CN109364758A - A kind of high-performance reverse osmosis composite membrane of chlorine-resistant and preparation method thereof - Google Patents
A kind of high-performance reverse osmosis composite membrane of chlorine-resistant and preparation method thereof Download PDFInfo
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- CN109364758A CN109364758A CN201811387123.XA CN201811387123A CN109364758A CN 109364758 A CN109364758 A CN 109364758A CN 201811387123 A CN201811387123 A CN 201811387123A CN 109364758 A CN109364758 A CN 109364758A
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- chlorine
- reverse osmosis
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- 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
- B01D67/0006—Organic membrane manufacture by chemical reactions
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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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a kind of polymeric membrane for separation, in particular to the high-performance reverse osmosis composite membrane and preparation method of a kind of chlorine-resistant, which is made of micropore supporting layer, polyamide separating layer, chlorine-resistant protective layer.The present invention deposits silane coupling agent protective coating on polyamide-based reverse osmosis membrane surface first, is fixed in film surface with reacting for N-H in amido bond followed by coating.The present invention has the advantages that the osmotic resistance of (1) chlorine-resistant protective layer is smaller, conventional method deposition protective layer is avoided the problem that and bring permeation flux sharp fall；(2) chlorine-resistant coating is reacted with amido bond N-H, while reducing Active Chlorine attack site, chlorine-resistant protective layer is fixed on reverse osmosis membrane surface in a manner of chemical bond, overcomes the problems, such as that conventional coating is easy to be lost, effectively extension guard time；(3) deposition of chlorine-resistant coating can carry out at normal temperature, easy to operate, great industrial applications prospect.
Description
Technical field
The present invention relates to a kind of polymeric membrane for separation, in particular to a kind of high-performance reverse osmosis composite membrane of chlorine-resistant, this hairs
The bright preparation method for further relating to above-mentioned composite membrane.
Background technique
Reverse osmosis technology is a kind of high efficiency, low energy consumption, easy-operating Novel filtration technology, it can be achieved that sea-water brackish water is light
Change, cycling utilization of wastewater and effective recycling of high added value substance etc..
And the core as the technology, the development of reverse osmosis membrane then experienced homogeneous symmetric membrane, asymmetric membrane, composite membrane three
A stage: the 1950s, the homogeneous reverse osmosis membrane of 6 μ m-thicks was prepared using cellulose acetate by Reid, indicated reverse osmosis
The beginning of membrane material research, but be eliminated in practical applications since homogeneous membrane mass transfer velocity is extremely low；In the early 1960s,
First acetic acid with high-throughput, high rejection in the world is prepared using new filming technology in Loeb and Sourirajan
Cellulose asymmetry reverse osmosis membrane, the film of the type only 0.2 μm or so of epidermis be it is fine and close so that mass transfer velocity improve it is close
3 orders of magnitude, become the milestone in membrane technology development history, and anisotropic membrane still uses in a certain range even to this day；20 generation
The filming technology that discipline the mid-1960s Riley and Cadoffe etc. are prepared with dense layer surface with loose supporting layer respectively is successfully developed
Compound reverse osmosis membrane out further promotes the permeation flux of reverse osmosis membrane；And 1987, Tao Shi Film Tec company successfully opens
Polyamide reverse osmose membrane is sent out, due to advantages such as its equipment with high desalinization, high throughput and low operating pressures, quickly in the reverse osmosis membrane in the whole world
Production and application field occupy leading position, and membrane technology and its application is made to obtain unprecedented development.
In actual use, in order to inhibit the breeding of microorganism in water body, need to add Active Chlorine, but the substance meeting
It destroys polyamide material and reverse osmosis composite membrane is made to lose separating property；Although currently used solution is at reverse osmosis place
The front end of reason removes chlorine residue using the modes such as activated carbon adsorption or reducing agent reduction, contacts to avoid with membrane material.But which
On the one hand, increase the complexity and operating cost of technique, on the other hand there are still accidental chlorine residue it is untreated cause completely it is reverse osmosis
The risk that film is scrapped.Therefore, the chlorine resistance of reinforced polyamide class reverse osmosis membrane for prolong the service life, reduce operating cost,
Simplify pretreating process and all has very important meaning.
With the further investigation to polyamide mechanism of chlorination, although the theory that every researcher is proposed is not quite similar,
Gradually formed some common recognitions: 1. direct phenyl ring chlorination replaces, which mainly occurs in strongly acidic solution, at this time with
Cl2In the presence of irreversible direct chlorine easily occurs with the phenyl ring of polyamine side and replaces, to influence the separating property of reverse osmosis membrane.Mirror
It is not used under strong acid generally in reverse osmosis, therefore the less generation of the process.2. invertibity amide N-Cl replace and it is irreversible
Orton rearrangement reaction mainly exists in the form of HClO under the conditions of neutral or meta-alkalescence, positively charged Cl in molecule
And the H on the ketonic oxygen and amide N on negatively charged O difference attack amido bond, transition state is formed, subsequent generation rearrangement is simultaneously complete
At the substitution of H atom on amide N, the N-Cl chemical bond that is formed at this time is simultaneously unstable, still can be again if contacted with reducing agent
Dechlorination is reduced into amide N-H structure.But then under the influence of the electronic effect of phenyl ring another amino, Cl atom is easily from amide
It is irreversibly transferred on N on the phenyl ring skeleton, i.e. Orton is reset.Due to the N-H key of amido bond and the chlorination of aromatic ring, make film
Surface hydrophilicity decline, the amido bond flexibility of film surface enhance and generate " compacted fill ground ", the polyamide function after final chlorination
Ergosphere decomposes and loses separating property.
In order to solve the problems, such as that reverse osmosis membrane chlorine resistance is bad, there is researcher to attempt using other chlorine-resistant membrane materials from basic
The chlorine resistance, including sulfonated polysulfone, teritary amide polymer, modificationization secondary amide polymer etc. of upper enhancing reverse osmosis membrane, but such
Material is difficult to surmount the polyamide-based composite membrane of interfacial polymerization preparation on preparation process ease or membrane separating property, at present
Still come out without preferable commercially produced product.It is modified to promote its chlorine-resistant property that surface is carried out to existing polyamide-based reverse osmosis membrane
It mainly include protective layer coating or chemically grafting and modifying.Protective layer coating will mainly be dissolved with the hydrophilic polymer of chlorine-resistant property
Object solution is contacted with reverse osmosis membrane, and polymer is made to be gradually deposited at film surface, to form uniform protective layer in film surface, is exempted from
It is destroyed in by Active Chlorine, but this method is also easy to improve osmotic resistance, and in the actual process since hydraulic blow may be with
Polyamide functional layer separates and loses chlorine-resistant property.
Chemically grafting and modifying mainly from polyamide chlorine mechanism of degradation, is subtracted using the compound that can be reacted with amide N-H
Few Active Chlorine attack site, thus the chlorine-resistant property of reinforced polyamide class reverse osmosis membrane.Such as Zhang is first with formaldehyde and reverse osmosis
The amido bond reaction of permeable membrane surface introduces N-CH2OH then passes through glutaraldehyde for N-CH2OH is cross-linked to form more stable ehter bond,
Enhance stability when it is contacted with Active Chlorine.But the process is relatively complicated, needs to use crosslinking agent and a degree of
Heat treatment.
Summary of the invention
In order to solve the above technical problems, the present invention provides high-performance reverse osmosis composite membrane and its preparation side of a kind of chlorine-resistant
Method deposits the silane coupling agent containing amino or acyloxy in polyamide-based composite film surface by Hyarogen-bonding, and utilizes
Base catalyst reacts-Si-OH with the N-H in amido bond, while reducing Active Chlorine attack site, by protective layer with chemical bond
Mode is fixed on film surface, extends effective protecting time.
In order to achieve the above objectives, the present invention is achieved by following technical proposals:
A kind of high-performance reverse osmosis composite membrane of chlorine-resistant, which is characterized in that micropore support membrane surface recombination has a strata acyl
Amine macromolecule desalination layer, is deposited with silane coupling agent coating on it, is formed by Hydrogen Binding Adsorption-room temperature base catalysis.
Preferably, above-mentioned polyamide-based macromolecule is Wholly aromatic polyamide or aromatic polyamides-urea or aromatics-rouge
Race's mixed polyamide；
Preferably, the above-mentioned silane coupling agent containing amino or acyloxy is 3- aminopropyl triethoxysilane, 3- ammonia
Hydroxypropyl methyl diethoxy silane, 3- aminopropyl trimethoxysilane, 3- aminopropyltriethoxy dimethoxysilane, N- (2- ammonia second
Base) -3- aminopropyl triethoxysilane, N- (2- aminoethyl) -3- aminopropyl trimethoxysilane, N- (2- aminoethyl) -3- ammonia
Hydroxypropyl methyl dimethoxysilane, 3- diethylenetriamine hydroxypropyl methyl dimethoxysilane, N- phenyl -3- aminopropyl trimethoxy
Silane, n-butyl amine base propyl trimethoxy silicane, 3- methacryloxypropyl trimethoxy silane, 3- methacryloxypropyl
One of base propyl-triethoxysilicane, 3- methacryloxypropylmethyl dimethoxysilane are a variety of；
Preferably, above-mentioned base catalyst is ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, one in sodium bicarbonate
Kind is a variety of；
A kind of high-performance reverse osmosis composite membrane preparation method of chlorine-resistant, its step are as follows: first will be polyamide-based reverse osmosis
Composite membrane is immersed in the amino containing 0.1-5.0wt% or acyloxy silane coupling agent aqueous solution 10-30 minutes, is used after taking-up
Deionized water rinses 10 minutes；Treated reverse osmosis composite membrane is then immersed in the alkaline solution of pH=8.0-12.0
It is 10-30 minutes middle, it is rinsed 10 minutes after taking-up with deionized water, obtains the high-performance reverse osmosis composite membrane of chlorine-resistant.
Compared with prior art the invention has the benefit that the invention firstly uses the amino or acyl in silane coupling agent
Oxygroup and polyamide-based macromolecule formation hydrogen bond action, the silane coupling agent coating of depositing homogeneous on reverse osmosis composite membrane surface,
And cause permeation flux fall is big to lack when removing extra silane coupling agent by rinsing to avoid conventional method coating
It falls into；Then, under room temperature using base catalysis make the silicon oxygen bond in silane coupling agent hydrolyze and with the amide in polyamide-based macromolecule
N-H in key reacts, and fixes silane coupling agent coating in a manner of chemical bond while reducing Active Chlorine attack site
On reverse osmosis membrane surface, overcome the problems, such as that conventional coating is easily lost in use, effectively extension guard time.
Specific embodiment
Implementation of the invention is illustrated below:
Modifying compound film surface:
By the polyamide-based reverse osmosis composite membrane through deionized water rinsing processing, successively it is handled as follows:
(1) polyamide-based reverse osmosis composite membrane is immersed in the amino containing 2.0wt% or acyloxy silane coupling agent water
30 minutes in solution, rinsed 10 minutes after taking-up with deionized water；
(2) treated reverse osmosis composite membrane is immersed in the ammonia spirit of pH=10.0 20 minutes, after taking-up
It is rinsed 10 minutes with deionized water, obtains the high-performance reverse osmosis composite membrane of chlorine-resistant.
Compound membrane separating property evaluation:
Salt rejection rate and permeation flux are two important parameters for evaluating reverse osmosis compound film separating property, are permeated by cross-flow
Mode is evaluated, and the NaCl aqueous solution that specific selection 2000mg/l and pH are 7.0~8.0 controls operation as feeding liquid
Pressure is 1.55MPa and temperature is 25 DEG C, the results are shown in Table 1.
The evaluation of composite membrane chlorine-resistant property:
The chlorine-resistant property of reverse osmosis membrane is carried out by way of static immersing, it is specific that select temperature be 25 DEG C, pH 8.0,
It impregnates after a certain period of time, takes out and with deionized water rinsed clean in the NaClO aqueous solution that concentration is 2000mg/l, test its point
From performance, it the results are shown in Table 2.
As a result:
Table 1: different silane coupling agents are selected treated reverse osmosis membrane performance
Examples detailed above 1-5 shows: after Wholly aromatic polyamide reverse osmosis composite membrane is impregnated using different silane coupling agents
It is handled again through ammonia spirit base catalysis, the permeation flux of reverse osmosis composite membrane has different degrees of reduction, but amplitude is respectively less than
10%, it is minimum only to reduce by 4.8%；And NaCl removal efficiency then slightly increases, wherein using N- (2- aminoethyl) -3- aminopropyl front three
When oxysilane, salt rejection rate has 99.3% to be increased to 99.5%, and flux only reduces by 7.0%；Example 5-8 then shows using phase
Same silane coupling agent is catalyzed after impregnating through different aqueous slkalis, and the influence to separating property is smaller.
Salt rejection rate (unit: %) of each reverse osmosis composite membrane of table 2 after sodium hypochlorite handles different time
| Handle the time | 0h | 1h | 2h | 3h | 4h | 5h |
| Comparative example 1 | 99.3 | 98.8 | 97.9 | 96.5 | 93.7 | 91.5 |
| Embodiment 1 | 99.4 | 99.4 | 99.3 | 99.2 | 99.1 | 98.9 |
| Embodiment 2 | 99.4 | 99.2 | 99.0 | 98.8 | 98.5 | 98.1 |
| Embodiment 3 | 99.5 | 99.3 | 99.2 | 99.0 | 98.7 | 98.5 |
| Embodiment 4 | 99.4 | 99.1 | 98.9 | 98.7 | 98.6 | 98.3 |
| Embodiment 5 | 99.4 | 99.3 | 99.3 | 99.2 | 99.0 | 99.0 |
| Embodiment 6 | 99.4 | 99.2 | 99.3 | 99.2 | 99.0 | 99.0 |
| Embodiment 7 | 99.4 | 99.3 | 99.2 | 99.2 | 99.1 | 99.0 |
| Embodiment 8 | 99.4 | 99.2 | 99.2 | 99.1 | 99.1 | 98.9 |
The chlorine-resistant of reverse osmosis composite membrane experiments have shown that, 1 polyamide reverse osmosis composite film of comparative example of non-surface modification treatment
After the NaClO immersion treatment of 2000mg/l, film extends rapid decrease with soaking time to the salt rejection rate of sodium chloride, works as processing
When time is 5h, salt rejection rate drops to 91.5% from 99.3%；And through silane coupling agent, treated that each reverse osmosis composite membrane passes through
After NaClO processing, film is smaller with the extended amplitude of variation of soaking time to the salt rejection rate of sodium chloride, after 5h processing,
Also salt rejection rate can be maintained 98.1% or more, there is excellent Active Chlorine tolerance.
Comparative examples 1 and embodiment 1-8, high-performance reverse osmosis composite membrane prepared by the present invention not only have excellent
Active Chlorine tolerance, and salt rejection rate with higher.
Claims (6)
1. a kind of high-performance reverse osmosis composite membrane of chlorine-resistant, which is characterized in that micropore support membrane surface recombination has a strata amide
Class macromolecule desalination layer, is deposited with silane coupling agent coating in desalination layer, is catalyzed shape by Hydrogen Binding Adsorption-room temperature base catalyst
At.
2. a kind of high-performance reverse osmosis composite membrane of chlorine-resistant according to claim 1, it is characterised in that the polyamide
Class macromolecule is Wholly aromatic polyamide or aromatic polyamides-urea or aromatic-aliphatic mixed polyamide.
3. a kind of high-performance reverse osmosis composite membrane of chlorine-resistant according to claim 1, it is characterised in that the silane is even
Connection agent contains amino or acyloxy, specifically: 3- aminopropyl triethoxysilane, 3- aminopropyltriethoxy diethoxy silane, 3-
Aminopropyl trimethoxysilane, 3- aminopropyltriethoxy dimethoxysilane, N- (2- aminoethyl) -3- aminopropyl-triethoxy silicon
Alkane, N- (2- aminoethyl) -3- aminopropyl trimethoxysilane, N- (2- aminoethyl) -3- aminopropyltriethoxy dimethoxysilane, 3-
Diethylenetriamine hydroxypropyl methyl dimethoxysilane, N- phenyl -3- aminopropyl trimethoxysilane, n-butyl amine base propyl trimethoxy
In base silane, 3- methacryloxypropyl trimethoxy silane, 3- methacryloxypropyl or
One of 3- methacryloxypropylmethyl dimethoxysilane is a variety of.
4. a kind of high-performance reverse osmosis composite membrane of chlorine-resistant according to claim 3, it is characterised in that described contains ammonia
The silane coupling agent of base or acyloxy are as follows: N- (2- aminoethyl) -3- aminopropyl trimethoxysilane.
5. a kind of high-performance reverse osmosis composite membrane of chlorine-resistant according to claim 1, it is characterised in that the base catalysis
Agent is one of ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate or a variety of.
6. a kind of high-performance reverse osmosis composite membrane preparation method of chlorine-resistant, its step are as follows: first will be polyamide-based reverse osmosis multiple
It closes film to be immersed in the amino containing 0.1-5.0wt% or acyloxy silane coupling agent aqueous solution 10-30 minutes, be spent after taking-up
Ionized water rinses 10 minutes；Then treated reverse osmosis composite membrane is immersed in the alkaline solution of pH=8.0-12.0
It 10-30 minutes, is rinsed 10 minutes after taking-up with deionized water, obtains the high-performance reverse osmosis composite membrane of chlorine-resistant.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113230912A (en) * | 2021-04-29 | 2021-08-10 | 浙江理工大学 | Preparation method of chlorine-resistant composite nanofiltration membrane |
| CN113522065A (en) * | 2020-04-22 | 2021-10-22 | 万华化学集团股份有限公司 | Chlorine-resistant and pollution-resistant polyamide reverse osmosis composite membrane and preparation method thereof |
| CN114504956A (en) * | 2022-02-17 | 2022-05-17 | 北京碧水源分离膜科技有限公司 | Chlorine-resistant nanofiltration membrane and preparation method thereof |
| CN115093055A (en) * | 2022-07-14 | 2022-09-23 | 重庆海通环保科技有限公司 | Reverse osmosis membrane coating and reverse osmosis membrane body suitable for strong acid solution |
| CN115337800A (en) * | 2022-09-21 | 2022-11-15 | 万华化学集团股份有限公司 | High-desalination antioxidant polyamide reverse osmosis membrane, and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113522065A (en) * | 2020-04-22 | 2021-10-22 | 万华化学集团股份有限公司 | Chlorine-resistant and pollution-resistant polyamide reverse osmosis composite membrane and preparation method thereof |
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| CN115093055A (en) * | 2022-07-14 | 2022-09-23 | 重庆海通环保科技有限公司 | Reverse osmosis membrane coating and reverse osmosis membrane body suitable for strong acid solution |
| CN115093055B (en) * | 2022-07-14 | 2023-10-31 | 重庆海通环保科技有限公司 | Reverse osmosis membrane coating and reverse osmosis membrane body suitable for strong acid solution |
| CN115337800A (en) * | 2022-09-21 | 2022-11-15 | 万华化学集团股份有限公司 | High-desalination antioxidant polyamide reverse osmosis membrane, and preparation method and application thereof |
| CN115337800B (en) * | 2022-09-21 | 2024-05-03 | 万华化学集团股份有限公司 | High-desalination antioxidant polyamide reverse osmosis membrane, preparation method and application thereof |
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Application publication date: 20190222 |