IMPROVEMENTS AND MODELING OF THE RWGS PROCESS

The Reverse Water Gas Shift (RWGS) reaction, which has been known since the mid-1800s, has been combined with water electrolysis (WE) to provide a testbed for the development of autonomous control software, to produce data to model the RWGS/WE system, and to develop process improvements at Kennedy Space Center, see Figure 1. The RWGS reaction combines carbon dioxide (CO2) with hydrogen (H2) over a copper catalyst at 673 K in an endothermic reaction (H = 37.6 kJ/mol) to produce water (H2O) and carbon monoxide (CO). The H2O is electrolyzed to produce oxygen (O2) and H2, which is recirculated to the RWGS reactor. This system would be a useful tool on Mars where atmospheric CO2 is a convenient raw material. The system is important even if water is present on Mars, since it provides not only O2, but also CO, which is a useful raw material for metal oxide reduction and production of hydrocarbons and other organic materials. Therefore, we have continued to develop our understanding of the RWGS/WE system, with a primary objective to reduce the system complexity and improve the overall efficiency of the process. The baseline data for the system are given in Table I, which provide a matrix of operating parameters, including the reactor feed to raw material (RM) feed ratio with the compressor. Table I. Test Matrix for the RWGS Baseline Run CO2 H2 Temp T2 Number sLpm sLpm C 1 0.5 0.5 400 2 1.0 1.0 400 3 3.0 3.0 400 4 1.0 2.0 400 5 2.0 1.0 400 6 1.0 1.0 350 7 1.0 1.0 375 8 1.0 1.0 425 9 1.0 1.0 450 10 1.0 1.0 400 11 1.0 1.0 400 12 1.0 1.0 400 13 1.0 1.0 400 14 1.0 1.0 400 15 1.0 1.0 400 16 0.5 0.5 400 17 0.5 0.5 400 Pressure psia 45 45 45 45 45 45 45 45 45 16 30 45 45 45 45 45 45 Reactor Feed RM Feed Single Pass Single Pass Single Pass Single Pass Single Pass Single Pass Single Pass Single Pass Single Pass Single Pass Single Pass 12.5 14.0 12.8 11.0 22.5 13.4 % Conversion CO/CO2 20.5 22.1 19.8 15.0 30.2 16.9 19.8 23.7 24.7 22.2 22.3 52.5 63.3 95.8 99.1 66.6 100.0

Several trends in the RWGS reaction are shown by the data in Table I. For example, as the total flow rate increases (runs 1-3) the conversion is almost unchanged; as the ratio CO2 of to H2 increases (runs 2, 4, 5) the conversion increases; as the reactor temperature increases (runs 2, 69) the conversion increases; as the pressure in the reactor increases (runs 2, 10-11) the conversion remains unchanged; and as the reactor feed to RM feed ratio increases the conversion

appears to go through a maximum. These data in Table I will be used to select the optimum operating conditions for the system. One of the initial problems with the design of the reactor was illustrated by the temperature differential across the bed, which ranged from 40 to 50 C. Since the bed was heated from the outside and the reaction is endothermic, was difficult to transfer heat across the bed. This difference is made worse by the insulating characteristics of the catalyst bed, which is copper impregnated -alumina. To correct the problem copper turnings were added to the catalyst and the temperature difference dropped to less that 10 degrees. Other changes in the initial design include a change in the method of analysis, which was changed from a mass spectrometer to a gas chromatograph. The gas chromatograph used two detectors for the analysis, which eliminate the need to switch carrier gas for analysis. In the final analytical method CO and CO2 were analyzed with a thermal conductivity detector and H2 was analyzed with a helium ionization detector. Additional changes are planned for the RWGS system, which could eliminate the recycle loop and reduce the complexity of the process. The primary change under investigation is to remove water directly from the reactor, thus shifting the equilibrium so the reactants are consumed before they leave the reactor.

Figure 1. The RWGS testbed developed at KSC Key accomplishments: Improved the temperature control reactor by adding copper turning and a PID control on the heater

Added a gas chromatograph to analyze the composition of the reactions and products at critical control points

Contact: Dr. C. F. Parrish (clyde.parrish-1@ksc.nasa.gov), YA-D2, (321) 867-8763 Participating Organizations: NASA (D. Keenan, M. Haddad), Dynacs Inc., (C. Goodrich, J. Surma, T. Hodge), Florida Institute of Technology (Dr. J. Whitlow)