Chemicals From Lignin

Hao Luo and Mahdi M Abu-Omar, University of California, Santa Barbara, CA, United States
Ó 2017 Elsevier Inc. All rights reserved.

Introduction

In the past two decades growth in the US chemical industry has led to an estimated revenue of $820 billion in 2016 (Global Business
Reports [GBR], 2016, pp. 8–10), compared to $367 billion in 1995, an increase of 4% per year (American Chemistry Society [ACS],
1996). A DOE report in 2010 indicated that the US chemical industry contributed 2.1% of the total US GDP (Department of Energy
[DOE], 2010), and over 17% of the manufacturing sector (Political Economy Research Institute [PERI], 2011). Over 95% of all
manufactured products today rely on chemistry (International Council of Chemical Associations [ICCA], 2010).
This great success of the chemical industry worldwide, however, comes at a significant cost in energy and adverse, often irrevers-
ible, effects on the environment. World energy consumption in 2013 was estimated to be 5.7
1020 J (International Energy Agency
[IEA], 2015), and was heavily reliant on nonrenewable fossil fuels. Three major fossil fuels (coal, oil, and natural gas) contributed to
over 87% of the total global energy supply in 1973, and this number has only slightly decreased to 81% in 2013 (IEA, 2015). As the
largest industrial energy user, the petrochemical sector accounts for roughly 10% of the total worldwide energy consumption (IEA,
2013). Half of that energy is used by the chemical industry to provide heat, power, and electricity generation; and the other half as
feedstock in manufacturing high-value products (Patt and Banholzer, 2009). Nonrenewable fossil fuels natural gas, coal, and
liquefied petroleum gases account for 53% of the energy supply, while petroleum and natural gas provide the feedstock supply
(DOE, 2007).
Despite the advantages of high energy density and low-cost, nonrenewable feedstocks release greenhouse gases (GHG),
which contribute to global climate change. World GHG emission in 2012 was approximately 48 billion tons of CO2 equivalent
(EPA, 2016). The chemical and petrochemical sector is responsible for 7% of the total emission, roughly 3.4 billion tons of CO2
equivalent (IEA, 2013).
With current rates of energy use, it is likely that both energy demand and CO2 emission will double by 2050. Actions must be
taken to curb GHG emissions. Development of high energy-efficient technologies and utilization of renewable resources help
reduce CO2 emission. According to EIA (US Energy Information Administration [EIA], 2016), about 10% of the total US energy
consumption is based on renewable energy source in 2015. Nonedible lignocellulosic biomass as an earth abundant renewable
resource contributed 50% of the total renewable energy use (Fig. 1). The average energy content for dry lignocellulosic biomass
is around 17–20 MJ kg 1; nonedible lignocellulose is a promising feedstock for making liquid fuels and valuable chemicals
(Agrawal et al., 2007; Singh et al., 2010). Making efficient utilization of biomass is an integral part of solving the energy challenge
and GHG emissions.

Lignin Basics: Structure and Isolation

Lignin in the Biosphere
Lignocellulosic biomass is composed of three major biological polymers: cellulose, hemicellulose (or xylan), and lignin.
Chemical and biological conversion of carbohydrates (cellulose and hemicellulose) has been advanced extensively over the

Fig. 1 Illustration of US energy consumption by energy source, 2015. Adapted from US Energy Information Administration [EIA], (2016). Monthly
energy review. Available at: http://www.eia.gov/totalenergy/data/monthly/archive/00351604.pdf (Accessed on April, 2016).

Encyclopedia of Sustainable Technologies, Volume 3 http://dx.doi.org/10.1016/B978-0-12-409548-9.10235-0 573

574 Chemicals From Lignin

past decade (Xing et al., 2011; Hu et al., 2012; Rose et al., 2015), while lignin remains largely underutilized. The majority of
lignin produced annually by the pulp and paper industry and by biorefineries (estimated at more than 70 billion kg) is burned
for heat at a value of $80 per ton ($0.08 per kg). Lignin is the only natural polymer made of aromatics (Li et al., 2015). It
represents ca. 30% of nonfossil carbon on earth, and is the largest natural reservoir of solar energy (Frost and Sullivan, 2012).
Nevertheless, lignin is often discarded only for its heat value, due to its inherent complex structure and underdeveloped lignin
valorization technologies (Tuck et al., 2012).
Natural abundance of lignin in the biosphere is around 300 billion tons (3.0
1014 kg), and increases by 20 billion tons
(2.0
1013 kg) every year (Frost and Sullivan, 2012). This represents a huge opportunity for deriving value-added products from
lignin feedstock. Currently, annual production of kraft lignin worldwide is around 100 Mtons (1.0
1011 kg) with about 70 Mtons
(7.0
1010 kg) of that coming from the paper and pulp industry. Only 2% out of the 70 Mton was isolated and commercially
utilized, the remaining 98% was burnt for fuel (National Non Food Crops Centre (UK) [NNFCC], 2011). Global production of
isolated lignin is expected to increase to 1.7 Mtons (1.7
109 kg) by 2022 positioning the total lignin market revenue to reach
$6.2 billion (Global Market Insights [GMI], 2016a; Grand View Research [GVR], 2015).

Lignin Structure: Building Blocks and Interlinkages

Lignin is an amorphous three-dimensional phenolic polymer composed of methoxylated propyl phenyl units. The exact structure
and molecular weight of native lignin are not known. Lignin is the major component of support tissue in plants, providing mechan-
ical strength and rigidity (Martone et al., 2009). In plant cell walls, lignin cross-linked with carbohydrates acts as the glue holding
the lignocellulose matrix, cell wall, together (Zakzeski et al., 2010). Biosynthesis of lignin macromolecules is thought to be through
random radical-based polymerization of three monophenolic building blocks: p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S),
which are derived from coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol, respectively (Fig. 2). Softwoods have the highest
lignin content, followed by hardwood, and grass species have the least lignin content (Zakzeski et al., 2010). Lignin monomers are
connected irregularly through in situ interlinkages. The type of linkage varies from species to species, but in general, over two-thirds
are ether linkages (Pandey and Kim, 2011) (Fig. 3). b-O-4-Aryl ether bond is the most abundant linkage among all species,
accounting for 45%–60% of monomers connectivity. Other linkages with relatively high abundance are the 5–5 linkage (10%–
20%) and b-5 linkage (10%–12%).

Lignin Isolation Technologies

The recalcitrant nature of lignocellulosic biomass renders lignin resilient to biodegradation, which hinders the efficient utilization of
lignin (Zhao et al., 2012). In order to make more efficient use of lignin, a pretreatment approach is feasible to separate the different
components of biomass from lignin, and consequently converts native lignin into technical grade lignin. Herein, native lignin refers
to its form in raw biomass, and technical grade lignin to isolated forms post biomass treatment. The latter is often chemically modi-
fied. Research by Lora et al. indicated that structure and component differences of lignin among different species are minor, while
the major differences come from pretreatment processes to isolate lignin (Lora and Glasser, 2002). Isolation techniques which can
derive lignin with high quality and purity are desirable. In detail, isolation of lignin from lignocellulosic biomass generally falls into
two categories. The first one is to dissolve cellulose and hemicellulose, leaving lignin as an insoluble residue. The second approach is

Fig. 2 The three phenolic building blocks that make up lignin and their precursor corresponding to phenolic alcohols.
 Chemicals From Lignin 575

Fig. 3 Common interunit linkages within lignin macromolecules.

Table 1 Comparison of different technical grade lignins and their properties

Kraft Lignosulfonate Soda Organosolv

Lignin purity High Low-medium High Very high

Sulfur content (%) 1–3 3–8 0 0
Molecular weight (kg mol 1) 1.5–5 (up to 25) 1–50 (up to 150) 0.8–3 (up to 15) 0.5–5
Solubility Water, Alkali Water Alkali Organic solvents
Separation techniques Precipitation (pH change) Ultrafiltration Precipitation (pH change) Precipitation (addition of nonsolvent)

Adapted from Frost and Sullivan (2012). High-value opportunities for lignin: Unlocking its potential. Santa Clara, CA: Frost and Sullivan. Available at: http://www.frost.com/sublib/
display-market-insight-top.do?id¼269017995; Kai et al. 2016.

to first dissolve lignin, leaving cellulose and hemicellulose insoluble, followed by recovery of lignin from the solution (Pandey and
Kim, 2011). In industry there are four primary methods of isolating lignin from biomass with all of the methods using techniques to
solubilize and extract lignin first: the Kraft, Sulfite, Soda, and Organosolv processes (Strassberger et al., 2014). The first two are
sulfur-based processes and the latter two are sulfur-free processes. A brief summary of the four technical lignins is provided in
Table 1.

Kraft process
The Kraft process is currently the most dominant technique employed in wood pulping. Wood chips are treated in a hot mixture of
high pH solution, which includes water, sodium hydroxide (NaOH), and sodium sulfide (Na2S) (the mixture of this solution is
called white liquor), at temperatures 423–453 K for approximately 2 h (Pacific Northern National Laboratory [PNNL], 2007).
Lignin is recovered from the final combined liquid (referred to as black liquor), by lowering the pH with CO2. Low pH precipitates
Kraft lignin, which is filtered, dried, and washed to give technical grade lignin. The Kraft process relies heavily on lignin itself as fuel
to operate the relatively expensive chemical recovery boiler system. Consequently, it is unlikely for the lignin produced from the
Kraft process to be largely used in commercial markets or in biorefinery operations for the production of high-value chemicals
(PNNL, 2007). The Kraft process introduces aliphatic thiol groups to the lignin side chains, giving the isolated lignin a sulfur content
1%–3%, which is relatively small compared to the high sulfur environment during treatment (Kai et al., 2016). Lignin sulfonation
can be controlled by adjusting the temperature; this control of the extent of sulfonation can lead to tuning product properties to
either be different or similar to those of lignin isolated from the sulfite process, another widely employed treatment (PNNL, 2007).

Sulfite process
The sulfite process is also used by the paper and pulp industry for producing lignosulfonates. The pulping solution employs salts of
sulfurous acid, either salts of sulfites (SO23 ), or bisulfites (HSO23 ). The common counterions are single-valent sodium (Naþ),
potassium (Kþ), and ammonium (NHþ 2þ 2þ
4 ), and doubly-valent calcium (Ca ) and magnesium (Mg ). The sulfite process can be
carried out in a wide range of pH, 2–12, depending on the cationic counterions. In most cases, the sulfite process is performed under
acidic conditions, using calcium or magnesium as counterions. High pH conditions are rare, but use sodium, potassium, and
576 Chemicals From Lignin

ammonium counterions (PNNL, 2007; Kai et al., 2016). The sulfite process is performed at temperature 403–433 K, for 4–14 h.
Lignosulfonates are recovered from the cooking liquor stream. They are highly water soluble, with high sulfur content (usually
3%–8%) and higher molecular weights compared to lignin produced from the Kraft process (Kai et al., 2016). Lignosulfonates
have low purity. Lignin content is usually 70%–75%, with the remaining mass being carbohydrate, ash, and inorganic salts. Further
commercial and biorefinery utilization requires the removal of sulfur, which would add cost (PNNL, 2007).

Soda process
The soda process uses sodium hydroxide as the cooking liquor to dissolve lignin at approximately 433 K (Upton and Kasko, 2016).
It resembles the Kraft process, except being sulfur free. The soda process is the main method for pulping nonwood biomass (straw,
sugar cane bagasse, etc.) (Lora and Glasser, 2002). Compared with lignin from wood biomass, the nonwood lignin recovered from
the soda process is rich in p-hydroxyl units and lower in molecular weight (Wormeyer et al., 2011). Soda lignin is sulfur free, thus
has high purity and is closer to the composition of native lignin. These properties of soda lignin make it suitable for direct utilization
without need for further purification. Examples of applications of soda lignin include the production of phenolic resins, animal
nutrition, and dispersants (Vishtal and Kraslawski, 2011).

Organosolv process
The organosolv process employs organic solvents as the cooking liquid to treat wood chips. Acetic acid, formic acid, ethanol, and
organic peroxide have all been used in organosolv lignin production (Kai et al., 2016). In the 1990s, a Canadian pilot plant demon-
strated the Alcell organosolv process using both ethanol and ethanol/water as solvents (Lora and Glasser, 2002). Although this
process successfully produced organosolv lignin and wood pulp for papermaking, it is no longer operational due to financial
constraints. One of the major advantages of organosolv is that it produces separate streams of cellulose, hemicellulose, and lignin
(PNNL, 2007). Organosolv lignin recovered from the pulping solvent is sulfur free and shows poor water solubility. It is of high
quality and purity, which makes it ideal for both direct use and upgrading into high-value chemicals. Organosolv lignin typically
has low molecular weight, which can be attractive for making low molecular weight phenols and other aromatic products (Lora and
Glasser, 2002). Despite all of the earlier-mentioned advantages, the high cost in handling and recovering the organic solvents has
limited the development of this treatment technique (PNNL, 2007).

Lignin Valorization: Conversion Into Value-Added Materials

There has been a long-standing saying in industry that “One can make everything from lignin, except money” (Ragauskas et al.,
2014). This embarrassing situation has driven significant amount of effort in the valorization of lignin. In 2007, a report from
DOE reviewed the role of lignin as a renewable material source, and evaluated the technical barriers to lignin utilization (PNNL,
2007). This report identified opportunities for commercialization of lignin products in the near-term (current uses and those
seem possible within 3–10 years), medium-term (5 to perhaps 20 years), and long-term opportunities (more than 10 years and
requiring significant new fundamental knowledge and technology development).
The macromolecular structure of lignin gives it the potential to be valorized into a wide range of different high-value products.
Several review articles appearing recently in the primary literature have discussed different valorization techniques for making high-
value products from lignin. The details of these conversion methods are beyond the scope of this article and will not be discussed
here (Zakzeski et al., 2010; Pandey and Kim, 2011; Wang et al., 2013; Xu et al., 2014; Li et al., 2015). Generally speaking, the valo-
rized products from lignin fall into three categories: power/fuel, macromolecules, and aromatics, based on the commercial value of
these products (Scheme 1). While this section will mainly focuses on the value-added products in these three categories, as well as
some of the routes and obstacles for making commercial progress, examples will be given in each category.

Power/Fuel
Combustion
So far, combustion is the simplest technology for utilization of isolated lignin. Lignin combustion or cocombustion as fuel to
provide energy and heat is widely practiced today in the pulping industry. The average heat value of dry lignin is around 25 MJ kg 1
(2.5
107 J kg 1) (The Bioenergy System Planners Handbook [BISYPLAN], 2012), which is comparable to that of coal 24–
30 MJ kg 1 (2.6–3.0
107 J kg 1) (the Engineering Toolbox). Lignin cofiring with coal was largely used in operation of fired pulp-
ing boilers. Current configurations of the cofiring systems can be divided into direct cofiring, parallel cofiring, and indirect cofiring
(Joint Research Centre [JRC], 2006). Compared with the sole use of fossil fuels, cofiring with lignin was reported to increase the
combustion system efficiency by 38%, and decrease GHG emission by as much as 60% (Khitrin et al., 2012; Scown et al.,
2014). Despite these advantages, combustion still remains as one of the lowest value applications of lignin.

Gasification
Gasification is an important approach for lignin valorization. It is a thermochemical treatment of lignin in the presence of oxygen,
air, and/or steam to produce syngas (when oxygen in use) or producer gas (when air in use). Syngas is a mixture of H2, CO, and
 Chemicals From Lignin 577

Scheme 1 General illustration of lignin valorization process.

a very small amount of CO2; producer gas has higher level of N2 and lower level of H2, CO, and CO2 compared with syngas
(Sikarwar et al., 2016).
Theoretically, 62 mol of hydrogen and 53 mol of carbon monoxide could be generated from gasification of 1 kg of isolated
lignin (Azadi et al., 2013). However, these numbers are never reached in practice due to decreased efficiency during the gasification
process caused by tar formation and several other factors (Huber et al., 2006). Tar is a side product during gasification; it is a black
mixture of condensed hydrocarbons, which includes single ring to 5-ring aromatic compounds (Devi et al., 2003). Tar blocks the
pipes and valves, contaminates the gasification equipment, and is the most severe issue affecting commercialization of lignin gasi-
fication processes (Milne et al., 1998; Qin et al., 2010). The removal or reduction of tar is one of the greatest technical challenges;
successfully handling tar would greatly increase commercial viability of the gasification process. Currently, several practical methods
have been reported to efficiently reduce tar formation, which can be categorized as: modification of operation conditions; use of
gasifier bed additives; and gasifier design modification (Table 2) (Devi et al., 2003).
Temperature and pressure are two of the main parameters that affect tar formation. Generally speaking, increasing the operation
temperature to 1073 K (Narvaez et al., 1996; Yu et al., 1997) and pressure to at least 2.0
106 Pa (Knight, 2000; Wang et al., 2000)
significantly decreases tar formation by 40%–74%. Introducing catalysts into gasification systems has resulted in reducing tar forma-
tion (Sutton et al., 2001). The most widely studied catalysts include Ni-based catalysts, calcined dolomites and magnesites, zeolites,
olivine and iron catalysts (Devi et al., 2003). The efficiency of tar reduction varies with catalyst and loading amount. For example,
a 3 wt.% of calcined dolomite resulted in 40% reduction of tar (Narvaez et al., 1996); a comparable amount of olivine gave a reduc-
tion of tar as high as 90% (Rapagna et al., 2000). Design of the gasifier plays a crucial role in the formation of tar. Gasifiers with
typical designs produce tar in the range of 1.0
103 mg m 3 to 1.0
105 mg m 3 (Milne et al., 1998; Huber et al., 2006). A pref-
erable tar concentration for the gasification engines was evaluated to be less than 10 mg m 3 (Bui et al., 1994), and all of the typical
designs far exceed this evaluated limit. Modification of the typical gasifiers includes introduction of a secondary air injection to the
gasifier, making it a two-stage gasifier (Fig 4.) (Devi et al., 2003). The gasification performed in a two-stage gasifier by Asian Institute
of Technology (AIT) resulted in a final tar content of only 50 mg m 3, which is a significant improvement (Table 2) (Bui et al.,
1994).
Syngas utilization is one of the most technically developed areas. Some of the well-known syngas conversion processes to value-
added products include: production of pure hydrogen through water–gas technology; production of methanol/dimethyl ether
(DMT), and production of diesel as biofuel through Fischer–Tropsch (F–T) technology (Huber et al., 2006).

Table 2 Comparison of different tar removal methods and their efficiency

Operation condition
modification Gasifier bed additives Gasifier design modification

Operation details Temperature  1073 K Addition of catalysts: Ni-based catalysts, calcined Introduction of secondary air injection
Pressure  2.0
106 Pa dolomites and magnesites, zeolites, olivine and iron
catalysts
Tar removal Tar reduction in range of Tar reduction in range of 40%–90% Final tar concentration as low as 50 mg m 3
efficiency 40%–70%
578 Chemicals From Lignin

Fig. 4 Simplified illustration of typical gasifier and secondary gasifier. (A) Typical gasifier. (B) Secondary gasifier. Adapted from Devi, L., Ptasinski,
K. J., and Janssen, F. J. J. G. (2003). A review of the primary measures for tar elimination in biomass gasification processes. Biomass and Bioenergy
24, 125–140; Huber, G. W., Iborra, S., and Corma, A. (2006). Synthesis of transportation fuels from biomass: Chemistry, catalysts, and engineering.
Chemical Reviews 106, 4044–4098.

Scheme 2 Water gas shift (WGS) reaction for hydrogen production.

Production of high purity H2 ( 99.99%) is the largest use of syngas through water gas shift (WGS) reaction (Scheme 2) (Spath
and Dayton, 2003). H2 is a clean high energy source with a heating value of 140 MJ kg 1. The cost of raw material (lignocellulosic
biomass) is generally $2–3 GJ 1, taking into consideration the energy consumption and other factors, this number rises up to $5–
8 GJ 1. In comparison, the commercial value of pure H2 is about $14–21 GJ 1 (Spath and Dayton, 2003).
Methanol is produced from syngas through a high temperature, high pressure catalytic pathway. The first catalyst, developed by
BASF in 1923, utilized ZnO/Cr2O3, and required harsh conditions (623 K, 2.5
106–3.5
106 Pa) (Huber et al., 2006). A new form
of Cu/ZnO/Al2O3 catalyst could catalyze methanol formation under milder condition (493–548 K, 0.5
106–1.0
106 Pa) (Fiedler
et al., 2003; Spath and Dayton, 2003). Methanol is one of the most widely used organic chemicals, and its conversion to other value-
added products are well established, such as production of formaldehyde, methyl tertiary-butyl ether, acetic acid, methanol to gaso-
line conversion, methanol to olefin conversion, etc. (Wender, 1996; Keil, 1999; Dybkjaer and Christensen, 2001). Commercial
value of methanol is about $ 13–14 GJ 1 (without distribution costs and taxes).
F–T synthesis is another main valorization technique for syngas conversion into liquid hydrocarbons. This technique was first
introduced by Fischer and Tropsch in the 1920s, with Fe and Co catalysts. Other group VIII transition metal oxides were later found
to be efficient for catalyzing F–T synthesis (Adesina, 1996). Temperature of F–T reaction is kept below 673 K, usually in the 473–
623 K range; pressure is controlled in the range of 1.0
106–4.0
106 Pa (Spath and Dayton, 2003). One of the world premiere
examples in using F–T technique to convert syngas is the Sasol Oryl plant, located in Qatar. It has the capability to produce
5406 m3 of gasoline and diesel per day from biomass-derived syngas (Lin and Huber, 2009). F–T products have a wide range of
prices. Generally, they are within the range of $13–30 GJ 1, without distribution costs and taxes (Tijmensen et al., 2002).

Pyrolysis
Pyrolysis of lignin is a thermal depolymerization treatment in the absence of oxygen, and produces noncondensable gases, liquid
oil, and solid as products. There is a wide temperature range for pyrolysis, which is generally from 623 K to as high as 1273 K (Li
et al., 2015). Pyrolysis is one of the most straightforward way to break down lignin for the production of bio-oil. Technically, pyrol-
ysis can be subdivided into six different categories, based on different process conditions: fast pyrolysis, slow pyrolysis, intermediate
pyrolysis, flash pyrolysis, vacuum pyrolysis, and ablative pyrolysis (Patel et al., 2016). Among them, fast pyrolysis is the most widely
used technique in terms of lignin valorization into liquid bio-oils. It has the advantages of moderate operation temperature (673–
823 K) and low residence time (Iribarren et al., 2012; Isahak et al., 2012).
Liquid bio-oil is the main product from lignin fast pyrolysis. It is a complex mixture of aromatic and nonaromatic compounds,
with a wide molecular weight distribution (Azadi et al., 2013). Addition of catalysts into the pyrolysis system is one way to signif-
icantly enhance the selectivity toward value-added hydrocarbon products. Zeolites (ZSM5, H-ZSM5, and H-USY) showed to be
 Chemicals From Lignin 579

among the most efficient catalysts in shifting the products toward more deoxygenated compounds: about 75 wt.% liquid products,
which are aromatic hydrocarbons (Ma et al., 2012). Raw liquid bio-oil from lignin pyrolysis is corrosive and highly oxygenated
(Brown et al., 2013). It is upgraded through technologies such as fluid catalytic cracking (Corma et al., 2007) and hydroprocessing
(Elliott et al., 2009). The refined bio-oil can be further used for generation of electricity (Martone et al., 2009), commodity chem-
icals (Nowakowski et al., 2010), and renewable gasoline and diesel (Ahmad et al., 2010). Commercial value of upgraded bio-oil is
affected by several factors including labor, material transportation, facility maintenance, and utility costs (Jahirul et al., 2012). One
example using bio-oil as fuel is estimated to have a minimum fuel selling price of $2.6 gal 1 ($ 0.7 L 1) (Brown et al., 2013).
All of the approaches discussed so far fall within the near-term opportunities categorized by DOE, meaning that the technologies
are currently available, but the value of the valorization products remain relatively low. One major competition in the fuels area is
price competitiveness with fossil fuels.

Macromolecules
Being a polymer, lignin has potential for commercialization in materials applications. Currently, around three quarters of the
commercial products from lignin take advantage of this property (PNNL, 2007). The recalcitrant nature of lignin makes the depo-
lymerization process energy intensive and economically costly. Thus, the direct use of lignin polymer as precursor for the production
of value-added materials without additional depolymerization is promising (Upton and Kasko, 2016). Some of the well-studied
lignin-based macromolecular materials include carbon fiber and polyurethane (Strassberger et al., 2014).

Carbon fiber
Carbon fiber as of 2011 has an annual global market of 46,000 metric tons valued at $1.6 billion. This market is expected to increase
to 140,000 metric tons with a value of $4.5 billion by the year 2020 (Frost and Sullivan, 2012). Currently, the main constraint on
carbon fiber market growth is its high price, $18 kg 1 (Frost and Sullivan, 2012). The reason for the high price is the high cost of its
precursor polyacrylonitrile (PAN), which costs $15 kg 1 (SAE International, 2013) Lignin as a natural low-cost carbon source with
high carbon content (over 60% carbon by mass), has been proven to be an ideal low price precursor for carbon fiber synthesis
(Mainka et al., 2015).
The process to obtain carbon fiber from lignin includes several techniques: melting spin of isolated lignin; oxidative stabilization
of lignin fiber; carbonization under N2; surface treatment and sizing (Baker and Rials, 2013; Ragauskas et al., 2014). Compared with
PAN, two of the advantages for using lignin as a precursor are lower melting temperature and faster stabilization capability (Baker
and Rials, 2013). However, as the major source of lignin comes from Kraft lignin, the difficulty in recovering pure lignin leads to
lignin-based carbon fiber with poor mechanical properties compared with traditional PAN-based carbon fiber (Ragauskas et al.,
2014). Highly amorphous structure of lignin results in formation of disordered glassy carbon during pyrolysis (Saha et al.,
2013). Nowadays, the major technical challenge for using lignin as carbon fiber precursor comes from the difficulty in melt spinning
(DOE, 2016). Several research techniques have been developed to address this problem include purification and chemical modi-
fication of lignin. Organic solvent purified lignin (Baker et al., 2012) proved to have excellent spinnability characteristics as
a precursor for producing carbon fiber compared with untreated lignin. In addition, chemical modification of lignin using acid
anhydrides (acetic, succinic, phthalic, and maleic) with tetrahydrofuran and methanol as a solvent showed similarly favorable
results (Chatterjee et al., 2014).
A promising market for carbon fiber is the automotive industry. It has been reported that 40%–50% of structural steel could be
replaced with carbon fiber composite materials (Ragauskas et al., 2014). However, compared with the price $4 kg 1 for regular steel
and $8 kg 1 for high strength steel (Jahn et al., 2012), carbon fiber from PAN has an obvious disadvantage due to its high price.
Furthermore, market research has shown that the automotive industry would not pay more than $7–11 kg 1 for carbon fiber mate-
rial (Frost and Sullivan, 2012). Oak Ridge National Laboratory (ORNL) is currently the leader in developing high-quality, low-cost
lignin-based carbon fiber. A recent estimation by ORNL indicated that the lignin-based carbon fiber could be sold at a commercial
value of $12 kg 1, which is quite close to the target range for the automotive industry (Frost and Sullivan, 2012).

Polyurethane
Polyurethane is one of the most versatile polymers with a wide variety of applications. Its global industry revenue was $52 billion in
2015, and the value is expected to increase to $77 billion by 2023 (Global Market Insights [GMI], 2016b). A typical polyurethane
synthesis pathway includes the reaction of diisocyanates and polyols with terminal hydroxyl groups (Scheme 3) (Engels et al.,
2013). Polyurethane exists both in a rigid form and a flexible form. Rigid polyurethanes are commonly used as insulation and

Scheme 3 Typical synthesis of polyurethanes by using diisocyanate and hydroxyl group terminated polyols.
580 Chemicals From Lignin

floating material, while the flexible variants are used more for cushioning and packaging material (United Nations Environment
Programme [UNEP], 1996). Lignin as a polymer with large numbers of hydroxyl groups has been shown to be able to replace poly-
ols in synthesizing polyurethane (Zhang et al., 2015).
Lignin can be directly incorporated as a polyol in polyurethane synthesis (Strassberger et al., 2014); or chemically modified
before the utilization (Nadji et al., 2005). In order for lignin to incorporate successfully into polyurethanes with different properties,
several factors have to be adjusted, such as reaction conditions, the employed diisocyanates, and chemical modification on lignin
itself (Duong et al., 2014). For example, using Kraft lignin and methylene diphenyldiisocyanate, Duong et al., 2014) generated
a high molecular weight polyurethane (920,000 g mol 1) by controlling the reaction temperature at 80 C (353 K) and reaction
time to 3 h (Duong et al., 2014). Introducing amine groups into lignin improves its water solubility and reactivity with isocyanate.
The resulting modified waterborne polyurethane proved to have improved mechanical and antiaging properties. Compared with
traditional polyurethane, lignin incorporated polyurethanes show superior physical properties in some instances. One drawback
of using lignin or modified lignin in producing polyurethane is that the resulting product exhibited more rigid and brittle charac-
teristics compared to conventional polyurethane. Aniceto et al. (2012) indicated that a technique called oxypropylation could graft
the poly(propylene oxide) on lignin, consequently converting it into liquid polyols. In this scenario, the hydroxyl groups are opti-
mized for polyurethane formulation.

Other macromolecules
Lignin can also be used for other macromolecular materials such as polymer modifiers, adhesives, and resins (Lora and Glasser,
2002; Ragauskas et al., 2014; Strassberger et al., 2014; Upton and Kasko, 2016; Zhao and Abu-Omar, 2015). In all these cases, lignin
can be used directly as a macromonomer, or can be chemically modified before forming a final resin or thermoset (PNNL, 2007).
Since lignin from different biomass sources and isolation processes always has different properties, proper chemical and catalytic
processes need to be developed for each specific case. Thermoset and resin macromolecules have a large commercial market, and the
values of lignin valorized macromolecular materials are significantly higher than using lignin as a source for power and fuel. In
general, this category falls in the DOE’s medium-term opportunity (PNNL, 2007).

Aromatics
Lignin is the only natural source for aromatics (Li et al., 2015). At first glance, it may seem to be straight forward to convert lignin
into monomeric aromatic products, but the complex structure of lignin as well as the highly cross-linked biological matrix in ligno-
cellulosic biomass severely hinders conversion efficiency and selectivity. Monomeric aromatic compounds are among the highest
value lignin valorization products, and this area of research and development falls into DOE’s long-term opportunities (PNNL,
2007). So far, the vast majority of aromatic products are produced from petroleum feedstock. New technological developments
for efficient depolymerization of lignin and upgrading into aromatics should contribute to reducing our reliance on fossil resources
(Frost and Sullivan, 2012).

Depolymerization technologies
A large amount of research has focused on different technologies to depolymerize lignin, which can generally be categorized as:
pyrolysis, gasification, hydrogenolysis, chemical oxidation, or hydrolysis under supercritical conditions (Nakamura et al., 2007;
Zakzeski et al., 2010; Pandey and Kim, 2011; Wang et al., 2013; Li et al., 2015). In general, a depolymerization process breaks
the interunit linkages within the lignin macromolecule, converting complex lignin polymers into oligomers or monomeric aromatic
products to be upgraded to specialty fuels and chemicals. Among all the well-studied technologies, chemical treatment is considered
as one of the most effective depolymerization pathways, aiming to recover aromatic monomers from lignin. Chemical depolymer-
ization, especially using heterogeneous catalysts, has the advantages of high efficiency, product selectivity, moderate reaction condi-
tions, and ease of reaction control (Wang et al., 2013).
A broad range of transition metals have proven to be successful in catalyzing lignin depolymerization to phenolic products.
Examples are Pt, Ru, Rh supported on active carbon (Yan et al., 2008), Cu/Mg/Al (Matson et al., 2011), ZrO2–Al2O3–FeOx (Yoshi-
kawa et al., 2012); 4.4 wt.% formic acid together with 0.15 wt.% Pd (Liguori and Barth, 2011); g-Al2O3-supported Ru, Ni, NiMo,
CoMo (Partil et al., 2011), Co–Mo–S supported by Al2O3 (Jongerius et al., 2012); bimetallic catalysts NiPt/C, NiCu/C, and Zn/Pd/C
(Song et al., 2012; Parsell et al., 2015); and Ni/C (Song et al., 2013; Luo et al., 2016). Under heterogeneous catalytic treatment, the
depolymerized products are in the range C6–C9 aromatics, the product selectivity varies case by case, depending on the catalyst and
specific reaction conditions. However, due to the expense of noble metal catalyst, difficulties in separations of multiphase reaction
streams, and required high pressures, most of these treatments have been limited to research scale.

Aromatic products from lignin

Examples of some high-value aromatic products that can be derived from lignin depolymerization include benzene, toluene, xylene
(BTX), phenol, and vanillin (PNNL, 2007).

BTX
BTX represented a $120 billion market in 2010, and is projected to grow at the rate of c. 4.4% per year from 2010 to 2020 (Frost and
Sullivan, 2012). Currently, all of the BTX comes from petroleum. The global production of BTX was around 100 million metric tons
 Chemicals From Lignin 581

(1.0
1011 kg) in 2010 (Frost and Sullivan, 2012). Lignin-based BTX production is currently in the R&D stage, and is expected to
reach commercial markets in 10–20 years (ACC, 2011). The technology to convert lignin into BTX is a two-step process: the first step
includes lignin depolymerization into oxygenated monomer aromatics through CeO bond cleavage; followed by a second step of
hydrodeoxygenation (HDO) and demethoxylation (Jongerius, 2013). However, with some of the most common noble metal cata-
lysts (Pt, Rh, Pd, Ru), the above pathways always result in over hydrogenation of the aromatic products, leading to the formation of
cyclic alkanes (Lee et al., 2012; Zhao and Lercher, 2012). In 2013, Jongerius reported that by using a novel catalyst system (CoMo/
Al2O3 and Mo2C/CNF), lignin after liquid phase reforming treatment could be effectively converted to BTX. BTX are used as precur-
sors for the production of a series of materials, such as resins, nylon fibers, polyurethane, and polyester. Efficient technologies to
derive BTX from lignin have the potential to increase the value of traditionally wasted material.

Phenol
Phenol is mostly made from cumene, which in turn is produced from alkylation of benzene. The global market for phenol is around
8 million metric tons (8
109 kg), valued at $12 billion in 2010 (Frost and Sullivan, 2012). Similar to BTX, the lignin to phenol
depolymerization also needs 10–20 years to reach commercial markets. Lignin is rich in both aliphatic and phenolic hydroxyl
groups, the HDO of lignin produces phenolic products with different methoxylation degrees. Methoxy groups can be removed
through demethoxylation by using catalysts such as Mo2N and CoMo/Al2O3 (Sepulveda et al., 2011; Jongerius, 2013). Phenols
are widely used in the formation of formaldehyde resins as well as polyurethane (Frost and Sullivan, 2012). Today, the price of
phenol is directly affected by oil, getting the technology of converting lignin into phenol commercialized could significantly expand
the use of naturally derived phenols and expand their commercial market.

Vanillin
Vanillin has been reported to be commercially produced from lignin since 1937. The global market for vanillin in 2011 was esti-
mated to be 16,000 metric tons (1.6
1011 kg), with a value of $230 million. About 20% of the synthetic vanillin comes from valo-
rization of lignin, and the remaining 80% comes from crude oil (Frost and Sullivan, 2012). The difference between vanillin and BTX
or phenol is that it is considered as an end product, rather than a platform chemical. Vanillin is well known for its use as the world’s
largest flavoring agent (Strassberger et al., 2014). Another difference between vanillin and BTX or phenol is that production of
vanillin from lignin is through oxidative catalytic pathway, instead of hydrogenolysis pathway (Werhan et al., 2011). Borregarrd
is the industry leader in commercial production of vanillin from lignin, which utilizes oxidative depolymerization of lignosulfonate
from sulfite pulping (Frost and Sullivan, 2012). The increased demand for natural vanillin is driving industrial interest in efficient
production of high-quality vanillin form lignin.

Environmental and Sustainability Benefits

Our heavy reliance on fossil fuels has led to significant increase in GHG, which is the main cause of climate change. In the United
States alone, GHG emission was estimated to be 5.1
1012 kg in 2012 (EPA, 2015). Coal combustion as the single largest contrib-
utor is responsible for the release of 1.6
1012 kg GHG (EPA, 2015). Moreover, fossil fuels are not renewable and will eventually
reach unsustainable levels, which would become a threat to our global energy system. All of these factors point to the importance
and urgency in developing renewable energy sources and sustainable technologies. Using nonedible lignocellulosic biomass to
provide fuels and materials is part of the solution to sustainability. In the coming decades, society will see a shift from fossil
feedstock-based chemical industry to one that relies on renewable feedstock for making fuels, chemicals, and materials. The US
Departments of Agriculture and Energy have set up ambitious goals to derive 20% of the US transportation fuel and 25% of the
US chemical commodities from biomass by 2030 (Zakzeski et al., 2010).
Lignin combustion or cocombustion with different fossil fuels presents the near-term opportunity to reduce a significant amount
of gaseous pollutants such as CO, CO2, NOx, and SO2. As indicated by Farrell et al. and Scown et al., a general GHG emission by
gasoline combustion is 95 g CO2 eq MJ 1, while using lignin as a substitute energy source, this emission is reduced by 60% (Farrell
et al, 2006; Scown et al., 2014). Lignin cofiring with coal in a general power plant can also result in a 40% reduction in life-cycle
water consumption (Scown et al., 2014).
Renewable products from lignin gasification and pyrolysis are used as clean and high efficient energy source in comparison with
traditional fossil fuels. H2 has very high heating value (140 MJ kg 1), much higher than common fossil fuels (normally 10–
50 MJ kg 1), and its combustion causes no environmental pollution (World Nuclear Association [WNA], 2016). However, despite
advantages, there is an intense debate on hydrogen utilization, mainly focused on the environmental impacts during the production
process (Zehner, 2012). Methanol derived from lignin gasification syngas has also been proven to result in reduction of toxic gas
emissions: addition of methanol in a spark engine together with gasoline results in a reduction of up to 40% in CO emission and
20% in hydrocarbon emission (Spath and Dayton, 2003). Compared to conventional fuels, F–T fuels and diesels from lignin pyrol-
ysis contain no sulfur and low aromatics, consequently resulting in superior combustion characteristics and less emissions of CO
and NOx (Spath and Dayton, 2003). Incorporating these renewable sources into traditional facilities, which are operated by burning
fossil fuels, will deliver environmental benefits.
Lignin as a renewable precursor, utilized in producing macromolecules, can potentially replace fossil-based materials and toxic
chemicals. Use of lignin-based carbon fiber in the automotive industry can significantly reduce vehicle weight and improve fuel
582 Chemicals From Lignin

economy (PNNL, 2007). Recent research has illustrated a novel pathway for producing polyurethanes with lignin and soybean oil,
avoiding the use of environmentally hazardous isocyanates (Lee and Deng, 2015). Lignin’s aromaticity makes it a promising feed-
stock for producing aromatic products. However, due to current technological limitations, the vast majority of aromatic products
being used are derived from petroleum. With the development of new technologies on the lab scale for deriving monomeric
aromatics from lignin, commercialization can be realized eventually and in the long-term lignin may play an important role in
decreasing the demand for oil.

Conclusion and Perspective

Lignin, traditionally a waste byproduct of paper and pulp and biorefining, is now attracting more attention than ever. The field of
lignin valorization has seen significant growth and advances in the past decade. Lignin’s aromatic properties has strong market
potential. Lignin utilization is both environmentally and sustainably beneficial. However, with current technologies, lignin utiliza-
tion is still largely limited to relatively low value fuel and power supply. Commercialization of lignin as precursor for high perfor-
mance macromolecular materials and aromatic products requires further research and development. There are still barriers existing
between the analysis of intrinsic lignin structure, processing of lignin depolymerization, and final product application. Each of these
areas is being studied exhaustively, but there is serious lack in synergy and collaborations. The translation of new laboratory trans-
formations and reactions to scalable commercial products requires a strong collaboration across different disciplines in science and
engineering, and better understanding of the economics of the entire supply chain. There is also always the question of feedstock
variability from location to location as well as from one growing season to another. Nevertheless, with these challenges comes an
opportunity in which lignin can be a substitute to traditional fossil-based feedstock for many products. Furthermore, governments
can play an important role in catalyzing commercialization by setting bold policies that push for fossil feedstock replacements.
Multidisciplinary and collaborative team research in lignin valorization is expected to continue to grow and thrive in the near future.

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Relevant Websites

http://bisyplan.bioenarea.eu/html-files-en/04-01.html.
http://www1.eere.energy.gov/manufacturing/pdfs/v2020_alternate_feedstock_report.pdf.
http://www.eia.gov/totalenergy/data/monthly/archive/00351604.pdf.
https://www3.epa.gov/climatechange/Downloads/ghgemissions/US-GHG-Inventory-2015-Main-Text.pdf.
https://www.epa.gov/sites/production/files/2016-08/documents/climate_indicators_2016.pdf.
http://www.frost.com/sublib/display-market-insight-top.do?id¼269017995.
https://assets.kpmg.com/content/dam/kpmg/pdf/2016/02/global-business-reports-us-chemicals-2016.pdf.
https://www.gminsights.com/industry-analysis/lignin-market-report.
https://www.gminsights.com/industry-analysis/polyurethane-PU-market.
http://www.grandviewresearch.com/industry-analysis/lignin-market.
https://www.iea.org/publications/freepublications/publication/ETP2012_free.pdf.
http://www.osti.gov/bridge.
http://www.nnfcc.co.uk/publications/nnfcc-renewable-chemicals-factsheet-lignin.
http://www.engineeringtoolbox.com/coal-heating-values-d_1675.html.
http://www.world-nuclear.org/information-library/facts-and-figures/heat-values-of-various-fuels.aspx.
http://www.articles.sae.org/11618/.
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Further Reading
McCarl, B.A., Peacocke, C., Chrisman, R., Kung, C.C., Sands, R.D., 2009. Economics of biochar production, utilization and greenhouse gas offsets. In: Lehmann, J., Joseph, S.
(Eds.), Biochar for environmental management. Earthscan, London.
The Engineering Toolbox. Available online at: http://www.engineeringtoolbox.com/coal-heating-values-d_1675.html.
International Energy Agency [IEA]. (2012). Energy technology perspective. Paris: OECD/IEA. Available at: https://www.iea.org/publications/freepublications/publication/ETP2012_
free.pdf.