Mathematical programming model for synthesis of heat exchanger network for distillation unit is established. MINLP problem for heat exchanger network is solved by branch-bound method. Two kinds of heat exchanger network with splitting stream and without splitting stream are obtained. 142 heat exchangers, 8 coolers and 4 heaters are needed in the heat exchanger network without splitting stream. 34 heat exchangers, 8 coolers, 4 heaters, 11 splitters and 11 mixers are needed in the heat exchanger network with splitting stream. The matching situation including heat load, heat exchange area, duty of utilities, flow fraction of splitting, temperature of inlet and outlet, etc. for cold and hot streams in the heat exchanger network with splitting stream is presented in detail, Analysis the relationship between total heat exchange area, total heat load, total capital cost and annual operation cost of the heat exchanger network. Taking the number of heat exchangers and operational flexibility of heat exchange network into consideration, the heat exchanger network with splitting stream is suggested to be selected.