METHOD FOR MODULARING IONIC FORCE

专利摘要:
water system with variable ionic strength and one-solute separation method. The present invention relates to a method and system for reversibly converting water between an initial ionic strength and an increased ionic strength, using a switchable additive. the disclosed system and method can be used, for example, in the free distillation of water from solutes, solvents, or solutions. after extracting a solute from a medium by dissolving it in water, the solute can be isolated from the aqueous solution or "salinized", converting the water into a solution having an increased ionic strength. the solute then separates the solution from the increased ionic strength as a separate phase. once the solute is, for example, decanted, the aqueous solution of increased ionic strength can be converted back to water having its original ionic strength and reused. switching from lowest to highest ionic strength is easily achieved using low energy methods such as bubbling with co2, cs2 or cos. switching from highest to lowest ionic strength is easily accomplished using low energy methods such as bubbling with air, heating, stirring, introducing a vacuum or partial vacuum, or any combination of these.
公开号:BR112012020112B1
申请号:R112012020112-3
申请日:2011-02-10
公开日:2021-08-24
发明作者:Philip G. Jessop；Sean M. Mercer；R. Stephen Brown；Tobias Robert
申请人:Queen's University At Kingston；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[0001] The field of the invention is solvents and specifically an aqueous solvent composition that can be reversibly converted between low ionic strength and high ionic strength. BACKGROUND OF THE INVENTION
[0002] Conventional solvents with fixed physical properties can cause significant limitations in their use as a medium for reactions and separations. Many chemical production processes involve multiple reactions and separation steps, and often the type of solvent that is ideal for any step is different from one that is best for the next step. Thus, it is common for the solvent to be removed after each step and a new solvent added in preparation for the next step. This removal and replacement greatly increases the economic cost and environmental impact of the overall process. Therefore, there is a need for a solvent that can change its physical properties.
[0003] Solvents are commonly used to dissolve material in manufacturing, cleaning, dyeing, extracting and other processes. In order for a solvent to dissolve a material quickly, selectively and in sufficient quantity, it is generally necessary for the solvent to have specific physical properties. Ionic strength, hydrophobicity, hydrophilicity, dielectric constant, polarization, acidity, basicity, viscosity, volatility, hydrogen bonding capacity, hydrogen bonding capacity, and polarity are examples of such properties. At some point in this process after dissolution, separation of the material from the solvent may be desired. This separation can be expensive to achieve, especially if the solvent is removed by distillation, which requires the use of a volatile solvent, which can lead to significant vapor emission losses and resulting in environmental damage, for example, through formation of mist.
[0004] In addition, distillation requires a large input of energy. Therefore, it would be desirable to find a non-distilling route for removing solvents from the products.
[0005] Water is a particularly desirable solvent because of its low price, non-toxicity, non-flammability and lack of negative impact on the environment, but separating water from a product or other material by distillation is particularly costly in terms of energy because of the high heating capacity of water and the high heat of vaporization of water. Therefore, the need for a non-distilling route for separating water, products or other materials is particularly strong.
[0006] A common method for separating water from moderately hydrophobic yet water-soluble materials is "refill", a method in which a salt is added to an aqueous solution that includes a dissolved moderately hydrophobic compound, in amounts sufficient to increase the ionic strength of the fraction aqueous. High ionic strength considerably decreases the solubility of some compounds in water; Thus, most of the selected compound or material is forced out of the aqueous phase. The compound or material precipitates (forms a new solid phase) cream, (forms a new liquid phase) or partitions into a pre-existing hydrophobic liquid phase, if any. This "refill" method does not require distillation, but is not preferred because of the expense of using large amounts of salts and, more importantly, because of the expense of removing the salt from the water later. SUMMARY OF THE INVENTION
[0007] An object of the present invention is to provide water with a switchable ionic strength. In one aspect, a system for alternating the ionic strength of water or aqueous solution is provided, comprising: means for providing an additive that includes at least one nitrogen that is sufficiently basic to be protonated by carbonic acid; means for adding the additive to water or aqueous solution to form an aqueous mixture with switchable ionic strength; means for exposing the mixture with switchable ionic strength to an ionizing trigger such as CO2, COS, CS2 or a combination thereof to increase the ionic strength of the mixture; and means for exposing the mixture with high switchable ionic strength to i) heat, (ii) gas release, (iii) a vacuum or a partial vacuum, (iv) agitation or (v) any combination thereof, to reform the mixture aqueous with switchable ionic strength. In specific embodiments, this system is used to remove water from a hydrophobic liquid or solvent or in a desalination process.
[0008] In another aspect, a system is provided to control the amount, or presence and absence, of salt dissolved in an aqueous mixture, composed of a compound that reversibly converts to a salt in contact with an ionizing trigger in the presence of water , the compound with general formula (1):
where R 1 , R 2 and R 3 are independently: H; a substituted or unsubstituted C 1 -C 8 aliphatic group that is linear, branched or cyclic, optionally, in which one or more C of the alkyl group is replaced by {-Si(R 10 ) )2-O-} up to and including 8 C is being replaced by 8 {-Si(R10)2-O-}; a substituted or unsubstituted CnSim group, where neither is independently a number from 0 to 8 and n+m is a number from 1 to 8; a substituted or unsubstituted C4-C8 aryl group where aryl is optionally heteroaryl, optionally in which one or more C is substituted by {-Si(R10)2-O-} a substituted or unsubstituted aryl group having from 4 to 8 ring atoms, optionally including one or more {-Si(R10)2-O-}, where aryl is optionally heteroaryl; a chain -Si(R10)2-O)p- in which p is from 1 to 8 which is terminated by H, or is terminated by a substituted or unsubstituted C1-C8 aliphatic and/or aryl group; or one of the substituted or unsubstituted group (C1-C8 aliphatic)-(C4-C8 aryl) where aryl is optionally heteroaryl, optionally, where one or more C is substituted by a {-Si(R10)2-O- }; where R10 is a substituted or unsubstituted C1-C8 aliphatic group, a substituted or unsubstituted C1-C8 alkoxy, substituted or unsubstituted C4-C8 aryl where aryl optionally is heteroaryl, a substituted or unsubstituted aliphatic-alkoxy group, a substituted or unsubstituted aliphatic-aryl group or substituted or unsubstituted alkoxy-aryl groups; and where one substituent is independently: alkyl; alkenyl, alkynyl, aryl; aryl halide; heteroaryl; cycloalkyl; Si(alkyl)3; Si(alkoxy)3; halo; alkoxyl, amino; alkylamino; alkenylamino; amide; amidine; hydroxyl; thioether; alkylcarbonyl; alkylcarbonyloxy; arylcarbonyloxy; alkoxycarbonyloxy; aryloxycarbonyloxy; carbonate; alkoxycarbonyl; aminocarbonyl; alkylthiocarbonyl; amidine, phosphate; phosphate ester; phosphonate; phosphinate; cyan; acylamino; imino; sulfhydryl; alkylthio; arylthio; thiocarboxylate; dithiocarboxylate; sulfate; sulfate; sulfonate; sulfamoyl; sulfonamide; nitro; nitrile, azide; heterocyclyl; ether; ester; fractions containing silicon; thioester; or a combination thereof; and a substituent may be further substituted, in which when an increase in ionic strength, or the presence of salt is desired, the compound is exposed to the ionizing trigger in the presence of water, resulting in protonation of the compound, and in which when a decrease when ionic strength, or the absence of salt, is desired, any ionizing trigger in said mixture is at a level that is not sufficient to convert the compound to or maintain the compound in protonated form.
[0009] In another aspect a system is provided, comprising: means to provide switchable water, which is an aqueous liquid composed of an additive, which has switchable ionic strength; means for exposing the switchable water to an ionizing trigger in the presence of water to thereby protonate the additive to form protonated ionic additives, which are water-miscible or water-soluble, so that switchable water forms an aqueous ionic liquid; means for exposing the aqueous ionic liquid to i) heat, (ii) gas release, (iii) a vacuum or a partial vacuum, (iv) agitation or (v) any combination thereof, thus expelling the ionizing trigger from the ionic aqueous liquid which causes the deprotonation of protonated additives so that the switchable water forms a non-ionic aqueous liquid; and optionally, means for separating a selected compound from the aqueous ionic liquid prior to formation of the non-ionic aqueous liquid.
[00010] In another aspect a system is provided for the removal of a selected compound from a solid material, comprising: means for contacting a mixture of solid material and selected compound with switchable water, comprising a mixture of water and a switchable additive in its non-protonated form, ionic form, so that at least a fraction of the selected compound becomes associated with the switchable water to form a non-ionic aqueous solution; optionally, means for separating the solution from residual solid material; means for contacting the solution with an ionizing trigger in the presence of water to convert a substantial amount of switchable additive from its non-protonated form to its protonated form, resulting in a two-phase liquid mixture having a liquid phase that includes the compound selected and an aqueous phase of ionic liquid, composed of water and the protonated ionic additive; and means for separating the selected compound from the liquid phase.
[00011] Yet another aspect provides a system for modulating an osmotic gradient across the membrane, which includes: a semipermeable membrane; a switchable water, comprising an additive having a switchable ionic strength on one side of such semipermeable membrane; means for contacting the semipermeable membrane with feed stream; and means for contacting the switchable water with an ionizing trigger to ionize the additive and thereby increase the concentration of solute in switchable water and modulate the osmotic gradient.
[00012] One aspect provides a desalination system, which includes: a semi-permeable membrane that is selectively permeable to water; a withdrawal solution composed of an additive having switchable ionic strength and water; means for introducing an ionizing trigger to the withdrawal solution to ionize the additive; means for contacting the semipermeable membrane with a feed stream of an aqueous salt solution to allow water to flow from the aqueous salt solution through the semipermeable membrane to the withdrawal solution which includes ionized additive; and means for separating the additive from the water.
[00013] Another aspect provides a system for the concentration of a dilute aqueous solution, comprising: a semipermeable membrane that is selectively permeable to water; a withdrawal solution composed of an additive having switchable ionic strength; means for introducing an ionizing trigger to the withdrawal solution to ionize the additive; means for contacting the semipermeable membrane with a dilute aqueous solution feed stream to allow water to flow from the dilute aqueous solution through the semipermeable membrane to the withdrawal solution which includes ionized additive; and optionally, means for separating the additive from the water.
[00014] Another aspect provides a method of separating a solute from an aqueous solution, composed by combining in any order: water; a solute; C02, COS, CS2, or a combination thereof; and an additive comprising at least one nitrogen atom that is sufficiently basic to be protonated by carbonic acid; and which allows the separation of two components: a first component comprising an ionic form of the additive in which the nitrogen atom is protonated and optionally water; and a second component that makes up the solute; in which the solute is not reactive with the additive, CO2, COS, CS2, or a combination thereof.
[00015] In yet another aspect, a method for modulating ionic strength is provided, comprising providing an aqueous solution of low ionic strength composed of water and the additive comprising at least one nitrogen that is sufficiently basic to be protonated by the carbonic acid; contacting the aqueous solution of low ionic strength with CO2, COS, CS2 or a combination to form a solution of superior ionic strength; subjecting the solution of greater ionic strength to heat, contact with a release gas or heat, and contact with a discharge gas; and reforming the low ionic strength aqueous solution.
[00016] In one aspect, a method is provided for destabilizing or preventing the formation of a dispersion, comprising combining in any order to form a mixture: water; a water-immiscible or water-insoluble ingredient; an additive comprising at least one nitrogen that is basic enough to be protonated by carbonic acid; and CO2, COS, CS2, or a combination thereof; and allowing the mixture to separate into two components, a first component comprising the water-immiscible ingredient and a second component comprising water and an ionic form of the additive.
[00017] It is to be understood for all aspects and modalities thereof that the use of an additive as described in this application includes the use of more than one additive.
[00018] In embodiments of the above aspects, the additive is a compound of the formula
substituted or unsubstituted C 1 -C 8 aliphatic which is linear, branched or optionally cyclic, in which one or more C of the alkyl group is replaced by {-Si(R 10 ) 2 -O-} up to and including 8 C being replaced by { -Si(R10)2 -O-}; a substituted or unsubstituted CnSim group, where neither is independently a number from 0 to 8 and n+m is a number from 1 to 8; substituted or unsubstituted C4-C8 aryl group where aryl is optionally heteroaryl, optionally, where one or more C is replaced by a {-Si(R10)2-O-}; a substituted or unsubstituted aryl group having from 4 to 8 ring atoms, optionally including one or more {-Si(R 10 )2-O-}, where aryl is optionally heteroaryl; a -(Si(R10)2-O)p- chain in which p is from 1 to 8 which is terminated by H, or is terminated by a substituted or unsubstituted C1-C8 aliphatic and/or aryl Group; or a substituted or unsubstituted group (C1-C8 aliphatic) group (C4-C8 aryl) where aryl is optionally heteroaryl, optionally, in which one or more C is replaced by {-Si(R10)2-O-} ; where R10 is a substituted or unsubstituted C1-C8 aliphatic group, a substituted or unsubstituted C1-C8 alkoxy group, a substituted or unsubstituted C4-C8 aryl group where aryl optionally is heteroaryl, a substituted or unsubstituted aliphatic-alkoxy group , a substituted or unsubstituted aliphatic-aryl group or a substituted or unsubstituted alkoxy-aryl group; and where a substituent is independently: alkyl; alkenyl, alkynyl, aryl; aryl halide; heteroaryl; cycloalkyl; Si(alkyl)3; Si(alkoxy)3; halo; alkoxyl; amino; alkylamino; dialkylamino, alkenylamino; amide; amidine;hydroxyl; thioether; alkylcarbonyl; alkylcarbonyloxy; arylcarbonyloxy; alkoxycarbonyloxy; aryloxycarbonyloxy; carbonate; alkoxycarbonyl; aminocarbonyl; alkylthiocarbonyl; phosphate; phosphate ester; phosphonate; phosphinate; cyan; acylamino; imino; sulfhydryl; alkylthio; arylthio; thiocarboxylate; dithiocarboxylate; sulfate; sulfate; sulfonate; sulfamoyl; sulfonamide; Nitro; nitrile; azide; heterocyclyl; ether; ester; fractions containing silicon; Thioester; or a combination thereof; and a substituent can be further substituted.
[00019] In certain embodiments of the above aspects, the ionic form of the additive is a compound of formula (2)
where R 1 , R 2 and R 3 are defined for the compound of formula (1) above, and E is O, S or a mixture of O and S.
[00020] In certain embodiments of the compounds of formulas (1) and (2), one or more of R1, R2 and R3 make up one or more nitrogen that is sufficiently basic to be protonated by carbonic acid. As would be readily appreciated by the person skilled in the art, each of the one or more nitrogens that are sufficiently basic to be protonated by carbonic acid are associated with a corresponding E3CH- counterion in the compound of formula (2).
[00021] In certain embodiments of the compounds of formulas (1) and (2), two of R1, R2 and R3, together with the nitrogen to which they are connected, are joined to form a heterocyclic ring. In some embodiments, the heterocyclic ring has 4 to 8 ring atoms. In certain embodiments of formula (1) R 1 , R 2 and R 3 can be H. R 1 , R 2 and R 3 can be a substituted or unsubstituted C 1 -C 8 alkyl group that is linear, branched or cyclic, optionally containing from 1 to 8 { -Si(R10)2-O-}. R1, R2 and R3 may be substituted or unsubstituted C2-C8 alkene which is linear, branched or cyclic, optionally containing from 1 to 8 {-Si(R10)2-O-}. R1, R2 and R3 can be a substituted or unsubstituted CnSim group, where neither is independently a number from 0 to 8 and n+m is a number from 1 to 8. R1, R2 and R3 can be substituted or unsubstituted C5- C8 aryl optionally containing from 1 to 8 {-Si(R10)2-O-}. R 1 , R 2 and R 3 may be a substituted or unsubstituted heteroaryl group having 4 to 8 atoms in the aromatic ring optionally containing from 1 to 8 {-Si(R 10 ) 2 -O-}. R1, R2 and R3 can be a -(Si(R10)2-O)p- chain in which p is from 1 to 8 which is terminated by H or by a substituted or unsubstituted C1-C8 alkyl group which is linear, branched, or cyclic. R1, R2 and R3 may be substituted or unsubstituted C1-C8 Alkylene - C5-C8 aryl group optionally containing from 1 to 8 {-Si(R10)2-O-}. R1, R2 and R3 may be substituted or unsubstituted C2-C8 alkenylene - C5-C8 aryl group optionally containing from 1 to 8 {-Si(R10)2-O-}. R1, R2 and R3 may be substituted or unsubstituted C1-C8 Alkylene-heteroaryl group having 4 to 8 atoms in the aromatic ring optionally containing from 1 to 8 {-Si(R10)2-O-}. R 1 , R 2 and R 3 may be substituted or unsubstituted C 2 -C 8 alkenylene - heteroaryl group having 4 to 8 atoms in the aromatic ring optionally containing from 1 to 8 {-Si(R10)2-O-}. R10 may be a substituted or unsubstituted group: C1-C8 alkyl, C5 C8 aryl, heteroaryl, having from 4 to 8 carbon atoms in the aromatic ring or C1-C8 alkoxy moiety.
[00022] In embodiments of the above aspects, the additive is a compound of formula (6),
where R1, R2, R3and R4 independently are: H; a substituted or unsubstituted C1-C8 aliphatic group that is linear, branched or cyclic, optionally, in which one or more C of the alkyl group is replaced by the {-Si(R10)2-O-} up to and including 8 C is being substituted by 8 {-Si(R10)2-O-}; a substituted or unsubstituted CnSim group, where neither is independently a number from 0 to 8 and n+m is a number from 1 to 8; substituted or unsubstituted C4-C8 aryl group where aryl is optionally heteroaryl, optionally, in which one or more C is substituted by {-Si(R10)2-O-}; a substituted or unsubstituted aryl group having from 4 to 8 ring atoms, optionally including one or more {-Si(R10)2-O-}, where aryl is optionally heteroaryl; a -(Si(R10)2-O)p- chain in which p is from 1 to 8 which is terminated by H, or is terminated by a Substituted or unsubstituted C1-C8 aliphatic and/or aryl group; or a substituted or unsubstituted (C1 C8 aliphatic)-(C4 C8 aryl) group of the group where aryl is optionally heteroaryl, optionally, where one or more C is substituted by a {-Si(R10)2-O-} ; where R10 is a substituted or unsubstituted C1-C8 aliphatic group, a substituted or unsubstituted C1-C8 alkoxy group, substituted or unsubstituted C4-C8 aryl where aryl optionally is heteroaryl, a substituted or unsubstituted aliphatic-alkoxy group, a substituted or unsubstituted aliphatic-aryl group or a substituted or unsubstituted alkoxy-aryl group; and where a substituent is independently: alkyl; alkenyl, alkynyl, aryl; aryl halide; heteroaryl; cycloalkyl; Si(alkyl)3; Si(alkoxy)3; Halo; alkoxyl; amino; alkylamino; alkenylamino; Amide; amidine; hydroxyl; thioether; alkylcarbonyl; alkylcarbonyloxy; arylcarbonyloxy; alkoxycarbonyloxy; aryloxycarbonyloxy; carbonate; alkoxycarbonyl; aminocarbonyl; alkylthiocarbonyl; amidine, phosphate; phosphate ester; phosphonate; phosphinate; cyan; acylamino; imino; sulfhydryl; alkylthio; arylthio; thiocarboxylate; dithiocarboxylate; sulfate; sulfate; sulfonate; sulfamoyl; sulfonamide; Nitro; nitrile; azide; heterocyclyl; ether; ester; fractions containing silicon; Thioester; or a combination thereof; and a substituent can be further substituted.
[00023] In certain embodiments of the above aspects, the ionic form of the additive is a compound of the formula (6'):
where R 1 , R 2 , R 3 and R 4 are defined for the compound of formula (6) above, and E is O, S or a mixture of O and S.
[00024] In embodiments of the above aspects, at least one nitrogen sufficiently basic to be protonated by carbonic acid is at least one nitrogen having a conjugate acid with a pKa range of about 6 to about 14, or about 8 to about 10.
[00025] In certain embodiments of the above aspects, the additive is MDEA (N-methyl diethanol-amine); TMDAB (N,N,N',N'-tetramethyl-1,4-diaminobutane); THEED (N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine); DMAPAP (1-[bis[3-(dimethylamino)]propyl]amino]-2-propanol); HMTETA (1,1,4,7,10,10-hexamethyl triethylenetetramine) or DIAC (N',N''-(butane-1,4-diyl)bis(N,N-dimethylacetimidamide).
[00026] In an embodiment of certain aspects, the dilute aqueous solution is waste water.
[00027] In certain embodiments of the aspect of a method for destabilizing or preventing the formation of a dispersion, the combination in any order comprises forming a mixture by adding additive to an aqueous solution comprising the solute; and contacting the mixture with CO2, COS, CS2 or a combination of these. In another embodiment, combining in any order comprises forming a mixture by adding solute to water or aqueous solution; contact the mixture with CO2, COS, CS2 or a combination thereof; and addition of additive. In another embodiment, combining in any order comprises forming a mixture by adding solute to an aqueous solution comprising the additive; and contacting the mixture with CO2, COS, CS2 or a combination of these. In another embodiment, combining in any order comprises adding a mixture composed of solute and additive to an aqueous solution comprising CO2, COS, CS2 or a combination thereof. In another embodiment, combining in any order comprises forming a mixture by adding solute to an aqueous solution comprising CO2, COS, CS2 or a combination thereof and adding additive.
[00028] In certain embodiments of this aspect, the solute is composed of a product of a chemical reaction. The first component can further include a water-soluble catalyst. The solute can include a catalyst. In another embodiment of certain aspects, the combination further comprises combining water, the solute, the additive and CO2, COS, CS2 or a combination thereof, with a hydrophobic liquid, where after the separation step the second component comprises the hydrophobic liquid.
[00029] In certain modalities, a mixture of water, the solute and the additive is a homogeneous liquid. In other embodiments, a mixture of water and the ionic form of the additive is a homogeneous liquid. In another embodiment, a mixture of water and the ionic form of the additive is a suspension. In another embodiment, a mixture of water and the ionic form of the additive is a solid. In certain modalities the solute is miscible in aqueous solutions of low ionic strength or soluble and insoluble or immiscible in aqueous solutions of high ionic strength.
[00030] Some modalities further comprise isolating the first component, and subjecting it to a trigger to form an aqueous solution composed of additive, in which the trigger is hot, bubbling with a release of gas, or heat and bubbling with a release of gas. In certain embodiments, isolation includes centrifuging, decanting, filtering, or a combination of these. In certain modalities, the additive is miscible with water in its ionized form and its non-ionized form, or soluble in water. In certain embodiments, only the ionized form of the additive is water-miscible or water-soluble and the non-ionized form is water-insoluble or immiscible.
[00031] In certain embodiments of the above aspects, the number of moles of water in the aqueous solution and the number of moles of basic nitrogen in the additive in aqueous solution are approximately equivalent. In other embodiments of the above aspects, the number of moles of water in the aqueous solution is greater than the number of moles of basic nitrogen in the additive in the aqueous solution.
[00032] In an embodiment of the aspect about a method for destabilizing or preventing the formation of a dispersion, the dispersion is an emulsion and the water-immiscible ingredient is a liquid or a supercritical fluid. In other embodiments, the dispersion is an inverse emulsion and the water-immiscible ingredient is a liquid or supercritical fluid. In another embodiment of this aspect, the dispersion is a foam and the water-immiscible ingredient is a gas. In other embodiments of this aspect, the dispersion is a suspension and the water-immiscible ingredient is a solid. In embodiments of the aspects described herein, a mixture may further include a surfactant.
[00033] In a modality of the aspect about the ionic strength modulation method, the method is used as a CO2, COS or CS2 sensor; a CO2, COS or CS2 detector; a chemical switch; a surfactant deactivator; or to conduct electricity.
[00034] In other embodiments of the aspect regarding a method of separating a solute from an aqueous solution, the aspect regarding ionic strength modulation and the aspect regarding a method for destabilizing or preventing the formation of a dispersion are used to remove water from a hydrophobic liquid or a solvent.
[00035] In other modalities, methods of these aspects are used in a wastewater treatment process or a desalination process. BRIEF DESCRIPTION OF THE DRAWINGS
[00036] Embodiments of the invention will now be described, by way of example, with reference to the accompanying drawings.
[00037] Figure 1 shows a chemical reaction equation and a scheme of the switching reaction between different forms of ionic strength of an aqueous solution of an amine.
[00038] Figure 2 shows the chemical structures of the various tertiary amines useful as additives in the present invention.
[00039] Figure 3 shows several 1H NMR spectra of MDEA commutability study performed in D2O at 400 MHz. Spectrum A was captured with no CO2 treatment, spectrum B was captured after 20 minutes of CO2 bubbling, and spectrum C was captured after 300 minutes of N2 bubbling. This is discussed in example 4 below.
[00040] Figure 4 shows several 1H NMR spectra from a study of switchability of DMAE in D2O at 400 MHz. Spectrum A was captured with no CO2 treatment, spectrum B was captured after 30 minutes of CO2 bubbling, and spectrum C was captured after 240 minutes of N2 bubbling. This is discussed in example 4 below.
[00041] Figure 5 shows several 1H NMR spectra from an HMTETA switchability study performed on D2O at 400 MHz. Spectrum A was captured with no CO2 treatment, spectrum B was captured after 20 minutes of CO2 bubbling, and spectrum C was captured after 240 minutes of N2 bubbling. This is discussed in example 4 below.
[00042] Figure 6 shows several 1H NMR spectra from a DMAPAP switchability study performed on D2O at 400 MHz. Spectrum A was captured with no CO2 treatment, spectrum B was captured after 20 minutes of CO2 bubbling, and spectrum C was captured after 120 minutes of N2 bubbling. This is discussed in example 4 below.
[00043] Figure 7 shows the conductivity spectra for water responses and 1:1 v/v H2O:DMAE; 1:1 v/v H2O:MDEA; and 1:1 w/w H2O: THEED solutions for a CO2 trigger over time. This is discussed in example 5 below.
[00044] Figure 8 shows the conductivity spectra for the 1:1 v/v H2O:DMAE responses; 1:1 v/v H2O:MDEA; and 1:1 w/w H2O: THEED solutions, which were switched with a CO2 trigger, to remove CO2 by bubbling nitrogen over time. This is discussed in example 5 below.
[00045] Figure 9 shows a representation of the degree of protonation of 0.5 M solutions of DMAE and MDEA in D2O and a 0.1 M aqueous solution of THEED in D2O resulting from exposure to a CO2 trigger over time . This is discussed in example 6 below.
[00046] Figure 10 shows a representation of the degree of deprotonation of 0.5 M solutions of DMAE and MDEA in D2O and a 0.1 M solution of THEED in D20 that was switched with a CO2 trigger for trigger removal by bubbling nitrogen over time. This is discussed in example 6 below.
[00047] Figure 11 shows the conductivity spectra for the 1:1 v/v H2O: Amine solutions for a CO2 trigger over time, where the amine is TMDAB (♦), HMTETA (■) and DMAPAP (▲). This is discussed in example 7 below.
[00048] Figure 12 shows the conductivity spectra for the 1:1 v/v H2O responses: Amine solutions, switched with a CO2 trigger, for removal of the trigger by nitrogen bubbling over time, in which the amine is TMDAB (♦), HMTETA (■) and DMAPAP (▲). This is discussed in example 7 below.
[00049] Figure 13 shows five photographs A-E representing different phases of an experiment that shows how the switchable ionic strength characteristic of TMDAB amine additive can be used to interrupt an emulsion of water and n-decanol. This is discussed in example 8 below.
[00050] Figure 14A-C schematically depict studies carried out to monitor clay settling in switchable water according to various modalities (fig. 14A; Study 1 of example 12; fig. 14B study 2 of example 12; and fig. 14C study 3 of example 12).
[00051] Figure 15A-D shows the results of mixing switchable water with fine particles of kaolinite clay and treatment with CO2, followed by treatment with N2 (fig. 15A clay+1 mM TMDAB; fig. 15B clay+1 mM TMDAB after 1 h CO2; fig. 15C clay+1 mM TMDAB - CO2 by adding N2 for 1 h; fig. 15 photographs of mixtures+TMDAB, then CO2 and N2).
[00052] Figure 16A-B shows the results of mixing switchable water with kaolinite clay particles and treatment with CO2 in the presence of clay (fig. 16A clay+1 mM TMDAB after 1 h CO2; and fig. 16 photographs of mixtures +TMDAB then CO2 and then N2).
[00053] Figure 17A-C shows the results of mixing a filtrate treated with CO2 (obtained from a mixture of switchable water with kaolinite clay particles) with clay (fig. 17A filtered 1h CO2+ clay; fig. 17B blanket of CO2+clay (control); Fig. 17C photographs of filtered mixtures of CO2+clay and CO2+clay blanket (control)).
[00054] Figure 18 shows a standard system for desalination of seawater using osmosis below.
[00055] Figure 19 shows a system and process of desalination by osmosis below, followed by reverse osmosis, using a switchable water ("active AC" refers to the bicarbonate form of switchable water and "non-active AC" refers to if the non-ionized form of switchable water).
[00056] Figure 20 shows an alternative system and the process of desalination by osmosis below, followed by removal of CO2 (by heat or non-acid gas bubbles) causing separation of most or all of the additive from the water, using a water Switchable ("active AC" refers to the switchable form of bicarbonate of water and "non-active AC" refers to the non-ionized form of switchable water). In this process, if the separation of the additive switchable water from the water is incomplete, reverse osmosis or nanofiltration can be used to remove the remaining additive from the water.
[00057] Figure 21 shows a system that includes means for reversibly converting a non-ionized form of switchable water to an ionized form of switchable water.
[00058] Figure 22 shows a system for obtaining at least one compound from a mixture of compounds using switchable water that is reversible from its non-ionic form to ionized form. DETAILED DESCRIPTION OF THE INVENTION Definitions
[00059] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by a common skill in the art to which this invention belongs.
[00060] As used in the specification and claims, the verb form "a", "the" and "an/a" include plural references unless the context clearly dictates otherwise.
[00061] The term "Comprising" as used herein means that the following list is indicative and may or may not include any other suitable additional items, for example, one or more further characteristics, component(s) and/or ingredient(s) as per appropriate.
[00062] As used herein, "aliphatic" refers to straight, branched or cyclic hydrocarbon moieties, may be alkyl, alkenyl or alkynyl and may be substituted or unsubstituted. "Alkenyl" means a hydrocarbon group that is linear, branched or cyclic and contains at least one carbon-carbon double bond. "Aryl" means a moiety including a substituted or unsubstituted aromatic ring, including heteroaryl moieties and the moieties with more than one conjugated aromatic ring; Optionally, it can also include one or more non-aromatic rings. "C5-C8 aryl" means a moiety including a substituted or unsubstituted aromatic ring having from 5 to 8 carbon atoms in one or more conjugated aromatic rings. Examples of aryl phenyl fractions are examples.
[00063] "Heteroaryl" means a moiety including a substituted or unsubstituted aromatic ring, having from 4 to 8 carbon atoms and at least one heteroatom in one or more conjugated aromatic rings. Here, "chain" refers to non-carbon and non-hydrogen atoms, such as, for example, O, S and N. Examples of heteroaryl moieties include pyridyl tetrahydrofuranyl and thienyl.
[00064] "Alkylene" means a bivalent alkyl radical, for example -CH- where f is an integer. "Alkenylene" means a bivalent alkenyl radical, for example, -CHCH-. "Arylene" means a bivalent aryl radical, for example -C6H4. "Heteroarylene" means a bivalent heteroaryl radical, for example, -C5H3N-. "Alkylene-aryl" means a bivalent alkylene radical attached at one of its two free valences to an aryl radical, eg, -CH2-C6H5. "Alkenylene-aryl" means a bivalent alkenylene radical attached at one of its two free valences to an aryl radical, eg, -CHCH-C6H5. "Alkylene-heteroaryl" means a bivalent Alkylene radical, attached at one of its two free valences to a heteroaryl radical, eg, -CH2-C5H4N. "Alkenylene-heteroaryl" means a divalent alkenylene radical attached to one of its two free valences to a heteroaryl radical, eg, -CHCH-C5H4N.
[00065] "Alkylene-arylene" means a divalent alkylene radical bonded in one of its two free valences to one of the two free valences of a bivalent arylene radical, eg, -CH2-C6H4-. "Alkenylene-arylene" means a divalent alkenylene radical attached in one of its two free valences to one of the two free valences of a bivalent arylene radical, for example, -CHCH-C6H4-. "Alkylene-heteroarylene" means a bivalent alkylene radical attached in one of its two free valences to one of the two free valences of a bivalent heteroarylene radical, for example, -CH2-C5H3N-. "Alkenylene-heteroarylene" means a divalent alkenylene radical attached in one of its two free valences to one of the two free valences of a divalent heteroarylene radical, for example, -CHCH-C5H3N-.
[00066] "Substituted" means having one or more substituent moieties, the presence of which does not interfere with the desired reaction. Examples of alkyl, alkenyl, alkynyl, aryl, aryl halide, heteroaryl, cycloalkyl (non-aromatic ring), Si(alkyl)3, Si(alkoxy)3, halo, alkoxy, amino, alkylamino, alkenylamino, amide, amidine, hydroxyl, thioether, alkylcarbonyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carbonate, alkoxycarbonyl, aminocarbonyl, alkylthiocarbonyl, phosphate, phosphate ester, phosphonate, phosphinate, cyano, acylamino, imino, sulfhydryl, sulfate, carboxythio, aryl sulfate, thiocarboxythiolate , sulfonate, sulfamoyl, sulfonamide, nitro, nitrile, azido, heterocyclyl, ether and ester, fractions containing silicone, thioester or a combination thereof.
[00067] Preferred substituents are alkyl, aryl, heteroaryl and ether. It will be appreciated that aryl halides are acceptable substituents. Alkyl halides are known to be very reactive and are acceptable as long as they do not interfere with the desired reaction. Substituents themselves can be substituted. For example, an amino substituent can be mono or independently bi-substituted by additional substituents defined above, such as alkyl, alkenyl, alkynyl, aryl, aryl halide and cycloalkyl heteroaryl (non-aromatic ring).
[00068] "small chain aliphatic" or "lower aliphatic" refers to C1-C4 aliphatics. "long chain aliphatic" or "higher aliphatic" refers to C5-C8 aliphatic.
[00069] Here, the term "substituted" refers to any open valence of an atom being occupied by hydrogen. Also, if an occupant of an open valence position in an atom is not specified, then it is hydrogen.
[00070] As used herein, the term "polymer" means a molecule of high relative molecular mass whose structure is primarily composed of several repeats of units derived from molecules of low relative molecular mass. In this document, the term "oligomer" represents a molecule of intermediate relative molecular mass, whose structure is mainly composed of a plurality of small units derived from molecules of low relative molecular mass. A molecule can be considered to have a high relative molecular mass if the addition or removal of one or some of the units has a negligible effect on the molecular properties. A molecule can be considered to have an intermediate relative molecular mass if it has molecular properties that vary significantly with the removal of one or some of the units. (See lUPAC 1996 Recommendations in (1996) Pure and Applied Chemistry 68: 2287-2311.)
[00071] The term "switched" means that the physical properties, and in particular the ionic strength, have been modified. "Selectable" means capable of being converted from a first state with a first set of physical properties, eg a first state of a certain ionic strength, to another state with a second set of physical properties, eg a high state ionic strength. A "trigger" is a change in conditions (eg, introduction or removal of a gas, change in temperature) that causes a change in physical properties, eg, ionic strength. The term "reversible" means that the reaction can proceed in any direction (backward or forward) depending on the reaction conditions.
[00072] "Aerated water" means a water solution in which CO2 has been dissolved. "CO2 saturated water" means a water solution in which CO2 is dissolved as much as possible at that temperature.
[00073] As used herein, "a gas that substantially does not contain carbon dioxide" means that the gas has insufficient CO2 content to interfere with the removal of CO2 from the solution. For some applications, air can be a gas that has substantially no CO2. Untreated air can be used successfully, ie air in which the CO2 content is unchanged; This would provide cost savings. For example, air can be a gas that has substantially no CO2, because in some circumstances, about 0.04% by volume of CO2 present in the air is insufficient to hold a composite in a switched form, such that air can be a trigger used to remove CO2 from a solution and cause switching. Likewise, "a gas that substantially does not have CO2, CS2 or COS" has insufficient CO2, CS2 or COS content to interfere with the removal of CO2, CS2 or COS from the solution.
[00074] As used herein, "additive" refers to a compound that includes at least one amine or amidine nitrogen that is sufficiently basic that when it is in the presence of water and CO2 (which form carbonic acid), for example, the compound becomes protonated. When an aqueous solution that includes a switchable additive is triggered, the reversible additive alternates between two states, a non-ionized state, where nitrogen is trivalent and is discharged, and an ionized state, where nitrogen is protonated, becoming a positively charged 4-coordinated nitrogen atom. For your convenience here, the discharged or non-ionic form of the additive is generally not specified, while the ionic form is usually specified. The terms "ionized" or "ionic" as used herein in identifying an additive form only refer to the protonated or charged state of the amine or amidine nitrogen.
[00075] As would be readily appreciated by a person skilled in the art, as some protonation reactions proceeded to the conclusion, when a compound is known here as being "protonated" it means that all, or only most, of the compound's molecules are protonated. For example, when the additive has a single N atom, more than about 90%, or more than about 95%, or about 95% of the molecules are protonated by carbonic acid.
[00076] As used herein, "amine additive" (see compound of formula (1) below) refers to a molecule with a structure R1R2R3N, where R1 to R3 are independently hydrogen or aliphatic or aryl, which includes heteroaryl , as discussed below. The ionic form of an amine (see compound of formula (2) below) is called an "ammonia salt". The bicarbonate salt of an amine (see compound of formula (3) below) is called an "ammonium bicarbonate".
[00077] As used herein, "amidine additive" refers to a molecule with a structure R1N=C(R2)-NR3R4, where R1 to R4 are independently hydrogen or aliphatic or aryl, which includes heteroaryl, or siloxy, such as discussed below. The ionic form of an amidine (see compound of formula (6') below) is called an "amidine salt".
[00078] As used herein, the term "basic nitrogen" or "a nitrogen that is basic enough to be protonated by carbonic acid" is used to denote a nitrogen atom that has a lone pair of electrons available and susceptible to protonation. Although carbonic acid (CO2 in water) is mentioned, such a nitrogen would also be protonated by CS2 in water and COS in water. This term is intended to denote the basicity of nitrogen, and is not intended to imply which of the three trigger gases (CO2, CS2 or COS) is used.
[00079] "Ionic" means containing or surrounding or occurring in the form of positively or negatively charged ions, ie, charged fractions. "Nonionic" means composed substantially of molecules with no formal charge. Nonionic does not imply that there are no ions of any kind, but rather that a substantial amount of basic nitrogens are in a non-protonated state. "Salts" as used in this document are compounds with no net charge formed from positively and negatively charged ions. For disclosure purposes, "ionic liquids" are salts that are liquid below 100°C; such liquids are typically non-volatile, polar and viscous. "Non-ionic liquids" means liquids that do not consist primarily of formally charged molecules such as ions. Non-ionic liquids are available in a wide range of polarities and can be polar or non-polar; they are typically more volatile and less viscous than ionic liquids.
[00080] "The ionic strength" of a solution is a measure of the concentration of ions in the solution. Ionic compounds (ie salts) that dissolve in water will dissociate into ions, increasing the ionic strength of a solution. The total concentration of dissolved ions in solution will affect important properties of the solution, such as dissociation or solubility of different compounds. The ionic strength, I, of a solution is a function of the concentration of all ions present in the solution and is normally given by equation (A),
where ci is the molar concentration of the ion i in mol/dm3, zi is the charge number of this ion and the sum is taken over all the ions dissolved in the solution. In non-ideal solutions, volumes are not addable which is preferable to calculate the ionic strength in terms of molality (mol/kg H2O), such that the ionic strength can be given by equation (B),
where mi is the molality of the ion i in mol/kg of H2O and zi as defined in the previous paragraph.
[00081] A "polar" molecule is a molecule in which some separation of the centers of positive and negative charge (or partial positive and partial negative charge) within the molecule occurs. Polar solvents are typically characterized by a dipole moment. Ionic liquids are considered polar solvents, even when a dipole may not be present, because they behave the same way as polar liquids in terms of their ability to solubilize polar solutes, their miscibility with other polar liquids, and their effects on solvatochromic dyes. A polar solvent is generally better than a non-polar (or less polar) solvent at dissolving polar or charged molecules.
[00082] "Nonpolar" means having weak diluting power of polar or charged molecules. Nonpolar solvents are associated with having little or no charge separation, so positive or negative poles are not formed, or have a small dipole moment. A non-polar solvent is generally better than a polar solvent for dissolving non-polar, waxy or oily molecules.
[00083] "Hydrophobicity" is a property of a molecule that allows it to be repelled from a body of water. Hydrophobic molecules are typically non-polar and non-hydrogen bonded. Such molecules tend to associate with other neutral and non-polar molecules. The degree of a molecule's hydrophobic character, or hydrophobicity, can be quantified by a value of logP. The logP is the logarithm of the lipid-water division coefficient, P, of a molecule. The lipid-water division coefficient seeks to determine the relationship between the solubility of a molecule in a lipid environment and a hydrophilic aqueous environment. The lipid-water division coefficient is the equilibrium constant calculated as the ratio of the concentration of the molecule in the lipid phase divided by the concentration of the molecule in the aqueous phase.
[00084] "Moderately hydrophobic" is used in this document to refer to compounds that are moderately or completely soluble in aqueous solutions of low ionic strength, but which are much less soluble or essentially insoluble in aqueous solutions of high ionic strength. Such compounds can be liquid or solid; they can be organic or inorganic. An example of a moderately hydrophobic compound is tetrahydrofuran.
[00085] Partition coefficients can be determined using noctanol as a model of an aqueous phosphate buffer solution at pH 7.4 and the lipid phase as a model of the water phase. Because the division coefficient is a relationship, it is dimensionless. The division coefficient is an additive property of a molecule, because each functional group helps determine the hydrophobic or hydrophilic character of the molecule. If the value of logP is small, the molecule will be miscible with (or soluble in) water such that the water and the molecule form a single phase in more proportions. If the value of logP is large, the compound will be immiscible with (or insoluble in) water such that a two-phase mixture will be formed with the water and the molecule present as separate layers in most proportions.
[00086] It is theoretically possible to calculate logP values for many organic compounds due to the additive nature of the division coefficient arising from individual functional groups of a molecule. We have a number of computer programs to calculate logP values. The logP values described here are predicted using ALOGPS 2.1 software, which calculates the logP value for a given molecule using nine different algorithms and then averages the values. This computational method is fully described by Tetko I.V. and Tanchuk V.Y. in J. Chem. Computer Information Sci., 2002, 42, 1136-1145 and in J. Comput. Aid. Mol. Des., 2005, 19, 453-463, both of which are incorporated herein by reference.
[00087] In contrast to hydrophobicity, "Hydrophilicity" is a property of a molecule, allowing it to be dissolved in or miscible with a body of water, usually because the molecule is capable of transiently bonding with water through binding of hydrogen. Hydrophilic molecules are generally polar. Such molecules can thus be compatible with other polar molecules. Hydrophilic molecules can include at least one hydrophilic substituent that can transiently bond with water via hydrogen bonding. Hydrophilic substituents include amino, hydroxyl, carbonyl, carboxyl, ester, ether and phosphate moieties.
[00088] "Insoluble" refers to a poorly solubilized solid in a specified liquid such that when the solid and liquid are combined a heterogeneous mixture results. It is recognized that the solubility of an "insoluble" solid in a specified liquid cannot be zero, but instead would be less than that useful in practice. The use of the terms "soluble", "insoluble", "solubility" and the like does not imply that only a solid/liquid mixture is intended. For example, a statement that the additive is water-soluble is not to imply that the additive must be a solid; the possibility that the additive may be a liquid is not excluded.
[00089] "Miscibility" is a property of two liquids which when mixed together provide a homogeneous solution. In contrast, "immiscibility" is a property of two liquids which when mixed together provide a heterogeneous mixture, eg having two distinct phases (ie layers).
[00090] As used here, "immiscible" means unable to blend into a single phase. Thus, two liquids are described as "immiscible" if they form two phases when combined in one ratio. This does not imply that combinations of the two liquids will be two-phase mixtures in all proportions, or under all conditions. The immiscibility of two liquids can be detected if two phases are present, for example, through visual inspection. The two phases can be present as two layers of liquid or drops from one phase distributed in the other phase.
[00091] The use of the terms "immiscible", "miscible", "miscibility" and the like is not intended to imply that it is intended only for a liquid/liquid mixture. For example, a statement that the additive is miscible with water is not to imply that the additive must be a liquid; the possibility that the additive is a solid is not excluded.
[00092] As used herein, the term "contaminant" refers to one or more compounds intended to be removed from a mixture and is not intended to imply that the contaminant is of no value.
[00093] In this document the term "emulsion" means a colloidal suspension of a liquid in another liquid. Typically, an emulsion refers to a suspension of a hydrophobic liquid (eg oil) in water while the term "reverse emulsion" refers to a suspension of water in a hydrophobic liquid.
[00094] In this document the term "suspension" means a heterogeneous mixture of fine solid particles suspended in the liquid.
[00095] In this document the term "foam" represents a colloidal suspension of a gas in a liquid.
[00096] As used herein the term "dispersion" means a mixture of two components, in which one component is distributed as particles, drops or bubbles in another component and is intended to include the emulsion (i.e., liquid in liquid, liquid , supercritical fluid or supercritical fluid in liquid), suspension (ie solid in liquid) and foam (ie gas in liquid).
[00097] "NMR" means Nuclear Magnetic Resonance. "IR spectroscopy" means infrared spectroscopy. "UV spectroscopy" means ultraviolet spectroscopy.
[00098] The term "DBU" means 1,8-diazabicyclo-[5.4.0]-undec-7-ene. The term "DMAE" means N,N-(dimethylamino)ethanol. The term "MDEA" means N-methyl diethanolamine. The term "TMDAB" means N,N,N',N'-tetramethyl-1,4-diaminobutane. The term "TEDAB" means N,N,N',N'-tetraethyl-1,4-diaminobutane. The term "THEED" means N,N,N',N'-tetrakis(2-hydroxyethyl) ethylenediamine. The term "DMAPAP" means 1-[bis[3-(dimethylamino)]propyl]amino]-2-propanol. The term "HMTETA" means 1,1,4,7,10,10-hexamethyl triethylenetetramine. Structural formulas for these compounds are shown in figure 2.
[00099] The term "waste water" means water that has been used by a domestic or industrial activity and therefore now includes waste products.
[000100] Patent Application Publication No. US 2008/0058549 discloses a solvent that reversibly converts from a mixture of nonionic liquid to an ionic liquid in contact with a selected trigger such as CO2. The nonionic liquid mixture includes an amidine or guanidine or both and water, alcohol or a combination thereof.
[000101] Zhou K., et al., "Review of Polyelectrolyte Dynamics in Diluted Saltless Solutions, Creating and Using a Novel Neutral-Charged Neutral Reversible Polymer" Macromolecules (2009) 42, 71467154, discloses a polymer that can suffer a neutral-charged-neutral transition in DMF with 5% water. The transition between neutral and charged state is achieved by alternately bubbling CO2 and N2 through a mixture containing the polymer. switchable water
[000102] Provided here is a liquid mixture that includes an aqueous component in which the ionic strength can be reversibly varied between a low ionic strength and a high ionic strength, subjecting the mixture to a trigger. Simply put, such aspects provide water that can be reversibly switched between substantially salt-free and salt water, several times with substantially little or no energy input. The term "switchable water" is used in this document to refer to the aqueous component which is pure water mixed with an additive, or an aqueous solution mixed with an additive, in which the additive can alternate between an ionic form and a non-ionic form to increase or decrease the ionic strength of the water or aqueous solution, respectively.
[000103] Traditionally, after a salt was added to water, high energy input was required to recapture the water (eg as salt water had to be heated to its boiling point). Thus, certain aspects of this application provide methods of separating a compound from a mixture by solubilizing the compound in an aqueous solution of a first ionic strength (a switchable water) and then isolating the compound by switching to a solution of a second ionic force. Such methods use non-ionic aqueous solution and ionic liquids. Switchable water can be reused repeatedly in extracting a desired or selected compost.
[000104] Aqueous mixtures including switchable water as described herein are useful for extracting a solute from a mixture, a solution or a matrix. After use in its low ionic strength form, for example for extracting a solute from water soluble, the switchable water is triggered to change to its high ionic strength form to cause precipitation or solute separation. The switchable water can then be reused to return to its low ionic strength form. Extraction solutes are pure compounds or mixtures of compounds. They include the desired contaminants and materials. These solutes can be extracted from various compositions, including, without limitation, soil, clothing, rock, biological material (eg wood, pulp, paper, grain, seeds, meat, fat, bark, grass, crops, skins, natural fibers , corn stalk, oils), water, equipment, or manufactured materials (eg machined parts, molded parts, extruded material, chemicals, refined oils, refined fuels, fabrics, fibers, sheets and as materials, whether made of metal , mineral, plastic, inorganic, organic or natural materials or combinations thereof). Desired solutes to be extracted include, without limitation, medicinal compounds, organic compounds, intermediate compounds, minerals, synthetic reagents, oils, sugars, foods, flavors, fragrances, dyes, pesticides, fungicides, fuels, spices and similar materials.
[000105] Other examples without limitation of selected solutes include the following: plant extracts (eg, lignin, cellulose, hemicellulose, pyrolysis products, leaf extracts, tea extracts, petal extracts, Rosehip extracts, nicotine, extracts of tobacco, root extracts, ginger extracts, sassafras extracts, bean extracts, caffeine, gums, tannins, carbohydrates, sugars, sucrose, glucose, dextrose, maltose, dextrin); other bio-derived materials (eg proteins, creatines, amino acids, metabolites, DNA, RNA, enzymes); alcohols, methanol, ethanol, 1-propanol, 1-butanol, 2-propanol, 2-butanol, 2-butanol, t-butanol, 1,2-propanediol glycerol and the like; products of organic synthesis (eg ethylene glycol, 1,3 propanediol, polymers, polyvinyl alcohol), polyacrylamides, poly(ethylene glycol), polypropylene glycol)); industrially useful chemicals (eg plasticizers, phenols, formaldehyde, paraformaldehyde, surfactants, soaps, detergents, de-emusifying agents, anti-foam additives); solvents (for example THF, ether, ethyl acetate, acetonitrile, dimethylsulfoxide, sulfolene, sulfolane, dimethylformamide, formamide, ethylene carbonate, propylene carbonate, dimethylacetamide, hexamethylphosphoramide); fossil fuel products (eg creosote, coal tar, coal pyrolysis oil components, crude oil, water-soluble components of crude oil); colorants (eg dyes, pigments, organic pigments, stains, mordants); unwanted compounds and mixtures (eg dirt or stains on clothing or equipment).
[000106] Selected compounds that may be suitable for the extraction methods described herein include compounds that are soluble to different degrees in low ionic strength water and high ionic strength water. Certain selected solutes are more soluble in aqueous solutions as described in this document which have low ionic strength and include an amine additive than in pure water. Since the following description is about a reversible chemical reaction that proceeds from low ionic strength to high ionic strength and returns again, over and over, you must choose one of these two states to start the process. However, this choice is arbitrary, and as described below, it is possible to start with the state depending on the specific application. Switchable additive
[000107] The exemplary description below starts with the switchable water of low ionic strength, composed of water and a switchable additive in its non-ionic form which is considerably soluble in water. Switchable water with the non-ionic form of additive has little or no ionic strength. This switchable water can be used as a solvent to dissolve compounds that do not react with the additive. When it is desirable to separate dissolved compounds in non-ionic switchable water, a trigger is applied and the additive is converted to its ionic form. The resulting ionic switchable water has a high ionic strength.
[000108] According to an example, the non-ionic and ionic forms of switchable additive used in this reversible reaction are soluble in water, such that in the case of a liquid mixture they separate into two phases, a hydrophobic phase and an aqueous phase, substantially all of the additive remains in the aqueous layer, no matter whether they are in their non-ionic form or their ionic form. In this example, in contrast to the additive, certain compounds will no longer be soluble in the high ionic strength solution, and they separate into a phase that is distinct from the ionic aqueous phase. This distinct phase may be a pre-existing hydrophobic liquid phase (non-aqueous solvents).
[000109] According to the alternative example, only one ionic form of the switchable additive is soluble in water, such that when the additive is converted into its non-ionic form, two phases are formed, with the non-ionic form of the additive in the eventual phase . The non-aqueous phase can include only the non-ionic form of the switchable additive, or it can include a solvent that is not soluble or miscible with water, such as a pre-existing hydrophobic liquid phase (non-aqueous solvents).
[000110] The switchable additive (also referred to as "additive") is a compound consisting of an amine nitrogen that is sufficiently basic that when it is in the presence of water and CO2 (which form carbonic acid), for example, it becomes protonated . When an aqueous solution that includes a switchable additive is triggered, the reversible additive alternates between two states, a nonionic state, where the amine nitrogen is trivalent and is discharged, and an ionic state, where it is the amine nitrogen protonated, becoming a positively charged 4-coordinate nitrogen atom.
[000111] In this sense, the charged amine group has a negatively charged counterion associated with it in the solution. The nature of the counterion depends on the trigger used and will be described below. Aqueous solution, which comprises the additive in its ionic state, is distinguishable from an aqueous solution, which comprises the compound in its nonionic state, by comparing the ionic strength.
[000112] In certain embodiments, switchable water is composed of water and amine additive that is peralkylated. The term "peralkylated" as used herein means that the amine has alkyl or other groups attached to the nitrogen atoms that are sufficiently basic to be protonated by carbonic acid so that the molecule has no N-H bonds. Amine compounds of formulas (1) and (4) that do not have any N-H bonds are preferred because most primary and secondary amines are able to form carbamate during CO2 switching. Removing carbamate ions from water by heating and bubbling with a stream of gas to switch the salt back into the amine form can be difficult. This is evident in Comparative Example 2, in which it was determined that it was not possible to change certain primary and secondary amine additives in ionic form back to corresponding non-ionic amine forms using low energy input triggers. Thus, carbamate formation is undesirable because it can decrease the efficiency of reversing an ionic solution back to an aqueous amine solution (nonionic form). This concern with the formation of carbamate ions is not relevant if the amine is an aniline (ie, an aryl or heteroaryl group is directly attached to a nitrogen atom); in such a molecule, an N-H bond is not considered to be non-preferred.
[000113] Stable carbamate formation can be reduced considerably by using bulky substituents on primary and secondary amines to provide steric hindrance (Bougie F. and llliuta M.C., Chem Eng Sci, 2009, 64, 153-162 and references cited therein). The steric hindrance allows for easy CO2 desorption. Tertiary amines are preferred as their ionic forms do not include carbamates but are bicarbonate anions. However, in some embodiments, primary and secondary amines that have bulky substituents are preferred because the switching process can be faster than that observed with tertiary amines. As demonstrated in example 22 below, the inventors reasonably expect efficient reversible switching to be possible between nonionic and ionic forms with primary and secondary amines that have bulky substituents. The inventors also reasonably expected that the presence of a small amount of a primary or secondary amine that is capable of forming carbamate, in addition to a switchable additive compound of formula (1), would not inhibit additive switching. In some embodiments, the presence of a small amount of primary or secondary amine can increase the rate of change of the additive between its ionic and non-ionic forms.
[000114] In one embodiment, an additive primary amine can be used. However, reversion from the ionic form of the additive primary amine to the non-ionic form is very difficult to be of practical use in the application where reversion is required. Instead, an additive primary amine can be of great value in situations where additive ionization reversal is unnecessary.
[000115] In another embodiment, an additive secondary amine may be used. As demonstrated in example 22, certain secondary amine additives are reversibly switchable between an ionized and an unionized form.
[000116] Useful additives may include more than one nitrogen center. Such compounds are called, for example, Diamines, Triamines or Polyamines. Polyamines include polymers with nitrogens in the polymer backbone. Polyamines also include polymers with nitrogens in the pendant groups. Polyamines also include polymers with nitrogens in the polymer backbone and nitrogens in the pendant groups.
[000117] Polyamines also include small molecules (ie non-polymers) that have more than one nitrogen atom. Examples of polyamines include poly(vinylamine), poly(N-vinyl-N,N-dimethylamine), poly(allylamine) poly(N-allyl-N,N-dimethylamine), 1,2,3,4,5,6 -hexakis(N,N-dimethylaminomethyl)benzene (eg C6(CH2NMe2)6 ) and 1,2,3,4,5,6-hexakis(N,N-dimethylaminomethyl)cyclohexane (eg C6H6(CH2NMe2) 6).
[000118] An example of a method for preparing polyamine additive includes reacting homopolymers of propylene oxide or ethylene oxide with maleic anhydride under free radical conditions in solution or in solid state to produce graft material. As an alternative to homopolymers, random or block copolymers of propylene oxide and ethylene oxide can be used. Once prepared, the graft material is reacted with a diamine (eg, N 1 , N 1 -dimethylpropane-1,3-diamine) to form an amine additive which is useful as an additive in embodiments of the invention described herein. In some embodiments, the ratios of repeating units of ethylene oxide and propylene oxide of the polyamine are controlled such that, at a given temperature and pressure, the additive in its "deactivated" state is substantially insoluble in water and in its "activated state". " is soluble in water.
[000119] Another example of a method for preparing polyamine additive includes reacting an acrylic acid polymer (or a corresponding ester) with a diamine (eg, N1,N1-dimethylpropane-1,3-diamine) to form the additive through amide bond formation. As an alternative to the acrylic acid polymer, another polymer comprising the carboxylic acid (or a corresponding ester thereof) can be used. An example of such a polymer includes a random or block copolymers of polystyrene and a polymer composed of carboxylic acid. The amide bond is formed, for example, via dehydration, acid chloride reaction, catalytically or similarly. Any primary or secondary amide nitrogen atom can be alkylated to adjust the solubility properties of the additive. In some modalities, proportions of polyamine components are controlled so that, at a given temperature and pressure, the additive in its "deactivated" state is considerably insoluble in water and in its "activated" state, after exposure to CO2 and H2O, is soluble in water.
[000120] In certain embodiments the additive is immiscible or insoluble, or poorly miscible or poorly soluble in water, but is converted by a trigger to a form that is ionic and soluble or miscible with water. The immiscibility or insolubility of the additive in its non-ionized form is advantageous in some applications because the additive can be readily removed from the water, when such removal is desired, by removal of the trigger. TEDAB is an example of an additive that works according to this modality.
[000121] In certain aspects of the invention, the additive is a compound of formula (1),
where R1, R2, and R3 are independently: H; a substituted or unsubstituted C1-C8 aliphatic group which is linear, branched or cyclic, optionally in which one or more of the C alkyl group is replaced by a {-Si(R10)2-O-} moiety up to and including 8 units C, being substituted by 8 units {-Si(R10)2-O-}; a substituted or unsubstituted CnSim group, where neither is independently a number from 0 to 8 and n+m is a number from 1 to 8; substituted or unsubstituted C4-C8 aryl group where aryl is optionally heteroaryl, optionally, in which one or more C is substituted by a moiety {-Si(R10)2-O-}; a substituted or unsubstituted aryl group having from 4 to 8 ring atoms, optionally including one or more {-Si(R 10 )2-O-} moiety, where aryl is optionally heteroaryl; a -(Si(R10)2-O)p- chain in which p is from 1 to 8 which is terminated by H, or is terminated by a substituted or unsubstituted group C1-C8 aliphatic and/or aryl group; a substituted or unsubstituted group C1-C8 aliphatic-C4 C8 aryl group where aryl is optionally heteroaryl, optionally, in which one or more C is substituted by a {-Si(R10)2-O-} moiety; or wherein R10 is a substituted or unsubstituted C1C8 aliphatic, C1-C8 alkoxy, or C4C8 aryl group where aryl is optionally heteroaryl.
[000122] A substituent can be independently: alkyl; alkynyl; alkenyl; aryl; aryl halide; heteroaryl; cycloalkyl (non-aromatic ring); Si(alkyl)3;Si(alkoxy)3; halo; alkoxyl; amino, which includes diamine; alkylamino; alkenylamino; Amide; amidine; hydroxyl; thioether; alkylcarbonyl; alkylcarbonyloxy; arylcarbonyloxy; alkoxycarbonyloxy; aryloxycarbonyloxy; carbonate; alkoxycarbonyl; aminocarbonyl; alkylthiocarbonyl; phosphate; phosphate ester; phosphonate; phosphinate; cyan; acylamino; imino; sulfhydryl; alkylthio; arylthio; thiocarboxylate; dithiocarboxylate; sulfate; sulfate; sulfonate; sulfamoyl; sulfonamide; nitro; nitrile; azide; heterocyclyl; ether; ester; fractions containing silicon; thioester; or a combination of these. Substituents can be substituted. For example, if an amino substituent can be mono or independently disubstituted by additional substituents defined above, such as alkyl; alkynyl; alkenyl, aryl, aryl halide and heteroaryl cyclyl (non-aromatic ring).
[000123] A substituent can preferably be at least one hydrophilic group, such as Si(C1-C4-alkoxy)3, C1-C4-alkoxy, amino, C1-C4-alkylamino, C2-C4-alkenylamino, amino-substituted , C1-C4-alkylamino-substituted, C2-C4-alkenyl amino-substituted amide, hydroxyl, thioether, C1-C4-alkylcarbonyl, C1-C4-alkylcarbonyloxy, C1-C4-alkoxycarbonyloxy, carbonate, C1-C4-alkoxycarbonyl, aminocarbonyl, C1-C4-alkylthiocarbonyl, phosphate, ester phosphate, phosphonate, phosphinate, acylamino, imino, sulfhydryl, C1-C4-alkylthio, thiocarboxylate, dithiocarboxylate, sulfate, sulfate, sulfonate, sulfamoyl, sulfonamide, nitro, nitrile, C1-C4 - alkoxy-C1-C4-alkyl, fractions containing silicone, thioester or a combination thereof.
[000124] In some embodiments, compounds of formula (1) are water miscible or water soluble. In alternative embodiments, compounds of formula (1) are water insoluble or water immiscible, or only partially water soluble or water miscible.
[000125] In certain embodiments, each R1, R2 and R3 can be replaced by a tertiary amine, which is optionally basic enough to become protonated, when in the presence of water and CO2 (which form carbonic acid).
[000126] The present application further provides an ionic solution composed of water and a salt additive of the formula (2) where R1, R2 and R3 are defined for the compound of the formula (1) and E is O, S or a mixture of O and S,

[000127] In some embodiments, a compound of formula (2) is prepared by a method that includes contacting a compound of formula (1) with CO2, CS2 or COS in the presence of water, thereby converting the compound to the salt of formula ( two). In some embodiments, a compound of formula (2) is water soluble.
[000128] Any of R 1 , R 2 , and R 3 of the salt of formula (2) may be optionally substituted as discussed for the compound of formula (1). However, if the optional substituent must include a nitrogen of sufficient basicity to be protonated by carbonic acid, it may be present in its protonated form as it may be protonated by the ionizing trigger. For example, if the optional substituent is an amino group, such as a tertiary amino group, it may exist as a quaternary ammonium moiety in the salt of formula (2).
[000129] The present application further provides a switchable water composed of water and a salt of formula (3). In a preferred embodiment, in the presence of water and CO2, an Amine compound of formula (1) converts to an ammonium bicarbonate, shown as a salt of formula (3), as shown below
where R1, R2, and R3 are as defined above. In some embodiments, a compound of formula (3) is water soluble. There may be some carbonate anions present in addition to bicarbonate anions. If an optional substituent includes a basic nitrogen, it may be present in protonated form if it can be protonated by carbonic acid. For example, if the optional substituent is an amino group, such as a tertiary amino group, it may exist as a quaternary ammonium moiety in the salt of formula (3).
[000130] A water-soluble additive of formula (1) can provide a switchable water that is a single-phase mixture and can function as a solvent for water-soluble substances.
[000131] Although in theory an aqueous solution of the compound of formula (1), in the absence of other water-soluble components will have a zero ionic strength, provided that no charged species is present; in practice, the ionic strength may be small, but greater than zero, due to some dissolved impurities such as air or small amounts of salts. As the ionic strength is small or zero, a switchable water comprising a water miscible compound of formula (1) is particularly useful as a solvent for miscible substances or soluble in aqueous solutions of low ionic strength.
[000132] In some embodiments, both the nonionic additive of formula (1) and the salt additive of formula (2) are soluble in water and can each, therefore, form a single-phase aqueous solution when dissolved in water. This means that the non-ionic compound of formula (1) and salt of formula (2) can remain in aqueous solution as a single phase with water after changeover. Switching a non-ionic switchable water, the compound of the formula (1) comprising an ionic switchable water, which includes the salt of the formula (2) increases the ionic strength of the switchable water. Increasing the ionic strength of switchable water can be used to expel a dissolved substance, which is insoluble in an ionic strength increasing solution without the need for distillation or other energy intensive separation techniques.
[000133] Alternatively, insoluble or poorly water soluble additives of formula (1) can provide a water switchable which is a mixture of two phases. Although theoretically the water from the two-phase mixture, in the absence of other components, will have an ionic strength of zero as long as no charged species is present; in practice, the ionic strength may be small, but greater than zero, due to some dissolved impurities such as air or small amounts of salts. As the ionic strength is small or zero, a switchable water mixture composed of the immiscible or poorly water miscible additive of formula (1) is particularly useful as a solvent for miscible substances or soluble in aqueous solutions of low ionic strength.
[000134] In some embodiments, the nonionic additive of formula (1) is insoluble or sparingly soluble in water, and the salt additive of formula (2) is soluble in water, such that a single phase is formed only when the additive is switched to its ionic form. Switching a non-ionic switchable water, the compound of the formula (1) comprising an ionic switchable water, which includes the salt of the formula (2) increases the ionic strength of the switchable water. In the present embodiment, the fact that the nonionic form of the additive is insoluble or immiscible in water can be useful in situations where it is beneficial to remove the additive from the aqueous phase after changing to the nonionic form.
[000135] Under any modality, the salt of formula (2) can be switched to a non-ionic additive of formula (1) by removing the ionizing trigger, such as CO2, or by adding a non-ionizing trigger. This is advantageous as it allows the reuse of switchable water.
[000136] In certain embodiments, at least one of R1, R2 and R3 may be replaced by one or more tertiary amine groups. For example, R1 can be replaced by a tertiary amine, which can further be replaced by a tertiary amine. Thus, the present invention includes the use of an aqueous solution composed of water and a compound of formula (4), where R2 and R3 are independently as defined for the compound of formula (1);
R5 and R6 are selected independently from the definitions of R1, R2 and R3 of formula (1); R4 is a bivalent bridging group selected from a substituted or unsubstituted group for C1-C8 alkylene group which is linear, branched or cyclic; a substituted or unsubstituted C2-C8 alkenylene group that is linear, branched or cyclic; a substituted or unsubstituted group -CnSim- where neither is independently a number from 0 to 8 and n+m is a number from 1 to 8; a substituted or unsubstituted C5-C8 arylene group optionally containing from 1 to 8 {-Si(R10)2-O-} units; a substituted or unsubstituted heteroarylene group having 4 to 8 atoms in the aromatic ring optionally containing from 1 to 8 {-Si(R10)2-O-} units; the chain -(Si(R10)2-O)p- where "p" is from 1 to 8; a substituted or unsubstituted C1-C8 Alkylene - C5-C8 arylene group optionally containing from 1 to 8 {-Si(R10)2-O-} units; a substituted or unsubstituted C2-C8 alkenylene - C5-C8 arylene group optionally containing from 1 to 8 {-Si(R10)2-O-} units; a substituted or unsubstituted C1-C8 alkylene-heteroarylene group having 4 to 8 atoms in the aromatic ring, optionally containing from 1 to 8 {-Si(R10)2-O-} units; a substituted or unsubstituted C2-C8 alkenylene-heteroarylene group having 4 to 8 aromatic ring atoms, optionally containing from 1 to 8 {-Si(R10)2-O-} units; R10 is a substituted or unsubstituted group of C1-C8 alkyl, C5-C8 aryl, heteroaryl, having from 4 to 8 carbon atoms in the aromatic ring or C1-C8 alkoxy moiety; and "a" is an integer. In some embodiments, compounds of formula (4) are water soluble. Additives with large "a" values are likely to be more effective in increasing ionic strength when they are in their ionic forms, but may suffer from poor water solubility when they are in their nonionic forms. For the avoidance of doubt, it should be noted that when "a"> 0, in a repeating unit -N(R5)-R4-, R4 and R5 may have a different definition from the other such repeating unit.
[000137] In some embodiments, the additive is an oligomer or a polymer that contains one or more of a nitrogen atom that is basic enough to be protonated by carbonic acid in the repeating unit of the oligomer or polymer. In terms of an embodiment, the nitrogen atoms are within the backbone of the polymer. The additive of formula (4) is a specific example of such a polymer in which the nitrogen atom(s) is in the backbone of the polymer. In alternative embodiments, the additive is an oligomer or polymer that contains one or more of a nitrogen atom that is basic enough to be protonated by carbonic acid, in a pendant group, which is part of the repeating unit, but which is not situated along the backbone of the polymer or oligomer. In some embodiments, some or all of the nitrogen atoms that are basic enough to be protonated by carbonic acid are amidine groups. Such amidine groups can be part of the backbone of the polymer or oligomer or can be on pendant groups that form part of the repeating unit.
[000138] Examples of polymer additives having the formulas (5a-f) are shown below. In these formulas, "n" refers to the number of repeating units that contain at least one basic group and "m" refers to the number of repeating units with no basic group. Additives with large "n" values are likely to be more effective in increasing ionic strength when they are in their ionic forms, but may have low water solubility when in their nonionic forms. It is not necessary for the polymer backbone to be made entirely of carbon and hydrogen atoms; in some modalities, the main structure can include other elements. For example, the polymer can have a polysiloxane backbone with amine-containing subgroups, a polyether backbone with amine-containing subgroups, or the backbone can include amine groups. In some embodiments, it is preferred to have a main structure or subgroups that are reasonably hydrophilic or polar. Without wishing to be bound by theory, it is envisioned that a hydrophilic or polar subgroups or backbone may help the charged form of the additive to precipitate.

[000139] R1 can be substituted by a tertiary amine, which can be further substituted by a tertiary amine, according to the compound of formula (4). These tertiary amine sites can be protonated when in contact with CO2, CS2 or COS in the presence of water. Thus, in certain embodiments, the present invention provides an ionic solution composed of water and a salt of formula (4).
[000140] It is evident that when the polymer additive is in its ionized form, in order to balance the positive charges on the quaternary ammonia sites on the cation, a number of anions equivalent to the number of protonated basic sites must be present. For example, in the ionized form of the polymer additive of formula (4), there will be anionic counter ions (a+1) -E3CH for each cation having (a+1) quaternary ammonium sites in the salt of formula (4). Alternatively, some of the -E3CH ions are replaced by anions of the formula CE32-.
[000141] Each of R 1 , R 2 , and R 3 in the compound of formula (1) can be substituted by a tertiary amine which can be further substituted with a tertiary amine. These tertiary amine sites can be protonated when in contact with CO2, CS2 or COS in the presence of water. However, not all Amine compounds having more than one Amine site (ie, polyamines) may be capable of trigger protonation at each Amine site. Thus, Amine compounds of formula (4) cannot be protonated at each tertiary amine site when in contact with CO2, CS2 or COS. Therefore, it should not be assumed that all basic sites must be protonated to effectively increase the ionic strength of switchable water.
[000142] Furthermore, the pKaH (ie the pKa of the conjugate acid (ie the ionic form)) of the Amine compound of formula (1) should not be so high as to yield irreversible protonation. In particular, the ionic form of the additive must be capable of deprotonation through the action of the non-ionizing trigger (which is described below as eg heating, bubbling with gas flow, or heating and bubbling with gas flow). For example, in some embodiments, the pKaH is in a range of about 6 to about 14. In other embodiments, the pKaH is in a range of about 7 to about 13. In certain embodiments the pKaH is in a range from about 7.8 to about 10.5. In some embodiments, the pKaH is in a range of about 8 to about 10.
[000143] Additives useful in a switchable water may have higher aliphatic groups (C5-C8) and/or siloxyl groups. Monocyclic or bicyclic ring structures can also be used. A larger number of aliphatic groups can make the compound waxy and immiscible in water at room temperature. As described above, this can be advantageous if it means that the non-ionic form of the additive is immiscible with water, but the ionic form is miscible with water.
[000144] In certain modalities, the additive is liquid at room temperature.
[000145] It is preferred that the aliphatic and/or siloxy chain length is 1 to 6, more preferably 1 to 4. A siloxy group contains {-Si(R10)2-O-} units; where R10 is a substituted or unsubstituted C1-C8 alkyl-C5-C8 aryl, heteroaryl group having from 4 to 8 carbon atoms in the aromatic ring or C1-C8 alkoxy moiety. Conveniently, in some discussions in this document, the term "aliphatic/siloxyl" is used as a shorthand to encompass aliphatic, siloxy, and a chain that is a combination of aliphatic and siloxy units.
[000146] Optionally the additive is composed of a group that includes an ether or ester moiety. In preferred embodiments, an aliphatic group is alkyl. Aliphatic groups can be substituted with one or more moieties, such as, for example, alkyl, alkene, alkene, aryl, aryl halide, hydroxyl, heteroaryl, non-aromatic rings, Si(alkyl)3, Si(alkoxy)3, halo, alkoxy, amino, ester, Amide, amidine, guanidine, thioether, alkylcarbonate, phosphine, Thioester or a combination thereof. Reactive substituents like alkyl halide, carboxylic acid, anhydride, acyl chloride are not preferred.
[000147] Strongly basic groups like amidines and guanidines may not be preferred if their carbonic acid protonation is difficult to reverse.
[000148] In other embodiments of the invention, substituents are lower aliphatic/siloxy groups and preferably are small and non-reactive. Examples of such groups are lower (C 1 -C 4 ) alkyl groups. Preferred examples of lower aliphatic groups are CH3, CH2CH3, CH(CH3)2, C(CH3)3, Si(CH3)3, CH2CH2OH, CH2CH(OH)CH3 and phenyl. Monocyclic, or bicyclic, ring structures can also be used.
[000149] It is evident that in some embodiments R substituents may be selected from a combination of lower and higher aliphatic groups. Furthermore, in certain embodiments, the total number of carbon and silicon atoms in all R 1 , R 2 , R 3 and R 4 substituents (including optional substituents) of a water soluble compound of formula (1) may be in the range of 3 to 20, more preferably 3 to 15.
[000150] Referring to figure 1, a chemical scheme and schematic drawing are shown for a switchable ionic strength solvent system of a water miscible amine additive of formula (1) and water. The chemical reaction equation shows an additive (non-ionic form), which is an amine composed of formula (1) and water on the left and an ionic form of the additive as an ammonium bicarbonate salt of formula (3) on the right. . This reaction can be reversed as indicated. The schematic diagram shows the same reaction that takes place in the presence of tetrahydrofuran (THF), in which a single-phase aqueous solution of an Amine additive (eg a compound of formula (1)) that is miscible with water, water and THF is shown on the left side under a cloak of N2. A mixture of two phases (layers) is shown on the right side under a blanket of CO2. The two phases, being an aqueous solution of the formula (3) salt composed of THF, ammonium bicarbonate and water.
[000151] Referring to figure 2, structures of a number of compounds of formula (1) referring to figure 2 are provided. DMEA is N,N-(dimethylamino)ethanol, in formula (1) has R1 is methyl; R2 is methyl; and R3 C2H4OH). MDEA is N-methyl diethanolamine, which in formula (1) has R1 is methyl; R2 is C2H4OH; and R3 C2H4OH). Both compounds, DMEA and MDEA, are monoamines having a unique tertiary amine group. TMDAB is N,N,N',N'-tetramethyl-1,4-Diaminobutane, which, in formula (1), has R 1 is methyl; R2 is methyl; R3 is C4H8N(CH3)2). THEED is N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, which in formula (1) has R1 is C2H4OH; R2 is C2H4OH; and R3 C2H4N(C2H4OH)2). Compounds TMDAB and THEED are Diamines, having two tertiary amine groups. Compound DMAPAP is a triamine, having three tertiary amine groups, 1-[bis[3-(dimethylamino)] propyl]amino]-2-propanol, which, in formula (1), has R 1 is methyl; R2 is methyl; and R3 is C3H6N C3H6N(CH2CH(OH)CH3)C3H6N(CH3)2).
[000152] Compound HMTETA is a tetraamine, having four tertiary amine groups, 1,1,4,7,10,10-hexamethyl triethylenetetramine, which, in formula (1), has R 1 is methyl; R2 is methyl; and R3 C2H4N(CH3)C2H4N(CH3)C2H4N(CH3)2). These compounds are discussed further in the working examples.
[000153] Referring to figure 3, several 1H-NMR are found from an MDEA switchability study performed in D2O at 400 MHz. This is discussed in example 4 below.
[000154] Referring to figure 4, several 1H NMR are shown from a DMAE switchability study performed in D2O at 400 MHz. This is discussed in example 4 below.
[000155] Referring to figure 5, several 1H NMR are shown from an HMTETA commutability study performed in D2O at 400 MHz. This is discussed in example 4 below.
[000156] Referring to figure 6, several 1H NMR are shown from a DMAPAP switchability study performed in D2O at 400 MHz. This is discussed in example 4 below.
[000157] Referring to Figure 7, conductivity spectra are shown for the responses to a CO2 trigger over time in the following solutions: 1:1 v/v H2O:DMAE; 1:1 v/v H2O:MDEA; and 1:1 w/w H2O:THEED. Experimental details are discussed in example 5 below.
[000158] Referring to figure 8, conductivity spectra are shown for the responses of 1:1 v/v H2O:DMAE solutions; 1:1 v/v H2O:MDEA; and 1:1 p/p H2O:THEED, which had been changed with a CO2 trigger, for the removal of CO2 by bubbling nitrogen over time. Experimental details are discussed in example 5 below.
[000159] Referring to Figure 9, a representation of the degree of protonation of 0.5 M DMAE and MDEA solutions in D2O and an aqueous 0.1 M THEED solution in D2O resulting from exposure to a CO2 trigger over the course of of time is shown. This is discussed in example 6 below.
[000160] Referring to Figure 10, a representation of the degree of deprotonation of 0.5 M DMAE and MDEA solutions in D2O and a 0.1 M THEED solution in D2O, which was switched with a CO2 trigger, to Trigger removal by nitrogen bubbling over time is shown. This is discussed in example 6 below.
[000161] Referring to Figure 11, Conductivity spectra for 1:1 v/v H2O: Amine solutions to a CO2 trigger over time, where the amine is TMDAB (♦), HMTETA ( ■) and DMAPAP (▲) are shown. This is discussed in example 7 below.
[000162] Referring to figure 12, conductivity spectra for the 1:1 v/v H2O responses: Amine solutions, linked to the removal of the trigger by bubbling with nitrogen over time, where the amine is TMDAB ( ♦), HMTETA (■) and DMAPAP (▲), with a CO2 trigger, are shown. This is discussed in example 7 below.
[000163] Referring to Figure 13, five photographs A-E representing different phases of an experiment showing how the switchable ionic strength characteristic of TMDAB amine additive can be used to interrupt an emulsion of water and n-decanol are shown. This is discussed in example 8 below.
[000164] According to an alternative aspect, the switchable additive is an amidine having the formula (6)
where R1, R2 and R3 are each independently as defined above. The ionized form of the additive in formula (6) is:
where n is a number from 1 to 6 sufficient to balance the overall charge of the cation and amidine, and E is O, S or a mixture of O and S. Ionizing and non-ionizing triggers
[000165] As used here, a trigger is a change that leads to a chemical reaction or a series of chemical reactions. A trigger can be an ionizing trigger, which acts to convert the effect of an additive to its ionic form (eg, protonated), or a non-ionizing trigger, which acts to convert the additive's effect to its non-ionic form (by example, deprotonated).
[000166] As is known to a person skilled in the art, there are several ways to protonate a compound in the presence of water. Likewise, there are several ways to deprotonate a compound in the presence of water. According to some embodiments, an irreversible switch between a non-ionic state (eg Amine deprotonated) and an ionic state (protonated) is sufficient. In terms of other modalities, an irreversible switch between an ionic state (eg, protonated Amine) and a non-ionic state (deprotonated) is sufficient. In preferred embodiments switching between ionic and non-ionic states is reversible. In this regard, the following discussion will describe various triggers.
[000167] An example of a non-ionizing trigger to convert the ionic state (eg Protonated Amine) to the nonionic state (eg Deprotonated Amine) in aqueous solution that has little or no dissolved CO2 is the addition of a base for the aqueous solution. An example of an ionizing trigger to convert the nonionic state (eg, deprotonated amine) to the ionic state (eg, protonated amine) in aqueous solution is the addition of an acid to the aqueous solution.
[000168] The compound of formula (1) can be advantageously converted, in the presence of water, from a water-soluble non-ionic Amine form to the ionic form which is also water-soluble. Conversion occurs when the non-ionic aqueous solution is contacted with an ionizing trigger which is a gas that releases hydrogen ions in the presence of water. Hydrogen ions protonate the nonionic compound amine nitrogen to form a cation and, in the case of a CO2 trigger, bicarbonate anion acts as a counterion and a salt form is generated. This aqueous salt solution is a single-phase ionic aqueous solution. More particularly, the ionic form is an ammonium salt. A person skilled in the art will recognize that a small amount of carbonate anions also form and can act as counter ions for the protonated ammonium cations.
[000169] In the example where the additive is immiscible or insoluble, or poorly miscible or poorly soluble in water, it can be converted, in the presence of water into the ionic form, which is also soluble in water. For example, conversion can occur when the mixture of water and non-ionic additive is in contact with a trigger gas that releases hydrogen ions in the presence of water. Hydrogen ions protonate the amine nitrogen of the nonionic compound to form a cation and, in the case of a CO2 trigger, the bicarbonate anion acts as a counterion and a salt form is formed. This aqueous salt solution is a single-phase ionic aqueous solution. More particularly, the ionic form is an ammonium salt. A person skilled in the art will recognize that a small amount of carbonate anions will also form and can act as counter ions for the protonated ammonium cations.
[000170] As used here, "gases that release hydrogen ions" divide into two groups. Group (i) includes gases that release hydrogen ions in the presence of base, eg, HCN and HCI (water may be present but not required). Group (ii) includes gases that when dissolved in water react with water to release hydrogen ions, eg CO2, NO2, SO2, SO3, CS2 and COS. For example, CO2 in water will produce HCO3- (bicarbonate ion) and CO32- (carbonate ion) and against hydrogen ions, with bicarbonate being the predominant species at pH 7. A person skilled in the art will recognize that group gases (ii) will release a smaller amount of hydrogen ions into water in the absence of a base and will release a greater amount of hydrogen ions into water in the presence of a base.
[000171] Preferred gases that release hydrogen ions are those in which the salt form changes to its non-ionic form (Amine) when the same gas is expelled from the environment. CO2 is particularly preferred. Hydrogen ions produced by dissolving CO2 in water protonate the amine. In such a solution, the counterion for the ammonium ion is predominantly bicarbonate. However, some carbonate ions may also be present in the solution and the possibility cannot be excluded that, for example, two ammonium molecules, each with a single positive charge, associate a carbonate counterion. When CO2 is expelled from the solution, the ammonium cation is deprotonated and therefore converted to its non-ionic form (Amine).
[000172] Of group (ii) gases that release hydrogen ions, CS2 and COS behave in the same way as CO2 such that their reaction with Amine and water is easily reversed.
[000173] However, they are generally not preferred due to their use in conjunction with water and an amine that can cause the formation of highly toxic H2S. In some embodiments of the invention, alternative gases that release hydrogen ions are used in place of CO2, either in combination with CO2 or in combination with each other. Alternative gases that release hydrogen ions (eg, HCI, SO2, HCN) are generally less preferred because of the added costs to be supplied and recaptured if recovery is appropriate. However, in some applications one or more of these alternative gases may be readily available and therefore adding little or no extra cost. Many of these gases or acids generated from their interaction with water are likely to be so acidic that the reverse reaction, ie the conversion of the ammonium salt to the amine form, may not proceed to completion as easily as the corresponding reaction with CO2. Group (i) HCN and HCI gases are less preferred triggers because of their toxicity and because reversibility would likely require a strong base.
[000174] Contacting a water-soluble compound of formula (1) with a CO2, CS2 or COS trigger in the presence of water may preferably comprise: preparing a switchable water, composed of water and a water-soluble additive, of formula (1 ); and contact switchable water with CO2, CS2 or COS trigger. Alternatively, contacting a water-soluble compound of formula (1) with CO2, CS2 or COS in the presence of water may include: first preparing an aqueous solution of CO2, CS2 or COS in water; and thereafter mixing the aqueous solution with a water-soluble additive of formula (1) to form a switchable water. Alternatively, contacting a water-soluble additive of formula (1) with CO2, CS2 or COS in the presence of water may include: dissolving CO2, CS2 or COS in a water-soluble additive of formula (1) which is in a liquid state to provide a liquid; and mixing the non-aqueous liquid with water to form a switchable water.
[000175] Contacting a water-insoluble compound of formula (1) with a CO2, CS2 or COS trigger in the presence of water may preferably comprise: preparing a switchable water, composed of water and a water-insoluble additive, of the formula ( 1); and contact switchable water with CO2, CS2 or COS trigger. Alternatively, contacting a water-insoluble compound of formula (1) with CO2, CS2 or COS in the presence of water may include: first preparing an aqueous solution of CO2, CS2 or COS in water; and thereafter mixing the aqueous solution with a water-insoluble additive of formula (1) to form a switchable water. Alternatively, contacting a water-insoluble additive of formula (1) with CO2, CS2 or COS in the presence of water may include: dissolving CO2, CS2 or COS in a water-insoluble additive of formula (1 ) which is in a liquid state to provide a liquid; and mixing the non-aqueous liquid with water to form a switchable water.
[000176] Depletion of CO2, CS2 or COS from a switchable water is achieved by means of non-ionizing triggers such as: Heating the switchable water; expose switchable water to air; expose switchable water to vacuum or partial vacuum; stir the switchable water; exposing switchable water to a gas or gases with insufficient CO2, CS2 or COS content to convert the non-ionic state to an ionic state; releasing switchable water with a gas or gases with insufficient CO2, CS2 or COS content to convert the non-ionic state to an ionic state; or any combination of these. A gas that releases hydrogen ions can be expelled from a solution by simple heating or by passively contacting an unreactive gas ("gas flow") or with a vacuum, in the presence or absence of heating. Alternatively and conveniently, a gas flow can be employed by bubbling it through the solution actively releasing a gas which releases hydrogen ions from the solution. This shifts the balance from ionic form to non-ionic amine. In certain situations, especially if velocity is desired, gas flow and heat can be employed in combination as a non-ionizing trigger.
[000177] Preferred release gases are N2, air, air that has had its CO2 component substantially removed, and argon. Less preferred release gases are those gases that are expensive to supply and/or recover, as the case may be. However, in some applications one or more release gases may be readily available and therefore add little or no extra cost. In certain cases, the release of gases is less preferred due to their toxicity, eg carbon monoxide. Air is a particularly preferred choice as a discharge gas, where the CO2 level of the air (today commonly 380 ppm) is sufficiently low that an ionic form (ammonium salt) is not retained in its salt form. Untreated air is preferred because it is cheap and environmentally safe. However, in some situations it may be desirable to employ air that has had its CO2 component substantially removed as a non-reactive gas (flux release). By reducing the amount of CO2 in the release gases, less salt or amines can potentially be used. Alternatively, some environments may have air with a high CO2 content and such gas release would not be able to change the ionic form sufficiently to the non-ionic amine form. Thus, it may be desirable to treat such air to remove enough CO2 for use as a trigger.
[000178] CO2 can be supplied from any convenient source, eg a compressed (g) CO2 container or as a product of a chemical reaction without interference. The amines of the invention are capable of reacting with CO2 at 1 bar or less to trigger the switch to their ionic form.
[000179] It will be understood by the person skilled in the art that the regeneration of a water-miscible compound of formula (1) from an ionic aqueous solution of a salt of formula (2) can be achieved by active or passive means. Regeneration can be achieved passively if an insufficient concentration of an ionizing trigger, such as CO2, is present in the environment to maintain the additive in ionic form. In this case, an ionizing trigger such as CO2 could be gradually lost from the aqueous solution by natural release. No non-ionizing triggers such as heating or active contact with gas streams would be required. Heating or contacting the release of gases would be faster, but could be more expensive.
[000180] In the studies described here (see example 7), efficient contact between gas and solution was obtained using a fritted glass apparatus. Heat can be supplied from an external heat source, preheated non-reactive gas, exothermic dissolution of gas in ionic aqueous solution, or an exothermic process or reaction that takes place within the liquid. In early studies, the non-ionizing trigger used to expel CO2 from solution and change its ionic form to Amine was heat. However, CO2 was expelled and the Amina salt was converted by coming into contact with a gas stream, specifically nitrogen. It is also expected that CO2 is expelled from the ionic solution by passively exposing the solution to air.
[000181] In some embodiments the amine additive in its nonionic state is a liquid, in other embodiments the amine additive in its nonionic state is a solid. Whether liquid or solid, they can be miscible or immiscible with water.
[000182] In some embodiments the ionic form of the additive (eg ammonium bicarbonate) is a liquid, in other embodiments the ionic form of the additive is a solid. Whether liquid or solid, they can be miscible or immiscible with water.
[000183] It is not significant whether pure ammonium bicarbonate salt is a solid or a liquid, as long as it is soluble in water that a single phase solution of the ionic aqueous solution is offered. It is evident that at least one molar equivalent of water is needed to react with CO2 to provide carbonic acid to protonate a nitrogen site of the amine group of the compound of formula (1) to form the ammonium cation.
[000184] In embodiments where a pure ammonium bicarbonate of formula (3) is a solid and not a liquid, more than one molar equivalent of water in relation to the number of nitrogen sites must be present in the aqueous solution to ensure complete dissolution of the salt in the ionic aqueous solution. In some embodiments, the amount of water is 1 or more equivalents by weight relative to the compound of formula (1).
[000185] In some embodiments, the molar ratio of water and basic nitrogen sites to the amine capable of protonation is at least approximately equimolar. It is evident to one skilled in the art that when the ionic form is prepared from this mixture, there will still be little or no unreacted reagent(s) and therefore little or no water after conversion to the salt form.
[000186] In other embodiments, the proportion of non-gaseous reactants is greater than equimolar, that is, the number of moles of water is greater than the number of moles of basic nitrogen sites in amine capable of protonation. This provides additional unreacted water, which is not consumed in the switching reaction. This may be necessary to ensure a single-phase liquid mixture if the resulting pure salt is a solid, thus providing a single-phase aqueous solution. In some embodiments, a very high ratio of moles of water to moles of nonionic additive (Amine) is preferred so that the cost of the aqueous solvent can be reduced; it is assumed that the Amine additive is more expensive than water. It is preferable that there is enough water to dissolve the salt formed after the change so that an ionic aqueous solution is obtained.
[000187] If there is insufficient water to solubilize a solid ammonium bicarbonate formed after the changeover, the solubilized non-salt will be present as a precipitate. For example, if the ratio of {moles of water} to {moles of basic nitrogen sites in amine capable of protonation} is equimolar, substantially all of the water could be consumed in a complete switching reaction. If the salt is a solid, rather than an ionic liquid, this solid would form as a precipitate. Formation of the salt as a precipitate may be advantageous in some circumstances because it is easily recoverable, for example, by filtration. Systems and methods that employ switchable water
[000188] As briefly described above, one aspect presented here is a method and system for binding the ionic strength of water or aqueous solution. The method comprises the step of mixing water or aqueous solution with a switchable additive, before, after or simultaneously with the introduction of an ionizing trigger ionizing the switchable additive and consequently increasing the ionic strength of the mixture of water or aqueous solution and switchable additive. Optionally, the method further comprises the step of introducing a non-ionizing trigger to reverse ionization of the switchable additive.
[000189] Also provided is a switchable water system comprising: means for providing a switchable additive comprising at least one nitrogen that is sufficiently basic to be protonated by carbonic acid; means for adding the additive to water or aqueous solution to form an aqueous mixture with switchable ionic strength; means for exposing the water or aqueous solution of an ionizing trigger, such as CO2, COS, CS2 or a combination thereof, to increase the ionic strength of the aqueous mixture with switchable ionic strength; and, optionally, means for exposing the mixture with ionic strength to a non-ionizing trigger, such as (i) heat, (ii) gas release, (iii) a vacuum or partial vacuum, (iv) agitation (v) or any combination thereof, to reform the aqueous mixture with switchable ionic strength. As will be appreciated, the means for exposing the water or aqueous solution to the ionizing trigger can be employed before, after or during the addition of the additive to the water or aqueous solution.
[000190] Figure 21 provides an example of a switchable water system as described above. In the embodiment of the system shown in Figure 21, the system includes means for contacting the non-ionized form of switchable water with the ionizing trigger, which in this example is CO2. Upon contact with the ionizing trigger, reversible switchable water is converted to its ionic form. As also depicted in Figure 21, the system in this example further comprises a means for introducing a non-ionizing trigger for the ionized form of switchable water. In this example, the non-ionizing trigger is air.
[000191] The following is a non-limiting list of applications of systems and methods employing switchable water: 1. In osmosis (either by forward osmosis (FO) or by forward osmosis followed by reverse osmosis (FO/RO)) a. For freshwater production, desalination of seawater or brackish water. B. For partial dehydration of wastewater, process water or other industrial aqueous solutions (waste or a process). Osmosis concentrates the aqueous solution of industrial wastewater/process water and produces a stream of purified water that can be directly recycled or disposed of, or repurified or processed for recycling or disposal. 2. In forcing immiscibility a. for drying (ie, removing water from) organic liquids, forcing the water content in the organic liquid to form a second liquid phase. B. for the recovery of organic liquids from water, forcing the organic content in the water to form a second liquid phase. ç. to force two immiscible aqueous phases to form (for separating water soluble polymers such as polyethylene glycol (PEG) from salts or for concentrating solutions of water soluble polymers such as PEG). 3. On forcing insolubility a. for recovery of a solid compound or compounds (eg an organic product, eg an active pharmaceutical ingredient (API) or a contaminant) from water or an aqueous mixture. The solid compound or more compounds recovered can be the target compound or compounds or a compound or more undesirable compounds (such as contaminants or by-products). This can be useful, for example, after an organic synthesis in water; after extracting an organic in water; for the recovery of proteins from water; for decontamination of contaminated water; to cause a coating, dye or mordant to result from the aqueous solution and coalesce into a solid. B. To adjust the solubility of salts in water (ie the solubility of the salt would be different in ionic switchable water than in non-ionic switchable water). Possibly useful in mining or in separations involving salts. ç. To adjust the division coefficient of solutes between an aqueous phase and a liquid organic phase. Certain systems and methods employing switchable water are useful in catalysis, extractions, product washing, mixture separations, etc. 4. In breaking up dispersions a. to break down emulsions. It can be useful, for example, in the oil industry during or after improved oil recovery, during or after the passage in pipelines of heavy crude oils or bitumen, during or after effluent treatment, in the treatment of waste layers, b . to break the suspensions. It can be useful, for example, for removing suspended solids/particles from water (eg waste water or rain). For example, the present systems and methods can be used in the processing of oil sands and tailings ponds, in mining, in the treatment of mining wastewater, in the processing of minerals and separation, in the treatment of wastewater from other industries. , in latex, preparation, manipulation and precipitation, in emulsion/microemulsion/miniemulsion/suspension/polymerization. In a specific example, the methods and systems can be used to remove fine clay particles from water. ç. to break up foams. It can be useful, for example, in the petroleum industry to suppress foam, in mineral separations, in the treatment of aqueous streams after mineral separations. 5. To cause change of other properties of aqueous solutions a. to modify the density. The density of the ionic form of a switchable water must be different from the density of the non-ionic version. This density change can be useful in separating solid materials such as polymers because some will float and some would sink at each density and modifying the density can allow for the separation of different polymers at different densities. B. To modify conductivity, for example, in sensors, liquid changes. ç. To modify viscosity. The viscosity of the ionic form of a switchable water solution is different from the non-ionic version.
[000192] In specific embodiments, this system and method are used, for example: - to remove water from a hydrophobic liquid or solvent; - removing, or isolating a solute from an aqueous solution; - removing, or isolating hydrophobic liquid or solvent from an aqueous mixture; - to remove salt and/or generate fresh water in a desalination process; - destabilize or interrupt micelles or deactivate a surfactant; - provide a switchable antifreeze, a switchable electrolyte solution, a switchable conductive solution, or an electrical switch; or - provide a CO2, COS, CS2 sensor.
[000193] In an embodiment, there is a method of extracting a selected substance from a starting material that makes up the selected substance. In some embodiments, the selected ingredient is soluble in aqueous solution, which comprises the nonionic form of a switchable water (which includes a nonionic form of switchable additive) with zero or low ionic strength and the selected substance is insoluble in aqueous solution which comprises the ionic form of switchable water (comprising the ionized form of the additive), which has a high ionic strength. For example, the starting material can be a solid impregnated with the selected substance. For another instance, raw materials can be a mixture of selected substance and a hydrophobic liquid. This method of extracting a selected substance is particularly effective if the selected ingredient is soluble in non-ionic aqueous solution. The selected content, which can be a liquid or a solid, dissolves in a non-ionic aqueous solution composed of an additive of formula (1) and thus can be easily separable from any remaining water-insoluble raw materials (by for example by filtration) and can be separated from the hydrophobic liquid (for example by decantation). Once the non-ionic aqueous solution comprising the selected compound is isolated, the selected substance can be separated from the aqueous phase (i.e., "stretch"), converting the non-ionic aqueous solution into the ionic aqueous solution. The selected substance will then separate and can be isolated.
[000194] Using methods and systems described in this document, it is possible to separate certain selected water-soluble compounds from an aqueous solution. Since selected compounds are dissolved in aqueous solution and optionally separated from other non-soluble compounds by, for example, filtration, selected compounds can be isolated from aqueous solution without the need to input a large amount of energy. to boil the water. Conveniently, this separation is done by increasing the ionic strength (amount of charged species) in aqueous solution (more commonly known as "relaunch") resulting in a separation of the selected compound from the distinct aqueous phase. The selected compound can be isolated from the aqueous solution to be decanted or filtered, as appropriate. Thus, an aqueous solution whose ionic strength changes when in contact with an appropriate trigger can dissolve or separate from a selected compound in a controlled manner. Importantly, this reset method is easily reversible, unlike the conventional reset method (eg adding NaCl to water). A system for employing this method includes, in addition to the set of components defined above, means for mechanically separating solids from a liquid mixture.
[000195] In one embodiment, the present invention provides a method of removing water (ie drying) from hydrophobic liquids such as solvents. As described in detail in this document, additives form a salt in the presence of water and CO2, COS or CS2, Consequently, additives added to the wet solvent and an ionizing trigger gas (in any combination) cause all the water that was in the solvent be separated out as a distinct ionic component in an aqueous phase. A system for employing this method includes, in addition to the above set of external components, means for extracting a water-immiscible liquid phase from an aqueous solution.
[000196] A conceptual model of such a system is shown in figure 1, which shows the reversible separation of tetrahydrofuran (THF) from an aqueous solution of a compound of formula (1). This figure shows that when THF is mixed with a nonionic aqueous solution, THF is miscible with the nonionic aqueous solution, providing a single phase. As discussed in working examples 1 and 2, THF was experimentally shown to be miscible with the non-ionic aqueous solution. Furthermore, the THF was isolated from the mixture, switching the additive in the solvent from its non-ionic form to its ionic form (ammonium bicarbonate) in order to increase the ionic strength and force the THF from the aqueous solution.
[000197] Specifically, as discussed in working examples 1 and 2, the aqueous solution was contacted with CO2 to switch the amine to its ammonium bicarbonate form (ionic form), as shown by formula (3). The contact was accomplished by treating a miscible mixture of THF, water and water-soluble amine compound of formula (1) with carbonated water or actively exposing the mixture to CO2. The THF then formed a non-aqueous layer and the ammonium bicarbonate remained in an aqueous phase of increased ionic strength ("water+salt (3)"). The aqueous and non-aqueous layers are immiscible and have formed two distinct phases, which can be separated by settling, for example. Once separated, the non-aqueous and aqueous layers provide an isolated non-aqueous phase comprising THF and an isolated aqueous phase comprising the ammonium bicarbonate form of additive in the switchable solvent. In this way, the solvent is separated from THF without distillation. While it is unlikely that every single THF molecule will be forced out of the aqueous phase, most of the THF could be forced out by this method. The amount of THF remaining in the aqueous phase will depend on several factors, including the nature and concentration of the additive, temperature, effect of other species in solution, amount of CO2 (or other gas(es) that release(s) ) protons in water) in water and the number of basic sites in the additive that are protonable by carbonic acid.
[000198] The ammonium bicarbonate salt of formula (3) in the aqueous phase was switched back to its non-ionic form. The aqueous salt solution (3), which has been switched to a non-ionic aqueous solution, can then be used to dissolve or extract more THF.
[000199] Note that the capacity of the liquid mixture of water and amine additive (eg compounds of formula (1)) to dissolve a selected compound may be greater than the capacity of pure water to dissolve the same selected compound, as the additive can help the desired compound to dissolve in the aqueous solution. This may be due to an amine polarity reducing effect, because of preferential solvation of the desired compound molecules by the additive amine molecules, and/or because of a bridging miscibility effect in which the addition of a polarity compound Intermediate increases the mutual miscibility between a low polarity liquid and a high polarity liquid.
[000200] When aqueous solutions with switchable ionic strength are alternated between their low ionic strength state and their high ionic strength state, the characteristics of the solution are changed. Such characteristics include: conductivity, melting point, boiling point, ability to dissolve certain solutes, ability to dissolve gases, osmotic pressure, and may also be a change in vapor pressure. As discussed in this document, the switchable ionic strength also affects surfactants, altering their critical micelle concentration and affecting their ability to stabilize dispersions. Variation of such characteristics can be used, for example, the reversibly switchable ionic strength solution can be a reversibly switchable antifreeze, a reversibly switchable electrolyte solution or a reversibly switchable conduction solution.
[000201] Another aspect provides a non-ionic switchable water mixture that is largely non-conductive (or only weakly conductive) of electricity, that it becomes more conductive when it is converted to its ionic form, and that this change is reversible. This difference in conductivity would allow the mixture to serve as an electrical switch, as a switchable medium, as a CO2, COS or CS2 detector, or as a CO2, COS or CS2 presence sensor, This ability of the ionic liquid to conduct electricity it can have applications in electrochemistry, in liquid switches and in detectors and/or sensors. Common, affordable CO2 sensors are typically effective at 2 to 5% CO2, CO2 sensors that work at 2 to 100% are generally large and prohibitively expensive. A chemical method based on switchable ionic strength solutions can cost much less.
[000202] A method for maintaining or interrupting the miscibility of two liquids is further provided, wherein the first liquid is miscible in water of low ionic strength, but is not miscible in water of high ionic strength and the second liquid is the aqueous solvent of reversibly switchable ionic strength described in this document. In a mixture of the first and second liquids, these are miscible when the switchable solvent is in its non-ionic form. To stop miscibility, a trigger is applied, causing the ionic strength of the switchable solvent to increase and newly immiscible liquids to separate.
[000203] Alternatively, the first liquid can be a liquid that is miscible in aqueous solutions of high ionic strength and immiscible in aqueous solutions of low ionic strength. In that case, the ionic and non-ionic forms of the switchable solvent must be used to maintain and disturb the miscibility, respectively.
[000204] Another aspect provides a method of deactivating surfactants. Surfactants (also known as detergents and soap) stabilize the interface between hydrophobic and hydrophilic components. In aqueous solutions, detergents act on clean oily surfaces and clothing producing oil (hydrophobic) more water-soluble (hydrophilic) by its action at the oil-water interface. Once the cleaning work is completed, soapy water with hydrophobic contaminants remains. To recover oil from soapy water, salt can be added to the water and most of the oil will separate from the salt water. With the switchable ionic strength aqueous solution of the present invention, after a cleaning job, the oil can be recovered from the solution with soapy water just by applying a trigger to reversibly increase the ionic strength of the solutions. The trigger causes the ionic strength to increase, thereby deactivating the surfactant. Many surfactants are unable to function properly (effectively stabilize dispersions) under conditions of high ionic strength. The oil is then separated from the aqueous phase and can be decanted away. The aqueous solution can be fired to reduce ionic strength. Regenerated soapy water can be reused, over and over.
[000205] Another aspect provides switchable water of switchable ionic strengths that is used to stabilize and destabilize emulsions, which may include stabilized surfactant emulsions. Oil and water emulsions that include surfactants are used in the oil industries to control viscosity and transport of oil (as an emulsion) through pipelines. Once the emulsion has been transported, however, it is convenient to separate the supported surfactant emulsion and recover the oil which is substantially free of water. In its non-ionized form, the amine additive does not significantly interfere with the stability of an emulsion of water and a non-water miscible liquid (eg, hexane, crude oil). However, once its ionic form has changed, the increase in the ionic strength of the solution interferes with the stability of the emulsion, resulting in a break in the emulsion. In surfactant-stabilized emulsions, the high ionic strength solution can interfere with the surfactant's ability to stabilize the emulsion. This reversible switch from lower to higher ionic strength is preferable over destabilizing emulsions by traditional means (ie, increasing ionic strength by adding a traditional salt such as NaCl). This preference is due to the increase in ionic strength caused by the addition of a traditional salt that is difficult to reverse without a large input of energy.
[000206] Creating an emulsion it is possible, for example, to add a non-water miscible liquid to the switchable aqueous solution of low ionic strength as described above, to form two phases. Then, a surfactant that is soluble in the aqueous phase must be added at a concentration above the critical micelle concentration of the surfactant. Shearing or stirring the mixture then creates an emulsion. As discussed above, the resulting emulsion can be destabilized by treatment with an ionizing trigger, such as bubbling in CO2, COS or CS2 to increase the ionic strength of the aqueous phase. Further removal of CO2, COS or CS2 by treatment with a non-ionizing trigger, such as bubbling the mixture with a discharge gas and/or heating to lower ionic strength, allowing the system to return to initial conditions.
[000207] Non-limiting examples of emulsions include mixtures of water with: crude oil; crude oil components (eg gasoline, kerosene, bitumen, pitch, asphalt, coal-derived liquids); oil (including oil derived from the pyrolysis of coal, bitumen, lignin, cellulose, plastic, rubber, tires or waste); vegetable oils; seed oils; nut oils; linseed oil; tung oil; Castor oil; canola oil; Sunflower oil; safflower oil; peanut oil; Palm oil; coconut oil; rice bran oil; fish oils; animal oils; tallow; or tallow. Other non-limiting examples of emulsions include water with colloidal particles, colloidal catalysts, colloidal pigments, clay, sand, minerals, soil, fine coal particles, ash, mica, latex, paints, nanoparticles including metallic nanoparticles, nanotubes.
[000208] Another aspect provides aqueous solutions of switchable ionic strength, or switchable water, which are used to stabilize and destabilize the reverse emulsions.
[000209] A suspension is a finely divided solid that is dispersed but not dissolved in a liquid. In one aspect of the invention, aqueous solutions of switchable ionic strength are used to stabilize and destabilize the suspension of solids in water, which may include stabilized surfactant suspensions. In its non-ionized form, the additive amine does not interfere with suspension stability. However, once the additive is switched to its ionic form, the increased ionic strength can significantly destabilize a suspension and/or can inhibit the ability of a surfactant to stabilize a suspension, resulting in the coagulation of solid particles. This reversible switch from lower to higher ionic strength is preferable to destabilize the suspension by adding traditional salts (eg NaCl), because the increase in ionic strength caused by adding a traditional salt is difficult to reverse without a large input of energy. Typical examples of such suspensions can include polymers (eg polystyrene), colloidal dyes and nanoparticles, including metallic nanoparticles. Increasing the ionic strength of the solution by applying a trigger causes small solid particles to aggregate or clot to form larger particles that are deposited at the bottom of the solution. Applying a trigger to convert from higher ionic strength to lower ionic strength (eg CO2 removal) allows for the redispersion of particles, regenerating the suspension.
[000210] In an alternative aspect, aqueous solutions are provided, comprising switchable water of switchable ionic strength which are used to stabilize and destabilize the foam (ie gas in liquid), which may include stabilized surfactant foams. In its non-ionized form, the switchable additive does not interfere with foam stability. However, once the additive is switched to its ionic form, the increase in ionic strength interferes with foam stability and/or inhibits the surfactant's ability to stabilize a foam, resulting in foam breakage. This reversible switch from lower to higher ionic strength is preferable for destabilizing foams by adding a traditional salt (eg NaCl) because the increase in ionic strength caused by adding a traditional salt is difficult to reverse without a large input of energy .
[000211] A gas in the liquid emulsion may exist in an aqueous solution of low ionic strength that includes an amine additive. When a trigger is applied to increase the ionic strength of the solution, the foam is destabilized. Applying a trigger to convert it from the high ionic strength solution to the low ionic strength solution causes a newly generated foam to be stabilized in the solution. In this situation, a non-ionizing trigger to release CO2, COS or CS2 would preferably be the application of a discharge gas (eg N2, Ar). In one embodiment of the method of separating the solute from an aqueous solution, instead of separating the solute into a pure form, it is possible to add a non-water miscible liquid (eg n-octanol) to the mixture. In the form of low ionic strength, the solute has a certain partition between the aqueous phase and the hydrophobic phase. With the application of a trigger, the aqueous phase converts to a high ionic strength solution, which causes more solute to partition into the hydrophobic phase. In this modality, instead of the solute, forming its own phase, the solute is dissolved in the hydrophobic phase. If desired, another trigger (eg CO2 removal) reduces the ionic strength, allowing the solute to return to the aqueous phase. A system for employing this method would include, in addition to the components described above, means for providing the water-immiscible liquid and means for extracting a water-immiscible liquid phase from an aqueous solution.
[000212] In another aspect, switchable ionic strength aqueous solutions are provided which are used to create two-phase aqueous/aqueous systems. A low ionic strength aqueous solution with amine additive and a water soluble polymer (eg poly(ethylene glycol) exists as a single phase. With the application of a trigger, the aqueous phase converts to a high solution ionic strength, which causes the mixture to form two separate phases. Specifically, the phases are polymer and water it carries with it as it is quite soluble in water and high ionic strength aqueous solution. If desired, another trigger (by eg removal of CO2) reduces the ionic strength, causing the system to recombine into a single aqueous phase.
[000213] In an embodiment of this aspect, there are two solutes in the aqueous solution of switchable ionic strength that comprises a water-soluble polymer (eg poly(ethylene glycol). The two solutes can be, for example, two different proteins. Each protein will separate from the high ionic strength aqueous solution (ie, "sink into a layer of salt") with a distinct and specific ionic strength. If a trigger increases the ionic strength of the switchable solution so that only one of the two proteins separates from the high ionic strength aqueous phase, the one protein will partition in the water and water soluble polymer layer so that it is separated from the other protein. As described above, with another trigger to reduce ionic strength, the aqueous solution can be used over and over again.
[000214] In another embodiment of this aspect, a solute can partition from the aqueous solution of high ionic strength in water with the water-soluble polymer layer in the form of a solid.
[000215] Another aspect of the invention is a method of drying hydrophobic liquids, separating the hydrophobic liquid from its water contaminants. As described in this document, this separation is accomplished by the addition of an additive that forms a salt in the presence of water and CO2, COS or CS2. The salt can be isolated from the hydrophobic liquid by eliminating its contaminants from the water. Non-limiting examples of hydrophobic liquids include solvents, alcohols, mineral oils, vegetable oils, fish oils, seed oils.
[000216] Yet another aspect of the invention provides a method for reversibly reducing a boiling point of an aqueous solution. Another aspect of the invention provides a method of reversibly increasing a boiling point of an aqueous solution.
[000217] Another aspect of the invention provides a method to reversibly reduce the boiling point of the aqueous solution. Another aspect of the invention provides a method of reversibly raising the boiling point of an aqueous solution.
[000218] One aspect of the invention provides a reversibly switchable antifreeze.
[000219] One aspect of the invention provides a reversibly switchable electrolyte.
[000220] In preferred embodiments, the conversion of the compound of formula (1) into the salt is complete. In certain embodiments, the conversion to salt is not complete; however, enough of the amine is converted to the salt form to change the ionic strength of the liquid. Similarly, in some embodiments, the conversion of the ionic form of the amine compound of formula (1) which is miscible with water may not be complete; however, a sufficient amount of salt is converted to the amine compound of formula (1) which is miscible with water to reduce the ionic strength of the solution.
[000221] An advantage of switchable water described in this document is that it can facilitate syntheses and separations, eliminating the need to remove and replace the water or aqueous solution after each reaction step. With triggers that are capable of causing a drastic change in the ionic strength of the water or aqueous solution while still in the reaction vessel, it is possible to use the same water or aqueous solution for multiple consecutive reaction steps or separation. This would eliminate the need to remove and replace the solvent water or aqueous solution. For example, a chemical reaction that requires an aqueous solvent can be carried out using switchable water while in its amine form as the solvent. When the reaction is complete, the solvent may switch to its high ionic strength form substantially incapable of dissolving a product and/or a side product of the reaction. This would force the product to precipitate if solid or become immiscible if liquid. The solvent could then be separated from the product by physical means, such as, for example, filtration or decantation. The solvent could then be returned to its low ionic strength form, switching the ionic form to the water miscible amine and reused. This method allows the use of an aqueous solvent without the need for an energy intensive distillation step to remove the solvent. Such distillation steps can be complex as the solvent and product can have similar boiling points.
[000222] The reuse and recycling of solvents of the invention provide economic benefits. The time required to switch solvents between high and low ionic strength is short, as demonstrated by studies described in examples 6 and 7, In example 6, an incomplete switch between additive in ionic form and non-ionic form can occur within 300 minutes with heating . Example 6 also shows that in excess of about 90% of the ionic forms of MDEA and THEED were converted back to their non-ionic forms. THEED was 98% deprotonated after 120 minutes of heating (75°C) and bubbling with N2 using a single needle. As shown in figure 12 and described in example 7, the conductivity of TMDAB was reduced by approximately 95% in 90 minutes when heated to 80°C and N2 was bubbled through a glass filter. This result demonstrated a dramatic reduction in ionic strength.
[000223] It is advantageous to convert amine from non-ionic form to ionic form and then return again (or vice versa). The solvent comprising water and additive in its amine form could be miscible in another liquid, and then the solvent could be switched to form of increased ionic strength to allow separation of the two resulting liquid components. Liquid components may or may not appear as distinct layers. Methods of separating the components may include decanting, or centrifugation followed by decanting. After separation, it is desirable to convert an ionic form of the additive back to its non-ionic amine form in water. In this way, the solvent can be reused.
[000224] According to a specific embodiment, a system is provided, as shown in figure 22, to isolate or purify one or more compounds from a mixture. The system includes a means 10 for introducing switchable non-ionic water to a mixture of compounds. In this example, the first compound is miscible in the non-ionic form of switchable water and the second compound is insoluble. In this sense, the system further comprises means 20 for mechanically collecting the second compound which is insoluble in switchable non-ionic water. For example, the system may include means for collecting or removing the second compound by filtration, thereby leaving a mixture 30 that includes non-ionic switchable water and the first compound. The system shown in Figure 22 further comprises means for contacting the mixture 30 with an ionizing trigger (e.g. CO2) to increase the ionic strength of the switchable water and generate a two-phase mixture 40 wherein the first compound does not it is more miscible in switchable water. The system shown in Figure 22, furthermore, comprises means 50 for collecting the first non-miscible compound. For example, the system can include means for decanting or otherwise collecting the surface layer of the mixture 40, wherein the top layer includes the first compound. Optionally, this system additionally includes means for reversing the increase in ionic strength of switchable water by introducing a non-ionizing trigger, such as air, to reform the non-ionic form of switchable water 60,
[000225] Switchable water can also be useful in water/solvent separations in two-phase chemical reactions. The separation of a liquid from a switchable solvent can be accomplished by switching the switchable solvent to its high ionic strength form. This ability to separate solvents can be useful in many industrial processes where, upon completion of a reaction, the solvent can be switched to its high ionic strength form with the addition of a trigger allowing for easy separation of the two distinct phases. Thus, a switchable ionic strength solvent can be used in its low ionic strength form as a medium for a chemical reaction. Upon completion of the reaction, the chemical is easily separated from the solution, switching the solvent to its high ionic strength form. Switchable water solvent can be recovered and reused.
[000226] To obtain a better understanding of the invention described in this document, the following examples are set forth. It should be understood that these examples are for illustrative purposes only. Therefore, they shall not limit the scope of this invention in any way.
[000227] In the following working examples, a variety of tertiary amines have been studied for their properties, such as switchable additives in aqueous solutions of switchable ionic strength (ie switchable water).
[000228] The results presented in the working examples, figures and tables show that six tertiary amines, selected from monoamines, diamines, triamines and tetraamines exhibited reversible switching ionic strength procedure. All these compounds were miscible in water, in aqueous solution and in the presence of CO2 for ammonium bicarbonate salt forms that were soluble in the aqueous phase.
[000229] Variations to the structure of these amine compounds are well within the skill of the person skilled in the art with reference to the invention. These include small substitutions, varying the length of a hydrocarbon chain, and the like.
[000230] As described in the working examples, various salts of formulas (2) and (3) and polyamines were formed according to the invention by reacting CO2 with aqueous solutions of water-miscible amine compounds of formulas (1) and ( 4). The water system advantageously provides a rapid reaction rate to form the ammonium bicarbonate compounds from water-miscible compounds of formulas (1) and (4) and allows the dissolution of the ammonium bicarbonate compounds to be solid at the separation temperature. . WORK EXAMPLES
[000231] The following compounds were used when received: ethanolamine, 2-(methylamino)ethanol, chloroform-d (99.8+ atom%d), D2O (99.9+ atom%d), acetonitrile-d3 (99, 8+ atom%d), methanol-d4 (99.8+ atom%d), 1,4-dioxane (99+%), DMAE, MDEA, TMDAB, THEED, DMAPAP and HMTETA (Sigma-Aldrich of Oakville, Ontario , Canada, "Aldrich" or TCI of Portland, Oregon, USA); THF (99+%) and ethyl acetate (99.5+%) (Caledon Laboratories, Ontario, Canada); hydrochloric acid (~12M, Fischer Scientific, Ottawa, Ontario, Canada); and DMSO-d6 (99.9+ atom%d) Cambridge Isotope Labs, St Leonard, Canada).
[000232] Diethyl ether was purified using a dual column solvent purification system (Innovative Technologies Incorporated, Newbury Port, USA). Compressed gases were from Praxair (Mississauga, Ontario, Canada): grade 4.0 CO2 (99.99%), grade 5.0 Air (99.999%), supercritical grade CO2 (99.999%, H2O < 0.5 ppm), nitrogen (99.998%, H2O < 3 ppm) and argon (99.998%, H2O < 5 ppm).
[000233] Unless otherwise specified, the water used in the studies described in this document was municipal tap water from Kingston, Ontario, Canada which was distilled by reverse osmosis and channeled through a MilliQ Synthesis A10 apparatus (Millipore SAS, Molsheim , France) for further purification.
[000234] DBU (Aldrich, Oakville, Ontario, Canada, 98%) grade was dried by refluxing over CaH2 and distilled under reduced pressure over 4Â molecular sieves and then deoxygenated by repeated cycles of freeze/vacuum/thaw or by bubbling CO2 followed by filtration to remove any bicarbonate precipitate.
[000235] The 1H NMR and 13C NMR spectra were collected at 300 K in a Bruker AV-400 spectrometer at 400.3 and 100.7 MHz, respectively. Comparative Example 1: amidine and water system
[000236] Bicyclic amidine DBU (1,8-diazabicyclo-[5,4,0]-undec-7-ene), having the following structure, was investigated as an additive to provide aqueous solutions of switchable ionic strength.

[000237] DBU in the form of nonionic amidine was soluble in water to provide a single-phase aqueous solution. It was found to be able to switch to a water-soluble amidinium bicarbonate salt form in the presence of water and a CO2 trigger.
[000238] Initial experiments with a solution of DBU in water confirmed that compounds of THF and 1,4-dioxane were miscible in the aqueous solution of DBU (nonionic form) in the absence of CO2 and immiscible in the aqueous solution in the presence of CO2 in that the amidine has been switched to its ionic form of amidinium bicarbonate. However, it was found that it was not possible to release CO2 from the ionic solution with moderate heating. The two-phase mixture of non-aqueous THF and non-aqueous amidinium bicarbonate generated from exposure to CO2 could not be converted into a single-phase aqueous solution of DBU (non-ionic form) and THF.
[000239] Specifically, a 1:1:1 (v/v/v) mixture of DBU, water and compound was added to a six drachma flask with a magnetic stirrer and equipped with a rubber septum. To introduce gas into the solution, a single narrow gauge steel needle was inserted and gas was bubbled through without interruption. A second narrow gauge steel needle was added to allow venting of the gas phase.
[000240] When the compound was THF, a mixture of miscible liquids in a single phase was observed. After CO2 had been bubbled through the solution for 15 minutes, the mixture was separated into two phases, an aqueous phase, which includes a DBU amidinium bicarbonate salt solution and a non-aqueous phase comprising THF. Bubbling N2 through the mixture for several hours at 50°C caused the phases to recombine.
[000241] Similarly, a 1:1:1 (v/v/v) mixture of DBU, 1,4-dioxane, was found to be a mixture of single-phase miscible liquids. After CO2 has been bubbled through the solution for 60 minutes, the mixture is separated into two phases, an aqueous phase comprising an amidinium bicarbonate salt solution of DBU and a non-aqueous phase comprising 1,4-dioxane. Bubbling N2 through the mixture for several hours at 50°C caused the phases to recombine.
[000242] Thus, although an aqueous solution of amidine DBU can be switched from a low ionic strength form to a high ionic strength form to force THF or 1,4-dioxane out of solution, the change was not found be reversible under certain experimental conditions. It is likely that with high energy input, such as high temperatures, reversibly switchable switching is possible. Comparative Example 2: primary and secondary amine systems and water
[000243] A primary amine, ethanolamine, and a secondary amine, 2(methylamino)ethanol were investigated as additives to provide aqueous solutions of switchable ionic strength. A six drachma vial comprising 3:3:1 (v/v/v) mixtures of H2O, amine, and compound were prepared as described by comparative example 1.
[000244] A 3:3:1 (v/v/v) mixture of H2O, ethanolamine, and THF showed a single phase solution. This solution separated into two phases after CO2 has been bubbled through the liquid mixture for 30 minutes, with an aqueous phase and a non-aqueous phase comprising THF. However, the two separate phases were not recombined into a miscible layer even after N2 had been bubbled through the liquid mixture for 90 minutes at 50°C.
[000245] A 3:3:1 (v/v/v) mixture of H2O, ethanolamine, and DMSO was found to be a single phase solution. This solution was not separated into two phases after CO2 had been bubbled through the liquid mixture for 120 minutes, however, turbidity was observed.
[000246] A 3:3:1 (v/v/v) mixture of H2O, 2-(methylamino)ethanol, and THF, a single phase solution was observed. This solution separated into two phases after CO2 has been bubbled through the liquid mixture for 10 minutes, with an aqueous phase and a non-aqueous phase comprising THF. However, the two separate phases were not recombined in a miscible layer until N2 had been bubbled through the liquid mixture for 90 minutes at 50°C.
[000247] Thus, in preliminary studies, certain additives of primary and secondary amines do not show reversibly switchable ionic strength character. Although switching from low ionic strength to high ionic strength, they have not been successfully switched from high to low ionic strength forms using the low energy input conditions of bubbling N2 through mixing liquids for 90 minutes at 50°C. Note that the higher temperatures were not used due to the limitation represented by the THF boiling point of 66°C. N2 bubbling at a higher temperature may have led to the reverse reaction; however, THF evaporation would have been a problem. While not intended to be bound by theory inventors suggest that this irreversibility may be as a result of carbamate formation resulting from the reaction of available NH groups on primary and secondary amines with CO2, Removal of carbamate ions in water to provide nonionic amines heating and bubbling a non-reactive gas can be difficult. Example 1: Reversible Solvent Switching in Tertiary Amine/Water Systems
[000248] Three tertiary amines, DMAE, MDEA and THEED were investigated as additives for switchable ionic strength solutions. DMAE and MDEA are monoamines and THEED is a diamine.
[000249] A six drachma flask containing a magnetic stirrer and equipped with a rubber septum were prepared with 1:1:1 w/w/w solutions of water, THF and a tertiary amine compound additive of formula (1) . To introduce gas into the solution, a single narrow gauge steel needle was inserted and gas was bubbled through without interruption. A second narrow gauge steel needle was added to allow venting of the gas phase.
[000250] The solutions were tested for the character of switchable ionic strength by bubbling CO2 through mixtures. The time taken to observe the separation of THF from the aqueous solution of ionic bicarbonate salt was recorded and is shown in table 1. It was determined that it normally takes 30 minutes of bubbling with CO2 to separate THF from the aqueous phase.
[000251] After separating the THF into a distinct non-aqueous phase it was observed that nitrogen was then bubbled through two-phase solutions at a temperature of 50°C to remove CO2 from the aqueous phase and at least a part of the form of Ionic bicarbonate salt returned to the non-ionic tertiary amine form. If the switching reaction was sufficiently reversible to reduce the ionic strength of the aqueous phase to a level that allows for miscibility with THF, conversion of the two-phase mixture to a single aqueous phase has been observed.
[000252] As shown in table 1, all tested tertiary amine additives could be switched back from their ionic forms allowing recombination of the two-phase mixtures to a single phase. Example 2: Quantitative determination of compound and additive separation until switching
[000253] The three switchable aqueous solution systems of example 1 were further investigated by 1H NMR spectroscopy to quantify the amount of THF separated from the aqueous phase until additive switching to its high ionic strength ammonium bicarbonate form and quantify the amount of additive retained in the aqueous solution after switching.
[000254] To measure the degree of THF, being forced out of an aqueous phase by an increase in ionic strength and the amounts of amine, which remained in the aqueous phase, 1:1:1 w/w/w solutions of water, THF, and amidine additive were prepared in graduated beakers and the beakers were covered with rubber septa. After 30 minutes of bubbling CO2 through the liquid phase at a flow rate of 3 to 5 ml. min-1) measured by J&W Scientific ADM 2000 Intelligent Flow Meter, from a single narrow gauge steel needle a visible phase separation was observed. The volumes of each phase were recorded. Aliquots of the aqueous and non-aqueous layers were taken and dissolved in d3-acetonitrile in NMR tubes. A known amount of ethyl acetate was added to each NMR tube as an internal standard.
[000255] 1H NMR spectra were acquired on an AV-400 Bruker NMR spectrometer at 400.3 MHz for several repeated solutions of each mixture, and through the integration of ethyl acetate standard, a concentration of THF or additive was calculated and sized to reflect the total volume of the aqueous or non-aqueous phase providing a percentage of the compound being forced out or retained. The results are shown in table 2,
[000256] The choice of tertiary amine additive was found to determine the amount of THF separated from the aqueous phase after switching with CO2, as shown in table 2. When the tertiary amine was MDEA, 74 moles of THF were separated from the aqueous phase after CO2 bubbling through the solution, while 90.7 mols of the additive (in ionic form) were kept in the aqueous phase.
[000257] In some embodiments, it is preferable that substantially all of the additive remains in the aqueous phase, rather than entering the non-aqueous phase. This is because the usefulness of such solutions as reusable solvent systems would be increased if losses of the additive from the aqueous phase could be minimized. In the case of MDEA, 90.7 mols of MDEA remained in the aqueous phase. Thereby, 9.3 mols of MDEA were transferred to the non-aqueous phase comprising THF. Interestingly, THEED had the best retention of the aqueous phase at approximately 98.6 moles, although it was less successful in forcing about 67.7 moles of THF out of solution.
[000258] Subsequent bubbling of N2 through the mixture reduced the ionic strength and allowed the THF and aqueous phases to become miscible and to be recombined. At 50°C, it took about 30 minutes for the MDEA/THF/water mixture (table 1). The recombination rate would increase at higher temperatures, but this was not attempted in this case because of the low boiling point of THF (boiling point 66°C).
[000259] These experiments were also conducted using air instead of nitrogen as non-reactive gas to expel CO2 from the aqueous solution and switch at least a part of an additive from ionic form to non-ionic form. The time required for recombination of the aqueous and non-aqueous phases was approximately the same for air as it was for N2 for each additive. Example 3: Quantitative determination of compound and additive separation after switching with different additive loads
[000260] Reversible solvent switching in amine/water systems was explored for different loads of five additives, keeping the THF:water ratio at a constant 1:1 w/w. The additives were all tertiary amines, selected from monoamines DMAE and MDEA, diamine TMDAB, triamine DMAPAP and tetraamine HMTETA.
[000261] To measure the degree of THF being forced out of an aqueous phase by an increase in ionic strength, and the amounts of amine that remained in the aqueous phase, 1:1 w/w water:THF solutions were prepared in beakers graded and the appropriate amount of amine additive added. The graduated beakers were covered with rubber septa. This comparison involved bubbling CO2 through a single narrow gauge steel needle for 30 minutes at a rate of 3 to 5 ml. min-1 as measured by a J&W Scientific ADM 2000 Intelligent Flow Meter to switch tertiary amine in aqueous solution with THF to ionic form. A second narrow gauge steel tube was provided to vent the gas phase. A visible phase separation into two liquid phases occurred, resulting in a non-aqueous and an aqueous phase. Aliquots of the aqueous and non-aqueous layers were taken and mixed with a known amount of ethyl acetate to act as an internal standard and the amounts of THF and additive were quantified by integration of 1H NMR as discussed in example 2. The results are shown in table 3,
[000262] It is evident that an increase in additive loading generally resulted in an increase in THF separated from the aqueous solution after switching, as would be expected. It can also be seen that the diamine compound TMDAB at a loading of 9% by weight (ie 5:5:1 THF:H2O:amine) forced 87% of THF out of the aqueous phase after switching while 99.6% of the additive were retained in the aqueous phase. Even with a 3% by weight charge of TMDAB (15:15:1 THF:H2O:amine), 74% of the THF was forced out after switching. In comparison, the monoprotonated additives DMAE and MDEA were only effective at higher loads and had higher additive losses to the THF phase (Table 3).
[000263] In all experiments, the effect of increasing ionic strength after switching with CO2 could be reversed; so that the THF phase was recombined with the aqueous phase to regenerate a one-phase system, when the mixture was heated and sparged with N2 or air to remove CO2, Example 4A: Qualitative determination of selected compound separation (THF) and additive (amine) after switching with equivalent additive loads
[000264] A qualitative comparison of reversible solvent switching in the five amine/water systems of example 3 was performed with equivalent additive loadings to determine by 1H NMR spectroscopy the relative switching efficiency of each nonionic amine additive to sodium bicarbonate. ammonium and return to non-ionic amine forms. Aqueous (0.80 molar) solutions of DMAE, MDEA, TMDAB, THEED, DMAPAP, HMTETA additives were added to 1:1 w/w solutions of THF:D2O in NMR tubes, which were sealed with rubber septa. 1H NMR spectra were acquired for each sample before any gas treatment, and are shown as A spectra in figures 4, 5, 6 and 7 for DMAE, TMDAB, HMTETA and DMAPAP, respectively. Two narrow gauge steel needles were inserted and the trigger gas was gently bubbled through one of the needles into the solution at a rate of 4 to 5 bubbles per second. The second needle served as a vent for the gas phase, which was maintained at a positive pressure above atmospheric by bubbling.
[000265] CO2 was used as the trigger to switch the amine from its nonionic to ionic form. 1H NMR spectra were acquired for each sample, after switching with CO2,
[000266] The spectrum obtained after switching from DMAE for 20 minutes of bubbling at 25°C with a CO2 trigger is shown as spectrum B in figure 4. Subsequently, the additive was returned to non-ionic form by bubbling a CO2 gas trigger nitrogen through the solution for 300 minutes at 75°C and the spectrum is shown as spectrum C in figure 4,
[000267] The spectrum obtained after switching TMDAB for 30 minutes of bubbling at 25°C with a CO2 trigger is shown as spectrum B in figure 5. Subsequently, the additive was returned to non-ionic form by bubbling a CO2 trigger. nitrogen through the solution for 240 minutes at 75°C and the spectrum is shown as spectrum C in figure 5,
[000268] The spectrum obtained after switching from HMTETA for 20 minutes of bubbling at 25°C with a CO2 trigger is shown as spectrum B in figure 6. Subsequently, the additive was returned to non-ionic form by bubbling a CO2 trigger. nitrogen through the solution for 240 minutes at 75°C and the spectrum is shown as spectrum C in figure 6,
[000269] The spectrum obtained after changing from DMAPAP for 20 minutes of bubbling at 25°C with a CO2 trigger is shown as spectrum B in figure 7, Subsequently, the additive was returned to non-ionic form by bubbling a CO2 trigger. nitrogen through the solution for 120 minutes at 75°C and the spectrum is shown as spectrum C in figure 7, Example 4B: Quantitative determination of separation of selected compound (THF) and additive (amine) after switching with equivalent additive charges
[000270] To measure the amount of THF being separated from an aqueous phase, increasing its ionic strength, and the amounts of amine remaining in the aqueous phase, 1:1 w/w solutions of THF and water were prepared in graduated cylinders. The appropriate mass of amine additive to result in a 0.80 ml molar solution was added and the beakers covered with rubber septa. After 30 minutes of bubbling CO2 through the liquid phase from a single narrow gauge steel needle, a visible phase separation was observed. The two phases were a non-aqueous phase comprising THF, which was forced out of the aqueous solution of increased ionic strength, and an aqueous phase comprising the additive in ionic form. The volumes of each phase were recorded. Aliquots of the aqueous and non-aqueous layers were taken and dissolved in d3-acetonitrile in NMR tubes. A known amount of ethyl acetate was added to each NMR tube as an internal standard. 1H NMR spectra were acquired as for the fully protonated additives, and through the integration of standard ethyl acetate, a concentration of THF or additive was calculated and sized to reflect the total volume of the aqueous or non-aqueous phase, providing a percentage of the compound which is forced out or withheld. The results are shown in table 4,
[000271] TMDAB, triamine DMAPAP and tetraamine HMTETA additives exhibited superior THF separation compared to monoamine additives DMAE and MDEA. This observation can be explained by the increase in the ionic strength, due to the greater charge on the quaternary ammonium cations, resulting from the protonation of several basic nitrogen centers into diamine, triamine and tetraamine. It is evident from equation (C) that for an equimolar concentration of additive, an increase in the charge on the salt cation from 1 to 2 will give rise to a tripling in the ionic strength.
[000272] It should be noted that, although TMDAB and DMPAP contain more than two tertiary amine centers, only two of the basic sites in each molecule are capable of protonation as a result of switching with CO2, This means that equimolar solutions of the protonated salts of TMDAB, DMAPAP and HMTETA must each have a similar ionic strength and therefore similar THF separations, as is evident from table 4, Example 5: Reversible protonation of amine additives in H2O as monitored by conductivity
[000273] The protonation of aqueous solutions of three tertiary amine additives, DMAE, MDEA and THEED, in response to the addition of a CO2 trigger was performed and monitored by the conductivity meter.
[000274] Aqueous solutions of an additive with distilled, deionized H2O (1:1 v/v of H2O and DMAE, 1:1 v/v of H2O and MDEA and 1:1 w/w of H2O and THEED) were prepared in sample beakers. 1:1 w/w H2O and THEED was used as a 1:1 v/v solution was too viscous to accurately pour. A selected trigger gas of CO2, air or nitrogen was bubbled at identical flow rates through the solution through a narrow gauge steel tube and the conductivity of the solution was measured periodically using a Jenway 470 conductivity meter (Bibby Scientific, NJ, US) having a cell constant of 1.02 cm-1,
[000275] The results of bubbling a CO2 gas trigger through the additive solutions in water at room temperature are depicted in figure 7, As shown in this figure, the conductivity of each of the pinkish additive solutions such as amine has been converted to its ionic form, when it came in contact with the CO2 trigger, The aqueous DMAE solution showed the greatest increase in conductivity.
[000276] Note that conductivity is not simply a function of salt concentration; conductivity is also strongly affected by solution viscosity. Thus, even if the two separate additive solutions have identical numbers of basic sites that can be fully protonated and have identical concentrations in water, they may have different levels of conductivity.
[000277] The deprotonation reactions of ionic solutions of additives in water were monitored in a similar way, and the conductivity graph is shown in figure 8, Nitrogen gas was released through the solution at 80°C for the salts to return to their form of non-ionic tertiary amine. The residual conductivity levels exhibited showed that none of the additives were completely deprotonated by this treatment within 6 hours. Example 6: Reversible protonation of amine additives in D2O when monitored by 1H NMR spectroscopy
[000278] The degree of protonation of tertiary amine additives in contact with a CO2 trigger was investigated by 1H NMR spectroscopy. The diamine THEED, DMAE and MDEA and two monoamines were selected for study.
[000279] To establish the chemical changes of the protonated bases, molar equivalents of several strong acids, including HCl and HNO3, were added to different solutions of amines dissolved in D2O. 1H NMR spectra were acquired by a Bruker AV-400 NMR spectrometer at 400.3 MHz for three repeated solutions of each amine. An average value of each chemical change for each protonated base was calculated along with standard deviations. If the bases when reacted with the trigger for the ionic form show chemical changes within this error range, they will be considered 100% protonated within the experimental error. The 1H NMR chemical changes of non-protonated amines were also measured.
[000280] The extent of protonation by CO2 of each additive at room temperature at 0.5 M (except THEED was at 0.1 M) in D2O was monitored by 1H NMR. The amine was dissolved in D2O in an NMR tube and sealed with rubber septa. The spectrum has been acquired. Subsequently, two narrow gauge steel needles were inserted and gas was gently bubbled through one of them into solution at approximately 4 to 5 bubbles per second. The second needle served as a vent for the gas phase.
[000281] First, CO2 was bubbled through the solution for a required period of time and then the spectrum was reacquired. This process was repeated. Amine protonation was determined from observed chemical changes by determining the amount of movement of the peaks from the normal position for the non-protonated amine towards the expected position for the fully protonated amine.
[000282] The results shown in figure 9 indicate that DMAE and MDEA are fully protonated (the peaks are within the standard deviation of HCl and HNO3 salts) within 20 minutes when CO2 was bubbled through the solution. THEED is half protonated (49%) for 10 minutes, which means that only one of the two nitrogen atoms of this diamine has been protonated.
[000283] The reverse reaction was monitored in a similar way and the results shown in figure 10, Nitrogen gas was released through the solution at 75°C. Spectra demonstrated that none of the additives were completely deprotonated by this treatment within 5 hours (2 hours of THEED), with the ionic form of THEED reacting the fastest of the three, and with DMAE being the slowest. THEED was 98% deprotonated (ie, the ionic strength of the solution reduced 25-fold) after 2 hours of N2 bubbling,
[000284] The observed switching rates, as represented by the protonation and deprotonation processes, are affected by the way in which the CO2 or spray gas was introduced (for example, its introduction rate and the shape of the container containing the solution ). For example, a comparison of Figure 7 with Figure 9 shows that the reaction rate in the 1H NMR experiment was faster than in the conductivity experiment. This rate difference is due to the difference in equipment. The 1H NMR experiment was performed in a tall, narrow NMR tube, which is washed more efficiently with CO2 than the beaker used in the conductivity tests. Furthermore, it is very likely that the deprotonation rate and therefore the reduction in the ionic strength of the solution can be increased if N2 bubbling is done more efficiently than simple bubbling through a narrow gauge tube.
[000285] In this way, a 1:1 v/v mixture of MDEA and water can be brought to 100% protonated and returned to about 4.5% by bubbling protonation/sprinkling with N2. It is possible to calculate an approximate ionic strength 100% and 4.5% degrees of protonation of the amine additive. The density of MDEA is 1.038 g/ml, so a 1L sample of this mixture would contain 500 g of water and 519 g of MDEA (4.4 mols). Consequently, the concentration of MDEA would be 4.4 M. The ionic strength, assuming an ideal solution and assuming that the volume does not change when CO2 is bubbled through the solution, is 4.4 M at 100% protonation and 0.198 M at 4.5% 4.5% protonation (using equation (A) above). Example 7: Reversible protonation of amine additives in H2O as verified by conductivity
[000286] Three tertiary amine additives were selected for further investigation of additives for aqueous solutions of switchable ionic strength. TMDAB is a diamine, DMAPAP is a triamine and HMTETA is a tetraamine.
[000287] 1:1 v/v solutions of the various additives and distilled, deionized water were prepared in a six drachma glass vial and transferred to a fritted glass apparatus which acted as a reaction vessel. The fritted glass apparatus consisted of a long, narrow glass tube leading to thin glass frits approximately 4 cm in diameter. The other end of the glass frit was connected to a cylindrical glass tube that held the additive solution during contact with the trigger gas. This apparatus allowed multiple sources of trigger gas bubbles to come into contact with the solution, compared to the single point source in example 5,
[000288] A selected trigger gas of CO2, air or nitrogen was bubbled through the solution through the glass frits, with a flow rate of 110 ml min-1 as measured by JW Scientific ADM 2000 Intelligent Flowmeter (CA, USA ). For each conductivity measurement, the solution was transferred to a six drachma flask, cooled to 298 K and measured in triplicate. Conductivity measurements were performed using a Jenway 470 conductivity meter (Bibby Scientific, NJ, US) having a cell constant of 1.02 cm-1.
[000289] Figure 11 shows a graph of the conductivity changes resulting from the bubbling of CO2 through three solutions at 25°C. It is apparent that HMTETA (■) and DMAPAP (▲), tetraamine and triamine respectively, exhibit lower conductivities than TMDAB (♦), diamine. Furthermore, TMDAB exhibits the highest rate of increase in conductivity.
[000290] The reverse reaction was monitored in a similar way and the results shown in figure 12, Nitrogen gas was released through the solution at 80°C. It is evident that the conductivity of the HMTETA solution (■) in the ionic form returns to close to zero after 20 minutes, indicating substantial removal of CO2 from the solution and reversion of the additive to its non-ionic form. The rate of conductivity reduction is greater for TMDAB (♦), diamine, indicating that it can be reversibly switched between ionic and non-ionic forms at a greater rate than HMTETA and DMAPAP (▲).
[000291] The observed switching rates, as represented by changes in conductivity, appear to be affected by the way in which the CO2 or spray gas was introduced (for example, its introduction rate and the shape of the container holding the solution) . For example, a comparison of Figure 11 with Figure 7 shows that the reaction rate using the frit gas apparatus appears to be faster than releasing the trigger through a narrow gauge steel tube, although it is accepted that the different additives are being compared. This may be because the fritted glass apparatus is more efficiently washed with CO2 than the beaker used in conductivity tests. Example 8: Emulsion formation and disruption of solutions comprising a surfactant and switchable amine additive
[000292] Three vials were prepared, each containing 0.462 g of N, N, N, N-tetramethyl-1,4-diaminobutane (TMDAB) in 4 ml of water (providing a molar solution of 0.80 ml) and 20 mg of SDS (sodium dodecyl sulfate, non-switchable surfactant) in the load of 0.50% by weight. To each vial n-decanol (0.25 ml) was added and the vials were capped with rubber septa. Figure 13, photograph, "A" shows the three vials at this stage in the experiment. In each bottle, there are two liquid phases. The lower liquid aqueous phase has a greater volume and is clear and colorless. The upper liquid n-decanol phase has a smaller volume and is also colorless, but not as clear. n-Decanol is not miscible with pure water.
[000293] The three vials were then shaken by hand for 30 seconds. Figure 13, photograph "B" shows the appearance after shaking. All three vials show an opaque liquid mixture with foam and cloudiness typical of an emulsion, which is as expected due to the presence of the known SDS surfactant.
[000294] The gases were bubbled through the solutions for 30 minutes through a narrow gauge steel needle inserted through the septum and into the liquid mixture. For each vial, gas could vent out of the vial through a second small needle inserted into the septum, but not in liquid phase. The gas was CO2 for the left flask and N2 for the center and right flasks. Figure 13, photograph "C" shows the appearance after gas treatment. Only the two vials on the right show the typical cloudiness of an emulsion. The liquid in the left vial is now clean and foam free, showing that the conversion of the aqueous solution to the high ionic strength form has weakened the ability of EDS to stabilize emulsions and foams. The liquid contents of the center and right vials still show the cloudiness and foaming typical of an emulsion, indicating that the bubbling of N2 gas through the solution does not have the effect of weakening the ability of SDS to stabilize emulsions and foams. This is because N2 had no effect on the ionic strength of the aqueous phase.
[000295] Although the left flask was allowed to rest for 30 minutes without further treatment, CO2 gas was bubbled through the liquid phase of the central flask for 30 minutes and N2 was bubbled through the right flask. Figure 13, photo "D" shows the appearance of the three vials after this time. The liquids in the left and center vials are now largely clear and foam-free, showing that the conversion of the aqueous solution to the high ionic strength form has weakened the ability of EDS to stabilize emulsions and foams. Emulsion and foam still persist in the bottle on the right.
[000296] The N2 gas was bubbled through the liquid phases of the central and left flasks for 90 minutes to remove the CO2 from the system and thus decrease the ionic strength of the aqueous solution. Then the two vials were shaken for 30 minutes. During this gas and agitation treatment, the vial on the right was untouched. Figure 13, photograph "E" shows the appearance of the three vials after this time. All three exhibit the typical cloudiness of an emulsion, although foaming in the two vials on the left is not evident, presumably because the conversion of the aqueous solution back to a low ionic strength is not complete. In practice, substantial conversion of low ionic strength is not difficult. However, it can be more difficult to achieve full conversion. Example 9: Description of ionic strength
[000297] The ionic strength of the aqueous salt solution will vary depending on the salt concentration and the charge on the ammonium ion. For example, an amine B having n sites that can be protonated by carbonic acid to provide a quaternary ammonium cation of formula I
, may have a switching reaction shown in reaction (1):

[000298] If the amine molality in the aqueous solution is m, the ionic strength of the ionic solution after switching can be calculated from equation (C):

[000299] Thus, for a given molality m, the ionic strength of a diprotonated diamine (n=2) will be three times that of a monoprotonated monoamine (n=1). Similarly, the ionic strength of a triprotonated triamine (n=3) will be six times that of a monoprotonated monoamine and the ionic strength of a tetraprotonated tetraamine (n=4) will be ten times that of a monoprotonated monoamine. Thereby, by increasing the number of tertiary amine sites in the compound of formula (1) that can be protonated by the trigger, the ionic strength of a solution comprising the corresponding salt of formula (2) can be increased, for a given concentration.
[000300] Not all basic sites in a compound of formula (1) may be capable of protonation by a gas that generates hydrogen ions in contact with water. For example, when the gas is CO2, the balance between CO2 and water and the dissociated carbonic acid, H2CO3 is shown in reaction (2):

[000301] The equilibrium constant, Ka for this acid dissociation is calculated from the ratio of
in equilibrium - in dilute solutions the water concentration is essentially constant and therefore can be omitted from the calculation. The equilibrium constant Ka is conventionally converted to the corresponding pKa value by equation (D):
pKa for reaction (2) is 6.36, The corresponding equilibrium for the dissociation of a protonated amine base BH+ (ie conjugate acid) is provided by reaction (3),
reaction (3)
[000302] The equilibrium constant KaH, for the dissociation of conjugate acid BH+ is calculated by the proportion of
. The equilibrium constant KaH is conventionally converted to the corresponding pKaH value in an analogous way to equation (D). From the above, it is evident that the equilibrium constant for the switching reaction shown in reaction (1) above where n=1 can be [ BH+][ HCO; ] K calculated from the ratio of
, which is equivalent to
the reason for
it can also be expressed in terms of corresponding pK values as
. Thus, in the case of dissociation of CO2 in water, if the pKaH value of the conjugate acid
BH+ exceeds 6.36, the ratio of [B][CO2] is greater than 1, favoring the production of ammonium bicarbonate. Thus, it is preferable that a salt as used herein comprises at least one quaternary ammonium site having a pKaH greater than 6 and less than 14. Some modalities have at least one quaternary ammonium site having a pKaH in a range of about 7 to about 13, In some embodiments the salt comprises at least one quaternary ammonium site having a pKaH in a range of about 7 to about 11. In other embodiments, the salt comprises at least one quaternary ammonium site having a pKaH in the range of about 7.8 to about 10.5, Example 10: Synthesis of Switchable Diamine and Triamine Additives Example 10A: Synthesis of N,N,N',N'-tetraethyl-1,4-diaminobutane (TEDAB)
[000303] 4.658 g (63.4 mmols) of diethylamine were dissolved in 100 ml of dichloromethane and cooled to 0°C. 2.339 g (15.1 mmol) of succinyl chloride was added dropwise to the solution. The solution was warmed to room temperature and stirred for 18 hours.
[000304] An aqueous solution of 0.80 ml of concentrated HCl and 25 ml of H2O was added to the mixture to wash the organic layer. The organic layer was then removed and dried with MgSO4 . The solvent was removed in vacuo to yield 3.443 g of N,N,N,N-tetraethylsuccinamide in 99% yield. 1H NMR (400 MHz CDCl 3 ) - δ: 3.37 (q, 7 Hz, 8H), 2.69 (s, 4H), 1.20 (t, J 7 Hz, 6H), 1.11 (t, J 7Hz, 6H).
[000305] 3.443 g (15.1 mmols) of N,N,N,N-tetraethylsuccinamide are dissolved in 100 ml of THF, degassed with N2 and cooled to 0°C. 61.0 ml of 2.0 M LiAlH4 in THF solution (122 mmols) was added dropwise to the solution. The solution was then refluxed for 6 hours.
[000306] The solution was then cooled to 0°C and the excess of LiAlH4 was quenched by adding 4.6 ml of H2O, 4.6 ml, 15% of NaOH and 13.8 ml of H2O. The solution was warmed to room temperature and stirred for 12 hours. The precipitate was filtered off and washed with THF. The washes were combined with the original THF solution and dried over MgSO4. The solvent was removed in vacuo to yield 2.558 g of a brown liquid, resulting in an 84.6% yield of N,N,N',N'- tetraethyl-1,4-diaminobutane. 1H NMR (400 MHz CDCl3) - δ: 2.55 (q, = 7 Hz, 8H), 2.41 (t, J = 7 Hz, 4H), 1.43 (t, J = 7 Hz, 4H) , 1.02 (t, J = 7 Hz, 12H).
[000307] All other straight chain diamines, N,N,N',N'-tetrapropyl-1,4-diaminobutane and N,N'-diethyl-N,N'-dipropyl-1,4-diaminobutane, were synthesized in a similar manner using the appropriate starting materials. Succinyl chloride, diethylamine, dipropylamine, lithium aluminum hydride solution were all purchased from Sigma Aldrich and used when received. N-ethylpropylamine was purchased from Alpha Aesar and solvents and MgSO4 were purchased from Fisher and used when received. Example 10B: Synthesis of 1,1',1"-(cyclohexane-1,3,5-tri-yl)tris(N,N,-dimethylmethanamine) (CHTDMA)
[000308] 1.997 g (9.2 mmols) of 1,3,5-cyclohexane-tricarboxylic acid was taken up in 40 ml of dichloromethane to create a suspension. 3.84 g (29.8 mmols) of oxyl chloride and one drop of DMF were added to the solution. The solution was refluxed for 3 hours, giving a yellow solution with white precipitate. The mixture was cooled to room temperature and the solvent removed in vacuo resulting in 2.509 g of a solid which contained both the desired 1,3,5-cyclohexane tricarbonyl trichloride and unwanted salts. 1H NMR (400 MHz CDCh) - δ: 2.88 (t, J = 9 Hz, 3H), 2.69 (d, J = 13 Hz, 3H), 1.43 (q, J = 13 Hz, 3H) ).
[000309] 2.509 g of the solid mixture was taken up in 50 ml of THF and cooled to 0°C. 34.5 ml of a 2.0 M solution of dimethylamine in THF (69 mmols) was added. The solution was warmed to room temperature and stirred for 18 hours. The solvent was then removed in vacuo leaving a yellow solid. The solid was taken up in a solution of 2.081 g (37.1 mmols) KOH in 20 ml of H2O. The organic content was then extracted with 3 x 40 ml chloroform washes. The organic washes were collected and the solvent removed in vacuo to yield 1.930 g of a yellow liquid, N,N,N',N',N,N'-hexamethylcyclohexane-1,3,5-tricarboxamide in the yield of 70 ,two%. 1H NMR (400 MHz CDCl 3 ) - δ: 3.06 (s, 9h), 2.92 (s, 9h), 2.65 (q, J 8.15 Hz, 3H), 1.86 (t, J 8 Hz, 6 H).
[000310] 1.930 g (6.5 mmols) of N,N,N,N,N,N'-hexamethylcyclohexane-1,3,5-tricarboxamide was dissolved in 80 ml of THF and cooled to 0°C. 42.0 ml of 2.0 M LiAlH4 in THF solution (84 mmols) was added dropwise to the solution. The solution was then refluxed for 6 hours.
[000311] The solution was then cooled to 0°C and excess LiAlH4 was quenched by adding 3.2 ml of H2O, 3.2 ml of 15% NaOH and 9.6 ml of H2O. The solution was warmed to room temperature and stirred for 12 hours. The precipitate was filtered off and washed with THF. The washings were combined with the original solution and dried over MgSO4. The solvent was removed in vacuo to yield 1.285 g of a yellow liquid, resulting in a 54.4% yield of 1.1',1''-(cyclo- hexane-1,3,5-tri-yl)tris(N,N,-dimethylmethanamine). 1H NMR (400 MHz CDCl3) - δ: 2.18 (s, 18H), 2.07 (d, J 7Hz, 8h), 1.89 (d, J 12Hz, 3H), 1.52 , (m, J 4.7Hz, 3H), 0.48 (q, J 12Hz, 3H). M 255.2678, 255.2674 expected.
[000312] Other cyclic triamines, N,N,N',N',N,N'-1,3,5-benzenetrimethanamine, were synthesized in a similar manner using the appropriate starting materials. 1,3,5-Benzenetricarbonyl trichloride was purchased from Sigma Aldrich and used when received. 1,3,5-Cyclohexanetricarboxylic acid was purchased from TCI and used when received. Example 11: Control of the zeta potential of clay particles suspended in water
[000313] In a suspension of solid particles in a liquid, a zeta potential close to zero indicates that the particles have ineffective surface charge and, therefore, the particles will not be repelled by each other. The particles will then naturally penetrate each other, causing coagulation, increasing particle size and settling to the bottom of the container or floating to the top of the liquid. Thus, the suspension will normally not be stable if the zeta potential is close to zero. Therefore, having the ability to bring a zeta potential close to zero is useful for destabilizing suspensions such as clay suspensions in water. However, strategies such as the addition of calcium salts or other salts are sometimes undesirable because, while these strategies cause the destabilization of suspensions, the change in water chemistry is essentially permanent; the water cannot be reused for the original application because the presence of added salts interferes with the original application. Therefore, there is a need for a method to destabilize suspensions that is reversible. Experimental methods:
[000314] Fine clay particles were weighed and placed in individual vials (0.025 g, Ward's Natural Science Establishment). Kaolinite and montmorillonite were used when received, but when illite clay was ground into a powder using mortar and pestle. Solutions containing additives were made with deionized water (18.2 MQcm, Millipore) and 10 ml were added to the fine clay particles. The suspension was created using a vortex mixer and later dispensed into a folded capillary cell. Zeta potential was measured using a Malvern Zetasizer instrument. The errors reported in the zeta potential values were the standard deviations of the measured zeta potential peaks.
[000315] Unless otherwise specified, all carbon dioxide treatments were conducted with aqueous solutions prior to the addition of fine clay particles. For the applicable measurements, ultrapure carbon dioxide (Supercritical CO2 Chromatographic Grade, Paxair) was bubbled through the solutions using a syringe. Results: Ilita
kaolinite

Montmorillonite

[000316] For three of the tested clays, it was found that the switchable water additives, TMDAB and BDMAPAP were effective additives changing the clay zeta potential. After the addition of CO2, the absolute values of clay zeta potentials were reduced. This effect was observed even at low concentrations of the switchable water additive (at 1 mM).
[000317] The above data demonstrates the ability of switchable water to affect the zeta potential of clay suspensions, however, CO2 treatments were carried out in aqueous TMDAB solutions before the fine clay particles were added (a method known as " external switching"). Another experiment was carried out in which CO2 was bubbled through a 1 mM aqueous solution of TMDAB that already contained fine clay particles (a method known as "in situ switching"). The results with kaolinite clay are summarized in the table below. kaolinite clay

[000318] It was observed that the magnitude of the zeta potential of the clay surfaces decreased regardless of whether the external switching method or the in situ switching method was used. Furthermore, the zeta potential could be restored to its original value after treatment with nitrogen gas at 70°C. Example 12: Reversible destabilization of a clay suspension in water
[000319] Three variations of clay settlement experiments were performed with 1 mM TMDAB (TCI America, Batch FIB01) to elucidate the ability of this switchable ionic strength additive to affect the stability of clay suspensions. Experiment 1
[000320] As depicted in Figure 14A, fine particles of kaolinite clay (5 g) were added to 100 ml of 1 mM TMDAB in deionized water. The mixture was stirred for 15 minutes at 900 rpm before transferring it to a 100 ml graduated cylinder, which was subsequently sealed with rubber septa. Fixation of fine clay particles was monitored as a function of time using a cathetometer.
[000321] CO2 was bubbled through 100 ml of 1 mM TMDAB using a dispersion tube for 1 hour. Fine kaolinite particles (5 g) were added to the aqueous solution and the mixture was stirred for 15 minutes at 900 rpm before transferring to a 100 ml graduated cylinder and sealing with rubber septa. Fixation of fine clay particles was monitored. CO2 was bubbled through 100 ml of 1 mM TMDAB using a dispersion tube for 1 hour. The solution was heated to 70°C and N2 was bubbled through without interruption for 1 hour. After cooling to room temperature, fine kaolinite particles (5 g) were added and the mixture was stirred at 900 rpm for 15 minutes before transferring to a 100 ml graduated cylinder and sealing with rubber septa. Fixation of clay particles was monitored. Experiment 2
[000322] As depicted in Figure 14B, fine kaolinite clay particles (5 g, Ward's Natural Science Establishment) were added to 100 ml of 1 mM TMDAB in deionized water. The mixture was stirred for 15 minutes at 900 rpm before transferring it to a 100 ml graduated cylinder, which was subsequently sealed with rubber septa. Fixation of fine clay particles was monitored as a function of time.
[000323] CO2 was bubbled through the above suspension. The mixture was stirred for 15 minutes at 900 rpm before transferring it to a 100 ml graduated cylinder, which was subsequently sealed with rubber septa. Fixation of fine clay particles was monitored.
[000324] The above fine clay particles were re-suspended in the solution and the mixture was heated to 70°C. N2 was bubbled through without interruption for 1 hour. After cooling to room temperature, the mixture was stirred at 900 rpm for 15 minutes before transferring to a 100 ml graduated cylinder and sealed with rubber septa. Fixation of fine clay particles was monitored. Experiment 3
[000325] As shown in Figure 14, fine kaolinite clay particles (5 g, Ward's Natural Science Establishment) were added to 100 ml of 1 mM TMDAB in deionized water. The mixture was stirred for 15 minutes at 900 rpm before transferring it to a 100 ml graduated cylinder, which was subsequently sealed with rubber septa. Fixation of fine clay particles was monitored as a function of time.
[000326] The above suspension was filtered. CO2 was bubbled through the filtrate for 1 hour. Fine kaolinite clay particles (4.5 g) were added and the mixture was stirred for 15 minutes at 900 rpm before transferring to a 100 ml graduated cylinder, which was subsequently sealed with rubber septa. Fixation of fine clay particles was monitored. Control Experiment
[000327] CO2 was bubbled through 100 ml of deionized water for 1 hour. Kaolinite clay (5 g) was added and the mixture was stirred for 15 minutes at 900 rpm before transferring to a 100 ml graduated cylinder, which was subsequently sealed with rubber septa. Fixation of clay particles was monitored. Results
[000328] Experiment 1 was carried out to examine the effect of switchable water additive on the clay settlement procedure. The shift was carried out in the absence of clay to ensure the shift took place entirely without any clay impedance. The results are plotted in Figures 15A-C.
[000329] A stable suspension with kaolinite clay and 1 mM TMDAB was formed. However, kaolinite clay with TMDAB treated by CO2 to 1 mM resulted in the resolution of clay with a clean supernatant and a clear sediment line. A stable suspension with kaolinite clay and 1 mM TMDAB treated with 1 h CO2 followed by 1 h N2 treatment. Photographs were taken after each 1 hour treatment and are provided in Figure 15,
[000330] Experiment 2 was carried out to examine whether the switchable water additives would still change after adding CO2 in the presence of kaolinite clay.
[000331] Kaolinite clay and 1 mM TMDAB were initially mixed to provide a stable suspension. This suspension was treated with CO2, which resulted in penetration of clay particles, with a clean supernatant and a clear line of sediment. As shown in Figures 16A-B, the procedure observed exactly as observed for experiment 1. The penetrated clay was agitated to reform a suspension, which was treated with N2, after which the suspension remained stable. Experiment 3 was carried out to determine if the switchable ionic strength additive adheres to the clay surface and therefore would be lost after clay removal. The suspension, created with the treated CO2 filtrate, was established very similar to the two previous experiments. A clear line of sediment was observed, however, the liquid above the sediment line was cloudy and still contained fine clay particles (see Figures 17A and C). This behavior was also observed with deionized water, treated with CO2 in the absence of any switchable water additive (see Figures 17B and C). Example 13: Removal of water from an organic liquid
[000332] 2.710 g of THF (3.76 x 10-2 mol) and 0.342 g of H2O (1.90 x 10-2 mol) were mixed together in a graduated container to create a single phase solution of approximately 8: 1 THF:H2O (w/w). 0.109 g (7.56 x 10-4 mol) of N,N,N'N'-tetramethyl-1,4-diaminobutane (TMDAB) was added to the solution again generating a single phase solution. The THF:TMDAB ratio was approximately 25:1 (w/w). This solution containing three components had a composition of mol% as follows: 65.6% mol% THF, 33.1% mol% H2O, and 1.3% mol% TMDAB.
[000333] A stir bar was added to the solution in the graduated container and the container was capped with rubber septa. A long, narrow gauge steel needle was inserted through the septa and into the solution. A second needle was pushed through the septa, but not into the solution. CO2 was bubbled into the solution through the first steel needle at a flow rate of about 5 ml min-1 with stirring at ~300 RPM for 30 minutes. At the end of bubbling a clear, colorless aqueous phase at the bottom of the container had creamed off the original organic phase. The organic phase was separated from the aqueous phase by decantation.
[000334] 76.1 mg of the upper organic phase were extracted and placed in an NMR tube. The sample was diluted with deuterated acetonitrile and 32.3 mg of ethyl acetate was added to act as an internal standard. A 1H NMR spectrum was acquired. Using the integration of the H2O and TMDAB NMR signals against the known amount of ethyl acetate added, the calculated masses of 4.58 mg and 0.46 mg of H2O and TMDAB were acquired respectively. The remaining mass of 71.06 mg corresponds to the THF in the sample.
[000335] The "dry" organic THF phase had a mole composition as follows: 79.3% by mole of THF, 20.5% by mole of H2O and 0.3% by mole of TMDAB. Example 14: Using a switchable additive to expel an organic compound from the water and then removing much of the additive from the aqueous phase
[000336] In some embodiments, the non-ionized form of the additive is immiscible with water. This makes it possible to create high ionic strength of the water while CO2 is present, in order to achieve some goal, such as expelling an organic compound from the aqueous phase and then removing the CO2 to recover most of the additive from the water. . This document describes the expulsion of THF from a water/THF mixture and subsequent recovery of a large part of the water additive.
[000337] 1.50 g of H2O, 1.50 g of THF and 0.30 g of N,N,N'N'-tetraethyl-1,4-diaminobutane (TEDAB) were mixed in a graduated container to generate a single-phase solution. The solution had a total volume of 3.54 ml. A small stir bar was added to the solution and the container was capped with rubber septa. The following procedure was performed in triplicate with a new sample (of the same content shown above) each time.
[000338] A long narrow gauge steel needle was inserted through the septa into the solution. A second small needle was inserted into the septa, but not into the solution itself. CO2 was bubbled through the solution at a flow rate of about 5 ml/min for 45 minutes, with stirring until a second phase foamed off on top of the aqueous phase. The CO2 bubbling was stopped and the needles removed. The cylinder was immersed in a hot water bath for a few seconds to facilitate separation of the liquid phases. Both phases were clear and yellow in color. The upper organic layer had a volume of 1.50 ml and the remaining aqueous layer had a volume of 2.04 ml.
[000339] The organic phase was decanted out giving a mass of 1.253 g (density 0.84 g/ml). The aqueous phase had a mass of 1.94 g (density 0.98 gml) resulting in a loss of 0.12 g due to solution transfer or extraction.
[000340] An example of 39.1 mg of the organic phase was placed in an NMR tube with deuterated acetonitrile and 50.2 mg of ethyl acetate to act as an internal standard. A 66.2 mg sample of the aqueous phase was placed in a second deuterated acetonitrile NMR tube with 22.3 mg ethyl acetate to act as an internal standard. A 1H NMR spectrum was acquired and knowing the amount of ethyl acetate in each corresponding sample the resulting amounts of THF in the aqueous sample and additive in the organic sample can be calculated. Knowing the mass, volume and density of each layer, the total amount of THF or additive in a respective layer can be calculated.
[000341] It was found that an average of 77.2±3.5 of THF was removed from the aqueous phase with 91.1±3.7 of TEDAB residing in the aqueous phase.
[000342] 1.943 g (1.90 ml) of the aqueous phase was returned to the same graduated container. The needles and septa were placed back in the container and the container was immersed in a water bath at 60°C. N2 was introduced in the same form as preformed CO2 above and the N2 was bubbled through the solution for 90 minutes, whereupon the organic phase foamed out of the aqueous phase.
[000343] The new organic phase had a volume of 0.17 ml leaving an aqueous phase of 1.57 ml. The organic layer was decanted away giving 0.09 g of mass, while the remaining aqueous phase had a mass of 1.507 g (density 0.96 g/ml). A 37.9 mg sample was collected from the aqueous phase in an NMR tube with deuterated acetonitrile and 41.5 mg of ethyl acetate to act as an internal standard. A 1H NMR spectrum was acquired and using the same procedure to compare integrations as performed above, it was found that 49.3±6.3 of the TEDAB was removed from the aqueous phase. It was also found that the overall 90.0±2.1 of total THF had been removed from the aqueous phase at the end of the procedure.
[000344] Using N,N'-diethyl-N,N'-dipropyl-1,4-diaminobutane instead of N,N,N'N'-tetraethyl-1,4-diaminobutane (TEDAB) in the above procedure caused the expulsion of 68% THF from the aqueous phase after the CO2 treatment. After the N2 treatment from the separated aqueous phase, 81% of N,N'-diethyl-N,N'-dipropyl-1,4-diaminobutane was removed from the aqueous phase. Example 15: Determining miscibility of diamines and triamines with water in the presence and absence of CO2
[000345] In some embodiments, the non-ionized form of the additive is immiscible with water, while the charged form is miscible with water or soluble in water. The following experiments were carried out in order to identify whether certain diamines and triamines have this phase behavior.
[000346] A 5:1 w/w solution of water and liquid additive (total volume 5 ml) was mixed in a glass vial at room temperature. Whether the mixture formed from one or two liquid phases was observed visually. Then CO2 was bubbled through the mixture through a single narrow gauge steel needle at a flow rate of ~5 ml min-1 for 90 minutes. Whether the formed mixture of one or two phases was observed visually. The results were as follows:
Example 16: Preparation and use of a polyamine for expelling acetonitrile from water Example 16A: Polyamine preparation:

[000347] Polyethyleneimine samples of three different molecular weights (M.W. 600, 99%; M.W. 1800, 99%; and M.W. 10,000, 99%) were purchased from Alfa Aesar. Formaldehyde (37% in H2O) and formic acid were purchased from Sigma-Aldrich. All reagents were used without further purification. IRA-400 (OH) Amberlite® ion exchange resin was purchased from Supelco.
[000348] For samples using polyethyleneimine M.W. 600 and 1800: A 250 ml round bottom flask was equipped with a 2 cm teflon stir bar and placed on a magnetic stir plate. 1.8 g (600 MW: 3.0 mmols, 1 eq, 1800 MW: 1.0 mmol, 1 eq) of polyethyleneimine was placed in the flask and 9.73 ml (120 mmols: MW 600:40 eq and MW 1800 120 eq) of formaldehyde solution and 4.53 ml (120 mmols: MW 600:40 eq and MW 1800 120 eq) of formic acid were added. The flask was equipped with a condenser and the reaction mixture was heated at 60°C for 16 hours with an oil bath. After 16 hours the mixture was allowed to cool to room temperature and the solvents were removed under reduced pressure. Then, the crude product was dissolved in 20 ml anhydrous EtOH and 4 g of Amberlite® resin was added to the solution. The resulting mixture was stirred for 4 h or 16 h at room temperature before the resin was filtered off and the EtOH removed under reduced pressure. The methylated polymer was obtained as a dark yellow oil (1.8 g of M.W. 600 sample and 1.7 g of M.W. 1800 sample).
[000349] For the sample using polyethyleneimine M.W. 10,000: A 250 ml round bottom flask was equipped with a 2 cm teflon stir bar and placed on a magnetic stir plate. 1.8 g (1.0 mmol, 1 eq) of polyethyleneimine was placed in the flask and 9.73 ml (120 mmol, 120 eq) of formaldehyde solution and 4.53 ml (120 mmol, 120 eq) of formic acid have been added. The flask was equipped with a condenser and the reaction mixture was heated at 60°C for 16 hours with an oil bath. After 16 hours the mixture was allowed to cool to room temperature and the solvents were removed under reduced pressure. Then, the crude product was dissolved in 20 ml of anhydrous EtOH and 4 g of Amberlite resin were added to the solution. The resulting mixture was stirred for 16 hours at room temperature, before the resin was filtered off and the EtOH removed under reduced pressure. The resulting crude product was dissolved in 10 ml of CH2Cl2 and 10 ml of a 2M aqueous solution of NaOH in water. The phases were separated and the aqueous layer was extracted three times with 10 ml of CH2Cl2. The organic phases were dried over MgSO4 and CH2Cl2 was removed under reduced pressure to yield methylated polyethyleneimine as a yellow oil. Methylated polyethyleneimine (600 MW before methylation): 1H NMR (CDCl3, 400 MHz): δ [pm] = 2.18-2.91 (m), no NH signal appears in the 13C NMR spectrum (CDCl3, 100.7 MHz) ): δ [pm] = 42.2 (q), 44.1 (q), 44.4 (q), 50.5-56.0 (m, t) Methylated Polyethyleneimine (MW 1800 before methylation) NMR 1H (CDCl3, 400 MHz): δ [pm] = 2.16 (s, CH3), 2.23 (bs, CH3), 2.44-2.64 (m), no NH signal appears in 13C NMR spectrum (CDCI3, 100.7 MHz): δ [pm] = 41.5 (q), 44.0 (q), 50.8-51.1 (m, t), 53.7 (t), 55, 0 (t) Methylated Polyethyleneimine (1800 MW before methylation) 1H NMR (CDCl3, 400 MHz): δ [pm] = 2.18 (s, CH3), 2.21 (s, CH3), 2.28-2 .62 (m), no NH signal appears in the 13C NMR spectrum (CDCl3, 100.7 MHz): δ [pm] = 42.9 (q), 43.0 (q), 45.9 (q), 46 .0 (q), 52.8-54.0 (m,t), 55.8-56.9 (m,t), 57.2-57.8 (m,t) Example 16B: use of polyamine to expel acetonitrile from water
[000350] The methylated polyamines were investigated as additives for solutions of switchable ionic strength. To measure the extent of acetonitrile being forced out of an aqueous phase by an increase in ionic strength and the amounts of amine remaining in the aqueous phase, 1:1 w/w solutions of acetonitrile and water (1.5 g each) were prepared in graduated beakers. 300 mg of non-ionic polyamine additive was added and the containers were capped with rubber septa. After 30 minutes of bubbling carbon dioxide through the liquid phase of a single narrow gauge steel needle at room temperature, a visible phase separation was observed. The volumes of each phase were recorded. Aliquots of the aqueous and non-aqueous layers were taken and dissolved in D2O in NMR tubes. A known amount of ethyl acetate or dimethylformamide (DMF) was added to each NMR tube as an internal standard. 1H NMR spectra were acquired and by integrating standard ethyl acetate or DMF, a concentration of acetonitrile or additive was calculated and sized to reflect the total volume of the aqueous or non-aqueous phase, providing a percentage of the compound being forced to leave. The results are shown in the table below.
99.9% of the polyamine was retained in the aqueous phase
[000351] Argon was then bubbled through the solution during heating at 50°C until the two phases were recombined into a single phase (usually 30 minutes). Bubbling CO2 through the mixture again for 30 minutes caused the liquid mixture to split into two phases and a subsequent bubbling of argon for 30 minutes caused the two phases to fuse again, which shows that the process is fully reversible. Example 17: Preparation and use of a tetra-amine for expelling THF from water Example 17A: Preparation of tetra-amine:

[000352] Spermine (97% purity) was purchased from Alfa Aesar, formaldehyde (37% in H2O), Zn powder from Sigma-Aldrich and acetic acid from Fisher Scientific.
[000353] A 250 ml round bottom flask was equipped with a 2 cm teflon stir bar and placed on a magnetic stir plate. 2.02 g (10 mmols, 1.0 eq) of spermine were placed in the flask and dissolved in 40 ml of water. Subsequently, 9.72 ml (120 mmols, 12.0 eq) of formaldehyde solution and 13.7 ml (240 mmols, 24.0 eq) of acetic acid were added and the solution was allowed to stir at room temperature for 15 minutes . Then 7.84 g (120 mmols, 12.0 eq) of Zn powder were added in small portions, which resulted in the formation of gases. A cold water bath was used to keep the vial temperature below 40°C. After the addition was complete the reaction mixture was vigorously stirred for 16 hours at room temperature. 20 ml of NH3 solution was added and the aqueous phase was extracted with ethyl acetate in a separatory funnel (3 times 25 ml).
[000354] The combined organic layers were dried over MgSO4, filtered through removed filter paper under reduced pressure. The crude product was purified by high vacuum distillation to yield 1.3 g (4.5 mmols, 42) of a yellow oil, which was formally named N1,N1-(butane-1,4-di-yl)bis( N1,N3,N3-trimethylpropane-1,3-diamine). As used herein, this compound is referred to as MeSpe (i.e., methylated spermine). 1H NMR (CDCl3, 400 MHz): δ [pm] = 1.36-1.44 (m, 4H, CH2), 1.55-1.66 (m, 4H, CH2), 2.18 (s, 6H, CH3), 2.19 (s, 12H, CH3), 2.21-2.27 (m, 4H, CH2), 2.28-2.35 (m, 8H, CH2); 13C NMR (CDCl3, 100.7 MHz): δ [pm] = 25.3 (t), 25.7 (t), 42.3 (q), 45.6 (q), 55.8 (t) , 57.8(t), 58.0(t); MS (EI): m/z (%) = 287.32 (7), 286.31 (41) [M]+, 98.08 (28), 86.08 (44), 85.07 (100) , 84.07 (41); HRMS (EI): caIc. for [M]+: 286.3097, established: 286.3091, Example 17B: Tetra-amine/water system reversible solvent switch
[000355] Methylated spermine has been investigated as an additive for switchable ionic strength solutions. To measure the degree of THF being forced out of an aqueous phase by an increase in ionic strength and the amounts of amine remaining in the aqueous phase, 1:1 w/w solutions of THF and water were prepared in graduated cylinders. The appropriate mass of amine additive to yield a 0.80 mole solution was added and the containers were capped with rubber septa. After 30 minutes of bubbling carbon dioxide through the liquid phase from a single narrow gauge steel needle, a visible phase separation was observed. The volumes of each phase were registered. Aliquots of the aqueous and non-aqueous layers were taken and dissolved in d3-acetonitrile in NMR tubes. A known amount of ethyl acetate was added to each NMR tube as an internal standard. 1H NMR spectra were acquired and through the integration of standard ethyl acetate, a concentration of THF or additive was calculated and sized to reflect the total volume of the aqueous or non-aqueous phase, providing a percentage of the compound being forced out or withheld. Next, argon was bubbled through the solution while heating at 50°C until the two phases were recombined (15 to 60 minutes). The entire switching process was repeated (30 minutes of CO2, sample taken, then another 30 minutes of Ar). The results are shown in the table below.
[000356] Experiments of sinking into a salt layer using methylated spermine (MeSpe).
Example 17C: NMR measurement of the degree of protonation of methylated spermine by sparkling water
[000357] The degree of protonation of tetra-amine (methylated spermine) in contact with a carbon dioxide trigger was investigated by 1H NMR.
[000358] To establish the chemical changes of the protonated bases, molar equivalents of several strong acids, including HCl and HNO3, were added to different solutions of tetra-amine dissolved in D2O. 1H NMR spectra were acquired on a Bruker AV-400 NMR spectrometer at 400.3 MHz for three repeated amine solutions. An average value of each chemical change for each protonated base was calculated along with standard deviations. If the base when reacted with the trigger for the ionic salt form shows chemical changes within this error range, it will be considered 100% protonated within the experimental error. Chemical changes of non-protonated amine 1 H NMR were also measured.
[000359] The extent of protonation of the additive at room temperature at 0.1 M in D2O was monitored by 1H NMR. The amine was dissolved in D2O in an NMR tube and sealed with rubber septa. The spectrum has been acquired. Subsequently, two narrow gauge steel needles were inserted and gas was gently bubbled through one of them into solution at approximately 4 to 5 bubbles per second. The second needle served as a vent for the gas phase.
[000360] First, CO2 was bubbled through the solution for the required period of time and then the spectrum was reacquired. This process was repeated. Amine protonation was determined from observed chemical shifts by determining the amount of movement of the peaks from the normal position of the non-protonated amine towards the position expected for the fully protonated amine.
[000361] The results show that the tetra-amine was protonated to a degree of 93%. Example 18: osmotic desalination system
[000362] The desalination of water by reverse osmosis is energetically expensive. An alternative that has been proposed in the literature is advanced osmosis (figure 18), and water flows through a membrane of salt water in a concentrated ammonium carbonate solution "(extracted solution"). Once the flow is complete, the extracted solution is removed from the system and heated to eliminate NH3 and CO2, the principle costs of the process are, the input of energy during the heating step and the supply of plywood ammonium carbonate. The limiting factors for the technology are according to a 2006 review of the field (Cath, T.Y.; Childress, A.E.; Elimelech, M.J. Membrane Sci. 2006, 281,70-87). "Lack of high-performance membranes and the need for an easily separable extracted solution."
[000363] Described in this example is a new easily separable extracted solution, which takes advantage of the present method of reversibly converting a switchable water from low to high ionic strength. The osmotic pressure of a switchable water must rise dramatically when the conversion from low ionic strength to high ionic strength takes place. Although the osmotic pressure of the solution before and after CO2 has not been measured, data from the literature (Cath, TY; Childress, AE; Elimelech, MJ Membrane Sci. 2006, 281.70-87) show that the osmotic pressure of a one solution 4M organic neutral such as sucrose is much lower (about 130 atm) than the osmotic pressure of a salt containing a dication such as MgCl2 (800 atm). This reversible change in osmotic pressure can be used in a water desalination method, as depicted in Figure 19.
[000364] The process depicted in figure 19 employs a water solution selectable in its ionic form as the extracted solution. After forwarding osmosis, the salt water is removed and CO2 is removed from the switchable water solution, dramatically dropping the osmotic pressure. Reverse osmosis produces fresh water from switchable water solution with little energy requirement due to low osmotic pressure.
[000365] The main advantages of this process over conventional advanced osmosis are that lower energy requirement is expected for the heating step (see predicted energy requirements table below) and easy and complete amine recycling. The main advantage of the proposed process over conventional reverse osmosis is the very low pressure requirement during the reverse osmosis step.
3Mucci, A.; Domain, R.; Benoit, RL Can. J.Chem. 1980, 58, 953-958,
[000366] A modification of this process, shown in figure 20, differs only in the last step, in which the switchable water additive in the solution is "free", or returns to its non-ionic form and is then removed by a method other than osmosis reverse. For example, if the nonionic form of the additive is insoluble or immiscible in water, it can be removed by filtration or decantation, with small amounts of additive remaining in the water being removed, passing the water through silica. The results showed the successful use of a separation process. Example 19: preparation and use of a diamidine for expelling THF from water Example 19: preparation of diamidine:

[000367] 1,4-diaminobutane was purchased from Sigma-Aldrich and dimethylacetamide dimethylacetal was purchased from TCI.
[000368] A 100 ml flask was equipped with a condenser and a 1 cm stir bar and then placed on a stir plate. 1.14 ml (1.0 g, 11.3 mmols, 1 eq.) of 1,4-diaminobutane and 3.64 ml (3.31 g, 24.9 mmols, 2.2 eq.) of dimethylacetal dimethylacetamide were placed in the flask. The reaction mixture was then stirred at 600 rpm and heated to 60°C. After 2 hours the reaction mixture was allowed to cool to room temperature and the resulting methanol was removed under reduced pressure to yield a yellow oil. This crude product was then purified by high vacuum distillation. The pure product was obtained as a pale yellow oil (2.32 g, 10.2 mmols, 91). The compound was named N,N-(butane-1,4-di-yl)bis(N,N-dimethylacetimidamide) and in this application was referred to as "DIAC" (i.e. diacetamidine)
1H NMR (CDCl3, 400 MHz): δ [pm] = 1.45-1.53 (m, 4H, CH2), 1.80 (s, 3H, CCH3), 2.79 (s, 6H, N( CH3)2), 3.09-3.19 (m, 4H, CH2); 13C NMR (CDCl3, 100.7 MHz): δ [pm] = 12.3 (q, CCH3), 30.2 (t, CH2), 37.9 (q, 2C, N(CH3)2), 50 .0 (t, CH2), 158.7 (s); MS (EI): m/z (%) = 227.22 (3), 226.21 (21), 198.16 (7), 182.17 (7), 141.14 (14), 140.13 (21), 128.11 (10), 127.10 (30), 114.11 (23), 113.11 (28), 112.09 (52), 99.09 (27), 70.07 ( 45), 56.05 (100); HRMS (EI): caIc. for [M]+: 226.2157, established: 226.2161, Example 17B: Reversible Solvent Switching of the Diamidine/Water System
[000369] Diamidine has been investigated as an additive for switchable ionic strength solutions. To measure the degree of THF being forced out of an aqueous phase by an increase in ionic strength and the amounts of amine, which remained in the aqueous phase, 1:1 w/w solutions of THF and water were prepared in graduated cylinders. The appropriate mass of amine additive to result in a 0.80 molar solution was added and the containers were capped with rubber septa. After 30 minutes of bubbling carbon dioxide through the liquid phase from a single narrow gauge steel needle, a visible phase separation was observed. The volumes of each phase were recorded. Aliquots of the aqueous and non-aqueous layers were taken and dissolved in d3-acetonitrile in NMR tubes. A known amount of ethyl acetate was added to each NMR tube as an internal standard. 1H NMR spectra were acquired and through the integration of standard ethyl acetate, a concentration of THF or additive was calculated and sized to reflect the total volume of the aqueous or non-aqueous phase, providing a percentage of the compound being forced out or withheld. The results showed that the amount of THF forced out of the aqueous phase was 54.5% and the amount of additive retained in the aqueous phase was 99.5%.
[000370] Next, argon was bubbled through the solution during heating at 50°C until the two phases were recombined (15 to 60 minutes). Example 20: Precipitation of an Organic Solid Using Switchable Water
[000371] Ten milliliters of water was pipetted into a glass centrifuge tube along with 2.038 g of TMDAB (~5:1 w/w solution). 68.2 mg of ()-camphor (used as from Sigma-Aldrich) was added to the solution. The solution was heated in a 70°C water bath to accelerate the dissolution of camphor. After complete dissolution of the solid (camphor) and cooling to room temperature (23°C), the solid remained dissolved in aqueous solution.
[000372] The centrifuge tube was capped with a rubber septum. CO2 was introduced into the solution through a single narrow gauge steel needle with a flow rate of about 5 mL min-1, a second needle was inserted into the tube, but not into the solution, to act as a gas outlet . After 30 minutes of CO2 bubbling through the solution, a white precipitate appeared throughout the aqueous solution.
[000373] The solution was centrifuged for 5 minutes, using a Fisher Scientific Centrific 228 centrifuge at a speed of 3300 RPM, so that all white solids were collected on top of the aqueous solution. White solids were collected by vacuum filtration and weighed on a Mettler-Toledo AG245 analytical balance. A mass of 24.0 mg was obtained, resulting in a recovery of 35.2% of the original dissolved solid. Example 21: Primary Amines as Switchable Additives
[000374] Primary amines have been tested as switchable water additives. The change from non-ionized form to charged form (which is probably a mixture of bicarbonate and carbamate salts) went well. Separation of an organic liquid was observed. However, the conversion from the ionic form back to the non-ionized form was successful. Primary amines, therefore, are only useful as additives in applications where a single switch to the ionic form, without conversion back to the non-ionized form, is sufficient. Thus, primary amine additives are not reversibly "switchable". Example 21A: Ethanolamine (5:5:1)
[000375] In a glass flask, 5.018 g of H2O, 1.006 g of ethanolamine, and 4.998 g of THF were mixed to generate a single, clear, colorless phase. A stir bar was added to the vial and the vial was capped with a rubber septum. CO2 was introduced into the solution through a single narrow gauge steel needle at a flow rate of about 5 mL min-1, a second needle was inserted through the septa, but not into the solution, to act as a gas outlet . CO2 was bubbled through the solution for 20 minutes until two liquid phases (aqueous and organic) were observed. By 1 H NMR spectroscopy, it was concluded that ~62% of the THF was forced out of the aqueous phase into the new organic phase.
[000376] The two-phase mixture was then placed in a water bath at 60°C, although N2 was bubbled through the mixture in a similar manner to the preceding CO2 bubbling, this was carried out for 60 minutes. Although some of the THF was boiled out, the two phases were not recombined. The temperature was raised to 75°C for 30 minutes, which seemed to boil off the remainder of the THF when the volume returned to the water and amine mixture. Some of ethanolamine may have boiled it out too. At this point, a single liquid phase was observed when the THF was boiled out, however the phase was cloudy and appeared to have a white precipitate (similar to carbamate salts).
[000377] The water bath temperature was then raised to 85°C and N2 bubbling was continued for 90 minutes, providing a total N2 treatment of 3 hours. No additional physical changes were observed. The solution remained cloudy white in color and some of the white precipitates had collected on the sides of the vial. Example 21B: ethylenediamine (18:18:1)
[000378] In a glass flask, 5.004 g of H2O, 0.283 g of ethylenediamine and 5.033 g of THF were mixed to generate a single, clear, colorless phase. A stir bar was added to the vial and the vial was capped with rubber septa. CO2 was introduced into the solution through a single narrow gauge steel needle at a flow rate of about 5 mL min-1, a second needle was inserted through the septa, but not into the solution, to act as a gas outlet . CO2 was bubbled through the solution for 10 minutes until two liquid phases (aqueous and organic) were observed. It was found by 1H NMR that ~67% THF was forced out of the aqueous phase into the new organic phase.
[000379] The two-phase mixture was then placed in a water bath at 60°C, although N2 was bubbled through the mixture in a similar manner to the preceding CO2 bubbling, this was carried out for 60 minutes, in which some of THF were boiled out, but the two phases were not recombined. The water bath temperature was then raised to 85°C and N2 bubbling was continued for 120 minutes, providing a total N2 treatment of 3 hours. It looked like all the THF had boiled out when the volume returned to the water and amine mixture. The solution turned into a single yellow liquid phase at this point, however a white precipitate (similar to carbamate salts) made the solution appear cloudy. Example 22: Sinking in a THF salt layer of water using switchable secondary amine additives
[000380] In general, from observations using primary amines, secondary amines were expected to be difficult to reverse, because primary and secondary amines tend to form carbamate salts. In addition to the bicarbonate salts when their aqueous solutions come into contact with CO2, however the following secondary amines have been found to be reversibly switchable. Without wishing to be bound by theory, it is possible that reversibility results from a tendency to form more bicarbonate than carbamate salts.
[000381] N-tert-butylethanolamine was purchased from TCI AMERICA and N-tert-butylmethylamine was purchased from Sigma-Aldrich. Both compounds were used without further purification.
[000382] N-tert-butylethanolamine and N-tert-butylmethylamine were investigated as additives for switchable ionic strength solutions. To measure the degree of THF being forced out of an aqueous phase by an increase in ionic strength and measure the amount of amine remaining in the aqueous phase, 1:1 w/w solutions of THF and water (1.5 g each) were prepared in graduated beakers. The appropriate mass to result in a 1.60 molar amine additive solution was added and the containers were covered with rubber septa. After 30 minutes of bubbling carbon dioxide through the liquid phase from a single narrow gauge steel needle, a visible phase separation was observed. The volumes of each phase were recorded. Aliquots of the aqueous and non-aqueous layers were taken and dissolved in d3-acetonitrile in NMR tubes. A known amount of ethyl acetate was added to each NMR tube as an internal standard. 1H NMR spectra were acquired and through the integration of standard ethyl acetate, a concentration of THF or additive was calculated and sized to reflect the total volume of the aqueous or non-aqueous phase, providing a percentage of the compound being forced out or withheld. Then argon was bubbled through the solution at 5 mL/min while heating at 50°C until the two phases were recombined (30 minutes for N-tert-butylethanolamine). Recombination of the phases when N-tert-butylmethylamine was used as an additive was not successful within 30 minutes, but was achieved for 2 hours at a higher Ar flow rate of 15 mL/min. THF was added after replacing the amount of THF being evaporated during the procedure. The entire switching process was repeated (30 minutes of CO2, sample taking, then another Ar treatment). The results are shown in the table below.
[000383] Sinking experiments in a salt layer using secondary amine additives

[000384] All publications, patents and patent applications mentioned in this specification are indicative of the skill level of those skilled in the art to which the present invention belongs and are incorporated herein by reference, to the same extent as if each individual publication , patents or patent applications were individual and specifically indicated to be incorporated by reference.
[000385] It will be understood by those skilled in the art that this description is made with reference to preferred embodiments and that it is possible to produce other embodiments employing the principles of the invention which fall within its spirit and scope as defined by the appended claims. All such modifications which would be obvious to one skilled in the art are intended to be included within the scope of the following claims. Table 1. Duration of CO2 bubbling required to separate aqueous phase, comprising additive, and duration of N2 bubbling required to recombine THF and THF aqueous phase
Table 2. Amount of THF separated out of the aqueous phase comprising the additive and the amount of additive retained in the aqueous phase
Table 3. Comparison of relative amounts of amine additive for separation of THF from 1:1 w/w solutions of THF and H2O and retention of amine in aqueous phase when reacted with CO2

[a] Determined by 1H NMR spectroscopy as discussed in Example 2. Table 4. Comparison of 0.80 molar capabilities of aqueous amine additive solutions to separate THF from 1:1 w/w solutions of THF and H2O and retention of amine additive in the aqueous phase when reacted with CO2
[a] Determined by 1H NMR spectroscopy as discussed in Example 1.

权利要求:
Claims (8)
[0001]
1. Method for modulating ionic strength, characterized in that it comprises: providing a switchable water comprising liquid water and a switchable additive and which has switchable ionic strength, the switchable additive comprising at least one amino nitrogen that is sufficiently basic to be protonated by carbonic acid; contacting switchable water with an ionizing trigger that is CO2, COS, CS2 or a combination thereof, protonating the switchable additive, and increasing the ionic strength of switchable water from a first ionic strength to a second ionic strength; and, subjecting the switchable water having the second ionic strength to (i) heating, (ii) a wash gas, (iii) a vacuum or partial vacuum, (iv) agitation, or (v) any combination thereof; and reforming the switchable water having the first ionic strength; where the switchable additive has the general formula (1): R2
[0002]
2. Method for destabilizing a dispersion or preventing the formation of a dispersion, characterized in that it comprises the steps as defined in claim 1 and further comprises: combining, in any order, to form a mixture of: water, an ingredient immiscible in steel water or water-insoluble, the switchable additive comprising at least one amino nitrogen atom that is sufficiently basic to be protonated by carbonic acid, and CO2, COS, CS2, or a combination thereof; and allowing the mixture to separate into two components, a first component comprising the water-immiscible ingredient and a second component comprising water and the protonated form of the switchable additive and optionally wherein (a) the dispersion is an emulsion and the water-immiscible ingredient is a liquid or a supercritical fluid; (b) the dispersion is an inverse emulsion and the water-immiscible ingredient is a liquid or a supercritical fluid; (c) the dispersion is a foam and the water-immiscible ingredient is a gas; or (d) the dispersion is a suspension and the water-immiscible ingredient is a solid; wherein the mixture optionally further comprises a surfactant.
[0003]
3. Method for desalinating an aqueous salt solution, characterized in that it comprises the steps as defined in claim 1 and further comprises the steps of: (a) providing a semi-permeable membrane that is selectively permeable to water and has in a switchable water side having switchable ionic strength as an extraction solution; (b) contacting the extraction solution with the ionizing trigger to protonate the switchable additive before or after association with the semipermeable membrane, thus increasing the ionic strength of the extraction solution; (c) contacting the semipermeable membrane with an aqueous salt solution feed stream to allow water to flow from the aqueous salt solution through the semipermeable membrane into the extracting solution of increased ionic strength; and (d) removing the switchable additive from the resulting dilute extraction solution.
[0004]
4. Method for concentrating a dilute aqueous solution, characterized in that it comprises the steps as defined in claim 1 and further comprises the steps of: (a) providing a semipermeable membrane that is selectively permeable to water and has on one side switchable water having switchable ionic strength as an extraction solution; (b) contacting the extraction solution with the ionizing trigger to protonate the switchable additive before or after association with the semipermeable membrane, thus increasing the ionic strength of the extraction solution; (c) contacting the semipermeable membrane with a feed stream of the dilute aqueous solution to allow water to flow from the dilute aqueous solution through the semipermeable membrane to the extract solution of increased ionic strength; and (d) optionally removing the switchable additive from the resulting dilute extraction solution.
[0005]
5. Method according to claim 3 or 4, characterized in that step (d) comprises reverse osmosis.
[0006]
6. Method according to claim 3 or 4, characterized in that when the switchable additive is immiscible with water after removal of the ionizing trigger, step (d) comprises decanting the switchable additive from the solution.
[0007]
7. Method according to claim 3 or 4, characterized in that when the switchable additive is insoluble in water after removal of the ionizing trigger, step (d) comprises filtering the non-ionized additive from the solution.
[0008]
8. Method according to any one of claims 1 to 7, characterized in that the switchable additive is: MDEA (N-methyl-diethanol-amine); TMDAB (N,N,N',N'-tetramethyl-1,4-diaminobutane); TEDAB (N,N,N',N'-tetraethyl-1,4-diaminobutane) EPDAB (N,N'-diethyl-N,N'-dipropyl-1,4-diaminobutane) THEED (N,N,N',N'-tetracis(2-hydroxyethyl)ethylenediamine); DMAPAP (1-[bis[3-(dimethylamino)]propyl]amino]-2-propanol), or HMTETA (1,1,4,7,10,10-hexamethyl triethylenetetramine). MeSpe (N1,N1'-(butane-1,4-di-yl)bis(N1,N3N3-trimethylpropane-1,3-diamine) Methylated polyethyleneimine HTDMA (1,1',1"-(cyclohexane-1) ,3, -tri-yl)tris(N,N-dimethylmethanamine) and/or; ionic form of the switchable additive is a compound of formula (2): wherein R 1 , R 2 and R 3 are as defined for the compound of formula (1) in claim 1, and E is O, S or a mixture of O and S.

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112012020112B1|2021-08-24|METHOD FOR MODULARING IONIC FORCE

---

BR112013014972B1|2020-12-29|method for removing a solute from the aqueous solution or for concentrating the diluted aqueous solution by modulating the ionic strength of an aqueous solution

---

Duan et al.2014|Treatment of wastewater produced from polymer flooding using polyoxyalkylated polyethyleneimine

---

US8710265B2|2014-04-29|Switchable solvents and methods of use thereof

---

Long et al.2015|Synthesis and application of ethylenediamine tetrapropionic salt as a novel draw solute for forward osmosis application

---

EP2493849A1|2012-09-05|Switchable hydrophilicity solvents and methods of use thereof

---

BRPI0620470A2|2011-11-08|reversibly convertible into a salt, surfactant reversibly to a non-surfactant, method for stabilizing an emulsion of two immiscible liquids or a liquid and a solid, method for separating two immiscible liquids or a liquid and a solid from an emulsion, and emulsion polymerization method

---

JP2013518718A5|2014-04-03|

---

Tang et al.2020|Recoverable deep eutectic solvent-based aniline organic pollutant separation technology using choline salt as adsorbent

---

Bouchal et al.2016|Alkylguanidinium based ionic liquids in a screening study for the removal of anionic pollutants from aqueous solution

---

Jessop et al.2020|CO2-switchable materials

---

CA2821789C|2020-12-29|Systems and methods for use of water with switchable ionic strength

---

Cherian2022|Switchable water

同族专利:

---

公开号 | 公开日

---

EP3653584A1|2020-05-20|

---

CA2789498A1|2011-08-18|

---

US20190315637A1|2019-10-17|

---

SG10201501027XA|2015-04-29|

---

SG183909A1|2012-10-30|

---

AU2011214865A1|2012-09-06|

---

BR112012020112A2|2020-08-11|

---

JP2018103180A|2018-07-05|

---

AU2011214865B2|2015-11-05|

---

CA2789498C|2019-04-02|

---

HK1177927A1|2013-08-30|

---

EP2534106A1|2012-12-19|

---

EP2534106B1|2019-10-16|

---

CN102892713B|2016-05-04|

---

WO2011097727A1|2011-08-18|

---

MX364273B|2019-04-22|

---

CN102892713A|2013-01-23|

---

JP2013518718A|2013-05-23|

---

JP2016128164A|2016-07-14|

---

IL221391A|2019-09-26|

---

US20130105377A1|2013-05-02|

---

EP2534106A4|2016-01-06|

---

IL221391D0|2012-10-31|

---

JP6431658B2|2018-11-28|

---

MX2012009296A|2012-11-06|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US2812333A|1954-09-27|1957-11-05|Union Carbide Corp|Process for the preparation of 1- imidazolidine-2|

---

US3088909A|1961-02-09|1963-05-07|Richard R Davison|Mixed solvents for saline water extraction|

---

US3925201A|1973-08-03|1975-12-09|Resources Conservation Co|Method of dewatering material containing solid matter and bound and unbound water|

---

JPH0220622B2|1982-07-28|1990-05-10|Tosoh Corp|

---

JPH037413B2|1985-04-01|1991-02-01|Kawasaki Heavy Ind Ltd|

---

JPH0446162B2|1985-05-07|1992-07-29|Kurita Water Ind Ltd|

---

EP0322924A1|1987-12-31|1989-07-05|Union Carbide Corporation|Selective H2S removal from fluid mixtures using high purity triethanolamine|

---

JPH0644972B2|1988-03-11|1994-06-15|ユニオン・カーバイド・コーポレーション|Tertiary alkanolamine absorbers containing ethylene amine promoters and methods of use thereof|

---

US5472638A|1992-04-27|1995-12-05|Mobil Oil Corp.|Corrosion inhibitor|

---

JPH062615A|1992-06-19|1994-01-11|Aqueous Res:Kk|Engine combustion system utilizing carbon dioxide|

---

JP3392646B2|1996-07-26|2003-03-31|三菱重工業株式会社|Method for recovering basic amine compound in decarbonation tower exhaust gas|

---

DE10036173A1|2000-07-25|2002-02-07|Basf Ag|Process for deacidifying a fluid stream and wash liquid for use in such a process|

---

US7510647B2|2003-11-19|2009-03-31|Intercat Equipment, Inc.|Mobile fluid catalytic cracking injection system|

---

US7662295B2|2004-11-05|2010-02-16|Hitachi, Ltd.|Method for removing organic material in oilfield produced water and a removal device therefor|

---

CA2527144C|2005-11-15|2014-04-29|Queen's University At Kingston|Reversibly switchable surfactants and methods of use thereof|

---

CN101326144A|2005-11-15|2008-12-17|金斯顿女王大学|Reversibly switchable surfactants and methods of use thereof|

---

JP5023512B2|2006-02-27|2012-09-12|三菱マテリアル株式会社|Gas separation and recovery method and apparatus|

---

CA2539418C|2006-03-13|2013-10-29|Queen's University At Kingston|Switchable solvents and methods of use thereof|

---

CA2654508C|2006-06-08|2014-07-29|Yale University|Multi stage column distillation method for osmotic solute recovery|

---

JP2008056642A|2006-09-04|2008-03-13|Research Institute Of Innovative Technology For The Earth|Method for producing highly concentrated piperazine-containing aqueous solution and method for recovering carbon dioxide|

---

JP2008238073A|2007-03-28|2008-10-09|Nippon Steel Chem Co Ltd|Carbon dioxide absorbent and carbon dioxide adsorbing method|

---

CN102026713B|2008-03-20|2013-10-16|耶鲁大学|Spiral wound membrane module for forward osmotic use|

---

EP2303436A4|2008-06-20|2012-08-15|Univ Yale|Forward osmosis separation processes|

---

CN102239231B|2008-12-08|2014-04-09|亨斯迈石油化学有限责任公司|Decreased presence of amine-derived contaminants in- and/or degradation of amine solvent solutions|

---

CN102892713B|2010-02-10|2016-05-04|金斯顿女王大学|There is the water of convertible ionic strength|CN103459439B|2010-12-15|2017-09-12|金斯顿女王大学|Use the system and method for the water with convertible ionic strength|

---

CN102892713B|2010-02-10|2016-05-04|金斯顿女王大学|There is the water of convertible ionic strength|

---

CN103153440B|2010-09-29|2015-11-25|富士胶片株式会社|Forward osmosis device and forward osmosis method|

---

US10363336B2|2011-08-26|2019-07-30|Battelle Energy Alliance, Llc|Methods and systems for treating liquids using switchable solvents|

---

NL2007353C2|2011-09-05|2013-03-07|Kwr Water B V|Solution comprising an osmotic agent and method of extracting water using said solution.|

---

CA2880645A1|2012-08-02|2014-02-06|Queen's University At Kingston|Micellar composition having switchable viscosity|

---

US10532319B2|2013-04-26|2020-01-14|Nanyang Technological University|Draw solute for forward osmosis|

---

US9399194B2|2014-07-16|2016-07-26|Battelle Energy Alliance, Llc|Methods for treating a liquid using draw solutions|

---

JP6512900B2|2015-03-31|2019-05-15|大阪瓦斯株式会社|Power generation equipment|

---

US11236250B2|2015-06-04|2022-02-01|Queen's University At Kingston|Switchable water-based paint or coating compositions|

---

MX2018001676A|2015-08-11|2019-04-22|Forward Water Tech|A switchable forward osmosis system, and processes thereof.|

---

CN105481744B|2015-11-25|2017-03-29|江南大学|CO2/N2‑H2O2Double stimuli responsive type surfactant and preparation method thereof|

---

TWI586681B|2016-08-30|2017-06-11|財團法人工業技術研究院|Ionic liquid for forward osmosis process and forward osmosis process|

---

JP6649310B2|2017-03-23|2020-02-19|株式会社東芝|Water treatment system and working medium|

---

JP6854196B2|2017-06-09|2021-04-07|株式会社Kri|Water absorption liquid, draw solution and forward osmosis water treatment method|

---

CN107376421A|2017-09-11|2017-11-24|扬州大学|A kind of method for carrying out extract and separate to the blend of organic matter and water using N methyl diethanolamines|

---

CN107596733A|2017-09-11|2018-01-19|扬州大学|A kind of method for carrying out extract and separate to the blend of organic matter and water using triethylamine|

---

CN108031144A|2017-12-25|2018-05-15|扬州大学|The method that extract and separate is carried out to the blend of organic matter and water using N-methylcyclohexylamine|

---

JP2019167331A|2018-03-22|2019-10-03|株式会社東芝|Amine compound, work medium and water treatment system|

---

US11235283B2|2019-12-30|2022-02-01|Industrial Technology Research Institute|Ionic liquid and forward osmosis process employing the same|

法律状态:
2020-08-25| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2021-01-12| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

---

2021-06-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2021-08-24| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 10/02/2011, OBSERVADAS AS CONDICOES LEGAIS. PATENTE CONCEDIDA CONFORME ADI 5.529/DF, QUE DETERMINA A ALTERACAO DO PRAZO DE CONCESSAO. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US30317010P| true| 2010-02-10|2010-02-10|

---

US61/303,170|2010-02-10|

---

US42345810P| true| 2010-12-15|2010-12-15|

---

US61/423,458|2010-12-15|

---

PCT/CA2011/050075|WO2011097727A1|2010-02-10|2011-02-10|Water with switchable ionic strength|

---