CN107138057A - A kind of preparation method of new reverse osmosis membrane - Google Patents
A kind of preparation method of new reverse osmosis membrane Download PDFInfo
- Publication number
- CN107138057A CN107138057A CN201710371617.8A CN201710371617A CN107138057A CN 107138057 A CN107138057 A CN 107138057A CN 201710371617 A CN201710371617 A CN 201710371617A CN 107138057 A CN107138057 A CN 107138057A
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- Prior art keywords
- reverse osmosis
- osmosis membrane
- mofs
- preparation
- film
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention discloses a kind of preparation method of new reverse osmosis membrane.The purpose of the present invention is realized as follows：By supporter (being typically milipore filter) by forming fine and close functional layer on support membrane surface after polyamine and the anti-raw reaction of polynary acyl chlorides.A kind of method of mofs crystal pre-seeding is used again, mofs is fixed on counterdie prepares the new reverse osmosis membrane containing complex functional layer and be characterized in that：Compared with cellulose acetate class reverse osmosis membrane, polyamide-based utilized thin film composite membranes (TMC) have the advantages such as equipment with high desalinization, high flux and relatively low operating pressure；The addition of Mofs materials makes the pore size controllable of functional layer, adds the screening of film, and specific surface area increase, anti-fouling performance increase, the introducing of inorganic metal particle improves the mechanical performance of film.
Description
Technical field
The present invention relates to reverse osmosis membrane preparation field, specially a kind of preparation method of reverse osmosis membrane.
Background technology
Membrane separation technique is a kind of isolation technics for being widely used in solution or gaseous matter separation, concentration and purification.Film
Wall micropore gathers, and stoste passes through membranous wall for filter liquor by the side of film, solvent and small molecule solute under a certain pressure, and big
Molecule solute is rejected by, and reaches the purpose of material separation and concentration.Membrane separating process is dynamic filtration process, macromolecular solute
Obstructed, flowed out with concentrate by membranous wall, film is difficult to be blocked, can continuously be used for a long time.Filter process can be transported under normal temperature, low pressure
OK, no phase-state change, energy-efficient.Reverse osmosis membrane is a kind of important form of seperation film.In recent years, reverse osmosis membrane is more and more wider
It is general be applied to pharmacy, brewage, food and drink, chemical industry, recycling municipal sewage, hospital, community wastewater reuse, the production and living such as papermaking it is dirty
Water process.Reverse osmosis membrane filtration technology is a kind of efficient low energy and easy-operating liquid separation technology than traditional method for treating water
Effect is good, can be achieved desalinization, waste water recycling and to utility it is effective reclaim.
Compared with cellulose acetate class reverse osmosis membrane, polyamide-based utilized thin film composite membranes (TMC) have equipment with high desalinization, high flux
And the advantage such as relatively low operating pressure.1987, Tao Shi Film T ec companies were invented after polyamide reverse osmose membrane, and it is very
Cellulose acetate class reverse osmosis membrane is instead of soon, is occupied predominantly in the counter-infiltration in the whole world and NF membrane production and application field
Position, makes membrane technology and its application obtain unprecedented development.But, the poor inoxidizability of polyamide-based reverse osmosis membrane, resistant
Dye and chlorine-resistant property, still govern its development and application.
The content of the invention
In order to overcome technical problem, it is an object of the invention to a kind of preparation method of reverse osmosis membrane.The purpose of the present invention
Realize as follows：Supporter (being typically milipore filter) is soaked with the aqueous solution of active monomeric polycarboxylic amine, then removed
Remove unnecessary aqueous phase monomers；This film is immersed in the organic solvent that another contains active monomer (polynary acyl chlorides) again；Polyamine and
The functional layer of densification is formed after the anti-raw reaction of polynary acyl chlorides on support membrane surface.A kind of side of mofs crystal pre-seeding is used again
Method, mofs crystal is dispersed in the oil phase containing low concentration (0.02%~0.05%) pyromellitic trimethylsilyl chloride, and counterdie is soaked in aqueous phase
Afterwards, add and a small amount of polyamide network structure formed around mofs oil phase, the solution of acid chloride mofs of low concentration, mofs because
This and be fixed on counterdie after to add oil phase and continue this method of film forming and obtain dispersiveness preferably mofs filling films
The supporter milipore filter can select different polymer material films, such as：Polyvinylidene fluoride film, polyvinyl chloride
Film, polysulfones, sulfonated polysulfone membrane etc.
The organic solvent range of choice of the active monomer of dissolving is wide, the mostly good polar organic solvent of solubility property
The species of the polyamine for preparing composite polyamide reverse osmosis membrane is a lot, and the most frequently used has m-phenylene diamine (MPD) (MPD)；
O-phenylenediamine (OPD) and p-phenylenediamine (PPD)
The polynary acyl chlorides has a variety of, the most frequently used for pyromellitic trimethylsilyl chloride (TMC)
The selection wide variety of the mofs is optional, such as MIL-100 (Fe), MIL-53 (Fe), UIO-66, HKUST-1 etc..
The final filling film can be Flat Membrane, hollow-fibre membrane, rolled film etc..
Compared with prior art, new reverse osmosis membrane of the present invention has the characteristics that：
1. compared with cellulose acetate class reverse osmosis membrane, polyamide-based utilized thin film composite membranes (TMC) have equipment with high desalinization, high pass
The advantage such as amount and relatively low operating pressure；
The addition of 2.Mofs materials makes the pore size controllable of functional layer, adds the screening of film, and specific surface area increases
Plus.Anti-fouling performance increase.
3. the introducing of inorganic metal particle improves the mechanical performance of film.
Embodiment
The present invention is further discussed below with reference to embodiment：
Specific embodiment of the invention given below, these specific embodiments are only used for being further discussed below the present invention, not
Limit the present patent application scope of the claims.
The G ＆ W on surface is removed by support membrane of polysulfones, the aqueous solution containing m-phenylene diamine (MPD) is immersed, after immersion completely
In the organic solvent for taking out the moisture immersion 5- isocyanate groups-isophthaloyl chloride for removing excess surface, question response is formed afterwards completely
Functional layer composite membrane.A small amount of MIL-100 (Fe) is dispersed in the oil phase of 0.03% pyromellitic trimethylsilyl chloride, composite membrane is soaked
Certain time MIL-100 (Fe) is reacted in above-mentioned mofs oil phase to fix on a functional, forms complex functional layer.
Claims (7)
1. a kind of preparation method of new reverse osmosis membrane makes：By supporter (the being typically milipore filter) water of active monomeric polycarboxylic amine
Solution soaks, and then removes unnecessary aqueous phase monomers；This film is immersed another again and contains the organic of active monomer (polynary acyl chlorides)
In solvent；The functional layer of densification is formed after the anti-raw reaction of polyamine and polynary acyl chlorides on support membrane surface.A kind of mofs is used again
The method of crystal pre-seeding, mofs crystal is dispersed in the oil phase containing low concentration (0.02%~0.05%) pyromellitic trimethylsilyl chloride,
After aqueous phase immersion counterdie, add around mofs oil phase, the solution of acid chloride mofs of low concentration and form a small amount of polyamide
Network structure, mofs be therefore fixed on counterdie after add oil phase continue this method of film forming obtain dispersiveness compared with
Good mofs filling films.
2. a kind of preparation method of new reverse osmosis membrane as claimed in claim 1, it is characterised in that：
The supporter milipore filter can select different polymer material films, such as：Polyvinylidene fluoride film, polychloroethylene film gathers
Sulfone, sulfonated polysulfone membrane etc..
3. a kind of preparation method of new reverse osmosis membrane as claimed in claim 1, it is characterised in that：The active monomer of dissolving
Organic solvent range of choice it is wide, the mostly good polar organic solvent of solubility property.
4. a kind of preparation method of new reverse osmosis membrane as claimed in claim 1, it is characterised in that：It is described to prepare compound polyamides
The species of the polyamine of amine reverse osmosis membrane is a lot, and the most frequently used has m-phenylene diamine (MPD) (MPD)；O-phenylenediamine (OPD) and p-phenylenediamine
(PPD)。
5. a kind of preparation method of new reverse osmosis membrane as claimed in claim 1, it is characterised in that：The polynary acyl chlorides has many
Kind, it is the most frequently used for pyromellitic trimethylsilyl chloride (TMC).
6. a kind of preparation method of new reverse osmosis membrane as claimed in claim 1, it is characterised in that：The selection kind of the mofs
Class is various optional, such as MIL-100 (Fe), MIL-53 (Fe), UIO-66, HKUST-1 etc..
7. a kind of preparation method of new reverse osmosis membrane as claimed in claim 1, it is characterised in that：The final filling film
Can be Flat Membrane, hollow-fibre membrane, rolled film etc..
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710371617.8A CN107138057A (en) | 2017-05-22 | 2017-05-22 | A kind of preparation method of new reverse osmosis membrane |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710371617.8A CN107138057A (en) | 2017-05-22 | 2017-05-22 | A kind of preparation method of new reverse osmosis membrane |
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| CN107138057A true CN107138057A (en) | 2017-09-08 |
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| CN201710371617.8A Pending CN107138057A (en) | 2017-05-22 | 2017-05-22 | A kind of preparation method of new reverse osmosis membrane |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108636118A (en) * | 2018-05-16 | 2018-10-12 | 南京帝膜净水材料开发有限公司 | A kind of preparation method of complex reverse osmosis membrane |
| CN108855010A (en) * | 2018-07-12 | 2018-11-23 | 中南大学 | A kind of application of Uio-66/ poly aromatic composite material |
| CN108939935A (en) * | 2018-08-07 | 2018-12-07 | 哈尔滨工业大学 | A kind of preparation method of chlorine-resistant anti-pollution polyamide reverse osmose membrane |
| CN109110878A (en) * | 2018-09-09 | 2019-01-01 | 中国海洋大学 | A method of improving compound forward osmosis membrane water flux |
| CN109499397A (en) * | 2018-12-13 | 2019-03-22 | 天津工业大学 | A kind of modified Nano composite membrane and its preparation method and application |
| CN110639446A (en) * | 2018-04-11 | 2020-01-03 | 香港科技大学深圳研究院 | Metal organic framework-based micro-membrane reactor, preparation method and application |
| CN112055609A (en) * | 2018-05-02 | 2020-12-08 | 新加坡国立大学 | Thin film nanocomposite membranes comprising metal organic cages for desalination |
| CN112426890A (en) * | 2020-12-01 | 2021-03-02 | 赖枝帅 | Anti-pollution modified polyvinyl chloride composite membrane and preparation method thereof |
| CN115487693A (en) * | 2022-09-30 | 2022-12-20 | 浙江工业大学 | Polyamide/polyolefin mixed matrix nanofiltration membrane and preparation method thereof |
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| US20140336435A1 (en) * | 2013-05-07 | 2014-11-13 | Georgia Tech Research Corporation | Flow processing and characterization of metal-organic framework (mof) membranes in hollow fiber and tubular modules |
| CN104209021A (en) * | 2014-09-03 | 2014-12-17 | 北京林业大学 | Preparation method of aromatic polyamide film modified by ZIF-8 type metal-organic framework material |
| CN105148752A (en) * | 2015-09-29 | 2015-12-16 | 北京林业大学 | Polyamide reverse-osmosis composite membrane containing MIL type metal-organic framework material and preparation method thereof |
| CN105358238A (en) * | 2013-07-04 | 2016-02-24 | 巴斯夫欧洲公司 | Multiple channel membranes |
| CN106110908A (en) * | 2016-07-05 | 2016-11-16 | 浙江赛特膜技术有限公司 | The preparation method of aromatic polyamides hydridization NF membrane |
| US9994501B2 (en) * | 2013-05-07 | 2018-06-12 | Georgia Tech Research Corporation | High efficiency, high performance metal-organic framework (MOF) membranes in hollow fibers and tubular modules |
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Patent Citations (6)
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| US20140336435A1 (en) * | 2013-05-07 | 2014-11-13 | Georgia Tech Research Corporation | Flow processing and characterization of metal-organic framework (mof) membranes in hollow fiber and tubular modules |
| US9994501B2 (en) * | 2013-05-07 | 2018-06-12 | Georgia Tech Research Corporation | High efficiency, high performance metal-organic framework (MOF) membranes in hollow fibers and tubular modules |
| CN105358238A (en) * | 2013-07-04 | 2016-02-24 | 巴斯夫欧洲公司 | Multiple channel membranes |
| CN104209021A (en) * | 2014-09-03 | 2014-12-17 | 北京林业大学 | Preparation method of aromatic polyamide film modified by ZIF-8 type metal-organic framework material |
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| CN106110908A (en) * | 2016-07-05 | 2016-11-16 | 浙江赛特膜技术有限公司 | The preparation method of aromatic polyamides hydridization NF membrane |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110639446A (en) * | 2018-04-11 | 2020-01-03 | 香港科技大学深圳研究院 | Metal organic framework-based micro-membrane reactor, preparation method and application |
| CN112055609A (en) * | 2018-05-02 | 2020-12-08 | 新加坡国立大学 | Thin film nanocomposite membranes comprising metal organic cages for desalination |
| CN108636118A (en) * | 2018-05-16 | 2018-10-12 | 南京帝膜净水材料开发有限公司 | A kind of preparation method of complex reverse osmosis membrane |
| CN108855010A (en) * | 2018-07-12 | 2018-11-23 | 中南大学 | A kind of application of Uio-66/ poly aromatic composite material |
| CN108939935A (en) * | 2018-08-07 | 2018-12-07 | 哈尔滨工业大学 | A kind of preparation method of chlorine-resistant anti-pollution polyamide reverse osmose membrane |
| CN109110878A (en) * | 2018-09-09 | 2019-01-01 | 中国海洋大学 | A method of improving compound forward osmosis membrane water flux |
| CN109110878B (en) * | 2018-09-09 | 2021-11-05 | 中国海洋大学 | Method for improving water flux of composite forward osmosis membrane |
| CN109499397A (en) * | 2018-12-13 | 2019-03-22 | 天津工业大学 | A kind of modified Nano composite membrane and its preparation method and application |
| CN112426890A (en) * | 2020-12-01 | 2021-03-02 | 赖枝帅 | Anti-pollution modified polyvinyl chloride composite membrane and preparation method thereof |
| CN115487693A (en) * | 2022-09-30 | 2022-12-20 | 浙江工业大学 | Polyamide/polyolefin mixed matrix nanofiltration membrane and preparation method thereof |
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