CN105080369A - High rejection rate composite reverse osmosis membrane and preparation method thereof - Google Patents
High rejection rate composite reverse osmosis membrane and preparation method thereof Download PDFInfo
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- CN105080369A CN105080369A CN201410166443.8A CN201410166443A CN105080369A CN 105080369 A CN105080369 A CN 105080369A CN 201410166443 A CN201410166443 A CN 201410166443A CN 105080369 A CN105080369 A CN 105080369A
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Abstract
The present invention discloses a high rejection rate composite reverse osmosis membrane and a preparation method thereof. The composite reverse osmosis membrane preparation method comprises: dipping a porous supporting base membrane with an acetone aqueous solution, contacting the dipped porous supporting base membrane and a water phase of a compound containing two or more than two amino groups, removing the excess water phase solution, and carrying out interface polymerization on the obtained material and an organic phase solution of an acyl chloride compound containing two or more than two acyl chloride groups to prepare the composite reverse osmosis membrane. According to the present invention, the rejection rate of the prepared composite reverse osmosis membrane is improved while the high flux is maintained.
Description
Technical field
The present invention relates to technical field of membrane, furtherly, relate to a kind of complex reverse osmosis membrane and preparation method of high rejection.
Background technology
Complex reverse osmosis membrane compound one deck on porous support layer basement membrane is thin, different materials that is fine and close, that have special separation function, have higher solute separation rate and the transmission rates of water than integrated film, current most commercialization reverse osmosis membrane all adopts interface polymerization reaction to be prepared from.Complex reverse osmosis membrane oneself be widely used in the fields such as petrochemical industry, electronics, weaving, light industry, metallurgy, medicine, bioengineering, food, environmental protection.A kind of reverse osmosis membrane of satisfaction should have suitable infiltration capacity or salt rejection rate.
The technical process of complex reverse osmosis membrane has introduction in US Patent No. 4277344, namely first polysulfones is coated in the micropore counterdie that polyester non-woven fabric is formed, be immersed in diamines or the polyamines aqueous solution, then film excess surface amine aqueous solution is removed by methods such as wind pouring, roll-ins, be immersed in again in organic non-polar solution of polynary acyl chlorides with acyl chlorides generation interface polymerization reaction, thus the fine and close polyamide ultrathin active layer with separation function is formed on surface, after film forming, fully washing and suitable heat cure process can improve film properties.
The utilized thin film composite membranes that preparation has high flux and a high rejection is simultaneously the development trend of membrane for water treatment is also growth requirement.And in the method for various raising complex reverse osmosis membrane performance, the means adding additive in aqueous phase solution are quite convenient beyond doubt and maneuverable, a lot of patented invention is also had to launch around this method.Chinese patent CN101569836A improves the flux of film by the alcohols adding methyl-sulfoxide, methyl phenyl sulfoxide or some solubilities in aqueous phase, but rejection is all difficult to ensure, in the embodiment even had, rejection declines serious.And in Chinese patent CN101381125A, then propose and add quaternary ammonium salt additive if tetramethyl ammonium chloride, tri-n-octyl methyl ammonium chloride etc. are to improve flux and the rejection of reverse osmosis membrane in aqueous phase solution, but its modified film rejection is the highest still fails breakthrough 96%.US Patent No. 006162358A by adding the flux that phenol, o-cresol and guaiacol etc. improve complex reverse osmosis membrane in aqueous phase, but rejection increase rate is little or have decline.
In sum, the rejection basis how keeping flux not decline being improved reverse osmosis membrane is still the current technical issues that need to address.
Summary of the invention
For solving produced problem in prior art, the invention provides a kind of complex reverse osmosis membrane and preparation method of high rejection.Before being formed by complex reverse osmosis membrane dense functional layer, infiltration process is carried out to open support basement membrane aqueous acetone solution, while the complex reverse osmosis membrane rejection obtained is improved, keep higher flux again.
An object of the present invention is to provide a kind of high rejection complex reverse osmosis membrane.
Described complex reverse osmosis membrane is prepared by the method comprised the following steps:
Open support basement membrane aqueous acetone solution is infiltrated, contact with the aqueous phase solution of the compound containing two or more amino again, and after removing unnecessary aqueous phase solution, then obtain described complex reverse osmosis membrane with the organic phase solution of the chloride compounds containing two or more acid chloride group by interfacial polymerization.
Two of object of the present invention is to provide a kind of preparation method of complex reverse osmosis membrane of high rejection.
Comprise:
Open support basement membrane aqueous acetone solution is infiltrated, contact with the aqueous phase solution of the compound containing two or more amino again, and after removing unnecessary aqueous phase solution, then obtain described complex reverse osmosis membrane with the organic phase solution of the chloride compounds containing two or more acid chloride group by interfacial polymerization.
Specifically comprise the following steps:
A) by open support basement membrane through aqueous acetone solution infiltrate after, remove unnecessary solution;
B) aqueous phase solution of the open support basement membrane after above-mentioned steps process with the compound containing two or more amino is contacted;
C) aqueous phase solution unnecessary for the open support membrane surface after aqueous phase solution infiltrates is removed;
D) the open support basement membrane after step c process contacts with the organic phase solution of the chloride compounds containing two or more acid chloride group and obtains composite membrane;
E) drying, heat treatment, washing obtained described complex reverse osmosis membrane afterwards.
Described open support basement membrane is preferably the one in polysulfone porous support basement membrane, SPSF open support basement membrane, polyether sulfone open support basement membrane, sulfonated polyether sulfone open support basement membrane; The molecular cut off of open support basement membrane is preferably 3-5 ten thousand;
The described compound containing two or more amino is preferably one or more in aromatic series polyfunctional amine; Described aromatic series polyfunctional amine is preferably m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine (PPD), 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 3,5-diaminobenzoic acids, 2, at least one in 4-diaminotoluene, 2,4-diamino anisoles, amidol, xylylene diamine;
The described chloride compounds containing two or more acid chloride group is preferably one or more in the multifunctional chloride compounds of aromatic series; The multifunctional chloride compounds of described aromatic series is at least one in paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride, biphenyl dimethyl chloride, benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride.
The organic solvent of described organic phase solution is preferably one or more in n-hexane, cyclohexane, trifluorotrichloroethane, normal heptane, normal octane, toluene, ethylbenzene, ISOPAR solvent naphtha.
The volumetric concentration that described impregnating porous supports the acetone soln of basement membrane is 0.5%-30%; Be preferably 2%-15%, infiltrating time is 10-600 second, and be preferably 30-150 second, temperature is preferably 15-45 DEG C.
The concentration of the compound containing two or more amino in described aqueous phase solution is 1-60g/L.
The concentration of the chloride compounds containing two or more acid chloride group in described organic phase solution is 0.5-5g/L.
Surfactant and/or acid absorbent can also be comprised in described aqueous phase solution;
The concentration of described surfactant is preferably 1-5g/L; The concentration of described acid absorbent is preferably 1-30g/L.
The surfactant commonly used when described surfactant can adopt this area to prepare composite membrane, includes but not limited at least one in lauryl sodium sulfate, neopelex, DTAB;
The acid absorbent commonly used when described acid absorbent can adopt this area to prepare composite membrane, includes but not limited at least one in triethylamine, sodium carbonate, sodium acid carbonate, dibastic sodium phosphate, sodium phosphate, NaOH, potassium hydroxide.
The above aqueous phase and open support basement membrane and organic phase and open support basement membrane are preferably 10-150 second time of contact;
Described heat treatment temperature is preferably 30-120 DEG C; Heat treatment time is preferably 1-10 minute.
The present invention can be achieved through the following technical solutions:
A) first, aqueous acetone solution is poured over porous support membrane surface, makes itself and open support basement membrane time of contact be 10-600 second, be preferably 30-150 second, temperature is 15-45 DEG C;
B) redundant solution outwelled, and remove redundant solution further, method preferably but be not limited to roll-in method and wind drenches method;
C) contacted by the aqueous phase solution of the open support basement membrane through infiltrating with the compound containing two or more amino, time of contact is 10-150 second;
B) removed by aqueous phase solution unnecessary for the open support membrane surface after aqueous phase solution infiltrates, the method for removing redundant solution is chosen as but is not limited to wind drenches method, roll-in method etc.;
E) porous support membrane after aqueous phase solution infiltrates is contacted 10-150 second with the organic phase solution of the chloride compounds containing two or more acid chloride group, pass through interface polymerization reaction, at porous support membrane Surface Creation one deck dense functional layer, obtain composite membrane;
F) finally by after above-mentioned film in atmosphere natural drying, put into 30-120 DEG C of baking oven heat treatment 1-10 minute, after washing, namely obtain complex reverse osmosis membrane.
In the present invention, described complex reverse osmosis membrane has high flux and high retention ratio.The current relevant method that can improve rejection that can find, often along with the decline of flux.And while meaning of this invention is to improve the rejection of complex reverse osmosis membrane, keeps flux to maintain previous level and do not decline.
Detailed description of the invention
Below in conjunction with embodiment, further illustrate the present invention.
Complex reverse osmosis membrane prepared by the present invention is used for desalination, and salt rejection rate and water flux are two important parameters of evaluating combined reverse osmosis membrane, and salt rejection rate R is defined as:
Wherein, C
frepresent the concentration of salt in the front water of process; C
prepresent the concentration of salt in the rear permeate of process.
Water flux is defined as: under certain operating conditions, and through the volume of the water of per membrane area in the unit interval, its unit is L/m
2h.
The test condition adopted in the present invention is: concentration is the sodium-chloride water solution of 2000ppm, and operating pressure is 1.5Mpa, and operating temperature is 25 DEG C.
Embodiment is raw materials used:
The present invention is set forth further below in conjunction with embodiment, but not as limitation of the present invention.
Embodiment 1
Use polysulfone porous support membrane, (being poured on the support membrane fixed by solution) is contacted 60 seconds with the aqueous acetone solution prepared, described aqueous acetone solution concentration is 0.5%, outwell redundant solution, surface roll is done by blend rubber roller, again with aqueous phase solution wetting contact 60 seconds, wherein in aqueous phase solution containing the m-phenylene diamine (MPD) of 20g/L and the triethylamine (TEA) of 10g/L.After outwelling unnecessary aqueous phase solution, by clean rubber rollers, film surface roll is done, then film is contacted 15 seconds with the hexane solution of the pyromellitic trimethylsilyl chloride of 1g/L, then the aramid layer of formation is dried in atmosphere, be placed in the baking oven of 45 DEG C and process 5min, then rinsing 10 minutes in the water of 25 DEG C, obtains complex reverse osmosis membrane film, and the complex reverse osmosis membrane prepared is preserved in deionized water.
Operating pressure be 1.5Mpa, under temperature is 25 DEG C, pH value is the test condition of 6.5-7.5, working concentration is the performance that the sodium-chloride water solution of 2000ppm tests the complex reverse osmosis membrane of above-mentioned preparation.Test result is in table 1.
Embodiment 2
Except the aqueous acetone solution concentration that impregnating porous support basement membrane is used is adjusted to 10%, other processing step and test condition are all identical with embodiment 1, and the test result of prepared complex reverse osmosis membrane lists in table 1.
Embodiment 3
Except the aqueous acetone solution concentration that impregnating porous support basement membrane is used is adjusted to 30%, other processing step and test condition are all identical with embodiment 1, and the test result of prepared complex reverse osmosis membrane lists in table 1.
Comparative example 1
Support except basement membrane except without aqueous acetone solution impregnating porous, other processing step and test condition are all identical with embodiment 1, and the test result of prepared complex reverse osmosis membrane lists in table 1.
Table 1
As can be seen from the data of table 1, through the pretreated reverse osmosis membrane of acetone under the test condition selected by experiment, rejection is improved significantly compared to comparative example 1, and flux can maintain the level of comparative example 1 simultaneously.
Embodiment 4
Use polysulfone porous support membrane, 15 seconds are contacted with the aqueous acetone solution prepared, described aqueous acetone solution concentration is 10%, outwell redundant solution, surface roll is done by blend rubber roller, again with aqueous phase solution wetting contact 10 seconds, the sodium carbonate wherein containing the m-phenylene diamine (MPD) of 20g/L, the lauryl sodium sulfate of 1g/L and 10g/L in aqueous phase solution.After outwelling unnecessary aqueous phase solution, by clean rubber rollers, film surface roll is done, then film is contacted 10 seconds with the cyclohexane solution of the pyromellitic trimethylsilyl chloride of 5g/L, then the aramid layer of formation is dried in atmosphere, be placed in the baking oven of 60 DEG C and process 5min, then rinsing 10 minutes in the water of 25 DEG C, obtains complex reverse osmosis membrane film, and the complex reverse osmosis membrane prepared is preserved in deionized water.The test condition of prepared complex reverse osmosis membrane is identical with embodiment 1.Test result is in table 2.
Embodiment 5
The time supporting basement membrane except acetone soln impregnating porous is adjusted to except 150 seconds, and other processing step and test condition are all identical with embodiment 4, and the test result of prepared complex reverse osmosis membrane lists in table 2.
Table 2
Embodiment 4,5 is compared to embodiment 2, and basement membrane is infiltrated aqueous acetone solution different time, and aqueous acetone solution concentration is identical with embodiment 2, other operating conditions and step are all identical.Test result shows, no matter the length of infiltrating time, and the performance of complex reverse osmosis membrane obtained after infiltrating basement membrane with aqueous acetone solution is all better than the performance infiltrating the reverse osmosis membrane obtained with acetone soln.
Embodiment 6
Use polysulfone porous support membrane, 90 seconds are contacted with the aqueous acetone solution prepared, described aqueous acetone solution concentration is 12%, outwell redundant solution, surface roll is done by blend rubber roller, then with aqueous phase solution wetting contact 150 seconds, wherein in aqueous phase solution containing 1 of 20g/L, the sodium carbonate of 3,5-triaminobenzene and 5g/L.After outwelling unnecessary aqueous phase solution, by clean rubber rollers, film surface roll is done, then film is contacted 150 seconds with the IsoparE solution of the m-phthaloyl chloride of 1g/L, then the aramid layer of formation is dried in atmosphere, be placed in the baking oven of 70 DEG C and process 3min, then rinsing 10 minutes in the water of 25 DEG C, obtains complex reverse osmosis membrane film, and the complex reverse osmosis membrane prepared is preserved in deionized water.The test condition of prepared complex reverse osmosis membrane is identical with embodiment 1.Test result is in table 3.
Embodiment 7
Except aqueous solutes and organic phase solute are adjusted to outside 1,2,4-triaminobenzene, paraphthaloyl chloride respectively, other processing step and test condition are all identical with embodiment 6, and the test result of prepared complex reverse osmosis membrane lists in table 3.
Comparative example 2
Support except basement membrane except without aqueous acetone solution impregnating porous, other processing step and test condition are all identical with embodiment 6, and the test result of prepared complex reverse osmosis membrane lists in table 3.
Comparative example 3
Support except basement membrane except without aqueous acetone solution impregnating porous, other processing step and test condition are all identical with embodiment 7, and the test result of prepared complex reverse osmosis membrane lists in table 3.
Table 3
Comparative example 2 described in table 3,3 respectively with embodiment 6,7 corresponding, be basement membrane is infiltrated without acetone soln corresponding to each embodiment, the scheme that other operating conditions and step are all identical.Test result shows, embodiment is all high than corresponding comparative example rejection, and water flux does not decline.
Embodiment 8
Use polysulfone porous support membrane, 120 seconds are contacted with the aqueous acetone solution prepared, described aqueous acetone solution concentration is 6%, outwell redundant solution, surface roll is done by blend rubber roller, again with aqueous phase solution wetting contact 60 seconds, wherein in aqueous phase solution containing the p-phenylenediamine (PPD) of 1g/L and the sodium acid carbonate of 1g/L.After outwelling unnecessary aqueous phase solution, by clean rubber rollers, film surface roll is done, then film is contacted 60 seconds with the hexane solution of the pyromellitic trimethylsilyl chloride of 0.5g/L, then the aramid layer of formation is dried in atmosphere, be placed in the baking oven of 45 DEG C and process 5min, then rinsing 10 minutes in the water of 25 DEG C, obtains complex reverse osmosis membrane film, and the complex reverse osmosis membrane prepared is preserved in deionized water.The test condition of prepared complex reverse osmosis membrane is identical with embodiment 1.Test result is in table 4.
Embodiment 9
The mix concentration of confrontation phenylenediamine and organic phase solute pyromellitic trimethylsilyl chloride of dewatering is adjusted to outside 60g/L and 5g/L respectively, and other processing step and test condition are all identical with embodiment 8, and the test result of prepared complex reverse osmosis membrane lists in table 4.
Comparative example 4
Support except basement membrane except without aqueous acetone solution impregnating porous, other processing step and test condition are all identical with embodiment 8, and the test result of prepared complex reverse osmosis membrane lists in table 4.
Comparative example 5
Support except basement membrane except without aqueous acetone solution impregnating porous, other processing step and test condition are all identical with embodiment 9, and the test result of prepared complex reverse osmosis membrane lists in table 4.
Table 4
Table 4 state comparative example 4,5 respectively with embodiment 8,9 corresponding, be basement membrane is infiltrated without acetone soln corresponding to each embodiment, the scheme that other operating conditions and step are all identical.Test result shows, embodiment is all high than corresponding comparative example rejection, and water flux does not decline.
Embodiment 10
Use polysulfone porous support membrane, 60 seconds are contacted with the aqueous acetone solution prepared, described aqueous acetone solution concentration is 100ml/L, outwell redundant solution, surface roll is done by blend rubber roller, again with aqueous phase solution wetting contact 60 seconds, wherein in aqueous phase solution containing the acetone of 6%, the lauryl sodium sulfate of the m-phenylene diamine (MPD) of 15g/L and the triethylamine (TEA) of 1g/L, 0.75g/L.After outwelling unnecessary aqueous phase solution, by clean rubber rollers, film surface roll is done, then film is contacted 60 seconds with the hexane solution of the pyromellitic trimethylsilyl chloride of 1g/L, then the aramid layer of formation is dried in atmosphere, be placed in the baking oven of 30 DEG C and process 10min, then rinsing 10 minutes in the water of 25 DEG C, obtains complex reverse osmosis membrane film, and the complex reverse osmosis membrane prepared is preserved in deionized water.The test condition of prepared complex reverse osmosis membrane is identical with embodiment 1.Test result is in table 5.
Embodiment 11
Except heat treatment temperature and heat treatment time are adjusted to 120 DEG C and 1min respectively, other processing step and test condition are all identical with embodiment 10, and the test result of prepared complex reverse osmosis membrane lists in table 5.
Comparative example 6
Support except basement membrane except without aqueous acetone solution impregnating porous, other processing step and test condition are all identical with embodiment 10, and the test result of prepared complex reverse osmosis membrane lists in table 5.
Comparative example 7
Support except basement membrane except without aqueous acetone solution impregnating porous, other processing step and test condition are all identical with embodiment 11, and the test result of prepared complex reverse osmosis membrane lists in table 5.
Table 5
Comparative example 6 described in table 5,7 respectively with embodiment 10,11 corresponding, be embodiment corresponding infiltrate basement membrane without acetone soln, the scheme that other operating conditions and step are all identical.Test result shows, the embodiment rejection infiltrating basement membrane with acetone soln is all high than the comparative example of correspondence, and flux also has small elevation.
Claims (9)
1. a complex reverse osmosis membrane for high rejection, is characterized in that:
Described complex reverse osmosis membrane is prepared by the method comprised the following steps:
Open support basement membrane aqueous acetone solution is infiltrated, contact with the aqueous phase solution of the compound containing two or more amino again, and after removing unnecessary aqueous phase solution, then obtain described complex reverse osmosis membrane with the organic phase solution of the chloride compounds containing two or more acid chloride group by interfacial polymerization.
2. a preparation method for the complex reverse osmosis membrane of high rejection as claimed in claim 1, is characterized in that described method comprises:
Open support basement membrane aqueous acetone solution is infiltrated, contact with the aqueous phase solution of the compound containing two or more amino again, and after removing unnecessary aqueous phase solution, then obtain described complex reverse osmosis membrane with the organic phase solution of the chloride compounds containing two or more acid chloride group by interfacial polymerization.
3. preparation method as claimed in claim 2, is characterized in that described method comprises:
A) by open support basement membrane through aqueous acetone solution infiltrate after, remove unnecessary solution;
B) aqueous phase solution of the open support basement membrane after above-mentioned steps process with the compound containing two or more amino is contacted;
C) aqueous phase solution unnecessary for the open support membrane surface after aqueous phase solution infiltrates is removed;
D) the open support basement membrane after step c process contacts with the organic phase solution of the chloride compounds containing two or more acid chloride group and obtains composite membrane;
E) drying, heat treatment, washing obtained described complex reverse osmosis membrane afterwards.
4. preparation method as claimed in claim 3, is characterized in that:
Described open support basement membrane is the one that polysulfone porous supports in basement membrane, SPSF open support basement membrane, polyether sulfone open support basement membrane, sulfonated polyether sulfone open support basement membrane;
The described compound containing two or more amino is one or more in aromatic series polyfunctional amine;
The described chloride compounds containing two or more acid chloride group is one or more in the multifunctional chloride compounds of aromatic series;
The organic solvent of described organic phase solution is one or more in n-hexane, cyclohexane, trifluorotrichloroethane, normal heptane, normal octane, toluene, ethylbenzene, ISOPAR solvent naphtha.
5. preparation method as claimed in claim 4, is characterized in that:
Described aromatic series polyfunctional amine is m-phenylene diamine (MPD), o-phenylenediamine, p-phenylenediamine (PPD), 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 3,5-diaminobenzoic acids, 2, at least one in 4-diaminotoluene, 2,4-diamino anisoles, amidol, xylylene diamine;
The multifunctional chloride compounds of described aromatic series is at least one in paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride, biphenyl dimethyl chloride, benzene-disulfo-chloride, pyromellitic trimethylsilyl chloride.
6. preparation method as claimed in claim 2, is characterized in that:
The volumetric concentration of described aqueous acetone solution is 0.5%-30%; Infiltrating time is 10-600 second, and infiltration temperature is 15-45 DEG C.
7. preparation method as claimed in claim 6, is characterized in that:
The volumetric concentration of described aqueous acetone solution is 2%-15%, and infiltrating time is 30-150 second.
8. preparation method as claimed in claim 3, is characterized in that:
The concentration of the compound containing two or more amino in described aqueous phase solution is 1-60g/L;
The concentration of the chloride compounds containing two or more acid chloride group in described organic phase solution is 0.5-5g/L.
9. preparation method as claimed in claim 3, is characterized in that:
Described time of contact is 10-150 second;
Described heat treatment temperature is 30-120 DEG C; Heat treatment time is 1-10 minute.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257748A (en) * | 1998-12-24 | 2000-06-28 | 中国科学院长春应用化学研究所 | Alcohol-water system modifying process for inner interface of inverse osmosis membrane |
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2014
- 2014-04-24 CN CN201410166443.8A patent/CN105080369A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1257748A (en) * | 1998-12-24 | 2000-06-28 | 中国科学院长春应用化学研究所 | Alcohol-water system modifying process for inner interface of inverse osmosis membrane |
Non-Patent Citations (1)
| Title |
|---|
| 曹艳霞 等: "反渗透复合膜内界面改性对其性能的影响研究——(Ⅱ)理论分析", 《高分子材料科学与工程》 * |
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