We describe a simple-to-use "matrix" method for obtaining all the basic distillation configurations and additional thermally coupled configurations that separate a zeo-tropic multicomponent feed into essentially pure product streams. This provides an opportunity to rank-list the configurations for a given application subject to criteria of interest. The only information needed to generate the configurations is the number of components in the feed. We have successfully enumerated all the configurations for feeds containing up to eight components. The method can also be used to generate nondistillation and hybrid separation configurations, and even easy-to-retrofit configurations. We illustrate the use of this method by applying it to the highly energy-intensive problem of petroleum crude distillation. We have identified more than 70 new configurations that could potentially have lower heat duty than the existing configuration. A significant number of these could reduce the heat demand by nearly 50%. (C) 2009 American Institute of Chemical Engineers AIChE J, 56: 1759-1775, 2010