CHAPTER ONE

1.1 Introduction
Lignin is one of the most abundant renewable biopolymers on Earth, accounting
for approximately 15–30% of the total dry weight of lignocellulosic biomass. It is
second only to cellulose in terms of natural abundance and plays a crucial role in
providing structural integrity, rigidity, and resistance against microbial attacks in
vascular plants (Ragauskas et al., 2024). Structurally, lignin is a complex and
irregular three-dimensional polymer composed of phenylpropanoid units derived
primarily from three monolignols: p-coumaryl alcohol, coniferyl alcohol, and
sinapyl alcohol (Laurichesse & Avérous, 2024). These monolignols confer lignin
its characteristic aromatic nature, making it a unique natural source of aromatic
carbon.

Fig 1.1: Lignin Samples (Ragauskas et al., 2024)

In most industrial processes, particularly in paper pulping (kraft and sulfite
processes), and second-generation bioethanol production, lignin is treated as a low-

1
value byproduct and is often burned on-site to generate process heat and electricity
(Li et al., 2025). This underutilization has been a significant limitation in the
overall economic and environmental sustainability of lignocellulosic biorefineries.
However, in recent years, there has been a paradigm shift in how lignin is
perceived—from being a waste stream to a valuable feedstock for high-end
applications.
This renewed interest stems from lignin’s diverse chemical functionalities such as
hydroxyl, methoxyl, and carboxyl groups, which make it chemically versatile for
conversion into a wide array of materials and chemicals (Abu-Omar et al., 2021).
Additionally, lignin’s aromatic-rich structure sets it apart from other biopolymers
like cellulose and hemicellulose, positioning it as a potential renewable alternative
to fossil-derived aromatics used in plastics, resins, fuels, and fine chemicals (Tuck
et al., 2022).
Moreover, the increasing global emphasis on sustainability and circular
bioeconomy has amplified the demand for bio-based raw materials. Agricultural
biomass and agro-industrial residues (e.g., corn stover, wheat straw, sugarcane
bagasse, rice husk) are rich in lignin and widely available across the globe,
particularly in developing countries where such waste is abundant but
underutilized (Kumar & Sharma, 2017). Valorizing lignin from these sources can
not only reduce environmental pollution and carbon emissions but also create new
economic opportunities in rural and agricultural communities.
Therefore, leveraging lignin as a renewable and sustainable feedstock aligns with
global goals on waste reduction, carbon neutrality, and the development of green
technologies. Its wide-ranging applications—from bioplastics and resins to energy
storage materials and biomedical devices—make lignin a strategic resource for
future biorefineries.
2
 CHAPTER TWO
2.1 About Lignin
Lignin is found in all vascular plants, mostly between the cells, but also within the
cells, and in the cell walls. It makes vegetables firm and crunchy, and gives us
what we call "fiber" in our food. It functions to regulate the transport of liquid in
the living plant (partly by reinforcing cell walls and keeping them from collapsing,
partly by regulating the flow of liquid), and it enables trees to grow taller and
compete for sunshine and researchers see it as a disposal mechanism for metabolic
wastes (Del Río et al., 2022).
In nature it is very resistant to degradation, being held together with strong
chemical bonds; it also appears to have a lot of internal H bonds. It is bonded in
complex and various ways to carbohydrates (hemicelluloses) in wood. This picture
of usefulness and stability presents quite a contrast to the familiar lignin in
groundwood paper, which is so unstable and so troublesome in books and records
of value. The contrast can be explained by the radical effect of pulping and
bleaching on the lignin as it is separated from the fibers.
Lignin is actually not one compound but many. All are complex, amorphous, three-
dimensional polymers that have in common a phenylpropane structure, that is, a
benzene ring with a tail of three carbons. In their natural unprocessed form, they
are so complex that none of them has ever been completely described, and they
have molecular weights that my reach 15,000 or more (Del Río et al., 2022)
Lignins are not acids, though most of them contain certain carboxylic acids, and
wood gives off acids as it deteriorates, as do paper and board that contain lignin.
This deteriorates cellulose and other sensitive materials nearby, as well as the
cellulose fibers within the lignin-containing paper itself. This is why permanent
paper standards in the past have always specified that no groundwood or
3
unbleached fiber should be used to make the paper. Recently, though, it has been
recognized that calcium carbonate filler would effectively cancel this destructive
effect of lignin for an indefinite period of time, and the current draft of the ANSI
Z39.48 standard permits as much as 7.5% lignin. This specification is
controversial, and raises several questions having to do with measurement: How
reliably and easily can the purchaser test paper and board to see how much lignin it
contains? What research has been done on the permanence of paper that contains
both lignin and calcium carbonate? Are the forms of lignin in different types of
pulp equivalent, as far as their effect on permanence is concerned?
These questions are important. More and more lignin will be included in paper as
time goes on, because of the increasing use of recycled postconsumer fiber (from
which it is hard to exclude groundwood and other mechanical pulp papers) and the
growing international pulp shortage (which provides incentive for use of high-yield
pulps) (Kumar & Sharma, 2017).
Lignins as they occur in nature (protolignins) have been grouped into several types,
characteristic of hardwoods, softwoods and grasses. Within each type there is a lot
of variation: lignins differ from species to species, and from one tissue to the next
in the same plant--even within different parts of the same cell. The process of
removing them from the plant changes their form and chemical makeup to a
greater or lesser extent, which makes then hard to study and way account for the
large and growing number of analytical techniques in use. No one method is ideal
for all cases, and the limitations of each method have to be borne in mind when
results are interpreted.
Besides protolignins, there are lignin preparations or model compounds, which are
removed from the wood matrix by mild, relatively nondestructive means for lab
study and research. They retain the characteristic phenylpropane structure of
4
lignins. The lignin compounds that occur in paper, on the other hand, have been
treated rather roughly and do not retain that structure, so they are not what a purist
would call true lignins.
2.2 Sources and Composition of Lignin
A wide range of agricultural residues and plant-based wastes serve as rich sources
of lignin. These include:
1. Corn Stover
Corn stover includes the stalks, leaves, husks, and cobs left in the field after corn
grain harvest. It constitutes nearly 50% of the above-ground biomass of corn and is
produced in substantial quantities in countries like the United States, China, and
Nigeria (Tuck et al., 2022).

Fig 2.1: Corn Stover (Tuck et al., 2022)

2. Wheat Straw and Barley Straw
These are the fibrous residues remaining after cereal grain harvesting. Globally,
wheat straw is one of the most abundant residues, particularly in Europe and Asia
(Tuck et al., 2022).

5
Fig 2.2: Wheat Straw and Barley Straw (Tuck et al., 2022)
3. Rice Husk and Rice Straw
Rice processing generates two primary lignin-containing residues: rice
straw during harvesting and rice husk during milling (Tuck et al., 2022).

Fig 2.3: Rice Husk (Tuck et al., 2022)

4. Sugarcane Bagasse
Bagasse is the fibrous by-product remaining after sugarcane stalks are crushed to
extract juice. It is abundant in sugar-producing countries like Brazil, India, and
Nigeria (Kumar & Sharma, 2017).

6
Fig 2.4: Sugarcane Bagasse (Kumar & Sharma, 2017)
5. Coconut Husk and Palm Fronds
Coconut husk, a byproduct of the coconut industry, and palm fronds from oil palm
plantations are both lignin-rich biomass streams common in tropical countries
(Tuck et al., 2022).

Fig 2.5: Coconut Husk and Palm Fronds

6. Oil Palm Empty Fruit Bunches (EFBs)
EFBs are generated after the extraction of palm oil and represent one of the major
waste streams in palm oil processing (Kumar & Sharma, 2017).

7
Fig 2.6: Oil Palm Empty Fruit Bunches (EFBs) (Kumar & Sharma, 2017)
7. Forestry Residues: Sawdust, Bark, and Wood Chips
Forestry operations and sawmills generate vast amounts of wood-based residues,
which are traditionally used in low-value applications such as combustion or
mulch.

Fig 2.7: Forestry Residues: Sawdust, Bark, and Wood Chips (Kumar &
Sharma, 2017)
2.2 Composition and Structural Variability of Lignin
The composition and structure of lignin vary significantly based on the plant
species and the method used for its extraction. Lignin is primarily synthesized from
three monolignols:
i. Softwoods (Gymnosperms)
Softwood lignins are predominantly composed of guaiacyl (G) units, with
negligible or no syringyl content. This G-unit dominance leads to highly
8
 condensed lignin structures due to the reactive C-5 position in guaiacyl
rings, allowing more C–C linkages. As a result, softwood lignin is more
resistant to chemical degradation and more recalcitrant in biorefining
applications (Ralph et al., 2004). Example species: Pine, spruce, fir
ii. Hardwoods (Angiosperms – Dicotyledons)
Hardwood lignins typically consist of both guaiacyl (G) and syringyl
(S) units, with the S/G ratio varying by species. The higher syringyl
content results in a more linear and less cross-linked structure, due to the
lack of a free C-5 position in syringyl units. This makes hardwood
lignins more amenable to depolymerization and better suited for producing
monomeric aromatic compounds. Example species: Eucalyptus, oak, poplar
iii. Grasses (Monocots – Cereals and Herbaceous Plants)
Grasses, such as wheat straw, corn stover, rice straw, and sugarcane bagasse,
contain all three lignin units: H, G, and S. These lignins are unique in that
they contain substantial amounts of hydroxycinnamic acids,
especially ferulic and p-coumaric acid, ester-linked to lignin and
polysaccharides. These cross-linking acids contribute to lignin-carbohydrate
complexes (LCCs), further complicating delignification and enzymatic
hydrolysis. Grasses generally have a lower S/G ratio than hardwoods, but
their lignin is structurally more complex and heterogeneous (Del Río et al.,
2022).
These variations in lignin structure significantly influence its reactivity and
suitability for downstream applications. For example, syringyl-rich lignins
are generally more amenable to depolymerization due to their more linear
structure and fewer carbon-carbon linkages compared to guaiacyl-rich
lignins (Li et al., 2015).
9
2.3 Industrial Processing Methods and Their Impact on Lignin Composition
Lignin can be extracted through various industrial pretreatment processes, each
altering its structure and purity to some extent:
1. Kraft Process
The kraft process is the most widely used method for industrial pulping,
accounting for more than 80% of global lignin extraction during paper
manufacturing. Biomass is treated with sodium hydroxide (NaOH) and sodium
sulfide (Na₂S) at high temperatures (140–170°C) and pressures. Kraft lignin,
a sulfur-containing, chemically modified lignin, is obtained. The presence of sulfur
limits its use in biomedical and high-purity applications due to odor and
environmental concerns.
2. Soda Process
The soda pulping process uses only sodium hydroxide (NaOH) and is generally
applied to non-wood biomass such as bagasse, straw, and grasses. Soda lignin,
a sulfur-free lignin, is produced. Preferred for applications where toxicity and odor
control are critical.
3. Organosolv Process
The organosolv process uses organic solvents (e.g., ethanol, acetone, methanol)
often mixed with acid catalysts to solubilize lignin at elevated temperatures (120–
200°C). Organosolv lignin, which is low in impurities, sulfur-free, and structurally
closer to native lignin. High operational costs and solvent recovery requirements.
4. Acid and Enzymatic Hydrolysis (Bioethanol Industry)
In second-generation bioethanol production, cellulose and hemicellulose are
hydrolyzed using acid or enzymes, leaving behind lignin-rich solid residues.
The choice of biomass and extraction method therefore directly impacts
the physicochemical properties of lignin—such as molecular weight, functional
10
groups, and solubility—which in turn affect its processability and application
potential (Laurichesse & Avérous, 2024).
2.4 Importance of Source Selection
Selecting appropriate lignin sources is critical for targeted applications. For
instance:
Sugarcane Bagasse Lignin: Phenol–Formaldehyde Resins
Sugarcane bagasse, the fibrous residue left after juice extraction, is widely
available in sugar-producing countries such as Brazil, India, and Nigeria. Its lignin
content ranges from 20% to 25%, with a structure relatively rich in guaiacyl and
syringyl units.
2. Corn Stover and Wheat Straw Lignin: Bioplastics and Biochar
Agricultural residues such as corn stover and wheat straw are lignin-rich biomass
streams available in large quantities, especially in North America, Asia, and Sub-
Saharan Africa. Their lignins typically contain all three types of lignin units (H, G,
S), along with ferulic and p-coumaric acids, resulting in complex structures with
cross-links to hemicelluloses.
3. Organosolv-Treated Hardwood Lignin: Nanomaterials and Biomedical
Lignin extracted from hardwoods via organosolv processes (e.g., ethanol/water
mixtures) tends to have high purity, low molecular weight, and a high degree of
phenolic hydroxyl substitution.

11
 CHAPTER THREE
3.1 Composites and Corrosives: Emerging Applications of Lignin
3.1.1 Lignin-Based Composites
Lignin has garnered significant attention as a natural reinforcement and matrix
material in the development of sustainable composites. Its aromatic, thermoplastic,
and biodegradable properties make it an excellent candidate for use in bio-based
polymeric systems.
3.1.2 Bio-Composites
Lignin, when combined with other natural fibers (such as flax, hemp, or jute) and
biodegradable polymers (like PLA, PHA, or starch-based plastics), forms bio-
composites with desirable mechanical strength, UV resistance, and water
resistance. These materials are used in automotive interiors, packaging,
construction panels, and furniture (Kai et al., 2016).
3.1.3 Lignin as a Filler or Binder
It serves as a filler or partial replacement for synthetic resins in thermoset plastics
and wood adhesives. This helps reduce dependency on fossil-derived products and
lowers environmental impact. For example, phenol-formaldehyde resins can be
partially replaced by lignin, improving sustainability and reducing toxicity
(Norgren & Edlund, 2024).
3.1.4 3D Printing Filaments
Recent studies have explored the blending of lignin with PLA to develop 3D
printing filaments, offering eco-friendly alternatives in additive manufacturing
(Bian et al., 2019).
3.2 Corrosion-Resistant Materials
Lignin also shows promising potential in the development of corrosion inhibitors
and protective coatings, especially for metals.
12
3.2.1 Green Corrosion Inhibitors
Due to its polyphenolic structure and antioxidant properties, lignin can act as
a corrosion inhibitor for steel and other metals. Modified lignin derivatives have
been used in acidic environments (e.g., HCl) to mitigate corrosion in pipelines,
tanks, and machinery (Karthik et al., 2020).
3.2.2 Lignin-Based Coatings
Lignin can be chemically modified to produce hydrophobic and antioxidative
coatings that protect metal surfaces from oxidative degradation. Such coatings are
increasingly being considered for marine applications, construction infrastructure,
and agricultural equipment.
3.2.3 Anti-fouling and UV-Protective Coatings
Lignin’s natural UV-absorbing properties also make it suitable for use in coatings
designed to resist biofouling and ultraviolet degradation, especially when
combined with other biodegradable polymers (Ragauskas et al., 2024).
3.3 Extraction and Processing of Lignin
Lignin, though naturally embedded within plant cell walls, must be chemically or
enzymatically separated from cellulose and hemicellulose to be recovered for
industrial or research applications. The choice of extraction method significantly
influences the yield, purity, molecular weight, and functional group composition of
the recovered lignin — all of which impact its performance in downstream uses
such as adhesives, composites, fuels, and pharmaceuticals (Rinaldi et al., 2016).
3.3.1 Kraft Process
The Kraft process, also known as the sulfate pulping process, is the most widely
adopted method in the pulp and paper industry, accounting for approximately 90%
of commercial lignin production. Biomass is treated with a mixture of sodium
hydroxide (NaOH) and sodium sulfide (Na₂S) at high temperature (150–170°C)
13
and pressure. Though chemically modified and less pure, Kraft lignin is suitable
for carbon fibers, phenolic resins, and fuel applications (Vishtal & Kraslawski,
2011). Presence of sulfur restricts its use in high-purity biomedical or food
applications due to odor and potential toxicity.
3.3.2 Sulfite Process
The sulfite process is another pulping method that uses sulfurous acid
(H₂SO₃) combined with various base ions (e.g., Na⁺, Ca²⁺, Mg²⁺, or NH₄⁺) to
extract lignin in the form of lignosulfonates. Lignosulfonates, which are water-
soluble, anionic lignin derivatives, ideal for dispersion and binding.
Lignosulfonates are widely used as dispersants in concrete and dyes, animal feed
additives, and dust suppressants due to their high solubility and surface
activity (Gosselink et al., 2024). Lower thermal stability and high ash content limit
their utility in high-end polymers or thermoplastics.
3.3.3 Organosolv Process
The organosolv process is a chemical pulping technique that uses organic
solvents (e.g., ethanol, acetone, and methanol) with or without acid catalysts to
solubilize lignin at temperatures between 120°C and 200°C. Due to its high purity,
low polydispersity, and good reactivity, organosolv lignin is suited
for nanomaterials, biodegradable polymers, resins, and even pharmaceutical
applications (Zhang et al., 2020). High cost of solvents and recovery systems has
limited commercial-scale adoption.
3.3.4 Enzymatic Hydrolysis Residues
Enzymatic hydrolysis is commonly used in biorefineries to convert cellulose into
glucose for bioethanol production. The residual solid fraction, rich in lignin, is
referred to as Enzymatic Hydrolysis Lignin (EHL) or Residual Lignin. After acid
or alkaline pretreatment to disrupt the biomass structure, enzymes (e.g., cellulases)
14
hydrolyze cellulose, leaving behind lignin. While less pure than organosolv lignin,
EHL is useful for biochar, composite reinforcement, and low-cost adsorbents in
water treatment (Abu-Omar et al., 2021).

15
 CHAPTER FOUR
4.1 Emerging Applications of Lignin
Lignin, as the largest renewable source of aromatic structures on Earth, has gained
increasing attention for its potential in producing a wide range of bio-based
chemicals, advanced materials, and functional products. Traditionally underutilized
as boiler fuel or waste, modern biorefinery innovations have unlocked lignin's
value for high-performance, sustainable applications in energy, agriculture,
medicine, and the environment (Ragauskas et al., 2024; Tuck et al., 2022).
4.1.1 Bio-Based Chemicals and Fuels
Due to its aromatic polymer backbone, lignin is ideal for the production of
various platform chemicals and renewable fuels. Lignin-derived phenolic
compounds, such as vanillin, are commercially important flavoring agents and
precursors for pharmaceuticals and polymers. Borregaard, a Norwegian company,
already produces vanillin from lignosulfonates (Zhang et al., 2020).
Thermochemical methods such as pyrolysis and hydrothermal liquefaction convert
lignin into a complex mixture of bio-oil, rich in phenols, ketones, and
hydrocarbons, suitable for upgrading into fuels.
4.1.2 Polymer and Composite Materials
Lignin's polyphenolic structure allows its integration into various polymer
matrices: Lignin serves as a filler or binder in biodegradable plastics like polylactic
acid (PLA) or polyethylene, enhancing UV resistance, mechanical strength, and
antioxidant properties (Thakur et al., 2024). Lignin can partially replace bisphenol-
A (BPA) in epoxy formulations, producing greener alternatives for coatings and
adhesives (Ferdosian et al., 2016). Due to its high carbon content, lignin is being
16
developed as a low-cost precursor for carbon fibers, with applications
in automotive and aerospace industries (Baker & Rials, 2023).
4.1.3 Agriculture and Soil Amendment
Lignin-Based Biochar and Fertilizer Coatings
Pyrolyzed lignin-rich residues produce biochar, which improves soil aeration,
water retention, and nutrient availability, while also sequestering carbon (Lehmann
et al., 2021). Lignin serves as a coating material for controlled-release fertilizers,
regulating nutrient availability while minimizing leaching and volatilization losses
(Shi et al., 2018).
4.1.4 Biomedical Applications
Lignin Nanoparticles (LNPs): Exhibit antioxidant, antimicrobial, and UV-
blocking properties; suitable for drug delivery, topical formulations,
and biosensing (Figueiredo et al., 2018). Lignin-containing biopolymer films (e.g.,
chitosan-lignin, PVA-lignin) improve mechanical strength and provide barrier
protection against microbial infections. Due to their bioactivity and
biocompatibility, lignin-based hydrogels and films are used in burn treatment, skin
regeneration, and UV-shielding applications.
4.1.5 Environmental Applications
Lignin-based materials remove heavy metals (Pb²⁺, Cd²⁺, Cr⁶⁺) and dyes (e.g.,
methylene blue, Congo red) from wastewater via adsorption and chelation (Wang
et al., 2019). Chemically modified lignin acts as eco-friendly
flocculants for industrial wastewater treatment and as dispersing agents in ceramics
and paints.
4.1.6 Energy Storage and Electronics
Lignin-derived activated carbon exhibits high surface area, enabling fast charge–
discharge rates and good cyclic stability in electrochemical capacitors (Shao et al.,
17
2018). Lignin-based carbons serve as anode materials in Li-ion and Na-ion
batteries, offering structural stability and conductivity. Lignin composites with
conductive fillers (e.g., graphene, CNTs) are used in printed
electronics, biosensors, and flexible circuits.

18
 CHAPTER FIVE
5.1 Conclusion
Lignin, once considered a low-value byproduct of agricultural and industrial
biomass processing, is now recognized as a strategic renewable resource with
transformative potential across a wide spectrum of applications. Derived from
residues such as corn stover, wheat straw, rice husk, and sugarcane bagasse, lignin
offers a sustainable, non-food-based feedstock for industries aiming to reduce
reliance on fossil-based raw materials.
Advancements in fractionation technologies—such as the kraft, sulfite, organosolv,
and enzymatic hydrolysis processes—have enabled the selective recovery of lignin
with tailored properties suitable for high-value applications, including bio-based
chemicals, bioplastics, epoxy resins, carbon fibers, nanomaterials, and
even biomedical devices (Rinaldi et al., 2016; Figueiredo et al., 2018).
Moreover, lignin valorization directly supports the principles of green chemistry
and circular economy, turning agricultural waste streams into carbon-rich,
functional materials. Its ability to serve as a carbon sequestration agent (via
biochar), a bio-based binder, or a renewable aromatic precursor positions lignin as
a keystone molecule in the transition toward bio-based and low-emission
economies (Tuck et al., 2022; Ragauskas et al., 2024).
By shifting perceptions and practices from waste disposal to resource utilization,
lignin can bridge the gap between environmental responsibility and industrial
innovation. Strategic investments in lignin-based product development, biorefinery
integration, and market standardization are essential for realizing its full potential.

19
In conclusion, lignin from agricultural biomass and waste stands not only as
a versatile platform chemical but also as a cornerstone for future bio-industrial
systems, enabling sustainable pathways in energy, materials, agriculture, health,
and environmental protection.

20
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