281502 Bi-Reforming of Methane and Natural Gas Under High Pressure
Bi-Reforming of Methane and Natural Gas Under High Pressure
By choosing the right proportions between water, CO2 and CH4, the combination of steam and dry reforming of methane can generate syn-gas with a H2/CO ratio of 2 ideal for the synthesis of methanol.[1,2] This combination of steam and dry reforming has been named bi-reforming.
Bi-reforming could be advantageous in the use of natural gas sources containing substantial amounts of CO2. This CO2 would, otherwise, have to be separated to allow further processing of the natural gas. Some natural gas sources contain CO2 concentration from 5% up to 70%. In most cases, once separated, the CO2 is then released into the atmosphere. Only in few locations is CO2 sequestered. The natural gas at the Sleipner platform in Norway containing 9% CO2 is for example currently separated and sequestered beneath the North Sea in a deep saline aquifer.
To mimic conditions closer to commercial operations, the bi-reforming reaction was conducted at pressures up to 35 bars in a tubular reactor system specially built for this purpose and able to withstand both high pressure and high temperature in a gas mixture with a high carbon activity. The catalysts used were based on Ni deposited on various supports including alumina, alkali earth oxides and combinations thereof. Reaction temperatures ranging from 700°C to 870°C were investigated. A gas feed composition of CH4/CO2/H2O with a molar ratio of 3/1.2/2.4 was typically used. The reaction was followed by an online GC equipped with a TCD.
In general the catalysts were tested for at least 50 hours to determine their stability as a function of time. The conversion of methane as well as carbon dioxide was stable over the length of the experiments (Figure 1). The obtained H2/CO ratio of the reaction gases was close to the desired value of 2. Increasing the amount of water and CO2 compared to methane increased the methane conversion but did not significantly change the H2/CO ratio.
As expected from a thermodynamic point of view the methane conversion decreased with increasing pressure. To some extent this effect could be compensated by a higher reaction temperature and/or higher water and CO2 content in the feed gas.
Figure 1. Bi-reforming at 7 bars. Conversion of methane and carbon dioxide.
Support of our work by the Loker Hydrocarbon Research Institute and the United States Department of Energy is gratefully acknowledged.
 G. A. Olah, G. K. S. Prakash, A. Goeppert, J. Am. Chem. Soc. 2011, 133, 12881.
 G. A. Olah, A. Goeppert, G. K. S. Prakash, Beyond Oil and Gas: The Methanol Economy, 2nd ed., Wiley VCH, Weinheim, Germany, 2009.
See more of this Group/Topical: Topical D: Accelerating Fossil Energy Technology Development Through Integrated Computation and Experimentation