Chelating agent, kit thereof, and method of using the same

Abstract

The present invention provides a chelating agent for chelating non-aqueous moieties from an aqueous solution. The chelating agent may include a detergent; and a polymer, the polymer being useful for stabilizing the formation of detergent micelles, thereby allowing the detergent and the polymer to self-assemble into a nanonet when exposed to the aqueous solution. The present invention also provides a kit and a method for using the chelating agent and the kit.

Description

Technical Field

[0001] The present invention is in the field of chelation, and more particularly in the field of chelating materials from aqueous environments. Background Art

[0002] The decontamination and disposal of organic wastes (e.g., sewage sludge, animal manure, food processing waste, fracturing fluids, oil and gas, and other industrial wastewaters) presents both environmental and public health concerns. The treatment and disposal of contaminated water has significant social, environmental, and economic impacts. Currently, residual wastewater sludge is typically digested, incinerated, deposited in landfills, returned to the same environment, or used as a fertilizer through agricultural land application of the residual biosolids.

[0003] The encapsulation of inorganic particles with polymers has been demonstrated [E. Bourgeat-Lami and E. Duguet: Polymer encapsulation of inorganic particles; in Functional coatings, SK Ghosh (ed.); 2006, Wiley-VCH, Weinheim; Chapter 4, pp. 85-152]. In biomedical applications, the coating of inorganic nanoparticles with polymers or encapsulation thereof in a polymer matrix or detergent layer is important for properties such as solubilization [R. Ladj et al., Polymer encapsulation of inorganic nanoparticles for biomedical applications; Internat. J. Pharm. 2013 (458) 230-241]. In the field of physics and engineering, magnetic fluids composed of magnetic nanoparticles coated with polymers and / or surfactants to stabilize the particles in the bulk liquid have been studied. Various synthesis methods have been disclosed for the preparation of such systems [e.g., J. Sommertune et al., Polymer / Iron oxide nanoparticles composites—a straight forward and scalable synthesis approach; Int. J. Mol. Sci. 2015 (16) 19752-19768]. Summary of the invention

[0004] The present invention is based, at least in part, on the description of the properties of detergents and polymers that make them suitable for use together as chelating agents.

[0005] The present invention provides a new means of capturing non-aqueous parts, including but not limited to organic pollutants and emulsified non-aqueous pollutants (NAC) in water, which are then removed by simple aggregation and filtration or electromagnetic methods. The present invention further removes pollutants suspended and dissolved in water. In the present invention, a clarifier is directly added to an aqueous solution (such as but not limited to, contaminated water or contaminated materials). Organic pollutants are chelated and wrapped in detergent-oil-polymer particles, which facilitates their subsequent removal. Oil and detergent particles are removed via polymer aggregation by protonation or cationic chelation of maleic acid groups or other functional groups on the polymer. The formulation of this polymer detergent combination leads to the formation of gel-like aggregates that can capture organic pollutants within minutes. Chelating agents capture various pollutants (including but not limited to hydrocarbons and heavy metals) and treat wastes with smaller volumes more specifically. Functionalized styrene maleic acid (styrenemalic acid, SMA) polymers are generally particularly suitable due to the range of substances that can be removed. Polymers can also be regenerated and recycled from wastes, making the chelating agent itself environmentally friendly. Embodiments of the present invention may also be used to remove specific chemicals from an extraction mixture.

[0006] Exemplary embodiments of the present invention provide a chelating agent for chelating non-aqueous moieties from an aqueous solution, the chelating agent comprising: a) a detergent; and b) a polymer, the polymer being useful for stabilizing the formation of detergent micelles, thereby allowing the detergent and the polymer to self-assemble into a nanonet when exposed to the aqueous solution.

[0007] Exemplary embodiments of the present invention provide a kit for chelating non-aqueous moieties from an aqueous solution, the kit comprising: a) a detergent; b) a polymer that can be used to stabilize the formation of detergent micelles, thereby allowing the detergent and the polymer to self-assemble into a nanonet when exposed to the aqueous solution; and c) a precipitant.

[0008] Exemplary embodiments of the invention provide a chelating agent and / or a kit as described herein, further comprising a precipitating agent.

[0009] Exemplary embodiments of the invention provide a chelating agent and / or a kit as described herein, wherein the precipitating agent is selected from the group consisting of an acid, a divalent cation, and a mixture thereof.

[0010] Exemplary embodiments of the invention provide a chelating agent and / or kit as described herein, wherein the precipitating agent is selected from the group consisting of acetic acid, malic acid, hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, tartaric acid, fumaric acid and lactic acid.

[0011] Exemplary embodiments of the present invention provide a chelating agent and / or kit as described herein, wherein the detergent is selected from the group consisting of a nonionic surfactant, an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, and mixtures thereof.

[0012] Exemplary embodiments of the present invention provide a chelating agent and / or a kit as described herein, wherein the detergent is selected from the group consisting of: Triton TM (Triton TM ), Triton X-100 TM (Triton X-100 TM ), Triton X-305 TM (Triton X-305 TM ), N-dodecyl-β-D-maltoside (DDM), sodium oleate and mixtures thereof.

[0013] Exemplary embodiments of the invention provide a chelating agent and / or a kit as described herein, wherein the detergent does not form stable micelles in the absence of the polymer.

[0014] Exemplary embodiments of the invention provide a chelating agent and / or a kit as described herein, wherein the detergent forms stable micelles in the absence of the polymer.

[0015] Exemplary embodiments of the invention provide a chelating agent and / or a kit as described herein, wherein the detergent is a nonionic surfactant.

[0016] Exemplary embodiments of the invention provide a chelator and / or kit as described herein, wherein the polymer is a block copolymer.

[0017] Exemplary embodiments of the present invention provide a chelating agent and / or kit as described herein, wherein the polymer is selected from the group consisting of styrene-maleic acid (SMA), activated SMA, di-isobutyl maleic acid, and mixtures thereof.

[0018] Exemplary embodiments of the invention provide a chelating agent and / or a kit as described herein, wherein the polymer has a molecular weight in the range of 3000 g / mol to about 25,000 g / mol.

[0019] Exemplary embodiments of the invention provide a chelating agent and / or a kit as described herein, wherein the polymer has a molecular weight of about 22,000 g / mol.

[0020] Exemplary embodiments of the invention provide a chelator and / or kit as described herein, wherein the polymer is water soluble.

[0021] Exemplary embodiments of the invention provide a chelator and / or kit as described herein, wherein the polymer is biodegradable.

[0022] Exemplary embodiments of the invention provide a chelating agent and / or kit as described herein, wherein the ratio of detergent:polymer is in the range of about 1:0.5 to about 1:1.3.

[0023] Exemplary embodiments of the invention provide a chelating agent and / or kit as described herein, wherein the ratio of detergent:polymer is in the range of about 1:0.5 to about 1:1.0.

[0024] Exemplary embodiments of the present invention provide a chelator and / or kit as described herein, wherein the ratio of detergent:polymer is in the range of about 1:0.6 to about 1:0.8.

[0025] Exemplary embodiments of the invention provide a chelator and / or kit as described herein, wherein the ratio of detergent:polymer is about 1:0.7.

[0026] Exemplary embodiments of the invention provide a chelating agent and / or a kit as described herein, wherein the detergent is capable of forming micelles having a size of no less than about 10 kDa.

[0027] Exemplary embodiments of the invention provide a chelating agent and / or a kit as described herein, wherein the detergent is capable of forming micelles having a size of no less than about 40 kDa.

[0028] Exemplary embodiments of the invention provide a chelator and / or kit as described herein, wherein the detergent is capable of forming micelles having a size of no less than about 40 kDa and no greater than about 300 kDa.

[0029] Exemplary embodiments of the present invention provide a method for chelating a non-aqueous portion from an aqueous solution, the method comprising adding a chelating agent as described herein to the aqueous solution comprising the non-aqueous portion, thereby forming a treated aqueous solution, and then removing solid particles from the treated aqueous solution.

[0030] Exemplary embodiments of the present invention provide the methods described herein further comprising mixing prior to removing the solid particles.

[0031] Exemplary embodiments of the present invention provide the method described herein, wherein the removing of solid particles comprises at least one selected from the group consisting of: filtration, gravity separation, flotation, and electromagnetic attraction.

[0032] Exemplary embodiments of the present invention provide the method described herein, wherein the removing of solid particles comprises electromagnetic attraction, and the method further comprises adding a magnetic moiety to the treated aqueous solution prior to removing the solid particles.

[0033] Other aspects and features of the present invention will become apparent to those of ordinary skill in the art upon reading the following description of specific embodiments of the invention in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 A: Schematic diagram depicting the capture process of the chelating agent.

[0035] Figure 1 B: Schematic diagram depicting the release process of the chelating agent.

[0036] Figure 1 C: Schematic diagram depicting the application of magnetic nanoparticle seeding to enhance the dewatering of the resulting flocs.

[0037] Figure 2 A: The results of Table 3 in Example 4 are depicted in a graphical form.

[0038] Figure 2 B: The results of Table 4 in Example 4 are depicted in a graphical form.

[0039] Figure 2 C: The results of Table 5 in Example 4 are depicted in a graphical form.

[0040] Figure 2 D: The results of Table 6 in Example 5 are depicted in a graphical form.

[0041] Figure 3 A: Depicts Triton X-100 TM Chemical structure.

[0042] Figure 3 B: depicts Triton X-100 at 280 nm TM Absorbance standard curve.

[0043] Figure 3 C: The results of Table 8 in Example 8 are depicted in graphical form.

[0044] Figure 4 A: depicts the reaction of Example 7 with 0.1% Triton X-100 TM Results of titration of DIBMA (at 0.025%, 0.05% and 0.1%).

[0045] Figure 4 B: The results of Table 7 in Example 7 are depicted in graphical form.

[0046] Figure 4 C: Depicted is the chemical structure of the repeating functional unit of DIBMA.

[0047] Figure 5 A: depicts polymer SMA 2021 as described in Example 10 TM Elution chromatograms of the polymers are depicted together.

[0048] Figure 5 B: depicts the detergent Triton X-100 as described in Example 10 TM The elution chromatogram of , together with the detergent is depicted.

[0049] Figure 5 C: depicts a polymer SMA 2021 as described in Example 10 TM and detergent Triton X-100 TM Elution chromatograms of the nanonets are depicted together with the nanonets.

[0050] Figure 6 A: depicts polymer SMA 2021 as described in Example 11 TM Elution chromatograms of the polymers are depicted together.

[0051] Figure 6 B: Depicted is the elution chromatogram of the detergent sodium oleate as described in Example 11, together with the detergent.

[0052] Figure 6 C: depicts a polymer SMA 2021 as described in Example 11 TM and the elution chromatogram of the nanonet with the detergent sodium oleate, depicting the nanonet together.

[0053] Figure 7 A: Depicts the use of polymer (SMA 2000 TM ) and detergent forming micelles <20 kDa. Nanomesh formulation with β-octylglucoside, sodium oleate and lauryl dimethylamine.

[0054] Figure 7 B: Describes the above Figure 7 A. Results of the same experiment set up except that it was repeated and contained additional nanomeshes using dodecyl-maltoside (DDM) as detergent (indicated by arrows).

[0055] Figure 7 C: depicts the use of polymer (SMA 2000 TM), the results of acid-precipitated flocs formed by detergent mixtures each having micelles of different sizes (0.8 kDa, 4 kDa, 8 kDa, 17 kDa and 90 kDa).

[0056] Figure 7 D: Graph depicting eight different polymer blends (SMA 2000 TM +: No detergent (i.e. only SMA 2000 TM ), sodium cholate (cholate), sodium deoxycholate (DOC), β-octylglucoside (Beta-OG), lauryl dimethylamine n-oxide (LDAO), octylphenol ethoxylate (TX-305), n-dodecyl β-D-maltoside (DDM) and sodium oleate (oleate) floccules (stimulated by slight centrifugation) aggregates. The circles in the graph refer to the starting micelle size, and the squares in the graph refer to the relative turbidity. Note that the circles and squares of polymer + TX-305 are in approximately the same position and overlap each other.

[0057] Figure 8 A: Depicted is only Triton X-305 TM Results of the size exclusion chromatography trace.

[0058] Figure 8 B: depicts Triton X-305 at a polymer to detergent ratio of 1:1.4 (wt / wt). TM Results of size exclusion chromatography traces of the nanomesh formulations. The inset depicts the precipitation that resulted in coagulation and captured 2% N-decane.

[0059] Figure 8 C: depicts Triton X-305 at a polymer to detergent ratio of 1:0.7 (wt / wt) TM Size exclusion chromatography traces of the nanomesh formulations. The inset depicts the precipitation leading to coagulation and trapping of 2% N-decane.

[0060] Figure 8 D: Depicted is the size exclusion chromatography trace of polymer only. The inset depicts the precipitation in the presence of 2% N-decane. DETAILED DESCRIPTION

[0061] Embodiments of the present invention provide chelating agents for chelating non-aqueous moieties from aqueous solutions. The chelating agents according to the present invention comprise a detergent and a polymer. The polymer can be used to stabilize the formation of detergent micelles, thereby allowing the detergent and polymer to self-assemble into a nanonet when exposed to an aqueous solution.

[0062] As used herein, the term "aqueous solution" refers to a liquid environment in which water is the major component. Examples of aqueous solutions include, but are not limited to, wastewater, aqueous materials recovered from processes (e.g., sewage sludge, animal manure, food processing waste), oil and gas wastewater, used fracturing fluids, industrial sewage, groundwater, etc.

[0063] As used herein, the term "part" refers to a division or portion of an entirety, which is divisible and different from other divisions of the entirety. As used herein, a "part" can be a whole chemical molecule or can be a division of a chemical molecule. For example, in a sodium chloride aqueous solution, the entirety should be a solution and the portion should be water, sodium, chlorine and sodium chloride, and each of water, sodium, chlorine and sodium chloride is an independent part of itself. As used herein, the term "non-aqueous" part is a part that is not a water molecule. A "non-aqueous" part can be suspended, dissolved and / or otherwise present in an aqueous environment. A non-aqueous part can be physical, chemical, biological and / or radioactive material. Examples of "non-aqueous" parts include, but are not limited to, organic parts, emulsified non-aqueous parts, hydrocarbons, heavy metals, oils, dissolved solids, suspended solids, ions and heavy metals.

[0064] As used herein, the term "sequestering agent" refers to an agent capable of separating a non-aqueous portion from an aqueous environment in which the non-aqueous portion is found. The non-aqueous portion may be a contaminant or more than one contaminant that needs to be separated so that an aqueous solution is decontaminated, and / or may be a valuable portion that needs to be separated in order to obtain and / or purify the non-aqueous portion. In some embodiments of the present invention, the chelating agent is a nanomesh. In some embodiments, the chelating agent is a mixture of portions that can form a nanomesh when exposed to an aqueous environment. In some cases, a "chelating agent" may refer to a "clarifying agent," and generally the terms "chelating agent" and "clarifying agent" may be used interchangeably.

[0065] As used herein, the term "micelle" refers to an aggregation of molecules in a colloidal solution.

[0066] As used herein, the term "nanonet" refers to a structure in which micelles (formed by detergent and polymer interaction) and nanonets self-assemble in an aqueous environment. The self-assembly of the nanonet usually occurs by the initiation of interaction between the polymer and the micelle. Typically, the interaction between the polymer and the micelle leads to the stability of the micelle, thereby making the micelle more resistant to damage. In some embodiments, the polymer wraps the outer surface of the micelle. The polymer can wrap the entire outer surface of the micelle, a large part of the outer surface, or a portion of the outer surface.

[0067] As used herein, the term "detergent" refers to a surfactant or a mixture of surfactants. Typically, detergents have a cleaning property such that a surfactant is combined with a non-aqueous portion to increase the solubility of the non-aqueous portion. In addition, as used herein, "detergent" refers to a surfactant that can form micelles. Some of these micelles can be micelles that are stable in themselves, and others can be unstable unless a second material is present to stabilize the micelles. For those micelles that are unstable unless a second substance is present, typically, they can be added at a concentration at or above their critical micelle concentration, and after a polymer is added to the micelles, a nanonet is formed. Once a nanonet is formed, if dilution of the detergent occurs, the concentration of the detergent is reduced to a CMC below it, although the detergent is at a concentration below the CMC, the micelles in the nanonet remain stable.

[0068] Chelating agents according to the present invention include polymers. The polymers used for the chelating agents of the present invention are commercially available. Generally, polymers are water-soluble. Generally, polymers are biodegradable. Polymers generally have a molecular weight in the range of about 3000 g / mol to about 25,000 g / mol. Polymers generally have a molecular weight of about 22 kDa. Polymers can also be a mixture of suitable polymers. Polymers are generally block copolymers. The term "block copolymer" is used herein to refer to copolymers with two or more homopolymer subunits, such as di-isobutylene maleic acid copolymers (DIBMA). Generally, polymers are amphoteric, with a hydrophilic part and a hydrophobic part. Generally, block copolymers are composed of hydrophobic subunits and hydrophilic subunits. In some embodiments, the ratio of hydrophobic subunits to hydrophilic subunits is 1:1, 2:1, 3:1 or higher than 3:1, and any ratio between 1:1 and 3:1. In some embodiments, the polymer is a maleic acid polymer, a styrene-maleic acid (SMA) polymer, or an activated SMA polymer. SMA polymers are synthetic polymers built from styrene and maleic anhydride monomers. Activated SMA polymers are SMA polymers where styrene maleic anhydride has been hydrolyzed to maleic acid. Typically, the polymer is SMA2021 TM Typically, the polymer is SMA 2000 TM .

[0069] Chelating agents according to the present invention include detergents. In some embodiments, detergents can form micelles with a size of not less than about 10kDa. In some embodiments, detergents can form micelles with a size of not less than about 40kDa. In some embodiments, detergents can form micelles with a size of not less than about 40kDa and not more than about 300kDa. In some embodiments, detergents can form micelles with a size in the range of about 10kDa to about 3000kDa. In some embodiments, in the absence of and / or presence of polymers, detergents form stable micelles. In some embodiments, in the absence of polymers, detergents do not form stable micelles. In some embodiments, in the presence of polymers, detergents only form stable micelles. In some embodiments, in the absence of polymers, detergents form stable micelles.

[0070] Detergents suitable for use in the present invention have a critical micelle concentration. Critical micelle concentration (CMC) refers to the concentration of a detergent in an aqueous solution, above which micelles are formed and additional detergent molecules also form micelles and / or become part of micelles. Some non-aqueous portions found in aqueous solutions can destroy, disrupt, destabilize and / or generally interfere with the formation of micelles. The addition of polymers can stabilize micelle formation below the CMC and / or offset the interference of the non-aqueous portions. In order to make a detergent suitable for use in the present invention, when forming a nanonet, the CMC of the detergent should be used in the presence of a polymer.

[0071] In some embodiments, the detergent can be a nonionic surfactant, an anionic surfactant, a cationic surfactant, a zwitterionic surfactant, and / or a mixture thereof. In some embodiments, the detergent can be Triton. TM Detergent, Triton X-100 TM , Triton X-305 TM , N-dodecyl-β-D-maltoside (DDM), sodium oleate and / or a mixture thereof.

[0072] The chelating agent of the present invention comprises a certain proportion of detergent: polymer. As used herein, these detergents: the ratio of polymer is expressed in a 'wt / wt' ratio. That is, if the ratio is 1:1, each of the same weight (e.g., 1g of detergent and 1g of polymer) is used. In addition, if the ratio is 2:1, twice the weight of detergent (e.g., 4g of detergent and 2g of polymer) is used compared to the weight of the polymer used. In some embodiments of the present invention, the detergent: polymer ratio is in the range of about 1:0.5 to about 1:1.3. In some embodiments of the present invention, the detergent: polymer ratio is in the range of about 1:0.075 to about 1:1.4. Typically, the ratio is in the range of about 1:0.5 to about 1:1.0. In some embodiments of the present invention, the detergent: polymer ratio is in the range of about 1:0.6 to about 1:0.8. In some embodiments of the present invention, the detergent: polymer ratio is about 1:0.7. In some embodiments of the present invention, the detergent: polymer ratio is about 1:0.75.

[0073] In some embodiments of the present invention, the chelating agent comprises a detergent, a polymer and a precipitation agent. The precipitation agent can be used to promote and / or induce the aggregation of the chelating agent. Such aggregation promotes the removal of the chelating agent from the aqueous solution. In some embodiments, the precipitation agent promotes and / or induces the flocculation of the chelating agent. Usually, the precipitation agent is an acid, a divalent cation and / or a mixture thereof. Usually, the precipitation agent is acetic acid, malic acid, citric acid, tartaric acid, fumaric acid, lactic acid and / or a mixture thereof. In some embodiments, the precipitation agent is a magnetic part, which promotes aggregation when the magnetic force is exposed to the aqueous solution treated with the chelating agent of the present invention. Usually, the magnetic part is a part that can be chelated by the chelating agent. In some embodiments, the precipitation agent is a non-aqueous part, which is present in the aqueous solution and can be chelated by the chelating agent.

[0074] Polymers can be aggregated by protonation or cationic chelation of maleic acid groups or other functional groups on the polymer. When the polymer stabilizes the micelle of the detergent, this aggregation causes the formation of gelatinous aggregates that chelate the non-aqueous part in the aqueous solution. Usually, this occurs within a few minutes of protonation or cationic chelation. Mixing the chelating agent of the present invention in the aqueous solution can promote faster and more complete aggregation. The gelatinous aggregate can then be removed by various methods known in the art for separating solids from liquids, including filtration, gravity separation, flotation or electromagnetic methods. Once separated from the aqueous solution, the polymer can be regenerated and reused usually.

[0075] Embodiments of the present invention also provide kits. The kits of the present invention provide components for chelating non-aqueous moieties with aqueous solutions. Typically, the kits comprise detergents, polymers, and precipitants. Detergents, polymers, and precipitants suitable for use in the kits of the present invention are the same as those described herein for use in the chelating agents. Instructions for use of the components found in the kits may also be provided in the kits of the present invention. The kits of the present invention may comprise any one or more of the components of the chelating agents described herein, and may further comprise instructions for use of these components.

[0076] Examples of aqueous solutions suitable for treatment with the chelating agents of the present invention include, but are not limited to, wastewater, aqueous materials recovered from processes (e.g., sewage sludge, animal feces, food processing waste), oil and gas wastewater, used fracturing fluids, industrial sewage, groundwater, and the like. Typically, up to 60% of pollutants, or up to 70% of pollutants, or up to 80% of pollutants, or up to 90% of pollutants, or up to 95% of pollutants, or more than 99% of pollutants are concentrated. Use of the chelating agents of the present invention can result in an aqueous solution having a suspended solids content in the range of about 0.05% to about 5% after treatment; or about 0.05% to about 10% or about 05% to 30%. Although the starting pH of the aqueous solution to be treated can be any pH, it is generally preferred to have a pH in the range of about 2 to about 11, or more preferably about 3 to about 11, or most preferably about 4 to about 11. Furthermore, although the concentration of the alkaline earth metal in the aqueous solution to be treated may be any concentration, it is generally preferred to have a concentration of less than about 20 mM, or less than about 5 mM, or less than about 10 mM.

[0077] Embodiments of the present invention also provide a method for chelating non-aqueous parts from an aqueous solution. The method may include adding a chelating agent as described herein to an aqueous solution comprising a non-aqueous part, thereby forming a treated aqueous solution. Once the treated aqueous solution is formed, solid particles can be removed from the treated aqueous solution. The removal of solid particles can be to obtain a cleaner aqueous solution, or can be to obtain solid particles, or can be to obtain a cleaner solution and obtain both solid particles. In such methods, it is sometimes beneficial to mix and / or stir the treated aqueous solution before removing the solid particles. Such mixing can promote and / or improve the chelation of the non-aqueous part and / or can promote and / or improve aggregation.

[0078] In the method of the present invention, the removal of solid particles can be achieved by one or more of filtration, gravity separation, flotation and / or electromagnetic attraction. In the embodiment of the method comprising electromagnetic attraction, before the removal of solid particles, a magnetic part, such as iron oxide particles and / or nanoparticles, is optionally added. The addition of the magnetic part can be before or after adding detergent and / or polymer and / or precipitation agent and / or mixing. The magnetic part can be chelated by a chelating agent, and when a magnetic force is applied to the magnetic part, the magnetic part chelated by the chelating agent can be attracted by the magnetic force or repelled by the magnetic force, thereby promoting the concentration of the chelating agent, which can facilitate the removal of solid particles.

[0079] In some embodiments of the present invention, a method for decontaminating water is provided. The method may include adding a detergent to the contaminated water, adding a polymer, adding one or more precipitants to aggregate the contaminants into gel-like aggregates, and filtering the waste solids from the liquid.

[0080] In some embodiments of the present invention, a method for decontaminating water is provided. The method may include adding a detergent to the contaminated water, adding iron oxide nanoparticles coated in a polymer to the contaminated water, adding a precipitant, mixing to aggregate the contaminants into gel-like particles, and removing waste solids using magnetic forces.

[0081] In some embodiments, the method of the present invention may further include recovering the polymer after removing the solid particles. The method may include neutralizing the waste product with a base, dissolving the polymer, and filtering the waste product and / or using a two-phase oil / water extraction to capture the polymer dissolved in the aqueous solution.

[0082] In some embodiments of the present invention, a method for recovering high-value chemicals is provided. The method may include adding a detergent to an extraction mixture, adding a polymer, adding a precipitant to capture the high-value chemicals, mixing to aggregate the high-value chemicals into gel-like particles, and removing the gel-like particles.

[0083] Example

[0084] The following examples illustrate some of the embodiments of the invention described herein. These examples are not intended to limit the spirit or scope of the invention in any way.

[0085] Example 1

[0086] Preparation of hydrolyzed polymer. 3 g of SMA 2021 TMMix in 30 mL of 1 M KOH and reflux at 85° C. for 3 hours. Remove the polymer from the KOH solution by precipitation via the addition of 6 M HCl and vigorous stirring. Wash the precipitated polymer 3 times with 50 mM HCl before resuspending in dH20 and adjusting to pH 8 to facilitate dissociation.

[0087] Example 2

[0088] The clarifier formula (0.15% SMA 2021 TM , .1% Tx-100) was added to 1 mL of contaminated fresh water and mixed by vortexing for 10 seconds. Precipitation was promoted by adding 30 mM HCl and then mixing by tube inversion (3X).

[0089] Then, the aggregates were allowed to stand for 5 minutes to form a gel matrix.

[0090] Example 3

[0091] The clarifier described is a mixture of SMA and detergent in a ratio of 1:1 to 1.4:1. To find this ratio, Triton X-100 TM Titration was performed relative to a constant concentration of SMA (Table 1). TM At 0.05% (wt / vol and vol / vol, respectively), both formed gel aggregates that captured all the oil. TM The density of Triton X-100 is 1.07 g / L, so the actual ratio is 1:1.07 wt / wt. TM The gel aggregates began to disintegrate and the oil was left in solution. The reverse experiment was repeated with titration of SMA and once again, the optimal ratio for complete capture of oil and SMA was found to be 1:1.07 (wt / wt) (Table 2). Although the optimal ratio was found to be about 1:1 (wt / wt) in this experiment, the amount of SMA in the small tube was difficult to remove with the small inlet. Therefore, for future experiments, SMA was mixed with Triton X-100. TM The ratio was reduced to 0.7:1 without reducing the oil capture efficiency. In previous experiments, a 1.4:1 (SMA: Triton X-100) TM Therefore, the optimal ratio range can be 0.07:1 to 1.4:1 SMA: Triton X-100 TM (wt / wt).

[0092] Table 1: Effect of different detergent concentrations on the relative coagulation of emulsified oil. Triton X-100 TMEffect on oil capture with the described clarifiers. Before starting precipitation with 30 mM HCl, an increase in the inclusion of Triton X-100 TM The reported values ​​are the result of the precipitation after 5 minutes.

[0093]

[0094] Table 2: Effect of different polymer concentrations on the relative coagulation of emulsified oil. Effect of SMA on capture of oil with the described clarifiers. Increasing concentrations of SMA were included before starting precipitation with 30 mM HCl. The values ​​reported are the results of the precipitation after 5 minutes.

[0095]

[0096] Example 4

[0097] Styrene maleic acid (SMA) contains repeating maleic acid groups, making it susceptible to precipitation by acid or divalent cations. Two common divalent cations found in groundwater are Mg and 2+ and Ca 2+ Titration of the polymer in buffer A containing the corresponding cations revealed that at 5 mM Ca 2+ and 50 mM Mg 2+ 100% polymer precipitation occurred in Figure 2 A) Using Mn 2+ Additional titrations were completed showing 100% precipitation at concentrations ≥ 10 mM. This result suggests that divalent cations will show different precipitation strengths on polymers. Nevertheless, the clarifier was still effective from Mg containing concentrations up to 10 mM. 2+ and Ca 2+ Although precipitation occurred before the addition of acid, about 75% of the oil was still effectively recovered (Table 4 and Figure 2 B) However, as the divalent cation concentration increased, oil recovery decreased significantly, indicating that the clarifier could not perform as desired at divalent cation concentrations greater than 10 mM.

[0098] Table 3: Effect of divalent cations on polymer precipitation (%). Divalent cation mediated precipitation of SMA in the described clarifiers. The clarifier (0.075% SMA, 0.1% Triton X-100 TM ) were added to buffer A (50 mM Tris-pH 7.9, 50 mM NaCl) supplemented with divalent cations at the indicated concentrations. The solution was mixed by vortexing to ensure dispersion of large aggregates, and turbidity was then measured at 600 nm.

[0099]

[0100] Table 4: Effect of divalent cations on oil recovery efficiency (%) of clarifiers. Oil recovery efficiency of 2% N-decane in buffer A supplemented with indicated divalent cations.

[0101]

[0102] Due to the different salt concentrations of the different target water samples, the clarifiers were tested at 50 mM, 250 mM, and 500 mM NaCl. There was no significant effect on the oil recovery efficiency due to the increase in NaCl concentration (Table 5). Likewise, the recovery efficiency did not change significantly with temperature (Tables 5 and Figure 2 C). However, there was a clear change in the nature of the aggregates formed at 1 °C. At this temperature, the clarifier produced many smaller aggregates that concentrated at the air-water interface (data not shown), rather than a single gel-like aggregate. However, it is important to note that the clarifier still trapped the oil (Table 5). This is in contrast to the precipitation of SMA without detergent, which also produced small aggregates but did not trap the oil or concentrate itself at the surface of the water (Table 1). In addition, the concentration effect was more complete at the lower temperature, with all available precipitate rising to the top of the solution, whereas at the higher temperature some of the free SMA-Triton TM The precipitate remained suspended in solution and did not enter into gel aggregates. At higher temperatures, the formation of gel aggregates occurred at a much greater rate, with virtually no aggregates formed after 15 minutes of incubation on ice, whereas they formed after only 30 seconds at 34°C (Table 5).

[0103] Table 5: Effect of NaCl and temperature on oil recovery efficiency (%) of clarifiers. Oil recovery efficiency of 2% N-decane with clarifiers in the presence of increasing monovalent salt concentrations. The experiment was repeated three times at 1°C, 21°C and 34°C respectively. The precipitated oil / gel aggregates were physically removed from the surface of the solution with a spatula. At 1°C, the oil was effectively captured but the gel aggregates disintegrated when it was removed with a spatula. Therefore, for all experiments conducted at 1°C, the precipitate was removed from the surface with a pipette.

[0104]

[0105] Example 5

[0106] N-dodecyl β-D-maltoside (DDM) has similar properties to Triton X-100 TM (0.02% and ≈90 kDa, respectively) with similar critical micelle concentrations (0.01%) and micelle sizes (70 kDa). Interestingly, DDM was also able to function in the clarifier to form precipitated gel aggregates. This allowed slightly higher extraction efficiencies to be obtained at the three temperatures tested (Tables 6 and Figure 2 D).

[0107] Table 6: Effect of detergent replacement on oil recovery efficiency (%) of clarifiers at different temperatures. Comparison of effectiveness of clarifiers with alternative detergents. TM (0.1%) of the clarifier removes oil from the solution containing Buffer A.

[0108]

[0109] Example 6

[0110] Synthesis of iron oxide-SMA coated nanoparticles. A solution of 1.3 M FeCl2, 0.65 M Fe2SO4 was prepared in 0.4 M HCl. Unless otherwise stated, all solutions were degassed by bubbling with N2 for 30 min. Undissolved iron oxide was removed by Whatman TM ) filter paper. Then 20mL of the filtered solution was centrifuged at 3K for 10 minutes to further obtain small particles of aggregated or undissolved iron. 10mL of the supernatant was removed and added dropwise to (degassed) 0.9M NaOH under vigorous stirring over a 20-30 minute period. After the solution was fully added, the black precipitate was allowed to continue stirring for an additional 30 minutes. The iron particles were poured into a vial and the resulting magnetic particles were concentrated using a magnet. The particles were washed 3 times with degassed water by rotating the precipitated particles (3K for 10 minutes). The pellets were removed and then resuspended in .01M HCl (50mL). This should form small nanoparticles, so some of the particles will not be precipitated out by rotation at this time. The precipitated solution was rotated and the pellets were resuspended in 500uL of HCl0.01M HCl. The solution was added dropwise to 0.3% SMA (50mL) (degassed) at pH 9 at 90°C. The solution was bubbled at 90°C for 30 minutes to ensure particle formation. Remove heating, and separate particles by centrifugation (3K 10 minutes). Wash particles 2 times with MQ water, then put back in 20mL of MQ water. Use dynamic light scattering to analyze particle size. This will obtain a solution with low PDI (about 0.3), with an average particle size of 0.4nm. Once filtered with a 0.2uM filter (PVDF), PDI will be increased to 0.15, with an average particle size of 140nm. Confirm that particles are still affected by magnetic fields. If there is SMA, then in the presence of acid, particles should show a faster response to magnetic fields, because particles aggregate in acidic solutions due to SMA precipitation.

[0111] Example 7

[0112] Di-isobutylmaleic acid is another anionic block copolymer that is more susceptible to degradation due to the lack of aromatic groups.

[0113] Use 0.1% Triton X-100 TM Titration of DIBMA (at 0.025%, 0.05% and 0.1%) resulted in complete encapsulation of the oil at a concentration of 1:1. Figure 4 Shown in A.

[0114] Replacing SMA with DIBMA in the clarifier resulted in similar oil recovery efficiency (Table 7), indicating that other block copolymers containing hydrophobic functional groups as well as maleic acid can function in clarifiers.

[0115] Table 7: Effect of polymer replacement on oil recovery efficiency (%) of clarifier at room temperature (21°C). Di-isobutylene-co-maleic acid (DIBMA) can replace SMA to quickly coagulate and aggregate emulsified oil. Oil recovery from 0.5% oil-water mixture using a 1:1 formulation of polymer to detergent. Coagulated oil was removed by scooping the coagulated polymer from the water surface.

[0116]

[0117] Example 8

[0118] To ensure that both detergent and polymer were trapped in the flocs, the absorbance of the clear solution and the pelleted flocs was measured. It was thus found that 98% of the clarifier (polymer and detergent) was retained in the pellets, while only 1.9% was left in solution (Table 8).

[0119] Table 8: Detergent and SMA encapsulated in coagulated flocs. Clarifier additives completely destabilize upon addition of acid. Both Tx-100 and SMA absorb at 280 nm. Quantification of clarifiers (0.05% Tx-100, 0.05% SMA) before and after acid-induced aggregation is expressed as a percentage of the initial absorbance value. Coagulated flocs were removed by centrifugation, dissolved in an equal volume of base, and the absorbance was remeasured to confirm capture by Tx-100. Standard deviations from three independent experiments are reported.

[0120]

[0121] Example 9

[0122] Effect of clarifier on capture of n-decane and soil fines mixture. Addition of clarifier to suspended soil fines and sediment results in rapid clarification of solution. Since soil fines do not settle easily, coagulation increases their effective weight and can produce better clarification by simple solution settling (Table 9). Note that after addition of clarifier, almost all of the soil fines settled, so most of the measured turbidity was due to coagulated polymer that was not bound to the settled fines. However, the addition of a filtration step was able to effectively remove all of the soil fines as well as free-floating flocculants from the solution after coagulation (Table 9). In addition, the addition of SMA-coated magnetic nanoparticles, followed by the addition of clarifier, also resulted in more effective clarification of water by applying a magnetic field (Table 9). Without the clarifier, the effect of the magnetic nanoparticles was minimal to no effect, and the soil fines were too small to be effectively filtered (Table 9).

[0123] Table 9: Effect of clarifier treatment combined with removal methods on clarification of suspended soil fines. Water contamination is reported as relative turbidity (absorbance measured at 550 nm). Water purified by reverse osmosis has a relative turbidity of 0. Nanomagnet seeding involves the addition of SMA coated magnetic nanoparticles and the application of a magnetic field to accelerate the settling and clarification of the solution. Capture of suspended soil fines. The experimental setup for obtaining contaminated water was as follows: 5 grams of pre-wetted soil was contaminated with 200 microliters of n-decane. The water was purified by treatment with 0.1% Triton X-100. TM The soil was treated by washing with a solution. The subsequent eluate was treated with a clarifier to clarify the water and remove emulsified oil and suspended soil fines for processing. The soil wash eluate was diluted 2-fold in MQ water and 0.05% SMA was added before the addition of acid. The reported values ​​are turbidity measurements of the supernatant after the selected treatment of the soil eluate. Nanomagnet broadcasting combined with a magnetic field was used to rapidly dewater the flocs, producing a clear solution only in the presence of a clarifier.

[0124]

[0125] Example 10

[0126] With SMA 2021 TM and Triton X-100 TM Size exclusion elution profile of the formed nanonet.

[0127] Non-ionic detergent Triton X-100 TM With SMA polymer formulation (SMA2021 TM ) in a 1:1 mass ratio (0.02% mass / volume) to induce the self-assembly of the nanonet. SMA 2021 TMIt is a heterogeneous polymer preparation with Mn (g / mol) = 12,000 and Mw (g / mol) of 21,000. TM The detergent micelles dispersed when interacting with the column medium and were eluted later in the chromatography (4.5 mL, Figure 5 A). The addition of SMA polymer stabilized the detergent micelles, allowing the detergent and polymer to elute together, about 3.7 mL ( Figure 5 B). The SMA polymer alone was completely soluble and eluted as a sharp peak at 2.8 mL ( Figure 5 C).

[0128] Embodiment 11

[0129] SMA 2021 TM Size exclusion elution profile of nanonets formed with sodium oleate.

[0130] The ionic detergent sodium oleate was mixed with SMA polymer formulation (SMA 2021 TM ) were mixed in a 1:1 mass ratio (0.2% mass / volume) to induce self-assembly of the nanomesh. Alternatively, equal amounts of polymer only or detergent only were injected. SMA 2021 TM is a heterogeneous polymer preparation with Mn (g / mol) = 12,000, and Mw (g / mol) of 21,000. Sodium oleate detergent micelles are very large (30 nm) and elute in the blank of size exclusion chromatography (1.6 mL, Figure 6 A). The SMA polymer alone was completely soluble and eluted as a sharp peak at 2.8 mL ( Figure 6 B). The addition of SMA polymer caused the self-assembly of polymer and detergent micelles, so that the detergent and polymer were eluted together, about 1.7 mL ( Figure 6 C).

[0131] The following Examples 12 and 13 use at least one detergent in the following table, and the table provides some relevant properties of these detergents.

[0132]

[0133] Example 12

[0134] The micelle size of the starting detergent is important for nanonet formation.

[0135] Figure 7A depicts the results of size exclusion chromatography of a 1:1 (wt / wt) nanomesh formulation using a detergent that forms micelles <20 kDa. The nanomesh formulation with β-octylglucoside, sodium oleate, and lauryl dimethylamine was subjected to size exclusion chromatography in distilled water. The detergent was mixed with the same polymer SMA 2000. TM 1:1 TM Nanomeshes were prepared by mixing in a 1:1 wt / wt ratio in distilled water. The nanomeshes were tracked by UV absorption at 280 nm. The results for all three non-micelle forming detergents were essentially the same.

[0136] Figure 7 B depicts the above Figure 7 Results of the same experiment as set A, except that it was repeated and contained an additional nanomesh using dodecyl-maltoside (DDM) as the detergent (indicated by the arrow). The results for all non-micelle-forming detergents (β-octylglucoside, sodium cholate, and lauryl dimethylamine) were essentially the same and consistent with Figure 7 The results in A are essentially the same, but the DDM nanomesh that formed micelles showed an elution curve shifted to the left.

[0137] Figure 7 C depicts the use of polymer (SMA 2000 TM ) detergent mixtures. Each detergent tested formed micelles of different sizes (0.8 kDa, 4 kDa, 8 kDa, 17 kDa and 72 kDa as shown in Example 11). The results show that the nanomesh prepared with the micelles of 0.8 kDa, 4 kDa and 8 kDa did not show significant improvement in visible turbidity. The nanomesh prepared with the micelles of 17 kDa showed a small improvement in visible turbidity, while the nanomesh prepared with the micelles of 72 kDa showed a great improvement in flocculation, thus removing turbidity.

[0138] Figure 7 D graphically depicts eight different polymer blends (SMA 2000 TM +: No detergent (i.e. only SMA2000 TM), sodium cholate (cholate), sodium deoxycholate (DOC), β-octyl glucoside (β-OG), lauryl dimethylamine n-oxide (LDAO), octylphenol ethoxylate (TX-305), n-dodecyl β-D-maltoside (DDM) and sodium oleate (oleate) The relationship between the floccules aggregates (stimulated by slight centrifugation). The circles in the chart refer to the starting micelle size, and the squares in the chart refer to the relative turbidity. Note that the circles and squares of polymer + TX-305 are in about the same position and overlap each other. The mixture that only forms the nanomesh shows increased floc aggregation.

[0139] Example 13

[0140] Demonstration of the ratio of nanomesh formation and flocculation.

[0141] Using four different scales of SMA 2000 TM Polymer and Triton X-305 TM Four different chelating agents were prepared. Each of the four chelating agents was then added to a 2% N-decane solution. The first ( Figure 8 A) has a ratio of 0:1 (SMA:TX-305). The second ( Figure 8 B) has a ratio of 1:1.4 (SMA:TX-305), and because there is too much detergent in the mixture, the precipitation reaction is inefficient, resulting in poor flocculation. Figure 8 C) had a ratio of 1:0.7 (SMA:TX-305), and because the nanonet was formed efficiently, the flocculation was efficient and the resulting solution was clear and captured the oil. Figure 8 D) had a 1:0 ratio (SMA:TX-305), and because the polymer was extended, the polymer created a large sludge that was difficult to remove from solution and did not effectively capture the oil.

[0142] Although various embodiments of the present invention are disclosed herein, many adaptations and modifications can be made within the scope of the present invention according to the common knowledge of those skilled in the art. Such modifications include replacing any aspect of the present invention with known equivalents so as to obtain the same results in substantially the same manner. Numerical ranges include numbers that define the ranges. In addition, numerical ranges are provided so that in addition to specifically listing the individual values ​​within the ranges listed without a range, the ranges of values ​​are also listed. The word "includes" is used as an open term in this article, which is substantially equivalent to the phrase "including but not limited to", and the word "includes" has a corresponding meaning. As used herein, the singular form ("one / a kind (a)", "one / a kind (an)" and "the") includes plural references unless the context clearly indicates otherwise. Therefore, for example, referring to "a thing" includes more than one such thing. The references cited herein do not admit that such references are prior art of the present invention. In addition, the materials appearing in the background technology section of the specification do not admit that such materials are prior art of the present invention. Any priority documents are incorporated herein by reference as if each individual priority document was specifically and individually indicated to be incorporated by reference and as if fully set forth herein.The invention includes all embodiments and variations substantially as hereinbefore described and with reference to the examples and drawings.

Claims

1. A chelating agent for chelating non-aqueous moieties from an aqueous solution, comprising: a) a detergent capable of forming micelles having a size of not less than 10 kDa, wherein The detergent is selected from the group consisting of: O-[4-(1,1,3,3-tetramethylbutyl)phenoxy]polyethoxyethanol, N-dodecyl-β-D-maltoside, sodium oleate and a mixture thereof, and the structural formula of the O-[4-(1,1,3,3-tetramethylbutyl)phenoxy]polyethoxyethanol is: wherein n=9-10 or n=30; and b) a polymer having a molecular weight in the range of 3000 g / mol to 25,000 g / mol, said polymer being useful for stabilizing the formation of detergent micelles, thereby allowing said detergent and said polymer to self-assemble into a nanomesh when exposed to said aqueous solution, wherein said polymer is selected from the group consisting of styrene-maleic acid polymers, diisobutylene-maleic acid copolymers, and mixtures thereof.

2. The chelating agent of claim 1, further comprising a precipitant, wherein the precipitant is selected from the group consisting of acetic acid, malic acid, citric acid, tartaric acid, fumaric acid, lactic acid, hydrochloric acid, sulfuric acid, phosphoric acid, and mixtures thereof.

3. The chelating agent of claim 1, wherein the polymer has a molecular weight of 22,000 g / mol.

4. The chelating agent of claim 1, wherein the polymer is water soluble.

5. The chelating agent of claim 1, wherein the polymer is biodegradable.

6. The chelating agent of claim 1, wherein the ratio of detergent:polymer is in the range of 1:0.5 to 1:1.

3.

7. The chelating agent of claim 1, wherein the ratio of detergent:polymer is in the range of 1:0.5 to 1:1.

0.

8. The chelating agent of claim 1, wherein the ratio of detergent:polymer is in the range of 1:0.6 to 1:0.

8.

9. The chelating agent as claimed in claim 1, wherein the ratio of detergent:polymer is 1:0.

7.

10. The chelating agent of claim 1, wherein the detergent is capable of forming micelles having a size of not less than 40 kDa.

11. The chelating agent of claim 1, wherein the detergent is capable of forming micelles having a size of not less than 40 kDa and not more than 300 kDa.

12. The chelating agent of any one of claims 1 to 11, wherein the polymer is a block copolymer.

13. A kit for chelating non-aqueous moieties from aqueous solutions, the kit comprising: a) a detergent capable of forming micelles having a size of not less than 10 kDa, wherein The detergent is selected from the group consisting of: O-[4-(1,1,3,3-tetramethylbutyl)phenoxy]polyethoxyethanol, N-dodecyl-β-D-maltoside, sodium oleate and a mixture thereof, and the structural formula of the O-[4-(1,1,3,3-tetramethylbutyl)phenoxy]polyethoxyethanol is: Where n=9-10 or n=30; b) a polymer having a molecular weight in the range of 3000 g / mol to 25,000 g / mol, said polymer being useful for stabilizing the formation of detergent micelles, thereby allowing said detergent and said polymer to self-assemble into a nanomesh when exposed to said aqueous solution, wherein said polymer is selected from the group consisting of styrene-maleic acid polymers, diisobutylene-maleic acid copolymers, and mixtures thereof; and c) a precipitating agent selected from the group consisting of acetic acid, malic acid, citric acid, tartaric acid, fumaric acid, lactic acid, hydrochloric acid, sulfuric acid and phosphoric acid.

14. The kit of claim 13, wherein the detergent is a nonionic surfactant.

15. The kit of claim 13, wherein the polymer has a molecular weight of 22,000 g / mol.

16. The kit of claim 13, wherein the polymer is water soluble.

17. The kit of claim 13, wherein the polymer is biodegradable.

18. The kit of claim 13, wherein the ratio of detergent:polymer is in the range of 1:0.5 to 1:1.

3.

19. The kit of claim 13, wherein the ratio of detergent:polymer is in the range of 1:0.5 to 1:1.

0.

20. The kit of claim 13, wherein the ratio of detergent:polymer is in the range of 1:0.6 to 1:0.

8.

21. The kit of claim 13, wherein the ratio of detergent:polymer is 1:0.

7.

22. The kit of claim 13, wherein the detergent is capable of forming micelles having a size of no less than 40 kDa.

23. The kit of any one of claims 13 to 21, wherein the detergent is capable of forming micelles having a size of not less than 40 kDa and not more than 300 kDa.

24. A method of sequestering a non-aqueous fraction from an aqueous solution, the method comprising adding a sequestrant according to any one of claims 1 to 12 to the aqueous solution comprising the non-aqueous fraction, thereby forming a treated aqueous solution, and then removing solid particles from the treated aqueous solution.

25. The method of claim 24, further comprising mixing prior to removing the solid particles.

26. The method of claim 24 or 25, wherein the removing of solid particles comprises at least one selected from the group consisting of filtration, gravity separation, flotation, and electromagnetic attraction.

27. The method of claim 26, wherein said removing solid particles comprises electromagnetic attraction, and said method further comprises adding a magnetic moiety to said treated aqueous solution prior to removing said solid particles.

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