US 4,287,370 A · Hydroformylation process for the production of n-valeraldehyde

Abstract

n-Valeraldehyde is produced by hydroformylation of butene-1 in the presence of one or more of cis- and trans-butene-2 and iso-butylene using a rhodium complex catalyst such as HRh(CO)PPh.sub.3).sub.3. Reaction conditions include use of at least about 100 moles of free triorganophosphine per gram atom of rhodium, a temperature of about 80.degree. C. to about 130.degree. C., a total pressure of not more than about 50 kg/cm.sup.2 absolute, a partial pressure of carbon monoxide of not more than about 1.5 kg/cm.sup.2 absolute, and a partial pressure of hydrogen of from about 1.0 to about 7.5 kg/cm.sup.2 absolute. An n-/iso-ratio of 20:1 and a conversion efficiency of butene-1 to n-valeraldehyde of over 85% are possible under these conditions with essentially no resin formation despite the presence of iso-butylene. The n-/iso-valeraldehyde mixture can be aldolized and reduced without intermediate purification to give a commercially acceptable C.sub.10 -plasticizer alcohol.

Claims14

Dependent claims

A process for the production of n-valeraldehyde by selective hydroformylation of butene-1 in the presence of at least one other C.sub.4 -olefin which comprises contacting a C.sub.4 -olefin feedstock with carbon monoxide and hydrogen in a hydroformylation zone in the presence of a catalytic quantity of a rhodium complex catalyst, said C.sub.4 -olefin feedstock comprising butene-1 and at least one other C.sub.4 -olefin selected from cis-butene-2, trans-butene-2, and iso-butylene and said rhodium complex catalyst comprising rhodium in complex combination with carbon monoxide and a triorganophosphine ligand, and in the presence of at least about 100 moles of free triorganophosphine ligand per gram atom of rhodium, at a temperature in the range of from about 80.degree. C. to about 130.degree. C., and at a total pressure of not more than about 50 kg/cm.sup.2 absolute, the partial pressure of carbon monoxide being less than about 1.5 kg/cm.sup.2 absolute and the partial pressure of hydrogen being in the range of from about 1.0 to about 7.5 kg/cm.sup.2 absolute, and recovering from the hydroformylation zone unreacted C.sub.4 -olefins and n-valeraldehyde, said unreacted C.sub.4 -olefins including substantially all of said at least one other C.sub.4 -olefin present in the feedstock.

A process for the production of n-valeraldehyde by selective hydroformylation of butene-1 in the presence of at least one other C.sub.4 -olefin which comprises:

(i) providing a hydroformylation zone containing a liquid charge comprising (a) a rhodium complex catalyst wherein rhodium is in complex combination with carbon monoxide and a triorganophosphine, (b) excess free triorganophosphine in an amount of at least about 100 moles per gram atom of rhodium, (c) liquid n-valeraldehyde product, and (d) polymeric aldehyde condensation products;
(ii) feeding a liquid C.sub.4 -olefin feedstock to the hydroformylation zone, said C.sub.4 -olefin feedstock comprising butene-1 and at least one other C.sub.4 -olefin selected from cis-butene-2, trans-butene-2, and iso-butylene;
(iii) supplying make up hydrogen and carbon monoxide to the hydroformylation zone;
(iv) maintaining in the hydroformylation zone a temperature in the range of from about 80.degree. C. to about 130.degree. C., a total pressure of not more than about 50 kg/cm.sup.2 absolute, a partial pressure of butene-1 of less than about 4.0 kg/cm.sup.2 absolute, a partial pressure of carbon monoxide of less than about 1.5 kg/cm.sup.2 absolute and a partial pressure of hydrogen of from about 1.0 to about 7.5 kg/cm.sup.2 absolute;
(v) recovering from the hydroformylation zone a liquid reaction product;
(vi) reducing the pressure of the liquid reaction product;
(vii) thereafter flashing unreacted C.sub.4 -olefins and product n-valeraldehyde from the liquid reaction product, said unreacted C.sub.4 -olefins including substantially all of said at least one other C.sub.4 -olefin present in the feedstock;
(viii) recycling resulting liquid reaction residue, now depleted in the C.sub.4 -olefins and product n-valeraldehyde, to the hydroformylation zone;
(ix) condensing product n-valeraldehyde and unreacted C.sub.4 -olefins;
and
(x) recycling unreacted C.sub.4 -olefins to the hydroformylation zone.

8 more elements

Dependencies are inferred from the claim text.

Hydroformylation process for the production of n-valeraldehyde

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Hydroformylation process for the production of n-valeraldehyde

Life of this patent

Abstract

Claims14