CN112973466A - Preparation of hydrophilic oleophobic graphene oxide membrane - Google Patents
Preparation of hydrophilic oleophobic graphene oxide membrane Download PDFInfo
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- CN112973466A CN112973466A CN201911210357.1A CN201911210357A CN112973466A CN 112973466 A CN112973466 A CN 112973466A CN 201911210357 A CN201911210357 A CN 201911210357A CN 112973466 A CN112973466 A CN 112973466A
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- membrane
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- water separation
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- 239000012528 membrane Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002070 nanowire Substances 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 238000000967 suction filtration Methods 0.000 claims abstract description 7
- 239000002033 PVDF binder Substances 0.000 claims abstract description 5
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 5
- 238000001471 micro-filtration Methods 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims 1
- 239000002135 nanosheet Substances 0.000 abstract description 5
- 230000035699 permeability Effects 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 238000003828 vacuum filtration Methods 0.000 description 8
- 230000004907 flux Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005374 membrane filtration Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000002569 water oil cream Substances 0.000 description 1
Classifications
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- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/08—Thickening liquid suspensions by filtration
- B01D17/085—Thickening liquid suspensions by filtration with membranes
-
- 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
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
-
- 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
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0076—Pretreatment of inorganic membrane material prior to membrane formation, e.g. coating of metal powder
-
- 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
- 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
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
Abstract
The invention discloses a preparation method of an oil-water separation hydrophobic membrane. Inserting ZnO nanowires between graphene oxide GO nanosheets, taking PVDF microfiltration membranes as a basal layer, and performing suction filtration on a GO/ZnO nanowire mixed solution on the membrane surface by using a vacuum suction filtration device. The doped ZnO nanowires are inserted between GO nanosheets, so that the internal structure and surface properties of the GO film are changed, and the film performance is improved. The ZnO/GO film shows good permeability and has high-efficiency oil-water separation performance.
Description
Technical Field
The invention belongs to the field of membrane preparation.
Background
In recent years, water environment problems caused by oil pollution are increasingly frequent, and ecological damage and huge economic losses which are difficult to restore are caused. Therefore, the oil-water separation not only draws the attention of broad scholars, but also becomes a research hotspot of practical engineering application. The traditional oil-water separation technology mainly comprises gravity settling, air flotation separation, an oil skimming tank and the like, so that the separation efficiency is low, and emerging emulsion cannot be treated. The novel membrane filtration technology is applied to the field of oil-water separation due to the high-efficiency separation effect and treatment capacity of the novel membrane filtration technology. In the process of separating oil-water mixed liquid by adopting a membrane filtration technology, oil substances are adsorbed by a lipophilic membrane material and are continuously adhered and gathered on the surface, and meanwhile, tiny oil drops can penetrate into the inside of membrane holes to block the pores. These two types of contamination greatly reduce the permeability of the membrane and severely affect the efficiency of oil-water separation. The traditional membrane material is easy to be polluted by oil substances, the loss of membrane flux is serious in practical engineering application, oil pollution is difficult to remove, and the application of the traditional membrane material in oil-water separation engineering is greatly limited. Therefore, the development of a novel membrane material is very important for the application of the membrane separation technology in the treatment of the oily wastewater. The Graphene Oxide (GO) nano material has stable chemical properties, high specific surface area and good mechanical properties, and is applied to research and preparation of various materials. Graphene-based membrane materials built by stacked GO assembly are considered the most promising water treatment membranes. On the one hand, the GO membrane has relatively good hydrophobic capacity due to the extremely strong capillary adsorption force and ultra-low frictional resistance in the gap of the GO nanosheet layer. On the other hand, the nanogap between GO plays the role of a molecular sieve, and effectively intercepts the permeation of macromolecules in a gas or liquid state. However, high operating pressures can compress the GO layer spacing to a large extent, limiting its application in practical engineering. Research proves that the water delivery capacity of the GO thin film can be effectively improved by expanding the distance between GO films. And acidified multi-walled carbon nanotubes are inserted between GO nano-gaps, so that the water flux of the GO film is greatly improved. However, the results of the studies show that multi-walled carbon nanotubes are not effective in improving the anti-contamination performance of the membrane. The preparation of the oil-water separation membrane requires more suitable materials and methods.
Disclosure of Invention
The invention aims to insert ZnO nanowires between GO nanosheets to reconstruct the internal and surface morphology structures. The ZnO nanowire has good hydrophilicity and is an ideal functional composite film material.
The technical scheme of the invention is as follows:
preparation of an oil-water separation hydrophobic membrane, wherein (1) graphene oxide GO and ZnO nanowires are dried for 12 hours under 323K condition before use. (2) 20 g of GO powder was dissolved in 50mL of deionized water and sonicated for 30min to form a uniform GO dispersion. (3) Adding 5-20 wt.% ZnO nanowires into the GO dispersion liquid, performing ultrasonic treatment for 30min to completely disperse the nanowires and form a uniform mixing system (4), taking the PVDF microfiltration membrane as a substrate layer, and performing vacuum filtration on the GO/ZnO nanowire mixed solution on a membrane surface (5) by using a vacuum filtration device to perform vacuum drying on the membrane subjected to vacuum filtration at 313K for 24 h.
Oil-water separation test:
hexadecane is adopted to simulate oil pollutants, 0.2 g of hexadecane is added into 1L of deionized water and is subjected to ultrasonic treatment for 1 hour to prepare stable and dispersed emulsion, and the oil concentration of the emulsion is 200 mg/L. And (3) measuring the separation effect of the oil-water emulsion by using the prepared oil-water separation film. The filtrate was collected and subjected to TOC measurement to characterize its remaining oil content. In the same suction filtration device, 50mL of deionized water and 50mL of oil-containing emulsion are sequentially filtered by using a membrane sample, and then 50mL of deionized water is filtered after the oil-polluted membrane is fully washed by using the deionized water.
Advantageous effects
And successfully preparing the ZnO/GO film on the PVDF supporting layer by a vacuum filtration method. The doped ZnO nanowires are inserted between GO nanosheets, so that the internal structure and surface properties of the GO film are changed, and the film performance is improved. The ZnO/GO film has good permeability and high-efficiency oil-water separation performance, the oil content of effluent is lower than 5 mg/L, and the oil removal efficiency is as high as 99%.
Detailed Description
Example 1
(1) The prepared GO and ZnO nanowires are dried for 12h under 323K condition before use. (2) 20 g of GO powder was dissolved in 50mL of deionized water and sonicated for 30min to form a uniform GO dispersion. (3) Adding 5 wt.% of ZnO nanowires into the GO dispersion liquid, performing ultrasonic treatment for 30min to completely disperse the nanowires and form a uniform mixing system (4), taking the PVDF microfiltration membrane as a substrate layer, and performing vacuum filtration on a membrane subjected to vacuum filtration on the GO/ZnO nanowire mixed solution on a membrane surface (5) by using a vacuum filtration device to perform vacuum drying for 24h at 313K.
The ZnO/GO film shows good permeability, the pure water flux is up to 2100L/(m 2 h) under 70 kPa pressure, the ZnO/GO film has high-efficiency oil-water separation performance, the oil content of effluent is lower than 5 mg/L, and the oil removal efficiency is up to 99%; strong oil stain resistance, and the flux recovery rate is more than 80 percent when the oily wastewater with different concentrations is treated.
Example 2
(1) The prepared GO and ZnO nanowires are dried for 12h under 323K condition before use. (2) 20 g of GO powder was dissolved in 50mL of deionized water and sonicated for 30min to form a uniform GO dispersion. (3) Adding 20 wt.% ZnO nanowire into the GO dispersion liquid, performing ultrasonic treatment for 30min to completely disperse the nanowire and form a uniform mixing system (4), performing suction filtration on the GO/ZnO nanowire mixed solution on a membrane surface (5) by using a vacuum filtration device, and performing vacuum drying on the filtered membrane for 24h at 313K.
The ZnO/GO film shows good permeability, the pure water flux is 2500L/(m 2 h) under 70 kPa pressure, the high-efficiency oil-water separation performance is realized, the oil content of effluent is lower than 5 mg/L, and the oil removal efficiency is as high as 99%; strong oil stain resistance, and the flux recovery rate is more than 80 percent when the oily wastewater with different concentrations is treated.
Claims (2)
1. The preparation method of the oil-water separation hydrophobic membrane is characterized by comprising the following steps:
(1) drying the graphene oxide GO and the ZnO nanowire for 12 hours under 323K condition before use;
(2) dissolving 20 g of GO powder in 50mL of deionized water, and carrying out ultrasonic treatment for 30min to form a uniform GO dispersion system;
(3) adding ZnO nanowires of 5-20 wt.% into the GO dispersion liquid, and performing ultrasonic treatment for 30min to completely disperse the nanowires and form a uniform mixed system;
(4) taking a PVDF microfiltration membrane as a basal layer, and carrying out suction filtration on the GO/ZnO nanowire mixed solution on the membrane surface by using a vacuum suction filtration device; (5) the membrane after suction filtration is dried in vacuum at 313K for 24 h.
2. The preparation method of the hydrophobic membrane for oil-water separation as claimed in claim 1, wherein 5-20 wt.% of ZnO nanowires is added in step (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911210357.1A CN112973466A (en) | 2019-12-02 | 2019-12-02 | Preparation of hydrophilic oleophobic graphene oxide membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911210357.1A CN112973466A (en) | 2019-12-02 | 2019-12-02 | Preparation of hydrophilic oleophobic graphene oxide membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112973466A true CN112973466A (en) | 2021-06-18 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911210357.1A Pending CN112973466A (en) | 2019-12-02 | 2019-12-02 | Preparation of hydrophilic oleophobic graphene oxide membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112973466A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108722206A (en) * | 2018-07-04 | 2018-11-02 | 同济大学 | A kind of antipollution self-cleaning type GO/ZnO-PVDF films and preparation method thereof |
-
2019
- 2019-12-02 CN CN201911210357.1A patent/CN112973466A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108722206A (en) * | 2018-07-04 | 2018-11-02 | 同济大学 | A kind of antipollution self-cleaning type GO/ZnO-PVDF films and preparation method thereof |
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