CN108434788B - Separation method of oil-water emulsion - Google Patents
Separation method of oil-water emulsion Download PDFInfo
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- CN108434788B CN108434788B CN201810252657.5A CN201810252657A CN108434788B CN 108434788 B CN108434788 B CN 108434788B CN 201810252657 A CN201810252657 A CN 201810252657A CN 108434788 B CN108434788 B CN 108434788B
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- 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
- B01D17/04—Breaking emulsions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
Abstract
The invention relates to a method for separating oil-water emulsion. Adopting a freeze polymerization reaction, uniformly mixing polyethylene glycol diacrylate, polydivinylbenzene particles and an initiator in a solvent, introducing nitrogen to remove oxygen, transferring into an injector to seal, controlling the reaction temperature at-18 ℃, and reacting for 48 hours; the obtained product is fully washed by an elution solvent and is used for oil-water emulsion separation under the action of gravity only, the oil-water separation efficiency can reach 99.8 percent, the oil content in water is lower than 50ppm, and the adsorption capacity of the polymer material to the oil-water emulsion is higher than 2.8 g/g. The preparation method is simple and reliable, the post-treatment is simple, the obtained material is used for separating oil-water emulsion, the separation speed is high, the separation efficiency is high, the repeated utilization rate is good, and the adsorption capacity is large.
Description
Technical Field
The invention relates to a separation method of oil-water emulsion, belonging to the technical field of emulsion separation.
Background
Oily wastewater widely exists in various aspects of human life, from oil exploitation and product development to the influence of various oil leakage and ocean oil spill events which are increasingly frequent on the living environment of human beings, from the discharge of industrial wastewater to the threat of various wastewater generated in human daily life on human health. The development of materials and processes with high-efficiency separation capability on the oily wastewater has wide application value.
According to the form of oil-water composition, oily wastewater can be simply divided into two types, namely an oil-water mixture and an oil-water emulsion. At present, a large number of effective methods are reported for separating oil-water mixtures, and various high-efficiency oil-water separation materials are developed. Most of these materials are hydrophobic or even super-hydrophobic materials. For example: chinese patent document CN103203226A discloses a graphite powder-butyl rubber composite gel oil absorption material and a preparation method thereof, and the obtained porous material can rapidly absorb various oil substances, and the oil absorption multiplying power is close to 20. Chinese patent document CN106432563A discloses a super-macroporous polymer prepared by using hydrophobic monomer divinylbenzene as raw material, and the adsorption multiple of the obtained material to crude oil is more than 30. However, the separation of oil-water emulsion from the above materials is difficult to achieve, mainly because the oil-water emulsion has a large amount of surfactant attached to its surface, and can be uniformly and stably distributed in the water phase, and is not easily adsorbed or absorbed by hydrophobic materials.
Compared with the separation of oil-water mixture, the separation process of oil-water emulsion at least comprises two processes of demulsification and oil-water separation, and in specific industrial practice, due to the complex composition of the oil-water emulsion, the separation process can be realized by a synergistic process of multiple methods such as demulsification, coagulation, air flotation, adsorption, separation and the like, which is the difficult point of oil-water emulsion separation. For example: chinese patent document CN1206178C discloses a method for treating high-concentration emulsified oil wastewater, which comprises the steps of firstly removing upper-layer floating oil by an oil separation tank, and then completing the separation of oil-water emulsion through the steps of emulsion breaking, air flotation, electrolysis, biochemical treatment and the like. The process treatment process of the cooperation of the multiple methods is complex, long in time consumption and low in efficiency. In recent years, materials with specific interfacial wettability have been used for the separation of oil-water emulsions. For example: chinese patent document CN104548667A discloses a net membrane for oil-water emulsion separation and a preparation method thereof, which attaches a metal oxide having a micro-nano structure to the meshes and wires of a metal net to form a composite net membrane structure. The obtained composite net film has the properties of super-hydrophilicity and super-oleophylicity in air, super-hydrophobicity under oil and super-lipophobicity under water, and can realize the rapid separation of oil-water emulsion. However, since the adsorption capacity of the separation membrane is generally small, there is a limitation in the application of continuous large-scale oil-water emulsion separation.
Disclosure of Invention
Aiming at the problems and the defects of the prior art, the invention provides a method for separating an oil-water emulsion. The invention adopts the composite super-macroporous polymer material with special interface wettability to separate oil and water emulsion; the polymer is prepared in situ by introducing hydrophilic monomers and hydrophobic polymer particles, and freezing polymerization at a lower temperature under the pore-forming of organic solvent crystals, has the properties of super-hydrophilicity and super-lipophilicity in air, super-hydrophilicity under oil and underwater lipophobicity, and can realize the rapid separation of oil-water emulsion under the action of gravity.
The technical scheme of the invention is as follows:
a method for separating oil-water emulsion comprises the following steps:
adding water into the composite super-macroporous polymer for swelling and balancing, adding an oil-water emulsion to be separated, and separating the oil-water emulsion under the action of gravity;
the composite super macroporous polymer is prepared by the following method:
adding hydrophilic monomer polyethylene glycol diacrylate, hydrophobic polymer particle polydivinylbenzene and an initiator into a solvent, uniformly mixing, introducing nitrogen to remove oxygen, sealing, controlling the reaction temperature between minus 40 ℃ and 4 ℃, reacting for 12-96 hours, fully washing a product by using an elution solvent, and drying to obtain the composite super-macroporous polymer.
According to the present invention, preferably, the mass ratio of the polyethylene glycol diacrylate to the polydivinylbenzene is 1: (0.1-1.0), more preferably 1: (0.2-0.5).
According to the present invention, it is preferable that the number average molecular weight of the polyethylene glycol diacrylate is 258-700, and the average particle size of the polydivinylbenzene is 4 μm.
According to the invention, preferably, the initiator is a redox initiation system consisting of benzoyl peroxide and N, N-dimethylaniline;
preferably, the solvent is one or two of water, dodecanol, dimethyl sulfoxide and acetic acid;
preferably, the initiator accounts for 0.5-10% of the weight of the polyethylene glycol diacrylate;
preferably, the elution solvent is ethanol.
According to the invention, the reaction temperature is preferably between-20 ℃ and 4 ℃; the reaction time is 20-50 hours.
According to the invention, the oil-water emulsion refers to an oil-water emulsion containing no surfactant or an oil-water emulsion containing a surfactant (such as Tween 80).
According to the method for separating an oil-water emulsion of the present invention, a preferred embodiment is as follows;
the composite super-macroporous polymer is placed in a columnar container, after water is added for swelling and balancing, oil-water emulsion is added from the upper part of the columnar container, the oil-water emulsion flows through a polymer material under the action of gravity, the oil-water emulsion is demulsified when flowing through the column material, water can smoothly pass through the polymer material, and oil is remained in the polymer material, so that the separation of the oil-water emulsion is realized.
According to the invention, the composite super-macroporous polymer material can be recycled after being fully washed by ethanol. The oil-water separation efficiency is maintained to be more than 99.5 percent after the oil-water separator is repeatedly used for more than 8 times.
According to the invention, the preparation of the composite type super macroporous polymer comprises the following steps:
0.5mL of polyethylene glycol diacrylate, 250mg of polydivinylbenzene particles, 4.8 mu l N, N-dimethylaniline and 9.2mg of benzoyl peroxide are added into 9.5mL of dimethyl sulfoxide and mixed uniformly, nitrogen is introduced to remove oxygen, the mixture is transferred into an injector to be sealed, the reaction temperature is controlled at-18 ℃, and the reaction is carried out for 48 hours; and fully washing the obtained product by an elution solvent, and drying to obtain the compound type super macroporous polymer.
The invention has the following characteristics and beneficial effects:
1. the composite super-macroporous polymer material has a micron-sized super-macroporous structure, the pore diameter range of the composite super-macroporous polymer material is mainly distributed between 1 and 100 mu m, and the composite super-macroporous polymer material has the properties of super-hydrophilicity and super-oleophylicity in air, super-hydrophilicity under oil and underwater oleophobic property, is suitable for the separation of oil-water emulsion, can be implemented by the action of gravity in the separation process without an external pressure device, has the oil-water separation efficiency higher than 99.5 percent, the oil content in water lower than 50ppm, and the adsorption capacity of the polymer material to the oil-water emulsion higher than 2.8 g/g.
2. The method is simple and reliable, the post-treatment is simple, the obtained material is used for separating oil-water emulsion, the separation speed is high, the oil-water separation efficiency is high, the repeated utilization rate is high, the adsorption capacity is large, and the method is superior to the prior art.
Drawings
FIG. 1: scanning electron micrographs of the superporous polymeric material prepared in comparative example 1.
FIG. 2: scanning electron microscope images of the composite super macroporous polymer material prepared in example 1.
FIG. 3: example 1 oil-water emulsion separation process schematic.
FIG. 4: the recycling performance diagram of the composite super-macroporous polymer material prepared in the embodiment 1 is used for oil-water emulsion separation.
Detailed Description
The present invention will be further described, but not limited to, by the following specific embodiments in conjunction with the accompanying drawings.
Example 1
0.180mL (200mg) of polyethylene glycol diacrylate (number average molecular weight of 600), 100mg of polydivinylbenzene particles (average particle size of 4 μm), 0.5 μ L N, N-dimethylaniline and 1.0mg of benzoyl peroxide are added into 1.1mL of dimethyl sulfoxide and mixed uniformly, nitrogen is introduced to remove oxygen, the mixture is transferred into an injector and sealed, the reaction temperature is controlled at-18 ℃ and the reaction is carried out for 48 hours. And fully washing the obtained product by using an eluting solvent ethanol, and drying to obtain the compound type super macroporous polymer.
The scanning electron microscope image of the composite super macroporous polymer prepared in the embodiment is shown in fig. 2, and the schematic diagram of the oil-water emulsion separation process is shown in fig. 3.
The obtained composite super-macroporous polymer material is placed in an injector, water is added for swelling and balancing for 2 hours, 1mL of oil-water emulsion is added from the upper part of a column tube, the oil-water emulsion can flow through the polymer column material only under the action of gravity, water smoothly passes through the polymer column material, the time is 1 minute, oil is reserved in the column material, and the oil-water separation efficiency is 99.8%.
The polymer material is fully washed by ethanol and repeatedly used for more than 10 times, the oil-water separation efficiency is not lower than 99.5 percent, and the recycling performance is shown in figure 4. Therefore, the composite super-macroporous polymer has good recycling performance.
Example 2
0.36mL (400mg) of polyethylene glycol diacrylate (number average molecular weight 600), 40mg of polydivinylbenzene particles (average particle size 4 μm), 0.2 μ L N, N-dimethylaniline and 0.4mg of benzoyl peroxide were added into 1.6mL of dimethyl sulfoxide and mixed uniformly, nitrogen was introduced to remove oxygen, the mixture was transferred to an injector and sealed, the reaction temperature was controlled at-18 ℃ and the reaction was carried out for 48 hours. And fully washing the obtained product by using an eluting solvent ethanol, and drying to obtain the compound type super macroporous polymer.
The obtained composite super-macroporous polymer material is placed in an injector, water is added for swelling and balancing for 2 hours, 1mL of oil-water emulsion is added from the upper part of a column tube, the oil-water emulsion can flow through the polymer column material only under the action of gravity, water smoothly passes through the polymer column material, the time is 1 minute, oil is reserved in the column material, and the oil-water separation efficiency is 98.3%.
Example 3
0.135mL (150mg) of polyethylene glycol diacrylate (number average molecular weight 600), 150mg of polydivinylbenzene particles (average particle size 4 μm), 0.8 μ l N, N-dimethylaniline and 1.5mg of benzoyl peroxide were added into 1.09mL of dimethyl sulfoxide and mixed uniformly, nitrogen was introduced to remove oxygen, the mixture was transferred to an injector and sealed, the reaction temperature was controlled at-18 ℃ and the reaction was carried out for 48 hours. And fully washing the obtained product by using an eluting solvent ethanol, and drying to obtain the compound type super macroporous polymer.
The obtained composite super-macroporous polymer material is placed in an injector, water is added for swelling and balancing for 2 hours, 1mL of oil-water emulsion is added from the upper part of a column tube, the oil-water emulsion can flow through the polymer column material only under the action of gravity, water smoothly passes through the polymer column material, the time is 1 minute, oil is reserved in the column material, and the oil-water separation efficiency is 93.9%.
Comparative example 1
0.363mL (0.403mg) of polyethylene glycol diacrylate (number average molecular weight 600), 2.1 mu L N, N-dimethylaniline and 4.0mg of benzoyl peroxide are added into 1.45mL of dimethyl sulfoxide and mixed uniformly, nitrogen is introduced to remove oxygen, the mixture is transferred into an injector to be sealed, the reaction temperature is controlled at-18 ℃ and the reaction is carried out for 48 hours. And fully washing the obtained product by using an eluting solvent ethanol, and drying to obtain the compound type super macroporous polymer.
Placing the obtained polyethylene glycol diacrylate super-macroporous polymer material into an injector, adding water to swell and balance for 2 hours, adding 1mL of oil-water emulsion from the upper part of a column tube, wherein the oil-water emulsion can flow through the polymer column material only under the action of gravity, water passes through the polymer column material, the time is taken for 5 minutes, oil is reserved in the column material, and the oil-water separation efficiency is 83.5%.
The scanning electron microscope image of the super macroporous polymer prepared by the comparative example is shown in figure 1, and as polydivinylbenzene particles are not added, the oil-water separation efficiency of the obtained super macroporous polymer is seriously reduced.
Comparative example 2
0.090mL (100mg) of polyethylene glycol diacrylate (number average molecular weight is 600), 200mg of polydivinylbenzene particles (average particle size is 4 μm), 1.0 μ l N, N-dimethylaniline and 2.0mg of benzoyl peroxide are added into 1.09mL of dimethyl sulfoxide and mixed uniformly, nitrogen is introduced to remove oxygen, the mixture is transferred into an injector and sealed, the reaction temperature is controlled at-18 ℃ and the reaction is carried out for 48 hours. And fully washing the obtained product by using an eluting solvent ethanol, and drying to obtain the compound type super macroporous polymer.
The obtained composite super-macroporous polymer material is placed in an injector, after water is added for swelling and balancing for 2 hours, 1mL of oil-water emulsion is added from the upper part of a column tube, the oil-water emulsion rapidly flows through the polymer column material within 20 seconds only under the action of gravity, the oil-water emulsion does not obviously change before and after flowing through the composite material, and the oil-water separation efficiency is lower than 5%.
In the comparative example, the mass ratio of the polyethylene glycol diacrylate to the polydivinylbenzene is 1: 2, the addition amount of the polydivinylbenzene particles is too much, and the prepared composite super-macroporous polymer hardly has the capability of separating oil and water emulsions.
Claims (7)
1. A method for separating oil-water emulsion comprises the following steps:
adding water into the composite super-macroporous polymer for swelling and balancing, adding an oil-water emulsion to be separated, and separating the oil-water emulsion under the action of gravity;
the composite super macroporous polymer is prepared by the following method:
adding a hydrophilic monomer polyethylene glycol diacrylate, hydrophobic polymer particles polydivinylbenzene and an initiator into a solvent, and uniformly mixing, wherein the mass ratio of the polyethylene glycol diacrylate to the polydivinylbenzene is 1: (0.1-1.0), introducing nitrogen to remove oxygen, sealing, controlling the reaction temperature to be-40-4 ℃, reacting for 12-96 hours, fully washing a product by an elution solvent, and drying to obtain the composite super-macroporous polymer; the initiator is a redox initiation system consisting of benzoyl peroxide and N, N-dimethylaniline, and the solvent is one or two of water, dodecanol, dimethyl sulfoxide and acetic acid.
2. The method as set forth in claim 1, wherein the polyethylene glycol diacrylate has a number average molecular weight of 258-700.
3. The method for separating an oil-water emulsion according to claim 1, wherein the initiator is 0.5 to 10 wt% of the polyethylene glycol diacrylate.
4. The method for separating an oil-water emulsion according to claim 1, wherein the eluting solvent is ethanol.
5. The method for separating an oil-water emulsion according to claim 1, wherein the reaction temperature is between-20 ℃ and 4 ℃; the reaction time is 20-50 hours.
6. The method for separating an oil-water emulsion according to claim 1, comprising the steps of:
the composite super-macroporous polymer is placed in a columnar container, after water is added for swelling and balancing, oil-water emulsion is added from the upper part of the columnar container, the oil-water emulsion flows through a polymer material under the action of gravity, the oil-water emulsion is demulsified when flowing through the column material, water can smoothly pass through the polymer material, and oil is remained in the polymer material, so that the separation of the oil-water emulsion is realized.
7. The method for separating oil-water emulsion according to claim 1, wherein the preparation of the composite super macroporous polymer comprises the following steps:
0.5mL of polyethylene glycol diacrylate, 250mg of polydivinylbenzene particles, 4.8 mu l N, N-dimethylaniline and 9.2mg of benzoyl peroxide are added into 9.5mL of dimethyl sulfoxide and mixed uniformly, nitrogen is introduced to remove oxygen, the mixture is transferred into an injector to be sealed, the reaction temperature is controlled at-18 ℃, and the reaction is carried out for 48 hours; and fully washing the obtained product by an elution solvent, and drying to obtain the compound type super macroporous polymer.
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| CN110272090A (en) * | 2019-04-17 | 2019-09-24 | 济南大学 | A kind of method of multifunction magnetic hydrogel processing waste water |
| CN112354215A (en) * | 2020-09-18 | 2021-02-12 | 山东大学 | Super-macroporous super-amphiphilic chitosan polymer for oil-water separation and oil-water separation method |
| CN113533593A (en) * | 2021-06-28 | 2021-10-22 | 济南大学 | Separation analysis method for complex oil-water emulsion system |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1341030A (en) * | 1999-02-24 | 2002-03-20 | 陶氏化学公司 | Manufacture of superabsorbents in high internal phase emulsions |
| CN1356345A (en) * | 2000-11-28 | 2002-07-03 | 罗姆和哈斯公司 | Hydrophobic absorbing polymer and method |
| CN103374143A (en) * | 2012-04-28 | 2013-10-30 | 中国科学院过程工程研究所 | Super macroporous polymer microspheres and preparation method thereof |
| CN104558350A (en) * | 2013-10-12 | 2015-04-29 | 中国石油大学(华东) | Hydrophilic super-macroporous polymer microsphere and preparation method thereof |
| CN107617426A (en) * | 2017-09-25 | 2018-01-23 | 常州市宇科不绣钢有限公司 | A kind of preparation method of high adsorption capacity crystalline substance glue microsphere particle |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341030A (en) * | 1999-02-24 | 2002-03-20 | 陶氏化学公司 | Manufacture of superabsorbents in high internal phase emulsions |
| CN1356345A (en) * | 2000-11-28 | 2002-07-03 | 罗姆和哈斯公司 | Hydrophobic absorbing polymer and method |
| CN103374143A (en) * | 2012-04-28 | 2013-10-30 | 中国科学院过程工程研究所 | Super macroporous polymer microspheres and preparation method thereof |
| CN104558350A (en) * | 2013-10-12 | 2015-04-29 | 中国石油大学(华东) | Hydrophilic super-macroporous polymer microsphere and preparation method thereof |
| CN107617426A (en) * | 2017-09-25 | 2018-01-23 | 常州市宇科不绣钢有限公司 | A kind of preparation method of high adsorption capacity crystalline substance glue microsphere particle |
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