Abstract: The desulfurization technology during coal combustion in furnace has been a competitive choice for middle and small industrial boilers to meet the environmental protection requirements,with the advantage of low cost and convenient operation.The ordinary calcium-based sorbents such as limestone and calcium carbide residue have low desulfurization efficiency during coal combustion because of CaSO ₄ decomposition.The sulphation product BaSO ₄ which don’t decompose until 1580℃ has much better thermal stability than CaSO ₄ which rapidly decompose at about 1300℃.A new type of barium-based sorbent with high desulfurization efficiency was developed.ZCS intelligent sulfur determination analyzer was used to study sulfur capture mechanism during the high temperature combustion process of coal.In addition the dynamic sulfur capture process of the mixture of barium-based sorbent and calcium-based sorbent was studied in detail.Industrial grate furnace experiment revealed that the desulfurization efficiency of barium-based sorbents could reach 35.5%, which is higher than 13.88% of calcium-based sorbent.It implied that the desulfurization effect of barium salt was much better than calcium salt during coal combustion at about 1200～1300℃.