Bioresource Technology 271 (2019) 462–472

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Review

A review on lignin structure, pretreatments, fermentation reactions and T

biorefinery potential
Vinoth Kumar Ponnusamya,b,1, Dinh Duc Nguyenc,1, Jeyaprakash Dharmarajad, Sutha Shobanae,
J. Rajesh Banuf, Rijuta Ganesh Sarataleg, Soon Woong Changc, Gopalakrishnan Kumarh,
⁎

a
Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung City, Taiwan
b
Research Center for Environmental Medicine, Kaohsiung Medical University, Kaohsiung City, Taiwan
c
Department of Environmental Energy Engineering, Kyonggi University, Suwon, Republic of Korea
d
Division of Chemistry, Faculty of Science and Humanities, Sree Sowdambika College of Engineering, Aruppukottai, Tamil Nadu, India
e
Department of Chemistry and Research Centre, Aditanar College of Arts and Science, Virapandianpatnam, Tiruchendur, Tamil Nadu, India
f
Department of Civil Engineering, Regional Campus Anna University Tirunelveli, Tamilnadu, India
g
Research Institute of Biotechnology and Medical Converged Science, Dongguk University, Seoul, Ilsandong–gu, Goyang–si, Gyeonggi–do 10326, Republic of Korea
h
Green Processing, Bioremediation and Alternative Energies Research Group, Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Viet
Nam

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: In recent years, lignin valorization is commercially an important and advanced sustainable process for lig-
Lignocellulosic biomass nocellulosic biomass-based industries, primarily through the depolymerization path. The conversion of the lignin
Lignin moieties into biofuels and other high value-added products are still challenging to the researchers due to the het-
Biorefinery erogeneity and complex structure of lignin-containing biomass. Besides, the involvement of different microorgan-
Biofuel
isms that carries varying metabolic and enzymatic complex systems towards degradation and conversion of the
Hybrid–conversion
Sustainability
lignin moieties also discussed. These microorganisms are frequently short of the traits which are obligatory for the
industrial application to achieve maximum yields and productivity. This review mainly focuses on the current
progress and developments in the pretreatment routes for enhancing lignin degradation and also assesses the liquid
and gaseous biofuel production by fermentation, gasification and hybrid technologies along with the biorefinery
schemes which involves the synthesis of high value-added chemicals, biochar and other valuable products.

⁎
Corresponding author.
E-mail address: gopalakrishnankumar@tdtu.edu.vn (G. Kumar).
1
Authors have equal contribution to this work.

https://doi.org/10.1016/j.biortech.2018.09.070
Received 20 August 2018; Received in revised form 11 September 2018; Accepted 13 September 2018
Available online 18 September 2018
0960-8524/ © 2018 Elsevier Ltd. All rights reserved.
V.K. Ponnusamy et al. Bioresource Technology 271 (2019) 462–472

1. Introduction
Plant cell walls are composed of lignin which is a phenylpropanoid
biopolymer, giving mechanical strength to the plant structure. Cellulose
and hemicellulose make up the entire biomass and are firmly connected
to the lignin molecules via covalent and hydrogenic linkages which
make the structure extremely strong and recalcitrant to pretreatment
techniques. Lignocellulosic biomass is primarily comprised of cellulose
(38–50%), hemicellulose (23–32%) and lignin (12–25%) components
(Sun and Cheng, 2002; Gonzalo et al., 2016). The lignin component is
familiar as the second greatest inexhaustible natural organic polymer
which conveys the greatest energetic substance of all the above, em-
powers plants to build rigid chemical structures and also provides a
probability against hydrolysis of cellulose and hemicellulose in the
lignocellulosic biomass (Saake and Lehnen, 2012; Zakzeski et al.,
2010). Accordingly, certain novel course of reactions are desirable to
produce high value–added products from the lignin moieties (Kleinert
and Barth, 2008). At present, the most integrated bio–based refinery
techniques comprise four key divisions that include the harvesting and
storage of the feedstock, pretreatment, enzymatic hydrolysis and fer-
mentation process of the released sugar to biofuels (Dale and Ong,
2012). Moreover, lignin is the only large–volume renewable feedstock
that is comprised of an enormous number of aromatic monomers (Tuck
et al., 2012). The U.S. Energy Security and Independence Act of 2007
authorization announced that by 2022 the development of 79 billion
liters of second–generation biofuels wouldbe produced annually. Even
if specific basic research has been focused on the conversion of lignin to
the platform chemicals, materials and fuels, the efforts for commer-
cialization are based on the bioengineering of lignin to easerecovery
and conversion. Moreover, advances in coupling the analytical chem-
istry, computational designing and modelling dimensions of genetic
engineering for lignin pretreatment have rendered the lignin depoly-
merization and conversion easier (Ragauskas et al., 2014). It has also
been well demonstrated that lignin is more applicable trait than the
other existing ones of biomass and is attributed to the aromaticity and
side chains on the carbon backbone (Dale and Ong, 2012). In a nutshell,
the ease of extraction for lignin via a reduction in the cross–linkages
with the other polymers in the biomass and the depolymerization
pathways of the inherently complex lignin structure are two main
process considerations which determine the significance and value of
lignin biorefineries.
1.1. Green biomass processing
Lignin is a heterogeneous biopolymer and consists of phenylpro-
panoid moieties via the conjugation of a vast number of aromatic
monomers with different bonds derived from three mono lignols
(p–coumaryl, coniferyl and sinapyl alcohols) (Pandey and Kim, 2011).
Softwood lignin mainly comprises coniferyl alcohol, hardwood lignin
contains both coniferyl and sinapyl alcohols and grass lignin contains
all the above three moieties (Duval and Lawoko, 2014). Lignin has a
high recalcitrance to chemical and biochemical depolymerization due
to the existence of phenylpropanoid polymers, ether linkages (β–O–4)
(Azadi et al., 2013; Pandey and Kim, 2011) and a range of functional
groups namely methoxy, aliphatic and aromatic hydroxy, benzyl al-
cohol, ether and non–cyclic benzyl ether and carbonyls (Pandey and
Kim, 2011). Various green biomass processing procedures have been
adopted for the isolation of lignin from lignocellulosic biomass and
these procedures can generally be categorized according to the isolation
mechanisms. One category targets hydrolyzation/solubilization of cel-
lulose and hemicellulose except for lignin residue. Another one is based
on the dissolution of lignin residue (Azadi et al., 2013; Pandey and Kim,
2011). The isolated lignin is observed with different structural mod-
ifications like the isolation of organo-solv lignin (EOL) and is com-
paratively pure when the hydrolyzation/solubilization procedure is
followed and its interior structures also remain unchanged despite that
its formula weight is decreased because of partial cleavage of β–aryl
ether linkages (Bauer et al., 2012). The ethereal linkages get cleaved in
the degradation paths whilst new bonds are formed by way of con-
densation in the case of kraft lignin from the second category (Chakar
and Ragauskas, 2004). Such structural changes can be considered as the
most significant barriers for the prolificutilization of lignin (Bugg and
Rahmanpour, 2015). Moreover, the biorefineries together with the pulp
and paper industries produce a large quantity of lignin.
Moreover, the fungi and bacteriae significantly occupy vital role in
the metabolic systems for the destruction of lignin during biomass
processing. However, such lignin deconstruction processes often con-
stitute barriers for industrial applications where high yields and high
lignin utilization efficiencies are sought (McLeod et al., 2006; Nelson
et al., 2002). As a result, research in this direction had led to the iso-
lation of many enzymes which mediate lignin degradation with ac-
ceptably good yields and conversion efficiencies. Characteristically,
kraft and organo-solv lignins are the two appropriate candidates for
industrial applications for converting lignin to value–added chemicals
whereas ligno–sulphonates yield low–value chemicals which necessi-
tate complex processing. Since kraft lignin envelops a range of appli-
cations which include high value–added platform chemicals and pro-
ducts prodcution starting from the woody biomass by neans of pulping
and paper production processes., it is consequently considered as a
useful intermediate between ligno–sulphonates and organosolv lignin
for green biomass processing (Chen and Wan, 2017).

Table 1
Lignin valorization for aromatics and bio–oils.
Sl. No Lignin type Conditions Solvent used Catalyst Liquid products (%)

1 Klason birch lignin 200 °C, 15 h, 4 MPa H2 Methanol Pd/C 4–n–Propanolsyringol (35%)
2 Oxidized birch lignin 200 °C, 6 h, 1 MPa H2 Methanol Ni/MgAlO–C Mixed aromatics (22%)
3 Diphenyl ether 120 °C, 10 h, no H2 Isopropanol Ru/C Mixed aromatics (90–98%)
4 Acetophenone 320 °C, 2 h, no H2 Ethanol FeNiB Ethylbenzene (64%)
5 Alkali lignin 260 °C, 5 h, 4 MPa H2 Methanol Pd/C + CrCl3 Monomeric phenols (28.5%)
6 Enzymatic acidolysis lignins 260 °C, 4 h, 3 MPa H2 Methanol MoOx/Carbon nanotube Monomeric phenols (47%)
7 Lignin β–O–4 models 42 °C, 4 h, Ar Acetonitrile ZnIn2S4 Monomeric phenols (71–91%)
8 Vanillin 100 °C, 2 h, 1 MPa H2 Water Pd/PRGO/Ce–MOF 2–Methoxy–4–methylphenols (10%)
9 Poplar sawdust 200 °C, 3 h, 2 MPa H2 Methanol Pd/C – H3PO4 Monomeric phenols (45%)
10 Klason Miscanthus lignin 180 °C, 6 h, 1 MPa H2 Methanol Co@Nb2O5@Fe3O4 C20–C28 and C29–C37 fragments (54%)
11 2–Aryloxy–1–arylethanols 80 °C, 12 h, 10 mol % NaBH4 EtOAc Pd/C Aryl ketones (98%)
12 Olive tree lignin 80 °C, 12 h, no H2 Tetralin Ni10 % Al – SBA Monomers, dimmers and trimmers (17%)
13 Benzophenone 100 °C, 4 h, 2 MPa H2 Methanol [Pd(tpy)Cl]Cl Diphenylmethane (99%)
14 Guaiacylglycerol – guaiacyl ether 100 °C, 24 h, no H2 DMSO Vanadium Schiff base catalyst Monomeric phenols (90%)
15 1,3 – dilignol 160 °C, 16 h, no H2 o – xylene [Ru(Cl)(H)(PPh3)3)3 Guaiacol (89%)
16 Aryl ethers 80 – 100 °C, 2 – 10 h, 0.1 MPa H2 m – xylene Ni(o)/ligand Mixed aromatics (> 80%)

(Modified from source: Cao et al., 2018).

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V.K. Ponnusamy et al. Bioresource Technology 271 (2019) 462–472

1.2. Lignin valorization Table 2

Lignin content in various lignocellulosic biomass feedstocks.
Lignin has also been utilized in the synthesis of binding agents, Lignocellulosic biomass Lignin (%) References
dispersing or emulsifying agents, sequestrant agents as well as a raw
material for synthetic polymers such as phenol–formaldehyde resin, Bagasse 24.8 Kim (2018)
Barley hull 13.8–19.0 Isikgor and Becer (2015)
epoxy resin, polyurethane resin and polyester (Lin, 1983; Sen et al.,
Barley hull 19.3 Kim (2018)
2015). Lignin hence offers a remarkable platform for valorizing lig- Barley straw 6.3–9.8 Isikgor and Becer (2015)
nocellulosic biomass and promoting the lignin–based biorefineries Beech 20.0 Zhou et al. (2016)
(Bhaskar et al., 2015; Hatakeyama and Hatakeyama, 2010; Holladay Birch 22.0 Zhou et al. (2016)
et al., 2007). Lignin can also be a potential source of various aromatic Corn cobs 6.1–15.9 Isikgor and Becer, (2015)
Corn cobs 15.0 Bajpai (2016), Khalid et al. (2017)
compounds and chemicals (Table 1). However, chemically modified
Corn fiber 8.4 Kim (2018)
lignin can be used as a reinforcing agent or filler for polymer blends and Corn pericarp 4.7 Kim (2018)
composite materials (Kai et al., 2016). The syngas (CO + H2) products Corn stalks 17.5 Zhou et al. (2016)
derived from lignin can be transformed into methanol, dimethyl ether, Corn stalks 7.0–18.4 Isikgor and Becer (2015)
Corn stover 19.9 Zhou et al. (2016)
ethanol, blended or mixed alcohols, Fischer–Tropsch–fluids and C1–C7
Corn stover 18.6 Kim (2018)
gases. Lignin was oxidized under different oxidation conditions to Corn straw 11.0 Zhou et al. (2016)
produce vanillic acid, aliphatic acids, aromatic acids, aromatic alde- Corncob 20.8 Zhou et al. (2016)
hydes, quinones, cyclohexanol, dimethyl sulphoxide and β–keto adipate Douglas fir 27.0 Isikgor and Becer (2015)
(Bhaskar et al., 2015). The depolymerization of lignin has been assessed Eucalyptus 21.5 Isikgor and Becer (2015)
Fir 18.0 Zhou et al. (2016)
through the oxidation pathway in the presence of alkaline medium
Grasses 10.0–30.0 Isikgor and Becer (2015), Bajpai
using nitrobenzene or CuO as mild oxidants to produce phenolic alde- (2016), Khalid et al. (2017)
hydes like vanillin and syringaldehyde (Pandey and Kim, 2011; Villar Miscanthusgiganteus 12.02 Zhou et al. (2016)
et al., 2001; Zakzeski et al., 2010). Lignin can also be converted to Newspaper 18.0–30.0 Khalid et al. (2017)
certain high value–added products: aromatic hydrocarbons such as Nut shells 30.0–40.0 Khalid et al. (2017)
Oak 24.1 Isikgor and Becer (2015)
benzene, phenol, substituted phenols or polyols, catechols, cresols, Oat straw 10.0–15.0 Isikgor and Becer (2015)
eugenol, resorcinols, syringols, coniferols and guaiacols. In addition, Olive tree pruning 16.2 Kim (2018)
lignin can also find an application in the production of carbon fiber Paper 0.0–15.0 Khalid et al. (2017)
fillers, polymer extenders, substituted lignins, thermoset resins or gums, Pine 27.3 Zhou et al. (2016)
Pinewood 20.0 Isikgor and Becer (2015)
composites, adhesives or glues, binders, additives or preservatives,
Pinewood 27.7 Kim (2018)
pharmaceuticals bio–compounds and some other polyols (Bhaskar Pinewood 27.3 Zhou et al. (2016)
et al., 2015; Jong et al., 2012). The various existing linkages (ether, Poplar 15.5–16.3 Isikgor and Becer (2015)
CeC and ester) patterns in lignin have been catalytically depolymerized Poplar 29.1 Kim (2018)
into various aromatic value–added monomeric units or compounds Ray straw 9.9–24.0 Isikgor and Becer (2015)
Red maple 29.1 Kim (2018)
through cracking, hydrolysis, dehydroxygenation, reduction and oxi- Rice husks 15.4–20.0 Isikgor and Becer (2015)
dation processes to produce biofuels. Rice straw 17.0–19.0 Isikgor and Becer (2015)
Furthermore, there are a number of commercially essential phenolic Rice straw 13.3 Kim (2018)
compounds which can be efficiently derived from the degradation of Rice straw 12.2 Zhou et al. (2016)
Solid cattle manure 2.7–5.7 Khalid et al. (2017)
lignin (Fachuang, 2014). Using dehydroxygenation or zeolite up-
Sorghum straw 15.0–21.0 Isikgor and Becer (2015)
grading, lignin can be transformed to automobile or transportation Sorted refuse 20.0 Khalid et al. (2017)
fuels. For example, studies have been conducted to investigate the hy- Spruce 28.3 Kim (2018)
drogenation of C]C bonds and deoxygenation of CeO bonds under Spruce 27.9 Isikgor and Becer (2015)
sulfide NiMo/CoMo catalysts on Al2O3 (alumina) or Cr as well as aro- Spruce 28.2 Zhou et al. (2016)
Sugar cane 10.7 Zhou et al. (2016)
matic moieties or zeolite at 250–450 °C to produce oil form of phenol, Sugarcane bagasse 15.0–25.0 Isikgor and Becer (2015)
cyclohexane, benzene, naphthalene and phenanthrene (Fachuang, Sugarcane bagasse 11.4 Kim (2018)
2014; Oasmaa et al., 1993). Moreover, there is a vast growing en- Sweet sorghum bagasse 14.3 Kim (2018)
thusiasm for developing a novel lignin–based derivative by the fact that Switchgrass 15.0–20.0 Isikgor and Becer (2015)
Switchgrass 12.0 Bajpai (2016), Khalid et al. (2017)
lignin can be an alternate substitute of aromatic compounds to fossil
Switchgrass 17.8 Kim (2018)
resources (Isikgor and Becer, 2015). Waste papers from chemical 5.0–10.0 Khalid et al. (2017)
In this regard, intensive research efforts have been continually de- pulp
ployed to explore the potential routes for lignin valorization process. Wheat straw 12.0–16.0 Isikgor and Becer (2015)
This article reviews the current developments in the pretreatment Wheat straw 15.0 Bajpai (2016), Khalid et al. (2017)
Wheat straw 17.0 Kim (2018)
routes for enhancing lignin degradation and then assesses liquid and Wheat straw 18.0 Zhou et al. (2016)
gaseous biofuel production by fermentation, gasification and hybrid
technologies along with the biorefinery scheme which involves the
synthesis of highly value–added chemicals, biochar and other valuable towards microbial attack and oxidative stress, and contains well–built
products. cellulose microfibrils because of a different variety of alkyl–/aryl–ether
inter–unit linkages (Hu and Ragauskas, 2012). Generally, lig-
2. Structural characteristics of lignin nocellulosic biomass or its feedstocks mainly contain cellulose, hemi-
cellulose, lignin and a small amount of ash as well as extractives. The
Lignin is a complex, amorphous, three dimensional long–chain and lignin content present in different lignocellulosic biomass feedstocks is
heterogeneous high molecular weight (6 × 105–15 × 106 kg kM−1) shown in Table 2.
aromatic polymer of phenylpropanes of 3C attached with 6C atom
rings, methoxy groups and non–carbohydratic polyphenolic substances,
which are connected by ether linkages (Anwar et al., 2014). It is present 2.1. Lignin derivatives and chemistry
approximately about 10–25% of the biomass by weight in plant primary
cell wall and makes up a rigid, impermeable and resistant structure Lignin is an irregular and randomly cross–linked phenolic polymer

464
V.K. Ponnusamy et al.
which is composed of three different primary phenylpropanes monomer
or monolignol units of (i) p–coumaryl alcohol (abbreviated as “H” unit;
p–hydroxy phenyl propanol or 4–hydroxycinnamyl; grasses: 5%); (ii)
coniferyl alcohol (abbreviated as “G” unit; guaiacyl propanol or
3–methoxy4–hydroxycinnamyl; softwoods: 90–95%; hardwoods: 50%
& grasses: 75%) and (iii) sinapyl alcohol (abbreviated as “S” unit; syr-
ingyl alcohol or 3,5–dimethoxy 4–hydroxycinnamyl; softwoods:
5–10%; hardwoods: 50% & grasses: 25%) through a series of oxidation
steps (Brunow, 2004; Staley and Barlaz, 2009). The monolignol unit has
hydroxy (–OH) and methoxy(–OCH3) substituted phenylpropane unit
(Azadi et al., 2013; Boerjan et al., 2003; Weng et al., 2008) which are
joined through several dissimilar linkages to form the lignin structure.
The basic distinction in the latter three phenylpropane units are the
number of methoxy (–OCH3) groups appended to an aromatic ring.
Generally, softwood lignin has a rich (∼90%) content of guaiacyl or
p–coniferyl alcohol (G) unit with very low content of p–coumaryl al-
cohol (H) unit whereas hardwood lignin contains a blend of guaiacyl
(G) and syringyl (S) units and grass lignin contains a mixture of above
the three G, H and S units (Li et al., 2013; Zakzeski et al., 2010).
The phenylpropane building units or blocks of lignin distribution
depend on the types of plant biomass (Itoh et al., 2003; Suhara et al.,
2012). Herbaceous plants like grasses (10–19%) have the lowest lignin
contents which have all the three phenylpropane units collectively to-
gether with p–hydroxycinnamic acids (p–coumaric acid, ferulic acid and
sinapic acid) (Hendriks and Zeeman, 2009; Itoh et al., 2003) while
softwoods (25–35%) and hardwoods (18–25%) have the highest lignin
content (Silverstein et al., 2007; Valaskova et al., 2007). The digest-
ibility of biomass increases by applying suitable pretreatment techni-
ques (Vidal and Molinier, 1988) which can assist the deconstruction
and depolymerization of the lignin structural composition. Lignin can
be further classified into three types namely Type–G (softwood lignin),
Type–G–S (hardwood lignin) and Type–H–G–S (grass lignin). However,
these moieties can frame the lignin matrix through different linkages
(aryl– or alkyl–ether, ester and CeC) with various functional groups
(eOH, eOCH3, C]O, eCeOH, propyl moiety, etc) resulting in ex-
tremely convoluted lignin structures (Wang et al., 2017a).
2.2. Possible mechanism for lignin degradation
Lignin contains a different variety of alkyl– or aryl–ether inter–unit
linkages (∼60–70%), carbon–carbon (∼25–35%) and very low ester
bonds (< 5% in herbaceous plants) which includeβ–O–4, β–5, β–β, β–1,
β–5, β–6,α–β,α –O–4, α –O–γ, γ –O– γ, 1–O–4,4–O–5,1–5,5–5 and 6–5
(Holtman et al, 2007; Zakzeski et al, 2010). Based on the literature,
seven major linkages namelyβ–O–4–aryl ether (β–O–4), β–O–4–aryl
ether (β–O–4),4–O–5–diaryl ether (4–O–5), β–5–phenylcoumaran
(β–5),5–5–biphenyl (5–5), β–1–(1,2–diarylpropane) (β–1) and β –β
(resinol) are present in the lignin molecules (Dorrestijn et al., 2000;
Wang et al., 2017b; Zhou et al., 2016). The correct linkage structures in
native lignin of biomass are not completely known. But aryl– or alky-
l–ether linkages (CeOeC of βeOe4, αeOe4 etc.) are more pre-
dominant than the ester bonds or carbon–carbon bond linkages. Ad-
ditionally, lignin can act as an adhesive medium, among the dissimilar
components of lignocellulosic biomass cell walls, consequently making
it water–insoluble (Fengel and Wegener, 1984). The degradation path
of the lignin moiety involves hydrolysis followed by cleavage of aryl–/
alkyl–ether, ester and CeC bonds, demethoxylation, alkylation and
condensation reactions (Barbier et al., 2012). The cleavage of Cα–Cβ
bond is easier as well as the cleavage of βeOe4 ether bond is superior
to other bond cleavages (Ehara et al, 2002; Wang et al., 2009). How-
ever, the aromatic phenyl rings remain unaltered or unaffected and the
biphenyl type moieties persist in their stability (Ehara et al., 2002).
Under mild conditions of very low temperature with a short period of
reaction time, the phenolic monomeric and dimeric compounds are
derived from lignin, consequently a cleavage of the ether and CeC
bonds occur. At high temperatures (250–550 °C) and pressures
465
Bioresource Technology 271 (2019) 462–472
(5–25 MPa), the lignin is converted by way of demethoxylation and
alkylation reaction pathways to produce many desired compounds
(Singh et al., 2015).
3. Pretreatments for lignin separation and degradation
Pretreatments are vital to modify biomass particle size, its structure
and its chemical composition. It is essential for reducing the recalci-
trance of biomass to deconstruction. There are a number of studies
which support that pretreatments work by deconstructing the lignin
structure as well as subsequently expanding enzyme accessibility to
cellulose in the biomass for an effective separation from other bio
components especially from hemicellulose and cellulose (Li et al.,
2013). As part of the pretreatment steps, hydrolysis of the carbohydrate
part in the biomass materials into monomeric sugars can be accom-
plished more quickly and with higher yield of sugars. A perfect pre-
treatment strategy ought to endow a number of key advantages. The
main advantages are decrease in biomass particle size, quick enzymatic
hydrolysis to enhance the monosaccharide (glucose) yield to avoid the
degradation of carbohydrate, a decrease in enzymatic action inhibition
and in the energy needs (Duque et al., 2016; Parveen et al., 2009). In
general, the saccharification of lignocellulosic biomass without pre-
treatment can yield fewer than 20% of aggregate sugars. However, after
the pretreatment, the yield can ascend to 90% with various pretreat-
ment like biological, physical, chemical and physico–chemical
methods. The pretreatment methods are presumably the most en-
ergy–demanding activity in biomass conversion for biofuels and
synthesis of high value–added chemicals. Pretreatment of lignin taking
place in the biorefineries will probably be used for isolating all the
fractions of lignocellulosic biomass materials and obtain high purity
unadulterated feedstocks. However, the pretreated lignin in the pulp
and paper industries is an appropriate candidate which may be ex-
pected to support the lignin valorization process (Valaskova et al.,
2007). Moreover, the different lignin pretreatments utilize different,
and at times harsh, conditions of temperature, pressure, pH range and
solvents.
3.1. Biological pretreatment
Currently, the biological pretreatment of lignocellulosic biomass
materials has been received more and more research attention by
reason of its many favourable characteristics. The merits of this process
are the cost–effectiveness, eco–friendliness and high propensity in de-
grading plant cell materials. A relatively wide variety of microorgan-
isms are capable of degrading lignin by way of enzymatic and/or che-
mical pathways and make the plant biomass more amenable to
saccharification via the polysaccharide sugar units (Valaskova et al.,
2007). During biological pretreatment, there are also a number of fungi
which are capable of secreting enzymes that can subsequently degrade
the lignin, hemicellulose and polyphenols, present in the crude bio-
mass. White and soft–rot fungi have been associated in the degradation
of lignocellulose materials. However, white–rot fungi show remarkably
more significant effects, when compared to the red–rot fungi as they are
employed to mediate some form of biological pretreatment of lig-
nocellulosic biomass (Agbor et al., 2011; Sun and Cheng, 2002).
Brown–rot fungi, on the other hand, first attack the cellulose, while soft
and white–rot fungi attack both lignin and cellulose moieties through
lignin deconstruction pathways mediated by enzymes such as lignin
peroxidases, manganese–dependent peroxidases, polyphenoloxidases and
laccases which are capable of degrading the lignin effectively (Agbor
et al., 2011). Some of the selected white–rot fungi such as Phanerochaete
chrysosporium, Phlebia radiata, Dichmitus squalens, Rigidosporus lignosus
and Junguasepar abilima shows excellent delignification of wood and
wheat straw. By the latter, lignin depolymerization with the fungi
species takes a very long time but it can be very effective and selective
(Hatakka, 1994). Moreover, such fungal biomass depolymerization has
V.K. Ponnusamy et al.
also been found to save approximately 15–20% of the electrical energy
requirements needed for the ethanolysis of beech wood with white–rot
fungi (Itoh et al., 2003). Moreover, nearly fifty–one white–rot basi-
diomycetes of Punctularia sp. are available. TUFC20056 and
TUFC20057 have shown efficient and selective lignin degradation by
way of the enzymatic hydrolysis of bamboo culms for the production of
bioethanol (Suhara et al., 2012).
3.2. Physical pretreatment
In general, the physical pretreatment methods include mechanical
(e.g. grinding, chipping, milling, knife milling and scissor cutting),
microwave irradiation, low frequency ultrasound irradiation, steam
explosion and liquid hot water treatments. The mechanical pretreat-
ment methods lead to a reduction of particles size between 5 cm to few
millimeters which can further decrease the degree of crystallinity of
cellulose and thereby an eventual increase in the accessible surface area
and pore size of the substrate. However, the microwave irradiation
pretreatment has been found particularly efficient in increasing the
solubilization of lignin and cellulose, available from lignocellulosic
biomass. However, ultrasound and microwave irradiation pretreat-
ments have a number of demerits and these may be summarized in
terms of energy–insensitivity, production of possible inhibitory phe-
nolic acids like byproducts, complex operation procedures and strict
monitoring of equipments – that all collectively limit their commercial
applications.
3.3. Chemical pretreatment
Using strong acids (HCl, H2SO4 and HNO3), alkalis (NaOH, KOH, Ca
(OH)2, ammonia and hydrazine), organic solvents (benzene, ether, cy-
clohexane, hexane, ethanol and methanol), ozone (O3) and ionic liquids
(ILs), the chemical pretreatment methods have been reported to bring
significant positive effects on the native structure of lignocellulosic
biomass. Generally, the strong acids are not favoured because they are
more corrosive and may be cost–intensive. Similarly, the alkaline pre-
treatment disturbs the lignin structure and breaks the linkages (such as
aryl–ether, ester and CeC bonds), amongst the lignin and the other
sugars or carbohydrate fragments from lignocellulosic biomass and
thence making the starch in the heteromatrix more open (Saratale and
Oh, 2015). This pretreatment method is an excellent approach with
low–lignin content biomass like agricultural residues. In the chemical
pretreatment method, when cotton stalks were autoclaved with 2% of
sulfuric acid and hydrogen peroxide medium, a 25% and 30% decrease
in lignin content for 90 and 60 min at 121 °C/15 psi, respectively, were
recorded (Silverstein et al., 2007). The mnewspaper, pretreated with
35% acetic acid together with 2% nitric acid (HNO3) resulted in the
reduction of lignin by 80% (Vidal and Molinier, 1988). Ozone (O3)
pretreatment is another way of reducing the lignin content of lig-
nocellulosic wastes and this type of approach results in an increase of
the in vitro digestibility of the treated materials and it does not produce
any toxic residues. After the ozonolysis pretreatment of poplar sawdust
under enzymatic hydrolysis, the lignin content decreased from 29% to
8% (Xiao and Clarkson, 1997). In addition, the acid pretreatment can
be effectively utilized to remove hemicelluloses competently by
breaking ether bonds in lignin/phenolics–carbohydrates complexes
without dissolving the lignin. The pretreatment of cane bagasse with
hydrogen peroxide (H2O2) greatly enhances its susceptibility to enzy-
matic hydrolysis. About 50% of the lignin and most of the hemicellulose
were solubilized by 2% H2O2 at 30 °C within 8 h, and 95% efficiency of
glucose production from cellulose was achieved by the subsequent
saccharification by cellulases at 45 °C for 24 h (Azzam, 1989). Recently,
certain imidazonium salts of ionic liquids (ILs) are being widely used in
biomass fractionation (Agbor et al., 2011). Generally, ILs show very low
environmental impact because of their low–volatility, low vapour
pressure, high solvent power, non–toxic character, non–flammability
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Bioresource Technology 271 (2019) 462–472
and eco–friendly solvent characteristics in contrast to many other or-
ganic solvents. Thus, ILs can be expected to reduce the cost of solvent
usage and also be recycled (Agbor et al., 2011; Brodeur et al., 2011).
After the pretreatment with N–methylmorpholine–N–oxide, rice straw
substrates gave a 60–68% enhancement in methane production at
130 °C during 1 h (Teghammar et al., 2012). ILs can also selectively
extract the unaltered lignin from the lignocelluloses while simulta-
neously yielding a highly degradable cellulose fraction (Wyman et al.,
2009).
3.4. Hybrid pretreatment
Hybrid pretreatments in the case of deconstructing the lignin, a
number of studies have shown that a combination of two pretreatment
methods such as biological pretreatment with chemical or physical
method is more effective when compared to pretreatments with a
chemical or biological method alone. Ultrasound–assisted and oxidative
(H2O2) medium pretreatment procedures were studied by Yu et al.
(2009), in this work, combined pretreatment shows better lignin re-
moval than in the case of the one–step pretreatment with a 2% H2O2 for
48 h (Yu et al., 2009). The combined ultrasound and alkali pretreat-
ments of birch and pine saw dusts. Kadimaliev et al. (2003) explored
that there had been an increase in the intensity of lignin degradation.
Ultrasound treatment loosened the wood structure by weakening the
bonds amongst and within polysaccharide and lignin molecules and
therefore led to an increase in the accessibility of fungal enzymes. The
results in the work of Kadimaliev et al. (2003) indicated that the pre-
treatment of the lignocellulosic substrate with alkali or ultrasound is
essential for intensification for the bioconversion of lignin. In another
study, the hybrid pretreatment (which comprised both biological and
acid pretreatments) using Echinodontium taxodii or Antrodia sp. 5898
with 0.25% H2SO4 was found to be more effective than a one–step
pretreatment (Ma et al., 2010). In the later work, the reducing sugar
yield increased by 1.13–2.11 folds than in the case of the acid pre-
treated water hyacinth, and this result indicated that a hybrid combi-
nation of biological and mild acid pretreatment can be regarded to be
promising enough a strategy for the improvement of enzymatic hy-
drolysis and ethanol production from water hyacinth having low lignin
content.
4. Detrimental reactions in depolymerization of lignin
The depolymerization of lignin involves the formation of a con-
siderable amount of detrimental high molecular weight compounds
from the highly reactive intermediates like 4–vinylphenol, 2–methox-
y–4–vinylphenol, isoeugenol, quinone methide etc., after the main pri-
mary reaction path, a secondary repolymerization route mainly via
coupling of the odd electron species, condensation of vinyl functional
unit (Patwardhan et al., 2011; Ye et al., 2012). It is due to the fact that
some of the chief functional units of the lignin moiety like Ar–OH (free
aromatic hydroxyl), certain linkages like β–O–4 ether & Cα–Cβ bonds
and high reactivity of formaldehyde (phenol–formaldehyde resin) like
products from the cleavage of Cγ position in the lignin side chains play a
vital role in certain secondary reactions via condensation coupled re-
polymerization paths which lead to a substantial restriction in the vale
added as well as fuels yield and finally the decomposition of lignin
occurs (Bai et al., 2014; Fossey et al., 1995; Huang et al., 2015; Saisu
et al., 2003). In addition, the initially generated odd electron species
involve the paths viz abstraction, rearrangement and irreversible radi-
cal–radical coupling mechanistic reactions to yield a number of un-
desirable components (Kim et al., 2017). Thereby, inducing rapid sta-
bilization characteristics of the lignin derived intermediates can only
prevent such reaction pathways (Toledano et al., 2014). In this concern,
certain compounds have been used as capping agents like boric acid,
water–ethanol–phenol mixture etc, to block addition as well as con-
densation reactions among the primary products and stabilize the
V.K. Ponnusamy et al.
functional units Ar–OH, Cγ respectively etc. In addition, a rapid
quenching process of the reactive odd electron species and hydro-
genolysis in the presence of certain metal catalysts like Ru, Pt, Pd, Ni,
etc can minimize reactions of the lignin side chains (Deuss and Barta
2016; Sun et al., 2018).
5. Liquid and gaseous biofuel production
During the gasification of lignin, it is converted to hydrogen (H2),
carbon monoxide (CO), carbon dioxide (CO2) and methane (CH4). The
generalized and well recognized methods for gasification of lignin are
(i) conventional gasification at high temperatures and almost atmo-
spheric pressure with oxygen (O2) and/or water (> 800 °C, 1 bar), and
(ii) catalytic gasification in supercritical water at moderate tempera-
tures under high pressures (350–500 °C, 250 bar) (Yamaguchi et al.,
2008; Kang et al., 2015). Generally, temperature, pressure, steam,
concentration of oxygen (O2), heating rate, composition of lignin con-
tent and impurities present in the biomass materials affect the yield of
the products. The syngas products (CO + H2) from lignin materials
have already been developed in different industries and thus produced
syngas can be converted to a wide range of high value–added products
like alcohols, ethers, paraffin and aromatic hydrocarbons through the
Fischer–Tropsch (FT) synthesis reaction (Yamaguchi et al., 2012;
Farzaneh et al., 2014). Further, the lignin gasification is focused on the
conversion of black liquor or black alcohol (containing C, O, Na, S, H
and K) which is the direct byproduct of the papermaking process. At
very high temperatures (> 900 °C), the conventional gasification pro-
cess suffers from high corrosion due to soluble base or alkali com-
pounds and also diminishing the sulfur/sodium (S/Na) ratios of the
recouped chemicals, which eventually increase the separation charge or
cost.
In the conventional perspective of a biorefinery of lignin, the iso-
lated fragments are the monosaccharides of glucose and lignin. There
involves physical, chemical as well as biological pretreatments followed
by enzymatic hydrolysis. The carbohydrate sugar parts are then con-
verted into bio–alcohols like methanol, ethanol, butanol and other
bio–based value–added products. In general, the liquefaction of lignin
present in the lignocellulosic biomass occurs very quickly through the
early stages of the liquefaction process since lignin has an amorphous
structure and it is easily accessible for liquefaction (Ge et al., 2018). The
hydrothermal liquefaction of lignin moiety takes place via hydrolysis
and cleavage of aryl–/alkyl–ether, ester and CeC linkages. Thereby,
demethoxylation, alkylation and condensation reactions take place
(Barbier et al., 2012). Further, the lignin can be converted into phenolic
and several alkyl phenolic compounds through demethoxylation and
alkylation reactions by the side of high temperatures (250–550 °C) and
pressures (5–25 MPa) (Singh et al., 2015).
6. Biorefinery scheme
These days, the biorefineries are focusing on the production of
biofuels from the feedstocks with high sugar content. In this regard, the
valorization of lignin involves a new potent technique which is the
hybrid chem–biorefinery or hybrid biorefinery route that can bring the
merits of higher efficiency of lignin depolymerization through certain
chemical approaches and excellent selectivity of the targeted high va-
lue–added biocompounds or chemicals using green microbial ap-
proaches (Wild Paul, 2015; Wu et al., 2017).
Commercially, lignin has been mobilized around 300 million dollars
(Schutyser et al., 2018). The aggregates of lignin accessibility in the
biosphere surpass 300 billion tons and there are an every year incre-
ments by around 20 billion tons (Smolarski, 2012). With this economic
performance, lignin may be expected to turn into the principal sus-
tainable resource for both the biofuel and platform chemicals in-
dustries. Moreover, lignin can be utilized as an eco–friendly alternative
to numerous petro–derived substances, rubber additives, thermoplastics
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Bioresource Technology 271 (2019) 462–472
and pharmaceuticals (Zakzeski et al., 2010). Due to the lack of in-
novative processing techniques, there are some hurdles which hamper
the full–fledged development and implementation of lignin–based
biorefineries. As a result, the commercial productions of biochemicals
from lignin–based feedstocks become a complex process strategy.
6.1. High value–added chemicals production
The macromolecular structure of lignin brings the possibility to
valorize the lignin substrate into an extensive variety of high va-
lue–added products. Only a few articles are showing up the essentials of
the various valorization paths for making high value–added products
from the lignin (Pandey and Kim, 2011; Zakzeski et al., 2010). The
valorized products from lignin fall into two categories, namely, mac-
romolecules and aromatics.
6.1.1. Macromolecular products
At present, lignin–derived products are synthesized via the depoly-
merization pathways which include reductive catalytic fractionation,
non–reductive, reductive (mild, harsh and bifunctional hydroproces-
sing) with hydrosilanes, oxidative, acid– and base–catalyzed, solvolytic
and thermal processes (Holladay et al., 2007).
6.1.1.1. Carbon fibers. Carbon fiber, starting from 2011, has been
occupied a yearly worldwide market of about 46,000 metric tons
which valued itself at $1.6 billion and this market is projected to an
increment up to 140,000 metric tons through an estimation of $4.5
billion constantly with years by 2020 (Smolarski, 2012). However, the
fundamental processing is cost–intensive (Smolarski, 2012) and this is
due to the bioprocessing of its precursor polyacrylonitrile ($15 kg−1)
(SAE Automotive Engineering Magazine, 2013). Moreover, the lignin as
a characteristic natural, low–cost carbon source with high carbon
content of about more than 60% carbon by mass has been turned into
a cost–effective precursor for the synthesis of carbon fiber via melting
spin, oxidative stabilization of lignin fiber, carbonization under N2,
surface treatment and sizing (Baker and Rials, 2013; Ragauskas et al.,
2014). Two main advantages for the utilization of lignin are the lower
melting temperature and faster stabilization capability than the
polyacrylonitrile precursor (Baker and Rials, 2013). As the significant
source of lignin originates from kraft lignin, it is hard to recover the
pure lignin for further processing to get lignin–based carbon fiber of
poor mechanical properties in comparison with conventional
PAN–derived carbon fiber (Ragauskas et al., 2014). Exceptionally, the
shapeless amorphous structure of lignin brings about the development
of disordered glassy carbon, by the pyrolysis process (Saha et al., 2013).
These days, a significantly specialized challenge for the utilization of
the lignin as carbon fiber originates from the dilemma, arising in the
process of melt spinning (Department of Energy, 2007). A few research,
findings have been made which could be employed to deal with the
related issues of purification and structural modification of lignin.
Lignin that has been purified in an organic solvent which has been
found to have magnificent spin ability (Baker et al., 2012), making it a
precursor for the generation of carbon fiber in comparison with the
untreated lignin. Furthermore, structural modifications of lignin by the
utilization of acetic, succinic, phthalic and maleic like anhydrides with
tetrahydrofuran (THF) and methanol solvents indicate similar outcomes
(Chatterjee et al., 2014). It has been accounted for that about 40–50%
of auxiliary steel could be supplanted with carbon fiber composite
materials (Ragauskas et al., 2014) and this could occupy a crucial
commercial segment, especially in the automotive sector when
compared to the carbon fiber from PAN (Jahn et al., 2012).
Moreover, the statistical analysis has demonstrated that such sectors
would not pay more than $7–11 kg−1 for carbon fiber material
(Smolarski, 2012). The Oak Ridge National Laboratory (ORNL) is an
American multi–program science and technology national laboratory,
sponsored by the U.S. Department of Energy and is of now the pioneer
V.K. Ponnusamy et al.
in the production of lignin–based carbon fiber (Smolarski, 2012). It
constructs $8 per kg, which could be commercially available for about
$12 per kg. An ongoing estimation by ORNL showed that the
lignin–based carbon fiber could be sold at $12 kg−1 and this estimate
is very near to the objective range sale price in these sectors (Smolarski,
2012).
6.1.1.2. Polyurethane products. Polyurethanes are remarkable
polymeric compounds and are amongst the most flexible polymers for
their intended range of applications. Its commercial scope was in the
range of about $52 billion in 2015 and it is expected to gain $77 billion
by the year of 2023 (Global Market sights, 2016). The polyurethane
synthetic pathway incorporates the reaction of diisocyanates and
polyols with terminal hydroxyl functionals (Engels et al., 2013) and
polyurethane exists both in the rigid and flexible frames. Polyurethanes
are usually utilized as insulation and floating materials by the reason of
their rigid form and also in their flexible frames for cushioning and
packaging materials (UNEP (United Nation Environmental
Programme), 1996).
Additionally, the lignin can be consolidated as a polyol in poly-
urethane synthesis (Strassberger et al., 2014) and hence structurally
modified before being utilized. Such modifications depend on the dii-
socyanates moiety as the utilization of the kraft lignin and methylene
diphenyldiisocyanate (Duong et al., 2014) forms a high atomic weight
polyurethane (920,000 g mol−1) at a temperature at 80 °C for 3 h (Nadji
et al., 2005; Duong et al., 2014). Furthermore, in the synthesis of
polyurethane, the lignin polymer with hydroxyl (–OH) functional can
replace polyols effectively (Zhang et al., 2015). The incorporation of
amino functional (–NH2) into lignin enhances its water dissolvability
and reactivity with isocyanate, and consequently the formation of
polyurethane with enhanced mechanical, anti–aging, rigid and brittle
characteristics becomes possible in comparison with the conventional
one. Aniceto et al. (2012) demonstrated that oxypropylation could be
employed to graft polypropylene oxide into lignin and this procedure
eventually is leading to the formation of liquid polyols in which the
hydroxyl functional groups have been rationalized for polyurethane
characterization.
Fig. 1. Biorefinery scheme of lignin biopolymer (modified from Source: Schwartz et al., 2016).
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Bioresource Technology 271 (2019) 462–472
6.1.1.3. Other macromolecular products. Thermoset and resin
macromolecules have a large commercial market and the value of
lignin–valorized macromolecular materials is significantly higher than
using lignin as a source of power and fuel (Holladay et al., 2007). Lignin
can commercially be valorized for some other macromolecular
materials such as polymeric modifiers, adhesives and resins
(Ragauskas et al., 2014; Strassberger et al., 2014; Upton and Kasko,
2016; Zhao and Abu-Omar, 2015).
6.1.2. Aromatic compounds
6.1.2.1. Butane, toluene and xylene (BTX) moieties. Phenols, benzene,
toluene, xylene (BTX) and terephtalic acid can be synthesized more
efficiently from lignin than from fossil–based resources. The innovation
to change the lignin molecules into BTX is a two–step process. The
initial step incorporates a depolymerization of the lignin into
oxygenated aromatic monomers, then followed by a second step
hydrodeoxygenation (HDO) and demethoxylation (Jongerius, 2013).
The most employed noble metal catalysts in the latter BTX production
process are Pt, Rh, Pd and Ru. It results in cyclic aliphatic hydrocarbons
via hydrogenation of the aromatic monomers (Lee and Deng, 2015;
Zhao and Lercher, 2012; Jongerius, 2013) which demonstrates that the
application of a novel catalytic system namely Co–Mo/Al2O3 and
Mo2C/CNF could assist the lignin conversion effectively in to BTX,
after reforming treatment of liquid phase. Moreover, BTX is the
precursor for a series of materials such as resins, nylon fibers,
polyurethane and polyester. Productive advancement to get BTX from
lignin can possibly expand the utilization of lignin–based waste
materials. The worldwide generation of BTX was around 100 million
metric tons (1.0 × 1011 kg) in 2010 (Jongerius, 2013) and it is expected
to develop at the rate of ca. 4.4% CAGR (Compound annual growth
rate), every year from this year to 2020 (Smolarski, 2012). At present,
the greater part of the BTX originates from fossil derived oils are
becoming replaced by the lignin based biomass. Such a BTX generation
is at present in the R & D stage and is expected to reach the commercial
innovation stage within 10–20 years (ACC (American Chemistry
Council), 2011).
V.K. Ponnusamy et al.
6.1.2.2. Phenolic compounds. Phenol is mostly produced using cumene,
which is a product obtained from alkylation of lignin–derived benzene.
The worldwide market for phenol is around 8 million metric tons and
estimated to have a commercial value of about USD12 billion, out of the
year 2010 (Brzonova et al., 2014). Lignin–to–phenol depolymerization
needs a further one to two decades to capture the commercial market
stages. Lignin is rich in both aliphatic and phenolic hydroxyl functional
groups and the HDO process of lignin yields phenolics with various
methoxylation degrees. The methoxy functional group (–OCH3) can be
replaced through demethoxylation by utilizing certain catalysts namely
Mo2N and CoMo/Al2O3 (Liu et al., 2012; Wu et al., 2005). Phenols are
broadly utilized in the synthesis of formaldehyde resins and
polyurethanes (Freitas et al., 2009; Malaviya and Rathore, 2007).
Today, the cost of phenol is specifically influenced by oil, and hence
getting the innovation of transforming lignin into phenol.
6.1.2.3. Vanillin. Vanillin has been economically derived from lignin
since 1937, and the worldwide market for vanillin in 2011 was assessed
to be 16,000 metric tons with an estimated value of $230 million.
Around 20% of the manufactured vanillin originates from valorization
of lignin, and the remaining 80% originates from unrefined petroleum
(Borregaard, 2015). Vanillin is outstanding in its utilization as one the
world's mostly used flavoring agent (Yang et al., 2013) and is produced
from lignin through the oxidative catalytic pathway rather than the
hydrogenolytic pathway (Hua et al., 2007).
6.2. Biochar and other valuable products
Lignin is a precursor to lignite coal throughout a three–step geo-
chemical process that changes lignin into lignite coal. This procedure is
known as coalification, which incorporates microbiological degradation
of cellulose to transform the lignin into humic yield and inturn they
build coal particles (Miller, 2011). The lignin particle is evaluated to
understand a dehydroxylation procedure in which cleavage of the
βeOe4 etherial bond and a demethylation procedure to coalify lignin
into lignite coal have taken place (Hatcher and Clifford, 1997). Because
of the similitudes between lignin and lignite coal, lignin has the po-
tentiality as a feedstock for the generation of powdered activated
carbon for the mercury sequestration.
7. Perspectives and recommendations–biorefinery scheme
The biorefinery scheme of lignin biopolymer by depolymerizationis
is briefly depicted in Fig. 1. In general, the lignin derived compounds
are the mixture of lignin products obtained from depolymerization and
also isolation of the pure compounds is technically challenging as well
as the yield of individual derivative has economically low values.
During the depolymerization process of lignin the products like alkyl,
alkenyl, carbonyl, alcohol, carboxyl and ester compounds are utilized as
biorenewable fuels, solvents, polymers and aromatic chemical reagents.
One of the largest challenges associated with lignin valorization is that
there are economic pathways for conversion of lignin to value–added
fuels and chemicals. In primary core transformations that affect the
phenolic core is done through hydrodeoxygenation (HDO) i.e., HDO of
lignin depolymerization products often form an essential and primary
upgrading step. Fig. 1 clearly shows that the HDO constituents can be
divided in four sub–classes based on the targeted products like cy-
cloalkanes, aromatics, phenols and cyclohexanols/cyclohexanones and
also these four classes show a characteristic O/C and H/C ratio. The
lignin derived HDO products of cyclohexanes may serve as mid–range
fuel additives which are derived from methoxylated phenols through
the combined action of both noble (Ru, Pd, Pt) or nickel–based metal
catalysts (hydrogenation) followed by Bronsted acidity (dehydration
and/or demethoxylation) (Zhang et al., 2014, Luska et al., 2015). The
higher value HDO products of aromatic hydrocarbons like pro-
pylbenzene were obtained as selective deoxygenated aromatics
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Bioresource Technology 271 (2019) 462–472
followed by direct CeO hydrogenolysis which is preferred over ring
hydrogenation and also the selectivity is favored in gas phase at very
high temperature and low pressure (< 1 bar H2) under sulfided CoMo–
and NiMo–based catalysts (Joshi and Lawal, 2013, Ruiz et al., 2012) in
this transformation. Another higher value added lignin derived HDO
compounds of phenolics are also obtained from noble (Pd/C, Ru/C) and
base metal (Fe/C, MoCx/C, WP/SiO2) catalysts under selective de-
methoxylation (Sun et al., 2013). The last lignin derived HDO products
of cyclohexanols via demethoxylation followed by aromatic ring hy-
drogenation without removal of functionality under suitable selective
catalysts like Ni/CeO2, Raney Ni, CoNx/C, Ru–MnOx/C, etc can be uti-
lized for this transformation in liquid phase (Wang and Rinaldi, 2012,
Liu et al., 2016, Ishikawa et al., 2016). Moreover, the alkylated cyclo-
hexanols (like propylcyclohaxanol) can be oxidized towards the corre-
sponding cyclohexanones and successively converted into alkylated
caprolactone (via Baeyer–Villiger oxidation) which is a potential
polyester building block, adipic acid and caprolactam (Schutyser et al.,
2015). Furthermore, the side chain transformations can also be per-
formed separately, while leaving the phenolic core unchanged and the
high value–added products are obtained through oxidation, hydro-
genation, hydrogenolysis and dehydration processes (Schutyser et al.,
2018).
Lignin, usually a waste product of paper and pulp and biorefining
industries, is presently pulling in more consideration than ever. The
field of lignin valorization has seen critical development and advances
from the previous decades. The aromaticity of lignin has a solid com-
mercial potentiality. Its usage is both ecologically and economically
valuable. Current innovations with lignin usage are still to a great ex-
tent and constrained to moderately low fuel and power consumption.
Commercialization of lignin as a precursor for the selected macro-
molecular materials and aromatic products requires additional in-
novative effort. There are still hindrances existing between the ex-
amination of inherent lignin structure, handling of lignin
depolymerization, and applications of the final products. Even though
such a zone is being contemplated thoroughly. However, there are some
serious efforts needed, regarding a strong collaboration across different
disciplines in science and engineering. There is likewise dependably the
topic of feedstock fluctuation from area to area and in addition starting
with one growing season then onto the next. With these difficulties,
lignin can be a substitute for the fossil–based feedstock for some items.
Moreover, the government can assume an essential part in catalyzing
commercialization by setting strong approaches that push for fossil
feedstock substitutions. Multidisciplinary and shared collaborative
team look into the lignin valorization is relied upon to proceed, develop
and flourish sooner rather than later. At long last, to manage and en-
hance future research on fractionation/depolymerization, we might to
bring up a couple of basic comments as learnt from the above review,
the structure and reactivity of the detached lignins has to be adminis-
tered via the biomass kind, the fractionation strategy, and the nature of
the fractionation technique which decide the confined lignin yield or
assay. In this manner, reasonable examinations of basic qualities must
be made by decoupling these three deciding viewpoints from each
other.
An optimal valorization of lignin into chemicals requires optimal
use of the entire lignin portion in the feedstock, which thus necessitates
the combination of an effective (high yield) lignin isolation and depo-
lymerization step. Similarly, as for the depolymerization of lignin, the
viability depends on the facts that the depolymerization technique and
the chemical composition of the lignin substrate. Not only the im-
provement in the cost–effective approaches is at a standstill height due
to the complex characteristics of lignin which can influence strongly the
involved reaction pathways in the lignin valorization but also the im-
plicated processes considerably distort the structural individuality for
the lignin composition. Thereby, it has limited the yield towards the
production of the present and future biorefineries along with certain
high value added platform chemicals. Furthermore throughout the
V.K. Ponnusamy et al.
lignin conversion process, there are the possibilities for a certain det-
rimental reactions among the formed intermediate products. Though,
the isolation and utilization processes of the lignin were practiced back
to the near beginning of 1900s, the researchers yet are seeking the
successful lignin valorization techniques. A reasonable correlation be-
tween various depolymerization requires that the lignin substrate be
the same, and the other way around. At the point when these essentials
are satisfied, fractionation and depolymerization techniques can be
assessed over various investigations. In any case, an extra obstacle is a
variation in the analytical techniques that exist between different in-
vestigations, prompting various results. Subsequently, to encourage a
reasonable and dependable appraisal of the different fractionation and
depolymerization techniques, similar examinations that remembers the
proposed criteria and apply a similar analytical technique which can
give significant consideration. As last, we might want to fortify the
research towards lignin molecules to consider the whole (local) lignin
fraction in future fractionation and lignin depolymerization examina-
tions. An ideal valorization of lignin into synthetic products needs an
ideal utilization of the whole lignin from the feedstock, which in this
manner requires the blend of a powerful (high return) lignin confine-
ment and depolymerization process.
8. Conclusions
Lignin valorization to value added chemical and biofuels have been
discussed in a brief manner. Biorefinery approach is necessary towards
the practical considerations of depolymerization techniques.
Additionally, ideal valorization of lignin into synthetic chemicals, fuels
and products needs the utilization of the whole lignin from the feed-
stock, which in this manner requires the blend of a powerful (high re-
turn) lignin confinement and depolymerization process. In spite of such
challenges related to the asymmetrical structure of lignin, the valor-
ization of this aromatic biopolymer has been emerged that bring many
defined products via depolymerization in the presence of catalysts/
biocatalysts.
Acknowledgements
The authors thank the Ministry of Science and Technology-Taiwan
(MOST105-2113-M-037-019-MY2), Kaohsiung Medical University
(KMU)-Taiwan and Research Center for Environmental Medicine-KMU
for research grant supports. Author GK would like to acknowledge the
financial assistance from Ton Duc Thang University, Vietnam. This
work was supported by the New & Renewable Energy Core Technology
Program of the Korea Institute of Energy Technology Evaluation and
Planning (KETEP) granted financial resource from the Ministry of
Trade, Industry & Energy, Republic of Korea (No. 20173010092470).
One of the author RGS acknowledge Dongguk University Seoul, South
Korea under research fund 2018–2020.
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