Solid phosphorus-free scale and corrosion inhibitor composition for cooling water treatment - Patents.com

Abstract

A solid, phosphorus-free water treatment composition is provided that can be used in cooling water treatment applications. The composition may include a polycarboxylic acid, a polymeric dispersant, a soluble corrosion inhibitor, and a fluorescent tracer. The composition may be phosphorus-free and exhibit the properties of a solid having an effective pH such that when the composition is dissolved in water at a concentration of 2 weight percent to form a solution, the solution has a pH in the range of 1-5.

Description

[Technical field]

[0001] (cross reference) This application claims the benefit of U.S. Provisional Patent Application No. 63 / 243,927, filed September 14, 2021, the entire contents of which are incorporated herein by reference.

[0002] FIELD OF THEINVENTION FIELD OF THE DISCLOSURE The present disclosure relates to treatment compositions for water systems, and more particularly to phosphorus-free treatment compositions for cooling water systems. [Background technology]

[0003] Cooling water systems are used in various plants to cool process fluids through heat exchangers or condensers. The heat exchangers or condensers can corrode or grow scale or biofilm due to poor water management. Corrosion, scale, and biofilm growth on heat exchangers can lead to significant reductions in the efficiency and operational life of the heat exchangers. For these and other reasons, cooling water system operators may utilize chemical treatment programs to help prevent scale formation, microbial formation, sludge, and / or corrosion.

[0004] Cooling water treatment programs often use inexpensive inorganic phosphates. This includes the use of orthophosphates as anionic corrosion inhibitors and complex phosphates as cathodic inhibitors. When used, orthophosphates are often supplied in the form of phosphoric acid or one of its sodium or potassium salts.

[0005] Phosphate-containing treatments can help effectively manage water-containing systems, but phosphate is an important nutrient for microorganisms such as cyanobacteria and algae. Phosphorus is recognized as the primary growth-limiting nutrient for algae in surface waters, including lakes and rivers. Excessive biomass growth due to phosphorus nutrients in lakes and rivers can cause reduced light transmission, reduced organic matter growth, and subsequent oxygen depletion in the water. To help address these issues, local and national governments have promulgated increasingly stringent phosphorus discharge regulations. Summary of the Invention

[0006] In general, the present disclosure relates to solid, phosphorus-free water treatment compositions and related techniques for using such compositions to treat water, for example, in recirculating water systems. The water treatment compositions can inhibit the formation of scale and corrosive deposits on surfaces that the treated water source comes into contact with. The water treatment compositions are formulated from phosphorus-free components, allowing the water treatment compositions to be added to source water without increasing the phosphorus concentration of the source water. This is beneficial for maintaining compliance with phosphorus discharge regulations when the treated water source is subsequently discharged into a surface water body, for example, a river or lake.

[0007] The phosphorus-free water treatment composition of the present disclosure is specifically formulated to promote the formation of a solid treatment composition. In other words, the water treatment composition is provided as a solid phase composition. The solid water treatment composition can be introduced into the source water on-site using a dispenser. The dispenser may or may not size-reduce and / or dissolve the solid treatment composition with a diluent prior to introducing the treatment composition into the source water intended to be treated. Formulation of the phosphorus-free water treatment composition as a solid can reduce the volume of the composition compared to utilizing a liquid formulation, making the transportation and storage of the solid treatment composition easier and more economical than a comparable liquid formulation.

[0008] The solid, phosphorus-free water treatment composition can exhibit excellent dimensional stability over a range of storage conditions, including relatively high temperature and humidity conditions, during the expected storage period. Additionally, the solid, phosphorus-free water treatment composition can exhibit substantially complete solubility in water, ensuring that the solid, phosphorus-free water treatment composition is substantially completely solubilized in the source water to which the composition is added.

[0009] The solid, phosphorus-free water treatment composition may include one or more of a cathodic corrosion inhibitor, an anodic corrosion inhibitor, a film-forming corrosion inhibitor, a scale inhibitor, a dispersant, a fluorescent agent to control the concentration of active agents, a pH adjuster to ensure that all components remain soluble in the dispensed solution, a retention agent to prevent microbial growth in the dispensed solution, and / or a filler agent to aid in solid block formation. A given component may perform more than one of the foregoing functions.

[0010] For example, a solid, phosphorus-free water treatment composition may be formulated to include a polycarboxylic acid, a polymeric dispersant, a soluble corrosion inhibitor, and a fluorescent tracer. The water treatment composition may optionally have one or more additional components, such as a pH adjuster, a filler / binder, and / or a biocide. In some embodiments, a component may serve multiple functions within the composition, such as a pH adjuster and a filler. The solid, phosphorus-free water treatment composition may be pH controlled, for example, to provide a resultant solution upon dissolution of the water treatment composition that has a threshold pH. The pH of the solid, phosphorus-free water treatment composition may be pH controlled in a variety of ways, for example, by the selection and incorporation of one or more acidifying components in the formulated water treatment composition and / or by the incorporation of one or more pH adjusting components in the composition that function to modify the pH of the resultant solution formed from the solid composition.

[0011] In some embodiments, the solid phosphorus-free water treatment composition is pH controlled to produce a resultant solution having a pH in the range of about 1 to about 5 when the solid composition is dissolved at a concentration of 2 weight percent. For example, the solid phosphorus-free water treatment composition may be pH controlled to produce a resultant solution having a pH in the range of about 2 to about 4. Without being bound to any particular theory, it is believed that controlling the pH of the phosphorus-free water treatment composition to a target acidification range can help provide an effective solid phosphorus-free water treatment composition. Controlling the pH of the composition can help the solid composition maintain structural and dimensional stability prior to use, prevent premature disintegration of the solid, and can also promote substantially complete solubility of the composition in water during use.

[0012] In some embodiments, the solid phosphorus-free water treatment composition is formulated to provide a resulting solution with a pH sufficiently low to ensure substantially complete dissolution of the composition in the water. If the pH of the resulting solution exceeds an upper threshold, the solution may exhibit turbidity, indicating incomplete dissolution of the treatment composition. The portion of the solid water treatment composition that does not fully dissolve in the water being treated may not be available to impart treatment function to the water, resulting in undertreatment of the water and / or waste of the treatment composition. In some embodiments, the solid phosphorus-free water treatment composition is formulated to provide a resulting solution with a pH high enough to help prevent the formation of pH-related deposits, such as low pH corrosion formation, and / or to provide a resulting solution that is sufficiently safe for water treatment facility personnel.

[0013] In one example, a solid, phosphorus-free water treatment composition suitable for use in cooling water treatment is described. The composition includes a polycarboxylic acid in the range of 30 weight percent to 60 weight percent of the composition, a polymeric dispersant in the range of 15 weight percent to 30 weight percent of the composition, a soluble corrosion inhibitor in the range of 2 weight percent to 25 weight percent of the composition, and a fluorescent tracer. The example specifies that the composition exhibits solid properties, is phosphorus-free, and has an effective pH such that when the composition is dissolved in water at a concentration of 2 weight percent to form a solution, the solution has a pH in the range of 1 to 5.

[0014] In another example, a solid, phosphorus-free water treatment composition for cooling water treatment is described. The composition includes a polycarboxylic acid in the range of 30 weight percent to 60 weight percent of the composition, a polymeric dispersant in the range of 15 weight percent to 30 weight percent of the composition, a soluble corrosion inhibitor in the range of 2 weight percent to 25 weight percent of the composition, a fluorescent tracer, and a pH adjuster. This example specifies that the composition exhibits pressed solid properties, is phosphorus-free, has a pH effective such that when the composition is dissolved in water at a concentration of 2 weight percent to form a solution, the solution has a pH in the range of 2.5 to 4, and has a substantially uniform distribution of components throughout the composition.

[0015] In another example, a method of treating a cooling water system is described. The method includes adding a solid, phosphorus-free water treatment composition to a water source to form a solution. The solid, phosphorus-free water treatment composition includes a polycarboxylic acid in the range of 30% to 60% by weight of the composition, a polymeric dispersant in the range of 15% to 30% by weight of the composition, a soluble corrosion inhibitor in the range of 2% to 25% by weight of the composition, and a fluorescent tracer. The example specifies that forming the solution includes forming a solution having a pH in the range of 1 to 5. The exemplary method also includes applying the solution within the water-containing system.

[0016] The details of one or more examples are set forth in the description below. Other features, objects, and advantages will become apparent from the description, and from the claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] As used herein, the term "water" for treatment according to the present invention includes various sources such as fresh water, pond water, sea water, salt water or brine source, recycled water, etc. The term water is also understood to include both fresh water sources and recycled water sources, and optionally any combination of water for treatment with the composition of the present disclosure. In some embodiments, recycled water refers to a mixture of water including both water recycled from previous use (e.g., previous cycle of heat exchange as a heat transfer medium) and water not used when previously used (e.g., in a cycle of heat exchange as a heat transfer medium), e.g., fresh water, pond water, sea water, etc.

[0018] "No phosphorus", "phosphorus-free", and various terms thereof, as used herein, mean that no more than trace amounts of phosphorus are present in the composition, particularly less than 0.1% by weight, e.g., less than 0.05% by weight, less than 0.01% by weight, or less than 0.001% by weight.

[0019] The terms "weight percent," "wt-%," "percent by weight," "% by weight," and variations thereof, as used herein, refer to the concentration of a substance when the weight of that substance is divided by the total weight of the composition and multiplied by 100. As used herein, it is understood that "percent," "%," and the like, are intended to be synonymous with "weight percent," "% by weight," and the like.

[0020] As used herein, the term "about" to modify amounts, concentrations, and similar values ​​of ingredients in compositions, and ranges thereof, for example, when describing embodiments of the present disclosure, refers to variations in numerical amounts that may occur, for example, due to typical measuring and handling procedures used to make compounds, compositions, concentrates, or use formulations; due to accidental errors in these procedures; due to differences in manufacture, source, or purity of starting materials or ingredients used to carry out the methods, and similar approximation considerations. The term "about" also encompasses amounts that differ due to degradation of a formulation having a particular initial concentration or mixture, and amounts that differ due to mixing or processing a formulation having a particular initial concentration or mixture.

[0021] The present disclosure generally relates to phosphorus-free water treatment compositions provided in a solid phase and used to treat aqueous systems to inhibit the formation of scale and corrosion deposits in the aqueous systems. The aqueous systems treated with the treatment compositions may typically be cooling water systems that supply water to one or more processes in which thermal energy from a relatively high temperature process stream is transferred to a relatively low temperature water stream through a divided heat exchange surface. In some embodiments, the water treatment compositions according to the present disclosure can be used in open recirculating cooling water systems, for example, open recirculating cooling water systems that include one or more cooling towers that cool the water via evaporative cooling.

[0022] The solid phosphorus-free water treatment composition may generally include a polycarboxylic acid, a polymeric dispersant, and a soluble corrosion inhibitor. The polycarboxylic acid may function as a scale inhibitor. The soluble corrosion inhibitor may be a cathodic corrosion inhibitor, an anodic corrosion inhibitor, a combined cathodic and anodic corrosion inhibitor (e.g., bipolar membrane), and / or a film-forming inhibitor, in any case soluble in water. The composition may also include a fluorescent tracer for tracking and controlling the amount of treatment chemicals in the treated water system. Various additional components such as pH adjusters and / or fillers, biocides, and the like may be included in the water treatment composition. Each of the components included in the water treatment composition may be phosphorus-free. As a result, the entire solid water treatment composition may be phosphorus-free.

[0023] Each of the components of the water treatment composition may be provided in solid form and mixed together. After mixing and forming the resulting solid, phosphorus-free water treatment composition, the composition may be chemically homogenous throughout the solid. In other words, each portion of the solid water treatment composition may have the same components in substantially the same relative weight percentages as each other portion of the solid water treatment composition.

[0024] The solid water treatment composition according to the present disclosure includes at least one solid phosphorus-free polycarboxylic acid as a scale inhibitor. In different embodiments, the water treatment composition may include a single solid phosphorus-free polycarboxylic acid or may include a mixture of two or more solid phosphorus-free polycarboxylic acids. The polycarboxylic acid component of the water treatment composition may comprise about 25% to about 70% by weight of the water treatment composition, for example, about 30% to about 60% by weight, about 30% to about 40% by weight, about 40% to about 50% by weight, or about 50% to about 60% by weight, based on the total weight of the water treatment composition.

[0025] The polycarboxylic acid component may be a carboxylic acid or a residue of a molecule having at least two carboxyl moieties, e.g., a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid. In some examples, the polycarboxylic acid component is a copolymer. The copolymer may comprise, consist essentially of, or consist of polymerized residues of two or more monomers. The two or more monomers may include a first monomer that comprises, consists essentially of, or consists of a carboxylic acid or a residue thereof, and a second monomer that is different from the first monomer. The first monomer may comprise a carboxylic acid or a residue of a molecule having at least one carboxyl moiety, a salt thereof, or a conjugate base thereof. The carboxylic acid may comprise a single carboxyl moiety or multiple carboxyl moieties (e.g., a dicarboxylic acid such as maleic acid).

[0026] As used herein, the term "copolymer" refers to polymers formed from two, three or more monomers and having two, three or more different subunits in their polymer backbone. The composition may include (meth)acrylic polymers, such as acrylic acid homopolymers, methacrylic acid homopolymers, and / or copolymers formed from mixtures containing these two monomers.

[0027] Carboxylic acids suitable for use as the carboxylic acid component of the water treatment composition may, by way of example, comprise, consist essentially of, or consist of dicarboxylic acids, such as maleic acid or maleic anhydride, fumaric acid, itaconic acid; glutaconic acid, muconic acid, succinic acid, or any other unsaturated dicarboxylic acid or anhydride thereof; tricarboxylic acids or more, such as citric acid, aconitic acid, or any other carboxylic acid having three or more carboxylic acid moieties; or any other monomer having at least two carboxylic acid moieties.

[0028] In some examples, the carboxylic acid component is a copolymer that may comprise, consist essentially of, or consist of polymerized residues of two or more monomers. The two or more monomers may include at least one monomer that comprises, consists essentially of, or consists of a carboxylic acid or a residue thereof, and a second monomer that is different from the first monomer. Carboxylic acids suitable for use as the first monomer may, by way of example, comprise, consist essentially of, or consist of alkylacrylic acids, such as methacrylic acid, butenoic acid (e.g., crotonic acid), pentenoic acid, propenoic acid, or any other unsaturated monocarboxylic acid that can be polymerized; dicarboxylic acids, such as maleic acid or maleic anhydride, fumaric acid, itaconic acid; glutaconic acid, muconic acid, succinic acid, or any other unsaturated dicarboxylic acid or anhydride thereof that can be polymerized; tricarboxylic acids or more, such as citric acid, aconitic acid, or any other carboxylic acid having three or more carboxylic acid moieties; or any other monomer having at least one carboxyl moiety; salts of any of the foregoing, or conjugate bases of any of the foregoing. In some embodiments, the first monomer is formed from any one of the aforementioned carboxylic acids, their salts, or their conjugate bases. For example, the first monomer may include a carboxylate (e.g., a dicarboxylate) of any of the aforementioned carboxylic acids.

[0029] Specific examples of polycarboxylic acids that may be commonly used as the polycarboxylic acid of the solid water treatment composition include polyacrylic acid (PAA), polyacrylamide, acrylamidomethylpropanesulfonate / acrylic acid copolymer (AMPS / AA), polymaleic acid / acrylic acid copolymer (MA / AA), polymaleic acid / acrylic acid / acrylamidomethylpropanesulfonate terpolymer (PMA / AA / AMPS), hydrolyzed polymaleic anhydride, maleic acid-acrylic acid copolymer, acrylic acid-hydroxypropyl acrylate copolymer, butane tetracarboxylic acid, acrylamidosulfonic acid (AMPS), sodium styrenesulfonate (SSS), and / or sulfophenyl methallyl ether (SPME).

[0030] In some embodiments, polyaspartic acid (PASP) compounds are used as polycarboxylic acid components in solid water treatment compositions. The term "polyaspartic acid" refers to a copolymer in which the mole percentage of aspartic acid residues is at least about 20% of the total number of subunits in the polymer, such as at least about 60%, at least about 70%, or at least about 80% of the total number of subunits in the polyaspartic acid compound. In some examples, at least about 80% of the subunits of the polyaspartic acid are alpha and / or beta aspartic acid subunits. For example, the proportion of beta-type aspartic acid subunits can be greater than about 50%, such as greater than 70%.

[0031] In addition to having polyaspartic acid units, polyaspartic acid may also include other repeating units, such as malic acid subunits, maleic acid subunits, and / or fumaric acid subunits. In some embodiments, polyaspartic acid may include small amounts (typically no more than about 20% of the subunits, generally no more than about 10%) of one or more comonomers, such as glutamic acid, polybasic carboxylic acid, fatty acid, polybasic hydroxycarboxylic acid, monobasic polyhydroxycarboxylic acid, and sugar carboxylic acid based polymeric subunits.

[0032] Other examples of polyaspartic acid compounds include copolymers of polyaspartic acid prepared by reacting maleic acid, polycarboxylic acid, ammonia and polyamine, hydrolyzing the resulting polymer and converting it to a salt with an alkali metal hydroxide.Polycarboxylic acids suitable for use in such processes include adipic acid, citric acid, fumaric acid, malic acid, malonic acid, succinic acid, glutaric acid, oxalic acid, pimelic acid, itaconic acid, nonanedioic acid, dodecanedioic acid, octanedioic acid, isophthalic acid, terephthalic acid and phthalic acid.Suitable polyamines typically include polyamines with at least one primary amino group, such as diethylenetriamine, polyoxyalkyleneamine diamines and triamines, melamine, alkyl diamines (e.g., ethylenediamine and hexanediamine) and alkyl triamines.

[0033] A solid water treatment composition according to the present disclosure includes at least one solid, phosphorus-free polymeric dispersant. In some embodiments, the polymeric dispersant also includes a carboxylic acid moiety, and the polymeric dispersant component of the solid water treatment composition is different from the separate carboxylic acid component of the composition. The polymeric dispersant component of the water treatment composition may comprise from about 10% to about 40% by weight of the water treatment composition, for example, from about 15% to about 30% by weight, from about 15% to about 20% by weight, or from about 20% to about 30% by weight, based on the total weight of the water treatment composition.

[0034] Generally, polymeric dispersants are highly charged polymers that help prevent small particles from agglomerating into larger clumps, which will settle on surfaces more easily. The mechanism of dispersion can be by charge reinforcement or steric stabilization. Dispersion by charge reinforcement increases the negative charge that all particles in the solution have. For example, low molecular weight anionic polymers adsorb onto the surface of particles in water, increasing the negative charge of the particles. The increase in surface charge helps prevent solids from agglomerating and settling. Polymers adsorbed on the surface of particles also help prevent agglomeration by creating a physical barrier against other particles. This barrier acts like an elastic cushion that helps prevent particles from sticking to each other, and is a steric effect, depending on the structure and molecular weight of the adsorbed polymer.

[0035] Phosphorus-free polymeric dispersants can function through both electrostatic repulsion and steric stabilization. Some polymeric dispersants can function as dispersants to prevent the deposition of suspended solids without providing significant scale inhibition. Other polymers that function as polymeric dispersants can provide both scale inhibition and dispersant functions.

[0036] In some embodiments, the polymeric dispersant is a copolymer that is the polymerized residue of two or more monomers, one of which is a carboxylic acid or residue thereof and the second monomer is a sulfonated acid or residue thereof. The first monomer may comprise a carboxylic acid or a residue of a molecule having at least one carboxyl moiety, a salt thereof, or a conjugate base thereof. The carboxylic acid may comprise a single carboxyl moiety or multiple carboxyl moieties (e.g., a dicarboxylic acid such as maleic acid). Carboxylic acids suitable for use as the first monomer may, by way of example, comprise, consist essentially of, or consist of alkylacrylic acids such as methacrylic acid, butenoic acid (e.g., crotonic acid), pentenoic acid, propenoic acid, or any other unsaturated monocarboxylic acid that can be polymerized; dicarboxylic acids such as maleic acid or maleic anhydride, fumaric acid, itaconic acid; glutaconic acid, muconic acid, succinic acid, or any other unsaturated dicarboxylic acid or anhydride thereof that can be polymerized; tricarboxylic acids or more such as citric acid, aconitic acid, or any other carboxylic acid having three or more carboxylic acid moieties; or any other monomer having at least one carboxyl moiety; salts of any of the foregoing, or conjugate bases of any of the foregoing.

[0037] The first monomer comprises about 55 mol% or more of the copolymer, for example, about 55 mol% to about 99 mol%, about 60 mol% to about 98 mol%, about 70 mol% to about 95 mol%, about 80 mol% to about 99 mol%, about 90 mol% to about 97 mol%, about 93 mol% to about 99 mol%, about 96 mol% to about 99 mol%, about 92 mol% to about 94 mol%, about 83 mol% to about It may constitute about 87 mol%, about 88 mol% to about 92 mol%, about 93 mol% to about 96 mol%, about 95 mol% to about 98.5 mol%, about 60 mol%, about 70 mol%, about 80 mol%, about 85 mol%, about 90 mol%, about 92.9 mol%, about 93.3 mol%, about 95 mol%, about 96 mol%, about 96.4 mol%, about 98.4 mol%, or about 98.5 mol% or less.

[0038] The second monomer of the copolymer comprises, consists essentially of, or consists of a sulfonated acid or a residue thereof. The sulfonated acid may include a sulfonated acid moiety, a salt thereof, or a conjugate base thereof. Suitable sulfonated acids may include ATBS, sulfostyrene, vinyl sulfonic acid, methallylsulfonic acid, a salt of the foregoing (e.g., sodium methallylsulfonate or ATBS sodium salt), or a conjugate base of the foregoing (e.g., methallylsulfonate).

[0039] The second monomer is about 45 mol% or less of the copolymer, for example, about 0.01 mol% to about 45 mol%, about 1 mol% to about 40 mol%, about 20 mol% to about 30 mol%, about 0.01 mol% to about 15 mol%, about 0.01 mol% to about 10 mol%, about 0.01 mol% to about 5 mol%, about 2 mol% to about 4 mol%, about 1 mol% to about 5 mol%, about 5 mol% to about 15 mol%, about 10 mol% to about 5 mol%, about 15 ... mol% to about 15 mol%, about 5 mol% to about 10 mol%, about 18 mol% to about 22 mol%, about 13 mol% to about 17 mol%, about 8 mol% to about 12 mol%, about 3 mol% to about 7 mol%, about 2 mol%, about 3 mol%, about 3.6 mol%, about 3.7 mol%, about 4 mol%, about 5 mol%, about 10 mol%, about 15 mol%, about 20 mol%, about 20 mol% or less, or about 10 mol% or less.

[0040] As one specific example, the solid phosphorus-free polymeric dispersant may be a copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid (AA-AMPS). Other exemplary solid phosphorus-free polymeric dispersants that may be used include polyepoxysuccinic acid and / or copolymers of maleic acid and acrylic acid (MA / AA). In various examples, the solid phosphorus-free polymeric dispersant may include terpolymers and / or tetrapolymers.

[0041] The solid water treatment composition according to the present disclosure may also include at least one solid, phosphorus-free, water-soluble corrosion inhibitor. Generally, corrosion inhibitors protect metals by forming a passivation layer on the metal surface. This passivation layer wets the metal surface, which in turn protects the metal from contact with the corrosive properties of the fluid. Typically, the corrosion inhibitor formulation may contain a variety of aliphatic organic surfactant molecules, including amines, quaternary amines, imidazolines, amides, carboxylic acids, or combinations thereof.

[0042] Exemplary corrosion inhibitors that may be used in the solid phosphorus-free water treatment compositions include azoles (e.g., triazoles), zinc salts, molybdates, and combinations thereof. Specific examples of azoles include benzotriazole, tolyltriazole, and mercaptobenzothiazole. Specific examples of zinc salts include zinc chloride, zinc sulfate, and zinc nitrate. Specific examples of molybdates include alkaline earth metal molybdates, such as sodium molybdate.

[0043] In some embodiments, the corrosion inhibitor is or includes substituted and / or hydrogenated benzotriazoles and tolyltriazoles. For example, the corrosion inhibitor may include alkylbenzotriazoles, alkyltolyltriazoles, alkoxybenzotriazoles, alkoxytolyltriazoles, nitrobenzotriazoles, nitrotolyltriazoles, halobenzotriazoles, halotolyltriazoles, hydrogenated benzotriazoles, hydrogenated tolyltriazoles, acids or salts thereof, or combinations thereof. The corrosion inhibitor does not contain phosphorus.

[0044] The alkyl or alkoxy benzotriazole can have 1 to 6 alkyl substituents attached to the nitrogen atom of the azole or to a carbon atom of the aromatic ring, which can be a C1 to C12 alkyl group. For example, the alkyl benzotriazole can include butyl benzotriazole, pentyl benzotriazole, hexyl benzotriazole, heptyl benzotriazole, octyl benzotriazole, or combinations thereof.

[0045] The alkyltolyltriazole can have 1 to 5 alkyl substituents attached to the nitrogen atom of the azole or to a carbon atom of the aromatic ring, and the alkyl substituents can be C1 to C12 alkyl groups. For example, the alkyltolyltriazole can include butyltolyltriazole, pentyltolyltriazole, hexyltolyltriazole, heptyltolyltriazole, octyltyltolyltriazole, or combinations thereof.

[0046] The solid water treatment compositions may utilize other corrosion inhibitors in addition to or in place of the foregoing, such as imidazoline compounds, quaternary ammonium compounds, pyridinium compounds, or combinations thereof. The imidazolines may be, for example, imidazolines derived from diamines such as ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetraamine (TETA), and the like, and long chain fatty acids such as tall oil fatty acid (TOFA). Suitable quaternary ammonium salts include, but are not limited to, tetramethylammonium salts, tetraethylammonium salts, tetrapropylammonium salts, tetrabutylammonium salts, tetrahexylammonium salts, tetraoctylammonium salts, benzyltrimethylammonium salts, benzyltriethylammonium salts, phenyltrimethylammonium salts, phenyltriethylammonium salts, cetylbenzyldimethylammonium salts, hexadecyltrimethylammonium salts, dimethylalkylbenzyl quaternary ammonium salts, monomethyldialkylbenzyl quaternary ammonium salts, or trialkylbenzyl quaternary ammonium salts, where the alkyl group has from about 6 to about 24 carbon atoms, from about 10 to about 18 carbon atoms, or from about 12 to about 16 carbon atoms. The quaternary ammonium salt can be a benzyltrialkylquaternary ammonium salt, a benzyltriethanolamine quaternary ammonium salt, or a benzyldimethylaminoethanolamine quaternary ammonium salt.

[0047] The corrosion inhibitor component of the water treatment composition may comprise about 2% to about 25% by weight of the water treatment composition, for example, about 8% to about 25% by weight, about 10% to about 20% by weight, about 10% to about 15% by weight, about 12.5% ​​to about 17.5% by weight, or about 15% to about 20% by weight, based on the total weight of the water treatment composition. In one example, the solid water treatment composition includes only a single corrosion inhibitor selected from the group of zinc-containing compounds (e.g., zinc salts), molybdate-containing compounds (e.g., molybdates), and triazoles (e.g., benzotriazole, tolyltriazole). In another example, the solid water treatment composition includes a combination of multiple corrosion inhibitors including at least one of zinc-containing compounds (e.g., zinc salts) and molybdate-containing compounds (e.g., molybdates), and at least one triazole (e.g., benzotriazole, tolyltriazole).

[0048] For example, the solid water treatment composition may comprise at least one triazole in the range of 2% to 15% by weight of the composition, e.g., about 4% to about 6% by weight, about 5% to about 8% by weight, or about 10% to about 12% by weight, and at least one of a zinc-containing compound and a molybdate-containing compound in the range of 2% to 15% by weight of the composition, e.g., about 4% to about 6% by weight, about 5% to about 8% by weight, about 8.5% to about 11.5% by weight, or about 10% to about 12% by weight.

[0049] The solid water treatment composition according to the present disclosure may also include a fluorescent tracer. The inclusion of the fluorescent tracer allows the amount of the composition in the water being treated to be determined and / or monitored. This can help the operator determine how much of the treatment composition is being delivered to the water source and / or how much of the treatment composition is being used up during use. A fluorometer, UV spectrometer, or other fluorescent substance detection device can be used to determine the amount of the fluorescent tracer in the water source and thus the proportional amount of the water treatment composition therein. Such equipment can be used to constantly monitor the concentration of the fluorescent tracer in the system or can be used to monitor said concentration on demand (e.g., randomly or at selected intervals).

[0050] The fluorescent tracer may be provided in the composition as a separate solid component added to the composition and / or by adding a fluorescent tagging agent to one of the above-mentioned polymers. If provided as a separate component, the fluorescent tracer may comprise less than 5% by weight of the water treatment composition, such as less than 1% by weight, or less than 0.5% by weight, such as about 0.1% to about 1% by weight, or about 0.2% to about 0.8% by weight, based on the total weight of the water treatment composition. If the fluorescent tracer is provided by tagging a separate functionalized polymer component, the weight of the fluorescent tracer may be included as a portion of the weight of the separate functionalized polymer component in the composition.

[0051] Exemplary solid fluorescent tracers that may be used include 1,3,6.8-pyrenetetrasulfonic acid sodium salt, fluorescein, and naphthalene disulfonic acid sodium salt. In a specific example, the fluorescent tracer used in the solid water treatment composition is 1,3,6.8-pyrenetetrasulfonic acid sodium salt.

[0052] When a tagging agent is used, the polymeric compound is tagged (e.g., polymerized) with the tagging agent. The tagging agent can be polymerized into any of the polymers disclosed herein. Suitable tagging agents can include one or more monomers that are naphthalene-, anthracene-, quinoline-, isoquinoline-, indole-, pyrene-, benzimidazole-, coumarin-, fluorescein-, quinoxaline-, xanthylium-, boron-dipyrromethene-, bimane-, rhodamine-, or naphthalimide-containing. Specific monomers that can be used to fluorescently label the polymer include 4-methoxy-N-(3-N',N'-dimethylaminopropyl)naphthalimide (quaternary salt), N-allyl-4-(2-N',N'-dimethylaminoethoxy)naphthalimide (methyl sulfate quaternary salt), 4-methoxy-N-(3-N',N'-dimethylaminopropyl)naphthalimide (allyl chloride quaternary salt), 5-allyloxy-4'-carboxy-1,8-naphthoylene, 2'-benzimidazole, 6-vinylbenzyloxy-4'-carboxy-1,8-naphthoylene, 1',2'-benzimidazole, 4-methoxy-N-(3-N',N'-dimethylaminopropyl)naphthalimide (2-hydroxy-3-allyloxypropyl quat), dimethylaminopropyl methacrylamide, and the quaternary ammonium salt of 2-(chloromethyl)quinoline. , a quaternary ammonium salt of dimethylaminopropyl methacrylamide and 9-(chloromethyl)anthracene, a quaternary ammonium salt of dimethylaminopropyl methacrylamide and 2-(chloromethyl)benzimidazole, a quaternary ammonium salt of dimethylaminopropyl methacrylamide and 4-(bromomethyl)pyrene, a quaternary ammonium salt of dimethylaminopropyl methacrylamide and 1-(chloromethyl)naphthalene, a quaternary ammonium salt of dimethylaminopropyl methacrylamide and any additional quaternary ammonium salts of halo-alkyl derivatives of the fluorescent chromophores listed above, or any other fluorescent molecule that can be polymerized with any of the polymers, and the tagging agent may constitute less than about 10 mol % of the polymer, e.g., less than about 1 mol %, less than about 0.1 mol %, or less than about 0.01 mol % of the polymer.

[0053] The solid phosphorus-free water treatment compositions according to the present disclosure can be pH controlled, for example, to provide a solution obtained upon dissolution of the water treatment composition having a threshold pH. The pH of the solid phosphorus-free water treatment composition can be pH controlled in a variety of ways, for example, by the selection and incorporation of one or more acidifying and / or alkaline components in the formulated water treatment composition, and / or by the incorporation of one or more solid phosphorus-free pH adjusting components in the composition that function to modify the pH of the resulting solution formed from the solid composition. If used, the one or more solid phosphorus-free pH adjusting components may also function as a bulking agent in the composition, for example, to increase the volume of the water treatment composition in which the active components are dispersed.

[0054] In different formulations, the pH adjusting components included in the solid water treatment composition may be acids, bases, and / or neutral salts. The selection and relative amount of one or more pH adjusting components used in the composition may vary depending on the other specific components included in the composition and the solution pH provided by those other components. Exemplary pH adjusting components that may be used include, but are not limited to, alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, alkaline earth metal bicarbonates, alkali metal sulfates, alkaline earth metal sulfates, alkali metal bisulfates, alkaline earth metal bisulfates, alkali metal and / or alkaline earth metal silicates, mineral acids, sulfamic acid, and / or organic acids (e.g., lactic acid, acetic acid, formic acid, citric acid, oxalic acid, uric acid, malic acid, tartaric acid). In some embodiments, the one or more pH adjusting components used in the composition are selected from the group consisting of alkali metal sulfates, alkaline earth metal sulfates, alkali metal bisulfates, alkaline earth metal bisulfates, sulfamic acid, alkaline earth metal carbonates, citric acid, and combinations thereof.

[0055] The pH adjusting component(s) can be provided in solid form and can be incorporated into other components included in the solid water treatment composition. The pH adjusting component(s) can be in hydrous or anhydrous form. The use of an anhydrous pH adjusting component can help reduce the water absorption of the resulting solid water treatment composition, which can aid in the stability (e.g., during shipping and storage) of the solid water treatment composition.

[0056] The components of the solid phosphorus-free water treatment composition (with or without the addition of one or more pH adjusting components) can be effective to achieve a target pH threshold and / or form a resultant solution that is within a target pH range. For example, when the solid composition is dissolved at a concentration of 2 wt % (the weight of the solid composition in the solution divided by the combined weight of the solid composition and the water forming the solution), the pH of the resultant solution can be at least 0.5, such as at least 1.0, at least 1.5, at least 2.0, at least 2.5, at least 3.0, at least 3.5, at least 4.0, or at least 4.5. Additionally or alternatively, the pH of the resultant solution can be less than 6.0, such as less than 5.0, less than 4.5, less than 4.0, less than 3.5, less than 3.0, or less than 2.5. In some examples, the pH of the resulting solution is in the range of about 1.0 to about 5.0, such as about 1.5 to about 4.5, about 2.0 to about 4.0, about 2.0 to about 3.0, or about 3.0 to about 4.0. Although the foregoing pH values ​​are discussed at a specific example concentration of 2% by weight, the solid water treatment compositions can indeed be used at other concentration levels without departing from the scope of the present disclosure.

[0057] The amount of one or more pH adjusting components (if used) included in a solid water treatment composition can vary depending on the pH generated by the other components of the composition, as well as the target pH threshold and / or target pH range. In some examples, the pH adjusting component of the composition is present in an amount ranging from about 5% to about 30% by weight of the water treatment composition, for example, from about 5% to about 15% by weight, from about 8% to about 12% by weight, from about 12.5% ​​to about 17.5% by weight, or from about 20% to about 30% by weight, based on the total weight of the water treatment composition.

[0058] The solid phosphorus-free water treatment composition may include various other optional additives. As an example, the composition may include a biocide. The water treatment composition may have less than 1% by weight of the water treatment composition, such as less than about 0.5% by weight, or less than about 0.2% by weight, such as about 0.01% to about 0.2% by weight, of the biocide, based on the total weight of the water treatment composition. Suitable biocides include, but are not limited to, oxidizing and non-oxidizing biocides. Suitable non-oxidizing biocides include, for example, aldehydes (e.g., formaldehyde, glutaraldehyde, and acrolein), amine-type compounds (e.g., quaternary amine compounds and cocodiamine), halogenated compounds (e.g., 2-bromo-2-nitropropane-3-diol) (bronopol) and 2,2-dibromo-3-nitrilopropionamide (DBNPA), sulfur compounds (e.g., isothiazolones, carbamates, and metronidazole). Suitable oxidizing biocides include, for example, sodium hypochlorite, trichloroisocyanuric acid, dichloroisocyanuric acid, calcium hypochlorite, lithium hypochlorite, chlorinated hydantoins, stabilized sodium hypobromite, activated sodium bromide, brominated hydantoins, chlorine dioxide, ozone, and peroxides.

[0059] As another example, the solid phosphorus-free water treatment composition may include a surfactant. The composition may include about 0.1-10 wt.%, about 0.5-5 wt.%, or about 0.5-4 wt.% of a surfactant based on the total weight of the composition. Suitable surfactants include, but are not limited to, anionic surfactants and nonionic surfactants. Anionic surfactants include alkylaryl sulfonates, olefin sulfonates, paraffin sulfonates, alcohol sulfates, alcohol ether sulfates, alkyl carboxylates and alkyl ether carboxylates, and alkyl and ethoxylated alkyl phosphate esters, and mono- and dialkyl sulfosuccinates and sulfosuccinates. Nonionic surfactants include alcohol alkoxylates, alkylphenol alkoxylates, block copolymers of ethylene, propylene and butylene oxides, alkyl dimethylamine oxides, alkyl-bis(2-hydroxyethyl)amine oxides, alkyl amidopropyl dimethylamine oxides, alkyl amidopropyl-bis(2-hydroxyethyl)amine oxides, alkyl polyglucosides, polyalkoxylated glycerides, sorbitan esters and polyalkoxylated sorbitan esters, and alkyl polyethylene glycol esters and diesters. In another example, the composition is free of surfactants.

[0060] As another example, the solid phosphorus-free water treatment composition may include fillers and / or binders. Exemplary fillers and / or binders that may be used include hydrated chelating agents such as hydrated aminocarboxylates, hydrated polycarboxylates or hydrated anionic polymers, hydrated citrates or hydrated tartrates, along with alkali metal carbonates. For example, exemplary fillers that may be used include sodium sulfate, sodium chloride, silicates, starches, sugars, C1-C10 alkylene glycols such as propylene glycol, and the like. Exemplary binders that may be used include organic acetates such as carbonates, aminocarboxylates, and the like. In another example, the composition does not include a separate filler and / or binder.

[0061] Table 1 below provides exemplary components that may be used to formulate an exemplary solid, phosphorus-free water treatment composition according to the present disclosure. The table includes exemplary weight ranges for each component in the composition, as well as exemplary molecules that may be used one or more in each composition component. The composition may comprise, consist essentially of, or consist of the components and / or chemicals in the table. [Table 1]

[0062] The individual components of the solid phosphorus-free water treatment compositions according to the present disclosure can be combined and formed into a solid structure, such as a solid block. The solid can be formed by a variety of techniques, such as pressing, casting, and / or extrusion. The components can be obtained in liquid form and / or can be obtained in liquid form and dried (e.g., via spray drying, drum drying, oven drying, or other drying methods that convert the liquid components into a solid and powder).

[0063] Solid phosphorus-free water treatment compositions can be made by blending dry components in the appropriate ratios or agglomerating the materials in an appropriate agglomeration system. Pelletized materials can be produced by compressing solid granules or agglomerated materials in an appropriate pelletizing equipment to produce appropriately sized pelletized materials. Solid blocks and cast solid block materials can be made by introducing into a container either a block of pre-hardened material or a castable liquid that hardens into a solid block in the container. Examples of containers include disposable plastic containers or water-soluble film containers. Other suitable packaging for the compositions include flexible bags, packets, shrink wrap, and water-soluble films such as polyvinyl alcohol.

[0064] The solid phosphorus-free water treatment composition may be formed using a batch or continuous mixing system. In one example, a single or twin screw extruder is used to combine and mix one or more components at high shear to form a homogenous mixture. In some embodiments, the processing temperature is below the melting temperature of the components. The processed mixture may be dispensed from the mixer by molding, casting, or other suitable means, where the composition hardens into a solid form. The structure of the matrix may be characterized according to its hardness, melting point, material distribution, crystal structure, and other similar properties by methods known in the art. In general, the solid composition processed according to the present disclosure is substantially homogenous with respect to the distribution of components throughout its mass and is dimensionally stable.

[0065] In the extrusion process, one or more liquid and / or solid ingredients are introduced into a final mixing system and mixed continuously until the ingredients form a substantially homogenous semi-solid mixture distributed throughout its mass. The mixture is then discharged from the mixing system into or through a die or other shaping means. The product is then packaged.

[0066] In the casting process, one or more liquid and / or solid ingredients are introduced into a final mixing system and mixed continuously until the ingredients form a substantially homogenous liquid mixture distributed throughout its mass. Once mixing is complete, the product is transferred to a packaging container where solidification occurs.

[0067] In the press solid process, flowable solids such as granular solids or other particulate solids may be brought together under pressure. In the press solid process, the flowable solids of the composition are placed in a form (e.g., a mold or container). The method may include gently pressing the flowable solids in the form to produce the phosphorus-free water treatment composition. Pressure may be applied by a block machine or a rotary press, or the like. Pressure may be applied at about 1 to about 2000 psi, about 1 to about 300 psi, about 5 psi to about 200 psi, or about 10 psi to about 100 psi. In some embodiments, the method may use pressures as low as about 1 psi or more, about 2 or more, about 5 psi or more, or about 10 psi or more. As used herein, the term "psi" or "pounds per square inch" refers to the actual pressure applied to the flowable solids being pressed, and not to the gauge or water pressure measured at a point on the pressing device. The method may include a curing step to produce a solid phosphorus-free water treatment composition. As referred to herein, the uncured composition comprising the flowable solid is compressed to provide sufficient surface contact between the particles that make up the flowable solid for the uncured composition to solidify into a stable solid composition. A sufficient amount of particles (e.g., granules) in contact with each other provide effective bonding of the particles to each other to create a stable solid composition. The inclusion of a curing step can include allowing the pressed solid to solidify for a period of time, such as several hours, or about a day (or longer). In a further aspect, the method can include vibrating the flowable solid in the form or mold.

[0068] The term "solid" means that the hardened composition does not flow and substantially retains its shape under moderate stress or pressure or simple gravity. The solid may be in various forms, such as powders, flakes, granules, pellets, tablets, lozenges, disks, briquettes, bricks, solid blocks, unit doses, or another solid form known to those skilled in the art. The degree of hardness of the solid cast and / or pressed solid compositions may range from that of a relatively dense and hard fused solid product, such as concrete, to a density that is characterized as being a hardened paste.

[0069] In addition, the term "solid" refers to the state of the composition under the expected storage and use conditions of the solid composition. The solid composition according to the present disclosure may maintain dimensional stability under high temperature and humidity storage conditions. For example, the solid composition may maintain dimensional stability at a temperature of 50°C and a relative humidity of 70% for a period of at least one month, such as at least two months, at least six months, or at least one year (e.g., a period of one month to one year). The term "dimensional stability" means that the solid composition does not change in size by more than 1% in any measured dimension when exposed to the stated environmental conditions outside of the packaging protection for the period of interest.

[0070] The resulting solid phosphorus-free water treatment composition may take forms including, but not limited to, cast solid products; extruded, molded, or formed solid pellets, blocks, tablets, powders, granules, flakes; pressed solids, or the formed solids may then be crushed or formed into powders, granules, or flakes. In some examples, the water treatment composition is formed into a solid having a weight of at least 10 grams, e.g., at least 100 grams, at least 1 kg, or at least 10 kg. For example, the composition may be formed into a solid having a mass of 1 to 100 kilograms, e.g., 1 to 25 kg.

[0071] The solid composition provides a stabilized source of the functional material. In some embodiments, the solid composition can be dissolved, for example, in an aqueous medium to produce a concentrated solution. The solution can be directed to a water reservoir for later use and / or dilution, or can be applied directly to the point of use. For example, in cooling water applications, a solid phosphorus-free treatment composition can be dissolved to form a concentrated solution. The amount of solid composition dissolved in water can be effective to produce a concentrated solution having a concentration of the treatment composition ranging from 0.1% to 5% by weight to about 1% to about 3% by weight, based on the combined weight of the water and treatment composition. In many applications, the actual size of the sump can range from a few liters (e.g., 2-4 liters) to about 20 liters, although other size applications are also possible.

[0072] The solid phosphorus-free water treatment composition may be substantially completely soluble in the water to which the composition is added. Exemplary compositions may exhibit about 100% solubility in the water to which it is added. The composition may dissolve in the water to which the solid composition is added over a period of 1 hour or less, such as 30 minutes or less, 15 minutes or less, 10 minutes or less, 5 minutes or less, 2 minutes or less, 1 minute or less, 30 seconds or less, 20 seconds or less, 10 seconds or less, or 5 seconds or less. The water to which the solid composition is added may be optionally mixed to aid and accelerate dissolution. The temperature of the water to which the composition is added may vary and in some examples may range from 20°C to 80°C, such as 20°C to 30°C, 30°C to 40°C, 40°C to 50°C, 50°C to 60°C, 60°C to 70°C, or 70°C to 80°C.

[0073] The solid phosphorus-free water treatment compositions disclosed herein can be used in water-containing systems such as desalination systems, cooling systems (e.g., cooling towers, radiators, heat pipes, etc.), pipes, drilling equipment (e.g., drill strings, drilling muds, etc.), tracking and fracking equipment, paper or pulp processing systems, wastewater treatment systems, water purification systems, dishwashing, evaporators, condensers, filtration, mining, water softening, pumps, storage vessels, or any other system that uses or contacts one or more surfaces in a water source. During use, as the scale and / or forming and / or corrosion-promoting components of the water source concentrate (e.g., by evaporation) and / or thermal shock occurs, corrosive conditions intensify, corrosion is initiated, and scale deposits from the water source on the surfaces of the water-containing system in contact therewith. Such surfaces can include the interior of pipes, storage vessels, radiators, heat pipes, filters, digesters, condensers, the exterior of cooling towers, or any other surface that contacts a water source. Surfaces of the water-containing system may include metal, plastic, glass, rubber or latex, fiberglass, concrete or stone, or any other material suitable for holding, transporting, or filtering water.

[0074] The surfaces of water-containing systems treated with the solid phosphorus-free water treatment compositions disclosed herein may include metals such as iron, steel (e.g., stainless steel, carbon steel, or galvanized steel), copper, lead, zinc (e.g., anodized pipe), aluminum, or any other metal suitable for use in water-containing systems; plastics such as polyethylene (e.g., PEX), polypropylene, polytetrafluoroethylene, polyvinyl chloride, acrylonitrile butadiene styrene, and the like; glass (e.g., glass storage containers), rubber or latex (rubber hoses or rubber tubing); fiberglass; concrete or stone; or any other material suitable for holding, transporting, or filtering water. The term "carbon steel" refers to steel in which the major alloying component with iron is carbon, carbon steel containing from about 0.1% to about 2.1% carbon by weight.

[0075] The water source to be treated using the compositions disclosed herein may include one or more caustic / scale formers therein, including carbon dioxide, hydrogen sulfide, organosulfur compounds, metal cations, metal complexes, such as aqueous metal cations, metal chelates and / or organometallic complexes, aluminum ions, ammonium ions, barium ions, chromium ions, cobalt ions, cuprous ions, cupric ions, calcium ions, ferrous ions, ferric ions, hydrogen ions, lead ions, magnesium ions, manganese ions, molybdenum ions, nickel ions, potassium ions, sodium ions, strontium ions, titanium ions, uranium ions, vanadium ions, zinc ions, bromide ions, iodine ... In one embodiment, the present invention comprises, consists essentially of, or consists of an anion, an ... Each caustic / scale former or the total amount of one or more caustic / scale formers in the water source may be present at a concentration of at least about 10 ppm, e.g., at least about 50 ppm, at least about 100 ppm, at least about 300 ppm, at least about 500 ppm, at least about 1000 ppm, at least about 2000 ppm, at least about 5000 ppm, at least about 10,000 ppm, at least about 20000 ppm, or less than about 100,000 ppm.

[0076] The solid, phosphorus-free water treatment compositions disclosed herein can inhibit corrosion, for example, corrosion caused by contact of a surface with a water source containing corrosives or corrosive conditions that can cause corrosion. The solid, phosphorus-free water treatment compositions disclosed herein can also inhibit the formation of scale, such as scale formed from calcium carbonate; magnesium carbonate; calcium sulfate; barium sulfate; barium carbonate; calcium fluoride; calcium, magnesium, aluminum, or iron silicates; or any other scale known to form in aqueous systems. The solid, phosphorus-free water treatment compositions disclosed above perform these functions without the use of phosphorus or phosphorus-containing compounds (e.g., phosphates).

[0077] In some applications, the pH of the water source is 7 to 14, e.g., about 7 to about 10, about 10 to 14, about 9 to about 11, about 7 to about 9, or about 7 to about 8. In some other applications, the pH of the water source is 0 to 7, e.g., about 1 to about 6, 5 to 6, 4 to 5, 3 to 4, 2 to 3, or 1 to 2.

[0078] In some embodiments, the source water in which the solid phosphorus-free water treatment composition is used is a cooling system that includes one or more of a water jacket, radiator, pipes, heat pipes, pumps, cooling towers, and the like. As the water source circulates through the water-containing system and evaporates in one or more portions thereof, the total dissolved solids are gradually concentrated with each cycle through the system. The corrosive / scaling materials therein, if left untreated, can reach concentrations that begin to corrode and / or scale the surfaces they come into contact with. The solid phosphorus-free water treatment composition may be added to the source water to inhibit or prevent corrosion (e.g., pitting or oxidation) and / or scaling caused by the composition of the water source (e.g., pH and / or dissolved solids).

[0079] The water source and the phosphorus-free water treatment composition added thereto may be maintained in a closed or open system, may be augmented with additional water from outside the system (e.g., make-up water), and / or may be circulated from the system (e.g., blowdown water) and replaced with additional water and / or the phosphorus-free water treatment composition from outside the system. Such maintenance, augmentation, and removal of the water source and / or water treatment composition allows a user to selectively control the concentration of the composition in the water source and / or the amount or rate of corrosion or scaling in the water-containing system.

[0080] In one application, a method of inhibiting corrosion and scale includes dispensing a solid phosphorus-free water treatment composition, such as any of those disclosed herein. The method may include providing a water source, such as any of the water sources disclosed herein. The method includes dispensing a solid phosphorus-free water treatment composition into the water source. In some examples, the solid phosphorus-free water treatment composition is reduced in size by reducing larger solid blocks to powder or smaller solid blocks using a grinder or other mechanical device to increase the surface area of ​​the solids for dissolution. In either case, the solid composition can be mixed with the source water, for example, by placing the solids in the source water and / or spraying the source water onto the solids. A combination of the composition and the source water may be mixed. Mixing may include one or more of batch, continuous, or incremental (e.g., supplemental, on-demand, or monitored) addition.

[0081] The solid phosphorus-free water treatment composition may be present in the water source at various concentration levels, for example, from about 0.05 ppm to about 1000 ppm (e.g., 0.05 ppm to about 50 ppm), for example, from about 0.05 ppm to about 10 ppm, from about 0.05 ppm to about 3 ppm, from about 0.05 ppm to about 5 ppm, from about 1 ppm to about 5 ppm, from about 2 ppm to about 10 ppm, from about 5 ppm to about 20 ppm, from about 15 ppm to about 30 ppm, or from about 15 ppm to about 30 ppm. ppm, about 20 ppm to about 40 ppm, about 30 ppm to about 50 ppm, about 50 ppm to about 100 ppm, about 1 ppm to about 30 ppm, about 10 ppm to about 100 ppm, about 50 ppm to about 500 ppm, about 100 ppm to about 1000 ppm, less than about 1000 ppm, less than about 500 ppm, less than about 100 ppm, less than about 30 ppm, less than about 10 ppm, or less than about 5 ppm.

[0082] The method may include circulating the treatment composition and water through a water-containing system, such as any water-containing system or component thereof disclosed herein. For example, the mixture may be circulated through a water jacket or piping. In one embodiment, the method includes recirculating the mixture through the water-containing system and selectively enhancing the treatment composition content and / or water in the system to maintain, decrease, or increase the concentration of the treatment composition. The concentration of the treatment composition may be monitored during use by use of a fluorescent agent and an instrument (e.g., a fluorometer) to determine the concentration in the water source.

[0083] The following examples may provide further details regarding the compositions and techniques according to the present disclosure. EXAMPLES

[0084] A series of solid, phosphorus-free water treatment compositions were made containing N-(2-hydroxypropyl) methacrylamide (HPMA), tagged high stress polymer (tHSP2) commercially available from Nalco Water, Ecolab, benzotriazole, and zinc chloride. The compositions were dissolved in water at a concentration of 3% by weight. The compositions were dissolved in water at high pH. The pH was gradually adjusted from pH 10 to pH 2. The results of the tested parameter pH showed a turbid solution when the pH was above about 6, indicating incompatibility and / or incomplete dissolution between the components of the composition. Starting at a pH of about 6 or less, the solutions became clear, indicating complete dissolution of the components for good corrosion / scale control performance.

Claims

1. 1. A solid, phosphorus-free water treatment composition for cooling water treatment, said composition comprising: (a) a polycarboxylic acid in the range of 30 weight percent to 60 weight percent of the composition; (b) a polymeric dispersant in the range of 15 to 30 percent by weight of the composition; (c) a soluble corrosion inhibitor in the range of 2 to 25 weight percent of the composition; (d) a fluorescent tracer; Including, The composition comprises: (i) exhibiting solid state properties; (ii) does not contain phosphorus; (iii) A solid, phosphorus-free water treatment composition for cooling water treatment, having a pH effective such that when said composition is dissolved in water at a concentration of 2 weight percent to form a solution, said solution has a pH within the range of 1 to 5.

2. 10. The composition of claim 1, wherein the composition exhibits about 100% solubility in water and is dimensionally stable at a temperature of 50°C and a relative humidity of 70% for a period of at least one month.

3. 3. The composition of claim 1 or 2, wherein the polycarboxylic acid, the polymeric dispersant, the soluble corrosion inhibitor, and the fluorescent tracer are each substantially uniformly dispersed throughout the cross section of the solid.

4. 3. The composition of claim 1, further comprising an anhydrous pH adjuster.

5. The composition of claim 4, wherein the anhydrous pH adjusting agent comprises from 5% to 30% by weight of the composition.

6. The composition of claim 4 , wherein the anhydrous pH adjuster comprises an alkali metal salt.

7. 3. The composition of claim 1 or 2, wherein the composition has a pH effective such that when the composition is dissolved in water at a concentration of 2 weight percent to form the solution, the solution has a pH in the range of 2.5 to 4.

8. 3. The composition of claim 1 or 2, wherein the soluble corrosion inhibitor comprises at least one of a zinc-containing compound, a molybdate-containing compound, and a triazole.

9. 3. The composition of claim 1 or 2, wherein the soluble corrosion inhibitor comprises a triazole in the range of 2 weight percent to 15 weight percent of the composition, and at least one of a zinc-containing compound and a molybdate-containing compound in the range of 2 weight percent to 15 weight percent of the composition.

10. The composition of claim 1 or 2, wherein the solid comprises a pressed solid.

11. 3. The composition of claim 1 or 2, wherein the polycarboxylic acid is selected from the group consisting of polyaspartic acid (PASP), copolymers of maleic acid and acrylic acid (MA / AA), butanetetracarboxylic acid, hydrolyzed polymaleic anhydride (HPMA), polyacrylic acid (PAA), and combinations thereof.

12. 1. A method of treating a cooling water system, the method comprising: adding a solid, phosphorus-free water treatment composition to a water source to form a solution, the solid, phosphorus-free water treatment composition comprising: a polycarboxylic acid in the range of 30 weight percent to 60 weight percent of the composition; a polymeric dispersant in the range of 15 weight percent to 30 weight percent of the composition; a soluble corrosion inhibitor in the range of 2 weight percent to 25 weight percent of the composition; and a fluorescent tracer, wherein forming the solution comprises forming a solution having a pH in the range of 1 to 5; applying said solution in a water-containing system; 1. A method for treating a cooling water system, comprising:

13. 13. The method of claim 12, wherein adding the solid, phosphorus-free water treatment composition to the water source to form the solution comprises forming the solution in a water sump, and applying the solution within the water-containing system comprises dispensing the solution from the water sump into the water-containing system.

14. 14. The method of claim 12 or 13, wherein the composition further comprises an anhydrous pH adjuster.

15. the polycarboxylic acid is selected from the group consisting of polyaspartic acid (PASP), copolymer of maleic acid and acrylic acid (MA / AA), butane tetracarboxylic acid, hydrolyzed polymaleic anhydride (HPMA), polyacrylic acid (PAA), and combinations thereof; the polymeric dispersant is selected from the group consisting of a copolymer of acrylic acid and 2-acrylamido-2-methylpropanesulfonic acid (AA-AMPS) sodium salt; sodium polyepoxysuccinate; and a copolymer of maleic acid and acrylic acid (MA / AA); 14. The method of claim 12 or 13, wherein the soluble corrosion inhibitor comprises at least one of a zinc-containing compound, a molybdate-containing compound, and a triazole.