Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2001-02-07
2003-11-04
Richter, Johann (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S454000, C568S455000, C564S132000, C564S396000, C564S397000, C564S398000
Reexamination Certificate
active
06642420
ABSTRACT:
The present invention relates to a process for the preparation of aldehydes and/or alcohols or, if required, amines by reacting olefins with carbon monoxide and hydrogen in the presence or absence of ammonia or a primary or secondary amine and in the presence of a catalyst which is homogeneously soluble in the reaction medium and contains at least one element selected from cobalt, rhodium or ruthenium in the presence or absence of a phosphorus-, arsenic-, antimony- or nitrogen-containing ligand at elevated temperatures and at superatmospheric pressure with the use of a jet loop reactor.
About 7 million metric tonnes of various products are produced annually worldwide by the hydroformylation of olefins. These are aldehydes, alcohols or amines. Aldehydes are produced essentially by the hydroformylation of olefins with cobalt carbonyl compounds or rhodium carbonyl or ruthenium carbonyl complexes which are homogeneously soluble in the reaction medium, as a rule rhodium carbonyl complexes whose reactivity and selectivity have been modified with a phosphorus-, arsenic-, antimony- or nitrogen-containing ligand.
Hydroformylation is understood as meaning the reaction of olefins with H
2
/CO mixtures, generally referred to as synthesis gas, to give aldehydes according to equation (1)
in the presence of a catalyst from subgroup VIII of the Periodic Table of Elements. Furthermore, the hydroformylation under hydrogenating conditions, in which the aldehyde formed in the hydroformylation step is hydrogenated in situ in the hydroformylation reactor by the hydroformylation catalyst to give the corresponding alcohol, and the hydroformylation under aminating conditions, can be assigned to the area of hydroformylation reactions. Although it is also possible to use heterogeneous hydroformylation catalysts, the use of complexes of these elements which are homogeneously soluble in the hydroformylation medium has become established in the industrial application of the hydroformylation reaction. Usually, cobalt carbonyl, rhodium carbonyl, palladium carbonyl or ruthenium carbonyl compounds are used, these compounds being preferred with respect to their reactivity and chemoselectivity as a result of complexing with phosphorus-, arsenic-, antimony- or nitrogen-containing ligands.
The hydroformylation is usually carried out at elevated temperatures, and the preferred temperature ranges may vary depending on the type of hydroformylation catalyst used. Depending on the hydroformylation catalyst used and on the pressure range in which it is preferably employed in industry, a distinction is generally made between three types of hydroformylation, namely high-pressure hydroformylation, which is carried out at in general from 140 to 200° C. and from 100 to 600 bar, medium-pressure hydroformylation, which is effected in general at from 120 to 180° C. and from 30 to 100 bar, and low-pressure hydroformylation, in which temperatures at from 60 to 130° C. and a pressure of 1 to 30 bar are generally used.
In general, different catalysts are preferably used for these different hydroformylation processes, namely, carbonyl compounds or hydrocarbonyl compounds, preferably of cobalt or rhodium, which have not been modified with additional organic ligands and form from readily obtainable precursor compounds under the hydroformylation conditions, in the high-pressure process under the reaction conditions used, cobalt carbonyl complexes modified with phosphorus-containing ligands, in particular phosphine ligands, in the medium-pressure hydroformylation and preferably rhodium carbonyl complexes having preferably phosphorus-containing ligands, in particular having phosphine or phosphite ligands, in the low-pressure formylation [sic].
The individual catalysts used in the various hydroformylation processes differ not only in their hydroformulation activity but also in their chemoselectivity, i.e. in their property of preferentially forming a specific hydroformylation product from among the isomeric hydroformylation products shown in equation (1) and in their property of having, in addition to the hydroformylation activity, also further catalytic activities which can be more or less desirable depending on the olefin to be hydroformylated and on the desired hydroformylation product.
Thus, many of the known hydroformylation catalysts additionally have hydrogenation activity which, depending on the reaction conditions used, is not inconsiderable, and possess said activity both for C—C double bonds and C—O double bonds of the carbonyl group. While the secondary reaction of the C—O double bond is as a rule undesired since it leads to the formation of low-quality paraffins, the hydrogenation of the carbonyl groups of the aldehydes formed in the course of the hydroformylation to give the relevant alcohols may be entirely desirable since it dispenses with an additional hydrogenation stage which may be required. Such hydrogenation activity of the hydroformylation catalysts is also desired, for example, in the hydroformylation of olefins under aminating conditions, the imine or enamine formed from the resulting aldehyde or a primary or secondary amine present in the reaction medium being hydrogenated in situ to the desired amine.
Another secondary catalytic activity of some hydroformylation catalysts is the isomerization of double bonds, for example of olefins having internal double bonds, to &agr;-olefins, and vice versa.
Cobalt carbonyl complexes modified with phosphorus-containing ligands not only have, for example, hydroformylation activity but are additionally very effective as hydrogenation catalysts, and, depending on the CO/H
2
ratio employed in the synthesis gas used for the hydroformylation, the aldehydes formed in the hydroformylation of the olefins with such cobalt catalysts are therefore completely or partly hydrogenated to the corresponding alcohols, so that alcohols or aldehyde/alcohol mixtures are formed, depending on the reaction conditions used (cf. B. Cornils in J. Falbe, New Syntheses with Carbon Monoxide, Springer Verlag, Berlin [1980] page 1-181)
The degree of these secondary activities of the hydroformylation catalysts can be influenced in the desired manner in some cases by establishing specific hydroformylation conditions in the reaction medium. However, often only small deviations from the process parameters optimized for the respective starting olefin and the desired hydroformylation product can lead to the formation of considerable amounts of undesired secondary products, and establishing virtually identical process parameters over the volume of the entire reaction liquid in the hydroformylation reactor may therefore be of considerable importance for the cost-efficiency of the process. Owing to their special process engineering aspects, this is true in particular for medium-pressure and low-pressure hydroformylation processes, the improvement of which is the subject of the present invention.
In the hydroformylation of, for example, an &agr;-olefin, straight-chain aldehydes, i.e. n-aldehydes, or branched aldehydes, i.e. isoaldehydes, may be formed, depending on which carbon atom of the olefinic double bond is involved in the addition reaction with the carbon monoxide (cf. Equation 1). For example, n-butylaldehyde and isobutylaldehyde are formed in the hydroformylation of propene. The commercial demand for the respective n- and iso-products obtained in the hydroformylation of specific olefins differs. Attempts are therefore made to produce these isomeric aldehydes in a specific n/iso ratio which corresponds to the demand for the individual isomers. The n/iso ratio can be influenced to a certain extent by establishing specific reaction parameters in the hydroformylation reactor.
In general, in the hydroformylation of olefins with the aid of ligand-modified homogeneous catalysts, it is advantageous to establish an optimum concentration of hydrogen and carbon monoxide dissolved in the liquid reaction medium, in particular the concentration of dissolved carbon monoxide, also abbreviated to [
Paciello Rocco
Ulonska Armin
Zehner Peter
Keil & Weinkauf
Richter Johann
Witherspoon Sikarl A.
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