Water treatment system methods

Abstract

Treatment compositions for treating water sources and methods for treating water sources are described. [Solution] The composition comprises one or more of an inorganic salt, a treatment polymer, and particles. A flocculant may be added to the water source before or after the inorganic salt, treatment polymer, and particles. The method and composition can be used, for example, to treat wastewater.

Description

[Technical Field]

[0001] This disclosure relates to methods and compositions for treating wastewater. More specifically, this disclosure relates to compositions comprising inorganic salts and treatment polymers, and to methods for using these compositions to treat wastewater. [Background technology]

[0002] Wastewater is a major global problem. Many industries generate wastewater, which can cause serious environmental problems and health hazards. Industrial and agricultural wastewater cannot be discharged without treatment. Such environmental problems have constantly driven scientists and engineers to develop new materials and methods that can reduce the level of environmental pollution.

[0003] Coagulation plays a major role in wastewater treatment. For example, industrial wastewater can be treated with organic or inorganic coagulants such as vinyl polymers and natural polysaccharides (i.e., chitosan, and chitosan grafted with synthetic polymers) and inorganic coagulants. Coagulation is the process by which particles are formed as a result of destabilization, and these particles come together and come into contact with each other, thereby gradually forming larger clumps. In this case, destabilization is actually manifested by the fact that coagulation accelerates floc formation, affects the physical characteristics of the formed flocs (e.g., their strength, size, and density), and governs the final concentration of destabilized particles. Coagulation and flocculation phenomena are extremely important in wastewater treatment.

[0004] Flocculating agents (or flocculants) are essential components in water and wastewater treatment that induce flocculation, a process in which small particles are collected to form larger particles by adding small amounts of chemical substances. Flocculating agents are classified into inorganic and organic categories. In wastewater treatment, inorganic flocculants (also called coagulants) containing polyvalent metals such as aluminum and iron have been widely used. Organic flocculants based on acrylamide polymers such as polyacrylamide and its derivatives are also effective, offering advantages such as low dose requirements, ease of handling, non-interference with the pH of the suspension, and greater floc-forming ability. [Overview of the project]

[0005] A particular aspect of this disclosure relates to a method for removing suspended solids from a water source. The method comprises adding a treatment polymer and an inorganic salt to the water source, wherein the weight ratio of the inorganic salt to the treatment polymer added to the water source is about 0.05:1 to 100:1.

[0006] In some embodiments, the inorganic salt is selected from the group consisting of aluminum salts, ferric salts, and any combination thereof.

[0007] In some embodiments, a treatment polymer is added to the water source in concentrations of approximately 1 ppm to 10,000 ppm. In specific embodiments, an inorganic salt is added to the water source in concentrations of approximately 1 ppm to 10,000 ppm.

[0008] In some embodiments, the treated polymer has a Huggins constant of about 0.0 to 1. In some embodiments, the treated polymer has a conformation plot gradient of about 0.05 to about 1.

[0009] In certain embodiments, the aluminum salt is aluminum chloride, aluminum chloride hydrate, aluminum sulfate, alum, polyaluminum sulfate, PAC, aluminum chlorohydrate, Al n Cl (3n-m) (OH) mThe compounds are selected from the group consisting of compounds having the formula (wherein m is an integer from 0 to 100, n is an integer from 1 to 100, and m is less than 3n), and any combination thereof.

[0010] In some embodiments, the ferric salt is selected from the group consisting of ferric chloride, ferric sulfate, polyferric salts, and any combination thereof.

[0011] In some embodiments, the composition comprises a treated polymer and an inorganic salt, and further comprises a pH of about 1.0 to about 8.5.

[0012] In certain embodiments, the treated polymer is added to the water source before, after, and / or together with the inorganic salt. In some embodiments, the inorganic salt and the treated polymer are supplied together to the water source.

[0013] In some embodiments, the treated polymer includes monomers selected from the group consisting of anionic monomers, cationic monomers, nonionic monomers, zwitterionic monomers, and any combination thereof.

[0014] In certain embodiments, the treatment polymer comprises a monomer selected from the group consisting of acrylamide, methacrylamide, 2-(dimethylamino)ethyl acrylate (“DMAEA”), 2-(dimethylamino)ethyl methacrylate (“DMAEM”), 3-(dimethylamino)propyl methacrylamide (“DMAPMA”), 3-(dimethylamino)propyl acrylamide (“DMAPA”), 3-methacrylamidopropyl-trimethyl-ammonium chloride (“MAPTAC”), 3-acrylamidopropyl-trimethyl-ammonium chloride (“APTAC”), N-vinylpyrrolidone (“NVP”), diallyldimethylammonium chloride (“DADMAC”), diallylamine, 2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride (“DMAEA.MCQ”), 2-(methacryloyloxy)-N,N,N-trimethylethanaminium chloride (“DMAEM.MCQ”), N,N-dimethylaminoethyl acrylate benzyl chloride (“DMAEA.BCQ”), N,N-dimethylaminoethyl methacrylate benzyl chloride (“DMAEM.BCQ”), 2-acrylamido-2-methylpropane sulfonic acid (“AMPS”), 2-acrylamido-2-methylbutane sulfonic acid (“AMBS”), acrylamide tert-butyl sulfonate (“ATBS”), [2-methyl-2-[(1-oxo-2-propenyl)amino]propyl]-phosphonic acid, acrylic acid, methacrylic acid, maleic acid, itaconic acid, glyoxalated polyacrylamide (GPAM), polyvinylamine (PVAM), polyethyleneimine (PEI), polyamidoamine epichlorohydrin (PAE), salts of any of the foregoing monomer units, and any combination thereof.

[0015] In some embodiments, the treatment polymer is a linear polymer.

[0016] In some embodiments, the treatment polymer is cationic, anionic, zwitterionic, nonionic, amphoteric with a net positive charge, or amphoteric with a net negative charge.

[0017] In certain embodiments, the treatment polymer contains carboxylic acid. In some embodiments, the polymer contains from about 1 mol% to about 25 mol% carboxylic acid.

[0018] In some embodiments, the method further includes forming colloidal particles using the treatment polymer and an inorganic salt, and adding the colloidal particles to a water source. In some embodiments, the method further includes forming colloidal particles in the water source using the treatment polymer and an inorganic salt.

[0019] In certain embodiments, the colloidal particles include a treatment polymer embedded within a colloidal aluminum hydroxide complex and / or a colloidal ferric hydroxide complex.

[0020] In some embodiments, the colloidal particles are water-insoluble. In some embodiments, the colloidal particles have an average particle size in the range of about 0.01 to about 1,000 microns.

[0021] In certain embodiments, the water source is wastewater, raw water, or oil sand wastewater.

[0022] In some embodiments, the pH of the water source is adjusted to about 5 to about 14.

[0023] In some embodiments, the suspended solids include members selected from the group consisting of food waste, microorganisms, oil particles, grease particles, industrial waste, sand particles, gravel particles, chemical precipitates, fibrous materials, environmental pollutants, and any combination thereof. [[ID=​​​​​​The disclosure also provides a method for removing suspended solids from a water source. The method comprises adding a composition to the water source, the composition comprising colloidal particles, the colloidal particles comprising polymers embedded within colloidal aluminum hydroxide complexes and / or colloidal ferric hydroxide complexes.

[0026] Furthermore, this disclosure provides a method for reducing the turbidity of a water source. The method comprises adding a treatment polymer and an inorganic salt to the water source, wherein the weight ratio of the inorganic salt added to the water source to the treatment polymer is approximately 0.05:1 to 100:1.

[0027] In some embodiments, the inorganic salt is selected from the group consisting of aluminum salts, ferric salts, and any combination thereof.

[0028] In some embodiments, a treatment polymer is added to the water source in concentrations of approximately 1 ppm to 10,000 ppm. In specific embodiments, an inorganic salt is added to the water source in concentrations of approximately 1 ppm to 10,000 ppm.

[0029] In some embodiments, the treated polymer has a Huggins constant of about 0.0 to 1. In some embodiments, the treated polymer has a conformation plot gradient of about 0.05 to about 1.

[0030] In certain embodiments, the aluminum salt is aluminum chloride, aluminum chloride hydrate, aluminum sulfate, alum, polyaluminum sulfate, PAC, aluminum chlorohydrate, Al n Cl (3n-m) (OH) m The compounds are selected from the group consisting of compounds having the formula (wherein m is an integer from 0 to 100, n is an integer from 1 to 100, and m is less than 3n), and any combination thereof.

[0031] In some embodiments, the ferric salt is selected from the group consisting of ferric chloride, ferric sulfate, polyferric salts, and any combination thereof.

[0032] In some embodiments, the composition comprises a treated polymer and an inorganic salt, and further comprises a pH of about 1.0 to about 8.5.

[0033] In certain embodiments, the treated polymer is added to the water source before, after, and / or together with the inorganic salt. In some embodiments, the inorganic salt and the treated polymer are supplied together to the water source.

[0034] In some embodiments, the treated polymer includes monomers selected from the group consisting of anionic monomers, cationic monomers, nonionic monomers, zwitterionic monomers, and any combination thereof.

[0035] In certain embodiments, the treated polymer comprises monomers selected from the group consisting of acrylamide, methacrylamide, DMAEA, DMAEM, DMAPMA, DMAPA, MAPTAC, APTAC, NVP, DADMAC, diallylamine, DMAEA.MCQ, DMAEM.MCQ, DMAEA.BCQ, DMAEM.BCQ, AMPS, AMBS, ATBS, [2-methyl-2-[(1-oxo-2-propenyl)amino]propyl]phosphonic acid, acrylic acid, methacrylic acid, maleic acid, itaconic acid, salts of any of the aforementioned monomer units, and any combination thereof.

[0036] In some embodiments, the treated polymer is a linear polymer. In some embodiments, the treated polymer is cationic, anionic, zwitterionic, nonionic, amphoteric with a net positive charge, or amphoteric with a net negative charge. In certain embodiments, the treated polymer contains a carboxylic acid. In some embodiments, the polymer contains about 1 mol% to about 25 mol% of the carboxylic acid.

[0037] In some embodiments, the method further comprises forming colloidal particles using a treated polymer and an inorganic salt, and adding the colloidal particles to a water source. In certain embodiments, the method further comprises forming colloidal particles in a water source using a treated polymer and an inorganic salt.

[0038] In some embodiments, the colloidal particles include a treated polymer embedded within a colloidal aluminum hydroxide complex and / or a colloidal ferric hydroxide complex.

[0039] In some embodiments, the colloidal particles are water-insoluble.

[0040] In certain embodiments, the colloidal particles have an average particle size in the range of about 0.01 to about 1,000 microns.

[0041] In some embodiments, the water source is wastewater, raw water, or oil sands wastewater.

[0042] In some embodiments, the pH of the water source is adjusted to approximately 5 to 14.

[0043] The disclosure also provides a method for reducing the turbidity of a water source. The method comprises adding a composition to the water source, the composition comprising colloidal particles, the colloidal particles comprising polymers embedded within colloidal aluminum hydroxide complexes and / or colloidal ferric hydroxide complexes.

[0044] The foregoing has broadly outlined the features and technical advantages of the present disclosure so that subsequent embodiments for carrying out the invention may be better understood. Further features and advantages of the present disclosure, which form the subject matter of the claims of this application, are described below. It should be understood by those skilled in the art that the disclosed concepts and specific embodiments can be readily used as a basis for modifying or designing other embodiments to accomplish the same objectives as the present disclosure. It should also be recognized by those skilled in the art that such equivalent embodiments do not deviate from the spirit and scope of the present disclosure as expressed in the appended claims. [Brief explanation of the drawing]

[0045] [Figure 1] This graph shows the effect of pH on the viscosity of polyaluminum chloride (PAC) and carboxylic acid-containing polymer (CAP) blend samples.

[0046] [Figure 2] This graph shows the effect of various concentrations of PAC and CAP blend samples on the turbidity of dairy samples.

[0047] [Figure 3] The bar graph shows that a greater reduction in oil content is observed for a 1200 ppm composition of 95 / 5 PAC / CAP (PAC blend B in the graph; CAP is diallyldimethylammonium chloride (DADMAC) containing 10% acrylic acid) compared to a 1500 ppm treatment with PAC alone (CAS#12042-91-0 in the figure).

[0048] [Figure 4] This graph shows the ratio of turbidity to the dosage of the treatment composition compared to a conventional PAC composition in synthetic oil water. [Modes for carrying out the invention]

[0049] Various embodiments of the technology of this disclosure are described below. The relationships and functions of the various elements of the embodiments can be better understood by referring to the detailed description below. However, the embodiments are not limited to those expressly described below.

[0050] Unless otherwise indicated, alkyl groups described herein, either alone or as part of another group, are optionally substituted linear or branched saturated monovalent hydrocarbon substituents having, for example, 1 to about 60 carbon atoms in the main chain, e.g., 1 to about 30 carbon atoms. Examples of unsubstituted alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, and t-pentyl.

[0051] When used herein, either alone or as part of another group (e.g., arylene), the terms “aryl” or “ar” refer to optionally substituted allocyclic aromatic groups, such as monocyclic or bicyclic groups containing about 6 to about 12 carbon atoms in the ring portion, including phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl, or substituted naphthyl. The term “aryl” also includes heteroaryl functional groups. It is understood that the term “aryl” also applies to planar, cyclic substituents containing 4n+2 electrons, according to Huckel’s law.

[0052] "Cycloalkyl" refers to a cyclic alkyl substituent containing, for example, about 3 to about 8 carbon atoms, preferably about 4 to about 7 carbon atoms, more preferably about 4 to about 6 carbon atoms. Examples of such substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. The cyclic alkyl group may be unsubstituted or may be further substituted with alkyl groups such as methyl or ethyl groups.

[0053] A "heteroaryl" refers to a monocyclic or bicyclic 5- or 6-membered ring system. Heteroaryl groups are unsaturated and satisfy Hückel's rule. Non-restrictive examples of heteroaryl groups include furanyl, thiophenyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, 1,3,4-oxadiazole-2-yl, 1,2,4-oxadiazole-2-yl, 5-methyl-1,3,4-oxadiazole, 3-methyl-1,2,4-oxadiazole, pyridinyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, benzothiophenyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzoxazolinyl, benzothiazolinyl, and quinazolinyl.

[0054] The compounds of this disclosure may be substituted with preferred substituents. As used herein, the term “preferred substituent” is intended to mean a chemically acceptable functional group, preferably a portion that does not negate the activity of the compound. Such preferred substituents include, but are not limited to, halo groups, perfluoroalkyl groups, perfluoroalkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, hydroxy groups, oxo groups, mercapto groups, alkylthio groups, alkoxy groups, aryl or heteroaryl groups, aryloxy or heteroaryloxy groups, aralkyl or heteroaralkyl groups, aralkoxy or heteroaralkoxy groups, HO-(C=O)- groups, heterocyclic groups, cycloalkyl groups, amino groups, alkyl and dialkylamino groups, carbamoyl groups, alkylcarbonyl groups, alkoxycarbonyl groups, alkylaminocarbonyl groups, dialkylaminocarbonyl groups, arylcarbonyl groups, aryloxycarbonyl groups, alkylsulfonyl groups, and arylsulfonyl groups. In some embodiments, preferred substituents include halogens, unsubstituted C1-C12 12 Alkyl groups, unsubstituted C4-C6 aryl groups, or unsubstituted C1-C6 groups 10 An example is an alkoxy group. Those skilled in the art will understand that many substituents can be substituted with additional substituents.

[0055] The term "substituted", as in "substituted alkyl", means that in the group in question (i.e., this alkyl group), at least one hydrogen atom attached to a carbon atom is replaced by one or more substituents such as hydroxy (-OH), alkylthio, phosphino, amide (-CON(R A )(R B )(where R A and R B are independently hydrogen, alkyl, or aryl)), amino (-N(R A )(R B (where R A and R B are independently hydrogen, alkyl, or aryl)), halo (fluoro, chloro, bromo, or iodo), silyl, nitro (-NO2), ether (-OR A (where R A is alkyl or aryl)), ester (-OC(O)R A (where R A is alkyl or aryl)), keto (-C(O)R A (where R A is alkyl or aryl)), heterocyclo, etc.

[0056] When the term "substituted" introduces a list of possible substituents, this term is intended to apply to all members of that group. That is, the phrase "optionally substituted alkyl or aryl" should be interpreted as "optionally substituted alkyl or optionally substituted aryl".

[0057] As used herein, the term “aluminum salt” refers to an inorganic compound containing aluminum ions, including but not limited to alum, aluminum chloride, aluminum sulfate, polyaluminum sulfate, PAC, and aluminum chlorohydrate. Aluminum salts are compounds that contribute to aluminum ions in aqueous solutions. These include, but are not limited to, aluminum sulfate, aluminum chloride, aluminum phosphate, aluminum nitrate, and aluminum acetate.

[0058] As used herein, the term “ferric salt” refers to an inorganic compound containing ferric ions, including but not limited to ferric chloride, ferric sulfate, polyferric sulfate, and polyferric chloride. Ferric salts are compounds that contribute to ferric ions in aqueous solutions. These include, but are not limited to, ferric sulfate, ferric chloride, ferric phosphate, ferric nitrate, and ferric acetate.

[0059] Terms such as "co-feed," "co-feeding," and "co-fed" refer to the addition of two or more components, raw materials, chemicals, etc., to a reaction vessel and / or storage container, etc., at essentially / substantially the same time and location, although separately. For example, two components, such as a processing polymer and an inorganic salt, may be supplied to a reaction vessel, etc., through separate injection pipes. Each pipe may simultaneously and continuously or intermittently inject chemicals to a single location or to two or more locations within the reaction vessel that are very close to each other (e.g., within about 1 to 12 inches, e.g., about 1 to 10 inches, about 1 to 8 inches, or about 1 to 6 inches).

[0060] The term "degree of crosslinking" refers to the average number of linkage bonds that connect one polymer chain to another. For example, a polymer sample with an average chain length of 1,000 monomer units and 10 monomer units linked to another chain has a degree of crosslinking of 1%.

[0061] The term "weight-average molecular weight" refers to the average molecular weight of a polymer determined by static light scattering measurements, specifically by size-exclusion-chromatography (SEC) / multi-angle-laser-light-scattering (MALLS) techniques. The polymers in this disclosure have a weight-average molecular weight of approximately 10,000 to approximately 10,000,000 daltons.

[0062] The term "average particle size" refers to the average diameter of a particle determined by a dynamic light scattering particle size analyzer when the particle size is less than 10 microns, and by a laser diffraction size analyzer when the particle size is between 1 and 1,000 microns. The particles of this disclosure have an average particle size of about 0.01 to about 1,000 microns.

[0063] The term “water source” means water containing one or more target substances, which are preferably separated from, passivated, or encombined with the water. In certain embodiments, the water sources addressed herein are industrial water sources, i.e., water, raw water, or oil sands wastewater containing one or more target substances as a result of one or more industrial processes. As used herein, the term “separation” means phase separation, such as achieved by precipitation, coagulation, or liquid-liquid phase separation. As used herein, the term “passivation” means that the harmful effects of the target substance are neutralized, inactivated, or attenuated. As used herein, the term “encombination” means dissolution, dispersion, or emulsification. Industrial water sources include generated water from hydrocarbon reservoirs or mines, reused water used for cooling in industrial manufacturing processes, wastewater generated by one or more industrial processes such as papermaking or food processing, and other water sources generated by industrial processes.

[0064] The terms “wastewater” and “sluice” may be used interchangeably to refer to any solution that is a discharge or effluent having water as its primary component and containing one or more contaminants.

[0065] The term “target substance” means one or more substances dissolved, suspended, emulsified, or dispersed in a water source, such as an industrial water source, which are treated by the compositions and methods described herein. Exemplary but non-limiting examples of target substances and corresponding water treatment compounds and / or methods include: corrosive compounds targeted for corrosion protection; compounds that tend to separate from water and deposit on equipment surfaces for the purpose of preventing phase separation or deposition / sedimentation; emulsified hydrocarbon compounds targeted for emulsion decomposition (destruction); microorganisms targeted for antimicrobial treatment; and dispersed solids targeted for coagulation or aggregation. A target substance may also refer to a “contaminant,” which may be any or more substances, such as water, whose composition, material, location, etc., are undesirable. For example, substances that are not considered environmentally safe for direct discharge into wastewater or other drinking water systems may be considered contaminants. Such substances include, but are not limited to, ions, organic matter, biochemical reagents, heavy metals, heavy metal complexes, inorganic salts, inorganic reagents, dissolved and suspended natural organic matter, clay, silica, and any other chemically or biologically active substances.

[0066] The terms “to treat,” “the act of treating,” “treatment,” “treatment method,” or “treatment method” further refer to the process of treating a water source, such as an industrial water source, to separate a target substance from the water source, to passivate a target substance within the water source, or to entrain a target substance within the water source. Examples of exemplary but non-limiting treatments include: corrosion protection treatments to passivate metal surfaces from corrosive substances present in industrial water sources; emulsion disruption treatments to induce liquid-liquid phase separation of target substances from industrial water sources; scale prevention treatments to prevent calcium scale deposition on surfaces in contact with industrial water sources; antifreeze treatments to prevent solidification or phase separation of industrial water sources in environments where the temperature is near or below 0°C, or may be at such temperatures; paraffin inhibition treatments to prevent the deposition of waxy petroleum-based solids on surfaces in contact with hydrocarbon-containing industrial water sources; coagulation / solidification treatments to remove solid impurities from industrial water sources by precipitation; disinfection / sterilization treatments to neutralize or reduce microbial factors present in industrial water sources; purification treatments to remove various target substances from industrial water sources; and polymerization inhibition treatments to reduce or prevent the polymerization of hydrocarbon impurities present in industrial water sources. Specifically, in the context of the described compositions and methods for treating water sources, these terms refer to treatments that improve the liquid-solid separation process in a water source, such as an industrial water source, compared to conventional methods of treating water sources.

[0067] With respect to improved treatment of water sources, the terms “improved” or “improved” refer to better performance in removing target substances from water sources by treatment using the treatment compositions described herein compared to conventional treatment methods. The degree of improvement will vary depending on the properties and amount of the treatment composition present, but will be evident, for example, as a detectable improvement in the reduction of target substances such as contaminants from water sources such as wastewater. Preferably, the degree of improvement is greater than 2.5%, 5%, 10%, 25%, 50%, 75%, 90%, 95%, or 99% compared to conventional treatment methods.

[0068] The term "conventional treatment method" refers to the treatment of a water source using PAC or its derivative, polyDADMAC, alone. In certain embodiments, the conventional treatment method may refer to treatment with a mixture of PAC and homopolyDADMAC, where polyDADMAC does not have reactive carboxylic acid groups. This type of mixture is not pH-dependent.

[0069] The terms “treatment composition” or “treatment formulation” refer to products such as mixtures of compounds added to one or more water sources to treat, improve, promote, reduce, manage, control, maintain, optimize, modify, reduce, inhibit, or prevent a target substance. Treatment compositions or formulations described herein include metal-containing salts such as aluminum-based coagulants (e.g., PAC) or derivatives thereof and / or ferric-based coagulants or derivatives thereof, as well as treatment polymers such as CAP.

[0070] As used herein, “aggregation” refers to the destabilization of suspended particles in water caused by processes such as polymer crosslinking and / or electrostatic interactions and charge neutralization. Aggregation often involves the formation of discrete spheres of agglomerated particles together with a film of liquid carrier interposed between the agglomerated spheres, and as used herein, aggregation includes those described in ASTME 20-85 and those described in the Kirk-Othmer Encyclopedia of Chemical Technology, 5th edition, (2005), (published by Wiley, John & Sons, Inc.), all of which are incorporated herein by reference in their entirety for all purposes.

[0071] The term “flocculant” or “flocculating agent” may be used interchangeably and refers to a compound that, when applied to water containing multiple suspended / dispersed particles, can remove some of the particles from the suspended matter in the water to produce purer water. Flocculants can coagulate suspended particles. For example, a flocculant may be a polymer that, when applied to wastewater containing multiple suspended particles, can remove some of the particles from the suspended matter in the wastewater to produce purer water. Flocculants may be organic or inorganic. In this specification, flocculants are distinguished from “flocculents,” which refer to the materials that are coagulated by flocculants. Flocculants are classified into inorganic and organic categories. Inorganic flocculants (also called coagulants) include polyvalent metals such as aluminum and iron. Examples of organic flocculants include acrylamide polymers such as polyacrylamide and its derivatives.

[0072] The term "coagulant" refers to a treatment compound or derivative thereof used in a solid-liquid separation step to neutralize the charge of suspended solids / particles so that they can form clumps. Coagulants are classified into inorganic coagulants, organic coagulants, and blends of inorganic and organic coagulants. Inorganic coagulants include, but are not limited to, polyvalent metals, e.g., aluminum or iron salts, e.g., aluminum sulfate / chloride, ferric chloride / sulfate, polyaluminum chloride, and / or aluminum chloride hydrate. Organic coagulants include, but are not limited to, polyamines, polyquaternized polymers, polyDADMAC, epichlorohydrindimethylamine, and low molecular weight positively charged polymer compounds, as listed in the Kirk-Othmer Encyclopedia of Chemical Technology, 5th edition, (2005), (published by Wiley, John & Sons, Inc.).

[0073] The term "aluminum-based coagulant" refers to inorganic coagulants including aluminum, any compound containing aluminum metal, and derivatives of these compounds, such as PAC and its derivatives. PAC is a polyhydroxy polynuclear complex of an aluminum salt, with the general formula Al n Cl (3n-m) (OH) m The formula has the following properties (wherein m and n are integers between 0 and 100, and m < 3n). PAC can be in liquid or powder form. "Polyaluminum chloride derivative" or "PAC derivative" refers to the product of Al, Cl, OH in any ratio in the formula, containing aluminum chlorohydrate with different levels of OH content compared to the OH levels of PAC. Commercial PAC products typically differ in Al content and pH value.

[0074] The term “carboxylic acid-containing polymer” or “CAP” refers to a polymer having a carboxylic acid content (i.e., containing at least one monomer having a carboxylic acid group). In certain embodiments, CAP has a carboxylic acid content of up to 50 mol%. In certain other embodiments, CAP has a carboxylic acid content of up to 40 mol%, up to 30 mol%, up to 20 mol%, or up to 10 mol%.

[0075] The term "surfactant" refers to a surfactant that may be anionic, cationic, amphoteric, or nonionic. Examples of surfactants include fatty alcohol ethoxylates, alkylphenol ethoxylates, EO / PO block copolymers, Span and Tween® type surfactants, alkyl sulfates such as sodium lauryl sulfate and sodium laureth sulfate, quaternary ammonium salts such as docusate and cetrimonium bromide (CTAB), and dimethyldioctadecylammonium chloride.

[0076] The term "surfactant formulation" refers to a composition containing at least one surfactant. A flocculant / surfactant formulation is a form of surfactant formulation. "Flocculant / surfactant formulation" refers to a single composition containing a flocculant and a surfactant.

[0077] The terms “purer water” or “purified water” refer to water from which some or all of the target substances and / or contaminants have been removed. Water purity may be defined by the total organic carbon (TOC) content or by the transmission (percent transmittance, %T) of visible light at a wavelength of 550 nm through a water sample. When TOC is used to define water purity, “purer water” or “purified water” refers to water having at least 50% less TOC than the water before treatment with the described treatment composition, as measured by a 0.02 M potassium dichromate solution. When transmittance percentage is used to define water purity, “purer water” or “purified water” refers to water having at least 50% greater transmittance percentage than the water before treatment with the described composition. Since the contaminants in water depend on what is subjectively considered undesirable, it should be understood that pure water as used herein may also refer to water containing solutes and other materials not considered contaminants in the given context.

[0078] "Polymer crosslinking" refers to the binding of polymer chain segments to two or more particles in wastewater, which causes those segments to link together and induce aggregation.

[0079] As used herein, the terms “simultaneous” and “substantially simultaneous” mean less than one minute or less than one minute from each other. In the context of mixing materials or formulations into a composition or solution, substantially simultaneous means that the second material or formulation is added to the composition or solution before the first material or formulation is distributed into the composition or solution.

[0080] With respect to the described compositions, the term "non-crosslinked form" refers to dormant compositions of polymers and inorganic salts treated at a low pH to prevent crosslinking before use; that is, during the supply of the product, influent water with a higher pH automatically induces crosslinking interactions, resulting in better performance.

[0081] Certain aspects of the methods disclosed herein provide in-situ and / or on-site generation of structured coagulants or flocculants by utilizing the pH of process water as an inducing mechanism, relying on pH-dependent interactions between inorganic salts such as aluminum salts and / or ferric salts and a treatment polymer such as CAP. Methods for improving liquid-solid separation processes in industrial water treatment programs are described herein.

[0082] Surprisingly, compositions containing inorganic salts such as aluminum salts and / or ferric salts, and treatment polymers such as CAP, were found to exhibit improved water purification performance compared to conventional water treatments such as PAC treatment alone.

[0083] Specifically, when the PAC solution was mixed with the treated polymer at an acidic pH (e.g., pH of about 4.0 or less), the mixture reacted minimally and remained liquid. However, as the pH increased, the solution rapidly became viscous or gel-like. This change in viscosity indicates the formation of a new structured coagulant or complex (which in some embodiments may be referred to as "CAP-crosslinked PAC," "treated polymer-crosslinked PAC," or "colloidal particles") through interaction between the PAC and the treated polymer. In some embodiments, the treated polymer of the Disclosure is chemically and / or physically entangled and / or embedded in colloidal aluminum hydroxide and / or colloidal ferric hydroxide complexes, which may be the structured coagulant or colloidal particles mentioned above.

[0084] The pH-dependent interaction between the inorganic salt and the treated polymer provides a stable and concentrated composition at low pH (typically pH < 4.0), but induces a reaction at high pH (typically pH > 4.0) during application, generating a hybrid structural network that improves the performance of the composition compared to standard processing methods. In other words, by modifying the inorganic salt, such as modifying the polyaluminum structure of PAC or its derivatives, superior coagulants were produced. By applying this pH-induced mechanism, it was surprisingly found that novel formulations perform better than polyaluminum alone, with potential advantages such as lower chemical consumption, less sludge formation, and lower cost.

[0085] Furthermore, surprisingly, it was discovered that the same technique could be applied by co-supplying and / or sequentially supplying inorganic salts together with the treated polymer and inducing interactions in-situ.

[0086] Furthermore, using the same technology, unstable crosslinking or structured flocculants / coagulants can be produced, for example, by low-level blending or co-supplying of polyaluminum salts and / or polyferric salts (e.g., less than 10%) with carboxylate-containing flocculants.

[0087] In certain embodiments, the treatment compositions or formulations described herein contain, essentially consist of, or comprise inorganic salts such as aluminum salts and / or ferric salts or their derivatives, and treatment polymers such as CAP, the pH of the composition is pH 4 or less, and the composition is in a non-crosslinked or low-crosslinked form. When the treatment composition is introduced into a water source, improved treatment results are observed compared to treatment using conventional wastewater treatment compositions.

[0088] In some embodiments, the inorganic salt is a metal-containing salt such as an aluminum salt and / or a ferric salt.

[0089] Any suitable aluminum salt may be selected and used in conjunction with the innovations disclosed herein. In some embodiments, the aluminum salt is aluminum chloride, aluminum chloride hydrate, aluminum sulfate, alum, polyaluminum sulfate, PAC, aluminum chlorohydrate, or Al n Cl (3n-m) (OH) m The compounds are selected from the group consisting of compounds having the formula (wherein m is an integer from 0 to 100, n is an integer from 1 to 100, and m is less than 3n), and any combination thereof.

[0090] In certain embodiments, the aluminum-based coagulant may be PAC or a derivative thereof. A PAC derivative is a compound of Al n Cl (3n-m) (OH) m The compound may contain Al, Cl, and OH in any ratio based on (Equation 1) (wherein m and n are integers from 0 to 100, and m < 3n), and may be an aluminum chlorohydrate having an OH content at a different level than that of PAC.

[0091] Any suitable ferric salt may be selected and used in conjunction with the innovations disclosed herein. In some embodiments, the ferric salt is selected from the group consisting of ferric chloride, ferric sulfate, polyferric salts, and any combination thereof.

[0092] The treated polymers of the present disclosure may be chemically and / or physically entangled and / or embedded in colloidal aluminum hydroxide and / or colloidal ferric hydroxide complexes. The treated polymers may comprise one or more anionic monomers, one or more cationic monomers, one or more nonionic monomers, one or more zwitterionic monomers, or any combination thereof.

[0093] In some embodiments, the treated polymer has a net negative charge, and in other embodiments, the treated polymer has a net positive or neutral charge. In certain embodiments, the treated polymer is water-soluble. In some embodiments, the treated polymer contains a carboxylic acid group, which may be referred to herein as CAP.

[0094] For example, the treated polymer may contain about 1 mol% to about 50 mol%, such as about 1 mol% to about 40 mol%, about 1 mol% to about 30 mol%, about 1 mol% to about 20 mol%, about 1 mol% to about 10 mol%, about 10 mol% to about 50 mol%, about 20 mol% to about 50 mol%, about 30 mol% to about 50 mol%, or about 40 mol% to about 50 mol% of carboxylic acid.

[0095] In some embodiments, the treated polymer contains about 1 mol% to about 8 mol%, about 1 mol% to about 7 mol%, about 1 mol% to about 6 mol%, about 1 mol% to about 5 mol%, about 1 mol% to about 4 mol%, about 1 mol% to about 3 mol%, or about 1 mol% to about 2 mol%, for example, about 1 mol%, about 2 mol%, about 3 mol%, about 4 mol%, about 5 mol%, about 6 mol%, about 7 mol%, or about 8 mol% of carboxylic acid.

[0096] Exemplary and non-limiting examples of nonionic monomers that may be included in the processed polymer are selected from acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, N-vinylformamide, N-vinylmethylacetamide, N-vinylpyrrolidone, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, N-tert-butylacrylamide, N-methylolacrylamide, diallylamine, allylamine, and the like.

[0097] Exemplary and non-limiting examples of anionic monomers include acrylic acid and its salts (including, but not limited to, sodium acrylate and ammonium acrylate), methacrylic acid and its salts (including, but not limited to, sodium methacrylate and ammonium methacrylate), AMPS, sodium salts of AMPS, sodium vinylsulfonate, styrene sulfonate, maleic acid and its salts (including, but not limited to, sodium salts and ammonium salts), sulfonate itaconate, sulfopropyl acrylate or methacrylate, or other water-soluble forms thereof or other polymerizable carboxylic acids or sulfonic acids, sulfomethylated acrylamide, allyl sulfonate, sodium vinylsulfonate, itaconic acid, acrylamide methylbutanoic acid, fumaric acid, vinylphosphonic acid, vinylsulfonic acid, allylphosphonic acid, sulfomethylated acrylamide, phosphonomethylated acrylamide, and the like.

[0098] Exemplary and non-limiting examples of cationic monomers include dialkylaminoalkyl acrylates and methacrylates, and their quaternary or salt salts, for example, dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate sulfate, dimethylaminoethyl acrylate hydrochloride, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate sulfate, dimethylaminoethyl methacrylate hydrochloride, dialkylaminoalkylacrylamide or methacrylamide and their quaternary or salt salts, for example, acrylamidopropyltrimethylammonium chloride, dimethylaminoethyl methacrylate Examples include, but are not limited to, diethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamidopropyl trimethylammonium chloride, dimethylaminopropyl acrylamide methyl sulfate quaternary salt, dimethylaminopropyl acrylamide sulfate, dimethylaminopropyl acrylamide hydrochloride, methacrylamidopropyl trimethylammonium chloride, dimethylaminopropyl methacrylamide methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide sulfate, dimethylaminopropyl methacrylamide hydrochloride, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, diallyldiethylammonium chloride, and diallyldimethylammonium chloride.

[0099] Exemplary and non-limiting examples of zwitterionic monomers include N,N-dimethyl-N-acryloyloxyethyl-N-(3-sulfopropyl)-ammonium betaine, N,N-dimethyl-N-acrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine, N,N-dimethyl-N-acrylamidopropyl-N-(3-sulfopropyl)-ammonium betaine, N,N-dimethyl-N-acrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine, 2-(methylthio)ethylmethacryloyl-S-(sulfopropyl)-sulfonium betaine, 2-[(2-acryloylethyl)dimethylammonio]ethyl 2-methylphosphate, and 2-(acryloyloxyethyl)-2'-(tri Examples include methylammonium)ethyl phosphate, [(2-acryloylethyl)dimethylammonio]methylphosphonic acid, 2-methacryloyloxyethyl phosphorylcholine (MPC), 2-[(3-acrylamidopropyl)dimethylammonio]ethyl 2'-isopropyl phosphate (AAPI), 1-vinyl-3-(3-sulfopropyl)imidazolium hydroxide, (2-acrylooxyethyl)carboxymethylmethylsulfonium chloride, 1-(3-sulfopropyl)-2-vinylpyridinium betaine, N-(4-sulfobutyl)-N-methyl-N,N-diallylamineammonium betaine (MDABS), and N,N-diallyl-N-methyl-N-(2-sulfoethyl)ammonium betaine.

[0100] In some embodiments, the treated polymer comprises monomers selected from the group consisting of acrylamide, methacrylamide, DMAEA, DMAEM, DMAPMA, DMAPA, MAPTAC, APTAC, NVP, DADMAC, diallylamine, DMAEA.MCQ, DMAEM.MCQ, DMAEA.BCQ, DMAEM.BCQ, AMPS, AMBS, ATBS, [2-methyl-2-[(1-oxo-2-propenyl)amino]propyl]phosphonic acid, acrylic acid, methacrylic acid, maleic acid, itaconic acid, salts of any of the aforementioned monomer units, and any combination thereof.

[0101] In certain embodiments, the polymer includes GPAM, PVAM, PEI, PAE, or any combination thereof.

[0102] Additional examples of treated polymers can be found in Table 1.

[0103] [Table 1-1] [Table 1-2]

[0104] In Table 1, DAAM refers to diacetone acrylamide, AAEM refers to acetoacetoxyethyl methacrylate, and MAA refers to methacrylic acid. In some embodiments, the polymer contains about 90 mol% acrylamide, about 8 mol% DMAEA.MCQ, and about 2 mol% itaconic acid.

[0105] The molar percentage of each monomer in the treated polymer is not particularly limited. In some embodiments, the treated polymer contains about 1 mol% to about 99 mol% of cationic monomers. For example, the treated polymer may contain cationic monomers in amounts of approximately 1 mol% to 90 mol%, approximately 1 mol% to 80 mol%, approximately 1 mol% to 70 mol%, approximately 1 mol% to 60 mol%, approximately 1 mol% to 50 mol%, approximately 1 mol% to 40 mol%, approximately 1 mol% to 30 mol%, approximately 1 mol% to 20 mol%, approximately 1 mol% to 10 mol%, approximately 10 mol% to 99 mol%, approximately 20 mol% to 99 mol%, approximately 30 mol% to 99 mol%, approximately 40 mol% to 99 mol%, approximately 50 mol% to 99 mol%, approximately 60 mol% to 99 mol%, approximately 70 mol% to 99 mol%, approximately 80 mol% to 99 mol%, or approximately 90 mol% to 99 mol%.

[0106] In some embodiments, the treated polymer contains about 1 mol% to about 99 mol% of anionic monomers. For example, the treated polymer may contain about 1 mol% to about 90 mol%, about 1 mol% to about 80 mol%, about 1 mol% to about 70 mol%, about 1 mol% to about 60 mol%, about 1 mol% to about 50 mol%, about 1 mol% to about 40 mol%, about 1 mol% to about 30 mol%, about 1 mol% to about 20 mol%, about 1 mol% to about 10 mol%, about 10 mol% to about 99 mol%, about 20 mol% to about 99 mol%, about 30 mol% to about 99 mol%, about 40 mol% to about 99 mol%, about 50 mol% to about 99 mol%, about 60 mol% to about 99 mol%, about 70 mol% to about 99 mol%, about 80 mol% to about 99 mol%, or about 90 mol% to about 99 mol% of anionic monomers.

[0107] In some embodiments, the treated polymer contains about 1 mol% to about 99 mol% of nonionic monomers. For example, the treated polymer may contain about 1 mol% to about 90 mol%, about 1 mol% to about 80 mol%, about 1 mol% to about 70 mol%, about 1 mol% to about 60 mol%, about 1 mol% to about 50 mol%, about 1 mol% to about 40 mol%, about 1 mol% to about 30 mol%, about 1 mol% to about 20 mol%, about 1 mol% to about 10 mol%, about 10 mol% to about 99 mol%, about 20 mol% to about 99 mol%, about 30 mol% to about 99 mol%, about 40 mol% to about 99 mol%, about 50 mol% to about 99 mol%, about 60 mol% to about 99 mol%, about 70 mol% to about 99 mol%, about 80 mol% to about 99 mol%, or about 90 mol% to about 99 mol% of nonionic monomers.

[0108] In some embodiments, the treated polymer contains about 1 mol% to about 99 mol% of zwitterionic monomers. For example, the treated polymer may contain zwitterionic monomers in amounts of approximately 1 mol% to 90 mol%, approximately 1 mol% to 80 mol%, approximately 1 mol% to 70 mol%, approximately 1 mol% to 60 mol%, approximately 1 mol% to 50 mol%, approximately 1 mol% to 40 mol%, approximately 1 mol% to 30 mol%, approximately 1 mol% to 20 mol%, approximately 1 mol% to 10 mol%, approximately 10 mol% to 99 mol%, approximately 20 mol% to 99 mol%, approximately 30 mol% to 99 mol%, approximately 40 mol% to 99 mol%, approximately 50 mol% to 99 mol%, approximately 60 mol% to 99 mol%, approximately 70 mol% to 99 mol%, approximately 80 mol% to 99 mol%, or approximately 90 mol% to 99 mol%.

[0109] In certain embodiments, the treated polymers disclosed herein comprise about 1 mol% to about 10 mol% of cationic monomers and about 1 mol% to about 5 mol% of anionic monomers. For example, the treated polymer may comprise about 5 mol% to about 10 mol% of cationic monomers, e.g., about 6 mol%, about 7 mol%, about 8 mol%, or about 9 mol% of cationic monomers and about 1 mol%, about 2 mol%, about 3 mol%, about 4 mol%, or about 5 mol% of anionic monomers.

[0110] In some embodiments, the treated polymer is neither disaccharide nor polysaccharide. In certain embodiments, the treated polymer excludes monosaccharide monomers. In certain embodiments, the compositions or particles disclosed herein exclude polysaccharides and / or anionic polysaccharides. In some embodiments, the treated polymer excludes hydroxamic acid groups, isocyanate groups, N-bromoamines and / or N-chloroamines. In certain embodiments, the treated polymer contains unmodified / unreacted amide and / or amine side chains. In some embodiments, if the treated polymer contains amide and / or amine side chains, less than 10% of these side chains, e.g., 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, less than 1%, or 0% are modified with / reacted with other functional groups before the treated polymer is embedded in the colloidal aluminum hydroxide complex and / or colloidal ferric hydroxide complex.

[0111] In some embodiments, the treated polymers of the Disclosure are water-soluble amphoteric polymers containing carboxylic acid groups. In certain embodiments, the treated polymers of the Disclosure may be linear, branched, crosslinked, structured, synthetic, semi-synthetic, natural, and / or functionally modified. The treated polymers of the Disclosure may be, for example, in the form of a solution, a dry powder, a liquid, or a dispersion.

[0112] The weight-average molecular weight of the treated polymer is not particularly limited. In some embodiments, the treated polymer has a molecular weight in the range of about 1,000 Da to about 20,000,000 Da. For example, the treated polymer may have molecular weights in the ranges of about 1,000 Da to about 15,000,000 Da, about 1,000 Da to about 10,000,000 Da, about 1,000 Da to about 5,000,000 Da, about 1,000 Da to about 2,500,000 Da, about 1,000 Da to about 1,000,000 Da, and about 1,000 Da to Approximately 500,000 Da, approximately 1,000 Da to approximately 250,000 Da, approximately 10,000 Da to approximately 5,000,000 Da, approximately 10,000 Da to approximately 3,000,000 Da, approximately 10,000 Da to approximately 1,000,000 Da, approximately 10,000 Da to approximately 750,000 Da, approximately 10,000 Da to approximately 50 0,000Da, approximately 10,000Da to approximately 250,000Da, approximately 10,000Da to approximately 100,000Da, approximately 10,000Da to approximately 50,000Da, approximately 100,000Da to approximately 10,000,000Da, approximately 500,000Da to approximately 10,000,000Da, approximately 750,000Da to approximately 1 It may have a molecular weight in the range of 0,000,000 Da, approximately 1,000,000 Da to approximately 10,000,000 Da, approximately 3,000,000 Da to approximately 10,000,000 Da, approximately 5,000,000 Da to approximately 10,000,000 Da, or approximately 8,000,000 Da to approximately 10,000,000 Da.

[0113] As an additional example, the weight-average molecular weight of the treated polymer may range from approximately 200,000 Da to approximately 1,000,000 Da, for example, approximately 200,000 Da to approximately 800,000 Da, approximately 200,000 Da to approximately 600,000 Da, or approximately 300,000 to approximately 500,000 Da.

[0114] In some embodiments, the treated polymers of the Disclosure have a Huggins constant of about 0.0 to about 1.0. For example, the Huggins constants of the treated polymers disclosed herein may be about 0.1 to about 0.9, about 0.1 to about 0.8, about 0.1 to about 0.7, about 0.1 to about 0.6, about 0.1 to about 0.5, about 0.1 to about 0.4, about 0.1 to about 0.3, about 0.1 to about 0.2, about 0.2 to about 0.8, about 0.2 to about 0.7, or about 0.2 to about 0.6.

[0115] The Huggins formula is an empirical formula used to relate the reduced viscosity of a diluted polymer solution to the concentration of the polymer in the solution. The Huggins formula is as follows:

number

[0116] The Huggins formula is η s / c is a useful tool because it can be used to determine the intrinsic viscosity [η] or IV from experimental data by plotting it against the concentration of the solution, c.

[0117] The Huggins constant can be calculated as follows:

number

number

[0118] In the SEC / MALLS analysis described herein, the polymer solution was diluted to approximately 0.05% with an aqueous mobile phase (0.3 M NaCl, 0.1 M NaH2PO4, 25 ppm NaN3). Approximately 200 μL of the solution was injected into a set of TSKgel PW columns (TSKgel GMPW+GMPW+G1000PW) with a mobile phase flow rate of approximately 1.0 mL / min. Bovine serum albumin (BSA) was used as a standard for normalizing the multi-angle light scattering detector. The calibration constant of the RI detector was verified with sodium chloride (NaCl).

[0119] The linearity of a treated polymer can be defined using the Huggins constant, where a lower Huggins constant indicates a more linear polymer.

[0120] Certain treated polymers disclosed herein may have conformation plot gradients of about 0.05 to about 1.0. For example, polymers may have conformation plot gradients of about 0.1 to about 1.0, about 0.2 to about 1.0, about 0.3 to about 1.0, about 0.4 to about 1.0, about 0.5 to about 1.0, about 0.05 to about 0.5, about 0.05 to about 0.3, or about 0.05 to about 0.1.

[0121] SEC / MALLS characterizes long chain branching (LCB) in macromolecules through conformational plots. Conformational plots are defined by the rms radius (radius of rotation, R).g This is a log-log plot of (LCB) and molar mass (M). Light scattering performed as SEC / MALLS can effectively and quickly characterize branching in polymers. Polymers with LCBs show a lower slope than the corresponding linear polymers, which varies depending on the degree of LCB. Conformation plots can be constructed by SEC / MALLS analysis (see AN1005: Identifying short-chain branched polymers with conformational analysis, Wyatt Technology, Chris Deng, Ph.D., this disclosure is incorporated in its entirety into this application).

[0122] The conformation plot is obtained by taking the average radius of rotation calculated based on the molecular weight at each point and the corresponding molecular weight on the chromatogram, and the corresponding gradient is calculated from the conformation plot.

[0123] Linear polymers should have higher conformational gradients such as about 0.5–1, about 0.6–1, about 0.7–1, or about 0.8–1. Crosslinked polymers should have lower conformational gradients, typically less than about 0.5, for example, about 0–0.4, about 0–0.3, about 0–0.2, or about 0–0.1.

[0124] Exemplary and non-limiting examples of processed polymers of the present disclosure are listed in Table 2, along with their corresponding Huggins constants and conformation plot gradients.

[0125] [Table 2]

[0126] In some embodiments, the treated polymer may be crosslinked with aluminum or iron in an aluminum hydroxide complex or a ferric hydroxide complex. In some embodiments, the treated polymer has a degree of crosslinking of more than 1%, more than 2%, more than 3%, more than 4%, more than 5%, more than 6%, more than 7%, more than 8%, more than 9%, or more than 10%. In certain embodiments, the treated polymer has a degree of crosslinking of less than about 50%, less than about 40%, less than about 30%, or less than about 20%. For example, the treated polymer may have a degree of crosslinking of approximately 1% to 50%, 5% to 50%, 10% to 50%, 15% to 50%, 20% to 50%, 30% to 50%, 2% to 25%, 2% to 20%, 2% to 15%, 2% to 10%, 3% to 25%, 3% to 20%, 3% to 15%, 3% to 10%, 4% to 25%, 4% to 20%, 4% to 15%, or 4% to 10%.

[0127] In some embodiments, crosslinks are formed from interactions / reactions between anionic monomers and iron and / or aluminum. For example, the treated polymer may contain carboxylic acid groups, and crosslinks may be formed from reactions / interactions between carboxylic acid groups and iron and / or aluminum.

[0128] The aqueous medium may contain colloidal particles (thus forming an aqueous colloidal treatment composition), and the aqueous medium may have a pH of, for example, about 2 to about 8.5, about 4.5 to about 8.5, about 5.5 to about 8.5, about 5.5 to about 8, about 6 to about 8, or about 7 to about 8. In some embodiments, the aqueous medium contains a pH of about 3.5 to about 8.5. In some embodiments, the colloidal particles are water-insoluble.

[0129] In certain embodiments, colloidal particles are prepared by adding a treated polymer disclosed herein to an aqueous solvent such as water, and then adding an inorganic salt such as an aluminum salt and / or a ferric salt to the solvent. The treated polymer and metal salt may be added continuously, intermittently, and in any order. In some embodiments, the treated polymer and metal salt are supplied together in the solvent.

[0130] In some embodiments, the solvent comprises about 0.01% to about 10% by weight of the treated polymer, for example, about 0.01% to about 9% by weight, about 0.01% to about 8% by weight, about 0.01% to about 7% by weight, about 0.01% to about 6% by weight, about 0.01% to about 5% by weight, about 0.01% to about 4% by weight, about 0.01% to about 3% by weight, about 0.01% to about 2% by weight, or about 0.01% to about 1% by weight of the treated polymer.

[0131] In some embodiments, the solvent contains aluminum salt and / or ferric salt and the treated polymer in a weight ratio of about 0.05:1 to 100:1. For example, the solvent may contain aluminum salt and / or ferric salt and the treated polymer in weight ratios of about 0.1:1, about 0.5:1, about 1:1, about 5:1, about 10:1, about 20:1, about 30:1, about 40:1, about 50:1, about 60:1, about 70:1, about 80:1, or about 90:1. In some embodiments, the solvent contains more aluminum salt and / or ferric salt than treated polymer.

[0132] As an illustrative example, if the weight ratio of PAC (based on Al2O3) to the polymer is approximately 1:1, the aluminum ions will constitute approximately 159 mol% of the treated polymer. As an additional, non-limiting example, if the weight ratio of PAC to the treated polymer is approximately 0.1:1, the aluminum ions will constitute approximately 15.9 mol% of the treated polymer.

[0133] The aqueous solvent may have a pH of, for example, about 1.0 to about 6.5, and after the addition of at least some of the polymer and metal salts, the pH may rise to about 7.0, about 7.5, about 8.0, about 8.5, or higher. In some embodiments, the pH of the composition may be increased by adding a base such as sodium hydroxide, or by diluting the composition with water. In certain embodiments, the pH of the composition is increased by adding a base to the papermaking process water, and the pH of the papermaking process water may be, for example, about 6.5 to about 8.5. A certain amount of colloidal particles may form in the composition before the pH rises, but substantially the majority or all of the colloidal particles are formed after the pH rises.

[0134] The colloidal particles contain aluminum hydroxide and / or ferric hydroxide and the treated polymer in a weight ratio of about 0.1:99 to about 99:0.1. For example, the weight ratio may be about 0.1:50 to about 50:0.1, about 0.1:25 to about 25:0.1, about 0.1:10 to about 10:0.1, about 0.1:5 to about 5:0.1, or about 0.1:2 to about 2:0.1. In certain embodiments, the weight ratio of aluminum hydroxide and / or ferric hydroxide to the treated polymer is about 0.1:1 to about 2:1. In some embodiments, the weight ratio of aluminum hydroxide and / or ferric hydroxide to the treated polymer is about 0.1:1 to about 0.9:1 or 0.1:1 to about 0.5:1.

[0135] The colloidal particles contain about 1% to about 99% by weight of the treated polymer. For example, the colloidal particles may contain about 5% to about 99% by weight, about 5% to about 95% by weight, about 10% to about 99% by weight, or about 10% to about 90% by weight of the treated polymer.

[0136] The colloidal particles contain approximately 1% to 99% by weight of aluminum hydroxide and / or ferric hydroxide. For example, the colloidal particles may contain approximately 5% to 99% by weight, approximately 5% to 95% by weight, approximately 10% to 99% by weight, or approximately 10% to 90% by weight of aluminum hydroxide and / or ferric hydroxide.

[0137] The weight ratio of the treated polymer to the inorganic salt can be determined by other auxiliary components in the composition and / or the type of water source being treated. For example, if the water source is dairy water, the weight ratio may be from approximately 99:1 inorganic salt to treated polymer to 95:5 inorganic salt to treated polymer. However, this is more difficult to determine, and deciding which program to use is a case-by-case matter, but generally it is classified by the use of coagulants or flocculants as described in the following paragraphs.

[0138] In certain embodiments, the treatment composition or formulation is a "high inorganic salt composition," meaning that inorganic salts make up more than 90% and the treatment polymer is less than 10%. In this particular formulation, the inorganic salts function as a coagulant and a pH-induced crosslinking agent to produce structured high molecular weight inorganic salts such as PAC.

[0139] In certain other embodiments, the treatment composition may be a "low inorganic salt composition," meaning that the level of the treatment polymer is high, for example, less than 10% inorganic salt and more than 90% treatment polymer. In this particular formulation, the treatment polymer acts as a flocculant and the inorganic salt acts as a pH-induced crosslinking agent to produce a structured high molecular weight flocculant.

[0140] The colloidal particles have an average particle size in the range of approximately 0.01 to approximately 1,000 microns. For example, the average particle size may be approximately 0.05 to approximately 100 microns, approximately 0.05 to approximately 80 microns, approximately 0.05 to approximately 60 microns, approximately 0.05 to approximately 40 microns, approximately 0.05 to approximately 20 microns, approximately 0.05 to approximately 10 microns, approximately 0.1 to approximately 50 microns, approximately 0.1 to approximately 40 microns, approximately 0.1 to approximately 30 microns, approximately 0.1 to approximately 20 microns, or approximately 0.1 to approximately 10 microns.

[0141] As an additional example, the average particle size may range from approximately 50 nm to approximately 500 nm, for example, approximately 50 nm to approximately 400 nm, approximately 50 nm to approximately 300 nm, approximately 100 nm to approximately 200 nm, approximately 100 nm to approximately 300 nm, or approximately 100 nm to approximately 400 nm.

[0142] In some embodiments, the colloidal particles have a zeta potential in the range of about -50 to about +70 mV. For example, the colloidal particles may have a zeta potential in the range of about -40 to about +60, about -30 to about +50, about -20 to about +40, about -10 to about +30, or about 0 to about +30 mV.

[0143] In some embodiments, colloidal particles can be added to an aqueous medium such as wastewater at concentrations of approximately 1 ppm to 10,000 ppm based on the aqueous medium. For example, colloidal particles can be added at concentrations of approximately 1 ppm to 8,000 ppm, approximately 1 ppm to 6,000 ppm, approximately 1 ppm to 4,000 ppm, approximately 1 ppm to 2,000 ppm, approximately 1 ppm to 1,000 ppm, approximately 1 ppm to 500 ppm, approximately 1 ppm to 250 ppm, approximately 1 ppm to 100 ppm, approximately 50 ppm to 10, It can be added at concentrations of 000 ppm, approximately 100 ppm to 10,000 ppm, approximately 250 ppm to 10,000 ppm, approximately 500 ppm to 10,000 ppm, approximately 1,000 ppm to 10,000 ppm, approximately 3,000 ppm to 10,000 ppm, approximately 5,000 ppm to 10,000 ppm, or approximately 7,500 ppm to 10,000 ppm.

[0144] The treatment compositions provided herein may contain any components disclosed herein, such as particles, treatment polymers, and / or inorganic salts, and the treatment compositions may also contain any optional agents selected from pH adjusters, antifreezes, corrosion inhibitors, purifying agents, softeners, paraffin inhibitors, scale inhibitors, biocides, bactericides, stabilizers, emulsifiers, hydrotropes, emulsion disruptors, antifouling compounds, chelating agents, surfactants, oxygen scavengers, rheology control agents, surfactants, defoamers, antifoaming agents, hydrate inhibitors, dispersants, asphaltene inhibitors, sulfide inhibitors, and the like.

[0145] Scaling is a term used to describe the hard surface coating of calcium carbonate, magnesium carbonate, and their by-products that forms on metal surfaces within metal containment vessels carrying industrial water sources with high total dissolved solids content, such as generated water, brackish water, seawater, and other sources of divalent carbonates. Exemplary scale inhibitors include, but are not limited to, borates, carboxylates, phosphates, sulfonates, or oligomers and polymer compounds having other anionic moieties.

[0146] Examples of agents used to adjust the pH of a composition, or in the case of on-site or in-place treatment, include, but are not limited to, water, Brønsted acids, conjugate bases and their salts, and mixtures thereof, for providing a selected pH to the industrial water source being treated. The acids may be strong acids, i.e., acids with a pKa of less than about 4, and weak acids, i.e., acids with a pKa of about 4 or more. In some embodiments, the organic acid is a weak acid. The pH adjuster is used to adjust the pH of the water source to a selected value or range, which may be any of the pH values ​​from about 1 to 12.

[0147] Examples of antifouling compounds include, but are not limited to, copolymers of unsaturated fatty acids, primary diamines, and acrylic acid; copolymers of methacrylamidopropyltrimethylammonium chloride with acrylic acid and / or acrylamide; copolymers of ethylene glycol and propylene glycol; and blends of two or more thereof.

[0148] Examples of chelating agents include, but are not limited to, compounds effective in reducing or removing one or more metal ions from industrial water sources. Chelation involves the formation or presence of two or more separate coordinate bonds between a polydentate (multiple bond) ligand and a single central atom. These ligands are typically organic compounds and are called chelant, chelator, chelating agent, and / or metal ion sequestering agent.

[0149] Examples of antimicrobial agents include, but are not limited to, compounds that, when added to a water source, such as an industrial water source, have bacteriostatic, disinfectant, or sterilizing effects on that water source. Non-exclusive examples of antimicrobial agents include fungicides, antifungicides, and nematicides. Examples of fungicides include activated chlorine disinfectants such as hypochlorites and chlorine dioxide; phenols such as triclosan, phenol itself, and thymol; cationic surfactants such as quaternary ammonium surfactants and chlorhexidine; ozone, permanganates, colloidal silver, silver nitrate, copper compounds, iodine preparations, peroxides, and strong acids and strong alkalis, which bring the pH of the water source to about 12 or less than 1. Examples of fungicidal agents include, but are not limited to, compounds such as strobilurins (azoxystrobin, trifloxystrobin, and pyraclostrobin); triazoles and anilinopyrimidines (tebuconazole, cyproconazole, triadimefon, pyrimethanil); and compounds such as triadimefon, benomyl, captan, chlorothalonil, copper sulfate, cyproconazole, dozin, flusilazole, flutolanil, fosetyl-aluminum (fosetyl-al), galex, mancozeb, metalaxyl, prochloraz, propiconazole, tebuconazole, thiophanate-methyl, triadimefon, triphenyltin hydroxide, and ziram.

[0150] In certain embodiments, the optional agent may be present in the treatment composition in amounts ranging from about 0.1% to about 50% by weight, for example, about 0.1% to about 40% by weight, about 0.1% to about 30% by weight, about 0.1% to about 20% by weight, about 0.1% to about 15% by weight, about 0.1% to about 10% by weight, about 0.1% to about 5% by weight, or about 0.1% to about 2% by weight.

[0151] Furthermore, the compositions described herein may contain one or more additives or auxiliaries other than the optional agents. Additives or auxiliaries such as solvents, polymers, surfactants, oils, fillers, buffers, viscosity modifiers, masking agents, and colorants are optionally added to the treatment composition as determined by the operator in conjunction with a specific water source and other variables.

[0152] In certain embodiments, additives or auxiliaries may be present in the treated composition in amounts ranging from about 0.1% to about 50% by weight, for example, about 0.1% to about 40% by weight, about 0.1% to about 30% by weight, about 0.1% to about 20% by weight, about 0.1% to about 15% by weight, about 0.1% to about 10% by weight, about 0.1% to about 5% by weight, or about 0.1% to about 2% by weight.

[0153] This disclosure also provides methods for using the compositions and particles of this disclosure in wastewater treatment applications. In some embodiments, a composition containing particles is added to wastewater. For example, the treatment polymer may be pre-mixed with trivalent ions such as aluminum salts and / or ferric salts in an aqueous medium to form particles, and the resulting mixture may be added to the wastewater.

[0154] In some embodiments, the composition comprises a treated polymer and an inorganic salt such as an aluminum salt and / or a ferric salt. The composition may optionally contain colloidal particles as defined herein in amounts such as about 0% to about 20% by weight, about 0% to about 15% by weight, about 0% to about 10% by weight, about 0% to about 5% by weight, or about 0% to about 1% by weight.

[0155] The composition may be an aqueous composition having a pH of about 1 to about 14, for example, about 1 to about 10, about 1 to about 9, about 1 to about 8.5, about 3 to about 14, about 3 to about 10, about 3 to about 8.5, about 3.5 to about 8.5, about 5 to about 14, about 5 to about 10, or about 5 to about 8. In certain embodiments, the composition has a pH of about 1 to about 7, for example, about 3 to about 5.

[0156] In some embodiments, the composition contains aluminum salt and / or ferric salt and the treated polymer in a weight ratio of about 0.05:1 to 100:1. For example, the composition may contain aluminum salt and / or ferric salt and the treated polymer in weight ratios of about 0.1:1, about 0.5:1, about 1:1, about 5:1, about 10:1, about 20:1, about 30:1, about 40:1, about 50:1, about 60:1, about 70:1, about 80:1, or about 90:1. In some embodiments, the composition contains more aluminum salt and / or ferric salt than treated polymer.

[0157] In certain embodiments, the composition comprises about 0.01% to about 10% by weight of the treated polymer. For example, the composition may comprise about 0.01% to about 9% by weight, about 0.01% to about 8% by weight, about 0.01% to about 7% by weight, about 0.01% to about 6% by weight, about 0.01% to about 5% by weight, about 0.01% to about 4% by weight, about 0.01% to about 3% by weight, about 0.01% to about 2% by weight, or about 0.01% to about 1% by weight of the treated polymer.

[0158] In some embodiments, the treated polymer comprises one or more anionic monomers. The pH of the aqueous composition may be adjusted to be higher than the minimum pKa value of the monomers in the treated polymer. The pKa of anionic monomers is equal to the pH value, but 50% of anionic monomers have an anionic charge. When the pH of the solution is higher than the pKa, more anionic charge sites appear on the polymer chain that can facilitate interactions with trivalent ions and their derivatives. When the aqueous composition containing the treated polymer is added separately from the inorganic salt, for example, when the treated polymer and inorganic salt are co-supplied, the pH of the aqueous composition containing the treated polymer may be adjusted as described in the preceding paragraph.

[0159] In some embodiments, the treatment polymer and inorganic salt are co-supplied at a location, for example, a reaction vessel, a storage tank, and / or an aqueous medium, for example, wastewater. Other components, such as flocculants, corrosion inhibitors, and chelating agents, can also be co-supplied together with the treatment polymer and / or inorganic salt. In some embodiments, when the treatment polymer and inorganic salt are co-supplied at a location, particles are formed at a location such as a reaction vessel or storage tank. In some embodiments, the wastewater receiving the treatment polymer, inorganic salt, and / or colloidal particles has a near-neutral pH, for example, about 5.5 to about 8.5 or about 6 to about 8.

[0160] For example, an injection pipe may lead to a location in the wastewater, and the pipe may inject a treatment polymer into the wastewater. Adjacent pipes may exist, which may be used to add additional chemicals, such as inorganic salts. The addition of each chemical may be continuous or intermittent, for example. Since the injection pipes are adjacent or substantially adjacent to each other, the chemicals are supplied substantially simultaneously to substantially the same location in the wastewater. The chemicals may interact in the wastewater and form colloidal particles.

[0161] Therefore, in some embodiments, colloidal particles are formed in the wastewater, and optionally, colloidal particles are added to the wastewater additionally or alternatively. In some embodiments, colloidal particles may be formed in the composition before the composition is added to the wastewater, and optionally, colloidal particles may be formed in the wastewater. In certain embodiments, a flocculant may be added before, after, and / or with the colloidal particles, treatment polymer, and / or inorganic salts.

[0162] The composition, particles, treatment polymer, and / or inorganic salt may be added at any point or time during the wastewater treatment process. Two or more of the components may be added together, and / or two or more components may be co-supplied into the wastewater. For example, the composition, particles, treatment polymer, and / or inorganic salt may be added together, separately, and / or co-supplied into the wastewater.

[0163] In some embodiments, the treatment polymer is added to the wastewater treatment process before, after, and / or simultaneously with the inorganic salt. The treatment polymer and the inorganic salt may be added at the same and / or different locations.

[0164] In some embodiments, a composition comprising one or more of aluminum salts, ferric salts, treatment polymers, and particles is added during the wastewater treatment process. In some embodiments, one or more of the aluminum salts, ferric salts, treatment polymers, and particles may be added separately to the wastewater treatment process, such as by co-feeding. In certain embodiments, the aluminum and / or ferric salts, as well as the treatment polymer, are pre-mixed before being added to the wastewater.

[0165] The amount of treatment polymer and inorganic salt added to the wastewater is not particularly limited. In some embodiments, 1 ppm to about 10,000 ppm of inorganic salt is added to the wastewater. For example, about 1 ppm to about 8,000 ppm, about 1 ppm to about 6,000 ppm, about 1 ppm to about 4,000 ppm, about 1 ppm to about 2,000 ppm, about 1 ppm to about 1,000 ppm, about 1 ppm to about 750 ppm, about 1 ppm to about 500 ppm, about 1 ppm to about 250 ppm, about 10 ppm to about 250 ppm, about 10 ppm to about 500 ppm, about 10 ppm to about 750 ppm, about 10 ppm to about 1,000 ppm, about 10 ppm to about 2,000 ppm, or about 10 ppm to about 4,000 ppm of inorganic salt is added to the wastewater.

[0166] In some embodiments, approximately 1 ppm to 10,000 ppm of the treatment polymer is added to the wastewater. For example, approximately 1 ppm to 8,000 ppm, approximately 1 ppm to 6,000 ppm, approximately 1 ppm to 4,000 ppm, approximately 1 ppm to 2,000 ppm, approximately 1 ppm to 1,000 ppm, approximately 1 ppm to 750 ppm, approximately 1 ppm to 500 ppm, approximately 1 ppm to 250 ppm, approximately 10 ppm to 250 ppm, approximately 10 ppm to 500 ppm, approximately 10 ppm to 750 ppm, approximately 10 ppm to 1,000 ppm, approximately 10 ppm to 2,000 ppm, or approximately 10 ppm to 4,000 ppm of the treatment polymer is added to the wastewater.

[0167] The treatment composition is suitably applied to a water source in any form. In certain embodiments, the treatment composition is applied as a solution, emulsion, or dispersion. Thus, in certain embodiments, the treatment composition includes additional solvents or other additives to realize a fluid composition, as described above. Nevertheless, in some embodiments, the treatment composition may be 100% active ingredients, which include inorganic salts, treatment polymers, and / or particles, as described herein.

[0168] In some embodiments, the treated compound or treated composition is a concentrate ("treated concentrate"), and the total concentration of the treated compound in the treated concentrate is about 0.1% to 98% by weight of the whole composition; for example, about 1% to 75% by weight of the whole composition; about 10% to 75% by weight of the whole composition; or about 10% to 50% by weight of the whole composition.

[0169] In some embodiments, the treatment concentrate includes, for example, a treatment polymer, an inorganic salt, and / or particles as defined herein. In some embodiments, the treatment concentrate includes one or more additives or auxiliaries, such as a solvent, a polymer, a surfactant, an oil, a stabilizer, or other components suitable for combination with an industrial water source. If one or more components of the treatment concentrate include a solvent, the solvent is generally present in about 10% to 99.9% by weight of the treatment concentrate.

[0170] This specification describes a method for treating a water source with a described treatment composition in order to eliminate or reduce target substances such as pollutants in the water source.

[0171] In exemplary and non-limiting embodiments, the described compositions may be pre-mixed to obtain a solution / composition containing an inorganic salt such as PAC and a treatment polymer such as CAP, the resulting product having a pH of 4 or less and being in a non-crosslinked form. The resulting mixture can be added to a water source. The concentrated non-crosslinked or dormant product is supplied through a process in which the product is diluted to a degree sufficient to avoid gelation, while simultaneously inducing immediate crosslinking at concentrations where the pH of the dilution water is not too low. In the case of products containing both PAC and the treatment polymer, the product concentration is typically high (greater than 10% by weight), and the pH must be kept low, typically below 4, because a high pH can induce crosslinking within the product, potentially forming a gel and rendering the product unusable.

[0172] In further exemplary and non-limiting embodiments, the inorganic salt and the treated polymer may be added directly to the flow in which crosslinking occurs at optimal pH and concentration, which is then discharged to a water source. In this dual-feed program, crosslinking becomes less efficient due to the very low product concentration (typically less than several hundred ppm).

[0173] Specific embodiments relate to on-site or in-situ methods for treating a water source. The method involves introducing a treatment agent into a water source, comprising a treatment composition containing an inorganic salt or derivative thereof, such as PAC, and a treatment polymer, such as CAP, wherein the pH of the composition is approximately 4 or less. In specific embodiments, the pH of the treated water source can be measured or remeasured to determine whether follow-up treatment with the composition is necessary. Methods for measuring the pH of treated water are known to those skilled in the art. If the pH is measured to be pH 6 or approximately pH 6, the introduction into the water source may be adjusted and / or repeated as many times as necessary to purify the water source. The PAC and CAP (or either the inorganic salt and the treatment polymer, selected) in the composition interact to form a new structured CAP coagulant (i.e., CAP-crosslinked PAC, treatment polymer-crosslinked PAC, colloidal particles) (see Examples, and for example, the undiluted pH study and examples in Figure 1 to demonstrate the effect). This interaction between PAC and CAP is pH-dependent. Novel structured CAP flocculants improve treatment performance compared to conventional wastewater treatments where PAC or its derivatives, or poly-DADMAC, are typically used alone. In some cases, a mixture of PAC and homopoly-DADMAC can be used as a standard or conventional treatment, although poly-DADMAC does not have reactive carboxylic acid groups. This type of mixture is pH-independent.

[0174] In certain embodiments, the inorganic salt and the treatment polymer may be pre-mixed before the input step.

[0175] In certain embodiments, the inorganic salt and the treated polymer may be treated with diluted water at a pH of approximately 6 or higher to pre-induce crosslinking before the composition is discharged into a water source. Crosslinking is concentration-dependent; for example, if the interaction between the inorganic salt and the treated polymer is pre-induced at a higher concentration, crosslinking becomes more efficient.

[0176] In alternative exemplary embodiments, the method of the present disclosure includes a step of introducing a water source by co-supplying PAC or a derivative thereof and CAP. The pH of the treated water source may be measured after the introduction step or throughout the method to determine whether follow-up treatment / introduction with the composition is necessary. If the pH is measured to be less than pH 6, the introduction of the water source may be adjusted.

[0177] In certain embodiments, the co-supply of PAC and CAP may be simultaneous. In certain other embodiments, the co-supply may be sequential. For example, PAC may be added to the water source first, followed by CAP. Alternatively, CAP may be supplied to the water source before PAC is added.

[0178] When the described compositions and methods induce a highly coagulated process, any contaminants such as large amounts of bacteria and viruses from the water precipitate together with the suspended solids.

[0179] In certain embodiments, the treatment compositions disclosed herein are effective for treating water sources such as wastewater, raw water treatment, and oil sands wastewater. Wastewater may be obtained, for example, from agriculture, the food industry, the energy industry, the iron and steel industry, mining, and pulp and paper manufacturing.

[0180] In certain alternative embodiments, the compositions described may be for use in retained wastewater and flocculation (RDF). In certain further embodiments, the compositions described may be for use in mining. The compositions and methods described can be used to improve wastewater quality for regulatory compliance and system stability. The compositions and methods disclosed herein can also enable more precise chemical input to optimize performance, as well as alerts for system problems such as pump failure and empty chemical tanks, thereby reducing system malfunctions. The techniques disclosed herein can be used in a variety of wastewater automation processes, such as dissolved air flotation ("DAF") automation and clarification dose optimization.

[0181] The above can be better understood by referring to the following examples. These examples are illustrative and are not intended to limit the scope of the disclosure or its application in any way. [Examples]

[0182] Examples

[0183] material:

[0184] CAS# 12042-91-0; Aluminum hydroxide chloride (24% as Al2O3).

[0185] CAS# 14215-15-7; Polyaluminum chloride (27% AlCl3).

[0186] CAS# 1327-41-9; Chlorohydroxyaluminum.

[0187] CAS# 26100-47-0; Acrylamide / Acrylic Acid Copolymer.

[0188] CAS# 53694-17-0; DADMAC / Acrylic Acid Copolymer.

[0189] CAS# 69418-26-4; Cationic acrylamide copolymer.

[0190] CAS# 79-06-1; Acrylamide (Am)

[0191] CAS# 79-10-7; Acrylic acid (AA).

[0192] CAS# 15214-89-8; ATBS (2-acrylamido-2-methylpropanesulfonic acid).

[0193] CAS# 44992-01-0; N,N,N-trimethyl-2-[(1-oxo-2-propenyl)oxy]-ethaneaminium chloride (DMAEA.MCQ).

[0194] CAS# 48042-45-1. DADMAC, N,N-dimethyl-N-propenyl-2-propene-1-aminium chloride.

[0195] Example 1: PAC Blend Research

[0196] The following polymers (CAPs) were evaluated to determine the most suitable polymer for use in the described compositions.

[0197] [Table 3]

[0198] Example 2: Effect of pH on viscosity

[0199] 47.5 g of CAS#12042-91-0 (24% activity), 2.5 g of Polymer 2 (20% activity), and 10 g of deionized water were blended with stirring to obtain a clear solution, and the viscosity and pH of the solution were recorded (BV=19 cps, pH=3.8). When 0.5 g to 1.0 g of 50% sodium hydroxide was gradually added to the mixture while stirring, the pH of the mixture and the viscosity of the solution increased.

[0200] Figure 1 shows the effect of pH on solution viscosity. The results demonstrate that the PAC / CAP blend is stable and the PAC / CAP crosslinking reaction is minimized at pH levels of approximately 4 or lower, but the solution viscosity increases significantly at pH levels around 5 or higher, which suggests a significant PAC / CAP crosslinking reaction.

[0201] Example 3: Exemplary Blend

[0202] Table 2 below shows example blends of PAC (CAS#12042-91-0) and PAC.

[0203] [Table 4]

[0204] Exemplary blends of carboxylic acid-functionalized cationic flocculants blended with aluminum or zirconium compounds are provided in Table 3 below.

[0205] [Table 5]

[0206] Example 4: Ultra Dairy Water

[0207] Materials and methods:

[0208] Ultra dairy water samples were treated with 100, 200, 300, 400, 500, and 600 ppm PAC (CAS#12042-91-0); 95 / 5 PAC / CAP ("PAC Blend B," where CAP is polyDADMAC, polymer 2, containing 10% acrylic acid); 99 / 1 CAS#12042-91-0 / polymer 2 ("PAC Blend A"); and 95 / 5 CAS#12042-91-0 / polymer 8 ("PAC Blend G"). Compared to CAS#12042-91-0, it was observed that the dose required to achieve similar water clarity was reduced by 40-50% for PAC Blend B and PAC Blend G.

[0209] result:

[0210] Figure 2 shows a graph illustrating the effect of various concentrations of PAC and CAP blend samples on the turbidity of dairy samples.

[0211] Example 5: Protein Sample

[0212] Materials and methods:

[0213] The received wastewater sample was homogenized and transferred to two 2L beakers. Optimal doses of CAS#12042-91-0 and PAC Blend B were added to the beakers. The sample was mixed at high speed at 250 rpm for 1 minute, then at low speed at 50 rpm for 2 minutes, followed by 20 minutes of sedimentation. Aliquots were then taken to measure turbidity and oil content.

[0214] result:

[0215] Figure 3 shows that the 1200 ppm composition of 95 / 5 PAC / CAP (PAC blend B in the graph; CAP is polyDADMAC containing 10% acrylic acid) results in a 5% reduction in oil content compared to 1500 ppm treatment with PAC alone (CAS#12042-91-0 in the figure). No reduction in oil content was observed in the control ("blank") treatment.

[0216] Conclusion: PAC Blend B demonstrated similar performance to CAS#12042-91-0 at a significantly lower dose (20% dose reduction).

[0217] Example 6: Treatment of synthetic oil and water

[0218] Materials and methods:

[0219] Synthetic oilwater was prepared by emulsifying 300 ppm oleic acid and 300 ppm triolein in tap water to simulate actual dairy wastewater. The water was treated with PAC Blend B and compared to CAS#12042-91-0 in terms of activity base. Water samples to which the above doses of chemicals were added were mixed at high speed at 250 rpm for 1 minute, then at low speed at 50 rpm for 2 minutes, and after settling for 20 minutes, aliquots were taken for turbidity measurement.

[0220] result:

[0221] Figure 4 shows a graph of turbidity versus dose.

[0222] Conclusion:

[0223] PAC Blend B achieved similar performance with a 33% lower dose compared to CAS#12042-91-0.

[0224]

[0100] All compositions and methods disclosed and claimed herein can be prepared and performed without undue experimentation, taking into consideration this disclosure. The present invention can be embodied in many different forms, and certain preferred embodiments of the present invention are described in detail herein. This disclosure is illustrative of the principles of the present invention and is not intended to limit the present invention to the specific embodiments illustrated. In addition, unless expressly stated otherwise, the term "a" is intended to include "at least one" or "one or more." For example, "a polymer" is intended to include "at least one polymer" or "one or more polymers."

[0225]

[0101] Any range given, whether absolute or approximate, is intended to encompass both, and any definitions used herein are intended to clarify, not limit. Numerical ranges and parameters that specify the broad scope of the invention are approximate, but the numerical values ​​specified in specific examples are reported as accurately as possible. However, any numerical value inherently contains a certain degree of error, which is necessarily due to the standard deviation observed in their respective test measurements. Furthermore, all ranges disclosed herein should be understood to encompass all subranges contained therein (including all decimal values ​​and whole values).

[0226]

[0102] Any composition disclosed herein may include, consist of, or essentially consist of, any element, component, and / or raw material disclosed herein, or any combination of two or more of the elements, components, or raw materials disclosed herein.

[0227]

[0103] Any method disclosed herein may include, consist of, or essentially consist of, any method step disclosed herein, or any combination of two or more method steps disclosed herein.

[0228]

[0104] The transitional phrase "comprising," which is synonymous with "including," "containing," or "characterized by," is either comprehensive or open-ended and does not exclude additional unlisted elements, components, raw materials, and / or process steps.

[0229]

[0105] The transitional phrase "consisting of" excludes any elements, components, raw materials, and / or process steps not specified in the claims.

[0230]

[0106] The transitional phrase "consisting essentially of" limits the scope of the claims to specific elements, components, raw materials and / or processes, and does not substantially affect the fundamental and novel features of the claimed invention.

[0231]

[0107] Unless otherwise specified, all molecular weights mentioned herein are weight-average molecular weights, and all viscosities were measured at 25°C using neat (undiluted) polymers.

[0232]

[0108] As used herein, the term “approximately” means a cited value that is within the error resulting from the standard deviation found in each of those test measurements, and if those errors cannot be determined, “approximately” may mean, for example, within 5%, 4%, 3%, 2%, or 1% of the cited value.

[0233]

[0109] Furthermore, the present invention encompasses any possible combination of some or all of the various embodiments described herein. It should also be understood that various changes and modifications to the preferred embodiments of the present invention described herein will be obvious to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the invention and without diminishing its intended advantages. Accordingly, such changes and modifications are intended to be covered by the appended claims.

Claims

1. A method for removing suspended solids from a water source, wherein the method is: A method comprising adding a treated polymer and an inorganic salt to the water source, wherein the weight ratio of the inorganic salt added to the water source to the treated polymer is about 0.05:1 to 100:

1.

2. The method according to claim 1, wherein the inorganic salt is selected from the group consisting of aluminum salts, ferric salts, and any combination thereof.

3. The method according to claim 1 or 2, wherein the treated polymer has a Huggins constant of about 0.0 to about 1.

4. The method according to any one of claims 1 to 3, wherein the treated polymer has a conformation plot gradient of about 0.05 to about 1.

5. The aluminum salts include aluminum chloride, aluminum chloride hydrate, aluminum sulfate, alum, aluminum polysulfate, PAC, aluminum chlorohydrate, and Al. ｎ Cl （３ｎ－ｍ） (OH) ｍ The method according to claim 2, selected from the group consisting of compounds having (wherein m is an integer from 0 to 100, n is an integer from 1 to 100, and m is less than 3n) and any combination thereof.

6. The method according to claim 2 or 5, wherein the ferric salt is selected from the group consisting of ferric chloride, ferric sulfate, polyferric salts, and any combination thereof.

7. The method according to any one of claims 1 to 6, wherein the composition comprises the treated polymer and the inorganic salt, and further comprises the composition having a pH of about 1.0 to about 8.

5.

8. The method according to any one of claims 1 to 7, wherein the treated polymer is added to the water source before, after, and / or together with the inorganic salt.

9. The method according to any one of claims 1 to 8, wherein the treated polymer comprises a monomer selected from the group consisting of anionic monomers, cationic monomers, nonionic monomers, zwitterionic monomers, and any combination thereof.

10. The aforementioned processed polymers include acrylamide, methacrylamide, 2-(dimethylamino)ethyl acrylate ("DMAEA"), 2-(dimethylamino)ethyl methacrylate ("DMAEM"), 3-(dimethylamino)propyl methacrylamide ("DMAPMA"), 3-(dimethylamino)propyl acrylamide ("DMAPA"), 3-methacrylamidepropyl-trimethyl-ammonium chloride ("MAPTAC"), 3-acrylamidepropyl-trimethyl-ammonium chloride ("APTAC"), N-vinylpyrrolidone ("NVP"), diallyldimethylammonium chloride ("DADMAC"), diallylamine, 2-(acryloyloxy)-N,N,N-trimethylethaneaminium chloride ("DMAEA.MCQ"), 2-(methacryloyloxy)-N,N,N-trimethylethaneaminium chloride ("DMAEM.MCQ"), The method according to any one of claims 1 to 9, comprising a monomer selected from the group consisting of N,N-dimethylaminoethyl acrylate benzyl chloride ("DMAEA.BCQ"), N,N-dimethylaminoethyl methacrylate benzyl chloride ("DMAEM.BCQ"), 2-acrylamide-2-methylpropanesulfonic acid ("AMPS"), 2-acrylamide-2-methylbutanesulfonic acid ("AMBS"), acrylamide tert butylsulfonate ("ATBS"), [2-methyl-2-[(1-oxo-2-propenyl)amino]propyl]phosphonic acid, acrylic acid, methacrylic acid, maleic acid, itaconic acid, glyoxalized polyacrylamide (GPAM), polyvinylamine (PVAM), polyethyleneimine (PEI), polyamidoamine epichlorohydrin (PAE), salts of any of the above monomer units, and any combination thereof.

11. The method according to any one of claims 1 to 10, wherein the polymer is cationic, anionic, zwitterionic, nonionic, amphoteric with a net positive charge, or amphoteric with a net negative charge.

12. The method according to any one of claims 1 to 11, wherein the polymer is an amphoteric polymer.

13. The method according to any one of claims 1 to 12, wherein the polymer contains less than about 25 mol% of a carboxylic acid.

14. The method according to any one of claims 1 to 13, further comprising forming colloidal particles using the treated polymer and the inorganic salt, and adding the colloidal particles to the water source.

15. The method according to any one of claims 1 to 14, further comprising forming colloidal particles in the water source using the treated polymer and the inorganic salt.

16. The method according to claim 14 or 15, wherein the colloidal particles include the treated polymer embedded within a colloidal aluminum hydroxide complex and / or a colloidal ferric hydroxide complex.

17. The method according to any one of claims 1 to 16, wherein the water source is wastewater, raw water, or a combination thereof.

18. The method according to any one of claims 1 to 17, wherein the pH of the water source is adjusted to approximately 5 to approximately 14.

19. The method according to any one of claims 1 to 18, further comprising adding a coagulant to the water source.

20. A method for removing suspended solids from a water source, wherein the method is: A method comprising adding a composition to the water source, wherein the composition comprises colloidal particles, and the colloidal particles comprises polymers embedded within colloidal aluminum hydroxide complexes and / or colloidal ferric hydroxide complexes.

21. A method for reducing the turbidity of a water source, wherein the method is A method comprising adding a treated polymer and an inorganic salt to the water source, wherein the weight ratio of the inorganic salt added to the water source to the treated polymer is about 0.05:1 to 100:

1.

22. A method for reducing the turbidity of a water source, wherein the method is A method comprising adding a composition to the water source, wherein the composition comprises colloidal particles, and the colloidal particles comprises polymers embedded within colloidal aluminum hydroxide complexes and / or colloidal ferric hydroxide complexes.

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