Category → Research
What’s the difference between a bartender and a biofuels researcher? A bartender uses ethanol to make cocktails, while a biofuels researcher uses cocktails to make ethanol. Researchers at the Department of Energy’s Pacific Northwest National Lab have developed a probe to help create the most efficient cocktails for biofuels makers.
A biofuel-making cocktail is a blend of enzymes that break down biomass (like corn stalks). And apparently the fungus Trichoderma reesei is a veritable Swiss Army knife of enzymes. T.E., as we’ll call it, is a mesophilic soft-rot fungus which was famous in World War II as the stuff that chewed through military tents in the Pacific Theater. It contains 200 sugar molecule busting enzymes (glycoside hydrolases) including 10 that chomp cellulose and 16 that consume hemicellulose. This variety is helpful, because no single enzyme can profitably make ethanol from cellulose.
To make biofuels, companies either make or purchase custom blends of enzymes that function at the needed pH, temperature, nutrient environment, and chemical conditions. Companies like Novozymes sell optimized blends of enzymes.
But with PNNL’s probes, cocktail DIY’ers can get in on the action. Currently, enzyme assays only show the total mixture activity of all enzymes, not the activity of individual enzymes. But the activity-based probe method quickly identifies and quantifies the activity of individual enzymes in a mixture, allowing high throughput analysis with gel electrophoresis or LC-MS-based proteomics. The research showed that the different processing conditions had a significant impact on the activity of individual enzymes. Armed with this knowledge, an enzyme mixologist would be able to more quickly identify the best ingredients for their biofuels process.
Reference [free download with registration at RSC]: Lindsey N. Anderson, David E. Culley, Beth A. Hofstad, Lacie M. Chauvigné-Hines, Erika M. Zink, Samuel O. Purvine, Richard D. Smith, Stephen J. Callister, Jon M. Magnuson and Aaron T. Wright, Activity-based protein profiling of secreted cellulolytic enzyme activity dynamics in Trichoderma reesei QM6a, NG14, and RUT-C30, Molecular BioSystems, Oct. 9, 2013, DOI: 10.1039/c3mb70333a.
It sounds like something from a greenskeeper’s nightmare – certain folks have plans to grow algae and dandelions on purpose, and in large quantities.
Firstly, in the golf course-choked state of Florida, Algenol CEO Paul Woods is scouting a location for a $500 million algae-to-fuels plant. The company was founded and has been operating in the southern part of the state for years now. Its claim to fame is cheap ethanol made from cyanobacteria in a custom-designed bioreactor. Woods does not, as far as I know, have plans to re-purpose stagnant water traps for the purpose of growing his feedstock.
But Florida, though it is sunny and warm, might have missed out on this slimy opportunity. In recent months, Woods questioned the state’s commitment to biofuels. For example, Governor Rick Scott repealed a state law requiring 10% ethanol in gasoline. But now, according to Fort Myers ABC 7 News, the company has been persuaded to build in its home state – apparently the estimated 1,000 jobs was just the ticket to getting a warmer welcome. Algenol needs to be sited near a major CO2 source (i.e., factory or power plant emissions) and says potential partners have come forward.
Meanwhile, it’s called the Russian Dandelion, though it grows in Germany. This common lawn scourge is bringing about not curses, but praise, for its rubber producing capability. Tire makers are enthused about its white latex sap. The goo is expected to give the subtropical rubber tree a bit of competition. Making rubber from dandelions is not a new idea, but has been given new life by a project at the Fraunhofer Institute for Molecular Biology and Applied Ecology.
Fraunhofer scientists, in a collaboration with folks from tire firm Continental are working on a production process for making tires from the dandelions. In addition to the manufacturing process, the researchers are also using DNA markers to grow new varieties of the plant with higher rubber yields.
The project sounds kind of cute but the researchers behind it are dead serious. The partners have already begun a pilot project and plans are afoot to move to industrial scale. According to them, the first prototype tires made from dandelion rubber will be tested on public roads over the next few years.
You can read an earlier post on the history of dandelion rubber here.
In Solar, a novel by acclaimed author Ian McEwan, the protagonist, a physicist named Michael Beard, has been tasked to evaluate submissions from the public sent to a UK panel looking for new ideas for clean energy. He divides them into piles: those that violate the first law of thermodynamics, those that violate the second law, and those that violate both. This cleantech reporter could relate.
That’s why ideas that start with the laws of thermodynamics – rather than those that have to account for them later – are so attractive. Take entropy, for example. In our daily life we struggle against entropy – the iPod headphone wires that get totally knotted up in my handbag, the fact that the neatest person you know still has a junk drawer, and so on.
This week’s issue of C&EN explores research that tries to harness the universe’s arrow-like movement to disorder. When CO2 laden emissions from power plants are released into the atmosphere, the CO2 mixes into the ambient air mass. As Naomi Lubick explains, an electrochemical cell could harvest the energy that is released when these two gases mix. Researcher Bert Hamelers of the Dutch water treatment tech center Wetsus, has developed a lab scale device to do just that.
But Lubick points out that to implement such a solution would require overcoming at least two hurdles – one, the sulfur dioxide and nitrogen oxides may foul the system’s membranes. And two, it is no easy task to dissolve huge amounts of CO2 in liquid.
In fact, dissolving the gas uses quite a bit of energy. Which reminds me of another literary reference: the witches of Shakespeare’s MacBeth chant “Double, double, toil and trouble; Fire burn and cauldron bubble” – indeed, there is some toil and trouble involved.
I know that many other researchers and technology companies are working on these two problems. For example, there are programs working on carbon capture and storage that are using liquids, catalysts and membranes to grab components of power plant emission gases. And firms such as Calysta Energy and Lanzatech have plans to use microbes to make useful products out of gases such as methane and flue gas. For that, they need to dissolve the gas in water. It is not a trivial problem.
This week’s cover story – Seeking Biomass Feedstocks That Can Compete – discusses the competition that natural gas might bring to the young renewable fuels and chemicals industry. [You can also check out the YouTube video about Energy Cane]
The story discusses one positive that the rise of natural gas brings to biobased chemical makers – at least those that produce C4 chemicals (i.e. butanediol, butadiene). As the chemical industry swaps petroleum feedstocks for natural gas, their processes will generate a much smaller ratio of C4 chemicals. Firms that rely on those intermediates will seek other sources of C4s.
But there are a few other ways that the natural gas story intersects with the renewable industries – some obvious, and some not so obvious. One obvious way – cheaper energy from natural gas may help decrease operating costs at all chemical producers, including ones that use biomass feedstocks.
Less obvious – there is a group of renewable companies that use syngas as a feedstock. You know what makes an excellent syngas? Why, that’d be natural gas. Sure, you could gasify plant matter, old tires, construction debris, municipal waste (anything carbon based). Any of those feedstocks will make a flow of carbon monoxide and hydrogen. With chemical or biological catalysts, that syngas can be made into chemicals and fuels.
At least two firms that started out with plans to make syngas from biomass or waste sources now say they will ramp up on natural gas – Coskata, and Primus Green Energy. Coskata’s end product is ethanol, while Primus is targeting drop-in hydrocarbons. Presumably, with a working gasifier and catalysts, they could switch feedstocks whenever the cost basis dictates.
Newlight Technologies wants to make polymers from waste gases like methane from water treatment plants. But methane from under the ground would work well, too. The company says it can also make polymers from CO2 (with a helping hand from a hydrogen generator). Which brings us to…
BASF, which is not really a renewable company, but has got some irons in the fire. The chemical giant has a research project going to rip the hydrogen off of natural gas, and mix that with waste CO2 to make a custom-blended syngas. The firm says getting hydrogen this way is cheaper than other ways (tearing up water molecules, etc). Waste CO2 is something many industries – especially in Europe – would like to do something with. LanzaTech is also in the waste CO2 business. Not sure what its natural gas plans are.
Lastly, two stalwarts of the biobased chemicals industry, Genomatica and OPX Bio are getting a handle on natural gas. Genomatica is working with Waste Management to make C4s from syngas (derived from municipal waste). The syngas project came up in my interview with Genomatica’s CEO Christophe Schilling about natural gas.
More directly, OPX Bio, which is working to make acrylic acid from sugar, has a lab-scale project for its second product – fatty acids. The company says its process can use syngas made from all the usual suspects including natural gas. There is already a significant market for chemicals based on fatty acids; they can also be converted into nice things like jet fuel.
Natural gas is not a renewable resource, so one might wonder why these green tech firms would bother using it at all. I can think of three reasons: one – as a first feedstock to prove one’s catalyst technology, two, as an alternate feedstock to balance price and availability of biomass or waste, and three, as a way to fix the mass-balance of hydrogens and carbons in your syngas. If adding 10% of syngas increases yields by 20%, that might be tempting.
There is one way that natural gas as a feedstock might be considered “green.” This comes via Alan Shaw of Calysta. The company uses methane munching bacteria to capture natural gas, then enzymes in the cells can make desired products. Shaw suggests a good use of the technology would be to install small-scale units where there is so-called “stranded” natural gas. That would include oil wells that flare the natural gas that comes up with the crude oil in places like North Dakota.
Behold the Gribble – a true gutless wonder. The Gribble (pictured here) is a marine wood-boring creature of around 2 millimeters in size. Scientists at the UK’s Biotechnology and Biological Sciences Research Council have been spending quality time with the Gribble because of its exceptional innards.
The tiny animal eats wood that finds its way into the sea. The wood can come from mangrove swamps or wash into estuaries from land. Gribbles, also called ship borers, have also been known to chow on wooden sailing vessels (including, rather famously, those of the Columbus voyages). “I’m sure they’ve taken down a few pirate ships, too” says Simon J McQueen-Mason a BBSRC researcher and materials biology professor at the University of York.
Most critters that eat wood or other lignocellulose plant material rely on symbiotic relationships with a diverse population of gut microbes – called the microbiome – to break down the tough-to-digest meal. When news reports suggest that pandas may hold the key to biofuels breakthroughs because they can live on tough bamboo, it’s really the microbes, and the enzymes made by the microbes, that are of interest.
(You can read a C&EN cover story about pandas, microbiomes and biofuels )
But the Gribble has no microbiome. And it doesn’t have the squishy, absorptive digestive system that most animals have. In fact, it digests its meals of wood in a sterile, hard-sided chamber in its hind gut. McQueen-Mason likens the environment to “a steel container you might use in an industrial lab.”
Instead of microbial helpers, the gribble has a separate organ where it produces the key enzyme itself. Termites do not do this (they have microbes). The gribble “must use quite aggressive chemistry; the enzyme is so harsh that it would kill any microbes” that might otherwise occupy the space, McQueen-Mason says.
The research team found the mystery organ and looked at the genes expressed there. Many of them encoded instructions for making what is called GH7 cellulase. This is a family of enzymes that are normally found in wood-degrading fungi. “These cellulases are abundant but were never reported in an animal before,” McQueen-Mason notes. “We were able to express the genes in a lab fungus and describe the properties.”
They also used X-ray crystallography to discover the structure of the enzyme and show how it binds cellulose chains and breaks them into small sugar molecules.
The Gribble’s enzyme appears to be very rugged and long-lasting, which is a good quality for an enzyme that might be used in an industrial setting to make biofuels from wood or straw, McQueen-Mason points out. It works very well in highly saline conditions and may also function well in ionic liquids. The use of salt water and ionic liquids for biofuels processing may cut down on the use of expensive, precious fresh water. And like a true catalyst, the enzyme may be reusable.
You can see a video of the Gribble – which I highly recommend – it’s kind of cute.
For more on the enzyme, check out the journal paper: ‘Structural characterization of the first marine animal Family 7 cellobiohydrolase suggests a mechanism of cellulase salt tolerance’ www.pnas.org/cgi/doi/10.1073/pnas.1301502110.
Cleantech Chemistry HQ got an interesting e-mail yesterday. It stated that Qteros, an industrial biotech start-up of yore, has resurfaced. The firm had officially closed down earlier this year “because of adverse market conditions.”
Qteros’ technology was – and is – based on what the founders call the Q microbe. This critter is a two-in-one biofactory. It chomps down on biomass and also ferments the sugars into ethanol. It seemed that the firm’s microbe was well regarded, but the path to commercialization was murky. Cleantech Chemistry earlier reported that the firm was regrouping and maybe looking for a buyer.
That buyer, it turned out, was to be three of the company’s original founders. The firm was a tech spin off of the U. of Mass. Amherst. Original COO – and now CEO – Stephan Rogers of Amherst says “Having examined all the research, we now see an immediate pathway to commercialization with the current technology. The company is going to pursue a new and different, less capital-intensive business model. Part of our strategy to quickly get to market is to partner with others who have deep experience in microbial research to help us jump-start the process.”
Also at Amherst and still on the company’s scientific advisory board is Susan Leschine, who discovered the Q microbe. Qteros’ connection to the school will remain very cozy, it appears from the press release. It seems that the developers will move in with fellow researchers and will not seek out their own lab or office space until sometime in mid 2013. So it may be a little while before we hear more about the road forward.
It’s not too often that I get a press release with a New Zealand embargo time. Waste gas to fuels and chemicals firm LanzaTech got its start in New Zealand, but is currently headquartered in Illinois. Still, the company’s larger projects are all in Asia, and being on the opposite side of the world from Cleantech Chemistry blog HQ is not a problem for them.
Yesterday (which is today in New Zealand), LanzaTech CEO Jennifer Holmgren spoke to a conference of oil refiners in New Delhi. In her remarks, she announced that the firm has a new joint development agreement with Malaysia’s national oil company Petronas.
The two firms will work to produce chemicals from carbon dioxide – the first one being acetic acid. LanzaTech already has two facilities that make ethanol from CO. In all cases, the CO or CO2 comes from waste gases. LanzaTech’s proprietary microbes ferment the gas into various end products. The Petronas deal will get its CO2 from refinery off gases and natural gas wells.
Earlier this year, the venture arm of Petronas contributed to LanzaTech’s third round of venture funding. And it seems the two companies have been in cahoots ever since.
C&EN profiled LanzaTech this summer.
And there is another cleantech firm that aims to make acetic acid – Zeachem. Zeachem is building out its plant that will produce acetic acid – as well as ethanol – from hybrid poplar grown in Oregon.
[With a note on some confusion about wheat, and if it has been genetically modified (see below)]
The herbicide 2,4 D is pretty powerful stuff. It has recently been in the news because it kills weeds that have developed resistance to glyphosate (brand name Roundup). In May, I wrote about efforts by Dow AgroSciences to bring a new genetically modified corn to market that has been engineered to be tolerant to 2,4 D.
The idea is that the new corn would withstand applications of both glyphosate and 2,4 D, and that farmers would use those two herbicides, and presumably a rotation of at least one other chemical control, to kill weeds and prevent new occurrences of resistant weeds.
Along with the new corn, Dow scientists created a new version of 2,4 D, called 2,4 D Choline, that is less likely to drift off the fields where it has been applied. Now, one group of growers, the Save Our Crops Coalition, has issued a joint statement with Dow saying that the information Dow has supplied about reduced drift and volatility, along with the company’s pledge to investigate non-target claims, has gone a long way to satisfy its concerns about migrating herbicide. Both SOCC and Dow say they have “agreed to modify positions with respect to pending regulatory matters around 2,4-D tolerant crops.”
Prior to this agreement, the Save Our Crops Coalition had used the USDA’s open comment period to request an environmental impact statement to assess the likelihood of drift from 2,4 D applications.
They pointed out that since not all farmers will be growing 2,4 D tolerant crops, drift to non-intended targets could result in significant crop damage, since it would be applied during the growing season (imaging a field of vegetables that got smogged by 2,4 D – the plants would croak along with the weeds).
I reported on Dow’s work to reduce migration of 2,4 D in the C&EN feature story. Here’s the relevant background:
David E. Hillger, an application technology specialist at Dow AgroSciences, explains that rather than traditional ester or amine forms of the molecule, which can volatilize in the environment, the new version is a more stable quaternary ammonium salt.
In addition, Hillger says Dow’s proprietary manufacturing process produces a product with less particle drift when application directions are followed. Dow recently reported that field tests of the formula showed a 92% reduction in volatility and a 90% reduction in drift.
Crops that contain the 2,4-D tolerance- trait will also tolerate older versions of 2,4-D. However, Dow has developed a stewardship program that obligates farmers to use a premixed combination of 2,4-D choline and glyphosate. The program includes farmer education about using multiple herbicide modes of action, the requirement to use Dow’s new herbicide mixture, and labeling instructions for proper application. State pesticide regulations generally require farmers to follow labeling guidelines when using herbicides.
For now DowAgrosciences is waiting on regulatory authorizations for 2,4-D tolerant corn, but the company says it plans to get the green light in time for the 2013 growing season.
Certainly there are other criticisms of the 2,4 D-tolerant crops still out there. One important concern is that farmers may use chemical fertilizers in such a way as to promote even more herbicide-resistant weeds – ones that cannot be killed with 2,4 D or glyphosate. Another is the possibility that the amount of 2,4 D used on crops will dramatically increase (glyphosate, though used in large amounts, breaks down rather quickly in soil).
And of course, foes of all types of GMO crops abound, and anyone who is against Roundup Ready corn is not likely to be in favor of the new varieties.
Speaking of which, I’ve noted a number of commentaries relating to wheat lately, apparently due to the rise of anti-gluten eating. Many leave the reader with the impression that the U.S. is awash in genetically modified wheat. This is incorrect – there are many wheat hybrids on the market today, but none have been genetically engineered.
I find it handy to refer to an online USDA list – updated seemingly daily – which lists pending GM crops as well as those that have been approved already (in the section titled Determinations of Nonregulated Status). You may want to bookmark it, or have it printed on handy cards to give to people.
Sometimes when you dig a little on Google News you find fascinating nuggets in local news of the topics that we cover here at C&EN. A great example is in Knoxville’s alternative newsweekly Metro Pulse.*
Newshound Joe Sullivan digs into what ever became of $70 million that the state of Tennessee spent in the flush days of 2007 to start up a switchgrass and cellulosic ethanol industry in the state.
The good news on the project is that the promised 250,000 gal per year cellulosic ethanol plant did open, in Vonore, Tennessee. The bad news is that it has not been using any of the switchgrass grown on 5,000 surrounding acres. The switchgrass part of the project involved the University of Tennessee Institute of Agriculture. The state figured switchgrass would grow great there. And it seems to have been correct.
Sullivan reports that more than half of the $70 million project money went to build the pilot plant. But corporate partner DuPont (now DuPont Cellulosic Ethanol) has used the pilot plant to test and demonstrate its ability to make ethanol from corn stover. Corn stover is a feedstock that is available in huge quantities…. in Iowa. As it happens, DuPont’s first commercial-scale cellulosic ethanol plant is in Nevada, Iowa, and is set to come online soon.
C&EN has mentioned the Vonore plant a half dozen times (including in a previous post on this blog). The move away from switchgrass escaped our attention, but it is an important development for the UT folks and the farmers they have been working with.
So what will happen to the 50,000 tons of switchgrass that were harvested by Vonore-area farmers? Read the story to find out.
* Edited 8/28 to correct reference to Metro Pulse
It’s been a very busy summer, but I had a chance to catch up with Rick Eno, the CEO of Metabolix, last week. Metabolix makes a bio-based plastic that it calls Mirel, though chemists call it a polyhydroxyalkanoate polymer (PHA). We last heard from Metabolix in January when its commercial-scale partnership with Archer Daniels Midland dissolved.
The breakup was a significant blow to the company in terms of growing its business and selling Mirel to customers. The partnership with ADM was based around an ADM-financed production plant capable of making 50,000 tons of Mirel per year. Unfortunately, sales ramped up slowly and ADM said the market was too risky.
Since the breakup, Metabolix has decided to launch the biodegradable Mirel bioplastic under its own nameplate, says Eno. It has transferred inventory from ADM, and brought over all the business operations. Still, the company needs a production partner.
“Since Mirel was exclusive to ADM for so long, [after the breakup] we did get inbound calls and we also reached out to potential partners to establish potential manufacturing,” Eno told C&EN. He says that rather than try to sell enough Mirel to keep a huge plant busy, he’s now looking for something closer to a 10,000 ton per year scale.
“We’ve narrowed down a large number of potential opportunities to four. Now we’re looking at engineering detail for integration of our manufacturing technology to the partners’ asset sets,” Eno reports. “We’re deeply evaluating a short list of manufacturing options.” Without ADM to center the business, Metabolix can look outside the U.S. – for example, to be closer to customers. In fact, the firm has opened a sales office in Cologne, Germany to be close to the European market.
As Alex Tullo wrote in his recent cover story on biodegradable plastics, an important market niche is in organic waste handling – specifically in municipalities where organic waste is separated and hauled to composting facilities. Eno suggests this is both a good niche for PHA, and also a great reason to be in Europe where people rigorously sort their trash.
Eno followed up on his January comments that the company would look to higher-value markets that really require biodegradability, rather than try to compete with cheap and plentiful petro-based plastics. He said the company is focusing on agriculture and horticultural markets – for things like biodegradable plastic mulch; the consumer market for compostable bags and similar products for organic waste diversion; a broader packaging market; and a marine and aquatic segment where it is important that plastics biodegrade fully in oceans and streams.
The breakup with ADM somewhat ironically boosted Metabolix’s cash position (for some rather complicated accounting reasons). That will be a big help, because the company is still developing its upcoming portfolio of bio-based C3 and C4 chemicals, using different PHA molecules than Mirel uses as an intermediate. Example target chemicals are gamma butyrolactone and acrylic acid. The C4 program is the farthest along and has reached 60,000 liter fermenters in scale-up. Eno says the chemicals program has netted “significant partner interest.”
Also helping to pay the bills is a government grant backing the company’s efforts to put the bio-based plastic platform into purpose-grown plants. In a recent advance, Metabolix and its research partners have reported a new way to increase polyhydroxybutyrate (PHB) production in sugar cane.
So there you have it – Metabolix is still moving along. The next time we will hear from them, Eno says, it will be because they have a new production partnership to announce. Stay tuned.