A thermodynamic comparison of membrane-assisted processes for hydrogen production with integrated CO₂ capture

The energy efficiency of two novel process designs for the production of ultra-pure hydrogen with simultaneous capture of CO2 using CH4 as the feedstock, namely membrane-assisted chemical looping reforming (MA-CLR) and membrane-assisted sorption-enhanced reforming (MA-SER) has been compared. The modelling of the integrated network for mass and heat balances has been carried out using the ASPEN (R) Plus V10 process simulation tool to quantify the benefits and disadvantages of integrating hydrogen perm-selective membranes with either chemical looping or sorption-enhanced reforming. The evaluation of the MA-CLR process is carried out for a range of the following operating conditions: 10 < p(R) < 60 bar, 500 < T-R < 900(degrees)C, and 1.5 < H2O/CH4 < 3.0. On the other hand, for the MA-SER process the operation ranges of 1.0 < pR < 10 bar, 400 < TR < 900(degrees)C, and 2.5 < H2O/CH4 < 4.0 were considered. Within the operation window of the MA-SER process, no carbon formation is observed, as any carbon present in the system reacts with CaO in the form of CO2. However, in the case of the MA-CLR process, carbon formation can occur during the pre-reforming stage, particularly at low H2O/CH4 ratios. In terms of hydrogen yield, energy utilization and carbon capture, the MA-CLR outperforms the MA-SER plant. However, the MA-SER plant offers certain advantages over the MA-CLR system, such as a pure CO2 product stream and lower reactor design temperatures. In the MA-CLR system, a carbon capture rate of 99.8% and a hydrogen product yield of 74.4% are achieved, whereas the MA-SER plant achieves a carbon capture rate of 98.5% and a hydrogen product yield of 69.7%.