DE1041944B - Process for the preparation of acylated citric acid esters - Google Patents
Process for the preparation of acylated citric acid estersInfo
- Publication number
- DE1041944B DE1041944B DEH28210A DEH0028210A DE1041944B DE 1041944 B DE1041944 B DE 1041944B DE H28210 A DEH28210 A DE H28210A DE H0028210 A DEH0028210 A DE H0028210A DE 1041944 B DE1041944 B DE 1041944B
- Authority
- DE
- Germany
- Prior art keywords
- citric acid
- preparation
- acid esters
- acylated
- acid
- 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.)
- Pending
Links
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 title claims description 29
- 238000000034 method Methods 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 230000010933 acylation Effects 0.000 claims description 3
- 238000005917 acylation reaction Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000008043 acidic salts Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 3
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- -1 fatty acid ester Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MKXAREWNUVZNTJ-UHFFFAOYSA-N 5-acetyl-7-butyl-6-hydroxyundecane-4,5,6-tricarboxylic acid Chemical compound CCCCC(CCCC)(C(O)=O)C(O)(C(O)=O)C(CCCC)(C(C)=O)C(O)=O MKXAREWNUVZNTJ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 206010000210 abortion Diseases 0.000 description 1
- 231100000176 abortion Toxicity 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KTUQUZJOVNIKNZ-UHFFFAOYSA-N butan-1-ol;hydrate Chemical compound O.CCCCO KTUQUZJOVNIKNZ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
- C07C69/704—Citric acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Verfahren zur Herstellung von acylierten Citronensäureestern Gegenstand der Patentanmeldung H 25806 IV b/120 ist ein Verfahren zur Herstellung von acylierten Citronensäureestern durch gleichzeitige Acylierung und Veresterung, das dadurch gekennzeichnet ist, daß man mit einem Überschuß von Veresterungs- und Acylierungsmitteln arbeitet und als Katalysator einen aus einem Metall und einem sauren Metallsalz bestehenden Mischkatalysator verwendet.Process for the preparation of acylated citric acid esters Subject the patent application H 25806 IV b / 120 is a process for the preparation of acylated Citric acid esters through simultaneous acylation and esterification, which thereby is characterized in that one with an excess of esterifying and acylating agents works and as a catalyst one of a metal and an acidic metal salt existing mixed catalyst used.
Die Verwendung von reinen Ausgangsstoffen, z. B. kristallisierter Citronensäure, erfordert vor allem bei fermentativ gewonnenen Substanzen eine mit Energie-, Kosten- und Zeitaufwand verbundene Konzentrierung mit anschließendem Ausfällen der Säure als Salz sowie deren Isolierung. Aus technischen und wirtschaftlichen Gründen ist es in Fällen dieser Art erstrebenswert, die anfallenden wäßrigen Rohlösungen direkt verarbeiten zu können.The use of pure raw materials, e.g. B. crystallized Citric acid, especially for substances obtained by fermentation, requires a Energy, cost and time associated concentration with subsequent failures the acid as a salt and its isolation. For technical and economic For reasons of this kind, it is desirable to use the resulting crude aqueous solutions to be able to process directly.
Es wurde nun gefunden, daß man acylierte Citronensäureester herstellen kann, wenn man eine wäßrige Lösung von Citronensäure durch azeotrope Destillation mit einem Alkohol- und Fettsäureestergemisch in Gegenwart eines Veresterungskatalysators und eines Schleppmittels den Bedingungen einer gleichzeitigen Acylierung und Veresterung unterwirft und die Reaktionstemperatur dabei unterhalb der Zersetzungstemperatur der Säure hält.It has now been found that acylated citric acid esters can be produced can, if you an aqueous solution of citric acid by azeotropic distillation with an alcohol and fatty acid ester mixture in the presence of an esterification catalyst and an entrainer under the conditions of simultaneous acylation and esterification and the reaction temperature is below the decomposition temperature the acid holds.
Vorteilhaft kann man die wäßrige, bei der Gärung anfallende rohe Citronensäure ohne vorherige Reinigung oder Entwässerung verwenden.The aqueous crude citric acid obtained during fermentation can advantageously be used use without prior cleaning or draining.
Die wäßrige Säure wird mit einem Alkohol-Fettsäureestergemisch, z. B. mit einem Gemisch aus Butanol und Butylacetat, unter Zusatz eines Schleppmittels, z. B. Benzol, in Gegenwart eines aus Natriumbisulfat und Zinn bestehenden Mischkatalysators gemäß Patentanmeldung H 25806 IV b / 12 o verestert, wobei die nach dem Abtreiben der Hauptwassermenge sich einstellende Temperatur nicht über die Zersetzungstemperatur der Säure steigen darf. Der hierbei erhaltene Rohester wird dann zweckmäßig durch Destillation gereinigt, kann als Weichmacher verwendet werden und ist in seinen Eigenschaften mit den aus kristallisierter Säure erhaltenen Estern vergleichbar.The aqueous acid is mixed with an alcohol-fatty acid ester mixture, e.g. B. with a mixture of butanol and butyl acetate, with the addition of an entrainer, z. B. benzene, in the presence of a mixed catalyst consisting of sodium bisulfate and tin esterified according to patent application H 25806 IV b / 12 o, the after the abortion the temperature that is established for the main amount of water does not exceed the decomposition temperature the acid may rise. The crude ester obtained in this way is then expediently through Purified by distillation, it can be used as a plasticizer and is in its Properties comparable to the esters obtained from crystallized acid.
Die folgenden Beispiele erläutern die Erfindung: Beispiel 1 500g einer etwa 30°/oigen wäßrigen Lösung fermentativ gewonnener roher Citronensäure werden mit einem Gemisch aus 3,5 kg Benzol und 0a85 kg Äthylalkohol bis zur sirupösen Konsistenz entwässert. Der braune Sirup wird mit 222 g Butanol, 350 g Butylacetat, 12 g Natriumbisulfat und 5 g Zinn versetzt und bis zur Erreichung einer SZ von 5 mg KOH je g Substanz bei einer Temperatur von 140 bis 160° C verestert. Der Rohester wird nach Auswaschen mit 3%iger wäßriger Sodalösung und Wasser ohne vorherige Trocknung destilliert, wobei ein farbloses Destillat vom Kp. 0,s=160 bis 161° C anfällt.The following examples illustrate the invention: Example 1 500g one about 30% aqueous solution of crude citric acid obtained by fermentation with a mixture of 3.5 kg of benzene and 85 kg of ethyl alcohol to a syrupy consistency drains. The brown syrup is made with 222 g of butanol, 350 g of butyl acetate, 12 g of sodium bisulfate and 5 g of tin are added and an AN of 5 mg of KOH per g of substance is reached Esterified at a temperature of 140 to 160 ° C. The crude ester becomes after washing out distilled with 3% aqueous soda solution and water without prior drying, whereby a colorless distillate with a boiling point of 0, s = 160 to 161 ° C is obtained.
Ausbeute an Acetylcitronensäuretributylester 260 g, entsprechend 821/o der Theorie.Yield of tributyl acetylcitric acid 260 g, corresponding to 821 / o the theory.
Beispiel 2 70G g einer etwa 60%igen Citronensäurelösung werden wie im Beispiel 1 nach Zusatz von 444 g Butanol, 700 g Butylacetat, 200 g Benzol, 24 g Natriumbisulfat und 10 g Zinn erhitzt, wobei die Veresterungstemperatur nicht über 140° C steigen soll. Nach 24 Stunden wird mit Erreichen einer SZ von 1,9 mg KOH je g Ester die Reaktion abgebrochen, wobei sich insgesamt 485 g eines Wasser-Butanol-Gemisches abgeschieden haben. Der rohe Acetylcitronensäuretributylester wird ohne vorheriges Waschen destilliert und geht bei 174° C/1,5 mm als farblose Flüssigkeit über.Example 2 70 g of an approximately 60% citric acid solution are heated as in Example 1 after adding 444 g of butanol, 700 g of butyl acetate, 200 g of benzene, 24 g of sodium bisulfate and 10 g of tin, the esterification temperature not exceeding 140 ° C. After 24 hours, when an AN of 1.9 mg KOH per g ester is reached, the reaction is terminated, with a total of 485 g of a water-butanol mixture having separated out. The crude tributyl acetylcitric acid ester is distilled without prior washing and passes over as a colorless liquid at 174 ° C./1.5 mm.
Ausbeute 746 g, entsprechend 85 % der Theorie.Yield 746 g, corresponding to 85% of theory.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEH28210A DE1041944B (en) | 1956-09-28 | 1956-09-28 | Process for the preparation of acylated citric acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEH28210A DE1041944B (en) | 1956-09-28 | 1956-09-28 | Process for the preparation of acylated citric acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1041944B true DE1041944B (en) | 1958-10-30 |
Family
ID=7150804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEH28210A Pending DE1041944B (en) | 1956-09-28 | 1956-09-28 | Process for the preparation of acylated citric acid esters |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1041944B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6403825B1 (en) | 1997-05-12 | 2002-06-11 | Reilly Industries, Inc. | Processes for producing citrate esters |
| CN102417453A (en) * | 2011-12-16 | 2012-04-18 | 中粮生物化学（安徽）股份有限公司 | Preparation method of citric acid ester |
-
1956
- 1956-09-28 DE DEH28210A patent/DE1041944B/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6403825B1 (en) | 1997-05-12 | 2002-06-11 | Reilly Industries, Inc. | Processes for producing citrate esters |
| CN102417453A (en) * | 2011-12-16 | 2012-04-18 | 中粮生物化学（安徽）股份有限公司 | Preparation method of citric acid ester |
| CN102417453B (en) * | 2011-12-16 | 2014-04-02 | 中粮生物化学（安徽）股份有限公司 | Method for preparing citric acid ester |
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