During the storage process, liquefied natural gas (LNG) may undergo severe evaporation, stratification, and rollover in large storage tanks due to heat leakage, aging, or charging, causing major safety risks. Therefore, this article theoretically analyzes the causes and inducing factors of the LNG stratification and rollover phenomenon in the storage tank of coastal engineering. The computational fluid dynamics was used to establish a numerical model for the heat and mass transfer of LNG multicomponent materials in the imaginary layered interface of the storage tank, and the evolution process of LNG from spontaneous stratification to rollover was simulated. The accuracy of the mathematical model is verified by comparing numerical results with experimental data from open literature. The effects of the density difference between upper and lower layers, layering parameters, heat leakage parameters, and the baffles structure on the rollover process were studied. The effects of the interfacial surface variations are not included in this study. The results show that different baffle structures will form different boundary velocity fields, which will only affect the severity of the rollover, not the occurrence time. The larger the layering density difference, the earlier the rollover occurs. Under current conditions, the baffle structure that has the best suppression of rollover and the minimum boundary velocity is at 0.5 m above the stratified interface with the installation of the baffle at 5 degrees.