NL2007353C2 - Solution comprising an osmotic agent and method of extracting water using said solution. - Google Patents
Solution comprising an osmotic agent and method of extracting water using said solution. Download PDFInfo
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- NL2007353C2 NL2007353C2 NL2007353A NL2007353A NL2007353C2 NL 2007353 C2 NL2007353 C2 NL 2007353C2 NL 2007353 A NL2007353 A NL 2007353A NL 2007353 A NL2007353 A NL 2007353A NL 2007353 C2 NL2007353 C2 NL 2007353C2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000002357 osmotic agent Substances 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000012528 membrane Substances 0.000 claims abstract description 100
- 238000009292 forward osmosis Methods 0.000 claims abstract description 48
- 230000003204 osmotic effect Effects 0.000 claims abstract description 33
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 76
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 49
- 229960003237 betaine Drugs 0.000 claims description 37
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 17
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 15
- 125000005496 phosphonium group Chemical group 0.000 claims description 14
- 229920006395 saturated elastomer Polymers 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- 241001465754 Metazoa Species 0.000 claims description 6
- 229920002301 cellulose acetate Polymers 0.000 claims description 6
- 238000001728 nano-filtration Methods 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000001223 reverse osmosis Methods 0.000 claims description 5
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 4
- 229940024606 amino acid Drugs 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 3
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 claims description 3
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 3
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 claims description 3
- 229920001727 cellulose butyrate Polymers 0.000 claims description 3
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 3
- 229960001231 choline Drugs 0.000 claims description 3
- 229960002449 glycine Drugs 0.000 claims description 3
- 229960002429 proline Drugs 0.000 claims description 3
- 238000000108 ultra-filtration Methods 0.000 claims description 3
- 229960004295 valine Drugs 0.000 claims description 3
- 239000004474 valine Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- 229920001747 Cellulose diacetate Polymers 0.000 claims 1
- 230000004907 flux Effects 0.000 description 44
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 36
- 239000012527 feed solution Substances 0.000 description 24
- 239000011780 sodium chloride Substances 0.000 description 18
- 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 14
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 14
- 229930006000 Sucrose Natural products 0.000 description 14
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 14
- 239000008103 glucose Substances 0.000 description 14
- 239000005720 sucrose Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 239000010865 sewage Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 6
- 239000008186 active pharmaceutical agent Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000035622 drinking Effects 0.000 description 2
- 235000015203 fruit juice Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000010841 municipal wastewater Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000000065 osmolyte Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- DFPOZTRSOAQFIK-UHFFFAOYSA-N S,S-dimethyl-beta-propiothetin Chemical compound C[S+](C)CCC([O-])=O DFPOZTRSOAQFIK-UHFFFAOYSA-N 0.000 description 1
- 108010077895 Sarcosine Proteins 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003295 industrial effluent Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000671 osmolytic effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229940043230 sarcosine Drugs 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- UYPYRKYUKCHHIB-UHFFFAOYSA-N trimethylamine N-oxide Chemical compound C[N+](C)(C)[O-] UYPYRKYUKCHHIB-UHFFFAOYSA-N 0.000 description 1
- -1 urine Substances 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
-
- 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
- C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/002—Forward osmosis or direct osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/002—Forward osmosis or direct osmosis
- B01D61/005—Osmotic agents; Draw solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/58—Multistep processes
-
- 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
-
- 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
- B01D69/107—Organic support material
-
- 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
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
- B01D71/14—Esters of organic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
Abstract
The present invention relates to a method of extracting water from an aqueous source by forward osmosis comprising the application of an osmotic pressure difference over a semi-permeable membrane by providing the aqueous source on one side of the membrane and a draw solution comprising an osmotic agent on the other side of the membrane, wherein the osmotic agent is an organic zwitterion and/or an organic compound comprising an onium group, or more than one carboxylic group.
Description
Solution comprising an osmotic agent and method of extracting water using said solution
The present invention relates to a method of 5 extracting water from an aqueous source by osmosis, a draw solution for use in the method and the use of osmotic agents in a draw solution.
Forward osmosis is a technologically applicable variant of osmosis, wherein water is naturally transported 10 through a semi-permeable membrane driven by an osmotic pressure difference generated by the two solutions on both sides of the membrane. In forward osmosis, water molecules migrate through the semi-permeable membrane from a low to high osmotic concentration corresponding to high to low 15 chemical potential. This phenomenon will continue until an osmotic equilibrium is reached, generally until the same concentration is reached on both sides of the membrane.
Whereas forward osmosis is an osmotically-driven membrane process, other membrane processes, such as 20 microfiltration, ultrafiltration, nanofiltration and reverse osmosis are driven by hydraulic pressure. In terms of energy consumption, forward osmosis requires no additional energy supply.
In present day forward osmosis applications, 25 forward osmosis mass transport is divided into: (i) a flux of water passing the membrane which dilutes the more concentrated draw side, and (ii) a reverse solute flux which concentrates the feed solution at the feed side. Both fluxes contribute to a decrease of the osmotic pressure difference 30 in this osmotic process. To increase the economic viability of the forward osmosis process, research goals are aimed at increasing the water flux towards the draw side and/or decreasing reverse flux of osmotic agents towards the feed 2 side .
Attention has been spent on the development of alternative draw solutions. Consequently, several osmotic agents are known in the field, which include salts (e.g.
5 NaCl, MgCl2, or KNO3) , sugars (e.g. sucrose, glucose or fructose), or volatile solutes (e.g. SO2) or certain mixtures thereof. However, the efficiency of these osmotic agents in draw solutions is suboptimal as a consequence of various drawbacks. For example, although it is in general observed 10 that inclusion of higher amounts of osmotic agents in the draw solution results in higher water fluxes, also an increased leakage of the osmotic agent is observed, i.e. draw solute leakage or reverse solute flux. Furthermore, there are difficulties in the recovery of the draw solute 15 using a reconcentration system, fouling of the membranes occurs during forward osmosis (both on the feed solution side and the draw solution side of the membrane) and internal concentration polarisation phenomena are observed when using such osmotic agents.
20 There is thus a need in the field of forward osmosis for identifying osmotic agents that can provide a high osmotic pressure difference on the one hand and exhibit improved characteristics with respect to at least reduction of solute leakage on the other.
25 It is an object of the present invention to, inter alia, provide a solution to the above-mentioned disadvantages .
This object, among others, is solved, completely or in part, by the invention according to the appended 30 claims.
More in particular, this object, or other objects, is achieved by the provision of a method of extracting water from an aqueous source by osmosis, preferably forward 3 osmosis, the method comprising the application of an osmotic pressure difference over a semi-permeable membrane by providing the aqueous source on one side of the membrane and a draw solution comprising an osmotic agent on the other 5 side of the membrane, wherein the osmotic agent is an organic zwitterion and/or an organic compound comprising a saturated positively charged group, preferably an onium group such as a quaternary ammonium group, sulfonium group or phosphonium group.
10 One advantage of the present invention is that the effectiveness of forward osmosis processes can now be enhanced, as the flux of water from the feed solution to the draw solution is improved. Furthermore, the reverse solute flux of the osmotic agent is minimized. Preferably though, 15 the osmotic agent causes both an improvement in the flux of water from the feed solution to the draw solution, while the reverse solute flux of the osmotic agent is minimized.
In an advantageous embodiment, the organic zwitterion used as the osmotic agent is selected from the 20 group consisting of a betaine comprising compound, a betaine and an amino acid. Herein, a betaine is a neutral chemical compound with a positively charged cationic functional group which bears no hydrogen atom, in particular an onium group (such as ammonium, phosphonium, sulfonium group), and 25 furthermore has a negatively charged functional group, such as a carboxylate group. A zwitterion herein is a neutral molecule having a positive and a negative electrical charge, at different locations within the molecule. For sake of clarity, zwitterions herein are distinct from dipoles.
30 Advantageously, the organic compound and/or organic zwitterion comprises an onium group such as a saturated quaternary ammonium group, sulfonium group or phosphonium group.
4
In a further advantageous embodiment, the quaternary ammonium useful as osmotic agent in the present invention comprises the structure presented as Formula I: R' R—N-"""" R R3
5 Formula I
wherein R1, R2 and R3 are independently selected from a lower alkyl, branched or linear, preferably a C1-C6 alkyl, and wherein R4 is selected from a carboxyl, an alcohol, 10 hydroxyl or a lower alkyl comprising a carboxyl, an alcohol or hydroxyl.
Advantageously, R1, R2 and R3 are each selected from methyl, ethyl, propyl, butyl, pentyl and hexyl, linear or branched. Preferably, R1, R2 and R3 are methyl.
15 In an advantageous embodiment, the osmotic agent used in the present invention is selected from the group consisting of glycine betaine, choline, valine, proline and glycine, or a combination thereof.
Alternatively, the osmotic agent according to the 20 invention is a natural osmolyte, meaning an organic compound produced by a cell which is used for osmotic purposes by the cell. Such compounds include trimethylamine N-oxide, dimethylsulfoniopropionate, trimethylglycine, sarcosine and the like.
25 In an advantageous embodiment, the method of the present invention relates to forward osmosis. This means that, besides the herein described structural definitions, the osmotic agent according to the invention provides a high osmotic pressure difference in forward osmosis and is at 30 least compatible with a forward osmosis membrane. The term 5 "forward osmosis" herein is meant to include direct osmosis, engineered osmosis, manipulated osmosis or pressure retarded osmosis. It is contemplated that, instead of using a forward osmosis membrane, it is also possible to use a reverse 5 osmosis or a nanofiltration membrane in the method of the present invention. Also, the method of the present invention preferably takes place without applying hydraulic pressure. And, the forward osmosis process takes place under any suitable ambient pressure and temperature wherein water is 10 or remains liguid.
According to a preferred embodiment, the osmotic agents of the present invention are sufficiently water soluble, exhibit no or low solute leakage, have a suitably small molecular weight, are sufficiently repelled by forward 15 osmosis membranes and provide a sufficient pull of water through these membranes. The latter feature implies that the osmotic agent has considerable osmotic power, meaning it creates enough osmotic pressure difference or chemical potential difference. The osmotic agent according to the 20 present invention, either used in the method of extracting water according to the present invention, or comprised by the draw solution according to the invention, is present in such a concentration that an osmotic pressure of at least 0.5 bar is generated by the osmotic agent and/or by a 25 combination of osmotic agents according to the present invention. In further embodiments, this osmotic pressure is at least 1 bar, at least 6 bar, at least 15 bar, at least 20 bar, or at least 24 bar These osmotic pressure values are derived from calculations based on the following Van 't Hoff 30 equation: n = iMRT. Herein is i the Van 't Hoff factor, M is the molarity, R is the gas constant: 0.0821 L atm K_1 mol-1, and T is the thermodynamic, absolute temperature (e.g.
20°C). It lies well within the capabilities of the skilled 6 person to calculate such osmotic pressure differences for any osmotic agent operating in forward osmosis under the herein mentioned conditions.
In a preferred embodiment, the semi-permeable 5 membrane is a membrane which is suitable for nanofiltration, reverse osmosis or preferably forward osmosis. Even though progress is made in the development of membranes for forward osmosis, the characteristics such membranes should have for them to be useful in forward osmosis processes are known by 10 the skilled person. Typically, such membranes are hydrophilic, charged, either positively or negatively, and have a determined pore size and specific molecular weight cut-off value.
Advantageously, the osmotic agent is compatible 15 with the semi-permeable membrane used in the process of the present invention. Compatibility herein is to be construed as that the osmotic agent according to the present invention and the semi-permeable membrane as used are selected such that the osmotic agent is repelled by the membrane and/or 20 excluded by size from passing the membrane. Such a selection can be based on charge differences between the membrane and osmotic agent, molecular weight or size of the agent versus the molecular weight cut-off value or pore size of the membrane as used and/or polarity differences exhibited by 25 the agent and the membrane.
The osmotic process that takes place under the influence of the draw solution according to the present invention occurs under suitable conditions, meaning i.a. that the pH of the solution lies between pH 2 and 10, 30 preferably between pH 3 and 8, most preferably between pH 4 and 6. Since the functionality of a charged compound is pH dependent, the pH of the draw solution is preferably selected such that the osmotic agent is not of the same 7 charge (or of opposite charge) as the semi-permeable membrane as used. Alternatively, the osmotic agent comprises a charged group which is not of the same charge as the semi-permeable membrane as used. Preferably, the osmotic agent 5 comprises a group which is of opposite charge of the semi-permeable membrane used.
Preferably, the semi-permeable membrane has a molecular weight cut-off less than 1000 Da, preferably less than 200 Da, more preferably less than 100 Da. Molecular 10 weight cut-off (MWCO) herein is defined as refers to the lowest molecular weight solute (in Da) in which 95% of the solute is retained by the membrane.
In a preferred embodiment, the semi-permeable membrane used in the method of the invention has a pore size 15 of between 0.001 and 0.0001 pm, preferably between 0.0003 and 0.0005 pm. Furthermore, the semi-permeable membrane comprises an active layer and/or a support layer.
Preferably, the semi-permeable membrane comprises a hydrophilic, cellulose comprising active layer, preferably 20 comprising cellulose acetate, cellulose di-acetate, cellulose tri-acetate, cellulose butyrate, cellulose acetate proprionate and/or mixtures thereof. Also, the semi-permeable membrane comprises a support layer or a polyester mesh or a micro-porous support. The semi-permeable membrane 25 can furthermore include or be a Thin Film Composite membrane .
The forward osmosis membrane according to the invention can be used in two orientations, one wherein the draw solution faces the active layer and the feed solution 30 faces the support layer, and vice versa. In the research that led to the invention, it was found that the osmotic agents of the present invention provide an improvement over present day draw solutions in both orientations. However, in 8 a preferred embodiment, the active layer faces the draw side since that orientation provides some improvement over the reverse orientation.
For certain applications it is preferred though to 5 operate in an active layer to feed side modus. This is in particular true for wastewater treatment since under those circumstances membrane fouling is expected to be less problematic .
The aqueous source, i.e. feed solution or the 10 aqueous target from which water is to be extracted, herein is in non-limiting examples, sewage, municipal wastewater, industrial (waste)water, effluent, leachate, surface water, ground water, brackish water, sea water (or other sources for high quality water or drinking/process water), bodily 15 fluids, urine, blood and/or an aqueous solution for animal or human consumption. These industrially-derived wastewaters can be from any source. The aqueous solutions for animal or human consumption are, in non-limiting examples, water for human consumption (e.g. recycled water used in space 20 travel), beverages, fruit juice. An advantage of using forward osmosis according to the method of the present invention is that fruit juices, or other aqueous solutions for human consumption, can be processed without including a heating or cooling step which might impair the quality or 25 affect the organoleptic properties of the aqueous solution for human or animal consumption.
In an advantageous embodiment, the osmotic agent according to the invention is reused after being used as draw solution. Reuse of the osmotic agent is possible due 30 its low solute leakage. Such reuse of the osmotic agent can be effectuated using the diluted draw solution as a starting point, using a reverse osmosis unit, a reconcentration unit, membrane distillation or nanofiltration.
9
In a non-limiting example, the osmosis membrane used in the method of the present invention can be used in a flat configuration, such as flat sheets, in a spiral configuration, a hollow fibre membrane or any other suitable 5 configuration.
Another aspect of the present invention relates to a draw solution for extraction of water by forward osmosis, comprising an organic zwitterion and/or an organic compound comprising a saturated positively charged group, preferably 10 a quaternary ammonium group, sulfonium group or phosphonium group as osmotic agent(s). The draw solution preferably comprises any one of the more specifically defined osmotic agents as mentioned herein.
An advantage of the osmotic agents according to 15 the present invention is that, when used in draw solutions, they provide an increased osmotic efficiency compared to small inorganic salts, such as NaCl. Another benefit of the present invention is that when using the draw solution in forward osmosis, a lower internal concentration polarization 20 is achieved, resulting in an increased forward osmosis efficiency (e.g. a lower reverse solute flux). Without being bound by theory, it is currently believed that the osmotic agents according to the present invention are not able, or at least to a lesser extent than existing agents (e.g.
25 NaCl), to enter the semi-permeable membranes used in forward osmosis. In particular, it is believed that the support layer comprised by such membrane is less accessible to the osmotic agents of the invention.
The present invention thus provides a draw 30 solution, encompassing organic zwitterions and/or organic compounds comprising a saturated positively charged group, preferably a quaternary ammonium group, sulfonium group or phosphonium group, as osmotic agents, with improved 10 characteristics in comparison to solutions which rely in essence only on NaCl, glucose or sucrose for their osmolytic properties. The draw solution of the present invention has a high osmotic efficiency, i.e. it is highly, or at least 5 sufficiently, soluble in water and generates a high osmotic pressure at the conditions encountered in forward osmosis.
In another embodiment, the draw solution further comprises one or more biocides to reduce degradation of the osmotic agent. Also, the draw solution and installed setup 10 may be sterile to reduce biodegradation of osmotic agents. The installed setup may also comprise an UV installation to disinfect the draw solution to prevent degradation.
Yet another aspect of the present invention relates to the use of an organic zwitterion and/or an 15 organic compound comprising a quaternary ammonium group as osmotic agent(s) in a solution, preferably in a draw solution .
This use of the draw solution preferably comprises any one of the more specifically defined osmotic agents as 20 mentioned herein.
The osmotic agent according to the present invention, or draw solution comprising said agent, can be used in applications wherein the obtainment of bulk amounts of purified water is the main purpose, for example in the 25 treatment of polluted sources such as in non-limiting examples, sewage, municipal wastewater, industrial (waste)water, effluent, leachate, surface water, ground water, brackish water, sea water (or other sources for high quality water or drinking/process water). Conversely, it can 30 be used in applications wherein the obtainment of a more concentrated feed solution is the main purpose, i.e. to concentrate liquids. Such more concentrated liquids comprise, in a non-limiting example, beverages for animal or 11 human consumption. Also, concentrating sewage in the production of biogas or any other aqueous solution containing a product that needs to be recovered or reused, is encompassed by the present invention.
5 As stated above, in forward osmosis, solutes can diffuse in two directions: from the feed solution into the draw solution (i.e. forward diffusion) and simultaneously from the draw solution into the feed solution (i.e. reverse diffusion). Due to internal concentration polarization (i.e. 10 the build-up of solutes within the osmosis membrane), nonlinear solute flux behaviour is observed (see Figure 1).
This internal concentration polarization results in a lower osmotic driving force.
In Figure 1, the higher concentration of solute in 15 the draw solution, CD, creates a chemical potential gradient that drives both the forward water flux Jw, and the solute flux Js. For the draw solute to permeate across the asymmetric membrane into the feed solution, where its concentration CF is negligible, it must be transported across 20 the support layer of thickness tA. C±s and C±A represent the draw solute concentrations on the support layer side and active layer side of the support layer-active layer interface, respectively.
By using a U-tube set-up, such as described in the 25 experimental section, it is possible to investigate and characterize fluxes of solutes and water in forward osmosis processes. Experimentally, the solute flux can be calculated using Equation I: , 1 A(cV)
Js = (Equation I) 30 Herein, A is the area of the active layer of the membrane and A(cV) the total solute amount that crosses the membrane during the interval At.
This set-up also allows calculation of the water 12 flux due to increase of the water volume in a measuring tube. The volumetric flow rate of water can be calculated from the water volume and the time interval. The flux of water in forward osmosis can be calculated experimentally 5 using Equation II:
Jw = (Equation II)
Herein, Jw is the water flux, A is the area of the active layer of the membrane and AV the total amount of water that crosses the membrane during the interval At.
10 Both fluxes, Js and Jw, allow the study of the efficiency of the forward osmosis process: a high water flux is required while the solute leakage is to remain as low as possible.
Osmotic agents according to the appended claims 15 have been found to exhibit both an improvement in the flux of water from the feed solution to the draw solution (as calculated by Equation II), while the reverse solute flux of the osmotic agent is minimized (as calculated by Equation I) • 20 In a broader respect, the invention relates to a method of extracting water from an aqueous source by osmosis, comprising the application of an osmotic pressure difference over a semi-permeable membrane by providing the aqueous source on one side of the membrane and a draw 25 solution comprising an osmotic agent on the other side of the membrane, wherein the osmotic agent is an organic zwitterion and/or an organic compound comprising a positively charged group, preferably a saturated positively charged group, such as an onium group preferably selected 30 from a quaternary ammonium group, sulfonium group or phosphonium group. In this broader respect, the invention also relates to a draw solution comprising an organic zwitterion and/or an organic compound comprising a 13 positively charged group, preferably a saturated positively charged group, such as an onium group preferably selected from a guaternary ammonium group, sulfonium group or phosphonium group.
5 The organic zwitterion in this broader respect, is selected from the group consisting of a betaine, a betaine comprising compound and an amino acid.
The quaternary onium group, in this broader respect, comprises the structure according to formula II: R1 R—R—R4 R3
10 K
wherein R5 is selected from N and P, preferably N+ , S+ and P+, R1, R2 and R3 are independently selected from H, a lower alkyl, branched or linear, preferably a alkyl, or aryl 15 and wherein R4 is selected from a carboxyl, an alcohol, hydroxyl, oxygen or a lower alkyl comprising a carboxyl, an alcohol, hydroxyl or oxygen.
Figures 20 Figure 1 schematically depicts draw solute leakage into the feed solution using a forward osmosis membrane. FS = Feed Solution 2, AL = Active Layer 4, SL = Support Layer 6, DS = Draw Solution 8, Jw = Water flux, Js = Solute flux, CD = Concentration of solute in draw solution, CiS = the draw 25 solute concentration on the support layer side of the support layer-active layer interface, CiA = the draw solute concentration on the active layer side of the support layer-active layer interface, CF = Concentration of solute in feed solution, tA = thickness of active layer, tS = thickness of 30 support layer.
14
Figures 2a and b show results obtained from experiments using various draw solutions comprising different osmotic agents. In Figure 2a, water flux and solute flux of glycine betaine (GB) is shown in comparison 5 to NaCl, glucose and sucrose. Membrane orientation: feed solution facing the active layer (AL to FS). In Figure 2b, ratio of glycine betaine (GB), NaCl, glucose and sucrose as measured during the experiment is shown (AL to FS).
Figures 3a and b show results obtained from 10 experiments using various draw solutions comprising different osmotic agents. In Figure 3a, water and solute flux of glycine betaine (GB) is shown and compared to NaCl, glucose and sucrose. Membrane orientation: draw solution facing the active layer (AL to DS). In Figure 3b, the ratio 15 of glycine betaine (GB), NaCl, glucose and sucrose as measured during the experiment is shown (AL to DS).
EXAMPLES
A standardized, laboratory-scale U-tube configuration was used to determine the forward osmosis 20 behaviour of various draw solutions and selected feed solutions over a vertically-positioned forward osmosis membrane. The U-tube configuration further comprised two pumps to allow continuous homogeneity of the draw and feed solutions and a measuring tube mounted on the draw side.
25 An asymmetric cellulose triacetate based-(CTA) forward osmosis-type membrane was used [the Expedition-type or HydroWell-type, Hydration Technology Innovations, Albany, OR, USA]. The forward osmosis membrane is hydrophilic with a thickness of less than 50 pm. It comprises a dense, 30 selective active layer and a porous support layer consisting of an embedded polyester mesh which provides mechanical support. Membranes were used in one of two different orientations: active layer facing feed side (AL to FS) or 15 active layer facing draw side (AL to DS) .
Forward osmosis experiments were carried out in the following experimental set-up.
The membrane, with an active area of 0.011 m2 was 5 placed in a membrane holder. A constant mixing rate of 5.5 L/min was applied to both the feed side and draw side to keep the solutions homogenous. The water flux (Jw) was determined by the volume increase within the measuring tube on the draw side, using Equation III. There is a dilution of 10 the draw solution over time due to an increase of water and also decrease of solutes (solute migration towards the feed side). The solute flux (Js) moving towards the feed side was determined by means of a conductivity meter (feed solution was deionised water), osmometer measurements or by using COD 15 kit (Chemical Oxygen Demand) kits. All experiments were carried out for 7 h and the temperature, unless otherwise stated, was normalised to 20 °C. Measurements were taken from the feed solution at various time intervals. The water height in the measuring tube was recorded and a 5 ml or 25 20 ml sample (depending on the analysis) was collected from the feed side. For each time interval, measurements were performed using an appropriate method. The solute flux was calculated using Equation II.
For each series of experiments, a new forward 25 osmosis membrane was used after soaking it for 30 minutes in DI water. After installing the membrane with the selected orientation, both compartments of the U-tube were quickly filled (first 3L feed solution at the feed side and then 3L draw solution at the draw side) to prevent hydraulic 30 pressure differences over the membrane and drying of the membrane .
EXAMPLE 1 - Active layer facing feed side (AL to FS) Deionised (DI) water was used as feed solution, either 16 to assess the osmotic performance of various different solutes or for reference purposes in comparison to water extraction from sewage. The fluxes of different draw solutions were tested in the forward osmosis system using 5 the following analytical grade solutes: NaCl, glycine betaine, sucrose and glucose. All solutions were prepared in DI water. For all experiments, unless otherwise stated, concentrations relating to an osmotic pressure of approximately 24 bar were used.
10 Figure 2a shows the results wherein water and solute flux of an organic osmolyte, glycine betaine, is compared to different draw solutions of NaCl, glucose and sucrose. Figure 2b demonstrates the relevant ratios for each draw solution.
15 From the results shown in Figure 2a, it can be concluded that with the forward osmosis membrane active layer facing the feed side, glycine betaine produced the highest water flux 4,5 LMH (Litre per square meter per hour, L/m2.h) by comparison with the electrolyte NaCl solution and 20 as well the higher molecular weight substances: glucose and sucrose solution. The solute leakage of glycine betaine is 0.1 g/1 per hour (GMH, grams/m2.h) compared to NaCl, glucose and sucrose which give 3.7 GMH, 2.1 GMH, and 1.1 GMH respectively. Figure 2b shows that glycine betaine as draw 25 solution gives the lowest ratio of 0.02 gram solute leakage per litre water extracted (g/1), while the highest ratio is observed with NaCl as draw solution, 0.8 g/1.
These results indicate that with the forward osmosis membrane active layer facing the feed solution, 30 glycine betaine exhibits the best performance among the other draw solutions studied with regards to its high water flux and low solute leakage.
17 EXAMPLE 2 - Active layer facing draw side (AL to DS) Figure 3a shows the water and solute flux of glycine betaine with comparison to the different draw solutions NaCl, glucose and sucrose. Figure 3b demonstrates the 5 relevant ratios of each draw solution.
From the results shown in Figure 3a it was concluded that with the forward osmosis membrane active layer facing draw side, glycine betaine produced the highest water flux of 7.3 LMH. NaCl, glucose and sucrose solution 10 all gave similar water fluxes of around 5.4 LMH. The solute leakage of glycine betaine has the lowest solute leakage 0.02 GMH (according to COD measurements), while NaCl, glucose, and sucrose gave 4.2 GMH, 2 GMH, and 1.7 GMH respectively. From Figure 3b, the glycine betaine as draw 15 solution gives the lowest ratio 0.02 g/1, while the highest ratio is observed with NaCl as draw solution, 0.8 g/1.
These results indicate that with the forward osmosis membrane active layer facing the draw side, glycine betaine has the best performance among the other draw 20 solutions studied with regards to its high water flux and extremely low solute leakage.
From the series of experiments (Figure 2 and Figure 3) it can be seen that glycine betaine has the highest water flux and lowest solute leakage for both 25 membrane orientations in comparison to the ionic solution
NaCl or the other higher molecular weight substances glucose and sucrose.
EXAMPLE 3 - Osmotic extraction of water from sewage Settled sewage was used as feed in combination with 30 glycine betaine as draw solution in the experimental U-tube set-up. The membrane orientation was such that the active layer faced the draw side. The osmotic pressure generated by glycine betaine as used in the experiments was 24 bar. DI
18 was used as reference feed solution.
Again, samples were taken at regular intervals over a 7 hour time period.
The experiments revealed that glycine betaine as 5 an osmotic agent in a draw solution behaved in a comparable manner with settled sewage as with deionised water. Results showed that water flux from sewage as feed is slightly lower (6.00 LMH) than DI water (7.30 LMH). Solute flux, measured by COD for sewage as feed, is slightly higher than DI water 10 (0.35 GMH vs. 0.14 GMH, respectively).
These results clearly demonstrate that extracting water from sewage is possible under the experimental conditions. It is contemplated that the slightly lower water fluxes and higher solute leakage is probably due to the more 15 complex nature and higher osmotic pressure of sewage as feed solution compared to deionised water. This results in fouling or external concentration polarization of the membrane .
19
Clauses 1. Method of extracting water from an aqueous source by osmosis, preferably forward osmosis, comprising 5 the application of an osmotic pressure difference over a semi-permeable membrane by providing the aqueous source on one side of the membrane and a draw solution comprising an osmotic agent on the other side of the membrane, wherein the osmotic agent is an organic zwitterion and/or an organic 10 compound comprising a saturated positively charged group, preferably a quaternary ammonium group, sulfonium group or phosphonium group.
2. Method according to clause 1, wherein the organic compound and/or organic zwitterion comprises a 15 saturated quaternary ammonium group, sulfonium group or phosphonium group.
3. Method according to clause 1, wherein the organic zwitterion is selected from the group consisting of a betaine, a betaine comprising compound and an amino acid.
20 4. Method according to clause 1, wherein the quaternary ammonium comprises the structure according to Formula I: R1 R—R4 R^
Formula I
25 wherein R1, R2 and R3 are independently selected from a lower alkyl, branched or linear, preferably a Ci~Ce alkyl, and wherein R4 is selected from a carboxyl, an alcohol, hydroxyl or a lower alkyl comprising a carboxyl, an alcohol or hydroxyl.
20 5. Method according to any of the clauses 1-4, wherein the osmotic agent is selected from the group consisting of betaine, glycine betaine, choline, valine, proline and glycine, or a combination thereof.
5 6. Method according to any of the clauses 1-5, wherein the semi-permeable membrane is suitable for forward osmosis, reverse osmosis, nanofiltration or ultrafiltration 7. Method according to any of the clauses 1-6, wherein said osmosis is forward osmosis.
10 8. Method according to any of the clauses 1-7, wherein the osmotic agent is compatible with the semi-permeable membrane.
9. Method according to any of the clauses 1-8, wherein the semi-permeable membrane has a molecular weight 15 cut-off less than 1000 Da, preferably less than 200 Da, more preferably less than 100 Da.
10. Method according to any of the clauses 1-9, wherein the semi-permeable membrane has a pore size of between 0.01 and 0.0001 ym, preferably between 0.001 and 20 0.0001 ym , more preferably between 0.0003 and 0.0005 ym.
11. Method according to any of the clauses 1-10, wherein the semi-permeable membrane comprises an active layer and/or a support layer.
12. Method according to any of the clauses 1-11, 25 wherein the semi-permeable membrane comprises a hydrophilic, cellulose comprising active layer, preferably comprising cellulose acetate, cellulose di-acetate, cellulose triacetate, cellulose butyrate, cellulose acetate proprionate and/or mixtures thereof.
30 13. Method according to any of the clauses 1-12, wherein the semi-permeable membrane comprises a support layer or a polyester mesh or a micro-porous support.
21 14. Method according to any of the clauses 1-13, wherein the osmotic agent is present in such a concentration that an osmotic pressure of at least 1 bar, at least 6 bar, at least 15 bar, preferably at least 20 bar, more preferably 5 at least 24 bar is generated over the membrane.
15. Method according to any of the clauses 1-14, wherein the aqueous source is sewage, wastewater, industrial water, effluent, and/or an aqueous solution for animal or human consumption.
10 16. Draw solution for forward osmotic extraction of water, comprising an organic zwitterion and/or an organic compound comprising a saturated positively charged group, preferably a quaternary ammonium group, sulfonium group or phosphonium group.
15 17. Use of an organic zwitterion and/or an organic compound comprising a saturated positively charged group, preferably a quaternary ammonium group, sulfonium group or phosphonium group, as an osmotic agent in a solution, preferably in a draw solution.
Claims (17)
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| NL2007353A NL2007353C2 (en) | 2011-09-05 | 2011-09-05 | Solution comprising an osmotic agent and method of extracting water using said solution. |
| PCT/NL2012/050612 WO2013036111A1 (en) | 2011-09-05 | 2012-09-05 | Solution comprising an osmotic agent and method of extracting water using said solution |
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| MX364273B (en) | 2010-02-10 | 2019-04-22 | Queens Univ At Kingston Star | Water with switchable ionic strength. |
| WO2012079175A1 (en) | 2010-12-15 | 2012-06-21 | Queen's University At Kingston | Systems and methods for use of water with switchable ionic strength |
| FR3004965B1 (en) * | 2013-04-30 | 2015-05-15 | Ederna | DEVICE AND METHOD FOR EXTRACTING BY OSMOTIC EVAPORATION |
| US9399194B2 (en) | 2014-07-16 | 2016-07-26 | Battelle Energy Alliance, Llc | Methods for treating a liquid using draw solutions |
| TWI586681B (en) * | 2016-08-30 | 2017-06-11 | 財團法人工業技術研究院 | Ionic liquid for forward osmosis process and forward osmosis process |
| JP6649309B2 (en) * | 2017-03-23 | 2020-02-19 | 株式会社東芝 | Water treatment system and working medium |
| JP2020127905A (en) * | 2017-04-28 | 2020-08-27 | 国立大学法人神戸大学 | Draw solution, power generator using the same, and water treatment equipment |
| JP7162308B2 (en) * | 2018-08-31 | 2022-10-28 | 株式会社日本触媒 | Draw solute and water treatment equipment |
| CN113905806A (en) * | 2019-05-31 | 2022-01-07 | 旭化成株式会社 | Concentrated system of raw materials liquid |
| US11502322B1 (en) | 2022-05-09 | 2022-11-15 | Rahul S Nana | Reverse electrodialysis cell with heat pump |
| US11502323B1 (en) | 2022-05-09 | 2022-11-15 | Rahul S Nana | Reverse electrodialysis cell and methods of use thereof |
| US11855324B1 (en) | 2022-11-15 | 2023-12-26 | Rahul S. Nana | Reverse electrodialysis or pressure-retarded osmosis cell with heat pump |
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| US3532621A (en) * | 1967-07-10 | 1970-10-06 | William Thomas Hough | Process for extracting solvent from a solution |
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| WO2007120198A2 (en) * | 2005-11-08 | 2007-10-25 | University Of Florida Research Foundation, Inc. | Materials and methods for improved microbial production of organic compounds |
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