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Petroleum displacement potential of next generation biofuels


approaching commercialization
Rafael Hernandez

Several thermochemical and biochemical biofuel production 21.10  1015 kJ (20  1015 Btu). Approximately 80% of a
processes will be operated commercially or at the barrel of crude is used to produce transportation fuels
demonstration scale over the next 5 years. The Department of (diesel, gasoline, and jet fuel) [4]. Since the energy
Energy has estimated the annual availability of 1.3 billion tons of content of a barrel of crude is 6.12  106 kJ (5.8  106
biomass that can sustainably be used as raw material to Btu) [5], and the US consumes 7.2  109 barrels of crude
produce next generation biofuels, which are defined as those per year [4], conversion of all available biomass into a
that rely on biomass, rather than corn, or vegetable oils and crude energy equivalent could theoretically displace 60%
animal fats, as the main feedstock. Energy efficiency of the petroleum currently consumed in the US to pro-
calculations of biomass preparation and conversion processes duce transportation fuels. This is the upper limit of
indicate petroleum displacements ranging from 3% to 40%, petroleum displacement that can be obtained using bio-
depending on the specific biofuel production process. mass to produce biofuels. However, actual overall process
Consideration of other energy consuming processes during efficiencies of current next generation biofuel production
fuel delivery could result in petroleum consumption instead of processes at the demonstration or commercial scale can
displacement for some of the proposed next generation biofuel significantly reduce this level of displacement. For
production processes. example, this calculation assumes that biomass conver-
sion into biofuels has the same energy efficiency as
Address conversion of petroleum into diesel, gasoline, and jet
Dave C. Swalm School of Chemical Engineering, Mississippi State fuel. Unfortunately, this is not the case. Previous studies
University, United States indicate that approximately 6–10% of the energy in
Corresponding author: Hernandez, Rafael
biomass is consumed during feedstock preparation (e.g.
(rhernandez@che.msstate.edu) 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 prep-
Current Opinion in Chemical Engineering 2011, 1:43–46 aration sites, and distances between preparation sites and
This review comes from the bio-refineries, which will directly impact the size of the
Inaugural Open Issue bio-refinery.

Available online 26th August 2011


Biomass conversion technologies
2211-3398/$ – see front matter Conversion technologies that will be implemented in bio-
# 2011 Elsevier Ltd. All rights reserved.
refineries can be essentially classified under two
DOI 10.1016/j.coche.2011.08.001 categories: thermochemical or biochemical [7,8].
Thermochemical processes consist of the application of
relatively high temperature and pressure to de-polymer-
ize lignocellulose into small molecular weight organic and
Introduction inorganic compounds, which can be catalytically reacted
Next generation biofuels are those that rely on lignocel- into hydrocarbons, alcohols, aromatics, and other organic
lulose, more generally known as biomass, rather than compounds directly associated with fuel mixtures. Bio-
corn, or vegetable oils and animal fats, as the main feed- chemical processes also require two steps: biomass gasi-
stock. Lignocellulose is the structural component of fication followed by microbial fermentation of the
biomass. Its main components are lignin, cellulose, and synthesis (syn) gas or biomass hydrolysis followed by
hemicellulose. The distribution of these components microbial fermentation [9,10,11]. The hydrolysis step
varies depending on the source of lignocellulose (e.g. de-polymerizes cellulose and hemicellulose to yield 6
energy crops, forestry residues, or corn stover) [1]. The and 5 carbon sugars (e.g. glucose and xylose, respect-
United States Department of Energy has estimated the ively). The hydrolyzate, containing the sugars and other
annual availability of 1.3 billion tons of biomass to pro- by-products, is then fermented into ethanol. Approxi-
duce biofuels (DoE) [2]. Over 80% of the biomass would mately 60% of the biomass can be converted into sugars.
be available as corn stover and cereal straw [1,2]. The The balance, containing lignin (30%), cannot be hydro-
energy content of this biomass can be estimated using a lyzed and becomes a solid by-product, usually counted as
heating value for corn stover of 17.91 kJ/g (7700 Btu/lb) an energy source within the ethanol production process.
[3]. The energy content of 1.3 billions tons of biomass is Fermentation of the hydrolyzate could be achieved using

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44 Inaugural Open Issue

microorganisms genetically modified to consume 5 carbon ENSOL process [10]. The reaction is usually conducted
sugars [12,13]. The hydrolyzate may need refining to using heterogeneous catalysts at a pressure of approxi-
remove by-products generated during hydrolysis that mately 30 bar and a temperature lower than 3508C. The
are inhibitory towards ethanol production, such as acetic reaction is exothermic, and thus, requires specific process
acid and furfural [14,15,16,17] heat control operations. Yields of ethanol of 30% (by mass)
have been reported in the literature, with the balance
Thermochemical biomass conversion composed of methanol, water, other alcohols, alkanes,
Presently, the most commonly applied thermochemical olefins, ketones, and acetic acid. In the US, Range Fuels
processes for conversion of biomass into biofuels are Inc. constructed a 30 million gallon commercial syn gas to
gasification and pyrolysis [7,8]. Gasification converts ethanol facility in Soperton, Georgia. Wood waste was the
biomass, usually dried and ground, into a gas mainly main feedstock. The company initiated operations in 2010,
composed of carbon monoxide (CO) and hydrogen but the process did not meet performance and economic
(H2) (also known as synthesis gas). Nitrogen could be targets, and discontinued operations the first quarter of
present at relatively high concentrations if the gasification 2011. Enerkem Inc. is planning to initiate construction of a
system is fed with air. Other syn gas impurities formed 20 million gallons syn gas to ethanol facility in Pontotoc,
during the process include tars and dust. Methane is also Mississippi in 2012. Even though the facility could handle
generated but it could be catalytically reformed into more multiple feedstocks, most of the ethanol will be generated
CO and H2. The process is operated at approximately using municipal solid waste. One of the main technical
10008C and 20 bar [7,8,10]. Impurities act as poisons challenges of current syn gas to ethanol technologies is the
to currently applied catalysts and thus need to be relatively low ethanol yield (<30%) of the process. Con-
removed from the syn gas before conversion into alcohols sequently, significant energy has to be spent during ethanol
(e.g. ethanol and methanol), or hydrocarbons by Fischer separation and purification. The calculated overall energy
Tropsch (FT) chemistry. Commercial technologies are efficiency of the syn gas to ethanol process is approximately
available for the required syn gas clean-up. Overall energy 55% [10]. The technology has the potential of displacing
efficiencies can be calculated taking into consideration 27% of consumed petroleum. This displacement may be
the heating value of the mass of fuel and biomass, and the further reduced because of the current ethanol distribution
net process energy, which is the addition of the net infrastructure. Ethanol is delivered by truck or rail, which is
chemical energy due to reactions and the thermodynamic more energy consuming, compared to FT fuels, which
energy required to operate each process [10]. could be distributed via pipeline.

The FT process was patented in 1935. It has been Biomass pyrolysis is the thermal de-polymerization of
commercially applied in South Africa (Sasol, Inc.) since biomass in the absence of oxygen. Fast pyrolysis, charac-
1980 to produce synthetic fuels. The Shell FT facility in terized by small residence times and fast heating rates,
Bintulu, Malaysia, has been operating since 1993 [11]. favors production of a liquid (bio-oil) that can be used to
The main reaction is given by [10]: produce transportation fuels [8]. This liquid is com-
posed of hundreds of oxygenated organic compounds
ð2n þ 1ÞH2 þ nCO ! Cn Hð2nþ2Þ þ nH2 O [19]. Its conversion into gasoline, diesel, and jet fuel
range organics and aromatics requires hydrodeoxygena-
FT product distribution can produce compounds ranging tion (HDO) reactions, and thus, addition of external
from gasoline (C5 to C8) to diesel (C16 to C20) and heavy oils hydrogen, which would be provided by methane reform-
(C21 to C30). The product can be refined using petroleum ing and increase the overall process energy consumption
refinery operations to separate the different product cuts. [8,10,19]. KiOR and Evergent, a joint venture be-
FT reaction is typically conducted at 150–3658C and 5– tween UOP and Ensyn, are two companies planning
40 bar [10]. Steam is introduced into the system to control commercial and demonstration facilities, respectively,
the CO:H2 ratio via the water gas shift reaction. The for producing a ready-for-refining bio-oil, which could
calculated overall energy efficiency (energy content of be fed to petroleum refineries as a renewable crude to
biomass compared to FT fuel) of FT fuel production produce fuels [20] (http://biomassmagazine.com/articles/
is approximately 70% depending on the feedstock 2013/uop-ensyn-to-form-joint-venture-company). The
[8,10,18]. If this efficiency, along with the 10% of the overall efficiency to produce HDO bio-oil is 65%
energy in biomass needed for feedstock preparation [8,10], which results in a petroleum displacement
are taken into consideration, application of the FT tech- potential of 33%, or approximately 50% of the theoretical
nology has the potential of displacing approximately 40% maximum.
of the petroleum consumed in the US for transportation
fuels. Biochemical biomass conversion
Most of the planned demonstration or commercial
Syn gas can also be converted into ethanol by direct biofuel facilities in the US include a biochemical process
conversion, methanol homologation, and the multi-step train to produce ethanol [9]. Companies like Abengoa

Current Opinion in Chemical Engineering 2011, 1:43–46 www.sciencedirect.com


Petroleum displacement potential of next generation Hernandez 45

Bioenergy, BlueFire Ethanol, Coskata, Dupont Danisco, hydrocarbons from glucose, and excreting the products to
and POET are in the final stages of pilot, demonstration, the fermentation medium, potentially reducing separ-
or commercial scale production [9]. Each of these ation costs [24,25]. No data have been reported on their
companies has developed variants of the two-step bio- energy efficiency, and hydrocarbon production rates from
chemical process mentioned above. Both processes have lignocellulosic sugars in the presence of potential inhibi-
advantages and disadvantages. The conversion of biomass tors like acetic acid and furfural. If successful, these
into syn gas before biochemical conversion can handle processes would significantly reduce mass transfer limita-
multiple feedstocks. Gasification is a well-established tion and energy consumption associated with product
technology. It is operationally simple in producing con- separation.
sistent quality syn gas from multiple biomass sources.
Furthermore biomass gasification does not yield a lignin Conclusion
solid that needs handling for energy recovery operations, In summary, current thermo-chemical processes to pro-
which is the case for biomass hydrolysis. However, fer- duce biofuels at the demonstration, pilot, or commercial
mentation of syn gas requires operation of fermentors at scale have higher potential for petroleum displacement
relatively high pressure to increase the solubility of the compared to biochemical processes. FT fuels have a track
gases in the fermentation mixture. The solubility of CO record of performance and technology development that
and H2 in water at 208C and atmospheric pressure are may be transferred successfully to production of FT fuels
0.028 and 0.0016 g per kg of water, respectively (http:// from biomass. The analysis presented above is not
www.engineeringtoolbox.com/gases-solubility-water-d_ intended to select or endorse any particular technology
1148.html). Low concentrations of CO and H2 in the for biofuel production. It is simply an estimate of
water, and consequently cell mass, create process con- petroleum displacement potential based on energy effi-
ditions in which growth of other non-ethanol producing ciencies reported in the literature. Other factors, such as
microbial competitors is difficult, especially at commer- total capital investment and interest, and operating cost,
cial scales. The relatively low reported ethanol yields type of feedstock, logistics, and chain supply economics
(<10%) also result in high-energy consumption for will have to be considered during final process selection.
ethanol separation [10,11].
References and recommended reading
Papers of particular interest, published within the period of review,
Hydrolysis of biomass followed by fermentation also have been highlighted as:
suffers from low ethanol yields, and consequently,
high-energy consumption during ethanol recovery. As  of special interest
 of outstanding interest
mentioned above, the microorganisms applied are geneti-
cally modified to convert both, C5 and C6 sugars, into 1. Soetaert W, Vandamme EJ: Biofuels. John Wiley & Sons, Ltd.;
ethanol. Several research groups have questioned the 2009:. ISBN 978-0-470-02674-8.
long-term stability of these genetically modified micro- 2. Perlack RD, Wright LL, Turhollow AF, Graham RL, Stokes BJ,
organisms [21–23]. The microorganisms could revert back  Erbach DC: Biomass as Feedstock for a Bioenergy and
Bioproducts Industry: The Technical Feasibility of a
to the wild type, which is the most stable form. Ethanol Billion-Ton Annual Supply. April 2005, Report Number
yields reported vary between 4% and 8% [10,11]. Yield DOE/GO-102005-2135
The authors establish the availability of approximately 1.3 billion tons of
variations are dependent on feedstock and hydrolysis biomass per year that could be used to produce transportation fuels. The
conditions. The consequence is an overall energy effi- objective of the report was to determine if there were sufficient biomass
resources in the US to replace 30% petroleum consumption by 2030. The
ciency of biochemical processes for ethanol production authors indicate that there is enough biomass in the US to meet this goal
that varies between 15% and 30%, depending on feed- sustainably via a combination of energy crops, agricultural wastes, and
stock and process conditions. Therefore, the petroleum forestry residues.
displacement potential varies between 3% and 12%. As 3. Pordesimo LO, Hames BR, Sokhansanj S, Edens WC: Variation in
corn stover composition and energy content with crop
mentioned above, this displacement may be further maturity. Biomass Bioenergy 2005, 28:366-374.
reduced because of the current ethanol distribution infra- 4. Energy Information Administration: http://www.eia.gov/
structure. Thus, there is the possibility of increasing energyexplained/index.cfm?page=oil_refining. Products Mades
petroleum consumption by producing ethanol from lig- from a Barrel of Crude Oil, 2010.
nocellulose via biochemical routes. Research and devel- 5. Energy Information Administration Calculator: http://www.eia.gov/
kids/energy.cfm?page=about_energy_conversion_calculator-
opment efforts need to focus on significantly increasing basics#oilcalc.
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and develop more cost effective and selective enzymes  biomass: the storage problem and multi-biomass supply
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The authors established the importance of biomass logistics, such as
planting, cultivation, harvesting, handling, and storage, on the economics
Other companies are evaluating biochemical processes of biorefineries. The authors emphasize the importance of biomass
storage considerations on biomass selection.
to directly produce hydrocarbons, or hydrocarbon precur-
7. Naik SN, Goud VV, Rout PK, Dalai AK: Production of first
sors. For example, LS9, Inc. and Amyris, have deve-  and second generation biofuels: a comprehensive review.
loped proprietary microorganisms capable of producing Renew Sust Energy Rev 2010, 14:578-597.

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46 Inaugural Open Issue

The paper presents the advantages of 2nd generation biofuels over 1st of biomass hydrolysis, while lignin-derived substances (phenolic com-
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production cost of bioethanol generated by biochemical or their process is a fluidized biomass catalytic cracking system,
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hydrocarbons using genetically modified microorganisms.
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