CS272102B1 - Method of fumaric acid production - Google Patents
Method of fumaric acid production Download PDFInfo
- Publication number
- CS272102B1 CS272102B1 CS876752A CS675287A CS272102B1 CS 272102 B1 CS272102 B1 CS 272102B1 CS 876752 A CS876752 A CS 876752A CS 675287 A CS675287 A CS 675287A CS 272102 B1 CS272102 B1 CS 272102B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- fumaric acid
- acid
- maleic
- thiourea
- water
- Prior art date
Links
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 title claims abstract description 32
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000001530 fumaric acid Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 12
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 12
- 239000011976 maleic acid Substances 0.000 claims abstract description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 4
- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 3
- 239000011707 mineral Substances 0.000 claims abstract description 3
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000013078 crystal Substances 0.000 description 6
- 238000000527 sonication Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Kyselina fumarová se vyrábí 1 maleinanhydridu a/nebo kyseliny maleinové za použití ultrazvuku v přítomnosti thiomoěoviny nebo thiomoCoviny v přítomnosti minerální kyseliny nebo thiosemikarbazidu při teplotách 10 - 50 °C. Získaná kyselina fumarová je ve vysoké kvalitě i výtěžku.Fumaric acid is produced by 1 maleic anhydride and / or maleic acid using ultrasound in the presence of thiourea or thiomoCovinyl in the presence of a mineral acid or thiosemicarbazide at 10 - 50 ° C. The fumaric acid obtained is high quality and yield.
Description
Vynález se týká způsobu výroby kyseliny fumarové z maleinanhydridu a/nebo kyseliny maleinové.The invention relates to a process for the production of fumaric acid from maleic anhydride and / or maleic acid.
Kyselina fumarové se v technologickém měřítku vyrábí izomerací kyseliny maleinové, která je snadno dostupná hydrolýzou maleinanhydridu. Ten se získává především katalytickou oxidací benzenu vzdušným kyslíkem, nebo také katalytickou oxidací n-butalenu nebo jejich směsí s n-butanem. Vzhledem k větší termodynamické stabilitě kyseliny fumarové (energeticky chudší trans izomer) oproti kyselině maleinové (cis izomer) probíhá izomerace poměrně snadno. literatura uvádí řadu postupů, při kterých je tato cis-trans-izomerace katalyzovány termicky, kyselinami (například kyselina chlorovodíková, kyselina jodovodíková), anorganickými solemi (například peroxidisíran amonný v kombinaci s bromidem amonným), sirnými sloučeninami, bromem atd. Při těchto katalytických izomeracích je nutná vyšší reakční teplota od 50 °C do teploty varu roztoků bučí za atmosferického tlaku, nebo za vyššího tlaku, čímž rostou energetické nároky na výrobu kyseliny fumarové a také vzrůstají nároky na výrobní zařízení.Fumaric acid is produced on a technological scale by isomerization of maleic acid, which is readily available by hydrolysis of maleic anhydride. This is obtained mainly by catalytic oxidation of benzene with atmospheric oxygen, or also by catalytic oxidation of n-butalene or mixtures thereof with n-butane. Due to the greater thermodynamic stability of fumaric acid (energy-poorer trans isomer) compared to maleic acid (cis isomer), isomerization proceeds relatively easily. the literature mentions a number of processes in which this cis-trans-isomerization is thermally catalyzed by acids (e.g. hydrochloric acid, hydroiodic acid), inorganic salts (e.g. ammonium persulphate in combination with ammonium bromide), sulfur compounds, bromine, etc. In these catalytic isomerizations a higher reaction temperature from 50 ° C to the boiling point of the solutions at atmospheric pressure or at a higher pressure is required, which increases the energy requirements for the production of fumaric acid and also increases the demands on the production equipment.
Uvedené nevýhody odstraňuje způsob výroby kyseliny fumarové katalytickou izomerací kyseliny maleinové podle vynálezu, jehož podstatou je, že se izomerace kyseliny maleinové provádí ultrazvukem při teplotě v rozmezí 10 až 50 °C v přítomnosti thiomočoviny nebo thiomočoviny v přítomností, minerální kyseliny nebo thiosemikarbazidu εοnokatalýzou.The process for the production of fumaric acid by catalytic isomerization of maleic acid according to the invention eliminates these disadvantages, which is carried out by sonication of maleic acid at 10 DEG to 50 DEG C. in the presence of thiourea or thiourea in the presence of mineral acid or thiosemicarbazide by ion catalysis.
Vychází se bučí z kyseliny maleinové, nebo z maleinanhydridu, který se snadno a rychle hydrolýzuje ultrazvukem za normální teploty na kyselinu maleinovou, která se bez isolace izomeruje.It is based either on maleic acid or on maleic anhydride, which is easily and rapidly hydrolyzed by ultrasound at normal temperature to maleic acid, which is isomerized without isolation.
Způsob výroby podle vynálezu poskytuje kyselinu fumarovou ve vysokém výtěžku a vyhovující čistotě.The process of the invention provides fumaric acid in high yield and satisfactory purity.
Vynález blíže objasňují následující příklady způsobu výroby podle vynálezu, které však rozsah vynálezu nikterak neomezují.The invention is further illustrated by the following examples of the production process according to the invention, which, however, do not limit the scope of the invention in any way.
Příklad 1Example 1
V otevřené baňce opatřené míchadlem a umístěné v ultrazvukovém generátoru (kmitočet 22 kHz) bylo smícháno 20 g maleinanhydridu a 85 ml vody. Za míchání a působení ultrazvuku byl maleinanhydrid zhydrolyzován během několika minut. K čirému roztoku byl přidán roztok 0,5 g thiomočoviny v 15 ml vody. Směs byla dále míchána při současném působení ultrazvuku. Teplota směsi se pohybovala v rozmezí 20 až 25 °C. Po několika minutách se z čirého roztoku vylučovaly bílé krystaly. Po 60 minutách působení ultra- . zvuku byly krystaly kyseliny fumarové odsáty a po promytí 3x 20 ml studené vody usušeny na vzduchu. Bylo získáno 22,05 g (93,1 ¢) kyseliny fumarové o teplotě tání 288 až 291 °C (stanoveno v zatavené kapiláře) a čistotě 99,5 % (GIC).20 g of maleic anhydride and 85 ml of water were mixed in an open flask equipped with a stirrer and placed in an ultrasonic generator (frequency 22 kHz). With stirring and sonication, maleic anhydride was hydrolyzed for several minutes. A solution of 0.5 g of thiourea in 15 ml of water was added to the clear solution. The mixture was further stirred while sonicating. The temperature of the mixture ranged from 20 to 25 ° C. After a few minutes, white crystals precipitated out of the clear solution. After 60 minutes of exposure to ultra-. At the same time, the fumaric acid crystals were filtered off with suction and, after washing 3 times with 20 ml of cold water, dried in air. 22.05 g (93.1%) of fumaric acid with a melting point of 288-291 ° C (determined in a sealed capillary) and a purity of 99.5% (GIC) were obtained.
Příklad 2Example 2
Provedení pokusu podle příkladu 1 (kmitočet 17 kHz), V baňce bylo smícháno 20 g maleinanhydridu a 85 ml vody. K roztoku byl přidán roztek 0,7 g thiomočoviny v 15 ml vody. Po 40 minutách, působení ultrazvuku při teplotě 27 až 35 °C byly krystaly po vychlazení odsáty, promyty studenou vodou a sušeny volně naCarrying out the experiment according to Example 1 (frequency 17 kHz). 20 g of maleic anhydride and 85 ml of water were mixed in a flask. A solution of 0.7 g of thiourea in 15 ml of water was added to the solution. After 40 minutes, sonication at 27-35 [deg.] C., the crystals were filtered off with suction after cooling, washed with cold water and dried freely on
CS 272 102 Bl vzduchu. Bylo získáno 22,8 g (96,3 kyseliny fumarové o teplotě tání 286 až 288 °C a čistotě 99,4 % (GLC).CS 272 102 Bl air. 22.8 g (96.3 g of fumaric acid) with a melting point of 286-288 DEG C. and a purity of 99.4% (GLC) were obtained.
Příklad 3Example 3
Provedení pokusu podle příkladu 1.Performing the experiment according to Example 1.
V baňce bylo smícháno 20 g maleinanhydridu a 100 ml vody. K tomuto roztoku bylo přidáno 0,2 g. thiosemikarbazidu. Po 90 minutách působení ultrazvuku při teplotě 30 až 35 °C byly krystaly pb vychlazení odsáty, promyty studenou vodou a sušeny volně na vzduchu. Bylo získáno 15,2 g (64,2 %) kyseliny fumarové o teplotě tání 281 až 282 °C a čistotě 99,1 % (GLC).20 g of maleic anhydride and 100 ml of water were mixed in the flask. To this solution was added 0.2 g of thiosemicarbazide. After sonication for 90 minutes at 30-35 [deg.] C., the pb crystals were filtered off with suction, washed with cold water and dried in free air. 15.2 g (64.2%) of fumaric acid with a melting point of 281-282 ° C and a purity of 99.1% (GLC) were obtained.
Příklad 4Example 4
Provedení pokusu podle příkladu 1.Performing the experiment according to Example 1.
V baňce bylo smícháno 20 g kyseliny maleinové a 80 ml vody. K roztoku byl přidán roztok 0,4 g thiomočoviny ve 20 ml vody. Po 60 minutách působení ultrazvuku při teplotě 25 až 30 °C byly krystaly po vychlazení odsáty, promyty studenou vodou a sušeny na vzduchu. Bylo získáno 19,1 g (95,5 %) kyseliny fumarové o teplotě tání 282 až 287 °C a čistotě 99,6 % (GLC).20 g of maleic acid and 80 ml of water were mixed in the flask. A solution of 0.4 g of thiourea in 20 ml of water was added to the solution. After 60 minutes of sonication at 25-30 [deg.] C., the crystals were filtered off with suction after cooling, washed with cold water and air-dried. 19.1 g (95.5%) of fumaric acid with a melting point of 282-287 DEG C. and a purity of 99.6% (GLC) were obtained.
Příklad 5Example 5
Provedení pokusu podle příkladu 1.Performing the experiment according to Example 1.
V baňce bylo smícháno 20 g maleinanhydridu a 85 ml vody. Ke směsi byl přidán roztok 0,5 g thiomočoviny v 15 ml vody a 2 ml kyseliny chlorovodíkové. Po 60 minutách působení ultrazvuku při teplotě 35 až 40 °C byly krystaly po vychlazení odsáty, promyty studenou vodou a sušeny volně na vzduchu. Bylo získáno 21,5 ε (91,0 %) kyseliny fumarové o teplotě tání 282 až 285 °C a čistotě 98,5 % (GLC).20 g of maleic anhydride and 85 ml of water were mixed in the flask. A solution of 0.5 g of thiourea in 15 ml of water and 2 ml of hydrochloric acid was added to the mixture. After 60 minutes of sonication at 35-40 [deg.] C., the crystals were filtered off with suction after cooling, washed with cold water and dried in free air. 21.5 ε (91.0%) of fumaric acid with a melting point of 282-285 ° C and a purity of 98.5% (GLC) were obtained.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS876752A CS272102B1 (en) | 1987-09-18 | 1987-09-18 | Method of fumaric acid production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS876752A CS272102B1 (en) | 1987-09-18 | 1987-09-18 | Method of fumaric acid production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS675287A1 CS675287A1 (en) | 1990-05-14 |
| CS272102B1 true CS272102B1 (en) | 1991-01-15 |
Family
ID=5415258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS876752A CS272102B1 (en) | 1987-09-18 | 1987-09-18 | Method of fumaric acid production |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS272102B1 (en) |
-
1987
- 1987-09-18 CS CS876752A patent/CS272102B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS675287A1 (en) | 1990-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| ATE82290T1 (en) | ALDITOLDIACETALS OF HIGH PURITY AND FREE OF ORGANIC SOLVENTS TRACES AND PROCESSES FOR THEIR PRODUCTION. | |
| JPH0684332B2 (en) | Method for optical resolution of a-isopropyl-p-chlorophenylacetic acid | |
| ES512933A0 (en) | A PROCEDURE FOR THE PRODUCTION OF MAGNESIC SALTS HYDRATED BY REACTION BETWEEN HYDROGEN PEROXIDE, AN ANHYDRIDE, A BASE AND WATER. | |
| CS272102B1 (en) | Method of fumaric acid production | |
| Sowden | A Convenient Method of Preparing 2-Deoxy-D-ribose1 | |
| JPS60255761A (en) | Manufacture of water-insoluble peroxycarboxylic acid | |
| US4104308A (en) | Synthesis of squaric acid | |
| US3803202A (en) | Process for the production of 2-cyano-3,4,5,6-tetrahalogenbenzoic acid alkyl esters | |
| JPS5946279A (en) | Method for producing N-formyl-L-aspartic acid anhydride | |
| US2376334A (en) | Synthesis of beta-alanine | |
| JPS5823661A (en) | Preparation of peroxide | |
| JP2002047270A (en) | Method for producing N-hydroxyimide | |
| US1953231A (en) | Production of monocarboxylic acids and their derivatives | |
| US3764611A (en) | N-(substituted sulfonamidomethyl)-2-pyrrolidinones | |
| KR890003289B1 (en) | Preparation of α-cyano-3-phenoxybenzyl-S-(+)-2- (4-chlorophenyl) -3-methylbutylate | |
| JPS6054311B2 (en) | Method for producing 2-isopropylaminopyrimidine | |
| CS273238B1 (en) | Method of fumaric acid production | |
| US3439024A (en) | Preparation of linalyl esters | |
| US3281462A (en) | Preparation of acetic anhydride by the catalyzed oxidation of acetaldehyde in the presence of amixture of boric acid and oxalic acid | |
| SU370869A1 (en) | Production Method 1 = acyl = 4 = (2 = hydroxyaryl) = semicarbazides | |
| KR850001474B1 (en) | Method for preparing 1-phenyl-3 (2,2-dialkoxy) ethyl-3,6-diazaheptan-4,7-dione derivative | |
| JPS6127396B2 (en) | ||
| SU66998A3 (en) | Method for preparing acyl dicyandiamides or their salts | |
| SU1721051A1 (en) | Method of producing 2-halogen-derivatives of furan | |
| SU497282A1 (en) | The method of obtaining mono - and / or polycarboxylic acids |