Efficient utilization of greenhouse gas in a gas-to-liquids process combined with carbon dioxide reforming of methane.

A process model for a gas-to-liquids (GTL) process mainly producing Fischer-Tropsch (FT) synthetic oils has been developed to assess the effects of reforming methods, recycle ratio of unreacted syngas mixture on the process efficiency and the greenhouse gas (GHG) emission. The reforming unit of our study is composed of both steam reforming of methane (SRM) and carbon dioxide reforming of methane (CDR) to form syngas, which gives composition flexibility, reduction in GHG emission, and higher cost-competitiveness. With recycling, it is found that zero emission of CO(2) from the process can be realized and the required amount of natural gas (NG) can be significantly reduced. This GTL process model has been built by using Aspen Plus software, and it is mainly composed of a feeding unit, a reforming unit, an FT synthesis unit, several separation units and a recycling unit. The composition flexibility of the syngas mixture due to the two different types of reforming reactions raises an issue that in order to attain the optimized feed composition of FT synthesis the amount of flow rate of each component in the fresh feed mixture should be determined considering the effects of the recycle and its split ratio. In the FT synthesis unit, the 15 representative reactions for the chain growth and water gas shift on the cobalt-based catalyst are considered. After FT synthesis, the unreacted syngas mixture is recycled to the reforming unit or the FT synthesis unit or both to enhance process efficiency. The effect of the split ratio, the recycle flow rate to the FT reactor over the recycle flow rate to the reforming unit, on the efficiency of the process was also investigated. This work shows that greater recycle to the reforming unit is less effective than that to the FT synthesis unit from the standpoint of the net heat efficiency of the process, since the reforming reactions are greatly endothermic and greater recycle to the reformer requires more energy.