[go: up one dir, main page]

WO2000020620A2 - Procede de recuperation d'acides carboxyliques dans un bouillon de fermentation - Google Patents

Procede de recuperation d'acides carboxyliques dans un bouillon de fermentation Download PDF

Info

Publication number
WO2000020620A2
WO2000020620A2 PCT/US1999/020901 US9920901W WO0020620A2 WO 2000020620 A2 WO2000020620 A2 WO 2000020620A2 US 9920901 W US9920901 W US 9920901W WO 0020620 A2 WO0020620 A2 WO 0020620A2
Authority
WO
WIPO (PCT)
Prior art keywords
acid
broth
extractant
group
fermentation broth
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/US1999/020901
Other languages
English (en)
Other versions
WO2000020620A8 (fr
WO2000020620A3 (fr
WO2000020620A9 (fr
Inventor
Gilbert H. Vice
Michael D. Staley
Louis Rebrovic
William G. Kozak
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.)
Henkel Corp
Cognis Corp
Original Assignee
Henkel Corp
Cognis Corp
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 Henkel Corp, Cognis Corp filed Critical Henkel Corp
Priority to AU63871/99A priority Critical patent/AU6387199A/en
Publication of WO2000020620A2 publication Critical patent/WO2000020620A2/fr
Publication of WO2000020620A3 publication Critical patent/WO2000020620A3/fr
Publication of WO2000020620A9 publication Critical patent/WO2000020620A9/fr
Publication of WO2000020620A8 publication Critical patent/WO2000020620A8/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/44—Polycarboxylic acids

Definitions

  • This invention relates to a process for recovering a carboxylic acid made by the biological oxidation of a substrate by a microorganism from a fermentation broth.
  • Standard methods for recovering carboxylic acids in general and polycarboxylic acids in particular from fermentation broths are based on the physical separation of the spent microorganism cells from the aqueous phase such as by alkalinization of the broth, followed by centrifugation and precipitation of the carboxylic acid as a result of pH reduction of the aqueous phase.
  • This method is unsatisfactory for a number of reasons, the most notable of which include the problem of physically separating the spent cells and then acidifying the cell-free broth to effect the precipitation of the carboxylic acid.
  • the precipitation of the carboxylic acid is time consuming and the separation and isolation of the precipitated carboxylic acid is not always clean.
  • the present invention is an improved process for the recovery of a carboxylic acid made by the biological oxidation of a substrate by a microorganism such as a yeast. It has been surprisingly discovered that carboxylic acids can be recovered from a fermentation broth by a simple process that is comprised of extracting the broth with a liquid extractant without the need for first removing the spent microorganism cells. After employing a standard fermentation procedure to produce a carboxylic acid, the viscosity of the broth is adjusted, preferably by heating the broth, to form a flowable liquid and can be optionally heated further to a temperature sufficient to enhance protonation of the carboxylic acid in the fermentation broth.
  • the pH of a fermentation broth which contains one or more carboxylic acids is then optionally adjusted to a value of from at least about 7.0 to about 1.5.
  • the next step involves contacting the carboxylic acid containing broth with a suitable extractant to extract the carboxylic acid. This method allows the easy isolation of the carboxylic acid by means of a simple extraction without separating the spent microorganism.
  • FIG. 1 is a graph representing the relationship between pH of the broth and the percent of carboxylic acids recovered at the given pH using 2-octanol as the extractant.
  • FIG. 2 is a graph representing the relationship between the number of extractions using 2-octanol and the percent of carboxylic acids recovered.
  • percent, "parts" of, and ratio values are by weight; the description of a group or class of materials as suitable or preferred for a given purpose in connection with the invention implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred; description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description or of generation in situ by chemical reactions specified in the description, and does not necessarily preclude other chemical interactions among the constituents of a mixture once mixed; and the term "mole” and its grammatical variations may be applied to elemental, ionic, and any other chemical species defined by number and type of atoms present, as well as to compounds with well defined molecules.
  • a carboxylic acid is any compound containing one or more carboxyl groups.
  • a polycarboxylic acid is any compound having two or more carboxyl groups.
  • a suitable liquid extractant is a liquid organic solvent which is not miscible with the fermentation broth but in which the carboxylic acids to be recovered from the fermentation broth are soluble.
  • the extractant is preferably chosen such that when cooled the carboxylic acid will crystallize out of solution.
  • a flowable liquid is a fluid whose molecules are free to move past one another while remaining in sliding contact.
  • the process for the recovery of a carboxylic acid comprises fermenting a microorganism in a culture medium which is comprised of a nitrogen source, and at least an organic substrate and then recovering the carboxylic acid by contacting the broth with a suitable extractant.
  • the organic substrate can be any compound which can be oxidized to a compound having at least one carboxyl group by biooxidation.
  • the substrate can be any compound having at least one methyl group, a terminal carboxyl group and/or a terminal functional group which is oxidizable to a carboxyl group by biooxidation.
  • the substrate can also contain one or more carbon-carbon multiple bonds and/or one or more carbocyclic or heterocyclic aromatic rings.
  • the microorganism can be any microorganism that is capable of biologically oxidizing an organic substrate as set forth above to a compound having at least one carboxyl group.
  • the process for the recovery of a carboxylic acid is applicable to the production by fermentation of any carboxylic acid that has between 3 and 36 carbon atoms, preferably 5 to 36 atoms and more preferably 9 to 36 carbon atoms.
  • the process for the recovery of a carboxylic acid is particularly applicable to the production of polycarboxylic acids by fermentation and most particularly to the production of dicarboxylic acids.
  • dicarboxylic acids include, but are not limited to, oxalic acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid, azelaic acid, sebacic acid, dodecanedioic acid, brassylic acid, 9-octadecenedioic acid, C-36 dimer acid and isomers thereof.
  • the process is also applicable to the recovery of monobasic carboxylic acids which can be saturated, unsaturated or polyunsatu rated.
  • Examples of such monocarboxylic acids include, but are not limited to: caprylic, pelargonic, capric, undecylic, lauric, myristic, pentadecanoic, palmitic, heptadecanoic, stearic, arachidic, palmitoleic, oleic, erucic, linoleic, and linolenic and isomers thereof.
  • the microorganism can be any microorganism capable of biooxidizing the substrate as defined herein.
  • a microorganism will be a yeast.
  • yeast Several strains of yeast are known to excrete alpha, omega-dicarboxylic acids as a byproduct when cultured on alkanes or fatty acids as the carbon source. These strains are set forth in U.S. patent 5,254,466, the entire contents of which are incorporated herein by reference.
  • the microorganism is a beta-oxidation blocked C. tropicalis cell which has been genetically modified so that the chromosomal POX4A, POX4B and both POX5 genes have been disrupted.
  • the substrate flow in this strain is redirected to the omega-oxidation pathway as the result of functional inactivation of the competing ⁇ -oxidation pathway by POX gene disruption.
  • the strain may also have one or more reductase genes amplified which results in an increase in the amount of rate- limiting omega-hydroxylase through P450 gene amplification and an increase in the rate of substrate flow through the ⁇ -oxidation pathway.
  • the process for making a dicarboxylic acid comprises fermenting a microorganism in a culture medium comprised of a nitrogen source, an organic substrate and a cosubstrate wherein the substrate is a compound having one carboxyl group and one methyl group or is a compound having one methyl group and a functional group that can be at least partially hydrolyzed to a carboxyl group and optionally wherein the substrate is partially neutralized. Saponification may be desirable for some raw materials.
  • the nitrogen source is disclosed in U.S. patent 5,254,466.
  • the cosubstrate can be any fermentable carbohydrate such as glucose, fructose, maltose, glycerol and sodium acetate.
  • the preferred cosubstrate is glucose, preferably a liquid glucose syrup, for example, 95% dextrose- equivalent syrup, or even lower dextrose- equivalent syrups.
  • Such materials contain small amounts of disaccharides, trisaccharides, and polysaccharides which can be hydrolyzed during the fermentation by the addition of an amylase enzyme.
  • the organic substrate can be any compound having at least one methyl group which can be biooxidized.
  • One type of organic substrate includes alkanes having from 3 to 36 carbon atoms, preferably those having 9 to 36 carbons, examples of which include, but are not limited to, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane and their isomers.
  • the organic substrate can also be any saturated aliphatic compound having at least one terminal methyl group, a terminal carboxyl group and/or a terminal functional group which is oxidizable to a carboxyl group by biooxidation.
  • the organic substrate can also be any unsaturated aliphatic compound having at least one internal carbon- carbon double bond and at least one terminal methyl group, a terminal carboxyl group and/or a terminal functional group which is oxidizable to a carboxyl group by biooxidation.
  • the organic substrate is preferably any compound having one carboxyl group and one methyl group or is a compound having one methyl group and a functional group that can be at least partially hydrolyzed to a carboxyl group.
  • the organic substrate in this case can be any aliphatic saturated or unsaturated monocarboxylic acid except formic acid and acrylic acid.
  • carboxylic acid substrates include, but are not limited to: caprylic, pelargonic, capric, undecylic, lauric, myristic, pentadecanoic, palmitic, heptadecanoic, stearic, arachidic, palmitoleic, oleic, erucic, linoleic, and linolenic and isomers thereof.
  • the organic substrate can also be an aromatic monocarboxylic acid having a methyl group, the simplest example of which is o, m, or p-methyl benzoic acid.
  • the substrate can be optionally partially neutralized with a base, preferably an alkaline earth metal hydroxide prior to the addition of the substrate to the fermentation broth.
  • the preferred alkaline earth metal hydroxides are calcium and magnesium hydroxide.
  • the organic substrate will preferably be a monocarboxylic acid for the production of polycarboxylic acids, it can be any compound having one carboxyl group and one methyl group or having one methyl group and a functional group that can be at least partially hydrolyzed to a carboxyl group thereby permitting at least partial neutralization of the carboxyl group formed in the hydrolysis.
  • Particularly preferred monocarboxylic acids are oleic acid and pelargonic acid.
  • the process for the recovery of a carboxylic acid involves adjusting the viscosity of the broth preferably by heating the fermentation broth to form a flowable liquid and optionally to a higher temperature sufficient to enhance protonation of the carboxylic acid in the fermentation broth. Adjusting the viscosity of the broth allows for better contact between the broth and the extractant that will be used for the extraction. This improves the effectiveness of the extraction.
  • the preferred temperature to which the broth is heated is to from about 50°C to about 75°C and more preferably to
  • the temperature range to which the broth can be heated is
  • the broth can be heated to just under the boiling point of the liquid extractant used in the extraction step. Temperatures above the boiling point of the liquid extractant will cause flashing of the extractant. To avoid flashing the extractant the temperature of the broth is kept below the boiling point of the extractant.
  • the liquid extractant can optionally be heated. It has surprising been found that highest recovery of the carboxylic acids results when the pH of the fermentation broth is in a slightly acidic pH range.
  • An optional step of the process for the recovery of a carboxylic acid following the fermentation process is the adjustment of the pH of the fermentation broth to from about at least 7.0 to about 1.5, preferably in the range from about 4.5 to about 7, and more preferably in the range from about 5 to about 6.
  • the pH value of the broth will fall in the range of from 5.0 to 7.5 but may be higher than 7.5 depending upon the fermentation conditions, the nature of the substrate, cosubstrate, the microorganism and the carboxylic acid formed in the fermentation.
  • the pH adjustment takes place after the fermentation process.
  • carboxylic acids recovered by the process are unsubstituted aliphatic carboxylic acids. These acids will normally have a pKa in the range of from about 4 to about 5.
  • the acid used to adjust to pH should be a stronger acid then the carboxylic acid to be recovered from the fermentation broth, preferably a strong mineral acid.
  • a strong carboxylic acid can also be used. Acids having a pKa less than that of the carboxylic acid to be recovered can be used. The stronger the acid the lower the pKa value will be. The strong acid will shift the equilibrium of the carboxylic acid so that more of the carboxylic acid is in its protonated form, making it easier to extract with a extractant.
  • acids used to adjust the pH include, but are not limited to, arsenic, hydrobromic, hydrochloric, chloric, iodic, nitric, nitrous, phosphoric, phosphorous, hypophosphorous, pyrophosphoric, sulfuric, sulfurous, thiosulfuric, tellurous, formic, chloracetic, lactic, glycolic, citric and mixtures thereof.
  • the next step in the recovery part of the process is to contact the liquid extractant with the fermentation broth for a time sufficient to extract the carboxylic acids from the fermentation broth.
  • the extraction can be carried out at ambient temperature or reflux temperature of the extractant.
  • the liquid extractant is chosen such that it is immiscible with the fermentation broth and the carboxylic and polycarboxylic acids are readily soluble in the liquid extractant. Also the liquid extractant is preferably chosen such that upon cooling of the liquid extractant the polycarboxylic acids crystallize out and the monocarboxylic acids remain in solution.
  • liquid extractants include, but are not limited to, C 7 - C 16 straight chain hydrocarbons, examples of which include, but are not limited to, heptane, octane, nonane, decane, dodecane, tetradecane; C 8 - C 16 branched chain hydrocarbons, examples of which include, but are not limited to, iso-octane,
  • ketones examples of which include, but are not limited to, cyclohexanone, methyl isobutyl ketone; aromatic compounds such as benzene, alkyl benzenes, examples of which include but are not limited to, toluene, o-xylene, m-xylene, p-xylene; chlorinated alkanes, examples of which include, but are not limited to, methylene chloride, chloroform, carbon tetrachloride; dialkyl ethers, examples of which include, but are not limited to, diethyl ether, diisopropyl ether, di-tert-butyl ether; alkylcarbonates, examples of which include, but are not limited
  • liquid extractants include, but are not limited to, esters of the formula: ROOC-R' wherein R is a C, - C 10 linear or branched alkyl or alkenyl group, or a substituted or unsubstituted phenyl group and wherein R' is a C - C 10 linear alkyl or branched alkenyl group, or a substituted or unsubstituted phenyl group.
  • esters of the formula ROOC-R' include, but are not limited to ethyl acetate and methyl acetate.
  • any combination of the aforementioned extractants are contemplated as useful within the scope of the present invention.
  • the extraction can be carried out using a continuous liquid-liquid extraction or can be accomplished batchwise.
  • the preferred method is continuous liquid-liquid extraction.
  • the batch or continuous extraction can be repeated numerous times to enhance recovery.
  • carboxylic acid and polycarboxylic acids can be separated from the liquid extractant by way of distillation, crystallization, melt crystallization or any other suitable means.
  • the recovered carboxylic acids can be further purified by an additional crystallization step or other means.
  • the recovered unsaturated carboxylic acids can be further hydrogenated to remove double bonds.
  • the unsaturated carboxylic acids can also be further reacted with an oxidizing agent to oxidatively cleave the carbon-carbon double bonds to carboxyl groups to form a polycarboxylic acid.
  • the oxidative cleavage of the carbon- carbon double bonds may be achieved with any oxidizing agent known in the art which will oxidatively cleave a carbon-carbon double bond to form two carboxyl groups.
  • Such methods include but are not limited to reaction with ozone and subsequent oxidative work-up of the ozonides as described in U.S.
  • the extraction of the carboxylic acids from the fermentation broth can be carried out without adjusting the pH of the broth using 1-octanol or 2-octanol as the liquid extractant.
  • Recovery of the carboxylic acids from the broth when using 1-octanol or 2-octanol can be higher then 80% after only one batch extraction. The phases separate quickly without formation of emulsion.
  • Another preferred embodiment of the invention is the preparation of carboxylic acid by biooxidation of a crude mixture of oleic acid comprising a mixture of saturated and unsaturated carboxylic acids to form monocarboxylic and dicarboxylic acids, followed by extraction with 2-octanol as disclosed herein, recovery of the extracted carboxylic acids from the extractant by any conventional means, for example by recrystallization, followed by oxidation of the unsaturated carboxylic.
  • a particularly preferred crude mixture of oleic acid consists of the following % composition (GLC): 0.084 C 12 , 2.148 C 14> 0.487 C 14 1 , 0.190 C 15 , 0.149 C 151 , 4.458 C 16 , 5.096 C 16 1 , 0.150 C 17 , 0.731 C 18 , 71.21 C 18 1 , 9.36 C 182 , 0.513 C 183 , 1.271 C 20 1 , and 0.330 C 202 .
  • GLC % composition
  • Another preferred embodiment of the invention is the preparation of azelaic acid by biooxidation of oleic acid to form 9-octadecenedioic acid followed by oxidation of the 9-octadecenedioic acid to azelaic acid.
  • a typical technical grade oleic acid consists of the following carboxylic acids: 0.42% C 12 ; 2.7% C 14 ; 0.86% C 14 ,; 6.3% C 16 ; 4.6% C 1 ⁇ 1 ; 0.93% C 17 ; 2.8 C 18 ; 71.8% C 181 ; 8.3% C 182 ; 0.58% C 183 .
  • the oleic acid can also be a high grade oleic acid obtained from a fatty oil of a Helianthus annuus (sunflower seed oil) species described, for example, in U.S. Pat. No. 4,627,192, the entire contents of which are incorporated herein by reference.
  • Such oils are very rich in oleic acid and contain at least 80% by weight of oleic.
  • the pH adjustment of the broth is optional.
  • the preferred pH range is from about 5 to about 6.
  • the fermentation broth is heated to about 65°C.
  • the purpose for heating the broth is to reduce the viscosity to allow for better contact between the broth and the extractant.
  • the broth is then contacted with the extractant.
  • the preferred means of contacting the broth with the extractant is via a continuous liquid-liquid extraction.
  • the 9-octadecenedioic acid is recovered from the extractant by any standard means as for example recrystallization.
  • the 9-octadecenedioic acid After the 9-octadecenedioic acid has been obtained by the biooxidation and recovery methods disclosed herein, it is reacted with ozone and further treated under oxidative conditions to yield azelaic acid.
  • the mixed oxidation products are then further oxidized to azelaic acid as, for example, in the method disclosed in U.S. patent 5,420,316, the entire contents of which are incorporated herein by reference.
  • a number of variations of the above azelaic acid preparation are contemplated by the present invention.
  • simple esters of oleic acid such as methyl oleate, ethyl oleate, and the like can be used in place of the oleic acid in the production of 9-octadecenedioic acid as well as natural fats and oils having a relatively high oleic acid content.
  • a fermentor was charged with a semi-synthetic growth medium having the composition 75 g/l glucose (anhydrous), 6.7 g/l Yeast Nitrogen Base (Difco Laboratories), 3 g/l yeast extract, 3 g/l ammonium sulfate, 2 g/l monopotassium phosphate, 0.5 g/l sodium chloride. Components were made as concentrated solutions for autoclaving then added to the fermentor upon cooling: final pH approximately 5.2. This charge was inoculated with 5-10% of an overnight culture of C. tropicalis H5343 prepared in YM medium (Difco Laboratories) as described in the methods of Examples 17 and 20 of U.S. Patent 5,254,466.
  • a technical grade oleic acid having the following composition: 0.30% C 12 ; 2.4% C 14 ; 0.60% C 14:1 ; 4.7% C 16 ; 4.6% C 16:1 ; 0.20% C 17 ; 0.80C 18 ; 69.9% C 18:1 ; 10.50% C 18;2 ; 0.30% C 18:3 was added (100 g/l) batchwise and the glucose cosubstrate feed (1.6 g/l/hr) is started near the time the culture enters stationary phase to initiate omega oxidation. A small amount of caustic was added for pH control during the transformation to maintain the pH at 5.0. No foam was formed at any time during the transformation.
  • the microorganism C. tropicalis H5343 was fermented using the method of example 1.
  • the fermentation broth was fed a mixture of monocarboxylic acids having the following % composition (GLC): 0.084 C 12 , 2.148 C 14 , 0.487 C 14 1 , 0.190 C 15 , 0.149 C 15 1 , 4.458 C 16 , 5.096 C 16 1 , 0.150 C 17 , 0.731 C 18 , 71.21 C 18 1 , 9.36 C 182 , 0.513 C 183 , 1.271 C 20 1 , and 0.330 C 202 .
  • C l4 1 indicates a total of 14 carbons and one unsaturated linkage
  • C 202 indicates 20 carbons and two unsaturated linkages.
  • Monocarboxylic Acid % 0.404% of the total broth weight
  • the microorganism C. tropicalis H5343 was fermented using the method of example 1.
  • the fermentation broth was fed a mixture of monocarboxylic acids having the following % composition as analyzed by GLC: 0.125 C 10 , 0.173 C 12 ,
  • Dicarboxylic Acid % 9.73% of the total broth weight
  • Monocarboxylic Acid % 2.10% of the total broth weight
  • Combined % Recovery 84.9% of the total carboxylic acid weight in the broth Analysis of the extracted broth showed an additional 0.28% total carboxylic acids not extracted from the broth.
  • the iso-octane extract was distilled under vacuum to give 8.41 % dibasic and
  • microorganism C. tropicalis H5343 was fermented using the method of example 1. A quantity of fermentation broth was heated to 65 °C. The broth was then contacted with an equal volume of 1-octanol and shaken. The organic phase was then separated from the broth phase.
  • the octanol extract was distilled under vacuum via rotoevaporation.
  • the microorganism C. tropicalis H5343 was fermented using the method of example 1.
  • a quantity of fermentation broth was heated to 65 °C.
  • the broth was then contacted with an equal volume of 2-octanol and shaken.
  • the organic phase was then separated from the broth phase.
  • the 2-octanol extract was distilled under vacuum via rotoevaporation. 91.7% of solids recovered in the extract were carboxylic acids 95.1% of carboxylic acids identified in the broth were extracted
  • the microorganism C. tropicalis H5343 was fermented using the method of example 1.
  • the pH of a quantity of fermentation broth was adjusted to 2.5 and heated to 65°C.
  • the broth was then contacted with an equal volume of 1 - octanol and shaken.
  • the organic phase was then separated from the broth phase.
  • the 1 -octanol extract was distilled under vacuum via rotoevaporation.
  • the microorganism C. tropicalis H5343 was fermented using the method of example 1.
  • the pH of a quantity of fermentation broth was adjusted to 2.5 and heated to 65°C.
  • the broth was then contacted with an equal volume of 2- octanol and shaken.
  • the organic phase was then separated from the broth phase.
  • the 2-octanol extract was distilled under vacuum via rotoevaporation. 81.7% of solids recovered in the extract were carboxylic acids
  • the following method is an improvement over the method of Example 1 in that it substantially shortens the apparent induction period by partially saponifying the oleic acid to form a metal soap prior to addition to the fermentor.
  • a fermentation conducted as in Example 1 was modified by first adding 0.0098g KOH and 0.04g water per gram of oleic acid to partially saponify the oleic acid. This mixture was added to the fermentation to give 50 g/l oleic acid in the fermentation broth.
  • the saponification reaction is conveniently integrated with a thermal sterilization of the feed, if so desired, to drive the saponification reaction to completion.
  • dibasic acid accumulation began within 24 hours after the addition of the partially saponified fatty acids. After 115 hours transformation time, 66.7% of the total C 18:1 area counts appeared as the dibasic acid. Some foaming occurred early during transformation which was easily handled by chemical or mechanical means.
  • Dibasic acid from Example 10 is treated with a gas containing 5 v/o of ozone with the balance O 2 at a rate to supply 0.00644 mmole of O 3 per minute of oleic acid present in the acid mixture per minute for 2.5 - 3.0 hours at 23 - 25°C.
  • the gas is supplied through a conventional sparger with a pore size of 147 - 174 ⁇ m. Afterwards, nitrogen gas is sparged into the post-reaction mixture for 15 minutes, in order to free the mixture substantially from either form of gaseous oxygen.
  • the reactor is placed in a temperature controlled water bath and initially sparged with nitrogen while the temperature is maintained about 10°C below the desired reaction temperature of 60°C.
  • the temperature controller for the water bath is then set to increase the temperature up to the desired reaction temperature.
  • the gas flow is changed from nitrogen to oxygen at a rate of 350 ml/min.
  • the reaction is continued until the peroxide content reached about 0.25 mmole O-O/gram by the method described in Example 10 of U.S. 5,420,316.
  • the product should contain azelaic acid substantially free of pelargonic acid.
  • the microorganism C. tropicalis H5343 was fermented using the method of example 1. Aliquots, of 200 gm each, of fermentation broth was acidified to the test pH value. The temperature of the broth was 65 °C. The broth was contacted with 2-octanol as in example 7. The extract was analyzed for carboxylic acids. The results of the extractions at various pH values are shown in Figure 2. The figure shows that the percent of carboxylic acids recovered maximizes between pH values of about 4.7 to about 6.0.
  • the microorganism C. tropicalis H5343 was fermented using the method of example 1. 200 gm of fermentation broth was warmed to 65 °C. The broth was then contacted with 50 ml of 2-octanol and shaken. The organic phase was then separated from the broth phase. The broth was contacted with 50 ml of 2- octanol three more times. Each of the four of 2-octanol extracts were distilled under vacuum via rotoevaporation and analyzed for carboxylic acids. The results are displayed in Figure 2. Figure 2 shows that after 4 extractions substantially all of the carboxylic acids have been recovered from the fermentation broth.

Landscapes

  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biotechnology (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Des acides carboxyliques sont récupérés dans un bouillon de fermentation en réglant la viscosité du bouillon de fermentation, puis en mettant en contact le bouillon de fermentation avec un agent d'extraction liquide en vue d'extraire les acides carboxyliques de ce bouillon.
PCT/US1999/020901 1998-10-05 1999-10-05 Procede de recuperation d'acides carboxyliques dans un bouillon de fermentation Ceased WO2000020620A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU63871/99A AU6387199A (en) 1998-10-05 1999-10-05 Process for recovering carboxylic acides from a fermentation broth

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US16604598A 1998-10-05 1998-10-05
US09/166,045 1998-10-05
US32861299A 1999-06-09 1999-06-09
US09/328,612 1999-06-09

Publications (4)

Publication Number Publication Date
WO2000020620A2 true WO2000020620A2 (fr) 2000-04-13
WO2000020620A3 WO2000020620A3 (fr) 2000-07-27
WO2000020620A9 WO2000020620A9 (fr) 2000-09-08
WO2000020620A8 WO2000020620A8 (fr) 2001-03-22

Family

ID=26861916

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/020901 Ceased WO2000020620A2 (fr) 1998-10-05 1999-10-05 Procede de recuperation d'acides carboxyliques dans un bouillon de fermentation

Country Status (2)

Country Link
AU (1) AU6387199A (fr)
WO (1) WO2000020620A2 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001098521A3 (fr) * 2000-06-22 2002-03-21 Cognis Corp Isolement des acides carboxyliques d'un bouillon de fermentation
US6376223B1 (en) * 1999-08-04 2002-04-23 Cognis Corporation Process for purifying polycarboxylic acids
WO2006103531A1 (fr) * 2005-03-31 2006-10-05 Council Of Scientific And Industrial Research Procede de production d'acide succinique a partir du glucose
WO2010068904A2 (fr) 2008-12-12 2010-06-17 E. I. Du Pont De Nemours And Company Procédé de fabrication d'acides dicarboxyliques linéaires à partir de ressources renouvelables
JP2012115237A (ja) * 2010-12-03 2012-06-21 Mitsubishi Chemicals Corp 脂肪族ジカルボン酸の製造方法
WO2013033201A2 (fr) 2011-08-29 2013-03-07 E. I. Du Pont De Nemours And Company Roue composite pour un véhicule
JPWO2011087062A1 (ja) * 2010-01-15 2013-05-20 三菱化学株式会社 含窒素組成物およびその製造方法
WO2014047435A1 (fr) 2012-09-20 2014-03-27 E. I. Du Pont De Nemours And Company Procédé pour la fabrication d'alcanes linéaires à longue chaîne utilisant des charges de départ renouvelables
WO2014159490A1 (fr) 2013-03-14 2014-10-02 E. I. Du Pont De Nemours And Company Procédé de fabrication d'alcanes linéaires à chaîne longue à partir de matières premières renouvelables en utilisant des catalyseurs comprenant des hétéropolyacides
WO2014159484A1 (fr) 2013-03-14 2014-10-02 E. I. Du Pont De Nemours And Company Procédé de préparation d'alcanes linéaires à longue chaîne à partir de matières premières renouvelables à l'aide de catalyseurs comprenant des hétéropolyacides
US9434966B2 (en) 2011-05-03 2016-09-06 Verdezyne, Inc. Biological methods for preparing adipic acid

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2813113A (en) * 1953-05-07 1957-11-12 Emery Industries Inc Method of making azelaic acid
US4170595A (en) * 1976-08-06 1979-10-09 Hoffmann-La Roche Inc. 3-Ethyl-1,3-dihydro-3-methoxy-2H-indole 2-one
US5240850A (en) * 1987-10-23 1993-08-31 Pfizer Inc. Cultures for production of avermectin aglycones
US5254466A (en) * 1989-11-06 1993-10-19 Henkel Research Corporation Site-specific modification of the candida tropicals genome
US5104492A (en) * 1990-07-11 1992-04-14 The Regents Of The University Of California Recovery of carboxylic acids from water by precipitation from organic solutions
US5412126A (en) * 1991-04-17 1995-05-02 The Regents Of The University Of California Carboxylic acid sorption regeneration process
IT1256989B (it) * 1992-10-29 1995-12-27 Novamont Spa Procedimento per la preparazione di acidi carbossilici o loro esteri mediante scissione ossidativa di acidi grassi insaturi o loro esteri.

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6376223B1 (en) * 1999-08-04 2002-04-23 Cognis Corporation Process for purifying polycarboxylic acids
WO2001098521A3 (fr) * 2000-06-22 2002-03-21 Cognis Corp Isolement des acides carboxyliques d'un bouillon de fermentation
US6660505B2 (en) 2000-06-22 2003-12-09 Cognis Corporation Isolation of carboxylic acids from fermentation broth
WO2006103531A1 (fr) * 2005-03-31 2006-10-05 Council Of Scientific And Industrial Research Procede de production d'acide succinique a partir du glucose
US8753853B2 (en) 2008-12-12 2014-06-17 E I Du Pont De Nemours And Company Process for making linear dicarboxylic acids from renewable resources
WO2010068904A2 (fr) 2008-12-12 2010-06-17 E. I. Du Pont De Nemours And Company Procédé de fabrication d'acides dicarboxyliques linéaires à partir de ressources renouvelables
JPWO2011087062A1 (ja) * 2010-01-15 2013-05-20 三菱化学株式会社 含窒素組成物およびその製造方法
JP2012115237A (ja) * 2010-12-03 2012-06-21 Mitsubishi Chemicals Corp 脂肪族ジカルボン酸の製造方法
US9434966B2 (en) 2011-05-03 2016-09-06 Verdezyne, Inc. Biological methods for preparing adipic acid
WO2013033201A2 (fr) 2011-08-29 2013-03-07 E. I. Du Pont De Nemours And Company Roue composite pour un véhicule
US9765208B2 (en) 2011-08-29 2017-09-19 E I Du Pont De Nemours And Company Composite wheel for a vehicle
WO2014047435A1 (fr) 2012-09-20 2014-03-27 E. I. Du Pont De Nemours And Company Procédé pour la fabrication d'alcanes linéaires à longue chaîne utilisant des charges de départ renouvelables
WO2014159490A1 (fr) 2013-03-14 2014-10-02 E. I. Du Pont De Nemours And Company Procédé de fabrication d'alcanes linéaires à chaîne longue à partir de matières premières renouvelables en utilisant des catalyseurs comprenant des hétéropolyacides
WO2014159484A1 (fr) 2013-03-14 2014-10-02 E. I. Du Pont De Nemours And Company Procédé de préparation d'alcanes linéaires à longue chaîne à partir de matières premières renouvelables à l'aide de catalyseurs comprenant des hétéropolyacides

Also Published As

Publication number Publication date
WO2000020620A8 (fr) 2001-03-22
WO2000020620A3 (fr) 2000-07-27
AU6387199A (en) 2000-04-26
WO2000020620A9 (fr) 2000-09-08

Similar Documents

Publication Publication Date Title
US6777213B2 (en) Isolation of carboxylic acids from fermentation broth
US6660505B2 (en) Isolation of carboxylic acids from fermentation broth
US8703451B2 (en) Method for the production of free carboxylic acids
KR101770851B1 (ko) 식물성유의 연속식 산화적 분해 방법
US6288275B1 (en) Separation and purification of carboxylic acids from fermentation broths
Gu et al. Propionic acid production by extractive fermentation. I. Solvent considerations
US5962285A (en) Process for making polycarboxylic acids
Jeon et al. Microbial production of sebacic acid from a renewable source: production, purification, and polymerization
WO2000020620A2 (fr) Procede de recuperation d'acides carboxyliques dans un bouillon de fermentation
US20100203600A1 (en) Method for the coproduction of methyl 7-oxoheptanoate and undecylenic acid from ricinoleic acid
CA2396300A1 (fr) Procede de fermentation ameliore
US9024066B2 (en) Method for recovering and purifying propionic acid
EP0399494A1 (fr) Procédé de production de l'acide dihomo-gamma-linolénique et inhibiteur de la réaction insaturée à la position delta 5 de l'acide gras
JP6838968B2 (ja) ３−ヒドロキシプロピオン酸のエステルの製造方法
US7867736B2 (en) Method for preparing an organic amine—lactic acid complex
JP2014070031A (ja) 長鎖ジカルボン酸の製造方法
CN109641829A (zh) 制备纯化二羧酸的方法
US6245538B1 (en) Process for recovering carboxylic acids from a fermentation broth
JP2003055303A (ja) カプロラクタム製造工程で発生するアルカリ性廃液より炭素原子数４〜６のジカルボン酸のエステル類を製造する方法
WO2001032903A1 (fr) Procede de recuperation d'acides carboxyliques dans un bouillon de fermentation
EP1114174B1 (fr) Procede de fabrication d'acides polycarboxyliques
US10982237B2 (en) Microbial consortium for 1,3-propanediol production using high glycerol concentration
US3115442A (en) Microbial production of 10-hydroxystearic acid
WO2025141503A1 (fr) Production d'acides dicarboxyliques avec candida maltosa génétiquement modifié
JPH05317064A (ja) 脂肪酸の連続製造方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref country code: AU

Ref document number: 1999 63871

Kind code of ref document: A

Format of ref document f/p: F

AK Designated states

Kind code of ref document: A2

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
AK Designated states

Kind code of ref document: A3

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A3

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

AK Designated states

Kind code of ref document: C2

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: C2

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

COP Corrected version of pamphlet

Free format text: PAGES 1/2-2/2, DRAWINGS, REPLACED BY NEW PAGES 1/2-2/2; DUE TO LATE TRANSMITTAL BY THE RECEIVING OFFICE

AK Designated states

Kind code of ref document: C1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: C1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

WR Later publication of a revised version of an international search report
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase