CN103521090A - Production process of hydrophilic polyvinylidene fluoride hollow fiber membrane - Google Patents
Production process of hydrophilic polyvinylidene fluoride hollow fiber membrane Download PDFInfo
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- CN103521090A CN103521090A CN201310440669.8A CN201310440669A CN103521090A CN 103521090 A CN103521090 A CN 103521090A CN 201310440669 A CN201310440669 A CN 201310440669A CN 103521090 A CN103521090 A CN 103521090A
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Abstract
The invention discloses a production process of a hydrophilic polyvinylidene fluoride hollow fiber membrane, which is completed in a continuous production system. The process specifically comprises the following steps of uniformly mixing polyvinylidene fluoride resin, a pore-foaming agent, organic base polyethylene polyamine and a solvent in a reaction kettle for reacting so as to prepare a membrane casting solution, extruding the membrane casting solution through a spinning head to prepare a semi-finished product hollow fiber membrane, then sequentially conveying the semi-finished product hollow fiber membrane by a guide roller to pass through a first modification tank and a second modification tank to perform modification treatment, and then preparing the hydrophilic polyvinylidene fluoride hollow fiber membrane after modification treatment. According to the production process disclosed by the invention, the semi-finished product hollow fiber membrane is continuously conveyed by the guide roller into the first and second modification tanks for modification treatment, and the continuous and fast production of the hydrophilic polyvinylidene fluoride hollow fiber membrane can be realized, which is equivalent to the situation that the continuously extruded semi-finished product hollow fiber membrane is continuously washed in an on-line manner in a conveying process, so that the production period is short.
Description
Technical field
The present invention relates to hydrophilicity kynoar hollow-fibre membrane production field, be specifically related to a kind of production technology of hydrophilicity kynoar hollow-fibre membrane.
Background technology
Kynoar is a kind of macromolecular material of function admirable, has good chemical stability, heat endurance and mechanical strength, therefore as membrane material, is widely used in the fields such as ultrafiltration, micro-filtration, film distillation, gas separation membrane process.Because the film surface that Kynoar is made can be low, present stronger hydrophobicity, easily produce adsorptivity and pollute, hindered polyvinylidene fluoride film and further applied.In recent years, researcher is devoted at Kynoar main chain or film surface, to introduce various hydrophilic radicals to improve the hydrophily on polyvinylidene fluoride film surface by method of modifying always.Wherein, alkali treatment is to improve the effective method of polyvinylidene fluoride film hydrophilically, and the two keys that generate after processing have certain reactivity, and two keys can directly carry out graft reaction, or carry out graft modification with hydrophilic monomer again after being oxidized to hydroxyl, carboxyl.
Highly basic is processed polyvinylidene fluoride film to improve its hydrophily, the reaction that mainly utilizes Kynoar to be easy to remove hydrogen fluorine under alkali condition comes substep to carry out surface chemical modification, at present, the main two-step method that adopts is prepared hydrophilicity kynoar film, after being Kynoar film forming, then adopt inorganic strong alkali and oxidant to make hydrophilicity kynoar film.
goal of the invention
The object of the present invention is to provide a kind of production technology of hydrophilicity kynoar hollow-fibre membrane, it can carry out the production of hydrophilicity kynoar hollow-fibre membrane continuously, and with short production cycle.
The present invention adopts following technical scheme for achieving the above object:
A kind of production technology of hydrophilicity kynoar hollow-fibre membrane, it is to complete in continuous process system, continuous process system comprises reactor and the core flow container that mixes reaction for each raw material, the liquid outlet of the discharging opening of reactor and core flow container is connected with the charging aperture of spinneret respectively, the discharging opening place of spinneret arranges respectively the first modification groove of splendid attire liquor potassic permanganate and the second modification groove of splendid attire solution of sodium bisulfite successively, arranges respectively semi-finished product hollow-fibre membrane is carried out to the deflector roll of carrying continuously on first and second modification groove;
This technique specifically comprises the steps: that polyvinylidene fluoride resin, pore-foaming agent, organic base polyethylene polyamine and solvent are mixed to reaction in reactor is prepared into casting solution, casting solution is extruded and made semi-finished product hollow-fibre membrane by spinneret, then successively semi-finished product hollow-fibre membrane is carried and carried out modification by first and second modification groove by deflector roll, after modification, can make this hydrophilicity kynoar hollow-fibre membrane.
The present invention by carrying out the production of hydrophilicity kynoar hollow-fibre membrane in above-mentioned continuous process system, each raw material mixes reaction in reactor, mixing core liquid in reacted casting solution and core flow container is delivered to continuously spinneret simultaneously and pushes and obtain semi-finished product hollow-fibre membrane, semi-finished product hollow-fibre membrane is delivered to first continuously by deflector roll, in two modification grooves, carry out can making this hydrophilicity kynoar hollow-fibre membrane after modification, above-mentioned technique can realize hydrophilicity kynoar hollow-fibre membrane and produce fast continuously, the semi-finished product hollow-fibre membrane that it is equivalent to extrude continuously carries out continuous on-line cleaning in course of conveying, therefore with short production cycle.For the continuity that guarantees to produce, a plurality of reactors (more than two) can be set, the discharging opening of a plurality of reactors is connected and is connected with the charging aperture of spinneret respectively, in a reactor, casting solution unloads while discharging like this, in another reactor, drop into raw material and mix reaction, in each reactor, alternately to spinneret supply casting solution, assurance hydrophilicity kynoar hollow-fibre membrane is produced continuously.
Accompanying drawing explanation
Fig. 1 is the structural representation of the continuous process system that adopts of the present invention.
The specific embodiment
By concrete operation, the present invention is described in further detail below.
The production technology of hydrophilicity kynoar hollow-fibre membrane provided by the invention, its special feature, that this technique completes in continuous process system as shown in Figure 1, this continuous process system comprises the reactor 11 that mixes reaction for each raw material, the liquid outlet of the discharging opening of reactor 11 and core flow container 112 is connected with the charging aperture of spinneret 12, the discharging opening place of spinneret 12 arranges respectively the first modification groove 13 of splendid attire liquor potassic permanganate and the second modification groove 14 of splendid attire solution of sodium bisulfite successively, first, two modification grooves 13, on 14, arrange respectively semi-finished product hollow-fibre membrane is carried out to the deflector roll 131 of carrying continuously.Continuous process system also comprises the core flow container 183 that stores core liquid, the liquid outlet of core flow container 183 is connected and is connected with the feed liquor of spinneret 12 by connecting pipe, the liquid outlet of core flow container 183 is also provided with the second measuring pump 182, and core liquid is 0.5～2wt% potassium permanganate solution.The setting of deflector roll 131 should make the semi-finished product hollow-fibre membrane of its conveying contact mutually with the tank liquor of first and second modification groove 13,14, semi-finished product hollow-fibre membrane is carried out to modification, preferably make semi-finished product hollow-fibre membrane inner through the tank liquor of first and second modification groove 13,14.
During operation, taking polyvinylidene fluoride resin, pore-foaming agent, organic base polyethylene polyamine and solvent adds respectively in reactor 11, be heated to stir and evenly mix reaction 23～25h at 59～60 ℃ and be prepared into casting solution, the polyvinylidene fluoride resin, the pore-foaming agent of 2～10 wt% and the organic base of 2～30 wt% that in the casting solution of preparation, contain 12～30 wt%, surplus is solvent;
Then the discharging opening of opening reactor 11 is delivered to spinneret 12 by casting solution, the liquid outlet of simultaneously opening core flow container 183 is delivered to spinneret 12 by core liquid, through spinneret 12, be crushed to semi-finished product hollow-fibre membrane, then successively semi-finished product hollow-fibre membrane is carried and carried out modification by first and second modification groove 13,14 by deflector roll 131, can make this hydrophilicity kynoar hollow-fibre membrane.
Aforesaid operations method Raw pore-foaming agent can be one or more in polyvinylpyrrolidone, polyethylene glycol, lithium chloride, and solvent can be selected DMF, DMA or 1-METHYLPYRROLIDONE.
The tank liquor of first and second modification groove 13,14 interior splendid attires is respectively 1～5wt% liquor potassic permanganate and 2～6wt% solution of sodium bisulfite, better for semi-finished product hollow-fibre membrane modified effect to obtain, simultaneously, also can be by controlling the transporting velocity of 131 pairs of semi-finished product hollow-fibre membranes of deflector roll, control the profit reduction and reserving time of semi-finished product hollow-fibre membrane in first and second modification groove 13,14 tank liquors, to obtain best modified effect.
Concrete is: between reactor 11 and spinneret 12, be also provided with the filter 15 for casting solution is filtered, the charging aperture of filter 15 is connected and is connected with the discharging opening of reactor 11, and the discharging opening of filter 15 is connected and is connected with the charging aperture of spinneret 12.In the second described modification groove 14, be also provided with the reel storing roller 16 of storing of hydrophilicity kynoar hollow-fibre membrane to making, rotate on the cell wall of the second modification groove 14 at storing roller 16 two ends, storing roller 16 axially and axially the paralleling of deflector roll 131.Continuous process system also comprises is convenient to the conveying mechanism that the interior casting solution of reactor 11 is delivered to spinneret 12, conveying mechanism comprises a pressure gas source, pressure gas source output gas is discharged from the discharging opening of reactor 11 bottoms to the top area of absence extruding casting solution in reactor 11, and discharging opening place is provided with valve 19 and the first measuring pump 181.The hydrophilicity kynoar hollow-fibre membrane making so is just wound onto on storing roller 16, and the two ends of storing roller 16 should be detachable with the cell wall of the second modification groove 14 and are connected, and are convenient to unloading and the assembling of storing roller 16.Filter 15 is mainly that the impurity in casting solution is filtered, and guarantees the quality of the hydrophilicity kynoar hollow-fibre membrane of production.Pressure gas source can be a nitrogen cylinder 17 and forms when operation, the escape pipe of nitrogen cylinder 17 and reactor 11 internal communication, extruding by pressure gas source to casting solution, guarantees the conveying of casting solution between reactor 11 and spinneret 12 and in the interior extruding film forming of spinneret 12.The first measuring pump 181 and valve 19 can regulate the feed flow of casting solution, regulate the specification of the hydrophilicity kynoar hollow-fibre membrane making.
In a word, the present invention can effectively realize the continuous production of hydrophilicity kynoar hollow-fibre membrane, shortens the production cycle of hydrophilicity kynoar hollow-fibre membrane, improves the economic benefit that hydrophilicity kynoar hollow-fibre membrane is produced.
Claims (9)
1. the production technology of a hydrophilicity kynoar hollow-fibre membrane, it is to complete in continuous process system, continuous process system comprises the reactor (11) that mixes reaction for each raw material, the discharging opening of reactor (11) is connected with the charging aperture of spinneret (12), the discharging opening place of spinneret (12) arranges respectively the first modification groove (13) of splendid attire liquor potassic permanganate and the second modification groove (14) of splendid attire solution of sodium bisulfite successively, first, two modification grooves (13, 14) on, arrange respectively semi-finished product hollow-fibre membrane is carried out to the deflector roll (131) of carrying continuously,
This technique specifically comprises the steps: polyvinylidene fluoride resin, pore-foaming agent, organic base polyethylene polyamine and solvent to mix in reactor (11) reaction and is prepared into casting solution, casting solution is extruded and made semi-finished product hollow-fibre membrane by spinneret (12), then successively semi-finished product hollow-fibre membrane is carried and carried out modification by first and second modification groove (13,14) by deflector roll (131), after modification, can make this hydrophilicity kynoar hollow-fibre membrane.
2. the production technology of hydrophilicity kynoar hollow-fibre membrane as claimed in claim 1, is characterized in that: in casting solution, contain the organic base of the polyvinylidene fluoride resin of 12～30 wt%, the pore-foaming agent of 2～10 wt% and 2～30 wt%, surplus is solvent.
3. the production technology of hydrophilicity kynoar hollow-fibre membrane as claimed in claim 1, is characterized in that: casting solution makes after stirring and evenly mixing reaction 23～25h by polyvinylidene fluoride resin, pore-foaming agent, organic base polyethylene polyamine and solvent at 59～60 ℃.
4. the production technology of hydrophilicity kynoar hollow-fibre membrane as claimed in claim 1, is characterized in that: the interior splendid attire of the first modification groove (13) be 1～5wt% liquor potassic permanganate.
5. the production technology of hydrophilicity kynoar hollow-fibre membrane as claimed in claim 1, is characterized in that: the interior splendid attire of the second modification groove (14) be 2～6wt% solution of sodium bisulfite.
6. the production technology of hydrophilicity kynoar hollow-fibre membrane as claimed in claim 1, it is characterized in that: between reactor (11) and spinneret (12), be also provided with the filter (15) for casting solution is filtered, the charging aperture of filter (15) is connected and is connected with the discharging opening of reactor (11), and the discharging opening of filter (15) is connected and is connected with the charging aperture of spinneret (12).
7. the production technology of hydrophilicity kynoar hollow-fibre membrane as claimed in claim 1, it is characterized in that: in the second described modification groove (14), be also provided with the reel storing roller (16) of storing of hydrophilicity kynoar hollow-fibre membrane to making, rotate on the cell wall of the second modification groove (14) at storing roller (16) two ends, storing roller (16) axially and axially the paralleling of deflector roll (131).
8. the production technology of hydrophilicity kynoar hollow-fibre membrane as claimed in claim 1, it is characterized in that: continuous process system also comprises is convenient to the conveying mechanism that the interior casting solution of reactor (11) is delivered to spinneret (12), conveying mechanism comprises a pressure gas source, pressure gas source output gas is discharged from the discharging opening of reactor (11) bottom to the top area of absence extruding casting solution in reactor (11), and discharging opening place is provided with valve (19) and the first measuring pump (181).
9. the production technology of hydrophilicity kynoar hollow-fibre membrane as claimed in claim 1, it is characterized in that: continuous process system also comprises the core flow container (183) that stores core liquid, the liquid outlet of core flow container (183) is connected and is connected with the feed liquor of spinneret (12) by connecting pipe, the liquid outlet of core flow container (183) is also provided with the second measuring pump (182), and core liquid is 0.5～2wt% potassium permanganate solution.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114288878A (en) * | 2021-12-07 | 2022-04-08 | 武汉工程大学 | Hydrophilic modified PVDF membrane and green in-situ covalent hydrophilic modification method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357304A (en) * | 2008-09-24 | 2009-02-04 | 哈尔滨工业大学 | Surface modification method of polyvinylidene fluoride membrane |
| CN101912740A (en) * | 2010-08-30 | 2010-12-15 | 东华大学 | Method for performing hydrophilic modification on surface of polyvinylidene fluoride microporous membrane |
| CN102527262A (en) * | 2011-12-09 | 2012-07-04 | 西安建筑科技大学 | Method for preparing chemically perforated polyvinylidene fluoride hollow fiber ultrafiltration membrane |
| CN103263861A (en) * | 2013-05-30 | 2013-08-28 | 哈尔滨工业大学 | Hydrophilic modification method for polyvinylidene fluoride hollow fiber membrane |
| CN103272495A (en) * | 2013-06-22 | 2013-09-04 | 南昌航空大学 | Method for preparing hydrophilic polyvinylidene fluoride hollow fiber membrane |
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- 2013-09-25 CN CN201310440669.8A patent/CN103521090A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357304A (en) * | 2008-09-24 | 2009-02-04 | 哈尔滨工业大学 | Surface modification method of polyvinylidene fluoride membrane |
| CN101912740A (en) * | 2010-08-30 | 2010-12-15 | 东华大学 | Method for performing hydrophilic modification on surface of polyvinylidene fluoride microporous membrane |
| CN102527262A (en) * | 2011-12-09 | 2012-07-04 | 西安建筑科技大学 | Method for preparing chemically perforated polyvinylidene fluoride hollow fiber ultrafiltration membrane |
| CN103263861A (en) * | 2013-05-30 | 2013-08-28 | 哈尔滨工业大学 | Hydrophilic modification method for polyvinylidene fluoride hollow fiber membrane |
| CN103272495A (en) * | 2013-06-22 | 2013-09-04 | 南昌航空大学 | Method for preparing hydrophilic polyvinylidene fluoride hollow fiber membrane |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114288878A (en) * | 2021-12-07 | 2022-04-08 | 武汉工程大学 | Hydrophilic modified PVDF membrane and green in-situ covalent hydrophilic modification method thereof |
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Application publication date: 20140122 |