Turning waste methane into formaldehyde could be a big deal

Professor Kwang-jin Ahn (center) and his team in the School of Energy and Chemical Engineering at UNIST. From left are Jihyun Lee, and Dr. Chinh Nguyen-Huy.

The primary component of natural gas, methane, is itself a potent greenhouse gas. A recent study, affiliated with UNIST has unveiled a high performance catalyst for methane conversion to formaldehyde.

This breakthrough has been led by Professor Kwang-jin Ahn and his team in the School of Energy and Chemical Engineering at UNIST in collaboration with Professor Ja Hun Kwak (School of Energy and Chemical Engineering, UNIST), Professor Eun Duck Park from Ajou University, and Professor Yoon Seok Jung from Hanyang University.

In this work, the team has presented an excellent ‘methane oxidase catalyst’ consisting of nanomaterials. This material has a stable structure and high reactivity at high temperatures, increasing the efficiency of converting methane to formaldehyde more than twice as much as before.

Methane, like petroleum, can be converted into useful resources through chemical reactions. The main ingredient of shale gas, which is attracting attention in the US in recent years, is methane, and the technology to make high value-added resources with this material is also recognized as important. The problem is that the chemical structure of methane is so stable that it does not easily react to other substances. So far, methane has been used primarily as fuel for heating and transportation.

A high temperature above 600 ° C is required to effect a reaction that changes the chemical structure of methane. Therefore, a catalyst having a stable structure and maintaining reactivity in this environment is required. Previously, vanadium oxide (V2O2) and molybdenum oxide (MoO3) were known to be the best catalysts. When these catalysts were used, the formaldehyde conversion of methane was less than 10%.

Schematic image showing [email protected]@Al2O3 [email protected] nanostructures.

Professor Ahn made a catalyst that could convert methane to formaldehyde using nanomaterials. Formaldehyde is a useful resource widely used as a raw material for bactericides, preservatives, functional polymers and the like.

The catalyst has a core-shell structure consisting of vanadium oxide nanoparticles surrounded by a thin aluminum film, with the aluminum shell surrounding the vanadium oxide particles. The shell protects the grain and keeps the catalyst stable and maintains stability and reactivity even at high temperatures.

In fact, when the catalytic reaction was tested with this material, vanadium oxide nanoparticles without aluminum shells had a structural loss at 600 ° C. and lost catalytic activity. However, nanoparticles made from core-shell structures remained stable even at high temperatures. As a result, the efficiency of converting methane to formaldehyde increased by more than 22%. It turned methane into a useful resource with more than twice the efficiency.

“The catalytic vanadium oxide nanoparticles are surrounded by a thin aluminum film, which effectively prevents the agglomeration and structural deformation of the internal particles,” says Euiseob Yang from the Department of Chemical Engineering at UNIST partook as the first author of this study. “Through the new structure of covering the atomic layer with nanoparticles, Thermal stability and reactivity at the same time.”

Schematic preparation of [email protected]@Al2O3 [email protected] nanostructures.

This research is particularly noteworthy in terms of improvement in the catalyst field, which has not made great progress in 30 years. The catalytic technology to produce formaldehyde in methane has not made much progress since it was patented in the US in 1987.

“The high-efficiency catalyst technology has been developed beyond the limits of the technology that has remained as a long-lasting technology,” says Professor Ahn. “The value is high as a next-generation energy technology utilizing abundant natural resources.”

He adds, “We plan to expand the catalyst manufacturing technology and catalyst process process so that we can expand our laboratory-level achievements industrially. The catalyst technology has a considerable effect on the chemical industry and contributes to the national chemical industry. I want to develop a practical technology that can do it.”

Learn more: Researchers Find New Ways to Harness Wasted Methane



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Methane, normally flared off at remote sites, could be converted for use instead with new method

MIT chemistry professor Yogesh Surendranath and three colleagues have found a way to use electricity, which could potentially come from renewable sources, to convert methane into derivatives of methanol. The researchers developed a low-temperature electrochemical process that would continuously replenish a catalyst material that can rapidly carry out the conversion.
Courtesy of the researchers

Approach developed at MIT could help curb needless “flaring” of potent greenhouse gas.

Methane gas, a vast natural resource, is often disposed of through burning, but new research by scientists at MIT could make it easier to capture this gas for use as fuel or a chemical feedstock.

Many oil wells burn off methane — the largest component of natural gas — in a process called flaring, which currently wastes 150 billion cubic meters of the gas each year and generates a staggering 400 million tons of carbon dioxide, making this process a significant contributor to global warming. Letting the gas escape unburned would lead to even greater environmental harm, however, because methane is an even more potent greenhouse gas than carbon dioxide is.

Why is all this methane being wasted, when at the same time natural gas is touted as an important “bridge” fuel as the world steers away from fossil fuels, and is the centerpiece of the so-called shale-gas revolution? The answer, as the saying goes in the real estate business, is simple: location, location, location.

The wells where methane is flared away are primarily being exploited for their petroleum; the methane is simply a byproduct. In places where it is convenient to do so, methane is captured and used to generate electrical power or produce chemicals. However, special equipment is needed to cool and pressurize methane gas, and special pressurized containers or pipelines are needed to transport it. In many places, such as offshore oil platforms or remote oil fields far from the needed infrastructure, that’s just not economically viable.

But now, MIT chemistry professor Yogesh Surendranath and three colleagues have found a way to use electricity, which could potentially come from renewable sources, to convert methane into derivatives of methanol, a liquid that can be made into automotive fuel or used as a precursor to a variety of chemical products. This new method may allow for lower-cost methane conversion at remote sites. The findings, described in the journal ACS Central Science, could pave the way to making use of a significant methane supply that is otherwise totally wasted.

“This finding opens the doors for a new paradigm of methane conversion chemistry,” says Jillian Dempsey, an assistant professor of chemistry at the University of North Carolina, who was not involved in this work.

Existing industrial processes for converting methane to liquid intermediate chemical forms requires very high operating temperatures and large, capital-intensive equipment. Instead, the researchers have developed a low-temperature electrochemical process that would continuously replenish a catalyst material that can rapidly carry out the conversion. This technology could potentially lead to “a relatively low-cost, on-site addition to existing wellhead operations,” says Surendranath, who is the Paul M. Cook Career Development Assistant Professor in MIT’s Department of Chemistry.

The electricity to power such systems could come from wind turbines or solar panels close to the site, he says. This electrochemical process, he says, could provide a way to do the methane conversion — a process also known as functionalizing — “remotely, where a lot of the ‘stranded’ methane reserves are.”

Already, he says, “methane is playing a key role as a transition fuel.” But the amount of this valuable fuel that is now just flared away, he says, “is pretty staggering.” That vast amount of wasted natural gas can even be seen in satellite images of the Earth at night, in areas such as the Bakken oil fields in North Dakota that light up as brightly as big metropolitan areas due to flaring. Based on World Bank estimates, global flaring of methane wastes an amount equivalent to approximately one-fifth of U.S. natural gas consumption.

When that gas gets flared off rather than directly released, Surendranath says, “you’re reducing the environmental harm, but you’re also wasting the energy.” Finding a way to do methane conversion at sufficiently low cost to make it practical for remote sites “has been a grand challenge in chemistry for decades,” he says. What makes methane conversion so tough is that the carbon-hydrogen bonds in the methane molecule resist being broken, and at the same time there’s a risk of overdoing the reaction and ending up with a runaway process that destroys the desired end-product.

Catalysts that could do the job have been studied for many years, but they typically require harsh chemical agents that limit the speed of the reaction, he says. The key new advance was adding an electrical driving force that could be tuned precisely to generate more potent catalysts with very high reaction rates. “Since we’re using electricity to drive the process, this opens up new opportunities for making the process more rapid, selective, and portable than existing methods,” Surendranath says. And in addition, “we can access catalysts that no one has observed before, because we’re generating them in a new way.”

The result of the reaction is a pair of liquid chemicals, methyl bisulfate and methanesulfonic acid, which can be further processed to make liquid methanol, a valuable chemical intermediate to fuels, plastics, and pharmaceuticals. The additional processing steps needed to make methanol remain very challenging and must be perfected before this technology can be implemented on an industrial scale. The researchers are actively refining their method to tackle these technological hurdles.

“This work really stands out because it not only reports a new system for selective catalytic functionalization of methane to methanol precursors, but it includes detailed insight into how the system is able to carry out this selective chemistry. The mechanistic information will be instrumental in translating this exciting discovery into an industrial technology,” Dempsey says.

Learn more: A new way to harness wasted methane


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