WO2004108969A1 - Procede de raffinage du sucrose - Google Patents

Procede de raffinage du sucrose Download PDF

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Publication number
WO2004108969A1
WO2004108969A1 PCT/US2004/018014 US2004018014W WO2004108969A1 WO 2004108969 A1 WO2004108969 A1 WO 2004108969A1 US 2004018014 W US2004018014 W US 2004018014W WO 2004108969 A1 WO2004108969 A1 WO 2004108969A1
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WIPO (PCT)
Prior art keywords
liquid sucrose
product
exchange resin
activated carbon
sucrose
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PCT/US2004/018014
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English (en)
Inventor
James T. Ii Walsh
Dennis P. Byrne
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Cargill, Incorporated
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Publication of WO2004108969A1 publication Critical patent/WO2004108969A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B20/00—Purification of sugar juices
    • C13B20/12—Purification of sugar juices using adsorption agents, e.g. active carbon
    • C13B20/123—Inorganic agents, e.g. active carbon
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B20/00—Purification of sugar juices
    • C13B20/14—Purification of sugar juices using ion-exchange materials
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B20/00—Purification of sugar juices
    • C13B20/14—Purification of sugar juices using ion-exchange materials
    • C13B20/142—Mixed bed

Definitions

  • the present disclosure relates to refining raw sucrose to produce a more pure sucrose product.
  • raw liquid sucrose may be contacted with at least activated carbon to produce a first liquid sucrose intermediate product.
  • the first liquid sucrose intermediate product may be contacted with a strong base anion exchange resin and a weak acid cation exchange resin to produce a second liquid sucrose intennediate product.
  • the second liquid sucrose intermediate product may be contacted with at least one sensory-enhancing material selected from activated carbon or an ion exchange resin resulting in a refined liquid sucrose product.
  • raw liquid sucrose may be contacted with at least one media selected from activated carbon or an ion exchange resin to produce a first intermediate liquid sucrose product.
  • the first intermediate liquid sucrose product may be contacted with a strong base anion exchange resin and a weak acid cation exchange resin to produce a second intermediate liquid sucrose product.
  • the second intermediate liquid sucrose product may be ⁇ passed through an activated carbon column resulting in a refined liquid sucrose product.
  • raw liquid sucrose may be contacted with at least one media selected from activated carbon or an ion exchange resin to produce a first intermediate liquid sucrose product.
  • the first intermediate liquid sucrose product may be contacted with a strong base anion exchange resin to produce a second intermediate liquid sucrose product.
  • the second intermediate liquid sucrose product may be contacted with a weak acid cation exchange resin at a temperature of less than 40°C to produce a third intermediate liquid sucrose product.
  • the third intermediate liquid sucrose product may be contacted with at least one sensory- enhancing material selected from activated carbon or an ion exchange resin resulting in a refined liquid sucrose product.
  • raw liquid sucrose may be contacted with at least one media selected from activated carbon or an ion exchange resin to produce a first intermediate liquid sucrose product.
  • the first intermediate liquid sucrose product may be contacted with a strong base anion exchange resin to produce a second intermediate liquid sucrose product.
  • the second intermediate liquid sucrose product may be contacted with a homogeneous weak acid cation exchange resin bed to produce a third intermediate liquid sucrose product.
  • the third intermediate liquid sucrose product may be contacted with at least one sensory-enhancing material selected from activated carbon or an ion exchange resin resulting in a refined liquid sucrose product.
  • FIG. 1 is a schematic process flow diagram of one example of a process disclosed herein.
  • Ash refers to various organic and inorganic agents that may be present in a sucrose- containing composition. Ash includes potassium, ammonium, sodium, calcium, and magnesium cations; chloride, sulfate and phosphate anions; proteins; and organic acids such as lactic acid and succinic acid.
  • the ash content in any given sucrose-containing composition may be determined in accordance with conductivity ash procedures established by the International Commission for Uniform Methods for Sugar Analysis (“ICUMSA").
  • De-ashing involves removing ash impurities from a sucrose-containing composition such as liquid sucrose. De-ashing may by used interchangeably with de-mineralization in the industry. The use of “de-ashing” in this disclosure also encompasses de-mineralization to the extent that there is any distinction between the two terms.
  • De-colorization refers to removing color bodies or agents from a sucrose-containing composition such as liquid sucrose.
  • Color bodies or agents include, by the way of example, caramels, melanoidins, polyphenolics, flavanoids, and color precursors such as amino acids, hydroxy acids, aldehydes, iron compounds that complex with phenolics, 5-hydroxymethyl-2- furfural, 3-deoxy-d-glucose, and reducing agents.
  • Homogeneous ion exchange resin bed denotes a resin bed that contains only one class of ion exchange resin (e.g., a weak acid cation exchange resin).
  • a homogeneous bed is distinguished from a mixed bed that includes at least two different classes of ion exchange resins.
  • I.C.U is an abbreviation for "international color units" as determined in accordance with procedures established by the ICUMSA.
  • Invert sugar includes non-sucrose sugars such as glucose and fructose that typically are present in a sugar composition.
  • the invert sugars may be present as a result of hydrolysis of sucrose.
  • invert sugar does not necessarily imply that the glucose and fructose are present in equimolar proportions.
  • the amount of invert sugar in a given sugar material may be measured in accordance with several procedures such as high-pressure liquid chromatography, ion chromatography, or polarimetry, and is referred to herein as a weight percentage of invert sugar present in the composition, based on the total dry solids content.
  • Liquid sucrose refers to any material, batch, composition, or mixture that includes liquid sucrose as a significant, if not the primary, component.
  • the sucrose typically maybe at least partially, if not substantially, dissolved in a liquid medium or carrier (e.g., water). A portion of the sucrose may also be in the form of solids suspended in a liquid carrier phase (e.g., an aqueous slurry).
  • a liquid medium or carrier e.g., water
  • a portion of the sucrose may also be in the form of solids suspended in a liquid carrier phase (e.g., an aqueous slurry).
  • “Raw liquid sucrose” refers to liquid sucrose that is generally not commercially acceptable for human consumption, particularly for use by food and drink manufacturers. For example, raw liquid sucrose may be produced by extracting cane sugar juice from sugarcane. The cane sugar juice then is crystallized into brown sugar crystals.
  • raw liquid sucrose does not have a specific classification and can be made by dissolving any quality of raw sugar into water.
  • Raw liquid sucrose may include, but is not limited to, aqueous sucrose syrup.
  • “Refined liquid sucrose” refers to liquid sucrose that has been refined from raw liquid sucrose via at least one refining stage.
  • An illustrative example of a refined liquid sucrose is bottler's grade liquid sugar.
  • “Sensory-enhancing material” refers to a separation material that can remove agents or bodies that impart an unpleasant taste or odor to a liquid sucrose composition.
  • “Strong base anion exchange resin” denotes an anion exchange resin that is fully or strongly ionized as opposed to weakly ionized.
  • a distinguishing feature between weak base anion exchange resins and strong base anion exchange resins concerns their differing exchange capacity.
  • a strong base anion exchange resin has a fixed exchange capacity per resin bead across the pH range of the liquid in which the resin is in contact.
  • Weak base anion exchange resins vary from a negligible exchange capacity to a high exchange capacity depending upon the pH of the liquid in which the resin is in contact.
  • “Weak acid cation exchange resin” denotes a cation exchange resin that is weakly ionized as opposed to fully or strongly ionized.
  • a distinguishing feature between weak acid cation exchange resins and strong acid cation exchange resins concerns their differing exchange capacity.
  • a strong acid cation exchange resin has a fixed exchange capacity per resin bead across the pH range of the liquid in which the resin is in contact.
  • Weak acid cation exchange resins vary from a negligible exchange capacity to a high exchange capacity depending upon the pH of the liquid in which the resin is in contact.
  • Weak acid cation exchange resins typically are functionalized by hydrolyzing an ester group with an acid or base to produce a carboxyl ion exchange group.
  • strong acid cation exchange resins typically are functionalized via sulfonation to produce sulfonyl ion exchange groups.
  • the processes disclosed herein relate to producing a refined liquid sucrose product from raw liquid sucrose. Due to the unique combination of process modules involving ion exchange resins and, in certain embodiments, activated carbon, crystallization steps are not typically required during the refining process. Hence, the processes disclosed herein offer the possibility of substantially reduced costs. It should be recognized that the use of at least one crystallization step in conjunction with the refining processes disclosed herein is not necessarily excluded. Moreover, despite the lack of any crystallization purification steps, the refined liquid sucrose products disclosed herein exhibit product characteristics such as color, taste, odor (collectively referred to herein as "sensory" properties) and ash content that are substantially similar to those of commercially available liquefied crystal sugar that was refined using crystallization. The refined product also is produced in a liquid phase that can be supplied directly to customers in contrast to the current need to liquefy conventional crystal refined sugar to produce liquid sugar.
  • the processes disclosed herein are able to substantially minimize the production of invert sugar during the refining process.
  • Invert sugar is undesirable since it can reflect the degree of impurity in sucrose solutions or solids.
  • certain products such as liqueurs and candy demand the highest purity of sucrose as exemplified by Large Grain Granulated Sugar quality sucrose (see Chen and Chou, Cane Sugar Handbook).
  • the increase in the amount of invert sugar from the raw liquid sucrose to the refined liquid sucrose product may be less than about 1.0 weight %, particularly less than about 0.5 weight %, more particularly less than about 0.2 weight %, and most particularly less than about 0.1 weight %.
  • Certain process parameters have been identified in the present disclosure that can minimize the formation of invert sugar.
  • Especially sensitive process conditions effecting invert sugar formation include temperature, pH and the contact time with specific types of ion exchange resins as described below in more detail. Control of the pH during the process is particularly illustrative.
  • the system pH can be maintained above about 7.0, more particularly about 7.5, to minimize invert sugar formation, although a pH below these levels can be tolerated depending upon the temperature and/or resin contact time.
  • a sucrose process stream may experience a pH decrease or increase as it flows through a process module.
  • the various process modules are described below in detail. However, such a pH modulation is acceptable provided the pH is adjusted accordingly in a relatively short time after the sucrose stream exits the module and/or the sucrose stream retention time within the module unit equipment is sufficiently minimized. For example, the sucrose stream exiting a module could be immediately directed into a pH trim tank for pH adjustment.
  • the raw liquid sucrose can be provided with any invert sugar level.
  • concentration of invert sugar present in the feedstock should be known.
  • the invert sugar concentration in the refined liquid sucrose product is equal to, or slightly greater than the invert concentration in the feedstock.
  • the customer specifications for invert sugar concentration in the refined liquid sucrose product must be considered. If the respective customer requirements are known, the invert sugar concentration in the feedstock can be selected to meet the finished product requirements allowing for a small additional invert sugar creation in the process. However, if invert sugar levels are not of significant concern, then invert sugar level requirements in the feedstock can be relaxed.
  • the refined liquid sucrose product may have any amount of invert sugar. However, in certain instances, the refined liquid sucrose product may have an invert sugar level of less than about 1 weight %, more particularly less than about 0.5 weight %, and most particularly less than about 0.1 weight %.
  • the raw liquid sucrose initially is subjected to a pretreatment/de-colorization process module.
  • the pretreatment/de-colorization process module can selectively remove a substantial amount of color, odor and organic compound impurities from the raw liquid sucrose feedstock.
  • the pretreated liquid sucrose resulting from the pretreatment process module then enters a de-ashing process module.
  • the de- ashing process module can selectively remove a substantial amount of ash and an additional amount of color.
  • the substantially de-colorized/de-ashed sucrose resulting from the de-ashing process module then enters a polishing process module.
  • the polishing process module can selectively remove flavors and odors to provide a more sensory-enhanced refined liquid sucrose product.
  • Each one of these process modules may include one or more steps.
  • the raw liquid sucrose for use as the starting material or process feedstock may be produced from various biomaterials such as sugarcane, sugar beet, sorghum, honey, maple sap, corn, and mixtures thereof.
  • Cane or beet raw sugar is a particularly useful starting material because of their abundance and the feedstock for the present process can be produced with very few steps from the raw crop.
  • the invert sugar level of the feedstock may vary widely, but in the case of cane raw sugar, the invert sugar level, for example, may less than about 0.05 weight %, but it could range up to about 0.1 weight % or greater depending upon the desired invert sugar level in the refined liquid sucrose product.
  • the presently disclosed processes can accept a wide range of ash amount and color level in the raw sucrose feedstock and still meet bottler's grade qualities in the refined product.
  • the raw liquid sucrose feedstock may include as impurities or contaminants (in addition to invert sugar as described above), less than or equal to about 2.0 weight %, more particularly less than or equal to about 1.0 weight %, based on the total dry weight of raw sucrose feedstock.
  • the minimum amount of ash in the raw feedstock may be about 0.25 weight %, more particularly about 0.15 weight %.
  • the raw liquid feedstock may have an I.C.U. of less than or equal to about 3000, more particularly less than or equal to about 1500, although the maximum I.C.U. should only be limited by the maximum amount of space available for the separation vessels used in the process.
  • the solids content of the raw liquid sucrose can vary, although a high solids content can limit evaporation costs.
  • the raw liquid sucrose may have a Brix degree of about 30 to about 60, with a more particular minimum of about 50.
  • the solids content of the raw liquid sucrose feedstock may range, for instance, from about 40 weight % to about 60 weight %, more particularly from about 50 weight % to about 55 weight %.
  • the raw liquid sucrose feedstock may be provided as crystallized raw sucrose which is washed and/or affined and then liquefied prior to its introduction into the refining processes. Such liquefaction may be accomplished, for example, by melting the crystallized raw sucrose in an aqueous medium such as water or a sugar aqueous solution. However, as mentioned above, no crystallization steps are necessary during the refining process itself.
  • the initial refining may occur within a pretreatment/de-colorizing process module.
  • a primary component of the pretreatment/de-colorizing process module is a separation stage such as at least one activated carbon treatment and/or at least one ion exchange resin. If a combination of activated carbon and an ion exchange resin is used, the activated carbon stage and ion exchange resin stage may be arranged in any order relative to the flow direction of the sucrose feedstock.
  • the pretreatment process module may also include screening of the raw liquid sucrose to remove large-sized solid matter.
  • the ion exchange resin may be especially useful for de-colorizing.
  • the pretreatment process module includes an activated carbon column as a first stage and at least one. strong base anion exchange resin as a second stage.
  • the pretreatment process module includes at least one strong base anion exchange resin, but no activated carbon treatment.
  • the second process scheme could include a first strong base anion exchange resin that is tailored to absorb colorants in a high colorant-load sucrose stream followed by a second strong base anion exchange resin tailored to absorb colorants in a lower colorant-load sucrose stream.
  • the sucrose feedstock may be contacted with the activated carbon and/or ion exchange resin under conditions sufficient for removing a substantial amount of the color (e.g., up to about 90%), and a substantial amount of large organic molecules that could foul the ion exchange resins in the downstream process, hi the activated carbon column followed by strong base anion exchange resin approach, the activated carbon may remove about 50% to about 90% of the color in raw sucrose feedstock.
  • the de-colorizing resin then can remove another 50% to 90% of the color of the sucrose stream received from the activated carbon.
  • the activated carbon may lower the color level to about 150 to about 750 I.C.U, more particularly below about 300 I.C.U.
  • the de-colorizing resin then could lower the color level to about 40 to about 375 I.C.U., more particularly below about 501.C.U.
  • the pH of the raw sucrose feedstock may be adjusted as necessary to be at least about 7.0, more particularly about 7.5.
  • the pH adjustment may be accomplished be adding a base as appropriate to the raw sucrose.
  • Illustrative bases for pH adjustment in the disclosed processes include hydroxides and carbonates of sodium, potassium and magnesium.
  • the amount of sucrose feedstock flowing through the activated carbon and/or ion exchange resin varies depending upon parameters such as pH drop, plant volume and production rates.
  • the flowrate ranges for each process module are dependent upon each other but are not necessarily equal. For example, the flowrate through an activated carbon column may range from about 0.1 to about 1 bed volume hour ("BV/hr"), but could be outside this range depending upon the specific parameters.
  • the temperature of the feedstock flowing through the activated carbon may range from about 50°C to about 90°C, more particularly about 60°C to about 80°C, and the pH of the sucrose may range from about 6.5 to about 9, more particularly about 7.0 to about 8.5.
  • the pH may decrease by up to about 2 units as the sucrose flows through the activated carbon, and thus the pH of the incoming sucrose can be adjusted to take into account an anticipated pH drop.
  • the pH of the pretreated liquid sucrose may be adjusted at a point downstream from the activated carbon.
  • magnesite may be added to the activated carbon to minimize the pH drop.
  • the maximum temperature of the ion exchange resin (such as the de-colorizing ion exchange resin) in the pretreatment/de-colorizing process module should be less than the given temperature stability limits of a specific resin. In addition, higher temperatures can avoid microbial growth.
  • the temperature may range, for example, from less than about 40°C (e.g., down to about 10°C or 30°C) to about 80°C, more particularly about 50°C to about 80°C. In the case of a strong base anion exchange (type I) resin for the de-colorizing resin, the temperature may range from less than about 40°C to about 80°C.
  • the temperature may range from about less than about 40°C to about 60°C.
  • the pH of the sucrose feeding to the de-colorizing resin may range as described above for the activated carbon treatment.
  • the activated carbon may be thermally or chemically activated.
  • the activated carbon may be utilized in any fo ⁇ n such as a powdered, granular, shaped or as activated carbon cloth.
  • the activated carbon may be a specific type of surface modification that renders the activated carbon acidic, basic, hydrophilic, or amphoteric.
  • One example of an activated carbon is an acid- washed, granular activated carbon such as those grades commercially available from Calgon Carbon Corporation under the trade designation CPG.
  • the activated carbon may include an additive (e.g., magnesium hydroxide or magnesite) that imparts increased pH stability.
  • a useful activated carbon format is an activated carbon column. More particularly, the activated carbon is arrayed or packed within a cylindrical vessel.
  • an activated carbon column is a pulsed column.
  • a pulsed column typically operates in a counter-current configuration with the flow moving up the column. Periodically, slugs of spent activated carbon are extracted from the bottom and virgin or regenerated activated carbon is inserted into the top of the column. The flow of new to old carbon is in the direction opposite to the sucrose flow. Thus, the incoming sucrose composition is initially exposed to the most spent carbon and then moves through zones of cleaner activated carbon.
  • a portion, say 5 to 10%, of the activated carbon contained in the column may be removed from the bottom every day and an equal amount of regenerated carbon is put into the top.
  • the removed carbon is rinsed with water to remove sugar (creating sweetwater) and then it is regenerated in a furnace.
  • a batch operation may be used rather than a continuous column operation.
  • the activated carbon and the sucrose feedstock are mixed together in a vessel.
  • the resulting mixture then is filtered to remove the activated carbon fines.
  • the activated carbon should be regenerated as required for maintaining its operating efficiency.
  • Various regeneration techniques can be used such as thermal, chemical, hot gas, or solvent methods. Suitable conditions for regenerating these types of resins are known in the activated carbon industry.
  • the ion exchange resin that could be used in the pretreatment process module may be selected from any class of resins such as weak and strong-acid resins for removing cations, and weak and strong-base resins for removing anions.
  • Ion exchange resins typically are copolymers of at least one monoethylenically unsaturated monomer with at least one polyunsaturated monomer.
  • monoethylenically unsaturated monomers include polycyclic aromatics such as vinylnaphthalenes, monocyclic aromatics such as styrene and substituted styrene, and (meth)acrylic monomers.
  • polyunsaturated monomers include di- or trivinyl aromatics such as divinylbenzene, and di- or trimethacrylates such as ethylene glycol dimethacrylate.
  • a strong base anion exchange resin (either type I or II) may be especially suitable for de-colorizing.
  • An example of a commercially available strong base anion exchange resin useful in the pretreatment process module is a high porous (i.e., macroporous) resin available from Mitsubishi Chemical under the tradename Diaion HPA25.
  • Diaion HPA25 is a type I resin having a styrenic polymer backbone and a quaternary ammonium(Cr) ion exchange group.
  • regenerants can be used for the de-colorizing resin such as a caustic-brine solution (e.g., a mixture of NaCl and NaOH), a brine solution (e.g., NaCl), or a caustic solution (e.g., NaOH, KOH, or NH 4 OH).
  • a caustic-brine solution e.g., a mixture of NaCl and NaOH
  • brine solution e.g., NaCl
  • a caustic solution e.g., NaOH, KOH, or NH 4 OH
  • Specific illustrative aqueous regenerants include a 10% NaCl - 1% NaOH mixture, a 10% NaCl solution, and a l%-4% NaOH solution.
  • Such resins have a particularly strong affinity for colorants when regenerated with sodium hydroxide or a sodium hydroxide/brine solution.
  • the regenerant dose can vary as required depending upon the specific resin.
  • NaCl/ft 3 resin may be used with a contact time of greater than about 40-60 minutes and a flow rate of about 1 to about 2 BV/hr.
  • Certain ion exchange resins are described in more detail below.
  • the first liquid sucrose intermediate or pretreated liquid sucrose then can be subjected to the de-ashing process module.
  • the intermediate product targets may vary depending upon the feedstock and desired refined product, the conditions in the de-ashing module can be sufficient for generating a de-colorized/de-ashed liquid sucrose intermediate having an I.C.U. of less than about 35 (especially if the pretreated sucrose has an I.C.U. of about 50 to about 375).
  • the ash content of the de-colorized/de-ashed liquid sucrose intermediate may be, for example, less than about 0.03 weight %, more particularly less than about 0.01 weight %, measured as conductivity ash.
  • the de-ashing process module may at least include contacting the pretreated liquid sucrose with a strong base anion exchange resin and a weak acid cation exchange resin.
  • the strong base anion exchange resin and the weak acid cation exchange resin may be provided together in a mixed bed configuration.
  • separate beds may be provided for the strong base anion exchange resin and for the weak acid cation exchange resin.
  • the separate resin beds may be provided in separate vessels or they can be placed in a single vessel that includes a split bed design such that the resins do not undergo a mixing process but have a contacting boundary layer. With separate vessels, the strong base anion exchange resin bed and the weak acid cation exchange resin bed can be operated at independent temperatures if desired.
  • both the anion bed and the cation bed will operate at the same temperature.
  • the strong base anion exchange resin and the weak acid cation exchange resin may be placed serially in any order with respect to the flow direction of the pretreated liquid sucrose through the beds.
  • the pretreated liquid sucrose initially contacts the strong base anion exchange resin and thereafter contacts the weak acid cation exchange resin.
  • Suitable strong base anion exchange resins include resins having a backbone polymer or matrix of (meth)acrylic, (poly)styrenic, or similar polymers.
  • Strong base anion exchange resins typically are styrene-divinylbenzene copolymers onto which various functional groups can be bonded to provide ion exchange groups. For example, a styrene-divinylbenzene copolymer can undergo chloromethylation followed by amination to introduce ammonium groups into the resin structure.
  • a type I e.g., the ion exchange group is a quaternary ammonium that includes three methyl groups substituents on the nitrogen atom
  • type II e.g., the ion exchange group is a primary, secondary, tertiary, or quaternary ammonium group that includes a hydroxyethyl substituent on the nitrogen atom
  • a pre-used type II resin such as a resin that has been used in a fructose purification process, as opposed to a virgin type II resin, can be employed in the process.
  • the resin may be microporous (i.e., gel-type) or macroporous, and it may be in the form of beads or powdered.
  • Illustrative commercially available strong base anion exchange resins include those available from Thermax (e.g., Tulsion A-72 SBA, Tulsion A-72 MP, or Tulsion A-30 MP), Dow Chemical (e.g., various resins available under the DOWEX tradename such as DOWEX Marathon 11 or Marathon MSA), Rohm & Haas (e.g., various resins available under the AMBERLITE tradename such as AMBERLITE FPA 91), Purolite (e.g., A-500S) and Mitsubishi Chemical (e.g., under the tradename Diaion HPA25).
  • Thermax e.g., Tulsion A-72 SBA, Tulsion A-72 MP, or Tulsion A-30 MP
  • Dow Chemical e.g., various resins available under the DOWEX tradename such as DOWEX
  • the strong base anion exchange resin(s) may be configured as mixed beds or in serially arranged, separated homogeneous beds for a continuous flow operation.
  • the resin bed(s) can be provided in packed columns.
  • more than one bed of the same type of strong base anion exchange resin could be employed.
  • the resin and the sucrose may be mixed together and subsequently filtered to separate the impurity-loaded resin and the sucrose.
  • the strong base anion exchange resin should be regenerated as required for maintaining its operating efficiency.
  • regenerants can be used as described above in connection with the de-colorizing strong base anion exchange resin. Periodic cross regeneration of the resin using an acid (e.g., HC1) could be employed to remove fouling. Sodium hydroxide may be particularly effective for the de-ashing strong base anion exchange resin.
  • the regenerant dosage can vary. In one example, about 3 to about 6 pounds of NaOH/bed ft 3 can be employed, with a contact time of about 45 to about 75 minutes. In the case of a continuous operation employing a resin bed, the regenerant may be introduced through the bed in a countercurrent flow relative to the sucrose flow direction.
  • the amount of pretreated sucrose flowing through the de-ashing strong base anion' exchange resin varies depending upon other parameters such as ion load and cation to anion ratio in the sucrose stream, but may range from about 0.2 to about 5, more particularly about 0.5 to about 2, BV/hr.
  • the strong base anion exchange resin bed temperature may range from less than about 40°C (e.g., down to about 10°C or about 30°) to about 80°C (for a type I resin), and from less than about 40°C (e.g., down to about 10°C or about 30°) to about 50°C (for a type II resin).
  • the strong base anion exchange resin may be less than about 40°C.
  • the pH of the pretreated sucrose entering the strong base anion exchange resin may range from about 6 to about 8. There may be a pH adjustment at a point prior to entry into the strong base anion exchange resin.
  • the pH of the sucrose stream exiting the strong base anion exchange resin may range from about 6 to about 9.
  • a weak acid cation exchange resin may be the most effective ion exchange resin class for minimizing formation of invert sugar.
  • a weak acid action exchange resin bed temperature of less than about 40°C can be particularly suitable for this purpose.
  • Any suitable weak acid cation exchange resin may be used.
  • Suitable weak acid cation resins include resins having a backbone polymer or matrix of (meth)acrylic, (poly)styrenic, or similar polymers.
  • Weak acid cation exchange resins typically are copolymers of divinylbenzene with acrylic acid or methacrylic acid.
  • Various functional groups can be bonded to the copolymer network to provide ion exchange groups.
  • the resin may be microporous (i.e., gel-type) or macroporous, and it may be in the form of beads or powdered.
  • Particularly useful resin matrices include gel-type polyacrylics.
  • the carboxyl ion exchange group may be regenerated with an acid such as sulfuric acid so that the resin operates as in H + form, but other cation types such as Na + may also be used.
  • Resin particle sizes can vary depending upon the operating conditions. For example, the particle size can be greater than about 40 mesh when utilizing a mixed bed or split bed, but smaller particle sizes can be utilized in homogeneous beds.
  • Illustrative commercially available weak acid cation exchange resins include those from Purolite (e.g., Purolite C-104E, Purolite C-l 15E), Dow Chemical (e.g., various resins available under the DOWEX tradename such as MAC 3), and Rohm & Haas (e.g., IMAC HP 33 and various resins available under the AMBERLITE tradename).
  • Purolite e.g., Purolite C-104E, Purolite C-l 15E
  • Dow Chemical e.g., various resins available under the DOWEX tradename such as MAC 3
  • Rohm & Haas e.g., IMAC HP 33 and various resins available under the AMBERLITE tradename.
  • More than one specific type of weak acid cation exchange resin may be employed.
  • the different types of weak acid cation exchange resin may be configured as mixed beds, split beds, or in serially arranged, separated homogeneous beds for continuous flow operation.
  • the resin bed(s) may be provided in packed columns.
  • the weak acid cation exchange resin is provided as a homogeneous bed according to certain variants.
  • a homogeneous weak acid cation exchange resin bed allows the preceding anion exchange resin to be maintained at a higher temperature. Consequently, cooling only occurs across the cation exchange resin bed which minimizes the low temperature zone volume and may be more beneficial for inhibiting microbial growth.
  • more than one bed of the same type of weak acid cation exchange resin could be employed.
  • the resin and the sucrose may be mixed together and subsequently filtered to separate the impurity-loaded resin and the sucrose.
  • the weak acid cation exchange resin should be regenerated as required for maintaining its operating efficiency.
  • regenerants can be used such as an aqueous mineral acid (e.g., hydrochloric acid or sulfuric acid). Suitable conditions for regenerating these types of resins are known in the ion exchange resin industry.
  • a 1 to 4% HCl aqueous solution can be passed through the bed at about 4 to about 8 BV/hr with a contact time of about 30 to about 45 minutes.
  • the regenerant may be introduced through the bed in a countercurrent flow relative to the sucrose flow direction.
  • the amount of pretreated sucrose flowing through the weak acid cation exchange resin varies depending upon other parameters such as retention time and temperature, and should be balanced to minimize invert sugar formation.
  • the flow rate may range from about 2 to about 4 BV/hr to maintain the invert sugar increase to less than about 0.1 weight %.
  • the weak acid cation exchange resin bed , temperature may be less than about 46°C, more particularly less than about 40°C, and most particularly less than about 35°C.
  • the pH of the liquid sucrose composition entering the weak acid cation exchange bed may be about 6 to about 9.
  • the pH of the sucrose composition may be adjusted to be at least 8.
  • the de-ashing process module could include other classes of ion exchange resins in addition to the strong base anion exchange resin and the weak acid cation exchange resin.
  • a strong acid cation exchange resin could also be used for de-ashing.
  • the strong acid cation exchange resin could be provided in a mixed bed with the weak acid cation exchange resin or as a separate bed that is located in the flow direction either before or after the weak acid cation exchange resin.
  • the ion exchange resin separated bed order relative to the sucrose flow direction maybe a strong base anion exchange resin bed followed by a weak acid cation exchange resin bed.
  • the separated bed order may be a first strong base anion exchange resin bed, a second strong base anion exchange resin bed, and then a weak acid cation exchange resin bed.
  • the strong base anion exchange resin and the weak acid cation exchange resin can have significantly different sucrose throughputs.
  • the bed sizes and/or number of beds can be designed accordingly to accommodate this difference.
  • the anion resin bed can be up to six times larger than the cation resin bed or multiple anion resin beds can be employed. With the former option, then both the anion bed and cation bed could be taken out of service for regeneration at the same time. With the latter option, the anion resin beds could be rotated in and out of service as they reach their operating capacity. As one bed continues to remove ions, the other bed can be regenerated.
  • a recycle system can be employed around the de-ashing module or the de-ashing module and the pretreatment/de-colorizing module to minimize retention times, and thus minimize invert sugar formation.
  • Such a recycle stream also could be employed to achieve a minimum flowrate through a resin bed to minimize the resin particles from floating in a high brix sucrose process.
  • the de-colorized/de-ashed liquid sucrose intermediate product exiting the de-ashing process module may still include an amount of impurities such that its sensory quality is inadequate compared to commercially available sucrose refined with crystallization.
  • a polishing process module for improving the sensory characteristics may be instituted at the backend of the process flow.
  • the polishing process module includes contacting the de- colorized/de-ashed liquid sucrose intermediate product with at least one sensory-enhancing material such as activated carbon and/or an ion exchange resin.
  • the activated carbons and ion exchange resins disclosed above in connection with the pretreatment process module may also be used for polishing. However, it has been determined that at least one activated carbon column may be especially advantageous for polishing. If an ion exchange resin is used (either with or without an activated carbon treatment), the ion exchange process typically does not involve ion exchange chromatography (i.e., separation of mixed sugars into two or more fractions).
  • the amount of de-colorized/de-ashed sucrose flowing through the polishing module varies depending upon parameters such as temperature, contact time and pH drop, but may range from about 0.2 to about 2, more particularly about 0.2 to about 1, BV/hr.
  • the polishing module (activated carbon and/or ion exchange resin) temperature may range from about 50°C to about 90°C, and the pH of the sucrose may range from about 6.5 to about 9, more particularly about 7.5 to about 8.5.
  • the polishing module also could include a final step of adjusting the pH of the liquid sucrose product to be at least 8 so as to avoid invert sugar formation.
  • the pH may be adjusted in any suitable manner such as by continuously adding a base (e.g., NaOH) via a trim tank.
  • a base e.g., NaOH
  • Sweetwater generated in any of the process modules may be recycled to the pretreatment process module.
  • Sweetwater is created when a process module is exhausted or evacuated or a slug is removed from an activated carbon column. Water is used to displace the sucrose composition forward into the process system until the % Brix drops to a predetermined amount, typically about 10 to about 20%. At this point, the sucrose composition is diverted to a sweetwater system.
  • a regenerated unit can be sweetened-on with syrup until the syrup exiting the unit rises into the 10 to 20% Brix range. At this point, the regenerated unit is then inserted back into the product process flow. Temperature and/or pH control of the sweetwater may be applied to avoid inversion and microbial problems.
  • the disclosed refining processes may be performed in a continuous manner or in a batch manner.
  • the various process modules are typically carried out in an aqueous medium.
  • the ion exchange resins and activated carbon may be contacted with the sucrose stream via known techniques such as fixed beds, pulsed beds, fluidized beds or expanded beds.
  • the continuous flow method which can be utilized based on the present disclosure contemplates a multi-step process wherein the steps are performed in a manner such that a sucrose stream flows continuously through the modules (e.g., beds or columns) defined by the steps.
  • the continuous flow does not have to be on a constant 24/7 hours/days basis (i.e., there can be down times for maintenance, process adjustment or simple lack of demand).
  • An example of a specific refining process is depicted schematically in FIG. 1.
  • a raw sugar solution is initially passed through a pulsed column of activated carbon.
  • the raw sugar solution may be heated to reach the desired activated carbon column operating temperature set forth above.
  • the resulting first intermediate product then is filtered, particularly to remove carbon fines.
  • the filtered intermediate product then passes through a first strong base anion exchange resin for de-colorization.
  • the de-colorizing strong base anion exchange resin may be regenerated by a brine or caustic brine solution.
  • the substantially de-colorized intermediate product then passes through a second strong base anion exchange resin for de-ashing.
  • the de- ashing strong base anion exchange resin may be regenerated by an alkali solution.
  • the substantially de-colorized intermediate product may optionally undergo cooling to reduce the intermediate product stream temperature to satisfy the temperature requirements of the weak acid cation exchange resin if the de-ashing strong base anion exchange resin is within the same temperature zone as the weak acid cation exchange resin bed.
  • the partially de-ashed intermediate product then undergoes any additional required cooling to reduce the intermediate product stream temperature to less than about 46°C, more particularly less than about 40°C, and most particularly less than about 35°C.
  • the partially de-ashed intermediate product subsequently is passed through a de-ashing weak acid cation exchange resin.
  • the weak acid cation exchange resin may be regenerated by an acid solution.
  • the pH of the substantially de- ashed intermediate product then is heated and adjusted to be in a range of about 7 to about 9 prior to introduction into an activated carbon pulsed column for polishing.
  • the de-ashed intermediate product may be heated via a heat exchanger or some other heat source.
  • the resulting polished product then is filtered, particularly to remove carbon fines.
  • the final refined product then may undergo evaporation and/or cooling for storage purposes.
  • the refined liquid sucrose products described herein may have human sensory properties (particularly odor and taste) that are substantially similar to commercially available refined bottlers grade liquefied sugar.
  • the taste and odor of the refined liquid sucrose product should be clean or not unpleasant.
  • the refined sucrose product may have a unique ion contents profile.
  • the refined sucrose product can have a potassium ion content of less than about 15, more particularly less than about 10 mg g (dry); a magnesium ion content of less than about 5, more particularly less than about 1 mg/Kg (dry), and most particularly less than about 0.5 mg Kg (dry); and a total chloride and sulfate ion content of less than about 10, more particularly less than about 5 mg/Kg (dry). If KOH is used as pH adjuster, then potassium ion content will be higher, but the sodium ion content will be reduced.
  • the total ash content of the refined sucrose product may be less than about 0.020 weight %, more particularly less than about 0.015 weight % (as defined by conductivity ash).
  • the refined sucrose product may also have an I.C.U. of less than about 35, more particularly less than about 25.
  • the refined liquid sucrose product is particularly useful as a sweetener for the food and beverage industries (e.g., as bottler's grade liquid sugar), but could also be used for the pharmaceutical industry and for direct sale to consumers.
  • a raw liquid cane sugar feedstock (I.C.U. 1022, solids of 55% Brix, 0.2% ash) was subjected to an initial activated carbon treatment. This treatment involved mixing 3500 ml of the raw liquid cane sugar feedstock with 750 g of regenerated Calgon Carbon CPG activated carbon. The mixture was stirred for six hours at 75°C and then separated by filtration through a 0.7 micron filter to remove carbon fines.
  • the syrup batch from the carbon treatment was fed through 100 ml of Thermax A-72 strong base anion exchange resin (for de-colorizing) in the chloride form at 1 BV/hr and a feed temperature of 56°C and a pH of 8.0.
  • the strong base anion exchange resin was regenerated with 3 BV of a 10%NaCl-l%NaOH solution and rinsed with 5 BV of deionized water prior to treating the syrup batch.
  • the batch from the de-colorizing resin was collected in a period of about 3 hours.
  • the batch was protected by cooling as it was collected.
  • the batch from the de-colorizing resin was fed at a rate of 8 BV/hr (based on the BV of the cation resin), a temperature of 42°C, and a pH of about 7 to a first de-ashing column that contained 300 ml Thermax A-72 strong base anion exchange resin and then to a second de- ashing column that contained 20 ml Purolite G-104E weak acid cation exchange resin.
  • the anion resin was regenerated with 3 BV of a 4% NaOH solution at a flow rate of 3 BV/hr then rinsed with 5 BV of deionized water at 3 BV hr prior to treating the batch.
  • the cation resin was regenerated with 3 BV of a 7% HCl solution at a flow rate of 3 BV/hr followed by a 5 B V of deionized rinse water prior to treating the batch.
  • Example 2 is the analysis of the product from the de-ashing module with only the subsequent filtration and evaporation.
  • Example 1 was submitted to a post-treatment involving passing a portion of the sample through 30 ml of DOWEX
  • Optipore SD-2 adsorbent resin at 3 BV hr at 43°C.
  • the DOWEX Optipore SD-2 adsorbent resin had been previously regenerated with a weak caustic solution.
  • Example 3 was generated by passing a portion of the sample product through 400 g Calgon CPG regenerated activated carbon supported on a filter inside a funnel. The syrup was heated and then poured into the funnel for gravity feed for over an hour. All the samples were allowed to remain at room temperature for storage.
  • a comparison of the ion profile of refined liquid sucrose products produced according to Examples 1-3 to several commercially available sucrose products produced via crystallization is shown below in Table 1.
  • the exemplified refined liquid sucrose product is diluted to an aqueous solution that includes 10 weight % dry solids sucrose.
  • the commercially available crystal sugars are dissolved into solution at a 10 weight % dry solids sucrose level. Both the exemplified samples and the commercial samples can be analyzed for ion content using standard ion chromatography techniques.
  • a Dionex Ion Chromatograph with a conductivity detector can be used with a column temperature at room temperature, a conductivity cell temperature of 35°C, a suppressor current of 100 mA, and a KOH mobile phase flow rate of 1.0 mL/minute.
  • the same equipment and conditions can be used except that the mobile phase is a methane sulfonic acid solution. The results may then be extrapolated to a dry mg/Kg basis.
  • Ion acid amount (mg/Kg dry basis)
  • the presently disclosed refined liquid sucrose product can include a significantly lower amount of potassium, magnesium, calcium, chloride, and sulfate ions compared to several commercially available sucrose products produced via crystallization.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Saccharide Compounds (AREA)

Abstract

La présente invention concerne des procédés de raffinage de sucrose liquide brut qui consistent à mettre en contact le sucrose liquide brut avec du charbon activé et/ou une résine échangeuse d'ions de manière à obtenir un premier produit intermédiaire du sucrose liquide. Ce premier produit intermédiaire du sucrose liquide peut être mis en contact avec une résine échangeuse d'anions fortement basique et une résine échangeuse de cations faiblement acide afin d'obtenir un second produit intermédiaire du sucrose liquide. Ce second produit intermédiaire du sucrose liquide peut être mis en contact avec du charbon activé ou une résine échangeuse d'ions aux fins de l'obtention du produit raffiné de sucrose liquide.
PCT/US2004/018014 2003-06-06 2004-06-03 Procede de raffinage du sucrose WO2004108969A1 (fr)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006092432A2 (fr) * 2005-03-03 2006-09-08 Basf Aktiengesellschaft Procede d'appauvrissement en soufre et/ou en composes soufres de sucre, d'alditol et/ou d'acide succinique
WO2008056331A1 (fr) * 2006-11-08 2008-05-15 Tongaat Hulett Limited Traitement de jus de canne à sucre
WO2013082018A1 (fr) * 2011-12-02 2013-06-06 Amal Gamated Research Llc Système et procédé de raffinage du sucre
WO2014143753A1 (fr) * 2013-03-15 2014-09-18 Sweetwater Energy, Inc. Purification de carbone de courants de sucre concentré issus de biomasse prétraitée
US9499635B2 (en) 2006-10-13 2016-11-22 Sweetwater Energy, Inc. Integrated wood processing and sugar production
US10844413B2 (en) 2014-12-09 2020-11-24 Sweetwater Energy, Inc. Rapid pretreatment
EP3615213B1 (fr) 2017-04-28 2021-06-02 Dow Global Technologies LLC Traitement de solutions de sucres
US11692000B2 (en) 2019-12-22 2023-07-04 Apalta Patents OÜ Methods of making specialized lignin and lignin products from biomass
US11821047B2 (en) 2017-02-16 2023-11-21 Apalta Patent OÜ High pressure zone formation for pretreatment

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1296244A (fr) * 1969-07-07 1972-11-15
US4046590A (en) * 1976-09-08 1977-09-06 California And Hawaiian Sugar Company Process for the production of a colorless sugar syrup from cane molasses
EP0102256A2 (fr) * 1982-06-28 1984-03-07 Calgon Carbon Corporation Procédé de purification d'une solution d'édulcorant
US4523959A (en) * 1980-09-19 1985-06-18 Rhone-Poulenc Industries Purification of sugarcane juice
US4950332A (en) * 1988-03-17 1990-08-21 The Dow Chemical Company Process for decolorizing aqueous sugar solutions via adsorbent resins, and desorption of color bodies from the adsorbent resins
US4968353A (en) * 1988-07-15 1990-11-06 C. Itoh Sugar Co., Ltd. Method for refining sugar liquor
JPH0372900A (ja) * 1989-08-09 1991-03-28 Fuji Seito Kk 蔗糖液の精製方法及び処理設備

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1296244A (fr) * 1969-07-07 1972-11-15
US4046590A (en) * 1976-09-08 1977-09-06 California And Hawaiian Sugar Company Process for the production of a colorless sugar syrup from cane molasses
US4523959A (en) * 1980-09-19 1985-06-18 Rhone-Poulenc Industries Purification of sugarcane juice
EP0102256A2 (fr) * 1982-06-28 1984-03-07 Calgon Carbon Corporation Procédé de purification d'une solution d'édulcorant
US4950332A (en) * 1988-03-17 1990-08-21 The Dow Chemical Company Process for decolorizing aqueous sugar solutions via adsorbent resins, and desorption of color bodies from the adsorbent resins
US4968353A (en) * 1988-07-15 1990-11-06 C. Itoh Sugar Co., Ltd. Method for refining sugar liquor
JPH0372900A (ja) * 1989-08-09 1991-03-28 Fuji Seito Kk 蔗糖液の精製方法及び処理設備

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 0152, no. 31 (C - 0840) 12 June 1991 (1991-06-12) *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006092432A3 (fr) * 2005-03-03 2007-08-09 Basf Ag Procede d'appauvrissement en soufre et/ou en composes soufres de sucre, d'alditol et/ou d'acide succinique
WO2006092432A2 (fr) * 2005-03-03 2006-09-08 Basf Aktiengesellschaft Procede d'appauvrissement en soufre et/ou en composes soufres de sucre, d'alditol et/ou d'acide succinique
US9499635B2 (en) 2006-10-13 2016-11-22 Sweetwater Energy, Inc. Integrated wood processing and sugar production
WO2008056331A1 (fr) * 2006-11-08 2008-05-15 Tongaat Hulett Limited Traitement de jus de canne à sucre
AU2007318897B2 (en) * 2006-11-08 2011-07-21 Tongaat Hulett Limited Treatment of sugar juice
AP2511A (en) * 2006-11-08 2012-11-21 Tongaat Hulett Ltd Treatment of sugar juice
WO2013082018A1 (fr) * 2011-12-02 2013-06-06 Amal Gamated Research Llc Système et procédé de raffinage du sucre
US9080221B2 (en) 2011-12-02 2015-07-14 Amalgamated Research Llc System and process for refining sugar
WO2014143753A1 (fr) * 2013-03-15 2014-09-18 Sweetwater Energy, Inc. Purification de carbone de courants de sucre concentré issus de biomasse prétraitée
US9809867B2 (en) 2013-03-15 2017-11-07 Sweetwater Energy, Inc. Carbon purification of concentrated sugar streams derived from pretreated biomass
US10844413B2 (en) 2014-12-09 2020-11-24 Sweetwater Energy, Inc. Rapid pretreatment
US11821047B2 (en) 2017-02-16 2023-11-21 Apalta Patent OÜ High pressure zone formation for pretreatment
EP3615213B1 (fr) 2017-04-28 2021-06-02 Dow Global Technologies LLC Traitement de solutions de sucres
US11692000B2 (en) 2019-12-22 2023-07-04 Apalta Patents OÜ Methods of making specialized lignin and lignin products from biomass

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