DE1163789B - Process for the preparation of unsaturated aliphatic aldehydes or ketones. - Google Patents
Process for the preparation of unsaturated aliphatic aldehydes or ketones.Info
- Publication number
- DE1163789B DE1163789B DE1961D0035239 DED0035239A DE1163789B DE 1163789 B DE1163789 B DE 1163789B DE 1961D0035239 DE1961D0035239 DE 1961D0035239 DE D0035239 A DED0035239 A DE D0035239A DE 1163789 B DE1163789 B DE 1163789B
- Authority
- DE
- Germany
- Prior art keywords
- acid
- mercurosulfate
- propylene
- mercury
- olefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Internat. Kl.: C 07 cBoarding school Class: C 07 c
Deutsche Kl.: 12 ο -7/03 German class: 12 ο -7/03
Nummer: 1163 789 Number: 1 163 789
Aktenzeichen: D 35239IV b /12 ο File number: D 35239 IV b / 12 ο
Anmeldetag: 24. Januar 1961 Filing date: January 24, 1961
Auslegetag: 27. Februar 1964 Opening day: February 27 , 1964
Die Erfindung betrifft die Herstellung von ungesättigten aliphatischen Aldehyden oder Ketonen.The invention relates to the production of unsaturated aliphatic aldehydes or ketones.
Die Herstellung von Acrolein durch Umsetzung von Propylen mit wäßrigem saurem Mercurisulfat wurde bereits beschrieben. In diesem Verfahren wird das Quecksilbersalz reduziert, und es ist erforderlich, eine schwierige Reoxydation des Mercurosulf ates durchzuführen, bevor es wieder verwendet werden kann. Durch die vorliegende Erfindung soll nun diese Schwierigkeit beseitigt werden. Das erfindungsgemäße Verfahren zur Herstellung von ungesättigten aliphatischen Aldehyden oder Ketonen durch Oxydation von Olefinen mittels Quecksilberverbindungen in Gegenwart von Säuren ist nun dadurch gekennzeichnet, daß man das Olefin mit einer wäßrigen Suspension von Mercurosulfat bei einer Temperatur von 50 bis 150° C umsetzt, wobei die genannte Suspension noch eine starke Säure in einer Konzentration zwischen etwa 0,1- und lOnormal und das Mercurosulfat in einem Anteil zwischen 0,1 und 100 Gewichtsprozent (berechnet als Quecksilbermetall), bezogen auf das Gewicht der Säurelösung, enthält.The production of acrolein by reacting propylene with aqueous acidic mercury sulfate has already been described. In this process the mercury salt is reduced and it is necessary to perform a difficult reoxidation of the mercurosulfate before it can be used again can. The present invention is now intended to overcome this difficulty. The inventive Process for the preparation of unsaturated aliphatic aldehydes or ketones by oxidation of olefins by means of mercury compounds in the presence of acids is now characterized by that the olefin with an aqueous suspension of mercurosulfate at a temperature converts from 50 to 150 ° C, said suspension still a strong acid in a concentration between about 0.1 and 10 normal and the mercurosulphate in a proportion between 0.1 and 100 percent by weight (calculated as mercury metal) based on the weight of the acid solution.
Das in dem erfindungsgemäßen Verfahren verwendete Olefin ist vorzugsweise ein niedriges Monoolefin mit bis zu 6 Kohlenstoffatomen, beispielsweise Propylen, Buten-(l) oder Isobuten. Die Verwendung von Propylen, das zu Acrolein umgewandelt wird, wird besonders vorgezogen.The olefin used in the process of the invention is preferably a lower monoolefin with up to 6 carbon atoms, for example propylene, butene- (I) or isobutene. The usage propylene, which is converted to acrolein, is particularly preferred.
Für die vorliegende Erfindung geeignete starke Säuren sind unter anderem Perchlorsäure, p-Toluolsulfonsäure, Methansulfonsäure und vorzugsweise Schwefelsäure.Strong acids suitable for the present invention include perchloric acid, p-toluenesulfonic acid, Methanesulfonic acid and preferably sulfuric acid.
Die Reaktion kann entweder als einstufiges oder auch als zweistufiges Verfahren durchgeführt werden. In dem zweistufigen Verfahren wird beispielsweise Propylen in einer wäßrigen Suspension des Mercurosulfates absorbiert. Jedes sich in dieser Stufe bildende metallische Quecksilber wird zweckmäßigerweise entfernt, bevor in der zweiten Stufe, die aus dem Erwärmen der Reaktionsmischung in Anwesenheit der starken Säure besteht, das hierbei entstehende Acrolein abdestilliert wird. Die Destillation kann erleichtert werden, indem Propylen oder ein inertes Gas durch die Reaktionsmischung geleitet wird. In dem einstufigen Verfahren wird Propyleln durch eine erhitzte Suspension des Mercurosulfates in Anwesenheit der starken Säure geleitet, wobei das Acrolein aus dem abströmenden Gas gewonnen wird.The reaction can be carried out either as a one-step or as a two-step process. In the two-stage process, for example, propylene is used in an aqueous suspension of the mercurosulfate absorbed. Any metallic mercury that forms in this stage is expedient removed before in the second stage resulting from heating the reaction mixture in the presence the strong acid, the resulting acrolein is distilled off. The distillation can be facilitated by bubbling propylene or an inert gas through the reaction mixture. In The one-step process is propylene by a heated suspension of the mercurosulfate in the presence the strong acid, whereby the acrolein is obtained from the outflowing gas.
Die Reaktion kann gegebenenfalls unter Druck durchgeführt werden; dies erfolgt besonders in dem einstufigen Verfahren oder in der ersten Stufe des zweistufigen Verfahrens.The reaction can optionally be carried out under pressure; this is especially done in the single-stage process or in the first stage of the two-stage process.
Verfahren zur Herstellung von ungesättigten
aliphatischen Aldehyden oder KetonenProcess for the production of unsaturated
aliphatic aldehydes or ketones
Anmelder:Applicant:
The Distillers Company Limited, EdinburghThe Distillers Company Limited, Edinburgh
(Großbritannien)(Great Britain)
Vertreter:Representative:
Dr. W. Schalk, Dipl.-Ing. P. Wirth,Dr. W. Schalk, Dipl.-Ing. P. Wirth,
Dipl.-Ing. G. E. M. DannenbergDipl.-Ing. G. E. M. Dannenberg
und Dr. V. Schmied-Kowarzik, Patentanwälte,and Dr. V. Schmied-Kowarzik, patent attorneys,
Frankfurt/M., Große Eschenheimer Str. 39Frankfurt / M., Große Eschenheimer Str. 39
Als Erfinder benannt:Named as inventor:
John Bentley Williamson, Sutton, SurreyJohn Bentley Williamson, Sutton, Surrey
(Großbritannien)(Great Britain)
Beanspruchte Priorität:Claimed priority:
Großbritannien vom 30. Januar 1960 (Nr. 3377)Great Britain January 30, 1960 (No. 3377)
Gegenüber dem bekannten Verfahren unter Verwendung von Mercurisulfat ergibt sich erfindungsgemäß der Vorteil, daß zur Wiederherstellung des Katalysators nicht die schwierige Oxydation des Mercurosulfates in das Mercurisulfat durchgeführt werden muß, sondern daß nur das Quecksilber zum Mercurosulfat oxydiert werden muß, was wesentlich einfacher durchzuführen ist.Compared to the known method using mercuric sulfate, this results according to the invention the advantage that to restore the catalyst not the difficult oxidation of the Mercurosulfates must be carried into the mercury sulfate, but that only the mercury to the Mercurosulfate must be oxidized, which is much easier to do.
Es konnte dabei nicht vorausgesehen werden, daß für die Oxydation von z. B. Propylen zu Acrolein das Mercurosulfat in gleicher Weise wirksam sein würde wie das Mercurisulfat.It could not be foreseen that for the oxidation of z. B. propylene to acrolein the mercury sulfate would be equally effective as the mercury sulfate.
Die vorliegende Erfindung wird weiterhin durch die nachfolgenden Beispiele erläutert, in denen die Gewichts- und Volumteile im gleichen Verhältnis zueinander stehen wie Kilogramm zu Liter.The present invention is further illustrated by the following examples in which the Parts by weight and volume have the same relationship to one another as kilograms to liters.
Durch eine unter Rühren gehaltene Mischung aus 25 Gewichtsteilen Mercurosulfat (Hg2SO4) und Volumteilen Wasser wurde während 5V2 Stunden Propylen geleitet. Nach Ablauf dieser Zeit wurden aus der Reaktionsmischung 2,5 Gewichsteille metallisches Quecksilber entfernt. Der Mischung wurde hierauf konzentrierte Schwefelsäure zugegeben, um eine Konzentration von etwa 2 η zu erhalten. Anschließend wurde die Mischung auf 80° CPropylene was passed through a mixture, kept with stirring, of 25 parts by weight of mercurosulfate (Hg 2 SO 4 ) and parts by volume of water. At the end of this time, 2.5 parts by weight of metallic mercury were removed from the reaction mixture. Concentrated sulfuric acid was then added to the mixture to obtain a concentration of about 2η. The mixture was then heated to 80 ° C
409 510/535409 510/535
erhitzt und mit einer Geschwindigkeit von 90 Volumteilen je Minute ein Stickstoffstrom durch die Mischung geleitet.heated and at a rate of 90 parts by volume per minute a stream of nitrogen through the Mixture headed.
Nach 5 Stunden wurden aus dem abströmenden Gas 0,25 Gewichtsteile Acrolein gewonnen und aus der Lösung weitere 1,2 Gewichtsteile metallisches Quecksilber entfernt. Das hierbei erhaltene Acrolein entsprach einer Ausbeute von 100% der Theorie, bezogen auf das Gesamtgewicht des abgesonderten metallischen Quecksilbers.After 5 hours, 0.25 parts by weight of acrolein were obtained from the outflowing gas and removed the solution removed a further 1.2 parts by weight of metallic mercury. The acrolein obtained in this way corresponded to a yield of 100% of theory, based on the total weight of the separated metallic mercury.
IOIO
Durch eine auf 95° C erhitzte und unter Rühren gehaltene Mischung aus 25 Gewichtsteilen Mercurosulfat und 100 Volumteilen 1 η-Schwefelsäure wurde Propylen mit einer Geschwindigkeit von 90 Volumteilen je Minute geleitet. Hierbei wurden aus dem abströmenden Gas innerhalb von 30 Stunden 0,28 Gewichtsteile Acrolein gewonnen.By a mixture of 25 parts by weight of mercurosulfate heated to 95 ° C. and kept with stirring and 100 parts by volume of 1η-sulfuric acid became propylene at a rate of 90 parts by volume directed per minute. In this case, the outflowing gas became within 30 hours Gained 0.28 parts by weight of acrolein.
2020th
Claims (6)
USA.-Patentschriften Nr. 2197 258, 2270 705,Considered publications:
U.S. Patents Nos. 2197 258, 2270 705,
Deutsches Patent Nr. 1 109 659.Legacy Patents Considered:
German Patent No. 1 109 659.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB3377/60A GB918186A (en) | 1960-01-30 | 1960-01-30 | Production of unsaturated aliphatic aldehydes and ketones |
Publications (1)
Publication Number | Publication Date |
---|---|
DE1163789B true DE1163789B (en) | 1964-02-27 |
Family
ID=9757172
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE1961D0035239 Pending DE1163789B (en) | 1960-01-30 | 1961-01-24 | Process for the preparation of unsaturated aliphatic aldehydes or ketones. |
Country Status (2)
Country | Link |
---|---|
DE (1) | DE1163789B (en) |
GB (1) | GB918186A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3439043A (en) * | 1964-02-17 | 1969-04-15 | Shell Oil Co | Production of unsaturated carbonylic compounds |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2197258A (en) * | 1936-01-31 | 1940-04-16 | Du Pont | Preparation of acrolein |
US2270705A (en) * | 1939-09-27 | 1942-01-20 | Acrolein Corp | Production of acrolein |
US2334091A (en) * | 1938-07-27 | 1943-11-09 | Aerolein Corp | Production of acrolein |
-
1960
- 1960-01-30 GB GB3377/60A patent/GB918186A/en not_active Expired
-
1961
- 1961-01-24 DE DE1961D0035239 patent/DE1163789B/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2197258A (en) * | 1936-01-31 | 1940-04-16 | Du Pont | Preparation of acrolein |
US2334091A (en) * | 1938-07-27 | 1943-11-09 | Aerolein Corp | Production of acrolein |
US2270705A (en) * | 1939-09-27 | 1942-01-20 | Acrolein Corp | Production of acrolein |
Also Published As
Publication number | Publication date |
---|---|
GB918186A (en) | 1963-02-13 |
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