GB2043052A - The purification of dicarboxylic acids - Google Patents
The purification of dicarboxylic acids Download PDFInfo
- Publication number
- GB2043052A GB2043052A GB7943513A GB7943513A GB2043052A GB 2043052 A GB2043052 A GB 2043052A GB 7943513 A GB7943513 A GB 7943513A GB 7943513 A GB7943513 A GB 7943513A GB 2043052 A GB2043052 A GB 2043052A
- Authority
- GB
- United Kingdom
- Prior art keywords
- dicarboxylic acids
- solution
- water
- purification
- alcohol
- 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.)
- Granted
Links
- 238000000746 purification Methods 0.000 title claims abstract description 10
- 150000001991 dicarboxylic acids Chemical class 0.000 title abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000000855 fermentation Methods 0.000 abstract description 15
- 230000004151 fermentation Effects 0.000 abstract description 15
- 150000007513 acids Chemical class 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 3
- 241000894006 Bacteria Species 0.000 abstract description 2
- 240000004808 Saccharomyces cerevisiae Species 0.000 abstract description 2
- 239000012188 paraffin wax Substances 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- -1 specifically Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical class [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical class [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011777 magnesium Chemical class 0.000 description 1
- 229910052749 magnesium Chemical class 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biotechnology (AREA)
- Oil, Petroleum & Natural Gas (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
Long-chain dicarboxylic acids are purified by dissolving the acids or their salts in a lower aliphatic alcohol or tetrahydrofuran or an aqueous solution of the alcohol or tetrahydrofuran, removing insoluble solids from the solution and recovering the acids from the solids- free solution by precipitation and filtration. This method is particularly suitable for the purification of acids produced by fermentation of, for example, a normal paraffin substrate by means of a yeast fungi or bacteria. The method removes residual solids originating from the fermentation broth.
Description
SPECIFICATION
A method for the purification of dicarboxylic acids
This invention relates to the purification of long-chain dicarboxylic acids, specifically, dicarboxylic acids having from 10 to 1 8 carbon atoms.
Recently, a method for producing long-chain dicarboxylic acids from a hydrocarbon, such as a 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 by the following steps:
(1) the cells in the fermentation broth are removed by means of solid-liquid separation method such as centrifuging or filtration;
(2) dicarboxyiic acids or their salts are allowed to precipitate by making the aforesaid broth containing dicarboxylic acids either acidic or basic; and
(3) 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, the formation of 0.2 to 6.0 wt% 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 be 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.
For analysis of dicarboxylic acids in the broth, separation of the products from the broth before and after removal of the 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 diethyl ether, low flash point of the ether and requirement for a large-scale extraction equipment arise. Viewing from the economical as well as standpoint of safety, said method is unsuitable for use on a commercial basis.
In the light of the situation as described above, this invention has been made. Therefore, an object of this invention is to offer an advantageous method for purifying dicarboxylic acids produced by fermentation.
Dicarboxylic acids produced by fermentation which are to be purified by the method of this invention have from 10 to 1 8 carbon atoms.
According to this invention there is provided a method for the purification of a long-chain dicarboxylic acid having from 10 to 18 carbon atoms in the molecule comprising dissolving said long-chain dicarboxylic acid or a salt thereof in an aliphatic alcohol or tetrahydrofuran or in an aqueous solution of said alcohol or tetrahydrofuran, and removing insoluble matter from the solution.
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 making said cell-free fermentation broth acid or alkaline may be used as the starting material. Of the above mentioned, the use of crude dicarboxylic acids or their salts precipitated by means of acidification of salting-out technique is desirable. When salts of the dicarboxylic acid are used, it will be obvious that they must be soluble in low aliphatic alcohol or tetrahydrofuran. For example, the potassium'salt of tridecanedioic acid can be purified by the method of this invention but the salts of calcium and magnesium cannot because of their low solubility in said solvents.
As the aliphatic alcohol employed in this invention, there can be employed methanol, ethanol, n-propanol and isopropanol. The solubility of dicarboxylic acids, the target products, in these aliphatic alcohols or tetrahydrofuran or their aqueous solutions is high while the impurities described above dissolve only sparingly in these solvents. In addition, said solvents possess have the merits of: (a) giving good filterability to the dissolved dicarboxylic acids, (b) are safe in treatment, (d) have no corrosive action on the equipment and (d) do not influence the quality of the products even if a trace amount remains in dicarboxylic acids after purification.
if solubility was the only criterion for selection of the solvent acetone, acetic acid, furfural, dioxane, lauric acid and dimethyl sulfoxide could be used, but these do not possess the above mentioned merits, that is, good filterability, safety, non-corrosiveness and little influence on the quality of the purified products remaining as residue: thus these solvents are not practical.
Of said aliphatic alcohols, especially methanol and ethanol possess not only the above described merits but also are easy to evaporate after purification of the products and fractional distillation for recovery of the products. When methanol or ethanol is employed in aqueous solution, 100 parts by weight against 40 parts by weight or less of water for the former and 1 80 parts by weight against 67 parts by weight 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, 2.5Kg to 1 OKg of methanol (1 5Kg for 70% methanol aqueous solution) and 3.8Kg to 7.5Kg of ethanol (12Kg for 60% ethanol aqueous solution) can be used. It is desirable to warm said mixture at 400C to 500C in order to accelerate dissolution.
The alcohol solution containing dicarboxylic acids obtained by dissolution as described above
is allowed to pass through a cylindrical vessel filled with filter sand and diatomaceous earth to filter out impurities contained in said solution. The
resultant solution is filtered further through an
industrial filter paper followed by washing of said filter layer and the filter paper with the alcohol, thereafter mixing the washing with the filtered solution and finally evaporating alcohol and water from the mixed solution by conventional methods in order to obtain purified dicarboxylic acids.
The method of removing said impurities is not limited to the filtration described above: any conventional solid-liquid separation can be applied.
In this invention, besides the above described evaporation of alcohol and water for recovering dicarboxylic acids, there can be employed another method in which water or diluted solution of mineral acid, for example, aqueous solution of 1.OKg of methanol containing 0.2Kg of dicarboxylic acids (methanol: water = 9:1) is added with 3.6 to 7.2Kg of water to precipitate the dicarboxylic acids by reducing their solubility and then separating the products from said aqueous solution. This method has a merit in that it prevents a danger of explosion when drying the 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, the alcohol is easily recovered since there is no solid matter remaining in the solution.
The present invention will now be described in the following Examples.
EXAMPLE 1
Ten kilograms of crude tridecanedioic acid (containing 2.1 wt% water) produced by means of fermentation was dissolved in 50 litres of methanol (containing 3.5 wt% water) at 450C.
Said solution was passed through a sand layer which was contained within a cylindrical vessel with 20cm of internal diameter and 5cm in depth followed by filtration through an industrial filter paper in order to remove insoluble matter. Said sand layer and the filter paper were washed with 10 litres of methanol (containing 3.5 wt% water).
The filtrate and the washings were mixed and then the water and methanol in said mixture were evaporated by heating the mixture. The weight of the resultant purified tridecanedioic acid (with 0.3 wt% water) was 9.2Kg. The nitrogen contents of 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 0.49 wt% (3.3% as protein) and that of the purified tridecanedioic acid 0.02 wt% (below 0.13% as protein) respectively against the dry weight of the sample.
EXAMPLE 2
In 8.1 litres of ethanol (7.9 wt% water), 2.0Kg of crude tridecanedioic acid (4.6 wt% water) produced by means of fermentation was dissolved at 480 C. 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. The sand layer and the filter paper were washed with 2.5 litres of ethanol containing 7.9 wt% water, foilowed by mixing of the washings and the filtrate and the ethanol evaporated off. As a result, 1.81 Kg (0.2 wt% water content) of purified tridecanedioic acid were obtained. The nitrogen contents of the crude tridecanedioic acid and purified tridecanedioic acid were 0.37 wt% and below 0.02 wt% respectively against the dry weight of the sample.
EXAMPLE 3
Ten kg of tridencanedioic acid (43.8 wt%
water), obtained from a fermentation broth which
was acidified and filtered through a filter press
after cells were removed, were dissolved in 25
litres of methanol (below 2 wt% water) in order to
remove insoluble matter by the method described
in Example 1. To 34 litres of the mixture of the washings and filtrate 60 litres of water were added to precipitate tridecanedioic acid. Said
precipitate was filtered under pressure at room temperature, washed with water and dried at
600C. As a result, 4.9Kg of purified tridecanedioic acid (beiow 0.4 wt% water) were obtained. The
nitrogen contents of the crude tridecanedioic acid and the purified tridecanedioic acid were 0.32 wt% and below 0.02 wt% respectively.
Claims (6)
1. A method for the purification of a long-chain dicarboxylic acid having from 10 to 1 8 carbon atoms in the molecule comprising dissolving said long-chain dicarboxylic acid or a salt thereof in an aliphatic alcohol or tetrahydrofuran or in an aqueous solution of said alcohol or tetrahydrofuran, and removing insoluble matter from the solution.
2. A method according to claim 1, wherein the aliphatic alcohol is methanol.
3. A method according to claim 1, wherein the aliphatic alcohol is ethanol.
4. A method according to claim 1, wherein the aqueous solution of aliphatic alcohol comprising
100 parts by weight of methanol and less than 40 parts by weight of water.
5. A method according to claim 1, wherein the aqueous solution of aliphatic alcohol comprises 100 parts by weight of ethanol and less than 67 parts by weight of water.
6. A method according to any preceding claim, wherein water or an aqueous solution of mineral acid is added to the solution from which insoluble matter has been removed, so as to precipitate said long-chain dicarboxylic acid and the precipitate is separated from the solution.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16336778A JPS5592691A (en) | 1978-12-28 | 1978-12-28 | Purification of dicarboxylic acid produced by fermentation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2043052A true GB2043052A (en) | 1980-10-01 |
| GB2043052B GB2043052B (en) | 1982-12-15 |
Family
ID=15772530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7943513A Expired GB2043052B (en) | 1978-12-28 | 1979-12-18 | Purification of dicarboxylic acids |
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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8377661B2 (en) | 2008-07-10 | 2013-02-19 | Arkema France | Method for synthesising omega-amino-alkanoic acids or the esters thereof from natural fatty acids |
| US9023626B2 (en) | 2007-09-20 | 2015-05-05 | Arkema France | Methods for the synthesis of fatty diacids by the metathesis of unsaturated diacids obtained by fermentation of natural fatty acids |
Families Citing this family (8)
| 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 |
| EP1148132A3 (en) | 1998-10-05 | 2002-01-16 | Cognis Corporation | Cytochrome P450 monooxygenase and NADPH cytochrome P450 oxidoreductase genes and proteins related to the omega hydroxylase complex of Candida tropicalis and methods relating thereto |
| 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 |
| CN113480421B (en) * | 2021-06-30 | 2024-10-18 | 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 DE DE19792951177 patent/DE2951177A1/en not_active Withdrawn
- 1979-12-19 CA CA000342274A patent/CA1136159A/en not_active Expired
- 1979-12-24 BE BE0/198756A patent/BE880865A/en unknown
- 1979-12-27 FR FR7931785A patent/FR2445374A1/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9023626B2 (en) | 2007-09-20 | 2015-05-05 | Arkema France | Methods for the synthesis of fatty diacids by the metathesis of unsaturated diacids obtained by fermentation of natural fatty acids |
| US8377661B2 (en) | 2008-07-10 | 2013-02-19 | Arkema France | Method for synthesising omega-amino-alkanoic acids or the esters thereof from natural fatty acids |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1136159A (en) | 1982-11-23 |
| JPS6159720B2 (en) | 1986-12-17 |
| DE2951177A1 (en) | 1980-07-24 |
| FR2445374A1 (en) | 1980-07-25 |
| JPS5592691A (en) | 1980-07-14 |
| BE880865A (en) | 1980-06-24 |
| GB2043052B (en) | 1982-12-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |