CN102527254A - High-flux composite reverse osmosis membrane - Google Patents
High-flux composite reverse osmosis membrane Download PDFInfo
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- CN102527254A CN102527254A CN2012100072123A CN201210007212A CN102527254A CN 102527254 A CN102527254 A CN 102527254A CN 2012100072123 A CN2012100072123 A CN 2012100072123A CN 201210007212 A CN201210007212 A CN 201210007212A CN 102527254 A CN102527254 A CN 102527254A
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Abstract
The invention relates to a polymeric membrane for water treatment, in particular to a high-flux composite reverse osmosis membrane. An ultrathin desalination separation layer is compounded on a porous supporting membrane through interfacial polycondensation between a polyamine-containing aqueous solution and an organic solution containing aromatic polyacyl chloride; the polyamine is a mixture of metaphenylene diamine and sericin; and the aromatic polyacyl chloride is benzenetricarbonyl trichloride, 5-isocyanate- isophthaloyl chloride, 5-oxoformyl chloride-isophthaloyl chloride, isophthaloyl dichloride, paraphthaloyl chloride or 2,4-toluene diisocyanate. The high-flux composite reverse osmosis membrane has the advantages of readily available raw materials, low price and excellent selective separation property. The water flux of the high-flux composite reverse osmosis membrane is higher than that of the conventional polyamide composite reverse osmosis membrane. The high-flux composite reverse osmosis membrane has high membrane surface hydrophilicity and high pollution resistance. The high-flux composite reverse osmosis membrane has wide application.
Description
Technical field
The invention belongs to water technology, specifically is that high-flux composite reverse osmosis membrane is used in a kind of water treatment.
Technical background
Reverse osmosis technology is a kind of efficient, energy-conservation green isolation technics; Have outstanding features such as equipment is simple, operating condition is gentle, treating capacity is big, separative efficiency height; Separate with resource, biological products with brackish water desalination, wastewater treatment at seawater, environmental project, food, medicine and other fields be used widely, and obtained good economic and social benefit; In recent years, along with the water globe shortage of resources is serious day by day, water pollutes and increases the weight of day by day, reverse osmosis technology has obtained using widely and paying attention in desalinization and water reuse field.
The core of reverse osmosis technology is a reverse osmosis membrane, and asymmetric reverse osmosis membrane and complex reverse osmosis membrane are two types of high-performance reverse osmosis membranes of commercial applications at present, and complex reverse osmosis membrane then is the main product in present reverse osmosis membrane field.Complex reverse osmosis membrane is that one deck ultrathin functional layer is deposited to suitable micropore support membrane surface, aperture, and depositional mode mainly contains surface-coated, interfacial polycondensation and in-situ polymerization etc.Composite membrane can make every layer to reach optimum performance through optimization.Ultrathin functional layer can be optimized to desirable selection permeability, and support membrane can reach best intensity and pressure tightness.In addition, composite membrane can make the material that is difficult to form asymmetric membrane form ultrathin membrane, as because solvent limitation and crosslinking polymer can form composite membrane through in-situ polymerization or interfacial polycondensation.
Salt rejection rate and water flux are two important parameters estimating reverse osmosis membrane, and the size of the salt rejection rate of reverse osmosis membrane and water permeation flux is directly determining the efficient of reverse osmosis process.Salt rejection rate (R) is defined as: under certain operating condition, and feeding liquid salinity (C
f) with penetrating fluid in salinity (C
p) poor, again divided by the feeding liquid salinity.Concrete computing formula is following:
Water flux (F) is defined as: under certain operating condition, see through the volume (V) of the water of elementary membrane area (A) in the unit interval (t), its unit is l/m
2.h, concrete computing formula is following:
Cadotte etc. are in US Patent 4,277,344 in 1981; Through the interfacial polymerization between m-phenylene diamine (MPD) and the pyromellitic trimethylsilyl chloride; Compound one deck aromatic polyamides desalination layer on the polysulfones support membrane, the preparation complex reverse osmosis membrane, salt rejection rate is greater than 99%; But the permeation flux of such reverse osmosis membrane is not high, and the chemical structural formula of its ultra-thin desalination layer can be expressed as:
Uemura etc. are in US Patent 4,761,234 in 1988; Adopt interfacial polycondensation technology; Through the interfacial polymerization between equal benzene triamine and the m-phthaloyl chloride, the compound one deck aromatic polyamides film of reaction on porous polysulfones support membrane, preparation high desalination reverse osmosis composite membrane; The film salt rejection rate is greater than 99.0%, but its used equal benzene triamine is difficult to obtain.The chemical structural formula of the ultra-thin desalination layer of such compound reverse osmosis composite membrane can be expressed as:
In addition, US Patent 4,529,646, US Patent4,872; 984, US Patent4,948,507, US Patent5,576; 057, US Patent 5,989, and 426, US Patent 6,162; 358, US Patent 6,464, and patents such as 873 also are to adopt interfacial polymerization technology, and preparing permeation flux through the interface polymerization reaction between polyamine on the porous support membrane and polynary acyl chlorides is 30～40 l/m
2.h.MPa complex reverse osmosis membrane product
Thereby, adopt the interfacial polymerization prepared, through the interfacial polymerization between m-phenylene diamine (MPD) and the aromatic polycarboxylic acyl chlorides, can obtain the complex reverse osmosis membrane of high desalination rate, but its permeation flux is on the low side.Along with fields such as drink water purifying, middle water reuse, Treatment of Industrial Water improve constantly what the reverse osmosis membrane permeation flux required, the preparation high-flux composite reverse osmosis membrane is very necessary.
Summary of the invention
The technical issues that need to address of the present invention are, provide a kind of raw material to be easy to get, and are cheap, and salt rejection rate is high, the NEW TYPE OF COMPOSITE reverse osmosis membrane that flux is big.
The present invention is achieved through following technical proposals:
A kind of high-flux composite reverse osmosis membrane is characterized in that, the interfacial polycondensation between the aqueous solution through containing polyamine on the porous support membrane and the organic solution that contains the aromatic polycarboxylic acyl chlorides, compound one deck desalination functional layer.
Porous support membrane wherein is conventional support membrane, and its preparation method, membrane structure are general in the market film, can oneself prepare, also can on market, buy in the present invention.
As preferably, above-mentioned high-flux composite reverse osmosis membrane, described polyamine are the mixtures of m-phenylene diamine (MPD) and sericin, and its weight ratio is a m-phenylene diamine (MPD): sericin=50～1: 1; As better selection, described weight ratio is a m-phenylene diamine (MPD): sericin=30～5: 1.
As preferably, above-mentioned high-flux composite reverse osmosis membrane, described aromatic polycarboxylic acyl chlorides are pyromellitic trimethylsilyl chloride (TMC); Or 5-isocyanates-isophthaloyl chlorine (ICIC); Or 5-oxygen formyl chloride-isophthaloyl chlorine (CFIC), or m-phthaloyl chloride (IPC), or paraphthaloyl chloride (TPC); Or 2,4-vulcabond toluene (TDI).
As preferably, above-mentioned high-flux composite reverse osmosis membrane, the part by weight of polyamine is 1.0-4.0wt% in the described aqueous solution, and the part by weight of aromatic polycarboxylic acyl chlorides is 0.05-0.20wt% in the organic solution, and the used organic solvent of organic solution is Isopar
G, a kind of in trifluorotrichloroethane, n-hexane, normal heptane or the dodecane.As better selection, the weight concentration of polyamine is 1.5-3.0wt% in the aqueous solution.
As preferably; In above-mentioned a kind of high-flux composite reverse osmosis membrane; The organic solution that contains the aqueous solution of polyamine and contain the aromatic polycarboxylic acyl chlorides is after the porous support membrane interfacial polycondensation forms; Earlier complex reverse osmosis membrane is dried in the shade, again through two step heat treatments: the first step is to handle 3～5 minutes down at 60～70 ℃, and second step was to handle 3～5 minutes down at 80～110 ℃; Then carry out two step rinsings again: the first step is to be rinsing 10～20 minutes in the methanol aqueous solution of 15wt% at 30～50 ℃, weight ratio, and second step was rinsing 10～30 minutes in 40～50 ℃ water.
High-flux composite reverse osmosis membrane described in the present invention is a flat sheet membrane, or hollow-fibre membrane, or tubular membrane.
Beneficial effect: the water flux of high-flux composite reverse osmosis membrane of the present invention is higher than existing polyamide composite reverse osmosis membrane, and salt rejection rate is not less than existing polyamide composite reverse osmosis membrane, and the film surface hydrophilicity is good, antifouling property is good.
The specific embodiment
Specify in the face of enforcement of the present invention down:
Following examples provide explanation, preparation method and their separating property of high-flux composite reverse osmosis membrane.Yet these embodiment only provide as explanation rather than limit the present invention.
Porous support membrane preparation: by the conventional method preparation; The present invention is the UDEL PS3500 polysulfones with 13.5wt%; The water of 0.25wt% and the surfactant of 0.15wt% are dissolved in N; In the dinethylformamide, be coated with and scrape on polyester non-woven fabric, immerse then in the water and to remove that to obtain molecular cut off (MWCO) after desolvating be 100,000 polysulfones porous support membrane.Wherein surfactant comprises alkyl phenol polyoxy Acetoxon acid esters at least, a kind of in dodecyl sodium sulfate and the alkyl phenol polyoxy Acetoxon hydrochlorate.
The preparation of complex reverse osmosis membrane: the polysulfones support membrane of hygrometric state is immersed in contains in the polyamine aqueous solution that acid receives agent 1-5 minute, after extracting with squeegee roll extrusion support membrane surface, contact with the organic solution single face that contains the aromatic polycarboxylic acyl chlorides and to carry out interface polymerization reaction.Composite membrane dried in the shade in air 2-5 minute, and again through two step heat treatments: the first step is to handle 3～5 minutes down at 40～70 ℃, and second step was to handle 3～5 minutes down at 70～110 ℃.Then carry out two step rinsings again: the first step is to be rinsing 10～40 minutes in 15% the aqueous solution at 30～60 ℃ methyl alcohol part by weight, and second step was rinsing 10～40 minutes in 30～60 ℃ water.It is triethylamine that acid wherein receives agent, or NaOH, or sodium carbonate, or tertiary sodium phosphate, and content is 1.0-4.0wt%; Polyamine wherein is the mixture of m-phenylene diamine (MPD) and sericin, and its weight ratio is a m-phenylene diamine (MPD): sericin=50～1: 1, and content is 1.0-4.0wt%; Aromatic polycarboxylic acyl chlorides wherein is pyromellitic trimethylsilyl chloride (TMC); Or 5-isocyanates-isophthaloyl chlorine (ICIC), or 5-oxygen formyl chloride-isophthaloyl chlorine (CFIC), or m-phthaloyl chloride (IPC); Or paraphthaloyl chloride (TPC); Or 2,4-vulcabond toluene (TDI), content are 0.05-0.20wt%; The used organic solvent of organic solution wherein is Isopar
G, or trifluorotrichloroethane, or n-hexane, or normal heptane, or dodecane; The single face haptoreaction time wherein is 0.5-5 minute.
The complex reverse osmosis membrane separating property is estimated: adopt the sodium-chloride water solution of 2000ppm, operating pressure is 225psi, and operating temperature is 25 ℃, and the salt rejection rate and the water flux of prepared composite counter-infiltration are estimated.
Embodiment 1-6
UDELPS3500 polysulfones with 13.5wt%; The polyoxyethylene nonyl phenyl Acetoxon acid esters of the water of 0.25wt% and 0.15wt% is dissolved in N; In the N--dimethyl formamide, be coated with and scrape on polyester non-woven fabric, immerse then in the water to remove and obtain the polysulfones porous support membrane that molecular cut off is 9-10 ten thousand after desolvating.
The polysulfones porous support membrane of hygrometric state was immersed in the aqueous solution of the polyamine (m-phenylene diamine (MPD), sericin mixed liquor) that contains 3.0wt% triethylamine and 2.0wt% 3 minutes; With squeegee roll extrusion support membrane surface; After draining the aqueous solution and the support membrane surface being dried up, contact with the hexane solution single face that contains the 0.10wt% pyromellitic trimethylsilyl chloride and to carry out interface polymerization reaction 40 seconds with nitrogen.The composite membrane of gained dried in the shade in air 5 minutes, and again through two step heat treatments: the first step is to handle 3～5 minutes down at 60～70 ℃, and second step was to handle 3～5 minutes down at 80～110 ℃.Then carry out two step rinsings again: the first step is rinsing 10～20 minutes in 30～50 ℃ 15wt% methanol aqueous solution, and second step was rinsing 10～30 minutes in 40～50 ℃ water.The composite membrane of preparation is with the sodium-chloride water solution of 2000ppm, and operating pressure is 225psi, 25 ℃, pH 6.8 times, tests its salt rejection rate and water flux.These several embodiment are that polyamine is formed the complex reverse osmosis membrane Effect on Performance in the investigation aqueous solution.
| Embodiment | Polyamine and weight ratio thereof | Salt rejection rate % | Water flux l/m 2.h |
| Example 1 | M-phenylene diamine (MPD) | 98.0 | 38.0 |
| Example 2 | M-phenylene diamine (MPD): sericin=50: 1 | 98.2 | 52.0 |
| Example 3 | M-phenylene diamine (MPD): sericin=30: 1 | 98.5 | 80.0 |
| Example 4 | M-phenylene diamine (MPD): sericin=10: 1 | 98.7 | 75.0 |
| Example 5 | M-phenylene diamine (MPD): sericin=5: 1 | 97.8 | 72.0 |
| Example 6 | M-phenylene diamine (MPD): sericin=1: 1 | 94.5 | 60.0 |
Embodiment 7-12
Embodiment like before; As stated above; Employing contains the polyamine (m-phenylene diamine (MPD): aqueous solution sericin=25: 1) of 3.0wt% triethylamine and 1.0-4.0wt%; Contact with the n-heptane solution single face that contains the 0.10wt% pyromellitic trimethylsilyl chloride and to carry out interface polymerization reaction 60 seconds, the preparation complex reverse osmosis membrane.These several embodiment investigate in the aqueous solution polyamine content to the complex reverse osmosis membrane Effect on Performance.
| Embodiment | Polyamine content wt% | Salt rejection rate % | Water flux l/m 2.h |
| Example 7 | 1.0 | 98.0 | 58.0 |
| Example 8 | 1.5 | 98.5 | 62.8 |
| Example 9 | 2.0 | 98.9 | 62.0 |
| Example 10 | 2.5 | 98.8 | 66.5 |
| Example 11 | 3.0 | 99.1 | 62.0 |
| Example 12 | 4.0 | 98.5 | 50.0 |
Embodiment 13-18
Embodiment like before; As stated above; Employing contains the polyamine (m-phenylene diamine (MPD): aqueous solution sericin=25: 1) of 2.0wt% tertiary sodium phosphate and 2.0wt%; Contact with the trifluorotrichloroethane solution single face that contains the polynary acyl chlorides of 0.10wt% distinct fragrance and to carry out interface polymerization reaction 50 seconds, the preparation complex reverse osmosis membrane.These several embodiment investigate in the organic solution aromatic polycarboxylic acyl chlorides kind to the complex reverse osmosis membrane Effect on Performance.
| Embodiment | The aromatic polycarboxylic acyl chlorides | Salt rejection rate % | Water flux l/m 2.h |
| Example 13 | Pyromellitic trimethylsilyl chloride (TMC), | 98.3 | 59.5 |
| Example 14 | 5-isocyanates-isophthaloyl chlorine (ICIC) | 98.5 | 56.8 |
| Example 15 | 5-oxygen formyl chloride-isophthaloyl chlorine (CFIC) | 99.2 | 57.5 |
| Example 16 | M-phthaloyl chloride (IPC) | 98.2 | 72.5 |
| Example 17 | Paraphthaloyl chloride (TPC) | 98.3 | 76.0 |
| Example 18 | 2,4-vulcabond toluene (TDI) | 98.3 | 75.0 |
Embodiment 19-22
Like the embodiment of before, as stated above, adopt the polyamine contain 1.0wt% NaOH and 2.0wt% (m-phenylene diamine (MPD): aqueous solution sericin=25: 1), with the Isopar that contains the variable concentrations pyromellitic trimethylsilyl chloride
GThe contact of solution single face was carried out interface polymerization reaction 30 seconds, the preparation complex reverse osmosis membrane.These several embodiment investigate the content of aromatic polycarboxylic acyl chlorides in the organic solution to the complex reverse osmosis membrane Effect on Performance.
| Embodiment | Pyromellitic trimethylsilyl chloride content wt% | Salt rejection rate % | Water flux l/m 2.h |
| Example 19 | 0.05 | 98.8 | 79.5 |
| Example 20 | 0.1 | 99.0 | 59.8 |
| Example 21 | 0.15 | 99.2 | 50.5 |
| Example 22 | 0.2 | 99.0 | 45.5 |
Claims (5)
1. a high-flux composite reverse osmosis membrane is characterized in that, one deck desalination functional layer is arranged on porous support membrane, and the desalination functional layer is to form at the porous support membrane interfacial polycondensation through the aqueous solution that contains polyamine and the organic solution that contains the aromatic polycarboxylic acyl chlorides;
Described polyamine is the mixture of m-phenylene diamine (MPD) and sericin, and its weight ratio is a m-phenylene diamine (MPD): sericin is 50～1: 1, and the weight concentration of polyamine is 1.0-4.0wt% in the aqueous solution;
Described aromatic polycarboxylic acyl chlorides is pyromellitic trimethylsilyl chloride, 5-isocyanates-isophthaloyl chlorine, 5-oxygen formyl chloride-isophthaloyl chlorine, m-phthaloyl chloride, paraphthaloyl chloride or 2; A kind of in the 4-vulcabond toluene; The weight concentration of aromatic polycarboxylic acyl chlorides is 0.05-0.20wt% in the organic solution, and the used organic solvent of organic solution is Isopar
G, a kind of in trifluorotrichloroethane, n-hexane, normal heptane or the dodecane.
2. a kind of high-flux composite reverse osmosis membrane according to claim 1 is characterized in that, described m-phenylene diamine (MPD): the weight ratio of sericin is 30～5: 1.
3. a kind of high-flux composite reverse osmosis membrane according to claim 1; It is characterized in that; The organic solution that contains the aqueous solution of polyamine and contain the aromatic polycarboxylic acyl chlorides is after the porous support membrane interfacial polycondensation forms; Earlier complex reverse osmosis membrane is dried in the shade, again through two step heat treatments: the first step is to handle 3～5 minutes down at 60～70 ℃, and second step was to handle 3～5 minutes down at 80～110 ℃; Then carry out two step rinsings again: the first step is to be rinsing 10～20 minutes in the methanol aqueous solution of 15wt% at 30～50 ℃, weight ratio, and second step was rinsing 10～30 minutes in 40～50 ℃ water.
4. a kind of high-flux composite reverse osmosis membrane according to claim 1 is characterized in that, the weight concentration of polyamine is 1.5-3.0wt% in the aqueous solution.
5. a kind of high-flux composite reverse osmosis membrane according to claim 1 is characterized in that, the compound counter-infiltration of described high flux is a flat sheet membrane, or hollow-fibre membrane, or tubular membrane.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105617875A (en) * | 2014-11-03 | 2016-06-01 | 株洲时代新材料科技股份有限公司 | High-throughput hollow fiber composite nanofiltration membrane, and preparation method thereof |
| CN111841346A (en) * | 2020-07-21 | 2020-10-30 | 浙江奥氏环境科技有限公司 | Preparation method of reverse osmosis membrane |
| CN115007004A (en) * | 2022-05-16 | 2022-09-06 | 天津工业大学 | Preparation method of hydrophilic charged high-pressure reverse osmosis membrane based on chicken protein/aromatic polyamide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105617875A (en) * | 2014-11-03 | 2016-06-01 | 株洲时代新材料科技股份有限公司 | High-throughput hollow fiber composite nanofiltration membrane, and preparation method thereof |
| CN111841346A (en) * | 2020-07-21 | 2020-10-30 | 浙江奥氏环境科技有限公司 | Preparation method of reverse osmosis membrane |
| CN115007004A (en) * | 2022-05-16 | 2022-09-06 | 天津工业大学 | Preparation method of hydrophilic charged high-pressure reverse osmosis membrane based on chicken protein/aromatic polyamide |
| CN115007004B (en) * | 2022-05-16 | 2023-12-26 | 天津工业大学 | Preparation method of hydrophilic charged high-voltage reverse osmosis membrane based on egg albumin/aromatic polyamide |
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Application publication date: 20120704 |