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This paper presents optimal operational scheduling model and economic assessment of Li-ion battery energy storage systems installed in non-residential customers. The operation schedule of a BESS is determined to minimize electric bill, which is composed of demand and energy charges. Dynamic programming is introduced to solve the nonlinear optimization problem. Based on the optimal operation schedule result, the economics of a BESS are evaluated in the investor and the social perspective respectively. Calculated benefits in the investor or customer perspective are the savings of demand charge, energy charge, and related taxes. The social benefits include fuel cost savings of generating units, construction deferral effects of the generation capacity and T&D infra, and incremental CO2 emission cost impacts, etc. Case studies are applied to an large industrial customer that shows similarly repeated load patterns according to days of the week.