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ACS Symposium: Biofuels for Transportation

The 231st national meeting of the American Chemical Society featured a one-day symposium on Biofuels for Transportation during which fuel chemists and other scientists from across the United States and Europe presented research toward developing viable, cost-effective and high-performing biofuels.

Much of the focus on the one-day event was on biodiesel, although several presentations touched on cellulosic ethanol and hydrogen.

The fourteen presentations of the symposium included:

  • Factors affecting the stability of biodiesel sold in the United States. Researchers from the National Renewable Energy Laboratory surveyed biodiesel quality and stability in the United States. They collected 27 B100 samples from blenders and distributors nationwide., including 4 produced from waste oils, 1 from tallow, and the balance from soy.

    They then conducted a series of chemical analyses and oxidation stability tests to reveal the factors influencing B100 stability. A typical US biodiesel exhibits 5 mg/100 ml of deposits on the ASTM D2274 accelerated stability test and less than 1 hour induction time on the EN 14112 Rancimat stability test.

  • Oxidative stability of biodiesel and NMR. Researchers at the USDA Agricultural Research Service (ARS) used nuclear magnetic resonance (NMR) to study the composition of biodiesel oxidized in open vessels at elevated temperatures. The results show enrichment of monounsaturated fatty acid chains and a decrease of diunsaturated species. The results coincided with other methods such as kinematic viscosity and acid value.

  • A pipeline for evaluating novel soydiesel derived from biotechnology. Researchers at the University of Nebraska investigated the introduction of novel oil traits through genetic engineering as a way to produce industrial products in oil seeds, such as soybean.

  • A comparison of biodiesel combustion performance with that of three other diesel fuels in a homogeneous charge compression ignition engine. Researchers at the Oak Ridge National Laboratory assessed the performance of a 100% biodiesel fuel (methyl ester), derived from soy oil, compared to three other hydrocarbon diesel fuels in an HCCI engine. Findings indicate that biodiesel requires earlier combustion phasing for peak efficiency, a hotter charge for ignition, burns more rapidly, and exhibits higher combustion temperatures than the HC based fuels. Total HC, CO, and NOx are all higher for the biodiesel.

  • Low temperature ignition behavior of methyl decanoate. A team from Penn State investigated the low-temperature ignition behavior of methyl decanoate, a biodiesel-relevant compound.

  • A numerical investigation into the anomalous slight NOx increase when burning biodiesel; A new (old) theory. A team from UC Berkeley and Lawrence Livermore National Laboratory reviewed previously proposed theories for the slight NOx increase from burning biodiesel, including theories based on biodiesel’s cetane number, which leads to differing amounts of charge preheating, and theories based on the fuel’s bulk modulus, which affects injection timing. This paper proposes a new theory explaining this NOx increase; the increase in double bonds in biodiesel, compared to No. 2 diesel, increases its flame temperature, which in turn increases NOx.

  • Emissions characteristics of a light duty diesel engine fueled with a hydrogenated biodiesel fuel. Penn State researchers explored the approach of achieving a more saturated biodiesel fuel and observing its effects on NOx emissions blended as B50. They explored the effects of hydrogenation of soybean oil prior to transesterification. The resulting fuel has a higher percentage of oleic acid methyl ester, and a reduction in the linoleic and linolenic methyl esters. Emissions testing on a light duty diesel engine revealed a decrease in NOx levels for some engine modes and an increase for other modes.

  • Reformulating biodiesel to reduce NOx emissions. This paper from researchers at the US Department of Agriculture described two methods for reformulating of methyl soyate (commercial biodiesel in the U.S.) in an attempt to reduce NOx emissions by changing the properties that would change the bulk modulus.

  • Examination of the behavior of biodiesel soot. This work from Penn State shows that although soot derived from the combustion of soybean oil-derived biodiesel fuel (B100) possesses an initially ordered structure, it is 5 times more reactive than soot obtained from combustion of a Fischer-Tropsch (F-T) diesel fuel. The oxidation mechanism of the B100 soot is unique, leading to capsule type oxidation and eventual formation of graphene ribbon structures.

  • Reduction of oxygen on the cytochrome c oxidase modified electrode. In this paper, scientists at Virginia Commonwealth University investigated the mechanisms of a biofuel cell by immobilizing cytochrome c oxidase and cytochrome c/ cytochrome c oxidase complex into lipid bilayer membranes on the gold electrodes.

  • Bio-based oxygenate for biofuels and fossil fuels. A team from Lehigh University and Gibson Technologies explored the application of a new process for the manufacture of dimethoxymethane (DMM)—an oxygenate proven equivalent to ethanol (EtOH) and dimethyl ether (DME) in its ability to lower soot emissions from internal combustion engines operating on gasoline or diesel fuel—to the conversion of pulp and paper mill waste gases.

    The pulp mill waste gas becomes a renewable bio-source for DMM. In addition, the CO2 generated by the present incineration of pulp mill waste gas is eliminated thus yielding an environmental advantage.

  • Conversion of cellulose to glucose via alkyl glucosides. Researchers at Iowa State University described their process for converting cellulose to glucose via an acid catalyst.

  • Production of large, water-soluble intermediates from carbohydrate-derived compounds by sequential condensation/hydrogenation. A group from the University of Wisconsin (also involved in Virent—earlier post) introduced a bi-functional metal-base catalyst that is highly active, selective, hydrothermally stable and recyclable. The bi-functional catalyst allows a single-pot synthesis to produce large water-soluble organic molecules by aldol-condensation of carbohydrate-derived compounds over a base catalyst and subsequent hydrogenation over a metal catalyst. These water-soluble intermediates can be processed further by aqueous phase dehydration/hydrogenation to form liquid alkane fuels.

    The selectivity and overall yield of the process can be controlled by the choice of reaction temperature and appropriate molar ratio for co-reactants during the condensation reaction. Developing a stable/recyclable aldol-condensation catalyst with a bi-functional characteristic, which permits a single-reactor design, is a significant advance on the path to making this technology industrially feasible by reducing operating and capital costs.

  • Direct use of H2-poor bio-syngas model in Fischer-Tropsch synthesis over un-promoted and rhenium promoted alumina-supported cobalt catalysts. A Scandinavian team from Chalmers University of Technology, KTE-Royal Institute of Technology and NTNU-Norwegian University of Science and Technology put a syngas of H2 and CO of different molar H2/CO-ratios (2.1, 1.5 and 1.0) through a fixed bed Fischer-Tropsch (FT) reactor over Co/Al2O3 and Co-Re/Al2O3 catalysts.

    The FT-reaction requires a H2/CO-molar-ratio of approximately 2.1 above the catalyst surface. For the ratios lower than 2.1, a water-gas-shift activity is desired in order to increase the H2/CO-ratio.

    With lower H2/CO-ratios in the feed, the CO conversion and the CH4 selectivity decreased, while the C5+ selectivity and C3(olefin/paraffin) ratio were slightly increased. However, the catalysts studied had very low water-gas-shift activities.

    The Re-promoted was considerably more active and selective to longer hydrocarbons. The characterization of catalysts showed the positive effect of the Re in dispersion and reducibility of the catalysts. It is possible to utilize the advantages of an inlet ratio of 1.0 (higher selectivity to C5+, lower selectivity to CH4) if a low CO conversion is accepted.



When will the ethanol/biodiesel lobby be able to push for higher gas taxes to make their products more appealing cost wise?

nitesh damor

hello sir.
I am very happy after reading your report. i am looking for this give me genral idea,but i want to know more about bio desiel. I want to establish a firm which produce such kind of desiel. your support can guide me. so please help me.
Nitesh Damor


When Gas hits $3.00 a gallon this summer, that will make the others appealing enough. All this talk of making gas $5.00 is stupid. It is plenty high enough to make people want to change now. Why wreck the economy in the process?
Germany and France have over 12% percent unemployment, maybe even higher.
Don't want that here, no thanks.....


A BioDiesel distribution infrastructure is in place. It seems to me that is the way to go, at least for now.

Has anyone taken a look at the possibilities of mixing alcohol with diesel to extend and maybe improve the viability of both?

Certainly ether seems to improve the ignition of diesel in cold weather.



I have also been wondering if adding small amounts of ethanol (Up to 7%) to biodiesel would improve its emissions. See the example for E-diesel or O2 Diesel.


This is what I found at their website. Sure would like to have this confirmed.

The benefits of adding oxygenates to motor fuels are well documented, but it is only recently that new technology has made oxygenated diesel fuel economically and technically viable. Supported by its ethanol-blended diesel fuel, O2Diesel, Corp. is a leader in delivering cleaner-burning diesel fuels to global markets.

O2Diesel™ is a "fill and go" clean diesel technology available for centrally-fueled fleets in large urban areas plagued with air quality problems.
O2Diesel™ reduces diesel equipment regulated and unregulated exhaust emissions, including greenhouse gases.
O2Diesel™ reduces harmful emissions from diesel engine exhaust including particulate matter, oxides of nitrogen, carbon monoxide, and carbon dioxide.
O2Diesel™ provides cleaner combustion with decreased engine corrosion, reduced cylinder wear and extended lubricant life.
O2Diesel™ can be used engines designed for conventional diesel fuel without special modifications or changes.

Fleet Refueling
Working with experienced local distributors, O2Diesel, Corp. has perfected several cost-effective approaches to supplying fleet customers with O2Diesel™ that ensure product quality and complete safety. The fuel can be delivered to a fleet customer through:

Existing underground storage tanks
Above-ground fuel tanks, and
Mobile equipment refueling
O2Diesel, Corp. works with suppliers and customers to design & implement a complete supply & refueling program, including staff training, tech support, and service.

Copyright ©O2Diesel, Inc 2004.


high fuel prices aren't the cause of
high unemployment rate in DE;

its mainly because the restrictions and pretensions are too high;


Doesn't biodiesel already have a subsidy of about a buck a gallon?

All those unemployed keep emissions down. $3.00/gallon didn't accomplish much. We need five dollars a gallon and above.

Raise gasoline taxes and offset, with income tax credits and outright subsidies for the middle and lower classes. Make it a net increase of taxes of zero, unless, of course, you want to do something about this insane deficit. This ride on debt we are on is going to be over one way or another. The question is, do you want it to end with a thud or a crash.

We can make the transition away from oil in a relatively orderly and planned manner or we can just wait for the whole thing to come tumbling down on top of us.

Let's not stick our head in the oil sands. Raise gas taxes now!!


From DOE's web site:

Effective with 2005, fuel ethanol and biodiesel production receive a tax credit of $0.51 and $1.00 per gallon, respectively ($0.50 if biodiesel is made from recycled rather than virgin vegetable oil or animal fat). Ethanol has had a similar level subsidy for a number of years, and with it has been generally competitive with MTBE, the primary other option for boosting octane or meeting oxygenate requirements, and close to competitive with gasoline itself. Small (less than 30 million gallons per year capacity) ethanol producers are also eligible for an additional subsidy. This program was little used in the past, but new provisions should make it possible for more small producers to take advantage of it. The biodiesel subsidy is new and should make biodiesel competitive with petroleum-derived diesel and make a substantial difference in its sales.

Harvey D

PaulH....Isn't it a bit unfair to compare the USA and UE economies at this specific time. UE has to adjust to an expanding community and the transistion in Eastern Europe. The USA economy is a wartime economy with extremly high budget and trade decifits artificially supporting it. What will happen down the road when americans have to pay back? Pay back times are sometime difficult to manage. Lets hope that USA will do it right.


"All those unemployed keep emissions down. $3.00/gallon didn't accomplish much. We need five dollars a gallon and above."

In case you hadn't noticed, biodisel production tripled last year. And we are well on the way to exponential increases in the next few years. Prices right now make it competetive. Nothing more is needed.

Government involvement in this should be as small as possible.


I find it interesting that there is lots of demands to raise fuel taxes and other politically dogmatic statements, but there is not one commenting on the science of what has been discussed.

From what is presented here, it would seem that there are some environmental concerns dealing with biodiesel that need to be addressed, namely, the combustion and formulation conditions. Is it reasonably feasable to engineer the on-board injection systems to detect and compensate for the various biodiesels and biodiesel/petrodiesel blends, or will there be a need for more stringent standardization of the fuels and factory adjustments of the engines?

The Re/Co catalyst work looks pretty exciting. I look forward to reading the full paper.

An Engineer

"From DOE's web site:
Effective with 2005, fuel ethanol and biodiesel production receive a tax credit of $0.51 and $1.00 per gallon, respectively ($0.50 if biodiesel is made from recycled rather than virgin vegetable oil or animal fat)."

How stupid is that? DOE pays you $1.00/gal for making biodiesel from food, but only $0.50/gal for making biodiesel from waste. It should be the other way round! Unfortunately one can see the farm lobby's dirty hand in tilting the subsidy the wrong way.

Is DOE trying to create good energy policy, or trying to slip through another farm subsidy?


It's not specifically about biodiesel. Raising the tax on gas is about cutting oil consumption. I don't see biodiesel as a panacea, but a possibly short sighted program which may eventually threaten and compete with our food supplies and food prices. Conservation is necessary regardless of what fuel alternative is chosen.

I was surprised and disappointed too when I saw that virgin biodiesel got twice the subsidy of waste biodiesel. But then it's all about helping agribusiness, isn't it?

Rafael Seidl

tthomas -

in gasoline engines, fuel quality is estimated by analyzing the signal from the knock sensor with a DSP. Diesels don't knock so they do not normally feature such a sensor.

However, it's possible it could be used to tease out fuel-related variations in ignition lag and burn rate (~rate of pressure change) from a sufficiently large number of samples. There is a lot of natural variation cycle-to-cycle. The measured data would need to be compared to a database of acoustic fingerprints derived from calibrated tests in a lab. If successful, the engine controller could switch to the optimized map specifying intake swirl controls and injection pattern for the identified fuel at each point in the torque-angular vlocity domain.

I suspect, however, that the chemists and engine designers will try to make do with tweaking the fuel formulation and perhaps, the specification as well, to avoid all this additional expense.


In Ireland we have gasoline at 1.10 euros / litre ~ $5 / gallon (US) - below average by EU standards.
We have unemployment of 4.3%
There is no corrleation between fuel costs and unemployment. All it means is we tend to drive more efficient vehicles. (Diesel SUVs sadly).
The US could adapt to this reasonably easily. NO new technology is needed, just pick the models with the smaller engines.
The trick of this is that if you depress demand, the base price falls, and the gains go to your government, instead of the oil producers.
Thus, you end up funding one side of the war on terror, not both.



The US has quite a different geography than Ireland. We're huge. We have long distances to cover. We have a lower population density.

$5 a gallon will kill us. And we'll get there without being taxed anyway.

tom deplume

What this tells me is that biodiesel doesn't burn much different than petrodiesel. Pure ethanol though is a much cleaner fuel than any other liquid fuel.

An Engineer

Don't get to carried away with ethanol. Some of ethanol's properties are not so great:
1. It is hygroscopic. So corrosion becomes a big concern.
2. It has a much higher vapor pressure than gasoline. That does a number of things, such as cause more evaporative losses, fouling up the air in the process. Ethanol can also not be pumped across the country like oil products. Expensive (and unenvironment-friendly) trucking is an option...
3. It takes a lot of energy to separate ethanol from water, meaning that ethanol from fermentation will always have a relatively low energy efficiency.

Much better to convert biomass to hydrocarbon (via TCP, G/F-T or Aqueous Phase Dehydration/Hydrogenation [APD/H]) and maintain the many benefits that we already enjoy.

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