CN108176242A - A kind of method using micro-filtration porous protective layer modification ultrafiltration film outer surface - Google Patents
A kind of method using micro-filtration porous protective layer modification ultrafiltration film outer surface Download PDFInfo
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- CN108176242A CN108176242A CN201711416336.6A CN201711416336A CN108176242A CN 108176242 A CN108176242 A CN 108176242A CN 201711416336 A CN201711416336 A CN 201711416336A CN 108176242 A CN108176242 A CN 108176242A
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- Prior art keywords
- micro
- protective layer
- porous protective
- filtration porous
- film outer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
Abstract
The invention discloses a kind of methods using micro-filtration porous protective layer modification ultrafiltration film outer surface.The method of the present invention is to modify micro-filtration porous protective layer in ultrafiltration film outer surface, and the micro-filtration porous protective layer is inorganic-organic hybrid functional layer of the aperture at 3 500 microns, and thickness is 0.1 1mm；The micro-filtration porous protective layer is prepared as steps described below：The coating stoste formed using polymer substrate phase, inorganic particulate, macromolecular pore former and solvent, above-mentioned each component mass percent proportioning are：Polymer substrate phase 5 10%, inorganic particulate 15 30%, macromolecular pore former 15 30%, solvent 30 65%.The inorganic-organic hybrid structure of micro-filtration porous protective layer in the present invention has good wearability, effectively avoids scuffing of the conventional substances to ultrafiltration function layer.
Description
Technical field
Prepared the present invention relates to film product and technical field of membrane separation field, more specifically, be related to it is a kind of using micro-
The method for filtering porous protective layer modification ultrafiltration film outer surface.
Background technology
With the development of embrane method drinking water treatment technique, with no medicine (being not added with flocculant) and the short fluid layer work of pre-treatment is saved
Skill gradually causes great attention in the industry, batch production for waterworks and cost effective has great importance.To ensure
Drinking water safety, during abbreviated system is implemented, the safety of filtering accuracy and separating layer for ultrafiltration membrane proposes
Higher requirement.
The method of conventional enhancing ultrafiltration membrane is mainly the reinforcement for selecting mechanical property higher, such as non-woven fabrics or braided fabric
Deng, ultrafiltration membrane functional layer is enhanced, so as to avoid membrane body occur breakage (be exactly to avoid fracture of wire for hollow-fibre membrane
Generation).But the above method can not form protection for Ultra filtration membrane layer, for embrane method drinking water treatment field,
If breakage occurs for ultra-filtration and separation layer, even if entire membrane body keeps complete, the decline of whole system safety can not be also avoided.
Invention content
The technical problems to be solved by the invention are to overcome the deficiencies in the prior art, are provided a kind of using micro-filtration
The method that porous protective layer modifies ultrafiltration film outer surface.
A kind of method using micro-filtration porous protective layer modification ultrafiltration film outer surface of the present invention, is given by following technical proposals
To realize, micro-filtration porous protective layer is modified in ultrafiltration film outer surface, the micro-filtration porous protective layer is aperture at 3-500 microns
Inorganic-organic hybridization functional layer, thickness 0.1-1mm；The micro-filtration porous protective layer is prepared as steps described below：Using
The coating stoste that polymer substrate phase, inorganic particulate, macromolecular pore former and solvent form, above-mentioned each component mass percent
It matches and is：Polymer substrate phase 5-10%, inorganic particulate 15-30%, macromolecular pore former 15-30%, solvent 30-65%,
The grain size of middle inorganic particulate is 1-10 microns, and the molecular weight of macromolecular pore former is higher than 20,000；Above-mentioned coating stoste it is coated and
Curing obtains micro-filtration porous protective layer in coagulating bath,
The coagulating bath is water-bath.
The polymer substrate mutually for Kynoar (PVDF), polysulfones (PS), polyether sulfone (PES) it is one or more.
The macromolecular pore former is polyethylene glycol (PEG) of the molecular weight higher than 20,000, polyethylene glycol oxide (PEO), polyethylene
Pyrrolidones (PVP) it is one or more.
The inorganic particulate is sodium chloride (NaCl), lithium chloride (LiCl), calcium chloride (CaCl2), calcium carbonate (CaCO3), two
Silica (SiO2), titanium dioxide (TiO2) it is one or more.
The solvent be 60-120 DEG C at can be formed with polymer homogeneously, under room temperature with the liquid or liquid of polymer split-phase
Body mixture.
The solvent liquid is dimethylacetylamide (DMAC), dimethyl sulfoxide (DMSO) (DMF) or N-Methyl pyrrolidone
(NMP)。
The solvent liquid mixture is dimethylacetylamide (DMAC) and PEG200 mixtures or dimethyl sulfoxide (DMSO) (DMF)
With PEG200 mixtures.
It is described modification be ultrafiltration membrane preparation process carry out surface coating, solidified forming or ultrafiltration membrane forming or
It is made after product and carries out surface coating and solidified forming again.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention constructs micro-filtration porous protective layer in ultrafiltration membrane surface, has the characteristics that：
1. the inorganic-organic hybridization structure of micro-filtration porous protective layer has good wearability, effectively avoids conventional substances
Scuffing to ultrafiltration function layer.
2. constructing this appropriate thickening design of micro-filtration porous protective layer in ultrafiltration membrane surface, make micro-filtration porous protective layer
Safety increases.
3. the design of the 3-500 micron pore sizes of micro-filtration porous protective layer can effectively avoid protective layer for ultrafiltration membrane flux
Loss, while the macroporous structure of inorganic-organic hybridization also can effectively avoid micro-filtration protective layer in itself formed pollution after be not easy
The problem of backwash is removed.
Specific embodiment
The present invention is described in further detail below in conjunction with specific embodiment.It is it should be appreciated that described herein specific
Embodiment is only used to explain the present invention, is not intended to limit the present invention.
Embodiment 1
2kg PVDF, 4kg NaCl, 4kg PVP and 10kg DMAC are added in stirred tank, stood after agitated 6h de-
16h is steeped, mixed feed liquid is passed through in coated board, and it is 1m to take surface area2, aqueous solution middle-molecular-weihydroxyethyl 6000PEG rejections be
96% seperation film, and by seperation film with 0.05m2The speed of/s at the uniform velocity passes through coated board, and separation membrane surface coats a layered material
Seperation film after coated feed liquid is immersed fully curing and cleaning in water-filled coagulating tank, obtained more with micro-filtration by liquid
The seperation film of hole protective layer.
With the sand paper of 400 mesh with the direction reciprocating friction film surface parallel with film surface three times after, measure it to aqueous solution
The rejection of middle-molecular-weihydroxyethyl 6000PEG is still 96%.
Comparative example 1
It is 1m to take surface area2, aqueous solution middle-molecular-weihydroxyethyl 6000PEG rejections be 96% seperation film, with the sand paper of 400 mesh
With the direction reciprocating friction film surface parallel with film surface three times after, measure its retention to aqueous solution middle-molecular-weihydroxyethyl 6000PEG
Rate is down to 76%.
Embodiment 2：
By 15kg PVDF, 3kg PVP, 3kg PEG, 79kg DMAC are as mixing in film forming feed liquid merging stirred tank
20h deaerations are stood after 12h, 1kg PVDF, 4kg NaCl, 6kg PVP and 9kg DMAC are added to stirring as coating feed liquid
In kettle, the film forming feed liquid through deaeration is passed through spinneret and squeezed out to the coagulating bath for filling with water by standing and defoaming 16h after agitated 6h
Primary solidification, the PVDF hollow-fibre membranes access coated board through primary solidification are simultaneously uniformly applied in film surface in slot and in coagulating bath
One layer of coating material liquid material liquid is covered, will fully be cured in the water-filled coagulating tank of the immersion of the seperation film after coated feed liquid and clear
It washes, obtains the PVDF hollow-fibre membranes with micro-filtration porous protective layer.
After testing, the PVDF hollow-fibre membranes for obtaining having micro-filtration porous protective layer are to aqueous solution middle-molecular-weihydroxyethyl 20000
PEG rejections are 99%；With the sand paper of 400 mesh with the direction reciprocating friction film surface parallel with film surface three times after, measure it
PEG rejections to aqueous solution middle-molecular-weihydroxyethyl 20000 are 99%.
Comparative example 2
By 15kg PVDF, 3kg PVP, 3kg PEG, 79kg DMAC are as mixing in film forming feed liquid merging stirred tank
20h deaerations are stood after 12h, the film forming feed liquid through deaeration is passed through spinneret and are squeezed out into the coagulating tank for fill with water and solidifying
Gu fully curing in bath, and by fully cleaning, obtain PVDF hollow-fibre membranes.
After testing, the PVDF hollow-fibre membranes obtained are 99% to the PEG rejections of aqueous solution middle-molecular-weihydroxyethyl 20000；And
It three times and is remeasured in aqueous solution points with the direction reciprocating friction film surface parallel with film surface with the sand paper of 400 mesh afterwards
The PEG rejection effects of son amount 20000, rejection are down to 81%.
The above is only the preferred embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (9)
1. a kind of method using micro-filtration porous protective layer modification ultrafiltration film outer surface, it is characterized in that, it is repaiied in ultrafiltration film outer surface
Micro-filtration porous protective layer is adornd, the micro-filtration porous protective layer is inorganic-organic hybridization functional layer of the aperture at 3-500 microns, thick
It spends for 0.1-1mm；The micro-filtration porous protective layer is prepared as steps described below：Using polymer substrate phase, inorganic particulate,
The coating stoste of macromolecular pore former and solvent composition, above-mentioned each component mass percent proportioning are：Polymer substrate phase 5-
10%th, inorganic particulate 15-30%, macromolecular pore former 15-30%, solvent 30-65%, the wherein grain size of inorganic particulate are 1-10
Micron, the molecular weight of macromolecular pore former are higher than 20,000；Above-mentioned coating stoste is coated and to obtain micro-filtration more for curing in coagulating bath
Hole protective layer.
2. the method according to claim 1 using micro-filtration porous protective layer modification ultrafiltration film outer surface, it is characterized in that, institute
It is to carry out surface coating, solidified forming in the preparation process of ultrafiltration membrane or shaped or after product is made in ultrafiltration membrane to state modification
Surface coating and solidified forming are carried out again.
3. the method according to claim 1 using micro-filtration porous protective layer modification ultrafiltration film outer surface, it is characterized in that, institute
Coagulating bath is stated as water-bath.
4. the method according to claim 1 using micro-filtration porous protective layer modification ultrafiltration film outer surface, it is characterized in that, institute
State one kind or more that macromolecular pore former is polyethylene glycol of the molecular weight higher than 20,000, polyethylene glycol oxide, polyvinylpyrrolidone
Kind.
5. the method according to claim 1 using micro-filtration porous protective layer modification ultrafiltration film outer surface, it is characterized in that, institute
Inorganic particulate is stated as sodium chloride (NaCl), lithium chloride (LiCl), calcium chloride (CaCl2), calcium carbonate (CaCO3), silica
(SiO2), titanium dioxide (TiO2) it is one or more.
6. the method according to claim 1 using micro-filtration porous protective layer modification ultrafiltration film outer surface, it is characterized in that, institute
State polymer substrate mutually for Kynoar, polysulfones, polyether sulfone it is one or more.
7. the method according to claim 1 using micro-filtration porous protective layer modification ultrafiltration film outer surface, it is characterized in that, institute
Solvent is stated as that can be formed with polymer homogeneously at 60-120 DEG C, under room temperature with the liquid or liquid mixture of polymer split-phase.
8. the method according to claim 6 using micro-filtration porous protective layer modification ultrafiltration film outer surface, it is characterized in that, institute
Solvent liquid is stated as dimethylacetylamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone.
9. the method according to claim 6 using micro-filtration porous protective layer modification ultrafiltration film outer surface, it is characterized in that, institute
Solvent liquid mixture is stated as dimethylacetylamide and PEG200 mixtures or dimethyl sulfoxide (DMSO) and PEG200 mixtures.
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| CN201711416336.6A CN108176242A (en) | 2017-12-25 | 2017-12-25 | A kind of method using micro-filtration porous protective layer modification ultrafiltration film outer surface |
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| CN201711416336.6A CN108176242A (en) | 2017-12-25 | 2017-12-25 | A kind of method using micro-filtration porous protective layer modification ultrafiltration film outer surface |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111389233A (en) * | 2020-03-20 | 2020-07-10 | 北京碧水源膜科技有限公司 | Preparation method of microfiltration membrane repairing liquid for functional layer damage and microfiltration membrane repairing method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2390670Y (en) * | 1999-09-14 | 2000-08-09 | 天津市长城过滤设备厂 | Coaxial multi-core layer high density compaction filtering hybridized compound core |
| CN1759924A (en) * | 2004-06-25 | 2006-04-19 | 米利波尔公司 | Ultrafiltration membrane and preparation method thereof |
| CN101015773A (en) * | 2006-12-29 | 2007-08-15 | 浙江大学 | Porous polyvinylidene blending porous membrane and process for producing same |
-
2017
- 2017-12-25 CN CN201711416336.6A patent/CN108176242A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2390670Y (en) * | 1999-09-14 | 2000-08-09 | 天津市长城过滤设备厂 | Coaxial multi-core layer high density compaction filtering hybridized compound core |
| CN1759924A (en) * | 2004-06-25 | 2006-04-19 | 米利波尔公司 | Ultrafiltration membrane and preparation method thereof |
| CN101015773A (en) * | 2006-12-29 | 2007-08-15 | 浙江大学 | Porous polyvinylidene blending porous membrane and process for producing same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111389233A (en) * | 2020-03-20 | 2020-07-10 | 北京碧水源膜科技有限公司 | Preparation method of microfiltration membrane repairing liquid for functional layer damage and microfiltration membrane repairing method |
| CN111389233B (en) * | 2020-03-20 | 2022-07-01 | 北京碧水源膜科技有限公司 | Preparation method of microfiltration membrane repairing liquid for functional layer damage and microfiltration membrane repairing method |
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Application publication date: 20180619 |