Procedure for the recovery of cobalt and organic Phosphinen, which do not form water-soluble salts, from distillation residues of the Oxo synthesis

The subject of the invention is a procedure for the recovery of cobalt and organic Phosphinen, which do not form water-soluble salts, from DestRlafionsrückständen of the Oxo Synthase, which enthaken with such organic Phosphinan modified Kobaltcarbonylkomplexe. The Katalysatorbestandtefle contained in the Oxo Reakfionsprodukten must wiedergewormen to become, on the one hand thereby it not be lost, on the other hand because they disturb the Welterverarbeitung of the Oxo Reaktionsprodukte. Well-known methods are e.g. the thermal decomposition of Carbonylkomplexen, whereby the catalyst metal is separated firmly. In another procedure the Oxo-Rea_kfionsprodukt in presence of aqueous acids with Oxydationsrnitteln is bahmldelt, whereby cobalt is won as wö serige Salztösung. Both procedures cannot be used, as soon as beside the Schwermetallcarbonylen Moditqzlerungsmittel, like Phosphine, are contained. From the USA patent specification Nr.3, 4! 8,35! a procedure is well-known, with that phosphimnodifizierte Metal! carbony omplexe into an insoluble compound to be transferred and from the Oxo Reaktionsprodukt be separated in such a way. The procedure has the disadvantage that does not succeed in this way, develops for Phosphinoxyde, which during the Oxo reaction from the Phosphinen, to separate. The technical task was posed, to Kobak and organic Phosphine, which do not form water-soluble salts, from distillation residues of the Oxo synthesis voilst ndig vfiederzugewinnen, whereby moose timely Phosphinoxyde are separated. It was now found that one recovers cobalt and organic Phosphlne, which do not form water-soluble salts from DestiUatlonsrückständen of the Oxo synthesis, which receive with such organic Phosphlnen of modified Kobaltcarbonylkomplexe more favourably than so far, if one treats the Desfillationsrückstände under exclusion of molecular oxygen at increased temperature with aqueous solutions not oxidizing mineral acids, which separates mixture into an aqueous and an organic phase, from the aqueous phase the cobalt a) contained in it by treating with alkalis as hydroxide ausf'älk or b) as lipoidlös! iches salt with hydrocarbons or higher A!! mnolen extracted and from the organic phase the organic Phosphlne mentioned through £ral fionierte Desti! lation abtrem1 t. The new procedure has the advantage that cobalt and organic Phosphine are recovered in a simple manner, whereby the not desired Phosphinoxyde is separated. Preferential Destillatinnsrückstände of the Oxo synthesis is such, which one receives after Abdestillieren of the aldehydes and alcohols from Oxo Reaktionsprodukten, which became to receive by Hydroformylieren from Olefinen with 3 to 20 carbon atoms with Carbon monoxide and Wasserstoff at temperatures from 60 to 220°C and under pressures from 20 to 700 in presence of cobalt Carbonylkomplexen. They essentially consist of acetals and esters of the appropriate aldehydes and A! kohole. The distillation residues contain generally 0.4 to 2 Gew. - % cobalt in the form of Carbonylkomp! exen and 0.4 to 4 Gew. - % phosphorus in the form of organic Phosphinen in particular terfi organic Phosphinen and Phosphlnoxyden ren. Preferred suitable DestiUafionsrückstände contains organic Phosphine, which Kol denstoffatomen long alkyl groups, preferably with altogether at least 20, when Substituentea have, e.g. Trioetylphosphin, Tridecylphosptün, Dirnethy! - alky [- (Czz Czs) - phosphJn. In other preferential Phosphinen an alkyl group can have also a Carbalkoxygmppe mi 7 to 20 carbon atoms than Subsdtuenten, e.g. Decylester of the Dimethy! - (10 carboxydecyl) phosphins. Whether the appropriate organic Phosphine does not form water-soluble salts, is easy in each case by a simple attempt to determine. The distillation residues are e.g. treated under exclusion of molecular oxygen, air, at increased temperature with aqueous solutions not oxidizing mineral acids. One favourably leads the treatment at temperatures from 80 to! 20°C, in particular 95 to 105°C, through. Preferential one, not oxidizing mineral acids are sulfuric acid, S hydrochloric acid or phosphoric acid. Completely particularly hydrochloric acid proved as suitably. One turns at least sovie favourably! at mineral acids mentioned, like on for the education Kobaltund Phosphinsalze necessarily is. Generally one uses dle mineral acids in 10 to gew. - %iger aqueous solution. The treatment takes place in usual way, which ensures a good Durchmisehung. In such a way received mixture separated into an aqueous and an organic phase, e.g. by Dekantation. The organic phase with a fresh quantity of aqueous solutions becomes favourable not oxidizing mineral acids nachbehandeR. From in such a way received aqueous phase ward cobalt by treating with alkalis, e.g. aqueous solutions of hydroxides of the first and second Hanptgruppe of the periodic system, in particular Natronund potash-long, when hydroxide ausgefänt. It understands itself that one at least so much AlkalJ! eye to use must, so that the not oxidizing Minemlsäure contained in the aqueous phase is neutralized and the contained cobalt quantity in its hydroxide is äbergef'ührt. Another possibility of winning the cobalt from the aqueous solution consists of that one extracts the cobalt into a lipoidlösliches salt transferred and this with hydrocarbons or higher Alkanolen. Generally one leads clie cobalt salts contained in the aqueous solution by addition of fatty acids, in particular such with 6 to! 8 carbon atoms, into llpoidlösllche salts over; appropriately one uses 1 to 1.5 mol fatty acid per atomic gram cobalt. One keeps preferably a pH value from 6 to 9, in particular from 7 to 8. The attitude of the pH value takes place in usual way with Alkalioder alkaline-earth caustic solution. When one uses extracting agents liquid hydrocarbons, in particular the Olefme, which are used with the respective Oxo synthesis. Higher Alkanole, which is likewise suitable for the Extrakfion, has in particular 7 to 11 carbon atoms. Those alcohols, which result with the respective Oxo synthesis as product, are particularly suitable. The organic Phosphine contained in the organic phase is separated, after they were e.g. set appropriately by treating with at least the äqnivalenten quantity of alkalis alkali hydroxide or carbonate solutions from the Phosphoniumsalzen free, by fractionated distillation in usual way, whereby the organic Phosphine mentioned will keep use pure as such and again as modifying agents to find to be able. The procedure after the invention becomes the recovery of Kobak with Phosphinen, which are used as catalysts with the Oxo synthesis. The procedure after the invention is illustrated in the following examples. B e i s p i el i: 675 g DestillaUonsrückstand from the Hydroformylierung of a Cs-C10 - Olefingemi, which contains 5.23 g Kobak as Carbonylkomplex and 8.99 g phosphorus in the form of Trioctylphosphin and its Phosphinoxyd, 2 h with 100°C with 200 ml 17 become gew. under air exclusion - %iger hydrochloric acid intimately mixes. Subsequently, the organic and the aqueous phase are from each other separated and the organic phase is washed neutrally with 200 ml 5 of gew.o%iger sodium carbonate solution. In the organic phase analytically 5.5 g trivalent phosphorus are determined. By fractionated distillation of the arrears one receives with 165 to 175°C and 0.15 mm Hg a parliamentary group from 89 g, which Trioctylphosphin contains 51 g, corresponds to 78% of the total quantity at trivalent phosphorus. The aqueous phase is stopped with 20 gew. - %iger caustic soda solution to a pH value of 9, whereby cobalt fails as hydroxide. One receives 9.6 g cobalt hydroxide, which corresponds to a content of 5,12 g cobalt and thus 98% of the originally received cobalt quantity. B e i s p i e 1 2 • 150 g of katalysatorhalfigen arrears from oxidizing of Octen-1, which contains 1.2 g cobalt as Carbonylkomplex and 1,9g phosphorus in the form of Dimethyleicosylphosphin and its Phosphinoxyd, become under air exclusion 2 h long with 100°C with 50 ml 17 gew. - %iger hydrochloric acid intimately mixes. Subsequently, the organic and aqueous phase are separated and washed neutrally the organic phase with 60 ml 5% sodium carbonate solution. In the organic phase by gas chromatography 1.1 g trivalent phosphorus are determined. By fractionated distillation of the arrears one receives 16 g of a parliamentary group turning into with 195 to 205°/0,2 mm Hg, which contains 1.0 g trivalent phosphorus or about 11 g Dimethylenoxylphosphor after titration. Those are 91% of the total quantity at trivalent phosphorus. The aqueous phase is over-laminated with 50 g Octen, shifted with 7 g ethyl hexane acid and adjusted with caustic soda solution to pH 8. The Octenschicht colors itself rapidly low blue with mixing. In the Octenschicht by titration 1.1 g cobalt (92% of the original arrears correspond) are found. This solution is used immediately again for the Hydroforraylierung.