1

Pyrolysis Oil Overview of characteristics and utilization

A.A. Boateng USDA/ARS
Outline:
1. What is pyrolysis?
2. What are the products of pyrolysis?
3. What is bio-oil
a. Bio-oil characteristics
b. Bio-oil production equipment
4. What is biochar, the major coproduct and its role in agriculture & climate change
5. Bio-oil utilization
6. What is the current state of the art for pyrolysis in the US, what are the gaps towards use
of 2
nd
generation biofuels
7. Who are commercial players
8. What is the future of pyrolysis and role in the RFS2

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Pyrolysis Oil Overview of Characterization and Utilization

A. A. Boateng
*


USDA-ARS, Eastern Regional Research Center, 600 E. Mermaid Lane, Wyndmoor, PA 19038,
USA

Keywords: Pyrolysis; Catalytic pyrolysis, Pyrolysis oil; Bio-oil; Bio-oil stabilization


* To whom correspondence should be addressed. Tel.: 215 233 6493; fax: 215 233 6406.
E-mail address: akwasi.boateng@ars.usda.gov.
Mention of trade names or commercial products in this publication is solely for the purpose of providing
specific information and does not imply recommendation or endorsement by the U.S. Department of
Agriculture.

Abstract
The U.S. renewable fuels standard (RFS2) requires increasing the domestic supply of alternative
fuels to 36 billion gallons by 2022. This includes 15 billion gallons from corn-based ethanol and
21 billion gallons from advanced biofuels from lignocellolosic biomass. For the latter, we must
use biochemical and thermochemical conversion technologies to utilize the vast lignocellulosic
biomass resources that could be sustainably harvested from US fields and forests. While
biochemical conversion methodologies proposed for lignocelluloses await cost effective
technologies, thermochemical conversion technologies that are proven for coal can be
economically adopted for biomass. The most familiar thermal energy conversion of organic
matter is combustion because people associate it with the fire that comes with the visible flame.
However, preceding combustion are two sequential process steps i.e., pyrolysis and gasification
each of which can be a stand-alone process for the production of renewable energy carriers
respectively, pyrolysis liquid plus charcoal and syngas that can be sources of advanced biofuels
envisioned in the RFS. In this article we discuss pyrolysis liquid, its characteristics, current
utilization and future prospects as transportation fuel resource. Pyrolysis coproduct, biochar, will
be covered separately.

1.0 Overview of Characteristics
Pyrolysis is defined as heating in the absence of oxygen. It has been the traditional process for
making charcoal since the ancient times, producing pyrolysis liquids (also called bio-oil or bio-
crude), char (bio-charcoal, biochar) and non-condensable gases (synthesis gas or syngas) in
various proportions depending upon heating rate. The current technologies for biomass pyrolysis,
including the properties and uses of pyrolysis oil were recently reviewed (Mohan et al., 2006,
Huber et al., 2006). Depending on the feedstock used and the exact process conditions, as much
as 50-75 wt% of the biomass can be converted to pyrolysis oil. The coproducts could constitute
10-30 wt% biochar and 5-15 wt% syngas (Fig. 1). Pyrolysis oil yield may be maximized using
the fast pyrolysis process (also known as rapid pyrolysis) whereby the biomass is heated at rapid
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rates in excess of 1000 C/s, to temperatures in the 450-550 C range (Diebold, 2002). In contrast
to fast pyrolysis, slow pyrolysis which employs slower heat rates at the same temperature range,
maximizes char yield. Another slow pyrolysis process is torrefaction, a mild form of pyrolysis
with production temperatures ranging between 200-320 C (Prins et al., 2006) primarily for
densification of the feedstock which targets reducing their transportation costs due to moisture
removal and increasing gridability and heating values (Bourgois and Guyonnet, 1988),
generating a material amenable for coal-blending and subsequent co-combustion (Bridgeman et
al., 2010; Repellin et al., 2010; Phanphanich and Mani, 2011). Pyrolysis can be endothermic or
exothermic depending upon the temperature of the reactants. Because biomass fixed carbon is
high (40-50 wt% dry-ash-free basis), biochar formation is the predominant pathway for slow
pyrolysis hence the exothermicity of the reaction is quite high amounting to some 80 kJ/g-mol
making it the driving force behind the self-starting (autogeneous), self-sustaining reactions that
take place at low temperatures (Milosavljevic et al., 1996, Mok and Antal, 1983). This explains
why the ancient methods of charcoal making, whereby biomass was buried underground, could
carry on for days. It must be noted that research in slow/mild pyrolysis to biochar and torrefied
products is increasing substantially, but this process will be covered in other papers.
Currently, pyrolysis liquids are produced using modern reactor vessels that are capable of
achieving the high heat rates stated with vapor residence times of the order of a few seconds. A
handful of such reactors have been developed over the years. Among these old and new
technologies fluidized bed reactors with both bubbling and circulating media are popular for fast
pyrolysis (Sadaka and Boateng, 2009). Another popular reactor type is the auger system
arrangement which, although does not achieve the rapid heat-rate as fluidized bed reactors do,
has demonstrated simplicity and better controllability. For a review of reactors used in the art,
the reader is referred to (Sadaka and Boateng, 2009). Regardless of the reactor type, vapors
generated from fast pyrolysis, resulting from the depolymerization (the breakdown and
deconstruction) of the organic constituent of the biomass component structure i.e., cellulose,
hemicellulose and lignin, must be rapidly cooled and condensed to form the pyrolysis oil a
complex mixture of oxygenated organic compounds. It must be mentioned that these vapors are
not true vapors but are mixtures of true vapors and many micron-sized droplets or aerosols;
therefore once condensed as liquids they cannot be totally be distilled as vapors (Qiang Lu et al,
2009). Prolonging the reaction time promotes secondary reactions of the aerosols leading to
pathways that favor the formation of low molecular weight hydrocarbons (e.g., CH
4
, C
2
H
6
, etc.)
and concomitant increase in the synthesis gas component of the coproduct.
Pyrolysis oil contains several hundreds of individual organic compounds and water (about 15-
30 wt%). Although it has a physical appearance of petroleum crude it is not miscible with
petroleum-derived fuels. The liquid organics are oxygenated hydrocarbons including acids,
alcohols, aldehydes, esters, furans, ketones, sugars, phenols and many multifunctional
compounds. Collectively, pyrolysis oil is acidic with an overall pH in the 2-3 range making it
unstable and corrosive. On an elemental basis, however, its compositional analysis is similar to
the parent biomass hence it is at times dubbed liquid plant matter. Due to its high oxygen
content its fuel value is lower than that of most fossil fuels (Table 1). Typically the calorific
value is only about half the heating value of petroleum derived fuels (e.g. heavy fuel oil),
however, it contains less trace metals and sulfur making it attractive as low-emission combustion
fuel. Owing to the high concentration of reactive components in pyrolysis liquids condensation
and polymerization reactions continue during storage and over time, cause increases in the
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average molecular weight, viscosity and water content. Also, alkali metals sequestered in the fine
char particles that are usually sequested into the liquid tend to catalyze and thereby accelerate
ageing reactions, further contributing to its instability. This combination of negative attributes
presents transportation, pumping and storage challenges; hence pyrolysis oil has found little
practical use thus far. Because of its heterogeneity pyrolysis oil is unsuitable for ready use in
diesel engines although, direct injection engine trials have been carried out (Solantausta et al.,
1993; Shihadeh and Hochgreb, 2000). Also, instability has been the major factor limiting
pyrolysis oil refining in existing petroleum refineries and thus far has been the major barrier to
the commercialization of pyrolysis oil as a transportation fuel (Schwietzke et al., 2008).
2.0 Logistics and Economic Advantage
Notwithstanding the drawbacks, the pyrolysis process itself offers a greater advantage over
other conversion technologies for the fact that it is feedstock neutral and uses the entire biomass.
Although variations exist in pyrolysis oil composition as function of feedstock composition
(Table 2), the negative effects that feedstock composition has on pyrolysis efficiency pale in
comparison with the effect feedstock composition has on biochemical processes (Boateng et al.,
2008). The smaller footprint of pyrolysis reactor systems makes it amendable to the farm scale
with the potential to set up regional, distributed biorefinery systems across a wide variation of
agricultural feedstocks. For example, converting biomass to pyrolysis oil near the harvest site
offers a major logistic advantage. With a specific gravity greater than water, when stabilized,
pyrolysis oil could be more cost effectively transported for further processing than its low bulk
density biomass precurssor, offering a major cost advantage in a commercial biorefinery (Fig. 2).
It has been shown (Wright et al., 2008) that because of the transportation costs savings alone, a
regional biorefinery system comprising localized, distributed pyrolysis reactors and a centralized
gasification plant using pyrolysis oil as feedstock with Fischer-Tropsch (FT) synthesis could be
economically favorable. This is encouraging since the existing commercial coal-FT liquid
production has thus far eluded economical production without large economies of scale
(Tijmensen et al., 2002, Jager, 1997). Most recent economic models developed by others
including Department of Energy (DOE) such as the National Renewable Energy Laboratory
(NREL) and the Pacific Northwest National Laboratory (PNNL), and also companies such as
UOP, a Honeywell company and Conoco Phillips all favor distributed, smaller footprint
pyrolysis systems (Jones, et al., 2009).
3.0 Production and Current Uses
3.1 Commercial Production
Production of pyrolysis oils in commercial quantities is only recent and offered in North
America by two Canadian companies, Ensyn Technologies Inc ( http://www.ensyn.com/ ) and
Dynamotive Inc. ( http://www.dynamotive.com/ ). Ensyn reports to have constructed the first
commercial plant in 1989 and seven since in the US and Canada but their Renfrew, Canada plant
built in 2007, is the largest to date with capacity of some 200 green TPD (ton per day) or 100
dried TPD biomass. Until 2005 production of pyrolysis liquids by Ensyn was restricted to
applications other than fuel. Their website claims they have operated commercial facilities for
thermochemical liquification of biomass wastes since 1991 that have targeted bio-liquid products
such as specialty chemicals, binders, preservatives, and road de-icers and co-polymers. Now the
company targets its products for use as fossil fuels replacement. With their rapid thermal process
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(RTP), a circulating fluidized bed technology, Ensyns process is similar to that used in the UOP
fluid catalytic cracking (FCC) technology and well suited for catalytic cracking in future
production of fungible (transportable) fuels. It is hopeful that these could be adopted for biomass
if ash accumulation effects on catalysts life could be resolved but research is underway. In 2008
Ensyn and UOP formed a joint venture company, Envergent (http://www.envergenttech.com/ ),
to convert second generation biomass like forest and agricultural residues to pyrolysis oil for use
in power and heating applications and to accelerate research and development efforts to
commercialize upgrading technologies to refine pyrolysis oil into transport fuels including jet
grade fuels http://www.naylornetwork.com/ppi-
biotech/articles/index.asp?aid=115582&issueID=21815 . In 2005 Dynamotive Inc, of
Vancouver, Canada commissioned a 100 TPD biomass pyrolysis plant at Guelph, Canada mainly
for the production of fuel grade pyrolysis liquid. This was followed by a larger capacity with 200
TPD biomass input. To date the company claims they have the capacity to process 66,000 dry
tons of biomass per year with an energy output equivalent to 130,000 barrels of oil. Outside
Canada, smaller quantities of pyrolysis oils have been produced mainly through demonstration
plants. In 2005 a 2 ton/hour or 48 TPD pyrolysis liquid production plant was built in Malaysia
using a fluidized-bed technology developed by Biomass Technology Group of the The
Netherlands, (BTG) ( http://www.btgworld.com/). The goal was to produce pyrolysis oil for
power generation using empty fruit bunch (EFBas feedstock. Smaller production capacities at
various research labs have been demonstrated using various conversion technologies these
include VTT Technical Research Center, Finland (5 TPD), The Canada Center for Mineral and
Energy Technology (CANMET), National Renewable Energy Laboratory (NREL), PYTEC
Technologies (http://www.pytecsite.de/pytec_eng/index.htm), etc.
3.2 Fuel Utilization
With the energy content of half that of diesel fuel oil one would think that by now
combustion of pyrolysis oil in boilers, kilns, and stationary engines would have been an
established art with ready markets while research to upgrade it to hydrocarbon fuels take shape.
However, combustion of the liquid as is or as fuel oil substitute has met with challenges due to
the stability problems listed earlier among them, their acidity, high water content, high oxygen
content, wide volatility distribution and presence of char all of which cause atomization
problems (i.e., problems associated with the process of breaking down the liquid into small
droplets for spray combustion), ignition delay, propensity to coking, and particulate emissions
when burned as is. Combustion research carried out at Sandia National Laboratories under the
DOE Biomass Power Program (Shaddix, C.R., and Hardesty, D.R., 1999) and at the
Massachusetts Institute of Technology (MIT) (Shihadeh, and Hochgreb, 2000, 2002) among
others in the late nineties showed that droplet combustion rates of pyrolysis oils are about 2 or 3
factors lower than that of light diesel fuel. Although this results in high mass density and latent
heat of vaporization, the wide range of volatility of the numerous pyrolysis oil components
including those mentioned under instability results in droplet fragmentation and hence
microexplosion of these droplets. This phenomenon plays an important role in reducing its
burning rate. Estimated droplet evaporation and burning rates of some pyrolysis oils and their
admixtures are shown in Table 3 (from Shaddix and Hardesty, 1999). The reported low
combustion rate values typically characterize flames that are long and lazy, low intensity with
more soot formation than diesel fuel fired at similar conditions. Fig. 3 shows a pyrolysis oil
flame generated at Mississippi State Universitys pyrolysis research laboratory. Regardless of
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these shortcomings use of biomass-derived pyrolysis oil for commercial power generation has
not been without effort. Czernik and Bridgwater (2004) and Chiaramonti et al. (2007) among
others, have reviewed such body of work reporting on some field trials involving engine
manufacturers, stationary gas turbine operators and boiler operators interested in co-firing
pyrolysis oils with coal and/or natural gas. Leading on the promise of pyrolysis oil as diesel fuel
substitute, Wartsila, a large engine manufacturer ( http://www.wartsila.com/ ), carried out
extensive testing of pyrolysis oil as fuel substitutes in their VASA series of stationary engines.
However, a business proposition to package an energy production supply chain comprising a
wood-waste -> pyrolysis plant -> stationary diesel power was aborted due to insurmountable
problems associated with acid attack on storage tanks, gaskets and seals in pumps, including
preheating problems (oligomerization) lacquering at pistons and nozzles, and many more.
Similar tests at MIT, CANMET, PYTEC, etc using various internal combustion (IC) engine
types have all yielded similar unfavorable results. To successfully operate IC engines solely on
pyrolysis oils or admixtures thereof, a standard engine will have to be substantially modified
including changing the materials of construction; something engine manufactures find as an
uneconomic venture. Gas turbines and boiler co-firing have not performed better either due, in
part, to the same issues of materials of construction (Lopez and Salva Monfort, 2000;
Chiaramonti, et al., 2007). Nonetheless, some successes have been achieved in firing pyrolysis
oil in some industrial furnaces such as kilns and boilers (Li et al., 2004) and for this an American
Standard Test Method (ASTM) specification (D7544-09) has recently been released for guiding
the design and operation of industrial burners equipped to handle it. As expected, this
specification is not intended at the moment for use in residential heaters, small commercial
boilers, engines or marine applications. For detailed studies of specific engine combustion tests,
the reader is referred to Chiaramonti et al. (2007).

4.0 Where we are - Current research Outlook
Given the high yield and high concentration of oxygenated hydrocarbons including
aromatic compounds, pyrolysis oil shows promise of producing large amounts of fungible
biomass-based hydrocarbon fuels such as gasoline and diesel by employing conventional
petroleum refining techniques such as hydrotreating and hydrocracking. However for this
technology to be commercially viable there is the need to address the long term storage stability
problem that has plagued as-produced pyrolysis oil. There are two conceptual approaches to
addressing the stability problem. One approach is by influencing the chemistry of the molecular
fragments de-polymerizing from the biomass substrate during the initial pyrolysis step i.e., in-
situ upgrading and this can be done catalytically or non-catalytically. The other approach is to
manipulate the chemistry of the pyrolysis oil post pyrolysis ex-situ upgrading or refining. Both
approaches involve removal of oxygen, however, the former approach produces a stable
intermediate that can be shipped, stored and address the specific issues related to pyrolysis oil
viscosity increase over time during storage. It also could potentially make the final upgrading step
(the latter approach) more commercially viable; not to mention the importance of a stable
intermediate product in resolving some of the combustion problems stated earlier. Stabilization
and upgrading of pyrolysis oils offer the gateway to utilizing the vast lignocellulosic fedstocks to
producing advanced biofuels via pyrolysis as intended by the RFS2 rule. Therefore this has been
the driving force behind current pyrolysis research and development in the United States. Recent
7

support by DOE include a $7M award for pyrolysis oil stabilization (2008), a $3M grant awarded
in 2009 to Research Triangle International (RTI) with Archer Daniel Midland company (ADM)
for catalytic pyrolysis by ARPA-E (Advanced Research Projects Agency-Energy), a new United
States government agency set up to promote and fund research and development of advanced
energy technologies. Some catalytic pyrolysis activities are also part of the new DOEs $35M
($50M with cost share) award in 2010 to the National Advanced Biofuels Consortium (NABC)
led by NREL and PNNL for the development of infrastructure compatible, fungible biomass-
based hydrocarbon fuel intermediates, the so-called drop-in fuels. Additionally, a $12M grant
was awarded by the DOE under the Biomass Research & Development Innitiative (BRDi) to
W.R. Grace and Company of Maryland, PNNL-UOP, The Gas technology Institute (GTI) of
Illinois and Battelle Memorial Institute (Ohio) for pyrolysis oil upgrading in 2010 with another
$12M follow-up funding opportunity announcement (FOA) issued in 2011. Other grant
opportunities large and small have been made over the last five years by the Defense Advanced
Research Projects Agency (DARPA), USDAs Cooperative State Research, Education, and
Extension Service (CSREES) now National Institute of Food and Agriculture (NIFA), SunGrant,
etc to institutions of higher learning and small businesses for research and demonstration projects
in advanced biofuels via pyrolysis. In Europe, EU efforts have included the Biocoup project
designed to develop a chain of process steps, which would effectively allow biomass feedstock
to be co-fed to conventional oil refinery with energy and oxygenated chemicals as co-products.
Biocoup is funded by the European Commission at 7.6M Euros from 2006 through 2011
(http://www.biocoup.com/ ). International collaborations between North America and Europe on
pyrolysis oils development are through the efforts of the International Energy Agency (IEA)
Bioenergy Task 34 - Pyrolysis (http://www.ieabioenergy.com/).
4.1 Pyrolysis Oil Stabilization and Upgrading
The term upgrading is used to describe any of the technologies used to conditioning the
pyrolysis oil to some stable intermediate product or completely converting it to hydrocarbon
fuels. DOE defines stabilization as reduction of the viscosity increases associated with aging of
pyrolysis oil. The most effective method for achieving this is to reduce the oxygen content
within the various organic compounds collectively comprising pyrolysis oil, with a preference
toward rejecting the oxygen as an economically optimum balance between carbon oxides and
water. Removing the oxygen present as carboxylic acid groups will reduce acidity of the bio-oil
and increase stability by reducing the occurrence of acid catalyzed aging reactions. Other
stabilization techniques involve preventing or removing suspended char particles in the pyrolysis
oil since the presence of alkali metals, sequestered in char particles, catalyze the reaction
between various organic compounds present in pyrolysis oil, and lead to higher viscosities.
Oxygen and particle reduction are subjects of most recent R&D efforts cited earlier.
As mentioned earlier, upgrading can be (i) in-situ i.e., stabilization by influencing
pathways to removing oxygen during the initial pyrolysis or (ii) ex-situ post-pyrolysis treatment.
In-situ upgrading can be carried out by using either non-catalytic or catalytic approaches. Non-
catalytic approaches include modifications to process conditions such as residence times, heating
and quenching rates and also collection methodologies including char removal, condensation,
etc. All these can affect bio-oil composition and could theoretically shift the pathways to a more
stable product cost-effectively without added catalysts or done in combination with catalysts
(Oasmaa et al., 2005). Research is required to determine the best methodologies for condensing
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pyrolysis vapors such that the most reactive components would be eliminated or separated from
the product to increase stability. While cyclones are the most utilized option for particulates
separation, they are not 100% efficient so alternative particulate separation approaches such as
hot gas filtration may offer better technologies for completely removing trace elements that
catalyze ageing reactions in pyrolysis oil and such approaches have been the subject of research
in recent years (Fahmi et al., 2007). It must be noted that while these are all possibilities there are
associated penalties including low yields that might impact the economics and process life cycle.
Catalytic upgrading encompasses a variety of pathways and several methods have been
proposed and explored for converting pyrolysis oil into fungible (transportable) fuels (Huber et
al., 2006). Several thermochemical pathways were identified for upgrading at the 2007 NSF
(National Science Foundation) workshop, Breaking the Chemical and Engineering Barriers to
Lignocellulosic Biofuels in Washington DC (NSF, 2008), one of many forums that set the stage
for current US research and action plans for developing the so-called 2
nd
generation or advanced
biofuels. Representing pyrolysis oil with a compositional formula e.g.,
67 . 0 33 . 1
O CH (based on its
elemental composition) catalytic upgrading can involve any of the following reactions:
Catalytic Cracking:
2 2 . 1 4 8 6
4 . 1 6 . 4 CO CH O H C + ! (1)
Hydrogenation: O H CH H O H C
2 2 . 1 2 4 8 6
4 6 + ! + (2)
Aqueous Reforming:
2 2 2 4 8 6
6 12 8 CO H O H O H C + ! + (3)
Equation 1 involves cracking where heterogeneous acid catalysts have been used to change the
decomposition pathways to partially or fully deoxygenate the product. Catalytic cracking uses
heterogeneous catalysts such as zeolites that can be mixed directly with the biomass or held in
the reactor bed. This process does not require external hydrogen and operates at atmospheric
pressure but it has the disadvantage of high cokeformation i.e., unwanted carbon deposits formed
during the said reactions. However, experience in handling catalyst regeneration exists in
petroleum refineries with the advent of the fluid catalytic cracking (FCC) technologies. Catalytic
pyrolysis has been recently studied as a viable method to produce partially deoxygenated bio-oils
(Williams and Nugranad, 2000, Adam et al., 2005, Jackson et al., 2009, Zhang et al., 2009).
Partial deoxygenation should make pyrolysis oils more stable by reducing the concentration of
reactive oxygen containing functional groups and make downstream hydroprocessing more
facile, by improving catalyst life and reducing coke formation. Several catalysts have been
studied for the cracking reaction pathway including ZnO, phosphoric acid, and other salts, but
more often zeolites and porous silicates, with zeolites such as HZSM-5 receiving the most
attention. Huber used HZSM-5 to demonstrate evidence of producing gasoline range aromatic
hydrocarbons directly from biomass derived sugars on a small scale (Carlson et al., 2008).
Others have also obtained partially deoxygenated bio-oils from biomass. Several methods of
introducing heterogeneous catalysts into the pyrolysis reactor are possible. Mixing it with dry-
ground biomass or by mixing the catalysts and biomass suspended in water and then drying it
again before pyrolysis have been shown to provide intimate contact and reduce mass transfer
limitations. However, the cost of doing so may be very high as the catalyst will end up mixed
with the char, making it difficult and expensive to recover. Alternatively, catalysts can be
immobilized in a vessel on a support (The KIOR process), within the pyrolysis unit or made into
pellets and substituted for the sand as the heat transfer medium in fluidized or entrained bed
9

reactors. Additionally, a second stage process where pre-condensed pyrolysis vapors are
catalytically treated is also possible. In the latter cases, any necessary reactivation can be
achieved by intermittent combustion. Catalyst development is also an integral part of recent
R&D efforts in pyrolysis upgrading. US investigators working on catalytic pyrolysis include
RTI, UMASS (University of Massachusetts), ARS (U.S. Department of Agriculture, Agriculture
Research Service), NREL, Iowa State University and Conoco Phillips, PNNL, University of
Oklahoma, University of Colorado, Mississippi State University, to mention but a few.
Hydroprocessing (Eq. 2) is best for upgrading already produced pyrolysis liquids
although in-situ hydrogenation has been suggested and tested by others (GTI). With this
approach bio-oil is catalytically converted to hydrocarbons using hydrodeoxygenation processes
similar to that practiced in petroleum refineries (McCall, 2008). Historical developments in
pyrolysis oil hydrogenation have been reviewed by Furimsky (2000) and recently by Elliott
(2007). In this process, catalysts similar to petroleum hydrodesulfurization (HDS) catalysts such
as cobalt-molybdenum (CoMo) and nickel-molybdenum (NiMo) sulfides have been successfully
applied. The setback to hydroprocessing includes the need for high pressure systems which can
be an economic drawback. Also, high levels of coke formation cause catalyst deactivation and
reduce yield. Additionally, there can be over-consumption of expensive hydrogen due to
unnecessary hydrogenation of aromatic rings. Nonetheless, these hurdles are surmountable with
new catalysts development (including nano-catalysts) and by applying the experiences gained in
the petroleum refining industry e.g., FCC.
Aqueous reforming (Eq. 3) reforms bio-oil and char over nickel and related catalysts into
syngas which can be used in Fisher-Tropsch synthesis to produce hydrocarbon or alcoholic fuels
(Wang et al., 2007). Interest in this route has grown in Europe and commercial interests are
currently underway to build the first plant in Germany i.e., the Lurgi-Karlsruhe bioliq process
(Henrich et al., 2007).
Recent economic models at PNNL and NREL (Jones, 2009) developed for production of
gasoline and diesel from biomass, via hydrotreating and hydrocracking of fast pyrolysis oil have
predicted that several design cases will be economical. Minimum selling prices under $2 per
gallon have been predicted for a plant processing 2000 dry metric tons per day of wood chips (at
feedstock cost of $50.7/bone dry metric ton, delivered) and producing 76 million gallons per year
of gasoline and diesel. However, the production cost has been shown to be sensitive to stability,
scale, hydrogen use, and whether the hydrotreating step is integrated or co-located with an
existing refinery infrastructure. As a result, the goal of improving the stability and refinability of
the pyrolysis oil on-site, for possible use as blendstock in an existing oil refinery process off-site
(drop-in), is paramount and this is being addressed by most U.S. researchers.
As previously mentioned, use of bio-oil in internal combustion engines has not been very
successful. However, stabilized bio-oil may be able to address most of the challenges
encountered in using pyrolysis oil as diesel fuel blends in combustion systems such as IC
engines, gas turbines and as boiler and kiln fuels in the power and materials processing industries
replacing large amounts of coal. These initial applications can provide needed revenues and the
impetus for researching technologies for the eventual development of transportation fuels from
fast pyrolysis of biomass.
5.0 Chemical co-product (non-fuel uses)
10

For fractionation purposes, the chemical components in pyrolysis oil are often classified
as water-soluble components (WS, sometimes called, Py-C, because it consists mainly of the
products of degradation of carbohydrates) and water insoluble components (WIS, sometimes
called pyrolytic lignin, Py-L) (Dobele et al., 2009). Either fraction can be further fractionated by
various methods. One method involves separating the WIS fraction based on solubility in
dichloromethane (DCM). The DCM-soluble fraction consists of low-molecular mass lignin
material (generally less than 400 MW), while the DCM-insoluble fraction is referred to as high
molecular mass lignin (Oasmaa and Kuoppola, 2008).
Although the major thrust of pyrolysis oil development is to provide advanced biofuel
some research efforts are devoted to identifying pyrolysis oil components that may have unique
applications with a much higher value than fuel. These potential chemical co-products could
provide additional revenues to the pyrolysis operation and increase overall profitability. For
example, one of the co-product applications of pyrolytic lignin (unfractionated) is its use as an
adhesive (Chan et al., 2002). Other high-value components that have previously been identified
in bio-oils include food flavoring products sometimes called liquid smoke, (Simon et al., 2005)
antioxidants (Dobele et al., 2009), steroids (Pakdel and Roy, 1996) and lignans (Simonelt et al.,
1993). Pyrolysis oil is also known to contain a significant amount of monolignols (including p-
coumaryl alcohol, coniferyl alcohol, and sinapyl alcohols) which are breakdown products of
lignin (Garcia-Perez et al., 2007). Monolignols have value because they can be used as
precursors to industrial products such as coumarin, and the latter can be used to synthesize
pharmaceuticals such as warfarin (Holbrook et al., 2005). Research is needed to provide useful
information about the economic feasibility of pyrolysis of agricultural materials, including the
possible economic benefits of various non-fuel chemical coproducts.
6.0 Concluding Remarks
U.S. research in pyrolysis oil production and development into fungible, advanced
biofuel is underway and nearing maturity. While the use of pyrolysis oil as fuel substitutes have
met some road bumps due to stability issues it is still conceivable that pyrolysis oil can be
stabilized enough to overcome storage and aging problems and that internal and external
combustion fuel specifications can be achieved within a couple of years. Upgrading of pyrolysis
liquids into fungible transportation fuels including jet fuels have been successfully demonstrated.
A hydroplane test run was carried out in 2009 by UOP and Boeing using 100% renewable jet
fuel comprising 98% Bio-SPK (synthetic paraffinic kerosene from natural oils and fats) and 2%
renewable aromatics from upgraded woody pyrolysis oil. It is believed that it will take about 3
years to complete R&D and within 5 years pyrolysis oil fuel substitutes could be certified for use
as jet and other transportation fuels. The logistics for production and delivery of pyrolysis liquids
are favorable economically following the distributed approach allowing for the potential to set up
regional conversion systems. The similarities between pyrolysis oil upgrading and fossil fuel
refining allow for the use of existing refinery infrastructure to accept stabilized pyrolysis oil as a
blend stock or drop-in biocrude. All these make pyrolysis oil a nearer-term promise and the
potential exists for it to replace a large portion of fossil fuels with advanced biofuels of the kind.
Acknowledgement
11

Some sections of this article may contain excerpts from the Authors project plan outline ARS
Project 1935-41000-082-00D. Contributors included Charles Mullen, Robert Moreau, Leland
Dickey and Kevin Hicks.

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13


Figure 1. Pyrolysis product distribution courtesy of ARS Biochar Initiative.
16















Figure 2. Concept of Integrated Distributed Pyrolysis System (adopted from Wright et al., 2008)





Figure 3. Pyrolysis oil flame created in the laboratory, Mississippi State University.



Transport
Centralized refining
Distributed processing
(pyrolysis/liquefaction)
Distributed processing
(oil extraction)
17

Table 1. Dry Basis Elemental Analysis and High Heating Value of Bio-oils (ARS)
Oak Switchgrass alfalfa
stems
corn
stover
barley
straw
barley
hulls
chicken
litter
Total water
wt%
22.3 15.8 28.6 9.2 26.7 13.8 20.1
pH 2.6 3.1 - 2.9 2.4 2.5 6.9
Elemental Analysis (db)
C (wt%) 58.13 47.47 56.84 53.97 50.78 54.37 55.64
H (wt%) 6.07 6.96 7.86 6.92 3.20 5.32 7.19
N (wt%) 1.50 0.36 3.73 1.18 1.37 1.79 7.77
S (wt%) 0 -- 0.07 <0.05 0.00 0.09 0.70
O (wt%) 34.30 45.19 31.30 37.94 44.42 38.49 29.27
HHV
(MJ/kg)
18.1

18.4 20.6 24.3 17.7 20.8 23.3
HHV
(MJ/kg, db)
23.3 21.9 28.9 26.7 24.2 24.1 29.2
Source: Mullen, C.A., Strahan, G.D., and Boateng, A.A. Energy & Fuels 23:2707-2718. 2009.

18

1ab|e 2a. ercentage of nydrogen 8ased on
1
n NMk Ana|ys|s of 8|o-o|| from Iast yro|ys|s of
Var|ous Ieedstocks, grouped accord|ng to chem|ca| sh|ft range.
Chemlcal
ShlfLs
(ppm)

roLon
AsslgnmenL
swlLch-
grass
alfalfa
sLems
corn
sLover
guayule
-whole
guayule
bagasse
chlcken
llLLer
0.3-1.3
Alkanes
9.8 20.9 11.8 29.4 28.7 34.6
1.3-3.0

allphaLlcs o-Lo
heLeroaLom or
unsaLuraLlon
24.3 34.0 18.3 42.0 34.3 43.9
3.0-4.4

alcohols, methylene-
dibenzene
21.3 7.2 20.3 10.4 12.3 9.8
4.4-6.0

meLhoxy, carbohydraLes
23.7 2.3 30.3 6.8 9.7 1.8
6.0 - 8.3

(heLero-) aromaLlcs
17.3 13.1 13.1 11.2 13.6 7.9
9.3 - 10.1

aldehydes

1.3 - 1.7 0.2 0.3 -
19

Source: Mullen, C.A., Strahan, G.D., and Boateng, A.A. Energy & Fuels 23:2707-2718. 2009

1ab|e 2b. ercentage of Carbon 8ased on
13
C NMk Ana|ys|s of 8|o-o|| from Iast yro|ys|s of
Var|ous Ieedstocks, grouped accord|ng to chem|ca| sh|ft range.
*

Chemlcal
ShlfLs (ppm)
Carbon
asslgnmenLs
#

swlLch-
grass
alfalfa
sLems
corn
sLover
guayule -
whole
guayule
bagasse
chlcken
llLLer
0-28
shorL allphaLlcs
13.8 17.2 13.8 28.3 19.1 23.8
28-33

long and branched
allphaLlcs
7.3 12.2 10.3 24.4 29.0 21.8
0-33
1oLal
All of above 21.1 29.4 24.1 32.9 48.1 47.6
33-93

alcohols, eLhers,
phenollc-meLhoxys,
carbohydraLes sugars
24.7 16.1 30.8 6.7 7.7 13.6
93-163

aromaLlcs, oleflns
33.0 31.9 36.0 39.3 43.3 36.2
20

163-180

esLers, carboxyllc aclds
- 2.6 3.8 0.8 0.4 -
180-213

keLones, aldehydes
1.2 - 1.3 0.1 0.2 2.6

*) 1he sLrong aceLone solvenL resonances aL 30 ppm (CP
3
) and 207 ppm (C=C) were excluded from Lhls
analysls. Source: Mullen, C.A., Strahan, G.D., and Boateng, A.A. Energy & Fuels 23:2707-2718.
2009.

Table 3. Combustion characteristics of some pyrolysis oils and admixtures. From Shaddix,
C.R., and Hardesty, D.R., 1999. Need complete source at end of table
Liquid Fuel Density
(g/ml)
Heat of
Vap.,
qv (J/g)
Evap. Rate,
Kv (mm
2
/s)
A/F mass
ratio

Spec.
comb.
Enthalpy,
qc (J/g)
Burning
Rate
Kc,
(mm
2
/s)

diesel No. 2 0.86 267 0.56 12.6 41 0.99
water 1.0 2257 0.10 N/A* N/A N/A
NREL 154 (Oak) 1.2 613 0.25 5.6 17.6 0.52
NREL 175 (poplar) 1.2 711 0.23 6.3 16 0.45
NREL 157 (switchgrass) 1.2 887 0.19 8.2 19.3 0.4
NREL 175+ water* 1.18 842 0.20 5.7 14.6 0.42
NREL 175+ methanol* 1.16 738 0.23 6.3 16.3 0.45
NREL 175+ ethanol* 1.16 720 0.23 6.4 16.8 0.46


* assumes 10% addition (volume basis)
Source: Shaddix, C.R., and Hardesty, D.R. Final project report. Sandia National Laboratories,
Albuguerque, New Mexico, 1999