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Can graphene, the wonder material, build better batteries?

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In 1962, German researcher Hanns-Peter Boehm suggested the versatile carbon atom, which can form long chains, might be configured into a chicken-wire pattern to create a stable molecule one atom thick.

The idea remained a theoretical construct without even a name until 1987, when researchers started calling it “graphene.” Basically, graphene is two-dimensional graphite, the pure carbon material that makes up “lead” pencils. The term was also used to describe the carbon nanotubes that were beginning to attract attention for their ultra-solid properties. For a while there was talk of elevators reaching up into space until it became clear that creating nanotubes without impurities that degrade their properties was currently out of the reach of mass production.

Then in 2004, Andre Geim and Kostya Novoselov, two researchers at The University of Manchester, came up with something a little more prosaic. They applied Scotch tape – yes, ordinary Scotch tape – to pure graphite and found they could peel off the single layer of carbon in the chicken-wire pattern that Boehm had described. They called this substance “graphene” and were awarded the Nobel Prize in 2010.

The discovery of single-layer graphene has set off a stampede into research of its properties. Carbon is, after all, a versatile element, the basic building block of life that can also be packed into a material as hard as a diamond, which is also pure carbon. When stretched out into lattices a million times thinner than a human hair, however, it has the following remarkable properties:

  • It is the strongest material ever discovered, 300 times stronger than steel.
  • It is the most electrically conductive material ever discovered, 1,000 times more conductive than silicon.
  • It is the most thermally conductive material ever discovered.
  • It is bendable, shapeable and foldable.
  • It is completely transparent, although it does filter some light.

In short, graphene is now being touted as “material of the 21st century,” the substance that could bring us into an entirely new world of consumer products, such as cell phones that could be sewn into our clothes.

All this still remained somewhat theoretical, since no one had been able to produce graphene in dimensions larger than single tiny crystals. When these crystals were joined together, they lost most of their properties. Two weeks ago, however, Samsung announced that it has been able to grow a graphene crystal to the size of a wafer, somewhat on the same dimensions as the silicon wafers that produce computer chips. Thus, the first step toward a new world of electronics may be upon us. Graphene cannot be used as a semiconductor, since it is always “on” in conducing electricity, but combined with other substances it may be able to replace silicon, which is many researches believe is currently reaching its physical limits.

So what does this mean for the world of transportation, where we are always looking for new ways to construct automobiles and find alternative power sources to substitute for our gas tanks? Well, plenty.

Most obvious is the possibility of making cars out of much lighter-weight materials to reduce the power burden on engines. Chinese researchers recently came up with a graphene aerogel that is seven times lighter than air. A layer spread across 28 football fields would weigh only one ounce and a cubic inch of the material would balance on a blade of grass. All this would occur while it still retained its 300-times-stronger-than-steel properties. Graphene itself would not be used to construct cars, but it could be layered with other materials.

But the most promising aspect of graphene may be in the improvement of batteries. Lithium-ion batteries achieve an energy density of 200 Watt-hours-per-kilogram, which is five times the 40-Wh/k density of traditionally lead-acid batteries. That has won it the prime role in consumer electronics. But Li-ion batteries degrade over time, which is not a problem for a cell phone, but becomes prohibitive when the battery must undergo more than 1,000 charge cycles and is half the price of the car.

Lithium-sulfur batteries have long been thought to hold promise but they, too, deteriorate quickly, sometimes after only a few dozen charges. But recently, researchers at Lawrence Berkeley Labs in California modified a lithium sulfur battery by adding sandwiched layers of a graphene. The result is a battery that achieves 400 Wh/k – double the density of plain lithium-ion – and has gone through 1,500 charging cycles without deterioration. This would give an electric car a range of more than 300 miles, which is in the lower range of what can be achieved with the internal combustion engine.

And so the effort to improve electric vehicles is moving forward, sometimes on things coming out of left field. If graphene really proves to be a miracle substance, look for Elon Musk to be discussing its wonders as he prepares to build that “megafactory” that is supposed to produce lithium-ion batteries capable of powering an affordable new version of the Tesla.

Arctic Leaf

Is butanol the next big thing in biofuels?

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Fuel Freedom recently learned about a man named David Ramey who drove his 1992 Buick Park Avenue from Blacklick, Ohio to San Diego using 100 percent butanol, without making any adjustments to his engine.

Ordinarily this wouldn’t be big news. But with the EPA now considering cutbacks in the 2014 biofuels mandate, some producers of ethanol are starting to turn to butanol as a way of getting around the limitations of the 10 percent “blend wall” that is threatening to limit ethanol consumption. This could be another breakthrough in our efforts to limit foreign oil.

Butanol is the alcohol form of butane gas, which has four carbons. Because it has a longer hydrocarbon chain, butane is fairly non-polar and more similar to gasoline than either methanol or ethanol. The fuel has been demonstrated to work in gasoline engines without any modification to the fuel chain or software.

Since the 1950s, most butanol in the United States has been manufactured from fossil fuels. But butanol can also be produced by fermentation, and that’s where another opportunity for reducing our dependence on fossil fuels exists.

The key is a bacterial strain called Clostridium acetobutylicum, also named the Weizmann organism for pioneering biological researcher Chaim Weizmann, who first used it to produce acetone from starch in 1916. The main use for the acetone was producing Cordite for gunpowder, but the butanol, a byproduct, eventually became more important.

Once set loose on almost any substratum, Clostridium acetobutylicum will produce significant amounts of butanol. Anything used to produce ethanol — sugar beets, sugar cane, corn grain, wheat and cassava, plus non-food crops such as switchgrass and guayule and even agricultural byproducts such as bagasse, straw and corn stalks — can all be turned into butanol. (Of course, not all of these are economical yet.)

Given the modern-day techniques of genetic engineering, researchers are now hard at work trying to improve the biological process. In 2011, scientists at Tulane University announced they had discovered a new strain of Clostridium that can convert almost any form of cellulose into butanol and is the only known bacterium that can do it in the presence of oxygen. They discovered this new bacterium in, of all places, the fecal matter of the plains zebra in the New Orleans Zoo.

DuPont and BP are planning to make butanol the first product of their joint effort to develop next-generation biofuels. In Europe, the Swiss company Butalco is developing genetically modified yeasts from the production of biobutanol from cellulosic material. Gourmet Butanol, a U.S. company, is developing a process that utilizes fungi for the same purpose. Almost every month, plans for a new butanol production plant are announced somewhere in the world. Many refineries that formerly produced bioethanol are now being retrofitted to produce biobutanol instead. DuPont says the conversion is very easy.

What are the possible drawbacks? Well, to match the combustion characteristics of gasoline, butanol will require slight fuel-flow increases, although not as great as those required for ethanol and methanol. Butanol also may not be compatible with some fuel system components. It can also create slight gas-gauge misreadings.

While ethanol and methanol have lower energy density than butanol, both have a higher octane rating. This means butanol would not be able to function as an octane-boosting additive, as ethanol and methanol are now doing. There have been proposals; however, the proposals are for a fuel that is 85 percent ethanol and 15 percent butanol (E85B), which eliminate the fossil fuels from ethanol mixes altogether.

The only other objection that has been raised is that consumers may object to butanol’s banana-like smell. Other than that, the only problem is cost. Production of butanol from a given substratum of organic material is slightly lower than ethanol, although the increased energy content more than makes up for the difference.

Ironically, the EPA’s decision to cut back on the biofuels mandate for 2014 is now driving some refiners to convert to butanol, since its greater energy density will help it overcome the 10 percent “blend wall.”

“Michael McAdams, president of the Advanced Biofuels Association, an industry group, said butanol was a ‘drop-in’ fuel, able to be used with existing gasoline pipelines and other equipment because it does not have a tendency to take up water, as ethanol does,” The New York Times reported last October. “‘It’s more fungible in the existing infrastructure,’ he said. ‘You could blend it with gasoline and put it in a pipeline — no problem.’

“Butanol would also help producers get around the so-called blend wall, Mr. McAdams said…With the 10 percent limitation, ‘you don’t have enough gasoline to put the ethanol in,’ he said. ‘You don’t have that problem with butanol.’”

So here’s to butanol. It will be yet another big step in reducing our dependence in foreign fuels.

Arctic Leaf

Take me shopping for eggs, copper and corn starch

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Good news for a world often filled with bad news has recently been generated by two major U.S. universities, both in regards to the efficacy of alternative fuels. Maybe the announcements will lend confidence that America can find a way to balance economic growth with environmental concerns. Increasing success over time will mean that (paraphrasing in part, the late Sen. Robert Kennedy) the nation will not have to accept “what is” with respect to the dominance of gasoline as a fuel, but can consider “what could be” concerning the use of alternative, cleaner, safer, environmental-better and cheaper fuels.

Stanford University professors, in a paper co-authored by Dr. Matthew Kanan, assistant professor of chemistry, announced that they have developed a copper catalyst that can efficiently convert carbon monoxide and water into ethanol. Quoting from a recent MIT Technology Review (April 2014), “while the work is still experimental, it’s significant because the group was able to synthesize ethanol and other desired products with so little energy input.” The Stanford researchers envision a “two-step process in which carbon dioxide is first converted into carbon monoxide using either existing processes or more energy-efficient ones that are currently under development. Then, the carbon monoxide would be converted to ethanol or other carbon-based compounds electrochemically. The key to the new catalyst is preparing the copper in a novel way that changes its molecular structure.”

How long will it take to get from idea to market? If the copper-based process survives further lab tests and evaluations, and if it is then converted into a prototype that is able to produce ethanol fuel, a big push to convert the prototype to real-world status from both the private sector and government would be warranted.

Stanford’s “breakthrough” — if the process becomes marketable and can generate lower-priced, environmentally-safe ethanol that is capable of fueling flex-fuel vehicles (FFVs) and older, converted FFVs — will be significant, even perhaps a disruptive technology. With the proper support, hopefully in the not-too-distant future, increased use of the copper catalyst will minimize and maybe even end the food vs. fuel and land-use allocation fights, as well as help resolve GHG emissions and other pollutant issues that have sometimes frustrated the use of corn-based ethanol and muted receptivity to natural-gas-based ethanol. Technological improvements concerning production reflected in recent life-cycle analysis of corn-based ethanol and reasonable assumptions concerning the cost and environmental benefits of natural-gas-based ethanol, combined with the success of Stanford’s copper catalyst approach, could offer owners of FFVs (both converted and new vehicles) a wider variety of alternatives to secure ethanol that, clearly, will be cheaper, safer and better for the environment.

Stanford’s good news was matched by Cornell’s. Dr. Yingchao You and Dr. Hao Chen announced that they had discovered that a component of corn starch and the yolk shell structure of eggs improve the durability and performance of lithium batteries. In this context, they note that lithium-sulfur batteries are a very solid alternative to lithium-ion batteries. Stabilization problems related to its capacity can be resolved by using amylopectin, a polysaccharide (mainly good old corn starch).

Enveloping the battery’s lithium sulfur cathodes, with an encasing resembling the shell of an egg yolk (sulfur coated with an inexpensive polymer) also apparently improves the battery’s durability and performance.

Cornell has initiated a startup company to take the new and improved starch, egg-yolk shell battery to market. Maybe sometime soon, moderate and middle-income owners of electric cars that are less expensive than what is now available will be able to reduce their fear of driving long distances and feel confident about the life and efficiency of the batteries in their vehicles.

I avoided chemistry, physics and engineering in college. I knew I was not destined to become neither city planner nor designer at MIT when my first student-planned bridge went under water instead of over it. While my efforts were applauded by the Malthusians among my colleagues, they were not regarded highly by professors. Since graduation, unless supported by respected colleagues with a background in relevant sciences and engineering, I have been hesitant to suggest approval of science-driven energy innovations. I am a policy and program person. However, after review and discussions with trusted experts, I believe the Stanford and Cornell initiatives have a good chance to see the light of day, or, more appropriate, see the light in the market place. If one or both do, we will all be better off and the number of feasible alternative transportation fuels available to the consumer will grow. Hooray for copper, starch and eggs.

Arctic Leaf

Of myths, oil companies and a competitive fuel market

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I do not wish to join the intense dialogue concerning whether or not the government should allow exports of crude oil. Others are already doing a good job of confusing and obscuring the pros and cons of selling increased amounts of America’s growing oil resources overseas.

What I do want to do is just focus on the logic of one of the oil industry’s major arguments for extending the permitting of exports — again, not on the wisdom of exporting policy. Permit me to do so in the context of the industry’s long-standing argument concerning the pricing of gasoline to U.S. consumers. The argument is that more oil drilling in the U.S. will lower the price of gas and put America on the path to oil “independence.”

In somewhat of circuitous manner, oil companies are using the opposite of their domestic advocacy for “drill, baby, drill” policy as a way to keep prices lower at the pump. Their yin is that producing more oil in the U.S. and sending significant amounts overseas, combined with declining vehicular fuel demand, will lower gas prices. Economist Adam Smith would applaud the simplicity if he were alive and well. Their yang presents a bit more complicated set of “ifs.” That is, the industry presumes that fulfillment of the yen (excuse another pun) to export will result in more U.S. oil being drilled because of increased world demand generated by the assumed ability of the U.S. to produce oil at less costs than the world price for oil. It will also help foster infrastructure development in the U.S. to break up current log jams concerning oil transportation. Finally, it will facilitate more efficient refineries, allowing them to specialize in different types of oil. The yin and yang will result in (marginally) lower prices of gasoline — so goes the rhetoric and oil-industry-paid-for studies.

Paraphrasing Dr. Pangloss in “Candide,” the oil companies hope for the “best of all possible worlds.” But, before Americans run out and buy stock, note the price of gasoline does not directly reflect oil production volume. Indeed, gas prices, despite increased supplies, have gyrated significantly and now hover nationally over $4 a gallon. Generally, oil and gas prices relate to international prices, tension in the Middle East and investor and banker speculation — not always or directly domestic costs. Stockholders and executives of oil companies function not on patriotism but on profit and to the extent that the law permits, they will sell overseas to get the best price — in effect, the best dollar over payment for a barrel of oil. Consumers, I suspect, are rarely a significant part of their opportunity costing.

Unfortunately, lack of strong empirical evidence tempers the company’s argument that increased world demand will stimulate good things like refinery efficiency and log-jam-ending infrastructure. Maybe if the price per barrel is right (clearly, higher than it is now) and seems predictable for more than a small period of time, refinery and infrastructure developments will be positive. But, the costs to the consumer, in this context, will be higher. It will also be higher because shale oil is tight oil and more risky and costly to drill.

Oil independence is a myth suggested by oil industry and a non-analytical media. Certainly, the oil boom and less vehicular demand have generated less imports and less dependency. But we still buy nearly 300 billion dollars’ worth of oil every year to respond to need and we still produce far less than demand.

Somewhere in the dark labyrinth of each major oil company is a pumped-up (another pun), never-used, secret justification for franchise agreements impeding the sale of alternative fuels in their retail outlets. To alleviate guilt, it may go something like this: “Monopolies at the pump will allow us to make larger profits. You know we will someday soon want to give back some of the profits to consumers by lowering the price of gasoline.” If you believe this still-secret beneficence, let me sell you the Brooklyn Bridge.

There is another way to steady the gasoline market and lower consumer costs. Inexpensive conversions to allow older vehicles to use safe, cheaper and environmentally better alternative fuels (as opposed to gasoline), combined with expanded use by flex-fuel owners of alternative fuels, would add competition to the fuel market and likely reduce prices for consumers. Natural-gas-based ethanol is on the horizon and methanol, once the EPA approves, will follow, hopefully shortly thereafter. Electric cars, once costs are lower and distance on single charges is higher, will be a welcome addition to the competitive mix.

Arctic Leaf

Is Elon Musk the next Henry Ford?

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Elon Musk doesn’t mind making comparisons between himself and Henry Ford. Others are doing it as well.

In announcing his plans for a “Gigafactory” to manufacture batteries for a fleet of 500,000 Teslas, Musk said it would be like Ford opening his famous River Rouge plant, the move that signaled the birth of mass production.

The founder of PayPal and current titular leader of Silicon Valley (now that Steve Jobs is gone), Musk is not one for small measures. The factory he is now dangling before four western states would produce more lithium-ion batteries than are now being produced in the entire world. And that’s not all. He’s designing his new operation to mesh with another cutting-edge, non-fossil-fuel energy technology – solar storage. His partner will be SolarCity (where Musk sits on the board), run by his cousin Lyndon Rive. Together they are looking beyond mere automobile propulsion and are envisioning a world where all this solar and wind energy stuff comes true.

So, is Musk a modern-day Prometheus, bringing the fire to propel an entirely new transportation system? Or, as many critics charge, is he just conning investors onto a leaky vessel that is eventually going to crash upon the shores of reality? As the saying goes, we report, you decide.

One investor that is already showing some qualms is Panasonic, which already supplies Tesla with all its batteries and would presumably help the company fill the gap between the $2 billion it just raised from a convertible-bond offering and the $5 billion needed to build the plant. “Our approach is to make investments step by step,” Panasonic President Kazuhiro Tsuga told reporters at a briefing in Tokyo last week. “Elon plans to produce more affordable models besides [the] Model S, and I understand his thinking and would like to cooperate as much as we can. But the investment risk is definitely larger.” Of course, this is Japan, where “the nail that sticks out gets hammered down.” Corporate executives are not known for sticking their necks out.

Another possible investor is Apple, which has mountains of cash and, at least under Steve Jobs, was always willing to jump into some new field – music, cell phones – to try to set it straight. This is a little more ambitious than the Lisa or the iPod and Jobs is no longer around to steer the ship, but Apple and Musk officials held a meeting last spring that stirred a lot of talk about a possible merger. A much more likely scenario, according to several commentators, is that Apple would become a major player in the Gigafactory.

And a Gigafactory it will be. Consider this. The three largest battery factories in the country right now are:

1)    The LG Chem factory in Holland, Mich. is 600,000 square feet, employs 125 people and produces 1 gigawatt hour (GWH) of battery output per year.

2)    The Nissan factory in Smyrna, Tenn. is a 475,000 square-foot facility with 300 employees puts out 4.8 GWH per year.

3)    A123 Systems’ battery factory in Livonia, Mich. is 291,000 square feet, employs 400 people and produces 0.6 GWH per year.

Both LG and Nissan received stimulus grants from the Department of Energy, built to overcapacity and are now operating part-time.

Now here’s what Musk is proposing. His Gigafactory would cover 10 million square feet, employ 6,500 people and produce 35 GWH per year of battery power. Basically, Musk’s operation is going to be ten times better anything ever built before, at a time that most of what exists isn’t even running fulltime. Does that sound like something of Henry-Ford proportions? Similar to Ford’s $5 a day wages, perhaps?

There are, of course, people who think all of this is crazy. In the Wall Street Journal blog, “Will Tesla’s $5 Billion Gigafactory Make a Battery Nobody Else Wants?,” columnist Mike Ramsey expresses skepticism over whether Tesla’s strategy of using larger numbers of smaller lithium-ion is the right approach. “Every other carmaker is using far fewer, much larger batteries,” he wrote. “Tesla’s methodology – incorrectly derided in its early days as simply using laptop batteries — has allowed it to get consumer electronics prices for batteries while companies like General Motors Co. and Nissan Motor Co. work to drive down costs without the full benefits of scale. Despite this ability to lower costs, no other company is following Tesla’s lead. Indeed, in speaking with numerous battery experts at the International Battery Seminar and Exhibit in Ft. Lauderdale a few weeks ago, they said that the larger cells would eventually prove to be as cost effective, and have better safety and durability. This offers a reason why other automakers haven’t gone down the same path.

But Musk has managed to produce a car that has a range of 200 miles, while the Leaf has a range of 85 miles and the Chevy Spark barely makes 82. Musk must be doing something right. And with Texas, Arizona, Nevada and New Mexico all vying to be the site of the Gigafactory, it’s more than likely that the winning state will be kicking in something as well. So, the factory seems likely to get built, even on the scheduled 2017 rollout that Tesla has projected.

At that point, Musk will have the capacity to produce batteries to go in 500,000 editions of the Tesla Model E, which he says will sell for $35,000. Sales of the $100,000 Model S were 22,000 last year. Does this guy think big or what?

To date, Silicon Valley doesn’t have a terribly good record on energy projects. Since Kleiner Perkins Caufield & Byers fell under Al Gore’s spell in 2006, its earnings have been virtually flat and the firm is now edging away from solar and wind investments. Venture capitalist Vinod Khosla’s spotty record in renewables was also the subject of a recent 60 Minutes segment. But, as venture capitalists say, it only takes one big success to make up for all the failures.

Will Tesla’s Model E be the revolutionary technology that, at last, starts making a dent in oil’s grip on the transportation sector? At least one investor has faith. “I’d rather leave all my money to Elon Musk that give it to charity,” was the recent evaluation of multi-billionaire Google founder Larry Page.

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Outnumbered 100-to-1, Methanol Is Upbeat

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“Why is it that we hear every day some new story about Elon Musk’s electric car, about Clean Energy Fuel’s efforts to build a CNG highway, or about some laboratory breakthrough that is at last going to bring us cellulosic ethanol, yet with methanol now cheaper than gasoline, you still never hear anything about it?”

That’s the question I posed to the three-member panel while serving as moderator for the wrap-up session at the 2014 Methanol Policy Forum in Washington last week.  The sponsors were the Methanol Institute, the Institute for the Analysis of Global Security (IAGS) and the Energy Security Council.

Anne Korin, co-director of IAGS, who earlier had moderated an even bigger panel that included former U.S. Senator J. Bennett Johnston, former National Security Advisor Robert McFarlane and former Ambassador to the European Union Boyden Gray, had a very unusual answer.  “If I may be permitted to be a bit cynical here,” she said, “I think the reason may be because methanol doesn’t require any subsidies.”  The implication, of course, is that those who come to Washington begging for money receive a lot more attention from Senators and Congressmen than those who don’t.

The question of politics versus economics had been raised at the outset of the daylong conference by Korin’s co-director at IAGS, Gal Luft, in his opening remarks.  “We’ve all heard this business about the circular firing squad and how the various alternatives to foreign oil shouldn’t be fighting each other,” he told the audience of about 400.  “But you have to acknowledge the importance of what goes on in Washington.  You can’t just talk about production ― you need money.  If you’re not at the table, that means you’re probably on the menu.

Luft showed a chart illustrating that while corn ethanol production exceeds methanol production by a factor of only 5-to-1 (14 billion gallons/year as compared with 2 bg/yr), the amount of money spent lobbying for ethanol is 50-to-1 (less than $100,000 vs. $5 million).  “When you add in the politics of the farm belt, it’s probably closer to 100-to-1,” he added.

So was anyone discouraged?  Not at all.  The news from industry executives is that methanol production is ramping up everywhere due to the bonanza of the fracking revolution.  It seems like only a matter of time before the idea of replacing large portions of our fuel imports with domestically produced methanol begins to command attention.

“In the past decade we closed down five methanol plants in the U.S. and moved them all to China,” John Floren, CEO of Methenex told the gathering of 400 at the Capital Hilton.  “The price of gas had become just too high.  Now we’ve moved two plants back from Chile and are looking at a third relocation.  We’ve got 1000 people working on our Louisiana site.  The chemical industry is starting to build as well.”

Tim Vail, the CEO of G2X, another methanol producer, had a similar take.  “The U.S. is a great place to invest right now,” he told the audience.  “The argument was always that you had to go to the ends of the earth to build methanol plants because that gas wasn’t available here.  Now all that has changed.  Our big worry is labor shortages but the construction industry is responding to our needs.  It takes away a lot of anxiety about having your assets appropriated by other countries.  China may seem like a good place to invest, but can you really trust the rule of law?”

Philip Lewis, chief technology officer of Zero Emission Energy Plants (ZEEP) was equally upbeat.  “I think the whole shale thing is being underestimated,” he said at the close of the morning session.  “It’s another industrial revolution.  And it won’t happen anywhere else because we have the thing that makes it work – private ownership of the resource.  In France, the government owns all the mineral rights and no one wants drilling on their land.”

But governments do have control over other things in this country and there was some questioning of whether federal agencies will be receptive to methanol as a fuel substitute or additive.  Matt Brusstar, deputy director of the EPA’s National Vehicle and Fuel Emissions Laboratory, claimed that his agency had been in the lead of methanol development for 30 years.  “Charlie Grady, who was in our department, was a big supporter of methanol,” said Brusstar.  “He even wrote a book about it.”  (Unfortunately, a Google search for Charlie Grady and methanol turns up no mention of Grady or his book.)  Patrick Davis, the director of the Fuel Cell Technologies Office in the Department of Energy, was even less encouraging.  “The Office of Science does not currently have any projects to create methanol as an end fuel,” he said.  “It could take a decade to sell enough methanol-compatible vehicles before a widespread distribution network would be feasible.”

When I queried Brusstar about Robert Zubrin’s documentation of the multi-thousand-dollar fines that the EPA is imposing for unauthorized conversions of engines to methanol, [See “Making the Case for Mars and Methanol,” Feb. 11] several government officials, plus Fuel Freedom Foundation director of research Mike Jackson, argued that faulty conversions can increase air pollution.

Despite the notable lack of enthusiasm from government agencies, however, there was a strong sense among the rank-and-file that methanol may be about to find a place in the sun.  “This is a much bigger crowd than we’ve ever had,” said one veteran of previous conferences.  “It’s a very exciting time for methanol.”

 

 

 

 

 

 

 

 

 

 

 

 

 

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Can New Catalysts Turn the Corner for Methanol?

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The concept of converting our abundant natural gas supplies into liquid methanol in order to replace oil in our gas tanks has had trouble gaining traction for several reasons, all of which are about to face change.

The first reason is that most of the attention towards additives has been focused on ethanol made from corn. Driven by highly specific government mandates, corn ethanol — which now consumes 45 percent of the country’s corn crop — has taken up whatever role industrial methanol might have been chosen to play as a gasoline additive.

Secondly, there’s the problem of the Environmental Protection Agency. Not only has the EPA not approved methanol for gas tanks, the organization actually imposes huge fines on anyone who converts a gasoline engine to methanol without its permission.

The third, and less distinguishable explanation for methanol’s difficult implementation, is that the whole idea has never been very sexy. Methanol has little to do with the “Cutting Edge” or the “New Age Economy.” The manufacturing of methanol is a 60-year-old process practiced doggedly by dozens of industrial facilities around the world. They produce 33 billion gallons a year at the reasonable price of $1.50 per gallon; the energy equivalent of $2.35 gas. Meanwhile, Elon Musk seems to announce a new milestone for the Tesla, or some “breakthrough” in battery technology or cellulosic ethanol emerging from the university laboratories each week, making methanol appear rather plain-Jane and old fashioned. In effect, the solution to our gas tank woes has been hiding before us in plain sight.

Now an announcement from the Scripps Howard Research Institute and Brigham Young University may change everything. In a paper published last week in Science, a team led by Roy Periana of the Scripps Florida Center and Professor Daniel Ess of Brigham Young University say they have found catalysts made from the common elements of lead and thallium that facilitate the conversion of gaseous methane to liquid methanol, potentially making the process even cheaper and more accessible.

The hydrogen bonds in the alkanes (methane, ethane, propane, etc) are among the strongest in nature. To break them involves a heat-driven process invented in the 1940s that is conducted at 900 degrees Celsius. For more than two decades, the Scripps team has been looking for catalysts that would shorten this heat requirement. In the 1990s they came up with a series of catalysts employing platinum, palladium, rhodium and gold, but quickly realized that these elements were too rare and expensive for commercial application. So it was back to the drawing boards in search of something more useful.

Last week in Science they reported success:

The electrophilic main-group cations thallium and lead stoichiometrically oxidize methane, ethane, and propane, separately or as a one-pot mixture, to corresponding alcohol esters in trifluoroacetic acid solvent.
The process reduces the heat requirement to only 200 degrees Celsius, which introduces enormous potential for energy savings. That “one-pot” notation is also crucial. Methane, ethane and propane all come out of the Earth together in natural gas. Currently, they must be separated before the heat-driven process can begin, With the new catalysts, no separation will be necessary. This means that methanol could become significantly cheaper to harvest than it already is. More importantly, these findings signify that methanol conversion will be able to weather the inevitable price increases that will result as demand for natural gas supplies multiplies.

Periana says the process is three years from commercialization. Reports Chemical & Engineering News:
The team is in discussion with several companies and entrepreneurs and would ideally like to jointly develop the technology with a petrochemical company or spin off a startup.

Periana also claims that “Initial targets would be higher-value, lower-volume commodity chemicals such as propylene glycol or isopropyl alcohol directly from propane.” He told reporter Stephen Ritter:

The next target could be to develop lower-temperature processes for higher-volume chemicals, such as converting methane to methanol and ethane to ethanol or ethylene as inexpensive sources for fuels and plastics.

An enormous portion of the world’s energy consumption is still tethered to oil, particularly the transportation sector, where oil constitutes 80 percent of consumption. As oil becomes more and more difficult to find, natural gas use is escalating. In addition, 25 percent of the world’s gas is still flared off because it has been uneconomical to capture. All this could change rapidly if a low-cost conversion to methanol becomes a reality. Reuters grasped the implications of this development when it reported that the new catalytic processes “could lead to natural gas products displacing oil products in the future.”

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Bio-processing of Gas-to-Liquids: A Report Card

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If finding microbes that can convert cellulose plant material into ethanol is of the holy grails of biofuels, an equally elusive goal is using microbes to make liquid fuels out of natural gas.

Almost everyone agrees that the best way to apply our now-abundant natural gas resources to transportation would be to convert it into a “drop-in” liquid fuel that would fit easily into our current gas-station infrastructure. T. Boone Pickens’ CleanFuels Corp. and others are trying to supply compressed natural gas to diesel trucks, but the effort has obvious impediments and will require a whole new infrastructure.

Much easier would be the direct conversion of natural gas to methanol, the simplest alcohol, which is now produced at a rate of 33 billion gallons per year for industrial purposes. But methanol still suffers from its Prohibition-Era reputation as poisonous “wood alcohol” (although gasoline is equally poisonous) and has run into stiff EPA regulations on converting contemporary engines to burn alternative fuels. (See “Making the Case for Mars and Methanol”) And so the vision has arisen that a golden gas-to-liquids pathway can be carved by the nation’s laboratories working with nature’s existing microbial stock.

A year ago, ARPA-E, the fast-track research funding agency modeled on the Defense Department’s Advanced Research Project Agency, announced a new initiative: REMOTE – the Reduced Emissions Using Methanotrophic Organisms for Transportation Energy.  Methanotrophic organisms are microbes that feast on methane, the simplest carbohydrate, and can convert it into more complex molecules such as butane or formaldehyde, which can in turn be synthesized by other microbes into butanol, methanol or other liquids that can be cleanly burned as fuels.  As the agency wrote in its Funding Opportunity Announcement (FOA):

The benefits of converting natural gas to liquid fuels for use in transportation have long been recognized. First, the existing transportation infrastructure is based on liquids, and such fuels can be conveniently “dropped in” without substantial changes in vehicles. Second, liquid fuels from methane have lower emissions than petroleum-based fuels. Liquid fuel produced from methane decreases emissions by up to 50%, compared to unconventional petroleum, and decreases particulate matter by up to 40%, compared to combustion of conventional diesel. Further, methane is responsible for 10% of the nation’s greenhouse gas emissions (on a CO2 equivalent basis), in part because its global-warming potential is 20 times greater than that of CO2 over a 100-year period. Technologies capable of capture and conversion of methane will help mitigate the global-warming potential of these emissions.

There are several interesting things going on here. First, ARPA-E has chosen the goal of reducing emissions rather than reducing dependence on foreign oil as the motivating force of the project. Alcohols do burn cleaner than gasoline. In fact, the whole California effort that put 15,000 methanol cars on the road in the 1990s was aimed at reducing air pollution, not replacing oil imports. This may satisfy environmentalists, who tend to see natural gas as just another fossil fuel and would prefer to pursue cellulosic ethanol in order to remain “carbon neutral.”

Second, although the chemical synthesis of methanol, butanol and other potential fuels is already economical, employing biotechnology gives the whole plan a “green” tinge. Chemical processes are regarded as “old economy” and unlikely to attract investment from Silicon Valley and other centers of venture capital, whereas biotechnology has a New Age sheen to it. Already ARPA-E has handed out $20 million to small startups and others have been forthcoming.

Finally, by latching onto natural gas flaring, ARPA-E is addressing a problem that is gaining more and more attention, particularly the publication of a paper in Science last week claiming that will be no climate benefits in switching from diesel and other crude-oil-based fuels to natural gas derivatives. Indeed, flaring is now said to consume the equivalent of one-third of America’s consumption of crude oil. Obviously, anything that addresses this will get attention.

So how are thing going?  Last week Robert J. Conrado and Ramon Gonzalez, two researchers in the Department of Energy, issued a progress report in Science. Basically, the news is that while there’s still lots of optimism about the idea, nothing much has been accomplished yet.

Conrado and Gonzalez note that the process of biological conversion involves three steps:   1) the “activation” of the stable methane molecule so it becomes chemically receptive; 2) the conversion of methane to formaldehyde and other intermediates; and 3) the synthesis of these intermediates into alcohols and other fuels through bioreactors. All three steps need improvement. “To access small-scale and time-varying resources [i.e., flared gas at remote wells], process intensification leading to an order-of-magnitude increase in volumetric productivities is needed and will require technological breakthroughs in [all] three areas.”

One institution that is working on the problem is the Sandia National Laboratory in New Mexico. Blake Simmons, manager of the lab’s biofuels and biomaterial science group, says the challenges are daunting but he remains optimistic. “There have been plenty of investigations into this in the past since there are plenty of organisms in nature that thrive and multiply off natural gas,” he said in an interview with Phys.org. “The problem, though, is that they exist in unique, tailored environments and are typically very slow at what they do. People have been trying to express this class of enzymes for a couple of decades, so this won’t be a slam dunk. But we have the collective experience and capabilities at Sandia to figure it out.”

And so the search for a clean, green conversion of methane to a liquid fuel goes on. In the meantime, however, it might be worth opening the door to methanol and other chemically synthesized products just as a placeholder.

Arctic Leaf

Can Sochi Lead To A New Alternative Energy Coalition?

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During the late 1980s, I had the good fortune, thanks to the Rockefeller Foundation, to lead and facilitate an Aspen Global Forum between Russian and U.S. leaders in Sochi; the site of the present Olympics. The subject was economic development in the then already fragmenting, Soviet Union.

Sochi was beautiful but back then was a relatively small resort city for vacationing Russian nomenklatura. I have three memorable funny stories (at least for me) related to Sochi. I will try linking them, for better or worse, with the need for alternative fuels.

Getting to Sochi at the time provided a unique experience. The U.S. delegation which included a former U.S. Senator, several Wall Street titans, the editor of a major national newspaper, leading members of the Denver business community and myself (I was a Dean at the University of Colorado at the time) were told when we arrived at the Moscow airport in a snowstorm, we had to fly out of Moscow’s second smaller airport. We all dutifully were taken by shuttle, very slowly given the snow, to what seemed like an old, a very old facility. We quickly boarded what appeared to be a jet plane on its last legs. It was late at night and the snow was still blowing strong. The plane’s seats were broken and the bathrooms didn’t work. The cabin crew was nice but spoke only in difficult to understand broken English. Not an auspicious start to the trip. Two members of our delegation asked the pilot for 10 minutes to go into the terminal (an exaggeration of the term) to buy two or three bottles of vodka to give us courage and calm our nerves. They did get permission. It turned into a fun flight.

After we checked into the Intourist Hotel in Sochi, we all went to bed. One of the members of our delegation was a smart, tough, but very funny reporter and op-ed writer for the Rocky Mountain News. She came down the next morning and indicated most of her winter clothes were stolen from the room, while she was sleeping. I went up to the Manager of the hotel and told him what had happened. He was dutifully contrite. Every day while we were there, the reporter received a nice gift of new winter clothing to wear in the snow. At the end of the week, I thanked him and said, next time, have them take my clothes!  He laughed. I was serious!

The Russian delegation hosted us in the summer home of an apparently famous Russian oligarch, whose name I forget, about 100 or so miles from Sochi. They took us there in big Army helicopters. We flew over and between the mountains and valleys of the Caucasus. The mountains were covered with much snow and looked gorgeous. One of the Russian guides opened the door so we could get a closer view. A big mistake! A member of the U.S. delegation, a well-known war experienced woman journalist, based I believe at the time in D.C, shouted close the f….n door. “I have covered many wars and been shot at. I survived. I don’t want to go down in a helicopter. We can look at the snow through a window.” She was right. At that point the helicopter seemed tilted at a significant angle to please us. We all were a bit scared but didn’t want to hurt our Russian hosts. She had no such fear. The door was closed.

If anything, except fuzzy memories, ties these stories together, it’s the snow and the mountains and a thought about building a coalition around alternative and renewable fuels to save the beauty of both and to the jobs they provide both up and down stream.

Based on the over 50 degree temperatures in Sochi during the current Olympics and the lack of abundant snow, The New York Times indicated that Daniel Scott, a professor of global change and tourism at the University of Waterloo in Ontario, was stimulated to project the future of winter sports. He noted that with a rise of global temperature possible by 2100 of 7 degrees Fahrenheit, there might not be many snowy regions left to hold the Winter Olympics.  He concluded “that of the 19 cities that have hosted the Winter Olympics, as few as 10 might be cold enough by midcentury to host them again. By 2100 the number will shrink to six.”

Of the 960,000 winter sports industry jobs are supported by winter sports in the U.S. 27,000 have already been lost because of lack of snow, according to a recent NRDC report. More will be gone next season if snow fall totals continue to decline.

If we can easily check the box on one or more of the following: concern for the health of the economy, concern for the environment, concern for the quality of our water supply and the availability of water, concern for the future of the ski industry and winter sports off and on mountains, then even if we don’t ski, and even if greenhouse gas is not a top priority for some , we should be able to foster a strong coalition between environmentalists, business, nonprofits,  natural gas and renewable fuel  advocates. Its mandate would be to work on speeding up use of alternative natural gas based transitional fuels  and helping place electric cars on a faster and cleaner track to market acceptance. The strategy is not perfect by any stretch of the imagination but it will at least get the country started on a path that will reduce harmful environmental impacts of gasoline including significant GHG emissions and other pollutants. It may also help slow down the browning of our mountain areas and the closure of winter resorts and the manufacturing and retail sectors that serve them.

America needs a good dose of pragmatism and probability curves to guide its fuel policies. Advocates of natural gas based fuels and renewables should be able to coalesce around the President’s agenda with respect to weaning the nation off gasoline (one of the biggest carbon emitters) and gasoline only vehicles.

Assuming electric utilities continue to switch from coal to cleaner natural gas; scholars suggest that electric cars will be of help in reducing total carbon emissions. But EV’s are not yet ready for prime time for most low, moderate and middle class households, in light of the relatively low mileage secured on a single battery charge, the absence of retail distributers, the small vehicle size and price. When they are, let the competition begin, remembering all the while that real change in emissions and reduction of pollutants, will come after the conversion of large numbers of existing cars to flex fuel vehicles and their ability to use natural gas based fuels. Back to Sochi and indeed to the mountains throughout America, when we are asked every Christmas whether there is a Santa Claus, lets us be able to look up at magnificent snow-capped mountains and collectively say, yes there is a Santa Claus and then sing loudly, Let it snow, Let it snow, Let it snow.

 

Arctic Leaf

Can Butanol Be the New Ethanol?

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Even as the ethanol industry is wobbling over the Environmental Protection Agency’s decision to cut back on the ethanol mandate in 2014, a new candidate has emerged as an additive to gasoline – butanol.

Virgin Airways founder and CEO Richard Branson has announced that his Virgin Green Fund will be cosponsoring a groundbreaking butanol manufacturing plant in Luverne, Minnesota.  “Butanol is the future of renewable fuel,” said Branson, who is already using renewable jet fuel for his airline.  “It’s hugely versatile and can be used to produce gasoline fuel blends, rubbers, solvents, and plastics, which gives us scope to enter a range of markets,” he said in an interview with Bloomberg.

Corn ethanol now dominates the $26 billion gasoline additive market, drawing the glucose content out of 45 percent of the nation’s corn crop (the protein is fed to animals).  Branson’s butanol would use a similar feedstock – corn, sugar cane or cellulosic biomass – but would produce a fuel that has 84 percent of gasoline’s fuel density compared to ethanol’s 66 percent, although ethanol has a higher octane rating.  The implication is that butanol could be mixed at higher blends, giving it almost the same range as gasoline.

Both butanol and ethanol are made through a process that employs yeasts to ferments the glucose from organic material into alcohols.  Methanol, the simplest alcohol, has one carbon joined to a hydroxyl ion while ethanol has two carbons and butanol has four.  Octane, the principal ingredient in gasoline, has eight carbons without the hydroxyl ion.

As far a butanol is concerned, it’s not as if people haven’t tried this before.  Both BP and Royals Dutch Shell have experimented with producing butanol from organic material but have found the process harder than they anticipated.  “There is certainly a potential, but there have been quite considerable problems with the technology,” Clare Wenner, of the London-based Renewable Energy Association, told Bloomberg.  “It’s taking a lot longer than anybody thought years ago.”

Gevo’s plant in Minnesota, for instance, has been running at only two-thirds of its 18 million gallon-a-year capacity because of a contamination in its yeast fermenting facility in September 2012.  Similar instabilities in the microbial-based process have dogged the efforts to break down cellulose into simple molecules.  There operations can often be performed in the laboratory but become much more difficult when moved up to a commercial scale.

Branson is confident these obstacles can be overcome.  He’s already got Silicon Valley investor Vinod Khosla on board in Gevo and Total, the French oil company, has also taken a stake.  Together they have enlisted big ethanol producers such as Big River Resources and Siouxland Ethanol to commit to switching their manufacturing process to butanol.  Butamax Advanced Biofuel, another Minnesota refiner funded by Dupont and BP, is also in the process of retrofitting its ethanol plant to butanol.  Taken together, these facilities would be able replace 1 billion of the 14 billion gallons of ethanol now being produced every year.

Whether this would be enough to make a bigger dent in America’s oil import budget remains to be seen.  The 14 billion gallons of ethanol currently substitutes for 10 percent of our gasoline and about 6 percent of our total oil consumption.  The Environmental Protection Agency has limited ethanol additives to 15 percent of the blend, mainly to protect older cars.  (In Iowa, newer cars are running on an 85 percent blend.)  Now the reduction in the 2014 mandate is making the ethanol industry nervous about overcapacity.  Butanol is less corrosive of engines and the 16 percent blend could give it an edge.

On another front, T. Boone Pickens’ Clean Energy Fuels announced this week that it may turn a profit for the first time since its founding in 1997.  Clean Fuels is concentrating on supplying compressed natural gas for trucks, signing major contracts with Frito-Lay, Proctor & Gamble, United Parcel Service and Ryder.  It is also attempting to set up a series of filling stations on the Interstate Highway System.  The use of CNG requires an entirely new infrastructure, however, rather than the easy substitution of liquid and butanol.

The dark horse here is methanol, which is liquid and fits easily into our present infrastructure but would be synthesized from natural gas.  Somehow, methanol has not attracted the attention of Branson’s biofuels and Pickens’ CNG.     All of these efforts hold promise, however, and would make a huge dent in our annual $350 billion bill for oil imports, which constitutes the bulk of our $450 billion trade deficit.  So good luck to all and may the best fuel win – or all of them, for that matter.