CN111111476A - Super-hydrophobic nanofiber membrane for oily sewage treatment and preparation method thereof - Google Patents
Super-hydrophobic nanofiber membrane for oily sewage treatment and preparation method thereof Download PDFInfo
- Publication number
- CN111111476A CN111111476A CN202010096276.XA CN202010096276A CN111111476A CN 111111476 A CN111111476 A CN 111111476A CN 202010096276 A CN202010096276 A CN 202010096276A CN 111111476 A CN111111476 A CN 111111476A
- Authority
- CN
- China
- Prior art keywords
- parts
- weight
- nanofiber membrane
- oily sewage
- sewage treatment
- 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.)
- Withdrawn
Links
Classifications
-
- 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
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of sewage treatment, and provides a super-hydrophobic nanofiber membrane for oily sewage treatment and a preparation method thereof. The super-hydrophobic nanofiber membrane is obtained by modifying nano silicon dioxide and glass beads with methacryloxypropyl trimethoxy silane, then carrying out copolymerization reaction with ethylene and tetrafluoroethylene, preparing a spinning solution, and carrying out electrostatic spinning. Compared with the traditional method, the nanofiber membrane prepared by the method disclosed by the invention is excellent in super-hydrophobic property, high in oil removal rate when used for treating oily sewage, not easy to damage a micro-nano structure and long in service life of a membrane material.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and provides a super-hydrophobic nanofiber membrane for oily sewage treatment and a preparation method thereof.
Background
Oily sewage is widely available, such as petrochemical, oil extraction, transportation, mechanical processing, leather, textile, food, medicine, and the like. Every year, 500-1000 million tons of oil in the world flows into the ocean through various ways. Because the oily sewage has high Chemical Oxygen Demand (COD) and serious environmental pollution, the oily sewage is required to be effectively separated no matter environment treatment, oil recovery and water reuse, and therefore, the research and application of a membrane separation technology and materials thereof become a hot topic.
Conventional methods for treating oily sewage generally include gravity separation, skimming, flotation, demulsification, flocculation, and the like. Some of the traditional treatment methods have low separation efficiency, and some of the traditional treatment methods add too much chemical agents to cause secondary pollution, and also have too high energy consumption and high cost. In recent years, the membrane separation technology is mainly used for separating stable emulsified oil, and has a wide application range. In the separation process, although the change of the material flow can affect the yield, the separation quality is not affected, no chemical agent or only a few chemical agents are added, and the oil is relatively easy to recover. The separation process is carried out at normal temperature without phase change, the device is small, the energy consumption is low, and the separation process can be highly automated, so the method is popular.
The super-hydrophobic membrane is a common material for membrane separation technology, and at present, the preparation of the super-hydrophobic membrane usually forms a micro-nano rough structure similar to the lotus leaf surface on the surface of a membrane material to obtain a super-hydrophobic surface. However, after long-term use, the micro-nano structure on the surface is damaged due to various reasons, especially under the condition that the combination of the micro-nano particles and the membrane material is poor, the super-hydrophobicity of the membrane material is reduced, the oil removal rate is reduced, and therefore the membrane material cannot be used for a long time, namely, the defect of short service life exists.
Disclosure of Invention
Therefore, after the super-hydrophobic membrane in the prior art is used for a long time, the super-hydrophobicity is reduced due to the fact that the micro-nano structure is damaged, the oil removal rate is reduced, and the service life of the membrane material is short. Aiming at the situation, the invention provides a super-hydrophobic nanofiber membrane for treating oily sewage and a preparation method thereof, acryloxy groups with polymerization reaction activity are introduced on the surfaces of nano silicon dioxide and glass beads, so that nano silicon dioxide particles and glass beads participate in copolymerization of ethylene and tetrafluoroethylene, firm combination of the nano silicon dioxide and the glass beads and an ethylene-tetrafluoroethylene copolymer is realized in a chemical bonding mode, particle agglomeration is prevented, and the obtained fiber membrane can keep a micro-nano structure from being damaged after long-term use, keeps a large contact angle and good super-hydrophobicity, and therefore has long service life.
The invention relates to a specific technical scheme as follows:
a preparation method of a super-hydrophobic nanofiber membrane for oily sewage treatment comprises the following specific steps:
(1) adding tetraethoxysilane and methacryloxypropyltrimethoxysilane into dimethyl sulfoxide, stirring and mixing uniformly, heating to 60-65 ℃, adding hydrochloric acid and deionized water, stirring and reacting for 4-5 hours to obtain modified nano-silica sol, and dialyzing to remove dimethyl sulfoxide to obtain modified nano-silica;
(2) adding methacryloxypropyl trimethoxy silane into deionized water to prepare a silane solution, mixing the silane solution with glass beads, stirring for 1-2 hours, and then placing in an oven for drying to prepare modified glass beads;
(3) adding modified nano-silica, modified glass beads, sodium stearate and diethyl malonate into n-octane, uniformly mixing, heating to 60-70 ℃, introducing ethylene and tetrafluoroethylene, maintaining the pressure at 4-6 MPa, adding dibenzoyl peroxide, carrying out polymerization reaction for 6-7 hours, cooling, filtering, washing and drying after the reaction is finished, thus obtaining the ethylene-tetrafluoroethylene copolymer/nano-silica/glass bead composite material;
(4) adding an ethylene-tetrafluoroethylene copolymer/nano silicon dioxide/glass bead composite material into a mixed solution of triethyl phosphate and triolein, heating to 180-200 ℃, stirring for 2-3 h, adding an irradiation sensitizer, and continuously stirring for 0.5h to prepare a spinning solution;
(5) and adding the spinning solution into an electrostatic spinning machine, spinning to obtain a nanofiber membrane, and performing irradiation crosslinking by adopting gamma rays under the protection of nitrogen to obtain the super-hydrophobic nanofiber membrane for treating oily sewage.
The method comprises the following steps of (1) preparing nano silicon dioxide particles in situ by a sol method, modifying the nano silicon dioxide particles by adopting methacryloxypropyltrimethoxysilane in the preparation process, and grafting acryloxy on the surfaces of the nano particles to enable the surfaces of the nano particles to be subjected to copolymerization reaction with double bonds of ethylene and tetrafluoroethylene. Preferably, the raw materials in the step (1) comprise, by weight, 8-12 parts of tetraethoxysilane, 1-1.5 parts of methacryloxypropyltrimethoxysilane, 60-70 parts of dimethyl sulfoxide, 2-4 parts of hydrochloric acid and 20-25 parts of deionized water.
Similarly, the purpose of the step (2) is to modify the surface of the glass microsphere through methacryloxypropyltrimethoxysilane, so that the surface of the glass microsphere is grafted with acryloxy groups, and the glass microsphere is endowed with the capability of participating in the copolymerization reaction of ethylene and tetrafluoroethylene. Preferably, the raw materials in the step (2) comprise, by weight, 30-40 parts of glass beads, 3-5 parts of methacryloxypropyltrimethoxysilane and 60-70 parts of deionized water; and (3) drying the drying oven in the step (2) at the temperature of 102-105 ℃ for 4-6 h.
And (3) performing free radical copolymerization reaction of ethylene and tetrafluoroethylene, wherein an initiator adopts dibenzoyl peroxide, and in the process, modified nano silicon dioxide and modified glass beads participate in the reaction due to the polymerization activity of surface acryloyloxy groups, so that in the prepared composite material, nano silicon dioxide particles and glass beads are firmly combined with the ethylene-tetrafluoroethylene copolymer in a covalent bonding mode and are uniformly dispersed in the ethylene-tetrafluoroethylene copolymer. Preferably, the raw materials in the step (3) comprise, by weight, 2-4 parts of modified nano-silica, 1-3 parts of modified glass beads, 15-25 parts of ethylene, 20-30 parts of tetrafluoroethylene, 0.5-1 part of sodium stearate, 0.2-0.5 part of diethyl malonate, 0.5-1 part of dibenzoyl peroxide and 100 parts of n-octane.
The prepared ethylene-tetrafluoroethylene copolymer/nano silicon dioxide/glass bead composite material is diluted by triethyl phosphate and triolein to prepare spinning solution, after a fiber membrane is prepared by electrostatic spinning, nano silicon dioxide particles and glass beads form a micro-nano coarse structure on the surface of the fiber membrane, and a tetrafluoroethylene polymerization chain segment which is one of main membrane forming substances endows the fiber membrane with low surface energy, so that the fiber membrane has excellent super-hydrophobic property, and can realize the separation of oil in oil-containing sewage.
Preferably, the radiation sensitizer in step (4) is triallyl isocyanate; the weight parts of the raw materials in the step (4) are 30 parts of ethylene-tetrafluoroethylene copolymer/nano silicon dioxide/glass bead composite material, 50-55 parts of triethyl phosphate, 15-20 parts of triolein and 5-8 parts of radiation sensitizer.
Preferably, the spinning voltage of the electrostatic spinning in the step (5) is 12-15V, the aperture of a spinning opening is 0.5-1 mm, and the receiving distance is 15-20 cm; and (5) the irradiation dose of the irradiation crosslinking in the step (5) is 80-120 kGy, and the time is 5-10 min.
The invention also provides the super-hydrophobic nano-fiber membrane for oily sewage treatment, which is prepared by the preparation method. The super-hydrophobic nanofiber membrane is prepared by modifying nano silicon dioxide and glass beads with methacryloxypropyl trimethoxy silane, then carrying out copolymerization reaction with ethylene and tetrafluoroethylene, preparing a spinning solution, and carrying out electrostatic spinning.
The invention provides a super-hydrophobic nanofiber membrane for oily sewage treatment and a preparation method thereof, and compared with the prior art, the super-hydrophobic nanofiber membrane has the outstanding characteristics and excellent effects that:
(1) according to the nanofiber membrane prepared by the preparation method disclosed by the invention, a micro-nano rough structure is constructed on the surface of the fiber membrane through the nano silicon dioxide particles and the glass beads, and the tetrafluoroethylene polymerization chain segments endow the fiber membrane with low surface energy, so that the fiber membrane has excellent super-hydrophobic property and large contact angle, and the oil removal rate is high when the fiber membrane is used for treating oily sewage.
(2) According to the invention, acryloxy groups with polymerization activity are introduced on the surfaces of nano silicon dioxide and glass beads through modification of methacryloxypropyltrimethoxysilane, and in the process of free radical copolymerization of ethylene and tetrafluoroethylene, nano silicon dioxide particles and glass beads can also participate in the reaction, so that firm combination of the nano silicon dioxide particles and the glass beads and the ethylene-tetrafluoroethylene copolymer is realized through a chemical bonding mode, and particle agglomeration is prevented, therefore, the fiber membrane can keep a micro-nano structure from being damaged after long-term use, and keeps a large contact angle and good superhydrophobicity, and therefore, the service life is long.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Adding tetraethoxysilane and methacryloxypropyltrimethoxysilane into dimethyl sulfoxide, stirring and mixing uniformly, then heating to 65 ℃, adding hydrochloric acid and deionized water, stirring and reacting for 4 hours to obtain modified nano-silica sol, and dialyzing to remove dimethyl sulfoxide to obtain modified nano-silica; the weight parts of the raw materials are 12 parts of tetraethoxysilane, 1 part of methacryloxypropyltrimethoxysilane, 60 parts of dimethyl sulfoxide, 4 parts of hydrochloric acid and 20 parts of deionized water;
(2) adding methacryloxypropyl trimethoxy silane into deionized water to prepare a silane solution, mixing the silane solution with glass beads, stirring for 1 hour, and then placing in an oven for drying to prepare modified glass beads; the weight parts of the raw materials are 30 parts of glass microspheres, 3 parts of methacryloxypropyltrimethoxysilane and 70 parts of deionized water; the drying temperature of the oven is 105 ℃, and the drying time is 4 hours;
(3) adding modified nano-silica, modified glass beads, sodium stearate and diethyl malonate into n-octane, uniformly mixing, heating to 70 ℃, introducing ethylene and tetrafluoroethylene, maintaining the pressure at 4MPa, adding dibenzoyl peroxide, carrying out polymerization reaction for 7 hours, cooling after the reaction is finished, filtering, washing and drying to obtain the ethylene-tetrafluoroethylene copolymer/nano-silica/glass bead composite material; the weight parts of the raw materials are 2 parts of modified nano silicon dioxide, 3 parts of modified glass beads, 15 parts of ethylene, 30 parts of tetrafluoroethylene, 0.5 part of sodium stearate, 0.5 part of diethyl malonate, 1 part of dibenzoyl peroxide and 100 parts of n-octane;
(4) adding the ethylene-tetrafluoroethylene copolymer/nano silicon dioxide/glass bead composite material into a mixed solution of triethyl phosphate and triolein, heating to 180 ℃, stirring for 3 hours, adding an irradiation sensitizer, and continuously stirring for 0.5 hour to prepare a spinning solution; the radiation sensitizer is triallyl isocyanate; the weight parts of the raw materials are that 30 parts of ethylene-tetrafluoroethylene copolymer/nano silicon dioxide/glass microsphere composite material, 50 parts of triethyl phosphate, 20 parts of triolein and 5 parts of radiation sensitizer;
(5) adding the spinning solution into an electrostatic spinning machine, obtaining a nanofiber membrane through spinning, and performing irradiation crosslinking by adopting gamma rays under the protection of nitrogen to obtain a super-hydrophobic nanofiber membrane for treating oily sewage; the spinning voltage of electrostatic spinning is 12V, the aperture of a spinning opening is 1mm, and the receiving distance is 15 cm; the irradiation dose of irradiation crosslinking is 120kGy, and the time is 5 min.
Example 2
(1) Adding tetraethoxysilane and methacryloxypropyltrimethoxysilane into dimethyl sulfoxide, stirring and mixing uniformly, heating to 62 ℃, adding hydrochloric acid and deionized water, stirring and reacting for 5 hours to obtain modified nano-silica sol, and dialyzing to remove dimethyl sulfoxide to obtain modified nano-silica; the weight portions of the raw materials are 8 portions of tetraethoxysilane, 1.2 portions of methacryloxypropyltrimethoxysilane, 61 portions of dimethyl sulfoxide, 2 portions of hydrochloric acid and 24 portions of deionized water;
(2) adding methacryloxypropyl trimethoxy silane into deionized water to prepare a silane solution, mixing the silane solution with glass beads, stirring for 2 hours, and then placing the mixture in a drying oven for drying to prepare modified glass beads; the weight parts of the raw materials are 30 parts of glass microspheres, 4 parts of methacryloxypropyltrimethoxysilane and 63 parts of deionized water; the drying temperature of the oven is 102 ℃, and the drying time is 6 hours;
(3) adding modified nano-silica, modified glass beads, sodium stearate and diethyl malonate into n-octane, uniformly mixing, heating to 60 ℃, introducing ethylene and tetrafluoroethylene, maintaining the pressure at 6MPa, adding dibenzoyl peroxide, carrying out polymerization reaction for 6 hours, cooling after the reaction is finished, filtering, washing and drying to obtain the ethylene-tetrafluoroethylene copolymer/nano-silica/glass bead composite material; the weight parts of the raw materials are 2 parts of modified nano silicon dioxide, 1 part of modified glass microsphere, 18 parts of ethylene, 26 parts of tetrafluoroethylene, 0.7 part of sodium stearate, 0.5 part of diethyl malonate, 0.5 part of dibenzoyl peroxide and 100 parts of n-octane;
(4) adding the ethylene-tetrafluoroethylene copolymer/nano silicon dioxide/glass bead composite material into a mixed solution of triethyl phosphate and triolein, heating to 200 ℃, stirring for 2 hours, adding an irradiation sensitizer, and continuously stirring for 0.5 hour to prepare a spinning solution; the radiation sensitizer is triallyl isocyanate; the weight parts of the raw materials are that 30 parts of ethylene-tetrafluoroethylene copolymer/nano silicon dioxide/glass microsphere composite material, 52 parts of triethyl phosphate, 20 parts of triolein and 5 parts of radiation sensitizer;
(5) adding the spinning solution into an electrostatic spinning machine, obtaining a nanofiber membrane through spinning, and performing irradiation crosslinking by adopting gamma rays under the protection of nitrogen to obtain a super-hydrophobic nanofiber membrane for treating oily sewage; the spinning voltage of electrostatic spinning is 12V, the aperture of a spinning opening is 0.5mm, and the receiving distance is 20 cm; the irradiation dose of irradiation crosslinking is 80kGy, and the time is 5 min.
Example 3
(1) Adding tetraethoxysilane and methacryloxypropyltrimethoxysilane into dimethyl sulfoxide, stirring and mixing uniformly, then heating to 60 ℃, adding hydrochloric acid and deionized water, stirring and reacting for 4.5 hours to obtain modified nano-silica sol, and dialyzing to remove dimethyl sulfoxide to obtain modified nano-silica; the weight portions of the raw materials are that tetraethoxysilane 10 portions, methacryloxypropyltrimethoxysilane 1.5 portions, dimethyl sulfoxide 62 portions, hydrochloric acid 3 portions and deionized water 24 portions;
(2) adding methacryloxypropyl trimethoxy silane into deionized water to prepare a silane solution, mixing the silane solution with the glass beads, stirring for 1.5 hours, and then placing the mixture in a drying oven for drying to prepare modified glass beads; the weight parts of the raw materials are 38 parts of glass beads, 4 parts of methacryloxypropyltrimethoxysilane and 68 parts of deionized water; the drying temperature of the oven is 104 ℃, and the drying time is 5 hours;
(3) adding modified nano-silica, modified glass beads, sodium stearate and diethyl malonate into n-octane, uniformly mixing, heating to 62 ℃, introducing ethylene and tetrafluoroethylene, maintaining the pressure at 5MPa, adding dibenzoyl peroxide, carrying out polymerization reaction for 6.5 hours, cooling after the reaction is finished, filtering, washing and drying to obtain the ethylene-tetrafluoroethylene copolymer/nano-silica/glass bead composite material; the weight parts of the raw materials are 3 parts of modified nano silicon dioxide, 2 parts of modified glass beads, 22 parts of ethylene, 28 parts of tetrafluoroethylene, 0.7 part of sodium stearate, 0.4 part of diethyl malonate, 0.5 part of dibenzoyl peroxide and 100 parts of n-octane;
(4) adding the ethylene-tetrafluoroethylene copolymer/nano silicon dioxide/glass bead composite material into a mixed solution of triethyl phosphate and triolein, heating to 190 ℃, stirring for 2.5 hours, adding an irradiation sensitizer, and continuously stirring for 0.5 hour to prepare a spinning solution; the radiation sensitizer is triallyl isocyanate; the weight parts of the raw materials are that 30 parts of ethylene-tetrafluoroethylene copolymer/nano silicon dioxide/glass microsphere composite material, 55 parts of triethyl phosphate, 17 parts of triolein and 8 parts of radiation sensitizer;
(5) adding the spinning solution into an electrostatic spinning machine, obtaining a nanofiber membrane through spinning, and performing irradiation crosslinking by adopting gamma rays under the protection of nitrogen to obtain a super-hydrophobic nanofiber membrane for treating oily sewage; the spinning voltage of electrostatic spinning is 13V, the aperture of a spinning opening is 0.8mm, and the receiving distance is 18 cm; the irradiation dose of irradiation crosslinking is 100kGy, and the time is 7 min.
Example 4
(1) Adding tetraethoxysilane and methacryloxypropyltrimethoxysilane into dimethyl sulfoxide, stirring and mixing uniformly, heating to 63 ℃, adding hydrochloric acid and deionized water, stirring and reacting for 5 hours to obtain modified nano-silica sol, and dialyzing to remove dimethyl sulfoxide to obtain modified nano-silica; the weight parts of the raw materials are 8 parts of tetraethoxysilane, 1 part of methacryloxypropyltrimethoxysilane, 70 parts of dimethyl sulfoxide, 3 parts of hydrochloric acid and 25 parts of deionized water;
(2) adding methacryloxypropyl trimethoxy silane into deionized water to prepare a silane solution, mixing the silane solution with glass beads, stirring for 2 hours, and then placing the mixture in a drying oven for drying to prepare modified glass beads; the weight parts of the raw materials are 40 parts of glass beads, 5 parts of methacryloxypropyltrimethoxysilane and 60 parts of deionized water; the drying temperature of the oven is 102 ℃, and the drying time is 5 hours;
(3) adding modified nano-silica, modified glass beads, sodium stearate and diethyl malonate into n-octane, uniformly mixing, heating to 68 ℃, introducing ethylene and tetrafluoroethylene, maintaining the pressure at 5.5MPa, adding dibenzoyl peroxide, carrying out polymerization reaction for 7 hours, cooling after the reaction is finished, filtering, washing and drying to obtain the ethylene-tetrafluoroethylene copolymer/nano-silica/glass bead composite material; the weight parts of the raw materials are 2 parts of modified nano silicon dioxide, 3 parts of modified glass beads, 15 parts of ethylene, 22 parts of tetrafluoroethylene, 0.5 part of sodium stearate, 0.2 part of diethyl malonate, 1 part of dibenzoyl peroxide and 100 parts of n-octane;
(4) adding the ethylene-tetrafluoroethylene copolymer/nano silicon dioxide/glass bead composite material into a mixed solution of triethyl phosphate and triolein, heating to 185 ℃, stirring for 2 hours, adding an irradiation sensitizer, and continuously stirring for 0.5 hour to prepare a spinning solution; the radiation sensitizer is triallyl isocyanate; the weight parts of the raw materials are that 30 parts of ethylene-tetrafluoroethylene copolymer/nano silicon dioxide/glass microsphere composite material, 50 parts of triethyl phosphate, 18 parts of triolein and 6 parts of radiation sensitizer;
(5) adding the spinning solution into an electrostatic spinning machine, obtaining a nanofiber membrane through spinning, and performing irradiation crosslinking by adopting gamma rays under the protection of nitrogen to obtain a super-hydrophobic nanofiber membrane for treating oily sewage; the spinning voltage of electrostatic spinning is 14V, the aperture of a spinning opening is 0.6mm, and the receiving distance is 18 cm; the irradiation dose of irradiation crosslinking is 110kGy, and the time is 6 min.
Example 5
(1) Adding tetraethoxysilane and methacryloxypropyltrimethoxysilane into dimethyl sulfoxide, stirring and mixing uniformly, heating to 60 ℃, adding hydrochloric acid and deionized water, stirring and reacting for 4 hours to obtain modified nano-silica sol, and dialyzing to remove dimethyl sulfoxide to obtain modified nano-silica; the weight parts of the raw materials are 10 parts of tetraethoxysilane, 1.5 parts of methacryloxypropyltrimethoxysilane, 60 parts of dimethyl sulfoxide, 2 parts of hydrochloric acid and 25 parts of deionized water;
(2) adding methacryloxypropyl trimethoxy silane into deionized water to prepare a silane solution, mixing the silane solution with glass beads, stirring for 2 hours, and then placing the mixture in a drying oven for drying to prepare modified glass beads; the weight parts of the raw materials are 32 parts of glass microspheres, 4 parts of methacryloxypropyltrimethoxysilane and 65 parts of deionized water; the drying temperature of the oven is 103 ℃, and the drying time is 4.5 h;
(3) adding modified nano-silica, modified glass beads, sodium stearate and diethyl malonate into n-octane, uniformly mixing, heating to 60 ℃, introducing ethylene and tetrafluoroethylene, maintaining the pressure at 6MPa, adding dibenzoyl peroxide, carrying out polymerization reaction for 6 hours, cooling after the reaction is finished, filtering, washing and drying to obtain the ethylene-tetrafluoroethylene copolymer/nano-silica/glass bead composite material; the weight parts of the raw materials are 4 parts of modified nano silicon dioxide, 2 parts of modified glass beads, 20 parts of ethylene, 20 parts of tetrafluoroethylene, 0.7 part of sodium stearate, 0.2 part of diethyl malonate, 1 part of dibenzoyl peroxide and 100 parts of n-octane;
(4) adding the ethylene-tetrafluoroethylene copolymer/nano silicon dioxide/glass bead composite material into a mixed solution of triethyl phosphate and triolein, heating to 180 ℃, stirring for 2.5 hours, adding an irradiation sensitizer, and continuously stirring for 0.5 hour to prepare a spinning solution; the radiation sensitizer is triallyl isocyanate; the weight parts of the raw materials are that 30 parts of ethylene-tetrafluoroethylene copolymer/nano silicon dioxide/glass microsphere composite material, 50 parts of triethyl phosphate, 20 parts of triolein and 5 parts of radiation sensitizer;
(5) adding the spinning solution into an electrostatic spinning machine, obtaining a nanofiber membrane through spinning, and performing irradiation crosslinking by adopting gamma rays under the protection of nitrogen to obtain a super-hydrophobic nanofiber membrane for treating oily sewage; the spinning voltage of electrostatic spinning is 15V, the aperture of a spinning opening is 0.5mm, and the receiving distance is 15 cm; the irradiation dose of irradiation crosslinking is 120kGy, and the time is 7 min.
Comparative example 1
In the preparation process, the nano silicon dioxide and the glass beads are not modified, and other preparation conditions are consistent with those of example 6.
And (3) performance testing:
(1) initial contact angle: taking the nanofiber membrane, testing the surface hydrophobic property by adopting an OCA20 optical contact angle tester under the condition of room temperature and the size of the used water drop of 5 mu L, respectively measuring at more than 5 different positions and calculating the average value;
(2) initial oil removal rate: the nanofiber membrane is adopted for oily sewage treatment, diesel oil is used as simulation oil and is mixed with water to obtain an oily sewage sample, n-hexane is used as an extracting agent to extract the diesel oil in the water, a UV1101 type ultraviolet spectrophotometer is adopted to detect the absorbance of the extraction liquid, the concentration of the diesel oil is obtained according to a standard curve of different concentrations of the diesel oil in the n-hexane corresponding to the absorbance, the oil content of the oily sewage sample before and after passing through an oil-water separation membrane is respectively tested, the oil removal rate n = (X1-X2)/X1 is calculated, X1 is the initial oil content, and X2 is the oil content after separation;
(3) durability: the nanofiber membrane is adopted to continuously treat oily sewage, and contact angles and oil removal rates after 7d, 30d and 60d are tested according to the method.
The data obtained are shown in Table 1.
Table 1:
Claims (10)
1. a preparation method of a super-hydrophobic nanofiber membrane for oily sewage treatment is characterized by comprising the following specific steps:
(1) adding tetraethoxysilane and methacryloxypropyltrimethoxysilane into dimethyl sulfoxide, stirring and mixing uniformly, heating to 60-65 ℃, adding hydrochloric acid and deionized water, stirring and reacting for 4-5 hours to obtain modified nano-silica sol, and dialyzing to remove dimethyl sulfoxide to obtain modified nano-silica;
(2) adding methacryloxypropyl trimethoxy silane into deionized water to prepare a silane solution, mixing the silane solution with glass beads, stirring for 1-2 hours, and then placing in an oven for drying to prepare modified glass beads;
(3) adding modified nano-silica, modified glass beads, sodium stearate and diethyl malonate into n-octane, uniformly mixing, heating to 60-70 ℃, introducing ethylene and tetrafluoroethylene, maintaining the pressure at 4-6 MPa, adding dibenzoyl peroxide, carrying out polymerization reaction for 6-7 hours, cooling, filtering, washing and drying after the reaction is finished, thus obtaining the ethylene-tetrafluoroethylene copolymer/nano-silica/glass bead composite material;
(4) adding an ethylene-tetrafluoroethylene copolymer/nano silicon dioxide/glass bead composite material into a mixed solution of triethyl phosphate and triolein, heating to 180-200 ℃, stirring for 2-3 h, adding an irradiation sensitizer, and continuously stirring for 0.5h to prepare a spinning solution;
(5) and adding the spinning solution into an electrostatic spinning machine, spinning to obtain a nanofiber membrane, and performing irradiation crosslinking by adopting gamma rays under the protection of nitrogen to obtain the super-hydrophobic nanofiber membrane for treating oily sewage.
2. The method for preparing the superhydrophobic nanofiber membrane for oily sewage treatment according to claim 1, wherein in the step (1), by weight, 8-12 parts of tetraethoxysilane, 1-1.5 parts of methacryloxypropyltrimethoxysilane, 60-70 parts of dimethyl sulfoxide, 2-4 parts of hydrochloric acid and 20-25 parts of deionized water are used.
3. The method for preparing the superhydrophobic nanofiber membrane for oily sewage treatment according to claim 1, wherein in the step (2), by weight, 30-40 parts of glass beads, 3-5 parts of methacryloxypropyltrimethoxysilane and 60-70 parts of deionized water are added.
4. The preparation method of the superhydrophobic nanofiber membrane for oily sewage treatment according to claim 1, wherein the drying temperature of the oven in the step (2) is 102-105 ℃, and the drying time is 4-6 hours.
5. The method for preparing the superhydrophobic nanofiber membrane for oily sewage treatment according to claim 1, wherein in the step (3), the modified nano silica is 2 to 4 parts by weight, the modified glass beads are 1 to 3 parts by weight, the ethylene is 15 to 25 parts by weight, the tetrafluoroethylene is 20 to 30 parts by weight, the sodium stearate is 0.5 to 1 part by weight, the diethyl malonate is 0.2 to 0.5 part by weight, the dibenzoyl peroxide is 0.5 to 1 part by weight, and the n-octane is 100 parts by weight.
6. The method for preparing the superhydrophobic nanofiber membrane for oily sewage treatment according to claim 1, wherein the radiation sensitizer of step (4) is triallyl isocyanate.
7. The method for preparing the superhydrophobic nanofiber membrane for oily sewage treatment as claimed in claim 1, wherein in the step (4), the ethylene-tetrafluoroethylene copolymer/nano silica/glass bead composite material is 30 parts by weight, the triethyl phosphate is 50-55 parts by weight, the triolein is 15-20 parts by weight, and the radiation sensitizer is 5-8 parts by weight.
8. The method for preparing the superhydrophobic nanofiber membrane for oily sewage treatment according to claim 1, wherein the electrostatic spinning in the step (5) has a spinning voltage of 12-15V, a spinning opening aperture of 0.5-1 mm, and a receiving distance of 15-20 cm.
9. The preparation method of the superhydrophobic nanofiber membrane for oily sewage treatment according to claim 1, wherein the irradiation dose of irradiation crosslinking in the step (5) is 80-120 kGy, and the time is 5-10 min.
10. The super-hydrophobic nano-fiber membrane for oily sewage treatment prepared by the preparation method of claims 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010096276.XA CN111111476A (en) | 2020-02-17 | 2020-02-17 | Super-hydrophobic nanofiber membrane for oily sewage treatment and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010096276.XA CN111111476A (en) | 2020-02-17 | 2020-02-17 | Super-hydrophobic nanofiber membrane for oily sewage treatment and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111111476A true CN111111476A (en) | 2020-05-08 |
Family
ID=70491262
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010096276.XA Withdrawn CN111111476A (en) | 2020-02-17 | 2020-02-17 | Super-hydrophobic nanofiber membrane for oily sewage treatment and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111111476A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111850722A (en) * | 2020-07-16 | 2020-10-30 | 浙江理工大学 | Preparation method of strawberry-shaped organic/inorganic crosslinked microsphere oriented filling reinforced chemical fiber |
| CN115198442A (en) * | 2022-06-17 | 2022-10-18 | 青岛大学 | Preparation method and application of nano-film with directional water transmission and efficient antibacterial functions |
| CN117861466A (en) * | 2024-03-12 | 2024-04-12 | 安徽先材科技有限公司 | Functional composite membrane based on trimesic acid chloride and preparation method thereof |
-
2020
- 2020-02-17 CN CN202010096276.XA patent/CN111111476A/en not_active Withdrawn
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111850722A (en) * | 2020-07-16 | 2020-10-30 | 浙江理工大学 | Preparation method of strawberry-shaped organic/inorganic crosslinked microsphere oriented filling reinforced chemical fiber |
| CN111850722B (en) * | 2020-07-16 | 2021-08-13 | 浙江理工大学 | Preparation method of strawberry-shaped organic/inorganic crosslinked microsphere oriented filling reinforced chemical fiber |
| CN115198442A (en) * | 2022-06-17 | 2022-10-18 | 青岛大学 | Preparation method and application of nano-film with directional water transmission and efficient antibacterial functions |
| CN115198442B (en) * | 2022-06-17 | 2024-04-12 | 青岛大学 | Preparation method and application of nano film with directional moisture transmission and efficient antibacterial functions |
| CN117861466A (en) * | 2024-03-12 | 2024-04-12 | 安徽先材科技有限公司 | Functional composite membrane based on trimesic acid chloride and preparation method thereof |
| CN117861466B (en) * | 2024-03-12 | 2024-05-17 | 安徽先材科技有限公司 | Functional composite membrane based on trimesic acid chloride and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111111476A (en) | Super-hydrophobic nanofiber membrane for oily sewage treatment and preparation method thereof | |
| CN107162154B (en) | Ternary combination flooding produced water load type reverse demulsifier and preparation method thereof | |
| CN108939952B (en) | PMIA super-hydrophobic nanofiber membrane for oil-water separation and preparation method thereof | |
| CN103990384B (en) | A kind of preparation method of hybrid inorganic-organic microporous separation membrane | |
| CN110023251A (en) | The biological beads controlled for biofouling in membrane bioreactor | |
| CN104262521A (en) | Preparation method of styrene-divinylbenzene copolymer hydrophobic catalyst support | |
| CN109126205B (en) | Preparation method of PS/PMMA (polystyrene/polymethyl methacrylate) bionic super-hydrophobic membrane for oil-water separation | |
| CN106632922B (en) | The method of the preparation method and its modified polyvinilidene fluoride microfiltration membranes of block polymer containing hydrophilic segment | |
| CN112915816A (en) | MXene separation membrane capable of simultaneously separating oil and dye and preparation method and application thereof | |
| CN103071402A (en) | Hydrophilic polyaryletherketone blended hollow fiber ultrafilter membrane and preparation method thereof | |
| CN111530434A (en) | Silica gel adsorbent for adsorbing heavy metal ions and preparation method thereof | |
| Zakaria Djibrine et al. | An effective flocculation method to the kaolin wastewater treatment by a cationic polyacrylamide (CPAM): Preparation, characterization, and flocculation performance | |
| CN110559865B (en) | Method for repairing ultrafiltration membrane pollution or membrane damage | |
| CN107938345B (en) | Preparation method of hydrolyzed silk peptide modified viscose fibers | |
| CN113274890B (en) | Porous high-permeability polyethylene sewage treatment membrane and preparation method thereof | |
| Bai et al. | Superefficient removal of lignins from papermaking wastewater by polycationic adsorption and direct reuse of wastes: structure–activity relationships and interaction mechanisms | |
| CN111423902B (en) | Demulsification synergist for thickened oil and preparation method thereof | |
| CN107297157A (en) | A kind of hydrophiling, the preparation method of anti-pollution PVDF seperation film | |
| CN109248570B (en) | Preparation method of PAN/PAMS/ZnO oil-water separation membrane | |
| CN113101897A (en) | Self-regeneration porous carbon sphere composite material and preparation method and application thereof | |
| CN106731880A (en) | Visible light catalytic hollow fiber ultrafiltration membrane and preparation method based on dopen Nano ZnO | |
| CN114762797A (en) | Preparation method of functionalized halloysite nanotube modified ultrafiltration membrane | |
| CN112023897A (en) | Preparation method of nanocellulose microspheres with selective adsorption and adsorption application of nanocellulose microspheres to dye wastewater | |
| Nica et al. | Preliminary assessments about the sorbtive properties of new types of TEMPO-oxidized cellulose and Pullulan-PVA hybrid hydrogels: Organic dyes and metallic ions retentions | |
| CN114307686B (en) | High-flux modification method of polyamide composite membrane based on ether free radicals |
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 | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200508 |