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WO1998001413A1 - Procede de recuperation d'acide dicarboxylique - Google Patents

Procede de recuperation d'acide dicarboxylique Download PDF

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Publication number
WO1998001413A1
WO1998001413A1 PCT/GB1997/001811 GB9701811W WO9801413A1 WO 1998001413 A1 WO1998001413 A1 WO 1998001413A1 GB 9701811 W GB9701811 W GB 9701811W WO 9801413 A1 WO9801413 A1 WO 9801413A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
process according
dicarboxylic acid
adduct
anion exchanger
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.)
Ceased
Application number
PCT/GB1997/001811
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English (en)
Inventor
Avraham Baniel
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.)
WHALLEY KEVIN
Innova SA
Original Assignee
WHALLEY KEVIN
Innova SA
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 WHALLEY KEVIN, Innova SA filed Critical WHALLEY KEVIN
Priority to AU34510/97A priority Critical patent/AU3451097A/en
Priority to EP97930627A priority patent/EP0912483A1/fr
Publication of WO1998001413A1 publication Critical patent/WO1998001413A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock

Definitions

  • the present invention relates to a process for the recovery of a dicarboxylic acid from a feed aqueous solution containing salts thereof.
  • Dicarboxylic acids such as fumaric acid, malic acid and succinic acid can be produced by fermentation of carbohydrates such as dextrose, pure sucrose dissolved in an aqueous solution and sucrose in molasses. The fermentation is conducted at about neutral pH and a neutralizing agent is added for pH adjustment. Both pKa's of the dicarboxylic acids are below 7 and typically below 6. As a result, at the pH of fermentation, both carboxytic groups are neutralized. Thus, their recovery, in an acid form, from the fermentation liquor requires chemical conversion. Several processes were developed for such conversion.
  • the conversion could liberate the dicarboxylic acid in solution, e.g. by displacement with a strong, usually mineral, acid.
  • a strong, usually mineral, acid e.g., calcium fumarate is formed. Reacting the calcium fumarate containing fermentation liquor with sulfuric acid results in precipitation of gypsum and liberation of fumaric acid.
  • ammonium sulfate is the by-product salt. It can be used as a low grade fertilizer. The latter, however, does not pay for the ammonia and sulfuric acid consumed. Another difficulty is that of separating the liberated acid. Some of the dicarboxylic acids are of low water solubility and precipitate out of the solution due to the acidulation. Additional purification steps are required to remove impurities resulting from the broth. In some cases the by-product salt may coprecipitate as well. For soluble dicarboxylic acids one may consider distillation as such, distillation of their esters or extraction.
  • the extractant could be a relatively weak one and would allow the recovery of the product acid at a r elatively high concentration by back-extraction.
  • the known (and food approved) weak extractants to be considered are amine-based ones or solvating extractants (one may consider esters, ethers, ketones, etc., however alkanols are preferable).
  • the amine-based ones are more attractive for several reasons: (i) they are more selective and would therefore provide for higher product purity, (ii) their extraction capacity is higher and therefore the extractant flow will be lower, and (iii) the amine-based extractants provide for temperature sensitive distribution and therefore provide for the "uphill pumping" through back-extraction at a temperature that is higher than that of the extraction.
  • Acidulating neutral fermentation liquors by the addition of strong acids usually results in the formation of by-product salts such as gypsum, ammonium and sodium sulfate. Reagents are consumed and disposal of undesired by-products is required.
  • liquid-liquid extraction (LLE) is applied for salt splitting
  • LLE liquid-liquid extraction
  • US 5,132,456 suggests a way to solve this problem it comprises back-extraction with an aqueous solution of ammonia or low molecular weight alkyl amine, especially t ⁇ methyl amine (TMA).
  • TMA t ⁇ methyl amine
  • the resultant aqueous ammonium or alkylammomum carboxylate solution can be concentrated, if necessary, and the carboxylate can be thermally decomposed to yield the product carboxylic acid and ammonia or amine, which can be condensed and recycled.
  • TMA t ⁇ methyl amine
  • Urbas proposes , in his US patent 4,444,881 , a process for the recovery of an organic acid selected from the group consisting of propionic acid, butyric actd, lactic acid and citric acid, from an aqueous solution of its calcium salt, which comprises the steps of: (a) adding a molar equivalent of a water soluble tertiary amine carbonate to the calcium salt solution to form a trialkylammonium salt of the acid in solution and a precipitate of calcium carbonate; (b) concentrating the trialkylammonium salt solution; and (c) heating the concentrated trialkylammonium salt solution to obtain the acid and the tertiary amine.
  • Urbas' process reaches higher yields than that of King due to the fact that most of the acid could be bound to the amine, whiie the pH in the solution remains relatively low.
  • the liberated base does not accumulate in the aqueous solution as calcium carbonate forms and precipitates.
  • the reaction does take place in the basic pH range and, in order to form the trialkylammonium salt of the organic acid, the tertiary amine should be a strong one. That is why Urbas selects water soluble amines. Separating the organic acid from the tertiary amine is therefore as problematic as in King's process.
  • a process for the recovery of a dicarboxylic acid from an aqueous feed solution containing at least one salt of said acid comprising the steps of: (a) reacting said feed solution with C0 2 and with an anion exchanger, said anion exchanger being water immiscible in both free base and salt form, whereby said dicarboxylic acid forms an adduct with said anion exchanger and a carbonate of said salt's cation is formed in the resulting aqueous solution; (b) separating said dicarboxylic a ⁇ d-anion exchanger adduct from the resulting aqueous solution, and (c) recovering said dicarboxylic acid from said adduct by methods known per se.
  • said salts of said dicarboxylic acid contained in said aqueous feed solution can be mono- salts, di- salts and mixtures thereof and said formed carbonate can be a carbonate or a bicarbonate
  • Said recovery of said dicarboxylic acid can be effected by various methods including distillation, neutralization and displacement by another acid.
  • step (c) ts effected by contacting said adduct with an aqueous medium to effect the back extraction and recovery of said acid.
  • step (c) is effected by reacting said adduct with known reagents to form a compound of said acid.
  • step (c) said recovery in step (c) is effected by contacting said adduct with another acid, whereby said dicarboxylic acid is displaced by said acid.
  • IMI Israel Mining Industries - Institute for Research and Development
  • the aqueous feed to the reaction should be saturated and should stay nearly saturated throughout the reaction.
  • the salt of the dicarboxylic acid would first have to be crystallized from the fermentation liquor and that the crystalline salt would have to be added to the reaction medium.
  • Another problem is indicated by the method of recovering the acid and regenerating the solvent.
  • the hydrochloric acid carrying solvent is reacted with a rather strong mineral base such as magnesium oxide or hydroxide.
  • the mineral base is stronger than the active component of the ion exchange solvent, the amine, and displaces it from the amine hydrochloride formed on the reaction.
  • the solvent is thereby regenerated.
  • the magnesium chloride formed is decomposed at high temperature to the magnesium base and to HCI Similar separation of the bound acid and regeneration of the anion exchanger would be very difficult to implement in the case of the dicarboxylic acids, which have high boiling points and are sensitive to thermal decomposition
  • It claims a process for the recovery of lactic acid from a lactate feed solution comprising the extraction step of combining said lactate feed solution with an extractant comprising at least one water immiscible trialkyl amine having a total of at least 18 carbon atoms in the presence of carbon dioxide at a partial pressure of at least 50 psig to form an aqueous phase and an organic phase containing extracted lactic acid and said extractant and separating lactic acid from said organic phase.
  • Urbas extracts carboxylic acids by water soluble amines. Those amines are strong ones, having a pKa of 9 to 11. They are stronger bases than the carboxylates of the monocarboxylic acids specified in Urbas' patent and stronger than all three carboxylates of citric acid. These amines neutralize the carboxylic groups in the extracted acids and the formation of calcium carbonate during the extraction is not surprising.
  • the amines used in Israeli patent 33,552 and in US patent 5,510,526 are water immiscible tertiary amines with an apparent basicity equivalent to pKa of about 4. They are much stronger bases than the chloride anion in Israeli 33,552 and of about similar basicity to the lactate anion. The acids in the organic phase are neutralized and the bicarbonate formed in these two inventions is therefore expected to exist.
  • Lactic acid is a monocarboxylic acid with a single pKa of 3.86.
  • Typical dicarboxylic acids of interest are: adipic (4.43, 5.41), fumaric (3.03, 4.44), glutaric (4.31, 5.41), itaconic (3.85, 5.45), malic(3.40, 5.11) and succinic (4.16, 5.61 ).
  • One of the carboxylates is a weaker base than the amine and is neutralized by the latter.
  • the second carboxylate of those acids is a stronger base than the amine and would not react with it.
  • aqueous solution comprising 19% di sodium fumarate was introduced into a pressure reactor along with an extractant comprising 50% Alamine 336 (a tricaprylyl amine produced by Henkel), 30% octanol and 20% kerosene.
  • the aqueous to organic phase ratio was 4 to 1.
  • a C0 2 pressure of 25 atmospheres was applied and the phases were mixed for 4 hours at a temperature of 25C.
  • the organic phase was then removed from the pressure vessel while still under pressure and analyzed for fumaric acid content. It was about 0.17 mole/Kg.
  • the pressure vessel was opened and solid sodium bicarbonate was found along with the aqueous solution.
  • aqueous solution comprising 27% di sodium succinate was introduced into a pressure reactor along with an extractant comprising 50% Alamine 336 (a tricaprylyl amine produced by Henkel), 30% octanol and 20% kerosene.
  • the aqueous to organic phase ratio was 5 to 1.
  • a CO 2 pressure of 25 atmospheres was applied and the phases were mixed for 4 hours at a temperature of 25C.
  • the organic phase was then removed from the pressure vessel while still under pressure and analyzed for succinic acid content. It was about 0.15 mole/Kg.
  • the pressure vessel was opened and solid sodium bicarbonate was found along with the aqueous solution.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention traite d'un procédé de récupération d'un acide dicarboxylique à partir d'une solution d'alimentation aqueuse contenant au moins un sel dudit acide. Le procédé comprend les étapes suivantes: a) faire réagir la solution d'alimentation aqueuse avec un CO2 et un échangeur d'anions, ledit échangeur d'anions étant de l'eau immiscible tant en base libre que sous forme de sel, procédé par lequel l'acide dicarboxylique forme un adduit avec l'échangeur d'anions et le cation dudit sel forme un carbonate dans la solution aqueuse obtenue; b) séparer l'adduit formé par l'acide dicarboxylique et l'échangeur d'anions de la solution aqueuse obtenue; et c) récupérer l'acide dicarboxylique à partir de l'adduit par des procédés habituels.
PCT/GB1997/001811 1996-07-05 1997-07-04 Procede de recuperation d'acide dicarboxylique Ceased WO1998001413A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU34510/97A AU3451097A (en) 1996-07-05 1997-07-04 A process for the recovery of dicarboxylic acid
EP97930627A EP0912483A1 (fr) 1996-07-05 1997-07-04 Procede de recuperation d'acide dicarboxylique

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IL11879696A IL118796A0 (en) 1996-07-05 1996-07-05 A process for the recovery of dicarboxylic acid
IL118796 1996-07-05

Publications (1)

Publication Number Publication Date
WO1998001413A1 true WO1998001413A1 (fr) 1998-01-15

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1997/001811 Ceased WO1998001413A1 (fr) 1996-07-05 1997-07-04 Procede de recuperation d'acide dicarboxylique

Country Status (4)

Country Link
EP (1) EP0912483A1 (fr)
AU (1) AU3451097A (fr)
IL (1) IL118796A0 (fr)
WO (1) WO1998001413A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008010373A1 (fr) * 2006-07-19 2008-01-24 Showa Denko K.K. Procédé de production d'acide succinique
JP2008043327A (ja) * 2006-07-19 2008-02-28 Showa Denko Kk コハク酸の製造方法
CN102408325A (zh) * 2011-11-29 2012-04-11 青岛琅琊台集团股份有限公司 一种从衣康酸发酵废母液中提取衣康酸的方法
CN102816056A (zh) * 2012-08-24 2012-12-12 青岛科海生物有限公司 一种萃取衣康酸发酵液提取衣康酸的方法
EP2694664A4 (fr) * 2011-04-06 2015-03-25 Univ New Hampshire Récupération d'un monomère d'acide vinylique
CN111808053A (zh) * 2011-08-16 2020-10-23 普拉克生化公司 可用于发酵液处理的通过用盐酸沉淀从羧酸镁盐中回收羧酸的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3228963A (en) * 1961-12-22 1966-01-11 Union Oil Co Process for purification of complex acids
US4282323A (en) * 1979-10-09 1981-08-04 E. I. Du Pont De Nemours And Company Removal and concentration of lower molecular weight organic acids from dilute solutions
WO1995025081A1 (fr) * 1994-03-16 1995-09-21 Yissum Research Development Company Of The Hebrew University Of Jerusalem Procede et composition d'extraction destines a extraire des acides
US5510526A (en) * 1993-06-29 1996-04-23 Cargill, Incorporated Lactic acid production, separation and/or recovery process

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3228963A (en) * 1961-12-22 1966-01-11 Union Oil Co Process for purification of complex acids
US4282323A (en) * 1979-10-09 1981-08-04 E. I. Du Pont De Nemours And Company Removal and concentration of lower molecular weight organic acids from dilute solutions
US5510526A (en) * 1993-06-29 1996-04-23 Cargill, Incorporated Lactic acid production, separation and/or recovery process
WO1995025081A1 (fr) * 1994-03-16 1995-09-21 Yissum Research Development Company Of The Hebrew University Of Jerusalem Procede et composition d'extraction destines a extraire des acides

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008010373A1 (fr) * 2006-07-19 2008-01-24 Showa Denko K.K. Procédé de production d'acide succinique
JP2008043327A (ja) * 2006-07-19 2008-02-28 Showa Denko Kk コハク酸の製造方法
US7915447B2 (en) 2006-07-19 2011-03-29 Showa Denko K.K. Process for producing succinic acid
EP2694664A4 (fr) * 2011-04-06 2015-03-25 Univ New Hampshire Récupération d'un monomère d'acide vinylique
CN111808053A (zh) * 2011-08-16 2020-10-23 普拉克生化公司 可用于发酵液处理的通过用盐酸沉淀从羧酸镁盐中回收羧酸的方法
CN102408325A (zh) * 2011-11-29 2012-04-11 青岛琅琊台集团股份有限公司 一种从衣康酸发酵废母液中提取衣康酸的方法
CN102816056A (zh) * 2012-08-24 2012-12-12 青岛科海生物有限公司 一种萃取衣康酸发酵液提取衣康酸的方法
CN102816056B (zh) * 2012-08-24 2014-07-09 青岛科海生物有限公司 一种萃取衣康酸发酵液提取衣康酸的方法

Also Published As

Publication number Publication date
AU3451097A (en) 1998-02-02
EP0912483A1 (fr) 1999-05-06
IL118796A0 (en) 1996-10-31

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