WO2016137787A1 - Séparation chromatographique de saccharides au moyen de billes de résine échangeuse de cations dotées d'une surface externe rugueuse - Google Patents

Séparation chromatographique de saccharides au moyen de billes de résine échangeuse de cations dotées d'une surface externe rugueuse Download PDF

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Publication number
WO2016137787A1
WO2016137787A1 PCT/US2016/018140 US2016018140W WO2016137787A1 WO 2016137787 A1 WO2016137787 A1 WO 2016137787A1 US 2016018140 W US2016018140 W US 2016018140W WO 2016137787 A1 WO2016137787 A1 WO 2016137787A1
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Prior art keywords
resin
cation exchange
saccharide
exchange resin
monomers
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PCT/US2016/018140
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English (en)
Inventor
Collin H. MARTIN
Jose A. TREJO O' REILLY
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Rohm And Haas Company
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Publication of WO2016137787A1 publication Critical patent/WO2016137787A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
    • B01D15/361—Ion-exchange
    • B01D15/362—Cation-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/04—Processes using organic exchangers
    • B01J39/05—Processes using organic exchangers in the strongly acidic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/26—Cation exchangers for chromatographic processes
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00—Glucose; Glucose-containing syrups
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K11/00—Fructose
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K3/00—Invert sugar; Separation of glucose or fructose from invert sugar

Definitions

  • the invention relates the use of strong acid cation exchange resins to chromatographically separate sugars including monosaccharides such as fructose and glucose.
  • the subject cation exchange resins are characterized by possessing "rough" outer surfaces.
  • the invention includes a method for chromatographically separating a first saccharide from a liquid (e.g. aqueous) eluent including the first saccharide and a second saccharide by passing the liquid eluent through a bed including a strong acid cation exchange resin.
  • the resin is provided in bead form and is characterized by having a rough surface, i.e. SIOz of at least 1 and more preferably at least 5 or even 6 as measured by confocal laser scanning microscopy.
  • the resin is gel-type and provided in calcium form with a uniform particle size.
  • Figures la-b are micrographs of a conventional bead-form strong acid, gel-type cation exchange resin and Figures lc-d are micrographs of a similar resin provided with "rough" outer surfaces as per the subject invention.
  • Figure 2 includes four chromatographic elution curves (Brix vs. Bed Volume (BV)) corresponding to Example 2 with the first two elution curves correspond to glucose and fructose, respectively, using sample resin B and the second two elution curves correspond to glucose and fructose, respectively, using sample resin A.
  • BV Bed Volume
  • the invention includes a method for chromatographically separating a first saccharide (analyte) from a liquid eluent including multiple saccharides, (e.g. a first and second saccharide).
  • a first saccharide analyte
  • the liquid eluent may include a variety of constituents, e.g. monosaccharides, disaccharides, oligosaccharides, organic acids, amino acids, inorganic salts, etc.
  • the first and second saccharides are preferably monosaccharides (e.g. glucose and fructose).
  • the liquid eluent typically includes an aqueous mixture of glucose (first saccharide) and fructose (second saccharide) along with various acids and salts.
  • first saccharide glucose
  • second saccharide fructose
  • the set up and operation of the bed is not particularly limited, e.g. moving, simulated moving and stationary beds may be used.
  • the first and second saccharides pass through the resin bed at different rates, thus allowing their separation.
  • fructose (second saccharide) more strongly interacts with the resin as compared with glucose (first saccharide).
  • glucose passes (elutes) through the bed more quickly followed by fructose as a separate product "cut".
  • the individual product cuts can then be collected and used or further treated as is customary in the art.
  • the resin used in the present invention is a strong acid cation exchange resin, preferably provided in bead form.
  • the cation exchange resin includes a crosslinked copolymer matrix that is functionalized (e.g. sulfonated) and which is preferably converted to a calcium form. While the crosslinked copolymer matrix may be macroporous or gel-type, gel-type copolymers are preferred.
  • gel-type and “macroporous” are well-known in the art and generally describe the nature of the copolymer bead porosity.
  • the term "macroporous" as commonly used in the art means that the copolymer has both macropores and mesopores.
  • microporous “microporous,” “gellular,” “gel” and “gel-type” are synonyms that describe copolymer beads having pore sizes less than about 20 Angstroms A , while macroporous copolymer beads have both mesopores of from about 20 A to about 500 A and macropores of greater than about 500 A .
  • Gel-type and macroporous copolymer beads, as well as their preparation are further described in US 4256840 and US 5244926 - the entire contents of which are incorporated herein by reference.
  • the crosslinked copolymer resin beads preferably have a median bead diameter from 100 to 2000 microns, and more preferably from 150 to 500 microns).
  • the beads may have a Gaussian particle size distribution but preferably have a relatively uniform particle size distribution, i.e. "monodisperse” that is, at least 90 volume percent of the beads have a particle diameter from about 0.9 to about 1.1 times the volume average particle diameter.
  • a representative example is AMBERLITETM SR1L available from The Dow Chemical Company and which may be converted to a calcium ionic form by way of conventional techniques known in the art.
  • a seeded polymerization process typically adds monomers in two or more increments. Each increment is followed by complete or substantial polymerization of the monomers therein before adding a subsequent increment.
  • a seeded polymerization is advantageously conducted as a suspension polymerization wherein monomers or mixtures of monomers and seed particles are dispersed and polymerized within a continuous suspending medium.
  • staged polymerization is readily accomplished by forming an initial suspension of monomers, wholly or partially polymerizing the monomers to form seed particles, and subsequently adding remaining monomers in one or more increments. Each increment may be added at once or continuously. Due to the insolubility of the monomers in the suspending medium and their solubility within the seed particles, the monomers are imbibed by the seed particles and polymerized therein. Multi-staged polymerization techniques can vary in the amount and type of monomers employed for each stage as well as the polymerizing conditions employed.
  • the seed particles employed may be prepared by known suspension polymerization techniques.
  • the seed particles may be prepared by forming a suspension of a first monomer mixture in an agitated, continuous suspending medium as described by F. Helfferich in Ion Exchange, (McGraw-Hill 1962) at pp. 35-36.
  • the first monomer mixture comprises: 1) a first monovinylidene monomer, 2) a first crosslinking monomer, and 3) an effective amount of a first free -radical initiator.
  • the suspending medium may contain one or more suspending agents commonly employed in the art. Polymerization is initiated by heating the suspension to a temperature of generally from about 50-90°C.
  • the suspension is maintained at such temperature or optionally increased temperatures of about 90-150° C until reaching a desired degree of conversion of monomer to copolymer.
  • Other suitable polymerization methods are described in US 4444961, US 4623706, US 4666673 and US 5244926 - each of which is incorporated herein in its entirety.
  • substituted styrene includes substituents of either/or both the vinylidene group and phenyl group of styrene and include: vinyl naphthalene, alpha alkyl substituted styrene (e.g., alpha methyl styrene) alkylene-substituted styrenes (particularly monoaikyl-substituted styrenes such as vinyltoluene and ethylvinylbenzene) and halo-substituted styrenes, such as bromo or chlorostyrene and vinylbenzyl chloride.
  • alpha alkyl substituted styrene e.g., alpha methyl styrene
  • alkylene-substituted styrenes particularly monoaikyl-substituted styrenes such as vinyltoluene and ethylvinylbenzene
  • Additional monomers may be included along with the monovinylidene aromatic monomers, including monovinylidene non-styrenics such as: esters of ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, particularly acrylic or methacrylic acid, methyl methacrylate, isobornyl- methacrylate, ethylacrylate, and butadiene, ethylene, propylene, acrylonitrile, and vinyl chloride; and mixtures of one or more of said monomers.
  • Preferred monovinylidene monomers include styrene and substituted styrene such as ethylvinylbenzene.
  • the term "monovinylidene monomer” is intended to include homogeneous monomer mixtures and mixtures of different types of monomers, e.g. styrene and isobornylmethacrylate.
  • the seed polymer component preferably comprises a styrenic content greater than 50 molar percent, and more preferably greater than 75, and in some embodiments greater than 95 molar percent (based upon the total molar content).
  • styrenic content refers to the quantity of monovinylidene monomer units of styrene and/or substituted styrene utilized to form the copolymer.
  • Substituted styrene includes substituents of either/or both the vinylidene group and phenyl group of styrene as described above.
  • the first monomer mixture used to form the first polymer component comprises at least 75 molar percent, preferably at least 85 molar percent and in some embodiments at least 95 molar percent of styrene.
  • crosslinking monomers i.e., polyvinylidene compounds
  • suitable crosslinking monomers include polyvinylidene aromatics such as divinylbenzene, divinyltoluene, divinylxylene, divinylnaphthalene, trivinylbenzene, divinyldiphenylsulfone, as well as diverse alkylene diacrylates and alkylene dimethacrylates.
  • Preferred crosslinking monomers are divinylbenzene, trivinylbenzene, and ethylene glycol dimethacrylate.
  • crosslinking agent crosslinker
  • crosslinking monomer crosslinking monomer
  • the proportion of crosslinking monomer in the copolymer seed particles is preferably sufficient to render the particles insoluble in subsequent polymerization steps (and also on conversion to an ion-exchange resin), yet still allow for adequate imbibition of an optional phase-separating diluent and monomers of the second monomer mixture. In some embodiments, no crosslinking monomer will be used.
  • a suitable amount of crosslinking monomer in the seed particles is minor, i.e., desirably from about 0.01 to about 12 molar percent based on total moles of monomers in the first monomer mixture used to prepare the seed particles.
  • the first polymer component e.g. seed
  • the first polymer component is derived from polymerization of a first monomer mixture comprising at least 85 molar percent of styrene (or substituted styrene such as ethylvinylbenzene) and from 0.01 to about 10 molar percent of divinylbenzene.
  • Polymerization of the first monomer mixture may be conducted to a point short of substantially complete conversion of the monomers to copolymer or alternatively, to substantially complete conversion. If incomplete conversion is desired, the resulting partially polymerized seed particles advantageously contain a free -radical source therein capable of initiating further polymerization in subsequent polymerization stages.
  • the term "free-radical source” refers to the presence of free -radicals, a residual amount of free -radical initiator or both, which is capable of inducing further polymerization of ethylenically unsaturated monomers.
  • the first monomer mixture it is preferable that from about 20 to about 95 weight percent of the first monomer mixture, based on weight of the monomers therein, be converted to copolymer and more preferably from about 50 to about 90 weight percent. Due to the presence of the free radical source, the use of a free-radical initiator in a subsequent polymerization stage would be optional. For embodiments where conversion of the first monomer mixture is substantially complete, it may be necessary to use a free-radical initiator in subsequent polymerization stages.
  • the free-radical initiator may be any one or a combination of conventional initiators for generating free radicals in the polymerization of ethylenically unsaturated monomers.
  • Representative initiators are UV radiation and chemical initiators, such as azo-compounds including
  • azobisisobutyronitrile azobisisobutyronitrile
  • peroxygen compounds such as benzoyl peroxide, t-butylperoctoate, t-butylperbenzoate and isopropylpercarbonate.
  • Other suitable initiators are mentioned in US 4192921, US 4246386 and US 4283499 - each of which is incorporated in its entirety.
  • the free-radical initiators are employed in amounts sufficient to induce polymerization of the monomers in a particular monomer mixture. The amount will vary as those skilled in the art can appreciate and will depend generally on the type of initiators employed, as well as the type and proportion of monomers being polymerized. Generally, an amount of from about 0.02 to about 2 weight percent is adequate, based on total weight of the monomer mixture.
  • the first monomer mixture used to prepare the seed particles is advantageously suspended within an agitated suspending medium comprising a liquid that is substantially immiscible with the monomers, (e.g. preferably water).
  • the suspending medium is employed in an amount from about 30 to about 70 and preferably from about 35 to about 50 weight percent based on total weight of the monomer mixture and suspending medium.
  • Various suspending agents are conventionally employed to assist with maintaining a relatively uniform suspension of monomer droplets within the suspending medium.
  • Illustrative suspending agents are gelatin, polyvinyl alcohol, magnesium hydroxide, hydroxyethylcellulose, methylhydroxyethyl cellulose methylcellulose and carboxymethyl methylcellulose.
  • Other suitable suspending agents are disclosed in US 4,419,245.
  • the amount of suspending agent used can vary widely depending on the monomers and suspending agents employed. Latex inhibitors such as sodium dichromate may be used to minimize latex formation.
  • seed particles comprising from about 10 to about 50 weight percent of the copolymer are preferably suspended within a continuous suspending medium.
  • a second monomer mixture containing a free radical initiator is then added to the suspended seed particles, imbibed thereby, and then polymerized.
  • the seed particles can be imbibed with the second monomer mixture prior to being suspended in the continuous suspending medium.
  • the second monomer mixture may be added in one amount or in stages.
  • the second monomer mixture is preferably imbibed by the seed particles under conditions such that substantially no polymerization occurs until the mixture is substantially fully imbibed by the seed particles.
  • the time required to substantially imbibe the monomers will vary depending on the copolymer seed composition and the monomers imbibed therein. However, the extent of imbibition can generally be determined by microscopic examination of the seed particles, or suspending media, seed particles and monomer droplets.
  • the second monomer mixture desirably contains from about 0.5 to about 25 molar percent, preferably from about 2 to about 17 molar percent and more preferably 2.5 to about 8.5 molar percent of crosslinking monomer based on total weight of monomers in the second monomer mixture with the balance comprising a monovinylidene monomer; wherein the selection of crosslinking monomer and monovinylidene monomer are the same as those described above with reference to the preparation of the first monomer mixture, (i.e. seed preparation).
  • the preferred monovinylidene monomer includes styrene and/or a substituted styrene.
  • the second polymer component i.e.
  • the second monomer mixture has a styrenic content greater than 50 molar percent, and more preferably at least 75 molar percent (based upon the total molar content of the second monomer mixture).
  • the second polymer component is derived from polymerization of a second monomer mixture comprising at least 75 molar percent of styrene (and/or substituted styrene such as ethylvinylbenzene) and from about 1 to 20 molar percent divinylbenzene.
  • seed particles comprising from about 10 to about 80 weight percent of the copolymer product are initially formed by suspension polymerization of the first monomer mixture.
  • the seed particles can have a free -radical source therein as previously described, which is capable of initiating further polymerization.
  • a polymerization initiator can be added with the second monomer mixture where the seed particles do not contain an adequate free radical source or where additional initiator is desired.
  • seed preparation and subsequent polymerization stages are conducted in-situ within a single reactor.
  • a second monomer mixture is then added to the suspended seed particles, imbibed thereby, and polymerized.
  • the second monomer mixture may be added under polymerizing conditions, but alternatively may be added to the suspending medium under conditions such that substantially no polymerization occurs until the mixture is substantially fully imbibed by the seed particles.
  • the crosslinked copolymer resin beads are sulfonated with a sulfonating agent, e.g. concentrated sulfuric acid (e.g. at least 96 wt ), oleum (fuming sulfuric acid), chlorosulfonic acid, sulfur trioxide or combinations thereof.
  • a sulfonating agent e.g. concentrated sulfuric acid (e.g. at least 96 wt ), oleum (fuming sulfuric acid), chlorosulfonic acid, sulfur trioxide or combinations thereof.
  • the sulfonation reaction is preferably conducted at elevated temperature, e.g. 110 to 150°C without a solvent.
  • An applicable sulfonation technique is described in US 2005/0014853. See also: in US 4500652, US 6228896, US 6750259, US 6784213, US 2002/002267 and US 2004/0006145.
  • Sulfonation of the resin in the absence of a solvent is believed to impart a wrinkled or dimpled surface to the resin bead.
  • this rough surface is believed to increase interaction of analytes with the bead, thus leading to faster elution rates.
  • Figures la-d are micrographs of two comparable gel-type strong acid cation exchange resins.
  • the resin shown in Figs.1 a) and b) was sulfonated using a traditional solvent (EDC) whereas the resin shown in Figs lc) and d) was sulfonated in the absence of a solvent.
  • Figures la-b are micrographs of AMBERLITETM 120 Na brand cation exchange resin available from The Dow Chemical Company. This resin has a gel-type, crosslinked,
  • FIGS lc-d are micrographs of AMBERLITETM SR1L brand cation exchange resin also available from The Dow Chemical Company. This resin is substantially similar to AMBERLITE 120 Na; however, this resin was sulfonated using H 2 S0 4 without solvent.
  • the sulfonated resins are subsequently converted to a calcium form using standard techniques as used with respect to ion exchange resins.
  • the sulfonated resin may be combined, agitated and soaked within a 1M solution of CaCl 2 .
  • the resin may then be optionally soaked within a saturated solution of Ca(OH) 2 followed by optionally pH adjustment, e.g. with a solution of H 3 P0 4 .
  • the treatment with CaCl 2 may be repeated multiple times to ensure a high level of conversion.
  • the cation exchange resins of the subject invention possess a rough outer surface. As shown in Figures lc-d, the surface appears wrinkled or dimpled.
  • the degree of roughness may be qualified by way of Confocal Laser Scanning Microscopy (CLSM), e.g. a Keyence VK-9700 microscope application viewer VK-Hl VIE with a 50x objective lens and superfine resolution) using a scanning violet laser (408 nm) light source for high resolution confocal surface profiling using a 283 ⁇ x 212 ⁇ sample surface area.
  • CLSM Confocal Laser Scanning Microscopy
  • a Keyence VK-9700 microscope application viewer VK-Hl VIE with a 50x objective lens and superfine resolution a scanning violet laser (408 nm) light source for high resolution confocal surface profiling using a 283 ⁇ x 212 ⁇ sample surface area.
  • the system provides simultaneous color, laser intensity, and height information to generate high-resolution images.
  • the CLSM is preferably operated with a 1 nm z resolution and 130 nm spatial resolution providing SEM-like images with a large 7mm through focus range.
  • CLSM the following parameters may be used to characterize the surface of a resin bead:
  • Sa the arithmetic mean deviation of the actual surface relative to the center plane fit to the data.
  • Sq the geometric mean derivation of the all points on the surface from the mean value of the data
  • SAD The difference in the surface area between the imaged surface and a flat surface of the same lateral size, expressed as a percentage.
  • SIOz the average difference between the 5 highest and 5 lowest points on the surface relative to the mean plane.
  • Smax the difference between the highest and lowest point on the surface relative to the mean plan.
  • the resin beads of the subject invention possess at least one and preferably all of the following surface characteristics: Sa > 1 (e.g. 1 to 3); Sq > 1 (e.g. 1-3), preferably > 1.2; SAD > 2 (e.g. 2 to 4); SIOz > 1, preferably >5 and more preferably >6 (e.g. 2 to 8); and Smax > 1, preferably >5 and more preferably >6 (e.g. 2 to 8).
  • CLSM Confocal Laser Scanning Microscopy
  • SAD or the surface area difference is the percent difference in the surface area of a resin bead versus that of a perfect sphere.
  • the surface area of smooth resin (A) shows approximately 0.95% increase in surface area versus that of a perfect sphere.
  • the wrinkly resin (B) shows approximately 2.10% increase in surface area.
  • a column was packed with the sample resin and heated to 60°C, and the individual sugar (glucose or fructose) to be pulsed were preheated to 60°C by placing a bottle containing the sugar in a heated water bath. Water was pumped through the column at the flowrate of the test (2.0 BV/hr) and the pressure in the column was maintained constant. To start the test, 0.05 BV (26.2 mL) of heated 30 Brix sugar was loaded into the injection valve using a syringe fitted with a blunt needle. The injection valve was then switched into the "inject" position and the sample loop containing the sugar was placed in-line to the column inlet stream.

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Abstract

L'invention concerne un procédé de séparation par chromatographie d'un premier saccharide à partir d'un éluant liquide comprenant le premier saccharide et un second saccharide en faisant passer l'éluant liquide à travers un lit comprenant une résine échangeuse de cations fortement acide sous forme calcique, laquelle résine est fournie sous la forme de billes et se caractérise par le fait qu'elle comprend une surface externe rugueuse.
PCT/US2016/018140 2015-02-27 2016-02-17 Séparation chromatographique de saccharides au moyen de billes de résine échangeuse de cations dotées d'une surface externe rugueuse WO2016137787A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN116459805A (zh) * 2023-04-27 2023-07-21 天津大学 锆基金属有机框架材料选择性吸附分离己糖的方法

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