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United States Patent Office Patented Nov 3,773,809 United States Patent Office Patented Nov. 20, 1973 2 mononitrile to organic dinitrile contained therein is less 3,773,809 than about 0.65 and preferably about 0.3 in order that SEPARATION OF ORGANIC PHOSPHORUS COM there is formed with the hydrocarbon solvent a multi POUNDS AND THER META, COMPLEXES FROM ORGANC NTRLES IN THE HYDRO phase mixture on which this method of separation de CYANATON OF OLEFNS pends. One method for effecting this is to control the Jack William Walter, Wilmington, Del, assignor to E. level of hydrocyanation of the mononitrile. For instance, du Pont de Nemours and Company, Wilmington, Del. to achieve a mole ratio of mononitrile to dinitrile less No Drawing. Continuation-in-part of abandoned applica than about 0.65, a degree of conversion of at least about tion Ser. No. 86,587, Nov. 3, 1970. This application 60 percent would be maintained. In some instances it may June 28, 1972, Ser. No. 267,106 be desirable to conduct the hydrocyanation at a lower level int. C. C07c 121/04 O of conversion of the organic mononitrile in which case U.S. C. 260-465.8 R 13 Claims the required mole ratio of mononitrile to dinitrile in the product fluid can be effected by removing mononitrile, for example, by flash distillation. Another approach for ABSTRACT OF THE DISCLOSURE achieving the required mononitrile/dinitrile ratio is to A process for separating an organic phosphorus com 5 introduce added quantities of the dinitrile until the re pound such as a phosphite or phosphonite or a zerovalent quired ratio is reached. The separation method of this in nickel complex of the organic phosphorus compound from vention is particularly adaptable to product fluids result a product fluid containing organic nitriles produced by ing from hydrocyanation of organic mononitriles such as hydrocyanating an ethylenically unsaturated organic 3-pentenenitrile or 4-pentenenitrile. The organic dinitriles mono-nitrile such as 3-pentenenitrile through extraction 20 contained in the product fluid are typified by adiponitrile, of the product fluid with a paraffin or cycloparaffin hydro methylglutaronitrile and ethylsuccinonitrile. carbon solvent at a temperature of about 0°C. to about The organic phosphorus compounds comprise those of 100° C. to produce a multiphase mixture wherein the or the formula PZ where Z is an R or OR group, R is an ganic phosphorus compounds and their metal complexes alkyl, aryl or alkoxyaryl group having up to 18 carbon are contained predominantly in the hydrocarbon phase 25 atoms and at least one Z is OR, wherein Z may be the and the organic mono- and dinitriles and degradation same or different and may be cojoined, and zerovalent products are contained in a separate phase. nickel complexes of the formula NiL4 wherein L is a sigma-pi bonding neutral ligand represented by PZ. Hy CROSS-REFERENCE TO RELATED APPLICATIONS drocyanations with these Zerovalent complexes are car 30 ried out at temperatures in the range of -25 C. to 200 This is a continuation-in-part of my U.S. application, C., preferably in the range of 0° C. to 150° C. Pressures Ser. No. 86,587, filed Nov. 3, 1970, now abandoned. in the range of 0.05 to 100 atmospheres can be employed; BACKGROUND OF THE INVENTION a range of 0.05 to 10 atmospheres is preferred. The hy In the hydrocyanation of nonconjugated ethylenically 35 drocyanations can be carried out conveniently at atmos unsaturated organic compounds such as 3-pentenenitrile pheric pressure. to produce dinitriles such as adiponitrile or methylglu Typical organic phosphorus compounds corresponding taronitrile in the presence of certain low valent nickel to PZ include complexes as described in U.S. Pats. 3,496,215, 3,496,- 217 and 3,496,218, as well as in the removal of certain 40 undesired by-products as described in U.S. Pat. 3,564,- 040, it is frequently necessary to remove the catalyst com plex from the reaction products for recycling of the cat alyst or for purification of the reaction products. Frac and tional distillation is in general a convenient method for 45 P(OCH) (CH) effecting such separations. However, in the case of the organic phosphorus compounds as well as some of the Nickel complexes of the type NiL include organic metal complexes, the elevated temperature re Ni(P(OCH5)3)4, Ni(P(OCH)3, Ni(P(OCH5)3)4, quired for fractional distillation has an adverse effect, causing disproportionation and in some cases degradation 50 Ne(o-KX-CH), of the organic phosphorus compounds and the organic NiP(OCH5)(CHg)), NiP(OCH5)(CH3)2] metal complexes as well as isomerization of reaction and products. NiP(OCH)2(CH5)4. STATEMENT OF THE INVENTION 55 Other zerovalent nickel complexes which are useful in Accordingly, it is an object of this invention to pro hydrocyanation reactions and which can be recovered by vide an improved method for separating organic phos the process of this invention are those of the formulae phorus compounds and their zerovalent nickel complexes Ni(PZ)R2-CN and Ni(PZ)2A wherein Z is R or OR, from hydrocyanation product fluids containing organic R is an alkyl or aryl radical having up to 18 carbon atoms dinitriles as well as unreacted organic mononitriles and 60 and at least one Z is OR, and the groups are so chosen degradation products of the organic phosphorus com that the ligand has a cone angle with an average value pounds and their metal complexes. between 130 and 170; wherein A is an unsaturated or This invention resides in the discovery of a process for ganic compound containing from 2 to 20 carbon atoms separating an organic phosphorus compound or its metal and having at least one olefinic carbon-carbon double complex from a hydrocyanation product fluid containing 65 bond and wherein R is of the class consisting of 2-butenyl predominantly organic dinitrile and unreacted organic and 3-butenyl radicals. The cone angle is determined as mononitrile and degradation products of the organic phos described by C. A. Tolman, J. Am. Chem. Soc. 92, 2956 phorus compounds and their metal complexes by extract (1970). Typical trivalent phosphorus ester ligands of this ing the product fluid with a paraffin or cycloparaffin hy type include tri-o-tolylphosphite (cone angle 141), drocarbon at a temperature in the range of about 0° C. 70 phenyl di-o-tolylphosphonite (cone angle 142), and tri to about 100° C. The composition of the product fluid (2,5-xylyl)-phosphite (cone angle 144). Typical corre must be controlled so that the molar ratio of organic sponding Zerovalent nickel complexes include 3,773,809 3 4 NiP(O-o-CHCH3)3(CH3CH=CHCHCN), of lower fatty acids of from 2 to 7 carbon atoms, HPO, HPO, CFCOO, CH15OSO, SO, etc. NiIP(O-o-CHCH)3 NC(CH2)CN), Also useful as a promoter in the hydrocyanation reac tion described above are the borohydrides and organo and NiP(O-o-CHCH3)2(CH4). These zerovalent boron compounds of the formulae B(R3) and B(OR3) nickel complexes and their use in hydrocyanation reac wherein R3 is of the class consisting of hydrogen, aryl tions are described in detail in U.S. patent application radicals of from 6 to 18 carbon atoms, aryl radicals sub Ser. No. 168,352, filed Aug. 2, 1971 by L. M. King, W. stituted with groups that do not interfere such as lower C. Seidel and C. A. Tolman. Such hydrocyanations are alkyl radicals of from 1 to 7 carbon atoms and lower carried out at a temperature in the range of -50° C. to 0 alkyl radicals of from 1 to 7 carbon atoms substituted 200° C. and at a pressure in the range of about 0.05 to with a cyano radical. Among the promoters of this type about 100 atmospheres. Preferred conditions are tempera triphenyl borane is especially preferred. As indicated ture in the range of about -15° C. to about 75 C. and above, the catalyst promoter can be recovered from the pressure in the range of about 0.05 to about 10 atmos pheres. organic nitrile either for re-use in further hydrocyanation 5 or for discard. In the multiphase mixture described above, the organic The extraction process described above can be carried phosphorus compounds and their zerovalent nickel com out as a batch process or it can be done continuously. A plexes are found predominantly in the hydrocarbon sol particularly useful technique comprises a continuous vent phase. The organic mono- and dinitriles, catalyst pro countercurrent operation. moter or residue of the catalyst promoter and degraded In these operations, the ratio of organic phosphorus nickel catalyst are found predominantly in at least one 20 compound to the nitrile being extracted may range from other phase distinct from the hydrocarbon phase. The 1/1000 parts to 90/100 parts; the ratio of hydrocarbon other phase (or phases) also contains degradation prod to organic phosphorus compound may range from 2/1 ucts of the organic phosphorus compounds in sufficient parts to 100/1 parts, all parts being by weight. The ex quantity to permit an efficient purge of these compounds tractions may be carried out at atmospheric pressure or from the organic phosphorus compounds and their zero 25 at elevated pressures to avoid undue evaporation of the valent nickel complexes recovered in the hydrocarbon sol solvents. vent phase. The degradation products of the organic phos A particular advantage of the process as set forth is phorus compounds comprise those wherein the phos that it provides not only means for recovering organic phorus atom is joined directly by covalent bands to four phosphorus compounds and organic mononitrile for re other atoms or groups.
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