This paper proposes a process scheme for the recovery of 1,3-Butadiene (BD) and methyl ethyl ketone (MEK) from the dehydration products of 2,3-Butanediol (BDO). BDO is produced via the bio-fermentation of the industrial-gas wastes from the steel industry and various biomasses. The suggested process is environmentally beneficial because it can extend the feedstock rather than petroleum, and it replaces the use of the industrial-plant gas wastes. The proposed process is composed of a catalytic-dehydration reactor, a quencher, a BD-purification unit, a decanter, a water-removal column, and an MEK-purification unit. Based on the proposed scheme, the BD- and MEK-recovery rates are approximately 94% and 98%, respectively. Most of the units in the process are well developed, except for the azeotropic distillation column (ADC) that is used in the MEK-purification unit. A pilot test is also performed, and the results are compared with those of a simulation for an analysis of the viability of an ADC. Through the use of the experimental ADC, a mixture of MEK and 2-methylpropanal (2-MPA) is obtained via the removal of water. The results of the pilot test show that a water trace, MEK 84.5%, and 2-MPA 15.5% are separated to the bottom stream, which is in sound agreement with the simulation data. Furthermore, the simulated temperature profile is consistent with the experimental data with an error range of only +/- 2%. (C) 2017 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.