Energy Conversion and Management 51 (2010) 1412–1421

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Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

The biorefinery concept: Using biomass instead of oil for producing energy
and chemicals
Francesco Cherubini *
Department of Energy and Process Engineering, Norwegian University of Science and Technology (NTNU), NO-7491 Trondheim, Norway

a r t i c l e i n f o a b s t r a c t

Article history: A great fraction of worldwide energy carriers and material products come from fossil fuel refinery.
Received 22 June 2009 Because of the on-going price increase of fossil resources, their uncertain availability, and their environ-
Accepted 29 January 2010 mental concerns, the feasibility of oil exploitation is predicted to decrease in the near future. Therefore,
Available online 6 March 2010
alternative solutions able to mitigate climate change and reduce the consumption of fossil fuels should be
promoted. The replacement of oil with biomass as raw material for fuel and chemical production is an
Keywords: interesting option and is the driving force for the development of biorefinery complexes. In biorefinery,
Biorefinery
almost all the types of biomass feedstocks can be converted to different classes of biofuels and biochem-
Biomass
Biofuels
icals through jointly applied conversion technologies. This paper provides a description of the emerging
Biochemicals biorefinery concept, in comparison with the current oil refinery. The focus is on the state of the art in bio-
Green chemistry fuel and biochemical production, as well as discussion of the most important biomass feedstocks, conver-
sion technologies and final products. Through the integration of green chemistry into biorefineries, and
the use of low environmental impact technologies, future sustainable production chains of biofuels
and high value chemicals from biomass can be established. The aim of this bio-industry is to be compet-
itive in the market and lead to the progressive replacement of oil refinery products.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Background and introduction
Our strong dependence on fossil fuels comes from the intensive
use and consumption of petroleum derivatives which, combined
with diminishing petroleum resources, causes environmental and
political concerns. There is clear scientific evidence that emissions
of greenhouse gases (GHG), such as carbon dioxide (CO2), methane
(CH4) and nitrous oxide (N2O), arising from fossil fuel combustion
and land-use change as a result of human activities, are perturbing
the Earth’s climate [1]. The Intergovernmental Panel on Climate
Change (IPCC) Fourth Assessment Report highlighted that the
world’s growing population and per capita energy demand are
leading to the rapid increase in greenhouse gas (GHG) emissions.
In particular, over the past 10 years, transport has shown the high-
est rates of growth in GHG emissions in any sector [2].
The world’s primary source of energy for the transport sector
(and production of chemicals as well) is oil. World demand is
approximately 84 million barrels a day and is projected to increase
to about 116 million barrels a day by 2030, with transport account-
ing for some 60% of such a rising demand [3]. While the transport
sector continues to expand in the US and Europe, growth in the
emerging economies of India and China is predicted to be substan-
* Tel.: +4773598942; fax: +4773598943.
E-mail address: francesco.cherubini@ntnu.no.
tially greater, growing by at least 3% per year [4]. Concerning
chemicals, their dependence on fossil resources is even stronger.
The majority of chemical products are produced from oil refinery
and almost 4% of oil is worldwide used for chemical and plastic
production [5].
In order to simultaneously reduce the dependence on oil and
mitigate climate change in transport and chemical sectors, alterna-
tive production chains are necessary. It is increasingly recognized
that there is not a single solution to these problems and that com-
bined actions are needed, including changes in behavior, changes
in vehicle technologies, expansion of public transport and intro-
duction of innovative fuels and technologies [6].
Recently, society began to recognize the opportunities offered
by a future sustainable economy based on renewable sources and
has been starting to finance R&D activities for its implementation.
It is increasingly acknowledged globally that plant-based raw
materials (i.e. biomass) have the potential to replace a large frac-
tion of fossil resources as feedstocks for industrial productions,
addressing both the energy and non-energy (i.e. chemicals and
materials) sectors [7].
At national, regional and global levels there are three main driv-
ers for using biomass in biorefinery for production of bioenergy,
biofuels and biochemicals. These are climate change, energy secu-
rity and rural development. The political motivation to support
renewable sources of energy and chemicals arises from each

0196-8904/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2010.01.015
 F. Cherubini / Energy Conversion and Management 51 (2010) 1412–1421
individual driver or combinations. Policies designed to target one
driver can be detrimental to another. For example, policies aimed
at ensuring energy security may result in increased GHG emissions
where local coal reserves are preferentially exploited at the ex-
pense of imported oil or gas. In addition, electricity and heat can
be provided by a variety of renewable alternatives (wind, sun,
water, biomass and so on), while biomass is very likely to be the
only viable alternative to fossil resources for production of trans-
portation fuels and chemicals, since it is the only C-rich material
source available on the Earth, besides fossils. As a consequence,
the sustainable biomass production is a crucial issue, especially
concerning a possible fertile land competition with food and feed
industries.
This paper investigates the possibilities to use biomass feed-
stocks as raw materials in biorefinery. Firstly, an overview of the
current status in biofuel production is provided and then the
emerging biorefinery concept is described. The latter is done
through an overview of the most promising biomass feedstocks,
technological processes and final products. The current oil refinery
industry is taken as benchmark throughout the paper. Finally, after
reviewing the strategic role played by green chemistry in estab-
lishing sustainable conversion technologies, some guidelines for
future biorefinery complexes are proposed.
2. State of the art in biofuel production
Currently, transportation fuels based on biomass (i.e. biofuels)
are identified as 1st and 2nd generation biofuels. First generation
biofuels usually refer to biofuels produced from raw materials in
competition with food and feed industries. Because of this compe-
tition, these biofuels give rise to ethical, political and environmen-
tal concerns. In order to overcome these issues, production of
second generation biofuels (i.e. from raw materials based on waste,
residues or non-food crop biomass) gained an increasing world-
wide interest in the last few years as a possible ‘‘greener” alterna-
tive to fossil fuels and conventional biofuels. As a development of
2nd generation biofuel production, the use of biomass in biorefin-
ery complexes is expected to ensure additional environmental ben-
efits and implement national energy security, thanks to the
coproduction of both bioenergy and high value chemicals.
2.1. First generation biofuels
First generation biofuels are produced from sugar, starch, vege-
table oil or animal fats using conventional technologies. The basic
feedstocks are often seeds and grains such as wheat, corn and rape-
seed. The most common first generation biofuels are bioethanol,
biodiesel and starch-derived biogas, but also straight vegetable
oils, biomethanol and bioethers may be included in this category.
Bioethanol is recovered from biomass feedstocks such as sugar-
cane, sugar beet and starch crops (mainly corn and wheat). In 2006,
total world production reached 51.3 billion litres. USA is currently
the largest producer of bioethanol with a production of 19.8 billion
litres per year, with corn as primary feedstock. Sugarcane is used as
primary feedstock in Brazil, currently the world’s second largest
producer (17.8 billion litres per year). The European Union pro-
duces 3.44 billion litres of bioethanol, mainly from sugar beet
and starch crops [8].
Biodiesel is produced from oil based crops such as rapeseed,
sunflower, soybean but also from palm oil and waste edible oils.
World biodiesel production surpassed 6 billion litres in 2006. Ger-
many led biodiesel production in 2006, producing 2.5 billion litres
mainly from rapeseed and sunflower. The USA are the second larg-
est producer with 0.86 billion litres, but other countries (France,
Italy, Austria) are increasing their biodiesel production [8].
1413
Biogas is produced after anaerobic digestion of mixtures of corn
derived starch, manure, organic waste and grasses. However, when
biogas is mainly derived from waste and residues can be catego-
rized as 2nd generation biofuel, because its feedstock is not in com-
petition with the food and feed industry. The production of biogas
is common in most world countries, and in the last few years it has
been strong implemented in countries with economic subsides for
electricity generation from biogas (especially European countries).
In some countries (such as Germany and Sweden), biogas is also
used as transportation biofuel, after upgrading to biomethane.
For instance, Sweden leads the world in automotive biogas produc-
tion, with a total fleet of approximately 4500 vehicles with 45% of
its fuel supplied by biomethane [9].
The main advantages of first generation biofuels are due to the
high sugar or oil content of the raw materials and their easy con-
version into biofuel. Many biofuel production chains have been
analysed by means of Life Cycle Assessment (LCA) in order to point
out their environmental performances [10–12]. With the exception
of a few studies, most LCAs have found a net reduction in global
warming emissions and fossil energy consumption when the most
common transportation biofuels (bioethanol and biodiesel) are
used to replace conventional diesel and gasoline [13–15]. Several
LCA studies have also evaluated life cycle impacts under other
environmental aspects, including local air pollution, acidification,
eutrophication, ozone depletion, land use, etc. These environmen-
tal burdens are much more affected by site specific assumptions
than GHG and energy balances, showing that it is not that easy
to draw simplified conclusions. Studies that have examined these
other environmental issues have concluded that most, but not
all, biofuels substituting fossil fuels lead to increased negative im-
pacts [16,17].
In addition, 1st generation biofuels are in competition with food
and feed industries for the use of biomass and agricultural land,
giving rise to ethical implications: as prices for fossil fuels increase,
a larger proportion of cereals or agricultural land will be dedicated
to biofuel production instead of using it to produce food.
In conclusion, first generation biofuels currently produced from
sugars, starches and vegetable oils cause several concerns: these
productions compete with food for their feedstock and fertile land,
their potential availability is limited by soil fertility and per hectare
yields and the effective savings of CO2 emissions and fossil energy
consumption are limited by the high energy input required for crop
cultivation and conversion [18,19]. These limitations are expected
to be partially overcome by developing the so-called 2nd genera-
tion biofuels [20].
2.2. Second generation biofuels
Second generation biofuels are produced from a variety of non-
food crops. These include the utilization of lignocellulosic materi-
als, such as residues from agriculture, forestry and industry and
dedicated lignocellulosic crops. In the scientific literature, the term
2nd generation shows wide variation in usage and can variably re-
fer to feedstocks (e.g. lignocellulosic material), conversion routes
(e.g. thermochemical, flash pyrolysis, enzymatic, etc.) and end
products (e.g. gas or synthetic liquid biofuels).
Contrarily to first generation biofuels, where the utilized frac-
tion (grains and seeds), represents only a small portion of the
above-ground biomass, second generation biofuels can rely on
the whole plant for bioenergy production. In fact, rapeseed grain
yield is 3.4 t/ha but the oil content of the grain is only 40%, thus
the ‘effective’ yield is reduced to 1.35 t/ha [21].
Second generation biofuels (e.g. Fisher Tropsch (FT)-diesel from
biomass and bioethanol from lignocellulosic feedstock) promise
advantages over 1st generation biofuels in terms of land-use effi-
ciency and environmental performance, according to most of the
1414 F. Cherubini / Energy Conversion and Management 51 (2010) 1412–1421
LCA studies published in the literature [22,23]. Thanks to technol-
ogy development, environmental performances of 2nd generation
biofuels could benefit of the use of high quantities of lignocellu-
losic residues and waste which are already available: they can con-
stitute the main raw material sources, which can be also
supplemented with non-food crops such as perennial grasses,
and short-rotation forestry. Most processes and technologies for
2nd generation biofuels from biomass residues are still at a pre-
commercial stage, but could enter the market within 10–15 years
if corresponding investments (R&D, infrastructure) are achieved.
On the one side the raw material situation is optimum (wide-
spread, relatively cheap and easily available); on the other side,
their use could allow the coproduction of valuable biofuels, chem-
ical compounds as well as electricity and heat, leading to better en-
ergy, environmental and economic performances through the
development of biorefinery concepts [24].
3. The biorefinery concept
3.1. Definition and perspectives
Among the several definition of biorefinery, the most exhaus-
tive was recently performed by the IEA Bioenergy Task 42 ‘‘Biore-
fineries” [25]: ‘‘Biorefining is the sustainable processing of biomass
into a spectrum of marketable products and energy”.
The biorefinery concept embraces a wide range of technologies
able to separate biomass resources (wood, grasses, corn. . .) into
their building blocks (carbohydrates, proteins, triglycerides. . .)
which can be converted to value added products, biofuels and
chemicals. A biorefinery is a facility (or network of facilities) that
integrates biomass conversion processes and equipment to pro-
duce transportation biofuels, power, and chemicals from biomass.
This concept is analogous to today’s petroleum refinery, which pro-
duces multiple fuels and products from petroleum.
A forward looking approach is the stepwise conversion of large
parts of the global economy/industry into a sustainable biobased
society having bioenergy, biofuels and biobased products as main
pillars and biorefineries as the basis. Such a replacement of oil with
biomass will require some breakthrough changes in the today’s
production of goods and services: biological and chemical sciences
will play a leading role in the generation of future industries and
new synergies of biological, physical, chemical and technical sci-
ences must be developed [24].
The efficient production of transportation biofuels is seen as one
of the main promoting factors for the future development of bior-
efineries [26]. In fact, the transportation sector is growing steadily
and the demand for renewable (bio-)fuels, which can only be pro-
vided from biomass, grows accordingly. As a consequence, the
main challenge for biorefinery development seems to be the effi-
cient and cost effective production of transportation biofuels,
whereas from the coproduced biomaterials and biochemicals addi-
tional economic and environmental benefits can be gained.
The main biobased products are today obtained from conver-
sion of biomass to basic products like starch, oil, and cellulose. In
addition, chemicals like lactic acid and amino acids are produced
and used in the food industry. Other already commercially avail-
able biobased products include adhesives, cleaning compounds,
detergents, dielectric fluids, dyes, hydraulic fluids, inks, lubricants,
packaging materials, paints and coatings, paper and box board,
plastic fillers, polymers, solvents, and sorbents. Some examples
of biorefinery and non-conventional biomass industries which
are already competitive in the market are listed in Cherubini
et al. [27], along with some existing pilot and demo plant.
Most of the existing biofuels and biochemicals are currently
produced in single production chains and not within a biorefinery
concept, and usually require materials in competition with the
food and feed industry. Their exploitation is thereby limited. By
contrast, lignocellulosic crops reduce the competition for fertile
land, since they can be grown on land which is not suitable for
agricultural crops. Moreover, in comparison with conventional
crops that can contribute only with a small fraction of the above
standing biomass, biorefineries based on lignocellulosic feedstocks
can rely on larger biomass per hectare yields, since the whole crop
is available as feedstock [24,28].
Concerning the conversion plant, consumption of non-renew-
able energy resources during biorefinery processing should be
minimized, along with related environmental impacts, while the
complete and efficient biomass use should be maximized. This eco-
logical perspective requires:
 analyses of three important agricultural and forestry cycles,
namely carbon (respiration, photosynthesis, and organic matter
decomposition), water (precipitation, evaporation, infiltration,
and runoff) and nitrogen (N fixation, mineralization, denitrifica-
tion) and their interdependencies [29],
 system performance evaluations at plant scale [30],
 environmental impact evaluations carried out by means of Life
Cycle Assessment [31].
Biorefinery industries are expected to develop as dispersed
industrial complexes able to revitalize rural areas. Unlike oil refin-
ery, which almost invariably means very large plants, biorefineries
will most probably encompass a whole range of different-sized
installations. In this context, several bio-industries can combine
their material flows in order to reach a complete utilization of all
biomass components: the residue from one bio-industry (e.g. lig-
nin from a lignocellulosic ethanol production plant) becomes an in-
put for other industries, giving rise to integrated bio-industrial
systems. In addition, biomass resources are locally available in
many countries and their use, may contribute to reduce national
dependence on imported fossil fuels.
3.2. Feedstocks
The term ‘‘feedstock” refers to raw materials used in biorefin-
ery. The biomass is synthesized via the photosynthetic process that
converts atmospheric carbon dioxide and water into sugars. Plants
use the sugar to synthesize the complex materials that are gener-
ically named biomass. An important stage in biorefinery system is
the provision of a renewable, consistent and regular supply of feed-
stock. Initial processing may be required to increase its energy den-
sity to reduce transport, handling and storage costs.
Renewable carbon-based raw materials for biorefinery are pro-
vided from four different sectors:
1. agriculture (dedicated crops and residues),
2. forestry,
3. industries (process residues and leftovers) and households
(municipal solid waste and wastewaters),
4. aquaculture (algae and seaweeds).
A further distinction can be done between those feedstocks
which come from dedicated crops and residues from agricultural,
forestry and industrial activities, which can be available without
upstream concerns. The main biomass feedstocks can be grouped
in 3 wide categories: carbohydrates and lignin, triglycerides and
mixed organic residues.
3.2.1. Carbohydrates and lignin
Carbohydrates (from starch, cellulose and hemicellulose) are
molecules of carbon, hydrogen, and oxygen and are by far the most
 F. Cherubini / Energy Conversion and Management 51 (2010) 1412–1421
common biomass component found in plant feedstocks. Six-car-
bon, single-molecule ‘‘monosaccharide” sugars (C6H12O6) include
glucose, galactose and mannose, while the most common 5-carbon
sugars (C5H10O5) are xylose and arabinose. The two most impor-
tant sugar crops are sugar cane and sugar beet which, together
with corn (a starch crop), supply almost all the ethanol that is pro-
duced today [32].
Starch (C6H10O5)n is a very large polymer molecule composed of
many hundreds or thousands of glucose molecules (polysaccha-
rides), which must be broken down into one or two molecule
pieces prior to be fermented. The most widespread starch crops
are wheat and corn. Once sugars have been depolymerized (for
starch crops) or extracted (for sugar crops) they can be easily fer-
mented to ethanol or used as a substrate for chemical reactions
leading to a wide range of chemical products.
Lignocellulosic biomass has three major components: cellulose,
hemicellulose and lignin. Cellulose (C6H10O6)n has a strong molec-
ular structure made by long chains of glucose molecules (C6 sugar).
The distinction with starch is given by the configuration of the
bonds formed across the oxygen molecule that joins two hexose
units. Starch can be readily hydrolyzed by enzymes or acid attack
to the single sugar monomers, while cellulose (30–50% of total lig-
nocellulosic dry matter) is much more difficult to hydrolyze and
set free individual glucose monomers. Hemicellulose (C5H8O5)n is
a relatively amorphous component that is easier to break down
with chemicals and/or heat than cellulose; it contains a mix of
C6 and C5 sugars. It is the second main component of lignocellu-
losic biomass (20–40% of total feedstock dry matter). Lignin
(C9H10O2(OCH3)n), is essentially the glue that provides the overall
rigidity to the structure of plants and trees and is made of phenolic
polymers. While cellulose and hemicellulose are polysaccharides
that can be hydrolyzed to sugars and then fermented to ethanol,
lignin cannot be used in fermentation processes, but it may be use-
ful for other purposes (chemical extraction or energy generation).
Lignin (15–25% of total feedstock dry matter) is the largest non-
carbohydrate fraction of lignocellulose.
Lignocellulosic biomass can be provided either as a crop or as a
residue. Large amounts of cellulosic biomass can be produced via
dedicated crops like perennial herbaceous plant species, or short
rotation woody crops. Other sources of lignocellulosic biomass
are waste and residues, like straw from agriculture, wood waste
from the pulp and paper industry and forestry residues. The use
of waste biomass offers a way of creating value for society, displac-
ing fossil fuels with material that typically would decompose, with
no additional land use for its production [33].
3.2.2. Triglycerides
Oils and fats are triglycerides which typically consist of glycerin
and saturated and unsaturated fatty acids (their chain length
ranges between C8 and C20, but 16, 18 and 20 carbons are the most
common). The sources of oils and fats are a variety of vegetable and
animal raw materials. Soybean, palm, rapeseed and sunflower oil
are the most important in terms of worldwide production
[34,35]. Vegetable oils are nowadays used for production of biodie-
sel by reacting with an alcohol, usually methanol. However, they
can also be used as a substrate for chemical reactions thanks to
two chemically reactive sites: the double bond in the unsaturated
fatty acid chain and the acid group of the fatty acid chain [36]. Like
sugar and starch crops, oilseed crops are characterized by low yield
and high use of inputs. In the future, non-edible crops like Jatropha
curcas and Pongamia pinnata, which require lower inputs and are
suited to marginal lands, may become the most widespread oil
crops for biorefinery purposes, especially in dry and semiarid re-
gions [32,37]. Other sources of vegetable oil for biofuel conversion
can be found in waste streams of food industry, where waste edible
oil is mainly generated from commercial services and food process-
1415
ing plants such as restaurants, fast food chains and households
[38].
3.2.3. Mixed organic residues
Other types of biomass sources that do not fall within the pre-
vious categories are organic fraction of the Municipal Solid Waste
(MSW), manure, wild fruits and crops, proteins and residues from
fresh fruit and vegetable industries. The physical and chemical
characteristics of this wide spectrum of biomass resources vary lar-
gely. Certain streams such as sewage sludge, manure from dairy
and swine farms and residues from food processing are very wet,
with moisture contents over 70%. Therefore, these feedstocks are
more suited for an anaerobic digestion process to generate biogas,
rather than other fuels or chemicals. Other streams, such as organic
MSW, may be more or less contaminated with heavy metals or
other elements, but represents a high potential for energy recovery
[39]. Clearly, the different properties and characteristic of the bio-
mass waste require the application of different conversion
technologies.
3.3. Technological processes in biorefinery
The aim of technological process in biorefinery is depolymeriz-
ing and deoxygenating the biomass components. In order to con-
vert biomass feedstock into valuable products within a
biorefinery approach, several technological processes must be
jointly applied. They can be divided in four main groups: thermo-
chemical, biochemical, mechanical/physical and chemical
processes.
3.3.1. Thermochemical processes
There are two main thermochemical processes for converting
biomass into energy and chemical products. The first is gasifica-
tion, which consists in keeping biomass at high temperature
(>700 °C) with low oxygen levels to produce syngas, a mixture of
H2, CO, CO2 and CH4 [40,41]. Syngas can be used directly as a sta-
tionary biofuel or can be a chemical intermediate (platform) for the
production of fuels (FT-fuels, dimethyl ether, ethanol, isobutene. . .)
or chemicals (alcohols, organic acids, ammonia, methanol and so
on). The second thermochemical pathway for converting biomass
is pyrolysis, which uses intermediate temperatures (300–600 °C)
in the absence of oxygen to convert the feedstock into liquid pyro-
lytic oil (or bio-oil), solid charcoal and light gases similar to syngas
[42,43]. Their yields vary with process conditions and for biorefin-
ery purposes the treatment which maximizes the production of li-
quid bio-oil is the most desirable (flash pyrolysis). The application
of bio-oil as a transportation biofuel is nowadays problematic and
its use as a source of chemicals is still under development [44,45].
Together with charcoal, it is generally best suited as a fuel for sta-
tionary electric power or thermal energy plants. In addition to gas-
ification and pyrolysis, direct combustion is also included among
the thermochemical processes. This is the most common and old-
est form of biomass conversion that involves burning biomass in an
oxygen-rich environment mainly for the production of heat [46].
3.3.2. Biochemical processes
Unlike thermochemical processes, biochemical processes occur
at lower temperatures and have lower reaction rates. The most
common types of biochemical processes are fermentation and
anaerobic digestion. The fermentation uses microorganisms and/
or enzymes to convert a fermentable substrate into recoverable
products (usually alcohols or organic acids). Ethanol is currently
the most required fermentation product, but the production of
many other chemical compounds (e.g. hydrogen, methanol, succi-
nic acid, among others) is nowadays object of many research and
development activities. Hexoses, mainly glucose, are the most fre-
1416 F. Cherubini / Energy Conversion and Management 51 (2010) 1412–1421
quent fermentation substrates, while pentoses (sugars from hemi-
cellulose), glycerol and other hydrocarbons required the develop-
ment of customized fermentation organisms to enable their
conversion to ethanol [47]. Anaerobic digestion involves the bacte-
rial breakdown of biodegradable organic material in the absence of
oxygen over a temperature range from about 30 to 65 °C. The main
end product of these processes is biogas (a gas mixture made of
methane, CO2 and other impurities), which can be upgraded up
to >97% methane content and used as a surrogate of natural gas
[48].
3.3.3. Mechanical processes
Mechanical processes are processes which do not change the
state or the composition of biomass, but only perform a size reduc-
tion or a separation of feedstock components. In a biorefinery path-
way, they are usually applied first, because the following biomass
utilization requires reduction of the material size within specific
ranges, depending on feedstock specie, handling and further con-
version processes. Biomass size reduction is a mechanical treat-
ment that refers to either cutting or commuting processes that
significantly change the particles size, shape and bulk density of
biomass. Separation processes involve the separation of the sub-
strate into its components, while with extraction methods valuable
compounds are extracted and concentrated from a bulk and inho-
mogeneous substrate [49]. Lignocellulosic pre-treatment methods
(e.g. the split of lignocellulosic biomass into cellulose, hemicellu-
lose and lignin) fall within this category, even if some of hemicel-
lulose is also hydrolyzed to single sugars [50].
3.3.4. Chemical processes
Chemical processes are those processes which carry a change in
the chemical structure of the molecule by reacting with other sub-
stances. The most common chemical processes in biomass conver-
sion are hydrolysis and transesterification, but this group also
includes the wide class of chemical reactions where a change in
the molecular formula occurs. Hydrolysis uses acids, alkalis or en-
zymes to depolymerise polysaccharides and proteins into their
component sugars (e.g. glucose from cellulose) or derivate chemi-
cals (e.g. levulinic acid from glucose) [50]. Transesterification is the
most common method to produce biodiesel today and is a chemi-
cal process by which vegetable oils can be converted to methyl or
ethyl esters of fatty acids, also called biodiesel. This process in-
volves the coproduction of glycerine, a chemical compound with
diverse commercial uses [34]. Other important chemical reactions
in biorefining are Fisher–Tropsch synthesis, methanisation, steam
reforming, among others.
4. From oil refinery to biorfinery
4.1. Biomass vs. fossils as raw materials
The structure of biorefinery raw materials is totally different
from that on which the current oil refinery is based. In fact, the
crude oil is a mixture of many different organic hydrocarbon com-
pounds. The first step of oil refinery is to remove water and impu-
rities, then distil the crude oil into its various fractions as gasoline,
diesel fuel, kerosene, lubricating oils and asphalts. Then, these frac-
tions can be chemically changed further into various industrial
chemicals and final products.
Unlike petroleum, biomass composition is not homogeneous,
because the biomass feedstock might be made of grains, wood,
grass, biological waste and so on, and the elemental composition
is a mixture of C, H and O (plus other minor components such as
N, S and other mineral compounds). Chemical and elemental com-
position of some lignocellulosic biomass feedstocks is reported in
Table 1. If compared to petroleum, biomass generally has too little
hydrogen, too much oxygen, and a lower fraction of carbon.
The compositional variety in biomass feedstocks is both an
advantage and a disadvantage. An advantage is that biorefineries
can make more classes of products that can petroleum refineries
and can rely on a wider range of raw materials. A disadvantage is
that a relatively larger range of processing technologies is needed,
and most of these technologies are still at a pre-commercial stage
[51].
In order to be used for production of biofuels and chemicals,
biomass needs to be depolymerized and deoxygenated. Deoxygen-
ation is required because the presence of O in biofuels reduces the
heat content of molecules and usually gives them high polarity,
which hinders blending with existing fossil fuels [19]. Chemical
applications may require much less deoxygenation, since the pres-
ence of O often provides valuable physical and chemical properties
to the product.
Unlike petroleum, biomass experiences seasonal changes, since
harvesting is not possible throughout the entire year. A switch
from crude oil to biomass may require a change in the capacity
of chemical industries, with a requirement to generate the materi-
als and chemicals in a seasonal time-frame. Alternatively, biomass
may have to be stabilized prior to long-term storage in order to en-
sure continuous, year-round, operation of the biorefinery [52].
Biorefinery represents a change from the traditional oil refinery
based on large exploitation of natural resources and large waste
production towards integrated systems in which all resources are
used. An example of how the biorefinery of the future will evolve
can be found in the history of the existing corn wet-milling indus-
try [53]. Initially the corn wet-milling industry produced starch as
the major product. As technology developed and the need for high-
er value products drove the growth of the industry, the product
portfolio expanded from various starch derivatives such as glucose
and maltose syrups to high fructose corn syrup. Later on, fermen-
tation products derived from the starch and glucose such as citric
acid, gluconic acid, lactic acid, lysine, threonine and ethanol were
added. Many other by-products, such as corn gluten, corn oil, corn
fiber and animal feed are now being produced. The final picture is
that the development of the technical, commercial and political
infrastructure of a biomass refinery (biorefinery) makes it similar
to the current oil refinery concept.
4.2. Current chemical platforms in oil refinery
Today’s chemical industry processes crude oil into a limited
number of base fractions [54]. Using numerous cracking and refin-
ing catalysts and using distillation as the dominant separation pro-
cess, crude oil is refined into fractions such as naphtha, gasoline,
kerosene, gas oil and residues. The relative volumes of the fractions
formed depend on the processing conditions and the composition
of the crude oil. The naphtha fraction is subsequently used as a
feedstock for the production of just a few platform chemicals from
which all the major bulk chemicals are subsequently derived. An
important characteristic of the naphtha feedstock is that, unlike
biomass, it is very low in oxygen content. The majority of bulk
chemicals can be produced starting from these few platform chem-
icals (see Fig. 1):
 ethylene,
 propylene,
 C4-olefines,
 the aromatics benzene, toluene and xylene (often referred to as
BTX).
These hydrogen- and carbon-containing platform chemicals are
subsequently used, for instance as solvents (benzene, toluene),
 F. Cherubini / Energy Conversion and Management 51 (2010) 1412–1421 1417

Table 1
Difference in composition of some lignocellulosic feedstocks.

Parameter Unit (dry) Softwood Switchgrass Corn stover Wheat straw Petroleum
Water % 15 15 15 15
LHV MJ/kg 19.6 18.6 18.5 17.6
Cellulose % 44.5 35.4 38.1 32.6
Glucan (C6) % 44.5 35.4 38.1 32.6
Hemicellulose % 21.9 26.5 25.3 22.6
Xylan (C5) % 6.3 22.4 20.2 19.2
Arabinan (C5) % 1.6 2.73 2.03 2.35
Galactan (C6) % 2.56 0.96 0.74 0.75
Mannan (C6) % 11.4 0.39 0.41 0.31
Lignin % 27.7 18.2 20.2 16.8
Acids % 2.67 2.15 4.84 2.24
Extractives % 2.88 11.5 4.78 12.9
Ash % 0.32 4.28 8.59 10.2
C % 50.3 46.9 46.7 43.9 83–87
H % 5.98 5.54 5.49 5.26 10–14
O % 42.1 42 38.4 38.7 0.1–1.5
N % 0.03 0.62 0.67 0.63 0.1–2
S % 0.01 0.7 0.1 0.16 0.5–6

Sources: softwood [47]; switchgrass [62] (biomass sample type: switchgrass alamo whole plant #94); corn stover [62] (biomass sample type: corn stover zea mays stalks and
leaves w/o cobs #55); wheat straw [62] (biomass sample type: wheat straw (Triticum aestivum) thunderbird whole plant #154); petroleum [63].

Fig. 1. Platform chemicals in oil refinery and their main derivatives.

starting material for polymers (ethylene, propylene, butadiene) or
are further functionalized via the introduction of elements such as
oxygen, nitrogen or chlorine [55].
4.3. Expected chemical platforms in biorefinery
A biorefinery industry aiming at producing bulk chemicals from
biomass will be based on a different selection of simple platforms
than those currently used in the petrochemical industry. Given the
chemical complexity of biomass, there is some choice of which
platform chemicals to produce since, within limits, different pro-
cessing strategies of the same material can lead to different break-
down products.
Although, in principle, all oil refinery platform chemicals can be
also derived from biomass, but with lower yields and higher costs
(as depicted in [55]), the future biorefineries are expected to be
1418 F. Cherubini / Energy Conversion and Management 51 (2010) 1412–1421
based on a limited number of platforms, from which all the other
commodity and bulk chemicals can be derived. In particular, the
carbohydrate fraction of biomass feedstock (i.e. cellulose and
hemicellulose in lignocellulosic biomass) is expected to play the
biggest role as a renewable carbon source for biochemical prod-
ucts. In fact, biomass polysaccharides can be effectively hydrolyzed
to monosaccharides (e.g., glucose, fructose and xylose) which can
then be converted, via fermentations or chemical synthesis, to an
array of bio Platform Molecules (bPM – building block chemicals
with potential use in the production of numerous value-added
chemicals), analogous to the petro-platform molecules of the cur-
rent oil refinery.
In 2004, a list of the most promising bPMs was compiled by the
US Department of Energy, with the intention that research into the
area of bPM utilization would focus on those molecules highlighted
(Fig. 2) [56]. Some chemicals, such as lactic acid, citric acid and eth-
anol, were omitted from the list as research into their use was con-
sidered to be already extensive and at an advanced stage.
Several functional groups are available from this list, offering a
huge choice of potential reactions and products. When considering
the type of reactions to perform on bPM’s, the chemist should ide-
ally consider those that are greenest. Addition reactions are more
favourable than substitutions or eliminations as atom economy is
higher. Pericyclic reactions, such as Diels–Alder, are also inherently
green, typically with atom economies of 100%. Any reactions
involving extensive use of auxiliaries, such as solvents or stoichi-
ometric reagents, or hazardous species should be avoided. Cata-
lysts should be incorporated into every step, as long as they are
recoverable and reusable [57].
In comparison to oil-derived platform molecules (e.g., ethylene,
benzene, etc.), bPMs have much higher oxygen content. This will
result in an interesting shift in chemistries from the often harsh
and environmentally damaging oxidation procedures to largely
greener reduction chemistry; for example using hydrogen gas over
Fig. 2. Top 14 biomass platform molecules [56].
a heterogeneous catalyst. As opposed to adding functionality, as it
normally occurs in the petroleum-based chemical industry, there
will be a switch to where a large part of the desired functionality
or pre-functionality is already present in the substrate [57].
An example of the applications of one of these biobased plat-
form chemicals is the following. Levulinic acid (C5H8O3) is formed
by acid hydrolysis of C6 sugars and can be converted to a large
number of chemical derivatives thanks to its high reactivity: since
it has both a ketone carbonyl group and an acidic carboxyl group, it
can react as a ketone and as a fatty acid. Firstly, cellulose is hydro-
lyzed to C6 sugars and then levulinic acid is obtained through
hydroxymethylfuran (HMF) with an efficiency of 50% [58]. Then,
levulinic acid is converted to the desired products, either chemicals
or fuel additives. Among the possible alternatives, the main inter-
esting derivatives are [58,59]:
 methyltetrahydrofuran (MTHF, a biofuel which can be blended
with gasoline and is obtained by dehydratation and hydrogenta-
tion of levulinic acid),
 d-aminolevulinic acid (a herbicide which can be produced after a
chemical synthesis process),
 diphenolic acids (a polymer constituent produced by reaction of
levulinic acid with phenols),
 ethyl levulinate (a transportation biofuel, produced after reac-
tion with ethanol, which can be added to conventional diesel
without engine modifications).
5. Biorefinery products
The products of biorefinery systems can be grouped in two broad
categories: material products and energy products. Energy products
are those products which are used because of their energy content,
providing electricity, heat or transportation service. On the other
hand, material products are not used for an energy generation
 F. Cherubini / Energy Conversion and Management 51 (2010) 1412–1421
purpose but for their chemical or physical properties. In some cases,
a further distinction for the characterization of products is needed
because some products like biohydrogen or bioethanol might be
used either as fuels or as chemical compound in chemical synthesis.
In these cases, it is necessary to identify the addressed markets, for
instance the transportation sector for H2 and bioethanol.
The products of a biorefinery must be able to replace fossil fuel
based products coming from oil refinery, both chemicals and en-
ergy carriers. Concerning the chemicals, this objective can be met
by producing the same chemical species from biomass instead of
from fossils (e.g. phenols), or producing a molecule having a differ-
ent structure but an equivalent function. Concerning the fuels, a
biorefinery must replace conventional fossil fuels (mainly gasoline,
diesel, heavy oil, coal and natural gas) with biofuels coming from
biomass upgrading.
The most important energy products which can be produced in
biorefineries are:
 gaseous biofuels (biogas, syngas, hydrogen, biomethane),
 solid biofuels (pellets, lignin, charcoal),
 liquid biofuels for transportation (bioethanol, biodiesel, FT-fuels,
bio-oil).
The most important chemical and material products are the
following:
 chemicals (fine chemicals, building blocks, bulk chemicals),
 organic acids (succinic, lactic, itaconic and other sugar
derivatives),
 polymers and resins (starch-based plastics, phenol resins, furan
resins),
 biomaterials (wood panels, pulp, paper, cellulose),
 food and animal feed,
 fertilizers.
6. The role of green chemistry
In order to establish a sustainable future production of these bio-
fuels and biochemicals, the integration of green chemistry into bior-
efineries, along with the use of low environmental impact
technologies, is mandatory. Green chemistry can be considered as
a set of principles for the manufacture and application of products
that aim at eliminating the use, or generation, of environmentally
harmful and hazardous chemicals. It offers a tool kit of techniques
and underlying principles that any researcher could, and should, ap-
ply when developing the next generation of biorefineries. The overall
goal of green chemistry combined with a biorefinery is the produc-
tion of genuinely green and sustainable chemical products [52].
Green chemistry offers a protocol when developing biorefinery
processes and may play an important role in facilitating production
of commodity chemicals from biomass. During chemical product
manufacture, and indeed during the whole product life cycle, en-
ergy demands should be minimized, safer processes used, and haz-
ardous chemical use and production avoided. The final product
should be non-toxic, degradable into innocuous chemicals and
with minimum production of waste.
Green chemistry methodologies and techniques can be used to
reach these goals. For instance, supercritical carbon dioxide is rec-
ognized as a green solvent, since it is non-flammable, non-toxic,
available as byproduct of many conversion technologies (e.g. bio-
mass fermentation) and gives no solvent residues. Other technolo-
gies with great potential as energy efficient extraction methods are
microwaves and ultrasounds [60].
In addition, there are numerous natural polymers directly avail-
able from biomass with potential for physical and chemical modi-
fications. These include starches, cellulose, hemicellulose, lignin,
1419
proteins and lipids. Modification of natural polymers is of extreme
interest, since they can replace fossil derived polymers like plastics
and textiles. For instance, lignin is a highly complex matrix of aro-
matic units and can be a renewable source of aromatic compounds
so widely used in chemical industry. Breakdown of lignin to indi-
vidual aromatic units, such as vanillin, is object of research and
development activities, but current technology is low-yielding
even under extreme conditions [61].
The range of chemicals and materials that future biorefineries
could produce is extensive, and with further research the selection
will become larger. As argued by Clark et al., environmental impact
evaluation methodologies like LCA and metrics such as atom econ-
omy should become as important in measuring the sustainability
of a chemical process as yield and selectivity are today [52].
7. Guidelines for future biorefineries
With all this, some final guidelines for the development of
biorefinery complexes can be elaborated. A biorefinery, similarly
to what occurs in oil refinery, should be based on feedstock
upgrading processes, where raw materials are continuously up-
graded and refined. This means that a biorefinery should separate
all the biomass feedstock components, and leading, through a
chain of several processes, to a high concentration of pure chem-
ical species (e.g. ethanol) or a high concentration of molecules
having similar, well identified functions (e.g. the mixture of C al-
kanes in FT-fuels). As a consequence, a feedstock cannot be di-
rectly burnt without any previous treatment, since the aim of a
biorefinery is to increase the value of the different biomass com-
ponents as material and energy source: the most desirable option
is to send to combustion, for heat and electricity production, only
the residues and leftovers of previous technological treatments
and conversion processes. This concept leads to the following
remarks:
 a biorefinery should produce at least one high value chemical/
material product, besides low-grade and high-volume products
(like animal feed and fertilizers), according to the specifications
given above,
 a biorefinery should produce at least one energy product besides
heat and electricity; the production of at least one biofuel
(liquid, solid or gaseous) is then required.
A biorefinery plant should also aim at running in a sustainable
way: all the energy requirements of the several biomass conver-
sion processes should be internally supplied by the production of
heat and electricity from combustion of residues (within a properly
sized set of processes/technologies). For instance, in a lignocellu-
losic ethanol plant, lignin, after separation from cellulose and
hemicellulose, can be burnt to provide the heat and electricity re-
quired by the plant. Since lignin can also be used to produce chem-
icals and polymers, direct external fossil energy inputs are allowed
if they ensure overall economic benefits and do not unduly burden
the life-cycle environmental concerns.
Similarly, solid, liquid and gaseous waste should be minimized.
This target can be achieved in two ways: using all the different bio-
mass components for producing a wide spectrum of multiple prod-
ucts in one location, or setting up industrial ‘‘bio-clusters”, where
material flow exchanges among different plants are promoted in
order to transform a downstream residue of a plant into an up-
stream raw material for another plant.
8. Conclusions
The use of biomass as raw materials for bioenergy and biochem-
ical production is encouraged by a reduction of fossil CO2
1420 F. Cherubini / Energy Conversion and Management 51 (2010) 1412–1421
emissions, the need for a secure energy supply, and a revitalization
of rural areas. Biomass energy and material recovery is maximized
if a biorefinery approach is considered, where many technological
processes are jointly applied to different kinds of biomass feed-
stock for producing a wide range of bioproducts. A lot of biorefin-
ery pathways, from feedstock to products, can then be established,
according to the different types of feedstock, conversion technolo-
gies and products. Biorefinery concept is analogous to today’s
petroleum refinery, which produces multiple fuels and products
from petroleum.
A key driver for the development and implementation of biore-
fineries is the growth in demand for energy, fuels, and chemicals.
Accordingly, the aim of research is in developing new technologies
and creating novel processes, products, and capabilities to ensure
the growth is sustainable from economic, environmental and social
perspectives. Further research and technology adoption will indi-
cate which new products and processes contribute to more sus-
tainable performances compared to conventional fossil based
systems. The term itself of sustainability needs an agreement on
a common definition and criteria for its evaluation. This will be
necessary for communication with nongovernmental organiza-
tions (NGOs), the general public, regulators and policy makers
about, for example, CO2 reductions.
When developing chemistry for future biorefineries, it is impor-
tant that the methods and techniques used minimize impact to the
environment and the final products are truly green and sustain-
able. The use of sustainable feedstock is not enough to ensure a
prosperous future for later generation; protection of the environ-
ment using greener methodologies is also required.
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