CH642942A5 - Process for the preparation of acetonitrile - Google Patents
Process for the preparation of acetonitrile Download PDFInfo
- Publication number
- CH642942A5 CH642942A5 CH294080A CH294080A CH642942A5 CH 642942 A5 CH642942 A5 CH 642942A5 CH 294080 A CH294080 A CH 294080A CH 294080 A CH294080 A CH 294080A CH 642942 A5 CH642942 A5 CH 642942A5
- Authority
- CH
- Switzerland
- Prior art keywords
- sep
- catalyst
- paraldehyde
- ammonia
- mol
- Prior art date
Links
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 21
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229960003868 paraldehyde Drugs 0.000 claims abstract description 21
- 239000011787 zinc oxide Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000008262 pumice Substances 0.000 claims description 16
- 239000004575 stone Substances 0.000 claims description 14
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000012876 carrier material Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000012043 crude product Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 230000007306 turnover Effects 0.000 claims description 2
- 239000002912 waste gas Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The process for the preparation of acetonitrile from paraldehyde and ammonia is carried out in the presence of a catalyst containing, preferably, zinc oxide at temperatures of from 400 to 500 DEG C.
Description
**WARNUNG** Anfang DESC Feld konnte Ende CLMS uberlappen **.
PATENTANSPRÜCHE
1. Verfahren zur Herstellung von Acetonitril, dadurch gekennzeichnet, dass man Paraldehyd mit Ammoniak in Gegenwart eines Katalysators bei 400 bis 500 C umsetzt.
2. Verfahren gemäss Patentanspruch 1, dadurch gekennzeichnet, dass man pro Mol Paraldehyd 5 bis 10 Mol, vorzugsweise 6 bis 8 Mol, Ammoniak einsetzt.
3. Verfahren gemäss Patentansprüchen 1 und 2, dadurch
Es ist bekannt aus der CH-PS 339 918, aliphatische Ni trile durch Umsatz von Ammoniak mit einem aliphatischen
Alkohol oder Aldehyd bei Temperaturen zwischen 300 und
650 "C in Gegenwart eines mindestens zum Teil aus Zink oxid bestehenden Katalysators herzustellen. Versuchte man mit dieser Methode, das Acetonitril aus Acetaldehyd herzu stellen, so führte das zu Verharzungen infolge der Polymerigekennzeichnet, dass man einen Zinkoxid enthaltenden Katalysator verwendet.
4. Verfahren gemäss Patentansprüchen 1 bis 3, dadurch gekennzeichnet, dass man Zinkoxid auf Bimsstein als Katalysator verwendet.
5. Verfahren gemäss Patentansprüchen 1 bis 4, dadurch gekennzeichnet, dass man pro Liter Katalyt und Stunde einen Durchsatz von 0,4 bis 0,6 Mol Paraldehyd einhält.
sation des aus unvollständiger Reaktion des Acetaldehyds mit Ammoniak gebildeten Imins.
Aufgabe der Erfindung ist es, diesen Nachteil zu vermeiden und ein Herstellungsverfahren für Acetonitril vorzuschlagen, das einen optimalen Umsatz gewährt.
Erfindungsgemäss wurde das durch ein Verfahren gemäss Patentanspruch 1 erreicht.
EMI1.1
<tb>
Die <SEP> Reaktion <SEP> folgt <SEP> der <SEP> Gleichung: <SEP> CH <SEP> 3
<tb> <SEP> o- <SEP> CH3
<tb> <SEP> CH3 <SEP> -/o <SEP> + <SEP> 3NH3 <SEP> - <SEP> > <SEP> 3C2H3N <SEP> + <SEP> 3H20 <SEP> + <SEP> 3H2
<tb> <SEP> 0n
<tb> <SEP> CH3
<tb>
In der Praxis wird man zweckmässig pro Mol Paraldehyd 5 bis 10 Mol, vorzugsweise 6 bis 8 Mol, Ammoniak anwenden.
Der Katalysator kann ganz aus Zinkoxid, aufgetragen auf ein Trägermaterial, bestehen. Es ist aber auch möglich, dem Katalysator weitere Bestandteile, wie Zinkpulver, Zinkamalgan, Quecksilber oder Quecksilberoxid, beizumischen.
Als Trägermaterial für den Katalysator eignen sich beispielsweise Bimsstein, Aluminium- oder Siliciumoxid. Der Bimsstein, das Aluminium- oder Siliciumoxid wird vorteilhaft in Form von Körnern oder Ringen mit einem Durchmesser von 3 bis 20 mm angewendet.
In einer vorzugsweisen Ausführungsform verwendet man als Katalysator Zinkoxid auf Bimsstein, wobei das Verhältnis von Träger zu aktiven Bestandteilen pro kg Bimsstein 0,2 bis 0,4 kg Zinkoxid beträgt.
Das Verfahren wird derart ausgeführt, dass man Paraldehyd und Ammoniak zusammenführt, in einem Vorerhitzer verdampft und über den Katalysator leitet. Der Katalysator kann in ein Reaktionsrohr gefüllt sein, das in einem Salzbad angeordnet ist.
Eine Verweilzeit von 30 bis 60 Sekunden, bezogen auf das Normalvolumen des Gasgemisches und den leeren Katalytraum, ist für eine vollständige Reaktion ausreichend.
Dabei soll pro Liter Katalyt und Stunde ein Durchsatz von 0,4 bis 0,6 Mol Paraldehyd eingehalten werden. Die bevorzugte Reaktionstemperatur liegt bei 460 bis 490 -C.
Die Reaktionsprodukte werden entweder kondensiert oder in Wasser absorbiert; der gebildete Wasserstoff kann als Abgas weggeführt werden.
Der Katalysator hat eine Standzeit von über 150 Stunden und kann leicht durch Überleiten von Luft bei Reaktionstemperatur regeneriert werden.
Beispiele
1. 141 g (1,07 Mol) Paraldehyd und 144 g (8,5 Mol) Ammoniak in Dampfform wurden bei 480 0C über einen mit Zinkoxid belegten Träger aus Bimsstein geleitet. Die Verweilzeit bezüglich Normalbedingungen betrug 47 Sekunden.
Durch Kondensieren erhielt man 216 g einer 56%igen Roh Acetonitrillösung, entsprechend einer Rohausbeute von 92%. Neben Acetonitril enthielt das Rohprodukt hauptsächlich Wasser und Ammoniak.
2. 143 g (1,08 Mol) Paraldehyd und 143 g (8,4 Mol) Ammoniak wurden während 7 Y2 Stunden bei 480 "C über einen aus 200 g Zinkoxid pro Liter Reaktionsvolumen auf einem Träger aus Bimsstein bestehenden Katalysator geleitet. Bei vollständigem Umsatz betrug die Ausbeute 86%.
3. 167 g (1,26 Mol) Paraldehyd wurden zusammen mit 130 g (7,6 Mol) dampfförmigem Ammoniak über eine Schicht von Zinkoxid enthaltenden Bimsstein geleitet. Der spezifische Paraldehyddurchsatz betrug 0,5 Mol/l Kat.h.
Dabei konnte Acetonitril in einer Ausbeute von 87% erhalten werden.
** WARNING ** beginning of DESC field could overlap end of CLMS **.
PATENT CLAIMS
1. A process for the preparation of acetonitrile, characterized in that paraldehyde is reacted with ammonia in the presence of a catalyst at 400 to 500 ° C.
2. The method according to claim 1, characterized in that 5 to 10 moles, preferably 6 to 8 moles, of ammonia are used per mole of paraldehyde.
3. The method according to claims 1 and 2, characterized
It is known from CH-PS 339 918, aliphatic Ni trile by conversion of ammonia with an aliphatic
Alcohol or aldehyde at temperatures between 300 and
To produce 650 "C in the presence of a catalyst consisting at least partially of zinc oxide. Attempting to use this method to prepare the acetonitrile from acetaldehyde led to resinification due to the polymer, which indicates that a catalyst containing zinc oxide is used.
4. The method according to claims 1 to 3, characterized in that zinc oxide on pumice is used as a catalyst.
5. The method according to claims 1 to 4, characterized in that a throughput of 0.4 to 0.6 mol of paraldehyde is maintained per liter of catalyst.
sation of the imine formed from incomplete reaction of acetaldehyde with ammonia.
The object of the invention is to avoid this disadvantage and to propose a production process for acetonitrile which ensures optimal conversion.
According to the invention this was achieved by a method according to claim 1.
EMI1.1
<tb>
The <SEP> reaction <SEP> follows <SEP> from the <SEP> equation: <SEP> CH <SEP> 3
<tb> <SEP> o- <SEP> CH3
<tb> <SEP> CH3 <SEP> - / o <SEP> + <SEP> 3NH3 <SEP> - <SEP>> <SEP> 3C2H3N <SEP> + <SEP> 3H20 <SEP> + <SEP> 3H2
<tb> <SEP> 0n
<tb> <SEP> CH3
<tb>
In practice, 5 to 10 moles, preferably 6 to 8 moles, of ammonia are expediently used per mole of paraldehyde.
The catalyst can consist entirely of zinc oxide, applied to a support material. However, it is also possible to add further constituents, such as zinc powder, zinc amalgan, mercury or mercury oxide, to the catalyst.
Pumice stone, aluminum oxide or silicon oxide, for example, are suitable as carrier material for the catalyst. The pumice stone, the aluminum or silicon oxide is advantageously used in the form of grains or rings with a diameter of 3 to 20 mm.
In a preferred embodiment, zinc oxide on pumice stone is used as catalyst, the ratio of carrier to active components per kg of pumice stone being 0.2 to 0.4 kg of zinc oxide.
The process is carried out by combining paraldehyde and ammonia, evaporating them in a preheater and passing them over the catalyst. The catalyst can be placed in a reaction tube placed in a salt bath.
A residence time of 30 to 60 seconds, based on the normal volume of the gas mixture and the empty catalytic space, is sufficient for a complete reaction.
A throughput of 0.4 to 0.6 mol of paraldehyde should be maintained per liter of catalytic agent per hour. The preferred reaction temperature is 460 to 490 -C.
The reaction products are either condensed or absorbed in water; the hydrogen formed can be carried away as waste gas.
The catalyst has a service life of over 150 hours and can easily be regenerated by passing air over it at the reaction temperature.
Examples
1. 141 g (1.07 mol) of paraldehyde and 144 g (8.5 mol) of ammonia in vapor form were passed at 480 ° C. over a pumice stone support covered with zinc oxide. The residence time under normal conditions was 47 seconds.
Condensation gave 216 g of a 56% crude acetonitrile solution, corresponding to a crude yield of 92%. In addition to acetonitrile, the crude product mainly contained water and ammonia.
2. 143 g (1.08 mol) of paraldehyde and 143 g (8.4 mol) of ammonia were passed for 7 Y2 hours at 480 ° C. over a catalyst consisting of 200 g of zinc oxide per liter of reaction volume on a pumice stone support Turnover, the yield was 86%.
3. 167 g (1.26 mol) of paraldehyde together with 130 g (7.6 mol) of vaporous ammonia were passed over a layer of pumice stone containing zinc oxide. The specific paraldehyde throughput was 0.5 mol / l cat.h.
Acetonitrile was obtained in a yield of 87%.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH294080A CH642942A5 (en) | 1980-04-16 | 1980-04-16 | Process for the preparation of acetonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH294080A CH642942A5 (en) | 1980-04-16 | 1980-04-16 | Process for the preparation of acetonitrile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH642942A5 true CH642942A5 (en) | 1984-05-15 |
Family
ID=4245054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH294080A CH642942A5 (en) | 1980-04-16 | 1980-04-16 | Process for the preparation of acetonitrile |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH642942A5 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000073261A1 (en) * | 1999-05-27 | 2000-12-07 | The Standard Oil Company | Ammoxidation of a mixture of ketones to acetonitrile and hydrogen cyanide |
-
1980
- 1980-04-16 CH CH294080A patent/CH642942A5/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000073261A1 (en) * | 1999-05-27 | 2000-12-07 | The Standard Oil Company | Ammoxidation of a mixture of ketones to acetonitrile and hydrogen cyanide |
| US6413485B2 (en) | 1999-05-27 | 2002-07-02 | The Standard Oil Company | Ammoxidation of a mixture of ketones to acetonitrile and HCN |
| EP1520852A3 (en) * | 1999-05-27 | 2005-09-21 | The Standard Oil Company | Ammoxidation of a mixture of ketones to acetonitrile and hydrogen cyanide |
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| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased | ||
| PL | Patent ceased |