Volume 94 Issue 13 | p. 7 | News of The Week
Issue Date: March 28, 2016 | Web Date: March 25, 2016

Carbon dioxide hydrogenated to methanol on large scale

Supported indium oxide catalyst could boost lab-scale process to an industrial level
Department: Science & Technology
News Channels: Environmental SCENE, Organic SCENE
Keywords: catalysis, carbon dioxide, CO2, hydrogenation, methanol, CH3OH
Vacancies on the surface of a ZrO2-supported In2O3 catalyst play a key role in converting CO2 to CH3OH.
Credit: Adapted from Qingfeng Ge & Javier Pérez-Ramírez
Vacancies on the surface of a ZrO2-supported In2O3 catalyst play a key role in converting CO2 to CH3OH.
Credit: Adapted from Qingfeng Ge & Javier Pérez-Ramírez

Manufacturers generally produce methanol, a key chemical building block and fuel, from petroleum-derived syngas, a mixture of carbon monoxide and hydrogen. Direct hydrogenation of the greenhouse gas carbon dioxide would be a more efficient and environmentally sustainable route to methanol. But practical catalysts capable of making this reaction happen on an industrial scale have been unavailable.

Scientists had shown earlier that indium oxide catalyzes the direct hydrogenation of CO2 to CH3OH on a lab scale. Javier Pérez-Ramírez of ETH Zurich and coworkers now demonstrate that zirconium oxide-supported In2O3 catalyzes the process under conditions similar to those required for industrial production (Angew. Chem. Int. Ed. 2016, DOI: 10.1002/anie.201600943).

The supported catalyst can convert CO2 and H2 to CH3OH over at least 1,000 hours of continuous use and outperforms most other hydrogenation catalysts. The researchers proved experimentally that oxygen vacancies on the catalyst surface make the reaction possible—a mechanism predicted by theoretical calculations from a team led by Qingfeng Ge of Southern Illinois University and Tianjin University (ACS Catal. 2013, DOI: 10.1021/cs400132a).

The ETH Zurich group optimized the reaction by adding CO to the starting materials and varying the temperature, both of which tuned the number of vacancies. The technique is “a long-sought breakthrough with the potential to realize continuous CO2 conversion to methanol on a commercial scale,” Ge says.

Pérez-Ramírez and coworkers have filed patent applications on the technology in collaboration with French energy firm Total, which has started pilot studies of the process.

Chemical & Engineering News
ISSN 0009-2347
Copyright © American Chemical Society
P. DE WET  (March 26, 2016 5:47 AM)
If you acchieve this feat to Carbon dioxide hydrogenated to methanol on large scale then I think you will acchieve something remarkable. Do you want to use Carbon dioxide in gas form or liquid form. Is there a supply chain demand? Do you create surpluss energy or use more energy to produce than the product can deliver? How much benefit will there be for the environment. At the end of the cycle and after burning the fuel you will create are you co2 negative to the environment or did you merely recycle carbon dioxide?
Oliver Martin  (March 29, 2016 8:25 AM)
The sustainability of methanol production will be determined by a life-cycle analysis which needs to consider the modelling of all production chain steps involved and multiple other factors (such as feedstock, energy in- and outputs, catalyst manufacture, or final use of the product). We definitely aim at a process which avoids more CO2 than it produces. This might require an additional input by renewables as energy and/or feedstock supply.
C. Well  (March 28, 2016 12:14 AM)
I'm just a chemistry PhD student, not affiliated with the authors of this article, but I try to answer your question:

If you'd create a surplus of energy by reacting a low energy compund to a high energy one, you'd have a perpetuum mobile. As you suggest, it recycles CO2. Crudely it goes like this: CO2 + energy --> methanol (the water plays no role, as its oxidation numbers stay the same. the catalyst s not used up, so doesd nt appear either).
You can then burn the methanol to reverse the reaction: methanol --> CO2 + energy. Both processes of curse run t less than 100 % efficiency, so with each cycle, yu lose energy in the form of heat to the environment, but that is simple thermodynsmicsand the ultimate fate of all energy transformations. We can live with that, however.

It should be understood that this reaction is no energy source. Making methanol, because of its intrinsic value (which it does not have, really), is also not the point. The point is the convert power plant energy into a liquid storage medum, you can use to run combustion
engines. If we don't manage battery-powered cars, and do not want to run cars linked to electrical cables like trains, we need a way to transport power plant energy (after peak oil). e are totally spoiled having had "free" liquid energy at our disposal for almost 200 years. We won't get that again. Every drp of whatever fuel we want to combust, has to be
created from scrach by using other energy sources. Therefore, the next generations of humans will have the twofold challenge: find an energy source in the first place (renewable? nuclear fusion...?) AND finding a way to store the energy for later (and mobile) use. Unless we cover the Sahara full of solar panels and use the electricity at once to power the
reaction in this article, then transferring the mehtanol by pipeline to shore and into tankers (from there, cntinue like it was petrol), this will be a challenge, to say the least.

P.S.: To prevent climate change getting out of hand, we should not burn all the methanol made in this way, but simply store a fraction, so that global CO2 levels slowly decrease. Yup, life's gonna get expensive.
C Walton  (March 28, 2016 11:21 AM)
From the reaction sequences shown, the same amount of CO2 is released as introduced, so what net value is there (even if the "source" of Oxygen in the final CH3OH is from the CO2)? Still need just as much syngas.
Oliver Martin  (March 29, 2016 8:26 AM)
Co-feeding CO is only one tool besides temperature and surface reduction by H2 to enhance the amount of oxygen vacancies, the active sites of our In2O3-based catalysts. In our study we demonstrate that even without CO the process works efficiently, i.e., featuring 100% selectivity at high reaction rates stable for 1000 h. In addition, several studies indicate that CO and H2 could be produced from renewables (e.g., through thermochemical conversion of H2O and CO2) in the future to result in a net CO2 consumption for MeOH production and use.
Riza Dervisoglu  (March 31, 2016 5:00 AM)
In addition to Oliver Martin's remark, a solid oxide fuel cell (SOFC) type setup can be used for the reducing surface, hence eliminating the need for specific "CO+H2" pair (still H2 is needed). For instance, Y2O3 stabilized ZrO2 is a well-known O ion conductor and a good support for many catalysts as well, which can be used as the electrolyte of the SOFC. Then the question is what type of electrode are we going to use with the activity of In2O3, as In2O3 is an insulator? Well, there are some problems to be polished out but in principle, we have the freedom to play around with new ideas.
Tom Blackburn  (April 4, 2016 1:44 AM)
The downside is that H2 comes from petroleum. Unless we get H2 from water, what are we saving in environmental costs?
Oliver Martin  (April 6, 2016 2:55 AM)
Our work focused on the manageable problem of CO2 conversion. We are aware that the H2 supply is a critical factor for the sustainable prodution of methanol. Other groups demonstrated successfully among various options how to obtain the H2 from alternative sources to oil and gas, e.g., solar-driven thermochemical splitting of H2O. Sustainability will likely not be accomplished through the realization of a single process, but it demands the progressive integration of renewable energy and other sources of C and H2 into the current industrial network.
Chemist  (April 27, 2016 8:22 AM)
Conversion of CO2 or CO into mehanol or methane will require a certain amount of energy. Burning these fuels will give the same amount of energy. Using a catalyst in fuel production will lower the amount of energy needed for producing the fuel. This means you will get more energy than than you have put in. This could be source of "free energy" isnt it? How about connecting a system like this to a car, and use the CO2 bubbled through water, heated by the exhaust system, affected by the catalyst, to produce alternative fuel, added to the combustion? Even if it is not free energy, it can surely make combustion engines more efficient by using less fuel. Even the heat alone could be used to create steam from water, but instead this energy is wasted through a radiator.
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