Functional resin particles

Abstract

A mass of resin particles, wherein the resin particles comprise one or more polymers, the polymers comprising methylene bridging groups between aromatic rings, the polymers comprising amino groups attached to the resin particles in a total amount of 0.1 to 1.4 equivalents per liter of the mass of resin particles, and quaternary ammonium groups attached to the polymers are either absent or are present in an amount of 0.05 equivalents or less per liter of the mass of resin particles, the resin particles having a water retention capacity of 40% to 50% by weight based on the weight of the mass of resin particles, and the resin particles having a water retention capacity of 100 ml 2 A mass of resin particles is provided having a surface area of ​​0.15 wt.

Description

Background Art

[0001] In the sugar purification process, it is often desirable to treat an aqueous solution containing one or more monosaccharides in order to remove color-imparting substances. One way to remove color is to pass the aqueous solution through a layer of adsorbent particles to adsorb the colored substances onto the particles. When such a method is used, it is desirable that the adsorbent particles can then be regenerated, i.e., that most or all of the adsorbed colored substances can be removed from the adsorbent particles. After regeneration, it is desirable that the adsorbent particles can be reused to remove colored substances. It is also desirable that the adsorbent particles exhibit good osmotic stability.

[0002] U.S. Patent No. 6,942,805 describes a method for decolorizing sugar juice using monodisperse ion exchange resins, preferably anion exchange resins, and their use for sugar juice decolorization.

Summary of the Invention

Problems to be Solved by the Invention

[0003] It is desirable to provide a specific classification of particles having specific characteristics such that resin particles effectively decolorize a sugar solution, particularly a solution containing one or more monosaccharides, and one or more of the following improvements: being more completely regenerable after adsorbing colored substances, and / or having improved osmotic stability.

Means for Solving the Problems

[0004] The following is an explanation of the present invention.

[0005] A first aspect of the present invention is an aggregate of resin particles, the resin particles contain one or more polymers, the polymers contain methylene bridging groups between aromatic rings, the polymers contain amino groups bonded to the resin particles in a total amount of 0.1 to 1.4 equivalents per liter of the aggregate of resin particles, The quaternary ammonium groups bonded to the polymer are either absent or, if present, present in an amount of 0.05 equivalents or less per liter of the aggregate of resin particles. The resin particles have a water retention capacity of 40% to 50% by weight based on the weight of the aggregate of resin particles. The resin particles are an aggregate of resin particles having a surface area of 100 m 2 / g or less.

[0006] A second aspect of the present invention is a method for treating an aqueous solution, wherein the aqueous solution contains dissolved sugar solids in an amount of 10% to 50% by weight based on the weight of the aqueous solution, the dissolved sugar solids contain monosaccharides in an amount of 1% to 99% by weight based on the weight of the dissolved sugar solids, the aqueous solution has an ionic conductivity of 100 to 10,000 μS / cm and a color component of 100 to 10,000 international color units, the method includes contacting the aqueous solution with an aggregate of resin particles, the resin particles contain one or more polymers, the polymer contains a methylene bridging group between aromatic rings, the polymer contains amino groups bonded to the resin particles in a total amount of 0.1 to 1.4 equivalents per liter of the aggregate of resin particles, the quaternary ammonium groups bonded to the polymer are either absent or, if present, present in an amount of 0.05 equivalents or less per liter of the aggregate of resin particles. The resin particles have a water retention capacity of 40% to 50% by weight based on the weight of the aggregate of resin particles. The resin particles are 2 a method having a surface area of 100 m / g or less.

Embodiments for Carrying Out the Invention

[0007] The following is a detailed description of the present invention.

[0008] As used herein, unless clearly indicated otherwise by context, the following terms have the specified definitions.

[0009] As used herein, "dissolved sugar solids" refers to all dissolved compounds that are monosaccharides, disaccharides, oligosaccharides, or polysaccharides. Monosaccharides are sugar compounds that cannot be hydrolyzed into simpler sugar compounds. Examples of monosaccharides include trioses, tetroses, pentoses, hexoses, and heptoses. Disaccharides are molecules formed when two monosaccharides are linked by a glycosidic bond. Oligosaccharides are molecules formed when 3 to 10 monosaccharides are linked by a glycosidic bond. Polysaccharides are molecules formed when 11 or more monosaccharides are linked by a glycosidic bond.

[0010] As used herein, "resin" is synonymous with "polymer". As used herein, a "polymer" is a relatively large molecule composed of the reaction products of smaller chemical repeating units. A polymer can have a structure that is linear, branched, star-shaped, loop-shaped, hyperbranched, cross-linked, or a combination thereof. A polymer can have a single type of repeating unit ("homopolymer") or it can have two or more types of repeating units ("copolymer"). Copolymers can have various types of repeating units arranged randomly, in an ordered manner, in blocks, in other sequences, or in any mixture or combination thereof. A polymer has a weight average molecular weight of 2,000 or more.

[0011] Molecules that can react with each other to form the repeating units of a polymer are recognized herein as "monomers". The repeating units thus formed are recognized herein as the "polymerized units" of the monomers.

[0012] The vinyl monomer has a non-aromatic carbon-carbon double bond that can participate in a free radical polymerization process. The vinyl monomer has a molecular weight of less than 2,000. Examples of vinyl monomers include styrene, substituted styrene, diene, ethylene, ethylene derivatives, and mixtures thereof. Examples of ethylene derivatives include vinyl acetate and unsubstituted and substituted types of acrylic monomers. "Substituted" means having at least one attached chemical group such as an 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.

[0013] A monofunctional vinyl monomer has exactly one polymerizable carbon-carbon double bond per molecule. A polyfunctional vinyl monomer has two or more polymerizable carbon-carbon double bonds per molecule.

[0014] As used herein, a vinyl aromatic monomer is a vinyl monomer that contains one or more aromatic rings.

[0015] The vinyl monomer is considered to form a polymer by a vinyl polymerization process in which the carbon-carbon double bonds react with each other to form polymer chains.

[0016] A polymer in which 90% by weight or more of the polymerized units, 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 50% by weight or more of the polymerized units, based on the weight of the polymer, are polymerized units of one or more vinyl aromatic monomers. A vinyl aromatic polymer that has undergone one or more chemical reactions to obtain one or more substituents (such as an amino group or a methylene crosslinking group, etc.) bonded thereto is still considered a vinyl aromatic polymer in this specification. Polymerized units of a vinyl aromatic polymer that have undergone one or more chemical reactions to obtain one or more substituents (such as an amino group or a methylene crosslinking group, etc.) bonded to the polymerized units are still considered polymerized units of a vinyl aromatic polymer in this specification.

[0017] If the polymer chain has sufficient branching points and the polymer does not dissolve in any solvent, in this specification, the resin is considered to be crosslinked. When it is stated in this specification that a polymer does not dissolve in a solvent, this means that less than 0.1 g of the resin dissolves in 100 g of the solvent at 25°C.

[0018] The term "amino group" as used in this specification refers to any of a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium group. A "non - quaternary amino group" is any of a primary amino group, a secondary amino group, or a tertiary amino group, but not a quaternary ammonium group.

[0019] When the nitrogen atom of an amino group is directly or indirectly covalently bonded to the resin, the resin is considered to contain an amino group. That is, the nitrogen atom of the amino group can be directly covalently bonded to an atom in the polymer main chain, or the nitrogen atom of the amino group can be covalently bonded to an intermediate chemical group, which can be covalently bonded to an atom in the main chain of the polymer. A non - quaternary amino group has the structure - NR 1 R 2 or the structure - N + HR 1 R 2has, and the open bond is directly or indirectly linked to an atom on the polymer backbone. In the formula, each R 1 and R 2 is independently hydrogen or a substituted or unsubstituted alkyl group. Neither R 1 nor R 2 is directly or indirectly bonded to an atom of the polymer backbone other than through the nitrogen atom of the amino group via the open bond shown in the above structure.

[0020] When the nitrogen atom of the quaternary ammonium group is directly or indirectly covalently bonded to the resin, in this specification, the resin is considered to contain a quaternary ammonium group. The quaternary ammonium group has the structure -N + R 1 R 2 R 3 has, and the open bond is directly or indirectly bonded to an atom on the polymer backbone. In the formula, each of R 1 , R 2 and R 3 is independently a substituted or unsubstituted hydrocarbyl group. Each of R 1 , R 2 and R 3 may or may not be directly or indirectly bonded to an atom of the polymer backbone via a series of covalent bonds that do not contain the nitrogen atom of the amino group.

[0021] A methylene group is the divalent chemical group -CH 2 -. When a carbon atom of the methylene group is bonded to a carbon atom of an aromatic ring and also to a carbon atom of a different aromatic ring, in this specification, the methylene group is considered to be a methylene bridging group between two aromatic rings. The methylene bridging group has the following structure (I):

Chemical formula

[0022] The water retention capacity of the aggregate of resin particles refers to the water content of the aggregate of resin particles. The water retention capacity is expressed as the weight percentage of water based on the total weight of the aggregate of resin particles, and this total includes both the resin particles and water.

[0023] The aggregate of resin particles can be characterized by the diameter of the particles. Non-spherical particles are considered to have a diameter equal to the diameter of a sphere with the same volume as the particle. A useful property evaluation of the aggregate of resin particles is D60, which is the diameter having the following properties: 60% by volume of the resin particles have a diameter less than D60, and 40% by volume of the resin particles have a diameter greater than or equal to D60. Similarly, 10% by volume of the resin particles have a diameter less than D10, and 90% by volume of the resin particles have a diameter greater than or equal to D10. The uniformity coefficient (UC) is obtained by dividing D60 by D10. The harmonic mean diameter (HMD) is given by the formula:

Number

[0024] The water retention capacity (WRC) of the aggregate of resin particles is a measure of the water molecules adhering to the resin particles when bulk liquid water is removed. WRC is measured by removing bulk liquid water from the aggregate of resin particles and equilibrating the aggregate of resin particles at room temperature (about 23 °C) using air with a humidity of 100% to produce wet resin that has been dehydrated. The dehydrated wet resin is weighed, dried, and weighed again. WRC is the weight loss divided by the initial weight and is expressed as a percentage.

[0025] The surface area of the aggregate of resin particles is determined using the Brunauer-Emmett-Teller (BET) method using nitrogen gas. The BET method using nitrogen gas is also used for the property evaluation of the total pore volume and average pore diameter of the aggregate of resin particles.

[0026] The ratios shown in this specification are characterized as follows. For example, when the ratio is said to be 3:1 or more, the ratio can be 3:1, or 5:1, or 100:1, but may not be 2:1. This characterization can be generally described as follows. When the ratio is said to be X:1 or more in this specification, it means that the ratio is Y:1, where Y is equal to or greater than X. As another example, when the ratio is said to be 15:1 or less, the ratio can be 15:1, or 10:1, or 0.1:1, but may not be 20:1. Generally, when the ratio is said to be W:1 or less in this specification, it means that the ratio is Z:1, where Z is equal to or less than W.

[0027] The resin particles of the present invention contain one or more polymers. The polymer contains an aromatic ring. A preferred polymer is a vinyl polymer, more preferably a vinyl aromatic polymer. Preferably, the total weight of the polymerized units of all vinyl aromatic monomers is 50% by weight or more of the polymer, more preferably 75% by weight or more, more preferably 90% by weight or more, more preferably 95% by weight or more.

[0028] Preferred vinyl aromatic monomers are styrene, alkylstyrene and polyfunctional vinyl aromatic monomers. Among alkylstyrenes, those having an alkyl group with 1 to 4 carbon atoms are preferred, and ethylvinylbenzene is more preferred. Among polyfunctional vinyl aromatic monomers, divinylbenzene is preferred. Preferably, the polymer contains polymerized units of a polyfunctional vinyl aromatic monomer in an amount of 0.5% by weight or more, more preferably 1% by weight or more, based on the weight of the polymer. Preferably, the polymer contains polymerized units of a polyfunctional vinyl aromatic monomer in an amount of 10% by weight or less, more preferably 8% by weight or less, based on the weight of the polymer.

[0029] Preferably, the polymer in the resin particles is crosslinked.

[0030] The aggregate of resin particles of the present invention contains both resin particles and water. Preferably, the total of the weight of the resin particles plus the weight of water is 80% or more, more preferably 90% or more, more preferably 95% or more, more preferably 98% or more as a ratio based on the total weight of the aggregate of resin particles (including resin particles, water and optional other components).

[0031] The polymer in the resin particles contains a methylene crosslinking group. The amount of the methylene crosslinking group is characterized by the weight of the methylene crosslinking group as a ratio of the weight of the polymer. The amount of the methylene crosslinking group is greater than zero. Preferably, the amount of the methylene crosslinking group is 4% or less.

[0032] The polymer in the resin particles has an amino group. More preferably, the polymer in the resin particles has a secondary or tertiary amino group. Preferably, R 1 and R 2 (as defined above) are both unsubstituted alkyl groups. Preferably, R 1 and R 2 each independently has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms. Preferably, R 1 and R 2 are the same as each other.

[0033] The total amount of all types of amino groups can be characterized by the equivalents of amino groups per liter (eq / L) of the aggregate of resin particles. Preferably, the polymer has an amount of amino groups of 0.1 eq / L or more, more preferably 0.4 eq / L or more, more preferably 0.7 eq / L or more, more preferably 1 eq / L or more, more preferably 1.2 eq / L or more. Preferably, the polymer has an amount of amino groups of 1.4 eq / L or less in total.

[0034] The polymer does not have a quaternary ammonium group or has an amount of quaternary ammonium group of 0.05 eq / L or less, preferably 0.025 eq / L or less, more preferably 0.015 eq / L or less as an equivalent per liter of the aggregate of resin particles.

[0035] Preferably, the polymer has no group containing any atom other than carbon, hydrogen, and nitrogen, or has a total amount of groups containing one or more atoms other than carbon, hydrogen, and nitrogen of 0.01 equivalents (eq / L) or less, more preferably 0.005 eq / L or less, and even more preferably 0.002 eq / L or less per liter of the aggregate of resin particles.

[0036] The resin particles of the present invention have a water retention capacity of 40% or more. The resin particles of the present invention preferably have a water retention capacity of 50% or less, more preferably 47% or less, and even more preferably 44% or less.

[0037] The particles of the present invention have a surface area of 100 m 2 / g or less, more preferably 50 m 2 / g or less. The particles of the present invention preferably have a surface area of 10 m 2 / g or more, more preferably 20 m 2 / g or more.

[0038] Preferably, the aggregate of resin particles has a harmonic mean diameter of 200 μm to 1,000 μm. Preferably, the aggregate of resin particles has a uniformity coefficient of 1.5 or less, more preferably 1.3 or less, and even more preferably less than 1.1.

[0039] The average pore diameter of the aggregate of resin particles is preferably 50 nm or less, more preferably 40 nm or less, even more preferably 35 nm or less, and even more preferably 32 nm or less. The average pore diameter of the aggregate of resin particles is preferably 20 nm or more, more preferably 25 nm or more, even more preferably 28 nm or more, and even more preferably 30 nm or more.

[0040] The aggregate of resin particles can be produced by any method. A preferred method for producing the aggregate of resin particles is to first produce an aggregate of polymer particles using aqueous suspension polymerization of a monomer mixture. Preferably, the monomer mixture contains one or more vinyl aromatic monomers. Preferably, the vinyl aromatic monomer is a hydrocarbon. More preferably, all monomers are hydrocarbons.

[0041] Preferably, the monomer mixture also contains one or more porogens. A porogen is a compound that is liquid at 23 °C and is soluble in the monomer mixture in the amount used at all temperatures from 23 °C to the polymerization temperature. The porogen does not effectively swell the polymer formed during polymerization, but instead forms pockets of porogen within the matrix of the polymer. After polymerization, the porogen is removed, leaving pores in the polymer particles.

[0042] Preferably, after polymerization, the amine functional group is added by a two-step process of halomethylation followed by amination.

[0043] Halomethylation can be achieved, for example, by reacting the polymer with a halomethylating agent such as methyl chloromethyl ether. The main reaction during the halomethylation step is thought to be the attachment of a halomethyl group (such as a chloromethyl group) to a carbon atom on the aromatic ring. Also, during halomethylation, a side reaction is thought to occur in which a methylene bridging group that connects the aromatic rings of the polymer (as described above in Structure (I)) is formed.

[0044] Amination of the halomethylated polymer can be achieved, for example, by reacting the polymer with an aminating agent such as dimethylamine. The main reaction during the amination process is thought to be the conversion of a halomethyl group to an amino group, such as the conversion of a chloromethyl group to a dimethylaminomethyl group. Also, during amination, a side reaction is thought to occur in which two halomethyl groups are linked to each other via a quaternary ammonium group, resulting in a structure such as the following.

Chemical formula

[0045] By appropriately controlling the halomethylation and amination processes, it is considered possible to control the degree to which side reactions occur, thereby imparting the characteristics that characterize the aggregate of resin particles of the present invention.

[0046] In the production of the aggregate of resin particles of the present invention, it is preferable that the chloromethylated polymer does not undergo a Friedel-Crafts chemical reaction. The Friedel-Crafts reaction involves reacting the polymer, for example, in the presence of a Friedel-Crafts catalyst such as FeCl 3 in the presence of a solvent such as ethylene dichloride. The Friedel-Crafts reaction causes the carbon atom in the -CH 2 Cl group of the benzyl chloride group to become unbonded from the chlorine atom and bond to an aromatic carbon atom located on a new aromatic ring, resulting in the formation of a methylene bridge.

[0047] The aggregate of resin particles of the present invention can be used for any purpose. A preferred purpose is the purification of an aqueous solution containing one or more monosaccharides.

[0048] The aqueous solution can be obtained from any source. Some suitable sources include high fructose corn syrup process streams, sugarcane or beet sugar process streams, fermentation broths, starch streams or extracts, and cellulose hydrolysates. High fructose corn syrup process streams and sugarcane or beet sugar process streams are preferred, and high fructose corn syrup streams are more preferred. In the case of a sugarcane or beet sugar process stream, preferably, the aqueous solution is obtained by a process including mechanical operations on the sugarcane or beet (such as one or more of grinding, slicing, pressing, or combinations thereof); forming a mixture of water and the sugarcane or beet or the product of the mechanical treatment; and optionally filtering the mixture. In the case of a high fructose corn syrup process, preferably, the aqueous solution is obtained by a process including grinding corn to extract starch; forming a mixture of water and the corn or the product of grinding; adding acid and / or enzyme to the mixture to decompose the starch into shorter-chain sugars; and filtering the mixture.

[0049] Preferably, the amount of sugar solids dissolved in the aqueous solution is 10% by weight or more, more preferably 20% by weight or more, still more preferably 25% by weight or more, based on the weight of the aqueous solution. Preferably, the amount of sugar solids dissolved in the aqueous solution is 70% by weight or less, more preferably 50% by weight or less, still more preferably 40% by weight or less, based on the weight of the aqueous solution.

[0050] Preferably, the total amount of all monosaccharides is 1% by weight or more, more preferably 5% by weight or more, still more preferably 20% by weight or more, still more preferably 90% by weight or more, still more preferably 92% by weight or more, based on the weight of the dissolved sugar solids. Preferably, the monosaccharides include glucose, fructose, or a mixture thereof, and more preferably, the monosaccharides include glucose. Preferably, the amount of glucose is 50% by weight or more, more preferably 70% by weight or more, still more preferably 92% by weight or more, based on the total weight of all monosaccharides.

[0051] Preferably, the total of the amount of water plus the amount of dissolved sugar solids is 50% by weight or more, more preferably 70% by weight or more, still more preferably 90% by weight or more, still more preferably 95% by weight or more, based on the weight of the aqueous solution.

[0052] The aqueous solution preferably has a conductivity of 100 μS / cm or more, more preferably 200 μS / cm or more. The aqueous solution preferably has a conductivity of 10,000 μS / cm or less, more preferably 5,000 μS / cm or less.

[0053] The aqueous solution has a color component of 100 International Color Units (ICU, as defined by the International Commission for Uniform Methods of Sugar Analysis (ICUMSA)) or more. Preferably, the aqueous solution has a color component of 10,000 ICU or less, more preferably 5,000 ICU or less, still more preferably 2,000 ICU or less.

[0054] The aqueous solution can be brought into contact with the aggregate of the resin particles of the present invention by any method. Preferably, after bringing the aqueous solution into contact with the aggregate of the resin particles, the solution is separated from the aggregate of the resin particles. After separation, it is considered that a small amount of the substance that colored the original aqueous solution remains on the aggregate of the resin particles, and the color components of the aqueous solution are significantly reduced.

[0055] A preferred method is to pass the aqueous solution through a fixed bed of the aggregate of the resin particles. The fixed bed is held in a container that holds the aggregate of the resin particles in a predetermined position, while allowing the aqueous solution to enter from an inlet, contact the aggregate of the resin particles, and exit from an outlet. A suitable container is a chromatography column.

[0056] After the aqueous solution has been brought into contact with the aggregate of the resin particles and then separated from the aggregate of the resin particles, the aqueous solution is regarded as "treated" herein. The treated aqueous solution can be used for any purpose. Preferably, one or more of the following operations are performed on the treated aqueous solution, namely contact with activated carbon; contact with one or more cation exchange media; contact with one or more anion exchange media in addition to the aggregate of the resin particles of the present invention; or a combination of these.

[0057] When the aqueous solution is produced as part of a process stream of sugar from beet or sugar cane, preferably one or more of the following operations are performed on the treated aqueous solution, namely crystallization of the sugar in the solution; contact with one or more cation exchange media; contact with one or more anion exchange media in addition to the aggregate of the resin particles of the present invention; contact with chromatography resin; or a combination of these.

[0058] When an aqueous solution is produced as part of a high fructose corn syrup manufacturing process, the following operations are preferably carried out on the treated aqueous solution, namely contact with one or more cation exchange media; contact with one or more anion exchange media in addition to the aggregate of resin particles of the present invention; isomerization for the conversion of some or all of the glucose to fructose; contact with a chromatography resin for separately producing a solution rich in glucose and a solution rich in fructose; or one or more of these combinations are carried out.

Examples

[0059] The following are examples of the present invention. Unless otherwise stated, the operations were carried out at room temperature (about 23 °C).

[0060] The following eight commercially available comparative resins were tested. "x" means "not tested".

[0061]

Table 1

[0062] The water retention capacity was measured as follows. Briefly, excess water was removed from the resin under humid air to produce a dehydrated but wet resin. The wet resin was weighed, dried, and weighed again. The relative weight loss after drying is the water retention capacity. Specifically, 50 mL of an aggregate of resin particles was mixed with 50 mL of deionized (DI) water. The mixture was placed in a Buchner funnel on a vacuum flask, and the water was drained from the sample under gravity. The sample was capped with a rubber stopper connected to a hose supplying air at 100% relative humidity from a humidifying tower. The vacuum flask was evacuated and an air flow of 4.0 L / min was supplied for 5 minutes. As a result, a dehydrated wet resin was obtained. Then, 4 - 5 g of the resin was weighed (Wm), then dried in an oven at 105 °C for 18 hours, and then weighed again (Wd). The water retention capacity (WRC) is WRC(%) = 100*(Wm - Wd) / Wm given by

[0063] The amino groups per liter and the quaternary ammonium groups per liter were determined as follows. Briefly, the resin was converted to the chloride form and the chlorides were removed by eluting with an NO 3 aqueous solution. The "total exchange capacity" (TEC, the sum of the amino groups per liter and the quaternary ammonium groups per liter) was obtained from the amount of chloride in the elution fluid. Then, the resin was converted back to the chloride form using basic NaCl and the chlorides were removed by eluting with an NO 3 aqueous solution. The quaternary ammonium groups per liter ("strong base dosage", also called SBC) were obtained from the amount of chloride in the elution fluid. Then, the amino groups per liter ("weak base dosage", also called WBC) were determined from WBC = TEC - SBC.

[0064] Specifically, wet resin dehydrated as tested for water retention capacity was prepared. Approximately 15 g of resin was weighed (Wm), then mixed with water to a total volume of 25 mL. 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 1.0 N HCl aqueous solution at 25 mL / min for 1 L, followed by treatment with 1 L of an alcohol mixture (5 / 95 methanol / ethanol by volume) at 25 mL / min. Then, 1 L of 0.5 N NaNO 3 aqueous solution was passed through the sample at 25 mL / min, collected and stored as solution "A". Then, the following were passed through the sample: 1.0 N NaOH aqueous solution at 25 mL / min for 1 L; DI water at 25 mL / min for 1 L; 1.0 N NaCl at 25 mL / min for 1 L; DI water at 25 mL / min for 1 L. Then, 1 L of 0.5 N NaNO 3 aqueous solution was passed through the sample at 25 mL / min, collected and stored as solution "B". Solution A was adjusted to pH 4 using 1 N HNO 3 aqueous solution or 1 N NaOH aqueous solution. Then, using a Mettler Toledo TM automatic titrator, model T90, solution A was titrated with 0.1 N AgNO 3 for chloride until the inflection point of conductivity was observed. The titration volume was Va (mL), and AgNO3 The normality of the solution was Nag (eq / L). Solution B was adjusted for pH and titrated in the same manner, and the titration volume Vb (mL) was determined. Thereafter, the same NaNO 3 solution was adjusted for pH and titrated in the same manner, and the titration volume Vblank (mL) was determined. TEC = 10 * (Va - Vblank) * Na / Vm SBC = 10 * (Vb - Vblank) * Na / Vm = Equivalent weight of quaternary ammonium groups per liter of resin WBC = TEC - SBC = Equivalent weight of amino groups per liter of resin

[0065] Conductivity was measured using an Orion 162A conductivity meter from Thermo Scientific TM

[0066] Brix was measured using an AR200 refractometer (manufactured by Reichert, Inc.) calibrated in Brix units.

[0067] The color components were measured using a Genesys 10S UV-vis spectrophotometer from Thermo Scientific with a cell having a path length of 1 cm. The color components were reported as described by the International Commission for Uniform Methods of Sugar Analysis (ICUMSA), which is TM ICU = 1000 * (Absorbance at 420 nm) / [(Path length) * (Concentration of sugar)] Concentration of sugar = Brix / [100 * (Density in g / cm 3 ) units] is. The ICUMSA value calculated above is reported as ICU for international colorimetry.

[0068] ​​An aqueous solution was prepared as follows. High fructose corn syrup (HFCS) was used in which 42% by weight of the dissolved sugar solids was fructose and about 55% by weight of the dissolved sugar solids was glucose. The HFCS was heated at 80 °C for 4 - 5 hours at pH 1 and then neutralized to pH 3 - 4 with an aqueous NaOH solution. The aqueous solution had the following properties. "Cond" is the conductivity.

[0069]

Table 2

[0070] The results obtained using this aqueous solution are considered to be the same as those obtained when the aqueous solution contains a higher proportion of glucose (for example, 90% by weight or more of the dissolved sugar solids). For example, if the aqueous solution is obtained from a high fructose corn syrup process stream (rather than from the experimental procedure described above), it is expected that the aqueous solution will have a relatively high proportion of glucose and a relatively low amount of fructose. When the method of the present invention is carried out using an aqueous solution obtained from a high fructose corn syrup process stream, it is expected to obtain advantages similar to those reported in this specification obtained using an aqueous solution produced by the experimental procedure described above.

[0071] Color removal was carried out as follows. 30 mL of resin particles were packed into a chromatography column with an inner diameter of 15 mm and a length of 300 mm. The quaternary amine groups of the functionalized resin were converted to the hydroxide form by stirring the resin with a 4% by weight aqueous sodium hydroxide solution corresponding to 3 times the resin volume at room temperature. After repeating this process a total of 3 times, the resin was thoroughly washed with deionized water to remove excess sodium hydroxide. The column, resin particles and aqueous solution were heated to 60 °C and the aqueous solution was passed through the column at 3 bed volumes (BV) per hour. To evaluate color removal, the ICUMSA color was measured again in the aqueous solution before entering the column and after exiting the column. Color removal is reported as "decolorization": Decolorization = (CA - CB) / CA In the formula, CA is the ICUMSA color before entering the column, and CB is the ICUMSA color after exiting the column. The decolorization was measured at 50 BV.

[0072] Regeneration was carried out as follows. After stopping the passage of the aqueous solution, 3 BV of 1 wt% aqueous NaOH solution was passed through the column at a rate of 3 BV / hr at 60 °C, and then 3 BV of deionized water was passed through at 3 BV / hr at 60 °C. All of the NaOH solution and deionized water were recovered after passing through the column and combined into one. The absorbance at 420 nm of the combined solution is reported.

[0073] The osmotic stability was tested as follows. 3 BV of an aqueous solution of 20 wt% lactic acid was passed through a resin bed containing 4 mL of resin particles at a flow rate of 1.0 mL / min for 12 minutes, and then the resin in the column was rinsed with 4 BV of deionized (DI) water at a flow rate of 1.0 mL / min for 15 minutes. Then, 3 BV of 4 wt% aqueous sodium hydroxide solution was passed through the resin at a flow rate of 1.0 mL / min for 12 minutes, and then rinsed with 4 BV of DI water for 15 minutes. This cycle was repeated 23 more times for a total of 24 cycles. After 24 cycles were completed, samples of each resin were collected, microscopic photographs of the beads were taken, and inspected to count the beads that remained intact. The osmotic strength is reported as the percentage of intact particles based on the total number of particles. The higher the percentage of intact beads, the greater the osmotic strength.

[0074] Synthesis Example 1: Synthesis of Resin Particles Copolymer particles were obtained. The copolymer was a copolymer of styrene, ethylvinylbenzene, and divinylbenzene produced by aqueous suspension polymerization from a suspension of droplets containing a mixture of monomer, initiator, and porogen. The monomer mixture contained more than 90 wt% styrene based on the total weight of all monomers. The droplets contained 20 wt% - 60 wt% porogen based on the weight of the droplets. This copolymer is suitable for use in standard industrial techniques for producing either known weak base ion exchange resins or known strong base ion exchange resins.

[0075] The copolymer was chloromethylated as follows. 60 g of the copolymer was added to 350 mL of chloromethyl methyl ether under stirring and swollen for 30 minutes. 3.6 g of the catalyst FeCl 3 was added and the heating profile was started. The heating temperature (jacket temperature) was set at 70 °C. Since the boiling point of the mixture was about 50 - 60 °C, depending on the sample, the reaction was maintained within this temperature range under reflux for 20 to 45 minutes. Since the chloromethyl ether was boiling and flying off, additional 50 ml - 200 ml of chloromethyl ether was added from time to time to maintain the fluidity during the reaction. After the holding time, heating was stopped, methanol was added to quench the reaction, and stirring was continued for 15 minutes. The reactor was cooled to room temperature (about 23 °C), and the solution was siphoned out from the reactor. The resin was washed with solvents in the order of methanol, methylal, and methanol to remove the residual ether. Methanol was siphoned out, methylal was added to swell the beads for 30 minutes. Methylal was siphoned out to prepare for the amination of the chloromethylated copolymer.

[0076] The chloromethylated copolymer was aminated as follows. 150 mL of chloromethylated beads was added to a mixed solution containing 58 g of 50 wt% aqueous NaOH solution and 60 g of 40 wt% aqueous dimethylamine (DMA) solution (the weight ratio of amine / copolymer was 0.5 - 0.6). The reaction was maintained at 100 °C for about 2 hours under reflux. When the reaction was completed, the solution was siphoned out. The resin was washed 3 times with DI water, followed by washing with 2N aqueous HCl solution for 30 minutes to remove all the residual amines. HCl was siphoned out, and the resin was backwashed with DI water until the effluent became neutral (pH about 7).

[0077] The following resins were produced. Resin numbers ending with "C" are comparative examples. The same copolymer was used for all 5 kinds of resins. The resins differed only in the chloromethylation and / or amination conditions.

[0078]

Table 3

[0079] Test Example 2: Decolorization and Regeneration Decolorization and regeneration were carried out as described above. The results were as follows.

[0080] [Table 4]

[0081] The decolorization of all the resins of the present invention was equivalent to or better than the decolorization of all the comparative samples. The regeneration of all the resins of the present invention was much better than the regeneration of all the comparative resins.

[0082] Test Example 3 The osmotic stability was tested. The results were as follows.

[0083] [Table 5]

[0084] The resins of the present invention exhibit better osmotic stability than all the comparative resins. (Aspect) (Aspect 1) An aggregate of resin particles, wherein the resin particles contain one or more polymers, the polymer contains a methylene crosslinking group between aromatic rings, the polymer contains amino groups bonded to the resin particles in a total amount of 0.1 to 1.4 equivalents per liter of the aggregate of the resin particles, either no quaternary ammonium groups are bonded to the polymer or, otherwise, they are present in an amount of 0.05 equivalents or less per liter of the aggregate of the resin particles, the resin particles have a water retention capacity of 40% to 50% by weight based on the weight of the aggregate of the resin particles, the resin particles have a surface area of 100 m 2 / g or less, an aggregate of resin particles. (Aspect 2) The aggregate of resin particles according to Aspect 1, having a ratio of D60 / D10 of less than 1.1. (Aspect 3) The aggregate of resin particles according to Aspect 1, wherein the methylene crosslinking group is present in an amount of 4% by weight or less based on the total dry weight of the resin particles.

Claims

1. An aggregate of resin particles having pores, wherein the resin particles consist only of one or more crosslinked vinyl aromatic copolymers, and the total weight of the polymerized units of all vinyl aromatic monomers is 90% by weight or more of the polymer, the polymer contains a methylene crosslinking group between aromatic rings, the polymer contains 1.0 to 1.4 equivalents per liter of the aggregate of the resin particles of amino groups bonded to the polymer, either no quaternary ammonium groups are bonded to the polymer or, if present, they are present in an amount of 0.05 equivalents or less per liter of the aggregate of the resin particles, the resin particles have a water retention capacity of 40% to 47% by weight based on the weight of the aggregate of the resin particles, The resin particles have a specific surface area of 100 m ２ / g or less, the weight of the aggregate of the resin particles is the total weight of the resin particles, water and any optional other components, an aggregate of resin particles.

2. The aggregate of resin particles according to claim 1, having a D60 / D10 ratio of less than 1.

1.

3. The aggregate of resin particles according to claim 1, wherein the methylene crosslinking group is present in an amount of 4% by weight or less of the methylene crosslinking group based on the total dry weight of the resin particles.

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