CS273238B1 - Method of fumaric acid production - Google Patents
Method of fumaric acid production Download PDFInfo
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- CS273238B1 CS273238B1 CS280988A CS280988A CS273238B1 CS 273238 B1 CS273238 B1 CS 273238B1 CS 280988 A CS280988 A CS 280988A CS 280988 A CS280988 A CS 280988A CS 273238 B1 CS273238 B1 CS 273238B1
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- CS
- Czechoslovakia
- Prior art keywords
- fumaric acid
- acid
- water
- acid production
- maleic anhydride
- Prior art date
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- 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 25
- 239000001530 fumaric acid Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims abstract 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 9
- 239000011976 maleic acid Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000006317 isomerization reaction Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 2
- 150000001342 alkaline earth metals Chemical class 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- -1 alkaline earth metal thiocyanate Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
<57) ŘeSení se týká způsobu výroby kyseleny fumarové z maleinanhydridu a/nebo kyseliny maleinové katalytickým působením thiokyanatanu alkalických kovů a kovů alkalických zemin při teplotách 60 až 150 °C. Získaná kyselina fumarová je ve vysoké kvalitě i výtěžku. 57 ) The present invention relates to a process for the preparation of fumaric acid from maleic anhydride and / or maleic acid by the catalytic action of alkali metal and alkaline earth metal thiocyanate at temperatures of 60 to 150 ° C. The fumaric acid obtained is of high quality and yield.
CS 273238 BlCS 273238 Bl
Vynález se týká způsobu výroby kyseliny fumarové z maleinanhydrldu a/nebo kyseliny maleinové.The invention relates to a process for the preparation of fumaric acid from maleic anhydride and / or maleic acid.
Kyselina fumarová se v technologickém měřítku vyrábí izomeraoí kyseliny maleinové, která je snadno dostupná hydrolýzou maleinanhydrldu. V literatuře jsou popsány četné postupy přípravy kyseliny fumarové.Fumaric acid is produced on an industrial scale by isomerism of maleic acid, which is readily available by hydrolysis of maleic anhydride. Numerous processes for the preparation of fumaric acid are described in the literature.
Vedle termického způsobu izomerace (Garro B.: Z. Anorg. Chem. 164, 81 (1927) to jsou hlavně postupy, kdy izomeréce probíhá v přítomnosti různých katalyzátorů.In addition to the thermal isomerization method (Garro B .: Z. Anorg. Chem. 164, 81 (1927)), these are mainly processes where isomerization takes place in the presence of various catalysts.
Jednu skupinu tvoři postupy využívající katalytického působeni silných minerálních kyselin jako je například kyselina chlorovodíková a kyselina bromovodíková (llozaki K., Ogg R. jr.: J. Am. Chem. Soc. £3, 2583 /1941/} čs. AO 196 951).One group consists of processes utilizing the catalytic action of strong mineral acids such as hydrochloric acid and hydrobromic acid (llozaki, K., Ogg, R. Jr., J. Am. Chem. Soc. ).
Další skupinu tvoří postupy využívající katalytického působení různých anorganických solí (Ger. 1 443 127, Ger 1 443 109, US pat. 2 914 559), bromu (GB pat. 775 912,Another group consists of processes utilizing the catalytic action of various inorganic salts (Ger. 1,443,127, Ger 1,443,109, US Pat. 2,914,559), bromine (GB Pat. 775,912,
GB 719 446, US 2 758 134) apod.GB 719,446, US 2,758,134) and the like.
Další postupy využívají jako katalyzátoru thiomočovinu (It. pat, 228 927, čs. AO 196 951, Ger. 1 768 629).Other processes employ thiourea as catalyst (It. Pat, 228 927, AO 196 951, Ger. 1 768 629).
Dosud známý způsob výroby kyseliny*fumarové se podle vynálezu zdokonaluje tím, že se izomeraee kyseliny maleinové provádí při teplotě 60 až 150 °C za katalytického působení thiokyanatanů obecného vzorce ·The presently known process for the preparation of fumaric acid is improved according to the invention by carrying out the isomerization of maleic acid at a temperature of 60 to 150 ° C under the catalytic action of thiocyanates of the formula
MSCN kde M Na, K, NH^, Ca, Mg, Ba.MSCN where M Na, K, NH 4, Ca, Mg, Ba.
Vychází se buí z kyseliny maleinové, nebo s výhodou z maleinanhydrldu, který se snadno a rychle hydrolyzuje za zvýšené teplotyna kyselinu maleinovou, která se bez izolace izomeruje.It starts with either maleic acid or preferably maleic anhydride, which is hydrolyzed easily and rapidly at elevated temperature to maleic acid, which isomerized without isolation.
Způsob výroby podle vynálezu poskytuje kyselinu fumarovou ve vysokém výtěžku a vyhovující čistotě.The process of the present invention provides fumaric acid in high yield and satisfactory purity.
Vynález blíže objasňující následující příklady provedení, které neomezují rozssh vynálezu.The invention is illustrated by the following non-limiting examples.
Příklad 1Example 1
V baňce opatřené zpětným chladičem a mechanickým míchadlem bylo smícháno 100 g maleinanhydrldu, 150 ml vody a 3 g thiokyanatanů draselného a směs byla za míchání ohřátá na 100 °C. Po několika minutách se z čirého roztoku vylučovaly bílé krystaly. Po 3 hodinovém zahřívání byl obsah baňky ochlazen na 20 °C, krystaly odfiltrovány, promyty 2 x 150 ml vody a sušeny při 100 °C. Bylo získáno 110,2 g (93,1 %) kyseliny fumarové o teplotě tání 289 až 291 °C (stanoveno v zatavené kapiláře) a čistotěIn a flask equipped with a reflux condenser and a mechanical stirrer, 100 g of maleic anhydride, 150 ml of water and 3 g of potassium thiocyanate were mixed and the mixture was heated to 100 ° C with stirring. After a few minutes, white crystals precipitated from the clear solution. After heating for 3 hours, the contents of the flask were cooled to 20 ° C, the crystals were filtered off, washed with 2 x 150 ml water and dried at 100 ° C. 110.2 g (93.1%) of fumaric acid having a melting point of 289-291 ° C (determined in a sealed capillary tube) and a purity was obtained
99,2 56 (GLC).99.2 56 (GLC).
Příklad 2Example 2
V baňce opatřené zpětným chladičem a mechanickým míchadlem bylo smícháno 100 g maleinanhydrldu, 150 ml vody a 2 g thiokyanatanů amonného a směs byla za míchání ohřátá na 100 °C. Po několika minutách se z čirého roztoku vylučovaly bílé krystaly. Po 4 hodinovém zahřívání byl obsah baňky ochlazen na 20 °C, krystaly odfiltrovány, promyty 2 x 150 ml vody a sušeny při 100 °C. Bylo získáno 111,7 g (94,4 %) kyseliny fumarové o teplotě tání 286 až 288 °C a čistotě 98, 5 56 (GLC),In a flask equipped with a reflux condenser and a mechanical stirrer, 100 g of maleic anhydride, 150 ml of water and 2 g of ammonium thiocyanate were mixed and the mixture was heated to 100 ° C with stirring. After a few minutes, white crystals precipitated from the clear solution. After heating for 4 hours, the contents of the flask were cooled to 20 ° C, the crystals were filtered off, washed with 2 x 150 ml water and dried at 100 ° C. 111.7 g (94.4%) of fumaric acid with a melting point of 286 DEG-288 DEG C. and a purity of 98.56 (GLC) were obtained,
CS 273238 Bl >&CS 273238 Bl> &
Příklad 3Example 3
Do autoklávu o obsahu 2 lt bylo vneseno 400 g maleinanhydridú, 600 ml vody a 8 g thiokyanatanu amonného a smés byla za míchání ohřátá na 150 °C. Po 2 hodinovém zahřívání byl obsah autoklávu ochlazen na 20 °C, krystaly odsáty, promyty 2 x 600 ml vody a sušeny při 100 °C. Bylo získáno 460,8 g (97, 3 %) kyseliny fumarové o teplotě tání 288 až 290 °C a čistotě 99,2 % (OLO).A 2 L autoclave was charged with 400 g of maleic anhydride, 600 ml of water and 8 g of ammonium thiocyanate, and the mixture was heated to 150 ° C with stirring. After heating for 2 hours, the contents of the autoclave were cooled to 20 ° C, the crystals were aspirated, washed with 2 x 600 ml of water and dried at 100 ° C. 460.8 g (97.3%) of fumaric acid with a melting point of 288 DEG-290 DEG C. and a purity of 99.2% (OLO) were obtained.
Příklad 4Example 4
V baňce opatřené míchadlem bylo smícháno 20 g maleinanhydridú, 40 ml vody a 0,4 g thiokyanatanu sodného a směs byla za míchání ohřátá na 70 °C. Po 4 hodinovém zahřívání byla směs vychlazena na 20 °C, krystaly odsáty, promyty 2 x 30 ml vody a sušeny volně na vzduchu. Bylo získáno 21,6 g (91,2 %) kyseliny fumarové o teplotě tání 288 až 291 °C a čistotě 99,0 % (GLC).In a flask equipped with a stirrer, 20 g of maleic anhydride, 40 ml of water and 0.4 g of sodium thiocyanate were mixed and the mixture was heated to 70 ° C with stirring. After heating for 4 hours, the mixture was cooled to 20 ° C, the crystals were aspirated, washed with 2 x 30 ml water and air dried. Fumaric acid (21.6 g, 91.2%), m.p. 288 DEG-291 DEG C. and a purity of 99.0% (GLC), was obtained.
Příklad 5Example 5
V baňce opatřené míchadlem a zpětným chladičem bylo smícháno 20 g kyseliny maleinové, 80 ml vody a 0,5 g thiokyanatanu amonného a směs byla za míchání ohřátá na 100 °C, Po 4 hodinovém zahřívání byla směs vychlazena na 20 °C, krystaly odsáty, promyty 2 x 30 ml vody a sušeny při 100 °G. Bylo získáno 18,9 (94,5 %) kyseliny fumarové o teplotě tání 284 až 286 °C a čistotě 98,6 % (GIG),In a flask equipped with a stirrer and a reflux condenser, 20 g of maleic acid, 80 ml of water and 0.5 g of ammonium thiocyanate were mixed and the mixture was heated to 100 ° C with stirring. After 4 hours the mixture was cooled to 20 ° C washed with 2 x 30 ml water and dried at 100 ° C. 18.9 (94.5%) of fumaric acid with a melting point of 284 to 286 ° C and a purity of 98.6% (GIG) was obtained,
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS280988A CS273238B1 (en) | 1988-04-26 | 1988-04-26 | Method of fumaric acid production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS280988A CS273238B1 (en) | 1988-04-26 | 1988-04-26 | Method of fumaric acid production |
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| Publication Number | Publication Date |
|---|---|
| CS280988A1 CS280988A1 (en) | 1990-07-12 |
| CS273238B1 true CS273238B1 (en) | 1991-03-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS280988A CS273238B1 (en) | 1988-04-26 | 1988-04-26 | Method of fumaric acid production |
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| CS (1) | CS273238B1 (en) |
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1988
- 1988-04-26 CS CS280988A patent/CS273238B1/en unknown
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| Publication number | Publication date |
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| CS280988A1 (en) | 1990-07-12 |
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