CN113121371A - Ionic liquids and forward osmosis processes utilizing same - Google Patents

Ionic liquids and forward osmosis processes utilizing same Download PDF

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CN113121371A
CN113121371A CN202010135929.0A CN202010135929A CN113121371A CN 113121371 A CN113121371 A CN 113121371A CN 202010135929 A CN202010135929 A CN 202010135929A CN 113121371 A CN113121371 A CN 113121371A
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ionic liquid
forward osmosis
solution
temperature
osmosis process
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CN113121371B (en
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刘柏逸
邵信
张敏超
陈意君
黄琼慧
何佳桦
王钧逸
洪仁阳
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Industrial Technology Research Institute ITRI
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/40—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton with quaternised nitrogen atoms bound to carbon atoms of the carbon skeleton
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • C07C55/16—Pimelic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • 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

Abstract

The present disclosure provides an ionic liquid. The ionic liquid has a structure shown in formula (I): ABnIn the formula (I), A is
Figure DDA0002397318080000011
n is 1 or 2; m is 0, or an integer from 1 to 7; r1And R2Independently methyl, or ethyl; k is an integer of 3 to 8; b is
Figure DDA0002397318080000012
Or
Figure DDA0002397318080000013
i is independently 1, 2, or 3; and j is 5, 6, or 7. The ionic liquid has the advantages of high molecular weight, high hydrophilicity, biocompatibility, low biotoxicity, low preparation cost, high environmental friendliness and the like. The present disclosure also provides a forward osmosis process using the above ionic liquid. The forward osmosis process is a desalination of brine (brine) in Forward Osmosis (FO) mode with an extraction fluid containing an ionic liquid. The forward osmosis process of the present invention has the advantages of high flux, low power consumption, low membrane blocking rate, low solute back diffusion, etc.

Description

Ionic liquids and forward osmosis processes utilizing same
Technical Field
The present disclosure relates to an ionic liquid and a forward osmosis process using the same.
Background
The technical principle of Forward Osmosis (FO) desalination is to use the osmotic pressure difference between the solutions or solutes at both ends of the semipermeable membrane as the driving force, i.e. to permeate the water at the feed water end of low osmotic pressure through the semipermeable membrane to the draw solution end of high osmotic pressure. The mixed solution of water and the extracting solution which passes through the semipermeable membrane can separate the water and the extracting solution by various separation and concentration modes, so that the extracting solution is recovered and pure water is generated. The forward osmosis technology applied to water treatment has the advantages of low energy consumption and low film blocking rate, and can greatly improve functional stability and cost benefit.
The extract has the characteristics of high osmotic pressure, good hydrophilicity, easy separation and the like, wherein the separation of the extract from the membrane water and the recovery of the extract are key factors for determining the energy consumption of the forward osmosis technology. At present, although many extracting solutions can generate enough high osmotic pressure, the extracting solutions are not suitable for practical popularization because of high energy consumption and toxicity.
Therefore, there is a need for a novel extraction solution for forward osmosis desalination process to solve the problems encountered in the prior art.
Disclosure of Invention
According to an embodiment of the present disclosure, an ionic liquid is provided. Wherein the ionic liquid can have a structure represented by formula (I):
ABnformula (I)
Wherein A is
Figure BDA0002397318060000021
Figure BDA0002397318060000022
n is 1 or 2; r1And R2Independently methyl, or ethyl; m is 0, or an integer from 1 to 7; k is an integer of 3 to 8; b is
Figure BDA0002397318060000023
Figure BDA0002397318060000024
i is independently 1, 2, or 3; and j is 5, 6, or 7.
According to the disclosed embodiment, when n is 1, a of the ionic liquid having the structure shown in formula (I) may be
Figure BDA0002397318060000025
m can be 0, 1, or 2; r1And R2Independently methyl, or ethyl; b can be
Figure BDA0002397318060000026
And j may be an integer of 5 to 7.
According to an embodiment of the present disclosure, when n ═ 1, a may be
Figure BDA0002397318060000031
m can be 5, 6, or 7; r1And R2Independent of each otherIs methyl, or ethyl; b can be
Figure BDA0002397318060000032
And i is independently 1, 2, or 3.
According to an embodiment of the present disclosure, when n is 2, a may be
Figure BDA0002397318060000033
k is an integer of 3 to 8; b is
Figure BDA0002397318060000034
And i is independently 1, 2, or 3.
According to an embodiment of the present disclosure, the ionic liquid may be
Figure BDA0002397318060000035
Figure BDA0002397318060000041
In accordance with an embodiment of the present disclosure, a forward osmosis process is provided. The forward osmosis procedure comprises the following steps: a semi-permeable membrane is used for separating an extraction liquid tank and a water inlet tank; introducing an extracting solution into the extracting solution tank, wherein the extracting solution comprises the ionic liquid disclosed by the disclosure; introducing saline water into a water inlet tank, wherein the osmotic pressure of the saline water is lower than that of the ionic liquid, so that the water in the saline water permeates through the semipermeable membrane and enters the extracting solution to obtain diluted draw solution; taking the diluted extract out of the extract tank; and, subjecting the diluted extract to a temperature control process (temperature controlled) to cause the diluted extract to separate into an aqueous layer and an ionic liquid layer.
According to an embodiment of the present disclosure, the extraction liquid includes water and the ionic liquid described in the present disclosure. Wherein the ionic liquid content of the extracting solution is 10 wt% to 70 wt% based on the total weight of the extracting solution.
According to an embodiment of the present disclosure, the temperature control process (temperature control process) may be a temperature reduction process. Here, ions for the extraction liquidThe liquid is
Figure BDA0002397318060000042
In addition, the diluted extract may have a high critical solution temperature (UCST) phase transition at a temperature of 10 ℃ to 35 ℃ or lower.
According to an embodiment of the present disclosure, the temperature control process may be a temperature raising process. Here, the ionic liquid used for the extraction liquid is
Figure BDA0002397318060000051
Figure BDA0002397318060000052
Furthermore, when the ionic liquid is
Figure BDA0002397318060000053
The diluted extract may have a Lower Critical Solution Temperature (LCST) phase transition above a temperature of 43 ℃ to 60 ℃; and, when the ionic liquid is
Figure BDA0002397318060000054
The diluted extract may have a Lower Critical Solution Temperature (LCST) phase transition above a temperature of 65 ℃ to 75 ℃.
According to an embodiment of the disclosure, the method further comprises introducing the ionic liquid layer into the extraction liquid tank after the temperature control process (temperature control process) is performed on the diluted extraction liquid.
Compared with the prior art, the invention has the advantages that: the ionic liquid of the invention utilizes the specific anionic group (B) to match with the specific cationic group (A), and has the characteristics of the ionic liquid (high dissolving capacity, extremely low vapor pressure, high thermal stability and electrochemical stability), and simultaneously has the advantages of higher molecular weight, high hydrophilicity, biocompatibility, low biological toxicity, low preparation cost, high environmental friendliness and the like. Therefore, the method can be widely applied to the fields of organic synthesis, separation and purification, electrochemistry and the like. On the other hand, by using the extracting solution containing the ionic liquid, the forward osmosis process of the invention has the advantages of high flux, low energy consumption, low membrane blockage rate, low solute back diffusion and the like, and can greatly improve the desalting stability and reduce the cost.
Drawings
FIG. 1 is a schematic diagram of a forward osmosis process in one embodiment of the present disclosure;
FIG. 2 is a graph of phase separation temperature versus ionic liquid concentration for an aqueous solution containing an ionic liquid of example 1;
FIG. 3 is a graph of conductivity versus ionic liquid concentration for an aqueous solution containing an ionic liquid of example 1;
FIG. 4 is a graph of the change in weight (water flux) of the water inlet tank and the extraction liquid tank as a function of the conductivity of the extraction liquid tank (using the ionic liquid of example 1) versus time;
FIG. 5 is a graph of phase separation temperature versus ionic liquid concentration for an aqueous solution containing an ionic liquid of example 3;
FIG. 6 is a graph of conductivity versus ionic liquid concentration for an aqueous solution containing an ionic liquid of example 3;
FIG. 7 is a graph of the change in weight (water flux) of the water inlet tank and the extraction liquid tank as a function of the conductivity of the extraction liquid tank (using the ionic liquid of example 3) versus time;
wherein, the notation:
11 a semi-permeable membrane; 13 a water inlet end;
15 extracting solution end; 17 saline;
19 an ionic liquid; 21 pure water;
100 forward osmosis system.
Detailed Description
According to an embodiment of the present disclosure, an ionic liquid is provided. The ionic liquid disclosed by the present disclosure is choline-based ionic liquid (choline-based ionic liquid).
According to the disclosed embodiments, the ionic liquid, which is composed of an anionic group (B) and a cationic group (a), may have a structure represented by formula (I):
ABnformula (I)
Wherein A is
Figure BDA0002397318060000071
Figure BDA0002397318060000072
n is 1 or 2; m is 0, 1, 2, 3, 4, 5, 6, or 7; r1And R2Independently methyl, or ethyl; k is 3, 4, 5, 6, 7, or 8; b is
Figure BDA0002397318060000073
Figure BDA0002397318060000074
i is independently 1, 2, or 3; and j is 5, 6, or 7. The ionic liquid disclosed by the invention utilizes the specific anionic group (B) to match with the specific cationic group (A), so that the ionic liquid has the characteristics of the ionic liquid (high dissolving capacity, extremely low vapor pressure, high thermal stability and electrochemical stability), and has the advantages of higher molecular weight, high hydrophilicity, biocompatibility, low biotoxicity, low preparation cost, high environmental friendliness and the like. Therefore, the method can be widely applied to the fields of organic synthesis, separation and purification, electrochemistry and the like.
According to an embodiment of the present disclosure, the ionic liquid may be represented by AB, wherein a may be
Figure BDA0002397318060000075
B can be
Figure BDA0002397318060000081
Figure BDA0002397318060000082
m is 0, 1, 2, 3, 4, 5, 6, or 7; r1And R2Independently methyl, or ethyl; i is independently 1, 2, or 3; and j is 5, 6, or 7.
In accordance with an embodiment of the present disclosure,the ionic liquid disclosed in the present disclosure may be AB2Wherein A may be
Figure BDA0002397318060000083
B can be
Figure BDA0002397318060000084
Figure BDA0002397318060000085
k is 3, 4, 5, 6, 7, or 8; i is independently 1, 2, or 3; and j is 5, 6, or 7.
According to an embodiment of the present disclosure, an extraction solution is provided for use in forward osmosis processes. The extract may be comprised of the ionic liquids described in the present disclosure. Furthermore, according to some embodiments of the present disclosure, the extraction liquid may comprise water and an ionic liquid as described in the present disclosure, wherein the ionic liquid content of the extraction liquid may be 5 wt% to 95 wt% (e.g., 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt%), based on the total weight of the extraction liquid. According to the disclosed embodiment, the ionic liquid content of the extract can be 10 wt% to 70 wt%. It should be noted that, since the extract of the present disclosure may be a forward osmosis extract, the concentration of the extract is not limited to a specific range, so long as the osmotic pressure of the extract at the concentration is greater than that of the saline, the effect of the forward osmosis extract can be achieved. In general, the greater the difference in osmotic pressure between the extract and the starting solution, the better the extraction effect, and therefore, a high-concentration aqueous solution can be used as the extract with a better extraction effect. However, from the viewpoint of cost, the osmotic pressure of the forward osmosis extract at that concentration may be higher than that of the raw material solution. Since the ionic liquid disclosed by the present disclosure is a liquid solution, the ionic liquid can be directly used as an extracting solution at a concentration of 100 wt%. However, depending on the magnitude of the osmotic pressure of the brine, aqueous solutions having different concentrations of ionic liquid may be optionally formulated as the extract solution. Although the ionic liquid has a larger molecular weight, the viscosity of the ionic liquid is low, so that the ionic liquid can be prepared into a high-concentration solution, and the prepared extracting solution has high osmotic pressure.
According to an embodiment of the present disclosure, the ionic liquid used for the extraction solution may be
Figure BDA0002397318060000091
Wherein m is 0, 1, or 2; r1And R2Independently methyl, or ethyl; and j is 5, 6, or 7. According to an embodiment of the present disclosure, the ionic liquid used for the extraction solution may be
Figure BDA0002397318060000092
Figure BDA0002397318060000093
Wherein m is 5, 6, or 7; r1And R2Independently methyl, or ethyl; and i is independently 1, 2, or 3. According to an embodiment of the present disclosure, the ionic liquid used for the extraction solution may be
Figure BDA0002397318060000094
Wherein k is 3, 4, 5, 6, 7, or 8; and i is independently 1, 2, or 3. Here, the ionic liquid may be mixed with water at room temperature to form a homogeneous aqueous solution, and the aqueous solution has high osmotic pressure, high conductivity, and temperature sensitive phase transition property (thermo-sensitive phase transition viewer), and is very suitable for preparing an extract (draw solution) used in a forward osmosis process.
In accordance with embodiments of the present disclosure, a forward osmosis process is also provided, wherein an extraction solution used in the forward osmosis process comprises an ionic liquid as described in the present disclosure. The forward osmosis process includes providing a forward osmosis system 100 (shown in FIG. 1), wherein the forward osmosis system 100 includes a semipermeable membrane 11 separating an inlet tank 13 and an extract tank 15. Next, saline (brine)17 is placed in the inlet tank 13, and an extract 19 is placed in the extract tank 15. Since the osmotic pressure of the brine 17 is lower than that of the extract liquid 19, pure water 21 in the brine permeates through the semipermeable membrane 11 and enters the extract liquid tank 15 to be mixed with the extract liquid 19 to form a diluted draw solution. When the diluted draw solution reaches a predetermined water content, the diluted draw solution is removed from the draw solution tank (e.g., a portion of the diluted draw solution is transferred from the draw solution tank to a processing tank). Then, the diluted extract is subjected to a temperature control process (e.g., heating or cooling) to separate the diluted extract into an aqueous layer and an ionic liquid layer. According to embodiments of the present disclosure, the predetermined water content of the diluted extract may be 30 wt% to 90 wt% (e.g., 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, or 90 wt%).
Since the ionic liquid used in the extracting solution disclosed herein is a temperature-sensitive polymer (i.e., the ionic liquid has a high critical solution temperature (UCST) or a Low Critical Solution Temperature (LCST)), which is characterized by being completely soluble above (or below) the critical solution temperature (LCST), the temperature of the diluted extracting solution can be adjusted to be lower than the high critical solution temperature (or higher than the low critical solution temperature), so that the ionic liquid generates an internal structural change (structural change) and reduces the affinity with water due to aggregation, and the diluted extracting solution is phase-separated (forming a water layer and an ionic liquid layer) (liquid-liquid separation), so that the purpose of recovering the extracting solution and producing pure water can be achieved.
According to the disclosed embodiment, the forward osmosis process may further comprise introducing the ionic liquid layer into the extraction liquid tank for recycling after the temperature control treatment (i.e. the diluted extraction liquid forms an aqueous layer and an ionic liquid layer) is performed on the diluted extraction liquid, so as to achieve the effect of recycling the ionic liquid. According to an embodiment of the present disclosure, the saline water may be continuously introduced into the inlet tank to maintain the osmotic concentration of the saline water in the inlet tank 13 constant. In this way, after the pure water 21 extracted from the brine permeates into the extraction liquid tank 15, the concentration and osmotic pressure of the brine 17 in the water inlet tank 13 are not increased, and the flux of the pure water 21 permeating into the extraction liquid tank 15 is prevented from being reduced. In accordance with embodiments of the present disclosure, the term "brine" as used herein is understood to mean an aqueous alkali metal and/or alkaline earth metal salt solution of natural or industrial origin. For example, the brine may be wastewater, the source of which may be a factory, home, or laboratory. Furthermore, according to embodiments of the present disclosure, the brine may be seawater.
According to an embodiment of the present disclosure, the temperature control process may be a temperature reduction process. In other words, the temperature of the diluted extract may be lowered to below room temperature during the temperature control treatment to cause phase separation of the diluted extract. Here, the ionic liquid used for the extraction liquid may be an ionic liquid having a high critical solution temperature (UCST), for example
Figure BDA0002397318060000111
Here, the aqueous solution containing the above ionic liquid may have a high critical solution temperature (UCST) phase transition at a temperature of 10 ℃ to 35 ℃ or lower.
According to an embodiment of the present disclosure, the temperature control process may be a temperature raising process. In other words, the temperature of the diluted extract may be raised to a temperature higher than room temperature to cause phase separation of the diluted extract during the temperature control treatment. Here, the ionic liquid used for the extraction liquid is
Figure BDA0002397318060000112
Figure BDA0002397318060000113
Furthermore, when the ionic liquid is
Figure BDA0002397318060000121
In the case, an aqueous solution containing the above ionic liquid may have a Lower Critical Solution Temperature (LCST) phase transition at a temperature of 43 ℃ to 60 ℃ or lower; and, when the ionic liquid is
Figure BDA0002397318060000122
In the presence of an aqueous solution containing the above ionic liquidTemperatures above 65 ℃ to 75 ℃ may have a Lower Critical Solution Temperature (LCST) phase transition.
According to the embodiment of the present disclosure, by using the extracting solution containing the ionic liquid of the present disclosure, the forward osmosis process of the present disclosure may have the advantages of high throughput, low energy consumption, low membrane blockage rate, and low solute back diffusion, which may greatly improve the desalination stability and reduce the cost.
In order to make the aforementioned and other objects, features, and advantages of the present disclosure more comprehensible, several embodiments accompanied with figures are described in detail below:
example 1:
firstly, (2-hydroxyethyl) octyldiethylammonium bromide, which has the structure of
Figure BDA0002397318060000123
) (hereinafter abbreviated as [ Ch228]][Br])：
52 g of (2-hydroxyethyl) diethylamine (2-hydroxyethy) diamine (0.44mole), 85 g of (1-octylbromide) (0.44mole) and 150 ml of acetonitrile (acetonitrile) were added to a reaction flask, and the resulting mixture was stirred at 80 ℃ for 24 hours. After cooling to room temperature, the product was slowly added dropwise to 1.5L diethyl ether, and a white solid was observed to precipitate. After filtration, the obtained filter cake was dried to obtain (2-hydroxyethyl) octyldiethylammonium bromide ([ Ch228] [ Br ]).
Then, [ Ch228] is reacted with an ion exchange resin][Br]Converted into (2-hydroxyethyl) octyl diethyl ammonium hydroxide (2-hydroxyethyl) octyildiethyl ammonium hydroxide with the structure of
Figure BDA0002397318060000131
) (hereinafter abbreviated as [ Ch228]][OH]). Next, 82.8 g of [ Ch228] were added][OH](0.335mol), 108 g of di (2-ethylhexyl) phosphate (0.335mmol) and 500ml of a water/ethanol mixture (1: 1 volume ratio of water to ethanol) were added to a reaction flask and stirred at room temperature for 12 hours. Then, the mixture was washed with 200 ml of dichloromethane(dichlomethane) the resulting solution was extracted, and the organic layer was collected. After water removal and concentration, the product ionic liquid (I) (with the structure as
Figure BDA0002397318060000132
Hereinafter abbreviated as [ Ch228][DEHP]. Analysis by NMR Spectroscopy [ Ch228][DEHP]The results are as follows:1H-NMR(500MHz in D2O):0.71～0.82(m,9H,CH3-)、1.09～1.29(m,26H,-CH2-)、1.31(m,2H,-CH-)、1.52(br,2H,N+CH2CH2-)、3.09(br,2H,N+CH2CH2-)、3.23(m,6H,N+CH2)、3.46(t,4H,-OCH2)、3.85(t,2H,-CH2OH)。
after mixing the ionic liquid [ Ch228] [ DEHP ] with water in different weight ratios, standing at room temperature for a period of time, observing whether phase separation occurred, and recording the critical solution temperature, the results are shown in FIG. 2. From the experimental results, it was found that the ionic liquid [ Ch228] [ DEHP ] is an ionic liquid having a Low Critical Solution Temperature (LCST). As can be seen from FIG. 2, when the content of the ionic liquid [ Ch228] [ DEHP ] is 10 wt% to 50 wt% (based on the total weight of the aqueous solution), the aqueous solution has a Lower Critical Solution Temperature (LCST) phase transition at a temperature of 43 ℃ to 60 ℃ or higher, at which time phase separation (liquid-liquid separation) of water from the ionic liquid occurs.
The osmolarity of aqueous solutions with different ionic liquid contents was measured using an osmometer (OSMOMAT 030, gototec) and the results are shown in table 1. The osmotic pressure of the aqueous solution is analyzed by a freezing point depression method, and the principle is that a rapid cooling freezing method is used for measuring the freezing point temperature. When 1 mole of a solute (e.g., ionic liquid) can lower the freezing point of 1 kg of water by 1.86 ℃, the osmotic pressure of the solute is defined as 1 Osmol/kg. As can be seen from Table 1, the osmotic pressure can be about 0.9Osmol/kg when the [ Ch228] [ DEHP ] concentration of the aqueous solution containing the ionic liquid [ Ch228] [ DEHP ] is 30 wt%. In addition, the osmolarity of the mixture containing high concentration of the ionic liquid [ Ch228] [ DEHP ] is beyond the range detectable by the instrument, so the osmolarity of the mixture containing 40 wt% of the ionic liquid [ Ch228] [ DEHP ] is further estimated by using the relationship obtained by the measured value of the osmolarity of the mixture containing 20-30 wt% of the ionic liquid [ Ch228] [ DEHP ], as shown in table 1. The experimental result shows that the osmotic pressure of the mixed liquid containing 40 wt% of the ionic liquid [ Ch228] [ DEHP ] is larger than that of seawater, and the mixed liquid can be used as the extracting solution for seawater desalination.
TABLE 1
[Ch228][DEHP]Concentration of 20％ 25wt％ 30wt％
Osmotic pressure (Osmol/kg) 0.279 0.502 0.882
Seawater osmotic pressure (0.6M NaCl) of 1.2Osmol/kg
The relationship between the ionic liquid concentration and the conductivity of the aqueous solution containing the ionic liquid [ Ch228] [ DEHP ] with different concentrations is shown in figure 3. Aqueous solutions containing high concentrations of ionic liquid [ Ch228] [ DEHP ] had initial conductivities of about 0.1mS/cm, however as the water content increased the conductivity increased. This is because the ionic liquid-rich phase (ionic liquid-rich) exists in the form of ion pair (ion pair), which reduces self-aggregation phenomenon with increasing water content, forming independent anions/cations. By the characteristics of the ionic liquid, the operation can be stable, and the forward osmosis water flux can be effectively improved.
Using self-assembled laboratory-level equipment with forward osmosis modules as flat panelsThe flow channel is designed into a two-channel internal circulation type, and a film (TW30-1812) produced by Dow-filmtec company is used, and the effective area of the film is 64cm2Pumping the solution at the water inlet end and the solution at the extraction liquid end with a sweep rate of 25cm/s, recording the weights of the water inlet tank and the extraction liquid tank at different time points, and calculating the water flux by the weight change, the area of the film and the experimental time, as shown in FIG. 4. Mixing ionic liquid [ Ch228][DEHP]Delivering to an extraction liquid tank, and delivering pure water (DI water) to a water inlet tank. In the early stages of the experiment, the conductivity and water flux increased with time. After 5 hours of stable operation, the water flux remained constant (average flux of 0.64 LMH).
Example 2:
first, 1,8-octanediyl-bis ((2-hydroxyethyl) diethylammonium bromide) was synthesized in the following procedure, and the structure was 1,8-octanediyl-bis (2-hydroxyethenyl) diethylammonium bromide)
Figure BDA0002397318060000151
) (hereinafter, abbreviated as [ DCh8-22]][Br2])：
52 g of (2-hydroxyethyl) diethylamine (2-hydroxyethyi) diamine (0.44mole), 60 g of 1,8-dibromooctane (1,8-dibromooctane) (0.22mole), and 100 ml of acetonitrile (acetonitrile) were added to a reaction flask, and the resulting mixture was stirred at 80 ℃ for 24 hours. After cooling to room temperature, the product was slowly added dropwise to 1.5L diethyl ether, and a white solid was observed to precipitate. After filtration, the obtained cake was dried to obtain 1,8-octanediyl-bis ((2-hydroxyethyl) diethylammonium bromide ([ DCh 8-22))][Br2])。
Next, [ DCh8-22] was purified by using an ion exchange resin][Br2]Converted into (2-hydroxyethyl) octyl diethyl ammonium hydroxide (2-hydroxyethyl) octyildiethyl ammonium hydroxide with the structure of
Figure BDA0002397318060000161
) (hereinafter, abbreviated as [ DCh8-22]][OH2]). Next, 45.25 g of [ DCh8-22] was added][OH2](0.15mol), 96.73 g of di (2-ethylhexyl) phosphate (0.3mmol) and 500ml of a water/ethanol mixtureThe resultant (water to ethanol volume ratio of 1:1) was added to a reaction flask and stirred at room temperature for 12 hours. Next, the resulting solution was extracted with 200 ml of dichloromethane (dichromethane), and the organic layer was collected. After water removal and concentration, the product ionic liquid (II) (with the structure as
Figure BDA0002397318060000162
Hereinafter abbreviated as [ DCh8-22]][DEHP]. Analysis by NMR Spectroscopy [ DCh8-22][DEHP]The results are as follows:1H-NMR(500MHz in D2O):0.71～0.80(m,24H,CH3-)、1.09～1.29(m,24H,-CH2-)、1.36(m,4H,-CH-)、1.54(br,4H,N+CH2CH2-)、3.50(br,4H,N+CH2CH2-)、3.31(m,12H,N+CH2-)、3.55(dd,4H,-OCH2)、3.85(t,4H,-CH2OH)。
after mixing the ionic liquid [ DCh8-22] [ DEHP ] with water in various weight ratios, the mixture was left at room temperature for a while to observe whether or not phase separation occurred, and the critical solution temperature was recorded, and the results are shown in Table 2. From the experimental results, it was found that the ionic liquid [ DCh8-22] [ DEHP ] is an ionic liquid having a Lower Critical Solution Temperature (LCST). When the ionic liquid [ DCh8-22] [ DEHP ] is present in an amount of 10 wt% to 30 wt% (based on the total weight of the aqueous solution), the aqueous solution has a Lower Critical Solution Temperature (LCST) phase transition above a temperature of 67 ℃ to 74 ℃ at which time the water phase separates from the ionic liquid (liquid-liquid separation).
TABLE 2
Figure BDA0002397318060000171
Example 3:
100 grams of choline hydroxide in water (46 wt% in water) (0.38 mole choline) was added to a reaction flask. Next, 74.42 grams of azelaic acid (nonanedioic acid) were slowly added to the reaction flask. After 24 hours of reaction at room temperature, the resulting solution was extracted with 200 ml of dichloromethane (dichloromethane) and collectedThe organic layers are collected. After water removal and concentration, the product ionic liquid (III) (with the structure as shown in the specification) is obtained
Figure BDA0002397318060000172
Hereinafter abbreviated as [ Ch][Aze]. Analysis by Nuclear magnetic resonance Spectroscopy [ Ch][Aze]The results are as follows:1H-NMR(500MHz in D2O):1.17(m,6H,-CH2-)、1.41(m,4H,-CH2-)、2.10(t,4H,-OOCCH2-)、3.03(s,9H,N+CH3)、3.35(t,2H,N+CH2CH2-)、3.90(m,2H,-CH2OH)。
after mixing the ionic liquid [ Ch ] [ Aze ] with water in different weight ratios, standing at room temperature for a period of time to see if phase separation occurred and recording its critical solution temperature, the results are shown in FIG. 5. From the experimental results, it was found that the ionic liquid [ Ch ] [ Aze ] is an ionic liquid having a high critical solution temperature (UCST). As can be seen from FIG. 5, when the content of the ionic liquid [ Ch228] [ DEHP ] is 5 wt% to 50 wt% (based on the weight of the aqueous solution), the aqueous solution has a high critical solution temperature (UCST) phase transition at a temperature of 10 ℃ to 35 ℃ or lower, at which time phase separation (liquid-liquid separation) of water from the ionic liquid occurs.
The osmolarity of aqueous solutions with different ionic liquid contents was measured using an osmometer (OSMOMAT 030, gototec) and the results are shown in table 3.
TABLE 3
Figure BDA0002397318060000181
Seawater osmotic pressure (0.6M NaCl) of 1.2Osmol/kg
As can be seen from Table 3, when the aqueous solution contained 30 wt% to 70 wt% of the ionic liquid [ Ch ] [ Aze ], the osmotic pressure of the aqueous solution was 2 to 15 times that of seawater. Therefore, the aqueous solution containing the ionic liquid [ Ch ] [ Aze ] has high osmotic pressure property, and is suitable as a forward osmosis extract.
The relationship between the ionic liquid concentration and the conductivity of the aqueous solution containing the ionic liquid [ Ch ] [ Aze ] with different concentrations is shown in FIG. 6. Aqueous solutions containing high concentrations of the ionic liquid [ Ch ] [ Aze ] had initial conductivities of about 1.1mS/cm, however as the water content increased the conductivity increased. This is because the ionic liquid-rich phase (ionic liquid-rich) exists in the form of ion pair (ion pair), which reduces self-aggregation phenomenon with increasing water content, forming independent anions/cations. By the characteristics of the ionic liquid, the operation can be stable, and the forward osmosis water flux can be effectively improved.
The self-assembly laboratory-level device is used, the forward osmosis module is a flat plate type, the flow channel is designed to be a double-channel internal circulation type, a film (TW30-1812) produced by Dow-filmtec company is used, and the effective area of the film is 64cm2Pumping the solution at the water inlet end and the solution at the extraction liquid end with a sweep rate of 25cm/s, recording the weights of the water inlet tank and the extraction liquid tank at different time points, and calculating the water flux by the weight change, the area of the film and the experimental time, as shown in fig. 7. Mixing ionic liquid [ Ch][Aze]Delivering to an extraction liquid tank, and delivering pure water (DI water) to a water inlet tank. In the early stages of the experiment, the conductivity and water flux increased with time. After stable operation for 5 hours, the water flux and the conductivity are maintained to be constant (the average flux is more than 3 LMH).
Although the present disclosure has been described with reference to several embodiments, it should be understood that the scope of the present disclosure is not limited to the embodiments described above, but is intended to be defined by the appended claims.

Claims (19)

1. An ionic liquid having a structure represented by formula (I):
ABnformula (I)
Wherein A is
Figure FDA0002397318050000011
Figure FDA0002397318050000012
n is 1 or 2; m is 0, or an integer from 1 to 7; r1And R2Independently methyl, or ethyl; k is an integer of 3 to 8; b is
Figure FDA0002397318050000013
Figure FDA0002397318050000014
i is independently 1, 2, or 3; and j is 5, 6, or 7.
2. An ionic liquid as claimed in claim 1, wherein n-1; a is
Figure FDA0002397318050000021
m is 0, 1, or 2; r1And R2Independently methyl, or ethyl; b is
Figure FDA0002397318050000022
And j is an integer of 5 to 7.
3. The ionic liquid of claim 2, wherein the ionic liquid is
Figure FDA0002397318050000023
4. An ionic liquid as claimed in claim 1, wherein n-1; a is
Figure FDA0002397318050000024
m is 5, 6, or 7; r1And R2Independently methyl, or ethyl; b is
Figure FDA0002397318050000025
And i is independently 1, 2, or 3.
5. The ionic liquid of claim 4, wherein the ionic liquid is
Figure FDA0002397318050000031
6. An ionic liquid as claimed in claim 1, wherein n-2; a is
Figure FDA0002397318050000032
k is an integer of 3 to 8; b is
Figure FDA0002397318050000033
And i is independently 1, 2, or 3.
7. The ionic liquid of claim 1, wherein the ionic liquid is
Figure FDA0002397318050000034
8. A forward osmosis procedure comprising:
separating the extraction liquid tank and the water inlet tank by a semi-permeable membrane;
introducing an extraction liquid into the extraction liquid bath, wherein the extraction liquid comprises the ionic liquid of claim 1;
introducing saline water into a water inlet tank, wherein the osmotic pressure of the saline water is lower than that of the ionic liquid, so that water in the saline water permeates through the semipermeable membrane and enters the extracting solution to obtain diluted extracting solution;
taking the diluted extract out of the extract tank; and
the diluted extract is subjected to temperature control treatment to separate the diluted extract into an aqueous layer and an ionic liquid layer.
9. The forward osmosis process of claim 8, wherein the extraction solution comprises water and the ionic liquid of claim 1.
10. The forward osmosis process of claim 9, wherein the ionic liquid content of the extraction solution is 10 wt% to 70 wt% based on the total weight of the extraction solution.
11. The forward osmosis process of claim 8, wherein the temperature control treatment is a temperature reduction treatment.
12. The forward osmosis process of claim 11, wherein the ionic liquid is
Figure FDA0002397318050000041
13. The forward osmosis process of claim 12, wherein the dilute extract solution has a high critical solution temperature phase transition below a temperature of 10 ℃ to 35 ℃.
14. The forward osmosis process of claim 8, wherein the temperature control process is a ramping process.
15. The forward osmosis process of claim 14, wherein the ionic liquid is
Figure FDA0002397318050000042
16. The forward osmosis process of claim 15, wherein the dilute extract solution has a low critical solution temperature phase transition above a temperature of 43 ℃ to 60 ℃.
17. The forward osmosis process of claim 14, wherein the ionic liquid is
Figure FDA0002397318050000051
18. The forward osmosis process of claim 17, wherein the dilute extract solution has a low critical solution temperature phase transition above a temperature of 65 ℃ to 75 ℃.
19. The forward osmosis process of claim 15, further comprising introducing the ionic liquid layer into the draw solution tank after the temperature control treatment of the dilute draw solution.
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