To address large scale industrial processes, a novel Lagrangian scheme is proposed to decompose a refinery scheduling problem with operational transitions in mode switching into a production subproblem and a blending and delivery subproblem. To accelerate the convergence of Lagrange multipliers, some auxiliary constraints are added in the blending and delivery subproblem. A speed-up scheme is presented to increase the efficiency for solving the production subproblem. An initialization scheme of Lagrange multipliers and a heuristic algorithm to find feasible solutions are designed. Computational results on three cases with different lengths of time horizons and different numbers of orders show that the proposed Lagrangian scheme is effective and efficient. (C) 2015 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.