CA1136159A - Method for the purification of dicarboxylic acids produced by fermentation - Google Patents
Method for the purification of dicarboxylic acids produced by fermentationInfo
- Publication number
- CA1136159A CA1136159A CA000342274A CA342274A CA1136159A CA 1136159 A CA1136159 A CA 1136159A CA 000342274 A CA000342274 A CA 000342274A CA 342274 A CA342274 A CA 342274A CA 1136159 A CA1136159 A CA 1136159A
- Authority
- CA
- Canada
- Prior art keywords
- dicarboxylic acids
- fermentation
- water
- solution
- purification
- 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.)
- Expired
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
- C12P7/44—Polycarboxylic acids
-
- 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
Abstract
ABSTRACT OF THE DISCLOSURE
Long-chain dicarboxylic acids, especially those produced by fermentation, are purified by a process involving dissolving the acid on a salt thereof in a lower aliphatic alcohol, tetrahydrofuran or aqueous solutions thereof, and removing insolubles from the solution so formed.
Long-chain dicarboxylic acids, especially those produced by fermentation, are purified by a process involving dissolving the acid on a salt thereof in a lower aliphatic alcohol, tetrahydrofuran or aqueous solutions thereof, and removing insolubles from the solution so formed.
Description
~3~i1S9 This invention relates to the purification of long-chain dicarboxylic acids, s~ecifically, dicarboxylic acids having 10 to 18 carbon atoms.
Recently, a method for producing long-chain dicarboxylic acids from hydrocarbon such as normal paraffin as a substrate by fermentation using a microorganism such as yeast, fungi or bacteria has been developed.
Heretofore, long-chain dicarboxylic acids ~hereinafter called dicarboxylic acids) produced by fermentation as described above, have been generally recovered through the following steps:
~1) the cells in the fermentation broth are removed by means of solid-liquid separation method such as centrifugation or ~iltration;
Recently, a method for producing long-chain dicarboxylic acids from hydrocarbon such as normal paraffin as a substrate by fermentation using a microorganism such as yeast, fungi or bacteria has been developed.
Heretofore, long-chain dicarboxylic acids ~hereinafter called dicarboxylic acids) produced by fermentation as described above, have been generally recovered through the following steps:
~1) the cells in the fermentation broth are removed by means of solid-liquid separation method such as centrifugation or ~iltration;
(2) dicarboxylic acids or their salts are allowed to precip;tate by acidifying or basifying the aforesaid broth containing dicarboxylic acids; and 13~ the precipitated dicarboxylic acids or their salts are separated from the broth and dried and recovered.
In the production of dicarboxylic acids by fermentation, however, forming of 0.2 to 6.0wt% of impurities cannot be prevented though the amount varies depending on the properties of the microorganism in use and cultural conditions. These impurities are presumed to be metabolic wastes excreted by the microorganism and substances emitted by the cells themselves.
Moreover, such impurities cannot b~ removed by the process of recovery of dicarboxylic acids from the fermentation broth described above. Accordingly, purification is a great problem in the production of dicarboxylic acids by means of fermentation.
a~
In the production of dicarboxylic acids by fermentation, however, forming of 0.2 to 6.0wt% of impurities cannot be prevented though the amount varies depending on the properties of the microorganism in use and cultural conditions. These impurities are presumed to be metabolic wastes excreted by the microorganism and substances emitted by the cells themselves.
Moreover, such impurities cannot b~ removed by the process of recovery of dicarboxylic acids from the fermentation broth described above. Accordingly, purification is a great problem in the production of dicarboxylic acids by means of fermentation.
a~
3~159 For analysis of dicarboxylic acids in the broth, separation of the products from the broth or from the same after removing cells has been conventionally employed. When said technique is applied to the purification of said dicarboxylic acids, however, problems such as low solubility of dicarboxylic acids in ethylether, low flash point of ethylether and requirement for a large-scale extraction equipment arise. Viewing from the economical as well as operational standpoint (for the prevention of disaster), said method is unsuitable to be employed on a commercial basis.
In the light of the situation as described above, this invention has been accomplished. Therefore, the purpose of this invention is to offer an advantageous method for purifying dicarboxylic acids produced by means of fermentation.
Thus according to the present invention, there is provided a method for the purification of long-chain dicarbox-ylic acids having from 10-18 carbon atons and produced by fermentation, wherein said long-chain dicarboxylic acids or their salts are dissolved in lower aliphatic alcohol or tetrahydrofuran or the aqueous solution of either of the aforesaid, and insoluble matters are removed from the solution.
Dicarboxylic acids produced by fermentation which are to be purified by the method of this invention have 10 to 18 carbon atoms.
In this invention, concentrated or dried fermentation broth containing dicarboxylic acids from which cells have been removed or crude dicarboxylic acids or their salts obtained by acidifying or basifying said cell-free fermentation broth are dissolved in low aliphatic alcohol or tetrahydrofuran or aqueous solution of either of them in order to purify dicarbox-ylic acids ~y removing impurities. Of the above mentioned, use ,~, ;, ~7 ~
113~55 of crude dicarboxylic acids or their salts precipitated by means of acidification or salting-out technique is desirable.
Regarding salts of dicarboxylic acids, it is necessary that these salts be soluble în low aliphatic alcohol or tetra-hydrofuran. For example, potassium salt of tridecanedioic acid can be purified by the method of this invention but the salts of calcium and magnesium are not appropriate to be used for purification by this invention because of their low solubility in said solvents.
As the lower aliphatic alcohol employed in this invention, there can be employed methylalcohol, ethylalcohol, n-propyl alcohol and isopropyl alcohol. The solubility of dicarboxylic acids, the target products, in these lower aliphatic alcohols or tetrahydrofuran or their aqueous solutions is high while impurities described above dissolve little in these solvents. In addit;on, said solvents possess following merits: giving ~ood filterbîlity to the dissolved dicarbox-ylic acids, safe in treatment, no corrosive action on the equipment and no influence on the quality of the products even 2~ if a trace amount remains in dicarboxylic acids after purification.
On the basis of solubility alone, methyl ketone, acetic acid, furfural, dioxane, lauric acid and dimethyl sulfoxide could be used, but being deficient in the above mentioned merits, that is, good filterbility, safety, non-corrosiveness and little influence on the quality of the purified products remaining as residue, said solvents are not practical.
113'~1~9 Of said lower aliphatic alcohols, especially methylalcohol and ethylalcohol possess not only the above described merits but also facilitate evaporation of the solvent after purification of the products and fractional distillation for recovery of the products. When methylalcohol or ethyla~x~ol is employed in aqueous solutîon lOOwt portion against 40wt portion or less of water for the former and lOOwt portion against 67wt portion or less of water for the latter are desirable.
In order to dissolve the concentrated or dried broth from which cells have been removed or the crude dicarboxylic acids or their salts obtained by precipitation in said alcohol or its aqueous solution, 2.5~g to lOkg of methyl alcohol ~lSkg for 70% alcohol aqueous solution) and 3.8kg to 7.Skg of ethylalcohol (12kg for 60% alcohol a~ueous solution) can be used. It is desirable to ~arm said mixture at 40C to 50C in order to accelerate dissolving speed.
The alcohol solution containing dicarboxylic acids obtained by dissolution as described above is allowed to pass through a cylindrical vessel filled with sands and diatomaceous 2Q earth to filter ou,t impurities contained in said solution. The resultant solution is filtered further through an industrial ~ilter paper followed by washing said filter layer and the filter paper with alcohol, thereafter mixing said alcohol with the filtered solution and finally evaporating alcohol and water from the mixed solution by the conventional method in order to o~tain purified dicarboxylic acids.
The method o~ removing said impurities is not limited to the filtration described above. Conventional solid~ uid separation methods can be applied.
113f~l59 In this invention, besides the above described evaporation of alcohol and water for recovering dicarbox-ylic acids, there can be employed another method in which water or diluted solution of mineral acid, for example, aqueous solution of l.Okg of methyl alcohol containing 0.2kg of dicarboxylic acids (methyl alcohol:water - 9:1) is added with 3.6 to 7.2kg of water to precipitate dicarboxylic acids by degrading the solubility and then separating the products from said aqueous solutio~.
This method has a merit in that it prevents a danger of explosion at dryi~g dicarboxylic acids because the products separated from the solution are made alcohol-free by washing with water prior to drying, and on the other hand, alcohol is easily recovered since there is no solid matter remaining in the solution.
The present invention will now be described specifically wit~ reference to preferred embodiments in the following specific but non-limiting examples.
Example 1 Ten kilograms of crude tridecanedioic acid ~containing 2.1wt% water) produced by means of fermentation was dissolved in 50 L of methylalcohol (containing 3.5wt~ water) at 45C.
Said solution was passed through a sand layer which was filled in a cylindrical vessel with 20cm of internal diameter and Scm in depth followed by filtration through an industrial filter paper in order to remove insoluble matters. Said sand layer 113~1~9 and the filter paper wer~ ~ashed with lOL of met~lalc~h~`l (containing 3.5wt% water). The filtrate described above and said wash solution were mixed and then water and methyl alcohol in said mixture were evaporated by heating the mixture.
The weight of the resultant purified tridecanedioic acid (with 0.3wt% water) was 9.2kg. Nitrogen contents in the crude tridecanedioic acid and the purified tridecanedioic acid were measured using Kjeldahl analytical method. It was found that nitrogen content of the crude tridecanedioic acid was 0.49wt~
~3.3% as protein) and that of the purified tridecanedioic acid 0.02wt% (below 0.13% as protein) respectively against the dry weight of the sample.
Example 2 In 8.lL of ethylalcohol ~7.9wt% water) 2.Okg of crude tridecanedioic acid ~4.6~t~ water~ produced by means of fermentation was dissolvea at 48C. The resultant solution was passed through a sand layer filled in a cylindrical vessel with 6cm internal diameter and 5cm deep. The filtered solution was further filtered through an industrial filter paper. Said sand layer and the filter paper were washed with 2.5L of ethylalcohol containing 7.9wt% water, followed by mixing said wash alcohol with the filtrate mentioned above in order to evaporate ethylalcohol. As a result, 1.81kg (0.2wt% water content) of purified tridecanedioic acid was obtained. Nitrogen contents of the crude tridecanedioic acid and purified tridecanedioic acid were ~.37wt~ and below 0.02wt% respectively against the dry weight of the sample.
Example 3 Ten kg of tridecanedioic acid ~43.8wt~ water) obtained 113~1~i9 from the fermentation broth which was acidified and filtered through a filter press after cells were removed was dissolved in 25L of methylalcohol ~elow 2wt% water) in order to remove insoluble matters with the method in Example 1. To 34L of the mixture of the wash alcohol and the filtrate 60L of water was added to precipitate tridecanedioic acid. Said precipitate was filtered by pressure at room temperature, washed with water and dried at 60C. As a result, 4.9kg of purified tridecanedioic acid (below 0.4wt% water) was obtained. Nitrogen contents of the crude tridecanedioic acid and the purified tridecanedioic acid were 0.32wt% and below 0.02wt% respectively.
In the light of the situation as described above, this invention has been accomplished. Therefore, the purpose of this invention is to offer an advantageous method for purifying dicarboxylic acids produced by means of fermentation.
Thus according to the present invention, there is provided a method for the purification of long-chain dicarbox-ylic acids having from 10-18 carbon atons and produced by fermentation, wherein said long-chain dicarboxylic acids or their salts are dissolved in lower aliphatic alcohol or tetrahydrofuran or the aqueous solution of either of the aforesaid, and insoluble matters are removed from the solution.
Dicarboxylic acids produced by fermentation which are to be purified by the method of this invention have 10 to 18 carbon atoms.
In this invention, concentrated or dried fermentation broth containing dicarboxylic acids from which cells have been removed or crude dicarboxylic acids or their salts obtained by acidifying or basifying said cell-free fermentation broth are dissolved in low aliphatic alcohol or tetrahydrofuran or aqueous solution of either of them in order to purify dicarbox-ylic acids ~y removing impurities. Of the above mentioned, use ,~, ;, ~7 ~
113~55 of crude dicarboxylic acids or their salts precipitated by means of acidification or salting-out technique is desirable.
Regarding salts of dicarboxylic acids, it is necessary that these salts be soluble în low aliphatic alcohol or tetra-hydrofuran. For example, potassium salt of tridecanedioic acid can be purified by the method of this invention but the salts of calcium and magnesium are not appropriate to be used for purification by this invention because of their low solubility in said solvents.
As the lower aliphatic alcohol employed in this invention, there can be employed methylalcohol, ethylalcohol, n-propyl alcohol and isopropyl alcohol. The solubility of dicarboxylic acids, the target products, in these lower aliphatic alcohols or tetrahydrofuran or their aqueous solutions is high while impurities described above dissolve little in these solvents. In addit;on, said solvents possess following merits: giving ~ood filterbîlity to the dissolved dicarbox-ylic acids, safe in treatment, no corrosive action on the equipment and no influence on the quality of the products even 2~ if a trace amount remains in dicarboxylic acids after purification.
On the basis of solubility alone, methyl ketone, acetic acid, furfural, dioxane, lauric acid and dimethyl sulfoxide could be used, but being deficient in the above mentioned merits, that is, good filterbility, safety, non-corrosiveness and little influence on the quality of the purified products remaining as residue, said solvents are not practical.
113'~1~9 Of said lower aliphatic alcohols, especially methylalcohol and ethylalcohol possess not only the above described merits but also facilitate evaporation of the solvent after purification of the products and fractional distillation for recovery of the products. When methylalcohol or ethyla~x~ol is employed in aqueous solutîon lOOwt portion against 40wt portion or less of water for the former and lOOwt portion against 67wt portion or less of water for the latter are desirable.
In order to dissolve the concentrated or dried broth from which cells have been removed or the crude dicarboxylic acids or their salts obtained by precipitation in said alcohol or its aqueous solution, 2.5~g to lOkg of methyl alcohol ~lSkg for 70% alcohol aqueous solution) and 3.8kg to 7.Skg of ethylalcohol (12kg for 60% alcohol a~ueous solution) can be used. It is desirable to ~arm said mixture at 40C to 50C in order to accelerate dissolving speed.
The alcohol solution containing dicarboxylic acids obtained by dissolution as described above is allowed to pass through a cylindrical vessel filled with sands and diatomaceous 2Q earth to filter ou,t impurities contained in said solution. The resultant solution is filtered further through an industrial ~ilter paper followed by washing said filter layer and the filter paper with alcohol, thereafter mixing said alcohol with the filtered solution and finally evaporating alcohol and water from the mixed solution by the conventional method in order to o~tain purified dicarboxylic acids.
The method o~ removing said impurities is not limited to the filtration described above. Conventional solid~ uid separation methods can be applied.
113f~l59 In this invention, besides the above described evaporation of alcohol and water for recovering dicarbox-ylic acids, there can be employed another method in which water or diluted solution of mineral acid, for example, aqueous solution of l.Okg of methyl alcohol containing 0.2kg of dicarboxylic acids (methyl alcohol:water - 9:1) is added with 3.6 to 7.2kg of water to precipitate dicarboxylic acids by degrading the solubility and then separating the products from said aqueous solutio~.
This method has a merit in that it prevents a danger of explosion at dryi~g dicarboxylic acids because the products separated from the solution are made alcohol-free by washing with water prior to drying, and on the other hand, alcohol is easily recovered since there is no solid matter remaining in the solution.
The present invention will now be described specifically wit~ reference to preferred embodiments in the following specific but non-limiting examples.
Example 1 Ten kilograms of crude tridecanedioic acid ~containing 2.1wt% water) produced by means of fermentation was dissolved in 50 L of methylalcohol (containing 3.5wt~ water) at 45C.
Said solution was passed through a sand layer which was filled in a cylindrical vessel with 20cm of internal diameter and Scm in depth followed by filtration through an industrial filter paper in order to remove insoluble matters. Said sand layer 113~1~9 and the filter paper wer~ ~ashed with lOL of met~lalc~h~`l (containing 3.5wt% water). The filtrate described above and said wash solution were mixed and then water and methyl alcohol in said mixture were evaporated by heating the mixture.
The weight of the resultant purified tridecanedioic acid (with 0.3wt% water) was 9.2kg. Nitrogen contents in the crude tridecanedioic acid and the purified tridecanedioic acid were measured using Kjeldahl analytical method. It was found that nitrogen content of the crude tridecanedioic acid was 0.49wt~
~3.3% as protein) and that of the purified tridecanedioic acid 0.02wt% (below 0.13% as protein) respectively against the dry weight of the sample.
Example 2 In 8.lL of ethylalcohol ~7.9wt% water) 2.Okg of crude tridecanedioic acid ~4.6~t~ water~ produced by means of fermentation was dissolvea at 48C. The resultant solution was passed through a sand layer filled in a cylindrical vessel with 6cm internal diameter and 5cm deep. The filtered solution was further filtered through an industrial filter paper. Said sand layer and the filter paper were washed with 2.5L of ethylalcohol containing 7.9wt% water, followed by mixing said wash alcohol with the filtrate mentioned above in order to evaporate ethylalcohol. As a result, 1.81kg (0.2wt% water content) of purified tridecanedioic acid was obtained. Nitrogen contents of the crude tridecanedioic acid and purified tridecanedioic acid were ~.37wt~ and below 0.02wt% respectively against the dry weight of the sample.
Example 3 Ten kg of tridecanedioic acid ~43.8wt~ water) obtained 113~1~i9 from the fermentation broth which was acidified and filtered through a filter press after cells were removed was dissolved in 25L of methylalcohol ~elow 2wt% water) in order to remove insoluble matters with the method in Example 1. To 34L of the mixture of the wash alcohol and the filtrate 60L of water was added to precipitate tridecanedioic acid. Said precipitate was filtered by pressure at room temperature, washed with water and dried at 60C. As a result, 4.9kg of purified tridecanedioic acid (below 0.4wt% water) was obtained. Nitrogen contents of the crude tridecanedioic acid and the purified tridecanedioic acid were 0.32wt% and below 0.02wt% respectively.
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1) A method for the purification of long-chain dicarboxylic acids having from 10-18 carbon atoms and produced by fermentation, wherein said long-chain dicarboxylic acids or their salts are dissolved in lower aliphatic alcohol or tetrahydrofuran or the aqueous solution of either of the aforesaid, and insoluble matters are removed from the solution.
2) A method according to Claim 1 wherein lower aliphatic alcohol is methylalcohol.
3) A method according to Claim 1 wherein lower aliphatic alcohol is ethylalcohol.
4) A method according to claim 1 or claim 2 wherein the aqueous solution of lower aliphatic alcohol comprises 100wt portion of methylalcohol and below 40wt portion of water.
5) A method according to claim 1 or claim 3 wherein the aqueous solution of lower aliphatic alcohol comprises 100wt portion of ethylalcohol and below 67wt portion of water.
6) A method for the purification of long-chain dicarboxylic acids produced by fermentation wherein water or an aqueous solution of mineral acid is added to the long-chain dicarboxylic acids in solution from which insoluble matters have been removed by the method described in claim 1, allowing said long-chain dicarboxylic acids to precipitate and separating the same from the solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16336778A JPS5592691A (en) | 1978-12-28 | 1978-12-28 | Purification of dicarboxylic acid produced by fermentation |
| JP53-163367 | 1978-12-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1136159A true CA1136159A (en) | 1982-11-23 |
Family
ID=15772530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000342274A Expired CA1136159A (en) | 1978-12-28 | 1979-12-19 | Method for the purification of dicarboxylic acids produced by fermentation |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5592691A (en) |
| BE (1) | BE880865A (en) |
| CA (1) | CA1136159A (en) |
| DE (1) | DE2951177A1 (en) |
| FR (1) | FR2445374A1 (en) |
| GB (1) | GB2043052B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3720261A1 (en) * | 1987-06-19 | 1988-12-29 | Henkel Kgaa | METHOD FOR SEPARATING DICARBONIC ACIDS |
| WO1991014781A1 (en) * | 1990-03-19 | 1991-10-03 | Henkel Research Corporation | METHOD FOR INCREASING THE OMEGA-HYDROXYLASE ACTIVITY IN $i(CANDIDA TROPICALIS) |
| CN1056882C (en) * | 1996-10-09 | 2000-09-27 | 中国石油化工总公司抚顺石油化工研究院 | Process for preparing high purity long chain dicarboxylic acid and its ester |
| DE19747791A1 (en) * | 1997-10-29 | 1999-05-06 | Basf Ag | Extraction of carboxylic acid from aqueous solution |
| ATE447028T1 (en) | 1998-10-05 | 2009-11-15 | Cognis Ip Man Gmbh | CYTOCHROME P450 MONOOXYGENASE GENE AND PROTEIN OF THE OMEGA-HYDROXYLASE COMPLEX OF CANDIDA TROPICALIS AND RELATED METHODS |
| FR2921363B1 (en) | 2007-09-20 | 2009-11-06 | Arkema France | PROCESSES FOR THE SYNTHESIS OF FATTY DIACIDES BY METATHESIS OF UNSATURATED DIACIDS OBTAINED BY FERMENTATION OF NATURAL FATTY ACIDS |
| FR2933696B1 (en) | 2008-07-10 | 2010-08-20 | Arkema France | PROCESS FOR THE SYNTHESIS OF OMEGA-AMINOALCANOIC ACIDS OR THEIR ESTERS FROM NATURAL FATTY ACIDS |
| FR2941694B1 (en) | 2009-02-05 | 2011-02-11 | Arkema France | PROCESS FOR SYNTHESIZING AN OMEGA-AMINOACIDE OR ESTERING FROM A MONO-UNSATURATED FATTY ACID OR ESTER |
| CN111099987B (en) * | 2018-10-26 | 2023-02-03 | 中国石油化工股份有限公司 | Refining method of long-chain dicarboxylic acid in fermentation liquor |
| CN113480421A (en) * | 2021-06-30 | 2021-10-08 | 中国石油化工股份有限公司 | System and method for preparing succinic acid by maleic anhydride hydrogenation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4823422B1 (en) * | 1970-04-09 | 1973-07-13 | ||
| JPS5331851A (en) * | 1976-09-06 | 1978-03-25 | Mitsubishi Rayon Co | Double structural wire |
-
1978
- 1978-12-28 JP JP16336778A patent/JPS5592691A/en active Granted
-
1979
- 1979-12-18 GB GB7943513A patent/GB2043052B/en not_active Expired
- 1979-12-19 CA CA000342274A patent/CA1136159A/en not_active Expired
- 1979-12-19 DE DE19792951177 patent/DE2951177A1/en not_active Withdrawn
- 1979-12-24 BE BE0/198756A patent/BE880865A/en unknown
- 1979-12-27 FR FR7931785A patent/FR2445374A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6159720B2 (en) | 1986-12-17 |
| GB2043052B (en) | 1982-12-15 |
| BE880865A (en) | 1980-06-24 |
| FR2445374A1 (en) | 1980-07-25 |
| JPS5592691A (en) | 1980-07-14 |
| GB2043052A (en) | 1980-10-01 |
| DE2951177A1 (en) | 1980-07-24 |
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Legal Events
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| MKEX | Expiry |