Patent Description:
<CIT> discloses a process for separating low molecular weight weak organic acids from liquid mixtures using ion exchange resins, which may be used to purify, for example, sugar solutions used in preparing foodstuffs.

<CIT> discloses a process for decolorizing an aqueous sugar solution by contacting the solution with an anion exchange resin.

A publication by the <NPL>) describes a macroporous anion exchange resin of medium basicity containing tertiary and low level of quaternary ammonium groups, based on polystyrene. It is desired to provide a new resin that is effective at removing dissolved acid from a solution of one or more monosaccharides in water. It is also desired that the new resin shows one or more of the following improvements over previously-known resins: being able to be more completely regenerated after adsorbing dissolved acid, having improved operating capacity, and/or having improved osmotic stability.

The following is a statement of the invention.

The present invention provides a collection of resin particles,.

Also described is a process for treating an aqueous solution,.

The following is a detailed description of the invention.

As used herein, the following terms have the designated definitions, unless the context clearly indicates otherwise.

As used herein, "dissolved sugar solids" refers to all dissolved compounds that are monosaccharides, disaccharides, oligosaccharides, or polysaccharides. A monosaccharide is a saccharide compound that cannot be hydrolyzed to a simpler saccharide compound. Monosaccharides include trioses, tetroses, pentoses, hexoses, and heptoses. A disaccharide is a molecule formed when two monosaccharides are joined by a glycosidic linkage. An oligosaccharide is a molecule formed when three to ten monosaccharides are joined by glycosidic linkages. A polysaccharide is a molecule formed when eleven or more monosaccharides are joined by glycosidic linkages.

"Resin" as used herein is a synonym for "polymer. " A "polymer," as used herein is a relatively large molecule made up of the reaction products of smaller chemical repeat units. Polymers may have structures that are linear, branched, star shaped, looped, hyperbranched, crosslinked, or a combination thereof; polymers may have a single type of repeat unit ("homopolymers") or they may have more than one type of repeat unit ("copolymers"). Copolymers may have the various types of repeat units arranged randomly, in sequence, in blocks, in other arrangements, or in any mixture or combination thereof. Polymers have weight-average molecular weights of <NUM>,<NUM> or more.

Molecules that can react with each other to form the repeat units of a polymer are known herein as "monomers. " The repeat units so formed are known herein as "polymerized units" of the monomer.

Vinyl monomers have a non-aromatic carbon-carbon double bond that is capable of participating in a free-radical polymerization process. Vinyl monomers have molecular weights of less than <NUM>,<NUM>. Vinyl monomers include, for example, styrene, substituted styrenes, dienes, ethylene, ethylene derivatives, and mixtures thereof. Ethylene derivatives include, for example, unsubstituted and substituted versions of the following: vinyl acetate and acrylic monomers. "Substituted" means having at least one attached chemical group such as, for example, alkyl group, alkenyl group, vinyl group, hydroxyl group, alkoxy group, hydroxyalkyl group, carboxylic acid group, sulfonic acid group, amino group, quaternary ammonium group, other functional groups, and combinations thereof.

Monofunctional vinyl monomers have exactly one polymerizable carbon-carbon double bond per molecule. Multifunctional vinyl monomers have two or more polymerizable carbon-carbon double bonds per molecule.

As used herein, vinyl aromatic monomers are vinyl monomers that contain one or more aromatic ring.

Vinyl monomers are considered to form polymers through a process of vinyl polymerization, in which the carbon-carbon double bonds react with each other to form a polymer chain.

A polymer in which <NUM>% or more of the polymerized units, by weight based on the weight of the polymer, are polymerized units of one or more vinyl monomers is a vinyl polymer. A vinyl aromatic polymer is a polymer in which <NUM>% or more of the polymerized units, by weight based on the weight of the polymer, are polymerized units of one or more vinyl aromatic monomer. A vinyl aromatic polymer that has been subjected to one or more chemical reactions that result one or more substituent groups (such as, for example, an amino group or a methylene bridge group) being attached to the vinyl aromatic polymer is still considered herein to be a vinyl aromatic polymer. A polymerized unit of a vinyl aromatic monomer that has been subjected, after polymerization, to one or more chemical reactions that result one or more substituent groups (such as, for example, an amino group or a methylene bridge group) being attached to the polymerized unit of the vinyl aromatic monomer is still considered herein to be a polymerized unit of a vinyl aromatic monomer.

A resin is considered herein to be crosslinked if the polymer chain has sufficient branch points to render the polymer not soluble in any solvent. When it is said herein that a polymer is not soluble in a solvent, it means that less than <NUM> gram of the resin will dissolve in <NUM> grams of the solvent at <NUM>.

As used herein, the term "amino group" refers to either a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium group. A "non-quaternary amino group" is either a primary amino group, a secondary amino group, or a tertiary amino group, but is not a quaternary ammonium group.

A resin is considered to contain an amino group when the nitrogen atom of the amino group is either directly or indirectly covalently bound to the resin. That is, the nitrogen atom of the amino group may be covalently bound directly to an atom in the main chain of the polymer, or the nitrogen atom of the amino group may be covalently bound to an intermediate chemical group that is, in turn, covalently bound to an atom in the main chain of the polymer. Non-quaternary amino groups have the structure -NR<NUM>R<NUM>, or the structure -N+HR<NUM>R<NUM>, where the open bond connects directly or indirectly to an atom on the main chain of the polymer; where each of R<NUM> and R<NUM> is independently hydrogen or a substituted or unsubstituted alkyl group. Neither R<NUM> nor R<NUM> is directly or indirectly bonded to an atom in the main chain of the polymer except through the nitrogen atom of the amino group via the open bond shown in the structure above.

A resin is considered herein to contain a quaternary ammonium group when the nitrogen atom of the quaternary ammonium group is either directly or indirectly covalently bound to the resin. A quaternary ammonium group has the structure -N+R<NUM>R<NUM>R<NUM>, where the open bond connects directly or indirectly to an atom on the main chain of the polymer; where each of R<NUM>, R<NUM> , and R<NUM> is independently a substituted or unsubstituted hydrocarbyl group. Each of R<NUM>, R<NUM> , and R<NUM> independently may or may not be directly or indirectly bonded to an atom in the main chain of the polymer through a set of covalent bonds that does not include the nitrogen atom of the amino group.

A methylene group is the divalent chemical group -CH<NUM>-. A methylene group is considered herein to be a methylene F group between two aromatic rings when the carbon atom of the methylene group is bonded to a carbon atom of an aromatic ring and is also bonded to a carbon atom of a different aromatic ring. A methylene bridge group is the -CH<NUM>- group shown in the following structure (I):
<CHM>.

A collection of resin particles may be characterized by the diameters of the particles. A particle that is not spherical is considered to have a diameter equal to the diameter of a sphere having the same volume as the particle. A useful characterization of a collection of resin particles is D60, which is a diameter having the following property: <NUM>% by volume of the resin particles have diameter below D60, and <NUM>% by volume of the resin particles have diameter of D60 or above. Similarly, <NUM>% of the resin particles by volume have diameter below D10, and <NUM>% of the resin particles by volume have diameter of D10 or above. The uniformity coefficient (UC) is found by dividing D60 by D10. The harmonic mean diameter (HMD) is defined by the following equation: <MAT> where i is an index over the individual particles; di is the diameter of each individual particle; and N is the total number of particles.

The Water retention capacity (WRC) of a collection of resin particles is a measure of the water molecules that adhere to the resin particles when bulk liquid water has been removed. WRC is measured by removing bulk liquid water from the collection of resin particles and allowing the collection of resin particles to come to equilibrium at room temperature (approximately <NUM>) with air having <NUM>% humidity to produce dewatered moist resin. The dewatered moist resin is weighed, dried, and weighed again. WRC is the weight loss divided by the initial weight, expressed as a percentage.

The surface area of a collection of resin particles is found using the Brunauer-Emmett-Teller (BET) method using nitrogen gas. The BET method with nitrogen gas is also used for characterizing the total pore volume and the average pore diameter of the collection of resin particles.

Ratios presented herein are characterized as follows. For example, if a ratio is said to be <NUM>:<NUM> or greater, that ratio may be <NUM>:<NUM> or <NUM>:<NUM> or <NUM>:<NUM> but may not be <NUM>:<NUM>. This characterization may be stated in general terms as follows. When a ratio is said herein to be X: <NUM> or greater, it is meant that the ratio is Y:<NUM>, where Y is greater than or equal to X. For another example, if a ratio is said to be <NUM>:<NUM> or less, that ratio may be <NUM>:<NUM> or <NUM>:<NUM> or <NUM>:<NUM> but may not be <NUM>:<NUM>. In general terms, when a ratio is said herein to be W:<NUM> or less, it is meant that the ratio is Z:<NUM>, where Z is less than or equal to W.

The resin particles of the present invention comprise one or more vinyl aromatic polymers. The total weight of polymerized units of all vinyl aromatic monomers is, by weight of the polymer, <NUM>% or more; preferably <NUM>% or more.

Preferred vinyl aromatic monomers are styrene, alkyl styrenes, and multifunctional vinyl aromatic monomers. Among alkyl styrenes, preferred are those in which the alkyl group has <NUM> to <NUM> carbon atoms; more preferred is ethylvinylbenzene. Among multifunctional vinyl aromatic monomers, preferred is divinylbenzene. Preferably the polymer contains polymerized units of multifunctional vinyl aromatic monomer in as amount, by weight based on the weight of polymer, of <NUM>% or more; more preferably <NUM>% or more. Preferably the polymer contains polymerized units of multifunctional vinyl aromatic monomer in as amount, by weight based on the weight of polymer, of <NUM>% or less; more preferably <NUM>% or less.

Preferably, the polymer in the resin particles is crosslinked.

The collection of resin particles of the present invention contains both resin particles and water. Preferably the sum of the weight of resin particles plus the weight of the water, as a percentage based on the total weight of the collection of resin particles (which includes the resin particles, water, and optionally other ingredients), is <NUM>% or more; more preferably <NUM>% or more; more preferably <NUM>% or more; more preferably <NUM>% or more.

The polymer in the resin particles contain methylene bridge groups. The amount of methylene bridge groups is characterized by the weight of methylene bridge groups as a percentage of the weight of the polymer. The amount of methylene bridge groups is greater than zero. Preferably the amount of methylene bridge groups is <NUM>% or less.

The polymer in the resin particles has amino groups. More preferably, the polymer in the resin particles has amino groups that are secondary or tertiary. Preferably both R<NUM> and R<NUM> (as defined above) are unsubstituted alkyl groups. Preferably each of R<NUM> and R<NUM> independently has <NUM> to <NUM> carbon atoms; more preferably <NUM> to <NUM> carbon atoms. Preferably R<NUM> and R<NUM> are the same as each other.

The total amount of all types of amino groups can be characterized by the equivalents of amino groups per liter of the collection of resin particles (eq/L). The polymer has amino groups in the amount of <NUM> eq/L or more; more preferably more than <NUM> eq/L; more preferably <NUM> eq/L or more; more preferably <NUM> eq/L or more; more preferably <NUM> eq/L or more. The polymer has total amino groups in the amount of <NUM> eq/L or less; more preferably <NUM> eq/L or less.

The resin particles have quaternary ammonium groups in an amount, as equivalents per liter of the collection of resin particles, <NUM> eq/L or more; more preferably <NUM> eq/L or more. The resin particles have quaternary ammonium groups in an amount, as equivalents per liter of the collection of resin particles, <NUM> eq/L or lower; preferably <NUM> eq/L or less.

Preferably, the polymer either has no groups that contain any atom other than carbon, hydrogen, and nitrogen or else has a total amount of groups that contain one or more atoms other than carbon, hydrogen, and nitrogen of <NUM> equivalents per liter of the collection of resin particles (eq/L) or less; more preferably <NUM> eq/L or less; more preferably <NUM> eq/L or less.

The resin particles of the present invention have water retention capacity of <NUM>% or more. The resin particles of the present invention preferably have water retention capacity of <NUM>% or less; more preferably <NUM>% or less; more preferably <NUM>% or less.

The particles of the present invention have a surface area of <NUM><NUM>/g or less; more preferably <NUM><NUM>/g or less. The particles of the present invention have a surface area of <NUM><NUM>/g or more; more preferably <NUM><NUM>/g or more.

Preferably the collection of resin particles has harmonic mean diameter of <NUM> micrometers to <NUM>,<NUM> micrometers. Preferably the collection of resin particles has uniformity coefficient of <NUM> or lower; more preferably <NUM> or lower; more preferably less than <NUM>.

The average pore diameter of the collection of resin particles is preferably <NUM> or smaller; more preferably <NUM> or smaller; more preferably <NUM> or smaller; more preferably <NUM> or smaller. The average pore diameter of the collection of resin particles is preferably <NUM> or larger; more preferably <NUM> or larger; more preferably <NUM> or larger.

The collection of resin particles may be made by any method. A preferred method of making the collection of resin particles is to first make a collection of polymer particles, using aqueous suspension polymerization of a monomer mixture. Preferably the monomer mixture contains one or more vinyl aromatic monomer. Preferably the vinyl aromatic monomers are hydrocarbons. More preferably, all monomers are hydrocarbons.

Preferably the monomer mixture also contains one or more porogen. A porogen is a compound that is liquid at <NUM> and that is soluble in the monomer mixture, in the amounts used, at all temperatures between <NUM> and the temperature of polymerization. A porogen does not effectively swell the polymer formed during polymerization but instead forms pockets of porogen within a matrix of the polymer. After polymerization, the porogen is removed, leaving pores in the polymer particle.

Preferably, after the polymerization, amine functional groups are added by a two-step process of halomethylation followed by amination.

Halomethylation may be accomplished, for example, by reacting the polymer with a halomethylating agent such as, for example, methylchloromethyl ether. It is considered that, during the halomethylation step, the predominant reaction is attaching a halomethyl group (such as, for example, a chloromethyl group) to a carbon atom on in aromatic ring. It is also considered that, during halomethylation, a side reaction also occurs, in which methylene bridge groups (as shown above in structure (I)) are formed that connect aromatic rings of the polymer to each other.

Amination of the halomethylated polymer may be accomplished, for example, by reacting the polymer with an amination agent such as, for example, dimethylamine. It is considered that the predominant reaction during the amination process is the conversion of halomethyl groups to amino groups, such as, for example, the conversion of chloromethyl groups to dimethylaminomethyl groups. It is also considered that, during amination, a side reaction occurs in which two halomethyl groups become linked to each other through a quaternary ammonium group, resulting in a structure like, for example, the following:
<CHM>.

It is contemplated that proper control of the halomethylation and amination processes can control the extent to which the side reactions occur and thereby impart the features that characterize the collection of resin particles of the present invention.

In making the collection of resin particles of the present invention, it is preferred that the chloromethylated polymer is not subjected to a Friedel-Crafts chemical reaction. A Friedel-Crafts reaction involves reacting the polymer in the presence of a solvent, such as, for example, ethylene dichloride, in the presence of a Friedel-Crafts catalyst such as, for example, FeCl<NUM>. The Friedel-Crafts reaction causes the carbon atom in the -CH<NUM>Cl group of a benzyl chloride group to become un-bonded from the chlorine atom and to become bonded to an aromatic carbon atom located on a new aromatic ring, thus forming a methylene bridge.

The collection of resin particles of the present invention may be used for any purpose. A preferred purpose is the purification of aqueous solutions that contain one or more monosaccharides.

The aqueous solution may be obtained from any source. Preferably, the aqueous solution is obtained by a process that includes contacting an intermediate aqueous solution that contains one or more monosaccharides and one or more dissolved ionic salts with a cation exchange medium. Preferably, the contact with the cation exchange medium removes some or all of the dissolved cations from the intermediate aqueous solution and replaces those cations with hydrogen ion, thus producing the aqueous solution at pH of <NUM> to <NUM>. A preferred type of cation exchange medium is a collection of resin particles that have acid-functional groups attached. Preferred acid-functional groups are carboxyl groups and sulfonic acid groups, more preferably sulfonic acid groups.

The intermediate aqueous solution, if used, may be obtained from any source. Preferably, the intermediate aqueous solution is obtained by a process that includes contacting a preliminary aqueous solution that contains one or more monosaccharides, one or more dissolved salts, and compounds that impart color to the solution with a decolorizing medium. Preferably, contact with the decolorizing medium removes some or all of the compounds that impart color from the preliminary aqueous solution. Preferred decolorizing media include activated carbon and collections of resin particles that have amino groups and/or quaternary ammonium groups attached. Among amino groups, preferred are secondary and tertiary; more preferred are tertiary.

Some suitable sources of the preliminary aqueous solution include high fructose corn syrup process streams, cane or beet sugar process streams, fermentation broths, starch streams or extracts, and cellulosic hydrolysates. Preferred are high fructose corn syrup process streams and cane or beet sugar process streams; more preferred are high fructose corn syrup streams. In cane or beet sugar process streams, preferably the aqueous solution is obtained by a process that includes mechanical operations on the beet or cane (such as one or more of milling, slicing, pressing, or a combination thereof); formation of a mixture of water with the cane or beet or with the product of the mechanical process; and optional filtration of that mixture. In high fructose corn syrup processes, preferably the aqueous solution is obtained by a process that includes milling the corn to extract starch; formation of a mixture of water with the corn or the product of the milling; addition of acid and/or enzymes to that mixture to break the starch down in to shorter-length saccharides; and filtration of the mixture.

Preferably the amount of dissolved sugar solids in the aqueous solution is, by weight based on the weight of the aqueous solution, <NUM>% or higher; more preferably <NUM>% or higher; more preferably <NUM>% or higher. Preferably the amount of dissolved sugar solids in the aqueous solution is, by weight based on the weight of the aqueous solution, <NUM>% or less; more preferably <NUM>% or less; more preferably <NUM>% or less.

Preferably the total amount of all monosaccharides is, by weight based on the weight of the dissolved sugar solids, <NUM>% or higher; more preferably <NUM>% or higher; more preferably <NUM>% or higher; more preferably <NUM>% or higher; more preferably <NUM>% or higher. Preferably the monosaccharides contain glucose, fructose, or a mixture thereof; more preferably the monosaccharides contain glucose. Preferably the amount of glucose is, by weight based on the total weight of all the monosaccharides, <NUM>% or higher; more preferably <NUM>% or higher; more preferably <NUM>% or higher.

Preferably, the sum of the amount of water plus the amount of dissolved sugar solids is, by weight based on the weight of the aqueous solution, <NUM>% or higher; more preferably <NUM>% or higher; more preferably <NUM>% or higher; more preferably <NUM>% or higher.

The aqueous solution preferably has pH of <NUM> or lower; more preferably <NUM> or lower; more preferably <NUM> or lower. The aqueous solution preferably has pH of <NUM> or higher. The aqueous solution contains one or more dissolved acids. The dissolved acid may be selected from one or more mineral acids, one or more organic acids, or a mixture thereof.

The aqueous solution preferably has conductivity of <NUM>/cm or higher; more preferably <NUM>/cm or higher. The aqueous solution preferably has conductivity of <NUM>,<NUM>/cm or lower; more preferably <NUM>,<NUM>/cm or lower.

Preferably, the aqueous solution has color content of <NUM>,<NUM> ICU or lower; more preferably <NUM>,<NUM> ICU or lower; more preferably <NUM>,<NUM> ICU or lower, more preferably <NUM>,<NUM> ICU or lower; more preferably <NUM> ICU or lower, more preferably <NUM> ICU or lower; more preferably <NUM> ICU or lower.

The aqueous solution may be brought into contact with the collection of resin particles of the present invention by any method. Preferably, after the aqueous solution has been brought into contact with collection of resin particles, the solution is then separated from the collection of resin particles. It is contemplated that, after the separation, some substances that imparted color to the original aqueous solution will remain on the collection of resin particles, and the color content of the aqueous solution will be significantly reduced.

A preferred method is to pass the aqueous solution through a fixed bed of the collection of resin particles. The fixed bed is held in a container that holds the collection of resin particles in place while allowing the aqueous solution to enter through an inlet, to make contact with the collection of resin particles, and to exit through an outlet. A suitable container is a chromatography column.

The following are examples of the present invention. Operations were performed at room temperature (approximately <NUM>) except where otherwise stated.

The following are examples of the present invention.

The following eight commercially available comparative resins were tested. "x" means "not measured.

Water retention capacity was measured as follows. In brief, excess water was removed from the resin under humid air to produce resin that is dewatered but damp. The damp resin was weighed, dried, and weighed again. The relative weight loss upon drying is the Water retention capacity. In detail, <NUM> of the collection of resin particles was mixed with <NUM> of deionized (DI) water. The mixture was placed in a Buchner funnel on a vacuum flask, and water was allowed to drain from the sample under gravity. The sample was covered with a rubber stopper that was connected to a hose that supplies air having <NUM>% relative humidity from a humidifying tower. Vacuum was applied to the vacuum flask to provide air flow of <NUM>/min for <NUM> minutes. The result is dewatered damp resin. Then <NUM> to <NUM> grams of resin was weighed (Wm), then dried in an oven at <NUM> for <NUM> hours, then weighed again (Wd). Water retention capacity (WRC) was given by <MAT>.

Amino groups per liter and Quaternary Ammonium groups per liter were determined as follows. In brief, the resin was converted to chloride form, the chloride was removed by elution with aqueous solution of NO<NUM>, and the quantity of chloride in the eluted fluid gave the "total exchange capacity" (TEC, the sum of amino groups per liter and quaternary ammonium groups per liter). Then the resin was again converted to chloride form using basic NaCl, then the chloride was removed by elution with aqueous solution of NO<NUM>, and the quantity of chloride in the eluted fluid gave the quaternary ammonium groups per liter (also called "strong base capacity," SBC). Then the amino groups per liter (also called the "weak base capacity", WBC) was found by WBC = TEC - SBC.

In detail, dewatered damp resin was prepared as in the test for Water retention capacity. Approximately <NUM> of resin was weighed (Wm), and then mixed with water to make a total volume of <NUM>. The resin was allowed to settle, and the volume of the resin was recorded (Vm). The resin was transferred to a fritted glass filter tube and then treated with <NUM> of <NUM> N HCl in water at <NUM>/min followed by <NUM> of alcohol mixture (<NUM>/<NUM> methanol/ethanol by volume) at <NUM>/min. Then <NUM> of. <NUM> N NaNO<NUM> in water was passed through the sample at <NUM>/min and collected and saved as solution "A. " Then the following were passed through the sample: <NUM> of <NUM> N NaOH in water at <NUM>/min; <NUM> of DI water at <NUM>/min; <NUM> of <NUM> N NaCl at <NUM>/min; <NUM> of DI water at <NUM>/min. Then <NUM> of. <NUM> N NaNO<NUM> in water was passed through the sample at <NUM>/min and collected and saved as solution "B. " Solution A was adjusted to pH <NUM> using either <NUM> N HNO<NUM> in water or <NUM> N NaOH in water. Then Solution A was titrated for chloride with <NUM> N AgNOs, using a Mettler Toledo™ autotitrator, model T90, until an inflection point in conductivity was observed. The titration volume was Va (mL) and the normality of the AgNOs solution was Nag (eq/L). Solution B was pH-adjusted and titrated in the same way, to find titration volume Vb (mL). Then the same NaNO<NUM> solution was pH-adjusted and titrated in the same way to find titration volume Vblank (mL). <MAT> <MAT> <MAT>.

Conductivity was measured with an Orion™ model 162A conductivity meter, from Thermo Scientific.

Brix was measured using an AR <NUM> refractometer (from Reichert, Inc. ), calibrated in Brix units.

Color content was measured using a Genesys™ <NUM> UV-vis spectrophotometer, from Thermo Scientific, using a cell having <NUM> path length. Color content is reported as described by the International Commission for Uniform Methods of Sugar Analysis (ICUMSA), where <MAT> The ICUMSA number calculated above is reported as ICU, for international color units.

Aqueous solution Number <NUM> (AQS1) was used for acid-removal testing. AQS1 was made immediately before acid-removal testing. AQS1 had the following contents and characteristics:.

It is considered that testing with AQS <NUM> is a useful assessment of the ability of the resin to remove acid, including mineral acids and/or organic acids, regardless of the method used to make the aqueous solution that contains acid. For example, aqueous solutions may contain mineral acid by direct addition of the mineral acid or by other methods, such as, for example, contacting an aqueous solution containing one or more mineral salts with a strong-acid cation exchange resin, which would exchange hydrogen ions for the cation of the mineral salt, resulting in an aqueous solution that contains mineral acid.

Removal of dissolved acid and assessment of "operating capacity" were performed as follows. <NUM> of resin was tapped into a glass chromatography column of <NUM> inside diameter and <NUM> length. The resin was preconditioned by passing <NUM> BV of an aqueous solution of <NUM> N NaOH through the column. Solution AQS <NUM> was passed through the column at <NUM>; pH and conductivity of the fluid exiting the column were continuously monitored, and the flow was stopped when conductivity rose to <NUM>/cm (the "breakthrough point"). The total number of bed volumes of AQS <NUM> that passed through prior to the breakthrough point was recorded (TBV). The total number of equivalents of acid in TBV was divided by the volume of the resin bed, and the quotient was reported as the "single-cycle capacity", in units of eq/L. Then <NUM> BV of water was passed through the column at <NUM> BV/hr at <NUM>.

After removal of dissolved acid, the resin was regenerated as follows. The column was cooled to room temperature (approximately <NUM>). A regeneration solution of <NUM>/L NaOH in water was prepared. The regeneration solution was passed through the column at <NUM> BV/hr for <NUM> BV. The resin was then slow-rinsed with deionized water at <NUM> BV/hr for <NUM> BV and then fast-rinsed with deionized water at <NUM> BV/hr for <NUM> BV.

The acid removal procedure was performed, followed by the regeneration procedure. Then a second acid removal procedure was performed, and the single-cycle capacity of the second acid removal procedure was reported as the "operating capacity" of the resin.

For testing the ability of a resin to be regenerated, a different aqueous solution was used. The regeneration test causes colored compounds to be adsorbed by the resin and then measures the completeness with which the colored compounds can be removed in a regeneration procedure. It is considered that performance in this color-based regeneration test will be an indicator of the ability of the resin to be regenerated following the use of the resin in removal of acid from an aqueous solution and an indicator of the regenerability of the resin in terms of organic impurities, linked to resins' long term performance.

For regeneration testing, aqueous solution AQS2 was made as follows. High fructose corn syrup (HFCS) was used in which <NUM>% by weight of the dissolved sugar solids were fructose and approximately <NUM>% by weight of the dissolved sugar solids were glucose. The high fructose corn syrup was heated at pH <NUM> at <NUM> for <NUM> to <NUM> hours and then neutralized with aqueous solution of NaOH to pH <NUM> to <NUM>. The aqueous solution had the following properties. "Cond" is conductivity.

It is contemplated that results obtained using this aqueous solution would be similar to results that would be obtained if the aqueous solution contained a higher proportion of glucose (for example, <NUM>% by weight or higher of the dissolved sugar solids). For example, if the aqueous solution were obtained from a high fructose corn syrup process stream (instead of from the laboratory procedure described above), it is expected that the aqueous solution could have a relatively high proportion of glucose and could have relatively little fructose. It is expected that performing the method of the present invention using an aqueous solution obtained from a high fructose corn syrup process stream would yield similar benefits to the benefits reported herein that were obtained by using the aqueous solution made in the laboratory procedure described above.

Color removal was performed as follows. <NUM> of resin particles were packed into a chromatography column of inside diameter <NUM> and length <NUM>. The quaternary amine groups in the functionalized resin were converted to hydroxide form by stirring the resin with three resin volumes' worth of a four weight percent solution of sodium hydroxide in water at room temperature. This process was repeated a total of three times, after which the resin was thoroughly washed in deionized water to remove excess sodium hydroxide. The column, the resin particles, and the aqueous solution were heated to <NUM>, and the aqueous solution AQS2 was passed through the column at <NUM> bed volumes (BV) per hour, for <NUM> BV. To assess color removal, the ICUMSA color was measured in the aqueous solution before entering the column and again after exiting the column. Color removal is reported as "decolorization": <MAT> where CA is the ICUMSA color before entering the column and CB is the ICUMSA color after exiting the column.

Regeneration was performed as follows. After passage of the aqueous solution was stopped, <NUM> BV at a rate of <NUM> BV/hr of an aqueous solution of <NUM> weight% NaOH was passed through the column at <NUM>, followed by <NUM> BV of deionized water at <NUM> BV/hr at <NUM>. All of the NaOH solution and the deionized water was collected after passage through the column and combined. The absorbance at <NUM> of that combined solution is reported as the "regenerability.

Osmotic stability was tested as follows. Three BV of a solution of <NUM> weight% lactic acid in water was passed through a resin bed containing <NUM> of resin particles at a flow rate of <NUM>/min for <NUM> minutes, followed by rinsing the resin in the column with <NUM> BV of deionized (DI) water at a flow rate of <NUM>/min over <NUM> minutes. Then, <NUM> BV of a solution of <NUM> weight% sodium hydroxide in water was passed through the resin at a flow rate of <NUM>/min for <NUM> minutes, followed by rinsing with <NUM> BV of DI water for <NUM> minutes. This cycle was repeated <NUM> additional times giving a total of <NUM> cycles. After <NUM> cycles were completed, the sample of each resin was collected, and a photomicrograph of the beads was taken and inspected to count the whole beads. Osmotic strength is reported as the percentage of particles that remain whole, based on the total number of particles. The higher percentage of whole beads represents higher osmotic strength.

Copolymer particles were obtained. The copolymer was a copolymer of styrene, ethylvinylbenzene, and divinylbenzene, made in aqueous suspension polymerization from a suspension of droplets that contained the mixture of monomers, initiator, and porogen. The mixture of monomers contained more than <NUM>% styrene by weight based on the total weight of all monomers. The droplets contained between <NUM>% and <NUM>% porogen by weight based on the weight of the droplets. The copolymer is suitable for use in standard industrial techniques that produce either previously-known weak base ion exchange resins or previously-known strong base ion exchange resins.

The copolymer was chloromethylated as follows. <NUM> of the copolymer was added to <NUM> chloromethyl methyl ether and swelled for <NUM>. under agitation. <NUM> grams of catalyst FeCl<NUM> was added, and the heating profile was started. The heating temperature (jacket temperature) was set at <NUM>. The boiling temperature of the mixture was about <NUM> to <NUM>, so the reaction was held through within this temperature window under reflux for <NUM> to <NUM> mins, depending on the sample. Since chloromethyl methyl ether is boiled out, additional <NUM> to <NUM> chloromethyl methyl ether was often added to keep the fluidity during the reaction. After the holding time, the heating was stopped, and methanol was added to quench the reaction, and the agitation was continued for <NUM>. The reactor was cooled to room temperature (approximately <NUM>), and the solution was siphoned out of the reactor. The resin was washed with solvent in a sequence of methanol, methylal, and methanol to removal residue ether. Methanol was siphoned out, and methylal was added to swell the beads for <NUM>. Methylal was siphoned out, and the chloromethylated copolymer was ready for amination.

The chloromethylated copolymer was aminated as follows. <NUM> chloromethylated beads was added to a mixture solution containing <NUM> of <NUM> weight% NaOH in water and <NUM> of <NUM> weight% Dimethylamine (DMA) in water (weight ratio of amine/copolymer was between <NUM> and <NUM>). The reaction was held at <NUM> was approximately <NUM> to <NUM> hours under reflux. When reaction was completed, the solution was siphoned out. The resin was washed with DI water for <NUM> times, followed by 2N HCl solution in water, washed for <NUM> mins to removal all residual amine. HCl was siphoned off, and the resin was backwashed with DI water until effluent was neutral (pH approximately <NUM>).

In some instances, the quaternary amine groups in the functionalized resin were converted to chloride form by stirring the resin with three resin volumes' worth of five molar sodium chloride in water at room temperature. This process was repeated a total of three times, after which the resin was thoroughly washed in deionized water to remove excess sodium chloride.

In some instances, the quaternary amine groups in the functionalized resin were converted to hydroxide form by stirring the resin with three resin volumes' worth of a four weight percent solution of sodium hydroxide in water at room temperature. This process was repeated a total of three times, after which the resin was thoroughly washed in deionized water to remove excess sodium hydroxide.

The following resins were made. Resin numbers ending in "C" are comparative. The same copolymer was used for all five resins; the resins differed only in the chloromethylation and/or amination conditions. "x" means "not measured.

Results of testing the various resins were as follows:.

Claim 1:
A collection of resin particles,
wherein the resin particles comprise one or more vinyl aromatic polymers, and the total weight of polymerized units of all vinyl aromatic monomers is <NUM>% or more by weight of the polymer;
wherein the polymer comprises methylene bridge groups between aromatic rings;
wherein the polymer comprises amino groups and the total amount of amino groups bonded to the resin particles is <NUM> to <NUM> equivalents or more per liter of the collection of resin particles, wherein an amino group has the structure -NR<NUM>R<NUM>, or the structure -N+HR<NUM>R<NUM>, where the open bond connects directly or indirectly to an atom on the main chain of the polymer; where each of R<NUM> and R<NUM> is an unsubstituted alkyl group, and neither R<NUM> or R<NUM> is directly or indirectly bonded to an atom in the main chain of the polymer except through the nitrogen atom of the amino group via the open bond shown in the structure above;
wherein quaternary ammonium groups bonded to the polymer are present in an amount of <NUM> to <NUM> equivalents per liter of the collection of resin particles;
wherein the resin particles have water retention capacity of <NUM>% to <NUM>% by weight of water based on the weight of the collection of resin particles;
and wherein the resin particles have surface area of from <NUM> to <NUM><NUM>/g, using the Brunauer-Emmett-Teller (BET) method using nitrogen gas.