Avantium Engine-Tests Furan-Based Biofuel
26 October 2007
|Avantium derives its Furanics fuels from the intermediate hydroxymethylfurfural. Illustration: Pacific Northwest National Laboratory|
Avantium, which spun-off from Shell in 2000, successfully completed an engine test to demonstrate the potential of its furan-based biofuels, or “furanics.” Furanics are heteroaromatic compounds derived from the chemical intermediate HMF (hydroxymethylfurfural, C6H6O3).
The cost-effective development of HMF and its fuel and chemical derivatives from biomass is of increasing research interest (earlier post, earlier post), given that the resulting fuels have significant advantages over first-generation biofuels.
For example, 2,5-dimethylfuran, one of the HMF-derived fuels being researched by Professor James Dumesic at the University of Wisconsin, has around a 40% higher energy density than ethanol, a higher boiling point (by 20 K), and is not soluble in water. Ethoxymethylfurfural (EMF, one of Avantium’s furanics examples) has an energy density of 8.7 kWh/L—very close to that of regular gasoline (8.8 kWh/L), nearly as good diesel (9.7 kWh/L) and significantly higher than ethanol (6.1 kWh/L).
Avantium is focused on the development of second generation biofuels and catalytic processes for the efficient production of novel bio fuels and bio-based chemicals. (The company also has a major focus in the pharmaceutical industry.)
By using its catalytic process development platform, Avantium has been able to find new and improved catalytic routes to specific furanics. Specifically, Avantium developed a one-step method for obtaining HMF derivatives in high yields from very hexose or hexose-containing starting materials such as sucrose and glucose.
The engine test. The engine test was performed by Intertek, in Geleen, The Netherlands, an independent test center. Using a Citroën Berlingo with a regular diesel engine, Avantium tested a wide range of blends of Furanics with regular diesel. The test yielded what the company termed positive results for all blends tested. The engine ran smoothly for several hours. Exhaust analysis uncovered a significant reduction of soot (fine particulates). Furanics do not contain any sulfur.
The excellent results of the engine test support the proof of principle of our next generation biofuel, and is an essential milestone for our biofuels development program. The significant reduction of soot in the car exhaust is encouraging, as soot emissions are considered a major disadvantage of using diesel today, because of its adverse environmental and health effects. We are developing a next generation biofuel that has superior fuel properties and process economics compared to existing biofuels. The production process of Furanics has an excellent fit with existing chemical process technology and infrastructure. Ultimately our ambition is to develop biofuels that are competitive with fossil based fuels.—Tom van Aken, Chief Executive Officer of Avantium
The company plans to undertake an additional, comprehensive engine tests in 2008 to study engine performance and long terms effects of Furanics. Commercialization will also require studies of toxicologic and environmental effects, such as emissions.
Avantium also announced the filing of over a dozen patent applications on the production and use of Furanics as part of the company’s strategy to build an extensive patent portfolio for its biofuels program. In September 2007, the first two key patents were published, that claim amongst others the use of furanics as a biofuel and its production routes from sugars.
(A hat-tip to Laurens at Biopact!)
Yuriy Román-Leshkov, Christopher J. Barrett, Zhen Y. Liu & James A. Dumesic (21 June 2007) “Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates” Nature 447, 982-985 | doi:10.1038/nature05923>
Haibo Zhao, Johnathan E. Holladay, Heather Brown, and Z. Conrad Zhang (15 June 2007) “Metal Chlorides in Ionic Liquid Solvents Convert Sugars to 5-Hydroxymethylfurfural” Science 316 (5831), 1597. doi:10.1126/science.1141199]
Avantium tests new generation of high energy density biofuels: 'Furanics' (Biopact)
European Patent EP 1834950: Method for the synthesis of 5-alkoxymethylfurfural ethers and their use
European Patent EP 1834951: Method for the synthesis of organic acid esters of 5-hydroxymethylfurfural and their use
So, I guess step one is figuring out a desirable liquid fuel output for the process, and step two is figuring out an efficient way to convert biomass into said output. If they're going catalytic, that sounds like it will have the same challenges as Fischer-Troph; lots of energy required to heat up the biomass, thus modest conversion efficiency.
It will have to compare favorably to the potential of enzymatic cellulosic butanol production, which also has some of the best qualities of alcahol and gasoline.
I guess the question for the early stages is this: On paper, which process has the highest potential usable energy output per unit input, and realistically how low can the production costs get?
Posted by: HealthyBreeze | 26 October 2007 at 02:28 PM
@ HealthyBreeze -
biobutanol is a potential replacement for gasoline, to be used in spark ignition engines. Furanics are one of a whole slew of second-generation biomass-derived diesel substitutes, suitable for CI engines. There's little point in a direct comparison of the two because they can't go into one and the same engine.
Fischer-Tropsch is actually quite exothermic, so that heat could be used to dry the biomass feedstock to some extent. Educt selectivity is also a problem, i.e. only a fraction of the liquid produced is suitable for motor fuel. Choren's BTL process does require fairly dry biomass but I'm not sure that's purely a question of the energy balance.
I suspect this particular catalytic process for furanics is also exothermic. If efficiency in terms of biomass energy in vs. fuel energy out proves to be poor, it is likely due to this chemistry rather than the heat needed to dry the feedstock.
The big advantage of catalytic conversion processes is that they are a little less finicky about the type of feedstock used and, they can be scaled up to industrial production levels more easily than enzymatic approaches.
Posted by: Rafael Seidl | 26 October 2007 at 03:35 PM
If furanics are similar to gasoline in energy density, but they are diesel substitutes, then they have meager energy density compared to diesel...hmmm.
Posted by: HealthyBreeze | 26 October 2007 at 03:59 PM
It is amazing to see how so many people are still stuck with 100+ years old inefficent dirty combustion engines.
Using sun energy to produce plants, to produce agrofuel feedstock, to produce ethanol, biofuel, butanol etc to feed inefficient ICE machines seems to be futile.
Let's convert sun energy directly into clean electrical energy and use high efficiency electric or mostly electric vehicles. Simple, clean and efficent. Since solar energy is so over abundant, the conversion efficiency does not have to be that high, 20% will do, until we find a way to increase the conversion efficiency to 40% or more.
It makes so much more sense.
Posted by: Harvey D | 26 October 2007 at 04:06 PM
We need to know the energy return and hope that it is at least 4.0 or so. Is this a candidate for jet fuel? It's a pity this sugar based fuel doesn't blend with cellulose based fuels.
As for the inefficiency of ICE engines the last I heard they cost $35 a kilowatt and run for 1000 hours when they can be fixed by backyard mechanics. Compare that to PEM fuel cells. This is part of the efficiency vs resilience trade-off.
Posted by: Aussie | 26 October 2007 at 04:59 PM
...Yeah, then we'll have stockpiles of inefficient, hazardous, mostly non-recyclable batteries all over the place. Gee, sure does make sense... :/
Until storage technology catches up (read: 25+ years), your utopia can't be a reality. Transportation will need a liquid hydrocarbon energy source for a long time to come.
Posted by: Joe | 26 October 2007 at 05:08 PM
Biofuel are not perfect (unfortunatly) just like batteries and we probably need both of them since they are more complementary than competitors. We can foresse a futur in personal transportation made of hybrid plug-in with downsized and improved ICEs fed by biofuel and reasonably sized batteries, well the total flex fuel vehicle along with weight reduction and impoved aerodynamic. But neither the biofuel only or electric only seems to be a credible solution so far.
Posted by: Treehugger | 26 October 2007 at 11:02 PM
@ HealthyBreeze -
yes, that is correct. Switching to furanics would reduce the operating radius of a vehicle with a CI engine by ~10% relative to dinodiesel. However, this is not a huge problem: the higher efficiency of a CI engine in part load means the same fuel volume will still propel you ~10% further than the same vehicle model can achieve with a comparable SI engine and gasoline.
@ Harvey D -
very early in the history of the automobile, electric drivetrains were common, precisely because they are clean and reliable. The issue for the past 90 years has been the poor storage capacity of batteries, compared to hydrocarbon fuels. It will take a combination of much improved technology and modified consumer expectations (especially wrt operating radius on a single charge) for true BEVs/PHEVs to capture significant market share.
Solar PV is expensive and suffers from the additional complication that it is available only during the day, whereas the most convenient time to charge up a BEV is at night.
Therefore, while your suggestion is sound from an energy balance perspective, it is not yet possible to implement it on a large scale. There's a fine line between vision and wishful thinking.
@ Joe -
lead-acid, NiMH and Li-ion batteries are all already being recycled today. I'm not sure which types you are referring to.
Posted by: Rafael Seidl | 27 October 2007 at 08:43 AM
Put it this way.
BioFuels will have a place.
But that will primarily be as a niche fuel for when there just isn't any alternative.
i.e. International Aviation, International Freight, and Military
Posted by: GreyFlcn | 27 October 2007 at 10:17 AM
Yes, relying on solar powered PHEV's is not possible today, but 25 years from now we'd be a lot further if there were proper leadership.
Just this week GE got $6 million to put toward development of efficient, higher output electric motors. Yet makers of these biofuels, especially corn-based ethanol, get hundreds of millions in subsidies. Politically expedient, but it doesn't really solve any problems.
If someone like Al Gore ran things we'd be on the way to having this problem licked. If the US and/or China put the emphasis that the UK does on cleaning cars up, something would actually happen.
Besides voting I'm not involved in politics, but I would so vote for Gore right now, it's not even funny.
Posted by: Elliot | 27 October 2007 at 10:33 AM
Quick charge, high performance batteries are not that far away.
Cost will come down when mass produced, specially in countries with much lower labor cost. This has already happened for smaller lithium batteries. Ex: A spare Lithium battery for my digital camera cost $50 four years ago. Two better one (50% more powerful) cost me $5 each last month. Apply the same reduction rate to large battery packs and the price should go down 10 times from $20 000 to ($1500 - $2000) within four to five years.
PHEVs can be used as an interim solution, (starting in 2010-11) to reduce liquid fuel consumption by up to 75+%.
BEVs will complement PHEVs to create a very low liquid fuel consumption mix sometime during the next decade.
Of course, batteries (and vehicles) should be recycled.
Posted by: Harvey D | 27 October 2007 at 10:40 AM
Catalytic convertion in the FT-process completely destroys every molecular bond in the feedstock, and then rebuilds it into the desired fuel. This (of course) is higly exotermic, thus not very efficient.
The catalytic processes described here only open a few atom-bonds of the sugar molecule and reorganize it into HMF. Since the majority of the atom-bonds are unaltered, the efficiency of this process is much higher.
The disadvantage of it (compared to FT) is that FT is much less specific, meaning that any form of carbon-containing feedstock can be used. In furan production, the feedstock can only be sugars (luckily, we have a lot of sugars in any plant material).
Posted by: Alain | 27 October 2007 at 12:02 PM
Thanks, Alain for clarifying the issue.
The only kind of sugars to be used for furan synthesis should come from cellulosic waste material. Grains for fuel is a big NO NO!
Eventually, with exhaustion of petroleum, these waste biomass would be too valuable for use as fuel, and should be reserved for the plastic and organic chemical industry and manufacturing industry.
Long-term renewable fuels (H2, CH4, NH3, etc.) should be synthesized from solar and wind energy. The potential of solar and wind energy is truly vast and can satisfy our current energy demand 10-100 folds over. We will just need to make steady investment in solar and wind energy, as well as more research on how to synthesize these simple gaseous fuels cheaply and efficiently. The advantage of gaseous fuel is the inefficiency in storage, forcing auto mfg's to strive for ever-increasing fuel efficiency in order to satisfy the customer with more than adequate range to gain sale advantage. Necessity is the mother of invention!
BEV will have an increasing niche role, but cannot take over the entire transportation sector, for obvious reasons.
Posted by: Roger Pham | 27 October 2007 at 07:51 PM
Furans are, generally, highly toxic substances, comparable with such nasty staff as dioxin. I would appreciate if somebody knowledgeable on the subject clarify how furanics biofuels score on that matter.
Posted by: Andrey | 28 October 2007 at 02:00 AM
like dioxins, furanes (also called furfurals) are a very large family. Some members are indeed extremely poisonous, others completely harmless or possibly beneficial.
Small quantities of hydroxymethylfurfural (HMF) are present in honey, UHT milk, toast and other foodstuffs. Because food safety is so important, a lot of research has been done on the health effects at very low doses, see e.g.:
However, I could find no data on the health impact of high concentrations of HMF. Chances are, those would not be good for you. Then again, neither is exposure to high concentrations of other fuels, including gasoline and diesel.
Posted by: Rafael Seidl | 28 October 2007 at 08:24 AM
The question probably is not that much the toxicity of high concentration of HMF, but the degree of biodegradability of HMF. Since it is present in many natural products it is probably adequately biodegradable. As diesel or gasoline are a mixture of different alifatic and aromatic molecules, many of them are much less biodegradable. HMF is even present at concentrations of 10mg/liter in INTRAVENOUS nutrition and doesn't seem to be toxic. HMF forms spontaneously when sugars are heated, so we eat them every day.
Posted by: Alain | 28 October 2007 at 02:24 PM
One chemical in this family, furfuryl alcohol, was used some decades ago as a rocket fuel. It has the property of igniting spontaneously (is 'hypergolic') with red fuming nitric acid, a nice property in a rocket engine where you seriously don't want oxidizer and fuel to accumulate in the thrust chamber before combustion begins.
As I recall, furfuryl alcohol was ultimately derived from oat hulls.
Posted by: Paul Dietz | 28 October 2007 at 02:25 PM
I'm not thrilled at the thought of using aromatic compounds as automotive fuel. They have a higher ozone-forming potential than fuel candidates like ethanol. And here's another point: The mass production of ethanol was motivated not only so much to substitute biomass-derived energy for fossil fuel energy, but for this reason:
When mother nature threw a frustrating showstoppper at us regarding methyl tertiary butyl ether (MTBE), we needed an oxygenate/octane improver to take its place. Ethanol, while undesirable if you get it into your system, is not as undesirable environmentally as MTBE. Its an oxygenate and octane-improver, as well as a source of energy.
So if we convert biomass into hydrocarbons with benzene-like ring structures, we negate part of the reason for mass-producing ethanol.
Given the problems that arise from using corn as a raw material for ethanol production, I hope, hope, hope that cellulosic ethanol (which can use non-food biomass like wood chips, switchgrass, etc) will become commonplace in the next few years.
Automobility for all,
Posted by: Alex Kovnat | 29 October 2007 at 06:50 AM
Well, the furans might be good fuels. But the real problem here is to get them cheaply on large scale. You get them from glucose, but where the glucose is going to come from? The same problem as with cellulosic ethanol - to break down cellulose. It can be done, but it is very messy, and not very efficient.
In contrast, gasification - Fischer-Tropsch gives you 40% of biomass energy as liquid hydrocarbons in a fairly simple process, biomass ashes is the only by-product.
And Choren does that right now - succesfully.
Posted by: green | 30 October 2007 at 05:15 AM
Recycling lowers the environmental impact of batteries but it still uses energy and creates waste.Batteries are toxic(so far)and most require mining.Cellulosic ethanol allows us to keep our current car.
Posted by: middleoroad | 30 October 2007 at 07:25 PM
HMF is as aromatic as glucose itself. I would prefer transforming cellulose to HMF, and then use the waste-biomass to produce FT-butanol.
This will probably have a much higher efficiency than doing FT-transformation on the total feedstock.
Posted by: Alain | 31 October 2007 at 02:06 PM
Well, what I mean is that it is much more efficient to gasify biomass in an simple gasifier and get pure synthesis gas rather than to chemically break down wood cellulose. First you need to separate it from lignin etc. This is done by chemicals (sulfides or something like that) as in paper mills. Then you have to hydrolize the cellulose. This means concentrated sulfuric acid. Lots of boiling, washing, filtering, lots of hazardous solutions of concentrated acids. The chemicals are all fairly expensive inputs in such a refinery. This is basically working with the methods of alchemists of the Middle ages. Yes, you can get the product, but you spend an enormous amount of effort to get there.
Posted by: green | 02 November 2007 at 06:13 AM
Alex wrote: "... Ethanol, while undesirable if you get it into your system, is not as undesirable environmentally as MTBE. Its an oxygenate and octane-improver, as well as a source of energy.
Ethanol is quite desirable to get it into your system...that's why there are bars and clubs everywhere and there are beers, wines and liquors on most restaurant menus. It is literally a real waste to use ethanol for your car.
green's observation is very keen. Gasification of waste biomass is much more efficient and cost-effective than hydrolysis of cellulosic bonds. But better still, why waste energy on further steps of F-T synthesis? Just go ahead to use the H2 as produced, or catalytically convert the syngas into methane and use it directly on NG-converted vehicles.
Posted by: Roger Pham | 03 November 2007 at 11:14 PM
Thanks, Roger, I totally agree that gasification is way more efficient than hydrolysis. And yes, the syngas can be shifted to hydrogen, converted to methane or anything else - ammonia, fertilizers, methanol, formaldehyde etc etc etc. It can be used as fuel or chemical feedstock.
But I think that the problem is that at present there are still way too more oil and gas available. And for obvious reasons it is way more easy to work with gas or oil than to collect biomass. That's why it is not being used at present.
But this can change in the future. More and more plants will eventually start to use biomass as the feedstock.
Choren does that now, let's see how it goes for them.
Posted by: green | 06 November 2007 at 07:21 AM