WO2024097329A1 - Séparateur smb pour purification d'acide organique à l'aide d'une résine cationique fortement acide - Google Patents

Séparateur smb pour purification d'acide organique à l'aide d'une résine cationique fortement acide Download PDF

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Publication number
WO2024097329A1
WO2024097329A1 PCT/US2023/036656 US2023036656W WO2024097329A1 WO 2024097329 A1 WO2024097329 A1 WO 2024097329A1 US 2023036656 W US2023036656 W US 2023036656W WO 2024097329 A1 WO2024097329 A1 WO 2024097329A1
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WO
WIPO (PCT)
Prior art keywords
acid
purifying
organic
organic acid
smb
Prior art date
Application number
PCT/US2023/036656
Other languages
English (en)
Inventor
Lily Crane
Peter FERRERO
Original Assignee
Amalgamated Research Llc
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
Priority claimed from US18/499,697 external-priority patent/US20240140899A1/en
Application filed by Amalgamated Research Llc filed Critical Amalgamated Research Llc
Publication of WO2024097329A1 publication Critical patent/WO2024097329A1/fr

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Classifications

    • 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
    • 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
    • B01D15/1828—Simulated moving beds characterized by process features
    • 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

Definitions

  • This disclosure relates generally to simulated moving bed (SMB) separation and purification systems and methods.
  • SMB simulated moving bed
  • this disclosure relates to systems and methods for an SMB separator for organic acid purification using a strong acid cation resin.
  • Organic acids such as lactic acid, malic acid, fumaric acid, and citric acid are widely used in the food industry as flavorings and acidulants.
  • Industrially the upstream process for producing many commercially available organic acids typically involves the fermentation of either cane or beat sugar molasses or corn syrups.
  • molasses is commonly used due to the integrated sugars, amino acids, and salts aiding in the growth of the bacteria or yeast to produce the desired organic acid.
  • the fermentation broth containing the organic acid product must undergo several purification steps to reduce the residual sugar, ash, and color content of the fermentation broth before crystallizing the organic acid. It is common to utilize a two-step precipitation process to remove most of the color and monovalent salts from the fermentation broth.
  • a technology that has been historically investigated into for the purification of these organic acids is ion exchange, as it would eliminate the gypsum byproduct waste of the gypsum purification process.
  • These methods use various types of anion exchange resin to bind the deprotonated organic acid followed by elution with salt, caustic, or acid as taught in EP2592952B1, US6641734, US5382681, US6087139, and US2664441 for which the contents of each are hereby incorporated by reference. This facilitates the removal of the residual sugar, ash, and color impurities in the fermentation broth.
  • anion exchange for organic acid purification is the high amount of chemical required during the elution step of the ion exchange cycle.
  • Strong acid cation (SAC) exchange resins have been extensively used to purify neutral sugars such as sucrose, glucose, and fructose in the sweetener industries using SMB chromatography.
  • the eluent for regenerating the SAC resin is simply condensate water produced elsewhere in the plant. This minimizes the amount of chemical consumed and disposed of compared to an ion exchange process.
  • organic acids could be purified from fermentation broths using a SAC resin instead of anion exchange as is typically practiced.
  • SAC resins are typically used to purify positively -charged compounds from impurities.
  • the use of a cation exchange resin to purify organic acids which tend to dissociate into negatively-charged compounds is not known to be used for purification by those skilled in the art.
  • Other drawbacks and inefficiencies also exist with current systems and methods.
  • An additional advantage from this process is that unlike anion exchange resins, cation exchange resins are resistant to organic foulants such as dextran and polysaccharides often found in fermentation broths. Furthermore, SAC resins are available in smaller resin particle sizes compared to anion exchange resins which further reduce the resin and eluent requirements for the SMB process utilizing a SAC resin.
  • Disclosed embodiments include processes for purifying an organic acid including separating an organic acid from a fermentation broth (FB) by adding an acid to the FB to form protonated organic acid, creating a solution of dissolved solids from the protonated organic acid, processing the solution of dissolved solids by using it as feedstock in a simulated moving bed (SMB) chromatography system that uses a dilute acid as an eluent and a strong acid cation (SAC) exchange resin, and wherein each step of the SMB chromatography system is divided into two sub-periods wherein a first sub-period encompasses a span of time where the feedstock and the eluent are injected into distinct columns within a recirculation loop and, concurrently, extract and raffinate fractions are also withdrawn from the SMB chromatography system at defined points and during a second sub-period an internal solids profile is recirculated within the SMB chromatography system without any additional material added or removed.
  • SMB
  • the FB comprises salt, color waste, fermentable sugars.
  • the organic acid is selected from the group including, but not limited to, citric acid, malic acid, fumaric acid, acetic acid, tartaric acid, glycolic acid, glucaric acid, lactic acid, xylonic acid, gluconic acid, galactaric acid, succinic acid, maleic acid, itaconic acid, malonic acid, terephthalic acid, phthalic acid, glutaric acid, adipic acid, 3-hydroxyproponic acid, formic acid, and oxalic acid.
  • the process of purifying an organic acid includes adding an acid to the FB to lower the pH of the FB to be substantially between 1.0-2.0. In some embodiments, the step of adding an acid to the FB includes adding 93% concentrated sulfuric acid.
  • the eluent used in the SMB chromatography system comprises acidified water where the acid used is a mineral acid.
  • the acidified water includes, but is not limited to, sulfuric acid, hydrochloric acid, nitric acid, or phosphoric acid.
  • the process of purifying an organic acid includes adjusting the pH of the acidified water to be substantially between 1.0-2.0.
  • Also disclosed are systems for purifying an organic acid including a simulated moving bed (SMB) chromatography system for processing a solution of dissolved solids by using it as feedstock and that uses a dilute acid as an eluent, a strong acid cation (SAC) exchange resin, and wherein each step of the SMB chromatography system is divided into two sub-periods wherein a first sub-period encompasses a span of time where the feedstock and the eluent are injected into distinct columns within a recirculation loop and, concurrently, extract and raffinate fractions are also withdrawn from the SMB chromatography system at defined points and during a second sub-period an internal solids profile is recirculated within the SMB chromatography system without any additional material added or removed.
  • SMB simulated moving bed
  • the solution of dissolved solids is formed by separating an organic acid from a fermentation broth (FB) by adding a mineral acid to the FB to form protonated organic acid.
  • the mineral acid is selected from the group including, but not limited to, sulfuric acid, hydrochloric acid, nitric acid, or phosphoric acid.
  • the FB comprises salt, color waste, fermentable sugars.
  • the organic acid is selected from the group including, but not limited to, citric acid, malic acid, fumaric acid, acetic acid, tartaric acid, glycolic acid, glucaric acid, lactic acid, xylonic acid, gluconic acid, galactaric acid, succinic acid, maleic acid, itaconic acid, malonic acid, terephthalic acid, phthalic acid, glutaric acid, adipic acid, 3-hydroxyproponic acid, formic acid, and oxalic acid.
  • system for purifying an organic acid included an acid added to the FB to lower the pH of the FB to be substantially between 1.0-2.0.
  • the acid added to the FB comprises 93% concentrated sulfuric acid.
  • the system for purifying an organic acid includes adjusting the pH of the mineral acid to be substantially between 1.0-2.0.
  • FIG. 1 illustrates the disclosed exemplary embodiments’ effectiveness of using a SAC resin in an SMB system to purify organic acids from sucrose, ash, and color.
  • FIG. 2 depicts an SMB system to produce purified organic acid from a fermentation broth according to embodiments of the disclosure.
  • a fermentation broth containing approximately 30,000 ppm salt, 275.0 absorbance units of color, 1-2 w/w% sucrose and 7-8 w/w% organic acid was adjusted with 93% concentrated sulfuric acid to lower the pH to between 1.0 - 2.0 to fully protonate the target organic acid to be purified.
  • the deionized (DI) water used as eluent was also pH adjusted to 1.0 - 2.0 pH with 93% concentrated sulfuric acid. Otherwise, the more neutral pH of DI water would raise the pH of the fermentation broth causing the citric acid to deprotonate. To stop this deprotonation from occurring it was also important that the starting fluid in the column be the pH adjusted eluent, and that the resin be soaked in the eluent prior to beginning a run of the process. The results from one of the exemplary runs are shown FIG. 1.
  • a SMB chromatography system was used to purify the organic acid from the various other impurities on a continuous basis.
  • a solution containing 30-40% total dissolved solids of a citric acid containing material was processed using the SMB system as configured in FIG. 2 in which items 1-6 indicate individual columns of the SMB.
  • a solution of diluted sulfuric acid at pH 1.5 was used as the eluent for the SMB system as indicated at 10 on FIG. 2.
  • step is herein defined as the subset of operation wherein the feedstock is introduced (e.g., injected) into a single column (e.g., 1-6) upon which at the end of the “step” the configuration of valves advances such that material is introduced into the next downstream column within the recirculation loop L.
  • the SMB separation of the SMB system was operated such that each step was divided into two subperiods as described in US5102553, the disclosure of which is incorporated by reference herein.
  • the first sub-period encompassed a span of time where the feedstock and eluent were injected into distinct columns within the recirculation loop (for example, as shown at column 1 and 4, respectively).
  • extract and raffinate fractions were also withdrawn from the SMB separator at defined points (for example, as shown between columns 2 and 3 and columns 4 and 5, respectively).
  • the SMB separator was filled with Mitsubishi UBK- 522M strong acid cation resin in the potassium form.
  • the SMB separator was loaded at approximately 45.9 lbs. dissolved solids per cubic foot resin per day (approximately 736 kilograms dissolved solids per cubic meter resin per day).
  • the total resin volume for this experiment was 0.65 cubic feet (18.5 liters) distributed amongst 6 columns.
  • Table 1 The product and by-product stream produced by the SMB chromatography system and the associated operating parameters of the system are listed in Table 1 below.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La divulgation concerne des systèmes et des procédés pour enrichir un acide organique d'un bouillon de fermentation contenant une couleur, des sels et des hydrates de carbone résiduel à l'aide d'une chromatographie sur lit mobile simulé ("SMB") pour produire un extrait d'acide organique de haute pureté. Un mode de réalisation du procédé purifie l'acide citrique d'un bouillon de fermentation en deux flux de produit : un premier flux de produit riche en impuretés de sel, de couleur et d'hydrates de carbone, et un second flux de produit comprenant un extrait enrichi en acide organique.
PCT/US2023/036656 2022-11-02 2023-11-02 Séparateur smb pour purification d'acide organique à l'aide d'une résine cationique fortement acide WO2024097329A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US202263421908P 2022-11-02 2022-11-02
US63/421,908 2022-11-02
US18/499,697 2023-11-01
US18/499,697 US20240140899A1 (en) 2022-11-02 2023-11-01 Smb separator for organic acid purification using a strong acid cation resin

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Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2389766A (en) 1941-04-22 1945-11-27 Fruit Growers Exchange Ca Process for production of calcium citrate
US2664441A (en) 1951-07-19 1953-12-29 Harry S Owens Separation of organic acids
US3798266A (en) 1971-09-20 1974-03-19 Montedison Spa Process for preparing citric acid
US5102553A (en) 1988-12-16 1992-04-07 The Amalgamated Sugar Company Time variable simulated moving bed process
US5382681A (en) 1992-10-07 1995-01-17 Cerestar Holding B.V. Process for the production of an alkali metal citrate
US6087139A (en) 1997-10-30 2000-07-11 Metallgesellschaft Aktiengesellschaft Process for producing citric acid and/or citrates
WO2002089946A1 (fr) * 2001-05-09 2002-11-14 Danisco Sweeteners Oy Procede de separation par chromatographie a lits mobiles simules
US6641734B2 (en) 2002-01-03 2003-11-04 A. E. Staley Manufacturing Co. Process for purifying an organic acid
EP2345632A1 (fr) * 2009-12-29 2011-07-20 Rohm and Haas Europe Services ApS Succursale France Procédé de séparation d'acides organiques et aminés à partir de la fermentation
WO2014106532A2 (fr) * 2013-01-03 2014-07-10 Thyssenkrupp Industrial Solutions Ag Procédé de purification d'acides carboxyliques issus de bouillons de fermentation
EP2592952B1 (fr) 2010-07-13 2014-09-03 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO Methodes et compositions de desacidification de jus de fruit
US9376364B2 (en) 2011-08-16 2016-06-28 Purac Biochem B.V. Acid/salt separation
US9776945B2 (en) 2014-09-29 2017-10-03 Rennovia Inc. Preparation and separation of a di-carboxylic acid-containing mixture
US10279282B2 (en) 2015-03-12 2019-05-07 Novasep Process Sas Process for purification of an organic acid including an electrodialysis treatment step
WO2019138338A1 (fr) * 2018-01-09 2019-07-18 Universidade Do Porto Procédé de séparation et de purification de dérivés du glycérol
WO2021226072A1 (fr) * 2020-05-05 2021-11-11 Amalgamated Research Llc Systèmes comprenant des séparateurs à lit mobile simulé pour la production de fructose de haute pureté et procédés associés

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2389766A (en) 1941-04-22 1945-11-27 Fruit Growers Exchange Ca Process for production of calcium citrate
US2664441A (en) 1951-07-19 1953-12-29 Harry S Owens Separation of organic acids
US3798266A (en) 1971-09-20 1974-03-19 Montedison Spa Process for preparing citric acid
US5102553A (en) 1988-12-16 1992-04-07 The Amalgamated Sugar Company Time variable simulated moving bed process
US5382681A (en) 1992-10-07 1995-01-17 Cerestar Holding B.V. Process for the production of an alkali metal citrate
US6087139A (en) 1997-10-30 2000-07-11 Metallgesellschaft Aktiengesellschaft Process for producing citric acid and/or citrates
WO2002089946A1 (fr) * 2001-05-09 2002-11-14 Danisco Sweeteners Oy Procede de separation par chromatographie a lits mobiles simules
US6641734B2 (en) 2002-01-03 2003-11-04 A. E. Staley Manufacturing Co. Process for purifying an organic acid
EP2345632A1 (fr) * 2009-12-29 2011-07-20 Rohm and Haas Europe Services ApS Succursale France Procédé de séparation d'acides organiques et aminés à partir de la fermentation
EP2592952B1 (fr) 2010-07-13 2014-09-03 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO Methodes et compositions de desacidification de jus de fruit
US9376364B2 (en) 2011-08-16 2016-06-28 Purac Biochem B.V. Acid/salt separation
WO2014106532A2 (fr) * 2013-01-03 2014-07-10 Thyssenkrupp Industrial Solutions Ag Procédé de purification d'acides carboxyliques issus de bouillons de fermentation
US9776945B2 (en) 2014-09-29 2017-10-03 Rennovia Inc. Preparation and separation of a di-carboxylic acid-containing mixture
US10279282B2 (en) 2015-03-12 2019-05-07 Novasep Process Sas Process for purification of an organic acid including an electrodialysis treatment step
WO2019138338A1 (fr) * 2018-01-09 2019-07-18 Universidade Do Porto Procédé de séparation et de purification de dérivés du glycérol
WO2021226072A1 (fr) * 2020-05-05 2021-11-11 Amalgamated Research Llc Systèmes comprenant des séparateurs à lit mobile simulé pour la production de fructose de haute pureté et procédés associés

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