by Nancy W. Stauffer (MIT Energy Initiative) MIT researchers are converting the plant material lignin into hydrocarbon molecules that could help make jet fuel 100 percent sustainable.
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Aviation fuel is a combination of two large classes of chemical compounds. Some 75 to 90 percent of it is made up of “aliphatic” molecules, which consist of long chains of carbon atoms linked together. “This is similar to what we would find in diesel fuels, so it’s a classic hydrocarbon that is out there,” explains Román-Leshkov (Yuriy Román-Leshkov, the Robert T. Haslam Professor of Chemical Engineering). The remaining 10 to 25 percent consists of “aromatic” molecules, each of which includes at least one ring made up of six connected carbon atoms.
In most transportation fuels, aromatic hydrocarbons are viewed as a source of pollution, so they’re removed as much as possible. However, in aviation fuels, some aromatic molecules must remain because they set the necessary physical and combustion properties of the overall mixture. They also perform one more critical task: They ensure that seals between various components in the aircraft’s fuel system are tight. “The aromatics get absorbed by the plastic seals and make them swell,” explains Román-Leshkov. “If for some reason the fuel changes, so can the seals, and that’s very dangerous.”
As a result, aromatics are a necessary component — but they’re also a stumbling block in the move to create sustainable aviation fuels, or SAFs. Companies know how to make the aliphatic fraction from inedible parts of plants and other renewables, but they haven’t yet developed an approved method of generating the aromatic fraction from sustainable sources. As a result, there’s a “blending wall,” explains Román-Leshkov. “Since we need that aromatic content — regardless of its source — there will always be a limit on how much of the sustainable aliphatic hydrocarbons we can use without changing the properties of the mixture.”
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For the past five years, understanding and solving the SAF problem has been the goal of research by Román-Leshkov and his MIT team — Michael L. Stone PhD ’21, Matthew S. Webber, and others — as well as their collaborators at Washington State University, the National Renewable Energy Laboratory (NREL), and the Pacific Northwest National Laboratory. Their work has focused on lignin, a tough material that gives plants structural support and protection against microbes and fungi. About 30 percent of the carbon in biomass is in lignin, yet when ethanol is generated from biomass, the lignin is left behind as a waste product.
Despite valiant efforts, no one has found an economically viable, scalable way to turn lignin into useful products, including the aromatic molecules needed to make jet fuel 100 percent sustainable. Why not? As Román-Leshkov says, “It’s because of its chemical recalcitrance.” It’s difficult to make it chemically react in useful ways. As a result, every year millions of tons of waste lignin are burned as a low-grade fuel, used as fertilizer, or simply thrown away.
Understanding the problem requires understanding what’s happening at the atomic level. A single lignin molecule — the starting point of the challenge — is a big “macromolecule” made up of a network of many aromatic rings connected by oxygen and hydrogen atoms. Put simply, the key to converting lignin into the aromatic fraction of SAF is to break that macromolecule into smaller pieces while in the process getting rid of all of the oxygen atoms.
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By reacting the biomass in the presence of a ruthenium-based catalyst, they are able to remove the lignin from the biomass and produce a black liquid called lignin oil. That product is chemically stable, meaning that the aromatic molecules in it will no longer react with one another.
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Ultimately, Román-Leshkov and his team found a special ingredient that would do the trick: a molybdenum carbide catalyst. “It’s actually a really amazing catalyst because it can perform those three actions very well,” says Román-Leshkov. “In addition to that, it’s extremely resistant to poisons. Plants can contain a lot of components like proteins, salts, and sulfur, which often poison catalysts so they don’t work anymore. But molybdenum carbide is very robust and isn’t strongly influenced by such impurities.”
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Two separate reactors containing independent catalyst beds would be connected in series, with the first pretreating the lignin oil and the second removing any oxygen that remains.
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“These molecules are not the typical aromatic molecules that you use in jet fuel,” says Román-Leshkov. “Preliminary tests with sample seals show that there’s no difference in how our lignin-derived aromatics swell the seals, but we need to confirm that. There’s no room for error.”
In addition, he and his team are working with their NREL collaborators to scale up their methods.
...
Román-Leshkov and his colleagues are now exploring the use of their approach with other types of biomass, including pine, switchgrass, and corn stover (the leaves, stalks, and cobs left after corn is harvested). READ MORE
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