Patent GB-1266187-A (GB)
IPC: C07C209/18
Filed: 1969-07-09
Abstract: 1,266,187. Recovering aniline from phenolaniline mixtures. HALCON INTERNATIONAL Inc. 9 July, 1969 [11 July, 1968], No. 34651/69. Heading C2C. The invention relates to a process for recovering high purity aniline from a mixture consisting essentially of aniline and phenol and containing at least one mole of aniline per mole of phenol which comprises fractionally distilling the mixture in a distillation zone having an overhead maintained at a pressure less than about 600 mm. Hg to obtain an overhead product comprising a high purity aniline stream. The invention also relates to a process for recovering high purity aniline from a mixture consisting essentially of aniline, phenol and water and containing at least one mole of aniline per mole of phenol and not more than 70 mole per cent of water, which process comprises the steps of: (a) fractionally distilling the mixture in a first distillation zone to form a first overhead product containing aniline and substantially all the water and a first bottoms product, which is an essentially water-free mixture of phenol and aniline containing more than one mole of aniline per mole of phenol; and, (b) fractionally distilling the first bottoms product in a second distillation zone, the pressure in the overhead of the second distillation zone being less than 600 mm. Hg, to form a second overhead product and a second bottoms product, the second overhead product being a high purity aniline stream and the second bottoms product being a mixture of aniline and phenol. The invention is described in conjunction with a phenol amination unit according to the flow diagram in which fresh phenol is fed to amination reactor 10 containing a suitable catalyst via conduit 11 and ammonia (via conduit 12) and a recycle stream containing both phenol and aniline (via conduit 13), whereby aniline is formed and the reactor conditions are controlled to give an effluent containing more than 1 mole of aniline per mole of phenol. The reaction products are withdrawn from reactor 10 via conduit 14 and are fed to a distillation column 20 to strip unreacted ammonia from the amination effluent which is withdrawn from the stripper via conduit 12, compressed, if necessary, and admixed with fresh ammonia introduced to the system via conduit 15 and finally recycled to the amination reactor. The reaction products, now essentially free of ammonia, are withdrawn from stripper 20 via conduit 21 and introduced to a fractional distillation tower 30 adapted to give an overhead product which is essentially the aniline-water azeotrope and a bottoms which is an essentially water-free mixture of phenol and aniline. The overhead vapour is withdrawn from drying column 30 via conduit 31, condensed in a heat exchanger 32 and passes to distillate drum 34 via conduit 33. Two liquid phases are formed in heat exchanger 32 and are separated one from the other under the influence of gravity in distillate drum 34, the aniline being withdrawn via conduit 35, and returned as reflux to drying column 30. Water rises, overflows weir 36 within distillate drum 34 and is withdrawn from the distillate drum via conduit 37. The essentially water-free phenolaniline mixture is withdrawn from the bottom of column 30 via conduit 38 and is fed to the phenol-aniline separation column 40 maintained at a pressure below about 600 mm Hg. The overhead product of this column is a highpurity aniline stream which can be used as such or, if desired; subjected to further purification. This stream is withdrawn from column 40 via conduit 41, is condensed in heat exchanger 42 and is then divided into two streams. A portion is returned to column 40 via conduit 43 as reflux, the balance is the net aniline product of the process and is withdrawn from the system via conduit 44. The phenol-aniline azeotrope being less volatile than aniline itself, concentrates in a lower portion of column 40 and is withdrawn therefrom via conduit 45, communicating with conduit 13 and hence is recycled to the amination reactor 10. Specified examples are given.