BE675583A - - Google Patents
Info
- Publication number
- BE675583A BE675583A BE675583DA BE675583A BE 675583 A BE675583 A BE 675583A BE 675583D A BE675583D A BE 675583DA BE 675583 A BE675583 A BE 675583A
- Authority
- BE
- Belgium
- Prior art keywords
- hydrogenation
- benzoic acid
- acid
- carboxylic acid
- cyclohexane
- Prior art date
Links
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 23
- 239000005711 Benzoic acid Substances 0.000 claims description 11
- 235000010233 benzoic acid Nutrition 0.000 claims description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 6
- NZNMSOFKMUBTKW-UHFFFAOYSA-N Cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229960000583 Acetic Acid Drugs 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- CPBZARXQRZTYGI-UHFFFAOYSA-N 3-cyclopentylpropylcyclohexane Chemical compound C1CCCCC1CCCC1CCCC1 CPBZARXQRZTYGI-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000005092 Ruthenium Substances 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N al2o3 Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052803 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
<Desc/Clms Page number 1>
"PROCEDE POUR L'HYDROGENATIO D'ACIDE BENZOIQUE
EN ACIDE CARBOXYLIQUE DE CYCLOHEXANE"
L'invention est relative à l'hydrogénation d'acide benzotque en acide carboxylique de cyclohexane.
R. Willstatter et E.W. Mayer (voir Ber. 41,1471 (1912)) ont réalisé, à l'aide d'un catalyseur de platine, l'hydrogénation d'acide benzoïque dans de l'acide acétique glacial servant d'agent de distribution. Comme l'acide acétique glacial est un agent de distribution peu intéressant pour l'appli- cation dans l'industrie, cette hydrogénation n'a pas été appliquée en pratique.
Or, des essais ont montré qu'on n'arrive pas à de bons résultats en supprimant l'acide acétique glacial pendant cette hydrogénation. L'hydro- génation d'acide benzoïque fondu, à l'aide d'un catalyseur de platine, est pratiquement nulle. Si l'on emploie d'autres catalyseurs d'hydrogénation comme le palladium, le ruthénium, le nickel ou le cobalt, l'hydrogénation d'acide benzoïque fondu en acide carboxylique de cyclohexane ne s'effectue pas non plus, ou bien elle est très faible.
Or, on a découvert qu'on peut hydrogéner l'acide benzoïque en acide carboxylique de cyclohexane sans formation de produits secondaires, si
<Desc/Clms Page number 2>
l'acide benzoïque est mis en contact, à l'état fondu et ensemble avec de l'hydrogène, avec du rhodium métallique.
On peut effectuer le procédé selon l'invention à la pression at- mosphérique, mais on peut appliquer aussi des pressions inférieures ou supérieures à celle-ci, p. e. de 10,25, 50 ou 100 atmosphères, ou une pression encore plus élevée. L'application d'une pression élevée nécessite un appareillage d'hydrogénation capable de résister à cette pression.
Les mesures servant à l'adduction des composants de réaction, au réglage de la température et de la pre ion, à l'évacuation du mélange de réaction, ainsi qu'à la réalisation en processus continu, sont celles usuelles pour la réalisation de processus d'hydrogénation, de sorte qu'une explication serait superflue.
De plus, il est possible, dans un processus continu, de faire recirculer l'acide benzoïque non converti, l'hydrogène non consommé et/ou le catalyseur.
Le catalyseur, qui est appliqué sous forme métallique, peut être aménagé sur un support, p.e. l'oxyde de thorium, l'oxyde d'aluminium, l'oxyde de magnésium, l'oxyde de zirconium, le bioxyde de silicium, le gel de silice, le kieselguhr ou le charbon.
Exemple
Dans un autoclave cylindrique, d'une capacité de 1 litre, muni d'un agitateur mécanique, on tient, à une température de 128 , un mélange se composant de 245 g d'acide benzolque et de 2,5 g de catalyseur (5 % de rho- dium sur du charbon) sous une pression d'hydrogène de 10 atm. Après 16 heures, l'acide benzoïque a été hydrogéné en acide carboxylique de cyclohexane.
Le produit de réaction est filtré à chaud pour éliminer le cata- lyseur. Le rendement est de 254 g d'acide carboxylique de cyclohexane (rendement de 99 %).
<Desc / Clms Page number 1>
"PROCESS FOR HYDROGENATIO OF BENZOIC ACID
OF CYCLOHEXANE CARBOXYLIC ACID "
The invention relates to the hydrogenation of benzotque acid to the carboxylic acid of cyclohexane.
R. Willstatter and EW Mayer (see Ber. 41,1471 (1912)) carried out, with the aid of a platinum catalyst, the hydrogenation of benzoic acid in glacial acetic acid serving as a stabilizing agent. distribution. As glacial acetic acid is an unattractive dispensing agent for industrial application, this hydrogenation has not been applied in practice.
However, tests have shown that good results are not obtained by removing glacial acetic acid during this hydrogenation. Hydrogenation of molten benzoic acid, using a platinum catalyst, is practically nil. If other hydrogenation catalysts such as palladium, ruthenium, nickel or cobalt are employed, the hydrogenation of molten benzoic acid to cyclohexane carboxylic acid either does not take place, or it is. very weak.
However, it has been discovered that benzoic acid can be hydrogenated to cyclohexane carboxylic acid without the formation of side products, if
<Desc / Clms Page number 2>
the benzoic acid is brought into contact, in the molten state and together with hydrogen, with metallic rhodium.
The process according to the invention can be carried out at atmospheric pressure, but it is also possible to apply pressures lower or higher than this, eg. e. of 10.25, 50 or 100 atmospheres, or even higher pressure. The application of a high pressure requires hydrogenation equipment capable of withstanding this pressure.
The measures used for the adduction of the reaction components, for the control of the temperature and the pre ion, for the evacuation of the reaction mixture, as well as for the carrying out in continuous process, are those customary for the realization of processes hydrogenation, so an explanation would be superfluous.
In addition, it is possible, in a continuous process, to recirculate the unconverted benzoic acid, unconsumed hydrogen and / or the catalyst.
The catalyst, which is applied in metallic form, can be arranged on a support, eg thorium oxide, aluminum oxide, magnesium oxide, zirconium oxide, silicon dioxide, gel of silica, kieselguhr or coal.
Example
In a cylindrical autoclave with a capacity of 1 liter, fitted with a mechanical stirrer, a mixture is kept at a temperature of 128, consisting of 245 g of benzolic acid and 2.5 g of catalyst (5 % rhodium on charcoal) under a hydrogen pressure of 10 atm. After 16 hours, the benzoic acid was hydrogenated to the carboxylic acid of cyclohexane.
The reaction product is filtered while hot to remove the catalyst. The yield is 254 g of cyclohexane carboxylic acid (99% yield).
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| BE675583A true BE675583A (en) |
Family
ID=208838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| BE675583D BE675583A (en) |
Country Status (1)
| Country | Link |
|---|---|
| BE (1) | BE675583A (en) |
-
0
- BE BE675583D patent/BE675583A/fr unknown
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2003506341A (en) | Catalytic hydrogenation of 3-hydroxypropanal to 1,3-propanediol | |
| EP1762554B1 (en) | Hydrogenation of acetone | |
| EP0135436A1 (en) | Process for the preparation of linear olefins from fatty acids or esters of saturated fatty acids | |
| BE675583A (en) | ||
| US4800227A (en) | Process for the production of lactams | |
| US4042599A (en) | Process for producing 2-pyrrolidone | |
| US5756865A (en) | Method for production of tetritols, specifically meso-erythritol | |
| US2683745A (en) | Preparation of 2-amino-alpha-methylbenzyl alcohol | |
| JP2714433B2 (en) | Method for producing gamma-butyrolactone | |
| US2040913A (en) | Process for producing a tolyl carbinol | |
| JP7206501B2 (en) | Method for producing halogenated cycloalkane compound | |
| US6329561B1 (en) | Impurities removal | |
| BE675582A (en) | ||
| EP1107952B1 (en) | Hydroperoxide decomposition process | |
| US4244877A (en) | Process for the preparation of hexahydrophthalic acid anhydride | |
| DE10160142A1 (en) | Process for the preparation of tetrahydrogeraniol | |
| BE608776A (en) | ||
| JP2516222B2 (en) | Process for producing 4- (4-hydroxyphenyl) -cyclohexanol | |
| BE718856A (en) | ||
| US2046011A (en) | Catalytic hydrogenation of aromatic aldehydes | |
| JPS5883645A (en) | Manufacture of beta-phenylethyl alcohol | |
| CA1312629C (en) | Process for the preparation of trifluoroethanol | |
| US5663433A (en) | Process for the preparation N-alkyl-N,O-diacetyl hydroxylamine | |
| BE494818A (en) | ||
| CN112707792A (en) | Method for increasing cis-dihydroterpineol content in terpineol hydrogenation reaction |