CN102389721A - Polyacrylonitrile membrane with supporting materials and preparation method thereof - Google Patents
Polyacrylonitrile membrane with supporting materials and preparation method thereof Download PDFInfo
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- CN102389721A CN102389721A CN2011102972451A CN201110297245A CN102389721A CN 102389721 A CN102389721 A CN 102389721A CN 2011102972451 A CN2011102972451 A CN 2011102972451A CN 201110297245 A CN201110297245 A CN 201110297245A CN 102389721 A CN102389721 A CN 102389721A
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Abstract
The invention discloses a polyacrylonitrile membrane with supporting materials and a preparation method thereof. The preparation method is characterized by comprising the following steps: taking calcium nitrate or lithium nitrate as an oxidant, polyethylene glycol or polyvinylpyrrolidone as a pore-forming agent and one or two of N,N-dimethylacetamide and N,N-dimethylformamide to prepare a polyacrylonitrile hollow fibrous membrane by a dry-wet method, ensuring monofilaments to enter into a spinneret via other inlets and carrying out blending to prepare the polyacrylonitrile hollow fibrous composite membrane with the supporting materials, wherein the monofilament fibrous materials are polyester, spandex, nylon 6, nylon 66 or polyurethane and have diameter of 0.01-2mm. The membrane and the preparation method have the following beneficial effects: the defect that the hollow fibrous membranes without supports have insufficient physical tensile strength and are easy to suffer from filament break is overcome; the physical tensile strength of the membrane disclosed by the invention is improved by more than several times compared with that of the hollow fibrous membranes without supports; support and membrane stripping can be avoided; the water flux and manufacturing cost of the membrane disclosed by the invention are equivalent to the water flux and manufacturing cost of the hollow fibers without supports; and the membrane can replace the existing hollow fiber products and has great economic and social benefits.
Description
Technical field
The present invention relates to composite, relate in particular to a kind of polyacrylonitrile film with backing material and preparation method thereof.
Background technology
Ultrafiltration is a kind of membrane process between micro-filtration and nanofiltration, is mainly used in big molecule, colloid and particulate in the separation solution, has the separation characteristic of high efficiency, low energy consumption.Along with the continuous development of membrane material and membrane process, hyperfiltration technique has become indispensable in an afternoon nap processing important operation and has wished in recent years.Membrane material and performance are the key factors that influences its application, for reaching high separative efficiency, realize the selectivity place to go of material in the water, and developing new membrane material or studying the new membrane material preparation process is one of focus of current water treatment worker.
Membrane material commonly used at present has cellulose acetate, polysulfones, polyether sulfone, polyacrylonitrile, Kynoar etc., but the cost performance of these materials is lower, has restricted the application of film to a certain extent.Therefore seek a kind of cheaply, good filtration effect, the membrane material that materialization stability is high are extremely important.
Polyacrylonitrile has good hydrophily, good anti-solvent, light resistance, weather, fungus resistance, heat endurance and chemical stability, and is suitable for dry-wet spinning.Yet the mechanical strength of polyacrylonitrile ultrafiltration film is not high, and therefore, preparation intensity polyacrylonitrile hollow-fibre membrane big, good hydrophilic property has important theory and realistic meaning.
Summary of the invention
The objective of the invention is deficiency, proposed a kind of polyacrylonitrile film with backing material and preparation method thereof to existing PAN doughnut membrane technology.
The polyacrylonitrile film of band backing material is: with the filter membrane of polyacrylonitrile material and 3 parallel blending formation of above monfil; Monfil is evenly distributed on the rete center after the film forming; Monfil is terylene, spandex, nylon 6, nylon 66 or polyurethane, and the diameter of monfil is the 0.01-2 millimeter.
The preparation method's of the polyacrylonitrile film of band backing material step is following:
1) concentration is that PAN, the concentration of 12-20 wt/v % are that 4.5-6.5 wt/v % oxidant, concentration are that 5 wt/v % pore formers, concentration are that the solvent of 65-89 wt/v % adds successively and dissolves in the material still; Open the shaft sealing of dissolving the material still and press the hurdle; Under 55-70 ℃; Stirring and evenly mixing removes bubble, obtains casting solution;
2) casting solution is clamp-oned tubular type doughnut spinning nozzle, 35-40 ℃ of casting solution temperature, core liquid is ultrafiltration water; 18-25 ℃ of core liquid temp, room temperature 18-25 ℃, indoor humidity 6-70%; Under the spinning speed of 15-60m/min; Casting solution is extruded by air pressure, gets into the spinning head casting solution through strainer filtering and measuring pump and gets into the hole, and gets into the hole from monfil and gets into the monfil of spinning head and get into deionized water the hole film-forming that after entering coagulating bath after the spinning head generation composite molding, is separated with core liquid; The coagulating bath gel media is the water of steady temperature, and the tank temperature is controlled at 18-25 ℃.
Described oxidant is: calcium nitrate or nitric acid reason.Described pore former is: polyethylene glycol or polyvinylpyrrolidone.The solvent of stating is: N, N-dimethylacetylamide or N, dinethylformamide.
The present invention's beneficial effect compared with prior art is:
1) the physics hot strength is high: because the monfil booster action as reinforcing bar is arranged, the physics hot strength of this product is minimum can be increased more than the several times, and can increase the next doughnut film strength that further increases of quantity of monfil.Usually 3-4 root monfil longitudinal tensile strength can reach more than 1 kgf;
2) membrane material can not peel off: adopt the blending hollow-fibre membrane of kernmantle, coating and kernmantle easy separation are peeled off, and lose filtering function; And adopt this product, because monfil and bulk material have certain compatibility, and, can not take place to separate and peel off, the service life of the film that increases greatly fully by polyacrylonitrile bulk material parcel;
3) cost is lower than the blending hollow-fibre membrane of kernmantle: in the blending hollow-fibre membrane material cost of kernmantle the kernmantle cost to account for over half, so cost will double above than this product;
4) loading density is higher than the blending hollow-fibre membrane of kernmantle, reduces volume, reduces the filter plant cost.The blending hollow-fibre membrane of kernmantle is owing to receive the external diameter size restriction of kernmantle, and often thicker, external diameter is generally more than 2 millimeters; And this product does not have this restriction; External diameter can be accomplished 1.2 millimeters, and the membrane area of unit volume can increase like this, reduces the filter plant volume;
5) because the monofilament of introducing has certain intermiscibility with membrane material, and the volume that is embedded in the film is little, only accounts for the 3-5% of membrane material volume, and is very little to the film forming structure influence, so the water flux of film can reach 280L/m
2H, 0.1MPa, 25 ℃ is more than 2 times of kernmantle structural membrane, suitable with no support hollow tunica fibrosa.
Description of drawings
Fig. 1 is the polyacrylonitrile membrane preparation method schematic flow sheet of band backing material;
Fig. 2 is blending polyacrylonitrile hollow-fibre membrane generalized section and existing two types of PES hollow-fibre membrane generalized sections.
The specific embodiment
The polyacrylonitrile film of band backing material is: with the filter membrane of polyacrylonitrile material and 3 parallel blending formation of above monfil; Monfil is evenly distributed on the rete center after the film forming; Monfil is terylene, spandex, nylon 6, nylon 66 or polyurethane, and the diameter of monfil is the 0.01-2 millimeter.
The preparation method's of the polyacrylonitrile film of band backing material step is following:
1) concentration is that PAN, the concentration of 12-20 wt/v % are that 4.5-6.5 wt/v % oxidant, concentration are that 5 wt/v % pore formers, concentration are that the solvent of 65-89 wt/v % adds successively and dissolves in the material still; Open the shaft sealing of dissolving the material still and press the hurdle; Under 55-70 ℃; Stirring and evenly mixing removes bubble, obtains casting solution;
2) casting solution is clamp-oned tubular type doughnut spinning nozzle, 35-40 ℃ of casting solution temperature, core liquid is ultrafiltration water; 18-25 ℃ of core liquid temp, room temperature 18-25 ℃, indoor humidity 6-70%; Under the spinning speed of 15-60m/min; Casting solution is extruded by air pressure, gets into the spinning head casting solution through strainer filtering and measuring pump and gets into the hole, and gets into the hole from monfil and gets into the monfil of spinning head and get into deionized water the hole film-forming that after entering coagulating bath after the spinning head generation composite molding, is separated with core liquid; The coagulating bath gel media is the water of steady temperature, and the tank temperature is controlled at 18-25 ℃.
Described oxidant is: calcium nitrate or nitric acid reason.Described pore former is: polyethylene glycol or polyvinylpyrrolidone.The solvent of stating is: N, N-dimethylacetylamide or N, dinethylformamide.
Embodiment 1:
1) concentration is that PAN, the concentration of 12 wt/v % are that 4.5 wt/v % calcium nitrate, concentration are that 5 wt/v % polyethylene glycol, concentration are the N of 65 wt/v %; The N-dimethylacetylamide adds to dissolve successively expects in the still; The hurdle is pressed in the shaft sealing of open dissolving the material still, under 55 ℃, and stirring and evenly mixing; Remove bubble, obtain casting solution;
2) casting solution is clamp-oned tubular type doughnut spinning nozzle, 35 ℃ of casting solution temperature, core liquid is ultrafiltration water; 18 ℃ of core liquid temps, 18 ℃ of room temperatures, indoor humidity 6%; Under the spinning speed of 15m/min; Casting solution is extruded by air pressure, gets into the spinning head casting solution through strainer filtering and measuring pump and gets into the hole, and gets into the hole from monfil and gets into the monfil of spinning head and get into deionized water the hole film-forming that after entering coagulating bath after the spinning head generation composite molding, is separated with core liquid; The coagulating bath gel media is the water of steady temperature, and the tank temperature is controlled at 18 ℃.
The polyacrylonitrile film internal diameter of gained band backing material is 1 millimeter, and external diameter is 1.3 millimeters, and average membrane pore size is 0.02 micron, and longitudinal tensile strength is greater than 2 kgfs, and burst pressure is greater than 0.3 MPa, under 0.1 MPa water flux be 240 liters/(square metre hour).
Embodiment 2:
1) concentration is that PAN, the concentration of 20 wt/v % are that 6.5 wt/v % nitric acid reason, concentration are that 5 wt/v % polyvinylpyrrolidones, concentration are the N of 89 wt/v %; Dinethylformamide adds to dissolve successively expects in the still; The hurdle is pressed in the shaft sealing of open dissolving the material still, under 70 ℃, and stirring and evenly mixing; Remove bubble, obtain casting solution;
2) casting solution is clamp-oned tubular type doughnut spinning nozzle, 40 ℃ of casting solution temperature, core liquid is ultrafiltration water; 25 ℃ of core liquid temps, 25 ℃ of room temperatures, indoor humidity 70%; Under the spinning speed of 60m/min; Casting solution is extruded by air pressure, gets into the spinning head casting solution through strainer filtering and measuring pump and gets into the hole, and gets into the hole from monfil and gets into the monfil of spinning head and get into deionized water the hole film-forming that after entering coagulating bath after the spinning head generation composite molding, is separated with core liquid; The coagulating bath gel media is the water of steady temperature, and the tank temperature is controlled at 25 ℃.
The polyacrylonitrile film internal diameter of gained band backing material is 1.1 millimeters, and external diameter is 1.3 millimeters, and average membrane pore size is 0.02 micron, and longitudinal tensile strength is greater than 2 kgfs, and burst pressure is greater than 0.3 MPa, under 0.1 MPa water flux be 250 liters/(square metre hour).
Embodiment 3:
1) polyacrylonitrile concentration 18 wt/v %, oxidant is calcium nitrate 5 wt/v %, and pore former is polyvinylpyrrolidone 5 wt/v %, and solvent is N, N-dimethylacetylamide (DMAc) 70 wt/v %.Under 65 ℃ of temperature, stirred 12 hours, standing and defoaming formed casting solution in 8 hours;
2) casting solution is clamp-oned tubular type doughnut spinning nozzle, core liquid is that temperature is 20 ℃ a ultrafiltration water, 36 ℃ of casting solution temperature; 20 ℃ of room temperatures; Indoor humidity 15%, under the spinning speed of 45m/min, casting solution is extruded by air pressure; Get into spinning head casting solution entering hole through strainer filtering and measuring pump; Get into the monfil of spinning head and get into deionized water the hole film-forming that after getting into coagulating bath after the spinning head generation composite molding, is separated with core liquid with get into the hole from monfil, the coagulating bath gel media is the water of steady temperature, and the tank temperature is controlled at 18 ℃.
Monfil is that diameter is 0.8 millimeter terylene, and quantity is 4.The coagulating bath gel media is the water of steady temperature, and the tank temperature is controlled at 20 ℃.
As shown in Figure 1; Casting solution is driven into spinning head through measuring pump; Monfil gets into spinning head from another inlet simultaneously, after polyacrylonitrile blending film forming, gets into behind the 30cm that under the spinning speed of 45m/min, aloft walks vertically downward in the coagulating bath ultrafiltration water; Film-forming after being separated carries out post processing at last.
The polyacrylonitrile film internal diameter of gained band backing material is 1 millimeter, and external diameter is 1.2 millimeters, and average membrane pore size is 0.02 micron, and longitudinal tensile strength is greater than 2 kgfs, and burst pressure is greater than 0.3 MPa, under 0.1 MPa water flux be 280 liters/(square metre hour).
Embodiment 4
1) concentration is that PAN, the concentration of 12 wt/v % are that 4.5 wt/v % calcium nitrate, concentration are that 5 wt/v % polyethylene glycol, concentration are the N of 65 wt/v %; The N-dimethylacetylamide adds to dissolve successively expects in the still; The hurdle is pressed in the shaft sealing of open dissolving the material still, under 55 ℃, and stirring and evenly mixing; Remove bubble, obtain casting solution;
2) casting solution is clamp-oned tubular type doughnut spinning nozzle, 35 ℃ of casting solution temperature, 18 ℃ of core liquid temps; 18 ℃ of room temperatures; Indoor humidity 6%, under the spinning speed of 15m/min, casting solution is extruded by air pressure; Get into spinning head casting solution entering hole through strainer filtering and measuring pump; Get into the monfil of spinning head and get into deionized water the hole film-forming that after getting into coagulating bath after the spinning head generation composite molding, is separated with core liquid with get into the hole from monfil, the coagulating bath gel media is the water of steady temperature, and the tank temperature is controlled at 18 ℃.
Monfil is that diameter is 1 millimeter a spandex, and quantity is 4.The coagulating bath gel media is the water of steady temperature, and the tank temperature is controlled at 18 ℃.
The polyacrylonitrile film internal diameter of gained band backing material is 0.8 millimeter, and external diameter is 1.2 millimeters, and average membrane pore size is 0.02 micron, and longitudinal tensile strength is greater than 2 kgfs, and burst pressure is greater than 0.25 MPa, under 0.1 MPa water flux be 260 liters/(square metre hour).
Embodiment 5
1) concentration is that PAN, the concentration of 20 wt/v % are that 6.5 wt/v % nitric acid reason, concentration are that 5 wt/v % polyvinylpyrrolidones, concentration are the N of 89 wt/v %; Dinethylformamide adds to dissolve successively expects in the still; The hurdle is pressed in the shaft sealing of open dissolving the material still, under 70 ℃, and stirring and evenly mixing; Remove bubble, obtain casting solution;
2) casting solution is clamp-oned tubular type doughnut spinning nozzle, 40 ℃ of casting solution temperature, 25 ℃ of core liquid temps; 25 ℃ of room temperatures; Indoor humidity 70%, under the spinning speed of 60m/min, casting solution is extruded by air pressure; Get into spinning head casting solution entering hole through strainer filtering and measuring pump; Get into the monfil of spinning head and get into deionized water the hole film-forming that after getting into coagulating bath after the spinning head generation composite molding, is separated with core liquid with get into the hole from monfil, the coagulating bath gel media is the water of steady temperature, and the tank temperature is controlled at 18 ℃.
Monfil is that diameter is 0.8 millimeter a nylon 6, and quantity is 3.The coagulating bath gel media is the water of steady temperature, and the tank temperature is controlled at 25 ℃.
The polyacrylonitrile film internal diameter of gained band backing material is 0.9 millimeter, and external diameter is 1.2 millimeters, and average membrane pore size is 0.02 micron, and longitudinal tensile strength is greater than 2 kgfs, and burst pressure is greater than 0.3 MPa, under 0.1 MPa water flux be 255 liters/(square metre hour).
Structure of the present invention is similar to reinforced concrete structure, and PAN is equivalent to concrete, and the monfil reinforcement is equivalent to reinforcing bar, forms quantity (common more than 3) and intensity that whole back physics hot strength depends on monfil, and the PAN material plays filtering function.
Because this product physics hot strength is high; Membrane material is incrust; Manufacturing cost and water flux are suitable with no supporter hollow-fibre membrane, can replace existing two types of hollow-fibre membranes (the blending hollow-fibre membrane of no supporter hollow-fibre membrane, kernmantle) fully; Be specially:
Adopt the Hollow Fiber Ultrafiltration assembly or the MBR membrane bioreactor of this production to compare, owing to do not exist fracture of wire problem, filter effect can guarantee that can significantly prolong service life with no supporter hollow-fibre membrane.
At last, what need particularly point out is that what more than to enumerate only is practical implementation case of the present invention.Obviously, the invention is not restricted to above-mentioned case study on implementation, can also many combinations.The all scenario that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
The present invention is a kind of advanced composite material (ACM), and strainability is good, but the PAN material that mechanical strength is short of to some extent mixes formed novel filter membrane with the monfil with excellent mechanical property with certain method.
Claims (5)
1. polyacrylonitrile film with backing material; It is characterized in that filter membrane with polyacrylonitrile material and 3 parallel blending formation of above monfil; Monfil is evenly distributed on the rete center after the film forming; Monfil is terylene, spandex, nylon 6, nylon 66 or polyurethane, and the diameter of monfil is the 0.01-2 millimeter.
2. the preparation method of an a kind of polyacrylonitrile film with backing material as claimed in claim 1 is characterized in that its step is following:
1) concentration is that PAN, the concentration of 12-20 wt/v % are that 4.5-6.5 wt/v % oxidant, concentration are that 5 wt/v % pore formers, concentration are that the solvent of 65-89 wt/v % adds successively and dissolves in the material still; Open the shaft sealing of dissolving the material still and press the hurdle; Under 55-70 ℃; Stirring and evenly mixing removes bubble, obtains casting solution;
2) casting solution is clamp-oned tubular type doughnut spinning nozzle, 35-40 ℃ of casting solution temperature, core liquid is ultrafiltration water; 18-25 ℃ of core liquid temp, room temperature 18-25 ℃, indoor humidity 6-70%; Under the spinning speed of 15-60m/min; Casting solution is extruded by air pressure, gets into the spinning head casting solution through strainer filtering and measuring pump and gets into the hole, and gets into the hole from monfil and gets into the monfil of spinning head and get into deionized water the hole film-forming that after entering coagulating bath after the spinning head generation composite molding, is separated with core liquid; The coagulating bath gel media is the water of steady temperature, and the tank temperature is controlled at 18-25 ℃.
3. the preparation method of a kind of polyacrylonitrile film with backing material according to claim 2 is characterized in that described oxidant is: calcium nitrate or nitric acid reason.
4. the preparation method of a kind of polyacrylonitrile film with backing material according to claim 2 is characterized in that described pore former is: polyethylene glycol or polyvinylpyrrolidone.
5. the preparation method of a kind of polyacrylonitrile film with backing material according to claim 2 is characterized in that described solvent is: N, N-dimethylacetylamide or N, dinethylformamide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103041717A (en) * | 2013-01-14 | 2013-04-17 | 海南立昇净水科技实业有限公司 | Yarn fiber reinforced double-layer tubular filtering membrane and method for preparing same |
| CN104548960A (en) * | 2014-11-05 | 2015-04-29 | 华文蔚 | Preparation method of hollow fibrous polyvinyl chloride resin microporous membrane |
| CN105544019A (en) * | 2015-12-16 | 2016-05-04 | 华南理工大学 | High oil-absorbing polyacrylonitrile hollow activated carbon fiber and preparation method thereof |
| EP3095508A1 (en) | 2015-04-20 | 2016-11-23 | Tianjin Polytechnic University | Method for preparing homogeneous braid-reinforced ppta hollow fiber membrane |
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| CN1887414A (en) * | 2005-06-28 | 2007-01-03 | 浙江四通环境工程有限公司 | Prepn process of ultrafiltering hollow fiber membrane with inner modified polyacrylonitrile layer |
| CN102151489A (en) * | 2011-03-21 | 2011-08-17 | 凌雪萍 | Multi-core hollow fiber porous membrane and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1504257A (en) * | 2002-11-29 | 2004-06-16 | 中国科学院生态环境研究中心 | Preparation method of high-flux porous membrane |
| CN1887414A (en) * | 2005-06-28 | 2007-01-03 | 浙江四通环境工程有限公司 | Prepn process of ultrafiltering hollow fiber membrane with inner modified polyacrylonitrile layer |
| CN102151489A (en) * | 2011-03-21 | 2011-08-17 | 凌雪萍 | Multi-core hollow fiber porous membrane and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103041717A (en) * | 2013-01-14 | 2013-04-17 | 海南立昇净水科技实业有限公司 | Yarn fiber reinforced double-layer tubular filtering membrane and method for preparing same |
| CN103041717B (en) * | 2013-01-14 | 2015-07-15 | 海南立昇净水科技实业有限公司 | Yarn fiber reinforced double-layer tubular filtering membrane and method for preparing same |
| CN104548960A (en) * | 2014-11-05 | 2015-04-29 | 华文蔚 | Preparation method of hollow fibrous polyvinyl chloride resin microporous membrane |
| EP3095508A1 (en) | 2015-04-20 | 2016-11-23 | Tianjin Polytechnic University | Method for preparing homogeneous braid-reinforced ppta hollow fiber membrane |
| CN105544019A (en) * | 2015-12-16 | 2016-05-04 | 华南理工大学 | High oil-absorbing polyacrylonitrile hollow activated carbon fiber and preparation method thereof |
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Application publication date: 20120328 |