## BP and DuPont to Partner on Next-Generation Biofuels; Biobutanol the First Product

##### 20 June 2006

BP and DuPont have created a partnership to develop, produce and market next-generation biofuels to help meet increasing global demand for renewable transport fuels.

The two companies have been working together since 2003 and are now ready to bring their first product to market: biobutanol, which will be introduced in the UK in 2007 as a gasoline bio-component.

The companies are leveraging DuPont’s biotechnology and bio-manufacturing capabilities with BP’s fuels technology expertise and market know-how. By pooling their knowledge and expertise, the two companies aim to be the world leaders in the development and production of advanced biofuels, driving the growth of biofuels, which today account for less than two percent of global transportation fuels. Current projections show that biofuels could represent up to 20-30% of the transport fuel mix in key markets.

Bio-butanol. Butanol (C4H10O) is a four-carbon alcohol in widespread use as an industrial solvent, with a US market size of some 370 million gallons per year at a price of about $3.75 per gallon (approximately$1.4 billion).

Originally produced by fermentation starting nearly 90 years ago (using Clostridia acetobutylicum), butanol shifted to becoming a petrochemically-derived product in the 1950s as the price of petrochemicals dropped below that of starch and sugar substrates such as corn and molasses. Virtually all of the butanol is use today is produced petrochemically.

Butanol’s energy content is closer to gasoline than ethanol’s. It is non-corrosive, can be distributed through existing pipelines, and can be—but does not have to be—blended with fossil fuels. Butanol itself could be reformed for hydrogen for use in fuel cells, and the production process itself produces hydrogen. (Earlier post.)

Bio-butanol’s low vapor pressure and its tolerance to water contamination in gasoline blends facilitate its use in existing gasoline supply and distribution channels. It has the potential to be blended into gasoline at larger concentrations than existing biofuels without the need to retrofit vehicles and it offers better fuel economy than gasoline-ethanol blends, improving a car’s fuel efficiency and mileage.

DuPont and BP are currently in the process of carrying out detailed calculations of biobutanol’s greenhouse gases Well-to-Wheel Life Cycle Analysis emission performance. Initial indications are that, on the same feedstock basis, biobutanol can deliver emission reductions that are at least as good as ethanol on the same basis.

Bio-butanol also enhances the performance of ethanol blends in gasoline by, amongst other things, reducing ethanol’s impact on vapor pressure, one of the issues which hampers a wider use of ethanol in existing gasoline distribution channels.

For the bio-butanol launch, BP and DuPont are working with British Sugar, a subsidiary of Associated British Foods plc, to convert the country’s first ethanol fermentation facility to produce bio-butanol. Additional global capacity will be introduced as market conditions dictate and a feasibility study in conjunction with British Sugar is already underway to examine the possibility of constructing larger facilities in the UK.

Transportation is an important area to address [for the reduction of greenhouse gases] since it accounts for around 20 per cent of global emissions and in the short to medium term increased blending of biocomponents represents one of the few real options for progress in this area on a global scale.

—Lord Browne, CEO of BP

Initial production of bio-butanol will be based on an existing technology, enabling early commercial market introduction. In addition, development work on a new biotechnology process which aims to produce bio-butanol competitively with ethanol is already underway.

Production is planned to utilize a range of feedstocks such as sugar cane or beet, corn, wheat, or cassava and, in the future, cellulosic feedstocks from fast growing energy crops such as grasses or agricultural byproducts such as straw and corn stalks. Since production of bio-butanol is similar to ethanol and uses similar feedstocks, existing ethanol capacity can be retrofitted to produce bio-butanol.

BP also recently announced it plans to spend $500 million over the next ten years to establish a dedicated biosciences energy research laboratory attached to a major academic center in the US or UK. (Earlier post.) Resources: ### Comments perfect! This is very good news, since it recognizes that butanol's fuel properties is better matched to demand than those of lower alcohols. It's good to hear BP is already hitting the ground running with its$500mm biofuels research project.

That said, it's becoming ever more apparent that the biofuel industry is based on multiple layers with interface conditions that allow each layer to be implemented independently. This is a proven approach used in many engineering disciplines incl. software development. Here's an attempt at summarizing the biofuel production routes I've come accross recently:

Fermentation route (spark ignition/diesel engines):
Feedstock crop agriculture/forestry
Option: cellulose extraction from black liquor
Option: cellulose to sugar
Sugar extraction
Fermentation into biogas (methane) or liquid alcohol:
methanol, ethanol, butanol (EEI)
Purification
Option: post-processing into synthetics
Delivery

Esterification route (diesel engine):
Feedstock crop agriculture/aquaculture (oil algae)
Oil extraction & titration
Option: waste processing via fermentation or synthetic
Esterification with methanol
Delivery

Synliquid route (aka TCP; for diesel engines):
Feedstock maceration in water
Pressure cooking
Product stream separation
Thermal cracking
Delivery

Syngas route (spark ignition/diesel engines):
a - Direct Process (MTG)
Methanol from fermentation / petrochemical
Dehydration into DME or gasoline
Distilaation
Delivery

b - Indirect Process (Fischer-Tropsch)
Preparation of biomass waste
Syngas production (*)
FT synthesis (cobalt or iron catalysts)
Distillation / cracking
Delivery

(*) syngas can also be produced from fossil fuels (e.g. natural gas, coal or tar sand)

This news has really put a smile on my face. I'm glad to see some action on butanol.

Couldn't agree more - this is big news. If EEI's estimates that 40% more energy (than from ethanol) can be obtained from the same feedstock proves to be true, this is a vast improvement. That's not even counting the Well-to-tank efficiency gains from being able to transport over pipelines!

It would be nice to see an automaker throw some support behind this. Optimally, Saab's Biopower concept. Given Butanol's even higher octane rating than ethanol, power could likely be raised even further (allowing further downsizing of engine displacement).

I am a harsh critic of corn ethanol, but butanol has some distinct advantages that might render it a decent biofuel. I worked in the chemical industry for 7 years, primarily on butanol production, and I wrote an essay on bio-butanol a couple of months ago:

Bio-butanol

RR

Thank you for the link, Robert. Do you have any insights on why it has taken so long for this to develop? I've been waiting for news on butenol production but I couldn't find much news on it anywhere.

Let me make sure I have this straight.

It's Carbon neutral,
it runs in any old car,
it mixes with regular gas,
you could make it from celulose.

If thats all true ... wow!!!

Neil -

(a) the prep step of getting from cellulose the sugars is not part of the EEI process afaik. However, Iogen/Shell/VW have announced a feasibility study for industrial-scale cellulose ethanol production. BP is devoting part of its \$500mm research fund to a cellulose to sugar process of its own.

(b) you will void your engine warranty if you use a fuel that has not been approved by the vehicle's manufacturer. Also, health & environment agencies have not yet approved its use as gasoline additive or replacement.

http://www.deh.gov.au/atmosphere/fuelquality/publications/paper2a.html
http://www.intox.org/databank/documents/chemical/butanol/cie51.htm

Note that there are four isomers of butanol; it's not clear to me which one(s) the EEI process produces, possibly only n-butanol which is the straight chain.

Octane numbers: RON MON
ethanol 130 96
n-butanol 96 78
t-butanol 105..109 89..94
sec-butyl alcohol 101 82*
gasoline 92..98 82..88

(*) The source (unep.org below) states "32" but this is almost certainly an OCR artefact of the document digitalization process.

In the US, the octane number quoted at the pump is (RON+MON)/2, in the EU it's just RON. The one that actually matters to engine designers is just MON. Go figure!

The data points do confirm that pure n-butanol has octane numbers similar to gasoline. I'd hesitate to try it in a new BMW, though (compression ration 11.5).

http://www.iupac.org/publications/pac/1989/pdf/6108x1373.pdf
http://www.unep.org/PCFV/Documents/PubGraboskiReport.pdf

So, EEI's octane numbers for Ethanol (92) and Butanol (94) are inaccurate?

If butanol so good, then why everybody is burning ethanol?

Butanol is very good. But people have been brewing ethanol for thousands of years. The beer and wine yeasts used to make ethanol have been under human selection for a long time. Huge distilleries for making whiskies and other ethanol spirits have been around for hundreds of years. Ethanol is an old friend and people are comfortable with the process of making it.

The bacteria that ferment butanol, on the other hand, are new and still being perfected. You understand it takes time to develop a new industry. When butanol really gets going, it will push ethanol back into the beverage category.

two questions:

1) does anybody know if butanol will meet the ethanol fuel requirements that several states have implemented?

2) how much energy is really available to produce biofuels? I mean, how much butanol could the US produce without significantly negatively impacting the agricultural sector or food supply? and how does this compare to our current fuel consumption?

Rafael:
Couple of suggestions to your scheme:
Black liquor is solution of lignin (kind of glue bonding cellulose fibers together) in caustic inorganic solvent, and has fairly small cellulose content. Lignin is not biodegradable under anaerobic conditions, and can not produce viable biofuel. Usually black liquor is concentrated and burned on the spot to recover inorganic chemicals and to fuel paper mill operation.
Biogas production is well-established process, where microbiological hydrolysis/acidification/methanogenesys usually are working together, reducing cellulose, proteins, and some others components to biogas. Arguably the best way to utilize biogas is to burn it on the spot with minimal purification to generate electricity, and waste heat is used to space heating and to warm-up anaerobic digestors. It is unlikely it will be source of transportation fuel.
Production of methanol from biogas is way less economical then direct thermal syntesis of methanol from wood waste, and yet production of methanol from regular NG is even cheaper.
So, most realistic fermentation scheme would be based on grain stock, in near future increasingly cellulose-bearing wastes, and resulting fuel for spark-ignition engines only would be ethanol and butanol.

As powerful octane booster, effective fuel system conditioner, and twice more potent oxygenate component, ethanol most likely will remain important gasoline and diesel additive, probably at E5 level. Further increase of biofuel content in gasoline most likely will be better served by butanol.

Time to rain on everybody's party.
Butanol, neurotoxic. Improperly processed, stinks like BO. Processed properly, still sinks (but necessary like additive to natural gas). If they do not improve their yields above 2.5 gallon per bushel, ethanol will catch up to them. Already, 2.9 gallons of ethanol per bushel has been reached. If ethanol reaches 3.5 gallons, they are par (btu per bushel). How butanol production fares with other feed stcks needs to be put into consideration as well.
Andrey
Ethanol and butanol would be needed to bring down NOX and particulates in biodiesel too.

Who cares if it stinks? So does gasoline.

It's neurotoxic. So is gasoline, that's why stupid people huff it to get a cheap high.

These are minor things. It's for your car, not something you're going to eat or take a bath in.

Some posters are forgetting what's most important from the consumer's viewpoint - they can use butanol 100% without having to modify their car's engine or fuel system. That's huge!

Shaun,
in response to your first question:

>1) does anybody know if butanol will meet the ethanol >fuel requirements that several states have implemented?

yes, I believe most of the "renewable fuels" bills that have passed recently include almost any biomass-derived fuel, including both ethanol and butanol. In the press, they tend to be presented as "ethanol legislation" simply because that's the only biofuel available on large-scale for spark ignition engines and so it's the one that people are familiar with.

there seems to be lots of comments on the use of butanol for auto fuel. EEI in Ohio claims to have driven 10,000 miles on nothing but butanol which he purchased but did not make. Information concerning making your own ethanol is readily available as well as still design. How come if butanol is such great stuff is there no information for bioreactor design or acid extraction to solvent. EEI is asking for money to setup a bioreactor to make butanol apparently so that they can compete with the oil companies. Do we really need another monopoly for fuel production. Butano; can be made in the backyard just like ethanol so why ia the formulation and technique being hidden -- money?

Ethanol is C2H5OH. Butanol is C4H9OH.

C2H5OH + C2H5OH = C4H9OH + H2O.

How much energy would that reaction cost? and does the result need to be distilled to remove water?

"Given Butanol's even higher octane rating than ethanol, power could likely be raised even further (allowing further downsizing of engine displacement)."
Octane ratings mean nothing in terms of increasing
energy output. High octane gasoline, for example, actually has less energy than regular. This is a near universal misconception about octane. High octane gas simply burns more slowly and is harder to ignite than lower octane gas, allowing a longer power stroke burn cycle, producing mor power per stroke, but also burning
more gasoline per stroke. There is NO energy gain
(actually probably a loss) from setting up an engine to run on high octane gas. High octane gasoline produces usually slightly less mileage than regular gas. Mileage also has very little to do with any small changes one could make in downsizing an engine. Mileage depends upon many things, engine size being relatively unimportant.

I think the high octane comment may have more to do with reducing the engine displacement and adding a turbo. The idea might be that you could get better milage if you can run a car on a 2 litre 4 cyclinder with a turbo using 91 octane (US) instead of a 3 litre V6 non-turbo using 87 octane (US).
The idea is something like variable compression ratio with the turbo. Keep your foot light on the pedal and not much turbo and better milage. Something like the 4/8 cyclinder idea for displacement on demand.

Schwartz:  You have your stoichiometry wrong.

2 C2H5OH -> C4H10O + H2O

(that's diethyl ether, not butanol.  DEE has a great cetane rating, but it makes a lousy substitute for gasoline and it has huge abuse potential.)

Sounds like the future fuel; ethanol should be used in industry and bio-butanol can be used for the automotive industry and Green Motor Sport. Gordon Foat www.GreenMotorSport.com

Who has a process flow diagram for biobutanol production? Pls post asap. tnx

"Octane ratings mean nothing in terms of increasing
energy output. High octane gasoline, for example, actually has less energy than regular."

That is correct, HOWEVER; The thermodynamic efficiency of an otto cycle engine increases albeit nonlinearly with compression ratio. The efficiency of the typical passenger car is limited somewhat by the maximum compression ratio that common pump gas will allow without detonation. The figure of merit for this property is the OCTANE RATING. Since efficiency increases with compression ratio, and the power delivered by a given engine displacement provides is also determined by compression ratio, it stands to reason that all else equal, an increase of compression ratio would produce a vehicle with a more efficient, lighter engine. THAT is the benefit. While I haven't run any hypothetical numbers, I would not be surprised at all if an engine could be produced to run off butanol which would meet, or exceed the performance and fuel efficiency of it's gasoline counterpart.

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