DE1224295B - Process for the hydroformylation of propylene - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C07c

German class: 12 ο-7/03

Number: 1224295

File number: J17832IV b / 12 ο

Filing date: March 16, 1960

Opening day: September 8, 1966

It is known to contain carbon monoxide and olefins To convert hydrogen at elevated pressure and elevated temperature to aldehydes and alcohols. This reaction is known as hydroformylation.

German Patentsohrjft 949 737 describes hydroformylation. of olefins at temperatures from 120 to 220 ° C in the presence of an aqueous cobalt sulfate solution. German patent specification 854,216 describes a similar process, the process being carried out at temperatures of 140 to 160 ⁰ C.

German Patent 869,794 describes the conversion of olefin in the oxygen-containing compounds by treating the olefins at elevated pressure and at temperatures of 50 to 25O ⁰ C and metal carbonyls, in particular in amounts stöchipmetrischen and a hydrogen containing gas.

The German patent specification 877 300 describes a process for the hydroformylation of olefins at temperatures of 80 to 200 ⁰ C, preferably 120 to 15O ⁰ C, wherein the are of the Group VIII existing catalyst in the form of a solution added of an organic compound of a metal in an organic solvent can.

The products of these known processes consist of a mixture of isomeric aldehydes and Alcohols. So if the olefin is propylene it will be a mixture of normal and isobutyraldehydes obtained, which give the corresponding alcohols on hydrogenation. Now is however normal butanol is more important in practice than isobutanol, and it is therefore essential that in the hydroformylation of propylene as high a yield as possible of normal butyraldehyde is obtained.

It is known that hydroformylation at temperatures below 100 ° C. promotes the formation of normal aldehyde, but the rate of conversion of the olefin is so slow that this process is of no practical importance. It has surprisingly been found that propylene can be hydroformylisigrt rapidly at temperatures of 110 to 13O ⁰ C to produce a high yield of normal butyraldehyde, if special conditions, the catalyst concentration and the ratio of propylene to be maintained solvent.

The invention thus relates to a process for the hydroformylation of propylene in the presence a soluble hydroformylation catalyst of Group VIII of the Periodic Table and a solution method for the hydroformylation of propylene

Applicant:

Imperial Chemical Industries Limited, London

Representative:

Dr. H. Fincke, Dipl.-Ing. H. Bohr

and Dipl.-Ing. S. Staeger, patent attorneys,

Munich 5, Müllerstr. 31

Named as inventor:
Reginald Edwin Goddard,
Geoffrey Harry Mansfield,
Norton-on-Tees, Durham (UK)

Claimed priority:

Great Britain March 18, 1959 (9353)

means at elevated pressure and elevated temperature, characterized in that the reaction at a Temperature between 110 and 130 ° C carried out, the catalyst in an amount of 0.2 to 0.8 g Metal used per 100 ml of solvent and the olefin to solvent volume ratio in the liquid Phase set to a value between 1: 1 and 5: 1 will.

The hydroformylation catalyst contains a Metal of group VIII of the periodic table, which is said to be able to react with carbon monoxide and To react hydrogen to form a metal carbonyl or metal carbonyl hydride. It is believed, that the metal carbonyl hydride is the active catalyst. The metal of group VIII can be in the hydroformylation zone are expediently introduced in the form of a salt, for example as Salt of an organic acid such as a naphthenate. The metal is preferably fed into the hydroformylation zone introduced as a preformed carbonyl or carbonyl hydride and is preferably cobalt.

It is preferred to have the hydroformylation catalyst in the reaction zone in the form of a To introduce a solution in a solvent which is liquid under the conditions of the hydroformylation. In the hydroformylation of propylene

609 659/422

it is preferred to use a solvent which under the conditions of the hydroformylation does not react or a product of hydroformylation is. Suitable solvents are saturated hydrocarbons or those obtained by hydrogenation of the product of hydroformylation and distillation the high-boiling residues obtained from the low-boiling alcohols prepared in this way.

The volume ratio of propylene to solvent in the liquid phase can expediently range from 1: 1 to 5: 1. To the in the To utilize the available space in the reaction zone as well as possible, it is desirable to use the ratio of Keep propylene to solvent as high as possible.

It is desirable that the catalyst solution be the equivalent of greater than 0.05 g of Group VIII metal per 100 ecm of solvent and preferably 0.2 to 0.8 g of metal of the VTII. Group per 100 ecm of solvent contains. It is desirable to use the more concentrated catalyst solutions in the presence of a high volume ratio from propylene to solvent use. It is very useful to use the hydroformylation process using a catalyst solution containing approximately 0.3 g of cobalt per 100 ecm of solvent and at one Carry out volume ratio of propylene to solvent in the range from 1: 1 to 3.5: 1.

The ratio of hydrogen to carbon monoxide can vary within a wide range, for example between 1: 1 and 4: 1.

The reaction pressure can expediently be between 100 and 500 at, for example between 200 and 300 at, but pressures higher than 500 at can be used. '

The product of the process according to the invention contains a mixture of isomeric aldehydes. These Aldehydes can by any of the known processes to a mixture of the corresponding Alcohols are hydrogenated.

example

The following tests were performed on the increased by the inventive control of the conditions of the hydroformylation process proportion of the obtained aldehydes of the type R-CH ₂ -CH ₂ -CHO, and / or alcohols of the type R - CH ₂ - CH ₂ - CH ₂ OH demonstrate . For comparison, test no. 6 was carried out, which is an example of the known process for the hydroformylation of propylene.

Residual oil (a high-boiling material which is produced as a post-fraction by hydrogenation and distillation of the Product of a previous experiment), which cobalt in the form of a dicobalt octacarbonyl additive Was contained, together with carbon monoxide, hydrogen and propylene under a pressure of 250 atm through a heated 6-1 pressure vessel directed. In each trial, liquid propylene was fed at a rate of 1.851 / hour. introduced into the pressure vessel. After cooling and releasing the pressure, the product was analyzed. The test results are shown in the following table:

Temperature CO + H ₂ Volume of CO Residual oil volume g Co per % Around Normal / iso- Ver rs door Volume H ₂ Residual oil 100 ecm
Residual oil change ratio
in the product search
No. ° c m ³ / hour 1 H. volume
fluid 110 1: 3 1.325 C ₃ H ₆ 0.30 70.9 4.4: 1 1 110 3.0 1: 3 0.620 1: 1.40 0.60 79 ", 6 4.2: 1 2 110 2.8 1: 2.3 0.997 1: 2.98 0.45 78.0 4.2: 1 3 120 3.7 1: 4 0.971 1: 1.72 0.31 86.9 3.7: 1 4th 130 3.4 1: 3 0.654 1: 1.76 0.63 77.6 3.8: 1 5 165 3.1 1: 3 1.346 1: 2.81 0.04 87.8 2.1: 1 6th 1: 1.37

55

Notes on the table:

1. The% conversion is the percentage of propylene, which is converted into butyraldehydes and butanols is converted.

2. The normal / iso ratio in the product is that Ratio of n-butyraldehyde and n-butanol to the corresponding iso compounds.

3. The flow rate of CO + H ₂ is expressed as the volume of gas at 20 ° C and atmospheric pressure.

A comparison of the results of tests No. 1 to 5 with the results of test No. 6 shows the considerably increased proportion of n-butyraldehyde and n-butanol that is used when carrying out the invention of the hydroformylation process is achieved.

Claims (3)

Patent claims: 1. Process for the hydroformylation of propylene in the presence of a soluble hydroformylation catalyst the VIII. group of the periodic table and a solvent at elevated pressure and temperature, characterized in that the reaction is carried out at a temperature between 110 and 130 ° C carried out, the catalyst in an amount of 0.2 to 0.8 g of metal per 100 ml of solvent is used and the olefin-solvent volume ratio in the liquid phase to a value is set between 1: 1 and 5: 1. 2. The method according to claim !, characterized in that that as a soluble hydroformylation catalyst a cobalt catalyst in the form a carbonyl, carbonyl hydride or a salt of an organic acid is used 5 6 3. The method according to claim 1 or 2, characterized in that the documents considered: characterized in that the hydroformylation German Patent Nos. 843 848, 849 737, catalyst in the form of a solution in a solution 854 216, 868 151, 869 794, 921 934, 935 844; solvent is used, which under the Asinger, chemistry and technology of the mono conditions the hydroformylation is liquid. 5 olefine (1957), pp. 657/658. 609 6S9 / 422 8.66 © Bundesdruckerei Berlin