Patent GB-689146-A (GB)
Title: Improvements in or relating to dispersion of solid cobalt catalysts
Filed: 1951-03-28
Abstract: In a continuous oxo synthesis an aqueous emulsion of an organic liquid having dispersed therein finely-divided cobalt-comprising solid is injected into the carbonylation zone.  Specified cobalt solids are ground cobalt metal cake obtained in the decobalter, the oxide, carbonate and hydroxide.  The organic liquid may be the olefine feed, bottoms from product distillations and crude aldehyde or alcohol product.  Emulsifiers may be present, the ratio of water to organic liquid being from 10/1 to 1/10 and the amount of cobalt in the emulsion from 1 to 10 per cent.  The proportion of cobalt suspended is about 0.1-0.8 per cent of the olefine feed.  In an illustration, the reaction is started with 1-3 per cent cobalt oleate based on olefine feed, the quantity of which is cut back as emulsion catalyst becomes available and is added at a 5 per cent concentration of cobalt and a rate of 0.5-1.5 lbs./barrels of olefine feed.  A gas mixture comprising 0.5-2 vols. of H2 per vol. of CO is supplied concurrently with liquid olefine and catalyst to the reactor where reaction ensues at 250-450 DEG  F. and 2500-3500 p.s.i.g., products are separated from gases and a portion of the liquid products may be returned to the reactor to aid temperature control, c.f. Specification 647,363, the remainder being treated in a decobalter by heating at 300-400 DEG  F. optionally in the presence of hydrogen, passed to a metal recovery zone, and finally hydrogenated in the usual way.  Metal and sludge from the recovery zone and decabalter, respectively, are ground with bottoms obtained in the distillation of the alcohol product, mixed with water, preferably at 50-150 DEG  F., optionally in the presence of emulsifying agents such as alkyl aryl sulphonates or polyether alcohols, to give a catalyst containing about 1-10 per cent of cobalt.  The emulsion catalyst may be used in addition to a dissolved catalyst.  When decobalting is effected with steam or water the aqueous cobalt solutions obtained may be used for forming the emulsion.  In an example a C7 fraction of polypropylene in the presence of 0.3 per cent of the following catalysts: cobalt oxide, cobalt metal, cobalt carbonate, cobalt formate and cobalt oxide emulsion is reacted with water gas containing equal amounts of H2 and CO at 350 DEG  F. and about 2700-2900 p.s.i., and the increase in reaction rate using the emulsion noted.  Specification 668,963 also is referred to.ALSO:An aqueous emulsion of a finely divided cobalt-containing solid in an organic liquid is used as catalyst in an oxo-synthesis. Specified cobalt solids are ground metal cake and sludge obtained in the decobalter, the oxide, formate, carbonate and hydroxide. The liquid may be the olefine feed, bottoms from product distillations and crude alcohol or aldehyde products. Emulsifiers, e.g. alkyl aryl sulphates or polyether alcohols, may be present.  The ratio of organic liquid to water is from 10/1 to 1/10 and the amount of cobalt in the emulsion from 1 to 10 per cent.  The proportion of cobalt suspended is about 0.1-0.8 per cent of the olefine feed.  In addition to the emulsion, catalyst may be added as a salt solution. When decobalting is effected with steam or water the aqueous cobalt solutions obtained may be used for forming the emulsion.