BE381976A - - Google Patents
Info
- Publication number
- BE381976A BE381976A BE381976DA BE381976A BE 381976 A BE381976 A BE 381976A BE 381976D A BE381976D A BE 381976DA BE 381976 A BE381976 A BE 381976A
- Authority
- BE
- Belgium
- Prior art keywords
- acid
- air
- mixture
- aldehyde
- crotonic
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- LDHQCZJRKDOVOX-NSCUHMNNSA-N Crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N fumaric acid Chemical compound OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- MLUCVPSAIODCQM-NSCUHMNNSA-N Crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VLAPMBHFAWRUQP-UHFFFAOYSA-L Molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000008262 pumice Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-Hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N Ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- -1 titanium anhydride Chemical class 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- UXJVWJGDHIZPLD-UHFFFAOYSA-O Ammonium vanadate Chemical compound [NH4+].O=[V-](=O)=O UXJVWJGDHIZPLD-UHFFFAOYSA-O 0.000 description 1
- OFJATJUUUCAKMK-UHFFFAOYSA-N Cerium(IV) oxide Chemical compound [O-2]=[Ce+4]=[O-2] OFJATJUUUCAKMK-UHFFFAOYSA-N 0.000 description 1
- LBFUKZWYPLNNJC-UHFFFAOYSA-N Cobalt(II,III) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L Potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J Titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L Tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 239000001120 potassium sulphate Substances 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium(0) Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Description
<Desc/Clms Page number 1>
Procédé pour la production d'acide et d'anhydride maléïque
On a trouvé que l'on obtient facilement et en bons rendements l'acide ou l'anhydride maléique en mettant en con- tact à une température élevée, comprise généralement entre 200 et 500 C, un mélange de vapeurs d'aldéhyde ou d'acide crotoni- que et d'oxygène ou de gaz qui en renferment, avec les cataly- seurs employés pour l'oxydation de composés organiques. La réaction a lieu à une température relativement basse: on ob- tient ainsi un bon rendement d'acide malélque par exemple vers 250 C. Un des avantages particuliers du procédé de la présente invention consiste en ce qu'on obtient l'acide malélque sous une forme très pure et exempte de produits secondaires gênants.
Au lieu de l'aldéhyde crotonique, on peut aussi employer l'al- dol, qui se transforme facilement en aldéhyde crotonique au chauffage.
<Desc/Clms Page number 2>
Comme catalyseurs appropriés on peut citer par exemple les acides vanadique, titanique et molybdique, qu'on peut employer chacun pour soi, en mélange entre eux ou avec d'autres catalyseurs tels que l'acide tungstique et l'oxyde de plomb. L'acide titanique est particulièrement ap@roprié, notamment en mélange avec les oxydes inférieurs du vanadium ou du molybdène, tels qu'ils prennent naissance par réduc- tion de l'acide vanadique ou molybdique au moyen d'une solu- tion aqueuse d'acide oxalique. Comme autres adjonctions appro- priées, on peut citer l'oxyde de zinc, l'oxyde de cériu, l'oxyde de chrome,l'oxyde de cobalt, la silice, etc.. On peut exécuter le procédé de la présente invention sous une pres- sion quelconque.
EXEMPLE 1.
-----------------
Diriger par heure un courant de 15 litres d'air à travers de l'aldéhyde crotonique chauffée à 30 C; on réunit ce courant avec un autre courant d'air, dont l'allure est de 150 litres par heure, et on fait passer le mélange vers 350 C sur un catalyseur formé par un mélange d'oxyde de vanadium et d'oxyde de molybdène, obtenu à partir de 10 parties de vana- date d'ammonium et de 5 parties d'acide molybdique et fixé sur de l'aluminium granulé. En refroidissant le mélange ga- . zeux après son passage sur le catalyseur, on obtient un bon rendement d'anhydride maléïque très pur.
En dirigeant sur le catalyseur indiqué plus haut, chauffé à 550 C, un mélange de va.peurs d'acide crotonique et d'air, obtenu en faisant passer par heure 150 litres d'air sur de l'acide crotonique chauffé à 90 C, il se forme égale- ment de l'anhydride maléique. Quand on emploie l'aldol, la. transformation en vapeur a lieu de préférence à une tempéra- ture comprise entre 80 et 90 C, au moyen d'un courant d'air
<Desc/Clms Page number 3>
de 5 à 10 litres par heure seulement ; on mélange alors les vapeurs avec une proportion d'air plus élevée avant de les faire passer sur le catalyseur.
E X E M P L E 2.
EMI3.1
-------------------
Diriger par heure 15 litres d'air à travers de l'al- déhyde crotonique à 87%, chauffée à 30 C. On réunit le courant d'air chargé des vapeurs de l'aldéhyde avec un autre courant d'air dont l'allure est de 220 litres par heure, et on dirige le mélange vers 300 C sur un catalyseur préparé de la manière suivante: on délaye¯20 gr d'acide molybdique, 8 gr d'acide vanadique, 10 gr d'anhydride titanique et 10 gr d'acide oxa- lique dans 100 cm3 d'eau distillée, on ajoute 100 cm3 de pierre ponce en grains de la grosseur d'un pois, et on évapore à sec tout en agitant.
Le mélange gazeux qui s'échappe de la chambre de réaction est refroidi, puis lavé avec de l'eau; on obtient ainsi 105 à 110 parties d'acide maléique pour 100 par- ties d'aldéhyde crotonique à 100%; environ 80% de l'acide se trouvent à l'état d'anhydride.
EXEMPLE 3.
@
Faire passer par heure un courant de 200 litres d'air sur de l'acide crotonique fondu à 90 C, puis diriger le mélan- ge gazeux vers 280 C sur un catalyseur obtenu à partir de 11 gr. de molybdate d'ammonium, de 3.2 gr d'acide vanadique, de 4gr d'anhydride titanique et de 4 gr d'acide oxalique, délayés dans 100 cm3 d'eau et appliqués sur 100 cm3 de pierre ponce granulée. Quand on refroidit les gaz après leur passage sur le catalyseur, il se dépose des cristaux d'anhydride maléTque pur ; pour récupérer la totalité du produit formé, on lave à l'eau les gaz refroidis.
@
<Desc/Clms Page number 4>
EXEMPLE 4.
------------------
Diriger par heure 200 litres d'air à travers de l'aldéhyde crotonique refroidie à 0 C. L'air chargé des vapeurs de l'aldéhyde est dirigé vers 400 C sur un catalyseur forme par un mélange intime de kieselguhr, de sulfate de potasse et d'acide vanadique. On sépare 'de façon usuelle l'acide maléï- que qui se trouve dans les gaz de la réaction.
EXEMPLE 5.
------------------
Diriger par heure, vers 0 C, un courant de 150 litres d'air à travers de l'aldéhyde crotonique à 87%. On dirige en- suite l'air chargé des vapeurs d'aldéhyde crotonique sur un ca- talyseur chauffé à 310 C, préparé en imprégnant 100 cm3 de pier- re ponce granulée d'une suspension de 20 gr d'anhydride titani- que de 5 gr de molybdate d'ammonium et de 3 gr d'acide oxali- que dans 100 cm3 d'eau. On sépare de façon connue l'acide ma- léïque formé. On obtient 65 parties d'acide maléique pour 100 parties d'aldéhyde crotonique à 100%.
<Desc / Clms Page number 1>
Process for the production of maleic acid and anhydride
It has been found that the acid or maleic anhydride is easily and in good yields by contacting at an elevated temperature, generally between 200 and 500 ° C., a mixture of aldehyde or vapor vapors. crotonic acid and oxygen or gases therein, together with the catalysts used for the oxidation of organic compounds. The reaction takes place at a relatively low temperature: a good yield of malelque acid is thus obtained, for example around 250 C. One of the particular advantages of the process of the present invention consists in that the malelque acid is obtained under a very pure form and free from annoying side products.
Instead of crotonic aldehyde, aldol can also be used, which easily converts to crotonic aldehyde on heating.
<Desc / Clms Page number 2>
As suitable catalysts, mention may be made, for example, of vanadic, titanic and molybdic acids, which can be used individually, as a mixture with one another or with other catalysts such as tungstic acid and lead oxide. Titanic acid is particularly suitable, especially in admixture with the lower oxides of vanadium or molybdenum, such as originate by reduction of vanadic or molybdic acid by means of an aqueous solution of. oxalic acid. As other suitable additions, there may be mentioned zinc oxide, cerium oxide, chromium oxide, cobalt oxide, silica, etc. The process of the present invention can be carried out under any pressure.
EXAMPLE 1.
-----------------
Direct a stream of 15 liters of air per hour through crotonic aldehyde heated to 30 C; this stream is combined with another stream of air, the rate of which is 150 liters per hour, and the mixture is passed to 350 ° C. over a catalyst formed by a mixture of vanadium oxide and molybdenum oxide , obtained from 10 parts of ammonium vanadate and 5 parts of molybdic acid and fixed on granulated aluminum. By cooling the mixture ga-. zeux after it has passed over the catalyst, a good yield of very pure maleic anhydride is obtained.
By directing on the catalyst indicated above, heated to 550 C, a mixture of vapors of crotonic acid and air, obtained by passing per hour 150 liters of air over crotonic acid heated to 90 C. , maleic anhydride is also formed. When we use aldol, the. conversion into steam takes place preferably at a temperature between 80 and 90 C, by means of a current of air
<Desc / Clms Page number 3>
from 5 to 10 liters per hour only; the vapors are then mixed with a higher proportion of air before they are passed over the catalyst.
E X E M P L E 2.
EMI3.1
-------------------
Direct per hour 15 liters of air through 87% crotonic aldehyde, heated to 30 C. The air stream charged with the vapors of the aldehyde is combined with another stream of air whose rate is 220 liters per hour, and the mixture is directed to 300 C on a catalyst prepared as follows: dilute20 gr of molybdic acid, 8 gr of vanadic acid, 10 gr of titanium anhydride and 10 gr of oxalic acid in 100 cm3 of distilled water, 100 cm3 of pumice stone in grains the size of a pea are added, and the mixture is evaporated to dryness while stirring.
The gas mixture which escapes from the reaction chamber is cooled, then washed with water; 105 to 110 parts of maleic acid are thus obtained per 100 parts of 100% crotonic aldehyde; about 80% of the acid is in the anhydride state.
EXAMPLE 3.
@
Pass per hour a stream of 200 liters of air over melted crotonic acid at 90 ° C., then direct the gas mixture to 280 ° C. over a catalyst obtained from 11 g. of ammonium molybdate, 3.2 g of vanadic acid, 4 g of titanium anhydride and 4 g of oxalic acid, diluted in 100 cm3 of water and applied to 100 cm3 of granulated pumice stone. When the gases are cooled after their passage over the catalyst, crystals of pure maleic anhydride are deposited; to recover all of the product formed, the cooled gases are washed with water.
@
<Desc / Clms Page number 4>
EXAMPLE 4.
------------------
Direct per hour 200 liters of air through crotonic aldehyde cooled to 0 C. The air charged with the vapors of the aldehyde is directed to 400 C over a catalyst formed by an intimate mixture of kieselguhr, potassium sulphate and vanadic acid. The maleic acid which is present in the reaction gases is separated in the usual way.
EXAMPLE 5.
------------------
Direct per hour, towards 0 C, a flow of 150 liters of air through 87% crotonic aldehyde. The air charged with crotonic aldehyde vapors is then directed onto a catalyst heated to 310 ° C., prepared by impregnating 100 cm 3 of granulated pumice stone with a suspension of 20 g of titanium dioxide. 5 g of ammonium molybdate and 3 g of oxalic acid in 100 cm3 of water. The malleic acid formed is separated off in a known manner. 65 parts of maleic acid are obtained per 100 parts of 100% crotonic aldehyde.
Claims (1)
Publications (1)
Publication Number | Publication Date |
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BE381976A true BE381976A (en) |
Family
ID=51444
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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BE381976D BE381976A (en) |
Country Status (1)
Country | Link |
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BE (1) | BE381976A (en) |
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- BE BE381976D patent/BE381976A/fr unknown
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