阅读说明：本技术 稳定离子交换树脂的方法 (Method for stabilizing ion exchange resins ) 是由 G·巴赫曼 马蒂·威尔克斯 于 2019-02-12 设计创作，主要内容包括：提供了稳定原始离子交换树脂材料的方法。该方法包括用包含非离子型去污剂的制剂清洗原始离子交换树脂材料。该方法包括用包含醇溶剂的制剂清洗原始离子交换树脂材料。该方法包括用脱氧水冲洗原始离子交换树脂材料。该方法包括将清洗过的/冲洗过的原始离子交换树脂材料引入到气体不可渗透的器皿中,并且将该器皿气密地密封。该方法包括将氧清除材料引入到气体不可渗透的器皿中,并且将该器皿气密地密封。还公开了一种通过提供在脱氧水中的清洗过的原始离子交换树脂材料来促进有相应需要的场所处的水处理的方法。(Methods of stabilizing virgin ion exchange resin materials are provided. The method comprises washing a virgin ion exchange resin material with a formulation comprising a non-ionic detergent. The method includes washing a virgin ion exchange resin material with a formulation comprising an alcohol solvent. The method includes rinsing the virgin ion exchange resin material with deoxygenated water. The method includes introducing the cleaned/flushed virgin ion exchange resin material into a gas impermeable vessel and hermetically sealing the vessel. The method includes introducing an oxygen scavenging material into a gas impermeable vessel and hermetically sealing the vessel. A method of facilitating water treatment at a location where there is a corresponding need by providing a washed virgin ion exchange resin material in deoxygenated water is also disclosed.)

1. A method of stabilizing a virgin ion exchange resin material, the method comprising:

washing the virgin ion exchange resin material with a formulation comprising the non-ionic detergent at a concentration below the critical micelle concentration of the non-ionic detergent to produce a washed virgin ion exchange resin material;

introducing the cleaned virgin ion exchange resin material into a gas impermeable vessel; and

the vessel is hermetically sealed.

2. The method of claim 1, further comprising rinsing the cleaned virgin ion exchange resin material with deoxygenated water.

3. The method of claim 1, wherein the non-ionic detergent comprises at least one of ethoxylated octylphenol, polysorbate, polyoxyethylene, and metabolites thereof.

4. The method of claim 3, wherein the formulation comprises less than about 0.125g/L ethoxylated octylphenol.

5. The method of claim 1, comprising introducing the cleaned virgin ion exchange resin material into a liquid-impermeable container of the gas-impermeable vessel.

6. A method of stabilizing a virgin ion exchange resin material, the method comprising:

washing the virgin ion exchange resin material with a formulation comprising an alcoholic solvent to produce a washed virgin ion exchange resin material;

introducing the cleaned virgin ion exchange resin material into a gas impermeable vessel; and

the vessel is hermetically sealed.

7. The method of claim 6, further comprising rinsing the cleaned virgin ion exchange resin material with deoxygenated water.

8. The method of claim 6, wherein the alcohol solvent comprises at least one of isopropanol, methanol, ethanol, n-butanol, isooctanol, methyl isobutyl carbinol, isoamyl alcohol, isobutanol, cyclohexanol, methylcyclohexanol, and ammonia.

9. The method of claim 8, wherein the formulation comprises less than about 0.5% isopropanol.

10. The method of claim 5, comprising introducing the cleaned virgin ion exchange resin into a liquid-impermeable container of the gas-impermeable vessel.

11. A method of stabilizing a virgin ion exchange resin material, the method comprising:

washing the virgin ion exchange resin material with a formulation comprising the non-ionic detergent at a concentration below the critical micelle concentration of the non-ionic detergent to produce a washed virgin ion exchange resin material; and

rinsing the cleaned virgin ion exchange resin material with deoxygenated water to produce a rinsed virgin ion exchange resin material.

12. The method of claim 11, comprising rinsing the washed ion exchange resin material with deoxygenated water having a dissolved oxygen concentration of less than about 10 ppb.

13. The method of claim 11, wherein the non-ionic detergent comprises at least one of ethoxylated octylphenol, polysorbate, polyoxyethylene, and metabolites thereof.

14. The method of claim 11, further comprising introducing the washed virgin ion exchange resin material into a gas-impermeable vessel, and hermetically sealing the vessel.

15. A method of stabilizing a virgin ion exchange resin material, the method comprising:

washing the virgin ion exchange resin material with a formulation comprising an alcoholic solvent to produce a washed virgin ion exchange resin material; and

rinsing the cleaned virgin ion exchange resin material with deoxygenated water to produce a rinsed virgin ion exchange resin material.

16. The method of claim 15, comprising rinsing the washed ion exchange resin material with deoxygenated water having a dissolved oxygen concentration of less than about 10 ppb.

17. The method of claim 15, wherein the alcohol solvent comprises at least one of isopropanol, methanol, ethanol, n-butanol, isooctanol, methyl isobutyl carbinol, isoamyl alcohol, isobutanol, cyclohexanol, methylcyclohexanol, and ammonia.

18. The method of claim 15, further comprising introducing the washed virgin ion exchange resin material into a gas-impermeable vessel and hermetically sealing the vessel.

19. A method of facilitating water treatment at a site in need thereof, the method comprising:

providing a cleaned virgin ion exchange resin material in deoxygenated water,

the cleaned virgin ion exchange resin material is a polystyrene-based ion exchange resin material and has less than about 25ppb of oxidized total organic carbon species.

20. The method of claim 19, further comprising providing the cleaned virgin ion exchange resin material and deoxygenated water in a liquid-impermeable compartment of a hermetically sealed gas-impermeable vessel.

21. The method of claim 20, further comprising providing an oxygen scavenging material positioned between an outer wall of the liquid-impermeable compartment and an inner wall of the gas-impermeable vessel.

22. The method of claim 21, further comprising providing an indicator of oxygen contamination.

23. The method of claim 19, comprising providing the deoxygenated water in an amount between about 40% and about 50% of the cleaned virgin ion exchange resin material.

24. The method of claim 19, comprising providing the deoxygenated water with less than about 10ppb dissolved oxygen.

Technical Field

Aspects and embodiments disclosed herein relate to stabilization of virgin ion exchange resin materials. More specifically, the disclosed aspects and embodiments relate to methods of reducing the rate of oxidative degradation of virgin ion exchange resin materials. Aspects and embodiments disclosed relate to the handling, storage and transport of stabilized virgin ion exchange resin materials.

SUMMARY

According to one aspect, a method of stabilizing a virgin ion exchange resin material is provided. The method may include washing a virgin ion exchange resin material with a formulation comprising a non-ionic detergent to produce a washed virgin ion exchange resin material. The formulation may comprise a non-ionic detergent at a concentration below the Critical Micelle Concentration (CMC) of the non-ionic detergent. The method may include introducing the virgin ion exchange resin material into a gas impermeable vessel (vessel). The method may include hermetically sealing the vessel.

In some embodiments, the method may further comprise rinsing the washed virgin ion exchange resin material with deoxygenated water.

The non-ionic detergent may comprise at least one of ethoxylated octylphenol, polysorbate, polyoxyethylene and metabolites thereof.

According to certain embodiments, the formulation may comprise less than about 0.125g/L ethoxylated octylphenol.

The method may include introducing the cleaned virgin ion exchange resin material into a liquid impermeable container (container) of a gas impermeable vessel.

In another aspect, a method of stabilizing a virgin ion exchange resin material is provided. The method can include washing a virgin ion exchange resin material with a formulation comprising an alcohol solvent to produce a washed virgin ion exchange resin material. The method may include introducing the cleaned virgin ion exchange resin material into a gas impermeable vessel. The method may include hermetically sealing the vessel.

In some embodiments, the method may further comprise rinsing the cleaned virgin ion exchange resin material with deoxygenated water.

According to certain embodiments, the alcohol solvent may include at least one of isopropanol, methanol, ethanol, n-butanol, isooctanol, methyl isobutyl carbinol, isoamyl alcohol, isobutanol, cyclohexanol, methylcyclohexanol, and aqua ammonia.

The formulation may comprise less than about 0.5% isopropyl alcohol.

In some embodiments, the method can include introducing the cleaned virgin ion exchange resin into a liquid-impermeable container of a gas-impermeable vessel.

According to another aspect, a method of stabilizing a virgin ion exchange resin material is provided. The method may include washing a virgin ion exchange resin material with a formulation comprising a non-ionic detergent to produce a washed virgin ion exchange resin material. The formulation may comprise a non-ionic detergent at a concentration below the critical micelle concentration of the non-ionic detergent. The method can include rinsing the cleaned virgin ion exchange resin material with deoxygenated water to produce a rinsed virgin ion exchange resin material.

The method can include rinsing the washed ion exchange resin material with deoxygenated water having a dissolved oxygen concentration of less than about 10 ppb.

In some embodiments, the non-ionic detergent may comprise at least one of ethoxylated octylphenol, polysorbate, polyoxyethylene, and metabolites thereof.

The method may further include introducing the flushed virgin ion exchange resin material into a gas-impermeable vessel, and hermetically sealing the vessel.

According to another aspect, a method of stabilizing a virgin ion exchange resin material is provided. The method can include washing a virgin ion exchange resin material with a formulation comprising an alcohol solvent to produce a washed virgin ion exchange resin material. The method can include rinsing the cleaned virgin ion exchange resin material with deoxygenated water to produce a rinsed virgin ion exchange resin material.

In some embodiments, the method may include rinsing the washed ion exchange resin material with deoxygenated water having a dissolved oxygen concentration of less than about 10 ppb.

The alcohol solvent may include at least one of isopropanol, methanol, ethanol, n-butanol, isooctanol, methyl isobutyl carbinol, isoamyl alcohol, isobutanol, cyclohexanol, methylcyclohexanol, and ammonia.

The method may further include introducing the flushed virgin ion exchange resin material into a gas-impermeable vessel, and hermetically sealing the vessel.

According to another aspect, a method of facilitating water treatment at a site in need thereof is provided. The method can include providing a cleaned virgin ion exchange resin material in deoxygenated water. The cleaned virgin ion exchange resin material may be a polystyrene-based ion exchange resin material. The cleaned virgin ion exchange resin material may have less than about 25ppb of oxidized total organic carbon species (oxidized total organic carbon species).

In some embodiments, the method may further comprise providing the cleaned virgin ion exchange resin material and deoxygenated water in a liquid-impermeable compartment of a hermetically sealed gas-impermeable vessel.

The method may further include providing an oxygen scavenging material positioned between an outer wall of the liquid-impermeable compartment and an inner wall of the gas-impermeable vessel.

In some embodiments, the method may further comprise providing an indicator of oxygen contamination.

The method may include providing deoxygenated water in an amount between about 40% and about 50% of the washed virgin ion exchange resin material.

The method may include providing deoxygenated water having less than about 10ppb dissolved oxygen.

Brief Description of Drawings

The figures are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures is represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. In the drawings:

fig. 1 is a schematic illustration of a vessel according to embodiments disclosed herein;

fig. 2 is a schematic diagram of a system including a vessel according to embodiments disclosed herein;

fig. 3 is a schematic illustration of a vessel according to embodiments disclosed herein;

FIG. 4 is a graph of comparative amounts of oxidized total organic carbon (oxidized total organic carbon) on ion exchange resins after washing with multiple detergents according to one embodiment disclosed herein;

FIG. 5A is a graph of the concentration of total organic carbon oxidized on ion exchange resins after washing with different concentrations of percarbonate;

FIG. 5B is a graph of the concentration of total organic carbon oxidized on the ion exchange resin after washing with different concentrations of isopropanol; and

figure 5C is a graph of the concentration of total organic carbon oxidized on the ion exchange resin after washing with various concentrations of ethoxylated octylphenol.

Detailed description of the invention

Ion exchange resins can generally be used to separate components contained in a liquid mixture. Conventional ion exchange resins can be prepared by functionalizing a copolymer matrix with groups having both cationic and anionic sites. When the resin is contacted with a liquid mixture, the anion or cation may be capable of exchanging or associating with an ion or molecule of the same charge in the liquid. The ions are exchanged stoichiometrically, maintaining the electrical neutrality of the system. Resins that exchange one positive ion (or a proportional amount based on valence) such as hydrogen for another positive ion such as copper, iron or sodium are cationic resins. Resins that exchange one anion (or a proportional amount based on valence) such as hydroxide for another anion such as chloride, sulfate, or chromate are anionic resins. In many cases, both types of resins are used to remove various salts from solution, such as sodium chloride or calcium sulfate. Mixed bed ion exchange resins include a combination of cationic and anionic resins to provide treated water of higher purity. The resin may be used until it becomes saturated with the removed ions. Many resins can also be regenerated and reused. For example, the resin used in water treatment can be regenerated by using strong acids (for cationic resins) or strong bases (for anionic resins).

Ion exchange is commonly used for water treatment, where ions in an aqueous solution typically displace hydrogen (H) bound to a substrate, such as an ion exchange resin⁺) Ions Or Hydroxides (OH)^-) Ions. This is sometimes referred to as "water desalination" or "water deionization". Ion exchange resins can be used in general in fields such as water purification, nuclear power generation, microelectronics manufacturing, semiconductor manufacturing, food processing, pharmaceuticals, chemical processing, and metal extraction.

Under certain conditions, the ion exchange resin may undergo oxidative degradation of the copolymer matrix over an extended period of time. For example, a liquid mixture placed in contact with a resin during purification of the liquid mixture may contain a significant amount of oxidizing species, such as molecular oxygen, dissolved chlorine, or may have an elevated temperature. Each of these may promote undesirable degradation of the copolymer matrix. In some cases, ion exchange resins may undergo oxidative degradation during handling, storage, or transportation prior to use. For example, water or air that is in contact with the ion exchange resin prior to use may also promote degradation of the copolymer matrix.

In particular, it is believed that during oxidative degradation, carbon-carbon bonds break, breaking crosslinks between individual polymer chains and/or linkages between individual styrene moieties. As used herein, "oxidative degradation" of an ion exchange resin material refers to the loss of crosslinked carbon-carbon bonds between individual polymer chains or styrene moieties of the copolymer matrix of the material. While not wishing to be bound by any particular theory, it is believed that loss of such bonds may result in an increase in water retention capacity and ultimately in the release of organic contaminants such as segments of functionalized linear polystyrene. Oxidative degradation of the copolymer matrix may be undesirable for commercial operation of ion exchange or chromatographic processes. For example, a resin that loses cross-linking may become relatively soft and swell to a greater extent. As a result of oxidative degradation, resin softness and increased swelling may ultimately result in one or more of increased bed pressure drop, decreased flow of the treated liquid mixture, and decreased operational capacity to remove chemicals from the liquid to be treated.

Furthermore, loss of crosslinking in the copolymer matrix may increase the release of organic contaminants into the column effluent, which may be unacceptable in some applications such as in the nuclear power generation industry. Organic contaminants, such as from degraded ion exchange resins, can create a potential source of corrosion to process equipment or contaminate other ion exchange resins associated with the process. Ionic contaminants may also be generated from degraded ion exchange resins. For example, in an exemplary treatment process, the cation exchange resin may contain a fixed sulfonic acid charge on the styrene backbone. Sulfonic acids are negatively charged. Positively charged ions, such as sodium or calcium, can be combined with another ion from the ion exchange resin, such as a hydrogen ion (H)⁺) The exchange results in the removal of sodium or calcium from the liquid being treated. However, in some cases, the resin may degrade to the extent that sulfate ions leach from the cation exchange resin. Leached sulfate ions can have a detrimental effect on the quality of the treated water.

Previously, industry has attempted to remedy oxidative degradation of ion exchange resins and their associated problems by increasing the amount of crosslinking monomer used to prepare the copolymer matrix. However, an increase in the number of cross-links generally renders the resulting resin beads less compatible with liquid mixtures, resulting in reduced diffusion into the beads and poor handling ability. Highly crosslinked resins may also exhibit poor regeneration efficiency and may be impermeable to macromolecules such as glucose, fructose, and other sugars. Furthermore, increasing the crosslink density may not solve the problems associated with the release of organic contaminants, as degradation may still occur.

Others in the industry have attempted to remedy oxidative degradation of ion exchange resins by replacing the hydrogen with a halogen at the tertiary carbon of the benzene ring adjacent to the styrene moiety. Briefly, as assumed in U.S. patent No. 3,342,755 (incorporated herein by reference in its entirety for all purposes), the possible mechanism of degradation of the copolymer matrix is related to the "weak linkage" identified at the tertiary carbon of the benzene ring adjacent to the styrene moiety. A tertiary carbon is considered a weak link because the hydrogen to which it is attached tends to form a hydroperoxide with an oxidizing agent such as molecular oxygen or chlorine. Hydroperoxides may eventually lead to cleavage of the carbon chains associated with the copolymer. In the' 755 patent, the inventors attempted to remedy the degradation by using monomers that do not contribute to resin stability, such as o-chlorostyrene.

When degradation of the ion exchange resin does occur, it is often possible to attempt to flush the degradation products from the ion exchange resin unless the resin performance has experienced a loss. When flushed with standard flush water (non-deoxygenated water), the ion exchange resin may continue to undergo oxidative degradation and/or contamination. During the polymerization and activation steps in the manufacture of ion exchange resins, residual polymer chips and impurities become entangled and will slowly leach out of the resin. In certain industrial applications, these must also be flushed to acceptable levels. Furthermore, in some cases, flushing ion exchange resins generates a large amount of waste. For example, in the nuclear industry, flushing ion exchange resins can produce large volumes of radioactive waste water, the disposal of which is complicated. There is a need to stabilize the original ion exchange resin while keeping it offline before use.

The ion exchange resin can be stabilized and oxidative degradation of the ion exchange resin can be prevented by limiting exposure of the resin to an oxidizing agent such as molecular oxygen, dissolved oxygen, or chlorine. Conventionally, ion exchange resins are typically stored in vessels containing moisture prior to being used to treat liquids. The present inventors have recognized that ion exchange resins can be stabilized prior to use by preventing exposure of the ion exchange resin to oxygen and/or chlorine dissolved in standard rinse water, and limiting the rate of oxidative degradation of the resin. In addition, conventional ion exchange resin storage vessels can typically allow air to enter the vessel, causing a rapid rate of oxidative degradation of the ion exchange resin. The present inventors have recognized that oxidative degradation of the ion exchange resin can also be further limited by stabilizing the ion exchange resin against contact with oxygen, for example from ambient air. Stabilization may allow the ion exchange resin to remain viable while offline for a predetermined period of time, as compared to ion exchange resins that are conventionally stored prior to use. The methods disclosed herein may also reduce the amount of wastewater generated during rinsing.

Polystyrene-based resins were analyzed to determine the nature of some contaminants released by oxidative degradation of the resin. Some of the contaminants identified included 5-methyl-3-hexanone, methoxyphenyl oxime, benzaldehyde, acetophenone, 2-methylbenzaldehyde, benzophenone imine, and tributylamine. While not wishing to be bound by any particular theory, it is believed that at least some of these contaminants result from the oxidation of the styrene and ortho-xylene moieties present in the production of the resin.

Such contaminants may have varying degrees of water solubility. For example, acetophenone, benzaldehyde and 2-methylbenzaldehyde have water solubilities of 5.5g/L, 3.0g/L and 1.2g/L, respectively. Contaminants with high water solubility can usually be washed away with water. However, contaminants with lower water solubility may not be rinsed off with water, or may only be partially rinsed off with water.

Aspects and embodiments disclosed herein relate to stabilization of virgin ion exchange resin materials. In some embodiments, stabilization of the ion exchange resin may refer to maintaining the stability of the ion exchange resin over time, for example, during handling, storage, and/or transport. The stabilization and maintained stability may be related to a decrease in the rate of oxidative degradation of the original ion exchange resin material. In particular, as used herein, a "stable" ion exchange resin material may refer to an ion exchange resin material having a reduced rate of oxidative degradation over a predetermined period of time.

Systems and methods for stabilizing virgin ion exchange resin materials are disclosed. A method of stabilizing an ion exchange resin can include rinsing a virgin ion exchange resin material with deoxygenated water to produce a rinsed virgin ion exchange resin material. A method of stabilizing an ion exchange resin may include introducing a flushed virgin ion exchange resin material into a gas impermeable vessel. A method of stabilizing a virgin ion exchange resin material may include hermetically sealing a gas impermeable vessel.

In some embodiments, a method of stabilizing an ion exchange resin may include rinsing a virgin ion exchange resin material with deoxygenated water having a dissolved oxygen concentration of less than about 10 ppb. A method of stabilizing an ion exchange resin may include rinsing a virgin ion exchange resin material with deoxygenated water having a dissolved oxygen concentration of about 1 ppb. A method of stabilizing an ion exchange resin can include rinsing a virgin ion exchange resin material with deoxygenated water having a chlorine concentration of less than about 10 ppb. A method of stabilizing an ion exchange resin may include rinsing a virgin ion exchange resin material with deoxygenated water having a chlorine concentration of about 1 ppb.

In certain embodiments, the methods disclosed herein may include rinsing the original ion exchange resin material by introducing deoxygenated water into a gas-impermeable vessel having the original ion exchange resin material, and removing interstitial deoxygenated water (anaerobic water) from the vessel. Rinsing with non-deoxygenated deionized water may be an improvement over not immediately rinsing with water prior to use at the customer site. The pre-flush may be designed to remove residual polymer and organic compound fragments that are entangled in the resin. Deoxygenation of the deionized water can minimize the incidence of oxygen decomposition of the resin itself in the deionized rinse water, which can generally contribute to the organic (as measured by total organic carbon-TOC) impurity levels from the ion exchange resin.

In some embodiments, the methods disclosed herein may include maintaining a moisture content in the washed virgin ion exchange resin material. Maintaining moisture content can be related to polymer crosslinking, minimizing leaching of organic compounds, and improving physical strength as required for resin function. For example, in some embodiments, the method may include maintaining a moisture content of at least about 40% in the washed virgin ion exchange resin material. In some embodiments, the method may include maintaining a moisture content of about 50% in the washed virgin ion exchange resin material. In some embodiments, the method may include maintaining a moisture content of between about 40% and about 50% in the washed raw ion exchange resin material.

According to certain embodiments, the methods disclosed herein may further comprise producing deoxygenated water. For example, deoxygenated water may be produced by deoxygenating non-deoxygenated water. Non-deoxygenated water may be deoxygenated by treatment to remove dissolved oxygen. In some embodiments, non-deoxygenated water may be deoxygenated by passing through a deoxygenated membrane. In some embodiments, the non-deoxygenated water may be deoxygenated by subjecting the non-deoxygenated water to vacuum degassing.

In some embodiments, the methods disclosed herein can include rinsing the virgin ion exchange resin material with deoxygenated water having a concentration of dissolved oxygen effective to reduce the rate of oxidative degradation of the virgin ion exchange resin material. For example, the rate of oxidative degradation may be reduced such that the first volume of water treated by the original ion exchange resin material contains less than about 10ppb of total organic carbon. In some embodiments, the rate of oxidative degradation may be reduced such that after maintaining the original ion exchange resin material in the vessel for a predetermined period of time, the first volume of water treated by the original ion exchange resin material contains less than about 10ppb of total organic carbon.

In some embodiments, the rate of oxidative degradation may be reduced such that the first volume of water treated by the original ion exchange resin material contains less than about 10ppb sulfate. In some embodiments, the rate of oxidative degradation may be reduced such that the first volume of water treated by the original ion exchange resin material contains less than about 10ppb of chloride. The rate of oxidative degradation may be reduced such that after maintaining the original ion exchange resin material in the vessel for a predetermined period of time, the first volume of water treated by the original ion exchange resin material contains less than about 10ppb of sulfate and/or less than about 10ppb of chloride. Organically bound chlorides and sulfates are commonly referred to collectively as TOC. The individual organic sulfates and organic chlorides in the original untreated resin may decompose to form ionic chlorides and sulfates. These compounds can be analytically measured by UV light which decomposes the organic compounds leaving ionic chlorides and sulfates which can be analyzed using conventional methods.

In some embodiments, the rate of oxidative degradation may be reduced such that after maintaining the original ion exchange resin material in the vessel for at least about 6 months, the first volume of water treated by the original ion exchange resin material contains less than about 10ppb of total organic carbon, less than about 10ppb of sulfate, and/or less than about 10ppb of chloride.

In some embodiments, the methods disclosed herein may further comprise unsealing the vessel and rinsing the original ion exchange resin material. The method may further include unsealing the vessel and rinsing the original ion exchange resin material after maintaining the original ion exchange resin material in the vessel for a predetermined period of time. For example, the method may further comprise unsealing the vessel and rinsing the original ion exchange resin material after maintaining the original ion exchange resin material in the vessel for at least about 6 months. The method may further comprise unsealing the vessel and rinsing the virgin ion exchange resin material with deoxygenated and/or deionized water (deoxygenated or non-deoxygenated) prior to use.

According to another aspect, a method of facilitating water treatment at a site in need thereof is provided. A method of facilitating water treatment at a site may include rinsing a virgin ion exchange resin material with deoxygenated water to produce a rinsed virgin ion exchange resin material. A method of facilitating water treatment may include introducing a flushed virgin ion exchange resin material into a gas-impermeable vessel. The method may include hermetically sealing the vessel. In some embodiments, the method may include providing a gas impermeable vessel containing the flushed virgin ion exchange resin material and residual moisture to a site, for example, to a water treatment site. The residual moisture content may include, for example, a moisture content between about 40% and about 50%.

In some embodiments, a method of facilitating water treatment at a location having a corresponding need may include rinsing a virgin ion exchange resin material with deoxygenated water having a dissolved oxygen concentration of less than about 10 ppb. A method of facilitating water treatment may include rinsing a virgin ion exchange resin material with deoxygenated water having a dissolved oxygen concentration of about 1 ppb. A method of facilitating water treatment may include rinsing a virgin ion exchange resin material with deoxygenated water having a chlorine concentration of less than about 10 ppb. A method of facilitating water treatment may include rinsing a virgin ion exchange resin material with deoxygenated water having a chlorine concentration of about 1 ppb.

According to certain embodiments, the methods disclosed herein may further comprise providing instructions. The method may include providing instructions to maintain the original ion exchange resin material in the hermetically sealed vessel for a predetermined period of time. For example, the method may include providing instructions to maintain the original ion exchange resin material in the hermetically sealed vessel until it is ready to be used. In some embodiments, the method may further comprise instructions to provide an unsealing vessel and rinse the original ion exchange resin material with deoxygenated water, for example, prior to use. The method may include providing instructions to unseal the vessel and flush the raw ion exchange resin material prior to use in, for example, water treatment.

According to another aspect, a vessel is provided comprising a virgin ion exchange resin material and deoxygenated water. In some embodiments, the vessel may be hermetically sealed. In some embodiments, the vessel may include deoxygenated water having less than about 10ppb dissolved oxygen. The vessel may include deoxygenated water having less than about 10ppb chlorine.

In some embodiments, the vessel may include a packaged desiccant media. For example, the vessel may include a packaged desiccant media within the vessel. In some embodiments, the vessel may be constructed of a gas impermeable material. For example, the vessel may be constructed from at least one of stainless steel and epoxy lined carbon steel.

In some embodiments, the starting ion exchange resin material may be a cation exchange resin. In some embodiments, the starting ion exchange resin material may be an anion exchange resin or a mixed cation exchange resin and anion exchange resin.

According to one aspect, a method of stabilizing a virgin ion exchange resin material is provided. The method includes rinsing a virgin ion exchange resin material with deoxygenated water to produce a rinsed virgin ion exchange resin material. The method may further comprise introducing the flushed virgin ion exchange resin material into a gas impermeable vessel. The method may include introducing the washed virgin ion exchange resin material into a designated compartment of the vessel, for example, into a liquid-impermeable compartment. The method may include introducing a preservative, an oxygen scavenging material, and/or an indicator of oxygen contamination into the gas impermeable vessel. The method may further comprise hermetically sealing the vessel. The method may further include purging oxygen in the gas-impermeable vessel. In certain embodiments, the method may include removing the preservative, oxygen scavenging material, and indicator of oxygen contamination prior to using the ion exchange resin.

Systems and methods for stabilizing virgin ion exchange resin materials are disclosed. The method can include rinsing the virgin ion exchange resin material with deoxygenated water to produce a rinsed virgin ion exchange resin material. The method can include introducing the flushed virgin ion exchange resin material into a liquid-impermeable compartment of a gas-impermeable vessel. The method may include hermetically sealing the vessel.

According to certain embodiments, the method may further comprise introducing an oxygen scavenging material into the gas impermeable vessel. The method can include positioning an oxygen scavenging material between an outer wall of the liquid-impermeable compartment and an inner wall of the gas-impermeable vessel.

In some embodiments, the method may include introducing the flushed virgin ion exchange resin material into a gas-impermeable vessel comprising at least one of polyethylene terephthalate, stainless steel, and epoxy-lined carbon steel.

The method can include rinsing the virgin ion exchange resin material with deoxygenated water having a dissolved oxygen concentration of less than about 10 ppb.

The method may include flushing the virgin ion exchange resin material in the gas-impermeable vessel.

According to another aspect, a method of stabilizing a virgin ion exchange resin material is provided. The method can include rinsing the virgin ion exchange resin material with deoxygenated water to produce a rinsed virgin ion exchange resin material. The method may include introducing the flushed virgin ion exchange resin material into a gas impermeable vessel. The method may include introducing an oxygen scavenging material into the gas impermeable vessel, the oxygen scavenging material being positioned such that it is not in direct contact with moisture. The method may include hermetically sealing the vessel.

In some embodiments, the method may further comprise introducing the washed virgin ion exchange resin material into a liquid-impermeable compartment of a gas-impermeable vessel. The method can include positioning an oxygen scavenging material between an outer wall of the liquid-impermeable compartment and an inner wall of the gas-impermeable vessel.

According to certain embodiments, the oxygen scavenging material may include iron containing compounds (ferrous compounds), catechol, ascorbate, ascorbic acid, sodium bicarbonate, citrus extract, oxidases, unsaturated hydrocarbons, polyamides, or combinations thereof.

The method may further comprise introducing an indicator of oxygen contamination. The indicator of oxygen contamination may be a pH7 and 25 ℃ having a redox midpoint potential E between about-0.05V and about +0.06V⁰The visual indicator of (1).

According to another aspect, a method of facilitating water treatment at a site in need thereof is provided. The method can include providing a washed virgin ion exchange resin material in deoxygenated water, the washed virgin ion exchange resin material positioned in a liquid-impermeable compartment of a hermetically sealed gas-impermeable vessel.

In some embodiments, the method may further comprise providing an oxygen scavenging material in the gas impermeable vessel, the oxygen scavenging material positioned such that it is not in direct contact with the deoxygenated water. The method may include providing an oxygen scavenging material positioned between an outer wall of the liquid-impermeable compartment and an inner wall of the gas-impermeable vessel. The method can include providing an oxygen scavenging material selected from the group consisting of iron-containing compounds, catechol, ascorbate, ascorbic acid, sodium bicarbonate, citrus extract, oxidase, unsaturated hydrocarbons, polyamides, and combinations thereof.

In some embodiments, the method may include providing deoxygenated water in an amount between about 40% and about 50% of the original ion exchange resin material.

The method may include providing deoxygenated water having less than about 10ppb dissolved oxygen.

In some embodiments, the method may include providing an indicator of oxygen contamination in a gas impermeable vessel.

According to another aspect, a hermetically sealed vessel is provided. The vessel may include virgin ion exchange resin material in deoxygenated water having less than about 10ppb dissolved oxygen. The vessel may also include an oxygen scavenging material.

In some embodiments, the original ion exchange resin material in the deoxygenated water may be positioned in a liquid-impermeable compartment of a hermetically sealed vessel.

The oxygen scavenging material may be positioned between an outer wall of the liquid-impermeable compartment and an inner wall of the vessel. The oxygen scavenging material can include iron-containing compounds, catechol, ascorbate, ascorbic acid, sodium bicarbonate, citrus extract, oxidase, unsaturated hydrocarbons, polyamides, and combinations thereof.

The vessel may be constructed of a material including at least one of polyethylene terephthalate, stainless steel, and epoxy lined carbon steel.

The vessel may also include an indicator of oxygen contamination. The indicator of oxygen contamination may comprise a redox midpoint potential E between about-0.05V and +0.06V at pH7 and 25 deg.C⁰The visual indicator of (1).

As used herein, a "virgin ion exchange resin" material may refer to an unused or virgin ion exchange resin material. The virgin ion exchange resin material may include newly manufactured resin and/or used resin that has been processed to meet the specifications required for the new use. For example, virgin or unrefined resins can be processed for new use by treatment with high purity water. The used resin may also be regenerated for reuse by treatment with strong acids or bases. The virgin ion exchange resin material may include cation exchange resins, anion exchange resins, and mixed cation exchange resins and anion exchange resins.

According to yet another aspect, systems and methods for stabilizing virgin ion exchange resin material are provided, including cleaning virgin ion exchange resin material. The virgin ion exchange resin material may be cleaned with a formulation containing a suitable cleaning agent.

As used herein, a "cleaned ion exchange resin" material may refer to an ion exchange resin material that has been treated to remove non-water soluble oxidized impurities (oxidized impurities). According to certain embodiments, the water insoluble oxidizing impurities may be those oxidatively degrading contaminants having a water solubility of less than about 10.0 g/L. The water insoluble oxidizing impurity may have a water solubility of less than about 7.0g/L, less than about 5.0g/L, less than about 4.0g/L, less than about 3.0g/L, less than about 2.0g/L, less than about 1.0g/L, or less than about 0.5 g/L.

The washed ion exchange resin may have an oxidized impurity or contaminant concentration of less than about 50ppb, as measured by total organic carbon oxidized (TOC). In some embodiments, the washed ion exchange resin may have less than 40ppb oxidized TOC, less than 30ppb oxidized TOC, less than 25ppb oxidized TOC, less than 20ppb oxidized TOC, less than 15ppb oxidized TOC, less than 10ppb oxidized TOC, or less than 5ppb oxidized TOC. The concentration of oxidized TOC in the ion exchange resin may generally depend on the particular cleaning agent, the concentration of cleaning agent in the formulation, and the cleaning method used.

The water insoluble oxidizing impurity may generally be an oxidized derivative molecule of the resin material. According to certain embodiments, the ion exchange resin material may be a polystyrene-based resin material. Exemplary oxidized derivative molecules of the polystyrene-based resin material include benzaldehyde and acetophenone. Other derivative molecules may result from oxidative degradation of polystyrene or other resinous materials. Such oxidized molecules can be similarly removed by the methods disclosed herein.

In certain embodiments, the ion exchange resin material may include one or more antioxidants from manufacture. For example, the polystyrene-based resin may include ortho-xylene. Exemplary oxygenated derivative molecules of such antioxidants include 5-methyl-3-hexanone, methoxyphenyl oxime, 2-methylbenzaldehyde, benzophenone imine, and tributylamine. Other oxidized derivative molecules may result from oxidative degradation of ortho-xylene or other resin molecular species. Such oxidized molecules can be similarly removed by the methods disclosed herein.

In some embodiments, the oxidizing impurities may include one or more of 5-methyl-3-hexanone, methoxyphenyl oxime, benzaldehyde, acetophenone, 2-methylbenzaldehyde, benzophenone imine, and tributylamine.

Water-soluble oxidizing impurities and contaminants can be removed by rinsing the ion exchange resin material with water.

Embodiments disclosed herein may incorporate rinsing the ion exchange resin material with deoxygenated water. Deoxygenated water is water that has been treated to remove molecular oxygen, such as dissolved oxygen. Typically, the non-deoxygenated water may contain more than about 1ppm of molecular dissolved oxygen, and up to about 20ppm of dissolved oxygen or more. Dissolved oxygen in water can fluctuate with changes in temperature, salinity, pH, conductivity, concentration of dissolved solids, and pressure. The concentration of dissolved oxygen can be measured by one or more of instrumentation, sensors, winklertration (winklertition), and colorimetry. Embodiments disclosed herein may incorporate measuring one or more of temperature, pressure, salinity, pH, conductivity, Total Dissolved Solids (TDS) concentration, and dissolved oxygen concentration of water.

According to certain embodiments, the methods disclosed herein may further comprise producing deoxygenated water. The deoxygenated water may be produced by deoxygenating non-deoxygenated water, such as from a source of non-deoxygenated water. Deoxygenated water may be produced by treating non-deoxygenated water to remove dissolved oxygen. In some embodiments, deoxygenating the non-deoxygenated water may remove at least about 75% of the dissolved oxygen. Deoxygenating the non-deoxygenated water may remove at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 99%, or about 100% of the dissolved oxygen from the non-deoxygenated water. Deoxygenating the non-deoxygenated water may remove between about 90% and about 100% of the dissolved oxygen from the non-deoxygenated water. Non-deoxygenated water may include deionized water, ultrapure water, high purity water, distilled water, microfiltered water, ultrafiltered water, water that has undergone reverse osmosis or ultraviolet oxidation, granular activated carbon treated water, or water that has been otherwise processed to remove contaminants.

Non-deoxygenated water may be deoxygenated by passing through a deoxygenating membrane. For example, the deoxygenation membrane may includeMembrane contactor (manufactured by 3MIndustrialGroup, Maplewood, MN). Briefly, deoxygenationThe membrane can remove dissolved gases from liquids using a mass transfer driving force. According to henry's law, the amount of gas dissolved in a liquid at equilibrium is proportional to the partial pressure of the gas in the gas phase in contact with the liquid. At standard temperature and pressure (25 ℃ and 1atm), at equilibrium, water may contain about 8.5ppm dissolved oxygen, 14.5ppm dissolved nitrogen, and some dissolved carbon dioxide. By reducing the partial pressure of the gas in contact with the liquid, the amount of gas dissolved in the liquid can be correspondingly reduced. The partial pressure of the gas may be reduced by reducing the total pressure of the gas phase or by changing the concentration of the gas in the gas phase. Each of these variations may be applied to the gas side of the membrane through which dissolved gas is removed from the liquid.

The non-deoxygenated water may be deoxygenated by undergoing vacuum degassing. Vacuum degassing can be accomplished with a vacuum degassing column or a dedicated vacuum chamber. In order to reduce the concentration of the gas dissolved in the liquid by vacuum degassing, the total pressure of the gas phase may be reduced by applying a vacuum to the gas. Mass transfer can remove dissolved gases from the liquid in contact with the gas.

Non-deoxygenated water may be deoxygenated by subjecting it to an oxygen scavenging resin. The oxygen scavenging resin may be contained in a column or other device. In some embodiments, the oxygen scavenging resin may include a catalyst. The catalyst may comprise a metal halide. In some embodiments, the catalyst may include sodium chloride. The catalyst may comprise palladium or a palladium compound, such as palladium chloride.

In some embodiments, the methods disclosed herein comprise rinsing the virgin ion exchange resin material with deoxygenated water having a concentration of dissolved oxygen effective to reduce the rate of oxidative degradation of the virgin ion exchange resin material. In general, a reduced rate of oxidative degradation may contribute to resin stability, ability to purify liquids, a reduced rate of cross-linking decomposition, a reduced incidence of impurities, improved bead integrity, and/or a reduced concentration of ionic contaminants in the treated liquid. For example, in some embodiments, the stable ion exchange resin may have a reduced rate of cross-link decomposition of between about 90% and about 70% over a predetermined storage time, such as a storage time of at least 6 months. The stable ion exchange resin may have a reduced cross-link decomposition rate of about 100%, a reduced cross-link decomposition rate of about 90%, a reduced cross-link decomposition rate of about 80%, a reduced cross-link decomposition rate of about 70%, or a reduced cross-link decomposition rate of about 60%. The% reduction in degradation (and de-crosslinking) may depend on the presence of oxidizing agents and the concentration of iron and other metals in or on the resin that act as catalysts for decomposition.

Water insoluble oxidizing impurities and contaminants can be removed by washing the ion exchange resin material with a surfactant. In some embodiments, water insoluble oxidizing impurities and contaminants may be removed with detergents, such as non-ionic detergents.

Embodiments disclosed herein may incorporate washing of ion exchange resin materials with formulations comprising non-ionic detergents. The formulation may be an aqueous formulation, or may contain a buffer or other solvent. Detergents generally include surfactants with cleaning properties, usually in dilute solutions. In some embodiments, the non-ionic detergent may include a Polyoxyethylene (POE), a polyethylene glycol (PEG), a polyethylene oxide (PEO), or a glycoside backbone with uncharged hydrophilic head groups. Suitable nonionic detergents include, for example, ethoxylated octylphenols, polysorbates, polyoxyethylenes, and metabolites thereof.

Soil release agents are typically foaming agents. The Critical Micelle Concentration (CMC) of a surfactant or detergent is the concentration at which micelles form. Thus, at concentrations above CMC, the surfactant may begin to form bubbles, which contribute to the oxidative degradation of the ion exchange resin. According to certain embodiments, the formulation may comprise a surfactant or detergent at a concentration below its CMC. For example, according to certain embodiments, the formulation may include ethoxylated octylphenol at a concentration of less than about 0.125 g/L. The CMC of a surfactant or detergent may vary with temperature and pressure. As disclosed herein, exemplary CMCs are formulations directed to temperatures at about room temperature (25 ℃) and about atmospheric pressure.

Additionally or alternatively, water insoluble oxidizing impurities and contaminants can be removed by washing the ion exchange resin material with an alcohol solvent.

Embodiments disclosed herein may incorporate washing the ion exchange resin material with a formulation comprising an alcohol solvent. The formulation may be an aqueous formulation, or may contain a buffer or other solvent. Alcohol solvents can be slightly polar, making them good solvents for non-polar hydrocarbons, polar organic molecules, and certain ionic compounds. Exemplary alcohol solvents may include, for example, isopropanol, methanol, ethanol, n-butanol, isooctanol, methyl isobutyl carbinol, isoamyl alcohol, isobutanol, cyclohexanol, methylcyclohexanol, and aqueous ammonia.

Isopropanol can be used as a solvent and cleaning agent for ion exchange resins because it is capable of removing non-water soluble contaminants while being substantially non-hazardous to the ion exchange resin. According to certain embodiments, the formulation may comprise less than 2.0% isopropanol. For example, the formulation may comprise less than about 1.5% isopropanol, less than about 1.0% isopropanol, less than about 0.5% isopropanol, or less than about 0.25% isopropanol.

In some embodiments, the stable ion exchange resin may comprise less than about 100ppm of metallic impurities (dry weight), including, for example, aluminum, copper, iron, sodium, and lead, and/or less than about 10ppm of organic impurities (soaking), including, for example, Total Organic Carbon (TOC), sulfate, and chloride, after a predetermined storage time, such as a storage time of at least six months. Specifically, the stabilized ion exchange resin can comprise less than or equal to about 50ppm of iron impurities, less than or equal to about 40ppm, less than or equal to about 30ppm, less than or equal to about 20ppm, less than or equal to about 10ppm, less than or equal to about 5ppm, or less than or equal to about 1ppm of iron impurities. The stabilized ion exchange resin may comprise less than or equal to about 5ppm TOC, sulfate, or chloride impurities, less than about 4ppm, less than about 3ppm, less than about 2ppm, less than about 1ppm, less than about 0.5ppm, or less than about 0.1ppm TOC, sulfate, or chloride impurities, less than about 1ppb TOC, and even less than about 0.5ppb TOC. These concentrations can be measured analytically in the flush water passing through the resin and/or soaking the resin, and the TOC in the effluent water is measured. The TOC level was measured to be less than 1ppb, and even less than 0.5 ppb. In some embodiments, a stable ion exchange resin material that has been stored for a predetermined storage time may be substantially similar to a new or regenerated ion exchange resin material, for example, in terms of bead integrity, concentration of impurities, and/or concentration of ionic contaminants in the treated liquid.

The methods disclosed herein may include a predetermined storage time. The predetermined storage time may generally include any time the ion exchange resin is stored in a hermetically sealed vessel. Storage time may include storage, handling, transport, or any purpose for maintaining the ion exchange resin within a hermetically sealed vessel. As used herein, the predetermined storage time may include a storage time of at least about 15 days, a storage time of at least about 30 days, a storage time of at least about one month, a storage time of at least about two months, a storage time of at least about three months, a storage time of at least about six months, a storage time of at least about nine months, a storage time of at least about 12 months, a storage time of at least about 18 months, or a storage time of at least about 24 months.

In some embodiments, the rate of oxidative degradation of the original ion exchange resin material may be reduced such that the first volume of water treated by the original ion exchange resin material contains from less than about 1ppb of TOC to less than about 10ppb of TOC. In some embodiments, the rate of oxidative degradation may be reduced such that after maintaining the original ion exchange resin material in the vessel for a predetermined period of time, the first volume of water treated by the original ion exchange resin material contains from less than about 10ppb of TOC to less than about 10ppb of TOC. For example, the first volume of treated water may comprise less than about 30ppb TOC, less than about 20ppb TOC, less than about 10ppb TOC, less than about 5ppb TOC, less than about 1ppb TOC, less than about 0.5ppb TOC, or less than about 0.1ppb TOC.

As disclosed herein, once the ion exchange resin material is placed on the wire to treat the water, the first volume of water treated by the ion exchange resin material comprises an initially monitored soak or rinse (initial monitored water or rinse) of the ion exchange resin material. In some embodiments, the concentration of the contaminant in the first volume of treated water may be measured from the water contacted with the ion exchange resin material. In other embodiments, the concentration of contaminants in the first volume of treated water may be measured downstream of the ion exchange resin material contact, for example, such that the water is diluted or concentrated in a downstream process. In some embodiments, the water may be diluted or concentrated by at least about 100-fold, about 200-fold, or about 300-fold. In such embodiments, the concentration of the contaminant measured in the diluted or concentrated water may be extrapolated to determine the concentration of the contaminant in the undiluted or unconcentrated first volume of treated water. Thus, as disclosed herein, the concentration of the contaminant in the first volume of treated water may refer to the undiluted and unconcentrated concentration of the contaminant. The first volume of treated water may include, for example, between about 25 gallons and about 150 gallons of treated water. In some embodiments, the undiluted, unconcentrated first volume of water treated comprises about 25 gallons, about 50 gallons, about 75 gallons, about 100 gallons, about 125 gallons, or about 150 gallons of water treated. Alternatively, the first 15 to 20 resin bed volumes of rinse water passing through the ion exchange resin material may contain high ppb or low ppm levels of organics, including organic sulfates and organic chlorides.

In some embodiments, the rate of oxidative degradation may be reduced such that the first volume of water treated by the original ion exchange resin material contains less than about 10ppb sulfate. The rate of degradation in use may be affected by temperature, nuclear radiation and/or oxidation, and the presence of metals on the resin. In some embodiments, the rate of oxidative degradation may be reduced such that the first volume of water treated by the original ion exchange resin material contains less than about 10ppb of chloride. The rate of oxidative degradation may be reduced such that after maintaining the original ion exchange resin material in the vessel for a predetermined period of time, the first volume of water treated by the original ion exchange resin material contains less than about 10ppb of sulfate and/or less than about 10ppb of chloride. For example, the first volume of water being treated may contain less than about 30ppb of sulfate or chloride, less than about 20ppb of sulfate or chloride, less than about 10ppb of sulfate or chloride, less than about 5ppb of sulfate or chloride, less than about 1ppb of sulfate or chloride, less than about 0.5ppb of sulfate or chloride, or less than about 0.1ppb of sulfate or chloride.

In some embodiments, the rate of oxidative degradation may be reduced such that after maintaining the original ion exchange resin material in the vessel for a predetermined storage time, e.g., at least about 6 months, the first volume of water treated by the original ion exchange resin material comprises less than about 10ppb TOC, less than about 10ppb sulfate, and/or less than about 10ppb chloride.

In some embodiments, the deoxygenated water may comprise less than about 0.1ppm dissolved oxygen. For example, the deoxygenated water may contain less than about 0.1ppm, less than about 50ppb, less than about 40ppb, less than about 30ppb, less than about 20ppb, less than about 10ppb, less than about 8ppb, less than about 6ppb, less than about 5ppb, less than about 4ppb, less than about 3ppb, less than about 2ppb, less than about 1ppb, or less than about 0.5ppb dissolved oxygen.

Deoxygenation may remove other dissolved gases in the water, such as dissolved carbon dioxide, dissolved nitrogen, and other ambient air gases. In some embodiments, the deoxygenated water may comprise less than about 0.1ppm dissolved carbon dioxide or dissolved nitrogen. For example, the deoxygenated water may contain less than about 0.1ppm, less than about 50ppb, less than about 40ppb, less than about 30ppb, less than about 20ppb, less than about 10ppb, less than about 8ppb, less than about 6ppb, less than about 5ppb, less than about 4ppb, less than about 3ppb, less than about 2ppb, less than about 1ppb, or less than about 0.5ppb dissolved carbon dioxide or dissolved nitrogen.

The methods disclosed herein may include treating deoxygenated or non-deoxygenated water to remove oxygenated contaminants. The deoxygenated or non-deoxygenated water may contain small amounts of other oxidizing contaminants such as chlorine, chloramines, and/or hydrogen peroxide. The deoxygenated or non-deoxygenated water may be treated with membrane filtration, reverse osmosis, high purity reducing agents (e.g., sodium bisulfite), or granular activated carbon to remove oxygenated contaminants, such as chlorine. In some embodiments, the deoxygenated or non-deoxygenated water may contain less than about 0.1ppm chlorine. For example, the deoxygenated water may contain less than about 0.1ppm, less than about 50ppb, less than about 40ppb, less than about 30ppb, less than about 20ppb, less than about 10ppb, less than about 8ppb, less than about 6ppb, less than about 5ppb, less than about 4ppb, less than about 3ppb, less than about 2ppb, less than about 1ppb, or less than about 0.5ppb of chlorine, chloramines, and hydrogen peroxide.

The methods disclosed herein may include rinsing the original ion exchange resin material by introducing deoxygenated water into a gas-impermeable vessel having the original ion exchange resin material, and removing interstitial (oxygenated) water from the vessel. For example, a vessel containing the original ion exchange resin material may be filled with deoxygenated water and the deoxygenated water substantially drained and the oxygenated water replaced with deoxygenated water. In some embodiments, the methods disclosed herein may include maintaining a moisture content in the washed virgin ion exchange resin material. As disclosed herein, moisture content may refer to the amount of liquid or water contained in the material. Moisture content can be defined as the ratio of the mass of liquid (e.g., water) in the sample to the mass of solid (e.g., ion exchange resin) in the sample, expressed as a percentage. Interstitial moisture is water in the void spaces between individual resin beads. The moisture of the beads themselves is the moisture (moisture) or hydration (hydration) within the resin beads, which is measured as% moisture. Most plastics (and other materials) have an inherent amount of moisture in the material that can be dried, and the difference in weight is measured. The deoxygenation portion of the methods disclosed herein is the displacement and otherwise removal of oxygenated water at two locations.

In some embodiments, the method comprises maintaining a moisture content of at least about 20% in the washed virgin ion exchange resin material. The method can include maintaining a moisture content of at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, or at least about 70% in the washed ion exchange resin material. In some embodiments, the method comprises maintaining a moisture content of less than about 50% of the washed virgin ion exchange resin material. The method can include maintaining a moisture content of less than about 80%, less than about 70%, less than about 60%, less than about 50%, less than about 40%, or less than about 30% in the washed ion exchange resin material. In some embodiments, the method comprises maintaining a moisture content of between about 20% and about 80%, between about 30% and about 60%, or between about 40% and about 50% in the washed original ion exchange resin material. The residual moisture content may be maintained in the original ion exchange resin material when the vessel is sealed, for example, when the vessel containing the rinsed original ion exchange resin material is handled, stored, or transported. In some embodiments, the moisture content may contribute to the stabilization of the washed virgin ion exchange resin material over time. For example, the moisture content may help to reduce the rate of oxidative degradation of the original ion exchange resin material.

Resins with a higher degree of crosslinking (cross-linking) may prevent significance of oxidative degradation (signalicicane). A higher degree of crosslinking contains entangled organics, resulting in a lower TOC level for a certain period of time. This effect may disappear as the oxidizing agent continues to be exposed to the resin.

In some embodiments, the methods disclosed herein may further comprise unsealing the vessel and rinsing the original ion exchange resin material. The method may further comprise unsealing the vessel and rinsing the original ion exchange resin material after maintaining the original ion exchange resin material in the vessel for a predetermined period of time, as previously described. For example, the method may further comprise unsealing the vessel and rinsing the original ion exchange resin material after maintaining the original ion exchange resin material in the vessel for at least about 6 months. The method may further comprise unsealing the vessel and rinsing the virgin ion exchange resin material prior to use. The virgin ion exchange resin material may be rinsed with deoxygenated water prior to use. In some embodiments, the raw ion exchange resin material may be flushed with deoxygenated water having any concentration of dissolved oxygen, dissolved gases, or oxygenated contaminants prior to use, as previously disclosed herein. The raw ion exchange resin material may be rinsed prior to use with deoxygenated water that has been produced by any of the methods previously disclosed herein.

According to another aspect, a method of facilitating water treatment at a site in need thereof is provided. Sites with corresponding needs may be associated with, for example, nuclear power generation, microelectronics manufacturing, semiconductor manufacturing, food preparation, pharmaceuticals, chemical processing and metal extraction, or any site requiring water treatment that may benefit from ion exchange water treatment technology.

A method of facilitating water treatment at a site may include providing a washed virgin ion exchange resin material in deoxygenated water, as previously described herein. The flushed virgin ion exchange resin material may be provided in a hermetically sealed gas impermeable vessel. In some embodiments, the washed virgin ion exchange resin material may be provided in a liquid-impermeable compartment of a hermetically sealed vessel. The method may further include providing one or more of a preservative, an oxygen scavenging material, or an indicator of oxygen contamination within the hermetically sealed vessel.

A method of facilitating water treatment at a site may include providing a washed virgin ion exchange resin material in deoxygenated water, as previously described herein. The cleaned virgin ion exchange resin material may be a polystyrene-based ion exchange resin material. As previously described, polystyrene-based resin materials can decompose to form oxidized impurities and contaminants in the form of Total Organic Carbon (TOC). In some embodiments, the provided cleaned virgin ion exchange resin material may have less than about 25ppb of oxidized TOC species. For example, the cleaned virgin ion exchange resin material provided can have less than about 20ppb oxidized TOC, less than about 15ppb oxidized TOC, less than about 10ppb oxidized TOC, or less than about 5ppb oxidized TOC.

The cleaned virgin ion exchange resin material may be provided in a hermetically sealed gas impermeable vessel. In some embodiments, the washed virgin ion exchange resin material may be provided in a liquid-impermeable compartment of a hermetically sealed vessel. The method may further include providing one or more of a preservative, an oxygen scavenging material, or an indicator of oxygen contamination within the hermetically sealed vessel. The cleaned virgin ion exchange resin material may be rinsed with deoxygenated water before being cleaned or after being cleaned.

In general, a method of facilitating water treatment at a site can include rinsing a virgin ion exchange resin material with deoxygenated water to produce a rinsed virgin ion exchange resin material. Additionally or alternatively, the method may comprise washing the virgin ion exchange resin material with a surfactant, a detergent, or an alcohol solvent. The method may include introducing a virgin ion exchange resin material into a gas-impermeable vessel, hermetically sealing the vessel, and purging oxygen in the vessel, as previously described herein. A method of facilitating water treatment may include providing a gas impermeable vessel containing a rinsed and/or cleaned virgin ion exchange resin material and residual moisture to a site, such as a water treatment site. In some embodiments, the method of facilitating water treatment may further comprise providing instructions to use a vessel comprising the virgin ion exchange resin material.

The residual moisture content may include maintaining a percentage of the moisture content in the washed ion exchange resin, as previously described. For example, the residual moisture content may include a moisture content between about 40% and about 50%. The residual moisture content may comprise a moisture content of between about 20% and about 80%, between about 30% and about 60%, or between about 40% and about 50% of the original ion exchange resin material that was washed, or any amount of moisture content as previously described.

In some embodiments, a method of facilitating water treatment at a location where there is a corresponding need may include rinsing a virgin ion exchange resin material with deoxygenated water, for example, having a dissolved oxygen concentration of less than about 10 ppb. In some embodiments, the raw ion exchange resin material may be flushed with deoxygenated water having any concentration of dissolved oxygen, dissolved gases, or oxygenated contaminants, as previously disclosed herein.

In some embodiments, a method of facilitating water treatment at a location where there is a corresponding need may include washing a virgin ion exchange resin material with, for example, a formulation of a non-ionic detergent having a concentration less than its CMC. For example, the method can include washing the virgin ion exchange resin material with a formulation having an ethoxylated octylphenol concentration of less than about 0.125 g/L. In some embodiments, the method may include washing the virgin ion exchange resin material with, for example, a formulation comprising an alcohol solvent. For example, the method can include washing the virgin ion exchange resin material with a formulation having an isopropanol concentration of less than about 0.5%. In some embodiments, the raw ion exchange resin material may be washed with a formulation having any concentration of surfactant, detergent, or alcohol solvent, as previously disclosed herein.

According to certain embodiments, the methods disclosed herein may further comprise providing instructions. The method may include providing instructions to maintain the original ion exchange resin material in the hermetically sealed vessel for a predetermined period of time. For example, the method may include providing instructions to maintain the original ion exchange resin material in the hermetically sealed vessel until it is ready to be used. The predetermined period of time may include any amount of storage, handling, and/or transport time required prior to use of the ion exchange resin. The predetermined period of time may include any predetermined period of time as previously described herein.

The methods disclosed herein may include providing instructions to maintain a hermetically sealed vessel under certain conditions. For example, the method can include providing instructions to maintain a vessel comprising a cation exchange resin at a temperature below at least about 210 ° f (99 ℃), below at least about 200 ° f (93 ℃), or below at least about 190 ° f (88 ℃). The method can include providing instructions to maintain a vessel comprising an anion exchange resin or a mixed anion exchange resin and cation exchange resin at a temperature below at least about 130 ° f (54 ℃) or below at least about 120 ° f (49 ℃) and as low as ambient temperature. The method may include providing instructions to maintain the hermetically sealed vessel at ambient pressure. The method may include providing instructions to avoid a temperature increase of more than 10 ℃, e.g., more than 7 ℃ or more than 5 ℃.

In some embodiments, the method may further comprise instructions to provide an unsealing vessel and rinse the original ion exchange resin material with deoxygenated water, for example, prior to use. The original ion exchange resin material may be flushed with deoxygenated water having any concentration of dissolved oxygen, dissolved gases, or oxygenated contaminants, as previously described herein. The methods disclosed herein may include instructions to flush the original ion exchange resin material immediately prior to use. In some embodiments, the method may include providing instructions to flush the original ion exchange resin material immediately prior to use while the ion exchange resin is still contained within the vessel. For example, the method may include providing instructions to fill the vessel with deoxygenated water and remove interstitial water from the vessel, thereby rinsing the original ion exchange resin material. The method may include providing instructions to unseal the vessel and flush the raw ion exchange resin material prior to use in, for example, water treatment.

In some embodiments, a method of facilitating water treatment may include instructions to return to a vessel after removal of ion exchange resin material. Such instructions may reduce waste of vessels and reduce operator time.

According to another aspect, a vessel is provided comprising a virgin ion exchange resin material and deoxygenated water. In some embodiments, the vessel may be hermetically sealed. The vessel may comprise an opening with an airtight seal. The vessel may further comprise an inlet and an outlet. The inlet and outlet may comprise a gas-tight seal. The inlet may be connected to a source of ion exchange resin material or a source of deoxygenated water. The outlet may be connected to a discharge port for deoxygenated water or to a point of use of the ion exchange resin material. For example, the outlet may be connected to a hose configured to deliver the ion exchange resin material to a point of use.

The vessel may be a container, tank, tub, basin, chamber, or reservoir configured to hold the ion exchange resin and deoxygenated water. The vessel may typically have a height of about 20 cubic feet (0.57 m)³) And about 50 cubic feet (1.42 m)³) The volume in between. For example, the vessel may have about 20 cubic feet (0.57 m)³) 25 cubic feet (0.71 m)³) 30 cubic feet (0.85 m)³) 35 cubic feet (1.0 m)³) 40 cubic feet (1.13 m)³) 45 cubic feet (1.27 m)³) Or 50 cubic feet (1.42 m)³) The volume of (a). The vessel may typically have a volume where the roof restrictions associated with the location where the ion exchange resin material is needed can be observed.

In some embodiments, the vessel may be constructed of a gas impermeable material. The vessel may be constructed of a material having a high flash point. For example, the vessel may be constructed of or lined with at least one of stainless steel and epoxy lined carbon steel. The vessel may be constructed of or lined with polyethylene terephthalate. Conventionally, ion exchange resin storage and transport vessels may be constructed from fiber, plastic, or wood. Such materials, while relatively inexpensive, are not gas impermeable and may contribute to oxidative degradation of the ion exchange resin material within the vessel. In addition, conventional materials may have a low flash point, which may be unsafe and/or undesirable in certain locations where ion exchange resin materials are needed.

The vessel may comprise one or more compartments. According to certain embodiments, the vessel may comprise a liquid-impermeable compartment. The virgin ion exchange resin and deoxygenated water may be packaged in a liquid-impermeable compartment. The liquid-impermeable compartment may include substantially no headspace or interstitial space between the resin bead and the water content. In some embodiments, the liquid-impermeable compartment may comprise a moisture content in the form of deoxygenated water of between about 40% and about 50%. In some embodiments, the liquid-impermeable compartment may also be gas-impermeable. The liquid-impermeable compartment may be constructed of the gas-impermeable materials described above. Alternatively, the liquid-impermeable compartment may be constructed of a liquid-impermeable polymeric material or a metallic material. In some embodiments, one or more compartments are integral with the vessel. In other embodiments, one or more compartments may be removable from the vessel. For example, the liquid-impermeable compartment containing the ion exchange resin may be an ion exchange resin package that is removable from the vessel.

In some embodiments, the vessel may contain deoxygenated water having any concentration of dissolved oxygen, dissolved gases, or oxygenated contaminants, as previously described herein. In some embodiments, the vessel may contain an interstitial volume of deoxygenated water. In some embodiments, the vessel may comprise deoxygenated water as residual moisture, e.g., as the moisture content previously described herein.

The vessel or compartment thereof may comprise a predetermined volume of void space, for example, the vessel or compartment may comprise interstitial void space between the ion exchange resin beads and/or the head space. In some embodiments, the void space is limited. The vessel or compartment may not substantially include a headspace and/or a limited interstitial space between the resin beads. Limiting the void space can contribute to the stability of the ion exchange resin stored, handled, or transported within the vessel.

In some embodiments, the vessel may include a preservative. The vessel may include a packaged desiccant media. For example, the vessel may include a packaged desiccant media contained within the vessel. The packaged desiccant media may be configured to remove oxygen from the void space within the vessel. In some embodiments, the desiccant/deoxidizer media is packaged in a fibrous pillow having a porous design capable of allowing oxygen exchange.

The preservative or desiccant/deoxidizer medium may be an oxygen scavenging material. The vessel may include an oxygen scavenging material. The oxygen scavenging material may be capable of removing or reducing the level of oxygen within the hermetically sealed vessel. In some embodiments, the oxygen scavenging material may be in the form of an oxygen chelating compound. For example, the oxygen scavenging material may be an oxidizing compound. In some embodiments, the oxygen scavenging material comprises an iron-containing compound, catechol, ascorbate, ascorbic acid, sodium bicarbonate, citrus extract, oxidase, an unsaturated hydrocarbon, a polyamide, or a combination thereof. The oxygen scavenging material may also include a catalyst to aid in oxidation. For example, the oxygen scavenging material may include a metal halide catalyst. The oxygen scavenging material may include sodium chloride or palladium.

The oxygen scavenging material may be packaged in a gas permeable vessel. The gas permeable vessel may be water permeable or water impermeable. The gas permeable vessel may comprise a gas permeable pouch, perforated vessel, fabric vessel, cardboard or paper vessel or polymeric vessel. In other embodiments, the oxygen scavenging material may be part of a packaging film or structure. For example, the oxygen scavenging material may line or be part of the vessel structure. A gas permeable vessel may be attached to a liquid impermeable compartment containing an ion exchange resin. In some embodiments, the gas permeable vessel may be contained on a layered strip (layered strip) around the liquid impermeable compartment. In some embodiments, a portion of the liquid-impermeable compartment may be removable to expose the oxygen scavenging material.

The vessel may include an indicator of oxygen contamination. In some embodiments, the indicator may comprise a redox indicator in a transparent package. When in the reduced form, the redox indicator can be a first color. Upon exposure to a predetermined concentration of an oxidizing agent, such as oxygen, the redox indicator may oxidize and change to a second color. Thus, the redox indicator can provide a visual indication of oxygen contamination within the vessel. The indicator of oxygen contamination may be positioned such that it reacts with the potential oxidizing agent within the vessel, but is visible from the exterior of the vessel, e.g., through a window. Thus, the indicator may be visible without opening the airtight seal of the vessel.

The indicator of oxygen contamination may have a redox midpoint potential E between about-0.05V and about +0.06V at pH7 and 25 deg.C⁰. For example, the indicator of oxygen contamination may have a redox midpoint potential E between about-0.05V and about-0.04V, between about-0.02V and about +0.02V, or between about +0.05V and about +0.06V at pH7 and 25 ℃⁰. Indicators of oxygen contamination may include, for example, indigo tetrasulfonic acid, methylene blue, or thionine.

The preservative, oxygen scavenging material, or indicator of oxygen contamination may be independently or collectively positioned in a designated compartment within the vessel. In some embodiments, the preservative, oxygen scavenging material, or indicator of oxygen contamination may be positioned within a gas-impermeable vessel, but outside of a liquid-impermeable compartment containing the ion exchange resin and deoxygenated water. Typically, the preservatives, oxygen scavenging materials, or indicators of oxygen contamination may be positioned such that they are not in direct contact with moisture. Thus, in some embodiments, a preservative, an oxygen scavenging material, or an indicator of oxygen contamination may be positioned between an outer wall of a liquid-impermeable compartment containing an ion exchange resin and deoxygenated water and an inner wall of a gas-impermeable vessel.

In some embodiments, the starting ion exchange resin material may be a cation exchange resin. In some embodiments, the starting ion exchange resin material may be an anion exchange resin. In yet other embodiments, the starting ion exchange resin material may be a mixed cation exchange resin and anion exchange resin. The storage conditions of the vessel, such as temperature, pressure, and/or concentration of dissolved gas in the deoxygenated water, may vary depending on the type of ion exchange resin contained in the vessel. For example, continuous exposure of the anionic resin to greater than about 0.05ppm of free chlorine should generally be avoided. At feed temperatures between about 5 ℃ and about 10 ℃, standard crosslinked anionic resins may be able to tolerate free chlorine levels up to about 0.3ppm, highly crosslinked anionic resins may be able to tolerate free chlorine levels up to about 0.5ppm, and macroporous anionic resins may be able to tolerate free chlorine levels up to about 1 ppm. At feed temperatures between about 20 ℃ and about 30 ℃, standard crosslinked anionic resins may only be able to tolerate free chlorine levels of less than 0.1ppm, highly crosslinked anionic resins may be able to tolerate free chlorine levels up to about 0.1ppm, and macroporous anionic resins may be able to tolerate free chlorine levels up to about 0.5 ppm. Some cation exchange resins, such as those available from Mitsubishi Chemical Corporation

The SK1B resin may have a free chlorine tolerance of about 0.6mg/L at a temperature between about 5 ℃ and about 10 ℃, and may have a free chlorine tolerance of about 0.1mg/L at a temperature between about 20 ℃ and about 25 ℃. The presence of a catalyst (e.g., iron or copper) can reduce the level of oxidant to which the resin can be exposed without significant degradation.

According to another aspect, a system is provided that includes a vessel containing a virgin ion exchange resin material and deoxygenated water. The vessel may be gas impermeable and can be hermetically sealed, as previously described. The vessel may be connected or connectable downstream of the source of deoxygenated water. The vessel may be connected or connectable downstream of the source of ion exchange resin material. In some embodiments, the vessel is connected or connectable upstream of the discharge of used deoxygenated water. The vessel may be connected or connectable upstream of the point of use of the original ion exchange resin material, for example via a hose.

In some embodiments, the system includes an oxygen monitor. An oxygen monitor may be connected to the vessel and configured to measure a concentration of oxygen within the vessel. The system may include a degasser, such as an in-line degasser. The deaerator may be a deaerating membrane. For example, the deoxygenation membrane may be made ofSupplied by a membrane contactor (3M Industrial Group, Maplewood, MN). The degasser may be a vacuum degasser. The degasser may be a column or other device containing an oxygen scavenging resin. The oxygen scavenging resin may include an oxygen scavenging material as previously described. In some embodiments, the oxygen scavenging resin may include a catalyst. The catalyst may comprise a metal halide. In some embodiments, the catalyst may include sodium chloride. The catalyst may comprise palladium or a palladium compound, such as palladium chloride. The degasser may be fluidly connected or connectable upstream of the vessel. The deaerator may be fluidly connected or connectable downstream of the source of non-deoxygenated water and configured to deaerate the non-deoxygenated water.

The system may also include a sensor or monitor, such as a pressure sensor or thermometer. The sensor and/or monitor may be positioned upstream of the vessel and configured to measure the temperature, pressure, pH, conductivity, and/or composition of the deoxygenated or non-deoxygenated water. The sensors and/or monitors may be electrically connected to the control module. The control module may be configured to control one or more parameters of the online degasser in response to measurements received from the sensors and/or monitors. The control module may be connected to an oxygen monitor. The control module may be configured to control one or more parameters of the online deaerator in response to measurements received from the oxygen monitor.

As shown in fig. 1, vessel 100 may include virgin ion exchange resin material and deoxygenated water. Vessel 100 may have an opening 110, an inlet 120, and an outlet 130. The opening, inlet and/or outlet may be capable of being hermetically sealed. The inlet may be connected to a source 140 of deoxygenated water or a source 150 of ion exchange resin material. The outlet may be connected to a drain 160 or point of use 170 of ion exchange resin material.

As shown in fig. 2, the system 200 may include a vessel 100 having an opening 110, an inlet 120, and an outlet 130. The system may also include an oxygen monitor 210, a degasser 220, a sensor or monitor 230, and a control module 240.

As shown in fig. 3, vessel 100 may have a compartment 105 configured to contain the original ion exchange resin material and deoxygenated water. A container 180 containing a preservative or oxygen scavenging material may be positioned in the interstitial space outside of the compartment 105. The indicator 190 of oxygen contamination may be visible through a viewing window 195 of the vessel 100. The vessel of fig. 3 may have an inlet and an outlet (not shown) in fluid communication with the reservoir 180. For example, the vessel may include an inlet or outlet in fluid communication with a liquid impermeable container containing the ion exchange resin and deoxygenated water.

Examples