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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.

2
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

gasoline-consuming car already on the road.

5
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.‖

26
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.

27
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.

28
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.
34
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.

35
Physical Property
Density at 20°C (g/cm³)

i-butanol

n-butanol

Ethanol

0.802

0.810

0.794

108

118

78

Boiling Point at 1 atm (⁰C)
Water Solubility at 20⁰C (g/100mL
water)
Net Heat of Combustion (BTU/gal)

8.0

7.7

Miscible

95,000

93,000

80,000

R+M/2

103.5

87

112

5.0

4.3

18-22

Blend RVP (psi at 100⁰F) 1

Biobutanol Projecting the 3rd
Wave

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Company Bug

Bug
Strategy

Molecule Fermentation Separation
Process
Strategy

Gevo

GMO UCLA
Valine
metabolism

iso-buoh

Yeast

Semi batch

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

Continuous modified vapor compression
ABE Fermentation
distillation

Tetra Vitae

Clostridium
beijerinckii

Non GMO
selected for
reduced etoh
production

Semi batch "AB"
Fermentation

Butyl Fuel

Clostridiums Aceto GMO & mutant n-buoh
& tyro
strain

Syngas Biofuels Fermentation of
Energy
Syngas

GMO

n-buoh and
acetone 2:1

n-buoh

Development
Status

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

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

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

Unknown

Thermochemical
catalyst

Unknown

NA

Status Butanol Companies

43
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

44

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Think fuel biobutanol

  • 1. Introduction to Biobutanol • Some literature on butanol by biochemical or ethanol conversion route is discussed briefly
  • 2. 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. 2
  • 3. 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) 3
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  • 5. 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 gasoline-consuming car already on the road. 5
  • 6. 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.. 6
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  • 26. 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.‖ 26
  • 27. 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. 27
  • 28. 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. 28
  • 29. 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. 29
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  • 34. 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. 34
  • 35. 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. 35
  • 36. Physical Property Density at 20°C (g/cm³) i-butanol n-butanol Ethanol 0.802 0.810 0.794 108 118 78 Boiling Point at 1 atm (⁰C) Water Solubility at 20⁰C (g/100mL water) Net Heat of Combustion (BTU/gal) 8.0 7.7 Miscible 95,000 93,000 80,000 R+M/2 103.5 87 112 5.0 4.3 18-22 Blend RVP (psi at 100⁰F) 1 Biobutanol Projecting the 3rd Wave 36
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  • 43. Company Bug Bug Strategy Molecule Fermentation Separation Process Strategy Gevo GMO UCLA Valine metabolism iso-buoh Yeast Semi batch 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 Continuous modified vapor compression ABE Fermentation distillation Tetra Vitae Clostridium beijerinckii Non GMO selected for reduced etoh production Semi batch "AB" Fermentation Butyl Fuel Clostridiums Aceto GMO & mutant n-buoh & tyro strain Syngas Biofuels Fermentation of Energy Syngas GMO n-buoh and acetone 2:1 n-buoh Development Status 2010 pilot 10-35k gpy 2011 demo 2-5m gpy 2012 commercial Carbon dioxide 2009 300 liter bench stripping continuous 2010 10,000 liter pilot in situ removal followed by distillation trains Continuous two stage stripping following dual path anaerobic immobilized cell fermentation bioreactors Unknown Thermochemical catalyst Unknown NA Status Butanol Companies 43
  • 44. 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 44