Introduction to Biobutanol

• Some literature on butanol by biochemical or ethanol conversion route is discussed briefly

o Butanol is a flammable alcohol that can be made from fossil fuels like petroleum. o Also, by a bioprocess from renewable sources such as corn grain or stalks, cobs, or other agro-wastes. o In the petroleum industry, butanol has been reserved mainly for the solvent and cosmetics markets, which tend to bring higher prices, rather than the motor fuel market. o The term biobutanol refers to butanol made from renewable resources such as grain or cornstalks by fermentation process.

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n-Butanol Applications
o Solvent –for paints, coatings, varnishes

o Plasticizers –to improve how a plastic material processes
o Coatings –as a solvent for a variety of applications, o Chemical intermediate or raw material –for other chemicals and plastics, o Textiles –as a swelling agent from coated fabric o Cosmetics –makeup, nail care products, shaving products o Drugs and antibiotics, hormones, and vitamins

o Gasoline (as an additive) and brake fluid (formulation
component)

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o Butanol can be used to power your car.
o It is safer than gasoline, will give you better

mileage
o It will increase the amount of energy derived

from biomass in comparison to ethanol—by
24–42%.

o We could mitigate CO2 emissions quickly by
doing something that is applicable to every
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gasoline-consuming car already on the road.

Reasons for not going for fuel butanol earlier:
o The A B E fermentation process yields only 1.3 gallons of butanol/bushel of corn, whereas yeast fermentation produces 2.52 gallons of ethanol/bushel of corn.

• Its low final concentration (0.6%) compares poorly with that of
ethanol from yeast fermentation (10–15%); the 1–2% alcohol concentration in the A B E- fermentation combination is sufficient to kill the fermenting bacteria. • Butanol’s boiling point (117°C) is higher even than that of water. At the 1–2% final batch concentration, there is a lot of water to boil off, which is expensive..
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Production breakthrough reported

• Environmental Energy, Inc.(EEI), an Ohio company led by David E. Ramey, reported on its website www.butanol.com a breakthrough _yields of 2.5 gallons of butanol per bushel of corn.”. • It has developed a process which makes ―fermentation-derived butanol more economically viable and competitive with current petrochemical processes and with the

production of ethanol.‖

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ButylFuel™.

David E. Ramey: ―How could butanol yield be increased

and production costs decreased?‖ I solved 3 major problems with the ABE process by: • increasing the yield of butanol from 1.3 gallons/bushel of corn to 2.5 (thus making it similar to that of ethanol by yeast fermentation); • overcoming the problem of the low final concentration of 1–2% by developing a recovery process that removes the solvents continuously and precludes accumulation to a level lethal to the microbe; and • solving the expensive recovery problem associated with the high boiling point by sparging carbon dioxide (produced by the fermentation) through the broth, stripping the butanol and then letting a gravity process increase the concentration before removing the remaining water.

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ButylFuel™.
In his butanol production method, Ramey takes the approach of using two types of microbes in two separate process steps. The first pass optimizes the production of hydrogen and butyric acid, while the second pass converts this acid into butanol. Each step utilizes a different Clostridium

strain. The article reported that other processes had
also tried the use of multiple bacteria strains, but

within the same slurry, making Ramey’s separation
approach unique.

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The patent EEI holds is U.S. No. 5,753,474: ―Continuous Two Stage, Dual Path Anaerobic Fermentation of Butanol and Other Organic Solvents Using Two Different Strains of Bacteria.‖ Some of the EEI work has been done through a

U.S. Department of Energy research grant, a
collaboration between Ramey and Shang- Tian

Yang, Department of Chemical and Biomolecular
Engineering at Ohio State University.
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New Catalysts to Convert Ethanol to Butanol Fuels Submitted by admin on April 23, 2013 by Chris Hanson (Ethanol Producer Magazine) Researchers from U.K.’s University of Bristol reported the development of new catalysts that are able to

convert ethanol to butanol at the national meeting
and exposition of the American Chemical Society.
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Duncan Wass, professor at the University of Bristol …and his group said  the new catalysts are similar to those used in modern petrochemical technology, potentially allowing existing ethanol producers to avoid high retrofitting costs while allowing for the production of both ethanol and butanol.  Unlike current technology, Wass said the new catalysts are more selective and yield 95 percent butanol out of the total products from each batch in laboratory-scale tests.

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Physical Property
Density at 20°C (g/cm³) Boiling Point at 1 atm (⁰C) Water Solubility at 20⁰C (g/100mL water) Net Heat of Combustion (BTU/gal) R+M/2 Blend RVP (psi at 100⁰F) 1

i-butanol
0.802 108 8.0 95,000 103.5 5.0

n-butanol
0.810 118 7.7 93,000 87 4.3

Ethanol
0.794 78 Miscible 80,000 112 18-22

Biobutanol Projecting the 3rd Wave

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Company Bug

Bug Strategy
GMO UCLA Valine metabolism

Molecule Fermentation Separation Process Strategy
iso-buoh Semi batch

Development Status

Gevo

Yeast

vacuum flash in situ 2010 Operating pilot in removal followed by St. Johns, MO. 2011 distillation trains Commercial

Cobalt Biofuels Clostridium

Non GMO strain n-buoh for reduced etoh blending and acetone w/gasoline, diesel, jet Non GMO selected for reduced etoh production n-buoh and acetone 2:1

Continuous modified vapor compression ABE Fermentation distillation

2010 pilot 10-35k gpy 2011 demo 2-5m gpy 2012 commercial

Tetra Vitae

Clostridium beijerinckii

Semi batch "AB" Fermentation

Carbon dioxide 2009 300 liter bench stripping continuous 2010 10,000 liter pilot in situ removal followed by distillation trains

Butyl Fuel

Clostridiums Aceto GMO & mutant n-buoh & tyro strain

Continuous two stage stripping following dual path anaerobic immobilized cell fermentation bioreactors

Unknown

Syngas Biofuels Fermentation of Energy Syngas

GMO

n-buoh

Thermochemical catalyst

NA

Unknown

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Status Butanol Companies

Many unknowns remain for the future of butanol.

Certainly the work of BP and DuPont and of
Environmental Energy, Inc. - and any others who enter

the butanol efforts - will be observed with interest.
Will butanol production reach a cost effective level? Will it reach commercial scale viability? If these milestones are achieved, does it compete with or complement ethanol? At this point, it’s more questions than answers on the butanol front. THANK YOU
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