EP3737484A1 - Procédé de séparation et de purification de dérivés du glycérol - Google Patents

Procédé de séparation et de purification de dérivés du glycérol

Info

Publication number
EP3737484A1
EP3737484A1 EP19708654.9A EP19708654A EP3737484A1 EP 3737484 A1 EP3737484 A1 EP 3737484A1 EP 19708654 A EP19708654 A EP 19708654A EP 3737484 A1 EP3737484 A1 EP 3737484A1
Authority
EP
European Patent Office
Prior art keywords
acid
solution
glycerol
water
port
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19708654.9A
Other languages
German (de)
English (en)
Inventor
Lucas CUNHA DUARTE COELHO
Alírio EGÍDIO RODRIGUES
Nelson MEDEIRO DE LIMA FILHO
Rui Pedro VIEIRA FARIA
Ana Mafalda Almeida Peixoto Ribeiro
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
UNIVERSIDADE FEDERAL DE PERNAMBUCO
Universidade do Porto
Original Assignee
Universidade Federal De Pernambuco
Universidade do Porto
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Universidade Federal De Pernambuco, Universidade do Porto filed Critical Universidade Federal De Pernambuco
Publication of EP3737484A1 publication Critical patent/EP3737484A1/fr
Pending legal-status Critical Current

Links

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
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
    • B01D15/1814—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns recycling of the fraction to be distributed
    • B01D15/1821—Simulated moving beds
    • B01D15/185—Simulated moving beds characterized by the components to be separated
    • 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
    • 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
    • B01D15/363—Anion-exchange
    • 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

Definitions

  • the present patent application relates to a novel method for the purification of glycerol derivatives, including dihydroxyacetone (DHA) , hydroxypyruvic acid (HPA) , glycolic acid (GCO) , oxalic acid (OXA) , mesoxalic acid (MEO) , tartronic acid (TTA) , glyceric acid (GCA) , glyceraldehyde (GLA) , glyoxalic acid (GOX) and unreacted glycerol by simulated moving bed chromatography.
  • DHA dihydroxyacetone
  • HPA hydroxypyruvic acid
  • GCO glycolic acid
  • OXA oxalic acid
  • MEO mesoxalic acid
  • TTA tartronic acid
  • GCA glyceric acid
  • GLA glyceraldehyde
  • GOX glyoxalic acid
  • biofuels such as biodiesel. Its production generates a byproduct, Glycerol, which represents around 10% in weight of the total biodiesel produced.
  • Glycerol represents around 10% in weight of the total biodiesel produced.
  • Crude Glycerol has very low commercial value due to its impurities, but as it can be converted in products of added value the feasibility of the biodiesel industry can be enhanced .
  • the purification step can determine the commercial viability of an industrial process. This means that, one route or an entire industrial process can be discarded if the purification is not energetically and commercially favorable. The difficulty is even greater in those cases in which the compounds of interest are produced at low concentrations or are chemically similar, as it is the case of DHA, HPA, GCO, OXA, MEO, TTA, GCA, GLA and GOX separation.
  • a starting material maleic acid, fumaric acid, tartaric acid, maleic acid anhydride, tartaric acid anhydride, or any of the water soluble esters of maleic acid, fumaric acid, or tartaric acid
  • a salt the resulting salt must have pH between 10 and 14
  • the OXA can be usually obtained through four methods :
  • a glucose solution obtained by hydrolysis of starch is placed in a reactor with sulfuric acid, vanadium pentoxide, iron (III) sulfate and nitric acid (65%) under vigorous stirring; Crude oxalic acid is obtained after cooling and centrifugation of the reaction mixture; The crude acid is again dissolved in hot water, passed through a grease separator and recrystallized; After a second centrifugation and drying, oxalic acid dihydrate is obtained;
  • an ethylene glycol solution is oxidized by an oxidizing mixture of sulfuric acid and nitric acid, in the presence of vanadium pentoxide and iron (III) salts. Crude oxalic acid is obtained after a crystallizer and separator steps. The final product is obtained after more steps, including: a dissolve with steam, crystallizer, separator and then a dryer;
  • a propene solution is introduced into a solution of nitric acid to produce water soluble intermediates of - nitratolactic acid and lactic acid.
  • the solution of these partially oxidized products is treated with oxygen in the presence of a catalyst. Oxalic acid is formed, crystallized, filtered and dried;
  • - carbon monoxide (CO) and a lower alcohol are reacted under pressure and in the presence of a catalyst to form the corresponding diester of oxalic acid.
  • a catalyst Palladium on charcoal and alkyl nitrites are employed as catalysts and the reaction is carried out at 10 - llMPa.
  • the diester is hydrolyzed in the second step to oxalic acid, which is crystallized and dried .
  • GCO acid is usually produced by hydrolysis of molten monochloroacetic acid with aqueous sodium hydroxide (Zhang and Meng 2013) .
  • the resulting glycolic salt may be removed by evaporative concentration, followed by extraction of the acid with acetone (LEUPOLD et al., 1979) .
  • Another process, which is commercially used in the United States produces GCO from the treatment of formaldehyde or trioxymethylene with carbon monoxide and water in the presence of acid catalysts at high pressure (>30MPa) and high temperature (140-220 oC) (Shattuck 1948; Larson 1939) (John 1939) .
  • the glycolic acid can be recovered from the concentrated solution by crystallization or separated from this crude mixture by distillation.
  • this new residue may be neutralized, e. g., with calcium carbonate, to convert the glycolic acid into a readily separable salt, or the residue may be sterilized with a suitable alcohol for removal of the glycolic acid as an ester. None of these use a production step followed by purification step, as does the process disclosed in the present application.
  • the DHA production process involves a microbial procedure (Green 1960; Charney 1978) . Although it is an industrial process, the fermentation is complete in up to 48 hours, numerous reagents are needed for the microbial growth and the whole process has low yields and low productivities. Moreover, it presents the common problems of industrial biotechnology: discontinuous processing, difficulties to maintain the microbial growth, contaminations by other microorganisms, high sterilization costs and high product recovery cost (Chen 2012) .
  • the product is isolated by known methods in the art, such as, filtration of the broth, removal of inorganic cations and/or anions (when present) via ion exchange resin adsorption, concentration of the resin effluent and crystallization of DHA from the concentrate. Again, it relates to a totally different process design from the one described in the present patent application.
  • US 4621153A (Hatch 1986) describes a method of recovering phenylalanine from an aqueous mixture comprising: providing calcium salt in the aqueous mixture; precipitating a complex of phenylalanine and Ca2+; separating the precipitated complex from the aqueous mixture; dissolving the precipitated complex in an aqueous solution at pH below 8.5; and separating the phenylalanine from the Ca2+.
  • the patent US5254729A (FUJIWARA et al . , 1993) reports a method for obtaining substantially colorless glycine from an aqueous glycine solution.
  • the method comprises the following steps: reacting glycolonitrile, carbon dioxide (gas) and ammonia in the presence of water to obtain a solution containing glycine; removing most of carbon dioxide and ammonia by adjusting the pH of the remaining alkaline aqueous glycine solution to 3.5-6 with an acid cation exchange resin; decoloring the aqueous glycine solution by contacting the solution with active carbon and; evaporating water from the solution to crystallize pure glycine crystals.
  • JP2003221359A (HIROYUKI and AKIHIRO 2003) describes a method for manufacturing dicarboxylic acid from the reaction mixture obtained by bringing a cycloalkane into contact with oxygen in the presence of an imide group compound.
  • An ion-exchange resin treatment is used to separate the dicarboxylic acid.
  • This ion-exchange resin treatment can be performed by supplying the liquid to be treated to a container filled with ion exchange resin (ion exchange resin treatment bath) .
  • the ion exchange resin treatment tank may be a tower type.
  • a fixed bed, a fluidized bed system or any other continuous treatment can be used.
  • the work discloses the separation of compounds containing an imide group or it's decomposition products from dicarboxylic acids obtained through the oxidation of a cycloalkane which comprise a completely different set of compounds to be separated comparing with those focused on the present patent application, which are obtained from different raw material, namely, glycerol. Moreover, it does not specify which continuous treatment is better in the reported invention.
  • the patent EP1441823B1 contemplates methods for the isolation of one or more specific components from a more complex material, but using a centrifugal chromatography device (CCD) described in the document.
  • CCD centrifugal chromatography device
  • the patent WO2016083455A1 (KOLFSCHOTEN and Sanders 2016) describes a process for the precipitation of one or more amino and/or organic acids from a liquid feed comprising a plurality of amino and/or organic acids.
  • a solution of amino and/or organic acids from a feed in a mixture of a solvent and an anti-solvent passes through a zone capable of selectively removing solvent and/or adding anti-solvent from an external source to the mixture.
  • the simulated moving bed (SMB) chromatography has been applied to a variety of industrial processes, as an alternative to discontinuous processes.
  • an SMB has two inlet streams (Figure 1), eluent ( Figure 1 - 5) and feed ( Figure 1 - 6), and two outlet streams, extract ( Figure 1 - 7) and raffinate ( Figure 1 - 8) .
  • These streams divide the unit into four sections or zones, each of which is responsible for a different function.
  • Section 1 Figure 1 - 1) the more-retained compound must move with the liquid to be collected in the extract port in order to regenerate the solid
  • Section 4 Figure 1 - 4
  • the less-retained compound must move with the solid to be collected in the raffinate in order to regenerate the liquid.
  • Sections 2 ( Figure 1 - 2) and 3 ( Figure 1 - 3) the more-retained compound must move with the solid to be collected in the extract port and the less-retained one must move with the liquid in the direction of the raffinate collecting point.
  • molasses consisting of molasses, vinasse, sulphite cooking liquid, fructose/glucose syrups, beet-derived juices, sugar beet molasses, xylitol run-off, invert sugar mixtures, starch hydrolysates, wood hydrolysates, milk whey solutions, lactose-containing solutions, solutions containing amino acids, fermentation broths containing organic acids, bagasse hydrolysates, inositol-containing solutions, mannitol- containing solutions, sorbitol-containing solutions, xylitol-containing solutions, erythritol-containing solutions, glutamic acid-containing solutions, and glycerol- containing solutions) .
  • the products to be recovered can include one or more of the following: glucose, fructose, sucrose, betaine, rhamnose, arabinose, mannose, raffiose, lactose, lactulose, maltose, maltiol, inositol, mannitol, glycerol, xylitol, xylose, sorbitol, erythritol, ribose, 6-O-ci-D- glucopyranosido-D-Sorbitol (1,6-GPS) and 1-O-ci-D- glucopyranosido-D-Mannitol (1,1-GPM), organic acids or amino acids, such as glutamic acid, the document limits them to the document limits them to the documents.
  • the patent document FR2900654A1 provides a process for separating an organic acid by passing this solution through a chromatographic bed filled with an anionic resin.
  • the method is also characterized in that the organic acid is the citric acid and the aqueous solution is a culture broth obtained by fermentation generating said organic acid.
  • US8951416B2 (SARMALA et al . , 2015) is based on the use of a combination of strong acid cation exchange resins (SAC) and weak acid cation exchange resins (WAC) in a specific order and in specified proportions in a chromatographic SMB separation system.
  • SAC strong acid cation exchange resins
  • WAC weak acid cation exchange resins
  • US8951416B2 relates to a method of separating betaine and at least one other component from a sugar beet based fermentation solution, in which the other compound to be separated can be glycerol, an organic acid or inositol.
  • the US20130345473A1 patent (ARCHER et al., 2013) disclosures a process for the separation of at least one di- carboxylic acid compound from a mixture comprising at least one mono-carboxylic acid compound and at least one di- carboxylic acid compound by a chromatography process.
  • ion- exchange chromatography is carried out using simulated moving bed (SMB) chromatography
  • SMB simulated moving bed
  • glycerol derivatives obtained from the catalytic chemical conversion of glycerol such as dihydroxyacetone, hydroxypyruvic acid, glycolic acid, oxalic acid, mesoxalic acid (MEO) , tartronic acid, glyceric acid, glyceraldehyde or glyoxalic acid , for instance, generating less chemicals waste, producing high purity compounds and providing high productivities.
  • the simulated moving bed chromatography method for separating a glycerol derivative from a feed solution comprising said glycerol derivative and one or more other glycerol derivatives, or impurities comprises:
  • a simulated moving bed chromatographic apparatus comprising at least two chromatographic columns interconnected in series; wherein said columns contain a separation media or a mixture of a variety of separation media, comprising ion exchange materials; sequentially comprising first a desorbent port, an extract port, a feed port and a raffinate port; and simultaneously,
  • the simulated moving bed chromatographic apparatus may further comprise additional raffinate or extract streams allowing to perform ternary, pseudo-ternary or higher order separations; withdrawing, through said outlet ports, a raffinate or extract stream comprising the fluid mobile phase, an acid solution or basic solution or water-organics mixture or water itself and mainly one of said glycerol derivative, and a lower percentage of said other glycerol derivative or any impurity present in said feed solution.
  • the simulated moving bed chromatographic apparatus may also comprise a second desorbent port to perform solvent gradients inside the unit; contacting, through said second desorbent port, an acid solution or basic solution or water-organics mixture or water itself with said separation material.
  • said glycerol derivative is selected from dihydroxyacetone (DHA) , hydroxypyruvic acid (HPA) , glycolic acid (GCO) , oxalic acid (OXA) , mesoxalic acid (MEO) , tartronic acid (TTA) , glyceric acid (GCA) , glyceraldehyde (GLA) , glyoxalic acid (GOX) , unreacted glycerol or any glycerol derivatives.
  • DHA dihydroxyacetone
  • HPA hydroxypyruvic acid
  • GCO glycolic acid
  • OXA oxalic acid
  • MEO mesoxalic acid
  • TTA tartronic acid
  • GCA glyceric acid
  • GLA glyceraldehyde
  • GOX glyoxalic acid
  • the feed solution is product of a chemical conversion of glycerol by a range of process such as selective oxidation, selective hydrogenolysis , catalyst dehydration, pyrolysis, gasification, selective glycerol transesterification and esterification, selective etherification and carboxylation .
  • the pH of said feed solution is between 1 and 13 by the addition of an acid or a basic species.
  • the pH of said feed solution is between 1 and 7 by the addition of an acid or a basic species.
  • the pH of said feed solution is between 1 and 5 by the addition of an acid or a basic species.
  • the feed solution is pretreated by any process suitable to obtain a solution of two or more glycerol derivatives with or without unreacted glycerol without impurities from the process of chemical conversion of glycerol including, but not limited to, ion exchange, distillation, centrifugation and filtration.
  • the chromatographic material is a cation or anion exchange chromatographic material, wherein said cation exchange chromatographic material is selected from alumina, magnesium silicates, silica, glass, controlled pore glass, carbon, porous graphitic carbon, zirconium phosphate, hydroxyapatite, calcium phosphate, magnesium carbonate, and polymers or resins.
  • said polymers or resins for the cation exchange chromatography are selected from hydroxyalkylmethacrolate, polyacrylamine, polymacrolate, poly (hydroxyethylmacrolate ) , polystyrene, styrene-divinylbenzine polymers, poly ( ethyleneglycoldimethacrolate ) , poly (vinylalcohol ) , Poly (vinylacetate) , and poly (vinylpyridine )
  • the cation exchange chromatographic material within each of chromatographic columns is equilibrated with an aqueous acid solution.
  • the anion exchange chromatographic material is selected from polymers, resins, silica, zirconia, carbon and alumina, wherein said polymers or resins for the anion exchange chromatography are selected from sulfonic acid, alkylsulfonic acid, phenylsulfonic acid, alkylphenylsulfonic acid, and salts thereof, poly (vinylalcohol ) , poly (methacrylates ) , hypercross-linked polystyrene and poly ( ethylene oxide) and styrene or ethylvinylbenzene polymers or copolymers cross-linked with divinylbenzene (e.g., ethylvinylbenzene-divinylbenzene (EVB-DVB) and styrene or polystyrene-divin
  • the said anion exchange chromatographic material within each of chromatographic columns is equilibrated with an aqueous basic solution.
  • the eluent is an acid or basic solution or water .
  • the simulated moving bed chromatography may be practiced with any simulated moving bed chromatographic apparatus, including but not limited to moving port and moving column systems .
  • the present patent application describes a simulated moving bed chromatographic method for separating a glycerol derivative, from a mixture feed solution, containing the glycerol derivative and at least another compound, such as other organic compound and/or other glycerol derivatives and/or unreacted glycerol and/or impurities, comprising:
  • a simulated moving bed chromatographic apparatus comprising at least two chromatographic columns interconnected in series; wherein said columns contain a separation media or a mixture of a variety of separation media, comprising ion exchange materials; sequentially comprising first a desorbent port, an extract port, a feed port and a raffinate port; and simultaneously,
  • the feed solution may be the stream containing glycerol (or the so called crude glycerol) from biodiesel production, which can be from multiple feedstocks or a solution of refined glycerol in any concentration, wherein the feed solution may also contain impurities.
  • the chromatographic material may be silicas, functionalized silicas, aluminas, carbons, zeolites functionalized and non- functionalized polystyrene, polyacrylamide, cross-linked polystyrenes, polyacrylates or other resins and the aqueous eluent may be water or an acid or basic solution.
  • the present patent application relates to a simulated moving bed chromatography method for separating one or more glycerol derivatives from a feed solution of chemically conversion processes of glycerol into said glycerol derivatives, comprising :
  • a simulated moving bed chromatographic apparatus comprising at least two chromatographic columns interconnected in series; wherein Said columns contain a separation media or a mixture of a variety of separation media, comprising ion exchange materials; sequentially comprising first a desorbent port, an extract port, a feed port and a raffinate port; and simultaneously,
  • the simulated moving bed chromatographic apparatus may further comprise additional raffinate or extract streams allowing to perform ternary, pseudo-ternary or higher order separations; withdrawing, through said outlet ports, a raffinate or extract stream comprising the fluid mobile phase, an acid solution or basic solution or water-organics mixture or water itself and mainly one of said glycerol derivative, and a lower percentage of said other glycerol derivative or any impurity present in said feed solution. It may also comprise a second desorbent port to perform solvent gradients inside the unit; contacting, through said second desorbent port, an acid solution or basic solution or water- organics mixture or water itself with said separation material .
  • feed mixtures containing various glycerol derivatives as mono- carboxylic acids or dicarboxylic acids
  • salt form of these acids such as sodium, potassium, calcium, and magnesium salts (e.g., tartronate, glycerate, oxalate, glycolate, dihydroxyacetonate) , or ketones or aldehydes or esters or ethers, among others.
  • the pH of said feed solution may be adjusted to a pH between 1 and 13, which may be between 1 and 7 or between 1 and 5, by the addition of an acid or a basic material.
  • the pH of the feed solution may be adjusted by the addition of any compound suitable to the production of an edible product.
  • Suitable acid compounds include, but are not limited to, hydrochloric acid, sulfuric acid and phosphoric acid. Preferable is sulfuric acid.
  • Suitable basic compounds include, but are not limited to, sodium hydroxide, potassium hydroxide, ammonium hydroxide and ammonia.
  • the second aspect of the present patent application is directed to a chromatographic separation process for separating a glycerol derivative, from a mixture containing the glycerol derivative, and one or more other component, which may be another glycerol derivatives and/or unreacted glycerol and/or impurities wherein the eluent can be an acid solution or basic solution or water-organics mixture or water itself and the stationary phase can be a chromatographic material .
  • the eluent may be an acid solution or basic solution or water-organics mixture or water itself . Any of these solutions must be prepared in order to have a pH between 1 and 13, ideally between 1 to 7 or between 1 and 3.
  • a chromatographic separation process that uses slightly acidified water as eluent is advantageous because it reduces the environment impacts and because additional equipment for separation of the glycerol derivative from the eluent may not be required.
  • the said column or columns may contain a cation exchange chromatographic material comprising a functional group selected from the group consisting of sulfonates, alkylsulfonates, phenylsulfonates, alkylphenylsulfonates and mixtures thereof.
  • the cation exchange chromatographic material may be a strong cation exchange resin.
  • the strong cation exchange chromatographic material may comprise a sulfonate .
  • the cation exchange chromatography material of the present patent application preferably comprises one or more chromatographic support materials (i.e., stationary phases) .
  • Suitable chromatographic support materials for the cation exchange chromatography include, but are not limited to, alumina, magnesium silicates, silica, glass, controlled pore glass, carbon, porous graphitic carbon, zirconium phosphate, hydroxylapatite, calcium phosphate, magnesium carbonate, and polymers or resins. d.
  • Suitable polymers or resins for the cation exchange chromatography include, but are not limited to, hydroxyalkylmethacrolate, polyacrylamine, polymacrolate, poly (hydroxyethylmacrolate ) , polystyrene, styrene-divinylbenzine polymers, poly ( ethyleneglycoldimethacrolate ) , poly (vinylalcohol ) , Poly (vinylacetate) , and poly ( inylpyridine ) .
  • Preferable are polymers or resins. More preferable are styrene-divinylbenzine polymers. e.
  • the cation exchange chromatographic material of the present patent application further comprises a plurality of ligands, selected from one or more functional groups suitable for ion exchange.
  • These functional groups include but are not limited to sulfonic acid, alkylsulfonic acid, phenylsulfonic acid, alkylphenylsulfonic acid, and salts thereof. Preferred are sulfonic acid functional groups and the salts thereof .
  • Specific examples of cation exchange silica-based chromatographic materials include ADSORBOSPHERE SCX, BAKERBOND SCX, PARTISIL SCX, SPHERISORB S SCX, SUPELCOSIL LC-3SCX, ULTRASILCX, and ZORBAX 300 SCX.
  • cation exchange polymers or resins that may be used include: AMBERLITE 200, AMBERLITE IR-118H, AMBERLITE IR-120PLUS, AMBERLITE IR- 122, AMBERLITE IR-130C, AMBERLITE 16641, AMBERLITE IRP- 69, DOWEX 50X1-100, DOWEX 50X2-100, DOWEX 50X2-200, DOWEX 50X2-400, DOWEX 50X4-100, DOWEX 50X4-200, DOWEX 50X4-200R, DOWEX 50X4-400, DOWEX 18880, DOWEX 50X8-100, DOWEX 50X8-200, DOWEX 50X8-400, DIAION 1-3561, DIAION 1-3565, DIAION 1-3570, DIAION 1-3573, DIAION 1-3577, DIAION 1-3581, DUOLITE D 5427, and DUOLITE D 5552, which are available from Sigma-Ald
  • AMBERLITE IR-120 Preferable are AMBERLITE IR-120, AMBERLITE IR-120B, AMBERLITE IR-200C, DOWEX C500ES, DOWEX XUS 43518, and DOWEX XUS 40406.00. Most preferable is DOWEX XUS 40406.00. h.
  • the said cation exchange chromatographic material within each of chromatographic columns may be equilibrated (conditioned) with an aqueous acid solution .
  • the anion exchange chromatography material of the present patent application preferably comprises one or more chromatographic support materials (i.e., stationary phases) .
  • chromatographic support materials i.e., stationary phases
  • Suitable chromatographic support materials for the anion exchange chromatography include, but are not limited to, polymers, resins, silica, zirconia, carbon and alumina. j .
  • Suitable polymers or resins for the anion exchange chromatography include, but are not limited to: poly (vinylalcohol ) , poly (methacrylates ) , hypercross- linked polystyrene and poly ( ethylene oxide) and styrene or ethylvinylbenzene polymers or copolymers cross- linked with divinylbenzene (e.g., ethylvinylbenzene- divinylbenzene (EVB-DVB) and styrene or polystyrene- divinylbenzene (DVB or PS-DVB) copolymer) of acrylonitrile, acrylic acid, or methacrylic acid.
  • poly (vinylalcohol ) poly (methacrylates )
  • the anion exchange chromatographic material of the present patent application further comprises a plurality of ligands, selected from one or more functional groups suitable for ion exchange. These functional groups are obtained through an amination procedure during the anion exchange chromatographic production process.
  • TMA trimethylamine
  • TAA trihexylamine
  • DMEA dimethylethanolamine
  • MA methylamine
  • DMA dimethylamine
  • MDEA methyldiethanolamine
  • TAA triethanolamine
  • anion exchange chromatographic materials include, but are not limited to, PRP-X100/"Hamilton", USA; PRP-X110/"Hamilton", USA; LCA01/"Sykam", Germany; Gelpack GL-IC-A23/"Hitachi", Japan; ICSep ANl/"Transgenomic", USA; ICSep AN1- SC/"Transgenomic", USA; ICSep AN300/"Transgenomic", USA; ICSep AN300B/"Transgenomic", USA; Star Ion A300/"Phenomenex", USA; Metrosep A Supp l/"Metrohm", Switzerland; Metrosep A Supp 1 HS/"Metrohm", Switzerland; Metrosep A Supp 3/"Metrohm", Switzerland; Metrosep A Supp 10/"Metrohm", Switzerland; Metrosep A Supp 15/"Metrohm", Switzerland; Metrosep A Supp 16/"M
  • separation processes disclosed herein can also include a selective membrane separation (e.g., nano-filtration membranes) in combination with the chromatographic separation processes described herein.
  • the selective membrane separation can be performed upstream and/or downstream of a chromatographic separation.
  • selective membrane separation techniques such as nano-filtration (NF) membrane separation can be used to reduce the amount of impurities contained in a mixture (e.g., a mixture obtained from an oxidation process for preparing the glycerol derivative from glycerol) prior feeding the mixture to a chromatographic separation.
  • NF nano-filtration
  • the feed solution may be from a chemical conversion of glycerol by a range of process such as selective oxidation, selective hydrogenolysis , catalyst dehydration, pyrolysis, gasification, selective glycerol transesterification and esterification, selective etherification and carboxylation .
  • the feed solution is pretreated by any process suitable to obtain a solution of two or more glycerol derivatives with or without unreacted glycerol without impurities from the process of chemical conversion of glycerol including, but not limited to, ion exchange, distillation, centrifugation and filtration.
  • the glycerol derivatives may be dihydroxyacetone (DHA) , hydroxypyruvic acid (HPA) , glycolic acid (GCO) , oxalic acid (OXA) , mesoxalic acid (MEO) , tartronic acid (TTA) , glyceric acid (GCA) , glyceraldehyde (GLA) or glyoxalic acid (GOX) .
  • DHA dihydroxyacetone
  • HPA hydroxypyruvic acid
  • GCO glycolic acid
  • OXA oxalic acid
  • MEO mesoxalic acid
  • TTA tartronic acid
  • GCA glyceric acid
  • GLA glyceraldehyde
  • GOX glyoxalic acid
  • the method disclosed herein may be practiced with any simulated moving bed chromatographic apparatus, including but not limited to moving port and moving column systems.
  • This example describes the purification of a binary mixture containing Glyceric Acid and Tartronic Acid produced from the catalytic oxidation of glycerol.
  • a solution of Sulfuric Acid 4mM was used as eluent and a Polystyrene Divinylbenzene (PS/DVB) resin (Dowex® 50WX-2), in hydrogen form (2%), mesh of 200-400, from The Dow Chemical Company (United States) was used as separation media.
  • PS/DVB Polystyrene Divinylbenzene
  • the SMB experiment was performed in a SMB unit containing 6 stainless steel columns of 100mm of height and 20mm of diameter packed with the acid resin Dowex® 50WX-2.
  • a mixture of Glyceric Acid (lOg/L) and Tartronic Acid (5g/L) was separated using a sulfuric acid solution (4mM) as eluent.
  • the flow rates were: 6.93mL/min for the eluent stream, 1.16mL/min for the feed stream, 4.81mL/min for the raffinate stream, 3.5mL/min for the extract stream and 8.4mL/min for the recycling stream.
  • the switching time was set at 2 min. Additionally, one column per section was used in sections 1 and 4 (of fig.
  • This example describes the purification of a pseudo-binary mixture, through which two fractions of glycerol derivatives (A and B plus C) can be purified.
  • fraction A Olalic Acid
  • fraction B Glyceric Acid and Unreacted glycerol
  • C Teartronic Acid
  • PS/DVB Polystyrene Divinylbenzene
  • the SMB separation was carried out in a SMB unit containing 6 stainless steel columns of 100mm of height and 20mm of diameter packed with the acid resin Dowex® 50WX-2.
  • This example describes the purification of a pseudo-ternary mixture, through which three fractions of glycerol derivatives (A, B and C) can be purified.
  • fraction A Olalic Acid
  • fraction B Gelar Acid and Unreacted glycerol
  • fraction C Teartronic acid
  • another SMB unit interconnected in series with the latter proceeded with the final purification between fraction B (Glyeric Acid and Unreacted glycerol) and fraction C (Tartronic acid) .
  • a solution of Sulfuric Acid 4Mm was used as eluent and a Polystyrene Divinylbenzene ( PS/DVB ) resin (Dowex® 50WX-2), in hydrogen form (2%), mesh of 200-400, from The Dow Chemical Company (United States) was used as separation media.
  • PS/DVB Polystyrene Divinylbenzene
  • the SMB separation was carried out in a SMB unit containing 6 stainless steel columns of 100mm of height and 20mm of diameter packed with the acid resin Dowex® 50WX-2.
  • a mixture of Tartronic Acid ( 7.83g/L) , Glyceric Acid (0.65g/L) and unreacted Glycerol ( 0.65g/L) was separated in the second SMB unit.
  • the flow rates were: 5.02mL/min for the eluent stream, 1.21mL/min for the feed stream, 2.69mL/min for the raffinate, 3.55mL/min for the extract stream and 9.07mL/min for the recycling stream.
  • the switching time was set at 2.00 min. Additionally, one column per section was used in sections 1 and 4 (of fig.l) (located between the desorbent and extract streams and between the raffinate and recycling streams, respectively) and two columns per section were used in sections 2 and 3 (of fig. 1) (located between the extract and feed streams and between the feed and raffinate streams, respectively) .
  • the internal concentration profile at the middle of the switching time after the cyclic steady state be achieved is shown in the FIG 4.
  • the main performance parameters are presented
  • FIG. 1 is a schematic diagram of the process of simulated moving bed chromatography as used for the separation of two water-soluble components, A and B.
  • Section 1 is the zone of potential water recovery, component B conceptually moves with the resin.
  • Section 2 is a zone in which component B moves with the water in an aqueous fluid, and component A conceptually moves with the resin.
  • Section 3 is a zone in which component B moves with the water in an aqueous fluid, and component A conceptually moves with the resin.
  • Section 4 is a section in which purified component A moves with the water in an aqueous fluid.
  • FIG. 2 show the internal concentration profile at the middle of the switching time after the cyclic steady state be achieved. Dashed lines for GCA and solid lines for TTA. The horizontal coordinate shows the axial position of the columns within the SMB equipment and the vertical coordinate shows the concentration (g/L) .
  • FIG. 3 show the internal concentration profile at the middle of the switching time after the cyclic steady state be achieved. Dashed lines for fraction A and solid lines for fraction B plus fraction C. The horizontal coordinate shows the axial position of the columns within the SMB equipment and the vertical coordinate shows the concentration (g/L) .
  • FIG. 4 show the internal concentration profile at the middle of the switching time after the cyclic steady state be achieved. Dashed lines for fraction C and solid lines for Fraction B. The horizontal coordinate shows the axial position of the columns within the SMB equipment and the vertical coordinate shows the concentration (g/L) .
  • the simulated moving bed chromatography method for separating a glycerol derivative from a feed solution comprising said glycerol derivative and one or more other glycerol derivatives, or impurities comprises:
  • a simulated moving bed chromatographic apparatus comprising at least two chromatographic columns interconnected in series; wherein Said columns contain a separation media or a mixture of a variety of separation media, comprising ion exchange materials; sequentially comprising first a desorbent port, an extract port, a feed port and a raffinate port; and simultaneously, (b) contacting, through said feed port, said feed solution with the separation media equilibrated with an acid or basic solution or water-organics mixture or water;
  • the simulated moving bed chromatographic apparatus may further comprise additional raffinate or extract streams allowing to perform ternary, pseudo-ternary or higher order separations; withdrawing, through said outlet ports, a raffinate or extract stream comprising the fluid mobile phase, an acid solution or basic solution or water-organics mixture or water itself and mainly one of said glycerol derivative, and a lower percentage of said other glycerol derivative or any impurity present in said feed solution.
  • the simulated moving bed chromatographic apparatus may also comprise a second desorbent port to perform solvent gradients inside the unit; contacting, through said second desorbent port, an acid solution or basic solution or water-organics mixture or water itself with said separation material.
  • said glycerol derivative is selected from dihydroxyacetone (DHA) , hydroxypyruvic acid (HPA) , glycolic acid (GCO) , oxalic acid (OXA) , mesoxalic acid (MEO) , tartronic acid (TTA) , glyceric acid (GCA) , glyceraldehyde (GLA) , glyoxalic acid (GOX) , unreacted glycerol or any glycerol derivatives.
  • DHA dihydroxyacetone
  • HPA hydroxypyruvic acid
  • GCO glycolic acid
  • OXA oxalic acid
  • MEO mesoxalic acid
  • TTA tartronic acid
  • GCA glyceric acid
  • GLA glyceraldehyde
  • GOX glyoxalic acid
  • the feed solution is product of a chemical conversion of glycerol by a range of process such as selective oxidation, selective hydrogenolysis , catalyst dehydration, pyrolysis, gasification, selective glycerol transesterification and esterification, selective etherification and carboxylation .
  • the pH of said feed solution is between 1 and 13 by the addition of an acid or a basic species. In a preferred embodiment the pH of said feed solution is between 1 and 7 by the addition of an acid or a basic species. In a more preferential embodiment the pH of said feed solution is between 1 and 5 by the addition of an acid or a basic species.
  • the feed solution is pretreated by any process suitable to obtain a solution of two or more glycerol derivatives without impurities; wherein the pretreatment process is a process selected from ion exchange, distillation, centrifugation and filtration.
  • the feed solution is pretreated by any process suitable to obtaining a solution of two or more glycerol derivatives without impurities from the process of chemical conversion of glycerol including, but not limited to, centrifugation and filtration including ultrafiltration.
  • the chromatographic material is a cation or anion exchange chromatographic material, wherein said cation exchange chromatographic material is selected from alumina, magnesium silicates, silica, glass, controlled pore glass, carbon, porous graphitic carbon, zirconium phosphate, hydroxyapatite, calcium phosphate, magnesium carbonate, and polymers or resins.
  • said polymers or resins for the cation exchange chromatography are selected from hydroxyalkylmethacrolate, polyacrylamine, polymacrolate, poly (hydroxyethylmacrolate ) , polystyrene, styrene-divinylbenzine polymers, poly ( ethyleneglycoldimethacrolate ) , poly (vinylalcohol ) , Poly (vinylacetate) , and poly ( inylpyridine )
  • the cation exchange chromatographic material within each of chromatographic columns is equilibrated with an aqueous acid solution.
  • the anion exchange chromatographic material is selected from polymers, resins, silica, zirconia, carbon and alumina, wherein said polymers or resins for the anion exchange chromatography are selected from sulfonic acid, alkylsulfonic acid, phenylsulfonic acid, alkylphenylsulfonic acid, and salts thereof, poly (vinylalcohol ) , poly (methacrylates ) , hypercross-linked polystyrene and poly ( ethylene oxide) and styrene or ethylvinylbenzene polymers or copolymers cross-linked with divinylbenzene (e.g., ethylvinylbenzene-divinylbenzene (EVB-DVB) and styrene or polystyrene-divinylbenzene (DVB or PS-DVB) copolymer) of acrylonitrile, acrylic acid, or methacrylic
  • the eluent is an acid or basic solution or water .
  • the simulated moving bed chromatography may be practiced with any simulated moving bed chromatographic apparatus, including but not limited to moving port and moving column systems .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)

Abstract

La présente demande de brevet concerne un nouveau procédé innovant pour la purification de dérivés de glycérol, par chromatographie en lit mobile simulé. Le procédé de la présente invention permet la séparation d'au moins un dérivé de glycérol présent dans une solution d'alimentation. Les dérivés de glycérol purifiés par le procédé de l'invention comprennent la dihydroxyacétone (DHA), l'acide hydroxypyruvique (HPA), l'acide glycolique (GCO), l'acide oxalique (OXA), l'acide mésoxalique (MEO), l'acide tartronique (TTA), l'acide glycérique (GCA), le glycéraldéhyde (GLA), l'acide glyoxalique (GOX) et le glycérol n'ayant pas réagi. Le procédé décrit ici peut être utilisé avec n'importe quel appareil chromatographique en lit mobile simulé comprenant, mais sans y être limité, des systèmes à orifices à colonnes mobiles.
EP19708654.9A 2018-01-09 2019-01-09 Procédé de séparation et de purification de dérivés du glycérol Pending EP3737484A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PT11050518 2018-01-09
PCT/IB2019/050161 WO2019138338A1 (fr) 2018-01-09 2019-01-09 Procédé de séparation et de purification de dérivés du glycérol

Publications (1)

Publication Number Publication Date
EP3737484A1 true EP3737484A1 (fr) 2020-11-18

Family

ID=65635757

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19708654.9A Pending EP3737484A1 (fr) 2018-01-09 2019-01-09 Procédé de séparation et de purification de dérivés du glycérol

Country Status (3)

Country Link
EP (1) EP3737484A1 (fr)
BR (1) BR112020014048A2 (fr)
WO (1) WO2019138338A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113956150B (zh) * 2020-07-21 2024-03-22 中国石油大学(华东) 一种甘油酸的制备方法
CN111909001B (zh) * 2020-09-04 2022-10-04 禾大西普化学（四川）有限公司 一种高纯甘油深度纯化方法
CN114712895B (zh) * 2022-03-08 2023-04-28 江南大学 提高模拟移动床产率的带额外色谱柱的双部分丢弃方法
WO2024097329A1 (fr) * 2022-11-02 2024-05-10 Amalgamated Research Llc Séparateur smb pour purification d'acide organique à l'aide d'une résine cationique fortement acide

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4621153A (en) 1985-02-27 1986-11-04 Biotechnica International, Inc. Purification and recovery of amino acids
US5254729A (en) 1990-05-31 1993-10-19 Mitsui Toatsu Chemicals, Inc. Method for purifying glycine
DE69112770T2 (de) 1990-11-02 1996-05-09 Mitsubishi Chem Corp Verfahren zur Abscheidung der organischen Säure oder Säuren aus einer organische Säuren enthaltenden Lösung.
US6224776B1 (en) 1996-05-24 2001-05-01 Cultor Corporation Method for fractionating a solution
US6942804B2 (en) 2001-11-09 2005-09-13 Kinetic Biosystems, Inc. Methods and compositions for chromatography
JP2003221359A (ja) 2002-01-29 2003-08-05 Daicel Chem Ind Ltd ジカルボン酸の製造方法
ES2396679T3 (es) 2003-02-25 2013-02-25 Dupont Nutrition Biosciences Aps Un sistema de lecho móvil simulado
FR2900654B1 (fr) 2006-05-05 2008-08-01 Applexion Procede de purification d'un acide organique par chromatographie
AU2008310307B2 (en) 2007-10-10 2013-04-18 Langtech International Pty Ltd Method to recover bioactive compounds
US8951416B2 (en) 2009-02-25 2015-02-10 Dupont Nutrition Biosciences Aps Separation process
US9487465B2 (en) 2011-12-14 2016-11-08 Rennovia Inc. Process for the separation of mono- and di-carboxylic acid compounds
AU2015323913A1 (en) * 2014-09-29 2017-03-02 Archer-Daniels-Midland Company Preparation and Separation of a Dicarboxylic Acid-Containing Mixture using a Dicarboxylate Form of an Anion Exchange Chromatography Resin
EP3224236A1 (fr) 2014-11-25 2017-10-04 Wageningen Universiteit Procédé de précipitation d'acides aminés et/ou organiques à partir d'une charge complexe et particules d'acides aminés et/ou organiques pouvant ainsi être obtenues

Also Published As

Publication number Publication date
BR112020014048A2 (pt) 2021-05-04
WO2019138338A1 (fr) 2019-07-18

Similar Documents

Publication Publication Date Title
WO2019138338A1 (fr) Procédé de séparation et de purification de dérivés du glycérol
US9233906B2 (en) Purification of succinic acid from the fermentation broth containing ammonium succinate
Din et al. Lactic acid separation and recovery from fermentation broth by ion-exchange resin: A review
Li et al. Recovery processes of organic acids from fermentation broths in the biomass-based industry
RU2634700C2 (ru) Способы обработки лигноцеллюлозных материалов
EP3200891B1 (fr) Préparation et séparation d'un mélange comprenant un acide dicarboxylique au moyen d'une résine chromatographique échangeuse d'anions sous forme carboxylate
US8802843B2 (en) Tagatose production using simulated moving bed separation
US10308582B2 (en) Process for making acrylic acid from dextrose
WO2017184545A1 (fr) Conversion de matières premières contenant du fructose en produit contenant de l'hmf
WO2014095080A2 (fr) Procédé pour la purification d'acides carboxyliques
JP2005520817A (ja) アスコルビン酸の製造方法
EP1213278B1 (fr) Procédé d'estérification dans un réacteur chromatographique
US6518454B1 (en) Preparation of esters of carboxylic acids
AU2006233711A1 (en) Method for recovering a basic amino acid from a fermentation liquor
CN109689852B (zh) 精制木质纤维素水解产物的方法
CN104610059A (zh) 一种酯交换-吸附脱甲醇合成(甲基)丙烯酸酯的方法
CN113121329B (zh) 一种从乳酸盐的含水原料中耦合转化与提取乳酸的方法
Ahmad et al. Acetic acid and co-chemicals production from syngas
CN111620774A (zh) 一种丙二酸钙制取高纯固体丙二酸的生产方法
EP3241820A1 (fr) Récupération de carboxylates à partir de la fermentation et la production d'esters utilisant des alcools expansés par co2
CN102070447A (zh) 一种普伐他汀钠化合物及其新制法
CN112771060A (zh) 三氯蔗糖的制备方法、粗产品溶液及三氯蔗糖
WO2023141455A2 (fr) E à 1,5-pentanediamine et séparation de diamines contenues dans des acides aminés et carboxyliques
AU2006233710A1 (en) Method for recovering a basic amino acid from a fermentation liquor II
CN116574147A (zh) 一种利用色谱技术分离纯化ump转化液的工艺

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20200810

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

RIN1 Information on inventor provided before grant (corrected)

Inventor name: ALMEIDA PEIXOTO RIBEIRO, ANA MAFALDA

Inventor name: EGIDIO RODRIGUES, ALIRIO

Inventor name: CUNHA DUARTE COELHO, LUCAS

Inventor name: MEDEIRO DE LIMA FILHO, NELSON

Inventor name: VIEIRA FARIA, RUI PEDRO

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20230824

RAP3 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNIVERSIDADE FEDERAL DE PERNAMBUCO

Owner name: UNIVERSIDADE DO PORTO