CN103933879A - Producing method for high-flux ultrafiltration membrane component capable of retaining endotoxin - Google Patents
Producing method for high-flux ultrafiltration membrane component capable of retaining endotoxin Download PDFInfo
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- CN103933879A CN103933879A CN201410128458.5A CN201410128458A CN103933879A CN 103933879 A CN103933879 A CN 103933879A CN 201410128458 A CN201410128458 A CN 201410128458A CN 103933879 A CN103933879 A CN 103933879A
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Abstract
The invention relates to a producing method for a high-flux ultrafiltration membrane component capable of retaining endotoxin. The producing method is characterized by comprising the following steps of feeding PES (polyether sulfone) serving as a membrane material, an NMP (non-methane product) serving as a solvent, a mixture which consists of one or two of PEG200, LiCl, PEG400, K17, K30, K60 and K90 and serves as a first additive, and a strong coagulation agent serving as a second additive according to the mass ratio of the membrane material to the solvent to the additives of (20-25):(40-60):(15-40), and stirring under a condition of 80 DEG C for 24 hours to perform uniform dissolving to form a membrane casting liquid; performing filtration, stewing for 48 hours, then defoaming the membrane casting liquid, and cooling to 45 DEG C; spinning the membrane casting liquid by adopting a conventional dry and wet method; washing membrane silk in flowing water for 6 hours, and aging the membrane silk to remove the solvent; performing moisture-retaining drying on the membrane silk, and preparing the conventional high-flux ultrafiltration membrane component. The pure water flux of the membrane component prepared by adopting the producing method disclosed by the invention is higher than 150L/m<2>.H, the pressure is 0.1MPa, and the temperature is 25 DEG C; municipal running water is filtered, and the endotoxin detection is smaller than 0.25EU/ml. The high-flux ultrafiltration membrane component can be used for purification of medicinal injection water, family water and the like, and the filtering effect and the filtering efficiency are guaranteed.
Description
Technical field
The present invention relates to a kind of production method that can hold back endotoxic large flux hyperfiltration membrane assembly, belong to membrane separation technique field.
Background technology
Ultrafiltration is one of membrane separation technique taking pressure as motive force.Taking large molecule and separation of small molecuies as object, membrane aperture is between 1-100nm.Industrial aspect, milipore filter is by a large number for engineering of water treatment.Hyperfiltration technique is being brought into play more and more important effect in fields such as counter-infiltration pretreatment, drinking water treatment, middle water reuses.Hyperfiltration technique, in degerming and the turbidity removal of drinks and beverage, all plays a key effect in the depyrogenation of medicine and food and pharmacy concentration process.Civilian aspect, hyperfiltration technique starts progressively to enter direct drinking link, family's link of purifying water.In hyperfiltration technique, membrane aperture and membrane flux are the existence of conflict.In the time that membrane aperture diminishes rejection effect rising, membrane flux is that filter efficiency declines.At present main flow hold back endotoxic milipore filter, molecular weight cut off is 6000, the pure water flux of film is 60-100L/ ㎡ H, 0.1MPa, 25 DEG C.The molecular weight cut off 80,000,100,000 that its aperture is commonly used little, flux is also little simultaneously, and in engineering, film usage quantity is more.Aspect civilian, can hold back endotoxic milipore filter because flux is lower, seldom use especially, be generally the larger larger film product in aperture thereupon of tendency flux.The wide-aperture product of these large flux, can effectively hold back bacterium, cannot effectively hold back endotoxin, equally also cannot hold back and similarly exotoxin of endotoxin size.Exotoxin is to cause the abnormal and central factors such as diarrhoea.Therefore there is certain potential safety hazard in large aperture film in theory.
Summary of the invention
The object of the invention is the problem and the defect that exist in order to overcome prior art, and provide a kind of production method that can hold back endotoxic large flux hyperfiltration membrane assembly, current to hold back endotoxic milipore filter flux less with solving for the method, is difficult to take into account the problem of filter effect, filter efficiency.
Technical scheme of the present invention is:
A kind of production method that can hold back endotoxic large flux hyperfiltration membrane assembly, it is characterized in that carrying out according to the following steps: 1) taking polyethersulfone resin (PES) as membrane material, 1-METHYLPYRROLIDONE (NMP) is solvent, Macrogol 200 (PEG200), LiCl, PEG400 (PEG400), polyvinylpyrrolidone PVP-K17(K17), polyvinylpyrrolidone PVP-K30(K30), polyvinylpyrrolidone PVP-K60(K60), polyvinylpyrrolidone PVP-K90(K90) in one or two or more kinds mixture be the first additive, causing by force solidifying agent is the second additive, according to quality than membrane material: the ratio of solvent: additive=20-25:40-60:15-40 feeds intake, under 80 DEG C of conditions, stir and within 24 hours, be uniformly dissolved formation casting solution, 2) filter rear standing 48H deaeration, and be cooled to 45 DEG C, 3) casting solution is pressed to existing dry-wet spinning, 4) the prepared film silk of step (3) is through the 6 hours aging desolventizings of washing that flow, 5) the film silk moisturizing of step (4) is dried to the conventional large flux hyperfiltration membrane assembly of rear preparation.
In described step (3) dry-wet spinning, coagulation bath temperature is 0-15 DEG C when spinning, and the first washing trough temperature is 15-45 DEG C, and the second washing trough temperature is 35-60 DEG C.
In described step (3) dry-wet spinning, coagulation bath temperature is 10-15 DEG C when spinning, the first washing trough 20-35 DEG C, the second washing trough 40-55 DEG C.
It is described that to cause by force solidifying agent be one or two or more kinds mixture in water, glycerine, ethylene glycol, acetic acid.
The assembly pure water flux that the present invention makes is greater than 150L/ ㎡ H, 0.1MPa, 25 DEG C.In film formulation, the second additive employing causes by force solidifying agent makes cortex thicker, hole densification, and the first additive is that membrane flux reaches maximum in suitable scope; And in production technology, low temperature coagulating bath makes fenestra enough little, the second washing trough of higher temperature is to impel solvent, pore-foaming agent etc. in film silk deviate from fast and form the hole of running through continuously, and film silk flux is maximized.
The membrane module of preparing with this method, holds back under endotoxic working condition and uses in routine, saves cost because flux can reduce film usage quantity more greatly.Aspect civilian water purification, can hold back and similarly exotoxin of endotoxin size, security is better, has preliminary use value.
Detailed description of the invention
Below in conjunction with example, invention is described further, but should limit the scope of the invention with this.
Embodiment 1
By quality ratio, PES:NMP:K30:K90:PEG400:H
2the proportional arrangement casting solution of O=23:50:1:1:21:4 stirs and within 24 hours, is uniformly dissolved formation casting solution at 80 DEG C, leaves standstill 48H deaeration, and be cooled to 45 DEG C after filtering; By existing dry-wet spinning; Coagulating bath, core liquid are water, and coagulating bath is 15 DEG C, and the first washing trough is 25 DEG C, and the second washing trough is 55 DEG C; Prepared film silk is through the 6 hours aging desolventizings of washing that flow; After making conventional large flux hyperfiltration membrane assembly after film silk moisturizing after desolventizing is dried, test, assembly effective film area 4 ㎡, flux is 600L/H, 0.1MPa, 25 DEG C.Do former water with running water, get production fluid after filtration, detect endotoxin according to gel method, result is less than 0.25EU/ml.
Comparative example 1-1
Cancel the first washing trough, all the other are identical with embodiment 1, and film silk surface occurs that projection etc. is bad.
Comparative example 1-2
Cancel the second washing trough, all the other are identical with embodiment 1, test after making assembly.Assembly effective film area 4 ㎡, flux is 320L/H, 0.1MPa, 25 DEG C.Do former water with running water, get production fluid after filtration, detect endotoxin according to gel method, result is less than 0.25EU/ml.
Embodiment 2
By quality ratio, the proportional arrangement casting solution of PES:NMP:K17:K30:PEG200: glycerine=22:50:1:1:20:6 stirs and within 24 hours, is uniformly dissolved formation casting solution at 80 DEG C, leaves standstill 48H deaeration, and be cooled to 45 DEG C after filtering; By existing dry-wet spinning; Core liquid is water, the aqueous solution of the NMP that coagulating bath is 40%, and coagulating bath is 10 DEG C, and the first washing trough is 20 DEG C, and the second washing trough is 50 DEG C; Prepared film silk is through the 6 hours aging desolventizings of washing that flow; After making conventional large flux hyperfiltration membrane assembly after film silk moisturizing after desolventizing is dried, test, assembly effective film area 4 ㎡, flux is 800L/H, 0.1MPa, 25 DEG C.Do former water with running water, get production fluid after filtration, detect endotoxin according to gel method, result is less than 0.25EU/ml.
Comparative example 2-1
Film silk formula is PES:NMP:K17:K30:PEG200=22:50:1:1:26, and all the other in the same manner as in Example 2.After making assembly, test.Assembly effective film area 4 ㎡, flux is 900L/H, 0.1MPa, 25 DEG C.Do former water with running water, after filtration, get production fluid, detect endotoxin according to gel method, detect reagent gel, defective.
Comparative example 2-2
Film silk formula is PES:NMP:K17:K30:PEG200: glycerine=22:50:1:1:14:12, and all the other in the same manner as in Example 2.After making assembly, test.Assembly effective film area 4 ㎡, flux is 500L/H, 0.1MPa, 25 DEG C.Do former water with running water, get production fluid after filtration, detect endotoxin according to gel method, result is less than 0.25EU/ml.
Embodiment 3
By quality ratio, the proportional arrangement casting solution of PES:NMP:K17:K60:PEG200: ethylene glycol=20:60:1.5:0.5:20:18, after discontinuous degassing, press existing dry-wet spinning, coagulating bath, core liquid are water, coagulating bath is 12 DEG C, the first washing trough is 35 DEG C, and the second washing trough is 40 DEG C, and prepared film silk is through the 6 hours aging desolventizings of washing that flow; After making conventional large flux hyperfiltration membrane assembly after film silk moisturizing after desolventizing is dried, test.Assembly effective film area 4 ㎡, flux is 700L/H, 0.1MPa, 25 DEG C.Do former water with running water, get production fluid after filtration, detect endotoxin according to gel method, result is less than 0.25EU/ml.
Embodiment 4
By quality ratio, the proportional arrangement casting solution of PES:NMP:LiCl:PEG200: acetic acid=25:40:1.0:10:4, after discontinuous degassing, press existing dry-wet spinning, coagulating bath, core liquid are water, coagulating bath is 15 DEG C, the first washing trough is 25 DEG C, and the second washing trough is 50 DEG C, and prepared film silk is through the 6 hours aging desolventizings of washing that flow; After making conventional large flux hyperfiltration membrane assembly after film silk moisturizing after desolventizing is dried, test.Assembly effective film area 4 ㎡, flux is 750L/H, 0.1MPa, 25 DEG C.Do former water with running water, get production fluid after filtration, detect endotoxin according to gel method, result is less than 0.25EU/ml.
Claims (4)
1. can hold back the production method of endotoxic large flux hyperfiltration membrane assembly for one kind, it is characterized in that carrying out according to the following steps: 1) taking polyethersulfone resin PES as membrane material, 1-METHYLPYRROLIDONE NMP is solvent, Macrogol 200, LiCl, PEG400, polyvinylpyrrolidone PVP-K17, polyvinylpyrrolidone PVP-K30, polyvinylpyrrolidone PVP-K60, the mixture of one or two or more kinds in polyvinylpyrrolidone PVP-K90 is the first additive, causing by force solidifying agent is the second additive, according to quality than membrane material: the ratio of solvent: additive=20-25:40-60:15-40 feeds intake, under 80 DEG C of conditions, stir and within 24 hours, be uniformly dissolved formation casting solution, 2) filter rear standing 48H deaeration, and be cooled to 45 DEG C, 3) casting solution is pressed to existing dry-wet spinning, 4) the prepared film silk of step (3) is through the 6 hours aging desolventizings of washing that flow, 5) the film silk moisturizing of step (4) is dried to the conventional large flux hyperfiltration membrane assembly of rear preparation.
2. a kind of production method that can hold back endotoxic large flux hyperfiltration membrane assembly according to claim 1, it is characterized in that: in described step (3) dry-wet spinning, coagulation bath temperature is 0-15 DEG C when spinning, the first washing trough temperature is 15-45 DEG C, and the second washing trough temperature is 35-60 DEG C.
3. a kind of production method that can hold back endotoxic large flux hyperfiltration membrane assembly according to claim 2, it is characterized in that: in described step (3) dry-wet spinning, coagulation bath temperature is 10-15 DEG C when spinning, the first washing trough 20-35 DEG C, the second washing trough 40-55 DEG C.
4. a kind of production method that can hold back endotoxic large flux hyperfiltration membrane assembly according to claim 1, is characterized in that: described to cause by force solidifying agent be one or two or more kinds mixture in water, glycerine, ethylene glycol, acetic acid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104888630A (en) * | 2015-06-04 | 2015-09-09 | 湖北中泉环保技术有限公司 | Manufacturing method of membrane component used in high-concentration aqueous alkali |
| CN105289319A (en) * | 2015-11-20 | 2016-02-03 | 湖南澳维环保科技有限公司 | Preparation method of polymer hollow fiber membrane |
| CN113996189A (en) * | 2021-11-30 | 2022-02-01 | 3E膜科技有限责任公司 | Preparation method of hollow fiber separation membrane with compact selective layer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04317726A (en) * | 1991-04-16 | 1992-11-09 | Nok Corp | Method for drying outside collecting type ultrafiltration membrane |
| JP2005137996A (en) * | 2003-11-05 | 2005-06-02 | Toyobo Co Ltd | Permselective separation membrane |
| CN103111189A (en) * | 2013-02-05 | 2013-05-22 | 江苏苏净集团有限公司 | High-flux polyvinylidene fluoride hollow fiber membrane |
-
2014
- 2014-04-01 CN CN201410128458.5A patent/CN103933879B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04317726A (en) * | 1991-04-16 | 1992-11-09 | Nok Corp | Method for drying outside collecting type ultrafiltration membrane |
| JP2005137996A (en) * | 2003-11-05 | 2005-06-02 | Toyobo Co Ltd | Permselective separation membrane |
| CN103111189A (en) * | 2013-02-05 | 2013-05-22 | 江苏苏净集团有限公司 | High-flux polyvinylidene fluoride hollow fiber membrane |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104888630A (en) * | 2015-06-04 | 2015-09-09 | 湖北中泉环保技术有限公司 | Manufacturing method of membrane component used in high-concentration aqueous alkali |
| CN105289319A (en) * | 2015-11-20 | 2016-02-03 | 湖南澳维环保科技有限公司 | Preparation method of polymer hollow fiber membrane |
| CN113996189A (en) * | 2021-11-30 | 2022-02-01 | 3E膜科技有限责任公司 | Preparation method of hollow fiber separation membrane with compact selective layer |
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