CN110508162A - Reverse osmosis membrane and its preparation method and application - Google Patents
Reverse osmosis membrane and its preparation method and application Download PDFInfo
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- CN110508162A CN110508162A CN201810497626.6A CN201810497626A CN110508162A CN 110508162 A CN110508162 A CN 110508162A CN 201810497626 A CN201810497626 A CN 201810497626A CN 110508162 A CN110508162 A CN 110508162A
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- polynary
- reverse osmosis
- osmosis membrane
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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
- 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
- B01D69/10—Supported membranes; Membrane supports
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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
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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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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to seperation film field, a kind of reverse osmosis membrane and its preparation method and application is disclosed.The reverse osmosis membrane includes the supporting layer being bonded to each other and polyamide separating layer, and the polyamide separating layer carries out interfacial polymerization with polynary acyl chlorides by the reaction product of polynary aminated compounds and acid anhydrides and obtains.Reverse osmosis membrane of the invention has high water flux and high salt-stopping rate simultaneously.
Description
Technical field
The present invention relates to reverse osmosis membranes, and in particular, to a kind of reverse osmosis membrane, the reverse osmosis membrane preparation method and should
Application of the reverse osmosis membrane in water treatment procedure.
Background technique
Complex reverse osmosis membrane be on open support basement membrane it is compound one layer thin, fine and close, have special separation function not
Same material, therefore have the transmission rates of higher solute separation rate and water than integrated film is more than 90% currently on the market
Reverse osmosis membrane is complex reverse osmosis membrane.Complex reverse osmosis membrane oneself be widely used in petrochemical industry, electronics, weaving, light industry, metallurgy, doctor
The fields such as medicine, bioengineering, food, environmental protection.Satisfied complex reverse osmosis membrane should have infiltration capacity appropriate or salt-stopping rate.
The technical process of complex reverse osmosis membrane is described in United States Patent (USP) US4277344, i.e., is first coated in polysulfones
The micropore counterdie formed on polyester non-woven fabric, is immersed in diamines or polyamines aqueous solution, then passes through the methods of wind leaching, roll-in
The extra amine aqueous solution of film surface is removed, then is immersed in organic non-polar solution of the chloride compounds containing more than two acid chloride groups
In with acyl chlorides interface polymerization reaction occurs, to form the fine and close polyamide ultrathin active layer with separation function on surface,
After film forming, sufficiently washing and heat cure appropriate processing can increase film properties.
It is also to send out that it is the development trend of membrane for water treatment that preparation has the high-throughput complex reverse osmosis membrane with high salt-stopping rate simultaneously
Exhibition demand.Existing number of ways is modified complex reverse osmosis membrane at present.Common method is included in aqueous solution, i.e. polyamine
Middle addition auxiliary agent improves film properties.It describes and a kind of is added into aqueous solution in the United States Patent (USP) US4950404 of Chau et al.
Method of the polar non-solute to improve reverse osmosis membrane flux, but the obtained reverse osmosis membrane salt-stopping rate of this method under
Drop.Being respectively mentioned in United States Patent (USP) US6024873, US5576057 of Hirose et al. and solubility parameters is added into water phase is 8-
14(cal/cm3)1/2Reagent and the reagents such as alcohols, ethers.Modified reverse osmosis membrane flux also increases, but same
The decline of ground salt-stopping rate.Therefore, it is necessary to the methods that the flux that gets a promotion does not influence the improvement film properties of salt-stopping rate still.
Summary of the invention
The purpose of the invention is to overcome the existing above problem of the prior art, a kind of reverse osmosis membrane and preparation are provided
Methods and applications, the reverse osmosis membrane have high water flux and high salt-stopping rate simultaneously.
To achieve the goals above, one aspect of the present invention provides a kind of reverse osmosis membrane, which includes being bonded to each other
Supporting layer and polyamide separating layer, the polyamide separating layer by the reaction product of polynary aminated compounds and acid anhydrides with it is polynary
Acyl chlorides carries out interfacial polymerization and obtains.
Preferably, the reverse osmosis membrane is 97% or more, preferably 97.5% or more to the salt-stopping rate of sodium chloride, more preferably
98% or more.
Preferably, the polynary aminated compounds is aromatic polyamine.
Preferably, the polynary aminated compounds be m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine, 1,3,5- triaminobenzenes,
1,2,4- triaminobenzene, 3,5- diaminobenzoic acid, 2,4 di amino toluene, 2,4- diamino anisole, amidol and benzene two
One of methanediamine is a variety of.
Preferably, the polynary acyl chlorides is aromatic polyvalent acyl chlorides.
Preferably, the polynary acyl chlorides is paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride, biphenyl diformazan
One of acyl chlorides, benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride are a variety of.
Preferably, the acid anhydrides is maleic anhydride, acetic anhydride, phthalic anhydride, sulfuric anhydride, nitric acid anhydride and acrylic anhydride
One of or it is a variety of.
Preferably, the mass concentration ratio of the polynary aminated compounds and the polynary acyl chlorides is 1-100:1, more preferably
5-50:1, further preferably 10-40:1 are still more preferably 15-35:1, are still more preferably 18-25:1.
Preferably, the molar ratio of the polynary aminated compounds and the acid anhydrides is 1:0.002-2, more preferably 1:
0.02-0.4。
Preferably, the supporting layer by polyacrylonitrile, Kynoar, the non-sulfonated polyether sulphone of phenolphthalein type, sulfonated polysulfone,
One of sulfonated polyether sulfone, polyether sulfone and polysulfones a variety of are made.
Preferably, the supporting layer with a thickness of 90-150 μm, preferably 100-120 μm.
Preferably, the polyamide separating layer with a thickness of 0.01-0.5 μm, preferably 0.05-0.3 μm.
Second aspect of the present invention provides a kind of preparation method of reverse osmosis membrane, method includes the following steps:
(1) aqueous solution of polynary aminated compounds is contacted with acid anhydrides, makes the amino and acid anhydrides in polynary aminated compounds
Reaction；
(2) by the aqueous solution that supporting layer is first obtained with step (1) carry out first contact after, then with contain the molten of polynary acyl chlorides
Liquid carries out the second contact, is then heat-treated, to form polyamide separating layer in supporting layer.
Preferably, after making the amino and anhydride reaction in polynary aminated compounds, the aqueous solution that reaction is obtained carries out dilute
It releases, then carries out first contact.
Preferably, in step (2), after supporting layer is carried out the first contact, extra water phase is removed, then carries out second again
Contact.
Preferably, the polynary aminated compounds is aromatic polyamine.
It is highly preferred that the polynary aminated compounds is m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine, 1,3,5- triamidos
Benzene, 1,2,4- triaminobenzene, 3,5- diaminobenzoic acid, 2,4 di amino toluene, 2,4- diamino anisole, amidol and benzene
One of dimethyl-p-phenylenediamine is a variety of.
Preferably, in the aqueous solution of the polynary aminated compounds, the content of the polynary aminated compounds is 50-
500g/L。
Preferably, the polynary acyl chlorides is aromatic polyvalent acyl chlorides.
It is highly preferred that the polynary acyl chlorides is paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride, biphenyl two
One of formyl chloride, benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride are a variety of.
Preferably, the concentration of polynary acyl chlorides is 0.5-5g/L in the solution containing polynary acyl chlorides.
Preferably, the acid anhydrides is maleic anhydride, acetic anhydride, phthalic anhydride, sulfuric anhydride, nitric acid anhydride and acrylic anhydride
One of or it is a variety of.
Preferably, in the solution obtained after the aqueous solution of polynary aminated compounds being contacted with acid anhydrides, the acid anhydrides contains
Amount is 0.05-40g/L, preferably 0.2-10g/L.
Preferably, the diluted multiple is 2-40 times, preferably 5-20 times.
Preferably, the mass concentration ratio of the polynary aminated compounds and the polynary acyl chlorides is 1-100:1, more preferably
5-50:1, further preferably 10-40:1 are still more preferably 15-35:1, are still more preferably 18-25:1.
Preferably, the molar ratio of the polynary aminated compounds and the acid anhydrides is 1:0.002-2, more preferably 1:
0.02-0.4。
Preferably, the supporting layer by polyacrylonitrile, Kynoar, the non-sulfonated polyether sulphone of phenolphthalein type, sulfonated polysulfone,
One of sulfonated polyether sulfone, polyether sulfone and polysulfones a variety of are made.
Preferably, the supporting layer with a thickness of 90-150 μm, preferably 100-120 μm.
Preferably, the polyamide separating layer with a thickness of 0.01-0.5 μm, preferably 0.05-0.3 μm.
Preferably, it is 40-150 DEG C that the condition of heat treatment, which includes: temperature, time 0.5-20min.It is highly preferred that at heat
The condition of reason includes: that temperature is 50-120 DEG C, time 1-10min.
Preferably, the time of first contact is 5-150s, preferably 10-60s；
Preferably, the time of second contact is 5-150s, preferably 10-60s.
The present invention also provides the reverse osmosis membranes that the preparation method by above-mentioned reverse osmosis membrane is prepared.
The present invention also provides application of the above-mentioned reverse osmosis membrane in water treatment procedure.
The present inventor is by further investigation discovery, by the way that acid anhydrides is added into aqueous solution used in interfacial polymerization
And make it with after the polynary amine monomer reaction in aqueous solution, then subsequent interface polymerization reaction is carried out, compound reverse osmosis obtained
Permeable membrane has higher water flux and has substantially no effect on the salt-stopping rate to ion.It has thus completed the present invention.Of the invention answers
It is simple to close reverse osmosis membrane preparation method, great prospects for commercial application.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
A kind of reverse osmosis membrane provided by the invention, the reverse osmosis membrane include the supporting layer being bonded to each other and polyamide separation
Layer, the polyamide separating layer carry out interfacial polymerization with polynary acyl chlorides by the reaction product of polynary aminated compounds and acid anhydrides and obtain
It arrives.
In the present invention, the polyamide separating layer be cross-linked with each other by polynary aminated compounds, acid anhydrides and polynary acyl chlorides and
At.Reverse osmosis membrane of the invention is 97% or more to the salt-stopping rate of sodium chloride, preferably 97.5% or more, more preferably 98% with
On.
Here, term " interfacial polymerization ", also known as " interfacial polycondensation ", refer to: two kinds of high response monomers are dissolved in two kinds respectively
In immiscible solvent, and the irreversible polymerization reaction carried out in the interface of two liquid phases.Interface polymerization reaction is obtained poly-
It closes object and does not dissolve in solvent, be precipitated in interface.
In the present invention, it is cross-linked with each other to obtain the polyamide point by polynary aminated compounds, acid anhydrides and polynary acyl chlorides
Absciss layer, the reverse osmosis membrane enabled to have higher water flux and salt-stopping rate.
According to the present invention, to the type of the polynary aminated compounds, there is no particular limitation, can be conventional for this field
Selection, preferably aromatic polyamine；It is highly preferred that the polynary aminated compounds is m-phenylene diamine (MPD), o-phenylenediamine, to benzene
Diamines, 1,3,5- triaminobenzene, 1,2,4- triaminobenzene, 3,5- diaminobenzoic acid, 2,4 di amino toluene, 2,4- diamino
One of methyl phenyl ethers anisole, amidol and xylylene diamine are a variety of.It is wherein preferably m-phenylene diamine (MPD).
According to the present invention, to the type of the acid anhydrides, there is no particular limitation, can be anti-with the polynary aminated compounds
Should, such as can be one of maleic anhydride, acetic anhydride, phthalic anhydride, sulfuric anhydride, nitric acid anhydride and acrylic anhydride
Or it is a variety of.
The reverse osmosis membrane of high water flux and salt-stopping rate in order to obtain, it is preferable that the polynary aminated compounds and the acid
The molar ratio of acid anhydride is 1:0.002-2, more preferably 1:0.02-0.4.By being used cooperatively polynary amine chemical combination within the above range
Object and acid anhydrides, the water flux and salt-stopping rate of the reverse osmosis membrane that can be further improved.
According to the present invention, for the type of the polynary acyl chlorides, also there is no particular limitation, can usually use for this field
In preparing chloride compounds used in polyamide, preferably aromatic polyvalent acyl chlorides；Such as can for paraphthaloyl chloride,
One of phthalyl chloride, o-phthaloyl chloride, biphenyl dimethyl chloride, benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride are a variety of.Its
In preferably pyromellitic trimethylsilyl chloride.
Dosage as the polynary aminated compounds and the polynary acyl chlorides can change in a larger range,
Preferably, the mass concentration ratio of the polynary aminated compounds and the polynary acyl chlorides is 1-100:1, more preferably 5-50:1,
Further preferably 10-40:1 is still more preferably 15-35:1, is still more preferably 18-25:1.As described polynary
The mass concentration ratio of aminated compounds and the polynary acyl chlorides can specifically be enumerated: 15:1,16:1,17:1,18:1,19:1,20:
1,21:1,22:1,23:1,24:1 or 25:1 etc..
In addition, the preferably described polynary acyl chlorides uses in the form of a solution when carrying out interfacial polymerization, contain the molten of polynary acyl chlorides
Solvent in liquid can be it is existing, it is incompatible with the solvent of the polynary aminated compounds of above-mentioned dissolution and to polynary acyl chlorides inertia
Solvent, for example, can be organic solvent, as the organic solvent be preferably n-hexane, hexamethylene, trifluorotrichloroethane,
One of normal heptane, normal octane, toluene, ethylbenzene, Isopar E, Isopar G, Isopar H, Isopar L and Isopar M
Or it is a variety of.
Polyamide separating layer of the invention is obtained as the polyamine and the polynary acyl chlorides are carried out interfacial polymerization
There is no particular limitation for mode, the various routines that polyamine can be made to use with the progress interfacial polymerization of polynary acyl chlorides for this field
The way of contact.In the present invention, it is preferred to by supporting layer successively with the reaction product containing polynary aminated compounds and acid anhydrides
Solution and containing polynary acyl chlorides solution contact, be then heat-treated.
According to the present invention, the type of the supporting layer is not particularly limited, can by it is existing it is various have it is certain
The intensity and material that can be used in reverse osmosis membrane is made, usually can be non-sulfonated by polyacrylonitrile, Kynoar, phenolphthalein type
One of polyether sulphone, sulfonated polysulfone, sulfonated polyether sulfone, polyether sulfone and polysulfones a variety of are made.Such as it can be turned by phase
The preparation of change method.In addition, the supporting layer can be single hole or porous structure.A kind of specific embodiment according to the present invention, institute
State supporting layer include non-woven polyester layer of cloth and be attached in the polyester non-woven fabric layer surface by polyacrylonitrile, polyvinylidene fluoride
Gather made of at least one of the non-sulfonated polyether sulphone of alkene, phenolphthalein type, sulfonated polysulfone, sulfonated polyether sulfone, polyether sulfone and polysulfones
Close nitride layer.The molecular cut off of the supporting layer is preferably 3-5 ten thousand.
It can be the conventional choosing of this field in addition, in the present invention, being not particularly limited to the thickness of the supporting layer
It selects, but in order to make that better coordinated can be played the role of between the supporting layer and the polyamide separating layer, makes to obtain
Reverse osmosis membrane have higher water flux and salt-stopping rate, the preferably described supporting layer with a thickness of 90-150 μm, more preferably
100-120μm.Thickness as supporting layer can specifically be enumerated: 90 μm, 95 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm,
125 μm, 130 μm, 135 μm, 140 μm, 145 μm or 150 μm etc..
In addition, in the present invention, the thickness of the polyamide separating layer as formation can change in a big way, in order to
So that between polyamide separating layer and the supporting layer can better coordinated, the reverse osmosis membrane enable has more
High water flux and salt-stopping rate, the preferably described polyamide separating layer with a thickness of 0.01-0.5 μm, more preferably 0.02-0.3 μm,
More preferably 0.05-0.3 μm.Thickness as polyamide separating layer can specifically be enumerated: 0.05 μm, 0.1 μm, 0.15 μm, 0.2 μ
M, 0.3 μm, 0.4 μm or 0.5 μm etc..
The present invention also provides a kind of preparation methods of reverse osmosis membrane, method includes the following steps:
(1) aqueous solution of polynary aminated compounds is contacted with acid anhydrides, makes the amino and acid anhydrides in polynary aminated compounds
Reaction；
(2) by the aqueous solution that supporting layer is first obtained with step (1) carry out first contact after, then with contain the molten of polynary acyl chlorides
Liquid carries out the second contact, is then heat-treated, to form polyamide separating layer in supporting layer.
In the present invention, it in order to make polynary aminated compounds, acid anhydrides and polynary acyl chlorides be cross-linked with each other, needs first to make polyamine
The aqueous solution and anhydride reaction of class compound, then the reaction product and polynary acyl chlorides are subjected to interface polymerization reaction, to obtain
Polyamide separating layer of the invention.
A preferred embodiment according to the present invention, after making the amino and anhydride reaction in polynary aminated compounds,
The aqueous solution that reaction obtains is diluted, first contact is then carried out.By by the polyamine of acid anhydrides and higher concentration
Class compound is reacted, and is then diluted the aqueous solution that reaction obtains, it can be ensured that acid anhydrides and polynary aminated compounds
It is reacted.
A preferred embodiment according to the present invention, in order to improve the efficiency of step (2), it is preferable that step (2)
In, after supporting layer is carried out the first contact, extra water phase is removed, then carries out the second contact again.The water extra as removal
The method of phase, such as the method that can use drain are specifically as follows wind leaching method, roll-in method etc..
According to the present invention, to the type of the polynary aminated compounds, there is no particular limitation, can be conventional for this field
Selection, preferably aromatic polyamine；It is highly preferred that the polynary aminated compounds is m-phenylene diamine (MPD), o-phenylenediamine, to benzene
Diamines, 1,3,5- triaminobenzene, 1,2,4- triaminobenzene, 3,5- diaminobenzoic acid, 2,4 di amino toluene, 2,4- diamino
One of methyl phenyl ethers anisole, amidol and xylylene diamine are a variety of.It is wherein preferably m-phenylene diamine (MPD).It is excellent in interfacial polymerization
Select the polynary aminated compounds to use in the form of a solution, as the solvent for dissolving the polynary aminated compounds, can for
The solvent of the aftermentioned polynary acyl chlorides of dissolution is incompatible and to the polynary inert solvent of aminated compounds.For example, can for water,
One of methanol and acetonitrile are a variety of.For the ease of reacting with acid anhydrides, the solvent of the polynary amine compound solution is
Water.
In addition, not special for the content of polynary aminated compounds in the polynary amine compound solution (before dilution)
Restriction, can be this field conventional selection.For example, the content of above-mentioned polynary aminated compounds can be 50-500g/L, it is excellent
It is selected as 100-400g/L.The content of above-mentioned polynary aminated compounds be specifically as follows 50g/L, 100g/L, 150g/L, 200g/L,
250g/L, 300g/L, 350g/L, 400g/L, 450g/L or 500g/L etc..Preferably, polynary amine in the solution after dilution
The content for closing object is 1-30g/L.
According to the present invention, to the type of the acid anhydrides, there is no particular limitation, can be anti-with the polynary aminated compounds
Should, such as can be one of maleic anhydride, acetic anhydride, phthalic anhydride, sulfuric anhydride, nitric acid anhydride and acrylic anhydride
Or it is a variety of.It is described in the solution (solution before diluting) obtained after the aqueous solution of polynary aminated compounds is contacted with acid anhydrides
The content of acid anhydrides is 0.05-40g/L, preferably 0.2-10g/L.Preferably, in the solution after above-mentioned solution being diluted, the acid
The content of acid anhydride is 0.02-5g/L, more preferably 0.1-1g/L.
The reverse osmosis membrane of high water flux and salt-stopping rate in order to obtain, it is preferable that the polynary aminated compounds and the acid
The molar ratio of acid anhydride is 1:0.002-2, more preferably 1:0.02-0.4.By being used cooperatively polynary amine chemical combination within the above range
Object and acid anhydrides, the water flux and salt-stopping rate of the reverse osmosis membrane that can be further improved.
In the present invention, as needed, the aqueous solution of the polynary aminated compounds can also include auxiliary agent, such as surface
Activating agent and/or acid absorbent.As above-mentioned auxiliary agent, can be used it is existing can be used in preparing the various of composite separating film help
Agent.It specifically, can be lauryl sodium sulfate, neopelex, dodecyl three as the surfactant
One of methyl bromide ammonium and laurel disulfonate acid are a variety of；As the acid absorbent, can for triethylamine, sodium carbonate,
One of sodium bicarbonate, dibastic sodium phosphate, sodium phosphate, sodium hydroxide and potassium hydroxide are a variety of.It is excellent as above-mentioned auxiliary dosage
Selection of land, the concentration of the surfactant are 0.1-5g/L；The concentration of the acid absorbent is 1-10g/L.
According to the present invention, for the type of the polynary acyl chlorides, also there is no particular limitation, can usually use for this field
In preparing chloride compounds used in polyamide, preferably aromatic polyvalent acyl chlorides；Such as can for paraphthaloyl chloride,
One of phthalyl chloride, o-phthaloyl chloride, biphenyl dimethyl chloride, benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride are a variety of.Its
In preferably pyromellitic trimethylsilyl chloride.
In addition, for the concentration of polynary acyl chlorides in the polynary solution of acid chloride, there is no particular limitation, can be this field
Conventional selection.For example, the concentration of polynary acyl chlorides can be 0.5-5g/L, preferably 0.8-2g/ in the polynary solution of acid chloride
L.In the polynary amine aqueous solution concentration of polyamine be specifically as follows 0.5g/L, 1/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L,
3.5g/L, 4g/L, 4.5g/L or 5g/L etc..
Dosage as the polynary aminated compounds and the polynary acyl chlorides can change in a larger range,
Preferably, the mass concentration ratio of the polynary aminated compounds and the polynary acyl chlorides is 1-100:1, more preferably 5-50:1,
Further preferably 10-40:1 is still more preferably 15-35:1, is still more preferably 18-25:1；As described polynary
The mass concentration ratio of aminated compounds and the polynary acyl chlorides can specifically be enumerated: 15:1,16:1,17:1,18:1,19:1,20:
1,21:1,22:1,23:1,24:1 or 25:1 etc..
In addition, the preferably described polynary acyl chlorides uses in the form of a solution when carrying out interfacial polymerization, contain the molten of polynary acyl chlorides
Solvent in liquid can be it is existing, it is incompatible with the solvent of the polynary aminated compounds of above-mentioned dissolution and to polynary acyl chlorides inertia
Solvent, for example, can be organic solvent, as the organic solvent be preferably n-hexane, hexamethylene, trifluorotrichloroethane,
One of normal heptane, normal octane, toluene, ethylbenzene, Isopar E, Isopar G, Isopar H, Isopar L and Isopar M
Or it is a variety of.
Polyamide separating layer of the invention is obtained as the polyamine and the polynary acyl chlorides are carried out interfacial polymerization
There is no particular limitation for mode, the various routines that polyamine can be made to use with the progress interfacial polymerization of polynary acyl chlorides for this field
The way of contact.
According to the present invention, in step (1), the polynary aminated compounds is contacted with the acid anhydrides, the reaction time
There is no particular limitation, such as can be 10-180s, preferably 20-90s；Temperature when above-mentioned contact can be 10-60 DEG C,
Preferably 20-40 DEG C (such as can be 25 DEG C).
In order to promote acid anhydrides to be reacted with polynary aminated compounds, it is preferable that the diluted multiple is 2-40 times, excellent
It is selected as 5-20 times.The content of acid anhydrides is 0.01-2g/L, preferably 0.04-0.5g/L in solution after diluting.
According to the present invention, in step (2), to the condition of the interface polymerization reaction, there is no particular limitation, can be this
The conventional selection in field, for example, it is described first contact time be 5-150s, preferably 10-60s (such as can for 10s,
20s, 30s, 40s, 50s or 60s)；It is described second contact time be 5-150s, preferably 10-60s (such as can for 10s,
20s, 30s, 40s, 50s or 60s).Temperature when above-mentioned contact can be 10-60 DEG C, preferably 20-40 DEG C (such as can be
25℃)。
In addition, the condition of the heat treatment includes: that the temperature of heat treatment is 40-150 DEG C, heat when carrying out above-mentioned heat treatment
The time of processing is 0.5-20min；Preferably, the temperature of heat treatment is 50-120 DEG C, heat treatment time 1-10min；It is more excellent
Selection of land, the temperature of heat treatment are 30-90 DEG C, heat treatment time 3-10min.As heat treatment temperature for example can for 50 DEG C,
60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C or 120 DEG C.Time as heat treatment for example can for 1min, 2min,
3min, 4min, 5min, 6min, 7min, 8min, 9min or 10min.Heat treatment can using existing any heating equipment into
Row, such as baking oven.
According to the present invention, the type of the supporting layer is not particularly limited, can by it is existing it is various have it is certain
The intensity and material that can be used in reverse osmosis membrane is made, usually can be non-sulfonated by polyacrylonitrile, Kynoar, phenolphthalein type
One of polyether sulphone, sulfonated polysulfone, sulfonated polyether sulfone, polyether sulfone and polysulfones a variety of are made.Such as it can be turned by phase
The preparation of change method.In addition, the supporting layer can be single hole or porous structure.A kind of specific embodiment according to the present invention, institute
State supporting layer include non-woven polyester layer of cloth and be attached in the polyester non-woven fabric layer surface by polyacrylonitrile, polyvinylidene fluoride
Gather made of at least one of the non-sulfonated polyether sulphone of alkene, phenolphthalein type, sulfonated polysulfone, sulfonated polyether sulfone, polyether sulfone and polysulfones
Close nitride layer.The molecular cut off of the supporting layer is preferably 3-5 ten thousand.
It can be the conventional choosing of this field in addition, in the present invention, being not particularly limited to the thickness of the supporting layer
It selects, but in order to make that better coordinated can be played the role of between the supporting layer and the polyamide separating layer, makes to obtain
Reverse osmosis membrane have higher water flux and salt-stopping rate, the preferably described supporting layer with a thickness of 90-150 μm, more preferably
100-120μm.Thickness as supporting layer can specifically be enumerated: 90 μm, 95 μm, 100 μm, 105 μm, 110 μm, 115 μm, 120 μm,
125 μm, 130 μm, 135 μm, 140 μm, 145 μm or 150 μm etc..
In addition, in the present invention, the thickness of the polyamide separating layer as formation can change in a big way, in order to
So that between polyamide separating layer and the supporting layer can better coordinated, the reverse osmosis membrane enable has more
High water flux and salt-stopping rate, the preferably described polyamide separating layer with a thickness of 0.01-0.5 μm, more preferably 0.02-0.3 μm,
More preferably 0.05-0.3 μm.Thickness as polyamide separating layer can specifically be enumerated: 0.05 μm, 0.1 μm, 0.15 μm, 0.2 μ
M, 0.3 μm, 0.4 μm or 0.5 μm etc..
In the present invention, the reverse osmosis membrane after heat treatment can be guaranteed reverse osmosis with operations such as further progress washings
The use of film, such as obtained reverse osmosis membrane can be impregnated into 2h or more in water, such as 24 hours.
The present invention also provides the reverse osmosis membranes being prepared by the method for aforementioned present invention.
The reverse osmosis membrane of aforementioned present invention is 97% or more, preferably 97.5% or more to the salt-stopping rate of sodium chloride, more preferably
It is 98% or more.
In addition, the application the present invention also provides the reverse osmosis membrane of aforementioned present invention in water treatment procedure.Such as it is drinking
With fields applications such as Water warfare, sewage treatment, sea water desalination, bioactive substance recycling, food concentrations.
The present invention will be described in detail by way of examples below.
Reverse osmosis membrane prepared by the present invention is used for desalination, and salt-stopping rate and water flux are two of evaluating combined reverse osmosis membrane
Important parameter, salt-stopping rate R is defined as:
Wherein, CfIndicate the concentration of salt in water before handling；CpAfter expression processing in permeate salt concentration.
Water flux is defined as: under certain operating conditions, the volume of the water of per membrane area is penetrated in the unit time,
Unit is L/m2·h。
The test condition used in the present invention are as follows: concentration is the sodium-chloride water solution of 2000ppm, and operating pressure is
1.5MPa, operation temperature are 25 DEG C.
Thickness measurement tests the cross-section morphology of diaphragm using scanning electron microscope (model S4800), and then obtains the thickness of film layer
Degree.
In addition, in following embodiment and preparation example, maleic anhydride, acrylic anhydride, acetic anhydride, m-phenylene diamine (MPD), 1,3,5-
Triaminobenzene, paraphthaloyl chloride, pyromellitic trimethylsilyl chloride are purchased from lark prestige Science and Technology Ltd.；N-hexane is purchased from western Gansu Province chemical industry
Co., Ltd；Other chemical reagent are purchased from Sinopharm Chemical Reagent Co., Ltd..
Comparative example 1
Using polysulfone porous support membrane (molecular cut off is 50,000, with a thickness of 110 μm, similarly hereinafter) and concentration between 20g/L
Phenylenediamine solution immersion contacts 60s.After outwelling extra aqueous solution later, film surface roller is done with clean rubber rollers, then will
The hexane solution of film and the pyromellitic trimethylsilyl chloride containing 1g/L contacts 60s, then in air by the polyamide separating layer of formation
It dries, is placed in 45 DEG C of baking oven and handles 5min, then rinsed 10 minutes in 25 DEG C of water, obtain complex reverse osmosis membrane and (divide
Absciss layer is with a thickness of 0.12 μm), it saves spare in deionized water.
Embodiment 1
Maleic anhydride is added in the m-phenylene diamine (MPD) aqueous solution that concentration is 200g/L, the amount of the maleic anhydride of addition guarantees
Concentration is 1.5g/L after it is added, and deionized water is added into solution after its reaction and dilutes ten times, that is, m-phenylene diamine (MPD) after diluting
Concentration is 20g/L, maleic anhydride concentration 0.15g/L.Using polysulfone porous support membrane, 60s is contacted with above-mentioned solution immersion.
After outwelling extra aqueous solution later, film surface roller is done with clean rubber rollers, then by film and containing the pyromellitic trimethylsilyl chloride of 1g/L
Hexane solution contact 60s, the aramid layer of formation is dried in air then, is placed in 45 DEG C of baking oven and handles
Then 5min is rinsed 10 minutes in 25 DEG C of water, obtain complex reverse osmosis membrane (separating layer is with a thickness of 0.12 μm), be stored in
It is spare in ionized water.
Embodiment 2-3
According to the method for embodiment 1, unlike, maleic anhydride is substituted for acetic anhydride, the acrylic anhydride of equivalent respectively,
Complex reverse osmosis membrane is obtained, is saved spare in deionized water.
Embodiment 4
Maleic anhydride is added in the m-phenylene diamine (MPD) aqueous solution that concentration is 20g/L, the amount of the maleic anhydride of addition guarantees
Concentration is 0.15g/L after it is added.60s is contacted using polysulfone porous support membrane and above-mentioned solution immersion.It is extra to outwell later
After aqueous solution, film surface roller is done with clean rubber rollers, then by the hexane solution of film and the pyromellitic trimethylsilyl chloride containing 1g/L
60s is contacted, the aramid layer of formation is dried in air then, is placed in 45 DEG C of baking oven and handles 5min, then at 25 DEG C
Water in rinse 10 minutes, obtain complex reverse osmosis membrane (separating layer is with a thickness of 0.14 μm), save it is spare in deionized water.
Test case 1
Under the test condition that operating pressure is 1.5MPa, temperature is 25 DEG C, the sodium chloride water for the use of concentration being 2000ppm
The performance of the complex reverse osmosis membrane of solution testing above-mentioned comparative example 1-2 and embodiment 1-3 preparation.The acquired results of test are shown in Table 1.
Table 1
Embodiment 5
Maleic anhydride is added in the m-phenylene diamine (MPD) aqueous solution that concentration is 200g/L, the amount of the maleic anhydride of addition guarantees
Concentration is 0.5g/L after it is added, and deionized water is added into solution after its reaction and dilutes ten times, that is, m-phenylene diamine (MPD) after diluting
Concentration is 20g/L, maleic anhydride concentration 0.05g/L.60s is contacted using polysulfone porous support membrane and above-mentioned solution immersion.
After outwelling extra aqueous solution later, film surface roller is done with clean rubber rollers, then by film and containing the pyromellitic trimethylsilyl chloride of 1g/L
Hexane solution contact 60s, the aramid layer of formation is dried in air then, is placed in 45 DEG C of baking oven and handles
Then 5min is rinsed 10 minutes in 25 DEG C of water, obtain complex reverse osmosis membrane (separating layer is with a thickness of 0.13 μm), be stored in
It is spare in ionized water.
Embodiment 6-8
According to the method for embodiment 5, unlike, maleic anhydride concentration is respectively 1g/L, 3g/L, 5g/L before diluting, i.e.,
Maleic anhydride concentration is respectively 0.1g/L, 0.3g/L, 0.5g/L after dilution, obtains complex reverse osmosis membrane, is stored in deionized water
In it is spare.
Test case 2
According to the method for test case 1, the performance of the complex reverse osmosis membrane of embodiment 5-8 is measured.The acquired results of test are shown in
Table 2.
Table 2
Embodiment 9
Maleic anhydride is added in the m-phenylene diamine (MPD) aqueous solution that concentration is 100g/L, the amount of the maleic anhydride of addition guarantees
Concentration is 0.75g/L after it is added, and deionized water is added into solution after its reaction and dilutes five times, that is, m-phenylene diamine (MPD) after diluting
Concentration is 20g/L, maleic anhydride concentration 0.15g/L.Polysulfone porous support membrane and above-mentioned solution immersion are contacted into 60s.It
After outwell extra aqueous solution after, film surface roller is done with clean rubber rollers, then by film and the pyromellitic trimethylsilyl chloride containing 1g/L
Hexane solution contacts 60s, then dries the aramid layer of formation in air, is placed in 45 DEG C of baking oven and handles 5min,
Then it is rinsed 10 minutes in 25 DEG C of water, obtains complex reverse osmosis membrane (separating layer is with a thickness of 0.13 μm), be stored in deionization
It is spare in water.
Embodiment 10
According to the method for embodiment 1, unlike, it is water-soluble that maleic anhydride is added to the m-phenylene diamine (MPD) that concentration is 400g/L
In liquid, concentration is 3g/L after the amount of the maleic anhydride of addition guarantees its addition, and deionized water is added into solution after its reaction
20 times are diluted, that is, m-phenylene diamine (MPD) concentration is 20g/L, maleic anhydride concentration 0.15g/L after diluting.Obtain complex reverse osmosis membrane
(separating layer is with a thickness of 0.11 μm) saves spare in deionized water.
Test case 3
According to the method for test case 1, the performance of the complex reverse osmosis membrane of embodiment 9-10 is measured.The acquired results of test are shown in
Table 3.
Table 3
Embodiment 11
Acetic anhydride is added in the m-phenylene diamine (MPD) aqueous solution that concentration is 160g/L, the amount of the maleic anhydride of addition guarantees it
Concentration is 1.2g/L after addition, eight times of deionized water dilution is added into solution after its reaction, that is, m-phenylene diamine (MPD) is dense after diluting
Degree is 20g/L, maleic anhydride concentration 0.15g/L.Polysulfone porous support membrane and above-mentioned solution immersion are contacted into 60s.Later
After outwelling extra aqueous solution, film surface roller is done with clean rubber rollers, then just by film and the pyromellitic trimethylsilyl chloride containing 1g/L
Hexane solution contacts 60s, then dries the aramid layer of formation in air, is placed in 45 DEG C of baking oven and handles 5min, so
It is rinsed 10 minutes in 25 DEG C of water afterwards, obtains complex reverse osmosis membrane, saved spare in deionized water.
Embodiment 12
Acrylic anhydride is added in the m-phenylene diamine (MPD) aqueous solution that concentration is 180g/L, the amount of the maleic anhydride of addition guarantees
Concentration is 1.2g/L after it is added, and deionized water is added into solution after its reaction and dilutes twelvefold, that is, isophthalic two after diluting
Amine concentration is 15g/L, maleic anhydride concentration 0.1g/L.Polysulfone porous support membrane and above-mentioned solution immersion are contacted into 60s.It
After outwell extra aqueous solution after, film surface roller is done with clean rubber rollers, then by film and the pyromellitic trimethylsilyl chloride containing 1g/L
Hexane solution contacts 60s, then dries the aramid layer of formation in air, is placed in 45 DEG C of baking oven and handles 5min,
Then it is rinsed 10 minutes in 25 DEG C of water, obtains complex reverse osmosis membrane, saved spare in deionized water.
Comparative example 2
The m-phenylene diamine (MPD) solution immersion that polysulfone porous support membrane and concentration are 15g/L is contacted into 60s.It is extra to outwell later
After aqueous solution, film surface roller is done with clean rubber rollers, then by the hexane solution of film and the pyromellitic trimethylsilyl chloride containing 1g/L
60s is contacted, the aramid layer of formation is dried in air then, is placed in 45 DEG C of baking oven and handles 5min, then at 25 DEG C
Water in rinse 10 minutes, obtain complex reverse osmosis membrane, save spare in deionized water.
Test case 4
According to the method for test case 1, the performance of the complex reverse osmosis membrane of embodiment 11-12 and comparative example 2 is measured.Test
Acquired results are shown in Table 4.
Table 4
It can be seen that the reverse osmosis membrane salt-stopping rate of the invention and comparative example 1-2 of embodiment 1-12 by the result of table 1-4
Substantially quite, but water flux significantly increases.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (17)
1. a kind of reverse osmosis membrane, which includes the supporting layer being bonded to each other and polyamide separating layer, which is characterized in that institute
Polyamide separating layer is stated to be obtained by the reaction product of polynary aminated compounds and acid anhydrides and the progress interfacial polymerization of polynary acyl chlorides.
2. reverse osmosis membrane according to claim 1, wherein the reverse osmosis membrane to the salt-stopping rate of sodium chloride be 97% with
On, preferably 97.5% or more, more preferably 98% or more.
3. reverse osmosis membrane according to claim 1, wherein the polynary aminated compounds is aromatic polyamine；
Preferably, the polynary aminated compounds be m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine, 1,3,5- triaminobenzenes, 1,2,
4- triaminobenzene, 3,5- diaminobenzoic acid, 2,4 di amino toluene, 2,4- diamino anisole, amidol and xyxylene
One of diamines is a variety of.
4. reverse osmosis membrane according to claim 1, wherein the polynary acyl chlorides is aromatic polyvalent acyl chlorides；
Preferably, the polynary acyl chlorides be paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride, biphenyl dimethyl chloride,
One of benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride are a variety of.
5. reverse osmosis membrane according to claim 1, wherein the acid anhydrides is maleic anhydride, acetic anhydride, phthalic acid
One of acid anhydride, sulfuric anhydride, nitric acid anhydride and acrylic anhydride are a variety of.
6. reverse osmosis membrane described in any one of -5 according to claim 1, wherein the polynary aminated compounds and described more
The mass concentration ratio of first acyl chlorides be 1-100:1, more preferably 5-50:1, further preferably 10-40:1, still more preferably for
15-35:1 is still more preferably 18-25:1；
Preferably, the molar ratio of the polynary aminated compounds and the acid anhydrides is 1:0.002-2, more preferably 1:0.02-
0.4。
7. reverse osmosis membrane described in any one of -5 according to claim 1, wherein the supporting layer is by polyacrylonitrile, poly- inclined
One of the non-sulfonated polyether sulphone of vinyl fluoride, phenolphthalein type, sulfonated polysulfone, sulfonated polyether sulfone, polyether sulfone and polysulfones or a variety of systems
At；
Preferably, the supporting layer with a thickness of 90-150 μm, preferably 100-120 μm；
Preferably, the polyamide separating layer with a thickness of 0.01-0.5 μm, preferably 0.05-0.3 μm.
8. a kind of preparation method of reverse osmosis membrane, which is characterized in that method includes the following steps:
(1) aqueous solution of polynary aminated compounds is contacted with acid anhydrides, makes the amino and anhydride reaction in polynary aminated compounds；
(2) by the aqueous solution that supporting layer is first obtained with step (1) carry out first contact after, then with contain the solution of polynary acyl chlorides into
Row second contacts, and is then heat-treated, to form polyamide separating layer in supporting layer.
9. preparation method according to claim 8, wherein after making the amino and anhydride reaction in polynary aminated compounds,
The aqueous solution that reaction obtains is diluted, first contact is then carried out；
Preferably, in step (2), after supporting layer is carried out the first contact, extra water phase is removed, second is then carried out again and connects
Touching.
10. preparation method according to claim 8, wherein the polynary aminated compounds is aromatic polyamine；
Preferably, the polynary aminated compounds be m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine, 1,3,5- triaminobenzenes, 1,2,
4- triaminobenzene, 3,5- diaminobenzoic acid, 2,4 di amino toluene, 2,4- diamino anisole, amidol and xyxylene
One of diamines is a variety of；
Preferably, in the aqueous solution of the polynary aminated compounds, the content of the polynary aminated compounds is 50-500g/L.
11. preparation method according to claim 8, wherein the polynary acyl chlorides is aromatic polyvalent acyl chlorides；
Preferably, the polynary acyl chlorides be paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride, biphenyl dimethyl chloride,
One of benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride are a variety of；
Preferably, the concentration of polynary acyl chlorides is 0.5-5g/L in the solution containing polynary acyl chlorides.
12. preparation method according to claim 8, wherein the acid anhydrides is maleic anhydride, acetic anhydride, phthalic acid
One of acid anhydride, sulfuric anhydride, nitric acid anhydride and acrylic anhydride are a variety of；
Preferably, in the solution obtained after the aqueous solution of polynary aminated compounds being contacted with acid anhydrides, the content of the acid anhydrides is
0.05-40g/L, preferably 0.2-10g/L；
Preferably, the diluted multiple is 2-40 times, preferably 5-20 times.
13. the preparation method according to any one of claim 8-12, wherein the polynary aminated compounds with it is described
The mass concentration ratio of polynary acyl chlorides be 1-100:1, more preferably 5-50:1, further preferably 10-40:1, still more preferably
It is still more preferably 18-25:1 for 15-35:1；
Preferably, the molar ratio of the polynary aminated compounds and the acid anhydrides is 1:0.002-2, more preferably 1:0.02-
0.4。
14. the preparation method according to any one of claim 8-12, wherein the supporting layer is by polyacrylonitrile, poly-
One of the non-sulfonated polyether sulphone of vinylidene, phenolphthalein type, sulfonated polysulfone, sulfonated polyether sulfone, polyether sulfone and polysulfones are a variety of
It is made；
Preferably, the supporting layer with a thickness of 90-150 μm, preferably 100-120 μm；
Preferably, the polyamide separating layer with a thickness of 0.01-0.5 μm, preferably 0.05-0.3 μm.
15. the preparation method according to any one of claim 8-12, wherein the condition of heat treatment includes: that temperature is
40-150 DEG C, time 0.5-20min；
Preferably, it is 50-120 DEG C that the condition of heat treatment, which includes: temperature, time 1-10min；
Preferably, the time of first contact is 5-150s, preferably 10-60s；
Preferably, the time of second contact is 5-150s, preferably 10-60s.
16. the reverse osmosis membrane that the method as described in any one of claim 8-15 is prepared.
17. application of the reverse osmosis membrane in water treatment procedure described in any one of claim 1-7 and 16.
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