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A concise review of current lignin production, applications, products and their

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 Industrial Crops & Products 139 (2019) 111526

Contents lists available at ScienceDirect

Industrial Crops & Products

journal homepage: www.elsevier.com/locate/indcrop

A concise review of current lignin production, applications, products and T

their environmental impact
D.S. Bajwaa,⁎, G. Pourhashemb, A.H. Ullahb, S.G. Bajwac
a
Department of Mechanical and Industrial Engineering, Montana State University, Bozeman, MT, USA
b
North Dakota State University, Fargo, ND, USA
c
Montana State University, Bozeman, MT, USA

ARTICLE INFO ABSTRACT

Keywords: Lignin is the second most abundant natural material on the earth. Commercially, it is generated as a waste
Lignin production product from the paper and ethanol production. The worldwide production of lignin is approximately 100
Organosolv lignin million tonnes/year valued at USD 732.7 million in 2015. It is expected to reach $913.1 million by 2025 with
Lignin applications compound annual growth rate (CAGR) of 2.2%. Two principal categories of lignin are ligno-sulphonate (˜88%)
Techno-economic analysis
and kraft lignins (˜9%), however a new category organosolv (˜2%) is now gaining popularity due to the pro-
Life-cycle assessment
duction of second generation biofuels (bioethanol production). The organosolv lignin segment is expected to
experience the highest growth over the coming years, at an estimated CAGR of over 5% from 2016 to 2025.
Chemically lignin is a polyaromatic macromolecule. The complexity and richness of its functional groups makes
it attractive for converting into a variety of value added products like high performance carbon fiber, bio-oil,
vanillin, and phenolic resin to name a few. Over the years lignin has been predominantly burnt as fuel for heat
and power. Less than 2% of the available lignin was sold, primarily in the formulation of dispersants, adhesives
and surfactants. However, in the last decade lignin-based research and new product development has picked
significant momentum due to the bio-refinery concept as aging pulp and paper mills need to diversify their
products portfolio to maintain their vitality. The emerging biofuel/bioenergy technologies are working to de-
velop value-added co-products from lignin and bio-oil as a means of making the processes more cost effective.
There is a resurgence in the demand for lignin for use in binders, adhesives, bioplastics, concrete admixtures and
biomedical applications. Effective “upstream” and “downstream” valorization techniques are facilitating fine
tuning of lignin as a building block for high value chemicals. Other market dynamics driving lignin use are
stringent regulations for dust control, demand for high quality concrete admixtures and dispersants, and carbon
rich products (activated carbon, carbon filer, resins etc.). To further accelerate development of lignin based
products consumer awareness and gap between research and development and consumer products need to be
reduced.

1. Introduction
Lignin is the second most abundant naturally occurring complex
organic material on the earth. Traditionally, it is considered as low-
value waste product. However, it has been established that lignin can be
used to make high-value products such as syngas, carbon fiber, phenolic
compounds, various oxidized products, and multifunctional hydro-
carbons (Agrawal et al., 2014; Luo and Abu-Omar, 2017; Ragauskas
et al., 2014; Ľudmila et al., 2015). Pulp and paper industry is known as
a traditional source of lignin, however, the advent of new cellulosic
biorefineries will introduce an excess supply of non-sulfonated lignin.
Currently 50–70 million tonnes of lignin is produced annually at pulp
and paper facilities world-wide (Luo and Abu-Omar, 2017; Mandlekar
et al., 2018). It is estimated by 2030, this number will increase by 225
million tonnes per year as the annual production of lignin, a byproduct
of biofuel production increases since Renewable Fuel Standard (RFS)
program has mandated the production of 60 billion gallons of biofuel
(EPA, 2018). This amount of biofuel requires 0.75 billion tonnes of
biomass, of which approximately 0.225 billion tonnes will remain in
the form of lignin rich byproduct during the conversion process
(Holladay et al., 2007). Therefore, it is essential to develop cost effec-
tive valorization technologies to ensure long term stability and vitality
of the biorefineries.
Despite the growing body of research on the possibilities of

⁎
Corresponding author.
E-mail address: Dilpreet.bajwa@montana.edu (D.S. Bajwa).

https://doi.org/10.1016/j.indcrop.2019.111526
Received 1 February 2019; Received in revised form 26 June 2019; Accepted 28 June 2019
Available online 25 July 2019
0926-6690/ © 2019 Elsevier B.V. All rights reserved.
D.S. Bajwa, et al.
converting lignin into commercial chemicals, materials, and fuel, cur-
rently most of the lignin produced from paper industry is burned as low-
value fuel to generate electricity and heat (Luo and Abu-Omar, 2017)
and only less than 2% is used for producing specialty chemicals such as
dispersants, adhesives, surfactants and other value added products. The
development of value-added lignin-derived co-product can help to
make the second generation biorefineries and paper industry more
profitable by valorizing their byproduct lignin. This review focuses on
recent advances into the valorization of the byproduct lignin generated
by second generation biorefineries and paper industry.
A.P. Candolle, the Swiss botanist, used the term “Lignin” for the first
time in 1813 (de Candolle and de Candolle, 1844). The word is derived
from lignum, which means “wood”. It is one of the major components of
lignocellulosic biomass. The other two major components of biomass
are cellulose, and hemicellulose. The typical percentage of these three
components in biomass varies by the plant source (Ragauskas et al.,
2014). For example, grass contains 17–24 wt% lignin, softwood con-
tains 18–25 wt% lignin, and hardwood contains 27–33 wt% lignin
(Calvo‐Flores and Dobado, 2010). Despite the fact that lignin has many
potential applications, and a lot of research has been conducted to
extract high-value lignin-derived products, lignin has yet not been
utilized at industrial scales. There are a few factors, which make use of
lignin in industrial scale challenging: lignin’s unique chemical re-
activity, the presence of various organic and inorganic impurities and a
non-uniform structure (Vishtal and Kraslawski, 2011).
The structure of lignin varies based on the extraction process, and
the presence of various functional groups. Lignin has different func-
tional groups such as: hydroxyl, methoxyl, carbonyl, and carboxyl etc.
Lignin has three basic types of monomers; coniferyl alcohol, sinapyl
alcohol, and p-coumaryl alcohol, also known as monolignols. To make
desired product from lignin, it is necessary to do controlled degradation
to make uniform structural lignin. Degradation of lignin can be done by
chemical (Hofrichter, 2002, 2002), thermal (Brebu and Vasile, 2010),
or enzymatic pathways (Bugg et al., 2011); (Crawford and Crawford,
1980). Even though many challenges exist in making products from
lignin, scientists are attempting to overcome these challenges by in-
venting different processes and pathways to convert lignin to valuable
products. The increasing trend of research papers and patents shown in
Fig. 1 demonstrates how researchers are moving forward by addressing
the lignin processing drawbacks.
The growing focus on lignin research is partially driven by the in-
creasing volume of lignin that is produced by different types of in-
dustries as a byproduct without being properly utilized. Another
Fig. 1. (a) Research Publications (Mandlekar et al., 2018) (b) Patent devoted to lignin applications (United States Patent and Trademark Office).
2
Industrial Crops & Products 139 (2019) 111526
driving force is the potential of lignin for providing an environmentally
and economically sustainable feedstock choice for materials, fuels and
chemicals. Traditionally, paper industry has been producing kraft and
lignosulfonates lignin for many years. However, recent emergence of
second generation biorefinery process has generated sulfur free orga-
nosolv lignin as a byproduct of biofuel that is gaining much popularity.
In both industries, it is known that lignin is burned for energy recovery.
This conventional practice, however, may not be economically and
environmentally optimum considering lignin can be potentially used as
a sustainable source to produce high value fuels and chemicals.
With the growing concern over the global effects of greenhouse gas
emission, biomass has been identified as an abundant and potentially
sustainable alternative source of energy and chemicals. In the US,
programs have been enacted to encourage the increase in percentage of
biomass in commodities from 5% in 2005 to 18% in 2020, and 25% by
2030 (BRDTAC, 2006; NRC, 2000). Examples of these program are
biopreferred and biorefinery, renewable chemical, and biobased pro-
duct manufacturing assistance programs.
The biomass reserves on the earth have been estimated to be ap-
proximately 1.85–2.4 × 1012 tonnes and 20% of this amount of biomass
is lignin (Rosillo-Calle et al., 2012). As a renewable component, lignin
can be used for producing a variety of products such as carbon fiber,
phenolic compounds, different oxidized product, multifunctional hy-
drocarbon and syngas that currently are derived from petroleum. In
addition to offering better environmental performance as compared to
their petroleum-derived counter parts, lignin derived materials and
fuels are light weight, fuel efficient, and more importantly have the
capability to lower cost (Hill et al., 2006; Ragauskas et al., 2014). For
example, automotive industry tends to use carbon fiber instead of steel
because carbon fiber is lighter with higher strength in comparison to
steel. But the high cost of carbon fiber, 15 USD/kg in USA (Gill et al.,
2016), is thwarting the use of carbon fiber in automotive industry. On
the other hand, lignin-derived carbon fiber would cost approximately 7
USD/kg (Baker and Rials, 2013). A study has reported that lignin based
carbon fiber has a value of 1.1 billion USD per 100 kilo tonnes (Cline
and Smith, 2017). A recent report published in 2015 by Radiant In-
sights predicted that the global lignin market will reach USD 6.19 bil-
lion by 2022 (Insights, 2015). Even though, lignin represents the largest
reservoir of aromatic compounds, existing industries are not optimized
based on production and use of lignin as byproduct. For example, the
paper industry focuses on producing paper at lowest possible price
without considering obtaining pure lignin. The primary goal for the
near future is to improve the technology for separating lignin efficiently
D.S. Bajwa, et al.
Fig. 2. Different sources of lignin and their current volume (Agrawal et al., 2014; Bruijnincx et al., 2016; Mandlekar et al., 2018; Ľudmila et al., 2015).
and economically. Since, recent research on lignin has established many
applications for this natural polymer, optimization of the facility con-
sidering lignin purification will help to develop high value products,
preparation in novel resins, plastic products, and low molecular weight
materials.
Nowadays, the demand for paper is decreasing due to online com-
munication. In the near future, many companies will further reduce
their dependency on paper. This reduction in demand for paper will
make existing paper industry difficult to survive. Also, new investors
want to invest in industries that have diverse product portfolios so that
the total revenue does not depend on only one product. To make
biorefineries and paper industry more profitable, lignin-derived pro-
ducts need to be produced at industrial scale. To encourage the industry
for developing lignin-derived product, there is still necessity of con-
ducting techno-economic assessments and life cycle analyses.
2. Source and types of lignin
The source and extraction process (Fig. 2) of lignin can influence its
properties and therefore selection of the best valorization path for
converting lignin to value added products. Most of the currently
available lignin in the market can be categorized based on the content
of sulfur. Sulfur free lignin is more environmentally friendly and has
more potential applications than sulfur containing lignin due to odor.
2.1. Sulfur containing lignin
Sulfur containing lignin contains inorganic compound sulfur after
extraction process. Most of the sulfur containing lignin comes from
paper and pulp industry. Kraft lignin, sulfite lignin and hydrolyzed
lignin are most common types of sulfur containing lignin.
The Kraft processing breaks down the lignin by cooking wood chips
in sodium hydroxide and sodium sulfide. One of the widely adopted
processes for isolating large quantities of kraft liginin from black liquor
is known as LignoBoost® developed by Innventia and Chalmers
University of Technology. Most recent advancement of LignoBoost
process has provided opportunity of large scale purification of lignin
from black liquor which is generated by Kraft process (Ten and
Vermerris, 2015). White liquor consists of sodium hydroxide (NaOH)
and sodium sulfide (Na2S) and is used to break the bond that links
lignin to cellulose. It converts the woody and non-woody materials into
pulp and black liquor that is then mixed with an acidic solution to
obtain the lignin (Mandlekar et al., 2018). The black liquor is a waste
3
Industrial Crops & Products 139 (2019) 111526
by-product, which is underutilized and commonly used as a fuel source
for heat generation. Generally, kraft lignin contains 7.0-3.0% sulfur and
0.5–3.0% ash. Kraft lignin is used in fertilizers, pesticides, carbon fibers,
binders and resins. Different types of chemicals are also produced from
kraft lignin, for example, vanillin, hydroxylated aromatics, quinine,
aldehydes and fatty acids.
The most abundant type of lignin available in the market is sulfite
lignin. It is processed with sulfur dioxide and a base calcium, sodium,
magnesium or ammonium (Mandlekar et al., 2018). The production of
lignosulfonates and sulfonated lignin is estimated to be around
800,000 tonnes and 15,000 tonnes respectively (Agrawal et al., 2014).
Lignosulphonates dominates the global lignin market due to rising de-
mand for lignin in building and construction industry. Borregaard
(Norway), Tembac (Canada), Nippon paper Industries (Japan), ALMT
(India) and, Domjo AB are some of the major companies those produce
lignosulphonates and deliver to building and construction industry
(Mandlekar et al., 2018). Sulfite lignin has high sulfur and ash contents
approximately 3.5–8% and 4.0–8.0% respectively. Different types of
product like colloidal suspension, stabilizer, dispersants, binders, de-
tergents, adhesive and component of feed, particle board, adhesive and
additives for cements can be produced from sulfite lignin (Ľudmila
et al., 2015).
Another type of sulfur containing lignin is obtained from enzymatic
hydrolysis and the process was first invented by (Yamasaki, 1981). The
process hydrolyzes and dissolutes carbohydrates by cellulolytic en-
zymes and keeps lignin as an insoluble residue. The residual lignin
sample contains 65–80% lignin and 7–8% carbohydrates and the re-
maining impurities are sulfur, ash and other impurities are generated
from proteins. The downside of this type of lignin is the existence of
carbohydrate that cannot be removed from the lignin by prolonged and
repetitive enzymatic treatment (Agrawal et al., 2014).
2.2. Sulfur-free lignin from biorefinery process
Sulfur free lignin exhibits distinct properties compared to sulfur
containing lignin. It is considered as an emerging class of lignin that can
be used in many applications. Most of the sulfur free lignin comes from
biomass conversion technologies, solvent pulping, and soda pulping
process (Lora and Glasser, 2002). Organosolv lignin and soda lignin are
considered as sulfur free lignin and are produced in industrial scale.
Also, second generation biorefinery process is another emerging source
of sulfur free lignin that has many applications in making high value
products (Cotana et al., 2014).
D.S. Bajwa, et al. Industrial Crops & Products 139 (2019) 111526

Organosolv lignin has low ash content, approximately 1.75% and
the lignin is soluble in organic solution but insoluble in water because
of its hydrophobicity (Ľudmila et al., 2015). It is obtained from the
solvent through precipitation. The most common organosolv processes
is based on ethanol/water pulping and pulping with acetic acid
(Mandlekar et al., 2018). Other extraction processes of organosolv
lignin include using formic acid, acetic acid and water that was de-
veloped by the French company CIMV (Wild et al., 2015).
Soda lignin originates from soda pulping process. Soda lignin does
not have any sulfur content, however the ash content is approximately
0.7–2.3%, which is relatively higher than the organosolv lignin
(Mandlekar et al., 2018). Annual plants like straw, flax, and hardwood
are used in soda based cooking method (Rodríguez et al., 2010). Soda
lignin is used for production of phenolic resins, animal nutrition, dis-
persant, and polymer synthesis.
The last category of sulfur-free lignin is the byproduct of lig-
nocellulosic biorefineries. Here, sulfur free lignin is generated during
hydrolytic pretreatment of biomass in addition to carbohydrate com-
ponents. Lignin is recovered from the solution by precipitation. Over
the last decade several biomass conversion technologies have been
implemented at pilot and industrial scales where lignin is produced as
byproduct.
adhesive, chemicals, and, binders etc. Some of these companies produce
materials from both sulfur containing and sulfur free lignin. In Asia,
China, Japan, and India are the key players in producing lignin-derived
products. There is a growing demand for lignin market in the emerging
economies like China, India, Japan, and Indonesia. Among all the
countries, China is currently leading in lignin-based chemical produc-
tion. The compound annual growth rate (CAGR) of lignin market in
china is 10%. China’s expanding industrial base has influenced the
demand growth for this niche market (Research, October 2018). Cur-
rently, the annual valorization rate of lignin is less than 2%, which
underscores the need for critical research to capitalize this abundant,
low-cost and underutilized biobased feedstock (Cao et al., 2018).
4. Current applications of lignin
Lignin research and its applications have been going on for decades.
Many studies have reported about the possibility to use lignin as high
value product (Agrawal et al., 2014; Luo and Abu-Omar, 2017; Ľudmila
et al., 2015). However, these applications have not yet reached the
industrial scale. So far, lignin use has been restricted to limited number
of low values uses. Table 2 highlights the major lignin derived mate-
rials, functional products and their potential applications.

3. Location, volumes, and pricing 4.1. Heat and power energy

It is estimated that the annual production of lignin on earth is in the
range of 5–36 × 108 tonnes (Gellerstedt and Henriksson, 2008; Saito
et al., 2012). Prices of lignin with low purity, lignin obtained from kraft
process and lignosulphonates vary between 50–280 USD/MT, 260–500
USD/MT, and 180–500 USD/MT, respectively. Relative to other types
of lignin available in the market, organosolv lignin has higher prices
starting at 280 USD/MT and ending at 520 USD/MT (Ľudmila et al.,
2015).
The lignin market is highly concentrated, with top five players ac-
counting for more than 85% share of the global market in 2015. Key
players operating in the lignin market include Borregaard LignoTech,
MeadWestvaco Corporation, Tembec Inc., Domtar Corporation, Domsjö
Fabriker AB, Changzhou Shanfeng Chemical Industry Co. Ltd, Nippon
Paper Industries Co. Ltd., UPMKymmene Corporation, Asian Lignin
Manufacturing Pvt. Ltd., Lignol Energy Corporation, Green Value and
Liquid Lignin Company (LLC) (Mandlekar et al., 2018). The industry in
North America and Europe has been very active in research to promote
lignin utilization at industrial scale. The examples in Table 1, adapted
from (Agrawal et al., 2014), highlights some of the recent industry
related developments.
To make lignin as valuable attractive raw material, most of the
companies are doing research and production simultaneously.
Companies in the USA, Canada, and Europe are producing different
types of lignin-derived products, for example, different types of
Lignin combustion is widely practiced in paper and pulp industry to
generate heat and electricity. Approximately 98% of the lignin pro-
duced is used as fuel for heat and electricity. The average heat value of
dry lignin is around 25 MJ/kg. On average, coal has an energy density
of 24–30 MJ/kg. Firing the lignin with coal has been largely used as fuel
for the pulping boiler (Luo and Abu-Omar, 2017). One study has re-
ported that co-firing lignin with coal increases the boiler efficiency by
38% compared to boiler fired with only black coal (Khitrin et al., 2012)
and reduces the carbon emission by 60% (Scown et al., 2014). The
market value of this heat is 6–10 USD/BTU (Holladay et al., 2007).
4.2. Pyrolysis and syngas products
Pyrolysis refers to thermal treatment of lignin where end products
are solid biochar, bio-oils or gases. The products obtained from this
process are highly dependent on the process conditions, feedstock type
and composition, reaction rates and additives (Pandey and Kim, 2011);
(Figueiredo et al., 2018). Depending on the process temperature and
time different products can be obtained from same biomass. Typically
low temperature and low heating rates result in char production,
whereas high heating rate and short residence time yields liquid pro-
ducts from biomass. High temperature, extended residence time and
low heating maximizes the gas production (Demirbas, 2007). Bio-oils
use has been limited due to their low heating value, incomplete

Table 1
Current industrial applications of lignin by leading global companies.
Company Name Country Product portfolio Sources of lignin

Alberta-pacific (Alpac) Canada Chemicals, materials Kraft pulping process

Innventia Sweden Carbon Fiber (Innventia, 2018) Kraft pulping
Domtar Corporation Canada Adhesives, Agricultural Films and Chemicals, Carbon Products (e.g. carbon fiber, graphene, graphite, –
activated carbon, etc.), Coatings, Dispersants, Fuels and Fuel Additives, Natural Binders, Plastics, Resins
(Domtar, April 2018)
Technaro GmbH Germany Thermo Plastics, Carbon fiber (TECNARO GmbH, 2010) –
Borregaard LignoTech USA Dispersing agents in concrete, textile dyes, pesticides, batteries and ceramic products – or as binding agents –
in animal feeds, briquetting and various dust suppression applications. (LIGNOTECH, 2018)
MeadWestvaco USA Propoxylated lignin polypols, animal feeds, particle board, wax emulsion,dyes, lead acid batteries, ceramics, Non sulfonated kraft
concrete, and refractories (Agrawal et al., 2014) lignin
Northway Lignin Chemicals Canada Emulsifiers, organic binders, dispersants, and liquid/powder agglomeration (Agrawal et al., 2014) Sulfur free kraft lignin
KMT lignin U.K. Concrete mixture, dust abatement, leather tanning, ceramics, insecticides sprays etc. (Agrawal et al., 2014)
Lennox Polymers Ltd. USA Formaldehyde-free resins, adhesives (Holladay et al., 2007)

4
D.S. Bajwa, et al. Industrial Crops & Products 139 (2019) 111526

volatility, acidity, instability and incompatibility with standard fossil

(Cao et al., 2018), (Grossman and Wilfred, 2019),

(Aro and Fatehi, 2017), (Figueiredo et al., 2018)

(Puziy et al., 2018) (Luo and Abu-Omar, 2017)
(Kalami et al., 2017) (Solt et al., 2018), (Wang
fuels, however catalytic upgrading can be performed to improve their

(Aso et al., 2013), (Cao et al., 2018), (Ouyang

et al., 2009), (Puziy et al., 2018), (Ge et al.,
acceptance.
Gasification is an important approach for lignin valorization. It

(Cao et al., 2018), (Puziy et al., 2018)

produces mixture of hydrogen (H2), carbon monoxide (CO), and a very
small amount of CO2. Syngas utilization is most technically developed

(Espinoza-Acosta et al., 2011)

area. Syngas can be used in many processes. For example, processes to
(Thakur and Thakur, 2015)

2018), (Cayla et al., 2016)

make DME (Methanol/Dimethyl ether), and Fischer Tropsch to produce
green diesel are well established. But the process to make syngas into
mixed alcohol has not been commercialized yet. The market value of
DME is 0.22 USD/L, mixed alcohol is 1-1.0 USD/L, and Fischer Tropsch
et al., 2019)
References

liquids are 0.42-0.57 USD/L (Holladay et al., 2007). Syngas can also be
used in heating, cooking and, generating electricity.
The complete gasification of lignin involves successive reactions
such as hydrolysis, polymerization, hydrogenation and methanation
(Figueiredo et al., 2018). Processing variables such as temperature,
Light-weight polymer composites, adsorbents,
multifunctional materials, building blocks for

Biomedical applications, tissue engineering,

agriculture, textiles, soil reclamation, water

reaction time, pressure, concentration and catalysts impact the gasifi-

Industrial chemicals, biobased adhesives,

Construction pavements, cement panels,

cation efficiency of lignin Alkali and alkali salt catalysts, metal oxides
electrochemical devices, automotives

are used to increase the hydrogen yield production and enhance reac-
Energy devices, battery, fuels cells

tion (Kang et al., 2013).

purification fire suppression

4.3. Lignin as binder

Potential Applications

biobased products

The water-soluble lignin salt is particularly suited for use as an

binder in water-based pigment printing compositions (Dilling and
drug delivery

Dimitri, 1990). Low-cost binders from lignin sulfonates are commonly

used in coal briquettes or ceramics, briquetting of mineral dust (fines,
shavings, turnings), and wood-related material such as plywood or
particle boards (Calvo‐Flores and Dobado, 2010). Lignin-derived bin-
Biochar, bio-oil, syngas, activated carbon, carbon fibers, carbon black

Soil conditioner, controlled release agent in fertilizers and pesticides,

ders can also be used in silicon anode. Silicon is the most promising
Li-ion, Na-Ion batteries (electrodes), super capacitators, solar cells
3D Printing resin (ationic surfactant), scaffolds, lignin nanotubes,

anode material for the next generation of lithium ion batteries. The
aromatic aldehydes, aromatic alcohols, acids, aryl ketones, anti-
Lignin monomers and dimers, aromatic phenols, alkyl phenols,

oxidants, dispersants, polyurethanes, phenolic resins, vanillin

main challenge in its application here is its significant volume changes

sequestering agent, contaminant absorbent, fire retardant

during lithium insertion and extraction. Hence, particular attention has

been given to the development of binder derived from lignin (Nirmale
bitumen, cement additive, dispersant, reinforcement

et al., 2017).
A list of major lignin derived material categories, functional products, and their potential applications.

4.4. Lignin as cement

The economically efficient use of lignin-derived cement have been

reported by several studies (Aso et al., 2013; Kamoun et al., 2003;
hydrogels, lignin nanotubes

Ouyang et al., 2009). Low levels of lignin and modified lignin is re-
ported to yield high performance concrete. It improves the strength,
eases grinding and reduces damage to external walls due to moisture
and acid rain. In addition, selective lignin can improve the compressive
strength of cement pastes. It is reported that sulfonation process helps
to add sulphate groups to lignin which makes lignin act like a dispersant
Products

in the cement matrix due to the high zeta potential. The high charge
creates electrostatic repulsion between cement particles (Meister,
2002).
Kraft, Sulfite, Soda,

Kraft, Sulfite, Soda,

Kraft lignin, Klason
Organosolv, Straw

5. Emerging applications of lignin

Klason, Kraft,

Kraft lignin,
Lignin Type

Organosolv

Organosolv

Organosolv

New applications are emerging for lignin-derived products in dif-

ferent fields. Lignin is being evaluated as a precursor for many new high
lignin

value chemicals. Most of the technologies are focused on lignin depo-

lymerization (hydrogenolysis, pyrolysis, oxidation, hydrolysis, and ga-
Aromatic macromolecules and fine

sification), synthesis of chemically active sites (hydroxyalkylation,

amination, nitration and sulfonation), functionalization of hydroxyl
Polymer and nano materials

groups (alkylation, phenolation, urethanization, and etherification) and

Carbon Materials, Biofuels

Specialized Applications

production of lignin graft copolymers. Lignin based carbon fibers, BTX,

phenol and oxidized products are some novel applications of lignin that
Building Materials
Material Category

have been reported (Baker and Rials, 2013; Gillet et al., 2017;
Energy Storage
chemicals

Langholtz et al., 2014). In addition lignin is finding uses in energy

storage devices, nanocomposites, drug delivery systems, tissue en-
Table 2

gineering and filtration and heavy metal capturing devices. Research is

underway to derive more valuable macromolecules and efficient

5
D.S. Bajwa, et al.
processes from lignin.
5.1. Carbon materials
All types of commercial lignin have potential applications as a
polyelectrolitic and polymeric material. This could be greatly expanded
for making higher value macro monomers for polymer application.
Recent developments about fundamental understanding of lignin re-
activity are helping to develop different types of macromolecules such
as: carbon fiber, polyurethane, polymer alloy, filler, and polymer ex-
tender.
It is estimated that by 2020, the global demand for carbon fiber will
be 140,000 tonnes with a value of 4.5 billion dollars (Smolarski, 2012).
In terms of application, the global use of carbon reinforced plastic will
be approximately 48.7 billion USD. However, the main challenge of
using carbon fiber is its high price. One study has reported the manu-
facturing cost of polyacrylonitrile (PAN) based carbon fiber to be 15
USD/kg in USA, 20 USD/kg in Germany, and 18 USD/kg in Japan (Gill
et al., 2016). The reason for such high prices is because of the high cost
of PAN. Lignin as a natural precursor with high carbon content can be
an ideal low cost source to produce carbon fiber (Mainka et al., 2015;
Ragauskas et al., 2014). Carbon fiber is widely used in sports, aerospace
industry. However, automotive industry could be a promising sector for
carbon fiber to replace the steel. Compared to the price of 4 USD/kg for
regular steel, 8 USD/kg for high strength steel, the price of the carbon
fiber needs to be around 7–11 USD/kg. Therefore, the idea is to use
lignin, which is readily available and has high carbon content as an
alternative to PAN. Due to the abundancy of lignin, lignin-derived
carbon fiber is predicted to be around 7 USD/kg (Baker and Rials,
2013). Different research institutes such as: Plasan, Ford Motor (USA),
BASF & SGL (Germany), DowAska (Netherlands), GrafTech (USA), Oak
Ridge National Lab (USA) are trying to develop high quality carbon
fiber from lignin.Lignin-based carbon fibers have been manufactured
using kraft lignin from hardwood and softwoods (Kadla et al., 2002);
(Norberg et al., 2013). A range of carbon materials including activated
carbons, structural carbon fibers, graphitic carbon or carbon black have
been target of recent studies. Lignin based carbon rich material have
been used as reinforcement in advance materials, energy storage,
electrodes in electrochemical applications, absorbent materials and
purifying gas an aqueous media from organic pollutants or heavy me-
tals (Puziy et al., 2018); (Wang et al., 2019); (Zhang et al., 2015);
(Mabrouk et al., 2017). The driving forces behind sustained research for
developing carbon fibers and related products from lignin has been the
energy efficiency, reduced environmental impact and its abundance.
However the heterogeneity of lignin molecule, ash content, and ther-
moplastic foaming behavior have been main challenges for manu-
facturing high quality carbon rich products.
5.2. Oxidized products
Lignin oxidation is a method used to derive high-value products like
aldehydes, vanillin, vanillic acid, dimethyl sulfoxide (DMSO), aromatic
acids, aliphatic acid, and cyclohexane. Organometal catalyzed oxida-
tion, biomometic oxidation, enzyme-based oxidation, and organic sol-
vent nanofiltration are some of the methods that has been established to
oxidize the lignin (Lange et al., 2013; Werhan et al., 2012). The pre-
sence of phenolic group makes it attractive for oxidation. Typically
oxidants such as nitrobenzene, metallic oxides and hydrogen peroxide
are used to maintain aromatic character.
Vanillin an aldehyde is the main component of the natural vanilla
extract. It is used as a flavoring agents in food, beverages, and phar-
maceuticals. Vanillin was commercially derived from eugenol since
1920 (Calvo‐Flores and Dobado, 2010). Twenty % of vanillin in the
market is produced from lignin and the rest of 80% is produced from
crude oil (Ľudmila et al., 2015). The oxidation of kraft lignin in alkaline
medium produces vanillin (Araújo et al., 2010; da Silva et al., 2009).
6
Industrial Crops & Products 139 (2019) 111526
Transitional metal and metal oxides are used as oxidant. The natural
vanilla market is characterized by very volatile prices because Mada-
gascar exports majority of vanilla extracted naturally. However, ex-
traction of lignin-derived vanillin is expected to reduce the volatility of
market. Further oxidation of vanillin yields vanillic acid. Vanillic acid
(4-hydroxy-3-methoxybenzoic acid) is a dihydroxybenzoic acid deri-
vative used as a flavoring agent. It is also an intermediate in the pro-
duction of vanillin from ferulic acid.
DMSO a by-product of the wood industry, has been used as a
commercial solvent since 1953. DMSO is a colorless polar aprotic sol-
vent that can dissolve polar and nonpolar molecules, including many
salts, so it is used as a solvent in many reactions, and shows very low
toxicity. DMSO is produced from dimethyl sulfide (DMS) through oxi-
dation. DMS is a byproduct of kraft pulping. Its market value is ap-
proximately 2.21 USD/kg (Holladay et al., 2007). Other oxidized pro-
ducts from lignin include aromatic acids, aliphatic acis and
cyclohexanol.
5.3. Phenolic compounds
Lignin can be transformed to phenolic compounds through synthesis
of new chemical sites via hydroxyalkylation. The reaction processes
include demethylation, phenolation, and methylolation. Phenols are
reactive compound and they are acidic in nature due to the presence of
−OH group. It is very easy to oxidize phenolic compound and form
polymers. The biosynthesis of lignin gives different forms of phenolic
compounds (Agrawal et al., 2014). Studies have shown that substitution
of 70–100% of the phenolic portion of phenolic adhesives is possible
when kraft lignin or lignin byproduct of 2nd generation biorefineries
are used (Kalami et al., 2017; Solt et al., 2018). Lignin phenol-for-
maldehyde resins have been synthesized to replace phenol for-
maldehyde resins (Kalami et al., 2017); (Laurichesse and Avérous,
2014). The introduction of methylol groups into the lignin is the basis
of methylolation modification process. The major focus is to develop
adhesives with good adhesive strength with low free formaldehyde
content, non-toxic with non-volatile nature.
Phenols are currently produced from petroleum-based benzene by
cumene process. The phenol derivatives are used in the preparation of
cosmetics including sun screens, hair coloring, and skin lightening
preparations. They also have potential application in chemical, phar-
maceutical, food, and perfumery industry (Agrawal et al., 2014). In
2012, the total demand for phenol reached 8 million tonnes and the
market price was 1,000–2,000 USD/tonnes (Ľudmila et al., 2015). The
price of petroleum derived phenol varies with oil price. A primary ad-
vantage of producing phenol from lignin is that it has a stable market
value with a price of 1.22–1.46 USD/kg. The application of phenolic
resins is predicted to grow to 16 billion USD by 2025 (Research, March
2017).
5.4. Hydrocarbons compounds
Lignin is one of the few biomass sources that can be used to make
hydrocarbons in an economical fashion. Hydrocarbons from klason
birch lignin, enzymatic acidolysis, organosolv and wood sawdust have
been obtained using heterogeneous or homogenous catalytic hydro-
genolysis processes (Cao et al., 2018). Their production highly depends
on the processing temperature and catalyst and feedstock (Shen et al.,
2015)). Fast pyrolysis process is mainly used to convert lignin into
valuable hydrocarbons like benzene, toluene, and xylene (BTX) (Laskar
et al., 2013). Production of BTX compounds requires breakage of CeO
and CeC bond through depolymerization. The complex structure of
lignin requires a variety of catalysts to achieve efficient depolymer-
ization.
BTX have wide range of applications. The global production of BTX
in 2010 was 100 million. Currently, all of the BTX are produced from
petroleum. BTX is the source of 60% of all aromatic volume and it has
D.S. Bajwa, et al.
24% of global petrochemical market with total value approximately
100 billion (Smolarski, 2012). Lignin based BTX could be a perfect
replacement for petroleum based BTX. However, lignin-based BTX
production is currently in the R&D stage, and is expected to reach
commercial market by 2020. The technology to convert lignin into BTX
requires two steps: (I) depolymerization and (II) hydrogeoxygenation.
(Luo and Abu-Omar, 2017). The approximate market value of lignin-
derived BTX and higher alkylates is expected to be 2 USD/gallons
(Holladay et al., 2007).
5.5. Urethanes and epoxy resins
Lignin can also be used as a raw material for the preparation of
environmentally friendly thermoset resin polyurethane. Polyurethane
has excellent strength to weight ratio, energy absorbing performance
and comfort features. It has important applications in shipbuilding in-
dustry, automotive industry, furniture insulation, and packaging in-
dustry (Banik and Sain, 2008). Conventional polyurethane is processed
using a diisocyanate and a diol, which is not an environmentally
friendly path. Production of polyurethane by biosynthesis of lignin can
make it biodegradable and therefore will be more environmentally
friendly (Lee and Deng, 2015). The polyurethane-based industry gen-
erates a revenue of 52 billion USD globally in 2015, which is expected
to increase to 77 billion USD by 2023 (Luo and Abu-Omar, 2017).
Urethanization reaction involves reacting hydroxyl groups with
isocyante groups to a urethane linkage. Lignin based polyurethane are
prepared by chemical modification on lignin by introducing polyols or
diols. Generally two approaches have been evaluated: First approach is
one step that involves adding diisocyanate and or adding diol as co-
monomer. Second approach is two-step process which involves pre-
polymer production using isocyanate and polyol followed by poly-
merization with lignin (Ahvazi et al., 2011)). Lignin based polyurethane
foam properties are reported to be better or same to conventional
polyurethanes (Mahmood et al., 2016). Lignin based polyesters are
produced by functionalization of hydroxyl groups through esterification
or etherification (Figueiredo et al., 2018). It is reported that type of
lignin and its extraction process influences the properties of composites,
which is related to density of hydrogen-bonding groups. Lignin-epoxy
resins are reported to add anti-aging properties to asphalt (Xin et al.,
2016).
5.6. Biomedical application
Lignin-derived products are becoming attractive materials in bio-
medical engineering, most of the research is still at proof of concept
stage. Major focus is to designing smart biobased nanocarriers where
active bio agent can be physically attached or encapsulated. Lignin
nanoparticles are showing promise in medical diagonistic and ther-
apeutic applications. Lignin-derived hydrogels and lignin-based nano-
tubes have important role in tissue engineering and DNA delivery.
Lignin based hydrogel is used in stem cell and cancer research, cell
therapy, tissue engineering, immunomodulation (Muir, 1996), and in
vitro diagnostics (Hoffman, 2012). Synthesis of lignin nanotubes (LNTs)
and lignin nanowires (LNWs) are considered as potential and cost ef-
fective vehicles for the delivery of DNA and therapeutic agents (Ten and
Vermerris, 2015). Lignin also has many pharmacological applications.
Epidemiological studies have shown that lignin has protective role
against many diseases like cancer. Lignosulfonates could also be used to
develop drugs to stimulate the immune system of the body by de-
creasing oxidative activity (Aro and Fatehi, 2017; Martinez et al.,
2012).
Recently, it was reported that lignin based hydrogels can be used in
drug delivery system, healing system, and water purification (Thakur
and Thakur, 2015; Vashist et al., 2014). Xanathan gum and lignin can
produce biodegradable hydrogels which offer more thermal chemical
reactivity with enhanced thermo-oxidative properties, and
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Industrial Crops & Products 139 (2019) 111526
antimicrobial activity (Raschip et al., 2011; Ten and Vermerris, 2015).
Lignin is also used in developing thermo-responsive hydrogels that
exhibits different gelling behavior at different temperatures. (Feng
et al., 2011).
5.7. Fire retardant and antioxidants
To meet the constant demand for fire protection, researcher have
investigated sustainable ways to manufacture natural fire retardants
instead of synthetic chemicals. A recent study suggested that lignin can
be used as natural flame retardant (Cayla et al., 2016). Lignin has also
received attention in making fire retardant polymer systems. It has been
investigated that the presence of lignin can effectively reduce the
flammability of polymers such as polypropylene, PBS, ABS, PET
(Mandlekar et al., 2018). Lignin-based synthetic polymers, and bio-
polymers show reduced flammability and smoke release.
The complex aromatic character of lignin due to presence of
methoxy and hydroxyl rings enables lignin to act as antioxidant. The
functional groups are responsible for termination of oxidative propa-
gation reaction through free radical scavenging activities. Lignin na-
noparticles are reported to have better antioxidant and UV-protection
properties than bulk lignin (Yearla and Padmasree, 2016). The lignin
nanoparticles are expected to find application in the cosmetics, phar-
maceutical and food industries.
5.8. Lignin as sequestering agent
The presence of heavy metals is a great threat to human health and
environment mainly due to their high toxicity. Heavy metal con-
tamination happens because of the release of waste from different in-
dustries such as metal plating, mining operations, tanneries, chloralkali
processing, smelting and alloy plants, and storage batteries industries.
Although active carbon is the most widely method to remove heavy
metals from the water, use of active carbon is very expensive (Hegazi,
2013). It is important to identify cost effective methods to remove toxic
heavy metal ion like lead Pb, Hg, Cd, Cr, As, Zn, Cu, and Ni. Researchers
have shown that modification of lignin structure can enhance its ab-
sorption abilities to remove heavy metals (Ge et al., 2018; Guo et al.,
2008).
Lignosulphonates are reported to be strong sequestering agents for
trapping metal ions and forming complexes. This property enables
lignosulphonates to be used for soil amelioration, soil conditioning or
removing harmful metals. Furthermore, lignin has been evaluated as a
control release agent in herbicides, pesticides and fertilizers
(Chowdhury, 2014). Lignin hydrogels have been tested as water storing
soil conditioner in agriculture and forestry operations. Lig-
nosulphonate-g-acrylic acid hydrogels with superabsorbent capacity
have demonstrated their contaminant absorption and dye (methylene
blue) removal potential from waste water (Yu et al., 2016). Addition of
lignin in the pesticides is reported to improve the stability against
photodegradation (Flores-Céspedes et al., 2015).
5.9. Lignin base nanomaterials
Recent advances in nano science and technology has demonstrated a
strong relationship between material structure, properties and their
performance. Nanoscale lignin modification to design high-value ma-
terials is still in its infancy stage. Researchers have turned the complex
macromolecular structure of lignin into nanoparticles, nanotubes and
nanofibers. This approach helps to transform lignin into more uniform
size and shape (Rangan et al., 2016). The high surface area to volume
ratio of nano particles helps to reinforce and strengthen polymer ma-
trices, and improve thermal stability through its anti-oxidant proper-
ties. Lignin nano particles also show superior dispersion and miscibility
in the hydrophobic matrices. The functional groups on lignin nano-
particles can be engineered for high value applications. The processing
D.S. Bajwa, et al.
methods such as interfacial crosslinking, polymerization, solvent ex-
change, and sonication are reported to influence the shape and size of
lignin nano particles (Figueiredo et al., 2018). The advances in the
hydrogel technology has also created a lot of interest in nano sized
lignin due to its biobased nature, biocompatibility, biodegradability,
enzymatic degradation and ecologically safe material. There are reports
of lignin based hydrogels being evaluated in drug delivery, wound care,
tissue engineering and contact lenses (Mishra and Wimmer, 2017).
5.10. Energy storage
The use of lignin in energy storage device is beneficial not only for
improving efficiency but also from the perspective of reducing toxicity,
cost and developing more eco-friendly device. The first research (Hirai
et al., 2006) on the use of lignin as energy source was reported in order
to show that lignosulfonate (LS) could be used as an expander (ad-
ditive) to the negative paste of a lead–acid battery to increase its effi-
ciency, cycle life, cold-cracking ability (CCA), and durability through
numerous charge and discharge cycles (Jung et al., 2015). Later, several
reports have been published on lignin as a potential element in making
environmental friendly electro chemical capacitor, super-capacitors
(Espinoza-Acosta et al., 2011); (Chang et al., 2016); (Nagaraju et al.,
2014), lignin and lignophenols in combination with conducting poly-
mers for solar cell (Aoyagi and Funaoka, 2004), and fuel cells (Zhang
et al., 2006); (Zhao and Zhu, 2016). The conventional primary lithium
battery (PLB) contain inorganic-compounds based cathode, an elec-
trolyte, and lithium- based anode are non-renewable, toxic, and costly.
However, Klason lignin extracted from sunflower husk and buck- wheat
husk (Gnedenkov et al., 2015) has been studied for the development of
low- cost cathode-active material for PLB. In order to reduce the
manufacturing time and cost of making lithium-ion batteries (LIBs), 3D
hierarchical porous carbon, carbon nanofibers, and carbon fibers mats
(CF mats) have been prepared using lignin as a raw material (Zhang
et al., 2015).
Superconductors has received much attention because they have
many advantages over batteries such as- high power density, fast
charge/discharge capability, and long durability. Lignin is considered
for making superconductor because activated carbon derived from re-
newable and abundant sources can be obtained by sustainable processes
at low cost (Ioannidou and Zabaniotou, 2007). For solar cells lignin has
been used to develop alternative photosensitizers of dye-sensitized solar
cells and polymer solar cells (Fonseca et al., 2017).
6. Environmental benefit and cost of commercialized lignin-
driven products
Climate change is one of the biggest environmental concerns in the
twenty first century. Reliance on fossil fuel has led to increase in
emission of greenhouse gases (GHGs). In 2016, the United States’ total
greenhouse gas emission was estimated at 6511 metric tonnes of carbon
dioxide equivalents (CO2e) (EPA, 2018). Over the past few decades,
countries around the world have been enacting policies and programs
to encourage a shift from fossil fuels to renewable-based industry.
Lignin-derived products can play an important role in increasing our
reliance on renewable-based chemicals, fuels, and materials and redu-
cing the carbon footprint of products and processes.
Renewable fuels derived from lignin can be used for producing heat,
electricity, and fuels (Demirbas, 2007; Nigam and Singh, 2011). Using
lignin as energy source is a traditionally assumed approach for using
lignin in lignin-generating industries. Studies have shown that onsite
combustion of biorefinery lignin helps to reduce the dependency on
fossil fuel as energy source. Combusting lignin in a cellulosic ethanol
biorefinery can reduce the biorefinery’s life cycle GHG emissions by
20 g CO2/MJ. While onsite lignin combustion may reduce the ethanol
biorefinery’s operating cost (Scown et al., 2014), it may add to its ca-
pital cost (Pourhashem et al., 2013). However, since this approach
8
Industrial Crops & Products 139 (2019) 111526
releases all the lignin carbon content to atmosphere, it may not be the
most sustainable use of lignin in long-term (Pourhashem et al., 2016).
Upgrading this byproduct lignin to products such as higher value che-
micals will further improve the overall environmental impact of bior-
efineries and provide a higher profit for the facility. Similarly, syngas
produced by gasification, and bio-oil produced by pyrolysis of lignin
will substantially reduce the greenhouse gas and other toxic gas emis-
sions compared to their petroleum-based counter parts (Halmann and
Steinfeld, 2006). In addition to potentially replacing fuel in transpor-
tation with lignin-based biofuels, implementing lignin-derived carbon
fiber in automotive industry can reduce vehicle weight and will result
in improved fuel economy therefore further lower the transportation
sector’s carbon footprint.
6.1. Techno-economic analysis
Before a commercialization decision is made for lignin-derived
products, a techno economic analysis of the facility is necessary. Techno
economic analysis studies combine engineering design and cost analysis
of the facility to evaluate the economic viability of the production and
estimate the minimum selling price of the product that can make the
facility profitable. In general, TEAs provide information on total capital
cost, operating cost, and revenue from selling the product. This in-
formation is generated based on engineering design specifications or
process simulation of plant using different software and models. To
date, there have been a few published studies on the techno-economic
studies of the lignin conversion to higher value products. Mabrouk et al.
(2017) evaluated the cost of producing a biobased chemical (catechol)
through depolymerization of lignin under alkaline condition. This
analysis shows that approximately 45% of total cost of catechol pro-
duction is associated with delignification stage. Depolymerization and
product separation has 27.83%, and 27.17% of total cost. For plant
capacity of feedstock 2544 kg/day and with valorization ratio of 3.2,
total cost of investment is 4.87 million (Mabrouk et al., 2017).
Another study by (Obydenkova et al., 2017) investigated the major
variables that impact the techno-economic cost of converting lignin to
transportation fuel through fast pyrolysis process. They took Project
Liberty (POET-DSM), DuPont and Abengoa as their case study. The
result suggests that for best economic outcomes, lignin should be pro-
cessed to fuel onsite. This study also suggests fast pyrolysis as the
pathway of choice for converting second generation lignin to fuel.
(Dessbesell et al., 2018) in a techno-economic study of producing
polymers from kraft lignin demonstrated that depolymerized kraft
lignin and oxypropylated depolymerized kraft lignin are feasible bio‐-
substitute for petroleum‐based polyols with a minimum selling price of
1440 and 1623 USD/tonne, respectively. They report that, however,
phenol produced from depolymerized kraft lignin may not be able to
compete in the market due to current low market prices of fossil-based
phenols.
A few studies have investigated the cost of making colloidal, micro
and nano lignin particles from pulp and paper lignin that can be used as
a replacement for petroleum-based feedstocks such as polyethylene,
polypropylene, polyethylene terephthalate (PET) and phenol (Ashok
et al., 2018; de Assis et al., 2018) estimated a production cost and
minimum selling price of 870–1170 USD/tonne and 1240–1560 USD/
tonne for lignin particles, respectively.
Since many of the lignin valorization technologies are emerging and
novel, the production costs could be much higher than the conventional
products. Therefore, one factor that could be considered for future scale
up the valorization processes are the size of the potential market (or
multiple markets) and the price volatility of the targeted product
(Rinaldi et al., 2016).
6.2. Life cycle assessment
To ensure that commercialization is done in a safe, responsible and
D.S. Bajwa, et al.
sustainable way, the environmental impacts of the commercialized
product should be investigated. Life cycle assessment (LCA) is a pow-
erful tool that helps in conducting a comprehensive environmental as-
sessment for a product. LCA evaluates the impacts generated by a
product from its every stage of production to its disposal. As the number
of proposed emerging lignin applications increases, it is necessary to
ensure pathways that have least environmental impacts before selecting
for future commercialization. Depending on the target criteria, goal and
audience, the investigated environmental impacts of a process or a
product may range from greenhouse emission, ozone depletion, smog,
acidification, eutrophication, and fossil fuel depletion. To date, due to
the novelty of many current researches on lignin upgrade to higher
value products, there has been limited LCA studies investigating the
environmental impacts of these products. Majority of these environ-
mental assessment studies investigate the use of lignin in production of
chemicals including phenolic compounds (Lettner et al., 2018) and fuel.
One recent study (Corona et al., 2018) compared the environmental
performance of adipic acid produced from fossil fuel and lignin through
different production scenarios. Their results showed that 1 kg of adipic
acid produced from lignin has a better environmental impact profile
than conventional fossil-based adipic acid. In their analysis, bio-based
adipic acid has carbon emission of 4.87 kg CO2/kg of acid, which is
78% and 62% less than conventional adipic acid produced with average
and maximum byproduct N2O capture, respectively. In another study of
lignin-based chemicals, Montazeri and Eckelman (2016) showed that
producing catechol from lignin versus petroleum, can overall reduce
the environmental impacts by 2%, 7%, and 59% in global warming
potential, ecotoxic effects, and fossil fuel depletion, respectively.
However, fossil-based catechol showed better results in the ozone de-
pletion category. Yuan and Guo (2017) showed that wooden composites
with lignin-based binders demonstrate better environmental perfor-
mance compared to conventional medium-density fiberboards (MDF).
The extent of using lignin as a substitute for petroleum-based
components, however, may also entail property and mechanical chal-
lenges. Thus, change in the composition of a final product such as a
composite may be needed when lignin-based components are used to
ensure equal functionally with full petroleum-based compositions.
Hilderbandt et al (2019) compared the environmental performance of 6
wood-based fiber laminate scenarios that used lignin-based phenolic
resins. They demonstrated that LCA can be used in conjunction with
composition design to optimize both technical and environmental
performance of the laminates by 80% compared to a non-optimized
one. Isola et al (2018) utilized a combination of LCA and green design
metrics to optimize the process and improve the sustainability of lignin-
based vanillin, another phenolic compound. They found catalyst se-
lection was a deterministic factor affecting the sustainability of the
lignin-based vanillin.
A number of studies have investigated how valorizing lignin by-
product to higher value products including fuel versus its traditional/
conventional use for energy recovery can impact the overall environ-
mental performance of pulp and paper facilities as well as biorefineries.
Secchi et al. (2019) studied the effect of partial removal of biorefinery
lignin byproduct for market sale and concluded that using natural gas, a
less carbon intense fuel compared to lignin, for electricity and heat
generation can improve the environmental performance of the facility.
However, their system boundary did not include any application for the
removed lignin byproduct. In another study, (Pourhashem and Bajwa,
2018) showed that if all 2nd generation biorefinery lignin is used as a
composite filler it can reduce the life cycle carbon emissions of ethanol
to −82 g CO2e/MJ of ethanol. In addition, while using this byproduct
lignin for land amendment leads to −2 g CO2e/MJ of ethanol, com-
busting it onsite or offsite with coal for energy production will result in
40 CO2e/MJ of ethanol (Pourhashem et al., 2013). Obydenkova et al.
(2017) investigated the sustainability of the lignocellulosic ethanol
plant if the lignin byproduct is upgraded to 1) marine fuel, and 2)
transportation fuel. Their finding shows that, assuming the total
9
Industrial Crops & Products 139 (2019) 111526
environmental impacts are allocated to both ethanol and lignin, if the
biorefinery uses corn stover to replace the lignin byproduct as an en-
ergy source, then both ethanol and lignin-derived marine fuel will be
able to comply to RFS. However, the lignin-derived transportation fuel
will not be able to comply with RFS unless the biorefinery uses natural
gas instead of corn stover as energy source. As more new lignin va-
lorization technologies emerge, using tools such as LCA is crucial in
guiding in selection of the most optimum lignin-based product design
for future commercialization.
7. Conclusion
Lignin is an abundant resource on earth and with pulp and paper
industry and second generation biorefineries generating large amounts
of lignin as coproduct, valorizing this resource can lead to higher profits
for these industries as well as better environmental performance. Many
viable products including, fuel, chemicals and materials obtainable by
lignin valorization have been demonstrated and many research efforts
have been done in developing processes that could produce valuable
lignin-derived compound. Lignin valorization can result in desired va-
luable chemical compounds with the use of right technology, and the
right equipment. Despite the significant number of research and pro-
mising results published, lignin is still underutilized in industry. Lignin-
derived products have shown so far that they have the potential to
significantly reduce the environmental impact of products. In addition,
to attract industry in producing lignin-derived products, a continued
investigation of cost-effective lignin valorization technologies is re-
quired. Using tools such as techno-economic analysis and life cycle
analysis can help in identifying benefits and challenges for a scaled up
production of lignin-based products and help bring the lignin valor-
ization technology from the infancy stage to the next step. Development
and design of lignin valorization based on the principle of eco-friendly
economy will help to grow integrated biorefinery industry and it will
also help to make the existing pulp and paper industry more profitable.
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