From the MASSACHUSETTS INSTITUTE OF TECHNOLOGY
A new way to harness wasted methane
Approach developed at MIT could help curb needless ‘flaring’ of potent greenhouse gas.
CAMBRIDGE, Mass. — 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.
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.
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The research team included postdoc Matthew O’Reilly and doctoral students Rebecca Soyoung Kim and Seokjoon Oh, all in MIT’s Department of Chemistry. The work was supported by the Italian energy company Eni S.p.A. through the MIT Energy Initiative.
ADDITIONAL BACKGROUND:
ARCHIVE: Turning greenhouse gas into gasoline http://news.mit.edu/2016/greenhouse-gas-into-gasoline-1115
The study: http://pubs.acs.org/doi/abs/10.1021/acscentsci.7b00342
The electricity could be generated from gas (Methane) turbines – it would be a more reliable energy source! 🙂
Insufficient quantities and variable compositions to be viable. However, the pumps to shift natural gas over long distances are often powered by gas turbines burning some of the product.
But there is no real evidence that CO2 has any effect on climate and plenty of scientific reasoning to support the idea that the climate sensivity of CO2 is zero. The radiant greenhouse has not been observed anywhere in the solar system including the Earth. The radiant greenhouse effect is science fiction.
A real inconvenient truth!
Another example of an otherwise meaningless university press release coattailed on CAGW. Essay Blowing Smoke has a classic example from 2014.
Great – an idea for converting a harmless byproduct into a highly toxic chemical which has to be transported from remote locations.
https://en.m.wikipedia.org/wiki/Methanol_toxicity
The electricity to power such systems could come from wind turbines or solar panels close to the site,
Or, from generators burning methane
“The electricity to power such systems could come from wind turbines or solar panels close to the site”
All that says is the authors are dumb as rock.
Frederic
What do you have against rock?
A small pile of sharp sand, after a Fohn has blown through, I suggest.
Auto – a bit vituperative tonight.
Sorry if I have offended Fohn fans.
Pump it back in the ground and store it. It would enhance oil prod a tiny bit and it may become more producible in 20years. If there is sulphur in it. Flare it!! Oh, that’s what they were doing!
It’s just another semi pie-in-the-sky press release. The oxidation of methane occurs in a solvent consisting of 98% sulfuric acid or fuming sulfuric acid and the reaction is at elevated temperature.
These are extremely corrosive conditions that require extremes of containment.
The reaction uses palladium (precious metal) catalyst, the reaction rates are slow, and the concentrations of products are very low.
The products are not methanol — CH3OH — but methane sulfonic acid (CH3SO3H) and methane sulfate (CH3OSO3H).
These products need further chemical processing to convert to methanol.
In other words, it’s an interesting laboratory demonstration that has no immediate technological significance. In fact, the process has no particular visible technological significance.
Hooking the idea as able to run off solar voltaic or wind power is utterly irrelevant. It’s just sustainability window-dressing meant to appeal to environmental sapism.
Here are the title and abstract: Matthew E. O’Reilly, R. Soyoung Kim, Seokjoon Oh, and Yogesh Surendranath “Catalytic Methane Monofunctionalization by an Electrogenerated High-Valent Pd Intermediate” DOI: 10.1021/acscentsci.7b00342
“Electrophilic high-valent metal ions are potent intermediates for the catalytic functionalization of methane, but in many cases, their high redox potentials make these intermediates difficult or impossible to access using mild stoichiometric oxidants derived from O2. Herein, we establish electrochemical oxidation as a versatile new strategy for accessing high-valent methane monofunctionalization catalysts. We provide evidence for the electrochemical oxidation of simple PdSO4 in concentrated sulfuric acid electrolytes to generate a putative Pd2III,III species in an all-oxidic ligand field. This electrogenerated high-valent Pd complex rapidly activates methane with a low barrier of 25.9 (±2.6) kcal/mol, generating methanol precursors methyl bisulfate (CH3OSO3H) and methanesulfonic acid (CH3SO3H) via concurrent faradaic and nonfaradaic reaction pathways. This work enables new electrochemical approaches for promoting rapid methane monofunctionalization.“
“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.”
There is about 3.5×10^12 tons of carbon dioxide in the atmosphere today. Adding 400 million more tons changes the total by 0.01%, assuming another mechanism of the carbon cycle doesn’t respond to take it out.
These people are staggered by absolute numbers, when they have no sense of proportion whatsoever.
And the whole methane capture objective is misconceived anyway, because free methane will naturally be oxidized in the atmosphere to water and carbon dioxide. It is not a persistent gas.
The only method of methane capture not mentioned above would be to pump it into cold water under pressure to form methane clathrate.
— 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 —
This is a good thing in and of itself. It gives an alternative, I’m hoping more efficient, method of turning methane to methanol. Maybe someday the method will be useful, maybe not.
The problem comes if someone mandates or artificially incentivizes its use.
If this pans out this would be great news.
You can safely assume that it won’t.
I think there is a lot of misunderstanding about why natural gas is flared. Oil companies don’t want to waste
a resource that has value.
In the case of a new gas well, extensive flaring can occur when a well is fraced using CO2 or N2. It’s the pipeline companies that determine how and when gas is put in their pipeline not the oil companies. If there is too much CO2 or N2 in the gas left over from the frac, it has to be flared until the gas meets pipeline specs. But it can take a lot of flaring to meet pipeline specs.
If the gas naturally contains H2S or CO2 ( and other inerts), that gas must be processed in a plant prior to entry into the sales gas line.
Continuous gas venting at oil wells usually happens when the well is remote and the oil is transported by truck and there is not a pipeline for the oil or gas to be delivered to a central battery where the gas can be captured and compressed into the sales pipeline. If there is a lot of oil and gas produced at the well, a pipeline will be built.
There is usually a lot less gas vented at new oil wells than a new gas well. But there are a lot more oil wells drilled.
Wild cat wells usually require more flaring. The oil company does more flow testing to determine the size and characteristics of the reservoir and size the surface production equipment needed.
There are other examples of why flaring is done but it would be an unusual situation where the oil company flared gas when it had an option of selling the gas for a profit.
There is a minor amount of gas vented on location. Usually to operate the pneumatic valves or coming off the condensate/oil tanks on a hot day.
If you flare a potent greenhouse gas, it is destroyed and no longer a potent greenhouse gas. It is water and carbon dioxide.
A few points about flaring.
It can never be completely eliminated. For one thing every refinery or processing plant must have a flare for safety reasons. This is so that any leakage of combustibles can be piped to a place where it can be safely combusted. NB. This also includes biogas plants.
Also a fair amount of the flaring you see in oil-fields are from wells that are not yet in production, or are in a production test phase. Nobody will ever build a complex processing plant for a well that might be abandoned and sealed up a few weeks hence.
The main method to achieve less flaring is more pipelines. By the way this is also one of the reasons the hottest area for “unconventional oil” is currently the Permian Basin. This is an old field that has been in production for a cetury and there is a good pipeline infrastructure.
If the location is remote enough to leave the gas economically stranded then what is the point in converting it to an even lower value product?
If the product fits in the same pipe used for oil, it makes sense
I don’t think it would be wise to send methanol thru a petroleum pipeline.
“The work was supported by the Italian energy company Eni”.
Oil companies people have been working on finding a use for flared gas for since the very beginning. Hence the boom in LNG, for instance.
They obviously are still working on it… Just fine, but don’t expect miracle
Possibly a stupid question. But why are we going so high tech? Run the flare gas through a boiler, use the steam generated to run an engine that powers a generator. One could probably mass produce a unit to do this.
Flares exist even in refineries that use boilers to operate. Even there it makes no sense, says it all
paqyfelyc
So, flare gasses in refineries are needed as a safety feature. When, not if but when a very high pressure reaction tower or tank loses electricity or has a problem, the thousands of pounds of explosive, high-pressure, semi-reacted gasses and chemicals MUST be vented off away from the tank before they explode, or before the chemicals kills thousands as in Bhopol. So, a flare tower several hundred feet tall, several hundred feet from other tanks and towers is kept continuously running. When an emergency happens, large pressure relief valves vent off the explosive/toxic gasses and liquids to the flare tower where they can burn off without exploding other tanks and pressure vessels. After burning, the flared gasses are no longer toxic – merely sulfates, fluorides and fluorates, CO2, and heat. Lots and lots of heat.
MIT wake up and do a bit of due diligence. There is a company, led by Dr. Robert Zubrin of the “Case for Mars” fame who is already doing this commercially.
http://www.pioneerenergy.com/about
Chemically interesting, but with caveats, some bigger than others. The usual problems such as catalyst poisoning, the expense of metals used (Palladium in this case), and the use of problematic aggressive/toxic reagents (concentrated sulfuric acid in this case) may not be insurmountable (in theory, at least)
But, more importantly, electrochemical-catalysis reaction conditions require solution phase chemistry. However, you are then faced with having to separate the catalyst from the reaction products in order to recycle the catalyst and use it again: Complicated, time consuming, probably low yield, expensive, messy.
The best industrially-useful catalysts are heterogeneous-phase, and can therefore be used in a continuous-flow process. Thus, for example, the catalyst in a car exhaust stays intact in one place while the exhaust gases pass over it, and away….the products thus being quickly and easily separated from the catalyst in ~100% separation-yield… But their process can’t work in this fashion because the electrochemistry requires reagents and catalyst dissolved in an electrolyte solution for current to flow.
“making this process a significant contributor to global warming”
The reason methane is a more powerful GHG is because it’s already at a very low level where the incremental effect while small, is larger than the tiny effect from incremental CO2. However; methane only affects a tiny part of the absorption spectrum, thus even if those bands were saturated, it would still have a total effect far less than either CO2 or H2O.
And, as I mentioned previously, methane is not a persistent gas; it naturally oxidizes in the air to form water and carbon dioxide. So, it will always be at a “low level.”
Another issue here is the nature of the international oil business. Basically international oil companies install oil facilities and produce oil for a host country because the host country is, for various reasons, unwilling or incapable of doing it on their own. A portion of the produced oil goes to the oil company to pay for the facility and for profit. From the host countries perspective/negotiation this portion is as small as possible. The significant remainder goes to the host country as basic income. The produced gas could be used to generate electricity for the host country (as is done in basically all ‘developed’ countries). However, producing, transmitting and distributing this electricity costs money which HAS to be paid for by the host country out of their oil income. In many cases they would rather spend the money on various local issues. Distribution of the ‘new’ power also has to be paid for and executed by the host country, which can be difficult is some countries. Getting third world consumers to pay is also difficult.