CN108854600B - Graphene oxide/polyurethane hollow fiber ultrafiltration membrane and preparation method thereof - Google Patents
Graphene oxide/polyurethane hollow fiber ultrafiltration membrane and preparation method thereof Download PDFInfo
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- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses a graphene oxide/polyurethane hollow fiber ultrafiltration membrane and a preparation method thereof, wherein the formula and the content of the membrane are calculated by mass percent and comprise the following components: 25-50% of polyurethane, 2-10% of chlorinated polyvinyl chloride, 1-5% of graphene oxide, 5-10% of a polyethylene glycol/polyvinylpyrrolidone mixture, 801-5% of tween-1 and 20-66% of dimethylacetamide. Preparing the components into a homogeneous membrane casting solution, penetrating and coating the membrane casting solution and the preheated composite woven tube by using a spinning die, passing through an air section, and then entering a coagulating bath to obtain the filter membrane. The coating formed by the casting solution disclosed by the invention is firmly attached to the surface of the braided tube, the membrane yarn flux is higher, the toughness and the impact resistance are good, and the membrane casting solution is suitable for backwashing under higher pressure; the graphene/polyurethane composite hollow fiber membrane prepared by composite modification has the functions of catalysis, antibiosis and the like.
Description
Technical Field
The invention relates to the field of preparation of fiber filter membranes, in particular to a graphene oxide/polyurethane hollow fiber ultrafiltration membrane and a preparation method thereof.
Background
The membrane bioreactor process (MBR) is a novel and efficient sewage treatment technology, and can simultaneously realize biocatalytic reaction and separation of water and degradation substances, so that water resources can be regenerated, and the standard of recycled water quality is realized. The MBR technology is a new modern advanced, high-efficiency and low-energy-consumption wastewater advanced treatment and regeneration and reuse technology. Wherein, the ultrafiltration membrane with high strength, strong pollution resistance and low cost is the core technology of the membrane bioreactor process. Compared with polyvinylidene fluoride (PVDF), polyvinyl chloride (PVC), polypropylene (PP), Polysulfone (PSF) and Polyacrylonitrile (PAN), Polyurethane (PUR) has higher mechanical strength, stable chemical property, good corrosion resistance and pollution resistance, and becomes a more ideal film-making substrate. At present, the graphene modified PUR hollow fiber membrane reinforced by the crocheted net tube with high strength, catalysis and antibacterial effects is rarely reported.
Disclosure of Invention
The invention aims to provide a graphene oxide/polyurethane hollow fiber ultrafiltration membrane suitable for being applied to a membrane bioreactor process and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
in a first aspect, the invention relates to a graphene oxide/polyurethane hollow fiber ultrafiltration membrane, and a formula and content of the membrane comprise, by mass:
preferably, the Polyurethane (PUR) has a weight average molecular weight of 350000 and the chlorinated polyvinyl chloride (CPVC) has a weight average molecular weight of 65000.
In another aspect, the invention also relates to a preparation method of the graphene oxide/polyurethane hollow fiber ultrafiltration membrane, which comprises the following steps:
s1, pretreatment of the polymer material: carrying out vacuum drying on polyurethane, chlorinated polyvinyl chloride and graphene oxide at the temperature of 60-80 ℃ for 12-15 h;
s2, preparing a casting solution: mixing polyurethane (P)1) Chlorinated polyvinyl chloride (P)2) Weighing the graphene oxide, the pore-forming agent, the hydrophilic agent and the solvent in proportion, sequentially placing the materials into a stirring kettle, stirring and dissolving at the temperature of 80-100 ℃, wherein the stirring time is 15-24 hours, the stirring speed is 80-120 rpm, vacuumizing and defoaming the obtained solution, and standing for more than 1 hour to obtain a casting solution for spinning;
s3, extrusion molding of the hollow fiber membrane: the composite weaving tube subjected to preheating treatment passes through a spinning nozzle by utilizing a spinning die and is coated with the casting solution for spinning, and the composite weaving tube enters a coagulating bath after passing through an air section to finally obtain the graphene/polyurethane hollow fiber membrane; the composite braided tube subjected to preheating treatment is subjected to heating treatment, and the temperature of the composite braided tube reaches 30-100 ℃;
s4, leaching of a pore-forming agent: immersing the graphene/polyurethane hollow fiber membrane prepared in the step S3 into a glycerol aqueous solution, removing a pore-forming agent in the membrane, wherein the temperature of the glycerol aqueous solution is 25-30 ℃, and the immersion time is 4-8 h;
s5, airing: and airing the soaked graphene/polyurethane hollow fiber membrane to obtain the graphene oxide/polyurethane hollow fiber ultrafiltration membrane.
Preferably, in step S1, the vacuum drying temperature is 60 to 70 ℃.
Preferably, the polyurethane is polyether polyurethane, and the hardness is Shore A90-95 ℃; the graphene oxide is dissolved to form a graphene oxide layer with a monolayer content of more than 99%, a microchip size of 0.5-2 mu m and a thickness of 0.55-1.20 nm.
Preferably, in step S3, the composite braided tube is a filament made of one or more of PET, PA, PE, PP, PEs, PTFE and carbon fiber.
Preferably, in step S3, the air passage means an air passage with a length of 2-5 cm.
Preferably, in step S3, the coagulation bath is performed in a mixed solution of water and a solvent; the solvent is one or a combination of several of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, and the mass proportion of the solvent in the mixed solution is not higher than 50%.
Preferably, in step S4, the glycerol in the glycerol aqueous solution is present in an amount of 10 to 50% by mass.
Preferably, in step S5, the airing is performed at room temperature; and the air humidity is not higher than 75% under the room temperature condition.
Compared with the prior art, the invention has the beneficial effects that:
1. the Polyurethane (PUR) material has wide sources, low price and simple manufacturing method, and is an ideal film material for replacing expensive polyvinylidene fluoride (PVDF) after composite modification;
2. the coating formed by the membrane casting solution is firmly attached to the surface of the braided tube, the membrane yarn flux is high, the toughness and the impact resistance are good, and the membrane casting solution is suitable for backwashing under higher pressure;
3. the prepared graphene/polyurethane composite hollow fiber membrane has the functions of catalysis, antibiosis and the like, and can play a role in accelerating the oxidative degradation of pollutants and preventing bacteria from breeding on the surface of the membrane in the sewage treatment process, so that the pollution resistance and the sewage treatment effect of the membrane are improved, and a high-performance membrane product can be provided for an MBR process.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a schematic view of a cross-sectional scanning electron microscope of a graphene oxide/polyurethane composite hollow fiber ultrafiltration membrane, wherein an outer layer is a composite filter membrane coating, and an inner layer is a composite braided tube as a supporting layer;
FIG. 2 is a schematic view of a surface scanning electron microscope of a graphene oxide/polyurethane composite hollow fiber ultrafiltration membrane;
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
Example 1
PET and PA monofilaments are woven into a composite braided tube which is evenly and mutually inserted according to the mass ratio of 49: 1, the inner diameter is 2.0mm, and the wall thickness is 0.2 mm. Stirring 35% of polyurethane, 5% of chlorinated polyvinyl chloride, 2% of graphene oxide, 8% of polyethylene glycol/polyvinylpyrrolidone (wt/wt: 1/1), 4% of tween-80 and 46% of dimethylacetamide, and dissolving at 90 ℃ for 3 hours to prepare a homogeneous membrane casting solution; the mixed braided tube was heated to 60 ℃ and passed through a spinneret, through a 3cm air section, and into a coagulation bath containing 25% N, N-dimethylacetamide. After the casting film liquid is led into a spinning nozzle through a material liquid pipeline, a material liquid pipeline valve and a weaving pipe are opened for uniform traction. Then uniformly coating the membrane casting solution on the surface of the composite braided tube by using a spinning die to obtain a graphene oxide/polyurethane composite hollow fiber ultrafiltration membrane; FIG. 1 is a schematic cross-sectional scanning electron microscope of a prepared graphene oxide/polyurethane composite hollow fiber ultrafiltration membrane, wherein an outer layer is a composite filter membrane coating, and an inner layer is a composite braided tube as a supporting layer; fig. 2 is a schematic view of a scanning electron microscope of the surface of the graphene oxide/polyurethane composite hollow fiber ultrafiltration membrane, and it can be seen from fig. 2 that the composite membrane has a smooth and flat surface structure and a good self-cleaning function.
The obtained enhanced graphene oxide/polyurethane composite hollow fiber ultrafiltration membrane has the strength far larger than 60N through a performance test, the pure water flux of 1200LMH, the initial bubble point of 0.28MPa, the membrane filaments subjected to backwashing air washing at 0.1MPa for about 5min, and the membrane filaments and the supporting layer are not separated. In the normal operation of the normal domestic sewage treatment, the COD (chemical oxygen demand) of inlet water is 500mg/L, the COD of produced water is 50mg/L, and the removal rate of the COD is 90 percent.
Example 2
PET and PTFE monofilaments are woven into composite braided tubes which are evenly and mutually interpenetrated according to the mass ratio of 40: 10, the inner diameter is 2.0mm, and the wall thickness is 0.2 mm. Then 38% of polyurethane, 4% of chlorinated polyvinyl chloride, 3% of graphene oxide, 10% of polyethylene glycol/polyvinylpyrrolidone (wt/wt: 1/1), 5% of tween-80 and 40% of dimethylacetamide are stirred and dissolved for 3 hours at 90 ℃ to prepare a homogeneous membrane casting solution; the mixed braided tube was heated to 60 ℃ and passed through a spinneret, through a 3cm air section, and into a coagulation bath containing 25% N, N-dimethylacetamide. After the casting film liquid is led into a spinning nozzle through a material liquid pipeline, a material liquid pipeline valve and a weaving pipe are opened for uniform traction. Then uniformly coating the membrane casting solution on the surface of the composite braided tube by using a spinning die to obtain a graphene oxide/polyurethane composite hollow fiber ultrafiltration membrane;
the obtained enhanced graphene oxide/polyurethane composite hollow fiber ultrafiltration membrane has the strength far larger than 60N through a performance test, the pure water flux is 1050LMH, the initial bubble point is 0.26MPa, the membrane filaments are back-washed and air-washed for about 5min under 0.1MPa, and the membrane filaments are not separated from the supporting layer. In normal operation of normal domestic sewage treatment, the COD (chemical oxygen demand) of inlet water is 500mg/L, the COD of produced water is 80mg/L, and the removal rate of COD is 84%.
Example 3
The PA monofilament and the PES monofilament are woven into a composite braided tube which is evenly and mutually interpenetrated according to the mass ratio of 50: 20, the inner diameter is 2.0mm, and the wall thickness is 0.2 mm. Then stirring 45% of polyurethane, 8% of chlorinated polyvinyl chloride, 5% of graphene oxide, 10% of polyethylene glycol/polyvinylpyrrolidone (wt/wt: 1/1), 5% of tween-80 and 27% of dimethylacetamide, and dissolving for 3 hours at 90 ℃ to prepare a homogeneous membrane casting solution; the mixed braided tube was heated to 60 ℃ and passed through a spinneret, through a 3cm air section, and into a coagulation bath containing 25% N, N-dimethylacetamide. After the casting film liquid is led into a spinning nozzle through a material liquid pipeline, a material liquid pipeline valve and a weaving pipe are opened for uniform traction. Then uniformly coating the membrane casting solution on the surface of the composite braided tube by using a spinning die to obtain a graphene oxide/polyurethane composite hollow fiber ultrafiltration membrane;
the obtained enhanced graphene oxide/polyurethane composite hollow fiber ultrafiltration membrane has the strength far larger than 60N through a performance test, the pure water flux is 950LMH, the initial bubble point is 0.29MPa, the membrane filaments are back-washed and air-washed for about 5min under 0.1MPa, and the membrane filaments are not separated from the supporting layer. In the normal operation of the normal domestic sewage treatment, the COD (chemical oxygen demand) of inlet water is 500mg/L, the COD of produced water is 60mg/L, and the removal rate of the COD is 88 percent.
Example 4
The PA monofilament and the PES monofilament are woven into a composite braided tube which is evenly and mutually interpenetrated according to the mass ratio of 40: 20, the inner diameter is 2.0mm, and the wall thickness is 0.2 mm. Then 50% of polyurethane, 6% of chlorinated polyvinyl chloride, 3% of graphene oxide, 8% of polyethylene glycol/polyvinylpyrrolidone (wt/wt: 1/1), 4% of tween-80 and 29% of dimethylacetamide are stirred and dissolved for 3 hours at 90 ℃ to prepare a homogeneous membrane casting solution; the mixed braided tube was heated to 60 ℃ and passed through a spinneret, through a 3cm air section, and into a coagulation bath containing 25% N, N-dimethylacetamide. After the casting film liquid is led into a spinning nozzle through a material liquid pipeline, a material liquid pipeline valve and a weaving pipe are opened for uniform traction. Then uniformly coating the membrane casting solution on the surface of the composite braided tube by using a spinning die to obtain a graphene oxide/polyurethane composite hollow fiber ultrafiltration membrane;
the obtained enhanced graphene oxide/polyurethane composite hollow fiber ultrafiltration membrane has the strength far larger than 60N through a performance test, the pure water flux is 1100LMH, the initial bubble point is 0.27MPa, the membrane filaments are back-washed for about 5min under 0.1MPa, and the membrane filaments are not separated from the supporting layer. In normal operation of normal domestic sewage treatment, the COD (chemical oxygen demand) of inlet water is 500mg/L, the COD of produced water is 80mg/L, and the removal rate of COD is 84%.
Example 5
The PA monofilament and the PES monofilament are woven into a composite braided tube which is evenly and mutually interpenetrated according to the mass ratio of 60: 10, the inner diameter is 2.0mm, and the wall thickness is 0.2 mm. Then, 40% of polyurethane, 8% of chlorinated polyvinyl chloride, 2% of graphene oxide, 9% of polyethylene glycol/polyvinylpyrrolidone (wt/wt: 1/1), 5% of tween-80 and 36% of dimethylacetamide are stirred and dissolved for 3 hours at 90 ℃ to prepare a homogeneous membrane casting solution; the mixed braided tube was heated to 60 ℃ and passed through a spinneret, through a 3cm air section, and into a coagulation bath containing 25% N, N-dimethylacetamide. After the casting film liquid is led into a spinning nozzle through a material liquid pipeline, a material liquid pipeline valve and a weaving pipe are opened for uniform traction. Then uniformly coating the membrane casting solution on the surface of the composite braided tube by using a spinning die to obtain a graphene oxide/polyurethane composite hollow fiber ultrafiltration membrane;
the obtained enhanced graphene oxide/polyurethane composite hollow fiber ultrafiltration membrane has the strength far larger than 60N through a performance test, the pure water flux is 1300LMH, the initial bubble point is 0.29MPa, the membrane filaments are subjected to backwashing air washing at 0.1MPa for about 5min, and the membrane filaments are not separated from the supporting layer. In normal operation of normal domestic sewage treatment, the COD (chemical oxygen demand) of inlet water is 500mg/L, the COD of produced water is 30mg/L, and the removal rate of COD is 94%.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (6)
1. The preparation method of the graphene oxide/polyurethane hollow fiber ultrafiltration membrane is characterized in that a membrane preparation formula comprises the following components in percentage by mass:
the weight average molecular weight of the polyurethane is 350000, and the weight average molecular weight of the chlorinated polyvinyl chloride is 65000; the polyurethane is polyether polyurethane, and the hardness is Shore A90-95 ℃; the graphene oxide is dissolved to form a single layer with the content of more than 99%, the size of a microchip is 0.5-2 mu m, and the thickness is 0.55-1.20 nm;
the method comprises the following steps:
s1, pretreatment of the polymer material: carrying out vacuum drying on polyurethane, chlorinated polyvinyl chloride and graphene oxide at the temperature of 60-80 ℃ for 12-15 h;
s2, preparing a casting solution: weighing and mixing polyurethane, chlorinated polyvinyl chloride, graphene oxide, a pore-forming agent, a hydrophilic agent and a solvent in proportion, stirring and dissolving at the temperature of 80-100 ℃, wherein the stirring time is 15-24 hours, the stirring speed is 80-120 rpm, the obtained solution is vacuumized and defoamed, and then standing for more than 1 hour to obtain a casting solution for spinning;
s3, extrusion molding of the hollow fiber membrane: the composite weaving tube subjected to preheating treatment passes through a spinning nozzle by utilizing a spinning die and is coated with the casting solution for spinning, and the composite weaving tube enters a coagulating bath after passing through an air section to finally obtain the graphene/polyurethane hollow fiber membrane; the composite braided tube subjected to preheating treatment is subjected to heating treatment, and the temperature of the composite braided tube reaches 30-100 ℃;
the composite braided tube is a filament made of one or more mixed materials of PET, PA, PE, PP, PES, PTFE and carbon fiber;
s4, leaching of a pore-forming agent: immersing the graphene/polyurethane hollow fiber membrane prepared in the step S3 into a glycerol aqueous solution, removing a pore-forming agent in the membrane, wherein the temperature of the glycerol aqueous solution is 25-30 ℃, and the immersion time is 4-8 h;
s5, airing: and airing the soaked graphene/polyurethane hollow fiber membrane to obtain the graphene oxide/polyurethane hollow fiber ultrafiltration membrane.
2. The method according to claim 1, wherein the vacuum drying temperature in step S1 is 60 to 70 ℃.
3. The method according to claim 1, wherein the step S3, the air passage is an air passage with a length of 2-5 cm.
4. The method according to claim 1, wherein in step S3, the coagulation bath is performed in a mixed solution of water and a solvent; the solvent is one or a combination of several of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone, and the mass proportion of the solvent in the mixed solution is not higher than 50%.
5. The method according to claim 1, wherein in step S4, the glycerol in the aqueous glycerol solution is present in an amount of 10 to 50% by mass.
6. The method according to claim 1, wherein the air-drying in step S5 is performed at room temperature; and the air humidity is not higher than 75% under the room temperature condition.
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| CN106139927A (en) * | 2016-07-28 | 2016-11-23 | 杭州天创环境科技股份有限公司 | A kind of high bond strength braided tube strengthens the preparation method of hollow fiber composite membrane |
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| CN102600734B (en) * | 2012-03-27 | 2014-12-10 | 南京工业大学 | Enhanced graphene oxide hollow fiber composite membrane and preparation method thereof |
| CN103480281A (en) * | 2013-08-09 | 2014-01-01 | 天津工业大学 | Organic-inorganic ultrafiltration composite membrane and preparation method thereof |
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