Chapter 27 - Development of Thermochemical and Biochemical Technologies For Biorefineries

C H A P T E R
27
Development of Thermochemical and
Biochemical Technologies for Biorefineries
Michael P. Garver, Shijie Liu*
Department of Paper and Bioprocess Engineering, College of Environmental Science and Forestry,
State University of New York, Syracuse, NY, USA
*Corresponding author email: sliu@esf.edu
O U T L I N E
Introduction 457 Steam Explosion 470

Ammonia Fiber Explosion 473
Characteristics of Lignocellulosic Biomass 458
Supercritical Carbon Dioxide Explosion 473
An Overview on Biomass Conversion 461 Biological Pretreatment 474
Acid Hydrolysis 474
PretreatmentdBiomass Size Reduction by Physical
Alkaline Hydrolysis 475
or Mechanical Methods 462
Mechanical PretreatmentdChipping, Grinding, Hydrolysis 476
Milling, Refining 463
BioconversiondConverting Sugars to Products 477
Irradiation Pretreatment by Electron Beam, Gamma
Ray, or Microwave 465 Thermochemical Conversion 478
Ammonia Recycle Percolation Pretreatment 465 Combustion 478
Ozonolysis Pretreatment 465 Gasification 478
Organosolv Pretreatment 466 Pyrolysis 481
Oxidation Pretreatment 466 Direct Liquefaction 481
Ionic Liquid Pretreatment 467
Conclusion 482
Sulfite Pretreatment to Overcome Recalcitrance
of Lignocelluloses 468 References 482
Hot Water 469
INTRODUCTION lignocellulosic biomass (LB). LB may originate from for-

est, herbaceous plants or organic waste streams such as
A biorefinery is a complex industrial system to sewage, food processing waste, or animal manure.
convert raw biologically derived materials into usable LB is a source of energy that can reduce the consump-
and valuable products. The actual design of a bio- tion of fossil fuels. Energy independence is an important
refinery depends on the desired product, the raw mate- economic and political goal. Renewable sources of
rials available, and the method of conversion desired. energy are also critical for a balanced ecological policy.
For the purposes of this chapter, the raw material Biorefineries may be designed to output a specific set
considered is woody biomass or more generally, of products and by-products. These products include
Bioenergy Research: Advances and Applications 457

http://dx.doi.org/10.1016/B978-0-444-59561-4.00027-9 Copyright Ó 2014 Elsevier B.V. All rights reserved.
458 27. DEVELOPMENT OF THERMOCHEMICAL AND BIOCHEMICAL TECHNOLOGIES FOR BIOREFINERIES
biofuels, adhesives, surfactants, biochemicals, biopoly- example, we currently look to use LB to reduce depen-
mers, food and medicine. This chapter will focus on dence on fossil fuels.
some common products such as acetic acid, ethanol, There are three families of LBs: grassy plants, shrubs,
butanol, acetone, hydrogen, and polyhydroxyalka- and trees, each possess four primary components: cellu-
noates. These products stem from the fermentation of lose, hemicellulose, lignin and extractives. Each species
sugars derived from LB or they may be derived from possesses these components in different proportions.
thermochemical conversion processes. Hardwood trees (angiosperms), shrubs and grassy
The first objective in any conversion is to reduce the plants (graminoids) usually possess less lignin than soft-
size and increase the surface area of the raw material. wood trees (gymnosperms) (Liu, 2012).
This enables subsequent treatment methods to attack Figure 27.1 illustrates the variation in cellular struc-
and exploit specific properties of LB more effectively ture between hardwood and softwood. Notice that in
to obtain sugars for bioconversion or obtain products both images the structure is porous, where the pores
from thermochemical conversion. are empty spaces and run longitudinally. Figure 27.2 is
Secondary treatment or conversion methodologies a compilation of sketches of wood cells. The cellular
include some form of hydrolysis, fermentation or any structure of each plant species is of different sizes and
of a variety of thermochemical conversion treatments. shapes and varies in the size and number of pores.
The objective of these methods is to break lignin and From Figure 27.1, one can note that there is no space
complex carbohydrates into either simple sugars or between the cells. Regardless of size and shape, each cell
intermediate products or even down to CO and H2 (syn- is glued tightly to its neighbors. The intercellular spaces
gas) for further fermentation (bioconversion) or thermo- are called middle lamellae. The great majority of the
chemical conversion. Fermentation is usually followed middle lamellae, over 80%, contain lignin (Liu, 2012).
by separations or filtrations as final steps in the acquisi- Lignin is the glue that binds the cells together and pro-
tion of a desired product in a bioconversion. vides the rigid structure of wood. The remaining volume
of the middle lamellae consists of hemicellulose and
extractives. Conversely, the cell wall is mostly made of
CHARACTERISTICS OF cellulose and to a much lesser degree contains lignin and
LIGNOCELLULOSIC BIOMASS hemicellulose. The great majority of biomass dry weight
is derived from the cell wall. A much smaller portion of
Understanding the characteristics of LB is necessary the biomass dry weight comes from the middle lamellae.
for the effective application of a conversion technology Most of the total lignin content of LB comes from the cell
or a pretreatment method. LB is the most abundant wall. Despite the high concentration of lignin in the
organic and renewable resource on the planet (Klass, middle lamellae, over 60% of the lignin from LB comes
1998). Man has been producing chemicals, materials, from the cell wall portion of the material (Liu, 2012).
and energy from LB since his origin. These activities Table 27.1 shows that cellulose is the largest portion
continue to be the most promising activities to pursue of LB. Cellulose, which represents between 40% and
in order to address our contemporary challenges. For 50% of the dry weight of wood, is a homopolymer of
(a) (b)
Softwood Hardwood
FIGURE 27.1 Typical structures of wood (a) Softwood (b) Hardwood. Source: Liu, 2012.
CHARACTERISTICS OF LIGNOCELLULOSIC BIOMASS 459
Southern
yellow pine
Western
Ray tracheid
hemlock
Softwood
Redgum Parenchyma
Hardwood cells
Birch 200 µm Oak early wood

Redgum
Aspen Alder
Eucalyptus Gmelina
Birch
Tracheid
Fiber Aspen
Oak Oak
tracheid late wood
Softwood fibers Hardwood fibers Hardwood vessel elements

FIGURE 27.2 Diagrams of major cell types in softwood and hardwood. All the diagrams are shown at the same magnification to illustrate
the relative sizes of these elements. Source: Parham, 1983.
b-D-glucopyranose where dehydration of the b-D- the exposed surface area of LB increases the effective-
glucose units forms a linear chain with a degree of poly- ness of these solvents, reagents and enzymes.
merization (DP) between a few hundred and several Hemicelluloses compose another large portion of LB,
thousand b-D-glycosidic bonds. The dehydration occurs between 20% and 30% of the dry weight of wood, see
between the one and four carbons of b-D-glucopyranose Table 27.1. These are heteropolymers, or heterosacchar-
units and leaves an oxygen atom to join the two units, ides of five- and six-carbon sugars. They are found
which is written as, b-1-O-4 glycosidic bonds. The for- mostly in the cell walls of LB. Common hemicellulose
mula for cellulose is He(C6H10O5)neOH, where “n” rep- sugars are D-glucose, D-mannose, D-galactose, D-xylose,
resents the DP. This highly ordered, tightly bound L-arabinose, and to a lesser degree, L-rhamnose. Hemi-
pattern is made of bonds that are quite strong and are cellulose has a low DP, around 100e200, and thus is
difficult to break. more easily hydrolyzed into their monomeric sugar
Cellulose grows into microfibrils with crystalline and components (Glaudemans and Timell, 1958; Goring
amorphous regions. The crystalline portions of the and Timell, 1960; Koshijima et al., 1965; Timell, 1960).
molecule line up side by side. Hydrogen bonds, between The structure of a hemicellulose tends to possess a
the hydroxyl groups, provide strong, sturdy and stable primary backbone, off of which might hang a variety
links between and within these crystalline units. When of residual units. These residual units are nonpolymeric
these microfibrils form macrofibrils and interact with acids and sugars. The degree of branching or number of
noncellulosic material in the cell walls of plants, the residual units depends on the origin or species of the
result is strength and rigidity. biomass. For hardwood, the backbone is xylan, contain-
While the crystalline regions are stable and strong, ing b-linked bonds at carbons one and four, like cellu-
the amorphous regions provide an opportunity to break lose. Unlike cellulose, residual units can hang off
down the large structure into smaller saccharides. Sol- from the other carbon positions. These residues may
vents, reagents and enzymes may be used to penetrate include those of acetic acid, glucuronic acid, mannose,
and hydrolyze the structure. Hydration requires the arabinose and galactose. Softwood is even more vari-
addition of energy or a strong acid. Alternatively, enable in that the backbone may be made of more diverse
zymes, such as cellulase, may facilitate the conversion. materials. The backbone is typically made of galacto-
Enzymatic hydrolysis tends to be much slower than glucomannan units or arabinoglucuronoxylan units.
acid hydrolysis. Reducing the chip size or increasing Galactoglucomannan is a polymer that is a primarily
TABLE 27.1 Major Components of Wood
Distribution, wt%
Type Softwoods Hardwoods
Cellulose OH OH 40e50 40e50

HO OH HO OH
O O
O O O OH
O
HO O HO OH O
OH
OH OH
Lignin 20e30 20e25
Phenolic eOH Per C6C3 unit 0.2e0.3 0.1e0.2
Aliphatic eOH Per C6C3 unit 1.15e1.2 1.1e1.15

Methoxyl eOCH3 Per C6C3 unit 0.9e0.95 1.4e1.6
Carbonyl >CaO Per C6C3 unit 0.2 0.15
Hemicellulose 25e30 25e35
Galactoglucomannan 5e8 0
(1:1:3)
(Galacto)glucomannan 10e15 0
(0.1:1:4)
The OH groups in the xylose units were partially substituted by OAc

on the C-2 or C-3 positions, i.e. RaCH3CO (Ac) or H
Glucomannan OH OH 0 2e5
(1:2 to 1:1) O HO O HO OH
O OH
O O O O
OH
HO O HO
OH O
OH
OH
Arabinoglucuronoxylan
7e10 Trace
Glucuronoxylan Trace 15e30
OH in the xylo-units were partially substituted by OAc on the C-2 or

C-3 positions (about 7 in 10 xylo-units), i.e. RaCH3CO (Ac) or
Extractives 5e8 2e4
Aliphatic and alicyclic Terpenes, terpenoids, esters, fatty acids, alcohols, etc.
Phenolics Phenols: p-cresol, p-ethylphenol, guaiacol, salicyl alcohol, eugenol, vanillin, coniferyl aldehyde, acetovanillone,
propioguaiacone, salicylic acid, ferulic acid, syringaldehyde, sinapaldehyde, and syringic acid; stilbenes: pinosylvin,
pinosylvin monomethyl and dimethyl ethers, 4-hydroxystilbene, 4-hydroxystilbene monomethyl ether; lignans;
hydrolyzable and condensed tannins; flavonoids; isoflavones or isoflavonoids
Carbohydrates Arabinose, galactose, glucose, xylose, raffinose, starch, pectic material

Inorganics Ca, K, Mg, Na, Fe, SO 2
4 , Cl , etc.
Others Cyclitols; tropolones; amino acids, protein, alkaloids, etc.
Ash 0.2e0.5 0.2e0.8
Source: Fengel, 1989.

AN OVERVIEW ON BIOMASS CONVERSION 461
linear and perhaps mildly branched chain. In hemicel- Given that LB is composed of a number of distinct
lulose, the residual units take the place of the strong components, there are a variety of treatment options
hydrogen bonding that occurred with cellulose available that one can use to change these components
components. into fuel, chemicals and other products.
Recall that cellulose is highly ordered and tightly With a harsh condition (high temperature, strong
bound and thus resistant to hydrolysis. Hemicellulose acid/base, strong solvents, or a combination of these
is not. Hemicellulose tends to be more randomly orga- agents), LB can be turned into small molecular units
nized with a more variable and loosely bound structure (such as C, CO2, CO, H2 and H2O) and then further con-
(amorphous). Therefore, it can be hydrolyzed by weaker verted to a desired product. Thermochemical conver-
or more dilute acids and bases, or at milder conditions. sion technologies usually employ this strategy to break
Lignin is the third largest component of LB at 25e35% down LB unselectively to accommodate further conver-
of the LB dry weight (Boerjan et al., 2003). Lignin is a het- sions either catalytically or biologically. Therefore, ther-
eropolymer with methoxylated phenylpropylene alcohol mochemical conversion technologies can be versatile.
units. Its structure tends to be amorphous and variable. The structure of wood (or LB in general) is sufficiently
These units are interconnected by stable ether and ester strong and complex that it is not feasible to attack the
linkages. It is hydrophobic and aromatic. It covalently whole complex at mild conditions in a single step, nor
links to hemicelluloses and cross-links different plant is it feasible to isolate the components and attack them
polysaccharides giving mechanical strength to the cell individually. When mild conditions are desired, one
wall (Mielenz, 2001). Additionally, lignin is highly resis- must attack at least one portion of the whole structure
tant to biological degradation and thus it protects cellulose and weaken it. Follow up with another treatment to
and hemicellulose from decay. break down the first component or attack a second
Lignin from different plant families vary in their component. Continue to treat the biomass until the
alcohol content and composition. These lignins are desired composition is obtained. These treatment op-
thus defined by these components into different types. tions are classified into mechanical, thermal, chemical,
The lignin precursor in gymnosperms is coniferyl or biological processes. These are not discrete classifica-
alcohol. The precursor in angiosperms is p-coumaryl tions. In other words, a process can be considered to
alcohol and sinapyl alcohol. The corresponding lignins belong to more than one category. For example, if one
are guaiacyl (G), p-hydroxyphenyl (H) and syringal were to saturate LB with water, then heat it under high
(S), respectively. Grasses tend to contain G while palm pressure and rapidly release the pressure, the hot water
trees contain mostly S (Sjöstrom, 1993). could vaporize into steam and thus explode apart
The next largest component of LB is the extractives. the woody cells it had penetrated. This is called steam
These make up between 2% and 8% of the total dry explosion and it uses a thermal process to accomplish
weight (Table 27.1). Extractives are compounds found a mechanical breakdown of the woody material. Steam
in LB that are soluble in neutral organic solvents or explosion will be discussed later in this chapter.
water at standard temperatures and atmospheric condi- While there are several LB conversion technologies
tions. Extractives vary in solubility. Some are lipophilic available, this chapter will focus on biochemical conver-
and others are hydrophilic. Lipophilic extractives that sion technologies with some discussions in thermo-
are soluble in nonpolar organic solvents are called chemical conversions.
resins. There is a large diversity in the number of extrac- These treatments may be applied at various points
tives. Additionally, the concentrations of extractives are across the process. The typical process to acquire fuel
highly variable throughout the plant depending on the products using a bioconversion methodology is gener-
tissue type, i.e. root, stem, bark, branch, needle or leaf. ally described in four parts: pretreatment, hydrolysis,
It is important to note that over 70 metal, earth elements, fermentation and distillation, separation and filtration.
and inorganic compounds may be found in LB. The As discussed previously, cellulose, hemicellulose and
extractives are the first components that can be extracted lignin are strong, stable structures. These structures are
from wood. This is advantageous for using LB as a biore- challenging for one to convert into fermentable compo-
mediation for toxic soil and wastewater in addition to nents (Mielenz, 2001). Of these three components, hemi-
being a source for biofuel and other products. cellulose is the most vulnerable and easiest to degrade.
Recall that compared to cellulose, hemicellulose is a
lower molecular weight and is less uniform as it is
AN OVERVIEW ON BIOMASS composed of a variety of sugar polymers and residual
CONVERSION units.
In bioconversions, the objective of pretreatment is to,
Conversion refers to the collection of processes as efficiently as possible, prepare LB for fermentation
employed to modify a feedstock into desired product(s). into products. The amount of energy required to break
FIGURE 27.3 Schemes of biochemical conversion to materials, chemicals and fuels: (1) sequential incremental deconstruction; (2) two-step
saccharification and fermentation; (3) simultaneous saccharification and fermentation; (4) gasification and fermentation. Source: Wang et al., 2012.
(For color version of this figure, the reader is referred to the online version of this book.)
down LB is fixed. No matter what suite of treatment Pathway 4 shows a gasification process to produce syn-
options used to convert LB to product, the thermody- gas. This is a thermochemical process. The sugars in syn-
namic barrier is the same. It requires the same amount gas are subsequently fermented into liquid fuels similar
of energy to completely biologically degrade wood as to those produced by the more biochemical methods.
it does to chemically treat it or gasify it. One trades off The four pathways shown vary in the number of steps,
time for allowing organisms to invest energy on one’s or time, required to acquire the product.
behalf versus applying heat or concentrated chemicals Figure 27.4 provides a slightly more detailed look at
to accomplish the same task more quickly. Additionally, pathway 1 from Figure 27.3. Different pretreatment
biological methods allow for greater selection of the methods have different desired characteristics (Limayem
portion of biomass to convert it into product, and usu- and Ricke, 2012). A summary of pretreatment methods to
ally by selecting a descending route of molecular chem- be discussed in this chapter and their characteristics is
ical energy or intermediates that are not down to shown in Table 27.2.
simplistic building blocks if possible (green chemistry).
By selecting only a portion of the LB to convert, one
lowers the amount of investment energy required. PRETREATMENTdBIOMASS SIZE
Biochemical processes operate at moderate or low tem- REDUCTION BY PHYSICAL OR
peratures. These milder conditions may be slightly MECHANICAL METHODS
more efficient than their thermochemical counterparts.
However, a burden of biological or biochemical pro- The first and most important step in any conversion
cesses could arrive for the need of detoxification. One process is to reduce the physical size of LB. In order to
must often remove toxic components resulting from obtain the high yields required for commercial success
the pretreatment methods employed. in bioconversion operations, it is vital to pretreat and
Figure 27.3 illustrates a set of four treatment path- reduce the biomass into an effective size (Mosier et al.,
ways to convert LB into various products. These are 2005). Reducing the LB size from a log to wood chips
not the only methods available but merely an example to even fine powders improves mass and heat transfer
of commonly used methods. This pathway represents as well as increases the surface area of the particle.
one of the most popular biorefinery designs used to bio- Increasing the surface area exposes a higher percentage
chemically convert LB into biofuels and bioproducts. of the glycosidic or ester bonds to the agents in solution
PRETREATMENTdBIOMASS SIZE REDUCTION BY PHYSICAL OR MECHANICAL METHODS 463
Lignocellulosic
biomass
Size reduction
Hemicelluloses Fermentation of
extraction Hemicelluloses
Hydrolysis hemicellulosic
(Pretreatment) extracts Ethanol
Detoxification sugars
Product butanol
& recovery biopolymer
neutralization Fermentation of ...
Residual Enzymatic cellulosic
biomass hydrolysis sugars
Residue
processing
Co-products
FIGURE 27.4 Schematic flow sheet for biomass conversion to bioproducts. Source: US DOE, 2006. (For color version of this figure, the reader
is referred to the online version of this book.)
(Mosier et al., 2005). Catalysts, such as a proton or an preferred method for reducing the size of wood. Chip-
enzyme, can only access active chemical bonds when ping reduces wood to 10e50 mm in two dimensions
exposed at the solideliquid interface (Liu, 2003; Yang and 5e15 mm in the third (Zhu and Pan, 2010). This is
and Liu, 2005). Smaller particles translate into faster, the minimum treatment necessary to begin conversion.
more uniform reactions and a more complete However, additional reduction is often performed. For
conversion. example, wood chips may subsequently be refined to fi-
The energy required to reduce the biomass into a bers such as that in fiber production, pulverized into
treatable size depends on the density of the biomass wood fibers or wood flour (Zhu and Pan, 2010). Pulver-
source. Herbaceous materials do not require as much ization requires much more energy than chipping (Zhu
processing to achieve the needed particle size as it and Pan, 2010).
does to reduce wood (Cadoche and Lopez, 1989). Since In addition to chipping and shredding, hammer mill-
LB reduction is much more energy intensive, it is imper- ing, knife milling, disk or attrition milling, and ball mill-
ative to adequately define the reduction process. This re- ing are viable alternatives to reduce biomass sizes.
quires an understanding of the quality and condition of Large-scale reduction operations have favored hammer
the source materials. Qualities such as moisture content, and disk milling (Tienvieri et al., 1999). Chip refining
soil particles, foreign matter, and initial cut length will is also an alternative as it can have a large throughput.
impact efficiency, energy requirements and downstream Hammer milling is primarily used for making wood
treatment conditions and requirements. Pretreatment is flours for composites and pellets. Disk milling is used
costly and greatly influences the cost and effectiveness for wood fiber production at a commercial scale, around
of downstream operations. It affects fermentation 1000 tons per day. Disk milling operations are depen-
toxicity, the rate of enzymatic hydrolysis, enzyme load, dent on environmental conditions and the quality of
powder mix, product concentration, product purity, source materials. The energy requirement and the
waste treatment requirements, energy requirements wood particle size and shape depend on these opera-
and a host of other process variables (Zhu and Pan, tional parameters (Tienvieri et al., 1999).
2010). Thus, it is important to begin the design process Milling operations have a significant impact on
with the end in mind. Much effort should be invested downstream energy requirements and the efficiency of
to design the whole process up front with specific source enzymatic cellulose saccharification. Since the goal of a
materials and conditions defined. biorefinery is to optimize the conversion process, to
reduce energy requirement and maximize the enzymatic
cellulose saccharification, it is important to attend to the
Mechanical PretreatmentdChipping, Grinding, biomass size reduction portion of the process. Failure at
Milling, Refining this stage amplifies the cost of energy requirements and
At the time of harvest, an operation is performed in reduces the effectiveness of subsequent treatments.
the field to presize the LB. Herbaceous biomass is pre- Since these mechanical processes can produce a range
pared by shredding or forage cutting. Chipping is the of particle sizes it is often necessary to control the
TABLE 27.2 Summary of Pretreatment Methods and Key Characteristics
Pretreatments Key Characteristics References
Dilute Acid (H2SO4, • Practical and simple technique. Does not require (Chandel et al., 2007; Chaudhary et al., 2012;
HCl (0.5e5%) thermal energy Gamez et al., 2004; Li et al., 2012; Lloyd and
• Effective hydrolysis of hemicelluloses with high Wyman, 2005; Schell et al., 2003; Um and van
sugar yield Walsum, 2012; Wyman et al., 2005; Yasuda and
• Generates toxic inhibitors Murase, 1995)
• Requires recovery steps
Hot Water • The majority of hemicelluloses can be dissolved (Banerjee et al., 2009; Hu et al., 2008;
• No chemicals and toxic inhibitors Kemppainen et al., 2012; Ladisch et al., 1998;
• Average solid load Laser et al., 2002; Lynd et al., 2002; Mosier et al.,
• Not successful with softwood 2005; Shupe and Liu, 2009; Weil et al., 1994)
Lime • High total sugar yield including pentose and (Kim and Holtzapple, 2006; Weil et al., 1994;
hexose sugars Zhu and Pan, 2010)
• Effective against hardwood and agricultural
residues
• High pressure and temperature hinder chemical
operation
• Commercial scalability problem
Ammonia Fiber • Effective against agricultural residues mainly (Bisaria and Ghose, 1981; Dale et al., 1984;
Explosion (AFEX) corn stover without formation of toxic end Hendriks and Zeeman, 2009; Jin et al., 2012; Lau
products and Dale, 2008; Speers and Reguera, 2012; Sun
• Not suitable for high-lignin materials and Cheng, 2002)
• Ammonia recovery
• No wastewaters
Ammonia Recycle • High redistribution of lignin (85%) (Drapcho et al., 2008; Gupta and Lee, 2009; Kim
Percolation (ARP) • Recycling ammonia and Dale, 2005)
• Theoretical yield is attained
Steam Explosion • Effective against agricultural residues and (Bisaria and Ghose, 1981; Bura et al., 2009; Galbe
with Catalyst hardwood and Zacchi, 2002; Kemppainen et al., 2012;
• High hemicelluloses fraction removal Lloyd and Wyman, 2005; Monavari et al., 2009;
• Not really effective with softwood Park et al., 2012)
Organosolv • High yield is enhanced by acid combination (Cybulska et al., 2012; Koo et al., 2012; Monavari
• Effective against both hardwood and softwood et al., 2009; Pan et al., 2005)
• Low hemicellulosic sugar concentration
• Formation of toxic inhibitors
• Organic solvent requires recycling
• High capital investment
Sulfite Pretreatment to • Effective against high-lignin materials, both (Li et al., 2012; Shuai et al., 2010; Tian et al., 2011;
Overcome Recalcitrance softwood and hardwood Wang et al., 2009; Zhu et al., 2010a,c, 2009; Zhu
(SPORL) • Highest pretreatment energy efficiency and Pan, 2010)
• Minimum of inhibitors formation
• Accommodate feedstocks versatility
• Steam explosion combined to SPORL in
presence of catalyst becomes effective against
softwood materials
• Cost-effective
Ozone • Effectively remove lignin from a wide range of (Garcı́a-Cubero et al., 2009; Mvula et al., 2009;
cellulosic material without generating inhibitors Sun and Cheng, 2002)
• Expensive
Alkaline Wet Oxidation • The combination of oxygen, water, high (Chaudhary et al., 2012; Klinke et al., 2004;
temperature and alkali reduce toxic inhibitors Monavari et al., 2009)
• High delignification and solubilization of
cellulosic material
• Low hydrolysis of oligomers
Fungal Bioconversion • Environmentally friendly (Dashtban et al., 2010; Nguyen et al., 2000)
• Low use of energy and chemical
• Slow bioconversion
particle size used in the biorefinery. Size characterization rate of enzymatic hydrolysis. Furthermore, irradiation
is accomplished using sieves, screens and imaging leads to a significant increase in sugar yield (Yang
analysis. The particle surface area is the most relevant et al., 2008).
determination of effectiveness, and thus, it is the quality An electron beam cuts biopolymers such as cellulose,
to be controlled. Specific surface area correlates to hemicellulose and lignin into smaller chains. Analysis
energy consumption and the efficiencies of a variety by powder X-ray diffractometer and Fourier transform
of size reduction processes have been compared infrared spectroscopy confirm the electron beam treat-
(Holtzapple et al., 1989). ments reduce the degree of crystallinity and improve
There is a limit to the effectiveness of size reduction. the sugar yields from enzymatic hydrolysis from treated
At this point, additional surface area increases, or parti- samples (Karthika et al., 2012).
cle size reductions will not improve substrate enzymatic Electron beam irradiation is preferred over irradia-
digestibility. This critical size is proportional to the pore tion using a radioisotope. First of all, electron beam is
size in and along the wood cells. Refer to Figures 27.1 safer. Turn off the power and the electron beam stops.
and 27.2. A common target size is one that maintains A radioisotope is continuous and thus requires signifi-
the cell structure while allowing for lignin removal cant safety precautions to handle and dispose of.
from the middle lamellae. Furthermore, dosages delivered by high-energy electron
Size reduction below the cell size will provide a more beam can be controlled and they can provide more po-
efficient conversion. To reduce particle size to this wer per dose. This is a feature that would be useful in
smaller level is done by comminution (Vidal et al., the continuous treatment of LB (Auslender et al., 2002).
2011). Comminution of biomass, especially at the final Compared with microwave and gamma ray treat-
sizing stage, is energy intensive and the product is of ments, treatment by electron beam is more energy
low value. Thus, there is much interest in finding the effective. The larger particle sizes, that it can treat, signif-
most efficient milling processes. icantly offset the negative effect of higher dosage. That
To that end, ball milling has been extensively studied. said, there still remains the challenge of the limitation
It has been shown to deliver excellent results in terms of of electron beam source and the potential limitation on
the hydrolysis rate and sugar yield. Additionally, this the scale of operations. Even though all these irradiation
pretreatment method is clean and easy to do. Vibratory options reduce the particle size and reduce the DP, they
ball milling has been shown to be more effective at are too expensive to use in full-scale operations.
breaking down the crystallinity of cellulose and Currently, the prospects of engaging an irradiation treat-
improving the digestibility of the biomass over ball mill- ment, even if in conjunction with other environmentally
ing alone (Millet et al., 1976). Mechanical milling requires friendly treatment options, does not look promising due
long operation times and a large amount of energy (Lynd to the excessive energy requirements. Table 27.3 shows a
et al., 1996). The smaller the desired particle size the comparison of these irradiation treatment methods on a
greater the comminution requirements will be in terms variety of wood species.
of time and energy (Cadoche and Lopez, 1989).
Ammonia Recycle Percolation Pretreatment
Irradiation Pretreatment by Electron Beam,
When aqueous ammonia, 10e15 wt%, is percolated
Gamma Ray, or Microwave through biomass at temperatures between 150 and
Irradiation is an option for biomass size reduction. 170 C with a fluid velocity of 1 cm/min and a residence
Following a gross procedure to reduce field supplies time of 14 min, lignin depolymerizes and the lignin-
into at least chip size, one can employ high-energy carbohydrate linkages break. This process is known as
radiation such as gamma radiation and/or microwave ammonia recycle percolation (ARP) (Iyer et al., 1996).
radiation to accomplish fine particle reduction This process is advantageous in that it does not inhibit
(Wasikiewicz et al., 2005). Not only does a high-energy downstream biological processes. A water wash is there-
radiation treatment produce fine particles, but it can fore not necessary (Kumar et al., 2009a). Additionally, it
also favorably alter the physical and chemical properties is possible to recover and recycle the ammonia. On the
of the biomass, depending on dosage (Bouchard et al., downside, ARP is inefficient when used to pretreat soft-
2006). Irradiation has been shown to decrease the DP wood pulp (Mosier et al., 2005) where lignin had already
(Bouchard et al., 2006) and make microstructural been removed.
changes to the irradiated cellulose pulp (Dubey et al.,
2004). These changes include an increase in the carbonyl
Ozonolysis Pretreatment
contents and an overall improvement in the vulnera-
bility of the cellulose crystalline regions to reagents A pretreatment option that is appropriate for
(Stepanik et al., 1998). This in turn leads to a higher grassy biomass and some softwood is ozonolysis.
TABLE 27.3 The Effects of Cellulose Conversion by Different Irradiation Pretreatments
Maximum Enzymatic Hydrolysis Cellulose

Wood Species Dose Particle Size Duration (h) Conversion
Electron Beam Irradiation Spruce 2 MGy 1e2 mm in thickness 72 0.89

(Khan et al., 1986) and 10e20 cm2
Gamma Irradiation Softwood 40 kGy 32e42 mesh 8 0.673 0.10
(Betiku et al., 2009) (Triplochiton scleroxylon)
Gamma Irradiation Hardwood 90 kGy 32e42 mesh 8 0.803 0.10
(Betiku et al., 2009) (Khaya senegalensis)
Microwave Beech 400 W 30e42 mesh 48 0.561
(Verma et al., 2011)
Source: Wang and Liu, 2012.
In this case, ozone is used to degrade the lignin and Raising the operational temperature above 185 C
hemicellulose in bagasse, green hay, peanut, pine, eliminates the need for a catalyst, either for an inorganic
cotton straw, wheat straw and poplar sawdust (Ben- acid or for an organic acid. At this condition, the amount
Ghedalia and Miron, 1981; Vidal and Molinier, 1988). of delignification is quite satisfactory. Adding acid
The process primarily acts on the lignin component yields a high quantity of xylose.
and only mildly affects the hemicellulose component, Since the organic solvents inhibit downstream biolog-
while cellulose is negligibly affected. Ozonolysis is ical processes, such as organism growth and enzymatic
notable in that it removes lignin effectively and the hydrolysis, it is necessary to remove these solvents
reactions take place at room temperature and stan- from the system. This is quite difficult as some quantity
dard pressure (Ben-Ghedalia and Miron, 1981). The of solvent is likely to reside in the system even after ef-
most significant advantage is that following an ozone forts to remove them. Organic solvents tend to evapo-
pretreatment where 60% of the lignin is removed rate into the atmosphere and are hazardous to the
from wheat straw, the rate of enzymatic hydrolysis environment and one’s health. Containing the solvent
increases by 500% (Ben-Ghedalia and Miron, 1981). is another challenge. Given these challenges, an organo-
The most notable drawback is that the process is solv pretreatment is not necessarily ideal for large-scale
expensive due to the large volume of ozone required or commercial operations.
(Sun and Cheng, 2002).
Oxidation Pretreatment
Organosolv Pretreatment
Oxidation is a pretreatment option whereby an oxi-
Take an organic or aqueous organic solvent such as dizing agent, such as hydrogen peroxide or peracetic
formic acid, acetic acid, methanol, ethanol, acetone, acid, is applied to LB. The result is the removal of hemi-
ethylene glycol, oxalic acid, triethylene glycol or tetrahy- cellulose and lignin and thus, an increased accessibility to
drofurfuryl alcohol and combine it with an inorganic cellulose to enzymatic hydrolysis. This result is the
acid catalyst such as hydrochloric acid or sulfuric acid culmination of several reactions: electrophilic substitu-
and one can eliminate the internal lignin and hemicellu- tion, displacement of side chains, cleavage of alkyl aryl
lose bonds. This is known as an organosolv process (Pan ether linkages, or the oxidative cleavage of aromatic
et al., 2006; Sarkanen, 1980; Thring et al., 1990). Alterna- nuclei (Hon and Shiraishi, 2001). Often the oxidative
tively, an organic acid, such as oxalic acid, acetylsalicylic agent is not selective and a significant loss of hemicellu-
acid and salicylic acid may be substituted for the inor- lose and cellulose may occur. Additionally, there is a high
ganic catalyst. risk of forming downstream inhibitors as soluble aro-
It has been observed that approximately 72% of matic compounds are formed while the lignin oxidizes.
xylose in untreated wood, in both its monomeric and When using hydrogen peroxide as the oxidative
oligomeric forms, could be recovered using an organo- agent on sugarcane bagasse, the rate of enzymatic hy-
solv pretreatment process (Pan et al., 2006). Pan et al. drolysis improves. In one study, hemicelluloses and
(2006) also investigated a bioconversion of hybrid pop- approximately 50% lignin were solubilized by 2%
lar to ethanol at 180 C, for 60 min, with 1.25% H2SO4, hydrogen peroxide at 30 C over 8 h. This was followed
and 60% ethanol. They observed that nearly 74% of the by enzymatic hydrolysis, or saccharification, using
lignin was removed as a precipitate in the ethanol cellulase at 45 C within 24 h. The result was 95% effi-
extraction. ciency in glucose production (Azzam, 1989).
In another study, peracetic acid was applied at In addition to particle size, dissolution efficiency is
ambient temperatures to a hybrid poplar and sugarcane also highly sensitive to the water content. Water attenu-
bagasse mixture (Teixeira et al., 2000). It was determined ates the dissolution effectiveness of an ionic liquid.
that peracetic acid was very selective for lignin and in Studies have shown that storing wood chips at warm
some cases, no significant carbohydrate was lost. temperatures, e.g. 50 C or 90 C, reduces the water con-
When peracetic acid was applied at 21%, the enzymatic tent of the wood and thus improves the pretreatment
hydrolysis of cellulose increased from 6.8% for un- effectiveness (Kilpeläinen et al., 2007; Sun et al., 2009).
treated biomass to 98% in the peracetic acid-pretreated Reducing the water content improves the dissolution
biomass. power of an ionic liquid regardless of the type of
wood being treated. However, if the wood becomes
too dry, the wood composition may change unfavorably.
Ionic Liquid Pretreatment
Determining the precise water content of LB is quite
Ionic liquids are strong solvents. They are able to difficult and is complicated due to the diversity of envi-
dissolve the components of LB at ambient to moderate ronmental conditions of the regions from which the
temperatures. Furthermore, ionic liquids are highly wood studied grew. Variables such as humidity and var-
tunable through the selection of anion and cation. iances in species present a challenge when comparing
Beyond toxicity and corrosivity, other considerations literature on the subject (Wang et al., 2012).
affecting the selection of an ionic liquid include price, The type of LB, dissolution time, temperature and
availability, water tolerance, biodegradability, and phys- ionic liquid to wood ratio, are all factors that contribute
ical properties such as viscosity, melting point, dipolar- to the dissolution power of an ionic liquid. That said,
ity and hydrogen bond basicity. An effective wood those ionic liquids that were effective at dissolving
dissolution is possible when both the ionic liquid and both lignin and cellulose were also excellent at overall
conditions are properly identified and employed. LB dissolution. One of the best solvents for wood chips
The most significant consideration for practical is the combination of 1-allyl-3-methylimidazolium chlo-
large-scale operations is the toxicity of the ionic liquid ride ([AMIM][Cl]) and [EMIM][OAc]. Ionic liquids
to be used. For example, 1-butyl-3-methylimidazolium derived from polycyclic amidine bases have been shown
chloride ([BMIM][Cl]) is a good solvent to use on to dissolve aspen wood chips completely (D’Andola
cellulose as it is only moderately toxic compared to et al., 2008). The ionic liquids used in this study
that of 1-ethyl-3-methylimidazolium chloride ([EMIM] were 1,8-diazabicyclo[5,4,0] undec-7-enium salt, and
[Cl]) (Swatloski et al., 2004; Wu et al., 2004). 1,8-diazabicyclo[5,4,0] undec-7-enium chloride [HDBU]
Corrosivity of the selected ionic liquid is also impor- [Cl] (D’Andola et al., 2008). It has been observed that
tant. It plays a large role in the economics of a commercial [AMIM][Cl] can effectively dissolve both hardwood
operation. One can minimize corrosivity by selecting an and softwood wood chips. However, the same solvent
ionic liquid that is halogen free. Good choices include only partially dissolved Norway spruce (Kilpeläinen
1-ethyl-3-methylimidazolium acetate ([EMIM][OAc]) et al., 2007). The efficiency of [AMIM][Cl] in dissolution
(Liebert, 2010) and 1,3-dimethylimidazolium-dimethyl- of wood is due to the presence of p-electrons both in the
phosphate ([MMIM][(MeO)2PO2]) (Zavrel et al., 2009). alkenyl chain as well as in the imidazolium ring.
Balancing the physical properties and operational Possible pep interactions may occur between the aro-
conditions is important to obtaining the most ideal disso- matic part of lignin and the ionic liquid (Hunter and
lution of LB. For example, if the viscosity of an ionic Sanders, 1990; Kilpeläinen et al., 2007). The highest sol-
liquid is high, it may be necessary to operate the pretreat- ubility of maple wood powder was achieved using
ment at a high temperature to obtain a practical dissolu- [AMIM][Cl] and [BMIM][Cl] (Lee et al., 2009).
tion. As a result, the reactions may become unstable and [EMIM][OAc] can completely treat three types of
may give rise to undesirable reactions and by-products. wood chips. It is used to treat spruce, beech and chestnut.
A solution to this problem is to reduce the viscosity of However, it only partially dissolves silver fir (Abies alba)
the ionic liquid by combining it with a cosolvent. A wood chips (Zavrel et al., 2009). A plausible explanation
good viscosity-reducing cosolvent is polyethylene glycol for this difference is that silver fir contains more cellulose
(Willauer et al., 2000). (50.3%) and lignin (27.7%) than the other wood species
The dissolution rate is inversely proportional to wood (Kuznetsov et al., 2002). When comparing the dissolution
chip sizes. For example, ball-milled wood powder effectiveness of [EMIM][OAc] to [BMIM][Cl] and control-
produces a higher dissolution rate than does sawdust. ling for species, wood chip size, and temperature one can
The dissolution rate for TMP fibers is higher than that obtain a 3.6-fold increase in dissolution effectiveness us-
for sawdust, which is much greater than that of wood ing [EMIM][OAc] vs [BMIM][Cl]. In this case, southern
chips (Kilpeläinen et al., 2007; Sun et al., 2009; Zavrel yellow pine wood chips were treated at 110 C. This
et al., 2009). 3.6-fold increase in dissolution effectiveness is
FIGURE 27.5 A process for the

Wood chips dissolution of wood and regeneration of
ionic liquid.Source: Sun et al., 2009. (For
color version of this figure, the reader is
referred to the online version of this
book.)
Ground wood
IL
IL
Cooking Recycle
Wood/IL solution
Cellulose-rich Filtration Regeneration

Acetone/H2O
materials Wash, dry
Lignin in solution
Evaporation of
acetone
Lignin
attributable to the basicity of the acetate anion, higher the pretreatment liquor and the temperature (Zhu
than that of the chloride anion. Thus, [EMIM][OAc] is et al., 2009).
stronger at breaking the intramolecular hydrogen bonds The first step in the process is to treat wood chips or
(Fort et al., 2007; Sun et al., 2009). another LB feedstock with a sulfite salt solution where
An opportunity for improvement in using ionic liq- the salt may be sodium, magnesium or calcium. This
uids is better recovery of solubilized cellulosic materials first step usually operates at a temperature between
and lignin. A significant drawback is that much of the 160 C and 190 C and at a pH between two and four
hemicellulose is washed away during the recovery pro- for 10e30 min. The second step is to fiberize the resul-
cess. Figure 27.5 illustrates the process. tant biomass using a disk mill. This yields a fine fibrous
Following pretreatment with an ionic liquid, an enzy- substrate suitable for robust saccharification and
matic hydrolysis pretreatment is applied to produce the fermentation (Shuai et al., 2010).
sugars for downstream fermentation. This pretreatment The typical acid charge on oven-dried wood is
can recover as much as 90% of the cellulose for enzy- 0.5e1% for hardwood and 1e2% for softwood. The
matic hydrolysis. While cellulose is recovered at a high typical bisulfite charge is 1e3% for hardwood and
rate, the hemicelluloses are not as they are washed 4e8% for softwood (Zhu et al., 2010b). More than 90%
away. As Figure 27.5 illustrates, the ionic liquids are of the cellulose was converted from SPORL-treated
recovered and recycled for reuse. Even so, the problems spruce chips. In this case the oven-dried wood chips
of price, toxicity, and the lost hemicellulose persist, were treated with an 8e10% bisulfate and 1.8e3.7% sul-
which inhibit wide adoption in industrial scale furic acid combination at 180 C for 30 min. The resul-
operations. tant material was treated with enzyme hydrolysis for
48 h using 14.6 cellulase and 22.5 b-glucosidase per
gram of substrate. Shuai et al., and Zhu et al., have per-
Sulfite Pretreatment to Overcome Recalcitrance formed comparative SPORL studies using dilute-acid
of Lignocelluloses pretreatments for both softwoods and hardwoods
Sulfites are found to be efficient agents for pretreating (Shuai et al., 2010; Zhu et al., 2010b). In these studies,
LB, in both hardwoods and softwoods (Zhu et al., 2009). it was observed that SPORL is better at saccharification
In sulfite pretreatment to overcome recalcitrance of lig- of hexoses and pentoses than was a dilute acid (DA)
nocelluloses (SPORL), the sulfite refers to any sulfite, treatment. In one case, where oven-dried spruce was
bisulfate or combination. A combination may contain treated at 180 C for 30 min with 1% H2SO4 at a 5:1
any two of the following three reagents: sulfite (SO2 3 ), liquor-to-wood ratio, 87.9% of the hexoses and pentoses
bisulfite (HSO 3 ), and sulfur dioxide (SO2, or H2SO3). were recovered using SPORL versus a similar DA treat-
The specific combination to use depends on the pH of ment where 56.7% of the saccharides were recovered.
TABLE 27.4 Comparison of Chemical Pretreatment Method on Lodgepole Pine Wood Chips
Pretreatment Initial Disk-Milling Energy Size Reduction

(180 C, 30 min) Liquid pH (kWh/ton wood) Energy Savings (%) (%)
Untreated 699 1.7

Hot Water 5.0 680 2.7 16.0
Acid 1.1 412 41.0 41.6
SPORL 4.2 594 15.0 75.1

SPORL 1.9 153 78.1 91.6
About 92.5% of the cellulose was recovered in an SPORL pretreatment methods (Amidon et al., 2008; Liu, 2010;
process utilizing a 9% sodium sulfite (w/w of wood) Mosier et al., 2005). High pressure is applied to keep
and 77.7% for the DA (Shuai et al., 2010). In another the water in a liquid state while it is at elevated temper-
study of aspen, or Populus tremuloides, a comparison atures (Hendriks and Zeeman, 2009). This enables the
was made between an SPORL pretreatment using a water to penetrate the cell structure of the biomass and
combination of sulfuric acid and sodium bisulfite and thus hydrate the cellulose and remove the hemicellu-
a dilute sulfuric acid (DA) pretreatment. It was observed loses. Another feature of water is that it has a high
that nearly 60% more ethanol was produced from the dielectric constant. This facilitates ionic substances to
SPORL-treated wood than from the DA-treated wood. disassociate and allows for the dissolution of hemicellu-
In both cases enzymatic hydrolysis was conducted using loses and a portion of the lignin.
10 FPU cellulase per gram glucan for 120 h (Zhu et al., When the water temperature exceeds 150 C, the
2010b). hemicellulose begins to solubilize. The degree to which
Table 27.4 highlights a handful of comparisons this occurs is determined by thermal, acid and alkali
between treatment methods and their effectiveness stability of the hemicellulose, which is dependent on
where the pretreatment conditions were L/W ¼ 3, the composition of the hemicellulose backbone and the
disk-milling solids loading ¼ 30% (the solid contents of branching groups. Temperature of the water can selec-
pretreated wood chips), and disk plate gap ¼ 0.76 mm. tively solubilize hemicelluloses. A 75% maximum xylan
Sodium bisulfite charge was 8% on oven-dried wood solubilization in the hot water extract of sugar maple
for the two SPORL runs; sulfuric acid charge was 2.21 was obtained at 175 C after 2 h, whereas only 30% of
(w/w) on oven-dried wood for the DA and low pH the initial xylan was removed from a 2 h treatment at
SPORL runs, and 0 for the hot water and high pH 152 C (Mittal et al., 2009). When the water temperature
SPORL runs. exceeds 180 C an exothermal reaction begins. It is most
SPORL is an attractive pretreatment method due to likely related to the solubilization of the hemicelluloses
several features. SPORL generates much less furfural (Brasch and Free, 1965).
and hydroxymethylfurfural (HMF) than does a simple Another result of the thermal process is that the pH of
DA pretreatment. SPORL significantly enhances the extract decreases to 3e4 (Gregg and Saddler, 1996a).
fermentation yields by weakening the hydrophobic rela- Portions of the hemicelluloses are hydrolyzed, which
tionship between lignin and enzymes and enhancing form acids such as acetic acid. These are released from
saccharification of cellulose. One of the products of acetylated polysaccharides in the wood. These acids
SPORL is a sulfonified lignin, which has potential eco- lower the pH and catalyze the additional hydrolysis of
nomic value as a directly marketable coproduct within hemicellulose (Liu and Wyman, 2003; Liu, 2008; Tunc
existing markets and for opening new markets. The and van Heiningen, 2008; Zhu et al., 2005).
energy consumption in the size reduction process is Depending on the intensity of the hot water extraction,
reduced by an order of magnitude. Lastly, SPORL has sugars may dehydrate. When hexose sugar dehydrates
demonstrated commercial scalability with low techno- HMF, also known as HFM or 5-hydroxymethyl-
logical and environmental risks (Zhu et al., 2010b). 2-furaldehyde, is formed. When pentose sugar dehy-
drates, furfural is formed. In addition to solubilizing
hemicellulose, hot water treatment can lead to solubiliza-
Hot Water tion of portions of lignin (Ramos, 2003). Regardless, the
Utilizing liquid water by itself, as the only pretreat- produced compounds are usually phenolic heterocyclic
ment reagent, is an option of interest as it is environmen- compounds such as vanillin, vanillin alcohol, furfural
tally friendly and inexpensive compared to other and HMF. This is especially true in strong acidic
conditions. Additionally, these compounds tend to water-saturated LB is suddenly exposed to low pres-
inhibit or toxify bacteria, yeast, methanogens and archae. sures, liquid water suddenly expands when vaporized
This is a significant disadvantage in using hot water to forcing LB to disintegrate into fine particles. The
extract cellulose and hemicellulose (Brownell et al., 1986). Masonite process was invented in 1926 (Mason, 1926)
Hot water extracts can be converted to desired employing this water to steam explosion process. Since
products as well, i.e. via separation and fermentation then, the steam explosion pretreatment (SEP) has been
(Liu et al., 2009; Shupe and Liu, 2009). Fermentation is a common technique (Mason, 1928). SEP is used to break
also strongly inhibited when a hydrolysate is produced the crystalline and lignocellulosic structure of biomass
from a treatment containing 3% or more of solids or the into its three major components, cellulose, hemicellulose
treatment temperature exceeded 220 C for 2 min. These and lignin. SEP enhances the resultant cellulose’s sus-
conditions likely yield furfural or soluble lignin com- ceptibility to enzymatic hydrolysis. High-pressure, satu-
pounds. At temperatures in excess of 250 C pyrolysis rated steam is applied to biomass for a brief period and
begins to take place (Laser et al., 2002). Therefore, one then allowed to rapidly decompress to atmospheric
should avoid these high temperatures. Another undesir- pressure, hence the term explosion.
able effect of thermal pretreatment is that it may increase The explosion breaks up solid particles and is used as
the crystallinity index (CrI) of cellulose (Weimer et al., a standard practice in chemical pulping operations. The
1995). It is important to remove the soluble lignin com- steam is vented and the biomass is discharged to a larger
pounds quickly. Since lignin is highly reactive, the vessel for rapid flash cooling (Mosier et al., 2005). SEP is
disengaged lignin will recondense and precipitate onto as much a mechanical process as it is a thermal process
the biomass (Liu and Wyman, 2003). This seems to be (Holtzapple et al., 1989). Regardless, the explosion per
more prevalent in cases where severe pretreatment con- se, whether it causes particle disintegration or not,
ditions are used. In these cases, more condensation and does not play a significant role in producing a product
precipitation of lignin compounds takes place and that is easily digested by enzymes (Brownell et al.,
sometimes, soluble hemicellulosic compounds such as 1986). A more likely mechanism at play is the treat-
furfural and HMF are also produced (Mittal et al., ment’s effect in removing hemicellulose (Mosier et al.,
2009) and polymerized (condensed) and deposited 2005). Applying acid catalysts, usually SO2 (or sulfite),
onto the extracted biomass. enhances this effect by reacting, in conjunction with wa-
Despite the undesirable effects above, when compared ter, within the interstitial spaces to form sulfuric acid
to other pretreatment methods, liquid hot water wood and thus catalyze hemicellulose degradation (Gregg
extraction still has a major advantage. Since a large vol- and Saddler, 1996b).
ume of water is used the solubilized hemicelluloses and SEP effectiveness and the chemical changes that take
lignin compounds appear in lower concentrations. As a place depend on residence time, temperature, chip size,
result, the risk of undesirable degradation products is and moisture content. Effectiveness is determined by the
reduced. The substances in the extract can be separated amount of hemicellulose solubilized and the rate of sub-
and converted to desired products. sequent enzymatic hydrolysis. Optimal outcomes are
Figure 27.6 illustrates the three methods of liquid hot obtained when pretreatment occurs at either high tem-
water reactors. They are differentiated by their configu- perature or short residence time, such as 270 C for
rations. One is cocurrent, another is countercurrent and 1 min, or at lower temperature and longer residence
the third is a flow-through reactor. time, such as 190 C for 10 min. Generally, initial treat-
Briefly, in cocurrent pretreatment, the biomass and ment pressures range from 0.69 to 4.83 MPa and treat-
water are heated and held at the desired conditions ment temperature ranges from 160 C to 260 C.
for a specific residence time prior to allowing it to At high temperatures water acts as an acid. Thus, dur-
cool. In the countercurrent design, water and lignocel- ing the treatment time, the hemicellulose hydrolyzes into
lulosic material flow in opposite directions through the soluble sugars. The hemicellulose is considered to auto-
reactor. The flow-through reactor is designed such that hydrolyze as a result of exposure to the acetyl groups
hot water is passed over a stationary bed of LB and in the organic acids formed at these high temperatures.
carries the hydrolysate and dissolved lignocellulosic Acetic acid is formed from the acetylated hemicelluloses.
components out of the reactor (Hendriks and Zeeman, The pH during SEP is kept quite low, near pH 3e4. SEP
2009). degrades a significant portion of the hemicellulose (Sun
et al., 2005). However, degradation of hemicellulose
may not stop at this point. If the treatment conditions
Steam Explosion
are severe, the solubilized hemicellulose may undergo a
LB is bulky and much of the volume is “empty” series of secondary reactions that yield furfural and
or saturated by air. Air in LB can be replaced by HMF. These severe conditions may be high temperature
liquid water at high temperature and pressure. When or a long incubation time. Furfural and HMF are
(a) Co-current reactor

Check valve
Pretreated
Water
biomass
Biomass
Steam
Insulated coil
(b) Counter-current reactor
Biomass Water with

dissolved extracts
Jacketed
reactor
Pretreated
biomass Water
(c) Flow-through reactor

Water
Jacketed
reactor
Biomass
Water with
dissolved extracts
FIGURE 27.6 Schematic diagram illustrating three types of liquid hot water reactors: (a) cocurrent, (b) countercurrent, (c) flow through.
(For color version of this figure, the reader is referred to the online version of this book.)
undesirable products that inhibit enzymatic hydrolysis the cellulose surface and thus improves the ability of
and limit the effectiveness of fermentation. the enzyme to attack the cellulose microfibrils (Alvira
Meanwhile, lignin is partially depolymerized, some et al., 2010). If the treatment conditions are severe,
lignin is redistributed within the material and some some degradation of cellulose to glucose can occur.
may be removed completely from the fibers, each of One study reported an enzymatic hydrolysis efficiency
which contribute to an improved exposure of the cellu- of 90% over 24 h using poplar chips using SEP. This
lose domains (Chen and Qiu, 2010). The reduction in was significantly better than the control where the enzy-
hemicellulose and partial removal of lignin exposes matic hydrolysis efficiency was 15% from untreated
poplar chips (Grous et al., 1986). That said, SEP is more without the addition of SO2. However, using a weak
effective on agricultural residues than in wood as a organic acid is more environmentally friendly than us-
result of the lower acetic acid content in the hemicellu- ing an inorganic acid as it would biodegrade in a waste
lose portion of the biomass. stream or be used for production of a biogas such as
Adding a supplemental acid to the SEP reduces both methane.
residence time and temperature. Adding an acid such as Particle size, by itself, is not a significant contributor
H2SO4 (or SO2) or CO2, typically 0.3e3% (w/w), im- to SEP effectiveness. Some studies report that larger par-
proves hydrolysis, decreases the production of inhibi- ticle size may improve the outcomes from SEP (Cullis
tory compounds and leads to a more complete et al., 2004). In these studies, pretreated Douglas fir, a
removal of hemicellulose (Kumar et al., 2009a). For the softwood, was milled to three particle sizes:
effective treatment of softwoods, adding an acid catalyst <0.422 mm screenings, 1.5 1.5 cm and 5 5 cm. They
is essential to make the substrate susceptible to enzy- were then steam exploded using SO2. It was observed
matic hydrolysis. Adding a supplemental acid also im- that the largest particle size suffered less from pretreat-
proves the enzymatic hydrolysis of the residual solids ment severity and had the highest cellulose recovery. It
and decreases the production of inhibitory compounds had larger quantities of solubilized carbohydrate and
(Morjanoff and Gray, 1987). contained fewer furan degradation products. The
These three parameters, the level of H2SO4 (or SO2) or smaller particle sizes produced outcomes containing
CO2, the residence time and the temperature, are the more solubilized hemicellulose and lignin. If the resul-
most influential parameters on total sugar yield. For tant biomass is further refined to particles of a finer
SEP treatment of sugarcane bagasse, the optimal condi- size by plate milling, with a 0.178 mm gap, the initially
tions are 1% H2SO4, 220 C; 30 s residence time, and a larger particle size showed a higher lignin removal
water-to-solids ratio of 2:1 (Holtzapple et al., 1989). After with peroxide washing and a greater rate of enzymatic
SEP treatment under these conditions sugar production hydrolysis. This is likely due to the reduction in lignin
was determined to be 65.1 g sugar/100 g. redeposition as a result of treatment severity.
A two-step SEP is a good pretreatment for softwood These findings were substantiated in studies of
(Söderström et al., 2003). In this case, the first step is to steam-exploded pine, another softwood (Ballesteros
optimize the amount of hydrolyzed hemicellulose by et al., 2000). The largest of the sizes exhibited a higher
employing low severity conditions where the biomass cellulose recovery and also a higher content of solubi-
is treated at 180 C for 10 min with 0.5% H2SO4. In the lized hemicellulose. Conversion of cellulose to glucose
second step, the solid material from the first step is was only slightly higher from the larger particle sizes.
washed and impregnated again with H2SO4. SEP is However, the total recovered glucose, including the sol-
applied again using more severe conditions. This time ubilized glucose from the steam explosion, was much
the biomass is treated at 180 Ce220 C for a longer higher when starting with the largest particle size
time, between 2 and 10 min, and with a higher concen- (Ballesteros et al., 2000).
tration of acid catalyst, 1e2% H2SO4. These treatments Starting with a herbaceous feedstock, such as Brassica
appear to hydrolyze a portion of the cellulose and carinata residues, produced different results. Although
make it more accessible to enzymatic attack (Sassner the cellulose recovery was still higher for the 8 and
et al., 2008). The most favorable conditions for 12 mm fractions, the smaller particle sizes performed
Salix wood is to impregnate it with 0.5% H2SO4 at better during enzyme hydrolysis. The 5e8 mm and
200 C for between 4 and 8 min. The yield is thus 2e5 mm fractions yielded 100% while the 8e12 mm
55.6 g glucose and xylose per 100 g dry biomass (Sassner fraction produced 85% (Ballesteros et al., 2002). This
et al., 2008). suggests that lignin condensation is not as influential
If one uses SO2 as the impregnating agent in spruce in herbaceous feedstock. It is a critical factor when
chips, the sugar yield is almost independent of impreg- pretreating softwood.
nation time and slightly increases with decreasing chip In softwood, the larger particle size produces a higher
size (Monavari et al., 2009). Shorter impregnation times maximum glucose yield, over 80%, compared to smaller
result in slightly lower mannose yields in larger chips. particle sizes with yields under 70% (Ballesteros et al.,
The optimum pretreatment conditions when using 2002). SEP-treated hardwood exhibited no difference in
SO2-catalyzed SEP for lodgepole and Douglas fir pine either enzyme digestibility or ethanol yield between
is 200 C for 5 min with 4% SO2 (w/w) (Ewanick et al., disparate particle sizes, in particular between 2e5 mm
2007; Kumar et al., 2010). and 12e15 mm (Negro et al., 2003). This indicates that
Another option for an impregnating agent is to use a the severity of the treatment plays a larger role than par-
weak organic acid, in particular, lactic acid (Monavari ticle size when using softwood. In these cases, smaller
et al., 2011). It was observed that it was not efficient particles increase the lignin condensation and recalci-
and resulted in lower sugar yields in spruce, with or trance to enzyme hydrolysis.
Overall, SEP is an attractive pretreatment method kenaf newspaper, alfalfa, wheat chaff, wheat straw,
considering the low amount of energy required to barley straw, rice straw, bagasse, coastal Bermuda grass,
reduce the biomass size compared to mechanical switchgrass, corn stover, and municipal solid waste. One
comminution. Conventional mechanical size reduction of the benefits is that AFEX only solubilizes a trivial
methods require 70% more energy than SEP to achieve amount of solid material. Also, compared to acid pre-
the same particle size reduction (Mittal et al., 2009). treatment and acid-catalyzed steam explosion, very little
Additionally, SEP is attractive because there are no recy- hemicellulose or lignin is removed. Lastly, the structure
cling or environmental concerns. This too lowers cost. of the material changes such that the result is an increase
SEP is thus recognized as one of the most cost-effective in water-holding capacity and improved digestibility.
pretreatment methods for hardwoods and agricultural Although physically modified, the chemical composi-
wastes. It has been extensively tested on a wide tion of the material following AFEX pretreatment is
array of lignocellulosic feedstock. It has been observed essentially unchanged from its original condition. The
that SEP is less effective for the pretreatment of benefit is illustrated as follows: over 90% hydrolysis of
softwoods. the cellulose and hemicellulose may be obtained after
The most significant limitations include the partial AFEX pretreatment of Bermuda grass where 5% of that
destruction of xylan, incomplete disruption of the is lignin. The result is similar for bagasse except 15%
lignin-carbohydrate matrix, low lignin removal, and of the hydrolysate is lignin (Holtzapple et al., 1992).
lignin redistributes over the surface of cellulose (Chen These low-lignin containing biomasses readily hydro-
et al., 2010). Additionally, there is a risk of producing un- lyze at near theoretical yields of sugars. The resulting
desirable compounds such as furfural, HMF and other sugars ferment rapidly with a high yield into a variety
soluble phenolic compounds. These undesirables inhibit of desired products. Since the AFEX treatment produces
microbial growth and enzymatic hydrolysis. Thus, prior very few inhibitors to the downstream biological pro-
to fermentation, SEP-treated LB must be washed with cesses, a water wash is not necessary (Dale et al., 1984;
water to remove these undesirable materials along Mes-Hartree et al., 1988).
with water-soluble hemicellulose. Unfortunately, this Materials with a high lignin content, around 25%,
wash lowers the overall effectiveness as it washes have proved to be recalcitrant to AFEX. Therefore,
away around 20e25% of the initial dry matter and a AFEX is a less effective pretreatment method for hard-
portion of the soluble sugars (Sun and Cheng, 2002). wood chips, some newspaper material, and nut shells
(Teymouri et al., 2005). AFEX does not require a small
particle size for it to be an effective treatment option
Ammonia Fiber Explosion
(Larson and King, 1986) like steam explosion and hot
Another explosion pretreatment is the ammonia fiber water treatments.
explosion (AFEX) process. Instead of using liquid water The most significant cost is that associated with recy-
under high pressure, liquid ammonia is used. AFEX is cling the ammonia following pretreatment (Kumar et al.,
an effective and somewhat economically attractive 2009a). Since pure ammonia is used in the process, more
method to increase the yields of fermentable sugars stringent environmental and recovery procedures are
from LB (Holtzapple et al., 1991; Holtzapple et al., required. Thus, recycling is necessary to reduce the envi-
1992). In this method LB is exposed to liquid ammonia, ronmental impact and the cost of the procedure. To
not ammonium hydroxide (i.e. no water/moisture), at recover the ammonia, a superheated ammonia vapor,
moderate temperatures and elevated pressures for a at temperatures upward of 200 C, is used to vaporize
longer period of time. After the appropriate residence and strip the residual ammonia from the pretreated
time, the system is rapidly vented allowing the liquid biomass. The evaporated ammonia is then drawn off
to vaporize and literally explode the fibrous material. the system by a pressure controller for final recovery
Typically, 1e2 kg of liquid ammonia is used for each (Holtzapple et al., 1990). Using this recovery method
kg of dry biomass. The system operates at temperatures has demonstrated that over 99% of the ammonia can
below 100 C, pressures above 3 MPa, and is quite be recycled successfully. Even so, the overall capital
tolerant of pH. Any pH under 12 appears suitable. The and operating costs are higher than other comparable
residence time is between 10 and 60 min. Under these methods.
conditions, the system forms few degraded sugar prod-
ucts yet gives a high yield of desirable sugar products
Supercritical Carbon Dioxide Explosion
(Mosier et al., 2005).
AFEX is an attractive treatment method for a variety To address the expense of the AFEX method, the su-
of herbaceous crops and grasses as it significantly im- percritical carbon dioxide explosion method was devel-
proves the saccharification rates. It has been tested on oped. Compared to steam explosion, the supercritical
a variety of LB including aspen chips, softwood and CO2 explosion method produces fewer inhibitory
compounds. Additionally, CO2 is much more environ- attention (Okano et al., 2005). The downside is that bio-
mental friendly than organic solvents used in the orga- logical pretreatment is too slow for some industrial ap-
nosolv method and the ammonia used in the AFEX plications and some material is lost to the
method. Because carbon dioxide is nontoxic, physiolog- microorganism as it is a consumer of hemicellulose, cel-
ically safe and inexpensive it is used in a variety of in- lulose and lignin (Bohlmann, 2006). The microorganisms
dustries, for example, in food and pharmaceutical are also susceptible to poisoning by lignin derivatives
production. The critical temperature of CO2 is 31.1 C (Hamelinck et al., 2003). Biological pretreatment by itself
and its critical pressure is 73 atm. The term supercritical may not be the best solution but it could provide value
refers to a fluid that at standard temperature and pres- when employed in conjunction with other pretreatment
sure would exist in its gaseous state. However, when options.
compressed using high pressures and at temperatures
above the critical point, the gas condenses into a liquid-
Acid Hydrolysis
like density. In this state it retains the characteristics of
mass transfer that are “gaslike” but with the solvating Water is a weak acid by itself; however, adding a salt
power that is “liquidlike” (Kim and Hong, 2001). Carbon to water will enhance the activity of the acid. Aqueous
dioxide molecules are small, like water and ammonia, acids, especially those with a salt, autoseparate into
and thus it penetrates the small pores of LB. It is believed hydrogen cations and hydroxyl anions, where one side
that CO2 forms carbonic acid and thus it should increase of the cleaved sugar polymer receives the hydrogen
the hydrolysis rate. Furthermore, at low temperatures it cation and the other receives the hydroxyl group. One
is thought to prevent significant decomposition of the can apply acid hydrolysis either as a pretreatment or
monosaccharides by the weak acid. However, the pri- as a main hydrolysis step. A variety of acids act well at
mary effect of supercritical carbon dioxide explosion is ambient temperatures to pretreat LB and prepare the
from the explosion whereby it disrupts the biomass material for anaerobic digestion. LB is eventually hydro-
structure and increases the surface area and improves lyzed into monosaccharides, furfural, HMF and other
its vulnerability to enzymatic attack (Conner and volatile products. The lignin, however, condenses and
Lorenz, 1986; Zheng et al., 1998). precipitates out as a result of the pretreatment (Esteghla-
Despite these advantages, the operating and capital lian et al., 1997; Liu and Wyman, 2003; Shevchenko et al.,
costs of the supercritical carbon dioxide explosion pre- 1999).
treatment option remain prohibitive. Concentrated acids are quite powerful, act at mild
temperatures and result in rapid reactions. However,
H2SO4, H3PO4 and HCl are highly toxic, corrosive, and
Biological Pretreatment hazardous. Reactors for acid hydrolysis need to resist
Perhaps the most natural pretreatment of biomass is a corrosion. Furthermore, recovering the concentrated
purely biological method. Nature commonly employs acid from the hydrolysis effluent is important to reduce
lignin-degrading microorganisms such as white, brown the negative environmental consequences and to reduce
or soft-rot fungi (Lee, 1997; McMillan et al., 1999). A costs.
study that investigated the effect of high-yield concen- Hydrolysis using a DA is an effective pretreatment
trated recombinant MnP (rMnP), produced from the for LB (Hinman et al., 1992). It produces high sugar
yeast Pichia pastoris on the biobleaching of kraft pulps yields from some hardwoods, like poplar and aspen.
found that rMnP applied at 30 U/g pulp for 24 h fol- In one study, poplar wood was pretreated with a 2%
lowed by alkali extraction removed a significant quan- sulfuric acid at 190 C for 1.1 min and this was followed
tity of lignin from both hardwood and softwood by an enzymatic hydrolysis (Wyman et al., 2009). In this
unbleached kraft pulps (Xu et al., 2010). The rMnP- particular study, the xylose yield was 18.5% and the
treated pulp was more susceptible to subsequent glucose yield was 64.3% where the raw material
peroxide bleaching compared to the control pulp. contained 25.8% xylose and 74.2% glucose (Wyman
More than 60% of the kappa number was reduced by et al., 2009). In another study of aspen wood, the wood
sequential rMnP treatments and alkaline extractions. was pretreated with a 1.1% sulfuric acid at 170 C for
When using white-rot fungi, such as Ceriporiopsis subyer- 30 min and followed by enzymatic hydrolysis (Tian
mispora, to treat sugar maple chips, the amount of et al., 2011). The xylose and mannose yield was 13 wt%
extracted hemicellulose can be increased (Barber, (18 wt% theoretical contents) and the glucose yield
2007). The biotreatment alters the physical and chemical was 85% following treatment (Tian et al., 2011). See
structures of the LB and removes a portion of the non- Table 27.5 for a comparison of concentrated and DA
carbohydrate mass. pretreatments.
Because biological pretreatment is safe, environmen- There are essentially two classes of DA pretreatment
tally friendly and energy saving it is gaining more processes: high-temperature continuous-flow and low
TABLE 27.5 Comparison of Concentrated and Dilute Acid Pretreatments
Wood Species Particle Size Acid Reaction Condition Effects and Results
Concentrated Hybrid poplar 40e60 mesh H3PO4 83e85.9% 50 C, 30e60 min Enzymatic cellulose
Acid (Zhang et al., 2007) digestibility 97% for 24 h
Douglas fir 40e60 mesh H3PO4 83e85.9% 50 C, 30e60 min Enzymatic cellulose
(Zhang et al., 2007) digestibility 75% for 24 h
Spruce 1e5 mm H2SO4 70 wt% 70 wt% H2SO4 74% pentoses, 69% hexoses
and 30 wt% (50 C, 2 h); 30 wt%
H2SO4 (80 C, 6 h)
Birch 1e5 mm H2SO4 70 wt% 70 wt% H2SO4 73% pentoses, 68% hexoses
and 30 wt% (50 C, 2 h); 30 wt%
H2SO4 (80 C, 6 h)
Dilute Acid Poplar 6.35 mm H2SO4 2% 190 C, 1.1 min 25.8% xylose 74.2% glucose
(Wyman et al., 2009)
Aspen (Tian et al., 2011) 6e38 mm H2SO4 1.1% 170 C, 30 min 72.2% pentoses 84% glucoses

Loblolly pine 35e60 mesh Trifluoroacetic 150 C, 60 min 70.3% pentoses, 22.9% hexoses
(Marzialetti et al., 2008) acid pH 1.65
Pine (Orozco et al., 2011) 1 mm H3PO4 2.5 wt% 175 C, 10 min 100% xylose 13% glucose
Source: Wang and Liu, 2012.
temperature batch processes. High-temperature systems dissolution or diffusion, is where the solvent surrounds
operate at temperatures over 160 C and are appropriate an ion, typically sodium dissolved in water. Traditional
for solutions with a low concentration of solids, between NaOH treatment requires high temperatures to be effec-
5% and 10%. Low-temperature systems operate under tive (Zhao et al., 2008). It may be supplemented with
160 C and are appropriate for solutions with a high urea to lower operational temperatures and improve
concentration of solids, between 10% and 40%. dissolution (Zhao et al., 2008).
Even though a simple acid pretreatment significantly The alkaline solvent then saponifies the intermolec-
improves the rate of a hydrolysis process, it costs higher ular ester bonds that cross-link xylan hemicelluloses
than other physicochemical pretreatment processes. One and other components including lignin and other hemi-
such process is steam explosion and was discussed celluloses. Removing these cross-links increases the
previously in this chapter. Another consideration for porosity of the lignocellulosic materials. This improves
an acid hydrolysis pretreatment is that one must the penetrability of the material to the solvent and
neutralize the hydrolysate prior to subsequent enzy- swelling of the biomass follows. The swollen biomass is
matic hydrolysis or fermentation (Sun and Cheng, 2002). thus more vulnerable to enzymatic and bacterial activity.
Compared with acid hydrolysis, alkaline hydrolysis
generally causes less sugar degradation. That said,
Alkaline Hydrolysis dissolution or solubilization of LB increases with alkali
Alkaline pretreatment is viewed as a viable treatment concentrations. At strong alkali concentrations, peeling
method because of its low energy requirement and low of end-groups may occur. This leads to alkaline hydroly-
capital equipment and operational costs (Zhao et al., sis and degradation of the dissolved polysaccharides.
2008). This process operates at lower temperatures and Furthermore, this may also produce unwanted byprod-
pressures than other pretreatment methods. However, ucts. However, there may be a downstream advantage in
at these conditions, the process is measured in hours subsequent conversion treatments. It increases the inter-
or days vs. minutes or seconds for high-temperature, nal surface area, decreases the DP, decreases crystallinity
high-pressure methods (Karr and Holtzapple, 2000). and separates linkages between lignin and carbohy-
Additionally, one may recover or regenerate many of drates causing an overall disruption of the lignin struc-
the caustic salts. ture (Fengel, 1984). This provides opportunity for
Alkaline pretreatment may follow an SEP and may be increased enzymatic and bacterial activity in down-
followed by an enzymatic hydrolysis pretreatment stream processes.
(Montane et al., 1994; Pan et al., 2006). The initial reac- An alternative process to improve sugar content is to
tions of alkaline pretreatment involve solvation and use aqueous potassium hydroxide, which selectively
saponification. Solvation, similarly associated with removes xylan. Keeping the temperature low, at or
below room temperature, prevents peeling (Hon and the ability of anaerobic organisms to digest the resultant,
Shiraishi, 2001). simpler sugars. Hydrolysis requires extended residence
It appears that monomeric forms of hemicelluloses time. Unfortunately, monosaccharides degrade into
are easily degradable to other volatile compounds. Glu- other nonsugar molecules when subjected for extended
comannans and xylans are particularly vulnerable to times to relatively high temperatures and acid condi-
peeling. However, by pretreating with a 3% NaOH tions (Hsu, 1996; Wyman et al., 2005). The hydrolysis
and 12% urea at 15 C one can achieve a 60% glucose reaction rate accelerates when either a chemical or an
conversion (Zhao et al., 2008). enzymatic catalyst is used and when the material to by
Calcium hydroxide, or slake lime, is yet another hydrolyzed is concentrated.
effective alkaline pretreatment agent. It is one of the Enzyme hydrolysis is highly specific and relatively
least expensive and it is highly recyclable (Karr and fast. Using an enzyme to act on its target polysaccharide
Holtzapple, 2000). Using common lime kiln technology, will convert it rapidly into its component monomers.
one can recover calcium hydroxide by regenerating it Additionally, this will convert the insoluble polysaccha-
from insoluble calcium carbonate. Lime pretreatment ride into a soluble monomer. Enzymatic hydrolysis is
removes lignin and hemicellulose and increases the CrI. best applied after other pretreatment methods that leave
Pretreatment with dilute NaOH decreases the lignin cellulose as a major component. The most common
content within a range of 24e55% to 20% and increases method of saccharification is enzymatic hydrolysis
the digestibility of NaOH-treated hardwood from 14% following acid hydrolysis (Harun, 2010).
to 55%. No effect was observed for softwoods with The enzyme cellulase converts cellulose into glucose.
lignin content greater than 26% (Bjerre et al., 1996). Cellulases are so specific that they only affect cellulose
Dilute NaOH pretreatment causes swelling, which, as and do not treat hemicelluloses in the LB (Wang et al.,
stated previously, has downstream benefits. 2012). There are five general types of cellulases. They
The overall effectiveness of alkaline pretreatment are classified by the reactions they catalyze. These five
depends on the lignin content of the biomass. Further- cellulases are endocellulases, exocellulases, cellobiases,
more, it changes the cellulose structure such that it is oxidative cellulases and cellulose phosphorylases (Bayer
less dense and more thermodynamically stable than et al., 1998). Table 27.6 summarizes the effectiveness
native cellulose (Hendriks and Zeeman, 2009; Liu and on the hydrolysis of wheat straw of Cellulase, alpha-
Wyman, 2003). Glucosidase and Xylananse from T. reesei, A. niger,
and T. longibrochiatum after various pre-treatments.
The high yields and mild conditions are attractive for
HYDROLYSIS commercial applications.
These enzyme structures are complex and can be
Hydrolysis is generally defined as the depolymeriza- found in various bacteria as organized supramolecular
tion of a substance via hydration. An aqueous acid’s ions complexes called cellulosomes (Bayer et al., 1998). These
act to cleave long polymers like cellulose, hemicellulose enzymes are commonly found in fungi such as Tricho-
and lignin into smaller chains. Pretreating LB to undergo derma reesei and Aspergillus niger and in bacteria such
hydrolysis or converting polysaccharides into monosac- as Clostridium cellulovorans (Arai et al., 2006). These
charides will enhance later fermentation by improving source organisms are either aerobic or anaerobic and
TABLE 27.6 Sugar Yield in the Enzymatic Hydrolysis of Wheat Straw after Various Pretreatments
Hydrolysis Sugar Yield, % Max.

Pretreatment Enzymes Mixture Source of Enzyme Condition g/g-DM Theoretical
Dilute H2SO4 Cellulase T. reesei 40 C; pH 5.0 0.612 99.6

Impregnation þ a-Glucosidase A. niger 96 h
0.75% (v/v) Cellulase T. reesei 45 C; pH 5.0 0.565 74
H2SO4, a-Glucosidase A. niger 72 h
121 C Xylananse T. longibrochiatum
2.15% (v/v) Cellulase T. reesei 45 C; pH 5.0 0.672 96.7

H2O2 a-Glucosidase A. niger 120 h
35 C Xylananse T. longibrochiatum
Fine Grinding þ Wet Cellulase T. reesei 50 C; pH 5.0 0.638 92
Oxidation a-Glucosidase A. niger 24 h
Source: Talebnia et al., 2010.

BIOCONVERSIONdCONVERTING SUGARS TO PRODUCTS 477
are either mesophilic or thermophilic. Commercial pro- and slows the rate of enzymatic hydrolysis. There is
duction of cellulase is focused on fungal sources because currently much research devoted to improving the over-
bacterial sources tend to be anaerobic and thus are slow all yield and maintaining a high rate of hydrolysis (Sun
to grow (Duff and Murray, 1996). and Cheng, 2002).
It appears that at least three classes of enzymes act Supplementing cellulase enzymes with other en-
together, synergistically, to hydrolyze cellulose: endocel- zymes is another area of current focus. Conjugating
lulase, exocellulase, and cellobiase. Endocellulase (EC the action of cellulases and hemicellulases is known to
3.2.1.4) randomly breaks internal (b-D-1,4) bonds at increase the rate of enzymatic hydrolysis and result in
amorphous sites that create new chain ends. Exocellu- an overall higher sugar yield. Cellulose is a homopoly-
lase (EC 3.2.1.91) cleaves two to four units from the saccharide, hemicelluloses are heteropolysaccharides.
ends of the exposed chains produced by the endocellu- To obtain a more complete hydrolysis of LB one must
lase and results in tetrasaccharides or disaccharides. consider a multiple-enzyme system and reap the yield
Lastly, the cellobiase (EC 3.2.1.21), otherwise known as of the combined activities.
b-glucosidase, hydrolyzes the exocellulase products
into individual monosaccharides (Coughlan and Ljung-
dahl, 1988; Galbe and Zacchi, 2002; Rabinovich et al., BIOCONVERSIONdCONVERTING
2002; Zhang et al., 2006). SUGARS TO PRODUCTS
The cellulase action occurs in three steps. The first is
adsorption of cellulase onto the surface of the cellulose. Following hydrolysis, converting the resultant
The second is biodegradation of cellulose into ferment- sugars to products is the next step. Fermentation is a bio-
able sugars. Lastly, desorption of cellulase occurs logical option and is the focus of this section. Both
completing the catalytic cycle. chemical/catalytic and biochemical conversions are
Enzyme activity is affected by a variety of environ- common.
mental and substantive conditions. Temperature and At this point, the pretreatment and hydrolysis activ-
pH are known to affect enzyme activity. Most cellulose ities were designed and executed all with the intent of
enzymes show an optimum activity at temperatures in optimizing and preparing for fermentation, the capstone
the range of 45e55 C and at pH values between 4 and process of the bioconversion (Gamage et al., 2010).
5 (Galbe and Zacchi, 2002). For LB applications, the Fermentation is referred to as anaerobic digestion.
optimum pH is shifted upward to between 5 and 6.5 Fermentation is the chemical breakdown of a substance
due to the presence of lignin in the system (Lucas by bacteria, yeasts, or other microorganisms to produce
et al., 2012). These are mild operational conditions. ethanol or other alcohols, lactic acid, lactose, and
These mild conditions lower the overall operational hydrogen (Chandel et al., 2007; Wheals et al., 1999).
costs compared to purely chemical hydrolysis methods. One of the most significant factors in fermentation is
Additionally, substrate concentration, product con- the choice of organism or modification to an organism to
centration, activators, inhibitors and cellulose structure acquire a desired product. Some organisms only metab-
are also significant determiners of enzyme effectiveness olize hexoses while others may metabolize both hexoses
(Detroy and Julian, 1982). and pentoses. Saccharomyces cerevisiae is an old and very
Cellobiase is itself an inhibitor to endo- and exocellu- popular strain of yeast used throughout the food and
lases. Thus, the b-glucosidase activity is crucial for the fuel industries. When added to a batch of material,
efficiency of the hydrolysis process (Coughlan and it will metabolize the glucose component, almost exclu-
Ljungdahl, 1988; Galbe and Zacchi, 2002; Rabinovich sively, into ethanol and carbon dioxide. It will generally
et al., 2002; Zhang et al., 2006). follow the Embden-Myerhof pathway under anaerobic
The structure of cellulose affects the rate of hydroly- conditions when the temperature is controlled around
sis. The cellulose features known to affect the rate of hy- 30 C (Limayem and Ricke, 2012). S. cerevisiae grows
drolysis include (1) molecular structure of cellulose, (2) optimally at this temperature and it also resists high os-
crystallinity of cellulose, (3) surface area of motic pressure and it is tolerant of pH as low as 4.0 and it
cellulose fiber, (4) degree of swelling of cellulose fiber, is tolerant of many inhibitory products (Hahn-Hagerdal
(5) DP, and (6) associated lignin or other materials (Det- et al., 2007). S. cerevisiae remains popular because of its
roy and Julian, 1982). The purer and more refined the high ethanol yield from hexose sugars; it generates
cellulose is, the more ideal the cellulase activity will 12.0e17.0% w/v, which is 90% of the theoretical
be. Higher enzyme activity lowers the enzyme load maximum (Bayrock and Ingledew, 2001; Claassen
and cost for the enzymatic hydrolysis process. et al., 1999).
Lastly, even under ideal conditions, the activity of the Despite all its great characteristics, S. cerevisiae
cellulase enzyme is affected by the age of the enzyme it- cannot metabolize both hexoses and pentoses and
self. The overall activity of the enzyme decreases rapidly thus it is not a great organism for converting LB. In
LB, there is a significant portion of the hydrolysate air, specifically oxygen, then the biomass will combust.
containing hemicelluloses, pentose sugars such as If the amount of air or elements of air is limited then
D-xylose, which may potentially enhance yields gasification will occur. Lastly, if no air is allowed then
(Martin et al., 2002). Identifying and employing an pyrolysis or hydrothermal liquefaction is the outcome.
optimal organism is a great opportunity in fermenta-
tion. The optimal organism ought to be high yielding,
Combustion
able to metabolize both hexose and pentose sugars,
tolerant to high ethanol concentration and tolerant to Combustion is a result of a complicated network of
chemical inhibitors left over from pretreatment and exothermic chemical reactions. The reaction generates
hydrolysis. There are numerous naturally occurring copious amounts of heat and radiation. The reaction
organisms that possess a subset of these characteristics, tends to be self-perpetuating and continues spontane-
but none are ideal. To develop a more advantageous ously due to the large amount of heat generated by the
organism one might have to genetically modify an reaction. Specifically, combustion is when carbon,
organism to achieve one’s goals. Table 27.7 lists several hydrogen, combustible sulfur, and nitrogen in LB react
naturally occurring organisms and their features and with oxygen. The process includes fusion, evaporation,
liabilities (Limayem and Ricke, 2012). pyrolysis, a gas phase, and surface reactions.
Reducing operating costs and product inhibition is Combustion of solids can take place in many forms
another important goal. There are strategies that including evaporation combustion, decomposition com-
combine hydrolysis and fermentation together. Simul- bustion, surface combustion, and smoldering combus-
taneous saccharification and fermentation (SSF) is one tion. Evaporation combustion is when fuel, with a
strategy that has just that in mind. The needed en- relatively low fusing point, fuses and evaporates by
zyme(s) and the corresponding organisms are added heating, and reacts with gaseous oxygen and burns.
together so that enzymatic saccharification of cellulose When gasses such as H2, CO, CmHn, H2O, and CO2 are
and subsequent fermentation of the resultant sugars produced by thermal decomposition and react with
takes place at the same time in the same reactor O2, it is called decomposition combustion. A common
(Dowe and McMillan, 2008). However, SSF requires by-product of evaporation and decomposition combus-
an overall compromise between saccharification and tion is char. Char burns by surface combustion. Surface
fermentation, usually resulting in a less optimum oper- combustion occurs when the material only contains car-
ation. Another strategy is to employ an organism that bon and small amounts of volatile compounds such as
is capable of making its own enzymes for hydrolysis charcoal, oxygen, carbon dioxide, or steam. When these
and of fermenting the resultant sugars. Consolidated compounds diffuse into pores inside or on the surface of
bioprocessing lowers the cost of bioconversion by the solid they burn in a reaction of the surface of the ma-
reducing enzymatic saccharification and fermentation terial. Lastly, smoldering combustion is a slower and
into a single step and eliminates the need for cellulase lower temperature reaction. It is a form of thermal
enzymes (Ladisch et al., 2010; Lynd et al., 2005). decomposition that takes place at a temperature below
Despite the number of prokaryotic and eukaryotic the ignition temperature of the volatile components of
microorganisms that convert sugars to ethanol, most the LB. If the temperature is forced up, smoke might
remain limited in terms of cofermentation, ethanol be produced or the reaction may ignite. If it ignites the
yields, and tolerance to chemical inhibitors, high reaction is referred to as flammable combustion. Indus-
temperatures and ethanol. trial LB conversion processes commonly employ decom-
position or surface combustion.
THERMOCHEMICAL CONVERSION Gasification

The process of converting LB to products using pri- Gasification is the conversion of LB from its solid
marily heat as the engine of conversion is thermochem- form to fuel gas or syngas. Syngas is simply a chemical
ical conversion. Thermochemical processing appears feedstock in its gas phase. These might be CO, H2, CH4,
more promising than bioconversion of the lignin frac- CO2 and N2 as well as char (Balat, 2008b; Demirbas,
tion of the LB in that it serves as a source of process 2004; Li and Suzuki, 2009).
energy and the coproducts have benefits in a life-cycle Gasification is a broad treatment method and pro-
context; however, it has a detrimental effect on enzy- duces a variety of different results depending on how
matic hydrolysis (Lynd et al., 1999, 2005; Lynd and it is controlled. Manipulating pressure, temperature,
Wang, 2004). This method differentiates on how much heating method, and conversion agent produces specific
air is supplied to the conversion, as shown in Figure 27.7. results. Pressure is usually controlled for either normal
If LB is heated in the presence of excessive amounts of pressure (0.1e0.12 MPa) or high-pressure conditions
TABLE 27.7 Advantages and Drawbacks of Potential Organisms in Lignocellulosic-Based Bioethanol Fermentation
Species Characteristics Advantages Drawbacks References
Saccharomyces cerevisiae Facultative anaerobic yeast • Naturally adapted to ethanol • Not able to ferment xylose (Gamage et al., 2010; Hahn-
fermentation and arabinose sugars Hagerdal et al., 2007; Jorgensen,
• High alcohol yield (90%) • Not able to survive high 2009; McMillan, 1994; Rogers
• High tolerance to ethanol (up temperature of enzyme et al., 2007; Talebnia et al., 2010)
THERMOCHEMICAL CONVERSION
to 10% v/v) and chemical hydrolysis
inhibitors
• Amenability to genetic
modifications
Candida shehatae Microaerophilic yeast • Ferment xylose • Low tolerance to ethanol (Banerjee et al., 2009; Ligthelm
• Low yield of ethanol et al., 1988; McMillan, 1994; Sun
• Require microaerophilic et al., 2011; Zaldivar et al., 2001)
conditions
• Does not ferment xylose
at low pH
Zymomonas mobilis Ethanologenic gram-negative • Ethanol yield surpasses • Not able to ferment xylose (Balat and Balat, 2008; Herrero,
bacteria S. cerevisiae (97% of the sugars 1983; Liu et al., 2010; McMillan,
theoretical) • Low tolerance to inhibitors 1994)
• High ethanol tolerance • Neutral pH range
(up to 14% v/v)
• High ethanol productivity
(fivefold more than S. cerevisiae
volumetric productivity)
modification
• Does not require additional
oxygen
Pichia stipites Facultative anaerobic yeast • Best performance xylose • Intolerant to a high (Jeffries et al., 2007; McMillan,
fermentation concentration of ethanol 1994; Nigam, 2001; Shupe and
• Ethanol yield (82%) above 40 g/L Liu, 2012; Zaldivar et al., 2001)
(Continued)
479
TABLE 27.7 Advantages and Drawbacks of Potential Organisms in Lignocellulosic-Based Bioethanol Fermentationdcont’d
480
Species Characteristics Advantages Drawbacks References
• Able to ferment most of • Does not ferment xylose

cellulosic-material sugars at low pH
including glucose, galactose, • Sensitive to chemical inhibitors
and cellobiose • Requires microaerophilic
• Possess cellulase enzymes conditions to reach peak
favorable to SSF process performance
27. DEVELOPMENT OF THERMOCHEMICAL AND BIOCHEMICAL TECHNOLOGIES FOR BIOREFINERIES

• Reassimilates formed ethanol
Pachysolen tannophilus Aerobic fungus • Ferment xylose • Low yield of ethanol (Zaldivar et al., 2001; Zayed and
• Require microaerophilic Meyer, 1996)
conditions
• Does not ferment xylose at low
pH
Escherichia coli Mesophilic gram-negative • Ability to use both pentose and • Repression catabolism (Gamage et al., 2010; Liu et al.,
bacteria hexose sugars interfere to cofermentation 2010; Weber and Boles, 2010;
• Amenability for genetic • Limited ethanol tolerance Zayed and Meyer, 1996)
modifications • Narrow pH and temperature
growth range
• Production of organic acids
• Genetic stability not proved
yet
• Low tolerance to inhibitors
and ethanol
Kluveromyces marxianus Thermophilic yeast • Able to grow at a high • Excess of sugars affect its (Banat et al., 1992; Kumar et al.,
temperature above 52 C alcohol yield 2009b; Weber et al., 2010)
• Suitable for SSF/CBP process • Low ethanol tolerance
• Reduces cooling cost • Fermentation of xylose is poor
• Reduces contamination and leads mainly to the
• Ferments a broad spectrum of formation of xylitol
sugars
modifications
Thermophilic bacteria Extreme anaerobic bacteria • Resistance to an extremely • Low tolerance to ethanol (Georgieva et al., 2008; Kumar
• Thermoanaerobacterium high temperature of 70 C et al., 2009b; Lynd et al., 2002;
saccharolyticum • Suitable for SSCombF/CBP Shaw et al., 2008; Zeikus et al.,
• Thermoanaerobacter ethanolicus processing 1981)
• Clostridium thermocellum • Ferment a variety of sugars
• Display cellulolytic activity
modification
CBP, consolidated bioprocessing.

THERMOCHEMICAL CONVERSION 481
FIGURE 27.7 Overview of thermo-
chemical conversion technologies. Source:
Thermochemical Bain, 2004.
conversion
No air
Excess air Partial air
pyrolysis
combustion gasification
hydrothermal liquefaction
(0.5e2.5 MPa). Temperatures are usually either operated break down the lignocellulosic bonds and crystalline
under low-temperature (<700 C) or high-temperature structure. By doing so under these conditions, new com-
(>700 C) conditions. High-temperature decomposition pounds are formed. Compounds such as char, bio-oil,
may occur at the ash fusion point or above. Indirect and gasses are produced (Thuijl et al., 2003). The bio-
gasification occurs when heating the raw material oil formed by pyrolysis is not easily stored because it
and gasification agent using an external heat source. is unstable and requires additional processing prior to
Direct gasification occurs when heat generated from long-term storage (Adam, 2005).
the reaction of partial gasification of raw material and There are three categories of pyrolysis: conventional,
oxygen is used as the heating source. The gasification fast and flash. Conventional pyrolysis produces solids,
agent is another variable with significant influence on liquids and gasses. Fast and flash pyrolysis produces
the product. An agent is any combination of air, oxygen, primarily liquid and gaseous products (Demirbas, 2005).
or steam. Additionally, carbon dioxide may be used for a
set period of time to affect the product.
There are a variety of gasifiers in use today. Fixed bed,
Direct Liquefaction
flow bed, circulating flow bed, entrained bed, mixing Direct conversion of LB to biofuels is liquefaction.
bed, rotary kiln, twin tower, and molten furnace are Typical products include biodiesel and heavy oils that
examples of industrial gasifiers (Yokoyama, 2008). are typically very viscous. Adding an alkali to the con-
Another method, supercritical water gasification version will enhance the liquefaction process (Itoh
(SCWG), is interesting because water under supercritical et al., 1994; Demirbas, 2005). Hydrothermal liquefaction
conditions has properties that facilitate the transport is an application where thermal depolymerization, or
processes of compounds while remaining a benign me- hydrous pyrolysis, is accomplished using superheated
dia for processing. It even acts as a catalyst for acid/ water under pressure.
base reactions under these conditions (Calzavara et al., Drying feedstock in unnecessary when using hydro-
2005; Nolen et al., 2003; Savage et al., 1995). Of note in thermal liquefaction. Consequently, it is suitable for con-
SCWG is that it takes place in either high- or low- verting any biomass regardless of its moisture content.
temperature conditions (Matsumura et al., 2005). How- Aquatic biomass, garbage, organic sludge as well as
ever, if one adds an alkali catalyst to the processing at LB are all good feedstock candidates for hydrothermal
low temperatures, it increases the conversion into oil liquefaction.
and gas. Additionally, the catalyst lowers the tempera- At the boiling point of water, 100 C, extraction of
ture at which the cellulose decomposes, or the onset of aqueous soluble components is possible. At tempera-
the gasification process (Minowa et al., 1997, 1995, tures above 150 C hydrolysis begins and biomass
1998a,b, Murakami et al., 2012). polymers, such as cellulose, hemicellulose, proteins,
and so on, degrade into monomers. Then at 200 C
and 1 MPa solidlike biomass changes into a slurry, a
Pyrolysis
process called liquidization. At higher temperatures
The conversion of LB by heating is pyrolysis (Balat, below the critical point of water, around 300 C and
2008a; Bridgwater, 2003; Mohan et al., 2006). Depending 10 MPa, liquefaction takes place and oily product is
on the desired product, one chooses the operational con- obtained. If one changes the reaction conditions such
ditions for pyrolysis. Factors such as heating rate, as reaction time or the catalyst, the main product can
reactor temperature, residence time and composition be changed to char, a process referred to as hydrother-
of the feedstock determine the product. The goal of py- mal carbonization. Finally, at a temperature around the
rolysis is to execute the process in the absence of oxygen critical point and in the presence of a catalyst, the
and thus avoid the burning of the feedstock and instead biomass will gasify.
CONCLUSION these pretreatments is to improve the quantity and qual-

ity of materials available to conversion, whether it is
Utilizing LB for energy and fuel production is as old bioconversion or thermochemical conversion. In order
as mankind. However, modern sources of fuel are to compete with contemporary and convenient sources
more cost-effective and convenient to drive and meet of energy it is important to maximize the pretreatment
our contemporary energy demands. Liberating carbon and conversion processes as well as to eliminate and
that has accumulated over millennia in such an unnatu- recycle waste and energy.
rally condensed period of time threatens to alter current The biorefinery holds great promise to enable the us-
climate conditions. Our economic engine has created de- age of biomass as a sustainable and reliable source of en-
pendencies on fossil fuels and has encouraged unhealthy ergy and fuel. The biochemical and thermochemical
relationships between highly industrialized societies like conversion options described here are by no means an
the United States and China and some energy suppliers exhaustive representation of all the studied methods.
around the world. The cycle of growing and using LB for Many more exist in the literature and maybe the best
fuel and energy is a closed and therefore, sustainable sys- methods are yet to come.
tem that consumes as much carbon dioxide as is liber-
ated. Finding technologies that can return modernized References
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C H A P T E R

Introduction 457 Steam Explosion 470

INTRODUCTION lignocellulosic biomass (LB). LB may originate from for-

Bioenergy Research: Advances and Applications 457

Birch 200 µm Oak early wood

Softwood fibers Hardwood fibers Hardwood vessel elements

TABLE 27.1 Major Components of Wood

Cellulose OH OH 40e50 40e50

Lignin 20e30 20e25

Phenolic eOH Per C6C3 unit 0.2e0.3 0.1e0.2

Aliphatic eOH Per C6C3 unit 1.15e1.2 1.1e1.15

The OH groups in the xylose units were partially substituted by OAc

Glucuronoxylan Trace 15e30

OH in the xylo-units were partially substituted by OAc on the C-2 or

Others Cyclitols; tropolones; amino acids, protein, alkaloids, etc.

Ash 0.2e0.5 0.2e0.8

Source: Fengel, 1989.

TABLE 27.2 Summary of Pretreatment Methods and Key Characteristics

Pretreatments Key Characteristics References

TABLE 27.3 The Effects of Cellulose Conversion by Different Irradiation Pretreatments

Maximum Enzymatic Hydrolysis Cellulose

Electron Beam Irradiation Spruce 2 MGy 1e2 mm in thickness 72 0.89

Source: Wang and Liu, 2012.

FIGURE 27.5 A process for the

Cellulose-rich Filtration Regeneration

Pretreatment Initial Disk-Milling Energy Size Reduction

Untreated 699 1.7

SPORL 4.2 594 15.0 75.1

(a) Co-current reactor

(b) Counter-current reactor

Biomass Water with

(c) Flow-through reactor

TABLE 27.5 Comparison of Concentrated and Dilute Acid Pretreatments

Source: Wang and Liu, 2012.

Hydrolysis Sugar Yield, % Max.

Dilute H2SO4 Cellulase T. reesei 40 C; pH 5.0 0.612 99.6

2.15% (v/v) Cellulase T. reesei 45 C; pH 5.0 0.672 96.7

Source: Talebnia et al., 2010.

THERMOCHEMICAL CONVERSION Gasification

Species Characteristics Advantages Drawbacks References

• Able to ferment most of • Does not ferment xylose

27. DEVELOPMENT OF THERMOCHEMICAL AND BIOCHEMICAL TECHNOLOGIES FOR BIOREFINERIES

CBP, consolidated bioprocessing.

CONCLUSION these pretreatments is to improve the quantity and qual-

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