Modified polyamines grafted onto particulate solid supports as sorbents for the removal of target substances from fluids - Patents.com

Abstract

SOLUTION: Provided are compositions for removal of a target substance from a fluid stream, the compositions comprising a polyamine and a covalently linked hydrophobic group, where the polyamine is covalently linked to a support material. Also provided are processes for removal of a target substance from a fluid stream, the processes comprising contacting the fluid stream with a composition comprising a polyamine and a covalently linked hydrophobic group, where the polyamine is covalently linked to a support material.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention provides a method for the detection of target substances using chemically modified filtration materials based on polyamines. The present invention relates to the removal of materials from fluids such as liquids, as well as methods for producing such materials. [Background technology]

[0002] Growing industrialization around the world combined with an increasing demand for cheaply produced products There is a significant and ongoing effort to remediate and recycle contaminated supplies of key solvents, including water. It contributes to the needs of the community by reusing existing resources rather than simply disposing of them. There is recognition that dwindling freshwater supplies need to be replenished with water due to pollution from industrial activities. As the environment is threatened by these factors, environmental protection regulations are becoming increasingly strict.

[0003] Important fluids used in industrial and agricultural processes include water, solvents, fuels, , lubricants, and hydraulic fluids. All of these liquids can be used to , through normal use in industrial processes or through exposure to waste products, For example, in industrialized countries, up to two-thirds of all water consumption typically occurs in industrial plants. At the international level, developed and developing countries are working to promote responsible water use. To ensure a commitment to sustainable environmental policies, including the use of It is no surprise that there are important initiatives, especially to support sustainable growth. Therefore, it is essential to develop better ways to get more out of each unit of water consumed. be.

[0004] improperly disposed wastewater from industrial plants and chemical processing facilities, agricultural areas Surface runoff containing fertilizers and pesticides used, as well as cleaning agents used in firefighting foams There are many sources of environmental pollutants that are harmful to the environment, including detergents and flame retardants. industrial chemical pollutants can persist in nature for years before breaking down, even at very low concentrations. It can cause great harm to plants, animals and humans. Its impact on ecosystems is also serious. Therefore, persistent environmental pollutants often become concentrated in the bodies of organisms higher up the food chain. Despite being banned in most industrialized countries in the late 1970s, polychlorinated biphenyls PCBs can be found at high levels in the tissues of many marine animals and interfere with normal endocrine processes. This is causing Seth confusion.

[0005] In addition to environmental pollutants that are harmful to the environment, The body contains precious metals, including silver or gold, palladium, and platinum group metals (Sharma et al. al, 2017, https: / / pubs.rsc.org / en / content / articlehtml / 2017 / ra / c7ra10153h), including lithium contain economically valuable elements or chemicals such as metals or small molecules, including pharmaceuticals In many situations, such chemicals are themselves harmful pollutants. Although it can often be considered lost, the removal and / or recycling of these contents It can also be valuable in that it can be reused rather than discarded. For example, waste from mining operations Water passing through the plant (such as rainwater) may contain dissolved minerals that are too low in content to be worth refining. It is present in concentrations that are too high, which can be harmful to the environment and potentially increase mining production. It can represent a variety of sources.

[0006] Therefore, it provides a novel and innovative solution to the problem of remediation of contaminated fluid streams, especially contaminated water. There is a significant need to provide

[0007] One particular class of persistent environmental pollutants is poly- and perfluorinated alkyl esters. These include halogenated organic compounds such as PFAS (Perfluorooctaphenylalanine-sulfonic acid). Although they are considered chemically inert, they persist in the environment and Their use is regulated in many countries by the Kyoto Protocol to the United Nations Framework Convention on Climate Change. PFAS include fluorosurfactants, fluoropolymers, and organofluorine reactants. It is also used as a precursor for the production of many derivative compounds that represent an environmental risk. Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are Widely used as a surfactant and flame retardant in fire-fighting foams and metal plating processes Both PFOS and PFOA are toxic PFAS compounds that have been used for a very long time. It persists in the environment for long periods of time and is recognized as a contaminant in most of the world's freshwater supplies. It is being done.

[0008] Adsorption of PFAS compounds, such as PFOS and PFOA, onto granular activated carbon removes them from contaminated water. represents the current best and recommended solution for removing In particular, charged short-chain PFAS environmental contaminants are difficult to remove by absorbing activated carbon beds. It "breaks through" quickly, meaning it requires very large amounts of activated carbon and becomes saturated with PFAS. They must be replaced frequently. The adsorbed PFASs are then transferred to activated carbon for "in situ" regeneration. Therefore, activated carbon is a key component in the removal of PFAS from contaminated water. They represent an expensive, disposable solution to the problem.

[0009] Some modified cellulose materials show better removal, but at high concentrations of perfluorinated interfaces It is only effective in reducing surfactants to lower levels, from >1 ppm to the specified Within regulatory limits (e.g., approximately 70 parts per trillion set by the U.S. Environmental Protection Agency) tps: / / www.epa.gov / ground-water-and-drink ing-water / drinking-water-health-advisori es-pfoa-and-pfos). Such materials are , effective only as a pre-treatment to extend the life of activated carbon, not a complete solution for PFC removal It also acts as a dispersed flocculant and is complex and proprietary to implement. (See, for example, Patent Document 1: EP2763790B1).

[0010] Special ion exchange resins are also a new solution, here modified with quaternary ammonium Styrene divinylbenzene polymer beads are used in packed beds as an alternative to activated carbon. These resins cannot be regenerated or can only be regenerated using toxic and flammable solvents. It can be regenerated (see, for example, Patent Document 2: WO2017180346A1). [Prior art documents] [Patent documents]

[0011] [Patent Document 1] European Patent No. 2763790 [Patent Document 2] International Publication No. 2017 / 180346 Brochure Summary of the Invention [Problem to be solved by the invention]

[0012] Therefore, low concentrations (<1 ppm) of target substances, especially valuable materials, or fluids such as wastewater Economical and reusable compositions and methods for removing environmental contaminants such as PFAS from streams There is a need to provide such a goal, particularly with current technology. It is clear that the present invention overcomes the current problems and meets these objectives. The purpose is to: [Means for solving the problem]

[0013] A first aspect of the present invention is a composition for removing a target substance from a fluid stream, comprising: comprises a polyamine and a covalently attached hydrophobic group, wherein the polyamine is covalently attached to a support material. The present invention provides a composition comprising:

[0014] The support material may typically be a porous, solid, and / or particulate support material. Preferably, the support material comprises cellulose, such as lignocellulose, microcrystalline cellulose, microcrystalline cellulose, The group consisting of fibrillated cellulose, bacterial cellulose, and cellulose derivatives Optionally, the support material is made of a material selected from one or more of the following: The pulp may be a powder or pulp such as a cellulose or lignocellulosic powder or pulp. If in particulate form, the support material may be, for example, a plurality of granules, flakes, beads, pellets, and and pastilles.

[0015] The support material may also be one or more members of the group consisting of silica, silica gel, and silica derivatives. can be selected from above.

[0016] In one embodiment of the present invention, the polyamine is selected from linear or branched polyamines. Preferably, the polyamine is polyethyleneimine (PEI), polypropyleneimine (PP I), poly(allylamine), poly(vinylamine), poly(N-methylvinylamine) A linear or branched polyamine selected from polylysine and poly(4-aminostyrene) be selected.

[0017] In an alternative embodiment of the present invention, the polyamine is poly(diallyldimethylammonium chloride). cationic polyamines such as polyhexamethylene guanidine or polyhexamethylene guanidine Guanidine polyamines such as Sanid, or poly(acrylamide-co-diallyldiamine) Polyamides such as poly(methylammonium chloride) or poly(methylene co-guanidine) The copolymer is selected from the group consisting of ethylenediaminetetraacetic acid copolymers.

[0018] In further embodiments, the hydrophobic group may be C2-C22 branched, linear, or cyclic, saturated, or Typically, the group is selected from the group consisting of: , C2 to C22 branched, linear, or cyclic alkyl, or aryl. Optionally, the C2 to C22 branched or linear alkyl group is butyl, hexyl, or octyl. Preferably, the C2 to C22 linear alkyl group is selected from isobutyl, isohexyl, C4-C8 branched or linear alkyl selected from silyl, cyclohexyl, or isooctyl groups. In certain embodiments of the present invention, the C2-C22 alkyl group is selected from the group consisting of cyclohexyl, ... and cycloalkyl selected from butyl, butyl, and cyclooctyl groups. In some embodiments, the aryl group is selected from the group consisting of phenol, benzene, or benzyl. In a further embodiment, the hydrophobic group is a C2-C22 poly- or perfluorinated group, preferably These include C8 perfluorooctane or C8 polyfluorinated, 6:2 fluorotelomer. Optionally, the sorbent molecule comprises multiple hydrophobic groups.

[0019] According to a particular embodiment of the invention, the polyamine group is bonded to the hydrophobic group via an amide bond. Alternatively, the polyamine and hydrophobic group may be bonded to a urea bond, a thiourea bond, an isothiourea bond, or a hydroxyurea bond. via a guanidinium bond, a guanidinium bond, or directly, by alkylation reactions, or by quaternary The bond can be formed via the Menshutkin reaction.

[0020] A second aspect of the present invention is a process for removing target substances from a fluid stream, comprising: contacting the stream with a composition comprising a polyamine and a covalently attached hydrophobic group, A process is provided in which the amine is covalently attached to a support material.

[0021] Typically, the fluid is a liquid, and optionally the liquid is water, an organic solvent, a liquid fossil fuel, a liquid lubricants, and hydraulic fluids.

[0022] In certain embodiments of the present invention, the target material is a pollutant. The pollutant may be one or more polysaccharides. and perfluorinated alkyl substances (PFAS), optionally including perfluorooctyl Perfluorobutane sulfonate (PFOA), perfluorobutane sulfonate (PFBS), perfluorobutane Perfluorohexane sulfonate (PFBA), Perfluorohexane sulfonate (PFHS), Perfluorohexane Perfluorooctane sulfonate (PFHA), Perfluorooctane sulfonate (PFOS), Perfluorooctane perfluorodecanoic acid (PFNA), and perfluorodecanoic acid (PFDA). or The contaminants are organic compounds, optionally diclofenac, erythromycin, estrogen a pharmaceutical product containing one or more selected from the group consisting of thiamethoxam, oxadiazon, and thiamethoxam; The compound may comprise a molecule or a pesticide molecule.

[0023] Alternatively, the contaminant is any of copper, iron, lead, mercury, chromates, or arsenates. The cation may be a metal or metalloid ion.

[0024] In another embodiment of the present invention, the target material comprises a valuable material, optionally gold, silver, rare earth gold, The term "platinum group metals" includes platinum group metals, or platinum group metals, or salts thereof.

[0025] In certain embodiments, the support material is disposed in a bed or packed column, and the fluid flow is directed through the bed or packed column. or through or across a packed column.

[0026] According to a further embodiment of the present invention, the process comprises the steps of: Preferably, the step of regenerating the composition further comprises regenerating the composition by adding an aqueous cleaning agent to the sorbent material or a series of cleaning agents. Optionally, regenerating the support material comprises: This includes applying a salt wash, or an acidic or basic wash, to the composition. The liquid may include a liquid having a pH greater than 9, or a pH less than 5. In some embodiments, regeneration of the support material may involve the use of other salt, basic, or acidic cleaners in addition to or in combination with other salt, basic, or acidic cleaners. Alternatively, use an aqueous ammonium hydroxide cleaner, an aqueous ammonium chloride cleaner, or an aqueous sulfur cleaner. The method includes applying an ammonium acid detergent to the composition.

[0027] A third aspect of the present invention is a method for making a composition for removing a target substance from a fluid stream. and providing a support material, and bonding the support material to a polyamine group, and b. and covalently attaching the target substance to a sorbent molecule comprising an attached hydrophobic group. do.

[0028] It is to be understood that the above description should be read in conjunction with the embodiments described in more detail below. It will be understood that each embodiment of the present invention may be used alone or in combination unless otherwise specified. may be used in combination with other embodiments. [Brief explanation of the drawings]

[0029] [Figure 1] 1 shows an electron microscope photograph of a composition according to an embodiment of the present invention. [Figure 2] 1 shows a graph comparing the adsorption rates of PFAS compounds between a composition according to the present invention (CGM) and bituminous granular activated carbon (GAC). [Figure 3] This demonstrates the improved binding capacity of PFAS compounds in simulated wastewater containing competing organic acids exhibited by a composition according to the present invention (CGM) compared to bituminous granular activated carbon (GAC) and Amberlite anion exchange resin. [Figure 4] 1 shows the performance of compositions according to the present invention in adsorbing PFOA and PFHS from batch tests at a range of pH values. [Figure 5] The PFHS removal performance of the composition of the present invention (CGM) and bituminous granular activated carbon (GAC) in a small-scale column test is shown. [Figure 6] 1 shows the recovery performance of PFOA, PFBA, and PFBS from the composition of the present invention (CGM). DETAILED DESCRIPTION OF THE INVENTION

[0030] Unless otherwise indicated, the practice of the present invention will be understood to be within the skill of those skilled in the art of chemistry, materials science, and process engineering. techniques that are within the capabilities of those skilled in the art.

[0031] Before describing the present invention, a number of definitions are provided to aid in the understanding of the invention. All references used are incorporated by reference in their entirety unless otherwise specified. All technical and scientific terms used herein are understood to be within the skill of the art to which this invention belongs. It has the same meaning as commonly understood by those in the art.

[0032] As used herein, the term "comprises" means that any of the listed elements "essentially consisting of" means that other elements may be optionally included as well. "Contains" means that the elements recited are necessarily included and that the invention substantially conforms to the basic and novel characteristics of the elements recited. This means that factors that affect the performance of the system are excluded and other factors may optionally be included. "Consisting of" means excluding all elements other than those listed. Embodiments defined by each of these terms are within the scope of this invention.

[0033] The term "target" or "target substance" as used herein refers to a substance that is to be removed or isolated from a fluid. The target substance is a substance or compound that is desired to be dissolved (i.e., a solute) in the fluid. , suspended, emulsified, dispersed or otherwise transportable, and therefore soluble in a fluid, As discussed below, the target substance may be partially soluble or insoluble in the target fluid. contain contaminants and / or valuable materials that it is desired to remove and possibly recover from It can be seen.

[0034] Target substances as contemplated herein are also known as "contaminants" or The present invention may contain "contaminant substances." In this context, a "pollutant" is a substance that may be harmful to human or animal health or to the environment. It is intended to encompass substances, and consequently, derivatives are defined accordingly, e.g. For example, a contaminated fluid is a fluid that contains contaminants. Typically, the contaminants are one or more particles. Fluoro- and polyfluoroalkyl substances (PFAS), typically consisting of one or more Fluorocarbons, optionally including perfluorooctanoic acid (PFOA), perfluoro Butane sulfonate (PFBS), Perfluorohexane sulfonate (PFHS), - Fluorohexanoic acid (PFHA), perfluorooctane sulfonate (PFOS), Perfluorononanoic acid (PFNA) and perfluorodecanoic acid (PFDA), 6:2 Fluorotelomer sulfonic acid (6:2 FTSA) In some embodiments, the perfluorinated anionic surfactant compound is selected from the group consisting of: In the present study, the contaminants are organic compounds, optionally diclofenac, erythromycin, estrogen, containing one or more selected from the group consisting of thiamethoxam, oxadiazon, and thiamethoxam , pharmaceutical molecules, or pesticide molecules. In some embodiments, the contaminant is copper, iron, lead, or a metal or metalloid ion selected from the group consisting of mercury, chromate, and arsenate; obtain.

[0035] The target material may be a valuable substance. If it contains a rare element or molecule, it may be difficult to produce. If it is a complex molecule, or in any other way economically valuable enough to want to recover it from the fluid, A substance can be valuable if it has value. As a result of the process, valuable substances may be present in the fluid. A valuable substance may itself be a pollutant if it is harmful to human or animal health or the environment. The valuable material is preferably a precious metal, a rare earth metal, a base metal, or a platinum group metal, or salts thereof. Precious metals include gold and silver. Platinum Among the group metals, mention may be made in particular of platinum and palladium. In some embodiments, it may be a small molecule such as a drug or fine chemical.

[0036] The term "fluid stream" or "fluid" refers to a fluid in which a target substance is dissolved, suspended, emulsified, or dispersed. Fluid refers to a flowable substance that is transported or otherwise carried. A fluid can be, for example, a liquid or a gas. Preferably, the fluid is a liquid, and optionally the liquid is water, an organic solvent, a liquid fossil fuel, The lubricant is selected from a liquid lubricant, an ionic liquid, a hydraulic fluid, and mixtures thereof.

[0037] The term "cellulose" refers to a group of glucose monosaccharides linked together with β(1→4) glycosidic bonds. It refers to a biological polymer that is a linear polysaccharide composed of hemimers. It also contains polysaccharides composed of cellulose, glucose and other monosaccharides, and is branched. It can refer to materials with shorter chains than those found in cellulose.

[0038] Lignocellulose, or lignocellulosic biomass, is a biomass composed of cellulose and lignocellulosic biomass. Lignocellulosic refers to biological materials containing cellulose, and may also contain hemicellulose and pectin. Because sucrose constitutes a large proportion of plant biomass, its high availability and decomposition potential are important. This resistance is due to the fact that lignin molecules are made up of ester and ether bonds. This is the result of creating cross-links between cellulose and hemicellulose chains through the lignocellulosic acid synthesis. Cellulose is found in any terrestrial plant that is harvested for a purpose, or in agriculture, forestry, construction, paper, and paper mills. Industrially relevant feedstocks or materials generated from sources such as fuel production, and biofuel production can be obtained from many sources, including waste biomass. Lullose is made from the small seeds, pods, husks, and stalks (leaves and stalks discarded after grain harvesting). In particular, lignocellulose is obtained from agricultural waste such as nut shells or fruit. Lignocellulose can be derived from the small seeds, kernels, seeds, or membrane pits of the plant. The powder is crushed and sieved to a predetermined particle size.

[0039] As used herein, "bacterial cellulose," "microbial cellulose," "nanocellulose," "Nocellulose," "Bacterial Cellulose," and "Bacterial Nanocellulose" The terms "bacteria" and "bacteria" are synonymous and refer to bacteria such as Gluconacetobacter species or It refers to cellulose produced by microorganisms or other organisms, and has high tensile strength, high tensile stiffness, and high elasticity. It is characterized by its biological purity, biocompatibility, and high water-to-cellulose ratio. Bacterial nanocellulose is a type of nanocellulose that is typically found in plant-derived cellulose such as lignin. "Microfibrillated cellulose" means cellulose that is substantially free of related molecules that are enzymatically or It refers to cellulose that has been treated by mechanical processing with or without chemical pretreatment. The material consists of long, thin fibers that are several micrometers in length. Decomposing the amorphous regions of cellulose through physical, chemical, or enzymatic means to form cellulose It refers to high-purity partially decomposed cellulose produced by leaving crystalline domains.

[0040] As used herein, the terms "modified cellulose" or "modified lignocellulose" The term "modified" in this context refers to cellulose that has been modified by the addition of chemical compounds. These compounds are formed by covalent, ionic, electrostatic, and Or they may bind to cellulose or lignocellulose through affinity interactions. is a chemical compound that is bound to cellulose or lignocellulose and then reacts with other compounds. In particular, cellulose may be modified by the reaction of the target substance. It is envisioned that the cellulose may be modified by the addition of sorbent molecules. The polyamine group is typically a polyethylenimine. The polyamine group may be linear or branched, and preferably is a branched polyethyleneimine. It may itself be further modified by the addition of further chemical groups such as hydrocarbon groups.

[0041] The term "silica" refers to a material composed of silicon dioxide, which has the formula SiO2. These may or may not be hydrated and are referred to as "silica gel" granules. Alternatively, the silica-based material may be a silicate such as sodium silicate. It may be a salt mineral.

[0042] As defined herein, the term "sorbent material" further includes sorbent functional groups. The sorbent material refers to a material containing a support material. The sorbent material is a target material, such as a contaminant, which may be a PFAS. whereby the target substance is adsorbed onto the sorbent material. , adsorbed into or otherwise taken up by the sorbent material. The agent material is disposed in a bed or packed column, and fluid flow is directed through the bed or packed column. Sorbent materials can be granular activated carbon or ion exchange resins. The sorbent may be disposed in a mixed bed in combination with any other adsorbent material. The spent sorbent material may be contained within a prepared component such as a cartridge. The sorbent material can be conveniently stored and similarly replaced or regenerated with fresh or regenerated sorbent material as needed. Alternatively, the sorbent material may be added to the fluid as a dispersion. is in particulate form, i.e., in the form of granules, flakes, beads, pellets, or pastilles The sorbent material may be a powder or pulp, especially cellulose, microfibrillated cellulose. It may be cellulose, microcrystalline cellulose, or lignocellulose powder or pulp. These may beneficially provide a higher accessible surface area. Sorbent materials may be used in membranes or In particular, the pulp can be incorporated into a membrane or membrane-like product. The usefulness of this type of filter is The functionalities can be fabricated with specific thicknesses and large surface areas while still being properly attached to the fluid flow paths. When applied, the purpose is to ensure that the fluid passes through. Typically, the sorbent material is in particulate or granular form, and preferably has an average particle or granule diameter size (particle (measured by the largest diameter of the Typically, it is less than about 1 mm, optionally less than about 500 μm.

[0043] As used herein, the terms "sorption," "sorb," "sorbent," and The derivative term refers to the removal of a target substance, such as a contaminant, by association of said target substance with said modified support material. Sorption refers to the removal of a substance from a fluid stream. Sorption by a material can occur, for example, by adsorption onto the surface of the material. This can occur by any means, including electrostatic attraction, covalent bond formation, ligation, chelation, Chemical interactions between the target substance and the support material, including van der Waals forces, hydrogen bonds, or other "Sorption" also refers to the absorption of a target substance onto a substance. Materials may be physically trapped within intermolecular spaces, pores, or other voids within the material. In particular, sorption is the chemical reaction between the target molecule and the sorbent molecule to which the sorbent material is modified. Adsorption can occur through the formation of chemical interactions. Such chemical interactions are called sorption. This results in the sequestration of the target substance within the agent material and out of the fluid stream. The use of the term or its derivatives is not intended to be bound by theoretical limitations. The term "sorption" is intended to include sorption by other means as defined above unless otherwise specified.

[0044] In one embodiment of the present invention, a method for removing target substances and / or contaminants from a fluid stream is provided. The composition is a sorbent comprising a support material covalently bonded to a target substance sorbent molecule. The support material has a high surface area to volume ratio and therefore facilitates collection of the target substance. Granular sorbent particles provide efficient support for molecules that can function as sorbents. The granules are designed to be deployed as a sorbent medium for wastewater treatment in packed beds. Although it has some degree of porosity, it is hard, durable, and resistant to degradation.

[0045] When the sorbent material comprises cellulose, the particles are agricultural materials such as stems, leaves, small seeds, and husks. It is produced from waste and can be processed into granular particles by crushing and sieving. As discussed, the target material is chemically modified with sorbent molecules and then placed in this manner. Like other media used (granular activated carbon or ion exchange resins), sorbent granules are packed in standard packings. The filter may be arranged in a filter bed or column, which is connected to a fluid stream, such as wastewater, containing the target substance. The fluid flow may be gravity fed, or may be pumped, vacuumed, or Alternatively, positive pressure or other suitable means may be used, such as by driving the fluid flow. The granules can be flowed over or through by the application of negative pressure. Sorption occurs, so the target material remains in place while the water flows through and removes it. The filter bed or column is free of organic matter or limescale that reduces flow rate. The system may be backflushed from time to time to remove any buildup of blockage.

[0046] According to one aspect of the invention, the sorbent molecule comprises a polyamine group. The sorbent molecules are typically 500-500 Polyamine-based polymers in the molecular weight range of 1,000 Daltons (Da) and above. The minimum average molecular weight of the polymer is typically at least 500, at least 1000, At least 2000, at least 3000, at least 5000, preferably at least 1 The maximum average molecular weight of the polymer is preferably 50,000 or less. , 45,000 or less, 40,000 or less, 35,000 or less, typically 30,000 These polymers can be linear or branched. Highly branched polyamine polymers, called "drimers," contain multiple groups on each polymer molecule. In certain embodiments, the polyamines utilized in the sorbent molecules of the present invention contain primary amino groups. When the amine contains at least one terminal amine, it is typically a dendrimeric polyamine. Advantageously, the sorbent molecules contain multiple terminal amines. Preferably, the sorbent molecules each contain two saturated Polyethylene, a polymer composed of multiple amine groups linked by carbon spacers imine "PEI" (also known as polyaziridine). Typically, The imine molecules are branched, i.e., they have a tertiary amine group at the branch point and a tertiary amine group at the end of each branch. Branched polyamines contain primary amine groups at the ends. They have lower melting points and higher solubility. In sorbent compositions, they have the ability to dissolve target molecules and provide benefits in the production process. Steric coupling using spatially positioned amines to allow cooperative interactions with the molecule In a further embodiment, the polyamine is a linear or branched polypropylene. In yet a further embodiment of the present invention, the polyamine may comprise Poly(allylamine), poly(vinylamine), poly(N-methylvinylamine) linear polyaniline such as, but not limited to, styrene, and poly(4-aminostyrene). In an alternative embodiment of the present invention, the polyamine may include poly(diallyldimethyl Cationic polyamines such as ammonium chloride, polyhexamethylene guanidine, etc. or guanidine polyamines such as polyhexanide, or poly(acrylamide-co -diallyldimethylammonium chloride) .

[0047] In water treatment, polyamines bound to solid support materials are effective in removing heavy metals and dyes. It has been shown that (see, for example, CN103041780B). While their effectiveness in removing anionic surfactants from water is surprising In particular, the flexible branched polyamine modified sorbent granules according to embodiments of the present invention Granules offer faster, more efficient sorption than activated carbon and lower cost than specialty ion exchange resins. In addition, activated carbon and resins can remove PFAS from wastewater up to regulatory limits. Unlike the conventional method, the sorbent material is then regenerated with an aqueous liquid detergent to recover the environmental contaminants. The sorbent material can be reused by using flexible branched polyamines. In addition, branched polyamines allow for stronger and more specific interactions with the It provides multiple amine groups that can be chemically substituted, eliminating the need for high levels of chemical modification of the cellulose itself. This tends to improve the sorption capacity of the target substance. do.

[0048] If it is necessary or desirable to activate the support substrate prior to addition of the target substance sorbent molecules This activation involves the addition of functional groups to the cellulose or silica surface. In the reaction, the target substance sorbent molecules then form bonds with the functional groups added during activation. , and bonded to the support material. The covalent bond may be an ester, ether, carbamate, or thiocatechin. In some embodiments, the cellulose support may be , activated by reaction with an acyl halide, typically bromoacetyl bromide. Chemically related groups of different chain lengths (e.g., methyl, propyl, butyl, pentyl) are also In another embodiment, the cellulose is prepared by the addition of a carbonyl with diimidazole or a crosslinker such as glutaraldehyde or epichlorohydrin These activated functional groups are the ones that ultimately modify the cellulose. These attachment points provide chemical attachment points for target substance binding molecules to the support. This may result in the presence of a short linker between the molecules. This linker may be, for example, the halo The residue left by acylation with acyl halide (-C(=O)-C-) could be.

[0049] In another embodiment, the granular porous silica gel substrate is (3-chloropropyl) trichloride. This allows the selected polymer to be activated in subsequent steps. A chemical attachment point is provided for the formation of a covalent bond to the triamine.

[0050] According to the present invention, the sorbent molecules are modified by the addition of further chemical groups, which are preferably short-chain hydrophobic groups. Typically, this further chemical group comprises a polyamine group which is itself modified by Reaction of alkyl or aryl acid halides or anhydrides with the amine groups of the polyamine groups. Optionally, the reaction The relationship between the hydrophobic group and the terminal primary amine group contained within the polyamine molecule is as follows: In embodiments, multiple hydrophobic groups react with multiple amine groups within a polyamine molecule. In this embodiment, substantially all of the terminal primary amine groups present in the polyamine molecule are sparsely Reacts with water radicals.

[0051] The resulting sorbent molecules have unique sorptive properties that can be tailored to the specific requirements of the sorbent material. Therefore, by modifying the chemical properties of the sorbent molecule, Materials are easily optimized to target specific substances and / or contaminants within the fluid stream This is an advantage of the present invention.

[0052] The primary targets in wastewater treatment are PFOA, PFOS, PFHA, PFHS, PFBA, and PF BS, and poly or perfluorinated surfactants such as 6:2 FTSA.

[0053] Other target materials, contaminants, or valuable materials (e.g., mining, refining, or manufacturing processes) wastewater treatment to remove metals (including precious or rare earth metals) present in wastewater from or the treatment of other fluids such as organic solvents and oils, or the removal of impurities from liquid product streams. In addition, it is contemplated that the sorbent material according to the present invention can be used to transport target substances in a gaseous form. It can be used as a sorbent to remove

[0054] Unlike other sorbents deployed in this manner for organic environmental contaminants, granular sorbent materials can be effectively regenerated in situ using aqueous liquid cleaners. , acidic cleaners, basic cleaners, or a combination of salt and acidic cleaners, etc. Preferably, the cleaning liquid comprises a liquid having a pH greater than 9 or less than 5. Optionally, the cleaning solution is an aqueous solution of ammonium hydroxide, ammonium chloride, or or aqueous ammonium sulfate. The possibility of recovery depends on whether it is recycled, recovered, or Enables removal of targeted materials for safe disposal while also allowing reuse of sorbent materials This method is particularly beneficial in that it allows the removal of targeted substances. The process further reduces costs and generates waste in the form of spent sorbent material.

[0055] The regeneration process involves removing the sorbent material from the fluid stream and treating it with an acid, base, and / or or a salt thereof. The acid may be hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, or the like. or ethanedioic acid, hexanoic acid, ethanedioic acid, or citric acid. The salts are preferably selected from the group consisting of chloride, sulfate, or phosphate salts. The salts are preferably selected from sodium, potassium, or magnesium salts of the cations. In some embodiments, the wash solution has a pH of less than 5, preferably less than 4, less than 3, or less than 2. It has.

[0056] Preferably, the regeneration process instead involves treating the sorbent material with a basic solution, typically ammonium hydroxide. Other suitable alkaline solutions include contacting the cellulose with an aqueous solution of sodium hydroxide. In some embodiments, the cleaning liquid may be selected from sodium hydroxide or potassium hydroxide. , greater than 8, preferably greater than 9 or greater than 10.

[0057] Without wishing to be bound by theory, it is believed that the targeting of the compositions described herein The adsorption of the protein is mainly due to electrostatic interactions with the polyamine and hydrophobic-phobic interactions with the covalently bound hydrophobic groups. This is likely the result of a combination of aqueous interactions. In the regenerated aqueous detergent solution, chlorides, sulfur Interaction with anions in cleaning agents, such as acid salts or hydroxides, results in the formation of anionic target substances. This replaces the electrostatic interaction of the target substance with the ion exchanger, releasing the target substance during cleaning. Lowering the pH changes the protonation of polyamines, resulting in electrostatic binding with the adsorbed target compounds. The presence of other ions, such as ammonium, can further reduce the binding interactions of the adsorbed target. This can improve the solubility of target compounds, further increasing their removal in the regenerated aqueous wash solution.

[0058] Another significant benefit of this system is its low cost and ease of production. using polyamine (PEI) and very low-cost support material (lignocellulose) , production of other forms of sorbent material such as granules or pulp, allowing for large scale (batch-by-batch) This allows for cost-effective production of materials for large-volume wastewater applications (approximately 1000 kg) In addition, the cellulose substrate and the target substance sorbent molecules Reactions involving the coupling with can be carried out economically on a large scale at room temperature and atmospheric pressure.

[0059] According to certain embodiments of the present invention, the filtration and removal of PFAS from a liquid stream includes: Lignocellulosic acid is then modified with amphiphilic groups to produce particularly useful derivative products. A process for the preparation of sucrose esters is provided. A particular advantage is that the process does not require high temperatures and the reaction can be carried out at room temperature. The advantage is that expensive catalysts, especially metal-containing catalysts, are not required. The process for this is relatively energy efficient and not resource intensive, making it Furthermore, the process allows the resulting product to be recycled after use, and the product It reduces overall consumption of sorbents and extends their useful working life over comparable sorbents, and This has the added benefit of allowing for the recovery of any valuable materials removed from the treated fluid stream. show.

[0060] In an embodiment of the present invention, the lignocellulosic / cellulose support material is prepared by the following reaction scheme: Bromoacetyl bromide in the presence of dimethylformamide (DMF) at room temperature according to scheme I It is activated by esterification with

[0061] [ka]

[0062] In an alternative embodiment, other acyl halides, preferably chloroacetyl chloro acetyl chloride, chloroacetyl bromide, and bromoacetyl chloride, or proton halides Different reactants are used, such as propionyl halides or butyryl halides. It will be understood that cellulose can be esterified in a similar manner.

[0063] To obtain highly substituted lignocellulose derivatives, bromo- The cetylated form further reacts with polyamines at room temperature, even in the presence of DMF. In embodiments, the amine utilized in the second step of the reaction is selected from the group consisting of: Branched polyethyleneimine (PEI):

[0064] [ka]

[0065] Polypropyleneimine (PPI), poly(allylamine), poly(vinylamine), poly Poly(N-methylvinylamine), polylysine, poly(4-aminostyrene), poly(diamond (C13-14C, C13-15C, C13-16C, C13-17C, C13-18C), polyhexamethylene guanidine, polyhexanide , poly(methylene-co-guanidine), or poly(acrylamide-co-diallyldi Linear PEI can also be used, as can other polyamines such as methylammonium chloride. It will be understood that it can be used.

[0066] In another embodiment, the particulate support material is silica gel. The surface was hydrated and then treated with trichloro(3-chloropropyl)silane in hexane solvent. The product is dried and then reacted with the following reaction scheme III: The polyamine is covalently attached by reaction in a methanol solvent with

[0067] [ka]

[0068] The substituted particulate solid support product is then reacted in a third step with, for example, an acylating agent, preferably In this embodiment of the invention, hexanoic acid is further reacted with an acyl or aryl acid halide. The acyl chloride is a substituted primary amine in the PEI group attached to the solid support. Hexanoyl chloride is dissolved in dichloromethane (DCM) and reacted as follows: As shown in Scheme IV, the base and catalyst diisopropylethylamine (DIPEA The reaction is carried out at room temperature in the presence of hydroxybenzoates, and the hydrophobic groups are bonded to the polyamines via amide bonds. do.

[0069] [ka]

[0070] In an alternative embodiment of the present invention, it is understood that the acylating agent may comprise a compound of the following formula: It will be done.

[0071] [ka]

[0072] During the ceremony, R1 is a C2-C22 branched, linear, or cyclic alkyl or aryl group . R2 is a halide.

[0073] Typically, R1 is a C2 to C22, preferably C4 to C8, straight chain saturated or unsaturated alkyl group. alkyl groups, most preferably butyl, hexyl, or octyl groups. Optionally, R1 is selected from an isopropyl, isobutyl, or isohexyl group. R1 includes a cycloalkyl selected from a cyclobutyl or cyclohexyl group. When R1 is aryl, typically the aryl is a phenol or benzene. The group is selected from the group consisting of aryl groups.

[0074] R2 is typically selected from chloride or bromide.

[0075] Alternatively, polyamines covalently bound to a granular solid support material can be prepared by one of the following reactions: It can be modified by covalent attachment of hydrophobic groups at C2 to C22 by

[0076] Reaction according to Scheme V, in which a polyamine group is attached to a hydrophobic group via a urea bond. R3NH represents a polyamine group, and R1=C2-C22. The reaction is carried out in an aprotic solvent. The reaction is carried out under basic conditions in a solvent system.

[0077] [ka]

[0078] Alternatively, the urea unit can be formed by the reaction shown in Scheme VI, where R3 R4NH represents a polyamine group, R1=C2-C22, and R2=H. The reaction is , using a carbonyldiimidazole derivative under basic conditions in an aprotic solvent system It will be carried out in.

[0079] [ka]

[0080] Alternatively, the urea unit can be formed by the reaction shown in Scheme VII, where R 2R3NH represents a polyamine group, R4=C2 to C22, R5=H, and R2 = hydrocarbon unit. The reaction is carried out under basic conditions in an aprotic solvent system. .

[0081] [ka]

[0082] The urea unit can be formed by the reaction shown in Scheme VIII, where R2R3N H represents a polyamine group, and R1=C2 to C22. The reaction is carried out in an aprotic solvent system and and the azide-containing reagent of step 1 is carried out under basic conditions.

[0083] [ka]

[0084] Alternatively, the hydrophobic groups at C2 to C22 can be converted to polyamines via a quaternization (Menshutkin) reaction. The polyamine nitrogens can be covalently bonded to up to three C2-C22 hydrophobic groups. This may be due to the reaction shown in Scheme IX, where X=halide. where R4=C2-C22 hydrophobic group, R1=part of a polyamine molecule, and R2 and R3 = R4, or the portion of the polyamine molecule represented by R1R2R3N be.

[0085] [ka]

[0086] The present invention is further illustrated by the following non-limiting examples.

[0087] Example 1 The novel custom granular media (CGM) compositions of the present invention are characterized by their unique structure (see FIG. 1). tion), resulting in significantly improved capacity for PFAS adsorption. This figure demonstrates the ability of the hydroxyl group at multiple C6 sites to be linked to the hydrophobic groups via reaction with hexanoyl chloride. Porous, solid polymer covalently bonded to polyethyleneimine (average molecular weight, 25,000). 1 shows an electron micrograph of a composition comprising solid, particulate, lignocellulosic material. , exhibiting surface roughness on the micrometer scale, allowing for the adsorption of large amounts of PFAS.

[0088] The absorption rate of the CGM composition of the present invention was compared with that of conventional bituminous granular activated carbon (GAC) media. In the assay, 0.05 g of each adsorbent (1 mm average diameter granules) was dissolved in 50 mL of DI water. The samples were immersed in 40 mL of ppb PFOA or PFHS. At specific times, aliquots of the solution were The samples were collected and the PFAS concentration was analyzed by liquid chromatography-mass spectrometry / mass spectrometry (LC- The results are shown in Figure 2. CGM was found to be highly sensitive to PFOA adsorption and PF It can be seen that HS has a much faster adsorption rate compared to GAC. The much superior speed seen with CGM leads to significantly reduced contact times for processing. This allows for higher fluid flow rates or the use of smaller vessels. Speed ​​allows flexible hydraulic load requirements to match any required pre- or post-treatment become.

[0089] Example 2 The binding capacity of the CGM compositions of the present invention for PFAS was evaluated using GAC and Amberlite (registered trademark). The adsorbent granules were tested in simulated wastewater in comparison with the anion exchange resin (Product No. 1001411). 0.05g of adsorbent granules were added to 2.5 ppm PFOS, PFOA in DI water containing 250 ppm competing organic acids Batch tests were conducted in which the samples were immersed in 40 mL of PFBA, PFBS, and PFBA. After 24 hours, The PFAS concentration in each solution was quantified using LC-MS / MS as in Example 1. The test results are shown in Figure 3. In all cases, the CGM composition of the present invention It was superior to previous sorbent media.

[0090] Example 3 The CGM compositions of the present invention may be administered to animals, such as those that may be encountered in effluents from industrial or agricultural sources. The adsorption performance was tested over a pH range from acidic to basic conditions. According to Say, 0.05g of adsorbent granules can be used to detect 2.5 ppm of PFOA or PFHS. The specimen was immersed in 40 mL of aqueous solution of I, and the pH was adjusted appropriately with NaOH or HCl. After 24 hours The PFAS concentrations in the solutions were quantified using LC-MS / MS according to Example 1. The results are shown in Figure 4. Thus, high levels of PFAS adsorption (>97%) were observed, and the test It remains remarkably stable over the entire pH range tested.

[0091] Example 4 The CGM compositions of the present invention were tested in a rapid, small-scale column test for the removal of the contaminant PFHS. The contaminated water influent (supply) contained 500 ppb of PFHS, and the CGM The composition and competitor's granular activated carbon (GAC) were pumped into a small packed bed. The time was 22 seconds and the linear velocity was 7.5 m / h. A sample of the effluent solution was taken and the PFHS was measured. The CGM composition was quantified by C-MS / MS. The results are shown in Figure 5. Removal of target contaminants to undetectable levels over 20,000 bed volumes (BV) of solution This was not achieved with GAC, where conventional sorbent media showed a solubility of approximately 50 The effluent concentrations rose rapidly to the ppb range.

[0092] Example 5 The CGM composition of the present invention was tested in batch tests to determine whether PFOA, PFBA, and PFBS The CGM composition was mixed with a contaminant solution containing 50 μg of total contaminants per gram of material. The substance was adsorbed (50 μg / g loading). The loaded CGM medium was then added to 8 ml of filled The bed was filled with a regeneration solution of 3% aqueous ammonium hydroxide, pumped over a contact time of 15 minutes. The total regenerated solution that passed through the column was collected and sampled every two bed volumes (8 ml). PFOA, PFBA, and PFBS concentrations were quantified by LC-MS / MS and analyzed by chemical analysis. The total recovery of the compound was calculated based on the initial loading amount. The results are shown in Figure 6. and PFBS were rapidly recovered, and after 6 bed volumes of regenerant solution, all target substances were transferred to the sorbent composition. The components are recovered from the spent regenerant solution.

Claims

1. 1. Use of a composition for removing contaminants from a fluid stream, comprising: the composition comprises a sorbent molecule, the sorbent molecule comprising a branched polyamine, the branched polyamine having a plurality of covalently bonded C2-C22 alkyl groups; contacting the fluid stream with the composition; Use of a composition for removing PFAS, wherein the branched polyamine is polyethyleneimine (PEI), polypropyleneimine (PPI), poly(allylamine), poly(vinylamine), poly(N-methylvinylamine), polylysine, poly(4-aminostyrene), poly(diallyldimethylammonium chloride), polyhexamethyleneguanidine, polyhexanide, poly(methylene-co-guanidine), or poly(acrylamide-co-diallyldimethylammonium chloride).

2. 2. The use of the composition for removing PFAS according to claim 1, wherein the branched polyamine is polyethyleneimine (PEI), and the molecular weight of PEI is 500 to 50,000 Da.

3. 3. The use of the composition for removing PFAS according to claim 1 or 2, wherein the C2 to C22 alkyl group is a C4 to C8 alkyl group.

4. 4. The use of the composition for removing PFAS according to claim 3, wherein said C4-C8 alkyl group is selected from the group consisting of butyl, hexyl, octyl, isobutyl, isohexyl and isooctyl groups.

5. The use of the composition for removing PFAS according to claim 3, wherein said C4-C8 alkyl group has a poly or perfluorinated group, C8 perfluorooctane, or C8 polyfluorinated 6:2 fluorotelomer.

6. The use of the composition for removing PFAS according to any one of claims 1 to 3, wherein said contaminants comprise one or more poly- and perfluorinated alkyl substances (PFAS).

7. The use of the composition for removing PFAS according to claim 6, wherein the PFAS comprises one or more perfluorinated anionic surfactant compounds selected from the group consisting of perfluorobutane sulfonic acid (PFBS), perfluorobutanoic acid (PFBA), perfluorohexane sulfonic acid (PFHS), perfluorohexanoic acid (PFHA), perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA) and 6:2 fluorotelomer sulfonic acid (6:2FTSA).

8. 8. The use of a composition for removing PFAS according to claim 7, further comprising regenerating said composition after removing contaminants from said fluid stream.

9. 9. The use of a composition for removing PFAS according to claim 8, wherein regenerating the composition comprises applying one or more aqueous liquid detergents to the composition, the aqueous liquid detergent being a salt detergent, and the salts are optionally selected from one or more of the group consisting of sodium, potassium, and magnesium salts having chloride, sulfate, or phosphate counterions.

10. 10. The use of a composition for removing PFAS according to claim 8 or 9, wherein regenerating the composition comprises applying one or more aqueous liquid detergents to the composition, the aqueous liquid detergent being an acidic detergent, and the acid being selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, ethanedioic acid, hexanoic acid, and citric acid.

11. The use of a composition for removing PFAS according to any one of claims 8 to 10, wherein regenerating the composition comprises applying one or more aqueous liquid detergents to the composition, the aqueous liquid detergent being a basic detergent, and the base being optionally selected from one or more of the group consisting of ammonium hydroxide, sodium hydroxide, and potassium hydroxide.

12. 1. A process for removing one or more poly- and perfluorinated alkyl substances (PFAS) from a fluid stream, comprising: contacting the fluid stream with a sorbent composition; the sorbent composition comprises a branched polyamine and a plurality of hydrophobic groups covalently bonded to the branched polyamine, the branched polyamine being covalently bonded to a support material; the support material is porous, solid, and particulate; A process for removing PFAS, wherein said covalently bonded hydrophobic groups are C2-C22 branched, linear or cyclic alkyl or aryl hydrophobic groups.

13. 13. The process of claim 12, wherein the branched polyamine is polyethyleneimine (PEI), and the molecular weight of the PEI is 500 to 50,000 Da.

14. the hydrophobic group has a C2 to C8 alkyl group; 14. The process of claim 13, wherein the C2 to C8 alkyl group is optionally selected from the group consisting of butyl, hexyl, octyl, isobutyl, isohexyl, and isooctyl groups.

15. 14. The process of claim 13, wherein the hydrophobic group comprises a poly or perfluorinated group, C8 perfluorooctane, or C8 polyfluorinated 6:2 fluorotelomer.

16. 16. The process of claim 13 or 15, wherein the support material is contained within a bed or packed column and the fluid stream passes through or across the bed or packed column.

17. 1. A composition for use in removing contaminants from a fluid stream, comprising: The composition comprises a porous, solid, and particulate support material; a sorbent molecule having a branched polyamine covalently attached to the support material; and A composition for removing PFAS, comprising: a branched polyamine; and a plurality of hydrophobic groups covalently attached to the branched polyamine.

18. the branched polyamine is polyethyleneimine (PEI), (1) The molecular weight of the PEI is 500 to 50,000 Da, and / or (2) The composition for removing PFAS according to claim 17, wherein the hydrophobic group has a C2 to C8 alkyl group or a poly- or perfluorinated group, and the C2 to C8 alkyl group is optionally selected from the group consisting of butyl, hexyl, octyl, isobutyl, isohexyl, and isooctyl groups.

19. 20. The composition for removing PFAS according to claim 18, wherein said poly or perfluorinated group is C8 perfluorooctane or C8 polyfluorinated 6:2 fluorotelomer.

20. A bed or packed column for use in removing contaminants from a fluid stream comprising sorbent molecules according to any one of claims 17 to 19.

21. 21. The bed or packed column of claim 20, wherein the contaminants comprise one or more poly- and perfluorinated alkyl substances (PFAS).

22. 22. The bed or packed column of claim 21, wherein the PFAS comprises one or more perfluorinated anionic surfactant compounds selected from the group consisting of perfluorobutanesulfonic acid (PFBS), perfluorobutanoic acid (PFBA), perfluorohexanesulfonic acid (PFHS), perfluorohexanoic acid (PFHA), perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), and 6:2 fluorotelomersulfonic acid (6:2FTSA).

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