Polymer fractionation by continuous chromatography

A review is given of general chromatographic theory, the factors affecting the performance of chromatographi c columns, and aspects of scale-up of the chromatographic process. The theory of gel permeation chromatography (g. p. c.) is received, and the results of an experimental study to optimize the performance of an analytical g.p.c. system are reported. The design and construction of a novel sequential continuous chromatographic refining unit (SCCR3), for continuous liquid-liquid chromatography applications, is described. Counter-current operation is simulated by sequencing a system of inlet and outlet port functions around a connected series of fixed, 5.1 cm internal diameter x 70 cm long, glass columns. The number of columns may be varied, and, during this research, a series of either twenty or ten columns was used. Operation of the unit for continuous fractionation of a dextran polymer (M. W. - 30,000) by g.p.c. is reported using 200-400 µm diameter porous silica beads (Spherosil XOB07S) as packing, and distilled water for the mobile phase. The effects of feed concentration, feed flow rate, and mobile and stationary phase flow rates have been investigated, by means of both product, and on-column, concentrations and molecular weight distributions. The ability to operate the unit successfully at on-column concentrations as high as 20% w/v dextran has been demonstrated, and removal of both high and low molecular weight ends of a polymer feed distribution, to produce products meeting commercial specifications, has been achieved. Equivalent throughputs have been as high as 2.8 tonnes per annum for ten columns, based on continuous operation for 8000 hours per annum. A concentration dependence of the equilibrium distribution coefficient, KD observed during continuous fractionation studies, is related to evidence in the literature and experimental results obtained on a small-scale batch column. Theoretical treatments of the counter-current chromatographic process are outlined, and a preliminary computer simulation of the SCCR3 unit t is presented.