CN101791522A - Hybridized composite reverse osmosis membrane containing carbon nano tubes and preparation method thereof - Google Patents
Hybridized composite reverse osmosis membrane containing carbon nano tubes and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hybridized composite reverse osmosis membrane containing carbon nano tubes and a preparation method thereof. The preparation method comprises the following steps of: adding the carbon nano tubes to a monomer solution for synthesizing a polyamide membrane; and preparing the hybridized composite reverse osmosis membrane containing the carbon nano tubes through an immersion method. The hybridized reverse osmosis composite membrane keeps the retention rate of a reverse osmosis membrane and also greatly increases the flux of the membrane by utilizing unique microcellular structures and good water channel action of the carbon nano tubes, and finally the reverse osmosis membrane with high flux and retention rate is prepared.
Description
Technical field
The present invention relates to the reverse osmosis composite membrane field, relate in particular to hybridized composite reverse osmosis membrane of a kind of carbon nanotubes and preparation method thereof.
Background technology
Counter-infiltration has obtained in the desalinization field using widely as realizing one of industrialized membrane technology the earliest, and at present, the whole world utilizes the fresh water daily output about 2 * 10 of hyperfiltration preparation
7Ton.Reverse osmosis membrane is the core content of reverse osmosis technology.Along with water resources problems is on the rise, reverse osmosis technology will be more and more widely in the application of water treatment field, be extended to fields such as wastewater treatment from the desalinization field just gradually, therefore reverse osmosis membrane also proposed new requirement, need improve existing reverse osmosis membrane.In recent years, on traditional reverse osmosis membrane basis, some new reverse osmosis membranes were continually developed:
Publication number is to disclose a kind of special selection polyamide reverse osmose membrane separatory and preparation method thereof that has in the Chinese patent of CN1817422A, utilize m-phenylene diamine (MPD) and 2, the aqueous solution of 4-diamino benzene sulfonic acid, carry out interface polymerization reaction with the organic phase solution of m-phthaloyl chloride and pyromellitic trimethylsilyl chloride, make reverse osmosis membrane.
Publication number is to disclose a kind of special selection polyamide reverse osmose membrane separatory and preparation method thereof that has in the Chinese patent application of CN1817423A, utilize the aqueous solution of m-phenylene diamine (MPD) and piperazine and the organic phase solution of pyromellitic trimethylsilyl chloride to carry out interface polymerization reaction, make reverse osmosis membrane.
Publication number is to disclose a kind of complex reverse osmosis membrane in the Chinese patent application of CN101601975A.By the aramid layer that on the polysulfone supporting layer of existing reverse osmosis membrane, adopts polyamine and the organic solution that contains acyl group to obtain having three cross-linked structures through the interface condensation; the performance of complex reverse osmosis membrane is further improved; membrane molecule has better compactness and stronger rigidity; thereby improve the salt rejection rate that compactness can improve film; can make film have the close voltinism energy of good resistance to compression and improve rigidity; thereby can reduce the rate of decay of film properties, prolong the service life of film.
Publication number is to disclose a kind of high-flux composite reverse osmosis membrane and preparation method thereof in the Chinese patent application of CN101569836A, is compounded with one deck PA membrane on porous support layer.When increasing polyamide reverse osmose membrane effective film area, improve the crosslinking degree of the two-phase monomer of reverse osmosis membrane, the result that salt rejection rate worsens thereby the membrane flux that the loose structure of having avoided the conventional composite reverse osmosis membrane to improve one's methods forming causes increases, finally prepare have high flux, the reverse osmosis membrane of high desalination rate.
From existing research, synthetic new monomer is normally introduced some new functional group, or cross-linked structure etc. is carried out some improve, and can only do part to the performance of film improves, and is difficult to realize the variation of essence.In addition,, reduce and transmit resistance and be difficult to realize, and the degree of cross linking that reduces aramid layer improves the rejection that membrane flux will certainly reduce film by reducing thickness because the separating layer of PA membrane is a superthin layer.Therefore, explore the preparation method of a kind of novel reverse osmosis composite membrane of invention, make it have the high flux high selectivity simultaneously, will have far-reaching economic benefit and social benefit.
Summary of the invention
The invention provides the hybridized composite reverse osmosis membrane of the high carbon nanotubes of a kind of membrane flux.
The present invention also provides the preparation method of the hybridized composite reverse osmosis membrane of low and the carbon nanotubes that can large-scale application of a kind of production cost.
A kind of preparation method of hybridized composite reverse osmosis membrane of carbon nanotubes comprises the steps:
(1), makes aqueous phase solution A with aromatic polyamine dissolving and be dispersed in the water;
The polynary acyl chlorides of aromatic series is dissolved in the organic solvent, stirs, make organic phase solution B;
Be dispersed with CNT among described aqueous phase solution A, the organic phase solution B one or both; Soon CNT is scattered in the described aromatic polyamine aqueous solution or is scattered in the polynary acyl chlorides organic solution of described aromatic series; Perhaps the part CNT is scattered in the described aromatic polyamine aqueous solution, remaining CNT is scattered in the polynary acyl chlorides organic solution of described aromatic series;
(2) the polysulfones support membrane being immersed aqueous phase solution A kept 1 minute-20 minutes, removal remains in the aqueous phase solution A on polysulfones support membrane surface, immerse this polysulfones support membrane among organic phase solution B again and kept 10 seconds-120 seconds, remove the organic phase solution B of film remained on surface, dry, obtain being compounded with the polysulfones support membrane of carbon nanotubes PA membrane, drying makes the hybridized composite reverse osmosis membrane of carbon nanotubes.
Described polysulfones support membrane selects for use commercially available prod commonly used, this area to get final product, and is generally the polysulfones support membrane that comprises nonwoven layer.
As preferably:
The mass percentage concentration of aromatic polyamine is 1%-2% among the described aqueous phase solution A.
Described aromatic polyamine is selected from one or both the mixture in phenylenediamine, the 5-sulfonic group m-phenylene diamine (MPD).
The weight ratio of phenylenediamine and 5-sulfonic group m-phenylene diamine (MPD) is 1-50 in described phenylenediamine and the 5-sulfonic group m-phenylene diamine (MPD) mixture: 1.
The mass percentage concentration of the polynary acyl chlorides of aromatic series is 0.05%-0.2% among the described organic phase solution B.
The polynary acyl chlorides of described aromatic series is selected from a kind of in a kind of or pyromellitic trimethylsilyl chloride in pyromellitic trimethylsilyl chloride, 5-isocyanates-isophthaloyl chlorine, the m-phthaloyl chloride and 5-isocyanates-isophthaloyl chloroformate mixture, pyromellitic trimethylsilyl chloride and the m-phthaloyl chloride mixture.
In described pyromellitic trimethylsilyl chloride and 5-isocyanates-isophthaloyl chloroformate mixture or pyromellitic trimethylsilyl chloride and the m-phthaloyl chloride mixture, the weight ratio of pyromellitic trimethylsilyl chloride and 5-isocyanates-isophthaloyl chlorine or m-phthaloyl chloride is 1-10: 1-10.
The mass percentage concentration of CNT is 0.005%-0.2% among described aqueous phase solution A or the organic phase solution B.
Described CNT is selected from SWCN, a kind of in double-walled carbon nano-tube, the multi-walled carbon nano-tubes.
Described organic solvent can select for use this area can dissolve the organic solvent of the polynary acyl chlorides of aromatic series, a kind of in preferred n-hexane, heptane, the trifluorotrichloroethane equal solvent.
Described baking temperature is 30 ℃-80 ℃.The restriction that the dry time is not strict reaches dry purpose and gets final product, general dry 15 minutes-20 minutes.
The hybridized composite reverse osmosis membrane of described carbon nanotubes can be used for desalinization, pure water preparation and organic matter separation field.
The characterizing method of the hybridized composite reverse osmosis membrane performance of carbon nanotubes of the present invention is as follows: hybridized composite reverse osmosis membrane is placed the conventional counter-infiltration testing arrangement in this area, 25 ℃ of separating properties of testing the sodium-chloride water solution of 2000ppm (mass concentration) down by the counter-infiltration testing arrangement.The film effective area is 38.46cm
2, under 1.6MPa, test behind the precompressed 1h.
Pure water flux (being membrane flux) computing formula is: F=V/ (St), wherein, F is the pure water flux (L/ (m of film
2H)), V is for seeing through the volume (L) of liquid, and S is the effective area (m of film
2), t is testing time (h).
Solute rejection calculates by concentration of raw material with through liquid concentration, and concrete formula is: R (%)=(1-C
p/ C
f) * 100, wherein R is a solute rejection, C
fBe the material liquid mass percentage concentration, C
pBe to see through the liquid mass percentage concentration.
The present invention has following effect effect:
CNT is good hydrone passage, fill it into and utilize its special cavity structure in the reverse osmosis membrane, improve the transmission of hydrone in film, increase is to the interception capacity of salt ion, the counter-infiltration nano hybridization composite membrane that is obtained is in conjunction with the advantage of inorganic particle and polymeric membrane, when keeping the reverse osmosis membrane rejection, improve the flux of film greatly, finally prepare have high flux, the reverse osmosis membrane of new generation of high rejection.Through characterizing the hybridized composite reverse osmosis membrane of finding high flux carbon nanotubes of the present invention, at 2000ppm NaCl, 25 ℃, pH value 6.5-7.5, under the pressure 1.6MPa condition, water flux can reach 71.43L/ (m
2H).
The specific embodiment
Embodiment 1
(1) preparation of aqueous phase solution A: with the dissolving of m-phenylene diamine (MPD) and multi-walled carbon nano-tubes be dispersed in the water, ultrasonic a period of time is uniformly dispersed it, is mixed with the m-phenylene diamine (MPD) mass percentage concentration and is 2%, the multi-walled carbon nano-tubes mass percentage concentration is 0.005% aqueous phase solution A;
(2) preparation of organic phase solution B: pyromellitic trimethylsilyl chloride is dissolved in the n-hexane, and ultrasonic agitation is even, is mixed with the pyromellitic trimethylsilyl chloride mass percentage concentration and is 0.2% organic phase solution B;
(3) the polysulfones support membrane being immersed aqueous phase solution A kept 20 minutes, removal remains in the aqueous phase solution on polysulfones support membrane surface, immerse this counterdie among organic phase solution B again and kept 40 seconds, remove the organic phase solution B of film remained on surface, be placed in the air 2-3 minute, dry, obtain being compounded with the polysulfones support membrane of carbon nanotubes PA membrane;
(4) the above-mentioned polysulfones support membrane that is compounded with the carbon nanotubes PA membrane is put in 60 ℃ the baking oven and kept 20 minutes, carry out post processing, take out then, obtain the hybridized composite reverse osmosis membrane of carbon nanotubes.
The hybridized composite reverse osmosis membrane of above-mentioned carbon nanotubes is carried out performance characterization, and test result is as shown in table 1.
Embodiment 2-3
Except the concentration of multi-walled carbon nano-tubes among the aqueous phase solution A was adjusted, all the other were operated with embodiment 1, prepare the hybridized composite reverse osmosis membrane of carbon nanotubes, and the The performance test results of the hybridized composite reverse osmosis membrane that makes is as shown in table 1.
Comparative Examples 1
Except to not adding among the aqueous phase solution A the multi-walled carbon nano-tubes, all the other are operated with embodiment 1, prepare the not hybridized composite reverse osmosis membrane of carbon nanotubes, and the test result of the hybridized composite reverse osmosis membrane that makes is as shown in table 1.
Table 1
| M-phenylene diamine (MPD) (wt%) | Multi-walled carbon nano-tubes (wt%) | Pure water flux (L/ (m 2·h)) | Rejection (%) | |
| Embodiment 1 | ??2.0 | ??0.005 | ??28.26 | ??92.23 |
| Embodiment 2 | ??2.0 | ??0.01 | ??31.77 | ??89.86 |
| M-phenylene diamine (MPD) (wt%) | Multi-walled carbon nano-tubes (wt%) | Pure water flux (L/ (m 2·h)) | Rejection (%) | |
| Embodiment 3 | ??2.0 | ??0.05 | ??45.92 | ??83.40 |
| Comparative Examples 1 | ??2.0 | ??0.00 | ??25.57 | ??94.21 |
Investigate in of the influence of aqueous phase interpolation CNT by above-mentioned several embodiment film properties.
As can be seen from Table 1: add CNT at aqueous phase, make it participate in polymerisation and form PA membrane, can increase the pure water flux of reverse osmosis membrane significantly, but rejection does not significantly decrease, and illustrates by preparing high-throughout reverse osmosis membrane to aqueous phase interpolation inorganic particulate to realize.
Embodiment 4-7
(1) preparation of aqueous phase solution A: the m-phenylene diamine (MPD) dissolving is dispersed in the water, and ultrasonic a period of time is uniformly dispersed it, is mixed with aqueous phase solution A;
(2) preparation of organic phase solution B: pyromellitic trimethylsilyl chloride and multi-walled carbon nano-tubes are dissolved in the n-hexane, and ultrasonic agitation is even, is mixed with organic phase solution B;
All the other operations make the hybridized composite reverse osmosis membrane of carbon nanotubes with embodiment 1, and the The performance test results of the hybridized composite reverse osmosis membrane that makes is as shown in table 2.
Table 2
| Pyromellitic trimethylsilyl chloride (wt%) | Multi-walled carbon nano-tubes (wt%) | Pure water flux (L/ (m 2·h)) | Rejection (%) | |
| Embodiment 4 | ??0.2 | ??0.005 | ??27.42 | ??91.38 |
| Embodiment 5 | ??0.2 | ??0.01 | ??34.56 | ??89.34 |
| Embodiment 6 | ??0.2 | ??0.05 | ??47.10 | ??84.76 |
| Embodiment 7 | ??0.2 | ??0.10 | ??67.92 | ??81.55 |
Investigate in organic facies by above-mentioned several embodiment and to add the influence of CNT film properties.
As can be seen from Table 2: in organic facies, add CNT, make it participate in polymerisation and form PA membrane, can increase the pure water flux of reverse osmosis membrane significantly, but rejection does not significantly decrease, and illustrates that preparing high-throughout reverse osmosis membrane by interpolation inorganic particulate in organic facies can realize.
Embodiment 8-10
(1) preparation of aqueous phase solution A: m-phenylene diamine (MPD) and multi-walled carbon nano-tubes dissolving are dispersed in the water, and ultrasonic a period of time is uniformly dispersed it, is mixed with aqueous phase solution A;
(2) preparation of organic phase solution B: pyromellitic trimethylsilyl chloride and multi-walled carbon nano-tubes are dissolved in the n-hexane, and ultrasonic agitation is even, is mixed with organic phase solution B;
All the other operations make the hybridized composite reverse osmosis membrane of carbon nanotubes with embodiment 1, and the The performance test results of the hybridized composite reverse osmosis membrane that makes is as shown in table 3.
Table 3
Investigate of the influence of the addition of CNT in water and organic facies by above-mentioned several embodiment to film properties.
As can be seen from Table 3: in water and organic facies, add CNT, participate in polymerisation and form PA membrane, pure water flux that can more significant increase reverse osmosis membrane illustrates by adding inorganic particulate to prepare high-throughout reverse osmosis membrane and can realize.
Embodiment 11-14
Except the kind of aromatic polyamine among the aqueous phase solution A and CNT and consumption are adjusted, all the other operations are with embodiment 1, prepare the hybridized composite reverse osmosis membrane of carbon nanotubes, the test result of the hybridized composite reverse osmosis membrane that makes is as shown in table 4.
Table 4
| Aromatic polyamine and weight ratio thereof (2.0wt%) | CNT (0.01wt%) | Pure water flux (L/ (m 2·h)) | Rejection (%) | |
| Embodiment 11 | M-phenylene diamine (MPD) | SWCN | ??29.49 | ??89.17 |
| Embodiment 12 | M-phenylene diamine (MPD)/5-sulfonic group m-phenylene diamine (MPD) (weight ratio is 20: 1) | Double-walled carbon nano-tube | ??30.39 | ??89.28 |
| Embodiment 13 | M-phenylene diamine (MPD)/5-sulfonic group m-phenylene diamine (MPD) (weight ratio is 10: 1) | Multi-walled carbon nano-tubes | ??32.58 | ??90.59 |
| Embodiment 14 | M-phenylene diamine (MPD)/5-sulfonic group m-phenylene diamine (MPD) (weight ratio is 5: 1) | Multi-walled carbon nano-tubes | ??34.24 | ??91.41 |
Investigate the influence of various aromatic polyamines and CNT by above-mentioned several embodiment to film properties.
As can be seen from Table 4: multiple aromatic polyamine coupling, pure water flux that can more significant increase reverse osmosis membrane keeps higher rejection simultaneously.
Embodiment 15-18
(1) preparation of aqueous phase solution A: the m-phenylene diamine (MPD) dissolving is dispersed in the water, and ultrasonic a period of time is uniformly dispersed it, is mixed with aqueous phase solution A;
(2) preparation of organic phase solution B: polynary acyl chlorides of aromatic series and multi-walled carbon nano-tubes are dissolved in the n-hexane, and ultrasonic agitation is even, is mixed with organic phase solution B;
All the other operations make the hybridized composite reverse osmosis membrane of carbon nanotubes with embodiment 1, and the The performance test results of the hybridized composite reverse osmosis membrane that makes is as shown in table 5.
Table 5
| The polynary acyl chlorides of aromatic series (0.2wt%) | CNT (0.01wt%) | Pure water flux (L/ (m 2·h)) | Rejection (%) | |
| Embodiment 15 | Pyromellitic trimethylsilyl chloride | Double-walled carbon nano-tube | ??30.47 | ??89.34 |
| Embodiment 16 | 5-isocyanates-isophthaloyl chlorine | Double-walled carbon nano-tube | ??30.94 | ??89.07 |
| Embodiment 17 | Pyromellitic trimethylsilyl chloride/5-isocyanates-isophthaloyl chlorine (weight ratio is 4: 1) | Multi-walled carbon nano-tubes | ??33.57 | ??90.53 |
| Embodiment 18 | Pyromellitic trimethylsilyl chloride/m-phthaloyl chloride (weight ratio is 4: 1) | Multi-walled carbon nano-tubes | ??32.19 | ??90.69 |
Investigate the influence of the polynary acyl chlorides of various aromatic series and CNT by above-mentioned several embodiment to film properties.
As can be seen from Table 5: the polynary acyl chlorides coupling of multiple aromatic series, pure water flux that can more significant increase reverse osmosis membrane keeps higher rejection simultaneously.
Embodiment 19-22
(1) preparation of aqueous phase solution A: m-phenylene diamine (MPD) and multi-walled carbon nano-tubes dissolving are dispersed in the water, and ultrasonic a period of time is uniformly dispersed it, is mixed with aqueous phase solution A;
(2) preparation of organic phase solution B: pyromellitic trimethylsilyl chloride and multi-walled carbon nano-tubes are dissolved in the n-hexane, and ultrasonic agitation is even, is mixed with organic phase solution B;
All the other operations make the hybridized composite reverse osmosis membrane of carbon nanotubes with embodiment 1, and the The performance test results of the hybridized composite reverse osmosis membrane that makes is as shown in table 6.
Table 6
Investigate the influence of aromatic polyamine, the polynary acyl chlorides of aromatic series and CNT concentration by above-mentioned several embodiment to film properties.
As can be seen from Table 6: when monomer concentration was low, the compactness of institute's film forming was not enough, caused rejection to reduce.And the CNT addition is when increasing, and membrane flux obviously increases.
Claims (10)
1. the preparation method of the hybridized composite reverse osmosis membrane of a carbon nanotubes comprises the steps:
(1), makes aqueous phase solution A with aromatic polyamine dissolving and be dispersed in the water;
The polynary acyl chlorides of aromatic series is dissolved in the organic solvent, stirs, make organic phase solution B;
Be dispersed with CNT among described aqueous phase solution A, the organic phase solution B one or both;
(2) the polysulfones support membrane being immersed aqueous phase solution A kept 1 minute-20 minutes, removal remains in the aqueous phase solution A on polysulfones support membrane surface, immerse among the organic phase solution B again and kept 10 seconds-120 seconds, remove the organic phase solution B of film remained on surface, dry, obtain being compounded with the polysulfones support membrane of carbon nanotubes PA membrane, drying makes the hybridized composite reverse osmosis membrane of carbon nanotubes.
2. preparation method as claimed in claim 1 is characterized in that, the mass percentage concentration of aromatic polyamine is 1%-2% among the described aqueous phase solution A.
3. preparation method as claimed in claim 1 or 2 is characterized in that, described aromatic polyamine is selected from one or both the mixture in phenylenediamine, the 5-sulfonic group m-phenylene diamine (MPD).
4. preparation method as claimed in claim 3 is characterized in that, the weight ratio of phenylenediamine and 5-sulfonic group m-phenylene diamine (MPD) is 1-50 in described phenylenediamine and the 5-sulfonic group m-phenylene diamine (MPD) mixture: 1.
5. preparation method as claimed in claim 1 is characterized in that, the mass percentage concentration of the polynary acyl chlorides of aromatic series is 0.05%-0.2% among the described organic phase solution B.
6. as claim 1 or 5 described preparation methods, it is characterized in that the polynary acyl chlorides of described aromatic series is selected from a kind of in a kind of or pyromellitic trimethylsilyl chloride in pyromellitic trimethylsilyl chloride, 5-isocyanates-isophthaloyl chlorine, the m-phthaloyl chloride and 5-isocyanates-isophthaloyl chloroformate mixture, pyromellitic trimethylsilyl chloride and the m-phthaloyl chloride mixture.
7. preparation method as claimed in claim 6, it is characterized in that, in described pyromellitic trimethylsilyl chloride and 5-isocyanates-isophthaloyl chloroformate mixture or pyromellitic trimethylsilyl chloride and the m-phthaloyl chloride mixture, the weight ratio of pyromellitic trimethylsilyl chloride and 5-isocyanates-isophthaloyl chlorine or m-phthaloyl chloride is 1-10: 1-10.
8. preparation method as claimed in claim 1 is characterized in that, the mass percentage concentration of CNT is 0.005%-0.2% among described aqueous phase solution A or the organic phase solution B.
9. as claim 1 or 8 described preparation methods, it is characterized in that described CNT is selected from SWCN, a kind of in double-walled carbon nano-tube, the multi-walled carbon nano-tubes.
10. as the hybridized composite reverse osmosis membrane of the carbon nanotubes of each described preparation method preparation of claim 1-9.
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