US 12,605,653 B2Granted

Anionic switchable hydrophilicity solvents

AssigneeQueen's University at Kingston

InventorsPhilip G. Jessop, Meghan McKeeman, Igor Tadeu da Cunha, Maedeh Ramezani, Alana Lloyd-Smith

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Abstract

Anionic switchable hydrophilicity solvents (ASHS) that can be reversibly converted between hydrophobic and hydrophilic forms are described. The ASHS comprise a carboxylic acid, a water-soluble base, water, and addition and removal of an acidic gas (CO2) effects the conversion between the hydrophobic and hydrophilic forms. A system and method for forming the ASHS are described, as well as applications utilizing the ASHS, including a method for separating a selected substance from a mixture, a method of removing gas from polymeric foam, and a method of extracting a hydrophobic material from a solid that is at least partially coated by the hydrophobic material.

Claims20

Dependent claims

A system for forming an anionic switchable hydrophilicity solvent comprising:

a carboxylic acid comprising a neutral form and an anionic form,
wherein the carboxylic acid is a water-immiscible liquid in its neutral form, and is water-soluble in its anionic form, at one or more selected temperatures within a selected temperature range, and/or
wherein the carboxylic acid is a liquid that is immiscible with water in its neutral form under an elevated pressure of CO2, and is water-soluble in its anionic form, at one or more selected temperatures within a selected temperature range:
a water-soluble base, wherein the water-soluble base is an amine, a basic salt containing a metal cation, a basic salt containing a quaternary ammonium cation, a basic salt containing a substituted or unsubstituted ammonium cation, a basic salt containing a quaternary phosphonium cation, a basic salt containing a substituted or unsubstituted phosphonium cation, ammonia, or a mixture thereof;
water;
and
a source of CO2;
wherein the carboxylic acid, the water-soluble base, and the water are combinable at one of the one or more selected temperatures such that the water-soluble base deprotonates the carboxylic acid and converts the carboxylic acid to its anionic water-soluble form, forming an aqueous solution;
and
contacting the aqueous solution with CO2 at one of the one or more selected temperatures results in the anionic form of the carboxylic acid being protonated and a biphasic mixture being formed, the biphasic mixture comprising:
an aqueous phase comprising water and the water-soluble base, and an organic phase comprising the carboxylic acid in its neutral form;
wherein when the water-soluble base is an amine, the ratio of the water-soluble base to the carboxylic acid is substoichiometric.

9 more elements

A method of forming an anionic switchable hydrophilicity solvent comprising:

(a) obtaining a carboxylic acid comprising a neutral form and an anionic form, wherein the carboxylic acid is a water-immiscible liquid in its neutral form, and is water-soluble in its anionic form, at one or more selected temperatures within a selected temperature range, and/or wherein the carboxylic acid is a liquid that is immiscible with water in its neutral form under an elevated pressure of CO2 and is water-soluble in its anionic form, at one or more selected temperatures within a selected temperature range;
(b) obtaining a water-soluble base, wherein the water-soluble base is an amine, a basic salt containing a metal cation, a basic salt containing a quaternary ammonium cation, a basic salt containing a substituted or unsubstituted ammonium cation, a basic salt containing a quaternary phosphonium cation, a basic salt containing a substituted or unsubstituted phosphonium cation, ammonia, or a mixture thereof;
(c) (i) combining in any order:
the carboxylic acid;
the water soluble base;
and water;
wherein the water-soluble base is configured to deprotonates the carboxylic acid and convert the carboxylic acid to its anionic water-soluble form to form an aqueous solution, wherein a temperature of the aqueous solution is one of the one or more selected temperatures within the selected temperature range;
wherein when the water soluble base is an amine, the ratio of the water-soluble base to the carboxylic acid is substoichiometric;
or
(c) (ii) combining:
a salt of the carboxylic acid and the water-soluble base and water to form an aqueous solution, wherein a temperature of the aqueous solution is one of the one or more selected temperatures within the selected temperature range;
wherein when the water-soluble base is an amine, the ratio of the water-soluble base to the carboxylic acid is substoichiometric;
and
(d) contacting the aqueous solution with CO2 to protonate the anionic form of the carboxylic acid to form a biphasic mixture, wherein a temperature of the biphasic mixture is one of the one or more selected temperatures within the selected temperature range, the biphasic mixture comprising:
an aqueous phase comprising water and the water-soluble base, and
an organic phase comprising the carboxylic acid in its neutral form;
and
(e) optionally, removing CO2 from the biphasic mixture, wherein when CO2 is removed from the biphasic mixture the carboxylic acid is deprotonated and converts to its anionic water-soluble form, re-forming the aqueous solution.

15 more elements

A method for separating a selected substance from a mixture using an anionic switchable hydrophilicity solvent, comprising:

(a) obtaining a carboxylic acid comprising a neutral form and an anionic form,
wherein the carboxylic acid is a water-immiscible liquid in its neutral form, and is water-soluble in its anionic form, at one or more selected temperatures within a selected temperature range, and/or
wherein the carboxylic acid is a liquid that is immiscible with water in its neutral form under an elevated pressure of CO2, and is water-soluble in its anionic form, at one or more selected temperatures within a selected temperature range;
(b) obtaining a water-soluble base, wherein the water-soluble base is an amine, a basic salt containing a metal cation, a basic salt containing a quaternary ammonium cation, a basic salt containing a substituted or unsubstituted ammonium cation, a basic salt containing a quaternary phosphonium cation, a basic salt containing a substituted or unsubstituted phosphonium cation, ammonia, or a mixture thereof,
(c) adding the carboxylic acid in its neutral form to a mixture comprising a selected substance that is water-immiscible or water-insoluble;
(d) allowing the carboxylic acid to solubilize the selected substance to form a second mixture;
(e) optionally isolating insoluble material from the second mixture;
(f) contacting the second mixture with water and the water-soluble base, wherein the water-soluble base deprotonates the carboxylic acid and converts the carboxylic acid to its anionic water-soluble form to form a two-phase mixture having:
a first hydrophobic phase comprising the selected substance, and
a second aqueous phase comprising the carboxylic acid in its anionic water-soluble form,
wherein a temperature of the two-phase mixture is one of the one or more selected temperatures within the selected temperature range, wherein when the water-soluble base is an amine, the ratio of the water-soluble base to the carboxylic acid is substoichiometric;
and
(g) separating the first hydrophobic phase from the second aqueous phase;
and
(h) optionally, contacting the second aqueous phase with CO:
to protonate the anionic form of the carboxylic acid to form a biphasic mixture, wherein a temperature of the biphasic mixture is one of the one or more selected temperatures within the selected temperature range, the biphasic mixture comprising:
an aqueous phase comprising water and the water-soluble base, and
an organic phase comprising the carboxylic acid in its neutral form;
and
(i) optionally, separating the organic phase from the aqueous phase to recover the carboxylic acid;
wherein the selected substance is not reactive with the carboxylic acid, the water-soluble
base, or a combination thereof.

19 more elements

A method of removing gas from polymeric foam using an anionic switchable hydrophilicity solvent, comprising:

(a) obtaining a carboxylic acid comprising a neutral form and an anionic form,
wherein the carboxylic acid is a water-immiscible liquid in its neutral form, and is water-soluble in its anionic form, at one or more selected temperatures within a selected temperature range, and/or
wherein the carboxylic acid is a liquid that is immiscible with water in its neutral form under an elevated pressure of CO2 and is water-soluble in its anionic form, at one or more selected temperatures within a selected temperature range;
(b) obtaining a water-soluble base,
wherein the water-soluble base is an amine, a basic salt containing a metal cation, a basic salt containing a quaternary ammonium cation, a basic salt containing a substituted or unsubstituted ammonium cation, a basic salt containing a quaternary phosphonium cation, a basic salt containing a substituted or unsubstituted phosphonium cation, ammonia, or a mixture thereof;
(c) contacting a polymeric foam with the carboxylic acid in its neutral form;
(d) allowing the carboxylic acid to solubilize the polymeric foam to form a solution;
(e) contacting the solution of (d) with water and the water-soluble base, optionally, wherein the solution of (d) is first contacted with water and then a resulting combination of the solution of (d) and water is subsequently contacted with the water-soluble base, wherein the water-soluble base deprotonates the carboxylic acid and converts the carboxylic acid to its anionic water-soluble form to form a two-phase mixture having:
a first solid phase comprising the polymer, and
a second aqueous phase comprising the carboxylic acid in its anionic water-soluble form,
wherein a temperature of the two-phase mixture is one of the one or more selected temperatures within the selected temperature range, wherein when the water-soluble base is an amine, the ratio of the water-soluble base to the carboxylic acid is substoichiometric;
and
(f) separating the first solid phase from the second aqueous phase;
and
(g) optionally, contacting the second aqueous phase with CO2 to protonate the anionic form of the carboxylic acid to form a biphasic mixture, wherein a temperature of the biphasic mixture is one of the one or more selected temperatures within the selected temperature range, the biphasic mixture comprising:
an aqueous phase comprising water and the water-soluble base, and an organic phase comprising the carboxylic acid in its neutral form;
and
(h) optionally, separating the organic phase from the aqueous phase to recover the carboxylic acid.

15 more elements

A method of extracting a hydrophobic material from a solid that is at least partially coated by the hydrophobic material using an anionic switchable hydrophilicity solvent, comprising:

(a) obtaining a carboxylic acid comprising a neutral form and an anionic form,
wherein the carboxylic acid is a water-immiscible liquid in its neutral form, and is water-soluble in its anionic form, at one or more selected temperatures within a selected temperature range, and/or
wherein the carboxylic acid is a liquid that is immiscible with water in its neutral form under an elevated pressure of CO2, and is water-soluble in its anionic form, at one or more selected temperatures within a selected temperature range;
(b) obtaining a water-soluble base,
wherein the water-soluble base is an amine, a basic salt containing a metal cation, a basic salt containing a quaternary ammonium cation, a basic salt containing a substituted or unsubstituted ammonium cation, a basic salt containing a quaternary phosphonium cation, a basic salt containing a substituted or unsubstituted phosphonium cation, ammonia, or a mixture thereof;
(c) combining the solid that is at least partially coated by a hydrophobic material with the carboxylic acid in its neutral form to form a mixture of the solid in a homogeneous single-phase liquid, said single-phase liquid comprising the carboxylic acid in its neutral form and the hydrophobic material;
(d) separating the solid from the single-phase liquid;
(e) contacting the single-phase liquid with water and the water-soluble base, wherein the water-soluble base deprotonates the carboxylic acid and converts the carboxylic acid to its anionic water-soluble form to form a two-phase mixture having:
a first hydrophobic phase comprising the hydrophobic material, and
a second aqueous phase comprising the carboxylic acid in its anionic water-soluble form,
wherein a temperature of the two-phase mixture is one of the one or more selected temperatures within the selected temperature range, wherein when the water-soluble base is an amine, the ratio of the water-soluble base to the carboxylic acid is substoichiometric;
and
(f) separating the first hydrophobic phase from the second aqueous phase;
and
(g) optionally, contacting the second aqueous phase with CO2 to protonate the anionic form of the carboxylic acid to form a biphasic mixture, wherein a temperature of the biphasic mixture is one of the one or more selected temperatures within the selected temperature range, the biphasic mixture comprising:
an aqueous phase comprising water and the water-soluble base, and
an organic phase comprising the carboxylic acid in its neutral form;
and
(h) optionally, separating the organic phase from the aqueous phase to recover the carboxylic acid;
wherein the hydrophobic material is not reactive with the carboxylic acid, the water-soluble base, or a combination thereof.

17 more elements

Dependencies are inferred from the claim text.

Facts

Application: 18/179,719Filed 7 Mar 2023 · us provisional application
Priority: CA 315265618 Mar 2022
Published: US 2023/0356114 A19 Nov 2023
Granted: 21 Apr 2026
Term ends: Not estimatedThe source records don’t support an estimate.

Classification11 codes

B01D 17/042
Breaking emulsions: by changing the temperature
B01D 19/0413
Characterised by the nature of the chemical substance: compounds containing N-atoms
B01D 11/028
Of solids: flow sheets
B01D 11/0288
Of solids: applications, solvents