 한국화학연구원 | Polyacrylonitrile/chitosan composite nanofiltration membrane containing graphene oxide and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103334096A (en) * | 2013-07-02 | 2013-10-02 | 江苏大学 | Method for preparing nano-silver-graphene composite film |
| CN106006609A (en) * | 2016-05-17 | 2016-10-12 | 西南民族大学 | Method for preparing graphene with step-by-step purification method |
| CN107626218A (en) * | 2017-10-24 | 2018-01-26 | 陕西省石油化工研究设计院 | A kind of preparation method of graphene oxide/nonwoven fabrics composite film |
| CN109012598A (en) * | 2018-09-12 | 2018-12-18 | 南昌航空大学 | A kind of preparation method based on manganese dioxide/stannic oxide/graphene nano composite material Ciprofloxacin absorption purifier |
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