CN109603587A - A kind of preparation method of anti-oxidant non-discolouring complex reverse osmosis membrane - Google Patents
A kind of preparation method of anti-oxidant non-discolouring complex reverse osmosis membrane Download PDFInfo
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- CN109603587A CN109603587A CN201811372299.8A CN201811372299A CN109603587A CN 109603587 A CN109603587 A CN 109603587A CN 201811372299 A CN201811372299 A CN 201811372299A CN 109603587 A CN109603587 A CN 109603587A
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- Prior art keywords
- reverse osmosis
- osmosis membrane
- discolouring
- complex reverse
- oxidant
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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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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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
- B01D67/0002—Organic membrane manufacture
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- 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
- B01D2325/30—Chemical resistance
Abstract
The present invention relates to UF membrane fields, relate more specifically to a kind of preparation method of anti-oxidant non-discolouring complex reverse osmosis membrane.The present invention is by the reverse osmosis membrane being made of non-woven fabrics supporting layer, polysulfone porous layer and polyamide separating layer, it is soaked in the sulfur-containing compound solution of certain mass concentration, it is dried after removing surplus liquid, obtains anti-oxidant non-discolouring complex reverse osmosis membrane.It is an advantage of the invention that significantly improving the anti-oxidant non-discolouring performance of complex reverse osmosis membrane, the permeation flux and rejection that complex reverse osmosis membrane separates sodium chloride brine simultaneously are held essentially constant, the present invention has simple and easy to do, it is easy to operate, it is low in cost, the phenomenon that solution complex reverse osmosis membrane changes colour in storage and use process to turn to be yellow, nigrescence.
Description
Technical field
The present invention relates to UF membrane fields, relate more specifically to a kind of preparation side of anti-oxidant non-discolouring complex reverse osmosis membrane
Method.
Background technique
Membrane technology is a separation technology having broad application prospects 21st century, it has grasps at normal temperature
Make, without phase-change, low energy consumption, pollutes the features such as small.As membrane technology is in fields such as chemical industry, medicine, food and drink and environmental protection
Using increasingly extensive, market needs film product also more and more.Complex reverse osmosis membrane is under a certain pressure can be selective
By the solute and the separated film product of solvent in solution, especially have to the sodium chloride brine containing monovalent ion higher
Rejection.Complex reverse osmosis membrane is widely used in sea water desalination, brackish water desalination, drink water purifying and industrial wastewater zero
In the water treatment technologies such as discharge.The separating layer of complex reverse osmosis membrane usually passes through m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride interfacial polymerization
It is formed, also remains a large amount of aqueous phase monomers m-phenylene diamine (MPD)s in separating layer at this time, this will lead to complex reverse osmosis membrane and is storing and using
There is discoloration jaundice in film surface in the process, or even the phenomenon that nigrescence, and then influences the separating property of product appearance and product.It is compound
Reverse osmosis membrane discoloration jaundice the main reason for be in interfacial polymerization remaining m-phenylene diamine (MPD) by the dioxygen oxidation in air at benzoquinones
Substance, and then discoloration jaundice is occurred according to m-phenylene diamine (MPD) content size, or even the phenomenon that nigrescence.Current existing production technology is logical
It crosses and washes amine technique and the residual amine of complex reverse osmosis membrane can be reduced into a part, but diaphragm still will appear during storage
Discoloration jaundice.Therefore the problem of diaphragm discoloration urgently to be resolved of the production technology of existing complex reverse osmosis membrane is turned to be yellow.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of anti-oxidant non-discolouring complex reverse osmosis membrane, improve compound reverse osmosis
The non-discolouring ability of the antioxygen of permeable membrane, even if by diaphragm place be to be exposed to the sun under outdoor solar light do not occur discoloration jaundice show
As, while diaphragm is not affected to the separating property of salting liquid, permeation flux and rejection are still kept and untreated diaphragm
Unanimously.
The preparation method of the anti-oxidant non-discolouring complex reverse osmosis membrane of one kind of the invention, it is characterised in that compound in this method
Reverse osmosis membrane is made of non-woven fabrics supporting layer, polysulfone porous layer and polyamide separating layer, and complex reverse osmosis membrane is soaked in and is contained
It in sulphur compound solution, is dried after removing surplus liquid, obtains anti-oxidant non-discolouring complex reverse osmosis membrane.
The present invention is achieved through the following technical solutions:
A kind of preparation method of anti-oxidant non-discolouring complex reverse osmosis membrane, which is characterized in that
(1) it is added in pure water by m-phenylene diamine (MPD), camphorsulfonic acid and dodecyl sodium sulfate, adjusts pH with triethylamine, prepare
Aqueous phase solution is obtained, it is spare；
(2) pyromellitic trimethylsilyl chloride is dissolved in Isopar G, is configured to organic phase solution, it is spare；
(3) the polysulfones support membrane that molecular cut off is 20000 or so is impregnated 60 seconds in aqueous phase solution, is removed after taking-up
The aqueous phase solution of excess surface；
(4) film in step (3) reacts 30 seconds in organic phase solution；
(5) film obtained in step (4) is heat-treated 6min in 100 DEG C of baking ovens, complex reverse osmosis membrane is prepared；
(6) reverse osmosis membrane that step (5) obtains is soaked in the solution for the sulfur-containing compound that mass concentration is 0.2-5wt%
It 2-5 minutes, is dried after then removing redundant solution in air dry oven, spin manifold temperature is 50-80 DEG C, drying time
It is 5-10 minutes, can be obtained anti-oxidant non-discolouring complex reverse osmosis membrane.
Preferably, the sulfur-bearing in the step of preparation method of the above-mentioned anti-oxidant non-discolouring complex reverse osmosis membrane of one kind (6)
Compound is thiodiglycolic acid, thio-2 acid, sodium thiosulfate, sodium sulfite, sodium hydrogensulfite, Hydros, or coke
The combination of one or more of sodium sulfite.As more preferably selecting, the sulfur-containing compound in step (6) is thiodiglycolic acid,
Mass concentration is 0.5wt%.
Preferably, the step of preparation method of the above-mentioned anti-oxidant non-discolouring complex reverse osmosis membrane of one kind (6) raising middle flask body temperature
Degree is 60 DEG C, and drying time is 10 minutes.
The utility model has the advantages that the present invention is handled by the chemical method carried out to complex reverse osmosis membrane separating layer, so that compound anti-
The anti-oxidant non-discolouring performance of permeable membrane is significantly improved, and diaphragm is exposed to outdoor solar light, and surface does not turn yellow nigrescence.It is multiple simultaneously
It closes permeation flux that reverse osmosis membrane separates sodium chloride brine and rejection is held essentially constant.The present invention has easy to be easy
Row, it is easy to operate, it is low in cost, it can be widely applied in the preparation process of complex reverse osmosis membrane, solve complex reverse osmosis membrane
The phenomenon that change colour jaundice in storage and use process, nigrescence.
Specific embodiment
A specific embodiment of the invention is illustrated below:
The present invention is described in more detail below in conjunction with embodiment, but the embodiment is not constituted to limit of the invention
System.It is associated from present disclosure or derived all deformations, is considered protection scope of the present invention, the field
Person skilled in the art can make some nonessential modifications and adaptations with content according to the present invention.
The preparation method of complex reverse osmosis membrane in the application:
M-phenylene diamine (MPD) (MPD), camphorsulfonic acid (CSA) and dodecyl sodium sulfate (SDS) are added in pure water first, with three
Ethamine (TEA) adjusts pH, prepares aqueous phase solution；Then pyromellitic trimethylsilyl chloride (TMC) is dissolved in isoparaffin (Isopar G)
It is configured to organic phase solution.Polysulfones support membrane (trapped molecular weight 20k or so) is impregnated into 60s in aqueous phase solution, after taking-up
The aqueous phase solution for removing excess surface, 30s is next reacted in organic phase solution, is then heat-treated in 100 DEG C of baking ovens
Complex reverse osmosis membrane is prepared in 6min.
The anti-oxidant non-discolouring processing method of composite membrane:
Complex reverse osmosis membrane is soaked in sulfur-containing compound solution 2-5 minutes that mass concentration is 0.2-5wt%, is removed more
It is dried after extraction raffinate body in air dry oven, spin manifold temperature is 50-80 DEG C, and drying time is 5-10 minutes.Resisted
Aoxidize non-discolouring complex reverse osmosis membrane.
The method of diaphragm performance test:
It is 7.5 as feeding liquid, film using 2000ppmNaCl aqueous solution pH under 25 DEG C and 1.55MPa test pressure conditions
The production water volume for passing through film effective area in certain time is collected after piece precompressed 30min, is tested and is intake using digital display conductivity meter
With production water conductivity, salt rejection rate and water yield are calculated.Salt rejection rate (R) is defined as: under certain operating conditions, charging salt solution is dense
Spend (Cf) with penetrating fluid in salinity (Cp) difference, then divided by feeding liquid salinity.Water flux is defined as: in certain operation item
Under part, through the volume of the water of per membrane area, unit L/m in the unit time2.h。
The anti-oxidant discoloration test of diaphragm: complex reverse osmosis membrane is cut into growth 40cm, the sample of wide 20cm is put into 60
In DEG C baking oven, humidity maintains 60-80%, daylight light irradiation is kept, every 24 hours observation film surface color changes, record film
The time of color change occurs.
Comparative example 1: the complex reverse osmosis membrane that will be prepared, without anti-oxidant non-discolouring processing, directly progress diaphragm separation
Performance test and the test of anti-oxidant discoloration, find the osmotic water flux of diaphragm and salt rejection rate are respectively 55L/m2.h and
99.5%, but obviously there is the phenomenon that discoloration jaundice after placing 72h in an oven in diaphragm, the longest record time is 30 days, i.e.,
Make not change colour and also stops experiment.
Embodiment 1-6 choose thiodiglycolic acid, thio-2 acid, sodium thiosulfate, sodium hydrogensulfite, Hydros and
Sodium pyrosulfite is 2 minutes as sulfur-containing compound, solution concentration 0.5wt%, soaking time, and drying temperature is 60 DEG C, is dried
The dry time is 10 minutes.
The diaphragm of implementation column 1-6 is subjected to diaphragm separation test and anti-oxidant discoloration experiment
Above-mentioned implementation column shows to impregnate complex reverse osmosis membrane, the permeation flux and salt rejection rate of diaphragm using sulfur compound solution
It is held essentially constant, and the ability of anti-oxidant discoloration is substantially improved, least raising is to original 2 times.
Embodiment 7-12
The diaphragm of implementation column 7-12 is subjected to diaphragm separation test and anti-oxidant discoloration experiment
Above-mentioned implementation column shows that, using sulfur compound solution immersion complex reverse osmosis membrane, solution concentration need to be controlled in 0.2-
The permeation flux and salt rejection rate of 5.0wt% diaphragm are held essentially constant, and the ability of anti-oxidant discoloration is substantially improved.
Embodiment 13-18
The diaphragm of implementation column 13-18 is subjected to diaphragm separation test and anti-oxidant discoloration experiment
Above-mentioned implementation column shows that, using sulfur compound solution immersion complex reverse osmosis membrane, solution soaking time need to be controlled in 2-
5 minutes, 50-80 DEG C of drying temperature, drying time was 5-10 minutes, and the permeation flux and salt rejection rate of diaphragm are held essentially constant,
And the ability of anti-oxidant discoloration is substantially improved.
Claims (4)
1. a kind of preparation method of anti-oxidant non-discolouring complex reverse osmosis membrane, which is characterized in that
(1) it is added in pure water by m-phenylene diamine (MPD), camphorsulfonic acid and dodecyl sodium sulfate, adjusts pH with triethylamine, with obtained water
Phase solution, it is spare；
(2) pyromellitic trimethylsilyl chloride is dissolved in Isopar G, is configured to organic phase solution, it is spare；
(3) the polysulfones support membrane that molecular cut off is 20000 or so is impregnated 60 seconds in aqueous phase solution, surface is removed after taking-up
Extra aqueous phase solution；
(4) film in step (3) reacts 30 seconds in organic phase solution；
(5) film obtained in step (4) is heat-treated 6min in 100 DEG C of baking ovens, complex reverse osmosis membrane is prepared；
(6) reverse osmosis membrane that step (5) obtains is soaked in the solution 2-5 for the sulfur-containing compound that mass concentration is 0.2-5wt%
Minute, it is dried after then removing redundant solution in air dry oven, spin manifold temperature is 50-80 DEG C, and drying time is
5-10 minutes, it can be obtained anti-oxidant non-discolouring complex reverse osmosis membrane.
2. the preparation method of the anti-oxidant non-discolouring complex reverse osmosis membrane of one kind according to claim 1, which is characterized in that step
Suddenly the sulfur-containing compound in (6) is thiodiglycolic acid, and thio-2 acid, sodium thiosulfate, sodium sulfite, sodium hydrogensulfite is low
The combination of one or more of sodium sulfite or sodium pyrosulfite.
3. the preparation method of the anti-oxidant non-discolouring complex reverse osmosis membrane of one kind according to claim 2, which is characterized in that step
Suddenly the sulfur-containing compound in (6) is thiodiglycolic acid, mass concentration 0.5wt%.
4. the preparation method of the anti-oxidant non-discolouring complex reverse osmosis membrane of one kind according to claim 1, which is characterized in that step
Suddenly spin manifold temperature is 60 DEG C in (6), and drying time is 10 minutes.
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| CN201811372299.8A CN109603587A (en) | 2018-11-16 | 2018-11-16 | A kind of preparation method of anti-oxidant non-discolouring complex reverse osmosis membrane |
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| CN201811372299.8A CN109603587A (en) | 2018-11-16 | 2018-11-16 | A kind of preparation method of anti-oxidant non-discolouring complex reverse osmosis membrane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110052170A (en) * | 2019-05-09 | 2019-07-26 | 万华化学集团股份有限公司 | A kind of reverse osmosis membrane and its preparation method and application of acid and alkali-resistance cleaning |
| CN110756061A (en) * | 2019-10-12 | 2020-02-07 | 万华化学集团股份有限公司 | Oxidation-resistant high-flux reverse osmosis membrane and preparation method and application thereof |
| CN114082307A (en) * | 2021-12-08 | 2022-02-25 | 湖南澳维环保科技有限公司 | Anti-oxidation reverse osmosis membrane and preparation method thereof |
| CN114082307B (en) * | 2021-12-08 | 2024-04-26 | 湖南澳维科技股份有限公司 | Antioxidant reverse osmosis membrane and preparation method thereof |
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| CN1046472A (en) * | 1987-06-08 | 1990-10-31 | 联合讯号有限公司 | Chlorine-resistant semipermeable membranes |
| CN104379243A (en) * | 2013-06-07 | 2015-02-25 | Lg化学株式会社 | Prolyamide-based water treatment separation membrane having excellent oxidation resistance and chlorine resistance and manufacturing method therefor |
| CN104474926A (en) * | 2014-12-12 | 2015-04-01 | 杭州水处理技术研究开发中心有限公司 | Preparation method of polyamide reverse osmosis membrane |
| WO2017146412A1 (en) * | 2016-02-26 | 2017-08-31 | 한양대학교 산학협력단 | Porous support for water treatment separation membrane, ultra-thin composite membrane comprising same, and manufacturing method therefor |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1046472A (en) * | 1987-06-08 | 1990-10-31 | 联合讯号有限公司 | Chlorine-resistant semipermeable membranes |
| CN104379243A (en) * | 2013-06-07 | 2015-02-25 | Lg化学株式会社 | Prolyamide-based water treatment separation membrane having excellent oxidation resistance and chlorine resistance and manufacturing method therefor |
| CN104474926A (en) * | 2014-12-12 | 2015-04-01 | 杭州水处理技术研究开发中心有限公司 | Preparation method of polyamide reverse osmosis membrane |
| WO2017146412A1 (en) * | 2016-02-26 | 2017-08-31 | 한양대학교 산학협력단 | Porous support for water treatment separation membrane, ultra-thin composite membrane comprising same, and manufacturing method therefor |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110052170A (en) * | 2019-05-09 | 2019-07-26 | 万华化学集团股份有限公司 | A kind of reverse osmosis membrane and its preparation method and application of acid and alkali-resistance cleaning |
| CN110052170B (en) * | 2019-05-09 | 2021-10-22 | 万华化学集团股份有限公司 | Acid and alkali cleaning resistant reverse osmosis membrane and preparation method and application thereof |
| CN110756061A (en) * | 2019-10-12 | 2020-02-07 | 万华化学集团股份有限公司 | Oxidation-resistant high-flux reverse osmosis membrane and preparation method and application thereof |
| CN110756061B (en) * | 2019-10-12 | 2022-01-07 | 万华化学集团股份有限公司 | Oxidation-resistant high-flux reverse osmosis membrane and preparation method and application thereof |
| CN114082307A (en) * | 2021-12-08 | 2022-02-25 | 湖南澳维环保科技有限公司 | Anti-oxidation reverse osmosis membrane and preparation method thereof |
| CN114082307B (en) * | 2021-12-08 | 2024-04-26 | 湖南澳维科技股份有限公司 | Antioxidant reverse osmosis membrane and preparation method thereof |
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Application publication date: 20190412 |