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Biochimie 91 (2009) 659–664

Contents lists available at ScienceDirect

Biochimie
journal homepage: www.elsevier.com/locate/biochi

Mini-review

Biorefinery: Toward an industrial metabolism


Stéphane Octave b, *,1, Daniel Thomas a
a
Service de la Recherche, Université de Technologie de Compiègne, Compiègne, France
b
UMR CNRS 6022 Génie Enzymatique et Cellulaire, Université de Technologie de Compiègne, Compiègne, Centre de Recherche de Royallieu, BP 20529, 60205 Compiegne Cedex, France

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

Article history: Fossil fuel reserves are running out, global warming is becoming a reality, waste recycling is becoming
Received 15 December 2008 ever more costly and problematic, and unrelenting population growth will require more and more
Accepted 20 March 2009 energy and consumer products. There is now an alternative to the 100% oil economy; it is a renewable
Available online 28 March 2009
resource based on agroresources by using the whole plant. Production and development of these new
products are based on biorefinery concept. Each constituent of the plant can be extracted and func-
Keywords:
tionalized in order to produce non-food and food fractions, intermediate agro-industrial products and
Plant biorefinery
synthons. Three major industrial domains can be concerned: molecules, materials and energy. Molecules
Industry
Lipids can be used as solvent surfactants or chemical intermediates in substitution of petrol derivatives. Fibers
Biotechnology can be valorized in materials like composites. Sugars and oils are currently used to produce biofuels like
Sustainable development bioethanol or biodiesel, but second-generation biofuels will use lignocellulosic biomass as raw material.
Lipids can be used to produce a large diversity of products like solvent, lubricants, pastes or surfactants.
Industrial biorefinery will be linked to the creation of new processes based on the twelve principles of
green chemistry (clean processes, atom economy, renewable feedstocks.). Biotechnology, especially
white biotechnology, will take a major part into these new processes with biotransformations (enzy-
mology, micro-organisms.) and fermentation. The substitution of oil products by biobased products will
develop a new bioeconomy and new industrial processes respecting the sustainable development
concept. Industrial biorefinery can be developed on the principle that any residues of one can then be
exploited as raw material by others in an industrial metabolism.
Ó 2009 Elsevier Masson SAS. All rights reserved.

1. Introduction substitution of fossil molecules requires the transformation of the


whole plant, especially parts not used as foodstuffs. This strategy
Fossil fuel reserves are running out, global warming is becoming leads to reduce as many as possible waste and by-products. The
a reality, waste recycling is becoming ever more costly and prob- whole plant valorization will induce the development of new
lematic, and unrelenting population growth will require more and industrial processes and a new chemistry based on plant deriva-
more energy and consumer products. There is now an alternative to tives molecules. The objective is to create a sustainable economic
the oil economy, it is a renewable resource based on plant biomass growth including new markets based on renewable products,
by using the whole plant. In this global context of fossil energy environmentally friendly. The use of agricultural produce for
dependence linked to oil and gas prices, it is essential to promote industrial ends is not new. As far back as two centuries ago, beet
and increase the part of biobased products. Production and provided 3000 tonnes of sugar in 1824 and 1.2 million tonnes in
development of these new products are based on the biorefinery 1840 [2]. The available biomass could contribute to the global
concept. energy needs only if major innovations occur [3]. Biorefineries
The biorefinery concept is based on the use of carbon molecules would provide energy (biofuel, heat.), molecules (fine chemistry,
extracted from plant in order to substitute carbons from oil and gas cosmetics, para-medicinal.), materials (plastics, composites.)
[1]. Considering the carbon cycle, a global use of biomass could and also food ingredients.
limit the impact of carbon dioxide on global warming. The Like crude oil, plants are composed of a huge number of
different molecules. Each constituent of the plant can be extracted
and functionalized in order to produce non-food and food fractions,
* Corresponding author. Tel.: þ33 3 44 23 44 09; fax: þ33 3 44 23 39 10.
E-mail address: daniel.thomas@utc.fr (S. Octave).
agro-industrial intermediate products and synthons, whose value
1
President of the French worldwide competitiveness cluster «Industries et is generally inversely proportional to their volume. Carbohydrates,
Agroressources» (www.iar-pole.com). lignin, proteins and fats represent 95% of plants. Five other percents

0300-9084/$ – see front matter Ó 2009 Elsevier Masson SAS. All rights reserved.
doi:10.1016/j.biochi.2009.03.015
660 S. Octave, D. Thomas / Biochimie 91 (2009) 659–664

are constituted by vitamins, dyes, flavors or other small molecules that can be used as bulk in biosynthesis pathway and substitute
that are also considered in biorefinery because of their high value. molecule derivates from fossil resources. The objective is to get
On the basis of these various plant components, different specific the same molecule when it is possible or develop different mole-
biorefineries can be outlined based on sugars (starch and sucrose), cules with the same chemical properties (functions, reactivity.).
lignocellulose and lipids as main sources of carbon molecules. Compounds with a high added-value are also included in this
The global scheme of each type of biorefinery consists in several category. Plant fibers and polymers are the elementary elements for
steps as described in Fig. 1. Biomass needs a first transformation a large family of biobased materials. Fibers may be incorporated in
with a huge separation or extraction of plant components by composites to substitute glass and carbon fibers. Biopolymers can
grinding followed by a fractionation or cracking by biological or also be used as matrix in composites. The final objective is to realize
physicochemical technologies. The aim of this step is to release composites with plant fiber and plant matrix with mechanical
molecules to make a second treatment that consists in a function- properties and characteristics as close as possible of usual
alization of biomass extracts. This leads to agro-industrial products composites. The last category concerns food industries that are fully
considered as intermediates in many industrial sectors. These involved in biorefinery by valorization of components or fabrica-
works on native biomass represents an industrial sector called first tion auxiliary.
transformation. The formulation of this intermediates leads to the
development of a large number of biobased products that can be 2. ‘‘Sugars biorefinery’’
separated in 4 categories. The most important in volume is Energy
with first generation biofuel like ethanol or biodiesel. Molecule Sugars represent the most important component of plant. By
derivates from biomass represent one of the most important considering their physiological rule, two classes can be defined. The
potential to produce chemical intermediates named bulk or syn- first one includes all sugars considered as reserve metabolites like
thons that could be the base of a new chemistry. The main objective starch and sucrose for example. These sugars are easily accessible
of plant chemistry is to obtain from biomass, chemical synthons by plant and are massively processed in food industries. The second

Fig. 1. Scheme of biorefinery including first transformation industries producing agro-industrial products used as feedstock by second transformation industries with applications
in numerous economic sectors. (Adapted from the Industries and Agroresources competitiveness cluster website www.iar-pole.com).
S. Octave, D. Thomas / Biochimie 91 (2009) 659–664 661

one is constituted of structural parts of the plant, especially ligno- the lignin and the cellulose fibers and gives more rigidity to the
cellulose containing more complex sugars harder to access. The cellulose – hemicelluloses – lignin network [17]. Lignocellulose has
first ‘‘generation’’ of biorefinery is focused on the first group of been selected during the evolution to be the key element of plant
sugars and based on the valorization of natural polymers like structure and consequently to be resistant to biotic and abiotic
starch, sucrose or simple sugars, like glucose. stresses. This characteristic involved some bottleneck in the
The first step consists in production of simple sugars by starch industrial processing of biomass.
depolymerization and polysaccharides fractionation. According Recalcitrance to saccharification is a major limitation for
to the white biotechnology definition, enzymes are the key tech- conversion of lignocellulosic biomass to ethanol [18]. The goal of
nology for this step. Digestion can be made by purified enzymes or pretreatment is to create an access to substrate for enzymes and
micro-organisms. Many works have been done to develop new micro-organisms and enhance its digestibility. Several methods
tools to increase yields during this step especially by metabolic have been developed like grinding to break structures [19] or
engineering of micro-organisms [4]. treatment with diluted acid. It consists in a 0.3–2% (w/w) acid
Glucose and hexoses are the basis of many applications like treatment at 150  C during 15–20 min followed by 1–5 min at
ethanol for biofuels. This first generation of biofuel is based on 240  C. This method leads to the dilution of hemicelluloses and
fermentation and new strains are developed to break the source a part of lignin. The result is that near of 90% of cellulose can be
specificity and obtain new tools able to use as many sugars as transformed by cellulase [20]. Other processes, like steam explo-
possible as carbon source [5]. Another application of glucose sion or liquid hot water can be used [21] but higher is the energy
transformation by micro-organisms is the production of lactic acid. involved, higher are the difficulties to realize following enzyme
This molecule is the basis of many synthesis ways in chemistry. actions.
Lactate esters are used as green solvents for coating and cleaning As mentioned above, lignocellulose has been selected during
industries. Lactic acid can be processed to make acrylic acid or 1,2 evolution to resist to external stress. The challenge for biotech-
propanediol used in polyester resins and polyurethane used as nology is to generate enzymes or microbial strains able to degrade
deicer or antifreeze [6]. Lactic acid can also be polymerized to make this polymer. The final objective is to develop clean processes in the
a biobased material usually call PLA. This polymer has many biological pathway.
industrial applications and an exponential economic development Cellulases, mainly endoglucanases and cellobiase can be
[7]. A very important derivative of glucose is succinic acid consid- produce by bacteria type Clostridiumn, Cellulomonas or Bacillus [22]
ered by chemical industries as a very important bulk and a very and by fungi [23]. Enzymatic degradation of hemicelluloses needs
reactive molecule able to substitute fossil molecules [8]. xylanase to break polymers and other enzymes able to act on side
Starch has many applications as a polymer especially in mate- groups like glucoronidases or esterases. The enzymatic digestion
rials. It can be used as filler in plastic to increase the part of leads to a mixture sugars like glucose, xylose, arabinose, galactose,
biodegradable component by incorporation of starch in low-density fucose.[24]. Simultaneous saccharification and fermentation
polyethylene [9]. Starch is a hydrophilic molecule and plastics are (SSF) has been developed to reduce costs in biofuel industries and
usually hydrophobic. Its chemical modification is essential to increases ethanol conversion. It consists in using for example
increase links between starch and plastic. Thermoplastics have been a cellulase extracted from Trichoderma reesei and in the same
developed and are constituted of starch and a plasticizer linked by batch Saccharomyces cerevisae for fermentation. Results indicate
a thermo-mechanical energy, liberate by extrusion or injection a conversion rate of 79.1% for poplar and 91.4% from switchgrass
molding. Hydrogen bonds are observed between starch and plas- [25]. An optimization of this process is the Direct Microbial
ticizer [10]. Plasticizer can also be biobased by using glycerol or Conversion or DMC. By metabolic engineering of yeast, a single
some polyols like sorbitol [11] or Xylitol [12]. It is not an exhaustive strain can make saccharification and fermentation [26].
list of agro-industrial application of sugars but they represent the S. cerevisae is unable to use five carbons sugars, affecting the
first major use of sugar in non-food industries. ethanol conversion rate. Fermentation of these sugars in ethanol
increases significantly the yield of bioethanol production.
3. ‘‘Ligno cellulosis biorefinery’’ Biotechnology has the challenge to find new enzymes to degrade
lignocellulose from unknown micro-organisms or by enzymes
Lignocellulose is the most abundant biomass representing near engineering (abzymes.). Another challenge is to develop a new
of 70% of the total plant biomass [13]. Classical uses of this raw DMC with strains able to make saccharification and fermentation of
material are for paper industries, building and textile that are using hexoses and pentoses.
only 2% of this type of biomass [14]. Important advantages of Increasing volume of ethanol will also increase the lignin volume
lignocellulose as feedstocks are its great abundance and the fact and it is necessary to develop its valorization. Lignin can be used as
that there is no concurrency with food industries. The second- fuel to produce heat but more complex applications can be done.
generation biofuel will be based on lignocellulose transformation Lignin can be incorporated in resins to substitute phenols [27] or
triggering the development of biorefineries based on by-products acting as a crosslinker in epoxy-resins [28]. New developments as
valorization [15]. Two different ways exist in lignocellulose adhesives are possible. Lignin incorporation in polyolefin increases
biorefinery. The first called thermo-chemical is based on a global resistance to UV without major modification in mechanical prop-
use of biomass without separation, by cracking and gasification to erties [29]. The utilization of lignin in chemical industries is also an
produce synthetic biofuel via the Fischer-Tropsch method [16]. The objective. Because of its structure with many phenol functions and
biological pathway is based on soft methods using enzymes and substitutions, lignin is a good candidate to get new synthons for
fermentation to transform biomass. The main difference with sugar chemistry.
biorefinery is the first step of pretreatment that consists in a first
separation between lignin and cellulose. This step is critical because 4. ‘‘Lipid biorefinery’’
of its direct impact on final yield in lignocelluloses biorefinery.
Lignocellulose contains microfibrils of cellulose, hemicelluloses, Oilseeds are commonly used to produce fatty acids and protein-
lignin and to a minor extent structural proteins, lipids and ash. rich cakes used to feed animals. Oilseeds provide a unique oppor-
Cellulose fibrils are mostly independent and weakly bound through tunity for the production of biofuel and high-value fatty acids
hydrogen bonding. Hemicellulose serves as a connection between that can replace petrol sources of specialty chemicals and other
662 S. Octave, D. Thomas / Biochimie 91 (2009) 659–664

applications like lubricants, or detergents. Plant oils contain various Modified oil esters can be used as a base stock for preparation of
triacylglycerol based on fatty acids with chains of 8–24 carbon environmentally friendly, rapidly biodegradable lubricants. Chem-
length. The most represented have chain of 16 and 18 carbon istry on the carbon chains is an opportunity to develop new
molecules. lubricants with specific characteristics as a function of the final use
Similarly to sugars and lignocelluloses, the first non-food [34]. Surfactants are able to reduce the surface tension of a liquid in
industrial use of oils is the production of biodiesel. Its production which they are dissolved. They are composed of a water-soluble
consists in an esterification by a primary alcohol (mainly methanol) group and a hydrocarbon chain. By these characteristics, fatty
to get fatty acid methyl ester used as biofuel. Sunflower, rape, acids are excellent candidates for the development of biobased
soybean or palm are the mostly used to make biodiesel. The impact surfactants.
on greenhouse gas is a reduction of 40% comparing to diesel from Food industries have also a great interest in plant lipids, espe-
fossil reserves [30]. Production of biodiesel generates glycerol as cially in non-usual lipids like poly-unsaturated fatty acids (PUFA).
a byproduct in a proportion of 1:9 (w/w). Some plant species are able to produce PUFA. Works on plant fatty
Therefore, development of new products based on glycerol acid biosynthesis (metabolism, enzymes.) will give new tools to
could give new opportunities to biodiesel producers. Oleochemis- manage lipid production in plant in order to facilitate their
try is an emulating sector that allows the development of various utilization by industries. PUFA, especially omega-3, could also be
products. Glycerol oxidation produces synthons for chemistry, produced by microalgae by using glycerol as a carbon source [35].
polyglycerols and esters can be used in coatings and adhesives. The use of plant reserves or plant structure as raw material
Glyceryl carbonate can also be valorized as plasticizers and glycerol determines a frontier between two kinds of biorefinery (Fig. 2). This
hydrogenolysis can produce propanediol and ethylene glycol useful separation induces also new technological bottlenecks linked to the
in polymers and solvents [31]. Recent studies are using glycerol as complex structure of lignocellulose. To develop the new biobased
a carbon source for microorganism. Some bacteria like Klebsiella economy, industries need new developments in pretreatments
planticola and a mutant of Enterobacter aerogenes are able to use and treatments by biotechnology (biochemistry, enzymology,
glycerol to produce ethanol with very interesting economic microbiology.).
performances [32].
Plant oils have very interesting physico-chemical character- 5. ‘‘Industrial metabolism’’
istics (inert, high viscosity index, low volatility) to promote them
as lubricants. Hydraulic fluids, open gear oils are some of their Bioproduction needs to reduce the gap between biology and
industrial uses [33]. New European legislations about working process engineering. Process engineering, derivates from chemical
situations in nature stimulate new markets for biodegradable engineering, split between a global modelisation of reactors and
lubricants. the elementary reactional events occurring into. This strategy

Fig. 2. Whole plant valorization in biorefinery, based on the function of plant components used as raw material.
S. Octave, D. Thomas / Biochimie 91 (2009) 659–664 663

considers reactors as a ‘‘blackbox’’. This approach can be a limiting European Union a PCRD6 project called ‘‘Biorefinery Euroview’’
factor in bioproduction because of the imperative necessity to take managed by the competitiveness cluster ‘‘Industries and Agro-
in account biological material specificities with kinetic of molec- resources’’ is in charge of mapping emerging industrial biorefineries
ular, cellular and metabolic events. in Europe [40]. Eight partners from member states are involved in
In the same time, molecular biology needs to become more this first approach. A cross-fertilization, based on a benchmarking,
quantitative and leave a kind of reductionism especially in the is needed between the achievement in US–Canada, China, Japan,
technological activation of biological functions. The development of Brazil and European Union.
a ‘‘systems biology’’ approach [36] will permit a better integration
with process engineering. The systems biology concept can be
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