Urea-SCR system, which converts nitrogen oxides to nitrogen and water in the presence of a reducing agent, usually AdBlue urea solution, is known as one of the powerful NOx reduction systems for mobile as well as stationary applications. For its consistent and reliable operation in mobile applications, such various problems as transient injection, ammonia slip, and freezing in cold weather have to be resolved. In this work, therefore, numerical study on three-dimensional unsteady heating problems were analyzed to understand the melting and heat transfer characteristics such as urea liquid volume fraction, temperature profiles and generated natural convection behavior in urea solution by using the commercial software Fluent 6.3. After validating by comparing numerical and experimental data with pure gallium melting phenomena, numerical experiment for urea melting is conducted with three different coolant heating models named CH1, 2, and 3, respectively. Finally, it can be found that the CH3 model, in which more coolant is concentrated on the lower part of the urea tank, has relatively better melting capability than others in terms of urea quantity of for start-up schedule.