CN101269301B - Method for preparing internal air pressure type hollow fiber compound film component - Google Patents
Method for preparing internal air pressure type hollow fiber compound film component Download PDFInfo
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- CN101269301B CN101269301B CN2008100530426A CN200810053042A CN101269301B CN 101269301 B CN101269301 B CN 101269301B CN 2008100530426 A CN2008100530426 A CN 2008100530426A CN 200810053042 A CN200810053042 A CN 200810053042A CN 101269301 B CN101269301 B CN 101269301B
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Abstract
The invention relates to a preparation method of internal pressure type hollow fiber composite membrane module, the preparation method comprises the following technical processes: 1. conventional equipment is adopted to weave an internal pressure type hollow fiber ultra-filtration membrane; 2. the membrane module is manufactured using the ultra-filtration membrane in the step 1 and leakage detection is performed; 3. the qualified membrane module is placed into coating solution for 30 seconds to 10 minutes for immersion coating and the temperature for immersion coating is 15 to 45 DEG C; 4. the inner wall of the membrane of the coated membrane module is blown and swept with dry and clean compressed air or N2, the water content of the membrane surface is controlled from 5 to 30 percent; 5. the cleaned membrane module is dipped in cross-linking fluid which is used for realizing interface reaction to produce the composite membrane or the cross-linking fluid is infused into the inner cavity of the membrane from the upper end of the membrane module to produce the composite membrane; 6. the membrane module which has completed cross-linking reaction is immediately immersed into water bathand is sealed up for future usage, thus, the internal pressure type hollow fiber composite membrane module is obtained.
Description
Technical field
The present invention relates to a kind of membrane preparation technology, be specially a kind of preparation method of inner pressed hollow fiber composite membrane assembly, international monopoly Main classification number plan is Int.Cl.B01D 69/00 (2006.01).
Background technology
Relevant hollow fiber composite membrane technology has report more.Applicant (or inventor) 4 patents or patent application (200510013569.2 formerly; 200510014733.1; 200510133639.8 and 200610013428.5) all relate to hollow fiber composite membrane.Wherein, related composite film material all is the prepolymer of acrylic compounds in preceding 3 patents, forms by interface-cross-linked method to have the active layer of separation function, and all is interior press molds.Because the prepolymer coating is thicker, the water flux of these hollow fiber composite membranes and the ability of separating inorganic salts are not ideal enough.The 4th above-mentioned application for a patent for invention is that the outer wall at the polysulfone hollow fibre milipore filter applies little molecule organic amide monomer, carries out the hollow fiber composite membrane of crosslinked preparation then.This film is external-compression type hollow fiber composite membrane (being called for short outer press mold, referring to Fig. 2).This composite membrane must be to film through water-soluble monomer on the hollow fiber ultrafiltration membrane coating machine in process of production, immerse then carry out in the crosslinking agent monomer organic solvent interface-cross-linked, realize the transition of film after, the bunchy pouring becomes corresponding assembly again.But this method can not be filming behind the basement membrane elder generation bunchy again, otherwise because outer surface has coating that doughnut is sticked together, and therefore wants complicated many on the production technology of membrane module, and cost is higher, and quality control is also difficult.
Summary of the invention
At the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is to propose a kind of preparation method of inner pressed hollow fiber composite membrane assembly.This preparation method is applicable to the high-performance inner pressed hollow fiber composite membrane of preparation active layer at the basement membrane inwall, and it is simple to have technology, and is with low cost, use equipment is simple, and energy consumption reduces, and the preparation film is easy, and good, the steady quality of film properties of product is suitable for characteristics such as heavy industrialization application.
The technical scheme that the present invention solves described preparation method's technical problem is: design a kind of preparation method of inner pressed hollow fiber composite membrane assembly, this preparation method comprises following technical process:
(1). adopt conventional equipment spinning inner pressed hollow fiber ultrafiltration membrane, its internal diameter is 0.4～0.65mm, and external diameter is 0.9～1.2mm, and molecular cut off is 20000～50000 dalton; The milipore filter of gained is in water-bath fully after the washing, and placing mass concentration is that 45～100% glycerine soaks 12～48h, and it is standby to control clean glycerine then; The material of described milipore filter can be selected a kind of in polysulfones, polyacrylonitrile, Kynoar, polyether sulfone or the cellulose acetate for use; Described milipore filter is that inner surface is the film of compacted zone;
(2). make membrane module with described milipore filter of (1) step, and hunt leak;
(3). the membrane module that is up to the standards is placed the coating liquid dip-coating, and time of immersion is 30 seconds～10 minutes, and the temperature of dip-coating circulation coating liquid is 15～45 ℃; Described coating liquid is that the shared volume ratio of ethanol is≤25% the aqueous solution, and contains first monomer and additive; Described first monomer is m-phenylene diamine (MPD), piperazine, a kind of in 2.5-two amido benzene sulfonic acids or the polymine, and first monomer shared weight ratio in coating liquid is 0.3～3.5%; Described additive is a kind of in isopropyl alcohol, triethylamine or the dodecyl sodium sulfate, and additive shared weight ratio in coating liquid is 0.15-3%.
(4). with compressed air or the N of the membrane module after the dip-coating with dried and clean
2Gas purges the inwall of film, and described compressed-air actuated pressure is 0.005～0.025MPa, and purge time is 0.5-2 minute, and the surperficial water content of controlling diaphragm is 5～30%, and can not retain drop on the inwall of film;
(5). the membrane module after the cleaning is immersed in the crosslinked fluid of realizing interfacial reaction produces composite membrane, perhaps the inner chamber that crosslinked fluid is injected described film from the membrane module upper end is produced composite membrane, will fully the flow through inwall of film of crosslinked fluid is realized interfacial reaction, and the crosslinked fluid of outflow reclaims; The mass concentration of crosslinked fluid is 0.1～1.5%, and crosslinking time is 10 seconds～2 minutes, and the cross-linking reaction temperature is 15～25 ℃, and is after reaction is finished that membrane module is upright, controls clean organic facies; Described crosslinked fluid is to be solvent with n-hexane, normal heptane or benzinum, and with m-phthaloyl chloride, a kind of in paraphthaloyl chloride or the pyromellitic trimethylsilyl chloride is the formulated solution of crosslinking agent monomer;
(6). the membrane module that will finish cross-linking reaction immerses in the water-bath immediately, and bath temperature is 25～35 ℃, embathe 1-4 hour after, implantation quality concentration is 0.5% NaHSO in membrane module
3The aqueous solution is as anticorrisive agent, seals up for safekeeping stand-byly, promptly makes described inner pressed hollow fiber composite membrane assembly.
With prior art the (as the aforementioned the 1st, 2,3 patents of invention are to utilize the inwall at the doughnut basement membrane at first to be coated with the last layer macromolecule prepolymer, form the method for functional layer again by interface-cross-linked method) compare, the preparation method of inner pressed hollow fiber composite membrane assembly of the present invention is at the direct dip-coating coating liquid of membrane module, make little molecule organic amide monomer wherein form functional layer by interface-cross-linked reaction, the ability of the water flux of the membrane module of the present invention of Chan Shenging and separating inorganic salts is better than prior art therefrom: under 0.7MPa pressure, membrane flux of the present invention is 40L/m
2H, prior art is 15L/m
2About h; The present invention is 1%MgSO to mass concentration
4MgSO in the aqueous solution
4Rejection about 95%, prior art is about 90%.In addition,
The preparation method of inner pressed hollow fiber composite membrane assembly of the present invention also has following tangible advantage:
1. preparation technology is simple, when for example preparing external-compression type hollow fiber composite membrane assembly, for preventing to cause adhesion because of outer wall has coating, after the composite bed film forming, must after suitable drying, could cast by bunchy, therefore need equipment (referring to patent application 200610013428.5) such as special-purpose coating machine, drying machine.And the coating process of inner pressed film of the present invention is very simple, only need on the hyperfiltration membrane assembly that makes, to apply water-soluble monomer, inject the crosslinking agent monomer solution in hollow fiber cavity then and carry out interfacial reaction, can finish transition from milipore filter to the composite membrane assembly, do not need special coating equipment, thereby technology is simple, and is with low cost, is suitable for industrialization promotion and uses.Being coated with method in this is an innovation part of the present invention.
2. preparation method's gained of the present invention be a kind of inner pressed hollow fiber composite membrane assembly, its work of separation ergosphere is attached to the inwall (referring to Fig. 1) of doughnut basement membrane.Because it is the doughnut form, so this film has bigger specific area, the loading density of membrane module is big.
3. preparation method's gained of the present invention be that a kind of inner pressed hollow fiber composite membrane assembly has the function of nanofiltration or counter-infiltration, can remove the water-soluble substanceses such as inorganic salts, colourity and COD in the water body, and can under low pressure operate, its operating pressure is below 1MPa, general work pressure is at 0.5～0.7MPa, therefore all optional engineering plastics of using such as the required pipeline of whole system, valve, system cost is cheap, is convenient to actual applying.
Description of drawings
Fig. 1 is the structural representation of inner pressed hollow fiber composite membrane of the present invention.Among Fig. 11 is supporting layer; 2 is composite bed.
Fig. 2 is the structural representation of the external-compression type hollow fiber composite membrane corresponding with inner pressed hollow fiber composite membrane of the present invention.Among Fig. 21 is supporting layer; 2 is composite bed.
The specific embodiment
Further narrate the present invention below in conjunction with embodiment and accompanying drawing thereof:
The preparation method (hereinafter to be referred as the preparation method) of the inner pressed hollow fiber composite membrane assembly of the present invention's design comprises following technical process:
1. adopt conventional equipment spinning inner pressed hollow fiber ultrafiltration membrane (hereinafter to be referred as milipore filter), its internal diameter is 0.4～0.65mm, and external diameter is 0.9～1.2mm, and molecular cut off is 20000～50000 dalton; The milipore filter of gained is in water-bath fully after the washing, and placing mass concentration is that 45～100% glycerine soaks 12～48h, and it is standby to control clean glycerine then; The material of described milipore filter can be selected a kind of in polysulfones (PSF), polyacrylonitrile (PAN), Kynoar (PVDF), polyether sulfone (PES) or the cellulose acetate (CA) for use; Described milipore filter is that inner surface is the film of compacted zone (being usually said single skin structure).
2. make membrane module with described milipore filter of the 1st step, be included in the milipore filter that fills the clean glycerine of control of the present invention in the shell of membrane module, two ends with epoxy adhesive pouring milipore filter, after curing and cutting, membrane module is fully washed, flush away glycerine up hill and dale, and membrane module hunted leak; Carry out faces end head plugging for the milipore filter that seepage is arranged;
3. the membrane module that is up to the standards is placed the coating liquid dip-coating, time of immersion is 30 seconds～10 minutes, and the temperature of dip-coating circulation coating liquid is 15～45 ℃; Described coating liquid is that the shared volume ratio of ethanol is≤25% the aqueous solution, and contains first monomer and additive; Described first monomer is m-phenylene diamine (MPD), piperazine, a kind of in 2.5-two amido benzene sulfonic acids or the polymine, and first monomer shared weight ratio in coating liquid is 0.3～3.5%; Described additive is a kind of in isopropyl alcohol, triethylamine or the dodecyl sodium sulfate, and additive shared weight ratio in coating liquid is 0.15-3%.
In the dip-coating process of the present invention, should guarantee that the inwall of every film fully contacts with coating liquid all, so that dip-coating or coating are evenly.
4. with compressed air or the N of the membrane module after the dip-coating with dried and clean
2Gas purges the inwall of film, and described compressed-air actuated pressure is 0.005～0.025MPa, and purge time is 0.5～2 minute, and the surperficial water content of controlling diaphragm is 5～30%, and can not retain drop on the inwall of film.
5. the membrane module after the cleaning is immersed in the crosslinked fluid of realizing interfacial reaction and produces composite membrane, perhaps the inner chamber that crosslinked fluid is injected described film from the membrane module upper end is produced composite membrane, will fully the flow through inwall of film of crosslinked fluid is realized interfacial reaction, and the crosslinked fluid of outflow reclaims; The mass concentration of crosslinked fluid is 0.1～1.5%, and crosslinking time is 10 seconds～2 minutes, and the cross-linking reaction temperature is 15～25 ℃, and is after reaction is finished that membrane module is upright, controls clean organic facies; Described crosslinked fluid is to be solvent with n-hexane, normal heptane or benzinum, and with m-phthaloyl chloride, a kind of in paraphthaloyl chloride or the pyromellitic trimethylsilyl chloride is the formulated solution of crosslinking agent monomer.
6. the membrane module that will finish cross-linking reaction immerses in the water-bath immediately, and bath temperature is 25～35 ℃, embathe 1-4 hour after, implantation quality concentration is 0.5% NaHSO in membrane module
3The aqueous solution is as anticorrisive agent, seals up for safekeeping stand-byly, promptly makes described inner pressed hollow fiber composite membrane assembly.
Film in the prepared membrane module of preparation method embodiment of the present invention is an inner pressed doughnut composite nanometer filtering film.Preparation method of the present invention forms crosslinked compacted zone or active layer by the interfacial polymerization with multi-functional two kinds of monomers on the inwall of hollow fiber ultrafiltration membrane, its aperture is several to tens
(10
-10M).The prepared composite nanometer filter membrane module of preparation method of the present invention can be operated under 1MPa pressure, generally can work under 0.5～0.7MPa pressure, belongs to the low-pressure membrane assembly; To the high price inorganic ions removal efficiency of water body 90～98%, to the removal efficiency of monovalence inorganic ions in the water body 30～90%; The removal efficiency of the coloring matter in the water body is 60～90%.When salt content when mass concentration is 0.1% left and right sides, the flux of water is 20L～60L/m
2.L, effect is remarkable.Not only described composite nanometer filtering film can be prepared with preparation method of the present invention, but also complex reverse osmosis membrane can be prepared.With the prepared reverse osmosis membrane of preparation method of the present invention to the removal efficiency of inorganic salts 95～99%, when salt content when mass concentration is 0.1% left and right sides, the flux of water is 20～50L/m
2H (0.7MPa), effect is obvious.
The present invention does not address part and is applicable to prior art.
Provide specific embodiments of the invention below.But claim of the present invention is not subjected to the restriction of embodiment:
Embodiment 1:
Adopting conventional method spinning basement membrane is molecular cut off 20000 daltonian polysulfone hollow fibre milipore filters, and the external diameter of gained hollow-fibre membrane is 1.2mm, and internal diameter is 0.8mm, and pure water flux is 700L/m
2H (25 ℃, 0.1MPa under); The pouring of gained film is become hyperfiltration membrane assembly, when washing removes glycerine in the striping and spinning, behind the residual additive, hunt leak, will have the film of leak source to block with epoxy resin; After confirming no leak source, under room temperature on the ultrafiltration apparatus, containing mass concentration in the circulation of the inner chamber of hollow-fibre membrane is that 1% triethylamine and mass concentration are the aqueous solution of 2% piperazine, pressure is controlled at 0.03MPa, circulated 4 minutes, inner chamber to hollow-fibre membrane is blown into compressed air then, and the air compressor machine outlet pressure is 0.05MPa, the every about 100L/m of doughnut air-blowing quantity
2H blew 1 minute, made the inwall of hollow-fibre membrane reach the state of substantially dry; Then membrane module immersed mass concentration and is in 0.5% the pyromellitic trimethylsilyl chloride n-heptane solution, soaked for 30 seconds, take out the clean organic solution of control, with membrane module immerse soak 12 hours in the deionized water after, promptly pour into anticorrisive agent and seal up for safekeeping standby.
Through check, the gained membrane module is 0.1%MgSO to mass concentration
4The aqueous solution is under 25 ℃, 0.06MPa intake pressure, and salt rejection rate is 97%, and water flux reaches 36L/m
2H; To mass concentration is that the salt rejection rate of the 0.1%NaCl aqueous solution reaches 30%.
Claims (1)
1. the preparation method of an inner pressed hollow fiber composite membrane assembly, this preparation method comprises following technical process:
(1). adopt conventional equipment spinning inner pressed hollow fiber ultrafiltration membrane, its internal diameter is 0.4～0.65mm, and external diameter is 0.9～1.2mm, and molecular cut off is 20000～50000 dalton; The milipore filter of gained is in water-bath fully after the washing, and placing mass concentration is that 45～100% glycerine soaks 12～48h, and it is standby to control clean glycerine then; The material of described milipore filter can be selected a kind of in polysulfones, polyacrylonitrile, Kynoar, polyether sulfone or the cellulose acetate for use; Described milipore filter is that inner surface is the film of compacted zone;
(2). make membrane module with described milipore filter of (1) step, and hunt leak;
(3). the membrane module that is up to the standards is placed the coating liquid dip-coating, and time of immersion is 30 seconds～10 minutes, and the temperature of dip-coating circulation coating liquid is 15～45 ℃; Described coating liquid is that the shared volume ratio of ethanol is≤25% the aqueous solution, and contains first monomer and additive; Described first monomer is m-phenylene diamine (MPD), piperazine, a kind of in 2.5-two amido benzene sulfonic acids or the polymine, and first monomer shared weight ratio in coating liquid is 0.3～3.5%; Described additive is a kind of in isopropyl alcohol, triethylamine or the dodecyl sodium sulfate, and additive shared weight ratio in coating liquid is 0.15-3%;
(4). with compressed air or the N of the membrane module after the dip-coating with dried and clean
2Gas purges the inwall of film, and described compressed-air actuated pressure is 0.005～0.025MPa, and purge time is 0.5-2 minute, and the surperficial water content of controlling diaphragm is 5～30%, and can not retain drop on the inwall of film;
(5). the membrane module after the cleaning is immersed in the crosslinked fluid of realizing interfacial reaction produces composite membrane, perhaps the inner chamber that crosslinked fluid is injected described film from the membrane module upper end is produced composite membrane, the crosslinked fluid inwall of will fully flowing through is realized interfacial reaction, and the crosslinked fluid of outflow reclaims; The mass concentration of crosslinked fluid is 0.1～1.5%, and crosslinking time is 10 seconds～2 minutes, and the cross-linking reaction temperature is 15～25 ℃, and is after reaction is finished that membrane module is upright, controls clean organic facies; Described crosslinked fluid is to be solvent with n-hexane, normal heptane or benzinum, and with m-phthaloyl chloride, a kind of in paraphthaloyl chloride or the pyromellitic trimethylsilyl chloride is the formulated solution of crosslinking agent monomer;
(6). the membrane module that will finish cross-linking reaction immerses in the water-bath immediately, and bath temperature is 25～35 ℃, embathe 1-4 hour after, implantation quality concentration is 0.5% NaHSO in membrane module
3The aqueous solution is as anticorrisive agent, seals up for safekeeping stand-byly, promptly makes described inner pressed hollow fiber composite membrane assembly.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102500244A (en) * | 2011-11-30 | 2012-06-20 | 杭州水处理技术研究开发中心有限公司 | Preparation method of reverse osmosis composite membrane for sea water desalinization |
| CN102643495B (en) * | 2012-04-27 | 2014-06-11 | 天津工业大学 | Preparation method of double-component polymer blend material |
| CN106659978B (en) | 2014-08-21 | 2020-07-03 | 旭化成株式会社 | Composite hollow fiber membrane module and method for producing same |
| CN105126650B (en) * | 2015-08-16 | 2017-08-08 | 哈尔滨工业大学宜兴环保研究院 | A kind of preparation method for separating antibiotic NF membrane |
| CN110917912B (en) * | 2019-12-09 | 2021-09-24 | 南京惟新环保装备技术研究院有限公司 | Internal pressure type composite hollow fiber nanofiltration membrane yarn and preparation method thereof |
| CN110935327A (en) * | 2019-12-30 | 2020-03-31 | 碧菲分离膜（大连）有限公司 | Internal pressure formula hollow fiber receives filter membrane production line |
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|---|---|---|---|---|
| CN1103814A (en) * | 1993-12-18 | 1995-06-21 | 中国科学院生态环境研究中心 | Method for fabricating composite hellow fibre ultrafiltration film and the products |
| CN1029822C (en) * | 1987-07-10 | 1995-09-27 | 联合碳化公司 | Composite membranes and their manufacture and use |
| CN1318127C (en) * | 2004-02-16 | 2007-05-30 | 中国科学院大连化学物理研究所 | Composite hollow fiber membrane and its preparation and application |
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2008
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1029822C (en) * | 1987-07-10 | 1995-09-27 | 联合碳化公司 | Composite membranes and their manufacture and use |
| CN1103814A (en) * | 1993-12-18 | 1995-06-21 | 中国科学院生态环境研究中心 | Method for fabricating composite hellow fibre ultrafiltration film and the products |
| CN1318127C (en) * | 2004-02-16 | 2007-05-30 | 中国科学院大连化学物理研究所 | Composite hollow fiber membrane and its preparation and application |
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