Patent GB-704449-A (GB)
Title: Improvements in or relating to the production of oxygenated organic compounds from hydrocarbon containing feedstocks and recovery of toluene therefrom
IPC: C07C45/50
Filed: 1950-07-04
Abstract: Plasticizers, especially for polyvinyl chloride, comprise esters, preferably with dibasic acids such as phthalic, adipic, sebacic, and pimelic acids, of alcohols obtained by reacting a toluene-containing gasoline cut, obtained by the catalytic cracking of a petroleum distillate, with carbon monoxide and hydrogen under the conditions of the OXO synthesis in the presence of a catalyst comprising a cobalt carbonyl (including carbonyl hydrides) and hydrogenating at least part of the product to form alcohols, the hydrogenation being carried out in the presence of toluene unchanged in the synthesis reaction, and then separating the toluene from the alcohols (see Group IV b).ALSO:A process for the production, from catalytically cracked gasoline, of alcohols suitable for use in the formation of plasticizers, with recovery of toluene, comprises reacting a toluene-containing gasoline cut, obtained by the catalytic cracking of a petroleum distillate, with carbon monoxide and hydrogen under the conditions of the OXO synthesis in the presence of a catalyst comprising a cobalt carbonyl (including carbonyl hydrides) the reaction being carried out in a synthesis zone operated without the introduction, before or during the reaction of cobalt metal or a cobalt compound in the solid phase, hydrogenating the product or a part thereof comprising aldehydes to form alcohols, the hydrogenation being carried out in the presence of toluene unchanged in the synthesis reaction, and then separating said toluene from the alcohols.  Suitable cracked gasoline fractions include the products of cracking gas oil or wax-containing fractions, e.g. a wax distillate or slack wax fraction and the gasoline fraction employed is preferably one which boils within the range 90 DEG -115 DEG C. The OXO synthesis is preferably operated at 100 DEG C.-180 DEG C. and at a pressure of at least 50 atmospheres, e.g. 50-250 atmospheres and particularly at 100-200 atmospheres.  Any cobalt carbonyl present in the OXO synthesis product is decomposed thermally in the presence or absence of a support material and the product freed from cobalt carbonyl may then be fractionated for removal of olefins either in the presence or absence of the cobalt metal or solid cobalt compounds produced by carbonyl decomposition.  The hydrogenation may be carried out on a metallic catalyst, such as nickel or cobalt usually supported on diatomaceous earth, at temperatures up to about 200 DEG C. and pressures up to about 200 atmospheres or more, or on copper-containing catalysts at about atmospheric pressure.  Toluene may be separated from the hydrogenation product by extractive distillation or solvent extraction.  The cracked gasoline fraction submitted to the OXO synthesis should preferably have a sulphur content less than 0.02 per cent. by weight.  The alcohol products may be esterified, preferably with dibasic acids such as phthalic, adipic, sebacic, or pimeltic acids, to yield plasticizers.  The esterification may be effected with phthalic anhydride in the presence of an acid catalyst, e.g. sulphuric acid, using excess alcohol; or by an interchange reaction with dimethyl phthalate. Conditions for the production of the cobalt carbonyl catalysts and for the operation of the OXO synthesis, product separation, and recovery stages may be as described in Specifications 702,191, 702,192, 702,195, 702,196, 702,197, 702,203, 702,204, 702,221, 702,222, 702,241 and 702,242. Specification 678,926 also is referred to.  The Provisional Specification includes an example wherein a gasoline cut having a boiling range of 70-120 DEG C. and containing by weight 19 per cent. olefin (estimated as C7), 14 per cent. toluene and 2 per cent. benzine, is submitted to the OXO synthesis reaction in the presence of water gas using cobalt carbonyl dissolved in the feedstock as catalyst.  The bulk of the hydrocarbon is removed from the reaction products by fractionation and the residue comprising the aldehyde product and hydrocarbons is then hydrogenated with Raney nickel as catalyst.  The hydrocarbons are removed from the produced alcohols by distillation and are combined with the hydrocarbons recovered by distillation of the aldehyde product and blended into gasoline from which the initial feed is fractionated.