CN113121371B - Ionic liquids and forward osmosis processes utilizing the same - Google Patents

Ionic liquids and forward osmosis processes utilizing the same Download PDF

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CN113121371B
CN113121371B CN202010135929.0A CN202010135929A CN113121371B CN 113121371 B CN113121371 B CN 113121371B CN 202010135929 A CN202010135929 A CN 202010135929A CN 113121371 B CN113121371 B CN 113121371B
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ionic liquid
forward osmosis
extract
temperature
water
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CN113121371A (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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    • 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 Table
    • 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
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    • 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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Abstract

The present disclosure provides an ionic liquid. The ionic liquid has a structure shown in a formula (I): AB (AB) n Formula (I) wherein A is
Figure DDA0002397318080000011
n is 1 or 2; m is 0, or an integer from 1 to 7; r is R 1 R is R 2 Independently methyl, or ethyl; k is an integer from 3 to 8; b is
Figure DDA0002397318080000012
Or (b)
Figure DDA0002397318080000013
i is independently 1, 2, or 3; and j is 5, 6, or 7. The ionic liquid has the advantages of higher molecular weight, high hydrophilicity, biocompatibility, low biotoxicity, low preparation cost, high environmental friendliness and the like. The disclosure also provides a forward osmosis process using the ionic liquid. The forward osmosis process is performed in a Forward Osmosis (FO) mode on a brine (brine) with an extract comprising an ionic liquid. The forward osmosis process of the invention has the advantages of high flux, low energy consumption, low membrane blocking rate, low reverse diffusion of solute and the like.

Description

Ionic liquids and forward osmosis processes utilizing the same
Technical Field
The present disclosure relates to an ionic liquid and a forward osmosis process using the same.
Background
The principle of Forward Osmosis (FO) desalination processes is to use the osmotic pressure difference between solutions or solutes across a semipermeable membrane as driving force, i.e. to permeate 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 extracting solution passing through the semi-permeable membrane can be separated from the extracting solution by various separation and concentration modes, so as to recover the extracting solution and produce pure water. The forward osmosis technology applied to water treatment has the advantages of low energy consumption and low membrane blocking rate, and can greatly improve the functional stability and the cost efficiency.
The extraction solution needs to have the characteristics of high osmotic pressure, good hydrophilicity, easy separation and the like, wherein the separation of the extraction solution and the membrane-passing water and the recovery of the extraction solution are key factors for determining the energy consumption of the forward osmosis technology. Many extracting solutions can generate high enough osmotic pressure at present, but are not suitable for practical popularization because of high energy consumption and toxicity.
Accordingly, there is a need in the art for a novel extract for use in forward osmosis desalination processes that addresses the problems encountered in the prior art.
Disclosure of Invention
According to an embodiment of the present disclosure, the present disclosure provides an ionic liquid. Wherein the ionic liquid may have a structure represented by formula (I):
AB n formula (I)
Wherein A is
Figure BDA0002397318060000021
Figure BDA0002397318060000022
n is 1 or 2; r is R 1 R is R 2 Independently methyl, or ethyl; m is 0, or an integer from 1 to 7; k is an integer from 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 an embodiment of the present disclosure, the ionic liquid having the structure shown in formula (I), when n=1, a may be
Figure BDA0002397318060000025
m may be 0, 1, or 2; r is R 1 R is R 2 Independently methyl, or ethyl; b may be
Figure BDA0002397318060000026
And j may be an integer from 5 to 7.
According to embodiments of the present disclosure, when n=1, a may be
Figure BDA0002397318060000031
m may be 5, 6, or 7; r is R 1 R is R 2 Independently methyl, or ethyl; b may be->
Figure BDA0002397318060000032
And i is independently 1, 2, or 3.
According to an embodiment of the present disclosure, when n=2, a may be
Figure BDA0002397318060000033
k is an integer from 3 to 8; b is->
Figure BDA0002397318060000034
And i is independently 1, 2, or 3.
According to embodiments of the present disclosure, the ionic liquid may be
Figure BDA0002397318060000035
Figure BDA0002397318060000041
According to an embodiment of the present disclosure, the present disclosure provides a forward osmosis process. The forward osmosis process comprises the steps of: separating an extraction liquid tank and a water inlet tank by a semi-permeable membrane; introducing an extraction liquid into the extraction liquid tank, wherein the extraction liquid comprises the ionic liquid disclosed in the disclosure; introducing a brine into a water inlet tank, wherein the osmotic pressure of the brine is lower than that of the ionic liquid, so that water in the brine permeates through the semipermeable membrane and enters the extracting solution to obtain a diluted extracting solution (diluted draw solution); taking out the diluted extract from the extract tank; and, subjecting the diluted extract to a temperature control process (temperature control treatment) to cause the diluted extract to delaminate into an aqueous layer and an ionic liquid layer.
According to an embodiment of the disclosure, the extraction solution comprises water and the ionic liquid disclosed herein. Wherein the ionic liquid content of the extracting solution is 10wt% to 70wt%, based on the total weight of the extracting solution.
According to an embodiment of the present disclosure, the temperature control process (temperature control)trom treatment) may be a cool down treatment. The ionic liquid used in the extract is
Figure BDA0002397318060000042
In addition, the diluted extract may have a high critical dissolution temperature (upper critical solution temperature, UCST) phase transition below a temperature of 10 ℃ to 35 ℃.
According to embodiments of the present disclosure, the temperature control process (temperature control treatment) may be a temperature ramp process. The ionic liquid used in the extract is
Figure BDA0002397318060000051
Figure BDA0002397318060000052
In addition, when the ionic liquid is
Figure BDA0002397318060000053
The diluted extract may have a low critical solution temperature (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 low critical solution temperature (lower critical solution temperature, LCST) phase transition above a temperature of 65 ℃ to 75 ℃.
According to an embodiment of the disclosure, after the temperature control treatment (temperature control treatment) of the diluted extract, the method further comprises introducing the ionic liquid layer into the extract tank.
Compared with the prior art, the invention has the advantages that: the ionic liquid provided by the invention has the characteristics of the ionic liquid (high dissolution capacity, extremely low vapor pressure, high thermal stability and electrochemical stability) and also has the advantages of higher molecular weight, high hydrophilicity, biocompatibility, low biotoxicity, low preparation cost, high environmental friendliness and the like because the specific anionic group (B) is matched with the specific cationic group (A). 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 film blocking rate, low solute back diffusion and the like, and can greatly improve the desalination stability and reduce the cost.
Drawings
FIG. 1 is a schematic diagram of a forward osmosis process in an embodiment of the present disclosure;
FIG. 2 is a graph of the phase separation temperature versus ionic liquid concentration for an aqueous solution containing ionic liquid according to example 1;
FIG. 3 is a graph of the conductivity of an aqueous solution containing an ionic liquid according to example 1 as a function of ionic liquid concentration;
FIG. 4 is a graph of the change in weight of the feed and extract tanks (water flux) versus conductivity of the extract tanks (using the ionic liquid of example 1) versus time;
FIG. 5 is a graph of the phase separation temperature versus ionic liquid concentration for an aqueous solution containing ionic liquid according to example 3;
FIG. 6 is a graph of the conductivity of an aqueous solution containing an ionic liquid according to example 3 as a function of ionic liquid concentration;
FIG. 7 is a graph of the change in weight of the feed tank and the extraction tank (water flux) versus conductivity of the extraction tank (using the ionic liquid of example 3) versus time;
wherein, the symbol illustrates:
11. a semipermeable membrane; 13 water inlet end;
15. extracting a liquid end; 17 brine;
19. an ionic liquid; 21 pure water;
100. a forward osmosis system.
Detailed Description
According to an embodiment of the present disclosure, the present disclosure provides an ionic liquid. The ionic liquid disclosed in the disclosure is choline-series ionic liquid (choline-based ionic liquid).
According to an embodiment of the present disclosure, the ionic liquid is composed of an anionic group (B) and a cationic group (a), and may have a structure represented by formula (I):
AB n formula (I)
Wherein A is
Figure BDA0002397318060000071
Figure BDA0002397318060000072
n is 1 or 2; m is 0, 1, 2, 3, 4, 5, 6, or 7; r is R 1 R is R 2 Independently 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 disclosure has the characteristics of the ionic liquid (high dissolution capacity, extremely low vapor pressure, high thermal stability and electrochemical stability) as well as the advantages of higher molecular weight, high hydrophilicity, biocompatibility, low biotoxicity, low preparation cost, high environmental friendliness and the like due to the fact that the specific anionic group (B) is matched with the specific cationic group (A). Therefore, the method can be widely applied to the fields of organic synthesis, separation and purification, electrochemistry and the like.
According to embodiments of the present disclosure, the ionic liquid of the present disclosure may be represented by AB, where a may be
Figure BDA0002397318060000075
B may be->
Figure BDA0002397318060000081
Figure BDA0002397318060000082
m is 0, 1, 2, 3, 4, 5, 6, or 7; r is R 1 R is R 2 Independently methyl, or ethyl; i is independently 1, 2, or 3; the method comprises the steps of,j is 5, 6, or 7.
According to an embodiment of the disclosure, the ionic liquid of the disclosure may be AB 2 Represented, wherein A may be
Figure BDA0002397318060000083
B may 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 embodiments of the present disclosure, an extract is provided for use in a forward osmosis process. The extract may be composed of the ionic liquid described in the present disclosure. Furthermore, according to certain embodiments of the present disclosure, the extract may comprise water and the ionic liquid described herein, wherein the ionic liquid content of the extract may be 5wt% to 95wt% (e.g., 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, or 95 wt%) based on the total weight of the extract. According to embodiments of the present disclosure, the ionic liquid content of the extract may be 10wt% to 70wt%. 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, and the effect of the forward osmosis extract can be exerted as long as the osmotic pressure of the extract at the concentration is greater than that of the brine. Generally, the greater the osmotic pressure difference between the extract and the raw material liquid, the better the extraction effect, so that a high-concentration aqueous solution can have a better extraction effect as the extract. However, from the viewpoint of cost, the osmotic pressure of the forward osmosis extract at this concentration may be larger than that of the raw material liquid. Since the ionic liquid is a liquid solution, the ionic liquid can be directly used as an extracting solution at the concentration of 100 wt%. However, water solutions with different ionic liquid concentrations can be optionally prepared as the extracting solution according to the osmotic pressure of the brine. The ionic liquid disclosed by the disclosure has larger molecular weight but low viscosity, so that the ionic liquid can be prepared into a high-concentration solution, and the prepared extracting solution has high osmotic pressure.
According to embodiments of the present disclosure, the ionic liquid used for the extraction solution may be
Figure BDA0002397318060000091
Wherein m is 0, 1, or 2; r is R 1 R is R 2 Independently methyl, or ethyl; and j is 5, 6, or 7. According to embodiments 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; r is R 1 R is R 2 Independently methyl, or ethyl; and i is independently 1, 2, or 3. According to embodiments of the present disclosure, the ionic liquid used for the extract 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 can 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 change properties (thermosensitive phase transition behavior), which are well suited for preparing the extraction solution (draw solution) used in the forward osmosis process (forward osmosis process).
According to an embodiment of the present disclosure, the present disclosure also provides a forward osmosis process, wherein the extraction solution used in the forward osmosis process comprises the ionic liquid described in the present disclosure. The forward osmosis process includes providing a forward osmosis system 100 (shown in FIG. 1), the forward osmosis system 100 comprising a semipermeable membrane 11 separating a feed tank 13 and an extract tank 15. Next, brine 17 is placed in the water 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 19, pure water 21 in the brine permeates through the semipermeable membrane 11 and enters the extract tank 15 to be mixed with the extract 19 to form a diluted extract (diluted draw solution). When the diluted extract reaches a predetermined water content, the diluted extract is removed from the extract tank (e.g., a portion of the diluted extract is transferred from the extract tank to a treatment tank). Then, the diluted extract is subjected to a temperature control process (such as a heating process or a cooling process) 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 30wt% to 90wt% (e.g., 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, or 90 wt%).
Since the ionic liquid for the extracting solution is a temperature-sensitive compound (thermoresponsive polymers) (i.e., the ionic liquid has a high critical solution temperature (upper critical solution temperature, UCST) or a low critical solution temperature (lower critical solution temperature, LCST)), and is characterized by being completely soluble (completely miscible) above (or below) the critical solution temperature (critical solution temperature), 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 can generate an internal structural change (conformational change) and reduce the affinity with water due to aggregation, and further the diluted extracting solution can generate phase separation (forming a water layer and an ionic liquid layer) (liquid-liquid separation), thereby achieving the purposes of recovering the extracting solution and generating pure water.
According to an embodiment of the disclosure, the forward osmosis process may further include re-introducing the ionic liquid layer into the extraction tank for recycling after the temperature control process is performed on the diluted extraction liquid (i.e., the diluted extraction liquid forms a water layer and an ionic liquid layer), so as to achieve the effect of recycling ionic liquid. According to embodiments of the present disclosure, the saline is introduced into the water inlet tank in a continuous manner to maintain a constant osmolarity of the saline in the water inlet tank 13. In this way, the concentration and osmotic pressure of the brine 17 in the water intake tank 13 are not increased after the pure water 21 extracted from the brine permeates into the extraction liquid tank 15, and the flux of the pure water 21 permeated into the extraction liquid tank 15 is prevented from being reduced. According to embodiments of the present disclosure, the term "brine" 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, a home, or a laboratory. Furthermore, according to embodiments of the present disclosure, the brine may be seawater.
According to an embodiment of the disclosure, the temperature control process may be a temperature reduction process. In other words, the temperature of the diluted extract may be reduced below room temperature to cause phase separation of the diluted extract when the temperature control process is performed. The ionic liquid used for the extraction liquid may here be an ionic liquid with a high critical dissolution temperature (upper critical solution temperature, UCST), for example
Figure BDA0002397318060000111
Here, the aqueous solution containing the above ionic liquid may have a high critical dissolution temperature (upper critical solution temperature, UCST) phase transition below a temperature of 10 ℃ to 35 ℃.
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 above room temperature to cause phase separation of the diluted extract during the temperature control process. The ionic liquid used in the extract is
Figure BDA0002397318060000112
Figure BDA0002397318060000113
In addition, when the ionic liquid is
Figure BDA0002397318060000121
When the aqueous solution containing the ionic liquid has a low critical solution temperature (lower critical solution temperature, LCST) phase transition below a temperature of 43 ℃ to 60 ℃; and when the ionic liquid is +>
Figure BDA0002397318060000122
When the aqueous solution containing the ionic liquid may have a low critical solution temperature (lower critical solution temperature, LCST) phase transition above a temperature of 65 ℃ to 75 ℃.
According to the embodiment of the disclosure, by using the extracting solution containing the ionic liquid, the forward osmosis process has the advantages of high flux, low energy consumption, low membrane blocking rate, low solute back diffusion and the like, and can greatly improve the desalination stability and reduce the cost.
In order to make the above and other objects, features and advantages of the present disclosure more comprehensible, several embodiments accompanied with figures are described in detail below:
example 1:
first, (2-hydroxyethyl) octyl diethyl ammonium bromide ((2-hydroxyyethyl) octyldiethylammonium bromide was synthesized according to the following procedure
Figure BDA0002397318060000123
) (hereinafter referred to as [ Ch228]][Br])：
52 g of (2-hydroxyethyl) diethylamine (0.44 mole), 85 g of (1-octylb romide) (0.44 mole) and 150 ml of acetonitrile (acetylstrength) were added to a reaction flask, and the resulting mixture was stirred at 80℃for 24 hours. After cooling to room temperature, 1.5L of diethyl ether (diethyl ether) was slowly added dropwise to the obtained product, and a white solid was observed to precipitate. After filtration, the obtained cake was dried to obtain (2-hydroxyethyl) octyl diethyl ammonium bromide ([ Ch228] [ Br ]).
Next, [ Ch228] was purified by ion exchange resin][Br]To (2-hydroxyethyl) octyl diethyl ammonium hydroxide (2-hydroxyyethyl) octyldiethyl ammonium hydroxide, of the structure
Figure BDA0002397318060000131
) (hereinafter referred to as [ Ch228]][OH]). Next, 82.8 g [ Ch228]][OH](0.335 mol), 108 g of di (2-ethylhexyl) phosphate (0.335 mmol) and 500ml of a water/ethanol mixture (volume of water and ethanol1:1) 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 (dichlormethane), and an organic layer was collected. After water removal and concentration, the product ionic liquid (I) is obtained (structure +.>
Figure BDA0002397318060000132
Hereinafter referred to as [ Ch228]][DEHP]. Analysis by Nuclear magnetic resonance Spectroscopy [ Ch228]][DEHP]The results were as follows: 1 H-NMR(500MHz in D 2 O):0.71～0.82(m,9H,CH 3 -)、1.09～1.29(m,26H,-CH 2 -)、1.31(m,2H,-CH-)、1.52(br,2H,N + CH 2 CH 2 -)、3.09(br,2H,N + CH 2 CH 2 -)、3.23(m,6H,N + CH 2 )、3.46(t,4H,-OCH 2 )、3.85(t,2H,-CH 2 OH)。
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 occurs or not, and recording the critical dissolution temperature, and the result is shown in FIG. 2. From the experimental results, it was found that the ionic liquid [ Ch228] [ DEHP ] was an ionic liquid having a low critical solution temperature (lower critical solution temperature, LCST). As can be seen from fig. 2, when the content of the ionic liquid [ Ch228] [ DEHP ] is 10wt% to 50wt% (based on the total weight of the aqueous solution), the aqueous solution has a Low Critical Solution Temperature (LCST) phase transition at a temperature above 43 ℃ to 60 ℃, at which time the water phase separates from the ionic liquid (liquid-liquid separation).
The osmotic pressure of aqueous solutions having different ionic liquid contents was measured using an osmotic pressure instrument (OSMOMAT 030, gostec) 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 the freezing point temperature is measured by a rapid cooling freezing method. When 1 mole of solute (e.g., ionic liquid) can lower the freezing point of 1 kg of water by 1.86 ℃, the osmotic pressure of this solute is defined as 1Osmol/kg. As can be seen from Table 1, when the [ Ch228] [ DEHP ] concentration of the aqueous solution containing the ionic liquid [ Ch228] [ DEHP ] is 30wt%, the osmotic pressure may be about 0.9Osmol/kg. In addition, the osmotic pressure of the mixed solution containing the high concentration of the ionic liquid [ Ch228] [ DEHP ] is beyond the detectable range of the instrument, so that the osmotic pressure of the mixed solution containing the ionic liquid [ Ch228] [ DEHP ] with the concentration of 20-30wt% is further estimated according to the relation obtained by the measured value of the osmotic pressure of the mixed solution containing the ionic liquid [ Ch228] [ DEHP ], and the osmotic pressure of the mixed solution containing the ionic liquid [ Ch228] [ DEHP ] with the concentration of 40wt% is further estimated as shown in the table 1. The experimental result shows that the osmotic pressure of the mixed solution containing 40wt% of ionic liquid [ Ch228] [ DEHP ] is larger than that of seawater, and the mixed solution can be used as an 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) is 1.2Osmol/kg
Aqueous solutions containing various concentrations of ionic liquids [ Ch228] [ DEHP ] with ionic liquid concentrations as a function of conductivity are shown in FIG. 3. The aqueous solution containing a high concentration of ionic liquid [ Ch228] [ DEHP ] had an initial conductivity of about 0.1mS/cm, however the conductivity increased with increasing water content. This is because the ionic liquid rich phase (ionic liquid-rich) exists in the form of ion pairs (ion pair) which decrease self-aggregation with increasing water content, forming independently occurring anions/cations. By means of the characteristic of the ionic liquid, the forward osmosis water flux can be stably operated and effectively improved.
The self-assembled laboratory-grade equipment is used, the forward osmosis module is flat plate type, the flow channel is designed into a double-channel internal circulation type, and a film (TW 30-1812) manufactured by Dow-filetec company is used, and the effective area of the film is 64cm 2 The water inlet end and the extraction liquid end solutions are conveyed by a pump, the sweeping flow rate is 25cm/s, the weights of the water inlet tank and the extraction liquid tank at different time points are recorded, and the water flux is obtained by the weight change, the film area and the experiment time, as shown in fig. 4. Ionic liquid [ Ch228]][DEHP]To the extraction tank, and pure water (DI water) to the water intake tank. In the initial stage 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) diethyl ammonium bromide) was synthesized according to the following procedure, and the structure was
Figure BDA0002397318060000151
) (hereinafter referred to as [ DCh8-22]][Br 2 ])：
52 g of (2-hydroxyethyl) diethylamine (0.44 mole), 60 g of 1,8-dibromooctane (0.22 mole) and 100 ml of acetonitrile (acetylide) were added to a reaction flask, and the resulting mixture was stirred at 80℃for 24 hours. After cooling to room temperature, 1.5L of diethyl ether (diethyl ether) was slowly added dropwise to the obtained product, 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)][Br 2 ])。
Next, the [ DCh8-22] was purified by using an ion exchange resin][Br 2 ]To (2-hydroxyethyl) octyl diethyl ammonium hydroxide (2-hydroxyyethyl) octyldiethyl ammonium hydroxide, of the structure
Figure BDA0002397318060000161
) (hereinafter referred to as [ DCh8-22]][OH 2 ]). Next, 45.25 g of [ DCh8-22]][OH 2 ](0.15mol), 96.73 g of di (2-ethylhexyl) phosphate (0.3 mmol) and 500ml of a water/ethanol mixture (volume ratio of water to ethanol 1:1) were added to a reaction flask and stirred at room temperature for 12 hours. Next, the resulting solution was extracted with 200 ml of dichloromethane (dichlormethane), and an organic layer was collected. After water removal and concentration, the product ionic liquid (II) is obtained (structure is
Figure BDA0002397318060000162
Hereinafter referred to as [ DCh8-22]][DEHP]. Analysis by Nuclear magnetic resonance Spectroscopy [ DCh8-22]][DEHP]The results were as follows: 1 H-NMR(500MHz in D 2 O):0.71～0.80(m,24H,CH 3 -)、1.09～1.29(m,24H,-CH 2 -)、1.36(m,4H,-CH-)、1.54(br,4H,N + CH 2 CH 2 -)、3.50(br,4H,N + CH 2 CH 2 -)、3.31(m,12H,N + CH 2 -)、3.55(dd,4H,-OCH 2 )、3.85(t,4H,-CH 2 OH)。
after mixing the ionic liquid [ DCh8-22] [ DEHP ] with water in different weight ratios, the mixture was allowed to stand at room temperature for a period of time, whether phase separation occurred or not was observed, and the critical dissolution temperature thereof was recorded, and the results are shown in Table 2. From the experimental results, it was found that the ionic liquid [ DCh8-22] [ DEHP ] was an ionic liquid having a low critical solution temperature (lower critical solution temperature, LCST). When the content of ionic liquid [ DCh8-22] [ DEHP ] is 10wt% to 30wt% (based on the total weight of the aqueous solution), the aqueous solution has a Low Critical Solution Temperature (LCST) phase transition above a temperature of 67 ℃ to 74 ℃, at which time water phase separates from the ionic liquid (liquid-liquid separation).
TABLE 2
Figure BDA0002397318060000171
Example 3:
100 g of an aqueous choline (choline hydroxide) (46 wt% in water) (0.38 mole choline) was added to a reaction flask. Next, 74.42 grams of azelaic acid (nonnadioic acid) was slowly added to the reaction flask. At room temperatureAfter the next reaction for 24 hours, the resulting solution was extracted with 200 ml of methylene chloride (dichlormethane), and the organic layer was collected. After water removal and concentration, the product ionic liquid (III) is obtained (structure is
Figure BDA0002397318060000172
Hereinafter referred to as [ Ch ]][Aze]. Analysis by nuclear magnetic resonance spectroscopy [ Ch][Aze]The results were as follows: 1 H-NMR(500MHz in D 2 O):1.17(m,6H,-CH 2 -)、1.41(m,4H,-CH 2 -)、2.10(t,4H, - OOCCH 2 -)、3.03(s,9H,N + CH 3 )、3.35(t,2H,N + CH 2 CH 2 -)、3.90(m,2H,-CH 2 OH)。
after mixing the ionic liquid [ Ch ] [ Aze ] with water in different weight ratios, standing at room temperature for a period of time, observing whether phase separation occurs or not, and recording the critical dissolution temperature, and the result is shown in FIG. 5. From the experimental results, it was found that the ionic liquid [ Ch ] [ Aze ] was an ionic liquid having a high critical dissolution temperature (upper critical solution temperature, UCST). As can be seen from fig. 5, when the content of the ionic liquid [ Ch228] [ DEHP ] is 5wt% to 50wt% (based on the weight of the aqueous solution), the aqueous solution has a high critical solution temperature (UCST) phase transition below a temperature of 10 ℃ to 35 ℃, at which time the water phase separates from the ionic liquid (liquid-liquid separation).
The osmotic pressure of the aqueous solutions with different ionic liquid contents was measured using an osmotic pressure instrument (OSMOMAT 030, gonotec) and the results are shown in table 3.
TABLE 3 Table 3
Figure BDA0002397318060000181
* Seawater osmotic pressure (0.6M NaCl) is 1.2Osmol/kg
As can be seen from Table 3, when the aqueous solution contains 30wt% to 70wt% ionic liquid [ Ch ] [ Aze ], the osmotic pressure of the aqueous solution is 2 to 15 times that of seawater. Therefore, the aqueous solution containing the ionic liquid [ Ch ] [ Aze ] does have the characteristic of high osmotic pressure, and is suitable as a forward osmosis extract.
The relationship between ionic liquid concentration and conductivity of the aqueous solution containing ionic liquids [ Ch ] [ Aze ] with different concentrations is shown in FIG. 6. The initial conductivity of the aqueous solution containing a high concentration of ionic liquid [ Ch ] [ Aze ] was about 1.1mS/cm, however the conductivity increased with increasing water content. This is because the ionic liquid rich phase (ionic liquid-rich) exists in the form of ion pairs (ion pair) which decrease self-aggregation with increasing water content, forming independently occurring anions/cations. By means of the characteristic of the ionic liquid, the forward osmosis water flux can be stably operated and effectively improved.
The self-assembled laboratory-grade equipment is used, the forward osmosis module is flat plate type, the flow channel is designed into a double-channel internal circulation type, and a film (TW 30-1812) manufactured by Dow-filetec company is used, and the effective area of the film is 64cm 2 The water inlet end and the extraction liquid end solutions were pumped at a sweeping flow rate of 25cm/s, the weights of the water inlet tank and the extraction liquid tank at different time points were recorded, and the water flux was determined by the weight change, the film area and the experimental time, as shown in fig. 7. Ionic liquid [ Ch ]][Aze]To the extraction tank, and pure water (DI water) to the water intake tank. In the initial stage of the experiment, the conductivity and water flux increased with time. After stable operation for 5 hours, the water flux and conductivity remained constant (average flux was above 3 LMH).
Although the present disclosure has been described with respect to several embodiments, it should be understood by those skilled in the art that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the disclosure as defined by the appended claims.

Claims (8)

1. An ionic liquid having a structure represented by formula (I):
AB n formula (I)
Wherein n=2;
a is
Figure FDA0004211141240000011
k is an integer from 3 to 8;
b is
Figure FDA0004211141240000012
i is independently 1, 2, or 3.
2. The ionic liquid according to claim 1, wherein the ionic liquid is
Figure FDA0004211141240000013
3. A forward osmosis process comprising:
separating the liquid extracting tank and the water inlet tank by a semi-permeable membrane;
introducing an extraction liquid into the extraction liquid tank, wherein the extraction liquid comprises the ionic liquid of claim 1;
introducing brine into a water inlet tank, wherein the osmotic pressure of the brine is lower than that of the ionic liquid, so that water in the brine permeates through the semipermeable membrane and enters the extracting solution to obtain diluted extracting solution;
taking out the diluted extract from the extract tank; and
and (3) performing temperature control treatment on the diluted extracting solution to separate the diluted extracting solution into a water layer and an ionic liquid layer.
4. The forward osmosis process of claim 3, wherein the extract comprises water and the ionic liquid of claim 1.
5. The forward osmosis process of claim 4, wherein the ionic liquid content of the extract is from 10wt% to 70wt%, based on the total weight of the extract.
6. The forward osmosis process of claim 3, wherein the temperature control process is a temperature increasing process.
7. The forward osmosis process of claim 6, wherein the ionic liquid is
Figure FDA0004211141240000021
8. The forward osmosis process of claim 7, wherein the diluted extract has a low critical solution temperature phase transition above a temperature of 65 ℃ to 75 ℃.
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