14 April 2016

Using methane rather than flaring it

Energy and Environment Media Releases

Chemists at ETH Zurich and the Paul Scherrer Institute have found a new, direct way to convert gaseous methane into liquid methanol. This offers industry the interesting prospect of using the gas, rather than simply burning it off, as is currently the case.

Methane is an abundant and inexpensive gas. Although it would be a suitable energy source and base material for the chemical industry, huge quantities of it are simply burnt off around the world – above all at oil fields and refineries. On satellite images of Earth at night, the Middle East is brightly illuminated. This is not because the region has an especially high number of large, brightly lit settlements, but rather because of methane flaring at the oil fields, says Jeroen van Bokhoven, Professor for Heterogeneous Catalysis at ETH Zurich and Head of the Laboratory for Catalysis and Sustainable Chemistry at the Paul Scherrer Institute PSI.

Another reason for this wasteful approach to methane is that, at present, it is not sufficiently profitable to convert the gas into methanol in liquid form, which is easier to transport and more reactive. On the industrial scale, this conversion is currently performed using an indirect, elaborate and energy-intensive method that involves the production of syngas as an intermediate step.

The stuff of many chemists’ dreams

Many chemists consider the easy, direct conversion of methane into methanol as a dream reaction, says van Bokhoven. He and his team have demonstrated a new approach to this in a recent study. The world of industry is also very interested in better utilising this abundant, inexpensive raw material, says the catalysis researcher. Rising global production of shale gas is resulting in the release of ever-greater volumes of methane.

In theoretical terms, at least, it is already possible to convert methane into methanol. This is achieved using crystalline, copper-containing silicon aluminium compounds (zeolites) as catalysts. The process involved is cyclical and is conducted at various temperatures: activating the catalyst requires very high temperatures, often up to 450 degrees Celsius. However, the actual reaction between methane and oxygen to form methanol cannot be carried out at temperatures significantly higher than 200 degrees, as otherwise any methanol formed would burn off immediately. The reaction vessel must therefore be heated and cooled repeatedly, which is why this approach has never made it out of the research lab and into industry.

High pressure instead of high temperatures

However, van Bokhoven and his colleagues have now demonstrated that this reaction cycle can also take place at a constant temperature of 200 degrees. They achieved this through a clever trick, using methane at a far higher pressure: 36 bars instead of under 1 bar, as previously used. Working at a constant temperature makes this a much easier process to implement in industry, says Patrick Tomkins, Master student in van Bokhoven’s group und first author of the current study.

Through analysis using X-ray absorption spectroscopy, the researchers were also able to show that, at the atomic level, the catalysed reaction in the new low-temperature/high-pressure method does not take place at the same position as it did in the existing high-temperature method. As a result of the high pressure, different active centres are utilised in the copper zeolites, says van Bokhoven.

The new approach is not yet suitable for direct application in industry, van Bokhoven makes clear, as the yield is not yet sufficient for industrial purposes. However, the approach opens up a new range of possibilities. In the past, catalysis scientists focused their research on copper zeolites for this reaction, because these are the most successful option in the high-temperature method. We also used these copper zeolites for the current study.

However, as the high-pressure method is catalysed differently at the atomic level, it is now worth investigating different catalysts, including those that haven’t been considered at all so far, says van Bokhoven. These might be even better suited to the high-pressure method. This is precisely what the catalysis researcher and his colleagues will work on in their future research, with a view to developing their own easy, direct and efficient process for converting methane into methanol – a dream come true for both the scientific community and the world of industry.

Text: ETH Zurich/Fabio Bergamin

About PSI

The Paul Scherrer Institute PSI develops, builds and operates large, complex research facilities and makes them available to the national and international research community. The institute's own key research priorities are in the fields of matter and materials, energy and environment and human health. PSI is committed to the training of future generations. Therefore about one quarter of our staff are post-docs, post-graduates or apprentices. Altogether PSI employs 1900 people, thus being the largest research institute in Switzerland. The annual budget amounts to approximately CHF 380 million. PSI is part of the ETH Domain, with the other members being the two Swiss Federal Institutes of Technology, ETH Zurich and EPFL Lausanne, as well as Eawag (Swiss Federal Institute of Aquatic Science and Technology), Empa (Swiss Federal Laboratories for Materials Science and Technology) and WSL (Swiss Federal Institute for Forest, Snow and Landscape Research).
(Last updated in February 2016)

About ETH Zurich

ETH Zurich is one of the leading international universities for technology and the natural sciences. It is well-known for its excellent education, ground-breaking fundamental research and for implementing its results directly into practice. Founded in 1855, ETH Zurich today has more than 18,500 students from over 110 countries, including 4,000 doctoral students. To researchers, it offers an inspiring working environment, to students, a comprehensive education. Twenty-one Nobel Laureates have studied, taught or conducted research at ETH Zurich, underlining the excellent reputation of the university.
(Last updated in February 2015)
Additional information
From methane to methanol
Prof. Dr. Jeroen van Bokhoven
Head of Laboratory for Catalysis and Sustainable Chemistry, Paul Scherrer Institute, 5232 Villigen PSI, Switzerland
Telephone: +41 56 310 50 46, e-mail: jeroen.vanbokhoven@psi.ch
Professor for Heterogeneous Catalysis, ETH Zurich, 8093 Zurich, Switzerland
Telephone: +41 44 632 55 42, e-mail: jeroen.vanbokhoven@chem.ethz.ch
Original Publication
Isothermal Cyclic Conversion of Methane into Methanol over Copper-Exchanged Zeolite at Low Temperature
P. Tomkins, A. Mansouri, S. E. Bozbag, F. Krumeich, M. B. Park, E. M. C. Alayon, M. Ranocchiari, J. A. van Bokhoven
Angewandte Chemie International Edition 24 March 2016
DOI: 10.1002/anie.201511065