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Petroleum displacement potential of next generation biofuels

approaching commercialization
Rafael Hernandez
Several thermochemical and biochemical biofuel production
processes will be operated commercially or at the
demonstration scale over the next 5 years. The Department of
Energy has estimated the annual availability of 1.3 billion tons of
biomass that can sustainably be used as raw material to
produce next generation biofuels, which are defined as those
that rely on biomass, rather than corn, or vegetable oils and
animal fats, as the main feedstock. Energy efficiency
calculations of biomass preparation and conversion processes
indicate petroleum displacements ranging from 3% to 40%,
depending on the specific biofuel production process.
Consideration of other energy consuming processes during
fuel delivery could result in petroleum consumption instead of
displacement for some of the proposed next generation biofuel
production processes.
Address
Dave C. Swalm School of Chemical Engineering, Mississippi State
University, United States
Corresponding author: Hernandez, Rafael
(rhernandez@che.msstate.edu)

Current Opinion in Chemical Engineering 2011, 1:4346

This review comes from the
Inaugural Open Issue
Available online 26th August 2011
2211-3398/$ see front matter
# 2011 Elsevier Ltd. All rights reserved.
DOI 10.1016/j.coche.2011.08.001

Introduction
Next generation biofuels are those that rely on lignocellulose, more generally known as biomass, rather than
corn, or vegetable oils and animal fats, as the main feedstock. Lignocellulose is the structural component of
biomass. Its main components are lignin, cellulose, and
hemicellulose. The distribution of these components
varies depending on the source of lignocellulose (e.g.
energy crops, forestry residues, or corn stover) [1]. The
United States Department of Energy has estimated the
annual availability of 1.3 billion tons of biomass to produce biofuels (DoE) [2]. Over 80% of the biomass would
be available as corn stover and cereal straw [1,2]. The
energy content of this biomass can be estimated using a
heating value for corn stover of 17.91 kJ/g (7700 Btu/lb)
[3]. The energy content of 1.3 billions tons of biomass is
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21.10  1015 kJ (20  1015 Btu). Approximately 80% of a

barrel of crude is used to produce transportation fuels
(diesel, gasoline, and jet fuel) [4]. Since the energy
content of a barrel of crude is 6.12  106 kJ (5.8  106
Btu) [5], and the US consumes 7.2  109 barrels of crude
per year [4], conversion of all available biomass into a
crude energy equivalent could theoretically displace 60%
of the petroleum currently consumed in the US to produce transportation fuels. This is the upper limit of
petroleum displacement that can be obtained using biomass to produce biofuels. However, actual overall process
efficiencies of current next generation biofuel production
processes at the demonstration or commercial scale can
significantly reduce this level of displacement. For
example, this calculation assumes that biomass conversion into biofuels has the same energy efficiency as
conversion of petroleum into diesel, gasoline, and jet
fuel. Unfortunately, this is not the case. Previous studies
indicate that approximately 610% of the energy in
biomass is consumed during feedstock preparation (e.g.
collection, drying, and grinding) before delivery to the
bio-refinery [1,6]. The specific energy will depend on the
type of biomass, distances between collection and preparation sites, and distances between preparation sites and
bio-refineries, which will directly impact the size of the
bio-refinery.

Biomass conversion technologies

Conversion technologies that will be implemented in biorefineries can be essentially classified under two
categories: thermochemical or biochemical [7,8].
Thermochemical processes consist of the application of
relatively high temperature and pressure to de-polymerize lignocellulose into small molecular weight organic and
inorganic compounds, which can be catalytically reacted
into hydrocarbons, alcohols, aromatics, and other organic
compounds directly associated with fuel mixtures. Biochemical processes also require two steps: biomass gasification followed by microbial fermentation of the
synthesis (syn) gas or biomass hydrolysis followed by
microbial fermentation [9,10,11]. The hydrolysis step
de-polymerizes cellulose and hemicellulose to yield 6
and 5 carbon sugars (e.g. glucose and xylose, respectively). The hydrolyzate, containing the sugars and other
by-products, is then fermented into ethanol. Approximately 60% of the biomass can be converted into sugars.
The balance, containing lignin (30%), cannot be hydrolyzed and becomes a solid by-product, usually counted as
an energy source within the ethanol production process.
Fermentation of the hydrolyzate could be achieved using
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44 Inaugural Open Issue

microorganisms genetically modified to consume 5 carbon

sugars [12,13]. The hydrolyzate may need refining to
remove by-products generated during hydrolysis that
are inhibitory towards ethanol production, such as acetic
acid and furfural [14,15,16,17]

Thermochemical biomass conversion

Presently, the most commonly applied thermochemical
processes for conversion of biomass into biofuels are
gasification and pyrolysis [7,8]. Gasification converts
biomass, usually dried and ground, into a gas mainly
composed of carbon monoxide (CO) and hydrogen
(H2) (also known as synthesis gas). Nitrogen could be
present at relatively high concentrations if the gasification
system is fed with air. Other syn gas impurities formed
during the process include tars and dust. Methane is also
generated but it could be catalytically reformed into more
CO and H2. The process is operated at approximately
10008C and 20 bar [7,8,10]. Impurities act as poisons
to currently applied catalysts and thus need to be
removed from the syn gas before conversion into alcohols
(e.g. ethanol and methanol), or hydrocarbons by Fischer
Tropsch (FT) chemistry. Commercial technologies are
available for the required syn gas clean-up. Overall energy
efficiencies can be calculated taking into consideration
the heating value of the mass of fuel and biomass, and the
net process energy, which is the addition of the net
chemical energy due to reactions and the thermodynamic
energy required to operate each process [10].
The FT process was patented in 1935. It has been
commercially applied in South Africa (Sasol, Inc.) since
1980 to produce synthetic fuels. The Shell FT facility in
Bintulu, Malaysia, has been operating since 1993 [11].
The main reaction is given by [10]:
2n 1H2 nCO ! Cn H2n2 nH2 O

ENSOL process [10]. The reaction is usually conducted

using heterogeneous catalysts at a pressure of approximately 30 bar and a temperature lower than 3508C. The
reaction is exothermic, and thus, requires specific process
heat control operations. Yields of ethanol of 30% (by mass)
have been reported in the literature, with the balance
composed of methanol, water, other alcohols, alkanes,
olefins, ketones, and acetic acid. In the US, Range Fuels
Inc. constructed a 30 million gallon commercial syn gas to
ethanol facility in Soperton, Georgia. Wood waste was the
main feedstock. The company initiated operations in 2010,
but the process did not meet performance and economic
targets, and discontinued operations the first quarter of
2011. Enerkem Inc. is planning to initiate construction of a
20 million gallons syn gas to ethanol facility in Pontotoc,
Mississippi in 2012. Even though the facility could handle
multiple feedstocks, most of the ethanol will be generated
using municipal solid waste. One of the main technical
challenges of current syn gas to ethanol technologies is the
relatively low ethanol yield (<30%) of the process. Consequently, significant energy has to be spent during ethanol
separation and purification. The calculated overall energy
efficiency of the syn gas to ethanol process is approximately
55% [10]. The technology has the potential of displacing
27% of consumed petroleum. This displacement may be
further reduced because of the current ethanol distribution
infrastructure. Ethanol is delivered by truck or rail, which is
more energy consuming, compared to FT fuels, which
could be distributed via pipeline.
Biomass pyrolysis is the thermal de-polymerization of
biomass in the absence of oxygen. Fast pyrolysis, characterized by small residence times and fast heating rates,
favors production of a liquid (bio-oil) that can be used to
produce transportation fuels [8]. This liquid is composed of hundreds of oxygenated organic compounds
[19]. Its conversion into gasoline, diesel, and jet fuel
range organics and aromatics requires hydrodeoxygenation (HDO) reactions, and thus, addition of external
hydrogen, which would be provided by methane reforming and increase the overall process energy consumption
[8,10,19]. KiOR and Evergent, a joint venture between UOP and Ensyn, are two companies planning
commercial and demonstration facilities, respectively,
for producing a ready-for-refining bio-oil, which could
be fed to petroleum refineries as a renewable crude to
produce fuels [20] (http://biomassmagazine.com/articles/
2013/uop-ensyn-to-form-joint-venture-company). The
overall efficiency to produce HDO bio-oil is 65%
[8,10], which results in a petroleum displacement
potential of 33%, or approximately 50% of the theoretical
maximum.

FT product distribution can produce compounds ranging

from gasoline (C5 to C8) to diesel (C16 to C20) and heavy oils
(C21 to C30). The product can be refined using petroleum
refinery operations to separate the different product cuts.
FT reaction is typically conducted at 1503658C and 5
40 bar [10]. Steam is introduced into the system to control
the CO:H2 ratio via the water gas shift reaction. The
calculated overall energy efficiency (energy content of
biomass compared to FT fuel) of FT fuel production
is approximately 70% depending on the feedstock
[8,10,18]. If this efficiency, along with the 10% of the
energy in biomass needed for feedstock preparation
are taken into consideration, application of the FT technology has the potential of displacing approximately 40%
of the petroleum consumed in the US for transportation
fuels.

Biochemical biomass conversion

Syn gas can also be converted into ethanol by direct

conversion, methanol homologation, and the multi-step

Most of the planned demonstration or commercial

biofuel facilities in the US include a biochemical process
train to produce ethanol [9]. Companies like Abengoa

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Petroleum displacement potential of next generation Hernandez 45

Bioenergy, BlueFire Ethanol, Coskata, Dupont Danisco,

and POET are in the final stages of pilot, demonstration,
or commercial scale production [9]. Each of these
companies has developed variants of the two-step biochemical process mentioned above. Both processes have
advantages and disadvantages. The conversion of biomass
into syn gas before biochemical conversion can handle
multiple feedstocks. Gasification is a well-established
technology. It is operationally simple in producing consistent quality syn gas from multiple biomass sources.
Furthermore biomass gasification does not yield a lignin
solid that needs handling for energy recovery operations,
which is the case for biomass hydrolysis. However, fermentation of syn gas requires operation of fermentors at
relatively high pressure to increase the solubility of the
gases in the fermentation mixture. The solubility of CO
and H2 in water at 208C and atmospheric pressure are
0.028 and 0.0016 g per kg of water, respectively (http://
www.engineeringtoolbox.com/gases-solubility-water-d_
1148.html). Low concentrations of CO and H2 in the
water, and consequently cell mass, create process conditions in which growth of other non-ethanol producing
microbial competitors is difficult, especially at commercial scales. The relatively low reported ethanol yields
(<10%) also result in high-energy consumption for
ethanol separation [10,11].
Hydrolysis of biomass followed by fermentation also
suffers from low ethanol yields, and consequently,
high-energy consumption during ethanol recovery. As
mentioned above, the microorganisms applied are genetically modified to convert both, C5 and C6 sugars, into
ethanol. Several research groups have questioned the
long-term stability of these genetically modified microorganisms [2123]. The microorganisms could revert back
to the wild type, which is the most stable form. Ethanol
yields reported vary between 4% and 8% [10,11]. Yield
variations are dependent on feedstock and hydrolysis
conditions. The consequence is an overall energy efficiency of biochemical processes for ethanol production
that varies between 15% and 30%, depending on feedstock and process conditions. Therefore, the petroleum
displacement potential varies between 3% and 12%. As
mentioned above, this displacement may be further
reduced because of the current ethanol distribution infrastructure. Thus, there is the possibility of increasing
petroleum consumption by producing ethanol from lignocellulose via biochemical routes. Research and development efforts need to focus on significantly increasing
ethanol yields from the different available feedstocks,
and develop more cost effective and selective enzymes
for hydrolysis.
Other companies are evaluating biochemical processes
to directly produce hydrocarbons, or hydrocarbon precursors. For example, LS9, Inc. and Amyris, have developed proprietary microorganisms capable of producing
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hydrocarbons from glucose, and excreting the products to

the fermentation medium, potentially reducing separation costs [24,25]. No data have been reported on their
energy efficiency, and hydrocarbon production rates from
lignocellulosic sugars in the presence of potential inhibitors like acetic acid and furfural. If successful, these
processes would significantly reduce mass transfer limitation and energy consumption associated with product
separation.

Conclusion
In summary, current thermo-chemical processes to produce biofuels at the demonstration, pilot, or commercial
scale have higher potential for petroleum displacement
compared to biochemical processes. FT fuels have a track
record of performance and technology development that
may be transferred successfully to production of FT fuels
from biomass. The analysis presented above is not
intended to select or endorse any particular technology
for biofuel production. It is simply an estimate of
petroleum displacement potential based on energy efficiencies reported in the literature. Other factors, such as
total capital investment and interest, and operating cost,
type of feedstock, logistics, and chain supply economics
will have to be considered during final process selection.

References and recommended reading

Papers of particular interest, published within the period of review,
have been highlighted as:
 of special interest
 of outstanding interest
1.

Soetaert W, Vandamme EJ: Biofuels. John Wiley & Sons, Ltd.;

2009:. ISBN 978-0-470-02674-8.

2.


Perlack RD, Wright LL, Turhollow AF, Graham RL, Stokes BJ,
Erbach DC: Biomass as Feedstock for a Bioenergy and
Bioproducts Industry: The Technical Feasibility of a
Billion-Ton Annual Supply. April 2005, Report Number
DOE/GO-102005-2135
The authors establish the availability of approximately 1.3 billion tons of
biomass per year that could be used to produce transportation fuels. The
objective of the report was to determine if there were sufficient biomass
resources in the US to replace 30% petroleum consumption by 2030. The
authors indicate that there is enough biomass in the US to meet this goal
sustainably via a combination of energy crops, agricultural wastes, and
forestry residues.

3.

Pordesimo LO, Hames BR, Sokhansanj S, Edens WC: Variation in

corn stover composition and energy content with crop
maturity. Biomass Bioenergy 2005, 28:366-374.

4.

Energy Information Administration: http://www.eia.gov/

energyexplained/index.cfm?page=oil_refining. Products Mades
from a Barrel of Crude Oil, 2010.

5.

Energy Information Administration Calculator: http://www.eia.gov/

kids/energy.cfm?page=about_energy_conversion_calculatorbasics#oilcalc.

6.


Rentizalas AA, Tolis AJ, Tatsiopoulos IP: Logistics issues of

biomass: the storage problem and multi-biomass supply
chain. Renew Sust Energy Rev 2009, 13:887-894.
The authors established the importance of biomass logistics, such as
planting, cultivation, harvesting, handling, and storage, on the economics
of biorefineries. The authors emphasize the importance of biomass
storage considerations on biomass selection.

7.


Naik SN, Goud VV, Rout PK, Dalai AK: Production of first
and second generation biofuels: a comprehensive review.
Renew Sust Energy Rev 2010, 14:578-597.
Current Opinion in Chemical Engineering 2011, 1:4346

46 Inaugural Open Issue

The paper presents the advantages of 2nd generation biofuels over 1st
generation biofuels, such as the use of biomass for transportation fuel
without competing with land resources for food production. The paper
emphasizes thermo-chemical technologies and the application of these
technologies to produce not only fuel but also chemicals.
8.


Huber GW, Iborra S, Corma A: Synthesis of transportation fuels

from biomass: chemistry, catalysts, and engineering. Chem
Rev 2006, 106:4044-4098.
This review describes the technical and economical challenges of 1st and
2nd generation biofuels. It presents information on potential production
rates, energy efficiencies, and cost of 2nd generation biofuels.

9.


Coyle WT: Next Generation Biofuels: Near Term Challenges

and Implication for Agriculture. Report from the Economic
Research Service, Report number: BIO 01-01, May 2010
The report list companies currently constructing demonstration or
commercial facilities for 2nd generation biofuels. It describes the technologies, and the technical and logistic challenges associated with
biofuel production.

10. International Air Transport Association: 2nd Generation Biomass

Conversion Efficiency. Report Published by McGill University
and IATA. The report shows detailed efficiency calculations of
thermo-chemical and biochemical processes to produce 2nd
generation biofuels, 2010.
11. Rapier R: Biofuel Pretenders, R2 Energy Blog, http://www.
consumerenergyreport.com/2009/08/31/biofuel-pretenders/. The
blog article describes the technical challenges of some of the
current 2nd generation biofuels being considered for commercial
scale. For example, the blog emphasizes the high cost of
production of algae oils, and the low yields, and consequently, high
production cost of bioethanol generated by biochemical or
thermo-chemical processes, August 2009.
12. Hahn-Hagerdal B, Karhumaa K, Fonseca C, Spencer-Martins I,
Gorwa-Grauslund wiMF: Towards industrial pentosefermenting yeast strains. Appl Microbiol Biotechnol 2007,
74:937-953.
13. Martin C, Marcet M, Almazan O, Jonsson LJ: Adaptation of a
recombinant xylose-utilizing Saccharomyces cerevisiae strain
to a sugarcane bagasses hydrolyzate with high content of
fermentation inhibitors. Bioresour Technol 2007, 98:1767-1773.
14. Diaz MJ, Ruiz E, Romero I, Cara C, Moya M, Castro E: Inhibition of

Pichia stipitis fermentation of hydrolysates from olive tree
cuttings. World J Microbiol Biotechnol 2009, 25:891-899.
The authors indicate that acetic acid is typically the most abundant
organic acid found in lignocellulose hydrolyzates obtained via the cleavage of the acetyl groups from hemicelluloses such as acetylxylan during
mild pretreatment conditions. The authors found that furfural concentrations in the order of 1 g/L already have negative effects on yeast viability,
specific growth rate, sugar consumption and volumetric fermentation rate
of ethanol producing yeast Pichia stipitis.
15. Wikandari R, Millati R, Syamsiyah S, Muriana R, Ayuningish Y:

Effect of furfural, hydroxymethylfurfural, and acetic acid on
indigenous microbial isolate for bioethanol production.
Agric J 2010, 5:105-109.
The authors found that acetic acid and furans (furfural and 5-hydroxymethylfurfural) are the most commonly produced degradation by-products

Current Opinion in Chemical Engineering 2011, 1:4346

of biomass hydrolysis, while lignin-derived substances (phenolic compounds) are normally found in concentrations well below 0.1 mM. These
compounds were found to exert inhibitory effects on the growth and
metabolism of microorganisms such as bioethanol-producing yeasts.
16. Gorsich SW, Dien BS, NIchols NN, Slininger PJ, Liu ZL, Skory CD:
Tolerance to furfural-induced stress is associated with
pentose phosphate pathway genes ZWF1, GND1, RPE1, and
TKL1 in Saccharomyces cerevisiae. Appl Microbiol Biotechnol
2006, 71:339-349.
It was found that overexpression of the gene zwf1, which is one of several
genes encoding for pentose phosphate pathway enzymes, allowed
Saccharomyces cerevisiae to grow a furfural concentrations that are
normally toxic.
17. Horvath IS, Franzen CJ, Taherzadeh MJ, Niklasson C, Liden G:
Effects of furfural on the respiratory metabolism of
Saccharomyces cerevisiae in glucose limited chemostats.
Appl Environ Microbiol 2003, 69:4076-4086.
18. Boerrigter H: Economy of Biomass to Liquids (BTL) Plants: An
Engineering Assessment. Energy Research Center of the
Netherlands, ECN C-06-019, May 2006.
19. Mohan D, Pittman CU, Steele PH: Pyrolysis of wood/biomass for
 bio-oil: a critical review. Energy Fuels 2006, 20(3):848-889.
The authors describe the challenges associated with pyrolysis oil production, handling, and conversion to biofuels. Additionally, the authors
provide alternatives for the application of pyrolysis oil as a feedstock to
produce specialty chemicals.
20. http://www.kior.com/content/?s=11&t=Technology. The website
describes KiORs commercialization plans. According to KiOR,
their process is a fluidized biomass catalytic cracking system,
which produces pyrolysis oil that is less acidic and with lower
oxygen content compared to conventional pyrolysis systems.
21. Keating JD, Panganiban C, Mansfield SD: Tolerance and
adaptation of ethanologenic yeasts to lignocellulose inhibitory
compounds. Biotechnol Bioeng 2006, 93:1196-1206.
22. Miller EN, Jarboe LR, Yomano LP, York SW, Shanmugam KT,
Ingram LO: Silencing of NAPDH-dependent oxidoreductases
(yqhD and dkgA)) in furfural-resistant ethanologenic
Escherichia coli. Appl Environ Microbiol 2009, 75:4315-4323.
The authors found that silencing the yqhD and dkgA genes in ethanologenic E. coli, which encode for products with low affinities for NADPH,
allowed the mutant strain to concurrently grow and reduce furfural to less
toxic products, such as furfuryl alcohol and furoic acid.
23. Zaldivar J, Nielsen J, Olsson L: Fuel ethanol production from
lignocellulose: a challenge for metabolic engineering and
process integration. Appl Microbiol Biotechnol 2001, 56:17-34.
24. http://www.ls9.com/. The website describes the technology being
developed by LS9, which is the conversion of sugars to
hydrocarbons using genetically modified microorganisms.
The hydrocarbons, once produced, are excreted into the cell
medium.
25. http://www.amyrisbiotech.com/. Amyris applies genetically
modified microorganisms to produce fuels and chemicals from
biomass.

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