CN103864179B - A kind of forward osmosis extracting solution and its preparation method and application - Google Patents
A kind of forward osmosis extracting solution and its preparation method and application Download PDFInfo
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- CN103864179B CN103864179B CN201410095615.7A CN201410095615A CN103864179B CN 103864179 B CN103864179 B CN 103864179B CN 201410095615 A CN201410095615 A CN 201410095615A CN 103864179 B CN103864179 B CN 103864179B
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- 238000009292 forward osmosis Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002105 nanoparticle Substances 0.000 claims abstract description 30
- 239000013535 sea water Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004005 microsphere Substances 0.000 claims abstract description 16
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 13
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 claims abstract description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 230000004043 responsiveness Effects 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 10
- 239000013505 freshwater Substances 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 6
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004160 Ammonium persulphate Substances 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 230000035515 penetration Effects 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229960002703 undecylenic acid Drugs 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 2
- 230000009977 dual effect Effects 0.000 abstract description 2
- 230000005426 magnetic field effect Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 238000000638 solvent extraction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 51
- 238000000034 method Methods 0.000 description 18
- 238000010612 desalination reaction Methods 0.000 description 9
- 239000012528 membrane Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000003204 osmotic effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 241000238366 Cephalopoda Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000116629 Ferula sumbul Species 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 229940030270 sumbul Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of forward osmosis extracting solution and its preparation method and application, it is the polymer composite microsphere solution having temperature-responsive and magnetic responsiveness concurrently, and the raw material of described polymer composite microsphere is Fe
3o
4nanoparticle, vinylbenzene, oligomeric ethylene glycol methyl ether methacrylate and N-isopropylacrylamide.Forward osmosis extracting solution of the present invention has temperature and magnetic field dual responsiveness.When temperature reaches LCST, in extracting solution, solute reunion is separated out; Under more low intensive externally-applied magnetic field effect, solute just can be separated rapidly.The two synergy makes the solute of extracting solution be easy to partitioning cycle use; Forward osmosis extracting solution of the present invention take polymkeric substance as main component, totally nontoxic, is separated product water quality high; Forward osmosis extracting solution of the present invention is used for sea water desaltination, and its processing unit is simple, cost is low, less energy consumption, meets the theory of Green Development.
Description
Technical field
The present invention is specifically related to a kind of forward osmosis extracting solution and its preparation method and application.
Background technology
Freshwater resources reserves only take up an area 2.5% ~ 3% of ball total Water, along with the increase of the size of population, growth in the living standard, the developing rapidly and the change of environment of industry, whole China and even the whole world all face the situation of serious shortage of fresh water, increasing countries and regions start to greatly develop desalination technology, want fresh water to ocean.
China's Coastal Areas is economically developed, populous, large to the demand of water resources, water resources is seriously deficient, in order to solve the water resources problems in China coast city, except taking water saving, retaining, water transfer, sea water desaltination solves the important channel of coastal cities shortage of fresh water by becoming.Sea water desaltination refers to the technical process being separated salt and water in seawater, by the most of salt in removing seawater, makes the seawater after process reach the standard of life and water of productive use.The desalinating process comparatively generally adopted in the world at present comprises multistage flash evaporation (Multi-stage flash, MSF), low temperature multiple-effect distillation (Multi-effect distillation, MED) and reverse osmosis method (Reverse osmosis, RO).But, the defect of these technology aspect such as all remarkable the and producing water ratio of ubiquity high cost, energy consumption is on the low side.
In recent years, forward osmosis membrane separation technique obtains and pays close attention to widely.Downward penetration (Forwardosmosis, FO) is different from traditional reverse-permeation process, but directly utilizes the permeable pressure head of film both sides solution to make impellent.FO desalination technology utilizes forward osmosis principle just, seawater is passed in the side of semi-permeable membranes, osmotic pressure " extracting solution " (Draw solution much larger than seawater is passed at opposite side, DS), water, by under the driving of film both sides osmotic pressure, enters extracting solution side from seawater side by semi-permeable membranes, and tunicle retains by the salinity in seawater, meanwhile, utilize other means to be separated by the water in extracting solution, just can obtain fresh water.Forward osmosis membrane separation technique has that cost is on the low side, energy consumption is less and producing water ratio advantages of higher, in this field, (the Kravath R E such as Kravath, Davis J A.Desalination of sea waterby direct osmosis [J] .Desalination, 1975,16 (2): 151-155.) adopt glucose solution as the extracting solution in forward osmosis technology, modulate certain density glucose extracting solution, directly from seawater, extract fresh water.This method obtains diluted glucose solution and as the nutrient supply of short-term, at sea liferaft can use, but does not solve the problem of extracting solution recycle.(the Frank B S.Desalination of sea water:US such as Frank, 1972:3670897 [P] .1972-06-20) utilize precipitable Tai-Ace S 150 as extracting solution solute, forward osmosis makes moisture enter extracting solution through film, then feeding lime water in the extracting solution after dilution is passed through, produce aluminium hydroxide and calcium sulfate precipitation, disgorging obtains clean water.But this method is comparatively large to the infringement of semi-permeable membranes, and cost is higher, is not suitable for actual popularization.(the McCutcheon J R such as McCutcheon, McGinnis R L, Elimelech M.A novelammonia-carbon dioxide forward (direct) osmosis desalination process [J] .Desalination, 2005,174 (1): 1-11.) etc. roatating packed bed ammonia and carbonic acid gas is utilized to make extracting solution, and then obtain and be greater than the osmotic pressure of seawater, and this extracting solution at a lower temperature (60
oc) decomposable asymmetric choice net goes out ammonia and carbonic acid gas again, and then recycles.This method effectively improves the recovery of solute, and reduce the energy expenditure in desalting process, but the industrialization facility structure of this method is complicated, fresh water post-processed is relatively loaded down with trivial details.(the M.M Ling such as Ling, T-S Chung, X Lu.Facile synthesis ofthermosensitive magnetic nanoparticles as " smart " draw solutes in forwardosmosis [J] .Chem.Commun, 2011,47:10788-10790.) report a kind of extraction solute, this solute simply wraps up N-isopropylacrylamide on magnetic particle surface, is reclaimed the recycle that can realize extracting solute by Magneto separate.But this extraction solute surface aggregate thing parcel less, wetting ability is poor, magnetic particle protection is not enough, and dispersiveness is also bad, easily reunites at low temperature, and impact uses.Sumbul draws Germania En Yeer (for the system and method for forward osmosis liquid purification, Chinese patent, publication number CN102325581A) to disclose extracting solution prepared by a kind of cloud point solute.When moisture infiltrate into from seawater extracting solution make its osmotic pressure be less than seawater time, to extracting solution improve temperature, cloud point solute just from " turbidity is out " extracting solution, can realize the recycle of forward osmosis liquid by means such as filtrations.This method is compared with traditional desalination technology, has the advantages such as energy consumption is less than normal, working temperature is lower, but it requires higher to solute filter membrane, and application is subject to certain restrictions.
Summary of the invention
The object of the invention is to overcome prior art defect, a kind of forward osmosis extracting solution is provided.
Another object of the present invention is to the preparation method that above-mentioned forward osmosis extracting solution is provided.
Another object of the present invention is the application providing above-mentioned forward osmosis extracting solution.
Concrete technical scheme of the present invention is as follows:
For a forward osmosis extracting solution for sea water desaltination, for having the polymer composite microsphere solution of temperature-responsive and magnetic responsiveness concurrently, the raw material of described polymer composite microsphere is Fe
3o
4nanoparticle, vinylbenzene, oligomeric ethylene glycol methyl ether methacrylate and N-isopropylacrylamide.
In a preferred embodiment of the invention, Fe described in described forward osmosis extraction
3o
4nanoparticle, styrene monomer, oligomeric ethylene glycol methyl ether methacrylate and N-isopropylacrylamide weight ratio are 1 ~ 5:2 ~ 5:1 ~ 5:5 ~ 10.
In a preferred embodiment of the invention, described polymer composite microsphere possesses nucleocapsid structure, and particle diameter is 50 ~ 80nm, and its core is the Fe of particle diameter 5 ~ 8nm
3o
4nanoparticle.
A preparation method for the above-mentioned forward osmosis extracting solution for sea water desaltination, comprises the steps:
(1) Fe is prepared
3o
4nanoparticle, and carry out surface modification to improve the hydrophobicity on its surface;
(2) under room temperature, by styrene monomer, Fe
3o
4nanoparticle puts into distilled water, adds initiator and be warming up to 55 ~ 60 DEG C of reaction 1 ~ 3h after stirring 0.5 ~ 1h;
(3) after the reaction of step (2) terminates, add oligomeric ethylene glycol methyl ether methacrylate and N-isopropylacrylamide, be warming up to 65 ~ 70 DEG C of continuation reaction 6 ~ 12h and namely obtain the described forward osmosis extracting solution for sea water desaltination.
In a preferred embodiment of the invention, described step (1) is specially: prepare magnetic Fe with chemical coprecipitation
3o
4nanoparticle, adds long-chain unsaturated fatty acid modification, improves Fe
3o
4the hydrophobicity of nanoparticle surface.
Preferred further, described long-chain unsaturated fatty acid is oleic acid, undecylenic acid or tridecylenic acid, and its consumption is Fe
3o
41 ~ 1.5 times of nanoparticle weight.
In a preferred embodiment of the invention, described initiator is Potassium Persulphate or ammonium persulphate.
In a preferred embodiment of the invention, described Fe
3o
4the content of nanoparticle, styrene monomer, oligomeric ethylene glycol methyl ether methacrylate, N-isopropylacrylamide and initiator is followed successively by: 1 ~ 5wt%, 2 ~ 5wt%, 1 ~ 5wt%, 5 ~ 10wt% and 0.001 ~ 1wt%, and surplus is distilled water.
The application of a kind of above-mentioned forward osmosis extracting solution in sea water desaltination.
In a preferred embodiment of the invention, adopt downward penetration, temperature when reclaiming the fresh water of load in described forward osmosis extracting solution is 31 ~ 36 DEG C, and magnetic field is 30 ~ 60mT; Temperature during concentrated described forward osmosis extracting solution is 25 ~ 33 DEG C and removes magnetic field.
The invention has the beneficial effects as follows:
(1) in forward osmosis extracting solution of the present invention, the particle diameter of complex microsphere is 50 ~ 80nm, and its core is the Fe of particle diameter 5 ~ 8nm
3o
4nanoparticle, specific surface area is large, and be rich in hydrophilic radical, osmotic pressure is high;
(2) forward osmosis extracting solution of the present invention has temperature and magnetic field dual responsiveness.When temperature reaches LCST, in extracting solution, solute reunion is separated out; Under more low intensive externally-applied magnetic field effect, solute just can be separated rapidly.The two synergy makes the solute of extracting solution be easy to partitioning cycle use;
(3) forward osmosis extracting solution of the present invention take polymkeric substance as main component, totally nontoxic, is separated product water quality high;
(4) forward osmosis extracting solution of the present invention is used for sea water desaltination, and its processing unit is simple, cost is low, less energy consumption, meets the theory of Green Development.
Accompanying drawing explanation
Fig. 1 is the TEM figure of complex microsphere in the forward osmosis extracting solution of embodiment 1 preparation;
Fig. 2 is the temperature sensitive lab diagram of complex microsphere in the forward osmosis extracting solution of embodiment 1 preparation;
Fig. 3 is the magnetic hysteresis loop figure of complex microsphere in the forward osmosis extracting solution of embodiment 1 preparation.
Embodiment
By reference to the accompanying drawings below by way of embodiment technical scheme of the present invention is further detailed and is described.
Embodiment 1
(1) MODIFIED Fe
3o
4the preparation of nanoparticle: by 23.83g FeCl
36H
2o and 7.31gFeSO
47H
2o is dissolved in 40mL deionized water, logical nitrogen deoxygenation 30min; Slowly add the NH of 15.3mL massfraction 25%
3h
2o, adds 5.1mL oleic acid after 60 DEG C of reaction 30min, is warming up to 80 DEG C of slaking 2h, obtains the magnetic Fe with superparamagnetism of size 5 ~ 8nm
3o
4nanoparticle.By modified magnetic Fe
3o
4nanoparticle by washing with alcohol 2 ~ 4 times to neutral, dry for standby.
(2) under room temperature, by 2g styrene monomer, 3g Fe
3o
4nanoparticle adds in 100mL distilled water, logical nitrogen, adds 0.04g ammonium persulphate and be warming up to 55 DEG C of reaction 2h after mechanical stirring 1h;
(3) add 5g oligomeric ethylene glycol methyl ether methacrylate, 10g N-isopropylacrylamide, be warming up to 65 DEG C of continuation reaction 12h and namely obtain described forward osmosis extracting solution.
Complex microsphere particle diameter in this forward osmosis extracting solution characterizes (as shown in Figure 1) via TEM, is about 65nm, has nucleocapsid structure, Fe
3o
4nanoparticle is embedded in microballoon inside; The magnetic property of complex microsphere measures (as shown in Figure 2) by SQUID superconductive quantum interference magnetometer, and result shows that residual magnetization and coercive force are all close to 0, almost exists without magnetic hysteresis, has superparamagnetism; The temperature-responsive of complex microsphere characterizes (as shown in Figure 3) by DLS, and result shows, cloud point temperature is about 32 DEG C.
Embodiment 2
Sea water desaltination simulated experiment
(1) take three cellulose acetate membrane as FO film, seawater side is simulated with NaCl solution.Setting NaCl solution concentration is 0.5molL
-1, the concentration of the forward osmosis extracting solution that embodiment 1 is obtained is 20gL
-1, recording water flux is 31.01Lm
-2h
-1, ratio of desalinization is 98.6%.
(2) after desalination terminates, extracting solution is warming up to the magnetic field of 35 DEG C and 50mT, the rate of recovery recording complex microsphere in extracting solution after 10min is 99.3%.
Embodiment 3 ~ 6
With embodiment 2 technique, the NaCl solution concentration changed in step (1) is followed successively by 1.0molL
-1, 1.5molL
-1, 2.0molL
-1, 2.5molL
-1, obtain experimental result as following table:
| Embodiment | Flux (Lm -2·h -1） | Ratio of desalinization (%) |
| 3 | 25.94 | 98.1 |
| 4 | 18.35 | 98.3 |
| 5 | 13.42 | 97.8 |
| 6 | 10.19 | 97.2 |
Embodiment 7 ~ 11
With embodiment 2 technique, fix N aCl strength of solution is 0.5molL
-1, extracting solution is reclaimed successively cycling and reutilization 1 time, 2 times, 3 times, 4 times, 5 times, obtains experimental result as following table:
| Embodiment | Flux (Lm -2·h -1） | Ratio of desalinization (%) |
| 7 | 30.92 | 98.3 |
| 8 | 29.21 | 98.1 |
| 9 | 29.34 | 97.9 |
| 10 | 28.76 | 97.2 |
| 11 | 27.87 | 97.4 |
Embodiment 12 ~ 16
With embodiment 2 technique, change temperature in step (2) and be followed successively by 31 DEG C, 32 DEG C, 33 DEG C, 34 DEG C, 36 DEG C, experimental results is as following table:
| Embodiment | The microballoon rate of recovery (%) |
| 12 | 23.4 |
| 13 | 24.7 |
| 14 | 93.3 |
| 15 | 99.4 |
| 16 | 99.2 |
Embodiment 17 ~ 19
With embodiment 2 technique, change magneticstrength in step (2) and be followed successively by 30mT, 40mT, 60mT, experimental results is as following table:
| Embodiment | The microballoon rate of recovery (%) |
| 17 | 74.2 |
| 18 | 86.8 |
| 19 | 99.5 |
Those skilled in the art are known, when described forward osmosis extracting solution processing parameter in the preparation changes in following scope, still can obtain identical or close technique effect:
(1) magnetic Fe is prepared with chemical coprecipitation
3o
4nanoparticle, adds long-chain unsaturated fatty acid modification, improves Fe
3o
4the hydrophobicity of nanoparticle surface.Described long-chain unsaturated fatty acid is oleic acid, undecylenic acid or tridecylenic acid, and its consumption is Fe
3o
41 ~ 1.5 times of nanoparticle weight.Described initiator is Potassium Persulphate or ammonium persulphate.
(2) under room temperature, by styrene monomer, Fe
3o
4nanoparticle puts into distilled water, adds initiator and be warming up to 55 ~ 60 DEG C of reaction 1 ~ 3h after stirring 0.5 ~ 1h;
(3) after the reaction of step (2) terminates, add oligomeric ethylene glycol methyl ether methacrylate and N-isopropylacrylamide, be warming up to 65 ~ 70 DEG C of continuation reaction 6 ~ 12h and namely obtain the described forward osmosis extracting solution for sea water desaltination.
Described Fe
3o
4the content of nanoparticle, styrene monomer, oligomeric ethylene glycol methyl ether methacrylate, N-isopropylacrylamide and initiator is followed successively by: 1 ~ 5wt%, 2 ~ 5wt%, 1 ~ 5wt%, 5 ~ 10wt% and 0.001 ~ 1wt%, and surplus is distilled water.
The above, be only preferred embodiment of the present invention, therefore can not limit scope of the invention process according to this, the equivalence change namely done according to the scope of the claims of the present invention and description with modify, all should still belong in scope that the present invention contains.
Claims (10)
1. a forward osmosis extracting solution, is characterized in that: for having the polymer composite microsphere solution of temperature-responsive and magnetic responsiveness concurrently, and the raw material of described polymer composite microsphere is Fe
3o
4nanoparticle, vinylbenzene, oligomeric ethylene glycol methyl ether methacrylate and N-isopropylacrylamide.
2. a kind of forward osmosis extracting solution as claimed in claim 1, is characterized in that: Fe described in described forward osmosis extracts
3o
4nanoparticle, styrene monomer, oligomeric ethylene glycol methyl ether methacrylate and N-isopropylacrylamide weight ratio are 1 ~ 5:2 ~ 5:1 ~ 5:5 ~ 10.
3. a kind of forward osmosis extracting solution as claimed in claim 1, is characterized in that: described polymer composite microsphere possesses nucleocapsid structure, and particle diameter is 50 ~ 80nm, and its core is the Fe of particle diameter 5 ~ 8nm
3o
4nanoparticle.
4. a preparation method for forward osmosis extracting solution according to claim 1, is characterized in that: comprise the steps:
(1) Fe is prepared
3o
4nanoparticle, and carry out surface modification to improve the hydrophobicity on its surface;
(2) under room temperature, by styrene monomer, Fe
3o
4nanoparticle puts into distilled water, adds initiator and be warming up to 55 ~ 60 DEG C of reaction 1 ~ 3h after stirring 0.5 ~ 1h;
(3) after the reaction of step (2) terminates, add oligomeric ethylene glycol methyl ether methacrylate and N-isopropylacrylamide, be warming up to 65 ~ 70 DEG C of continuation reaction 6 ~ 12h and namely obtain described forward osmosis extracting solution.
5. the preparation method of a kind of forward osmosis extracting solution as claimed in claim 4, is characterized in that: described step (1) is specially: prepare magnetic Fe with chemical coprecipitation
3o
4nanoparticle, adds long-chain unsaturated fatty acid modification, improves Fe
3o
4the hydrophobicity of nanoparticle surface.
6. the preparation method of a kind of forward osmosis extracting solution as claimed in claim 5, it is characterized in that: described long-chain unsaturated fatty acid is oleic acid, undecylenic acid or tridecylenic acid, its consumption is Fe
3o
41 ~ 1.5 times of nanoparticle weight.
7. the preparation method of a kind of forward osmosis extracting solution as claimed in claim 4, is characterized in that: described initiator is Potassium Persulphate or ammonium persulphate.
8. the preparation method of a kind of forward osmosis extracting solution as claimed in claim 4, is characterized in that: described Fe
3o
4the content of nanoparticle, styrene monomer, oligomeric ethylene glycol methyl ether methacrylate, N-isopropylacrylamide and initiator is followed successively by: 1 ~ 5wt%, 2 ~ 5wt%, 1 ~ 5wt%, 5 ~ 10wt% and 0.001 ~ 1wt%, and surplus is distilled water.
9. the application of a forward osmosis extracting solution according to claim 1 in sea water desaltination.
10. the application of a kind of forward osmosis extracting solution as claimed in claim 9 in sea water desaltination, is characterized in that: adopt downward penetration, temperature when reclaiming the fresh water of load in described forward osmosis extracting solution is 31 ~ 36 DEG C, and magnetic field is 30 ~ 60mT; Temperature during concentrated described forward osmosis extracting solution is 25 ~ 33 DEG C and removes magnetic field.
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