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The prediction and pre-evaluation of the thermal properties and combustion-related problems (e.g., emissions and ash-related problems) are critical to reducing emissions and improving combustion efficiency during the agricultural crop residues combustion process. This study integrated the higher heating value (HHV) model, specific heat model, and fuel indices as a new systematic approach to characterize the agricultural crop residues. Sixteen linear and non-linear regression models were developed from three main compositions of the ultimate analysis (e.g., C, H, and O) to predict the HHV of the agricultural crop residues. Newly developed HHV models have been validated with lower estimation errors and a higher degree of accuracy than the existing models. The specific heat of flue gas during the combustion process was estimated from the concentrations of C, H, O, S, and ash content under various excess air (EA) ratios and flue gas temperatures. The specific heat of agricultural crop residues was between 1.033 to 1.327 kJ/kg·K, while it was increased by decreasing the EA ratios and elevating the temperature of the flue gas. Combustion-related problems, namely corrosions, PM1.0 emissions, SOx, HCl, and ash-related problems were predicted using the fuel indices along with S and Cl concentrations, and ash compositions. Results showed that agricultural crop residues pose a severe corrosion risk and lower ash sintering temperature. This integrated approach can be applied to a wide range of biomass before the actual combustion process which may predict thermal-chemical properties and reduce the potential combustion-related emissions. [ABSTRACT FROM AUTHOR]