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Review
a r t i c l e
i n f o
Article history:
Received 11 July 2006
Received in revised form 18 May 2008
Accepted 20 May 2008
Available online 2 July 2008
Keywords:
Pretreatment
Lignocellulose
Digestibility
Fermentation
Bioenergy
a b s t r a c t
Lignocellulosic biomass represents a rather unused source for biogas and ethanol production. Many factors, like lignin content, crystallinity of cellulose, and particle size, limit the digestibility of the hemicellulose and cellulose present in the lignocellulosic biomass. Pretreatments have as a goal to improve the
digestibility of the lignocellulosic biomass. Each pretreatment has its own effect(s) on the cellulose, hemicellulose and lignin; the three main components of lignocellulosic biomass. This paper reviews the different effect(s) of several pretreatments on the three main parts of the lignocellulosic biomass to improve its
digestibility. Steam pretreatment, lime pretreatment, liquid hot water pretreatments and ammonia based
pretreatments are concluded to be pretreatments with high potentials. The main effects are dissolving
hemicellulose and alteration of lignin structure, providing an improved accessibility of the cellulose for
hydrolytic enzymes.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
2.1. Cellulose
For a long time research is being done to enhance the digestibility of lignocellulosic biomass for mainly the efcient conversion of
(hemi-) cellulose to ethanol, methane and, in the last years, also to
hydrogen. It is however not clear which characteristics of the lignocellulosic biomass are important, to determine a successful pretreatment. Further more additional problems, like production of
recalcitrant or inhibitory products, are to be solved.
A lot of literature is written about different pretreatment methods
to enhance the digestibility of lignocellulosic material. The objective
of this review is to nd out which characteristics of lignocellulosic
biomass determine which pretreatment method will be successful
and attractive to apply. This will be done by explaining the composition of lignocellulosic material, giving an overview of the methane
and ethanol production process, summarizing the effects of different
pretreatment methods on lignocellulosic biomass and the consequences of these effects on ethanol and methane production. Moreover, additional problems will be analyzed, and nally, conclusions
with respect to promising pretreatment techniques and needed future research are made. Hydrogen production is left out in this paper,
because it is still in the R&D phase (Reith et al., 2003).
2.2. Hemicellulose
Hemicellulose is a complex carbohydrate structure that consists
of different polymers like pentoses (like xylose and arabinose),
hexoses (like mannose, glucose and galactose), and sugar acids.
The dominant component of hemicellulose from hardwood and
agricultural plants, like grasses and straw, is xylan, while this is
glucomannan for softwood (Fengel and Wegener, 1984; Saha,
2003).
Hemicellulose has a lower molecular weight than cellulose, and
branches with short lateral chains that consist of different sugars,
which are easy hydrolyzable polymers (Fengel and Wegener,
1984). Hemicellulose serves as a connection between the lignin
and the cellulose bers and gives the whole cellulosehemicelluloselignin network more rigidity (Laureano-Perez et al., 2005).
The solubility of the different hemicellulose compounds is in
descending order: mannose, xylose, glucose, arabinose, and galactose. The solubilitys increase with increasing temperature. The solubilitys of higher molecular polymers could not be predicted,
because of unknown melting points (Gray et al., 2003). The solubilization of hemicellulose compounds into the water starts around
180 C under neutral conditions according to Bobleter (1994). Garrote et al. (1999) however mention that already from 150 C parts
of the hemicellulose solubalize. The solubilization of lignocellulose
components not only depends on temperature, but also on other
aspects like moisture content and pH (Fengel and Wegener, 1984).
The xylan of hemicellulose can be extracted quite well in an
acid or alkaline environment, while glucomannan can hardly be
extracted in an acid environment and needs a stronger alkaline
environment than xylan to be extracted (Balaban and Ucar, 1999;
Fengel and Wegener, 1984; Lawther et al., 1996b). Xylan appears
to be the part that can be extracted the most easily.
Of cellulose, hemicellulose and lignin the hemicelluloses are the
most thermal-chemically sensitive (Levan et al., 1990; Winandy,
1995). During thermalchemical pretreatment rstly the side
groups of hemicellulose react, followed by the hemicellulose backbone (Sweet and Winandy, 1999).
11
the hydrolysis step. The conversion of (hemi) cellulose to monomeric sugars can be done chemically by acids or enzymatically
by addition of cellulases (enzymes responsible for the hydrolysis
of cellulose). The produced monomeric hexoses (six carbon sugars)
can be fermented to ethanol quite easily, while the fermentation of
pentoses (ve carbon sugars) is only done by a few strains. Volatile
products are also not easily fermented to ethanol. A problem
occurring during the fermentation is that the formed product ethanol is an inhibitor for the yeasts/bacteria that perform the fermentation. This puts a limit to the concentration of fermentable
sugars. Latter is not the case for methane production as methane
escapes from the water phase. After the fermentation the ethanol
has to be recovered from the fermentation broth by distillation
(Mosier et al., 2005b).
Furfural and other inhibitors like (probably) soluble lignin compounds also form a problem for the fermentation step, because
such compounds can inhibit, or even stop the fermentation (Laser,
2001; Laser et al., 2002).
2.3. Lignin
Lignin is, after cellulose and hemicellulose, one of the most
abundant polymers in nature and is present in the cellular wall.
It is an amorphous heteropolymer consisting of three different
phenylpropane units (p-coumaryl, coniferyl and sinapyl alcohol)
that are held together by different kind of linkages. The main purpose of lignin is to give the plant structural support, impermeability, and resistance against microbial attack and oxidative stress.
The amorphous heteropolymer is also non-water soluble and
optically inactive; all this makes the degradation of lignin very
tough (Fengel and Wegener, 1984).
Lignin, just like hemicellulose, normally starts to dissolve into
water around 180 C under neutral conditions (Bobleter, 1994).
The solubility of the lignin in acid, neutral or alkaline environments depends however on the precursor (p-coumaryl, coniferyl,
sinapyl alcohol or combinations of them) of the lignin (Grabber,
2005).
3. Methane production by anaerobic digestion
The production of methane from lignocellulosic material can
consist of three phases, namely pretreatment, anaerobic hydrolysis
and methane production, and post-treatment of the liquid fraction.
A product separation step is not needed during the methane production step, because methane is, under normal conditions, a gas
and will separate itself from the liquid fraction.
Pretreatment can be done to improve the hydrolysis yield and
total methane yield. The hydrolysis of the lignocellulose and
conversion to methane is in general done in one reactor by a consortium of micro-organisms. Often only the second phase, hydrolysis and methane production is executed, for energy production and
recovery.
The advantage of using a mixture of micro-organisms is that almost all products, like pentoses, hexoses, volatile products and
even sometimes inhibiting compounds like furfural and soluble lignin compounds (in not too high concentrations) can be converted
to methane after a period of adaptation (Benjamin et al., 1984;
Fox et al., 2003; Noike and Niigata Eng., 2001).
4. Ethanol production by fermentation
The production of ethanol from lignocellulosic material consists
of mainly ve different steps, namely pretreatment, (enzymatic)
hydrolysis, fermentation, product separation, and post-treatment
of the liquid fraction. The pretreatment is necessary to improve
the rate of production and the total yield of monomeric sugars in
12
the lignocellulose in most cases by 525% (depends on kind of biomass, kind of milling, and duration of the milling), but also reduces
the technical digestion time by 2359% (thus an increase in hydrolysis rate) (Delgens et al., 2002; Hartmann et al., 1999). A particle
size reduction below 40 mesh however has little effect on the
hydrolysis yield as well as hydrolysis rate of the biomass (Chang
and Holtzapple, 2000).
6.2. Consequences for ethanol and methane production
Milling causes both an increased methane (525%; Delgens et
al., 2002) and ethanol yield and also increases the hydrolysis rate.
As no production of inhibitors (like furfural and HMF (hydroxymethylfurfural)) are produced, milling is suited for both methane
and ethanol production. It has however a high energy requirement
(Cowling and Kirk, 1976; Ramos, 2003) and was found therefore
not economically feasible as pretreatment in 1987 (Fan et al.,
1987). Taking into account the high energy requirements of milling
and the continuous rise of the energy prices, it is likely that milling
is still not economically feasible.
7. Thermal pretreatment
7.1. General thermal processes in lignocellulose
During this pretreatment the lignocellulosic biomass is heated.
If the temperature increases above 150180 C, parts of the lignocellulosic biomass, rstly the hemicelluloses and shortly after that
lignin, will start to solubalize (Bobleter, 1994; Garrote et al., 1999).
The composition of the hemicellulose backbone and the branching
groups determine the thermal, acid and alkali stability of the hemicellulose (see Section 2.2). From the two dominant components of
hemicelluloses (xylan and glucomannan), the xylans are thermally
the least stable, but the difference with the glucomannans is only
small. Above 180 C an exothermal reaction (probably solibilization) of the hemicellulose starts (Beall and Eickner, 1970; Domansky and Rendos, 1962). This temperature of 180 C is probably just
an indication of the temperature at which an exothermal reaction
of the hemicellulose starts, because the thermal reactivity of lignocellulosic biomass depends largely on its composition (Fengel and
Wegener, 1984; Hon and Shiraishi, 1991).
During thermal processes a part of the hemicellulose is hydrolyzed and forms acids. These acids are assumed to catalyze the further hydrolysis of the hemicellulose (Gregg and Saddler, 1996). Liu
and Wyman (2003) and Zhu et al. (2004, 2005) conclude that other,
so far unknown, factors than the catalyzing effect of in situ formed
acids play a role in the solubilization of hemicellulose.
Thermal pretreatment with temperatures of 160 C and higher,
causes, besides the solubilization of hemicellulose, also the solubilization of lignin. The produced compounds are almost always phenolic compounds and have in many cases an inhibitory or toxic
effect on bacteria, yeast and methanogens/archae (Gossett et al.,
1982). These soluble lignin compounds are very reactive and will,
if not removed quickly, recondensate en precipitate on the biomass
(Liu and Wyman, 2003). Especially too severe pretreatment conditions promote the condensation and precipitation of soluble lignin
compounds, sometimes even with soluble hemicellulosic compounds like furfural and HMF (Bobleter and Concin, 1979; Lora
and Wayman, 1978; Negro et al., 2003).
Heat pretreatment in which soluble (hemi) cellulose and lignin compounds are formed, has a risk of formation of phenolic
and heterocyclic compounds, like vanillin, vanillin alcohol, furfural and HMF, especially in acidic environments (Ramos, 2003).
These formed compounds can be inhibitory. When the solid concentration was 3% or higher and the temperature exceeded
13
8. Acid pretreatment
8.1. Process description and mode of action
Pretreatment of lignocellulose with acids at ambient temperature are done to enhance the anaerobic digestibility. The objective
is to solubilize the hemicellulose, and by this, making the cellulose
better accessible.
The pretreatment can be done with dilute or strong acids. The
main reaction that occurs during acid pretreatment is the hydrolysis of hemicellulose, especially xylan as glucomannan is relatively
acid stable. Solubilized hemicelluloses (oligomers) can be subjected to hydrolytic reactions producing monomers, furfural,
HMF and other (volatile) products in acidic environments (Fengel
and Wegener, 1984; Ramos, 2003). During acid pretreatment solubilized lignin will quickly condensate and precipitate in acidic
environments (Liu and Wyman, 2003; Shevchenko et al., 1999).
The solubilization of hemicellulose and precipitation of solubilized
lignin are more pronounced during strong acid pretreatment compared to dilute acid pretreatment.
Xiao and Clarkson (1997) showed that the addition of nitric acid
during acid pretreatment has a tremendous effect on the solubilization of lignin of newspaper.
8.2. Consequences for ethanol and methane production
The advantage of acid pretreatment is the solubilization of
hemicellulose and by this, making the cellulose more easily accessible for the enzymes. There is however a risk on the formation of
volatile degradation products and this carbon is in many cases lost
for the conversion to ethanol. Volatile products however can be
converted to methane. The condensation and precipitation of solubilized lignin components is an unwanted reaction, as it decreases
digestibility.
Strong acid pretreatment is for the ethanol production not
attractive, because there is a risk on the formation of inhibiting
compounds. Dilute acid pretreatment however is considered as
one of the promising pretreatment methods, because secondary
reactions during the pretreatment can be prohibited in dilute acid
pretreatment.
For methane production acid pretreatment is more attractive
than for ethanol production, because methanogens can handle
compounds like furfural and HMF to a certain concentration and
with an acclimatization period. For both the ethanol as well as
the methane production the chance on soluble lignin components
is a risk, because soluble lignin compounds are often inhibiting for
both processes. Methanogens are however capable of adapting to
such inhibiting compounds (Benjamin et al., 1984; Xiao and Clarkson, 1997).
When sulfuric or nitric acids are used in the acidic pretreatment, the methane production during anaerobic treatment will
14
9. Alkaline pretreatment
9.1. Process description and mode of action
During alkaline pretreatment the rst reactions taking place are
solvation and saphonication. This causes a swollen state of the biomass and makes it more accessible for enzymes and bacteria. At
strong alkali concentrations dissolution, peeling of end-groups,
alkaline hydrolysis and degradation and decomposition of dissolved polysaccharides can take place. Loss of polysaccharides is
mainly caused by peeling and hydrolytic reactions (Fengel and
Wegener, 1984). This peeling is an advantage for later conversion,
but, because lower molecular compounds are formed as a result,
the risk on degradation and loss of carbon, in the form of carbon
dioxide, also increases.
Xylan can be selectively removed with aqueous potassium
hydroxide. The temperature is kept low during extraction (room
temperature or lower) to prevent peeling (Hon and Shiraishi,
2001). Glucomannans and xylans can both be subject of the peeling
reaction. This itself is not a problem, but the higher the monomeric
hemicellulose fraction, the lower the total recovery of the hemicellulose (Laser et al., 2002). The monomeric forms of hemicellulose
are probably easily degradable to other (volatile) compounds and
for example furfural, which leads to losses of digestible substrate
for the ethanol process (Bobleter, 1994).
An important aspect of alkali pretreatment is that the biomass
on itself consumes some of the alkali. The residual alkali concentration after the alkali consumption by the biomass is the alkali
concentration left over for the reaction (Gossett et al., 1982). Pavlostathis and Gossett (1985) for example found during their experiments an alkali consumption of approximately 3 g NaOH/100 g TS.
Lime works remarkably better than sodium hydroxide (Gossett et
al., 1982).
Alkali extraction can also cause solubilization, redistribution
and condensation of lignin and modications in the crystalline
state of the cellulose. These effects can lower or counteract the positive effects of lignin removal and cellulose swelling (Gregg and
Saddler, 1996).
Another important aspect of alkaline pretreatment is the
change of the cellulose structure to a form that is denser and thermodynamically more stable than the native cellulose (Pettersen,
1984).
An oxidative pretreatment consists of the addition of an oxidizing compound, like hydrogen peroxide or peracetic acid, to the biomass, which is suspended in water. The objective is to remove the
hemicellulose and lignin to increase the accessibility of the cellulose. During oxidative pretreatment several reactions can take
place, like electrophilic substitution, displacement of side chains,
cleavage of alkyl aryl ether linkages or the oxidative cleavage of
aromatic nuclei (Hon and Shiraishi, 2001).
In many cases the used oxidant is not selective and therefore
losses of hemicellulose and cellulose can occur. A high risk on
the formation of inhibitors exists, as lignin is oxidized and soluble
aromatic compounds are formed.
Teixeira et al. (1999) have investigated the use of peracetic acid
at ambient temperatures as a pretreatment method for hybrid poplar and sugar cane bagasse. Peracetic acid is very lignin selective
and no signicant carbohydrate losses occurred. The enzymatic
hydrolysis of the cellulose increased from 6.8% (untreated) to a
maximum of about 98% (pretreated) at a 21% peracetic acid pretreatment. Teixeira et al. (1999) showed similar results for digestibility at using a mixture of NaOH and peracetic acid. The yields
during experiments carried out at ambient temperature were higher as compared to higher temperatures.
Gould (1984) demonstrated the use of H2O2 for delignication
with a maximum at pH 11.5. No substantial delignication occurred below a pH of 10.0. Hydrogen peroxide had no real effect
on the enzymatic digestibility at a pH 12.5 or higher. According
to Gould (1984) the hydrogen peroxide concentration should be
at least 1% and the weight ratio between H2O2 and biomass should
be 0.25 for a good delignication. The delignication is probably
caused by the hydroxyl ion (HO), which is a degradation product
of hydrogen peroxide with a maximum at pH 11.511.6. About half
of the lignin was solubilized in this way (temperature around 25 C
and a duration of 1824 h) (Gould, 1984).
A way to improve the effect of thermal steam or LHW pretreatment is to add an external acid. This addition of an external acid
catalyzes the solubilization of the hemicellulose, lowers the optimal pretreatment temperature and gives a better enzymatic
hydrolysable substrate (Brownell et al., 1986; Gregg and Saddler,
1996). The lignocellulose is often impregnated (soaked) with SO2
or H2SO4. During steam pretreatment the SO2 is converted to
H2SO4 in the rst 20 seconds of the process; after that, the catalytic hydrolysation of the hemicellulose starts. Another important
point is that gradual removal of hemicellulose and lignin can trigger reorientation of cellulose to a more crystalline form (Gregg
and Saddler, 1996). Latter is true for every pretreatment that
gradually removes hemicellulose and lignin. The effect of the
added acid is however still not clear. Tengborg et al. (1998)
showed a severe inhibition in the ethanol production step at a
15
16
Table 1
Effects of the different pretreatments on the physical/chemical composition or structure of lignocellulose (adapted from Mosier et al. (2005b))
Mechanical
ST/SE
LHW (batch)
LHW (ow through)
Acid
Alkaline
Oxidative
Thermal + acid
Thermal + alkaline (lime)
Thermal + oxidative
Thermal + alkaline + oxidative
Ammonia (AFEX)
CO2 explosion
Increase accessible
surface area
Decrystallization
cellulose
+
+
+
+
+
+
+
+
+
+
+
+
+
+
ND
ND
ND
ND
ND
ND
ND
+
Solubilization
hemicellulose
+
+
+
+
Solubilization
lignin
Formation furfural/
HMF
Alteration lignin
structure
+
+
+
+
+
+
+
+
+/
+/
+/
+/
+/
+/
+/
+
+ = major effect.
= minor effect.
ND = not determined.
hydrolysis, while such optimal enzyme mixture is difcult to produce articially (Schwarz, 2001). The production of the enzymes
by the thermophilic bacteria does not consume a lot of extra energy (Ng et al., 1977), the enzyme hydrolyses rate can be comparable with that of the enzymes of Trichoderma reesei (Lynd et al.,
1989). These bacteria can be adapted to higher ethanol concentrations (Baskaran et al., 1995; Bender et al., 1985; Herrero and
Gomez, 1980; Klapatch et al., 1994; Larsen et al., 1997; Rani et
al., 1996; Tailliez et al., 1989a, 1989b), and are maybe even capable of handling compounds like furfural and HMF or adapt to
them. Thermophilic conditions decrease the risk on infection
(Payton, 1984; Wiegel, 1980), and could create the possibility
of continuous distillation (Payton, 1984; Zeikus, 1980; Wiegel,
1980).
Acknowledgements
The authors would like to thank T. Fernandes, C. Pabon, K.
Grolle, V. de Wilde, and B. Willemsen for their experimental discussion and assistance throughout the investigation.
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