1 Sources of Lignin
Shayesteh Haghdan, Scott Renneckar and Gregory D. Smith
Department of Wood Science, Forest Sciences Centre, The University of British Columbia, Vancouver, BC, Canada
O U T L I N E
1. Introduction to Lignin
2. Lignin Functions
3. Sources of Lignin
3.1 Wood
3.2 Pulp and Paper Industry
1. Introduction to Lignin
The term lignin is derived from the latin name
lignum meaning wood (Mccarthy and Islam, 1999).
It was first isolated from wood in a scientific report
by the French scientist Payen (1838) and later given
its current name in 1857 by Schulze. Lignin was
initially described as an incrustant of cellulose, and
this point is insightful as lignification occurs after the
deposition of the polysaccharide framework. In an
extremely simplified view it is analogous to the
matrix material for a fiber-reinforced composite.
Lignin has several functions with the cell wall such as
changing the permeability and thermal stability, but it
has the primary function to serve as a structural
material that adds strength and rigidity to plant
tissue. In the sense lignin distinguishes lignocellu-
losic biomass from other polysaccharide-rich mate-
rials, by reinforcing the polysaccharide scaffolding of
the cell wall. Its performance is so effective that it
allows trees to outcompete other plants for sunlight
forming the largest organisms on the planet.
As lignin constitutes 15e40% of dry weight of
woody plants, it is the most abundant aromatic
polymer on the earth and the second most abundant
organic polymer after cellulose. Based on yearly
biomass growth rates, the overall production of
lignin is on the order of 5e36  108 tons (dos Santos
Lignin in Polymer Composites. http://dx.doi.org/10.1016/B978-0-323-35565-0.00001-1
Copyright © 2016 Elsevier Inc. All rights reserved.
1 3.3 Sugarcane Bagasse 6
3.4 Agricultural Residues 7
4
4. Lignin Potential 8
5
5 References 8
6
et al., 2014). Hence, lignin has the potential to be an
important source of aromatic chemicals for the
chemical industry, arising from the conversion of
modern era CO2, and its efficient utilization solves
a potential puzzle in creating valuable by-products in
a biorefinery scheme. This reasoning is because if
wood is converted to the billion ton scale for biofuels
and biochemicals, then there will be greater than
300 million tons of lignin potentially available. To
put this in perspective it is roughly the size of the
global polymer market.
As mentioned above, lignin is an aromatic poly-
mer. The monomeric precursors have a phenolic ring
with a three carbon side chain providing a basic nine
carbon structure commonly referred to as a C9-unit
and/or phenylpropane unit as shown in Figure 1.
The side chain is terminated with a primary
hydroxyl group on the Cg, while the Ca and Cb are
connected together with an unsaturated bond. The
phenolic ring is methoxylated (eOCH3) to various
degrees, dependent upon the species; p-coumaryl
alcohol, coniferyl alcohol, and sinapyl alcohol have
none, one, or two methoxyl groups at the 3- and
5-positions, respectively. Based on the lignin mono-
meric composition involved in polymerization, the
resulting lignin is classified into three types: (1) lignin
that contains mainly coniferyl alcohol is called
guaiacyl (G) lignin and is found predominantely in
1
2 L IGNIN IN P OLYMER C OMPOSITES

Figure 1 Examples of C9 monomers: p-coumaryl alcohol, coniferyl alcohol, and syringyl alcohol.

gymnosperms; (2) lignin formed from sinapyl alcohol
is called syringyl lignin (S) and mixtures of G and S
are found in angiosperm lignin; and (3) lignin which
incorporates p-coumaryl alcohol is p-hydroxyphenyl
(H) lignin, and the three types of monomers are
commonly found in grasses. Overall hardwoods have
a G:S ratio that approaches 1:2 and softwoods have
approximately 95% G lignin (Lin and Dence, 1992).
One simple way of determining this ratio is based on
the methoxy content of the lignin, while other tech-
niques can be used to identify the specific C9 struc-
tures either directly using nuclear magnetic
spectroscopy or determined from the derivatized
thioacidolysis products using gas chromatography.
The monomeric units are built into the macro-
molecule lignin from the oxidative radical coupling
of these substructures (Adam et al., 2011; Dinis et al.,
2009; De la Cruz, 2014; Bowyer et al., 2007).
Lignification is initiated when a phenolic hydroxyl
hydrogen atom is abstracted by the enzyme peroxi-
dase to form a phenoxy free radical, typically
referred to as dehydrogenative polymerization, as
described by Freudenberg and Neish (1968). This
phenoxy-free radical will then delocalize to both
aromatic and side chain carbon atoms by the process
of resonance stabilization (Figure 2).
Coupling of these radicals may form ether link-
ages, carbonecarbon bonds, and bonds occasionally
to more than one other phenylpropane unit. Based on
the stability of the radical at each location, there is
a higher probability that certain carbons will host the
free radical. This, in turn, will provide preferred
linkages between lignin units. It has been determined
that approximately 50% of these bonds are b-O-4
ether type (De la Cruz, 2014; Bowyer et al., 2007)
with other bonds associated such as b-5, b-1, b-b,

Figure 2 Resonance stabilization of radicals that lead to interunit linkages in lignin.

1: S OURCES OF L IGNIN
Figure 3 Examples of interunit connections in lignin. Note, the diagram is to simply illustrate possible linkages
and this structure is not a representative “segment” of lignin.
and 5-5 (Figure 3). It is evident that the Cg retains its
hydroxyl group through this process, providing the
native lignin opportunity to also retain a certain level
of hydrophilicity. Furthermore, as indicated in
Figure 3, the benzylic carbon (at the Ca) is typically
highly unstable and undergoes reactions with nucle-
ophilic compounds. These reactions can lead to the
formation of a secondary hydroxyl group at the Ca by
reaction with water which is a reactive site for link-
ages to carbohydrates creating ligninecarbohydrate
complexes. These linkages formed to the poly-
saccharides are both ether and ester linkages
dependent upon the functional groups of the mono-
saccharide (Fengel and Wegener, 1983).
Analysis of lignin impacts several changes to its
native state making it difficult to have an exact
structure of lignin within the cell wall. However,
there are isolation methods that can be used to get
a better idea of the characteristics of a less severely
modified lignin. One such method involves the
resizing of wood into a fine flour through ball milling,
using cellulose-degrading enzymes to remove the
bulk of the polysaccharides and then an acidolysis
reaction to break several of the lignin carbohydrate
linkages (Wu and Argyropoulos, 2003). The isolation
of this enzymatic mild acidolysis lignin (EMAL)
preserves several aspects about lignin and is used as
a standard to compare other lignin isolation methods.
3
When analyzed using quantitative nuclear magnetic
resonance (NMR) spectroscopy, it reveals that the
quantity of functional groups is based on the quantity
of lignin (Granata and Argyropoulos, 1995). It is also
revealed that most lignins have w4 mmol aliphatic
hydroxyl groups attached to the side chain per gram
of lignin and 0.2e1 mmol free phenolic groups per
gram of lignin (Pu et al., 2011). Furthermore, it is
possible to analyze lignin within the whole cell wall
without the need for isolation. This approach requires
the milling of wood into a fine powder and then using
special solvents for cell wall dissolution. Dissolved
wood material is analyzed using two-dimensional
(2D) 13Ce1H heteronuclear single quantum coher-
ence NMR spectroscopy (Mansfield et al., 2012). The
technique can determine the relative concentrations
of interunit lignin structures providing an insight into
the structure of lignin.
As may be inferred from the above description of
isolating EMAL, there are two processes that occur
during delignification. The first involves breakage of
key ligninecarbohydrate linkages. This bond
breakage will allow extractability of the lignin as
seen during mild acidolysis of lignin where dilute
hydrochloric acid is used to break these linkages.
The second process involves cleavage of some of
the interunit bonds of lignin that may reduce
the molecular weight. Hence, delignification
4 L IGNIN
technologies dramatically impact lignin function-
ality and molecular weight. As a result, the proper-
ties of lignin related to its solubility are modified.
Several studies have shown that lignin can be frac-
tionated by using several solvents with largely
different solvent parameters (Moerck et al., 1986). A
small fraction of lignin may be soluble in a nonpolar
solvent like toluene, nonhydrogen bonding solvents
like dichloromethane, while other fractions are
soluble in more polar solvents like aliphatic alco-
hols. The different solubility of the fractions shed
light on the heterogeneous nature of lignin even if it
is isolated from a softwood lignin that contains 95%
guaiacyl lignin. Delignification can modify the
lignin to appreciative degrees by the addition of the
reactants such as sulfur or alcohol to the lignin or
increase the molecular weight (or change the inter-
unit linkages) by reactions of lignin with itself
during delignification. These isolation processes
result in lignin that contains acidic groups, lose
aliphatic hydroxyl groups, increase the free phenolic
groups by breakage of the b-O-4 linkage, and
contain more carbonecarbon bonds between units
(which are referred to as condensed structures).
Because of the variety of intermolecular linkages
between the precursors, lignin is also a highly
heterogeneous polymer (Fengel and Wegener, 1983;
Baucher et al., 1996). The variety of bonds results in
a branched lignin polymer with a potentially cross-
linked three-dimensional structure (Schmidl, 1992).
The recent literature has suggested that lignin may be
more uniform than previous thought, with either
linear chain topologies (Crestini et al., 2011) or even
being capped by specific lignin monomers (Sangha
et al., 2014). However, it is clear that lignin poly-
merization is left up to the fates of thermodynamics
as the polymerization process occurs outside the
control of the cell cytoplasm (Ralph et al., 2004).
Hence, the cellular control is limited to the produc-
tion and release of the monomers involved in ligni-
fication and the enzyme-activated dehydrogenated
monomers will polymerize with the growing lignin
chain.
Another important aspect of polymeric materials is
their molecular weight. Absolute knowledge about
lignin’s molecular weight has been difficult to ach-
ieve as removing lignin to analyze it automatically
impacts the lignin structure. Additionally, lignin
molecular weight measurements suffer from issues
surrounding solubility, aggregation, adsorption, and
fluorescence making it one of the most difficult
IN P OLYMER C OMPOSITES
polymers to analyze. Early experiments looking into
the molecular weight of lignosulfonates suggested
that delignification occurred like breaking a network
polymer (Gorning, 1971). However, several different
isolated lignins have been analyzed with modern
analytical equipment, and lignin usually has
a bimodal distribution with number-average molec-
ular weight between 3000 and 10,000 and weight-
average molecular weight from 8000 to 80,000
dependent upon solution conditions, and lignin type
(Guerra et al., 2007). Many technical lignins
described in the literature either have lower molec-
ular weights because of fragmentation of lignin into
oligomers or much greater molecular weights. When
delignification occurs, a number of reactions can
occur but many involve radical formation and
subsequent radical coupling where lignin fragments
can become bonded, increasing the molecular weight.
Additional heterogeneity of lignin involves how
the structure of this polymer differs within a given
cell wall dependent on its location in the wall, plant
species (hardwood vs softwood), and growth
conditions, especially related to reaction wood
formation (Campbell and Sederoff, 1996; de Wild
et al., 2010). These differences arise from the
monomeric composition available during the ligni-
fication reactions. Overall, one can see the
complexity of trying to analyze a lignin that may be
different in various locations of the cell wall. Ter-
ashima has shown that lignin microstructure is
dependent upon its location in the cell wall. In the
cell wall corners, lignin forms spherical clusters,
while lignin in the secondary cell wall is greatly
reduced in dimensions surrounding the microfibril
lamellar structure of the cell wall layers as shown in
Figure 4 (Terashima et al., 2004). Work with the
Raman spectroscopy has indicated that lignin in
the secondary wall has a preferred orientation along
the microfibril structure (Atalla and Agarwal, 1985).
2. Lignin Functions
Lignin is part of the structural framework in
plants, forming part of the primary load-bearing
element of the cell wall. From an evolutionary
point of view, lignin has been credited as the terres-
trial adaption that permits significant vertical growth.
As an essential part of the cell, lignin supports the
plant by imparting rigidity to the cell wall. The plant
withstands natural environmental stresses because of
1: S OURCES OF L IGNIN
Figure 4 Cell corner region. Large globular modulus form aggregates at random, left and lignin modules (arrows)
are growing along cellulose microfibrils (CMFs) at an almost regular distance, right.
this cell wall building block (Lopes et al., 2011;
Sarkanen and Ludwig, 1971). Lignin not only
provides stiffness to the plant but in conjunction with
the heteropolysaccharides, it provides flexibility
which is fundamental for an appropriate response to
dynamic loads from wind and snow. In addition to
mechanical support, lignin modifies the poly-
saccharide network to make it resistant to outside
organisms. Lignin helps to protect woody tissue from
the microbial and fungal attack encasing the carbo-
hydrate structure, providing reduced accessibility of
enzymes for hydrolysis. Limited solubility and
complexity of the lignin make it resistant to degra-
dation by most microorganisms (Prasongsuk et al.,
2009; Bholay et al., 2012; Berg and Meentemeyer,
2002; Crow et al., 2009; Verma and Dwivedi, 2014).
One can imagine if lignin only contains a single
linkage that would become the cell wall’s Achilles’
Heal. However, with the variety of linkages wood-
destroying organisms require the breakage of both
aryl carbon bonds and aryl ether bonds needing to
expand the cost of production of specific enzymes or
develop nonspecific pathways for delignification. In
addition, lignin is less hydrophilic than the poly-
saccharides helping to change the permeability of the
cell wall by sealing it and enabling water transport
through the vascular tissue (Ten and Vermerris,
2013). Finally, the aromaticity of lignin lends itself to
enhance the thermal stability of wood providing char
layer. This has been exploited with isolated technical
lignin, turning it into carbon fiber material by
controlled high-temperature heating. While lignin is
seen as more thermally stable because of it, the native
structure of lignin is greatly impacted by the thermal
modification and researchers should be cautioned
5
that lignin structure can change during processing at
temperatures used in the production or some ther-
moplastic materials. Such modification includes
depolymerization, loss of the Cg hydroxyl, and
formation of new acidic groups.
3. Sources of Lignin
The source from which lignin is obtained, the
extraction methods and the secondary treatments
applied, have strong impacts on its physical and
mechanical properties (Garcia et al., 2011; Khanam
et al., 2006). Lignin can be derived from various
sources such as wood, pulp and paper, sugarcane
bagasse, and cereal straws using a variety of pulping
methods. In terms of weight, the lignin content in
woody plants from gymnosperms and angiosperms is
the highest with the order of 30e40% while other
sources only contain around 3e25% (Smolarski,
2012). The pulp and paper sector produces a large
amount of lignin (Jungmeier, 2010; Doherty et al.,
2011) with even greater potential from future ligno-
cellulosic biorefineries. Minimal lignin is recovered
from grass, branches, leaves, and solid waste in urban
and rural areas where their lignin content is estimated
to be less than 15% (Wang et al., 2011; Philippidis
and Hatzis, 1997).
3.1 Wood
Lignin has nonuniform thickness in the middle
lamella, and in the primary and secondary cell walls
depending on the plant species and cell type
(Figure 5). Approximately 70% of the total lignin
content of the cell wall is concentrated in the
6 L IGNIN
thickest layer of the secondary cell wall. Lignin
quantity and quality vary naturally among wood
species with 19e28% in hardwoods (angiosperms)
and 24e33% in softwoods (gymnosperms) (Fengel
and Wegener, 1983). In fact, hardwoods, in general,
contain more hemicellulose and less lignin than
softwoods (Bjornsson, 2014). Not only the amount
of lignin varies between hardwoods and softwoods,
the relative concentration also differs in the location
within a tree. The juvenile wood has a higher lignin
content than latewood (De la Cruz, 2014; Bowyer
et al., 2007). Lignin content is also variable within
populations of plants of the same genus. For
example, the average content of lignin ranges from
25% in Pinus monticola to 30% in Pinus palustris
within the genus Pinus. Reaction wood forms
mechanical stress and has different lignin content in
comparison with the normal wood depending on the
conditions and species (Tiimonen, 2007).
Lignin in hardwoods is syringyleguaiacyl type
and in softwoods is typically guaiacyl with limited
p-hydroxyphenyl lignin in both types. Both of these
structures have differences arising from the interunit
linkages. Guaiacyl lignin can undergo coupling
reactions at the 5-position of the phenylpropane unit,
and this provides a significant place for branching and
cross-linking reactions, especially occurring during
Figure 5 Wood cell wall including middle lamella (ML),
primary cell wall (P), layers of the secondary cell wall
(S1, S2, S3), and warty layer (W) (Sjostrom, 1993).
IN P OLYMER C OMPOSITES
delignification process. The presence of syringyl units
makes hardwood lignin more readily removed during
the pulping process by limiting lignin forming
condensed structures at the open methoxy position. In
the case of compression-wood lignin, it is more
difficult to hydrolyze because it contains a higher
proportion of condensed p-hydroxyphenyl units
(Campbell and Sederoff, 1996; Novaes et al., 2010).
3.2 Pulp and Paper Industry
Softwood and hardwood species, and certain types
of annual plants, have commercial interest as a source
of cellulose fibers for the production of paper and
board products. Lignin is not easy to isolate in the
native form from plant material (Leisola et al., 2012).
The pulp and paper industry is the primarily
commercial source of lignin, however, the delignifi-
cation process modifies lignin to various degrees. In
technical fiber liberation processes, such as alkaline
or sulfite pulping, huge quantities of lignin are dis-
solved as alkali lignin and lignosulfonates, respec-
tively. Large amounts of lignin are made available
annually from the pulp and paper industry as by-
products of the delignification process. These sulfite
or sulfate lignins have varying levels of covalently
bonded sulfur resulting in the polymer with different
characteristics than the original lignin (Sainsbury,
2013; Khanam et al., 2006; Lora and Glasser, 2002).
Typically, lignin impurities include low-molecular-
weight sugars and resin acids that are removed during
the purification process. For example, kraft lignin is
usually purified from kraft black liquors which are
complex mixtures of fibrous materials and dissolved
organics such as lignins, hemicelluloses, sugars, acids,
and resins and also inorganic salts such as ash (Wall-
berg et al., 2003). The recent technology in enhancing
lignin recovery from black liquor by CO2 acidification
has been transferred to the industry and has created
a readily available dry lignin powder stream (Ohman
et al., 2013; Kouisni et al., 2012). As shown in Table 1,
in all commercial pulping processes the lignin
extraction methods will affect the value of the products
that can be derived from it and will alter the structure of
the lignin in comparison with the native one (Smo-
larski, 2012).
3.3 Sugarcane Bagasse
Sugarcane bagasse is the fiber that remains after the
sugars have been extracted. As an agro-industrial
residue, sugarcane bagasse (Saccharum officinarum)
1: S OURCES OF L IGNIN
Table 1 Lignin Purity with Its Associated Sources (Holladay et al., 2007)
Lignin Type Lignin Puritya
Lignosulfonates Medium (some reducing sugar
(up to 20 wt%) and sulfur)
Kraft Medium (some ash and sulfur)
Organosolv High (sulfur free)
a
Presence of residual carbohydrates, ash, and proteins depends on feedstock and process.
is another source of lignin raw material. It is a by-
product of the sugarcane industry with approxi-
mately 32e34% cellulose, 19e24% hemicellulose,
25e32% lignin, 6e12% extractives, and 2e6% ash
(Sakdaronnarong and Jonglertjunya, 2012; Rezende
et al., 2011; Pandey et al., 2000). Chemical compo-
sition of sugarcane bagasse is similar to the other plant
cell walls. Each class of plants, grasses, softwoods,
and hardwoods produces a lignin rich in one type of
the phenylpropane repeat unit. Sugarcane bagasse
lignin has a higher proportion of H-type lignin, p-
hydroxyphenyl, and hence a lower methoxy content
than softwood and hardwood lignins (Doherty et al.,
2007). Approximately 250e280 kg of bagasse is
generated from processing each ton of sugarcane
which roughly yielded 54 million tons of bagasse
annually (Canilha et al., 2012). Currently, a large
amount of bagasse is burnt as a low-grade fuel for
energy recovery, and only a limited quantity has been
used to make pulps, board materials, and composites.
It is estimated that 200 million tons of lignin is
produced annually from bagasse (Singh et al., 2005).
3.4 Agricultural Residues
The advantages of using agricultural residues are
threefolds: economic, environmental, and techno-
logical. Unlike wood pulps, agricultural pulps can be
produced using more environmentally benign pro-
cessing and bleaching methods (Clancy-Hepturn,
1998). In the wood pulping process, most of the pulp
is bleached using chlorine or chlorine-based chem-
icals while straw can be treated with minimal addi-
tions of chlorine-free chemicals which results in no
production of toxic chemicals. Moreover, agricul-
tural residues have generally a more porous structure
and a lower lignin content than woody plants which
facilitate their pulping process. Examples of the
7
Potential Products
Dispersants, agricultural chemicals, emulsion
stabilizer, industrial binders, carbon black, ink
and pigments, and concrete additives
Dispersants, carbon fibers, emulsifiers,
activated charcoal, and binders
Aromatic polyols, new diacids, activated carbon,
phenolic resins, carbon fibers, vanillin, phenol
derivatives, and antioxidants
agricultural residues are rice and wheat straws which
are discussed in this section. Rice straw also called as
cereal straw is another source for lignin production.
Total world production of rice straw, Oryza sativa, is
525 million tons per year.
About 90% of the rice straw is produced in Asia.
China has the greatest capacity for pulping rice straw.
It has approximately 30e35% cellulose, 25e30%
hemicellulose, 15e28% lignin, and 4e7% ash
(Marques et al., 2010). The high ash content arises
from the silica in the cell wall limiting the ability to
burn this material without causing a significant envi-
ronmental nuisance. High silica content in rice straw,
as high as 18% in clean rice straw, makes the pulping
process more costly due to increased chemical
recovery difficulties and costs. In addition to rice
straw, wheat straw, Triticum aestivum, is annually
generated in abundance of 529 million tons per year.
When farmed intensively, wheat straw can be
produced in a larger scale. The amount of lignin of
wheat straw varies between 5% and 17% depending
on the geographical location of the plants which is
comparable to hardwoods (Buranov and Mazza,
2008). Wheat straw has one of the highest cellulose
contents of all of the agricultural fibers. Straw papers
are known to possess good printing qualities and are
made from pulp requiring low energy relative to that
required to process wood pulp. Researchers found that
wheat straw must be pulped under conditions of less
energy and fewer chemicals in comparison with the
wood pulps to maximize pulp yields (Clancy-Hepturn,
1998). To make the strongest product, papermakers
will likely combine some stronger hardwood, kenaf,
or hemp pulp with straw pulp. Despite the advantages
of using agricultural residues, the high collection,
transportation, and handling costs associated with
these resources, as well as their seasonal availability,
limit their applications in paper production.
8 L IGNIN
4. Lignin Potential
Currently around 50 million tons of lignin is
produced per year by the pulp and paper sector but only
2% of that is used for applications other than combus-
tion and energy production (de Wild et al., 2014; Fengel
and Wegener, 1983; Schmidl, 1992; Thielemans et al.,
2002). There are limitations in utilization due to the
lignin structure, heterogeneity, and the industrial pro-
cessing costs for delignification (Holladay et al., 2007;
Vanholme et al., 2010; Neutelings, 2011; El Hage et al.,
2009; Chiang, 2005). To improve upon these limita-
tions, different types of modifications are done to
increase its chemical reactivity and uniformity, reduce
the brittleness of lignin-derived polymers, increase its
solubility in organic solvents, and improve the ease of
processing the lignin (Argyropoulos, 2012). Lignin
potentials can also be considered in the production of
additives, resins, and coating materials (Jungmeier,
2010; Vishtal and Kraslawski, 2011). This renewable
aromatic polymer can equally be replaced with
synthetic polymers and aromatic chemicals (Zakzeski
et al., 2012). High antioxidant capacity of lignin and its
applications in polymer enhancement have been
experimentally proved (Piazza et al., 2014). The find-
ings of research on lignin depolymerization showed
that due to the ligninmacromolecular structure of lignin
with many phenolic units, lignin depolymerization can
be used as a large-scale source for production of valu-
able chemicals (Kleinert et al., 2009; Meier et al., 1992;
Horácek et al., 2012). Lignin also has potential to be
used in the fabrication of composite materials.
El Mansouri et al. (2007) showed that exterior-grade
particleboards made with lignin-based adhesives
successfully met the requirements of international
standards. The potential of lignin in polymeric
composites will be discussed in later chapters.
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