World energy consumption projections expect coal to stay one of the world’s main energy sources in the coming decades, and a growing share of it will be used in CT—the conversion of coal to liquid fuels (CTL). Researchers from the National Institute of Clean-and-Low-Carbon Energy in Beijing and Eindhoven University of Technology have developed iron-based catalysts that substantially reduce operating costs and open the door to capturing the large amounts of CO₂ that are generated by CTL. An open-access paper on their work is published in the journal Science Advances.

The conversion of coal to liquid fuels is especially relevant in coal-rich countries that have to import oil for their supply of liquid fuels—such as China.

China represents the largest coal market in the world and is expanding its coal-to-liquids (CTL) technology by ~2% per year. By 2020, CTL is expected to account for 15% of the coal use in China. Accordingly, there is a large incentive to improve current CTL technology, which can convert coal into liquid fuels and valuable chemicals.

—Wang et al.

The first stage in CTL is the conversion of coal to syngas—a mixture of carbon monoxide (CO) and hydrogen (H₂). Using the Fischer-Tropsch process, these components are converted to liquid fuels. But before that can be done, the composition of the syngas has to be changed to make sure the right products come out in the end. Some of the CO is taken out of the syngas (rejected) by converting it to CO₂, in a process called the water-gas shift.

In this chain the researchers tackled a key problem in the Fischer-Tropsch reactor. As in most chemical processing, catalysts are required to enable the reactions. CTL catalysts are mainly iron-based. Unfortunately, they convert some 30% of the CO to unwanted CO₂, a byproduct that in this stage is hard to capture and thereby often released in large volumes, consuming a lot of energy without benefit.

The Beijing and Eindhoven researchers discovered that the CO₂ release is caused by the fact that the iron-based catalysts are not pure, but comprise several components. They were able to produce a pure form of a specific iron carbide—epsilon iron carbide—that has a very low CO₂ selectivity.

The existence of ε-iron carbide was already known but until now it had not been stable enough for the harsh Fischer-Tropsch process. The Sino-Dutch research team has now shown that this instability is caused by impurities in the catalyst. The phase-pure epsilon iron carbide they developed is, by contrast, stable and remains functional, even under typical industrial processing conditions of 23 bar and 250 ˚C.

The new catalyst eliminates nearly all CO₂ generation in the Fischer-Tropsch reactor. This can reduce the energy needed and the operating costs by roughly €25 million per year for a typical CTL plant. The CO₂ that was previously released in this stage can now be removed in the preceding water-gas shift stage.

We are aware that our new technology facilitates the use of coal-derived fossil fuels. However, it is very likely that coal-rich countries will keep on exploiting their coal reserves in the decades ahead. We want to help them do this in the most sustainable way.

—lead researcher Professor Emiel Hensen of Eindhoven University of Technology

The research results are likely to reduce the efforts to develop CTL catalysts based on cobalt. Cobalt-based catalysts do not have the CO₂ problem, but they are expensive and quickly becoming a scarce resource due to cobalt use in batteries, which account for half of the total cobalt consumption.

Hensen expects that the newly developed catalysts will also play an import role in the future energy and basic chemicals industry. The feedstock will not be coal or gas, but waste and biomass. Syngas will continue to be the central element, as it is also the intermediate product in the conversion of these new feedstocks.

Resources

• Peng Wang, Wei Chen, Fu-Kuo Chiang, A. Iulian Dugulan, Yuanjun Song, Robert Pestman, Kui Zhang, Jinsong Yao, Bo Feng, Ping Miao, Wayne Xu, Emiel J. M. Hensen (2018) “Synthesis of stable and low-CO₂ selective ε-iron carbide Fischer-Tropsch catalysts” Science Advances Vol. 4, no. 10, DOI: 10.1126/sciadv.aau2947