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EP0912483A1 - Verfahren zur rückgewinnung der dicarbonsäure - Google Patents

Verfahren zur rückgewinnung der dicarbonsäure

Info

Publication number
EP0912483A1
EP0912483A1 EP97930627A EP97930627A EP0912483A1 EP 0912483 A1 EP0912483 A1 EP 0912483A1 EP 97930627 A EP97930627 A EP 97930627A EP 97930627 A EP97930627 A EP 97930627A EP 0912483 A1 EP0912483 A1 EP 0912483A1
Authority
EP
European Patent Office
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.)
Withdrawn
Application number
EP97930627A
Other languages
English (en)
French (fr)
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.)
Innova SA
Original Assignee
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 Innova SA filed Critical Innova SA
Publication of EP0912483A1 publication Critical patent/EP0912483A1/de
Withdrawn legal-status Critical Current

Links

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
  • 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.
  • 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.
  • 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.

Landscapes

  • 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)
EP97930627A 1996-07-05 1997-07-04 Verfahren zur rückgewinnung der dicarbonsäure Withdrawn EP0912483A1 (de)

Applications Claiming Priority (3)

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
PCT/GB1997/001811 WO1998001413A1 (en) 1996-07-05 1997-07-04 A process for the recovery of dicarboxylic acid

Publications (1)

Publication Number Publication Date
EP0912483A1 true EP0912483A1 (de) 1999-05-06

Family

ID=11069046

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97930627A Withdrawn EP0912483A1 (de) 1996-07-05 1997-07-04 Verfahren zur rückgewinnung der dicarbonsäure

Country Status (4)

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

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101489970B (zh) 2006-07-19 2012-08-08 昭和电工株式会社 琥珀酸的制备方法
JP5052234B2 (ja) * 2006-07-19 2012-10-17 昭和電工株式会社 コハク酸の製造方法
US8802404B2 (en) * 2011-04-06 2014-08-12 University Of New Hampshire Vinyl acid monomer recovery
CN108148027A (zh) * 2011-08-16 2018-06-12 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
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

Family Cites Families (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
IL109003A (en) * 1994-03-16 1999-09-22 Yissum Res Dev Co Process and extractant composition for extracting water-soluble carboxylic and mineral acids

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9801413A1 *

Also Published As

Publication number Publication date
WO1998001413A1 (en) 1998-01-15
AU3451097A (en) 1998-02-02
IL118796A0 (en) 1996-10-31

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