KR101953439B1 - Draw solute comprising 2 and more thermoresponsive compounds and method for water desalination using the same - Google Patents

Draw solute comprising 2 and more thermoresponsive compounds and method for water desalination using the same Download PDF

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KR101953439B1
KR101953439B1 KR1020160142855A KR20160142855A KR101953439B1 KR 101953439 B1 KR101953439 B1 KR 101953439B1 KR 1020160142855 A KR1020160142855 A KR 1020160142855A KR 20160142855 A KR20160142855 A KR 20160142855A KR 101953439 B1 KR101953439 B1 KR 101953439B1
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solute
induction
osmosis
temperature
iodide
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KR20180047117A (en
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안혜련
최원준
노영준
이연
노민우
박정선
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서울대학교산학협력단
두산중공업 주식회사
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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • 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

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The present invention relates to a temperature responsive solute for positive osmosis capable of achieving high water solubility and high osmotic pressure by mixing two or more temperature responsive substances and a desalination method using the solute.
In the induction solute for cleansing osmosis provided by the present invention, water solubility exceeding the maximum water solubility of each compound and osmotic pressure exceeding the maximum osmotic pressure of each compound can be realized by mixing two or more specific compounds, while temperature responsiveness is maintained, So that the desalination can be efficiently performed.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an induction solute for osmosis and a desalination method using the same,

The present invention relates to an induction solute for osmosis in which two or more temperature responsive substances are mixed to achieve a high water solubility and a high osmotic pressure, and a desalination method using the induction solute.

The current water shortage is becoming a global problem. Water supplies can not cope with demand, and water pollution also promotes the deficiency of available water. Currently, one-third of the world's population lives in water shortages, and by 2020, two-thirds of the world's population is in water shortages (RF Service, Science 313, 1088 (2006)). Therefore, research and development are actively carried out to obtain clean water by desalinating or purifying seawater, river water and polluted water.

Conventionally, commercially available techniques for obtaining clean water include distillation for boiling water and reverse osmosis using a semi-permeable membrane (hereinafter referred to as a semi-permeable membrane) which can not transmit particles other than water. However, the distillation method consumes a lot of energy to boil the water (distillation energy consumption: 10-16 kWh / m3), and the reverse osmosis method also requires a larger amount of energy than the osmotic pressure of the solution to be removed (reverse osmosis Consumption: 4-6 kWh / m 3 ).

Forward osmosis (FO), which is more energy efficient than the above-mentioned methods, has been attracting attention as a future water desalination and purification technology. In the first step, a solution having a higher osmotic pressure than the osmotic pressure of the species to be desalinated or purified is placed at the boundary of the semipermeable membrane (this solution is called a 'draw solution' And the solute constituting the inductive solution is referred to as the 'draw solute'), so that the osmotic phenomenon causes the water to migrate toward the induction solution without additional energy supply. Then, in the second step, the solute is technically removed from the derivatized solution which draws water. With these two steps, clean water can be obtained even with very small energy consumption.

Therefore, the key point in the positive osmotic process is to select an inducible solute having an appropriate osmotic pressure and to remove it from the clear water. Today, the most studied derivatized solute in the osmosis process is NH 4 HCO 3 (ammonium hydrogen carbonate), which is composed of ammonium ion (NH 4 + ) and hydrogen carbonate ion (HCO 3 - ). The high concentration of ammonium bicarbonate solution has a high osmotic pressure, so it can induce water through osmosis from seawater, river water and polluted water. After the water is drawn by using the ammonium hydrogen carbonate solute, high temperature of 60 ° C. is supplied to remove it. At this time, the ammonium hydrogen carbonate as the solute is vaporized by ammonia (NH 3 ) and carbon dioxide (CO 2 ) It is possible to obtain clean water.

However, there are various limitations to the positive osmosis method using ammonium bicarbonate. First, since the ammonium hydrogen carbonate solution is basic, the physical properties of a semipermeable membrane made of a polymer material may be deteriorated. Also, the temperature for removing the solute, which is 60 DEG C, is still a high temperature condition requiring high energy. Furthermore, it is a disadvantage of this method that the complex column distillation method must be used not only to maintain the temperature at 60 ° C. but also to remove the induced solute, and it is also problematic that complicated processes are required to reuse the removed induced solute to be. In addition, ammonium hydrogen carbonate, which has a small molar mass and hydrated ion size, also has a problem that a significant amount can be discharged through the semipermeable membrane.

Korean Patent Laid-Open Publication No. 2011-0091153 discloses a purified osmotic induction solution, specifically, an aqueous solution containing an anion and a cation as induction solute, wherein the induction solute is vaporized and separated from the aqueous solution, . However, the specific derivatized solute proposed in the above document is a salt-type compound containing mainly ammonium cations, and it has not only the problems of the above-mentioned positive osmosis method using ammonium hydrogen carbonate, but also the problems of 40 And a high energy consumption process requiring a high temperature of 90 to < RTI ID = 0.0 > 90 C. < / RTI >

Despite the disadvantages described above, satisfactory inducing solutes that can solve the problems of the prior art have not been presented so far. Therefore, it is necessary to develop a new concept of induction solute and a positive osmosis system using the induction solute.

It is an object of the present invention to provide a water treatment apparatus capable of realizing a high water solubility and a high osmotic pressure by mixing two or more specific types of temperature responsive materials so that a large volume of fresh water can be quickly separated from raw water of high concentration, After the process, it is intended to provide an induction solute which can be easily separated and recovered from fresh water by a simple and easy process.

Another object of the present invention is to provide a desalination method capable of rapidly separating a large amount of fresh water from high-concentration raw water using the induction solute.

According to one embodiment of the present invention, there is provided a derivatized solute for osmosis comprising two or more different compounds of the general formula:

[Chemical Formula 1]

X m Y n

In Formula 1,

m is an integer of 1 or 2, n is an integer of 1 to 3, and m and n are not simultaneously 2;

X is a cation represented by any one of formulas A-1 to A-3;

Figure 112016105784893-pat00001

Y is F - , Cl - , Br - , I - , BF 4 - , NO 3 - , ClO - , PF 6 - , CF 3 SO 3 - , CH 3 CH 2 SO 3 -

Figure 112016105784893-pat00002
,
Figure 112016105784893-pat00003
,
Figure 112016105784893-pat00004
,
Figure 112016105784893-pat00005
, CH 3 CO 2 - , CF 3 CO 2 - , HCO 3 - , SO 4 2- , CO 3 2- and the anions represented by any one of the following formulas B-1 to B-3;

Figure 112016105784893-pat00006

In the above formulas A-1 to A-3 and B-1 to B-3,

R 1 to R 9 are each independently hydrogen or a C 1 to C 10 alkyl group;

R 10 is a C 1 to C 11 alkyl group;

K 1 to K 4 are each independently a direct bond or a C 1 -C 10 alkylene, a C 2 -C 10 alkenylene, a C 2 -C 10 alkynylene, a -R 11 -C (═O) -R 12 - , -R 11 -OR 12 - and -R 11 -C (= O) (O) -R 12 -;

R 11 and R 12 are each independently a direct bond or C 1 -C 4 alkylene;

The alkyl group of R 1 to R 10 , the alkylene, alkenylene and alkynylene of K 1 to K 4 , and the alkylene of R 11 and R 12 are each independently selected from the group consisting of halogen, C 1 to C 4 alkyl, C 2 ~ C 4 alkenyl group, C 2 ~ C 4 of the alkynyl group, C 6 ~ C 10 aryl group, nuclear atoms of 5 to 10 heteroaryl group is substituted with a first substituent at least one selected from the group consisting of or being unsubstituted , When they are substituted with a plurality of substituents, they are the same as or different from each other.

In the present invention, when m is 2 and n is 1, X is a monovalent cation represented by the above formula (A-1), Y is SO 4 2- , CO 3 2- , 2 may be an anion.

Wherein m is 1 in the present invention, when n is 2, X is a divalent cation of the formula A-2, Y is F -, Cl -, Br - , I -, BF 4 -, NO 3 - , ClO - , PF 6 - , CF 3 SO 3 - , CH 3 CH 2 SO 3 - ,

Figure 112016105784893-pat00007
,
Figure 112016105784893-pat00008
,
Figure 112016105784893-pat00009
,
Figure 112016105784893-pat00010
, CH 3 CO 2 - , CF 3 CO 2 - , HCO 3 - and the above-mentioned formulas B-1 to B-2.

Wherein m is 1 in the present invention, when n is 3, X is a trivalent cation represented by the general formula A-3, Y is F -, Cl -, Br - , I -, BF 4 -, NO 3 - , ClO - , PF 6 - , CF 3 SO 3 - , CH 3 CH 2 SO 3 - ,

Figure 112016105784893-pat00011
,
Figure 112016105784893-pat00012
,
Figure 112016105784893-pat00013
,
Figure 112016105784893-pat00014
, CH 3 CO 2 - , CF 3 CO 2 - , HCO 3 - and the above-mentioned formulas B-1 to B-2.

In the present invention, when m is 2 and n is 3, X is a trivalent cation represented by the above formula (A-3) and Y is SO 4 2- , CO 3 2- or a group represented by the above formula 2 may be an anion.

In the present invention, X may be a divalent cation represented by the above formula (A-2).

In the present invention, the purified osmotic solute for osmosis may comprise two or more different compounds represented by the formula XY 2 .

The X in the present invention is a divalent cation of the formula A-2, Y is F -, Cl -, Br - , I -, BF 4 -, NO 3 -, ClO -, PF 6 -, CF 3 SO 3 - , CH 3 CH 2 SO 3 - ,

Figure 112016105784893-pat00015
,
Figure 112016105784893-pat00016
,
Figure 112016105784893-pat00017
,
Figure 112016105784893-pat00018
, CH 3 CO 2 - , CF 3 CO 2 - , HCO 3 - and the above-mentioned formulas B-1 to B-2.

In the present invention, in the cations represented by the above formulas A-1 to A-3, R 1 to R 9 may each independently be a C 1 to C 10 alkyl group.

In the present invention, in the cations represented by the above formulas A-1 to A-3, R 1 to R 9 may each independently be a C 1 to C 4 alkyl group.

In the present invention, in the cations represented by the above formulas A-2 and A-3, K 1 to K 3 may each independently be C 1 -C 10 alkylene.

In the present invention, the purified osmotic solute may have a temperature responsiveness at a concentration of 35 to 80% by weight.

In the present invention, the maximum osmotic pressure of the induction solute for positive osmosis may be 200,000 ppm or more.

In the present invention, the purified osmotic solute for osmosis may comprise two or more different compounds selected from the group consisting of the following compounds:

1) tetramethylammonium iodide;

2) N 1, N 1, N 1, N 6, N 6, N 6 - hexamethyl-1,6-hexane diamine, titanium iodide (N 1, N 1, N 1, N 6, N 6, N 6 -hexamethylhexane-1,6-diaminium iodide);

3) N 1, N 1, N 1, N 8, N 8, N 8 - hexamethyl-1,8-octane diamine, titanium iodide (N 1, N 1, N 1, N 8, N 8, N 8 -hexamethyloctane-1,8-diaminium iodide);

4) N 1, N 1, N 1, N 2, N 2, N 2 - hexamethyl-1,2-diamine urethane iodonium iodide (N 1, N 1, N 1, N 2, N 2, N 2 -hexamethylethane-1,2-diaminium iodide);

5) N 1, N 1, N 1, N 10, N 10, N 10 - hexamethyl-decane-1,10-diamine, titanium iodide (N 1, N 1, N 1, N 10, N 10, N 10 -hexamethyldecane-1,10-diaminium iodide)

6) tetramethylammonium 3-carboxypropanoate;

7) tetramethylammonium (E) -3-carboxyacrylate; tetramethylammonium (E) -3-carboxyacrylate;

8) tetramethylammonium (Z) -3-carboxyacrylate; tetramethylammonium (Z) -3-carboxyacrylate; And

9) tetramethylammonium tetramethylacetate.

According to another embodiment of the present invention, there is provided a method for producing a water-soluble organic solvent, comprising the steps of: 1) contacting an inducing solution containing raw water and a purified osmotic solute of the present invention through a semipermeable membrane;

2) the fresh water contained in the raw water is passed through the semipermeable membrane to the induction solution by the positive osmotic pressure phenomenon; And

3) separating the fresh water from the inductive solution.

In the present invention, in step 1), the concentration of the derivatizing solution may be higher than the raw water.

In the present invention, prior to the step of separating the fresh water, the temperature of the inductive solution is raised to be equal to or higher than the phase separation temperature of the induction solute for positive osmosis, or lowered to the phase separation temperature or less, Step < / RTI >

In the present invention, the term "alkyl" is a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isoamyl, hexyl And the like, but are not limited thereto.

In the present invention, the above-mentioned "alkylene" is a divalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 10 carbon atoms, and examples thereof include methylene, ethylene, propylene, isobutylene, sec- It is not limited.

In the present invention, the term "alkenylene" means a linear divalent hydrocarbon chain of 2 to 10 carbon atoms or a branched divalent hydrocarbon chain of 3 to 7 carbon atoms, having at least one double bond. Examples of alkenylene include ethenylene, 2,2-dimethylethanehenylene, prophenylene, 2-methylpropylene, and buteneylene.

In the present invention, the term "alkynylene" means a linear divalent hydrocarbon chain of 2 to 10 carbon atoms or a branched divalent hydrocarbon chain of 3 to 4 carbon atoms, having at least one triple bond. Exemplary alkynylenes include ethynylene, 2,2-dimethylethynylene, propynylene, 2-methylpropynylene, and butynylene.

In the present invention, the term " aryl " means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 10 carbon atoms in which a single ring or two or more rings are combined. In addition, it is also possible that two or more rings are condensed with each other, and only the carbon atom as the ring-forming atom (for example, the number of carbon atoms may be 8 to 10) and the whole molecule is a non-aromacity, Substituents may also be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl and anthryl.

In the present invention, the term "heteroaryl" means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 10 nuclear atoms. Wherein one or more carbons, preferably one to three carbons, of the ring are substituted with a heteroatom selected from N, O, P, S and Se. In addition, it is preferable that two or more rings are pendant or condensed with each other, and include hetero atoms selected from N, O, P, S and Se besides carbon as a ring-forming atom, < / RTI > aromacity). Examples of such heteroaryls include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; Polycyclic rings such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, and benzothiazole; Imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.

In the present invention, the term "halogen" means fluorine, chlorine, bromine or iodine.

The induction solute for cleansing osmosis provided by the present invention can be prepared by mixing two or more specific temperature-responsive compounds so that water solubility exceeding the maximum water solubility of each temperature-responsive compound and osmotic pressure exceeding the maximum osmotic pressure of each temperature- It is possible to efficiently desalinate or purify the raw water.

Also, the induction solute for positive osmosis provided in the present invention is a simple and easy process that maintains the temperature responsiveness even in the state of mixture and increases or decreases the temperature after the positive osmosis temperature, so that it can be recovered from the induction solution and recycled Do.

In addition, the induction solute for positive osmosis provided by the present invention has an advantage that the outflow through the semipermeable membrane can be minimized as compared with the conventional induction solute.

1 schematically shows a schematic diagram of a desalination process according to the present invention.
FIG. 2 is a graph showing the phase transition temperatures of the mixed induction solutions of Examples 1 to 5 at different concentrations in Experimental Example 1. FIG.
FIG. 3 is a graph showing the phase transition temperatures of the mixed induction solutions of Examples 6 to 10 according to their concentration in Experimental Example 3. FIG.
FIG. 4 is a graph showing the phase transition temperatures of the mixed induction solutions of Examples 11 to 15 according to the concentration in Experimental Example 4. FIG.
FIG. 5 is a graph showing the phase transition temperatures of the mixed induction solutions of Examples 16 to 22 according to their concentration in Experimental Example 5. FIG.

Hereinafter, preferred embodiments of the present invention will be described. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. Further, the embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.

The solubility of the solute which can dissolve in a maximum of 100 g of solvent at a certain temperature is called solubility. Especially when water is used as a solvent, it is expressed as 'water solubility'. In general, the water solubility of each compound is set at a specific value at a specific temperature and pressure, and when the solute is dissolved by the amount of solubility, it becomes a saturated solution.

However, the inventors of the present invention have found that when two or more temperature-responsive compounds of a specific kind are mixed, not only a high-concentration mixture above the water solubility of each compound can be obtained but also the high osmotic pressure above the maximum osmotic pressure of each compound I can implement it. Particularly, in the case of a mixture of certain combinations, a maximum osmotic pressure of 200,000 ppm or more could be achieved.

Therefore, when the mixture of the present invention is used, a large amount of fresh water can be rapidly introduced from raw water of high concentration such as seawater, industrial wastewater, etc. by the osmosis method. In addition, in the case of such a mixed inducing solute, the temperature responsiveness is maintained even in the mixture state, and even after the concentration is lowered due to dilution of fresh water after the positive osmosis, the mixture of the present invention can be easily separated and recovered The present invention has been accomplished on the basis of these findings.

According to one embodiment of the present invention, there is provided a derivatized solute for osmosis comprising two or more different compounds of the general formula:

[Chemical Formula 1]

X m Y n

In Formula 1,

m is an integer of 1 or 2, n is an integer of 1 to 3, and m and n are not simultaneously 2;

X is a cation represented by any one of formulas A-1 to A-3;

Figure 112016105784893-pat00019

Y is F - , Cl - , Br - , I - , BF 4 - , NO 3 - , ClO - , PF 6 - , CF 3 SO 3 - , CH 3 CH 2 SO 3 -

Figure 112016105784893-pat00020
,
Figure 112016105784893-pat00021
,
Figure 112016105784893-pat00022
,
Figure 112016105784893-pat00023
, CH 3 CO 2 - , CF 3 CO 2 - , HCO 3 - , SO 4 2- , CO 3 2- and the anions represented by any one of the following formulas B-1 to B-3;

Figure 112016105784893-pat00024

In the above formulas A-1 to A-3 and B-1 to B-3,

R 1 to R 9 are each independently hydrogen or a C 1 to C 10 alkyl group;

R 10 is a C 1 to C 11 alkyl group;

K 1 to K 4 are each independently a direct bond or a C 1 -C 10 alkylene, a C 2 -C 10 alkenylene, a C 2 -C 10 alkynylene, a -R 11 -C (═O) -R 12 - , -R 11 -OR 12 - and -R 11 -C (= O) (O) -R 12 -;

R 11 and R 12 are each independently a direct bond or C 1 -C 4 alkylene;

The alkyl group of R 1 to R 10 , the alkylene, alkenylene and alkynylene of K 1 to K 4 , and the alkylene of R 11 and R 12 are each independently selected from the group consisting of halogen, C 1 to C 4 alkyl, C 2 ~ C 4 alkenyl group, C 2 ~ C 4 of the alkynyl group, C 6 ~ C 10 aryl group, nuclear atoms of 5 to 10 heteroaryl group is substituted with a first substituent at least one selected from the group consisting of or being unsubstituted , When they are substituted with a plurality of substituents, they are the same as or different from each other.

In the present invention, when m is 1 and n is 1, X is a monovalent cation represented by the above formula (A-1), Y is F - , Cl - , Br - , I - , BF 4 - , NO 3 - , ClO - , PF 6 - , CF 3 SO 3 - , CH 3 CH 2 SO 3 - ,

Figure 112016105784893-pat00025
,
Figure 112016105784893-pat00026
,
Figure 112016105784893-pat00027
,
Figure 112016105784893-pat00028
, CH 3 CO 2 - , CF 3 CO 2 - , HCO 3 - and the above-mentioned formulas B-1 to B-2.

In the present invention, when m is 1 and n is 1, X is a divalent cation represented by the above formula (A-2), Y is SO 4 2- , CO 3 2- or the formula (B-3) It may be a divalent negative ion to be displayed.

In the present invention, when m is 2 and n is 1, X is a monovalent cation represented by the above formula (A-1), Y is SO 4 2- , CO 3 2- , 2 may be an anion.

Wherein m is 1 in the present invention, when n is 2, X is a divalent cation of the formula A-2, Y is F -, Cl -, Br - , I -, BF 4 -, NO 3 - , ClO - , PF 6 - , CF 3 SO 3 - , CH 3 CH 2 SO 3 - ,

Figure 112016105784893-pat00029
,
Figure 112016105784893-pat00030
,
Figure 112016105784893-pat00031
,
Figure 112016105784893-pat00032
, CH 3 CO 2 - , CF 3 CO 2 - , HCO 3 - and the above-mentioned formulas B-1 to B-2.

Wherein m is 1 in the present invention, when n is 3, X is a trivalent cation represented by the general formula A-3, Y is F -, Cl -, Br - , I -, BF 4 -, NO 3 - , ClO - , PF 6 - , CF 3 SO 3 - , CH 3 CH 2 SO 3 - ,

Figure 112016105784893-pat00033
,
Figure 112016105784893-pat00034
,
Figure 112016105784893-pat00035
,
Figure 112016105784893-pat00036
, CH 3 CO 2 - , CF 3 CO 2 - , HCO 3 - and the above-mentioned formulas B-1 to B-2.

In the present invention, when m is 2 and n is 3, X is a trivalent cation represented by the above formula (A-3) and Y is SO 4 2- , CO 3 2- or a group represented by the above formula 2 may be an anion.

According to a preferred embodiment of the present invention, in the cations represented by the above formulas A-1 to A-3, R 1 to R 9 may each independently be a C 1 to C 10 alkyl group.

According to a preferred embodiment of the present invention, in the cations represented by the above formulas A-1 to A-3, R 1 to R 9 may each independently be a C 1 to C 4 alkyl group.

According to a preferred embodiment of the present invention, in the cations represented by the above formulas A-2 and A-3, K 1 to K 3 each independently may be C 1 -C 10 alkylene.

In the present invention, in the monovalent anion represented by the above formula (B-1), R 10 is preferably a C 5 -C 11 alkyl group, but is not limited thereto.

In the present invention, in the monovalent anion represented by the above formula (B-2), K 4 is preferably C 1 -C 10 alkylene or C 2 -C 10 alkenylene, but is not limited thereto.

According to one preferred embodiment of the present invention, X is preferably a divalent cation represented by the above-mentioned formula (A-2) because it can realize high concentration and high osmotic pressure.

According to one preferred embodiment of the present invention, the compound may comprise two or more different compounds represented by the formula XY 2 . Here, X is a divalent cation represented by the above formula (A-2), more preferably R 1 to R 6 are each independently a C 1 -C 4 alkyl group, K 1 is a C 1 -C 10 alkylene Y is at least one selected from the group consisting of F - , Cl - , Br - , I - , BF 4 - , NO 3 - , ClO - , PF 6 - , CF 3 SO 3 - , CH 3 CH 2 SO 3 -

Figure 112016105784893-pat00037
,
Figure 112016105784893-pat00038
,
Figure 112016105784893-pat00039
,
Figure 112016105784893-pat00040
, CH 3 CO 2 - , CF 3 CO 2 - , HCO 3 - and the above-mentioned formulas B-1 to B-2.

According to one more preferred embodiment of the present invention, the compound is a first compound represented by the formula XY 2 ; And a second compound represented by the formula XY 2 . In the first compound, X is a divalent cation represented by the above formula (A-2), more preferably each of R 1 to R 6 is independently a C 1 to C 4 alkyl group, Y is F - Cl - , Br - , I - , BF 4 - , NO 3 - , ClO - , PF 6 - , CF 3 SO 3 - , CH 3 CH 2 SO 3 -

Figure 112016105784893-pat00041
,
Figure 112016105784893-pat00042
,
Figure 112016105784893-pat00043
,
Figure 112016105784893-pat00044
, CH 3 CO 2 - , CF 3 CO 2 - , HCO 3 - and the above-mentioned formulas B-1 to B-2. In the second compound, X is a monovalent cation represented by the above formula (A-2), more preferably R 1 to R 6 are each independently a C 1 to C 4 alkyl group, K 1 is a C 1 - C 10 alkyl, and alkylene, Y is F -, Cl -, Br - , I -, BF 4 -, NO 3 -, ClO -, PF 6 -, CF 3 SO 3 -, CH 3 CH 2 SO 3 -,
Figure 112016105784893-pat00045
,
Figure 112016105784893-pat00046
,
Figure 112016105784893-pat00047
,
Figure 112016105784893-pat00048
, CH 3 CO 2 - , CF 3 CO 2 - , HCO 3 - and the above-mentioned formulas B-1 to B-2. However, the first compound and the second compound are different from each other.

According to one preferred embodiment of the present invention, the compound may further comprise a compound represented by the formula XY in addition to two or more different compounds represented by the formula XY 2 . In the formula, X is a monovalent cation represented by the formula (A-1), more preferably R 1 to R 4 are each independently a C 1 -C 4 alkyl group, Y is F - , Cl - , Br - , I - , BF 4 - , NO 3 - , ClO - , PF 6 - , CF 3 SO 3 - , CH 3 CH 2 SO 3 -

Figure 112016105784893-pat00049
,
Figure 112016105784893-pat00050
,
Figure 112016105784893-pat00051
,
Figure 112016105784893-pat00052
, CH 3 CO 2 - , CF 3 CO 2 - , HCO 3 - and the above-mentioned formulas B-1 to B-2.

In the present invention, the purified osmotic solute for osmosis may comprise two or more different compounds selected from the group consisting of the following compounds:

1) tetramethylammonium iodide;

2) N 1, N 1, N 1, N 6, N 6, N 6 - hexamethyl-1,6-hexane diamine, titanium iodide (N 1, N 1, N 1, N 6, N 6, N 6 -hexamethylhexane-1,6-diaminium iodide);

3) N 1, N 1, N 1, N 8, N 8, N 8 - hexamethyl-1,8-octane diamine, titanium iodide (N 1, N 1, N 1, N 8, N 8, N 8 -hexamethyloctane-1,8-diaminium iodide);

4) N 1, N 1, N 1, N 2, N 2, N 2 - hexamethyl-1,2-diamine urethane iodonium iodide (N 1, N 1, N 1, N 2, N 2, N 2 -hexamethylethane-1,2-diaminium iodide);

5) N 1, N 1, N 1, N 10, N 10, N 10 - hexamethyl-decane-1,10-diamine, titanium iodide (N 1, N 1, N 1, N 10, N 10, N 10 -hexamethyldecane-1,10-diaminium iodide)

6) tetramethylammonium 3-carboxypropanoate;

7) tetramethylammonium (E) -3-carboxyacrylate; tetramethylammonium (E) -3-carboxyacrylate;

8) tetramethylammonium (Z) -3-carboxyacrylate; tetramethylammonium (Z) -3-carboxyacrylate; And

9) tetramethylammonium tetramethylacetate.

In the present invention, the pure osmotic solute may have a temperature responsiveness at a concentration of 35 to 80% by weight, preferably at a concentration of 40 to 80% by weight, more preferably at a concentration of 40 to 76% by weight, The osmotic pressure is at least the maximum osmotic pressure that can be achieved by each inducing solute, preferably 200,000 ppm or more, so that fresh water can be rapidly and rapidly separated even from a very high concentration of raw water.

The term "thermo-sensitive or thermo-responsive" as used in the present invention means that when a substance is in a state of aqueous solution and under a predetermined molar fraction, Refers to a property that a solubility is drastically reduced in the opposite region of the reference temperature and a phase transition occurs. Here, the reference temperature at which the phase separation is performed is referred to as a 'phase transition temperature'.

In the present invention, the induction solute for positive osmosis can be used as an induction solution for positive osmosis by dissolving the induction solute in a concentration of 35 to 80% by weight in a solvent, preferably water.

According to another embodiment of the present invention, there is provided a method for desalinating raw water using the induction solute for osmosis provided by the present invention, Contacting the inducing solution comprising the semipermeable membrane through a semipermeable membrane; 2) the fresh water contained in the raw water is passed through the semipermeable membrane to the induction solution by the positive osmotic pressure phenomenon; And 3) separating the fresh water from the inductive solution.

Two or more compounds provided by the present invention, preferably two or more different compounds represented by the formula XY 2 , wherein X is a divalent cation represented by the above formula (A-2), more preferably R 1 to R 6 is each independently an alkyl group of C 1 ~ C 4, K 1 is an alkylene C 1 -C 10 alkyl, Y is F -, Cl -, Br - , I -, BF 4 -, NO 3 -, ClO - , PF 6 - , CF 3 SO 3 - , CH 3 CH 2 SO 3 - ,

Figure 112016105784893-pat00053
,
Figure 112016105784893-pat00054
,
Figure 112016105784893-pat00055
,
Figure 112016105784893-pat00056
, CH 3 CO 2 - , CF 3 CO 2 - , HCO 3 - and monovalent anions selected from the group consisting of the above-mentioned formulas B-1 to B-2, And the maximum osmotic pressure is 200,000 ppm or more, it is possible to rapidly separate a large amount of fresh water from a high concentration of raw water.

In the present invention, the kind of raw water to be desalinated in the present invention is not particularly limited and includes various substances that can be filtered by a semipermeable membrane such as ions, colloids, microorganisms, water-soluble molecules, insoluble organic molecules, So long as osmosis water treatment is possible. Specific examples of the raw water include, but are not limited to, sea water, brackish water, ground water, and waste water. In a non-limiting example, the seawater may be treated with the above described osmosis water treatment apparatus to obtain drinking water.

In addition, in the present invention, the semipermeable membrane is water-permeable to water and is impermeable to a substance to be separated, and can be any semipermeable membrane conventionally used in the desalination or purification method by an osmosis method. But are not limited to, cellulose acetate-based or polyether sulfone-based semipermeable membranes.

In the present invention, the induction solution contains the induction solute for positive osmosis provided by the present invention at a concentration higher than that of the raw water to be purified and desalinated, whereby the fresh water contained in the raw water is passed through the semipermeable membrane . At this time, many of the conventional derivatized solutes including sodium hydrogencarbonate are likely to flow through the semipermeable membrane due to their low molar mass and small hydrate ion size, and to be discharged into the raw water. However, since the present invention has a relatively large molar mass and hydrate ion size, it is possible to greatly reduce the flow rate through the semipermeable membrane.

In the present invention, prior to the step of separating the fresh water, the step of raising the temperature of the inducing solution above the phase separation temperature of the induction solute for positive osmosis may further comprise phase separation of the induction solute for positive osmosis from the inducing solution .

The mixed compound contained in the induction solute for positive osmosis provided in the present invention has a temperature response of 35 to 80% by weight, preferably 40 to 80% by weight, more preferably 40 to 76% by weight, And since the phase separation temperature is relatively low at 0 to 90 캜, preferably 0 to 70 캜, relatively low thermal energy can be recovered easily and simply from the derivatizing solution.

In addition, the compound provided by the present invention may be a low-threshold dissolution-temperature-sensitive compound or a high-threshold dissolution-temperature-resistant compound. Here, the 'lower critical solution temperature (LCST)' is a phenomenon in which a homogeneous phase occurs at a temperature lower than the reference temperature and a phase separation phenomenon occurs when the temperature becomes higher than the reference temperature, The upper critical solution temperature (UCST) is a homogeneous phase at a temperature higher than the reference temperature and a phase separation phenomenon when the temperature is lower than the reference temperature.

Accordingly, in the present invention, when fresh water contained in raw water is passed through a semipermeable membrane and then transferred to an induction solution, the temperature of the induction solution is raised to a temperature above the phase separation temperature of the induction solute for pure osmosis or below the phase separation temperature, Can be easily recovered by phase separation and, if necessary, can be recycled as the induction solute for forward osmosis at the time of subsequent osmosis, which is economical advantage.

Since the osmotic pressure of the inducing solution is very low after the induction solute for positive osmosis is phase-separated from the induction solution as described above in the present invention, fresh water can be separated by low pressure or energy even using a conventional reverse osmosis method. Alternatively, physiological saline having saline concentration such as the inside of the human body and low salt water having a lower concentration than that of the human body can be used as a secondary induction solution to induce fresh water from the primary induction solution. Some of the induction solutes proposed in the present invention can be easily separated by centrifugation after centrifugation or ultrafiltration.

FIG. 1 schematically shows a schematic diagram of a desalination process according to the present invention. The schematic diagram of the desalination solution section of the forward osmosis reaction apparatus 10 separated into an inductive solution section 12 and a raw water section 13, The induction solution 2 containing the induction solute 1 for positive osmosis provided by the present invention can be supplied to the raw water section 12 and the raw water 3 to be purified can be supplied to the raw water section 13. At this time, when the induction solution and the raw water come into contact with each other through the semipermeable membrane, the fresh water 4 contained in the raw water is moved to the induction solution 2 through the semipermeable membrane by the osmosis phenomenon (S100). Thereafter, when the induction solution 2 is raised to a temperature higher than the phase separation temperature or lowered to a temperature not higher than the phase separation temperature (S200), the induction solute 1 for positive osmosis contained in the induction solution becomes phase separation and can be easily separated and recovered. The thus recovered purified osmosis solute 1 can be recycled as the inducing solute 1 in the subsequent forward osmosis process (S400). Further, after the induction solute 1 for pure osmosis is removed from the induction solution 2, the fresh water 4 can be further easily separated by a reverse osmosis process, a positive osmosis process, a centrifugal separation process or an ultrafiltration process S300).

Hereinafter, the present invention will be described more specifically by way of specific examples. The following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

Example

[ Manufacturing example  One] Tetramethylammonium  Iodide ( 테트라 메틸 암 모늄 iodide )

Figure 112016105784893-pat00057

The excess of 1-iodomethane was added to the primary amine, 1,6-diaminohexane, and the reaction was carried out in the presence of a base to obtain a methylated iodide salt.

[Preparation Example 2] N 1, N 1, N 1, N 6, N 6, N 6 - hexamethyl-1,6-hexane diamine, titanium iodide (N 1, N 1, N 1, N 6, N 6 , N 6 -hexamethylhexane-1,6-diaminium iodide)

Figure 112016105784893-pat00058

The excess of 1-iodomethane was added to the primary amine, 1,6-diaminohexane, and the reaction was carried out in the presence of a base to obtain a methylated iodide salt.

[Preparation Example 3] N 1, N 1, N 1, N 8, N 8, N 8 - hexamethyl-1,8-octane diamine, titanium iodide (N 1, N 1, N 1, N 8, N 8 , N 8 -hexamethyloctane-1,8-diaminium iodide)

Figure 112016105784893-pat00059

1-iodomethane was added to the primary amine, 1,6-diaminooctane in an excess amount, the base was added and the reaction was carried out under methanol to obtain a methylated form of iodide salt.

[ Manufacturing example  4] N One , N One , N One , N 2 , N 2 , N 2 - Hexamethylethane -1,2- Diamine  Iodine One , N One , N One , N 2 , N 2 , N 2 -hexamethylethane-1,2-diaminium iodide )

Figure 112016105784893-pat00060

To the primary amine, ethylenediamine, 1-iodomethane was added in excess and the base was added and the reaction was carried out under methanol to obtain the methylated form of the iodide salt.

[Preparation Example 5] N 1, N 1, N 1, N 10, N 10, N 10 - hexamethyl-decane-1,10-diamine, titanium iodide (N 1, N 1, N 1, N 10, N 10 , N 10 -hexamethyldecane-1,10-diaminium iodide)

Figure 112016105784893-pat00061

The primary amine, 1,6-diaminodecane, was added in excess of 1-iodomethane, the base was added, and the reaction was carried out under methanol to obtain a methylated iodide salt.

[ Manufacturing example  6] Tetramethylammonium  3- Carboxy propanoate  ( 테트라 메틸 암 모늄  3-carboxypropanoate < / RTI >

Figure 112016105784893-pat00062

Tetramethylammonium 3-carboxypropanoate was obtained by acid-base reaction by mixing tetramethylammonium hydroxide with succinic acid.

[ Manufacturing example  7] Tetramethylammonium  (E) -3- Carboxyacrylate  (tetramethylammonium (E) -3- carboxyacrylate )

Figure 112016105784893-pat00063

Tetramethylammonium (E) -3-carboxyacrylate was obtained by acid-base reaction by mixing tetramethylammonium hydroxide with fumaric acid.

[ Manufacturing example  8] Tetramethylammonium  (Z) -3- Carboxyacrylate  (tetramethylammonium (Z) -3- carboxyacrylate )

Figure 112016105784893-pat00064

Tetramethylammonium (Z) -3-carboxyacrylate was obtained by acid-base reaction by mixing tetramethylammonium hydroxide and maleic acid.

[ Manufacturing example  9] Tetramethylammonium Tetramethyl acetate  ( 테트라 메틸 암 모늄  tetramethylacetate

Figure 112016105784893-pat00065

Tetramethylammonium tetramethyl acetate was obtained by acid-base reaction by mixing tetramethylammonium hydroxide and tetramethyl acetic acid.

[ Example  1 to 5] For osmosis  Preparation of induction solution (1)

The induction solution was prepared by mixing two kinds of high critical temperature responsive materials with different solubilities. Specifically, the N 1, N 1, N 1 , N 6, N 6, N 6 - hexamethyl-hexane-1,6-dia minyum iodide (NMQHDA) 0.66g and N 1, N 1, N 1 , N 8 , And N 8 , N 8 -hexamethyloctane-1,8-diammonium iodide (NMQODA) were mixed in 1 g of water to obtain a 75 wt% mixed solution. However, the concentration of the saturated solution of NMQHDA was 40 wt% at room temperature, and the concentration of saturated solution of NMQODA was 70 wt% at room temperature. When these solutions were mixed, a mixed solution of 75 wt% concentration was obtained. Water was added to the thus obtained 75 wt% mixed solution to prepare mixed induction solutions having various concentrations as shown in Table 1 below.

division Concentration of mixed induction solution (wt%) NMQHDA (g) NMQODA (g) Amount of total water (H 2 O) (g) Example 1 37 0.66 (12 wt%) 2.3 (32 wt%) 5 (+1) Example 2 43 0.66 (14 wt%) 2.3 (37 wt%) 4 (+1) Example 3 50 0.66 (18 wt%) 2.3 (44wt%) 3 (+1) Example 4 60 0.66 (25 wt%) 2.3 (54 wt%) 2 (+1) Example 5 75 0.66 (40 wt%) 2.3 (70 wt%) One

[ Experimental Example  1] Phase transition temperature measurement of mixed induction solution

The mixed induction solutions prepared in Examples 1 to 5 were subjected to a change in transmittance (1 캜 / min) while lowering the temperature from a high temperature to a low temperature using an ultraviolet / visible ray spectrometer, and the results are shown in Fig.

Generally, the high-critical dissolution temperature material shows 100% permeability because the mixed solute is well dissolved in water at a high temperature. However, when the temperature is lowered to fall below the transition temperature, the solutes aggregate to form a large molecule and the permeability drops sharply. FIG. 2 is a graph of the phase transition temperature according to the concentration of the mixed induction solution according to the present invention, and the concentration range in which the phase transition temperature appears is 37 to 75 wt%.

[ Experimental Example  2] Osmotic pressure measurement of mixed induction solution

The osmotic pressure of the 75wt% mixed induction solution prepared in Example 5 was measured to be about 250.000 ppm (> 88atm).

The osmotic pressure of the mixed induction solution of 37 wt% prepared in Example 1 using the freezing point lowering type osmotic pressure measuring device was measured and found to be about 19,000 ppm (<15 atm), about 1/6 of the maximum osmotic pressure Respectively.

Accordingly, the mixed induction solution according to the present invention can realize a high osmotic pressure, so that it is possible not only to rapidly separate a large amount of fresh water from a high concentration raw water during a normal osmosis, It can be seen that only the solute can be separated and recovered.

[ Example  6 to 10] For osmosis  Preparation of induction solution (2)

The induction solution was prepared by mixing three kinds of high - temperature - responsive materials with different solubilities. Specifically, 0.053 g of tetramethylammonium iodide (TMA), 0.66 g of N 1 , N 1 , N 1 , N 6 , N 6 , N 6 -hexamethylhexane-1,6-diamine iodide (NMQHDA) 2.3 g of N 1 , N 1 , N 1 , N 8 , N 8 , N 8 -hexamethyloctane-1,8-diammonium iodide (NMQODA) were mixed in 1 g of water to obtain a 75 wt% mixed solution. However, when the concentration of the saturated solution of NMQHDA was 40 wt% and the concentration of the saturated solution of NMQODA was 70 wt% at room temperature, a mixed solution of 75 wt% concentration was obtained even when TMA was mixed into them. Water was added to the thus obtained 75 wt% mixed solution to prepare mixed induction solutions having various concentrations as shown in Table 2 below.

division Concentration of mixed induction solution (wt%) TMA (g) NMQHDA (g) NMQODA (g) Amount of total water (H 2 O) (g) Example 6 37 0.0531 (1.4 wt%) 0.66 (12 wt%) 2.3 (32 wt%) 5 (+1) Example 7 43 0.0531 (2.0 wt%) 0.66 (14 wt%) 2.3 (37 wt%) 4 (+1) Example 8 50 0.0531 (2.6 wt%) 0.66 (18 wt%) 2.3 (44wt%) 3 (+1) Example 9 60 0.0531 (3.4 wt%) 0.66 (25 wt%) 2.3 (54 wt%) 2 (+1) Example 10 75 0.0531 (5.0 wt%) 0.66 (40 wt%) 2.3 (70 wt%) One

[ Experimental Example  3] Phase transition temperature measurement of mixed induction solution

The mixed induction solutions prepared in Examples 6 to 10 were observed for changes in transmittance (1 캜 / min) while lowering the temperature from a high temperature to a low temperature using an ultraviolet / visible ray spectrometer, and the results are shown in FIG.

FIG. 3 is a graph showing the phase transition temperature according to the concentration of the mixed induction solution according to the present invention, and the concentration range in which the phase transition temperature appears is 46 to 75 wt%.

[ Example  11 to 15] For osmosis  Preparation of induction solution (3)

The induction solution was prepared by mixing three kinds of high - temperature - responsive materials with different solubilities. Specifically, 0.086 g of tetramethylammonium iodide (TMA), 0.51 g of N 1 , N 1 , N 1 , N 6 , N 6 , N 6 -hexamethylhexane-1,6-diamine iodide (NMQHDA) 1.8 g of N 1 , N 1 , N 1 , N 8 , N 8 , N 8 -hexamethyloctane-1,8-diammonium iodide (NMQODA) was mixed with 0.77 g of water to obtain a mixed solution of 76 wt%. However, when the concentration of the saturated solution of NMQHDA was 40 wt% and the concentration of the saturated solution of NMQODA was 70 wt% at room temperature, a mixed solution of 75 wt% concentration was obtained even when TMA was mixed into them. Water was added to the thus obtained 75 wt% mixed solution to prepare mixed induction solutions having various concentrations as shown in Table 3 below.

division Concentration of mixed induction solution (wt%) TMA (g) NMQHDA (g) NMQODA (g) Amount of total water (H 2 O) (g) Example 11 40 0.086 (2.3 wt%) 0.51 (13 wt%) 1.8 (34 wt%) 3.57 (+1) Example 12 48 0.086 (3.2 wt%) 0.51 (17 wt%) 1.8 (41 wt%) 2.57 (+1) Example 13 60 0.086 (5.2 wt%) 0.51 (25 wt%) 1.8 (53 wt%) 1.57 (+0.4) Example 14 67 0.086 (6.8 wt%) 0.51 (30 wt%) 1.8 (61 wt%) 1.17 (+0.4) Example 15 76 0.086 (5.0 wt%) 0.51 (40 wt%) 1.8 (70 wt%) 0.77

[ Experimental Example  4] Phase transition temperature measurement of mixed induction solution

The mixed induction solutions prepared in Examples 11 to 15 were subjected to a change in the transmittance (1 캜 / min) while lowering the temperature from a high temperature to a low temperature using an ultraviolet / visible ray spectrometer, and the results are shown in FIG.

FIG. 4 is a graph showing the phase transition temperature according to the concentration of the mixed induction solution according to the present invention, and the concentration range in which the phase transition temperature appears is 40 to 76 wt%.

[ Example  16 to 22] For osmosis  Preparation of induction solution (4)

The induction solution was prepared by mixing three kinds of high - temperature - responsive materials with different solubilities. Specifically, 0.18 g of tetramethylammonium iodide (TMA), 0.66 g of N 1 , N 1 , N 1 , N 6 , N 6 , N 6 -hexamethylhexane-1,6-diamine iodide (NMQHDA) 2.3 g of N 1 , N 1 , N 1 , N 8 , N 8 , N 8 -hexamethyloctane-1,8-diammonium iodide (NMQODA) was mixed with 1 g of water to obtain a mixed solution of 76 wt%. However, when the concentration of the saturated solution of NMQHDA was 40 wt% and the concentration of the saturated solution of NMQODA was 70 wt% at room temperature, a mixed solution of 75 wt% concentration was obtained even when TMA was mixed into them. Water was added to the thus obtained 75 wt% mixed solution to prepare mixed induction solutions having various concentrations as shown in Table 4 below.

division Concentration of mixed induction solution (wt%) TMA (g) NMQHDA (g) NMQODA (g) Amount of total water (H 2 O) (g) Example 16 37 0.18 (3.2 wt%) 0.66 (11 wt%) 2.3 (31 wt%) 5.3 (+1) Example 17 42 0.18 (3.9 wt%) 0.66 (13 wt%) 2.3 (34 wt%) 4.3 (+1) Example 18 49 0.18 (5.5 wt%) 0.66 (15 wt%) 2.3 (38 wt%) 3.3 (+1) Example 19 58 0.18 (7.1 wt%) 0.66 (20 wt%) 2.3 (47 wt%) 2.3 (+0.6) Example 20 65 0.18 (9.4 wt%) 0.66 (25 wt%) 2.3 (54 wt%) 1.7 (+0.5) Example 21 74 0.18 (13 wt%) 0.66 (35 wt%) 2.3 (65 wt%) 1.2 (+0.2) Example 22 76 0.18 (15 wt%) 0.66 (40 wt%) 2.3 (70 wt%) 1.0

[ Experimental Example  5] Phase transition temperature measurement of mixed induction solution

The mixed induction solutions prepared in Examples 16 to 22 were observed for changes in transmittance (1 캜 / min) while lowering the temperature from a high temperature to a low temperature using an ultraviolet / visible ray spectrometer, and the results are shown in FIG.

FIG. 5 is a graph showing the phase transition temperature according to the concentration of the mixed induction solution according to the present invention, and the concentration range in which the phase transition temperature appears is 40 to 76 wt%.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, It will be obvious to those of ordinary skill in the art.

1: induction solute for clearing osmosis 2: induction solution
3: enemy 4: fresh water
10: positive osmosis reaction apparatus 11: semipermeable membrane
12: Induced solution section 13: Raw water section

Claims (17)

An induction solute for positive osmosis comprising two or more different compounds of the formula (1) and having a temperature responsiveness and an ionicity:
[Chemical Formula 1]
X m Y n
In Formula 1,
m is an integer of 1 or 2, n is an integer of 1 to 3, and m and n are not simultaneously 2;
X is a cation represented by any one of formulas A-1 to A-3;
Figure 112018084907944-pat00066

Y is F - , Cl - , Br - , I - , BF 4 - , NO 3 - , ClO - , PF 6 - , CF 3 SO 3 - , CH 3 CH 2 SO 3 -
Figure 112018084907944-pat00067
,
Figure 112018084907944-pat00068
,
Figure 112018084907944-pat00069
,
Figure 112018084907944-pat00070
, CH 3 CO 2 - , CF 3 CO 2 - , HCO 3 - , SO 4 2- , CO 3 2- and the anions represented by any one of the following formulas B-1 to B-3;
Figure 112018084907944-pat00071

In the above formulas A-1 to A-3 and B-1 to B-3,
R 1 to R 9 are each independently hydrogen or a C 1 to C 10 alkyl group, or R 1 to R 4 are not both hydrogen,
R 10 is a C 1 to C 11 alkyl group;
K 1 to K 4 are each independently a direct bond or a C 1 -C 10 alkylene, a C 2 -C 10 alkenylene, a C 2 -C 10 alkynylene, a -R 11 -C (═O) -R 12 - , -R 11 -OR 12 - and -R 11 -C (= O) (O) -R 12 -;
R 11 and R 12 are each independently a direct bond or C 1 -C 4 alkylene;
The alkyl group of R 1 to R 10 , the alkylene, alkenylene and alkynylene of K 1 to K 4 , and the alkylene of R 11 and R 12 are each independently selected from the group consisting of halogen, C 1 to C 4 alkyl, C 2 ~ C 4 alkenyl group, C 2 ~ C 4 of the alkynyl group, C 6 ~ C 10 aryl group, nuclear atoms of 5 to 10 heteroaryl group is substituted with a first substituent at least one selected from the group consisting of or being unsubstituted , When they are substituted with a plurality of substituents, they are the same as or different from each other. The method according to claim 1,
When m is 2 and n is 1, X is a monovalent cation represented by the above formula (A-1), Y is SO 4 2- , CO 3 2- or a divalent anion represented by the above formula (B-3) Induced solute for pure osmosis. The method according to claim 1,
Case wherein m is 1, n is 2, X is a divalent cation of the formula A-2, Y is F -, Cl -, Br - , I -, BF 4 -, NO 3 -, ClO - , PF 6 - , CF 3 SO 3 - , CH 3 CH 2 SO 3 - ,
Figure 112016105784893-pat00072
,
Figure 112016105784893-pat00073
,
Figure 112016105784893-pat00074
,
Figure 112016105784893-pat00075
, CH 3 CO 2 - , CF 3 CO 2 - , HCO 3 - and monovalent anions selected from the group consisting of the above-mentioned formulas B-1 to B-2. The method according to claim 1,
Case wherein m is 1, n is 3, X is a trivalent cation represented by the general formula A-3, Y is F -, Cl -, Br - , I -, BF 4 -, NO 3 -, ClO - , PF 6 - , CF 3 SO 3 - , CH 3 CH 2 SO 3 - ,
Figure 112016105784893-pat00076
,
Figure 112016105784893-pat00077
,
Figure 112016105784893-pat00078
,
Figure 112016105784893-pat00079
, CH 3 CO 2 - , CF 3 CO 2 - , HCO 3 - and monovalent anions selected from the group consisting of the above-mentioned formulas B-1 to B-2. The method according to claim 1,
When m is 2 and n is 3, X is a trivalent cation represented by the above formula (A-3), Y is SO 4 2- , CO 3 2- or a divalent anion represented by the above formula (B-3) Induced solute for pure osmosis. The method according to claim 1,
And X is a divalent cation represented by the above formula (A-2). The method according to claim 1,
Wherein the induction solute for positive osmosis comprises two or more different compounds represented by the formula XY 2 . 8. The method of claim 7,
Wherein X is a divalent cation of the formula A-2, Y is F -, Cl -, Br - , I -, BF 4 -, NO 3 -, ClO -, PF 6 -, CF 3 SO 3 - , CH 3 CH 2 SO 3 - ,
Figure 112016105784893-pat00080
,
Figure 112016105784893-pat00081
,
Figure 112016105784893-pat00082
,
Figure 112016105784893-pat00083
, CH 3 CO 2 - , CF 3 CO 2 - , HCO 3 - and monovalent anions selected from the group consisting of the above-mentioned formulas B-1 to B-2. The method according to claim 1,
In the cation represented by any of Formulas A-1 to A-3, R 1 to R 9 are each independently a C 1 to C 10 alkyl group. The method according to claim 1,
In the cation represented by any one of formulas (A-1) to (A-3), R 1 to R 9 are each independently a C 1 to C 4 alkyl group. The method according to claim 1,
In the cations represented by the above formulas A-2 and A-3, K 1 to K 3 are each independently C 1 -C 10 alkylene. The method according to claim 1,
And the induction solute for normal osmosis has a temperature response at a concentration of 35 to 80 wt%. delete The method according to claim 1,
The induction solute for cleansing osmosis comprises at least two different compounds selected from the group consisting of the following compounds:
1) tetramethylammonium iodide;
2) N 1, N 1, N 1, N 6, N 6, N 6 - hexamethyl-1,6-hexane diamine, titanium iodide (N 1, N 1, N 1, N 6, N 6, N 6 -hexamethylhexane-1,6-diaminium iodide);
3) N 1, N 1, N 1, N 8, N 8, N 8 - hexamethyl-1,8-octane diamine, titanium iodide (N 1, N 1, N 1, N 8, N 8, N 8 -hexamethyloctane-1,8-diaminium iodide);
4) N 1, N 1, N 1, N 2, N 2, N 2 - hexamethyl-1,2-diamine urethane iodonium iodide (N 1, N 1, N 1, N 2, N 2, N 2 -hexamethylethane-1,2-diaminium iodide);
5) N 1, N 1, N 1, N 10, N 10, N 10 - hexamethyl-decane-1,10-diamine, titanium iodide (N 1, N 1, N 1, N 10, N 10, N 10 -hexamethyldecane-1,10-diaminium iodide)
6) tetramethylammonium 3-carboxypropanoate;
7) tetramethylammonium (E) -3-carboxyacrylate; tetramethylammonium (E) -3-carboxyacrylate;
8) tetramethylammonium (Z) -3-carboxyacrylate; tetramethylammonium (Z) -3-carboxyacrylate; And
9) tetramethylammonium tetramethylacetate. 1) contacting the inducing solution containing the raw water and the induction solute for positive osmosis according to any one of claims 1 to 14 through a semipermeable membrane;
2) the fresh water contained in the raw water is passed through the semipermeable membrane to the induction solution by the positive osmotic pressure phenomenon; And
3) separating the fresh water from the inductive solution. 16. The method of claim 15,
Wherein the concentration of the inducing solution in the step 1) is higher than the raw water. 16. The method of claim 15,
The step of separating the induction solute for positive osmosis from the inducing solution by separating the inducing solution from the inducing solution by raising the temperature of the inducing solution to a temperature higher than the phase separation temperature of the induction solute for positive osmosis or lowering it to a phase separation temperature or lower, Containing water.
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