Bioresource Technology 384 (2023) 129294

Contents lists available at ScienceDirect

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

Review

Lignin to value-added products: Research updates and prospects

Hongliang Guo a, 1, Ying Zhao a, 1, Jo-Shu Chang b, c, d, Duu-Jong Lee e, f, *
a
College of Forestry, Northeast Forestry University, Harbin 150040, China
b
Research Center for Smart Sustainable Circular Economy, Tunghai University, Taichung 407, Taiwan
c
Department of Chemical Engineering, National Cheng Kung University, Tainan, Taiwan
d
Department of Chemical and Materials Engineering, Tunghai University, Taichung 407, Taiwan
e
Department of Mechanical Engineering, City University of Hong Kong, Kowloon Tong, Hong Kong
f
Department of Chemical Engineering and Materials Science, Yuan Ze University, Chung-li 32003, Taiwan

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Composition-dependent effect of CoPd

alloys studied via pulsed laser
technique.
• Monophasic CoPd alloys for hydrazine
oxidation reaction as an anolyte in fuel
cell.
• In-situ/operando Raman probe reveals
the active-species and structural
transformation.
• Fabricated hydrazine coupled water
electrolyzer for energy-saving H2 fuel
production.
• Co1Pd9 ‖ Co1Pd9 requires only 0.22 V
for OHzS and 1.83 V for OWS.

A R T I C L E I N F O A B S T R A C T

Keywords: Due to the urgent need for renewable and clean energy, the efficient use of lignin is of wide interest. A
Depolymerization comprehensive understanding of the mechanisms of lignin depolymerization and the generation of high-value
Heat and mass transfer products will contribute to the global control of the formation of efficient lignin utilization. This review ex­
Lignin
plores the lignin value-adding process and discusses the link between lignin functional groups and value-added
Value addition
products. Mechanisms and characteristics of lignin depolymerization methods are presented, and challenges and
prospects for future research are highlighted.

1. Introduction manufacturing chemicals and fuels at high conversion efficiency (Jian

et al., 2022; Panke et al., 2022). Among numerous biomass sources,
With the rapid growth of the global economy, energy shortage is lignocellulose presents its potential to replace non-renewable coal,
becoming a severe problem (Jacobs et al., 2023; Aufischer et al., 2022). crude oil, and natural gas as a primary energy source (Llatance-Guevara
Biomass is a renewable energy source that can be useful in et al., 2022; Rawat et al., 2022). Lignocellulosic biomass is composed of

* Corresponding author at: Department of Mechanical Engineering, City University of Hong Kong, Kowloon Tong, Hong Kong.
E-mail address: [email protected] (D.-J. Lee).
1
These authors have contributed equally to this work and share the first authorship.

https://doi.org/10.1016/j.biortech.2023.129294
Received 6 May 2023; Received in revised form 3 June 2023; Accepted 6 June 2023
Available online 11 June 2023
0960-8524/© 2023 Elsevier Ltd. All rights reserved.
H. Guo et al. Bioresource Technology 384 (2023) 129294

lignin, cellulose, and hemicellulose, of which lignin has a sturdy and yields of phenolic monomers (Rinaldi et al., 2019). Lignin-priority bio­
sophisticated structure to limit lignocellulose hydrolysis (Gundekari and refineries utilize selective catalytic conversion of reaction intermediates
Karmee, 2022; Lofgren et al., 2022). To overcome this obstacle, depo­ or functionalization of natural structures to avoid the formation and
lymerization methods of lignin have been developed (Curran et al., coalescence of reactive intermediates, resulting in the efficient decon­
2022; Chin et al., 2022). In particular, lignin depolymerization has struction of biomass (Sultan et al., 2019). The lignin first biorefinery
emerged as a critical step for the success of biorefinery (Ullah et al., process focuses on a gentle fractionation strategy for the stabilization of
2022; Chen et al., 2022). A comprehensive understanding of lignin β-O-4 bonds and active stabilization of lignin monomers and in­
depolymerization methods is the basis for realizing efficient lignin termediates during fractionation to prevent lignin condensation (Abu-
economization (Shao et al., 2022). Omar et al., 2021). To stabilize the β-O-4 bond in the lignin structure,
Methods for lignin depolymerization have been extensively investi­ mild fractionation methods commonly used include ammonium-based
gated. In addition, production and refining of the value-added products fractionation and organic solvent techniques. Liquid ammonium frac­
from lignin depolymerization are also the focus of research (Gundekari tionation is performed under favorable conditions and, depending on
and Karmee, 2022). The lignin depolymerization process involves the the nature of the lignin, will dissolve instantly within a few hours
transport of intermediates and final products to and out of the lignin (Sadeghifar and Ragauskas, 2020). Tolesa et al. (2018) developed a
matrix, whose roles in the overall lignocellulosic depolymerization green method of ammonium-based ionic liquids to extract spent coffee
process have been rarely studied. This review provides a detailed husks while depolymerizing the extracted lignin into high-value-added
overview of the transport processes involved in lignin depolymerization, compounds. Organic solvent fractionation is a process that uses
and the potential for lignin value addition. organic solvents to dissolve lignin from biomass and recover lignin along
with the solvent (Liu et al., 2022c). A combination of alcohols, organic
2. Lignin structures and types acids, and catalytic solvents is commonly utilized for the organic solvent
fractionation of lignin (Zhou et al., 2022b). Gamma-valerolactone (GVL)
Understanding lignin’s complex structure is fundamental to pro­ is a green separator that can be used to dissolve lignin from biomass. By
ducing value-added products. Lignin is composed of three types of studying the structural changes of lignin during the treatment of poplar
benzene propane, namely p-hydroxyphenyl (H), guaiacyl (G), and using gamma-valerolactone, Cheng et al. (2023) showed that co-solvent-
syringyl (S), with p-coumaryl, pineol, and mustard alcohol as their assisted hydrolysis helps to retain more of the original ether bond
corresponding monomers, respectively (Azubuike et al., 2022; Wang structure of GVL-extracted poplar lignin, further improving the pro­
et al., 2023). The percentage of lignin in each plant species differs ductivity and quality of GVL-extracted lignin.
depending on the plant species and the growth environment/conditions. Catalytic hydrolysis is the most studied method for preferential
Softwoods have 25–35% of lignin, 20–25% for hardwoods, and herbs, refinement of lignin. Hydrolysis usually occurs at the β-O-4 molecule,
15–25% (Putra et al., 2022). Lignin monomers are conjugated by where the C-O bond is cleaved to produce lignin monomer and other
different bonds, such as β-O-4, β-5, 5–5, β-β and α-O-4, of which β-aryl intermediates. The use of catalytic hydrolysis reactions allows for the
ether (β-O-4) is the primary interunit linkage in the natural lignin efficient conversion of biomass under relatively mild conditions,
structure and the most abundant bond of monolignin (Mukherjee and yielding higher amounts of bio-oil and high-value aromatic hydrocarbon
Mukhopadhyay, 2023; Ullah et al., 2022). products (Zhang et al., 2021a). The study showed that the NiMo/MgO-
The industrial lignins (Kraft lignin, soda lignin, and lignin sulfonates) La experimental group had the highest total monomer yield of 26.4 wt%
are isolated lignin, primarily the byproducts of the paper and pulp in­ in the solvent-free hydrotreating of kraft lignin, including 15.7 wt% of
dustry (Pham et al., 2022; Mennani et al., 2023). Kraft lignin is a type of alkylphenolic yield (Margellou and Triantafyllidis, 2019). Bifunctional
lignin obtained by the Kraft process, which uses alkaline solutions hydrotreating of loaded metals on acidic materials was also identified as
(including sodium hydroxide and sodium sulfide) and other additives a particular case due to the acidic nature of the carrier, leading to alkane
(such as sodium carbonate and sodium sulfate) to dissolve and precipi­ production by further hydrolysis and dehydration reactions at temper­
tate lignin molecules out of solution through the breaking of ether atures below 320 ◦ C (Cheng et al., 2018). The introduction of various
bonds. This method can produce high-quality lignin and more applica­ catalysts can improve the efficiency of hydrogenolysis and significantly
tions (Li et al., 2022). The chemical composition of vellum lignin in­ affect the production of selective monomers (Mukherjee and Mukho­
cludes approximately 1–2% elemental sulfur and high content of padhyay, 2023). The conversion of kraft lignin to monomeric alkyl­
condensed structures (Wang et al., 2022b; Wang et al., 2020). The soda phenols can be achieved at 5 ◦ C using Cu/Mo-ZSM-220 catalysts in a
process obtains soda lignin, historically one of the oldest delignification water/methanol solvent system, and the presence of NaOH used to
processes, which is widely used in current industrial delignification of enhance the solubility of lignin through hydrogen produced by
non-wood biomass such as bagasse, grass, straw, and other agricultural reforming and water–gas shift reactions (Mukherjee and Mukho­
production wastes, with the advantage of lower molarity of separated padhyay, 2023).
lignin and higher purity (Cui et al., 2022; Pourmahdi et al., 2023).
Compared to kraft lignin and lignosulfonate, soda lignin is chemically 4. Lignin to value-added products (Lignin depolymerized
closer to natural lignin (Cui et al., 2022). Lignosulfonates are obtained products)
by the sulfite process, which uses different cations at various tempera­
tures and pHs to treat plant materials, such as sodium, calcium, or The depolymerization of lignin produces low molecular weight ar­
ammonium (Ridho et al., 2022). Experimental studies were recently omatic compounds, and among the various aromatic monomers pro­
conducted to explore the production of lignin sulfonates using a neutral duced, commercial vanillin production is about 3,000 tons per year
sulfite pulping method and to compare the effect of producing lignin (Londono-Zuluaga et al., 2018). Studies have shown that vanillin is
sulfonates from eucalyptus kraft lignin, by two different processes, sul­ widely adopted to prepare desserts and beverages, especially chocolate
fonation, and acidification. The study results showed that lignosulfo­ and ice cream. Vanillin is also used as a feed additive in poultry to
nates have a higher sulfur content and are less expensive, offering promote animal fattening (Zhou et al., 2022b). In addition, many re­
advantages over kraft lignin (Castro et al., 2022). searchers have reported vanillin’s potential beneficial health effects
(Zhang et al., 2023). For example, Zhou et al. (2023) used various
3. Lignin-first strategy antioxidant assays to assess the antioxidant activity of vanillin. Ac­
cording to the experimental results, vanillin exhibited practical antiox­
The lignin-first strategy has emerged as one of the most well- idant effects and was able to play a role in the 3-ethylbenzothiazoline-6-
researched prospective strategies, allowing for high selectivity and sulfonic acid radical cation scavenging assay and the oxidative

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H. Guo et al. Bioresource Technology 384 (2023) 129294

hemolysis inhibition assay. bacterial, fungal, and enzymatic depolymerization, chemical depoly­
Syringaldehyde is another aromatic aldehyde of interest produced by merization, including pyrolysis, acid catalysis, and base catalysis pho­
the depolymerization of lignin. Syringaldehyde is much less commer­ tocatalysis and electrocatalysis, and preferential refinement of lignin,
cially available than vanillin but has become an emerging lignin-derived mainly including fractionation and hydrogenolysis, are summarized in
chemical (Deepika et al., 2023). The experimental results showed that Table 1.
clove aldehyde exhibited higher potential in inhibiting colon cancer cell
proliferation. Eugenol also has potential as a food additive and natural 5.1.1. Biological depolymerization
health product and deserves further study (Becker and Wittmann, 2019). Biodegradation of lignin is achieved the action of fungi, bacteria, or
Ferulic acid belongs to the hydroxycinnamic acid family and is also a specific enzymes under mild conditions (Zhou et al., 2022b). Fungi, such
typical product of great value resulting from the depolymerization of as white and brown rot fungi, are widely used in lignin depolymerization
lignin. The methoxy, hydroxyl, and carboxylic acid groups on the ben­ by their efficient ligninolytic systems (Ullah et al., 2022). These white-
zene ring of ferulic acid provide the opportunity to stabilize phenoxy rot fungi completely degrade lignin to CO2 and H2O, while brown-rot
radical intermediates and even terminate radical chain reactions while fungi partially degrade lignin (Weng et al., 2021). Besides terrestrial
reacting with radicals. These functional groups make sodium ferulate an fungi, some marine fungi, such as the marine cnidarian fungus Clado­
effective scavenger of reactive oxygen and reactive nitrogen species sporium cladosporioides CBMAI 857 and Trichoderma reesei CBMAI 847,
(Goyal and Kaur, 2022). Researchers reported that the ferulic acid among others, can depolymerize lignin by synthesizing ligninolytic en­
produced by lignin increases the sun protection factor of sunscreens and zymes (Dashora et al., 2023). Many ligninolytic fungi have been used in
provides sun protection for body creams (Luis Espinoza-Acosta et al., applications such as bio-pulping and bio-refineries for the delignifica­
2022). tion of lignin biomass (Wan et al., 2022). Pleurotus strains can degrade
In addition, lignin can be used to replace conventional raw materials wheat straw and form eugenol, ferulic acid, and protocatechuic acid (Xu
in adhesives and used together with other biomass materials in the et al., 2018). However, the fungus’s harsh growth conditions and com­
production of biomass adhesives, such as lignin-soya protein adhesives plex genetic system greatly limit its wide application (Xu et al., 2018).
and lignin-based formaldehyde-free adhesives (Huang et al., 2022). The Bacteria can degrade lignin, although with low efficiency, achieving
use of lignin as a component of adhesives not only improves the effi­ a relatively high overall degradation rate by their capability of rapid
ciency of biomass utilization but also reduces the cost of manufacturing adaption and fast growth (Wang et al., 2022a). Lignin-degrading bac­
adhesives and reduces dependence on fossil resources, while effectively teria are frequently noted in lignin-rich environments, such as pulp and
reducing environmental pollution (Gong et al., 2022). Lignin can also be paper wastewater, soil, decaying wood, and termite intestines (Nandal
used as a functional additive. Due to its rigid structure and the presence et al., 2021). Different ligninolytic bacteria are known which can
of phenolic groups, lignin can be used as a lubricity additive in com­ dissolve both carbohydrates and lignin from lignocellulose, such as
mercial base oils and metalworking fluids, e.g., lignin modified with Thermobifica fusca, which can produce heterologously expressed alcohol
heterogeneous elemental rich groups can be used as a lubricity additive dehydrogenase, and using this enzyme; it can synthesize 1-propanol
in PEG200 lubricants (Zhang et al., 2022). Isnard et al. (2022) designed from untreated biomass like willowherb and corn stover (Lee et al.,
modified silicone (MS) sealants with enhanced UV and thermal stability 2019). After 12 weeks of fermentation with S. viridosporus T7A and
by incorporating lignin additives, and revealed that the lignin additive S. setonii 75Vi2, 30–45% of lignin was removed from softwoods, hard­
was a strong stabilizer even at low loadings. woods, and hardwoods and grasses (Weng et al., 2021).
There is experimental evidence that lignin modification and incor­ Enzymatic depolymerization of lignin has milder reaction conditions
poration of lignin into polymers can help to develop different textile and exhibits higher selectivity (Liu et al., 2021). Enzymes used in the
spinning techniques to improve the spinnability and compatibility of lignin depolymerization process include laccase, manganese peroxidase,
lignin with existing materials, thus producing fibers with better me­ and lignin peroxidase. Fig. 1 depicts the depolymerization mechanism of
chanical properties (Jin et al., 2021). Zhang et al. (2021b) summarized lignin peroxidase and manganese peroxidase. Vignali et al. (2022)
different methods of nano lignin preparation, emphasizing solvent pre­ designed and developed a laccase-Lig multi-enzymatic, multistep system
cipitation resistance, self-assembly, and interfacial cross-linking, con­ for lignin depolymerization. This system uses laccase from Bacillus
firming the existence of many potential high-value applications for nano licheniformis, Funalia trogii, and Lig from the sphingosine genus SYK-6 to
lignin, such as for food packaging, biomedicine, and biorefineries study primary and fractionated lignin. They showed that samples with
(Zhang et al., 2021b). low phenolic/aliphatic hydroxyl group ratios underwent net depoly­
merization while increasing phenolic/aliphatic hydroxyl group ratios
5. Value-adding process of lignin led to the polymerization of residual lignin (Vignali et al., 2022).
Mukhopadhyay et al. (2023) constructed a two-chamber microbial
Lignin is a complex biopolymer with a wide range of chemicals and peroxide-generating cell. After eight days of operation of this device,
energy sources to produce. Different functional groups in the lignin depolymerization products, including isoeugenol, acetyl vanillone, and
molecule can be modified by specific chemical modifications by selec­ methacrylic acid, were observed experimentally (Mukhopadhyay et al.,
tive modification of various reaction sites in lignin (Nadanyi et al., 2023). In addition, quinone reductase and lignin peroxidase combine a
2022). The value addition of lignin is achieved by depolymerization, promising method for lignin depolymerization. Adding quinone reduc­
modification, and purification. tase can limit lignin repolymerization by lignin peroxidase (Majeke
et al., 2021).
5.1. Lignin depolymerization
5.1.2. Chemical depolymerization
Lignin depolymerization decomposes complex lignin matrix com­ Chemical methods of lignin depolymerization include thermal py­
pounds into monomers or oligomers (Rocnik et al., 2022). Numerous rolysis, oxidative, photocatalytic, and alkali catalytic conversions (Tran
lignin depolymerization methods have been claimed to be commercially et al., 2022).
viable and are currently being performed on an industrial scale. Lignin is Pyrolysis converts lignin into biofuels with efficient decomposition
the most abundant natural aromatic polymer, and its valorization has capacity and reaction rate (Tran et al., 2022). In hydrothermal decom­
excellent potential, provided that an effective depolymerization process position, complex decomposition reactions, such as hydrolysis, decar­
is developed. So the development of green and economical depolymer­ boxylation, and oxidation, are substantially enhanced in reactive water
ization methods still holds great promise for the future. Biological de­ (Svarc-Gajic et al., 2022). Experimental studies have shown that hy­
polymerization’s mechanisms, advantages, and disadvantages include drothermal treatment can promote the cleavage of ether bonds while

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Table 1
Lignin depolymerization mechanism and its advantages and disadvantages.
No. Depolymerization Depolymerization mechanism Advantages Disadvantages References
method

1 Fungal Oxidative breakage of the propylene-based side Environmentally friendly Complex degradation process (Wan et al., 2022)
depolymerization chain to form benzoic acid, and low tolerance to the
Oxidative ring opening degrades the aromatic environment
ring to produce the target product.
2 Bacterial H, G, and S lignin units are converted by specific Bacteria are highly tolerant to Complex degradation process (Liu et al., 2022)
depolymerization reactions such as ether cleavage, double bond temperature, pH, and oxygen and low tolerance to the
cleavage, side chain cleavage, decarboxylation, limitations environment
oxidation, respectively.
3 Enzymatic Cα-dehydrogenase oxidizes the hydroxyl group, Environmentally friendly Poor selectivity, low yield of (Li & Zheng, 2020)
depolymerization β-Etherase cleaves the β-O-4 ether bond, depolymerization products,
oxidation of β-hydroxymalondialdehyde to difficult to commercialize
vanillin.
4 Pyrolysis Most of the ether bonds are broken at Simple and efficient for industrial Low yield of the obtained (Wang et al., 2023)
150–400 ◦ C, above 400 ◦ C strong bonds are production small molecule products, easy
broken and gasification starts simultaneously. to coke, and carbon
accumulation
5 Acid Catalysis Acid dissociation and breakage of aryl ether Promotes the formation of mono The high price and toxicity of (Tyagi & Sarma,
bonds in lignin polymers. phenolic compounds, helps oxidizers and reducers make 2022)
stabilizing depolymerization it difficult to scale up and
products, and inhibits commercialize
repolymerization reactions
6 Alkali catalysis Inhibit the occurrence of benzene ring Low-cost and abundant sources Difficult to achieve the (Xu et al., 2020)
hydrogenation reaction to obtain the target separation of catalyst and
product of phenols. product, polluting the
environment
7 Photocatalysis Under specific light irradiation energy, the Clean, efficient, energy-saving, Low light energy utilization (Abdelaziz et al.,
semiconductor photocatalytic material simple technology, relatively low cost 2022)
undergoes a redox reaction at the interface to
depolymerize lignin macromolecules.
8 Electrocatalysis Direct chemical interaction with the electrode Environmentally friendly, high High energy consumption, (Ayub & Raheel,
surface. selectivity, precise control of lignin high equipment cost 2022)
degradation, high oxidation capacity,
low reagent consumption, mild
reaction conditions
9 Microwave Assist Applying high-energy electromagnetic radiation Reduced reaction time and precise High energy consumption (Chio et al., 2019)
to lignin and biomass molecules causes rotation control of operation
and ionic conduction of polar molecules and
generates large amounts of heat.
10 Fractionation Stabilization of β-O-4 bonds and stabilization of Gentle, efficient, green Some organic solvents are (Thoresen et al.,
lignin monomers and intermediates to prevent more costly 2023)
lignin condensation.
11 Hydrogenolysis Reduction of target compounds by hydrogen or Mild conditions, high selectivity The process is more complex (Margellou &
hydrogen donor reactants. Triantafyllidis, 2019;
Zhang & Wang,
2020)

86.87% in the liquid recovery of guaiacol and alkylphenol (Xu et al.,

2023).
Oxidation is the preferred method in the industry because it produces
a cleaner end product (Casimiro et al., 2022). Lignin oxidation is
traditionally carried out using chlorine and nitrate, but both oxidants
are non-green and toxic (Scimmi et al., 2022). Therefore, the need for
environmentally benign oxidants has led to novel methods in substitu­
tion with water or other friendly media (Kumaravel et al., 2021). Elec­
trocatalytic oxidation is a promising lignin oxidative depolymerization
(Ayub and Raheel, 2022). In addition, metal loading can enhance the
oxidative depolymerization rates of lignin (Hu et al., 2022). The choice
of copper as an electrocatalyst for the depolymerization of lignin ob­
serves the dominance of aryl ethers and phenolic groups and reveals the
enhanced electrochemical stability of the metal (da Cruz et al., 2022).
Zhou et al. (2022a) prepared metal-based catalysts such as Ni/C-X for
Fig. 1. Depolymerization mechanism of lignin peroxidase (a) and manganese the oxidative value addition of lignin. Through the synergistic interac­
peroxidase(b). tion between nickel and carbon carriers, the Ni/C catalysts exhibited
excellent performance, which further enhanced the catalytic activity of
inhibiting carbon cycle disruption. Water molecules can catalyze the the oxidative lignin depolymerization reaction.
depolymerization reaction of lignin to produce more C4 molecules, thus Photocatalytic oxidation of lignin is a green oxidation technology
increasing the production of combustible gas resources (Jiang et al., that produces oxidizing substances, such as superoxide anion radicals,
2023). In addition, adding grinding beads during the pyrolysis process under the influence of light, without the assistance of external oxidants
promoted lignin depolymerization, resulting in a maximum increase of (Ku et al., 2023). Researchers found that N-phenyl phenothiazine (PTH),

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H. Guo et al. Bioresource Technology 384 (2023) 129294

a non-metallic photocatalyst, exhibits high efficiency and selectivity in and economical separation processes that are environmentally friendly
inducing the cleavage of lignin’s C-α-C-β bond for the production of are a vital aspect of future research efforts in the lignin biorefining in­
benzoic acid (Li et al., 2023a). Liu et al. (2022a) proposed a strategy of dustry (Sun et al., 2020).
photocatalytic pre-oxidation and ultrasonic cavitation in tandem to Li et al. (2019b) used GR95PP membranes for ultrafiltration sepa­
depolymerize lignin, using WO3/g-C3N4/h-BN (WCB) photocatalyst for ration to separate low molecular weight compounds (LMMC) from
the photocatalytic pre-oxidation of residual corn stover lignin in in­ depolymerized black liquor cutoffs (BLR) and to protect lignin mono­
dustrial bioethanol process. The experimental results showed that the mers, dimers, trimers, and others, from repolymerization. Moreover,
WCB-induced photocatalytic pre-oxidation led to a 26% increase in light after separation, about 60–70% of the lignin monomer is recovered into
oil yield and a 35% increase in phenolic monomer yield (Liu et al., the permeate, while less than 17% of the monomer remains in the cutoff
2022a). (Li et al., 2019b). It is worth noting that even though monomer recovery
is improved after membrane separation, there is still a 20% monomer
5.2. Lignin functional group modification loss.
The extraction process is also commonly used to separate the depo­
Lignin has diverse terminal groups, such as hydroxyl and carbonyl lymerization products. The standard extraction process mainly includes
groups. Their structures can be changed to prepare new products and water extraction, organic solvent extraction, and others (Alherech et al.,
expand the application areas of lignin (Li et al., 2023b). 2021). Water extraction uses water to separate water-soluble fractions,
One possible modification protocol is to perform epoxidation. which can achieve safe, “green” extraction. The main advantage of
Komisarz et al. (2023) proposed a chemical modification of lignin with water extraction is its low cost, but it has some limitations due to its low
epoxy groups, reacting epichlorohydrin with two lignin substrates under selectivity (Ren et al., 2019). Experiments show that organic solvent
alkaline conditions. They obtained two types of epoxidized lignin extraction can lead to increased recovery of monomers but still faces
products: a water-soluble liquid product and a water-insoluble solid some bottlenecks, such as potential toxicity hazards to humans and the
product. The reaction mixture was separated by centrifugation to get environment, poor selectivity, and recovery (Wang et al., 2019). In
two different phases. These phases were then washed using distilled addition, multi-stage condensation can be used directly in the lignin
water to remove unreacted substrates or impurities. Finally, the prod­ pyrolysis process to separate lignin derivatives, significantly reduce the
ucts were dried entirely at 30 ◦ C using vacuum drying. The experimental energy consumption in the bio-oil distillation process, and explore
results confirmed that hydroxymethylation and alkali lignin yielded effective combination technologies and study the appropriate collabo­
epoxidation products that can be used in composite formulations for ration conditions (Reshmy et al., 2022). The complex composition,
wood applications (Komisarz et al., 2023). various properties, and heterogeneous molecular weight distribution of
Another modification protocol way is to modify the hydroxyl groups lignin depolymerization products require the development of more
in the lignin molecule to change its nature or function. The structure of economical and rational separation methods to improve the purity of the
lignin contains hydroxyl and phenolic, among others. The reactivity of target products (Dashora et al., 2023).
hydroxyl groups varies due to intramolecular interactions within the
lignin structure, but phenolic hydroxyl groups are usually more reactive 6. Challenges and prospects
and significantly affect the reactivity. The generation of lignin polyol
derivatives can be achieved by modifying the hydroxyl groups with The growing global economy, the urgent need for renewable energy
different functional groups (Lauberte et al., 2019). The main focus is on sources, and a large amount of underutilized lignin in the pulp and paper
alkylation and phenolization. Alkylation reactions may occur at multiple industry have led researchers to enhance refining technologies to
positions in the lignin molecule, but generally, the hydroxyl and improve the utilization of lignin. There are still bottlenecks in the con­
carboxyl groups on the oxygen atom will be the primary targets of the version of lignin to value-added compounds, such as repolymerization
reaction (Guo et al., 2020). during lignin depolymerization (Lan and Luterbacher, 2019), separation
The dealkylation process of lignin is demethylation in the presence of of depolymerization products have not received sufficient attention (Wu
molten sulfur in an alkaline environment, producing dimethyl sulfide et al., 2022) and green and efficient depolymerization processes need to
and further oxidation. This process can increase lignin’s modified hy­ be developed (Ji et al., 2023).
droxyl groups, improving its reactivity (Ponnuchamy et al., 2020).
Phenolization reactions are usually performed using phenol or 6.1. Increase in project yields
phenolic derivatives in organic solvents and acidic environments, where
lignin undergoes a condensation reaction with the phenol present. This Lignin has a vital self-binding function due to the intense electron
modification usually increases the number of reactive positive and stabilization energy between various subunits in the lignin structure.
negative groups, thus improving the reactivity of the lignin. Experi­ This inherent structure makes lignin susceptible to adverse repolyme­
mental studies have shown that the products obtained by phenolization rization during lignin depolymerization and reduces the efficiency of
reactions are generally used to replace phenol in phenolic resins or, in lignin utilization (Cheng et al., 2018). Several methods have been
specific cases, can be used in polyurethane coatings to improve some researched to cope with this recombination phenomenon. Kim et al.
mechanical properties (Gao et al., 2021; Suzuki and Iwata, 2021). (2017) found that chemically selective methylation blocking of phenolic
hydroxyl (Ar-OH) groups inhibited secondary depolymerization and
5.3. Purification of depolymerization products charring during lignin depolymerization. Researchers introduced
capping agents to stabilize intermediates or reaction sites of lignin
Although much research has been conducted to develop efficient fragments, such as adding boric acid to lignin. This potent ligand could
depolymerization systems for the efficient use of lignin, methods to inhibit repolymerization reactions initiated by Ar-OH groups (Kim &
separate the depolymerization products have not received sufficient Kim, 2018).
attention, and effective separation processes should be developed in In addition, such repolymerization reactions can be reduced by
conjunction with depolymerization processes to improve upstream and introducing new processes, such as the development of new solvent
downstream processes for lignin value addition (Banu et al., 2019). The systems that perform under mild processing conditions without strong
recovery of aromatic compounds from lignin depolymerization has been acid or base catalysts, minimizing the condensation and repolymeriza­
found to involve a series of separation and purification processes. Most tion reactions induced by carbon positive ions and quinone methylations
separation and purification processes are labor- and financial-intensive (Kaur et al., 2022). Ethanol is an effective reagent to inhibit the repo­
and produce environmentally harmful reagents. Therefore, efficient lymerization reaction. Ethanol has two crucial roles in chemical

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H. Guo et al. Bioresource Technology 384 (2023) 129294

reactions: first, as a hydrogen supply solvent to stabilize the primary 2023). Lignin depolymerization usually produces aromatic mixtures,
products, and second, to form AR-OH groups through O-alkylation re­ and most of these aromatic compounds show significant inhibition of
actions, thereby inhibiting repolymerization reactions (Kim and Kim, ligninolytic strains (Wang et al., 2022a). Therefore, improving the
2018). Although significant efforts have been made to identify tech­ tolerance of strains is also a noteworthy aspect of future research. Using
nologies to utilize lignin better, developing economically effective pro­ lignin to efficiently and economically depolymerize into high-value
cesses remains challenging due to the complexity of lignin (Van den compounds will remain challenging.
Bosch et al., 2018).

6.3. Transport process in lignin depolymerization

6.2. Development of efficient depolymerization technology
Studies have found that multi-scale models must be considered to
Numerous depolymerization techniques have been developed, but all better understand the reaction kinetics and transfer processes during
lignin degradation methods, except for biodepolymerization, are either lignin depolymerization. The products must be assigned to different
expensive, consume more energy, or produce toxic byproducts; never­ stages for evaluation. This helps to differentiate the rates of specific
theless, biodepolymerization methods also face many challenges (Liu reactions and assess the effects of mass and heat transfer (Kannah et al.,
et al., 2022b). For example, the mechanism of action and the enzymatic 2021). Exploring the reaction mechanism and studying kinetic expres­
properties of many enzymes involved in the lignin depolymerization sions are the basis for optimizing the lignin depolymerization process.
process are still unknown. In this sense, genetic engineering and protein Extensive studies of kinetic models exist, but exploring mass and heat
engineering technologies are essential in the gradual industrialization of transfer during lignin depolymerization needs to be improved. There­
biological depolymerization methods (Li et al., 2019a). Study results fore, this section provides a detailed overview of the mass and heat
showed that deletion of the coumarin dehydrogenase gene of the R. jostii transfer processes, and the transport phenomena and the interphase
RHA1 strain could produce a mutant strain. The mutant strain accu­ transfer processes are depicted in Fig. 2.
mulated up to 96 mg/L of coumarin and 53 mg/L of 4-hydroxybenzalde­
hyde after 144 h of incubation (Saini et al., 2023). In addition, to obtain 6.3.1. Mass transfer
high yields of pyruvate and lactate, Agarwal et al. (2018) successfully The mass transfer process in lignin depolymerization is mainly a
engineered P. putida strains by replacing endogenous catechol with transfer phenomenon of compounds through the liquid or gas phase
exogenous catechol and altering the β-ketogluconate pathway (Agarwal within the catalyst or lignin particles (Joseph et al., 2022). Under­
et al., 2018). standing the effect of lignin structure and solvent properties on the ki­
Bioconversion is a potential platform for converting lignin into more netic rate of lignin depolymerization is, therefore, very important in
valuable products. However, the natural heterogeneity of lignin causes screening catalysts and studying reactor systems (Pu et al., 2020). Mass
its degradation to produce a variety of aromatic molecules, which pre­ transfer limitations in specific reaction media and systems can be pre­
vents the complete conversion of these molecules into high-value, value- dicted using coupled reaction–diffusion models. Such models consider
added products (Zuo et al., 2022). In this context, the synergy of mi­ chemical reactions and substance diffusion to determine which step
crobial and enzymatic systems and the application of microbial con­ dominates the reaction rate and assess possible limiting factors (Mor­
sortia are essential for constructing multifunctional biological systems. gana et al., 2021). Theoretically, the reaction reaches its maximum ki­
Moreover, more in-depth studies on the interactions between enzymes netic rates when the diffusion of material in the catalyst pores is
and microorganisms are needed to develop efficient lignin value-added eliminated. The concentration of lignin depolymerization reactants in
systems (Singhania et al., 2022). Weiland et al. (2023) metabolically the pores drops to zero. This means that the reaction rate is no longer
engineered Bacillus glutamicus to produce cis-muconic acid (MA) from limited by the material transport but mainly by the properties of the
these key aromatic hydrocarbons. This process resulted in the final reaction itself, such as the interaction of the reactants and the activity of
strain, MA-9, through a combination of genes that had biobased the catalyst. Therefore, to avoid mass transfer limitations, choose highly
methane from vanillin, vanillin ester, and seven structurally related dilute, low active site loading and small catalyst particles (Anderson
aromatic hydrocarbons with maximum selectivity (Weiland et al., et al., 2018).

Fig. 2. Interphase transfer at the gas–liquid interface and water diffusion pattern.

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H. Guo et al. Bioresource Technology 384 (2023) 129294

Researchers usually combine reactors to study mass transfer phe­ et al. (2020a) studied the kinetic properties of camphor pine. They
nomena during lignin depolymerization. The monomer yields of widely confirmed that the variation of activation energy values is the main
used intermittent reactors are typically low, and coke formation for reason for the different decomposition reactions of lignin at different
polymerization reactions is observed in intermittent reactors (Sahayaraj temperatures. Insufficient heat transfer time at high heating rates leads
et al., 2021). The reaction rate of lignin depolymerization in intermittent to increased temperature gradients inside the sample, which is more
systems is limited by internal mass transfer, which decreases with pronounced compared to low heating rate conditions; therefore, the
decreasing particle size (Pu et al., 2019). In addition, intermittent re­ temperature of the maximum exothermic peak should be higher than the
actors make it difficult to identify and separate quickly. Study transfer maximum pyrolysis temperature (Xu et al., 2020a). The increased heat
limitations, so to determine the actual activation potential of lignin and transfer efficiency allows the biomass pellets to reach the target tem­
eliminate the effect of depolymerization reactions, the concept of flow- perature level quickly but sufficiently to achieve the best results for the
through reactors was introduced, in which mass transfer depends only reaction (Rasaq et al., 2021). Therefore, heat transfer within the parti­
on solvent flow rate and biomass particle size and enables shorter pro­ cles is often overlooked, but its effect is minimal because the lignin is
cessing times, thus reducing overall energy consumption (Abdelaziz and dissolved before reaching the final reaction conditions.
Hulteberg, 2020; Anderson et al., 2018).
The effective diffusional coefficient can be used to estimate the
limitation of internal mass transfer by the concentration gradient inside 6.4. Research needs and future directions
the catalyst particle. This is because the reaction rate within the catalyst
particle depends on the rate of reactant diffusion in the pores, which is Conversion of lignin into value-added products is a challenging
limited by the concentration gradient. Using the effective coefficient, the process. This review describes the lignin valorization to generate high-
internal mass transfer process of the catalyst can be better understood value-added products and provides an overview of lignin depolymer­
and can help optimize the reaction conditions and catalyst design (Van ization, modification, and purification of the products. To make lignin a
der Zwan et al., 2019). Thornburg et al. (2020) presented a validated principal renewable energy source, the technical obstacles such as
simulation framework that considers the feedstock properties of occurrence of re-polymerization and lacking economical and green
methanol-based poplar extracts and determines the intrinsic kinetic depolymerization processes should be overcome. Lignin polymerization
parameters of lignin independent of transport (Thornburg et al., 2020). is considered a greener and more economical depolymerization method
The experimental results suggest that mass transfer resistance will than chemical depolymerization, but researches are needed to search for
dominate the solvation of poplar pellets longer than about 2 mm. In efficient strains and new enzymes with exploration of their mechanisms
response to this phenomenon, the researchers recommend using biomass of action.
particles less than approximately 0.2 mm in length for kinetic evaluation In addition, the transport phenomenon during lignin depolymeriza­
of lignin-preferred catalysts to avoid feedstock-specific mass transfer tion has not been sufficiently studied. This process is usually explored in
limitations in lignin conversion studies (Thornburg et al., 2020). the form of kinetic models, while the detailed process is hard to be
External mass transfer limitation refers to the effect of factors such as described by the kinetic models in lump-sum nature. A multi-scale
mass transfer at the gas–liquid interface and liquid–solid diffusion at the models should be developed to accurately describe the lignin depoly­
catalyst particle interface during the reaction, limiting the reaction rate merization process to optimal design and operations of the lignin-to-
by these mass transfer hindrances. Studies have shown that the effect of value-added product process.
external mass transfer can be eliminated by increasing the flow rate so
that the concentration in the reaction mixture is close to the concen­ 7. Conclusions
tration at the surface of the catalyst particles (Hafeez et al., 2020).
Studying internal and external mass transfer helps to understand the This review overviews the contemporary research into the valori­
transfer phenomena in conventional batch/fluid flow reactors. Deter­ zation of lignin to produce value-added products, including depoly­
mining and optimizing lignin depolymerization rates are critical for the merization, modification, and product purification. The mechanisms
most commonly used reactors (e.g., batch/fluid flow) (Godongwana, involved in the lignin depolymerization process are outlined. Challenges
2016; Rocnik et al., 2022). and prospects for further development are delineated. The efficient,
green, and economical lignin depolymerization process is the key to
6.3.2. Heat transfer lignin which remains unsatisfactorily developed. The structures of lignin
Lignin behaves poorly regarding heat transfer because of the undi­ functional groups can be prepared to yield new products, expand their
rected arrangement of individual molecules. Due to the low thermal application areas commercial values.
conductivity of lignin, significant temperature gradients develop inside
the particles, which are significantly influenced by particle size and
shape (Bayani et al., 2019). Lignin pyrolysis is an essential technology Declaration of Competing Interest
for producing renewable fuels and chemicals. If the heat transfer limi­
tations in lignin depolymerization can be overcome, it could play a The authors declare that they have no known competing financial
crucial role in the global energy mix (Tiarks et al., 2019). interests or personal relationships that could have appeared to influence
The heat transfer limitation is mainly generated by biomass pyrolysis the work reported in this paper.
conditions, where the heating rate is the critical factor affecting the
effective pyrolysis rate (Gadkari et al., 2017). Heating rates cannot be Data availability
measured experimentally but are usually evaluated by mathematical
models, and experimental studies have shown that spherical biomass No data was used for the research described in the article.
feedstocks do not accurately capture the thermal gradient in the pellets
and that even the pore structure between pine and poplar can cause Acknowledgments
differences in external heat transfer coefficients (Pecha et al., 2019).
Zhao et al. (2021) developed a model of thermal conductivity in wood The authors gratefully acknowledge funding supported by the
based on the pore structure relative to the vertical and parallel orien­ Fundamental Research Funds for the Central Universities
tation of the fibers in the wood, as well as the density and moisture (2572021BA01), Ecological and Environmental Protection project of
content, by which it is known that the thermal conductivity parallel to Heilongjiang Province (HST2022ST004), and City University of Hong
the fibers is approximately twice as high as the vertical orientation. Xu Kong grant No. 9380141.

7
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