Pre-treated ion exchange resin for heat transfer systems in alternative energy power sources requiring low-conductivity coolants.

Abstract

Methods and apparatus for pre-treated ion exchange resins, as well as alternative power sources such as heat transfer systems, fuel cells and battery systems, and their use in assemblies including such power sources. The apparatus may comprise a cooling system and a pre-treated ion exchange resin. The pre-treated ion exchange resin may include ion exchange resin treated with corrosion inhibitors and / or antioxidants. The cooling system may comprise a heat transfer fluid. The heat transfer fluid may comprise water, glycol-based freezing point depressants, and mixtures thereof. Examples of glycol-based freezing point depressants include ethylene glycol, propylene glycol, 1,3-propanediol, and mixtures thereof. The cooling system may comprise an ion exchange unit. The ion exchange unit may comprise a pre-treated ion exchange resin, an untreated ion exchange resin, a basic anion resin, an acidic cation exchange resin, and mixtures thereof.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Application No. 63 / 465,615, filed on 11 May 2023, entitled “Pre-treated ion exchange resin for a heat transfer system for an alternative energy power source requiring a low-conductivity coolant,” which is incorporated by reference in its entirety. Technical field

[0002] Aspects of this disclosure relate to pre-treated ion exchange resins. Aspects of this disclosure particularly relate to corrosion inhibitors and / or antioxidant-treated ion exchange resins, and their use in heat transfer systems, alternative power sources such as fuel cells and battery systems, and assemblies containing such power sources. [Background technology]

[0003] To control the heat generated during the operation of a power source, a heat transfer system connected to the power source is used. For example, automobiles use heat transfer fluids and cooling systems to transfer and dissipate the heat generated as a byproduct of the gasoline-driven internal combustion engine. In this case, the heat transfer fluids and cooling systems ensure that the engine operates in an optimal environment and is not exposed to undesirable high temperatures. Water is present in the heat transfer fluid at an average amount of 60-100% by weight relative to the total amount of heat transfer fluid. However, alternatives to conventional gasoline-driven internal combustion engines are now desired, particularly those that address public concerns regarding the environment and the management of natural resources. As a result, new power source technologies, especially those that bring about improvements in energy efficiency, continue to be developed. Examples of alternative power sources that have been developed include, but are not limited to, batteries, fuel cells, and solar power (or photovoltaic power). Such alternative power sources can be used alone or in combination, as is the case with hybrid vehicles. While such alternative power sources often bring about improvements in energy efficiency compared to gasoline-driven internal combustion engines, they still require the use of heat transfer systems and heat transfer fluids. In particular, heat transfer systems and fluids need to maintain optimal operating conditions, especially with respect to temperature.

[0004] Unfortunately, conventional prior art cooling systems and heat transfer fluids may not be suitable for use with alternative power sources, particularly those using electricity or electric charge. For example, conventional prior art heat transfer fluids typically feature extremely high electrical conductivity, often in the range of 3000 μS / cm or more. Using highly conductive heat transfer fluids with alternative power sources, especially electric-based alternative power sources, can result in electric shock, hydrogen release after battery pack damage, increased corrosion, and / or short circuits. Consequently, conventional heat transfer fluids may not be desirable for use with alternative power sources, especially electric-based alternative power sources.

[0005] Fuel cells and battery electric vehicles ("BEVs") are particularly attractive alternative power sources due to their clean and efficient operation. The electrochemical reactions that occur in fuel cells or battery electrodes are exothermic; that is, they generate heat. Therefore, it is necessary to control the heat generated during the electrochemical reactions. For example, to achieve optimal operating conditions, the normal operating temperature of proton exchange membrane or polymer electrolyte membrane ("PEM") fuel cell assemblies is controlled to remain within the range of 60°C to 95°C. To achieve optimal operating conditions during charging and discharging of the battery system, the temperature must remain within the range of 20°C to 40°C.

[0006] Due to the exothermic nature of electrochemical reactions, it is desirable to use a heat transfer fluid to maintain the electrode assembly at an operating temperature within the desired operating temperature range. However, the presence of electric charge makes it difficult to use fuel cells with prior art heat transfer systems and fluids. Furthermore, to generate sufficient power, fuel cell-based automotive engines may have many fuel cells connected in series to form a fuel cell stack. Individual fuel cells may have an operating voltage of 0.6 to 1.0 V DC. In one example, it is conceivable that any number of individual fuel cells, between 100 and 600, may be connected in series. Consequently, the DC voltage across the automotive fuel cell stack is high, typically in the range of 125 to 450 V DC. The same principle also applies to battery systems. These same voltages are applied in the heat transfer fluid systems of individual fuel cells used in the automotive fuel cell stack, or when the battery pack fails. To prevent or minimize the risk of electric shock, it may be desirable for the heat transfer fluid to have low conductivity. Low electrical conductivity in fuel cell heat transfer fluids can also be desirable to reduce flow divergence within the heat transfer fluid system and minimize the decrease in system efficiency. Therefore, it may be desirable to provide low-conductivity heat transfer fluids intended for use in heat transfer systems that are thermally connected to alternative power sources. In battery electric vehicles (BEVs), it is crucial to ensure that no ignition or hydrogen release occurs when the coolant is in direct contact with the battery system. This is best achieved by coolants with low electrical conductivity, particularly less than 100-300 μS / cm. Several international standards, e.g., GB 29743.2 and ASTM, address low-conductivity coolants for BEV applications. Various methods have been proposed for maintaining low electrical conductivity in heat transfer fluids.

[0007] Mobile applications, particularly fuel cells and / or batteries in automobiles, may require operation at low ambient temperatures, typically as low as approximately -40°C. Therefore, a coolant circuit with antifreeze measures may be desirable, and a freezing point depressant may be added to the heat transfer fluid. Particularly suitable examples of freezing point depressants include ethylene glycol, propylene glycol, and 1,3-propanediol. The freezing point depressant alcohol may be present in the heat transfer fluid at an average amount of 30–60% by weight relative to the total volume of the heat transfer fluid. Such freezing point depressants may oxidize during use, generating ionic substances such as glycolic acid and lactic acid. Furthermore, the decomposition rate may increase with temperature and in the presence of transition metals; for example, some stainless steel components may accelerate glycol decomposition, although they themselves may not corrode. Additionally, since the cooling subsystem is usually closed (sealed) when operating at temperatures above approximately 60°C, the coolant cannot be freely exposed to air to avoid rapid oxidation of glycol. Such ionic oxidation byproducts can increase the electrical conductivity of the coolant, potentially leading to a "short circuit" in the power source. The presence of these oxidation byproducts can also significantly accelerate corrosion within the coolant circulation loop. Ionic substances can also arise from impurities during manufacturing or from materials used in the assembly of the heat transfer system, such as flux residue from radiator brazing. Therefore, aluminum and plastic components may be used, but these must be screened to determine whether they accelerate glycol decomposition or corrode, producing soluble ionic impurities in the pure coolant. Consequently, ion exchangers or ion exchange resins are generally provided in the coolant pathways of fuel cell systems to remove any such ionic substances. Since ion exchangers are "consumed" during the removal of ionic substances, their capacity degrades over time. Periodically, the coolant and ion exchange resins must be replaced to prevent potential corrosion and accumulation of glycol decomposition products, which can lead to increased conductivity and potential system failure.Because ion exchange resins are composed of organic materials, they are susceptible to degradation. While cation exchange resins have a maximum operating range of up to 120°C, these hydroxide forms of anion exchange resins are often recommended for use only below 60°C. In some applications, 60°C is below the optimal operating temperature.

[0008] It is sometimes desirable for heat transfer fluids to be corrosion-resistant. Heat transfer systems often contain several metallic components. Exemplary metals found in fuel cell and battery cooling systems, as well as other heat transfer systems, include iron alloys and non-ferrous alloys such as stainless steel, aluminum, brass, and brazing alloys. Furthermore, the use of dissimilar metals in the coolant loop can lead to galvanic corrosion, which should be avoided whenever possible. However, such metals are susceptible to corrosion because they come into contact with the heat transfer fluid. Therefore, it is sometimes desirable to provide corrosion-resistant heat transfer fluids that minimize corrosion of metal heat transfer system components and extend the service life of fuel cell and battery cooling systems, as well as other heat transfer systems. However, many known corrosion inhibitors used in internal combustion engine coolants are usually highly conductive ionic species and may not be desirable for use in fuel cell heat transfer fluids. Examples of such corrosion inhibitors include inorganic silicates, nitrites, molybdates, nitrates, carboxylates, phosphates, and borates. Ion exchange resins can remove ionic corrosion inhibitors. As a result, fuel cell heat transfer fluids may lose their ability to prevent corrosion of metal components in fuel cell heat transfer systems. More specifically, there is still a need for low-conductivity heat transfer fluids that also prevent corrosion of heat transfer systems that are thermally connected to alternative power sources. Conventional inhibitors in low-conductivity coolants are triazole-based and / or contain organic silicate derivatives. Alkyl, hydroxyalkyl, and aromatic amines, or mixtures thereof, can also be used as corrosion inhibitors in coolants with limited conductivity.

[0009] Therefore, some conventional technologies have attempted to address these current challenges with coolants.

[0010] US 2003 / 0198847A1 describes fuel cell coolants containing alcohols and polyalkylene oxides.

[0011] WO 2000 / 017951 describes a cooling system for fuel cells in which a pure ethylene glycol / water mixture is used as the coolant in a 1:1 ratio, without additives. To provide corrosion prevention for materials present in the cooling system, the cooling circuit is equipped with an ion exchange unit to maintain the purity of the coolant and ensure low specific conductivity over long periods, thereby preventing short circuits and corrosion. Suitable ion exchangers mentioned include strongly alkaline hydroxyl-type anionic resins, sulfonic acid-based cationic resins, and other filter materials such as activated carbon.

[0012] WO 02 / 101848 A2 describes antifreeze compositions and concentrates thereof for cooling systems in fuel cell drive devices, comprising specific azole derivatives.

[0013] DE 10063951A1 describes a coolant for a cooling system in a fuel cell drive unit, containing orthosilicate ester as a corrosion inhibitor.

[0014] WO 2018 / 095759 relates to a coolant for a cooling system in an electric vehicle having a fuel cell and / or battery, based on alkylene glycol or a derivative thereof, comprising an additional corrosion inhibitor to improve corrosion protection in addition to a specific azole derivative.

[0015] US 8951689 describes a fuel cell system containing a coolant with an additive package. The ion exchange resin is prepared so that the adsorption of the additive on the ion exchange resin reaches saturation.

[0016] US 9587154 discloses a pretreated ion exchange resin in which at least 15% of the exchangeable groups are exchanged by at least one of ions, Lewis acids, or Lewis bases resulting from a heat transfer fluid component, based on the total number of exchangeable groups. The heat transfer fluid contains a corrosion inhibitor.

[0017] US 7344655 describes a fuel cell coolant containing a solution mixture of water and glycol as a base material and a rust inhibitor that functions to maintain the electrical conductivity of the coolant at a low level. Rust inhibitors include at least one of an alkaline ethanolamine additive and an acidic additive selected from the group consisting of triazole compounds, phosphoric acid compounds, and organic phosphoric acid compounds. US 7138199 relates to a coolant composition containing additives useful in fuel cells. The base composition is deionized water or a mixture of deionized water and a freezing point depressant. The additive package includes an organic corrosion inhibitor and a polymeric ion suppressor.

Prior Art Documents

Patent Documents

[0018]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

[0019] Pre-treated ion exchange resins, methods for maintaining low conductivity in heat transfer fluids, and methods for preparing pre-treated ion exchange resins are particularly disclosed. The pre-treated ion exchange resins may contain up to 100% of exchangeable groups, based on the total number of exchangeable groups, which are derived from treatment with a resin treatment fluid component having a pKa of 0 to 14 in an aqueous solution at 25°C, and which include at least one of ions, Brønsted acids, or Brønsted bases. In terms of performance requirements, various treated or untreated resins can be mixed and combined.

[0020] In some embodiments, a suitable resin treatment component may have a pKa of 0 to 14 in an aqueous solution at 25°C. In one embodiment, the resin treatment component may be a corrosion inhibitor and / or reducing agent. The corrosion inhibitor / reducing additive is a reagent that inhibits oxidation of the heat transfer fluid and prevents an increase in the electrical conductivity of the coolant composition, or a reagent that blocks ions eluting into the cooling system and prevents an increase in the electrical conductivity of the coolant composition. In some specific embodiments, the reducing agent may also be a corrosion inhibitor specific to ferrous metals and aluminum when released from the resin.

[0021] A method for producing a treated ion exchange resin is also disclosed, comprising contacting an anion and / or cation exchange resin with an aqueous treatment solution containing a resin treatment component having a pKa of 0 to 14 in an aqueous solution at 25°C for a period of time sufficient to exchange up to 100% of the exchangeable parts with the resin treatment component. A method for producing an anionic ion exchange resin that is resistant to high temperatures is also disclosed. [Brief explanation of the drawing]

[0022] The subject matter and merits of this disclosure will become clear when interpreted in conjunction with the accompanying drawings, taking into consideration the following detailed description. Throughout the accompanying drawings, the same reference numerals refer to the same parts.

[0023] [Figure 1] An exemplary chemical structure is shown, in accordance with the principles of this disclosure. [Figure 2] An exemplary chemical reaction in accordance with the principles of this disclosure is shown. [Figure 3] This document shows a photographic comparison of a substance treated with an ion exchange resin used in accordance with the principles of this disclosure, and a substance treated without such resin. [Figure 4] A photograph of a metal test specimen used in accordance with the principles of this disclosure is shown. [Figure 5] This photograph shows a comparison between a substance treated with an ion exchange resin used in accordance with the principles of this disclosure and a substance treated without using such a resin. [Figure 6] An illustrative schematic diagram is shown, in accordance with the principles of this disclosure. [Figure 7] An illustrative table is provided, including results obtained in accordance with the principles of this disclosure. [Modes for carrying out the invention]

[0024] Apparatus, method, and composition are disclosed. The composition may include a resin.

[0025] As used herein, the terms “heat transfer fluid” or “coolant” refer to a fluid capable of transferring and dissipating a certain amount of thermal energy from one location to another. In some embodiments, the heat transfer fluids disclosed may also be called antifreezes, as some of the heat transfer fluids can function as freezing point depressants. As used herein, the term “resin-treated fluid component” refers to reagents in aqueous solution used to treat, more specifically, precharge or pre-treat, ion exchange resins with reducing corrosion inhibitors and / or reagents. As used herein, water-glycol-based low conductivity heat transfer fluids may be used, which may contain inhibitors and / or corrosive salts commonly present when undeionized water is used in heat transfer fluid preparation. Furthermore, other means may be used to maintain the required purity of the coolant when undeionized water is used or when the heat transfer system is not specifically cleaned before use. For example, means for appropriately reducing the decomposition rate may be used and combined with means for removing ionic impurities. The alternatives described involve slowing the decomposition rate by removing oxygen from the circulating coolant, for example, by using a deoxidizing resin to remove dissolved oxygen or reduce the ionic species. Furthermore, means to maintain the required purity and corrosion prevention properties may be used with a pre-charged resin that has deoxidizing properties, which can also release corrosion inhibitors. From the user's perspective, this approach may allow the use of non-deionized water or less extensive system cleaning procedures in certain BEV and / or electrical system applications.

[0026] As used herein, the term "low conductivity" generally refers to an electrical conductivity of 200 μS / cm or less. In some embodiments, a suitable heat transfer fluid may have a conductivity of less than 150 μS / cm, while in some embodiments, a suitable heat transfer fluid may have a conductivity of less than 50 μS / cm. In other embodiments, a suitable heat transfer fluid may have an electrical conductivity of 0.02 μS / cm to 200 μS / cm or less. In some embodiments, the heat transfer fluid disclosed for use in fuel cells may have a conductivity of 0.2 μS / cm to 100 μS / cm. In some embodiments, the disclosed heat transfer fluid may have a conductivity of 0.05 to less than 50 μS / cm, while in some embodiments, the disclosed heat transfer fluid may have a conductivity of 0.05 to 25 μS / cm or less. In some embodiments, the disclosed heat transfer fluid may have an electrical conductivity of 0.05 to 10 μS / cm or less. In some embodiments, the disclosed heat transfer fluid may have an electrical conductivity of 0.05 to 5 μS / cm or less. The electrical conductivity of the disclosed heat transfer fluids can be measured using the test method described in ASTM D1125, namely, the "Standard Test Method for Electrical Conductivity and Resistivity of Water," or an equivalent method.

[0027] In some embodiments, the resin treatment components present in the pre-treated resin may be corrosion inhibitors and / or reducing agents. In some embodiments, pre-treated ion exchange resins, such as corrosion inhibitor and / or reducing agent-treated ion exchange resins, are produced by pre-treating the ion exchange resin with one or more of the above-described resin treatment components. In some embodiments, the resin treatment components may be corrosion inhibitors and / or reducing agents. In some embodiments, the disclosed corrosion inhibitor and / or reducing agent-treated ion exchange resins can be produced by contacting the ion exchange resin with an aqueous resin treatment fluid containing one or more treatment components, such as corrosion inhibitors and / or reducing agents. More specifically, the preparation device may include a supply container for supplying a solution containing a predetermined corrosion inhibitor and / or reducing reagent, a column or solution channel containing the ion exchange resin, a pump, and a recovery container. A flow meter can be used to control the pressure and absorption rate. It is recommended to use an inert material. The solution is passed through the ion exchange resin until no more additives are absorbed. The treatment results in the exchange of treatment components, such as inhibitors and / or reducing agents, on the ion-exchangeable resin using exchangeable groups. The resulting pre-treated ion-exchange resin, and in some embodiments, the corrosion inhibitor and / or reducing agent treated ion-exchange resin, can be washed with deionized water.

[0028] Suitable examples of ion exchange resins include anion exchange resins, cation exchange resins, mixed-bed ion exchange resins, and mixtures thereof. The selected ion exchange resin depends on the type of heat transfer fluid component used in the heat transfer fluid. Corrosion inhibitors and / or reducing agents, though used in the following discussion, should be understood as merely examples of the type of heat transfer fluid component suitable for use in the preparation and acquisition of treated ion exchange resins. Ion exchange resins suitable for use in the preparation of any of the pre-treated ion exchange resins disclosed herein generally have a polymer matrix and functional groups paired with exchangeable ionic forms. The exchangeable ionic forms are generally Na, depending on the type of ion exchange resin. + H + , OH -or Cl - It is one or more of these ions. These exchangeable ions are exchanged with ion species produced by one or more corrosion inhibitors and / or reducing agents present in the aqueous corrosion inhibitor treatment solution. These exchangeable ions are exchanged with any ion species produced by one or more corrosion inhibitors and / or reducing agents present in the aqueous inhibitor treatment solution, and optionally with ionic inhibitor species present in the corrosion inhibitor heat transfer fluid.

[0029] For example, when heat transfer fluid components such as corrosion inhibitors and / or reducing agents become negatively charged species in solution, the ion exchange resin should be a mixed bed resin, an anion exchange resin, or a mixture thereof. Commercially available anion exchange resins are typically in the form of OH - or Cl - In some embodiments, the selected anion exchange resin can be in the OH - form. Alternatively, when heat transfer fluid components such as corrosion inhibitors and / or reducing agents in the corrosion inhibitor heat transfer fluid become positively charged species in solution, a mixed bed resin, a cation exchange resin, or a mixture thereof should be used. Commercially available cation exchange resins are typically in the form of H + or Na + In some embodiments, the selected cation exchange resin can be in the H + form. In some embodiments, ion exchange resins in the form of Na + or Cl - are used only when treatment with an aqueous component solution, such as an aqueous corrosion inhibitor and / or reducing agent solution, will remove substantially all of the Na + or Cl - ions. For example, in some embodiments, ion exchange resins in the form of Na + or Cl -Various forms of ion exchange resins may be used. Examples of exemplary polymer matrices include polystyrene, polystyrene-styrene copolymer, polyacrylate, aromatic-substituted vinyl copolymer, polymethacrylate, phenol-formaldehyde, polyalkylamine, and combinations thereof. In some embodiments, the polymer matrix may be polystyrene-styrene copolymer, polyacrylate, or polymethacrylate, while in some embodiments, the polymer matrix may be styrene-divinylbenzene copolymer. Examples of exemplary functional groups in cationic ion exchange resins include sulfonic acid groups (-SO3H2) and carboxylic acid groups (e.g., -COOH, -(CH)=(CH)-COOH, etc.), and combinations thereof. Examples of exemplary functional groups in anion exchange resins include quaternary ammonium groups, e.g., benzyltrimethylammonium group (also called type I resin), benzyldimethylethanolammonium group (also called type II resin), trialkylbenzylammonium group (also called type I resin), or tertiary amine functional groups. In some embodiments, the functional group in the anion exchange resin may be trialkylbenzylammonium, trimethylbenzylammonium, or dimethyl-2-hydroxyethylbenzylammonium, while in some embodiments, the functional group in the anion exchange resin may be trialkylbenzylammonium.

[0030] Ion exchange resins can be classified into four distinct groups: strongly basic anion ("SBA"), weakly basic anion ("WBA"), strongly acidic cation ("SAC"), and weakly acidic cation ("WAC") ion exchange resins. Strongly basic anion and strongly acidic cation ion exchange resins strongly bind to their ionic counterions in solution via ionic interactions, while weakly acidic cation and weakly basic anion resins are typically in equilibrium with weakly basic ions, weakly acidic ions, Brønsted bases, and Brønsted acids in solution, respectively. The equilibrium constant K depends on the pKa and pKb values ​​of the functional groups bound to the resin matrix, as well as the pKa and pKb values ​​of the ionic species in solution. The pKa and pKb are bonded by the following equation: pKa+pKb=14 When reversible ion-exchange interactions with ion-exchangeable groups bonded to a resin are desired, ion-exchange resins, such as those containing weakly acidic cations (e.g., carboxylic acid (-COOH)) and / or weakly basic anions (e.g., tertiary amine (-NR3)), can be used in combination with weakly Brønsted acids or Brønsted bases present in the solution. For example, when a low concentration of a inhibitor containing a carboxylic acid functional group is required over time in a heat transfer fluid, a weakly basic anionic resin containing a tertiary amine group should be used. In this case, both the pKb and pKa of the functional groups bonded to the resin and the inhibitor in the solution are similar, thereby allowing the inhibitor in the solution to reach equilibrium. Ion-exchange resins are necessary to completely remove ions from the heat transfer fluid to SAC resins, such as those containing H-form sulfonic acid groups (-SO3H2), and SBA resins, such as those containing OH-form benzyltrimethylammonium groups.

[0031] An exemplary fuel cell coolant containing triazole and stabilized nonionic organic silicate derivatives was used. Strongly acidic cations and strongly basic anionic resins in their original H and OH forms were used in various anion / cation ratios. To simulate glycol oxidation conditions during operation, experiments were repeated in which a specific amount of glycolic acid (20 mg) was added to the exemplary fuel cell coolant. The total amount of resin was kept constant.

[0032] In our applications, specifically in fuel cells and BEVs, the use of strong mixed-bed ion exchange resins can enable low electrical conductivity over time. Several common corrosion inhibitors in low-conductivity coolants, such as benzotriazole and silicates, have low pKa values. Therefore, by carefully selecting the type and ratio of anionic and cationic ion exchange resins, filtering of the inhibitor can be prevented, and corrosion performance can be maintained. Benzotriazole, with a pKa of 8.2, exhibits weakly acidic properties. Silicic acid, i.e., Si(OH)4, is even weaker than benzotriazole, based on its pKa of 9.51. Both substances can bind to strong anionic exchange resins in their hydroxide forms. Due to the weaker acidity of silicic acid, benzotriazole can bind when both substances are provided at the same concentration and the amount of resin does not deplete the amount of inhibitor. When other ions, such as glycolic acid, are provided due to the oxidation of glycol, ions with stronger acidity, i.e., lower pKa, may replace benzotriazole and / or silicic acid, allowing the resin to release the corrosion inhibitor bound to it, and the resin may function as a semi-slow release inhibitor "depot".

[0033] Resin bonding properties do not depend solely on the pKa or pKb of the inhibitor in solution. SBA type II resins are less basic than SBA type I resins due to hydroxyethyl substitution with tetravalent nitrogen. This property results in benzotriazole or silicic acid weakly bonding to the resin or not bonding at all, leaving the corrosion inhibitor in the solution. Although not specifically shown here, low pKa values ​​and / or polyvalent ions (Fe) 3+ , Al 3+ Strongly acidic substances possessing these properties bond strongly and irreversibly to resins that are strongly anionic or strongly acidic.

[0034] In low-conductivity heat transfer environments, ion exchange resins function as a buffer for alkalinity. To operate the system within the appropriate pH range of 5.5–8.0, it is necessary to select a mixed-bed resin with a higher anion exchange resin ratio, resulting in a slightly basic or neutral environment. When using fuel cell or BEV heat transfer fluids containing benzotriazole and / or silicic acid derivatives as corrosion inhibitors, it is recommended to use type II strongly anionic resins, rather than type I, in hydroxide form. Therefore, different applications, particularly different heat transfer fluid technologies distinguished by the selection of corrosion inhibitors, may require different mixed-bed ion exchange resins or resin ratios for system and performance optimization. Results indicate that heat transfer fluids containing triazole and silicic acid derivatives can achieve best corrosion performance with type II strongly basic anionic mixed-bed resins, as the corrosion inhibitors are less likely to be filtered by the resin. This finding is particularly pronounced for silicic acids with low acidity. To ensure optimal corrosion performance, a mixed bed resin with an anion / cation ratio slightly greater than 1:1 molar equivalent may enable the lowest initial triazole concentration for yellow metal corrosion protection. The original low-conductivity heat transfer fluids contained 500 ppm benzotriazole ("BTZ") and 500 ppm tolyltriazole ("TTZ"). The original Si content was 100 ppm, as measured by inductively coupled plasma atomic emission spectroscopy ("ICP-OES"). [Table 1]

[0035] The ion exchange resin may be brought into contact with an aqueous treatment solution containing suitable resin treatment fluid components, such as corrosion inhibitors and / or reducing agents. It will be understood that other components, such as those described herein, may also be suitable for use. Suitable resin treatment components that can be used to produce pre-treated resins include any component that either forms ionic species or functions as a Brønsted acid or Brønsted base in an aqueous solution at 25°C. In some embodiments, suitable resin treatment fluid components may have a pKa of 2 to 12 in an aqueous solution at 25°C. In some embodiments, suitable resin treatment fluid components may have a pKa of less than 2 to 12 in an aqueous solution at 25°C. An example of a suitable resin treatment fluid component is a treatment corrosion inhibitor and / or reducing agent. Suitable treatment inhibitors and / or reducing agents for use in an aqueous treatment solution of the inhibitor include alcohols, or mixtures of one or more alcohols and water, or weakly ionic corrosion inhibitors that are soluble or dispersible only in water. In some embodiments, a suitable corrosion inhibitor for use as a treatment inhibitor may have a pKa value equal to or greater than 2 if it is a Brønsted acid in aqueous solution at 25°C. In some embodiments, a suitable treatment inhibitor may have a pKa value of 2 to 12. In some embodiments, a suitable acidic treatment inhibitor may have a pKa value of 2 to less than 12. If the treatment inhibitor is a Brønsted base, the pKb value of the suitable treatment inhibitor must be equal to or greater than 5 in aqueous solution at 25°C. In some embodiments, a suitable Brønsted basic treatment inhibitor may have a pKb value of 5 to 12. In some embodiments, a suitable Brønsted basic treatment inhibitor may have a pKb value of 5 to less than 12. In some embodiments, a suitable treatment inhibitor may have good stability in a mixture of alcohol and water under system operating conditions, i.e., typically at temperatures of about 40°C to about 100°C. In some embodiments, the treatment component, such as the treatment inhibitor, may contain at least a minimum number of functional groups that can form ionic species by hydrolysis in aqueous alcohol or alkylene glycol solution.In some embodiments, the treatment inhibitor may contain 1 to 10 ion-forming functional groups per molecule of the treatment inhibitor. In some embodiments, the treatment inhibitor may contain 1 to 5 ion-forming functional groups per molecule of the treatment inhibitor. Exemplary ion-forming functional groups may be selected from the group consisting of amine groups, heterocyclic aromatic groups, other N-containing groups, carboxylic acid groups, phosphoric acid groups, phosphite groups, hypophosphite groups, and sulfite groups, or from their sodium and potassium salts.

[0036] The aqueous inhibitor solution used to prepare corrosion inhibitor and / or reducing agent-treated ion exchange resins generally contains the above-mentioned treatment inhibitor at a concentration of at least 10,000 ppm. In some embodiments, the aqueous inhibitor solution may have a concentration of 1% to 90% by weight, while in some embodiments, the aqueous inhibitor solution may have a concentration of 2% to 10% by weight. In some embodiments, the aqueous inhibitor solution may be prepared with deionized water.

[0037] Pre-treated ion exchange resin may contain a treatment inhibitor. The treatment inhibitor may contain a reducing phosphorus compound. Examples of phosphorus compounds include H-PO(OH) n (OR) m Phosphorous acid, hypophosphorous acid, or organophosphorus compounds containing the structure, such as phosphonic acid esters, may be used, where R can be an alkyl, hydroxyalkyl, or aryl group, n and m can be 0-2, and n+m can be 2. Phosphonic acids and their esters may also function as antioxidants that bind to the pre-treated resin, potentially delaying glycol degradation. Monosodium or disodium, or monopotassium or dipotassium salts of the corresponding acids may also be used as resin treatment components. Phosphorus compounds typically bind strongly to SBA ion exchange resins. Nevertheless, phosphorus compounds may be released from the pre-treated resin by more strongly binding corrosive ions, such as sulfate or carbonate ions. When using corrosive water containing chloride as a heat transfer fluid, untreated mixed-bed ion exchange resin may be included to selectively bind to the chloride.

[0038] In some embodiments, the treatment inhibitor may include an amine. Specifically, a hydrazine derivative represented by the general formula R2N-NR2, or a carbohydrazide derivative represented by the general formula (R2N-NH)C=O(HN-NR2), may be used, where R can be -H, a C1-C6 alkyl, or an alkenyl. All derivatives can be symmetrically or asymmetrically substituted. R=-H may be one embodiment. When the hydrazine derivative reacts with oxygen, nitrogen and water may be released as oxidation byproducts. Therefore, hydrazine oxidation with oxygen can create its own inert atmosphere, thus avoiding the oxidation of glycol. In some cases, the use of a catalyst is recommended to enable the deoxidation reaction at ambient temperature.

[0039] Because hydrazine and its derivatives are basic, they bind to strongly acidic cationic resins in their H form. When the hydrazine derivative bound to the resin reacts with oxygen, nitrogen may be released, and the resin may return to its original state. Therefore, depending on the oxygen removal requirements and operating conditions, it is practical to frequently inject small amounts of hydrazine solution into the resin filter container. The term "operating conditions" may refer to the time when the pre-treated ion exchange resin comes into contact with the coolant.

[0040] Anthraquinone derivatives are known for their catalytic reduction / oxidation ("RedOx") properties and play a crucial role in chemical synthesis and energy storage, for example, in anthraquinone processes for hydrogen peroxide production, in the paper industry, in anthraquinone flow batteries described in WO 2015 / 048550 and EP 4106060, and in Soda QA processes using Fischer solutions, i.e., aqueous solutions of potassium hydroxide, sodium hydrosulfite, and sodium anthraquinone β-sulfonate, to remove oxygen from gas streams. Anthraquinone derivatives function as catalysts. Anthraquinone can be reduced to anthrahydroquinone derivatives by a reducing agent bonded to a resin. The anthrahydroquinone can then reduce ionic species to alcohol, preventing an increase in electrical conductivity. Alternatively, anthrahydroquinone can simply reduce oxygen to water, preventing corrosion. Anthraquinone or benzoquinone does not necessarily need to be charged, but it must be soluble in the heat transfer medium. The catalyst derivative may have the following structure (Figure 1).

[0041] [ka] In the formula, X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , and X 8 R can be independently selected from the group consisting of hydrogen atoms, halogen atoms, ether groups of the general formula -OR, linear, cyclic, or branched, saturated or unsaturated, optionally substituted hydrocarbon groups containing 1 to 10 carbon atoms, -OH groups, -NR2 groups, -SO3H groups, or -COOH carboxylic acid groups, or salts thereof. R may represent linear, cyclic, or branched, saturated or unsaturated, optionally substituted hydrocarbon groups containing 1 to 10 carbon atoms. R may also represent a hydrogen radical. Pyrogallol and catechol can also be used as catalysts.

[0042] Pre-treated ion exchange resins for corrosion prevention are provided. The pre-treated ion exchange resin may contain components. The components may be configured to undergo a change in oxidation state when the resin comes into contact with a heat transfer fluid. The components may be acidic phosphorus components. The acidic phosphorus components may be configured to undergo a change in oxidation state when the resin comes into contact with a heat transfer fluid. The components may be acidic or basic nitrogen components. The acidic or basic nitrogen components may be configured to undergo a change in oxidation state when the resin comes into contact with a heat transfer fluid. The components may be acidic sulfur components. The acidic sulfur components may be configured to undergo a change in oxidation state when the resin comes into contact with a heat transfer fluid. The components may be a mixture of two or more of the acidic phosphorus components, acidic or basic nitrogen components, and acidic sulfur components.

[0043] Pre-treated ion exchange resin may exist as a set of beads. A set of beads may contain untreated resin. Pre-treated ion exchange resin may exist as a first set of beads. A first set of beads may exist in a mixture. A mixture may contain a first set of beads and a second set of beads. The second set of beads may not contain pre-treated ion exchange resin.

[0044] The pre-treated ion exchange resin may contain a heat transfer fluid. Examples of heat transfer fluids include water. Examples of heat transfer fluids include glycol-based freezing point depressants. Examples of heat transfer fluids include a mixture of water and a glycol-based freezing point depressant. The glycol-based freezing point depressant may be ethylene glycol. The glycol-based freezing point depressant may be propylene glycol. The glycol-based freezing point depressant may be 1,3-propanediol. The glycol-based freezing point depressant may be a mixture of two or more of ethylene glycol, propylene glycol, and 1,3-propanediol.

[0045] The pre-treated ion exchange resin may be a basic anion exchange resin. The pre-treated ion exchange resin may be an acidic cation exchange resin. The pre-treated ion exchange resin may be a mixture of a basic anion exchange resin and an acidic cation exchange resin.

[0046] Pre-treated ion exchange resin may be present in the container. The container may be configured to receive a heat transfer fluid from a closed liquid heat transfer circuit. The container may be configured to supply a heat transfer fluid to a closed liquid heat transfer circuit. The container may be configured to receive a heat transfer fluid from a closed liquid heat transfer circuit and to supply a heat transfer fluid to a closed liquid heat transfer circuit.

[0047] The pre-treated ion-exchange resin may contain ion-exchangeable groups. The ion-exchangeable groups may contain one or more ions. The ion-exchangeable groups may contain one or more Brønsted acids. The ion-exchangeable groups may contain one or more Brønsted bases. The ion-exchangeable groups can be selected from ions, Brønsted acids, and Brønsted bases. At least one of the ion-exchangeable groups may have reducing properties.

[0048] Pre-treated ion exchange resins can be produced by reaction with aqueous solutions. Aqueous solutions may have a pKa of 0-14. Aqueous solutions may have a pKa of 0-12.

[0049] The aqueous solution may contain a treatment corrosion inhibitor. The treatment corrosion inhibitor may contain a phosphorus component. The phosphorus component may be phosphorous acid and / or its salts. The phosphorus component may be hypophosphorous acid and / or its salts. The phosphorus component may be an organophosphorus compound and / or its salts. The phosphorus component may be a phosphonic acid ester and / or its salts. The phosphorus component may be a mixture of two or more of phosphorous acid and / or its salts, hypophosphorous acid and / or its salts, organophosphorus compounds and / or their salts, and phosphonic acid esters and / or their salts. The phosphorus component may be H-PO(OH) n (OR) m The structure may include R, which can be selected from alkyl, hydroxyalkyl, and aryl groups. n and m can independently be 0 to 2. n+m can be 2.

[0050] Examples of pre-treated ion exchange resins include SBA ion exchange resins. SBA ion exchange resins contain HPO3 groups that can exchange phosphite ions. 2- It may include the following. When the pre-treated ion exchange resin comes into contact with the coolant, the phosphite ion exchangeable groups may have temperature stability up to 100°C.

[0051] The aqueous solution may contain a treatment corrosion inhibitor. The treatment corrosion inhibitor may contain a nitrogen component. The nitrogen component may be a hydrazine derivative represented by the general formula H2N-NH2. The nitrogen component may be a carbohydrazide derivative represented by the general formula (H2N-NH)C=O(HN-NH2). The nitrogen component may be a mixture of a hydrazine derivative represented by the general formula H2N-NH2 and a carbohydrazide derivative represented by the general formula (H2N-NH)C=O(HN-NH2).

[0052] The treatment corrosion inhibitor may contain a sulfur component. The sulfur component may be sulfurous acid and / or its salts. The sulfur component may be sulfite and / or its salts. The sulfur component may be bisulfite and / or its salts. The sulfur component may be metabisulfite and / or its salts. The sulfur component may be a mixture of two or more of sulfurous acid and / or its salts, sulfite and / or its salts, bisulfite and / or its salts, and metabisulfite and / or its salts.

[0053] The heat transfer fluid may contain a RedOx catalyst. The RedOx catalyst may be an anthraquinone derivative. The RedOx catalyst may be a benzoquinone derivative. The RedOx catalyst may be catechol. The RedOx catalyst may be pyrogallol. The RedOx catalyst may be a mixture of two or more of the anthraquinone derivative, the benzoquinone derivative, catechol, and catechol.

[0054] Examples of pre-treated ion exchange resins include SBA II type ion exchange resins in hydroxide form. The heat transfer fluid may contain a triazole-based corrosion inhibitor. The heat transfer fluid may contain an organic silicate derivative. The heat transfer fluid may contain a triazole-based corrosion inhibitor and an organic silicate derivative.

[0055] The heat transfer fluid may have a conductivity of less than approximately 200 μS / cm. The heat transfer fluid may have a conductivity of approximately 0.5 to approximately 10 μS / cm.

[0056] The aqueous solution may contain a fluid corrosion inhibitor. The fluid corrosion inhibitor may be reversibly bonded to the pre-treated ion exchange resin.

[0057] Pre-treated ion exchange resin may be present in the resin compound. More than 15% of the compound may be pre-treated ion exchange resin. More than 25% of the compound may be pre-treated ion exchange resin.

[0058] The heat transfer fluid may not contain corrosion-preventive components. The heat transfer fluid may be a low-conductivity heat transfer fluid.

[0059] A method for preparing a pre-treated ion exchange resin may be provided. The method may include contacting the ion exchange resin with an aqueous treatment solution. The aqueous treatment solution may contain a corrosion inhibitor. The method may include contacting the ion exchange resin with the aqueous treatment solution containing the corrosion inhibitor until the absorption rate of the corrosion inhibitor into the ion exchange resin decreases to nearly zero.

[0060] In some embodiments, the treatment inhibitor may include sulfites, bisulfites, metabisulfites, or mixtures thereof. 3,3'-thiodipropionic acid, 2,2'-thiodiglycolic acid, and thioglycolates are also suitable because they are reducing agents and can bind to anion-exchange resins through ionic interactions. Sulfur-containing reagents bound to the resin can function as antioxidants / reducing agents and can slow glycol degradation. Bisulfites are also known to undergo addition reactions with aldehydes or ketones to form so-called hydrogen sulfite adducts, where the sulfur of the hydrogen sulfite ion binds to the carbonyl group to form a hydroxyalkyl sulfone. In addition to the reducing properties of sulfites, this reaction mechanism can trap aldehydes and prevent further oxidation of the aldehyde to acid. This acid can lead to increased conductivity and corrosion. Sulfite and sulfate ions generated in situ from the oxidation process are corrosive when released from the resin. Therefore, due to their anticorrosive properties, phosphorus compounds may be preferred over inorganic sulfur reagents.

[0061] In some embodiments, the treatment inhibitor may include an azole compound. Suitable azole compounds may be five-membered heterocyclic compounds having 1 to 4 nitrogen atoms. Examples include imidazoles, triazoles, thiazoles, and tetrazoles (e.g., benzotriazole, tolyltriazole, alkylbenzotriazoles (e.g., 4-methylbenzotriazole, 5-methylbenzotriazole, and butylbenzotriazole, etc.), benzimidazole, halobenzotriazole (e.g., chloro-methylbenzotriazole), tetrazole, substituted tetrazole, thiazole (e.g., 2-mercaptobenzothiazole, etc.)). In some embodiments, the azole compound may be benzotriazole, tolyltriazole, mercaptobenzothiazole, or a mixture thereof. Azole compounds are non-reducing. Nevertheless, due to their weak resin-binding properties, triazole-treated resins may be used in place of untreated anionic and / or mixed-bed resins. Because benzotriazole exhibits weak basicity, it can bind to SAC ion-exchange resins. Nevertheless, because benzotriazole is more acidic, it can bind more strongly to SBA ion exchange resin. When benzotriazole-pretreated mixed bed resin is exposed to corrosive water containing chloride, sulfuric acid, and sodium carbonate salts, the aqueous solution may be deionized, benzotriazole may be released into the solution, and a pH neutral solution is obtained. When benzotriazole-pretreated SAC ion exchange resin is exposed to corrosive water, the present cations may release benzotriazole, causing a decrease in pH and resulting in a corrosive environment. An increase in pH can be caused by benzotriazole-treated SBA ion exchange resin.

[0062] For low-conductivity coolant applications, SBA exchange resins can be used in hydroxide form. Quaternary ammonium salts readily undergo Hoffmann elimination in the presence of hydroxide counterions. The strong basicity of the hydroxide facilitates the elimination reaction. The elimination reaction is catalyzed by heat, yielding ammonia and alkenes (see Figure 2). Hoffmann-amine decomposition has historically been an important method for elucidating the structures of nitrogen-derived natural products (alkaloids).

[0063] In anesthesiology, Hoffmann withdrawal is important in relation to the inactivation of certain muscle relaxants postoperatively.

[0064] When the quaternary ammonium function on the resin is lost, the strongly basic anion exchange resin loses its functionality to bind to ionic substances. The resin may also darken and emit an ammonia odor. Ammonia can also increase the pH, potentially causing other degrading side effects in the heat transfer system. When the hydroxide is replaced with a less basic anion, such as the phosphite anion mentioned above, Hoffmann elimination may be hindered, and the strongly basic anion resin may be exposed to high temperatures during operation. The advantage of replacing the hydroxide with a phosphite anion can be demonstrated by the fact that the color of the pre-treated resin remains unchanged. Compared to the original strongly basic anion exchange resin, no ammonia odor was also observed in deionized water after storage at 90°C. The color of the untreated strongly basic anion exchange resin changed from yellow to dark brown (see Figure 3 and Table 2, 3g of basic NEW). This effect is not limited to solution. In a container, "dried" SBA resin in OH form, stored at 50°C, rapidly generates a strong ammonia odor, while phosphite-form strongly basic anionic resins and benzotriazole-treated resins do not generate an ammonia odor (see Figure 3 and Table 2, 3g basic + Na2HPO3). [Table 2]

[0065] To test corrosion protection, pre-screened ASTM carbon steel specimens were immersed in 100 mL of ASTM 1384 corrosive water ("CW") and 3 g of pre-treated ion exchange resin was added. The corrosive water contained 148 ppm sodium sulfate, 165 ppm sodium chloride, and 138 ppm bicarbonate, with corrosive anions at 100 ppm each. The specimens were stored in a 33% glycol solution at 55°C for 3 days. The appearance of the specimens and solution was evaluated visually (see Figures 3-5) and by ion chromatography ("IC"). Deionized water and deionized water on 3 g of mixed bed resin were included as reference. Hydrogen phosphate pre-treated resin was also included in the screening. The table below (Table 3) shows that the pre-treated resin can protect ordinary carbon steel under corrosive conditions. Chlorides derived from corrosive water are not nucleophilic enough to replace phosphites in pre-treated resins. On the other hand, sodium can replace hydrazine derivatives in strongly acidic cationic resins. When using phosphite-pre-treated resins in combination with corrosive water, it is therefore recommended to use a combination of pre-treated and untreated resins, or a combination with triazole-pre-treated resins. When carbohydrazide-pre-treated resins were used, the test specimens had the appearance of "blue steel." Steel corrosion is susceptible to pH. Phosphite, i.e., HPO3 2- The pre-treated resin yielded optimal results. Carbon steel was chosen due to its tendency to corrode. Low-conductivity cooling systems can use stainless steel, aluminum, and copper, which are less likely to corrode.

[0066] [Table 3]

[0067] The disclosed pre-treated ion exchange resin is advantageous in that it can remove ionic species from the heat transfer fluid and maintain low conductivity. The composition may include a pre-treated ion exchange resin that maintains the low electrical conductivity of the coolant composition. The anticorrosive and deoxidizing, exchangeable ions suppress oxidation of the heat transfer fluid and prevent the elution of ions into the cooling system, thus preventing an increase in the conductivity of the coolant composition. Therefore, the pre-treated ion exchange resin maintains the low conductivity of the coolant composition over a long period. The pre-treated ion exchange resin thus enables the use of unprotected heat transfer fluids in alternative power source heat transfer systems while maintaining the low electrical conductivity of the heat transfer fluid.

[0068] In some embodiments, the disclosed pre-treated ion exchange resins may be used in cooling systems, particularly in fuel cell or BEV cooling systems. Exemplary types of suitable fuel cells include PEM fuel cells. However, it will be understood that the disclosed pre-treated ion exchange resins, and the heat transfer fluids that pass through such resins and maintain low conductivity, may be used in applications other than fuel cells or BEVs that require a heat transfer fluid. Suitable applications include cooling systems that require a low-conductivity heat transfer fluid. [Examples]

[0069] Example 1 The performance of the treated resin was evaluated using a modified ASTM 1384 compared to a standard ASTM corrosive aqueous solution in 33% glycol. Metal specimens (carbon steel, aluminum, copper, and brass) were prepared according to ASTM 1384. The yellow metal specimens were non-conductively connected to the carbon steel and aluminum specimens by plastic bolts with nuts and Teflon® washers, and placed in two Teflon® stands in a 1 L beaker equipped with ground glass joints and glass covers. Copper, brass, carbon steel, and aluminum were connected conductively, respectively. 750 mL of ASTM corrosive aqueous solution was then introduced. The initial electrical conductivity of the ASTM corrosive aqueous solution was 260 μS / cm. A filter bag containing 11.0 g of pre-treated resin was placed in the solution, and the solution was heated to 45°C at an airflow rate of 100 ± 10 mL / min for 14 days. pH, conductivity, and metal loss / visual inspection were evaluated before and after the test. ASTM D8485-23 "Corrosion Test of Electric Vehicle Coolant in Glassware" was also used, but no clear results were obtained due to the less severe conditions (stainless steel, aluminum, and transport fluids with low conductivity).

[0070] A means of maintaining the desired purity of the heat transfer fluid is to incorporate ion exchange resin into a circulating loop defining the flow path of the heat transfer fluid, and to incorporate ion exchange resin into a filter cartridge placed in the flow path so that the heat transfer fluid always flows through the ion exchange resin. The ion exchange filter cartridge needs to be located at the lowest temperature point in the circulating loop and, if necessary, need to be easily accessible for replacement. The filter cartridge may consist of a filter packaging material containing ion exchange resin beads. For efficient ion removal, a mixed-bed filter may be used. Separating the anion exchange resin and the cation exchange resin into separate filter cartridges may allow for easier regeneration of the resin when reuse is advantageous.

[0071] The size and particle size distribution of the beads, e.g., monodisperse and heterodisperse, determine the pressure drop, pump dimensional requirements, and ion exchange capacity. The amount of ion exchange resin, and therefore the size of the filter, can be determined by the volume of the heat transfer fluid, the initial contamination of the circulation loop, and the initial ion concentration of the water used to fill the circulation loop system. Since glycol decomposition becomes more severe at higher temperatures and during frequent hot-cold cycles, the size of the filter, and in particular the performance of the required resin, can be determined by the operating conditions.

[0072] The circulating loop can be thermally connected in any configuration that allows heat to be generated by an exothermic reaction. Examples of such configurations include fuel cells, battery systems, electric converters, electric inverters, generators, power electronics, and electrical devices. Different configurations and systems have different electrical conductivity requirements, which may necessitate different combinations of ion exchange resins and filter sizes.

[0073] The results in the table below (Table 4) and Figures 3-7 show that the ionic species were removed from the corrosive aqueous solution, and that the pre-treated ion exchange resin was able to protect the metal even under galvanic conditions. When triazole-pre-treated resin was used, triazole was detected in the heat transfer solution after the test. The test solution became clear after the test.

[0074] Figure 4 shows photographs of three metal test specimens treated with resin (1), i.e., untreated ion exchange resin, on the right, and three metal test specimens treated with load resin (2), i.e., pre-treated ion exchange resin, on the left.

[0075] Table 4 shows the results corresponding to metal test specimens treated with resin (1) and metal test specimens treated with load resin (2). [Table 4]

[0076] Figure 5 shows (a) a metal specimen 502 treated with a preventive fuel cell ("FC") coolant in monoethylene glycol ("MEG") and deionized water ("DI water") liquid 504 (darkest color) on the left, (b) a metal specimen 502 treated with resin (i.e., untreated ion exchange resin) in a resin bag 506 in MEG / DI water liquid 504 (somewhat dark color) on the center, and (c) a metal specimen 502 treated with load resin (i.e., pretreated ion exchange resin) in a resin bag 506 in MEG / DI water liquid 504 (lightest color / most transparent) on the right.

[0077] Figure 6 shows an exemplary ion exchange resin unit. The ion exchange resin unit may include electronic components 604. Electronic components 604, such as a fuel cell stack, battery, and AC / DC converter, may supply power to the ion exchange resin unit. The ion exchange resin unit may include a pump 606. The ion exchange resin unit may include a radiator 608. The ion exchange resin unit may include a replaceable filter 602. The replaceable filter 602 may be filled with an inhibitor / antioxidant ion exchange resin. Electronic components 604 may drive the pump 606. The pump 606 may push the coolant through the radiator 608. The coolant may flow through the filter housing. The filter housing may contain a replaceable filter 602. The coolant may flow through a closed loop.

[0078] Figure 7 shows a table containing results obtained in accordance with the principles of this disclosure.

[0079] In some embodiments, features shown or described in relation to the exemplary apparatus may be omitted. Some embodiments may have features not shown or described in relation to the exemplary apparatus. Features of the exemplary apparatus may be combined. For example, one exemplary embodiment may have features shown in relation to another exemplary embodiment.

[0080] Embodiments may include some or all of the features of the exemplary apparatus, or some or all of the steps of the exemplary method.

[0081] Exemplary apparatuses and methods are described herein with reference to the accompanying drawings, which form part of this specification. Other embodiments are available, and structural, functional, and procedural improvements can be made without departing from the scope and spirit of this disclosure.

[0082] Figure 1 shows an exemplary chemical structure in accordance with the principles of this disclosure.

[0083] Figure 2 shows an exemplary chemical reaction in accordance with the principles of this disclosure.

[0084] Figure 3 is a photograph showing a comparison between a substance treated with an ion exchange resin according to the principle of this disclosure and a substance treated without using such a resin.

[0085] Figure 4 shows a photograph of a metal test specimen used in accordance with the principles of this disclosure.

[0086] Figure 5 is a photograph showing a comparison between a substance treated with an ion exchange resin used in accordance with the principles of this disclosure and a substance treated without using such an ion exchange resin.

[0087] Figure 6 shows an exemplary schematic diagram in accordance with the principles of this disclosure.

[0088] Figure 7 shows an exemplary table, including results obtained in accordance with the principles of this disclosure.

[0089] As will be understood by those skilled in the art, the methods and apparatus described herein or referred to herein may be embodied, in whole or in part, by method, apparatus, or product-by-process.

[0090] All ranges and parameters disclosed herein should be understood to encompass all subranges, all numbers between endpoints, and endpoints contained therein. For example, the stated range "1 to 10" should be understood to include any subrange between (and including) the minimum value 1 and the maximum value 10, i.e., all subranges beginning with a minimum value greater than or equal to 1 (e.g., 1 to 6.1) and ending with a maximum value less than or equal to 10 (e.g., 2.3 to 9.4, 3 to 8, 4 to 7), and ultimately, each of the digits 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 contained within the range.

[0091] Accordingly, apparatus and methods for pre-treated ion exchange resins, as well as alternative power sources such as heat transfer systems, fuel cells and battery systems, and their use in assemblies including such power sources are provided. Those skilled in the art will understand that the present invention can be implemented in embodiments other than those described, which are presented for illustrative purposes only and not limitation, and that the present invention is limited only by the following claims. The present invention provides, for example, the following items: (Item 1) A pre-treated ion exchange resin for corrosion prevention, (a) The resin has an acidic phosphorus component configured to undergo a change in oxidation state when it comes into contact with a heat transfer fluid, (b) an acidic or basic nitrogen component configured to undergo a change in oxidation state when the resin comes into contact with the heat transfer fluid, (c) The resin is configured to undergo a change in oxidation state when it comes into contact with the heat transfer fluid, (d) A pre-treated ion exchange resin for corrosion prevention comprising a mixture of two or more of (a) to (c) and a component selected from the group consisting of (a) to (c). (Item 2) The ion exchange resin is the pre-treated ion exchange resin described in item 1, which exists as a set of beads. (Item 3) The beads are pre-treated ion exchange resins as described in item 2, including untreated resin. (Item 4) The aforementioned pre-treated ion exchange resin exists as a set of first beads, The first set of beads is, The first set of beads and, It is present in the mixture containing the second set of beads, The second set of beads is the pre-treated ion exchange resin described in item 1, which does not include the pre-treated ion exchange resin. (Item 5) The heat transfer fluid comprises a mixture of water and a glycol-based freezing point depressant. The glycol-based coagulation point depressant is (a) Ethylene glycol and (b) Propylene glycol and (c) 1,3-propanediol and (d) A pre-treated ion exchange resin as described in item 1, selected from the group consisting of two or more mixtures of (a) to (c). (Item 6) The aforementioned pre-treated ion exchange resin is Basic anion exchange resin, Acidic cation exchange resin, and A pre-treated ion exchange resin as described in item 1, selected from the group consisting of a mixture of a basic anion exchange resin and an acidic cation exchange resin. (Item 7) The pre-treated ion exchange resin described in item 1 is located in a container configured to receive the heat transfer fluid from a closed liquid heat transfer circuit and to supply the heat transfer fluid to the closed liquid heat transfer circuit. (Item 8) The aforementioned pre-treated ion exchange resin contains ion-exchangeable groups, The aforementioned ion-exchangeable group is, ion, Brønsted acid, and Selected from Brønsted bases, The pre-treated ion exchange resin according to item 1, wherein at least one of the ion-exchangeable groups is reducing. (Item 9) The pre-treated ion exchange resin is the pre-treated ion exchange resin described in item 8, which is produced by a reaction with an aqueous solution having a pKa of 0 to 14. (Item 10) The aqueous solution is a pre-treated ion exchange resin as described in item 9, having a pKa of 2 to 12. (Item 11) The aqueous solution contains a treatment corrosion inhibitor. The aforementioned treatment corrosion inhibitor contains a phosphorus component. The aforementioned phosphorus component is (a) Phosphite and / or salts thereof, (b) hypophosphorous acid and / or salts thereof (c) Organophosphorus compounds and / or salts thereof, (d) Phosphonic acid esters and / or salts thereof, (e) Selected from the group consisting of two or more mixtures of (a) to (d), The aforementioned phosphorus component is H-PO(OH) n (OR) m Including structure, R is selected from alkyl, hydroxyalkyl, and aryl groups. n and m are between 0 and 2. n+m is 2, pre-treated ion exchange resin as described in item 9. (Item 12) The aforementioned pre-treated ion exchange resin includes a strongly basic anion ("SBA") ion exchange resin. The aforementioned SBA ion exchange resin has a phosphite ion exchangeable group HPO3 2- Includes, The phosphite ion exchangeable group is the pre-treated ion exchange resin according to item 9, wherein the pre-treated ion exchange resin has temperature stability up to 100°C when the pre-treated ion exchange resin comes into contact with a coolant. (Item 13) The aqueous solution contains a treatment corrosion inhibitor. The aforementioned treatment corrosion inhibitor contains a nitrogen component, The aforementioned nitrogen component is (a) Hydrazine derivatives represented by the general formula H2N-NH2, (b) Carbohydrazide derivatives represented by the general formula (H2N-NH)C=O(HN-NH2), and (c) A pre-treated ion exchange resin as described in item 9, selected from the group consisting of (a) and (b). (Item 14) The aqueous solution contains a treatment corrosion inhibitor. The aforementioned treatment corrosion inhibitor contains a sulfur component, The aforementioned sulfur component is (a) Sulfites and / or salts thereof, (b) Sulfites and / or salts thereof (c) Bisulfite and / or salts thereof, (d) Metabisulfite and / or salts thereof, (e) A pre-treated ion exchange resin as described in item 9, selected from the group consisting of two or more mixtures of (a) to (d). (Item 15) The heat transfer fluid includes a reduction / oxidation ("RedOx") catalyst. The aforementioned RedOx catalyst is (a) Anthraquinone derivatives, (b) Benzoquinone derivatives, (c) Catechol, (d) Pyrogallol, and (e) A pre-treated ion exchange resin as described in item 1, selected from the group consisting of two or more mixtures of (a) to (d). (Item 16) A pre-treated ion exchange resin as described in item 1, comprising a hydroxide-form strongly basic anion ("SBA") type II ion exchange resin. (Item 17) The heat transfer fluid is Triazole-based corrosion inhibitors, and A pre-treated ion exchange resin as described in item 1, containing an organic silicate derivative. (Item 18) The heat transfer fluid is a pre-treated ion exchange resin as described in item 1, having a conductivity of less than approximately 200 μS / cm. (Item 19) The heat transfer fluid is a pre-treated ion exchange resin as described in the item, having a conductivity of approximately 0.5 to approximately 10 μS / cm. (Item 20) The pre-treated ion exchange resin according to item 9, wherein the aqueous solution contains a fluid corrosion inhibitor that reversibly binds to the pre-treated ion exchange resin. (Item 21) The aforementioned pre-treated ion exchange resin is present in the resin compound. The pre-treated ion exchange resin described in item 1, wherein 15% or more of the compound is a pre-treated ion exchange resin. (Item 22) The aforementioned pre-treated ion exchange resin is present in the resin compound. The pre-treated ion exchange resin described in item 1, wherein 25% or more of the compound is a pre-treated ion exchange resin. (Item 23) The heat transfer fluid is a pre-treated ion exchange resin as described in item 1, which does not contain corrosion-preventive components. (Item 24) The heat transfer fluid is a low-conductivity heat transfer fluid, and the pre-treated ion exchange resin is as described in item 1. (Item 25) A method for preparing a pre-treated ion exchange resin, The method comprising contacting the ion exchange resin with an aqueous treatment solution containing the corrosion inhibitor until the absorption rate of the corrosion inhibitor into the ion exchange resin decreases to nearly zero.

Claims

1. A pre-treated ion exchange resin for corrosion prevention, (a) The resin is configured to undergo a change in oxidation state when it comes into contact with the heat transfer fluid, (b) an acidic or basic nitrogen component configured to undergo a change in oxidation state when the resin comes into contact with the heat transfer fluid, (c) An acidic sulfur component configured such that the resin undergoes a change in oxidation state when it comes into contact with the heat transfer fluid, (d) A pre-treated ion exchange resin for corrosion prevention, comprising a mixture of two or more of (a) to (c) and a component selected from the group consisting of (a) to (c).

2. The ion exchange resin is a pre-treated ion exchange resin according to claim 1, wherein the ion exchange resin exists as a set of beads.

3. The pre-treated ion exchange resin according to claim 2, wherein the beads include an untreated resin.

4. The pre-treated ion exchange resin exists as a set of first beads, The first set of beads is The first set of beads, It is present in a mixture containing a second set of beads, The pre-treated ion exchange resin according to claim 1, wherein the second set of beads does not include the pre-treated ion exchange resin.

5. The heat transfer fluid comprises a mixture of water and a glycol-based freezing point depressant. The glycol-based coagulation point depressant is (a) Ethylene glycol and (b) Propylene glycol and (c) 1,3-propanediol and (d) A pre-treated ion exchange resin according to claim 1, selected from the group consisting of two or more mixtures of (a) to (c).

6. The aforementioned pre-treated ion exchange resin is Basic anion exchange resin, Acidic cation exchange resin, and A pre-treated ion exchange resin according to claim 1, selected from the group consisting of a mixture of a basic anion exchange resin and an acidic cation exchange resin.

7. The pre-treated ion exchange resin according to claim 1, wherein the pre-treated ion exchange resin is contained in a container configured to receive the heat transfer fluid from a closed liquid heat transfer circuit and to supply the heat transfer fluid to the closed liquid heat transfer circuit.

8. The aforementioned pre-treated ion exchange resin contains ion-exchangeable groups, The aforementioned ion-exchangeable group is, ion, Brønsted acid, and Selected from Brønsted bases, The pre-treated ion exchange resin according to claim 1, wherein at least one of the ion-exchangeable groups is reducing.

9. The pre-treated ion exchange resin is produced by a reaction with an aqueous solution having a pKa of 0 to 14, as described in claim 8.

10. The aqueous solution is a pre-treated ion exchange resin according to claim 9, having a pKa of 2 to 12.

11. The aqueous solution contains a treatment corrosion inhibitor. The aforementioned treatment corrosion inhibitor contains a phosphorus component. The aforementioned phosphorus component is (a) Phosphite and / or salts thereof, (b) Hypophosphorous acid and / or salts thereof (c) Organophosphorus compounds and / or salts thereof, (d) Phosphonic acid esters and / or salts thereof, (e) Selected from the group consisting of two or more mixtures of (a) to (d), The aforementioned phosphorus component is H-PO(OH) ｎ (OR) ｍ Including structure, R is selected from alkyl, hydroxyalkyl, and aryl groups. n and m are between 0 and 2. The pre-treated ion exchange resin according to claim 9, wherein n+m is 2.

12. The aforementioned pre-treated ion exchange resin includes a strongly basic anion ("SBA") ion exchange resin. The aforementioned SBA ion exchange resin is a group HPO that can exchange phosphite ions. ３ ２－ Includes, The pre-treated ion exchange resin according to claim 9, wherein the phosphite ion exchangeable group has temperature stability up to 100°C when the pre-treated ion exchange resin comes into contact with a coolant.

13. The aqueous solution contains a treatment corrosion inhibitor. The aforementioned treatment corrosion inhibitor contains a nitrogen component, The aforementioned nitrogen component is (a) General formula H ２ N-NH ２ Hydrazine derivatives represented by, (b) General formula (H ２ N-NH)C=O(HN-NH ２ Carbohydrazide derivatives represented by ) and (c) A pre-treated ion exchange resin according to claim 9, selected from the group consisting of (a) and (b).

14. The aqueous solution contains a treatment corrosion inhibitor. The aforementioned treatment corrosion inhibitor contains a sulfur component, The aforementioned sulfur component is (a) Sulfites and / or salts thereof, (b) Sulfites and / or salts thereof (c) Bisulfite and / or salts thereof, (d) Metabisulfite and / or salts thereof, (e) A pre-treated ion exchange resin according to claim 9, selected from the group consisting of two or more mixtures of (a) to (d).

15. The heat transfer fluid includes a reduction / oxidation ("RedOx") catalyst, The RedOx catalyst is (a) Anthraquinone derivatives, (b) Benzoquinone derivatives, (c) Catechol, (d) Pyrogallol, and (e) A pre-treated ion exchange resin according to claim 1, selected from the group consisting of two or more mixtures of (a) to (d).

16. The pre-treated ion exchange resin according to claim 1, comprising a hydroxide-form strongly basic anion ("SBA") type II ion exchange resin.

17. The heat transfer fluid is Triazole-based corrosion inhibitors, and A pre-treated ion exchange resin according to claim 1, comprising an organic silicate derivative.

18. The heat transfer fluid is a pre-treated ion exchange resin according to claim 1, wherein the heat transfer fluid has a conductivity of less than approximately 200 μS / cm.

19. The heat transfer fluid is a pre-treated ion exchange resin according to the claim, having a conductivity of about 0.5 to about 10 μS / cm.

20. The pre-treated ion exchange resin according to claim 9, wherein the aqueous solution contains a fluid corrosion inhibitor that reversibly binds to the pre-treated ion exchange resin.

21. The aforementioned pre-treated ion exchange resin is present in the resin compound. The pre-treated ion exchange resin according to claim 1, wherein 15% or more of the compound is a pre-treated ion exchange resin.

22. The aforementioned pre-treated ion exchange resin is present in the resin compound. The pre-treated ion exchange resin according to claim 1, wherein 25% or more of the compound is a pre-treated ion exchange resin.

23. The heat transfer fluid is a pre-treated ion exchange resin according to claim 1, wherein the heat transfer fluid does not contain corrosion-preventive components.

24. The pre-treated ion exchange resin according to claim 1, wherein the heat transfer fluid is a low-conductivity heat transfer fluid.

25. A method for preparing a pre-treated ion exchange resin, The method comprising contacting the ion exchange resin with an aqueous treatment solution containing the corrosion inhibitor until the absorption rate of the corrosion inhibitor into the ion exchange resin decreases to nearly zero.

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