WO2017095687A1 - Séparation chromatographique d'acides organiques au moyen d'un adsorbant macroporeux polymère - Google Patents

Séparation chromatographique d'acides organiques au moyen d'un adsorbant macroporeux polymère Download PDF

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Publication number
WO2017095687A1
WO2017095687A1 PCT/US2016/063220 US2016063220W WO2017095687A1 WO 2017095687 A1 WO2017095687 A1 WO 2017095687A1 US 2016063220 W US2016063220 W US 2016063220W WO 2017095687 A1 WO2017095687 A1 WO 2017095687A1
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Prior art keywords
acid
class
organic acids
liquid feed
feed mixture
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PCT/US2016/063220
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English (en)
Inventor
Daryl J. Gisch
Collin H. MARTIN
Stephen Pease
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Dow Global Technologies Llc
Rohm And Haas Company
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Application filed by Dow Global Technologies Llc, Rohm And Haas Company filed Critical Dow Global Technologies Llc
Priority to CN201680069448.6A priority Critical patent/CN108367212A/zh
Priority to BR112018010803-0A priority patent/BR112018010803B1/pt
Publication of WO2017095687A1 publication Critical patent/WO2017095687A1/fr

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    • 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
    • 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
    • B01D15/265—Adsorption chromatography
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms

Definitions

  • the invention relates the use of polymeric macroporous adsorbents (stationary phase) to chromatographically separate selected organic acids (analytes) from a common liquid feed mixture.
  • fermentation broths including saccharides such as glucose and fructose may degrade by bacteriological action to produce lactic acid, malic acid along with other weak organic acids. If not removed from the sugar solution, the taste and color of foodstuffs produced therefrom may be adversely affected.
  • Ion exchange resins have been used as a stationary phase in chromatographic separation of organic acids from fermentation broths. See for example US8664436, US5068418 and EP0481603. These separations rely upon ionic interactions between the acid and ion exchange groups present on the stationary phase resin. While effective at separating organic acids from a fermentation broth, these techniques do not readily separate various organic acids from one another.
  • Non-functionalized (non-ionic) crosslinked polymeric macroporous adsorbents have also been used to separate organic acids from fermentation broths. See for example US 4720579 and Thang et al., Green Biorefinery: Separation of Lactic Acid from Grass Silage Juice by Chromatography using Neutral Polymeric Resin, Bioresource Technology 99 (2008) 4368-4379. These separations rely upon pore size and other non-ionic interactions of the adsorbent (stationary phase) to preferentially separate an organic acid from the fermentation broth.
  • the present invention is at least partially based upon the unexpected ability of
  • the invention includes a method for chromatographically separating a first class of organic acids from a second class of acids which are both present in a liquid feed mixture.
  • the method includes the step of passing the liquid feed mixture through a bed including a non-functionalized polymeric macroporous adsorbent.
  • the first class of organic acids is selected from one or more of: propionic acid, lactic acid, itaconic acid, succinic acid, maleic acid, citric acid, ascorbic acid and a-ketoglutaric acid.
  • the second class of acids is selected from one or more of: glycolic acid, gluconic acid, malic acid, tartaric acid and saccharic acid.
  • Figure 1 is a plot of concentration (g/L) vs. column volume for selected compounds described in the Examples.
  • the invention includes a method for chromatographically separating a first class of organic acids from a second class of acids where both class of acids are present in a common liquid feed mixture.
  • organic acid refers to an organic molecule including at least one carboxylic acid functional group or a corresponding salt thereof.
  • the first class of organic acids is selected from one or more of: propionic acid, lactic acid, itaconic acid, succinic acid, maleic acid, citric acid, ascorbic acid and a-ketoglutaric acid.
  • the first class of organic acids is selected from at least one of: propionic acid, itaconic acid and maleic acid.
  • the second class of organic acids is selected from one or more of: glycolic acid, gluconic acid, malic acid, tartaric acid and saccharic acid.
  • the first class of organic acids is preferentially retained by the adsorbent with the second class of organic acids eluting through the adsorbent (stationary phase) more quickly than the first class, thus allowing for efficient chromatographic separation form a common liquid feed mixture (mobile phase).
  • the liquid feed mixture includes at least 1 g/L of an organic acid from the first class and at least 1 g/L of an acid from the second class.
  • the liquid feed mixture may addition include one or more carbohydrates including saccharides (e.g.
  • liquid feed mixtures include those of used in fermentation processes.
  • the liquid feed mixture (mobile phase) passes through a bed or stratum of adsorbent (stationary phase).
  • the set up and operation of the bed is not particularly limited, e.g. moving, simulated moving and stationary beds may be used.
  • the adsorbents used in the present include a well-known class of non-functionalized macroporous polymers, preferably derived from styrene and divinylbenzene.
  • a preferred example is AmberliteTMFPX66 available from The Dow Chemical Company.
  • Additional examples include alkylene-bridged adsorbents such as DOWEXTM OPTIPORETM V493 and V503 brand polymeric adsorbents. Methods for preparing and characterizing such adsorbents are well documented. See for example: US3531463, US3729457, US4297220, US4263407, US4297220, US4382124, US4720579 and US5460725 which are all incorporated in their entirety by reference.
  • the adsorbents of the present invention are non-functionalized, i.e. they have essentially no ion exchange capacity (e.g. less than 0.3 millequivalents per gram as measured by ASTM D2187-94 (reapproved 2009))
  • the subject adsorbents are preferably provided in bead form having a median diameter from 10 to 2000 microns, and more preferably from 100 to 1000 microns.
  • the beads may have a Gaussian particle size distribution or may 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 0.8 to about 1.2, and more preferably 0.85 to 1.15 times the volume average particle diameter.
  • the subject adsorbents are macroporous.
  • the term "macroporous" as commonly used in the art means that the polymer has both macropores and mesopores.
  • Mesopores have diameters of from about 20 A to about 200 A and macropores have diameters greater than about 200 A.
  • the subject adsorbents have surface areas, e.g. 300 to 2100 m 2 /g, and more preferably from 500 to 1500 m 2 /g).
  • Average pore size and surface area are determined by the nitrogen adsorption method in which dried and degassed samples are analyzed on an automatic volumetric sorption analyzer. The instrument works on the principle of measuring the volume of gaseous nitrogen adsorbed by a sample at a given nitrogen partial pressure. The volumes of gas adsorbed at various pressures are used in the B.E.T. model for the calculation of the surface area of the sample.
  • the average pore radius is calculated from the relationship between the surface area and the pore volume of the sample, assuming cylindrical
  • the adsorbents of the present invention are based upon a porogen-modified crosslinked copolymer matrix of at least one monovinyl aromatic monomer and a polyvinyl aromatic crosslinking monomer.
  • the crosslinked copolymer matrix may be further crosslinked by subsequent alkylene bridging.
  • Monovinyl aromatic monomers include styrene, vinyltoluenes, ethylvinylbenzenes and vinylnaphthalenes and may also include heterocyclic monomers such as vinylpyridine.
  • the preferred monovinyl aromatic monomers include styrene, vinyltoluene, ethylvinylbenzene and mixtures thereof. Styrene, ethylvinylbenzene and their mixtures are most preferred.
  • the monovinyl aromatic monomers comprise of from 45 to 80 weight percent of the total monomer mixture, preferably of from 65 to 80 weight percent of the total monomer mixture.
  • Monovinyl aliphatic monomers include derivatives of acrylic and methacrylic acids and acrylonitrile.
  • the preferred monovinyl aliphatic monomers include methyl methacrylate, acrylonitrile, ethyl acrylate, 2-hyroxyethyl methacrylate and mixtures thereof.
  • the monovinyl aliphatic monomers comprise of from 0 to 20 weight percent of the total monomer mixture. Since subsequent alkylene bridging occurs between aromatic rings, it is often preferable not to employ any monovinyl aliphatic monomer or to keeps its amount to a minimum.
  • Polyvinyl aromatic crosslinking monomers include divinylbenzene and trivinylbenzene with divinylbenzene being most preferred.
  • Commercial divinylbenzene typically consists of from 55 to 80 weight percent divinylbenzene in admixture with from 20 to 45 weight percent ethylvinylbenzene.
  • the actual polyvinyl aromatic crosslinking monomer comprises of from 20 to 35 weight percent of the total monomer mixture. In any given instance, the ratio of the monovinyl aromatic and aliphatic monomer to the polyvinyl aromatic crosslinking monomer is from 1.8 to 4. 0.
  • the crosslinked copolymer matrix which form the basis of the present invention are porogen-modified, i.e., they are prepared by suspension polymerization in the presence of a porogenic solvent or a mixture of two or more such porogenic solvents.
  • Porogenic solvents are those solvents which are suitable for forming pores and/or displacing the polymer chains during polymerization. The characteristics and use of such solvents in the formation of macroporous resins are described in US4224415.
  • a porogenic solvent is one which dissolves the monomer mixture being copolymerized but which does not dissolve the copolymer.
  • the porogenic solvents must be inert to the polymerization conditions, i.e., neither interfere with or enter into the polymerization.
  • aromatic hydrocarbons like toluene, xylene and ethylbenzene, C6-C 1 2 saturated aliphatic hydrocarbons like heptane and iso-octane and C4-C 1 0 alkanols like tert-amyl alcohol, sec-butanol and 2-ethylhexanol are particularly effective.
  • Aromatic hydrocarbons and C6-C 1 2 saturated aliphatic hydrocarbons and their mixtures are preferred; toluene alone or in mixtures with a Ce-Cs saturated aliphatic hydrocarbon is most preferred.
  • a sufficient concentration of porogenic solvent is required to effect phase separation or polymer chain displacement.
  • the porogenic solvent comprises of from 50 to 70 weight percent and preferably from 55 to 65 weight percent of the total weight of the monomer mixture and the porogenic solvent.
  • suspension polymerization is a term well known to those skilled in the art and comprises suspending droplets of the monomer or monomer mixture and of the porogenic solvent in a medium in which neither are soluble. This may be accomplished by adding the monomer or monomer mixture and the porogenic solvent with any additives to the suspending medium which contains a dispersing or suspending agent.
  • the suspending medium is usually water and the suspending agent a suspension stabilizer, e.g., gelatin, polyvinyl alcohol or a cellulosic such as hydroxyethyl cellulose, methyl cellulose or carboxymethyl methyl cellulose.
  • the organic phase disperses into fine droplets.
  • Polymerization is accomplished by heating in the presence of a free-radical initiator.
  • 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 like azobisisobutyronitrile; and peroxygen compounds such as benzoyl peroxide, t-butylperoctoate, t-butylperbenzoate and iso-propylpercarbonate. Only a catalytic amount of initiator is required.
  • the usual range is from about 0.01 to about 3 percent of initiator with reference to the weight of the monomer mixture.
  • the preferred range is from 0.1 to 1.5 percent.
  • the optimum amount of initiator is determined in large part by the nature of the particular monomers selected, the nature of the impurities present and the volume of porogen used. For example, when higher levels of polyvinyl aromatic crosslinking monomer is employed, it may be necessary to use a greater percentage of free-radical initiator, e.g. greater than 0.5 weight percent.
  • the organic phase containing monomer, porogenic solvent and initiator is suspended within an agitated aqueous medium.
  • the suspending medium is employed in an amount of from 30 to 70 weight percent, preferably from 35 to 50 weight percent based on the total weight of organic phase and suspending medium.
  • the polymerization is conducted at a temperature from between 30°and 130°C, preferably from between 70° and 110°C.
  • the adsorbent beads may be prepared by a seeded, continuous-addition process as described, for example, in US4419245, US4564644 and US5231115 which are incorporated herein by reference.
  • seed particles of crosslinked copolymer are suspended in an aqueous phase and swelled with an organic phase as described above, i.e., monomer mixture, porogenic solvent and initiator.
  • an organic phase as described above, i.e., monomer mixture, porogenic solvent and initiator.
  • a second organic phase is continuously added while polymerization continues.
  • the second organic phase can be the same as the first or different provided that the ratios of monovinyl aromatic monomer, polyvinyl aromatic crosslinking monomer and porogenic solvent are within the limitations of the present invention.
  • the second organic phase is devoid of initiator.
  • the adsorbents of the present invention may be prepared from the aforementioned crosslinked copolymer beads by additional alkylene-bridging (post-crosslinking) of individual polymer chains after polymerization.
  • Post-crosslinking may be achieved by first swelling the copolymer beads under non-reactive conditions with a swelling agent along with the haloalkylating agent and an effective amount of a Friedel-Crafts catalyst.
  • the haloalkylating agent advantageously has the Friedel-Crafts catalyst incorporated therein.
  • the swollen copolymer beads are then maintained at a temperature sufficient forthe haloalkylating agent to react with the copolymer beads until achieving a desired degree of reaction, usually from 0.6 to 0.7 haloalkyl groups per aromatic ring.
  • the reaction temperature can be from 20°C to 180°C. More preferably, the temperature is from 60°C to 85°C.
  • Methods for haloalkylating copolymer beads are described in: US2642417, US2960480, US2992544, US4191813, US4263407 and US4950332 which are incorporated herein by reference.
  • Friedel-Crafts catalysts are Lewis acids and include for example, AICI3, FeCk, BF3 and HF. AICI 3 and FeCl 3 are preferred.
  • Preferred haloalkylating agents include chloromethyl methyl ether and ⁇ , ⁇ '-dichloroxylene, with chloromethyl methyl ether being most preferred.
  • Suitable swelling agents are solvents which are substantially inert during post-crosslinking of the haloalkylated copolymer and include chlorinated hydrocarbons, such as dichloroethane, chlorobenzene, dichlorobenzene, methylene chloride, and propylene dichloride, or nitrogen-substituted aromatics, like nitrobenzene.
  • reaction of a chloromethyl group with the aromatic ring of an adjacent copolymer chain results in formation of an alkylene bridge or in this example, a methylene bridge, i.e., a (-CH2-) moiety.
  • the halo alkylating agent and swelling agent may be removed by conventional methods, such as solvent extraction, washing, drying, or a combination thereof. If a drying step is used, it is preferred to avoid an oxygen-containing atmosphere at temperatures above normal room temperature.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Fats And Perfumes (AREA)

Abstract

L'invention concerne un procédé de séparation par chromatographie d'une première classe d'acides organiques d'une seconde classe d'acides qui sont toutes deux présentes dans un mélange de charge liquide par le passage du mélange de charge liquide à travers un lit comprenant un adsorbant macroporeux polymère non fonctionnalisé, dans lequel: i) la première classe d'acides organiques est sélectionnée parmi un ou plusieurs des éléments suivants: acide propionique, acide lactique, acide itaconique, acide succinique, acide maléique, acide citrique, acide ascorbique et acide α-cétoglutarique; et ii) la seconde classe d'acides organiques est sélectionnée parmi un ou plusieurs des éléments suivants: acide glycolique, acide gluconique, acide malique, acide tartrique et acide saccharique.
PCT/US2016/063220 2015-12-01 2016-11-22 Séparation chromatographique d'acides organiques au moyen d'un adsorbant macroporeux polymère WO2017095687A1 (fr)

Priority Applications (2)

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CN201680069448.6A CN108367212A (zh) 2015-12-01 2016-11-22 使用聚合物大孔吸附剂色谱分离有机酸
BR112018010803-0A BR112018010803B1 (pt) 2015-12-01 2016-11-22 Método para separar cromatograficamente uma primeira classe de ácidos orgânicos de uma segunda classe de ácidos

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US201562261343P 2015-12-01 2015-12-01
US62/261,343 2015-12-01

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WO2019018406A1 (fr) * 2017-07-18 2019-01-24 Agrimetis, Llc Procédés de purification de l-glufosinate
WO2019154647A1 (fr) 2018-02-06 2019-08-15 Basf Se Procédé de préparation de monoalcanolamines en c2-c4 mettant en œuvre un échangeur de cations acide en tant que catalyseur

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
WO2019018406A1 (fr) * 2017-07-18 2019-01-24 Agrimetis, Llc Procédés de purification de l-glufosinate
US11634442B2 (en) 2017-07-18 2023-04-25 Basf Se Methods for the purification of L-glufosinate
US11897908B2 (en) 2017-07-18 2024-02-13 Basf Se Methods for the purification of L-glufosinate
US11897909B2 (en) 2017-07-18 2024-02-13 Basf Se Methods for the purification of L-glufosinate
US11976089B2 (en) 2017-07-18 2024-05-07 Basf Se Methods for the purification of L-glufosinate
WO2019154647A1 (fr) 2018-02-06 2019-08-15 Basf Se Procédé de préparation de monoalcanolamines en c2-c4 mettant en œuvre un échangeur de cations acide en tant que catalyseur
US11753364B2 (en) 2018-02-06 2023-09-12 Basf Se Method for producing C2-C4 mono alkanol amines using an acid cation exchanger as a catalyst

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