catalysts

Review
Catalytic Transfer Hydrogenolysis Reactions for
Lignin Valorization to Fuels and Chemicals
Antigoni Margellou 1 and Konstantinos S. Triantafyllidis 1,2, *
1 Department of Chemistry, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece;
amargel@chem.auth.gr
2 Chemical Process and Energy Resources Institute, Centre for Research and Technology Hellas,
57001 Thessaloniki, Greece
* Correspondence: ktrianta@chem.auth.gr




Received: 31 October 2018; Accepted: 10 December 2018; Published: 4 January 2019


Abstract: Lignocellulosic biomass is an abundant renewable source of chemicals and fuels. Lignin,
one of biomass main structural components being widely available as by-product in the pulp and
paper industry and in the process of second generation bioethanol, can provide phenolic and aromatic
compounds that can be utilized for the manufacture of a wide variety of polymers, fuels, and other
high added value products. The effective depolymerisation of lignin into its primary building blocks
remains a challenge with regard to conversion degree and monomers selectivity and stability. This
review article focuses on the state of the art in the liquid phase reductive depolymerisation of lignin
under relatively mild conditions via catalytic hydrogenolysis/hydrogenation reactions, discussing
the effect of lignin type/origin, hydrogen donor solvents, and related transfer hydrogenation or
reforming pathways, catalysts, and reaction conditions.

Keywords: lignin; catalytic transfer hydrogenation; hydrogenolysis; liquid phase reductive

depolymerization; hydrogen donors; phenolic and aromatic compounds

1. Introduction
The projected depletion of fossil fuels and the deterioration of environment by their intensive
use has fostered research and development efforts towards utilization of alternative sources of energy.
Biomass from non-edible crops and agriculture/forestry wastes or by-products is considered as
a promising feedstock for the replacement of petroleum, coal, and natural gas in the production
of chemicals and fuels. The EU has set the target of 10% substitution of conventional fuels by
biomass-derived fuels (biofuels) by 2020, and USA of 20% substitution by 2030 [1–3].
Lignocellulosic biomass consists mainly of cellulose, hemicellulose and lignin, all of which can
be converted into a wide variety of platform chemicals that can be further transformed to fuels,
engineering polymers, pharmaceuticals, cosmetics, etc. (Figure 1). Cellulose is a linear polymer
consisting of glucose molecules linked with β-1,4-glycosidic bonds and hemicellulose is branched
polysaccharide composed of C5 and C6 sugars [4]. Lignin is an amorphous polymer with p-coumaryl,
coniferyl, and sinapyl alcohols being its primary building units. Lignocellulosic biomass can be derived
from hardwoods (beech, birch, poplar, etc.), softwoods (pine, spruce, cedar, etc.), grasses (switchgrass,
miscanthus, etc.), as well as various agricultural byproducts/wastes (straws, husks, bagasse, etc.).
The percentage of cellulose, hemicellulose and lignin in lignocellulosic biomass depends on the nature
of the source as well as on the type of the individual member, i.e., hardwood vs. softwood and
poplar vs. beech within hardwoods. A number of pretreatment methods have been proposed for the
selective isolation of each biomass component. These include physical methods such milling [5–7],
sometimes combined with H2 SO4 , chemical methods such as acid (H2 SO4 , HCl, H3 PO4 ), alkaline

Catalysts 2019, 9, 43; doi:10.3390/catal9010043 www.mdpi.com/journal/catalysts

 Catalysts 2019, 9, 43 2 of 31

(NaOH), organosolv, ozone and oxidative treatment [6,8–11] and physicochemical such as ammonia
fiber, SO2 and steam explosion [6,12–14], wet oxidation [15] and hydrothermal methods [16,17].
The isolated fractions in the form of carbohydrate or phenolic biopolymers of varying molecular
weight, functionality, particle size and other physicochemical characteristics, can be utilized as such
in polymer composites, pharmaceutical formulations, etc. [18–20] Furthermore, the downstream
selective depolymerization of these biopolymers to their primary building units, i.e., glucose, xylose,
alkoxy-phenols, etc., and their consequent transformation to a wide variety of platform chemicals and
eventually to final products, may offer even higher value to biomass valorization, via the “biorefinery”
concept. Pyrolysis and hydrogenolysis/hydrogenation [21–24] represent probably the most studied
thermochemical biomass (or its components) depolymerization processes towards the production of
valuable compounds with a potential in fuels, chemicals and polymers industry [23,25,26].
The aim of this review is to focus on the heterogeneous catalytic transfer hydrogenation reactions
for the depolymerization of various types of lignins, including technical lignins deriving from
established industrial processes, i.e., kraft, soda or lignosulphonate lignin from the pulp and paper
or related industries, as well as enzymatic/acid hydrolysis and organosolv lignins as part of the 2nd
Catalysts 2018, 8, x FOR PEER REVIEW 3 of 31
generation bioethanol production process.

Figure 1. Cont.
 Catalysts 2019, 9, 43 3 of 31

Figure 1. Chemicals derived by the valorization of lignocellulosic biomass. Reproduced from reference [27]
Figure
with1.permission
Chemicals derived
from MDPI. by the valorization of lignocellulosic biomass. Reproduced from
reference [27] with permission from MDPI.
2. Lignin Chemistry
2. Lignin Chemistry
2.1. Lignin Structure and Isolation
Lignin
2.1. Lignin is an and
Structure amorphous
Isolationpolymer formed by the polymerization of p-coumaryl, coniferyl and
sinapyl alcohols via the phenylpropanoid pathway [28]. The structures of the three monolignols, being
Lignin is an amorphous
phenylpropene rings with onepolymer formed
(coniferyl), by the polymerization
two (sinapyl) or no (p-coumaryl)ofmethoxy-substituents,
p-coumaryl, coniferyl are and
sinapyl
shown
Catalysts
alcohols viaPEER
in 8,Figure
2018,
the
x FOR 2.
phenylpropanoid pathway [28]. The structures of the three monolignols,
Coniferyl
REVIEWalcohol (G units) is the main building block of softwood lignins with 4 of 31
being phenylpropene rings
up to ca. 90% content, withhardwood
whereas one (coniferyl), two (sinapyl)
lignins contain, in additionorto no (p-coumaryl)
coniferyl methoxy-
units, increased
amountsamounts
substituents,
increased of
aresinapyl
shownofalcohol (S alcohol
in Figure
sinapyl units), reaching
2. Coniferyl 50–75%.
alcohol
(S units), (GGrass
reaching lignin
units) isGrass
is the
50–75%. also
main composed
building
lignin ofblock
coniferyl
is also and of
of softwood
composed
sinapyl
lignins withand
coniferyl alcohol units,
upsinapyl
to ca. 90% exhibiting
content,
alcohol also traces
units,whereas of p-coumaryl
hardwood
exhibiting alcohol
lignins
also traces (H units)
contain, in
of p-coumaryl [29,30].
addition
alcohol to coniferyl
(H units) [29,30].units,

Figure
Figure 2.
2. Building blocksof
Building blocks oflignin.
lignin.

The
The building
building blocksofoflignin
blocks ligninare
are linked
linked via
via ether
etheror
orcarbon-carbon
carbon-carbonbonds
bondsformed
formedbetween
betweenthethe
aliphatic
aliphatic chain
chain ofofmonolignols
monolignolsand and the
the aromatic
aromatic moieties.
moieties. The
Themost
mostdominant
dominantlinkage is the
linkage β-O-4
is the β-O-4
aryl ether between the β-carbon of the aliphatic chain and the O-atom from the aromatic
aryl ether between the β-carbon of the aliphatic chain and the O-atom from the aromatic moiety, moiety, withwith
45–50% abundance in softwood and 60–62% in hardwood [29,31,32]. Other linkages appearing in
45–50% abundance in softwood and 60–62% in hardwood [29,31,32]. Other linkages appearing in
lignin are β-β (resinol), β-5 (phenylcoumaran), β-1 (spirodienone), α-O-4, 4-O-5 (diaryl ether), α-O-γ,
lignin are β-β (resinol), β-5 (phenylcoumaran), β-1 (spirodienone), α-O-4, 4-O-5 (diaryl ether), α-O-γ,
5-5 (bisphenyl) and dibenzodioxocin [29,31–33]. Representative schematic representations of
softwood and hardwood lignin structures, as well as the dominant linkages, are shown in Figure 3.
 The building blocks of lignin are linked via ether or carbon-carbon bonds formed between the
aliphatic chain of monolignols and the aromatic moieties. The most dominant linkage is the β-O-4
aryl ether between the β-carbon of the aliphatic chain and the O-atom from the aromatic moiety, with
45–50% Catalysts
abundance
2019, 9, 43in softwood and 60–62% in hardwood [29,31,32]. Other linkages appearing 4 of 31 in
lignin are β-β (resinol), β-5 (phenylcoumaran), β-1 (spirodienone), α-O-4, 4-O-5 (diaryl ether), α-O-γ,
5-5 (bisphenyl) andanddibenzodioxocin
5-5 (bisphenyl) [29,31–33].
dibenzodioxocin [29,31–33]. Representative
Representative schematic representations
schematic representations of softwood of
softwood and hardwood lignin structures, as well as the dominant linkages, are shown in Figure 3.
and hardwood lignin structures, as well as the dominant linkages, are shown in Figure 3.

Catalysts 2018, 8, x FOR PEER REVIEW 5 of 31

(a)

(b)
Figure 3.Figure 3. Schematic
Schematic representations
representations of of
(a)(a)softwood
softwood and
and(b)(b)
hardwood lignin
hardwood structures.
lignin Reprinted
structures. Reprinted
with permission from reference [3]. Copyright 2010, American Chemical Society.
with permission from reference [3]. Copyright 2010, American Chemical Society.
The methods of lignin isolation can be classified into two categories based on the solubilization
Theofmethods
lignin, as of ligninbyisolation
reported Kim and can be classified
co-workers [34]: theinto two categories
first category includes based on the
the methods in solubilization
which
of lignin,lignin
as reported
is isolatedby Kim andresidue
as insoluble co-workers
after the[34]: the first ofcategory
solubilization cellulose includes the methods
and hemicellulose while inin which
lignin is the second as
isolated category ligninresidue
insoluble is isolatedafter
in thethe
process solution leaving
solubilization cellulose and
of cellulose andhemicellulose in the while in
hemicellulose
insoluble solids. Each isolation process may result in varying lignin yields with different molecular
the second category lignin is isolated in the process solution leaving cellulose and hemicellulose in
weight and other properties, and possible contaminations, as can be observed in Table 1.
the insoluble solids. Each isolation process may result in varying lignin yields with different
molecular weight and other properties, and possible contaminations, as can be observed in Table 1.
Kraft lignin is produced by the treatment of wood feedstock with NaOH and Na2S at 170 °C for
2 h [3,33,35]. During kraft pulping, the hydroxide and hydrosulfide anions react with lignin, causing
its depolymerizaiton into smaller water/alkali soluble fragments [31]. Besides the depolymerization
Catalysts 2019, 9, 43 5 of 31

Table 1. Major lignin isolation processes and the properties of the obtained lignin [4].

Process Agent T (◦ C) MW (Da) Polydispersity Contamination

Kraft NaOH + Na2 S 170 1000–3000 2.5–3.5 Sulfur
Soda NaOH + anthraquinone 140–170 1000–3000 2.5–3.5 Sulfur
Sulfite sulfite salts 140–170 1000–50,000 4.2–7.0 Sulfur
Organosolv organic solvents 180–200 500–5000 1.5 Sulfur free

Kraft lignin is produced by the treatment of wood feedstock with NaOH and Na2 S at 170 ◦ C for
2 h [3,33,35]. During kraft pulping, the hydroxide and hydrosulfide anions react with lignin, causing its
depolymerizaiton into smaller water/alkali soluble fragments [31]. Besides the depolymerization via
the cleavage of aryl ether bonds, introduction of thiol group, stilbene and carbohydrate linkages can
occur [33,35]. Additionally, the isolated lignin is contaminated with carbohydrates from hemicellulose
and a small amount of sulfur [4]. Kraft pulping is the dominant process and constitutes about 85% of
total lignin production and is recognized as by-product in paper/pulp industry [36]. Similar to the
Kraft process, soda pulping is more often used for the fractionation of non-woody biomass e.g grass,
straw and sugarcane bagasse in the presence of NaOH or NaOH-anthraquinone at 140–170 ◦ C [4,33].
Lignin is partially depolymerized during soda pulping via the cleavage of α- and β-aryl ether bonds,
first in phenolic units and finally in non-phenolic units [35]. The resulting lignin is considered to be
free of impurities compared to the Kraft lignin.
Another industrial process for the isolation of lignin is the sulfite pulping where the lignocellulosic
biomass is digested at 140–170 ◦ C with an aqueous solution of a sulfite or bisulfate salt of Na+ , NH4 + ,
Mg or Ca [35]. This process can be carried out in the whole range of pH scale by selecting the appropriate
salt. During the sulfite pulping, the linkages between the lignocellulosic compounds as wells as the
ether bonds between lignin units can be cleaved by the nucleophilic attack of the sulfite anion [4,35].
As a consequence, sulfonation of the lignin aliphatic chain can occur.
The fractionation of lignocellulosic feedstocks via the organosolv process involves the treatment
of biomass in organic solvents at the temperature range of 180–200 ◦ C [4]. In this process a wide
variety of organic compounds such as alcohols, ketones, acids, ethers and their mixtures with water
have been used as solvents [37–41]. The fractionation can be improved by the addition of inorganic
acids (H3 PO4 , HCl, H2 SO4 [29,41,42]. Luterbacher et al. suggested the formaldehyde addition in the
organosolv process for the stabilization of lignin during biomass pretreatment [43]. The subsequent
hydrogenolysis of the extracted lignin resulted in 47–78% monomers, in contrast to the hydrogenolysis
of lignin extracted in absence of formaldehyde which led to only 7–26% monomers. The organosolv
pretreatment of biomass [11,44], as well as the recently reported hybrid steam explosion/organosolv
process [45], have been proven beneficial for the enzymatic saccharification of the remaining cellulose,
while at the same time achieving high yields of recovered lignin of relatively low molecular weight
and high purity [11,33,45].

2.2. Lignin Valorization

The chemical structure and composition of lignin offer numerous exploitation opportunities
towards the production of a vast variety of valuable products. For example, lignin itself can be used
either directly without modification or after chemical modification in the polymer industry. One of the
main applications of lignin is the substitution of phenol in the phenol-formaldehyde resins, without
modifying the properties of the final product. Furthermore, lignin can be mixed with polymers such as
polyolefins, polyesters and polyurethanes in the form of blends, copolymers and composites for the
production of eco-friendly plastics with improved properties [19,46,47]. After chemical modifications
lignin can be also added in epoxy resins. Another possible exploitation of lignin, is the thermochemical
conversion to carbon functional materials [48] and chemicals for pharmaceutical applications [49].
In addition to utilizing lignin as such, the platform chemicals/monomers, i.e., phenolics, aromatics,
alkanes that derive from various depolymerization processes may lead to the production of even
Catalysts 2019, 9, 43 6 of 31

higher added value fuels, chemicals and products, usually via more controlled selective catalytic
reaction pathways and related processes. Of course, the economics and sustainability of the integrated
technology and the final products depend greatly on the effectiveness of the initial depolymerization
process. The main thermochemical processes for lignin depolymerization can be divided into
three groups based on the temperature/energy requirements. i.e., pyrolysis and more specifically
fast pyrolysis leading mainly to the production of bio-oil (relatively high temperature/energy, ca.
400–700 ◦ C), hydrotreatment or hydroprocessing in the absence of solvents (moderate temperatures, ca.
350–450 ◦ C) and liquid phase depolymerization comprising various acid/base and reductive/oxidative
reactions (relatively low temperatures, ca. ≤ 400 ◦ C) [29]. The “lignin-first” process is a relatively new
strategy that applies directly on the lignocellulosic biomass and provides efficient lignin solubilization
and depolymerization in a single step/reactor, as described below.
In fast pyrolysis, lignin is heated up to 400–700 ◦ C under high heating/cooling rates in the absence
of oxygen, with or without catalyst [34,50]. The main products of no-catalytic, thermal fast pyrolysis of
lignin are bio-oil (containing substituted alkoxyphenols and few aromatics), char and gases (mainly
CO, CO2 , CH4 ). Despite being a high temperature/energy process that could lead to uncontrolled
depolymerization and breaking of C-O and C-C bonds, in a recent work of Lazaridis et al. it has
been shown on the basis of 2D HSQC NMR results that the composition profile in terms of G- or
S-units of the parent lignin is “transferred” to the composition of the produced thermal pyrolysis lignin
bio-oil [51]. On the other hand, the catalytic fast pyrolysis of lignin where the primary thermal pyrolysis
vapors/products are in situ converted to less oxygenated products via dehydration, decarbonylation,
dealkoxylation, cracking and aromatization reactions, may provide bio-oils with substantially altered
composition, containing mainly alkyl-phenols, mono-aromatics (BTX) and naphthalenes, depending
on the physicochemical characteristics of the catalysts [30,51,52]. Gasification is also an important
thermochemical process, widely studied with biomass as feedstock, showing also potential for lignin
valorization via synthesis gas production or hydrogen production and utilization [29]. The ratio of
the produced gases (H2 , CO, CO2 and CH4 ) is dependent upon process parameters, i.e., temperature,
pressure, presence of steam and oxygen, heating rate, and the elemental composition of feed lignin.
Due to the sulfur content of technical lignins, the gasification process can also produce H2 S.
With regard to the liquid phase depolymerization processes, various catalytic reaction
mechanisms have been proposed including acidic, alkaline, oxidative or reductive pathways. Lignin
depolymerization under acidic conditions has been mainly studied by the use of metal salts (metal
acetates, metal chlorides and metal triflates) with Lewis acid properties [53]. In supercritical water
at 400 ◦ C, the yield of products, composed mainly of oxygenated mono-aromatics, was in the range
of 6.2–6.9 wt.% with metal (Fe, Cu, Co, Ni, Al; max. yield with FeCl2 ) chlorides as acidic agent
and 7.1–7.9 wt.% with metal (Fe, Cu, Co, Ni; max. yield with Co(Ac)2 ) acetates. The conversion was
increased when the solvent changed from water to ethanol. Formic acid has also been studied as acidic
catalyst, in ethanol/water mixtures with relatively low yield of monomer phenolics [54], while H2 SO4
was successfully used on hydrolysis lignin (Mw > 20,000 g/mol), yielding ~75 wt.% of depolymerized
lignin with Mw of 1660 g/mol [55]. With regard to alkaline conditions, when NaOH and KOH were
used as homogeneous base catalysts, up to ~20 wt.% yield of oil was obtained, consisting of monomeric
phenolic compounds, such as catechol, cresols, syringol and guaiacol. However, the relatively low oil
production was attributed to substantial repolymerization reactions [56] Hulterberg and co-workers
have studied the base (NaOH)—catalyzed depolymerization of pine kraft lignin in a continuous flow
reactor [57]. The optimum conditions for higher production of monomeric phenolic compounds, less
char formation and partial deoxygenated dimeric/oligomeric fractions, were determined to be 240 ◦ C
for residence time of 2 min, using 5 wt.% lignin loading and NaOH/lignin ratio of ~1 (w/w).
The depolymerization of lignin under oxidative conditions has been studied by the use of
H2 O2 , O2 and nitrobenzene as oxidants and metal oxide catalysts (organometallic, single oxides
and perovskites) at low temperatures. The oxidation resulted in the cleavage of lignin C-O and
C-C bonds and the production of low molecular weight compounds mainly aldehydes, carboxylic
Catalysts 2019, 9, 43 7 of 31

acids and alcohols [30,47,58]. A well-known lignin oxidation process is the vanillin production from
Borregaard Company via the catalytic oxidation of lignosulfonates with O2 as oxidizing agent. A detailed
description of various lignin depolymerization/valorization processes can be found in previous
reviews of Zakzeski et al. [3], Pandey and Kim [34], Li et al. [30], Sun et al. [47], Xu et al. [59]
and Schutyser et al. [58]. Apart from the thermochemical depolymerization processes, enzymatic
deconstruction of lignin had been also proposed by the use of oxidative enzymes, mainly laccases and
peroxidase, from fungi and bacteria [59–61].
A more detailed analysis and overview of the reductive depolymerization processes with
emphasis on the use of hydrogen donor solvents and catalytic transfer hydrogenation/hydrogenolysis
methods is presented in the next sections.

3. Reductive Depolymerization
In contrary to the oxidative depolymerization, reductive depolymerization is taking place in the
presence of reducing agents and redox catalysts. Sels and co-workers have reported a categorization
of reductive depolymerization process based on hydrogen source and reaction temperature [50,58].
When H2 gas is used as the reducing agent, the process is called hydroprocessing and when hydrogen
donor solvents are used, the process is usually called liquid phase reforming. On the other hand,
there are many studies using hydrogen donor solvents which refer to transfer hydrogenation instead
of reforming, without however elaborating on the possible reaction steps and mechanism. Further
subcategories of hydroprocessing, in terms of the reaction temperature, are the mild (<320 ◦ C) and the
harsh hydroprocessing (>320 ◦ C). Mild hydroprocessing is performed in liquid phase with solvents
and catalysts leading to p-substituted methoxyphenols, while harsh hydroprocessing provides a
wider spectrum of products including demethoxylated phenolic species, deoxygenated aromatics,
alkanes, catechols and methoxy-phenols. Harsh hydroprocessing may also take place in the absence
of solvents. In the solvent-free hydroprocessing of Kraft lignin by the use of NiMo/MgO-La2 O3 at
350 ◦ C, 4 h reaction time and 100 bar initial H2 pressure, the conversion was 87% with the highest
total monomer yield 26.4 wt.% which included 15.7 wt.% alkyl-phenolics [62]. Similar results were
obtained for Alcell lignin by the use of supported noble metals at 400 ◦ C, for 4 h reaction time
and initial H2 pressure of 100 bar, with Ru/TiO2 , exhibiting the highest catalytic activity providing
bio-oil yield 78.3 wt.%, and 9.1 wt.% alkylphenolics, 2.5 wt.% aromatics, and 3.5 wt.% catechols [63].
The bifunctional hydroprocessing with metals supported on acidic materials has been also identified
as a separate case, leading to alkane production via additional hydrolysis and dehydration reactions
due to the acidic nature of the support, at temperatures below 320 ◦ C [50].

3.1. Reductive Depolymerization of Lignin Model Compounds

Due to the complex nature of lignin, many studies were carried out with model compounds
simulating the structure and the bonds of lignin, in order to elucidate the kinetics and pathways for
lignin depolymerization. As mentioned in Section 2.1, the most abundant linkage in lignin polymer is
the β-O-4 ether bond. The transformation of β-O-4 and 4-O-5 model compounds shown in Figure 4, is
discussed below.
Zhu et al. studied the hydrogenolysis of nine compounds containing different functional groups,
i.e., benzyl alcohol, aromatic methoxyl and phenolic hydroxyl groups, in methanol and formic acid,
acting as hydrogen donors, and Pd/C as the catalyst [64]. In the compounds without a benzyl alcohol
group, the β-O-4 linkages were cleaved directly and quickly, in contrast to the compounds that
contained benzylic alcohol group, where additional reactions, such as the dehydrogenation of the
benzyl alcohol group, hindered the cleavage of β-O-4 bonds to form aromatic monomer products.
The aromatic methoxyl and the phenolic hydroxyl groups had no impact on products distribution
but the aromatic methoxyl group in both non-phenolic and phenolic compounds seemed to promote
the cleavage of β-O-4 bonds, while the phenolic hydroxyl group had a small negative impact on the
cleavage of these bonds.
 Due to the complex nature of lignin, many studies were carried out with model compounds
simulating the structure and the bonds of lignin, in order to elucidate the kinetics and pathways for
lignin depolymerization. As mentioned in Section 2.1, the most abundant linkage in lignin polymer
is Catalysts
the β-O-4 ether bond. The transformation of β-Ο-4 and 4-O-5 model compounds shown in8 Figure
2019, 9, 43 of 31
4, is discussed below.

Figure
Figure Ligninmodel
4.4.Lignin modelcompounds
compounds studied
studied in
in the
the catalytic
catalyticreductive
reductivedepolymerization.
depolymerization.

The group of Zhang et al. screened a wide range of monometallic catalysts (Ru, Rh, Pd, Pt, Ir, Ag,
Zhu et al. studied the hydrogenolysis of nine compounds containing different functional groups,
Au, Cu, Fe, Co, Ni, Re and Sn) in the hydrogenolysis of 2-phenoxy-1-phenylethanol (130 ◦ C, 10 bar H2 )
i.e., benzyl alcohol, aromatic methoxyl and phenolic hydroxyl groups, in methanol and formic acid,
and Ni showed the highest selectivity towards monomers, i.e., 22% with 14% being cyclohexanol, but
acting as hydrogen donors, and Pd/C as the catalyst [64]. In the compounds without a benzyl alcohol
not the highest conversion (58%). The highest conversion (>99%) was observed by Ru and Rh [65].
group, the β-O-4 linkages were cleaved directly and quickly, in contrast to the compounds that
The catalytic activity of nickel increased by the addition of Ru, Rh, Pd, Pt and Au leading to full
contained benzylic alcohol group, where additional reactions, such as the dehydrogenation of the
conversion of 2-phenoxy-1-phenylethanol and the NiAu catalyst showed the highest monomer yield
benzyl alcohol group, hindered the cleavage of β-O-4 bonds to form aromatic monomer products.
71% (37% cyclohexanol). The optimum ratio Ni:Au was proved to be 7:3. The same group examined
The aromatic
further methoxyl activity
the synergistic and theof phenolic
NiM (M=Ru,hydroxyl groups
Rh, Pd) had no impact
and observed that Nion products distribution
85 Ru15 led to complete
butconversion
the aromatic methoxyl group in both non-phenolic and phenolic
of 2-phenoxy-1-phenylethanol with 58% monomer yield (32% cyclohexanol)compounds seemedatto130promote
◦ C,
the10cleavage of β-O-4 bonds, while the phenolic hydroxyl group had a small negative impact on the
bar H2 [66].
cleavage of these
The activity bonds.
of Pd-Ni bimetallic nanoparticles supported on ZrO2 was examined in the
The group ofofZhang et al. screened a widewith range of monometallic ◦ C.Ir,
hydrotreatment 2-phenoxy-1-phenylethanol NaBH 4 or H2 gas ascatalysts
hydrogen(Ru, Rh,atPd,
source 80 Pt,
Ag,TheAu, Cu, Fe, reaction
optimum Co, Ni, system
Re andcorresponded
Sn) in the hydrogenolysis
to Pd:Ni ratio of 2-phenoxy-1-phenylethanol
1:8, with H2 gas as hydrogen source (130 °C,at 10
◦
bar80 HC 2) for
and 12 Ni showed100%
h, yielding the formation
highest selectivity towards
of cyclohexanol [67].monomers,
The presence i.e.,of 22%
NaBH with 14% the
being
4 induced
cyclohexanol,
initial formationbut not the highest
of phenol which conversion
was further (58%). Thetohighest
converted conversion
cyclohexanol (>99%)NaBH
at increased was observed
4 amount. by
RuTheandcatalytic
Rh [65].activity of the same
The catalytic bimetallic
activity of nickelPd-Ni catalysts
increased by was also tested
the addition ofinRu,theRh,
hydrogenolysis
Pd, Pt and Au
of 2-phenethyl
leading phenyl ether
to full conversion in isopropanol at 210 ◦ C. Under
of 2-phenoxy-1-phenylethanol andinert
the atmosphere
NiAu catalyst theshowed
conversion
theof the
highest
monomer yield 71% (37% cyclohexanol). The optimum ratio Ni:Au was proved to be 7:3. The the
substrate reached 67% with 60% aromatic yield, whereas the addition of hydrogen gas increased same
conversion
group examined to 75% with 70%
further aromatic yield
the synergistic [68]. of NiM (M=Ru, Rh, Pd) and observed that Ni85Ru15
activity
led toThe hydrogenolysis
complete of 2-phenoxy-1-phenylethanol
conversion of 2-phenoxy-1-phenylethanolwith HCOOH withas hydrogen
58% monomer donor and carbon
yield (32%
supported metal catalysts at 80 ◦ C, resulted in the production of acetophenone and phenol [69].
cyclohexanol) at 130 °C, 10 bar H2 [66].
TheThepresence
activityof equivalent
of Pd-Ni amount
bimetallicof base (NH3 ) promote
nanoparticles the reaction
supported on and
ZrOamong the M/C (M=Pd,
2 was examined in the
Rh, Ir, Re, Ni) catalysts tested, Pd/C exhibited the highest activity. Changing the hydrogen source
hydrotreatment of 2-phenoxy-1-phenylethanol with NaBH4 or H2 gas as hydrogen source at 80 °C.
from HCOOH to propanol or hydrogen gas, the reaction was not performed. On the other hand, the
use of other amines, i.e., ethylamine, diethylamine and p-allylamine as bases instead of NH3 , can be
successfully applied resulting in >95% conversion. In another work by the same group, the effect of
other H-donor solvents was examined under redox-neutral reaction conditions and the NaBH4 was
proved to be the best H-donor with 100% substrate (2-phenoxy-1-phenylethanol) conversion [70].
The hydrogenolysis of 1-(2,4-dihydroxyphenyl)-2-(4-methoxyphenoxy)-ethanone (DHPMPE)
model compound in water/ethanol and Pt/C as catalyst at 275 ◦ C yielded quantitative amounts of
4-methoxypenol and a mixture of 6-hydroxy-3-coumaranone and 2,4 dihydroxyacetophenone [71].
The authors suggested that the reaction mechanism is based on β-O-4 bond cleavage and the cyclisation
of 2,4 dihydroxyacetophenone (produced via hydrogenolysis of the initially formed pentacyclic ether)
to 6-hydroxy-3-coumaranone favored by the presence of -OH group in α position of the aromatic ring.
In the hydrogenolysis reaction of guaiacylglycerol-β-guaiacylether (GGGE) under the same conditions,
 The hydrogenolysis of 1-(2,4-dihydroxyphenyl)-2-(4-methoxyphenoxy)-ethanone (DHPMPE)
model compound in water/ethanol and Pt/C as catalyst at 275 °C yielded quantitative amounts of 4-
methoxypenol and a mixture of 6-hydroxy-3-coumaranone and 2,4 dihydroxyacetophenone [71]. The
authors suggested that the reaction mechanism is based on β-O-4 bond cleavage and the cyclisation
of 2,4 dihydroxyacetophenone
Catalysts 2019, 9, 43 (produced via hydrogenolysis of the initially formed pentacyclic
9 of 31
ether) to 6-hydroxy-3-coumaranone favored by the presence of -OH group in α position of the
aromatic ring. In the hydrogenolysis reaction of guaiacylglycerol-β-guaiacylether (GGGE) under the
the reaction products were 2-methoxyphenol and 4-propyl-2-methoxyphenol [71]. The reactant and
same conditions, the reaction products were 2-methoxyphenol and 4-propyl-2-methoxyphenol [71].
product concentration profiles in the conversion of the DHPMPE and GGGE lignin model compounds
The reactant and product concentration profiles in the conversion of the DHPMPE and GGGE lignin
are shown in Figure 5.
model compounds are shown in Figure 5.

(a) (b)
Figure 5. 5.
Figure Reaction
Reaction profiles
profiles of (a) 1-(2,4-dihydroxyphenyl)-2-(4-methoxyphenoxy)-ethanone
of (a) 1-(2,4-dihydroxyphenyl)-2-(4-methoxyphenoxy)-ethanone (DHPMPE)
(DHPMPE) and (b) guaiacylglycerol-β-guaiacylether (GGGE) lignin model compounds
and (b) guaiacylglycerol-β-guaiacylether (GGGE) lignin model compounds in 50 vol.% ethanol in 50 vol.%+
ethanol
50 vol.%+water,
50 vol.% water,
Pt/C, ◦
275 Pt/C,
C, 80275
bar.°C, 80 bar. Reproduced
Reproduced from reference
from reference [71] with permission
[71] with permission from
from Elsevier.
Elsevier.
Rinaldi and co-workers examined the effect of solvent type as well as their hydrogen donor activity
(protic with/without
Rinaldi Lewis basicity
and co-workers andthe
examined aprotic
effectpolar/non
of solventpolar)
type in
as the
wellhydrogenolysis reaction
as their hydrogen of
donor
diphenyl ether, a compound containing 4-O-5 ether bond [72]. The hydrogenolysis
activity (protic with/without Lewis basicity and aprotic polar/non polar) in the hydrogenolysis reaction was
studied ◦ C under hydrogen pressure (50 bar) by the use of Raney Ni catalyst. Among the protic
reactionatof90diphenyl ether, a compound containing 4-O-5 ether bond [72]. The hydrogenolysis
solvents
reaction was studied at 90 2-propanol
with Lewis basicity, exhibited pressure
°C under hydrogen the highest conversion
(50 72.7%
bar) by the use(83% monomers–40.5%
of Raney Ni catalyst.
cyclohexanol)
Among the proticand the use of with
solvents Hex-F-2-PrOH as protic
Lewis basicity, solvent without
2-propanol Lewis
exhibited the basicity
highest led to full reactant
conversion 72.7%
conversion but with lower
(83% monomers–40.5% monomers yield
cyclohexanol) and (32.7%
the usemonomers–16.6%
of Hex-F-2-PrOHcyclohexanol). Among
as protic solvent the aprotic
without Lewis
solvents, 2-Me-THF
basicity led led to 61.1%
to full reactant conversion
conversion (74.2%
but with monomers–34.4%
lower monomers yield cyclohexanol) whereas full
(32.7% monomers–16.6%
conversion wasAmong
cyclohexanol). observed thebyaprotic
methylcyclohexane (44.6% monomers–22.8%
solvents, 2-Me-THF cyclohexanol),
led to 61.1% conversion despite the
(74.2% monomers–
fact that aprotic solvents are not hydrogen donor compounds. The ability of the above solvents to act
as hydrogen donors was also tested in the absence of hydrogen gas. In the case of 2-propanol, the
conversion decreased to 16.6% (100% monomers–49.8% benzene) while with the rest catalysts, the
reaction was not performed.
Apart from β-O-4 model compounds, experiments with other compounds, simulating aryl
ethers [71], carbon-carbon [71,73], and dibenzodioxocin [74] linkages, have also been carried out in
order to define the pathways for the hydrogenolysis of native lignin.

3.2. Lignin-First Strategy

Lignin first strategy refers to the reductive catalytic fractionation of the whole biomass feedstock
and not to the conversion of isolated lignins. Actually, this process is a combination of lignocellulosic
biomass fractionation and simultaneous conversion of lignin to monomers [50]. The composition
and the structure of the primary biomass influences significantly the obtained products. Klein et al.
compared the extent of lignin depolymerization during the reaction of birch, poplar and eucalyptus
wood in methanol under N2 atmosphere (2 bars), at 200 ◦ C and Ni/C as catalyst, and pointed out
that birch wood (hardwood) is a better feedstock, enabling the formation of more lignin-derived
products [75]. The preferred use of hardwood in this process is also remarked by Galkin et al. who
found the following ranking considering the monophenol yield: birch > poplar > spruce > pine
and attributed this effect to the relatively increased abundance of β-O-4 moieties in hardwoods
(Figure 6) [76]. When hardwoods were compared with softwoods and grasses, hardwoods showed
higher monomer yield and delignification amount, followed by grass and softwood [77]. Furthermore,
birch wood (hardwood) is a better feedstock, enabling the formation of more lignin-derived products
[75]. The preferred use of hardwood in this process is also remarked by Galkin et al. who found the
following ranking considering the monophenol yield: birch > poplar > spruce > pine and attributed
this effect to the relatively increased abundance of β-O-4 moieties in hardwoods (Figure 6) [76]. When
Catalysts 2019, 9, 43 10 of 31
hardwoods were compared with softwoods and grasses, hardwoods showed higher monomer yield
and delignification amount, followed by grass and softwood [77]. Furthermore, the ratio between S-
andtheG- units
ratio of lignin
between in biomass
S- and feedstock
G- units of lignin in was alsofeedstock
biomass correlated with
was alsothe respective
correlated withratio in the final
the respective
products
ratio in [77,78].
the final products [77,78].

Figure 6. 6.
Figure Yield
Yieldofofphenolic
phenoliccompounds
compounds produced by the
produced by the lignin-first
lignin-firstapproach
approachasas a function
a function of of 0
β-O-4′
β-O-4
moiety
moiety in in
thethe native
native ligninofofdifferent
lignin differentlignocellulose
lignocellulose substrates.
substrates. Reproduced
Reproducedfromfromreference [76]
reference[76] with
with
permission
permission fromJohn
from JohnWiley
WileyandandSons.
Sons.

The catalytic conversion of woody feedstocks under H2 gas pressure to lignin monomers is known
The catalytic conversion of woody feedstocks under H2 gas pressure to lignin monomers is
from the early 1940s. The group of Hibbert studied the digestion of maple wood and woodmeal in the
known from the early 1940s. The group of Hibbert studied the digestion of maple wood and
presence of 1,4 dioxane and Cu-CrO catalyst at 280 ◦ C under H2 pressure and found that the major
woodmeal in the presence of 1,4 dioxane and Cu-CrO catalyst at 280 °C under H2 pressure and found
products were 4-n-propylcyclohexanol and 3-(4-hydroxycyclohexyl)-propanol-1 [79]. Recently, the
that the major products were 4-n-propylcyclohexanol and 3-(4-hydroxycyclohexyl)-propanol-1 [79].
reductive catalytic fractionation of lignocellulosic feedstocks has been studied by the use of noble
Recently,
metals Pdthe[80–83],
reductive catalytic
Pt [80], fractionation
Ru [77], Rh [80] and oftransition
lignocellulosic
metals,feedstocks
mainly Nihas been studied
[75,84,85] by the
as catalysts.
useAof noble metals
comparative Pd of
study [80–83], Pt [80], Ruof
the performance [77],
Pd/CRh and
[80] Ru/C
and transition metals,
catalysts in mainly Ni
the reductive [75,84,85]
processing of as
catalysts. A comparative study of the performance of Pd/C and Ru/C catalysts
birch sawdust under H2 pressure, showed that the two catalysts resulted in almost the same monomerin the reductive
processing
yield andof birch sawdust
delignification under H
efficiency 2 pressure,
but showed
in completely that the
different two catalysts
product selectivityresulted in almostofthe
and OH-content
same monomer yield and delignification efficiency but in completely different product
lignin oil [86]. Pd/C favored the formation of para-propyl phenolics (75%) while Ru/C the formation selectivity
andof OH-content
para-propanol of phenolics
lignin oil (91%)
[86]. Pd/C favored the
and increased formationConsidering
OH-content. of para-propyl phenolics
catalyst stability,(75%) while
recovery
Ru/C the formation of para-propanol phenolics (91%) and increased OH-content.
and reuse, Sels and co-workers studied the performance of Ni-Al2 O3 pellets positioned in a basket Considering
within a stirred batch reactor [87].
As for the reaction medium, the most common solvents studied are H2 O [80,88],
alcohols [75,77,83–85,88] and mixture of organic solvents with H2 O [80–82,85]. The polarity of the
solvent was shown to influence delignification efficiency and formation of soluble mono-, di- and
oligomer phenolics in the Pd/C-catalyzed reductive liquid processing of birch wood. The major
phenolic monomers obtained were 4-propanolsyringol and 4-propanolguaiacol. The proposed ranking
of solvents was: H2 O > MeOH ≈ EG > EtOH > 1-Pr-OH > 1-BuOH >THF >Dioxane>Hexane, although
a too polar solvent like water caused significant solubilization of carbohydrates [88]. Song et al.
studied the conversion of birch sawdust into 4-propylguaiacol and 4-propylsyringol with a range of
alcohols over Ni/C catalyst and the highest conversion was 50% with >90% selectivity of the above
products [78]. The authors proposed that lignin is initially fragmented into smaller lignin species with
a molecular weight of m/z ca. 1100 to ca. 1600 via alcoholysis reaction, followed by hydrogenolysis
of the fragments into the phenolic monomers. Considering the formic acid, there is no need to be
added externally in the reaction, as it can be produced in situ from the acetyl groups in lignocellulosic
biomass [4,82].
In order to promote the fractionation of lignocellulose, Hensen et al. added Brønsted acid
co-catalysts (HCl, H2 SO4 , H3 PO4 and CH3 COOH) for a possible replacement of the expensive Al(OTf)3
in the process [89]. In the presence of Pd/C at 180 ◦ C, the best co-catalyst was the HCl, resulting in
44 wt.% lignin monomers from oak sawdust, being similar to the performance of Al(OTf)3 which
Catalysts 2019, 9, 43 11 of 31

provided 46 wt.% monomers. In a similar work, by Yan et al., H3 PO4 enhanced the efficiency of
lignin depolymerization from white birch wood sawdust with H2 in dioxane/water using Pt/C as
the catalyst, resulting in 46.4% monomer yield [80]. Among NaOH (alkaline), H3 PO4 (acidic) and
neutral conditions, H3 PO4 resulted in enhanced delignification (85 % with NaOH vs. 96% with H3 PO4 )
of poplar wood in methanol (MeOH) with Pd/C as the catalyst [90]. In the presence of H3 PO4 , the
lignin-derived oil was characterized by a narrow molecular weight distribution and a monomer yield
very close to theoretical whereas in the presence of NaOH, the monomer yield was lower due to
repolymerization. More detailed description of the lignin-first process can be found in the reviews
published by the groups of Samec [4], Barta [47] and Sels [58,91].

3.3. Depolymerization with External Hydrogen Source

Many groups examined the catalytic reductive depolymerization of various types of lignins
utilizing external hydrogen source (H2 gas). In these studies, the catalysts play a major role in the
conversion and the selectivity of the final products. The most widely used catalysts are Pd/C [81,92–96],
Ni/C [93–97], Pt/C [93–95,98], Pt/Al2 O3 [99], Cu-based porous oxides [100,101], supported NiW and
NiMo [102], Ru-based materials [93–96,103], bimetallic NiM (M = Ru, Rh, Pd) [66], Ni-Au [65,104],
WP [105], Rux Ni1-x /SBA-15 [106], modified SBA-15 and Al-SBA-15 [107], MoOx /CNT [108],
S2 O8 2− -KNO3 /TiO2 [109]. Another significant parameter in the reductive depolymerization
using molecular H2 is the reaction medium. The most widely used solvents are water [104],
alcohols [92–95,97,98,100–103,106,107] or mixtures of water with organic compounds [81,99,105] under
sub or super- critical conditions. In most cases, the beneficial effect of a hydrogen donor solvent is
aimed, as discussed in the following section. The conversion activity can be also enhanced by the
addition of other compounds which may facilitate lignin depolymerization and formation of phenolic
monomers, such as metal chlorides [92,93] and NaOH [104].

4. Catalytic Hydrogenolysis of Lignins Using Hydrogen Donors

4.1. Kraft Lignins

Ma et al. reported the complete ethanolysis of Kraft lignin by the use of α-MoC1−x /AC (280 ◦ C)
and the main products were phenols, phenyl and C6 alcohols and C8 -C10 esters [110]. The addition
of H2 gas in the reaction instead of the inert atmosphere had a negative impact on the formation
of liquid products, increasing the alcohols and decreasing the ester yield. Comparing ethanol,
methanol, isopropanol and water, ethanol was the most effective solvent providing more liquid
products. In a following paper, the effect of catalyst properties was examined in the depolymerization
of lignin under supercritical ethanol [111]. The activity sequence of the catalysts was: carbide >
metal > nitride > oxide and the main products were esters, alcohols and aromatics with different
ratios depended on the catalyst. Kraft lignin ethanolysis was also studied by the same group
using alumina-supported molybdenum catalysts at 280 ◦ C, reduced at different temperatures [112].
The depolymerization resulted in C6 alcohols (mainly hexanol), C8 -C10 esters (2-hexanoic acid ethyl
ester), monophenols (2-methoxy-4-methyl phenol), benzyl alcohols (O-methyl benzyl alcohol) and
arenes (xylene). The increase in the reduction temperature from 500 to 750 ◦ C resulted in a gradual
increase of total production yield reaching 1390 mg/g lignin but further increase to 800 ◦ C, decrease
the yield. The same trend was exhibited in each group of products. The inferior activity of the material
reduced at 750 ◦ C was correlated with the metallic phase of Mo and the lower activity of the material
reduced at 800 ◦ C with the collapse of porous structure due to sintering phenomena. The effect of
the reaction time was also studied. When the reaction time increased from 4 to 6 h the product yield
increased dramatically from 142 to 1390 mg/g lignin but when the time was prolonged to 10 h, the
product yield decreased.
The conversion of Kraft lignin into monomeric alkyl phenols was achieved over Cu/Mo-ZSM-5
catalysts at 220 ◦ C using hydrogen produced by reforming and water gas shift reactions taking place
dramatically from 142 to 1390 mg/g lignin but when the time was prolonged to 10 h, the product yield
decreased.
The conversion of Kraft lignin into monomeric alkyl phenols was achieved over Cu/Mo-ZSM-5
catalystsCatalysts
at 2202019,
°C 9,using
43 hydrogen produced by reforming and water gas shift reactions12taking of 31 place
in the water/methanol solvent system and in the presence of NaOH which was used for enhanced
lignin solubility [113]. If no NaOH,
in the water/methanol solvent methanol
system andor in water was used
the presence of NaOHin the reaction,
which was used low forconversions
enhanced were
observed,lignin
despite the [113].
solubility fact that
If no in the presence
NaOH, methanol orof methanol
water was usedorinwater high low
the reaction, selectivity
conversionsto were
phenol was
observedobserved,
but low despite
monomeric the factproduct
that in the presence
yield. Theofoptimum
methanol water:
or watermethanol
high selectivity
ratiostofor
phenol
the was
production
observed but low monomeric product yield. The optimum water: methanol
of monomeric products were determined to be 1:1 and 3:1. The first ratio (1:1) led to 95.7 ratios for the production of wt.%
monomeric products were determined to be 1:1 and 3:1. The first ratio (1:1) led to 95.7 wt.% conversion
conversion and 70.3% selectivity for phenol, 3-methoxy and 2,5,6 trimethyl phenol. The molecular
and 70.3% selectivity for phenol, 3-methoxy and 2,5,6 trimethyl phenol. The molecular weight of
weight ofEtOAc
EtOAc soluble
soluble products
products were
were 286.7 286.7Ing/mol.
g/mol. In all
all reaction reaction
systems, systems,
almost no char almost no char was
was observed,
observed,with
with
thethe exception
exception of the of the experiment
experiment in the
in the absence of absence
NaOH which of NaOH
resultedwhich
in high resulted in high char
char formation
formation(20.4 wt.%).
(20.4 The proposed
wt.%). mechanism
The proposed consisted of
mechanism four stepsof
consisted and is shown
four stepsinand
Figure 7.
is shown in Figure 7.

Figure 7. Possible mechanism for the selective formation of phenol, 3-methoxy, 2,5,6-trimethyl (PMT).
Reproduced from reference [113] by permission of The Royal Society of Chemistry.

The reductive depolymerization of kraft lignin was also examined in a water–ethanol mixture
50/50 (v/v) with formic acid as an in-situ hydrogen source, by the use of Ni-based catalysts compared
to 5% Ru/C [114]. The effectiveness of the formic acid is evident even in the absence of catalysts
(89 wt.% yield of liquid depolymerized lignin at 200 ◦ C). The catalysts resulted in decrease in
the molecular weight of the products but also in an unfortunate increase of solid residue due to
condensation reactions evoked by the acidic properties of the supports. 10% Ni/Zeolite led to a
slight increase of the yield up to 93.5 wt.%, decrease of Mw to 3150 g/mol and 9.3 wt.% solid residue.
The ability of formic acid to depolymerize Kraft lignin in the absence of any other catalyst was also
reported by the same group in a previous publication [115]. Under the optimum operating conditions
Catalysts 2019, 9, 43 13 of 31

of ca. 300 ◦ C, 1 h, 18.6 wt.% substrate concentration, 50/50 (v/v) water–ethanol medium containing
formic acid (FA) with FA-to-lignin mass ratio of 0.7, lignin (Mw ~ 10,000 g/mol) was effectively
de-polymerized towards a liquid product (DL, Mw 1270 g/mol) at a yield of ~90 wt.% and <1 wt.%
yield of solid residue (SR). Higher acidity caused condensation of the intermediate products. Higher
temperatures or prolonged reaction times resulted also in repolymerization. Formic acid as hydrogen
source has been also used by Liguori and Barth for the depolymerization of Kraft lignin to phenols
in water and with Pd-Nafion SAC-13 as catalyst at 300 ◦ C [116]. The main products obtained were
guaiacol, pyrocatechol and resorcinol. Nafion SAC-13 acted as a Brønsted acid, activating the lignin
aryl ether sites and promoting the hydrogenolysis to phenols.
A combination of a supported metal catalyst (Ru/C) with various MgO based catalysts was
studied in the depolymerization of kraft lignin in supercritical ethanol as hydrogen donor solvent [117].
In the absence of Ru/C, the most active catalyst proved to be MgO/ZrO2 with the highest bio-oil
yield (47.7 wt.%) consisting mainly of phenolic compounds, followed by MgO/C (43.3 wt.%) and
MgO/Al2 O3 (42.1 wt.%), as can be observed in Table 2. The number of base/acid sites of the MgO
based catalysts was found to be correlated with the catalytic activity: MgO/ZrO2 which possessed the
highest number of base sites and the less acid sites, exhibited the highest catalytic activity. In contrast,
the catalyst with the highest acidity, i.e., MgO/Al2 O3 , was the less active one. The addition of Ru/C led
to higher bio-oil yield in the range of 70.9–82.7 wt.%, rich in higher alcohols and aliphatic esters, while
the highest bio-oil yield (88.1 wt.%) and the lower solid residue (8.8 wt.%) was observed for Ru/C
when used alone. The unexpected increase of catalytic bio-oil molecular weights, compared to the
non-catalytic bio-oil, was attributed to the higher concentrations of heavy compounds. The addition
of hydrogen gas in the experiment catalyzed by Ru/C + MgO/ZrO2 did not improve the bio-oil
yield (76.9 wt.%). Upon replacement of Kraft lignin with organosolv lignin, the Ru/C + MgO/ZrO2
resulted in lower yield and lower molecular weight of bio-oil, with a higher yield of aromatic monomer.
The higher depolymerization efficiency of organsolv lignin was attributed to the less condensed
structure and the absence of catalyst-poising sulfur.

Table 2. Product yields, molecular weight averages of bio-oils, and monomer yields obtained from
the depolymerization of kraft lignin over MgO loaded on different supports (i.e., carbon, Al2 O3 , and
ZrO2 ), Ru/C, and physical mixtures of Ru/C and each MgO catalyst at 350 ◦ C after a reaction time of
60 min in the 40 mL batch reactor. Reproduced from reference [117] with permission from Elsevier.

Product Yield Molecular Weight of

Monomer Yield (wt.%)
Catalyst (wt.%) Bio-Oil (g/mol)
Mn Mw Phenolic Aliphatic
Bio-Oil SR Total
(g/mol) (g/mol) Monomers Esters
No catalyst 36.2 47.3 347 737 1.75 1.70 0.04
MgO/C 10% a 43.3 37.3 370 834 2.10 1.83 0.26
MgO/Al2 O3 10% 42.1 37.5 383 844 1.98 1.76 0.23
MgO/ZrO2 10% 47.5 32.7 365 776 4.22 3.90 0.32
Ru/C 10% 88.1 8.8 398 906 5.05 4.54 0.51
Ru/C 10% + MgO/C 10% 79.2 10.0 371 944 5.73 5.15 0.58
Ru/C 10% + MgO/Al2 O3 10% 70.9 21.0 434 1064 4.52 3.76 0.77
Ru/C 10% + MgO/ZrO2 10% 82.7 11.3 323 832 6.10 5.16 0.94
a Percent value indicates the catalyst loading amount with respect to lignin weight.

Esposito et al. synthesized two different nickel-based materials, TiN-Ni and TiO2 -Ni and tested
their activity in the hydrogenolysis of Kraft lignin in various alcohols, in a flow reactor system under
relatively mild temperature and pressure conditions, considering mainly the effect of alcohols on
lignin solubility, without discussing their potential hydrogen donating function [118]. Higher catalytic
activity exhibited by the TiN-Ni, was attributed to the better dispersion of Ni in TiN phase as well as to
the more favorable titanium oxidation state, i.e., being (III) in TiN compared to (IV) in TiO. Substituted
phenols (3.2 wt.%) and aromatic fragments (60 wt.%) with small molecular weights were obtained
for TiN-Ni.
their activity in the hydrogenolysis of Kraft lignin in various alcohols, in a flow reactor system under
relatively mild temperature and pressure conditions, considering mainly the effect of alcohols on
lignin solubility, without discussing their potential hydrogen donating function [118]. Higher
catalytic activity exhibited by the TiN-Ni, was attributed to the better dispersion of Ni in TiN phase
as well 2019,
Catalysts as to9,the
43 more favorable titanium oxidation state, i.e., being (III) in TiN compared to (IV) 14 of in
31
TiO. Substituted phenols (3.2 wt.%) and aromatic fragments (60 wt.%) with small molecular weights
were obtained for TiN-Ni.
Supercritical
Supercritical water/isopropanol systems were
water/isopropanol systems were applied
applied for
for the
the depolymerization
depolymerization of of Kraft
Kraft lignin
lignin
over Fe on Rh/La O /CeO
over Fe on Rh/La22O33/CeO2-ZrO 2 -ZrO [119].
2 [119].
2 Different ratios of water and isopropanol were
Different ratios of water and isopropanol were used to used to adjust
adjust
the optimum in
the optimum in situ
situ HH22production,
production,which
whichwaswascorrelated
correlatedwith
withthethe hydrogen
hydrogen donating
donating capability
capability of
of
water and isopropanol and the relative amount of Fe in the catalyst. Gradual increase in waterincontent
water and isopropanol and the relative amount of Fe in the catalyst. Gradual increase water
content
led to a led to a gradual
gradual decreasedecrease in H2 selectivity.
in H2 selectivity. Considering
Considering the products,
the products, the increase
the increase in water in water
content,
content,
resulted resulted in a progressive
in a progressive increaseincrease of aromatics
of aromatics and aliphatic
and aliphatic acid/esters
acid/esters while
while a sharp
a sharp decrease
decrease in
in hydrogenated cyclics was observed. The products distribution obtained
hydrogenated cyclics was observed. The products distribution obtained at the different ratioat the different ratio of
of
isopropanol/water
isopropanol/water can can be
be seen
seen in
in Figure
Figure 8.8. Apart
Apart from
from the
the liquid
liquid products,
products, similar
similar trends
trends were
were
observed in the gas products.
observed in the gas products.

Figure 8. Qualitative
Qualitative liquid
liquid products
products distribution
distribution from
from Kraft lignin depolymerization under the
different ratio
ratio of
ofisopropanol
isopropanoltotowater
water(0.1 g kraft
(0.1 lignin,
g kraft 40 wt.%
lignin, Rh/La
40 wt.% 2O3/CeO
Rh/La 2-ZrO22catalyst,
2 O3 /CeO 373 °C
-ZrO2 catalyst,
373 ◦
reaction temperature,
C reaction 2 h reaction
temperature, time time
2 h reaction and and
2 mmol
2 mmolFe).Fe).
Reproduced
Reproducedfrom reference[119]
fromreference [119] with
permission from Elsevier.
Elsevier.

Singh ◦ C by the use of

Singh etet al. studied the
al. studied the depolymerization
depolymerization of of Kraft
Kraft lignin
lignin inin methanol
methanol at at 220
220 °C by the use of
homogeneous (NaOH) and heterogeneous catalysts (HZM-5 and iron turnings from
homogeneous (NaOH) and heterogeneous catalysts (HZM-5 and iron turnings from lathe machining) lathe machining) [120].
Compared to the non-catalytic experiment, which resulted in 73.6 wt.% depolymerization
[120]. Compared to the non-catalytic experiment, which resulted in 73.6 wt.% depolymerization yield, the
homogeneous NaOH ledNaOH
yield, the homogeneous to 68.5ledwt.% yield,
to 68.5 wt.%5.1yield,
wt.%5.1 monomeric compounds
wt.% monomeric and 100–1000
compounds g/mol
and 100–1000
molecular weight distribution. The heterogeneous HZSM-5 resulted
g/mol molecular weight distribution. The heterogeneous HZSM-5 resulted in higher in higher depolymerization yield
of 85.1 wt.%, withyield
depolymerization lower ofmonomers amount
85.1 wt.%, with lower4.2monomers
wt.% and amount
the same 4.2molecular
wt.% and weight
the same distribution
molecular
while
weightthe iron turnings
distribution whileresulted in lower
the iron turningsdepolymerization
resulted in lower (44.4 wt.%) with 1.7 wt.%
depolymerization (44.4monomers
wt.%) withand1.7
100–2000 g/mol molecular weight distribution. In all cases, the main products
wt.% monomers and 100–2000 g/mol molecular weight distribution. In all cases, the main products were alkyl substituted
phenols.
were alkylIt was suggested
substituted that methanol,
phenols. in addition
It was suggested thattomethanol,
being a solvent in theto
in addition reaction,
being aacted also
solvent inas a
the
hydrogen donor. The hydrogen released due to thermal reforming of methanol-induced
reaction, acted also as a hydrogen donor. The hydrogen released due to thermal reforming of hydrogenolysis
of the ether linkageshydrogenolysis
methanol-induced in lignin resulting in ether
of the ligninlinkages
depolymerization and demethoxylation.
in lignin resulting in lignin depolymerization
and demethoxylation.
4.2. Soda Lignins
Hensen et al. carried out a thorough investigation of the reductive depolymerization of soda
lignin by the use of CuMgAlOx catalysts. In a first article, the group examined the influence of solvent,
reaction time, and catalyst [121]. The most effective combination proved to be CuMgAlOx with ethanol
at 300 ◦ C, resulting in 17 wt.% monomers yield, comprising of aromatic products with small amounts of
furans, hydrogenated substituted cyclic compounds and deoxygenated aromatics, as can be observed
in Figure 9. The Cu content of 20 wt.% in the CuMgAlOx mixed oxide was found to induce the
highest activity for Guerbet, esterification and alkylation reactions, resulting in higher monomers yield
 Hensen et al. carried out a thorough investigation of the reductive depolymerization of soda
lignin by the use of CuMgAlOx catalysts. In a first article, the group examined the influence of solvent,
reaction time, and catalyst [121]. The most effective combination proved to be CuMgAlOx with
ethanol at 300 °C, resulting in 17 wt.% monomers yield, comprising of aromatic products with small
amounts of furans,
Catalysts 2019, 9, 43 hydrogenated substituted cyclic compounds and deoxygenated aromatics, as can
15 of 31
be observed in Figure 9. The Cu content of 20 wt.% in the CuMgAlOx mixed oxide was found to
induce the highest activity for Guerbet, esterification and alkylation reactions, resulting in higher
and low repolymerization
monomers [122]. Both the non-catalytic
yield and low repolymerization [122]. Both experiment and the
the non-catalytic use of methanol
experiment and the resulted
use of
in low monomer yields (5 and 6 wt.%) and in the latter case the products
methanol resulted in low monomer yields (5 and 6 wt.%) and in the latter case the products were were mainly methylated
phenols and
mainly guaiacol-type
methylated compounds.
phenols Copper in MgAlO
and guaiacol-type x improved
compounds. the monomer
Copper in MgAlO production
x improved and the
the
formation of deoxygenated aromatics compared to the MgAlO
monomer production and the formation of deoxygenated aromatics compared to the MgAlOx,
x , NiMgAlO x , and PtMgAlO x catalysts.
Considering
NiMgAlO the repolymerization
x, and PtMgAlOx catalysts. via the phenolic hydroxyl
Considering groups, the authors
the repolymerization via thesuggested
phenolic that ethanol
hydroxyl
not only the
groups, actsauthors
as a hydrogen-donor
suggested that solvent,
ethanolbut also
not onlyas aacts
capping agent and formaldehyde
as a hydrogen-donor solvent, scavenger,
but also asas a
shown in Figure 10 [121,123]. In a following paper, they discussed the influence
capping agent and formaldehyde scavenger, as shown in Figure 10 [121,123]. In a following paper, of reaction temperature
on the productsthe [124]. At lower temperatures in theon range of 200–250 ◦ C, recondensation reactions
they discussed influence of reaction temperature the products [124]. At lower temperatures in
are dominant whereas at higher temperatures of 380–420 ◦ C, the char formation due to carbonization
the range of 200–250 °C, recondensation reactions are dominant whereas at higher temperatures of
played a major role. At the intermediate range of 300–340 ◦ C, the depolymerization of lignin is
380–420 °C, the char formation due to carbonization played a major role. At the intermediate range
enhanced,
of 300–340 resulting in the formation of
°C, the depolymerization of reactive
lignin isphenolic
enhanced, intermediates
resulting inwhich can be protected
the formation of reactiveby
alkylation, Guerbet and esterification reactions. CuO in the parent CuMgAlO
phenolic intermediates which can be protected by alkylation, Guerbet and esterification reactions. x catalyst favors the
alkylation
CuO in the reactions
parent CuMgAlOwhile itsx catalyst
progressive favors reduction to Cureactions
the alkylation may leadwhileto the its undesirable increased
progressive reduction
hydrogenation
to Cu may lead of to the
the aromatic
undesirablering. increased hydrogenation of the aromatic ring.

Figure 9. Product
Productdistribution
distributionfollowing
followingreaction:
reaction:(a)(a)
blank
blankreaction
reactionat 300 °C ◦for
at 300 4 h 4inhethanol,
C for (b)
in ethanol,
CuMgAlO
(b) CuMgAlOx at x300
at 300 ◦
°C forC 4for
h 4inhethanol, (c) CuMgAlO
in ethanol, (c) CuMgAlO x atx300
at 300 ◦
°C for 4 h4inh methanol,
C for in methanol,(d)(d)
CuMgAlO
CuMgAlO x at
x
300 °C◦for
at 300 8 h8 in
C for ethanol.
h in ethanol. The
The numbers
numbers ininthe
themolecules
moleculescorrespond
correspondtotothe themolecular
molecularweight,
weight, whereas
whereas
colors are used to facilitate the reading of the figure. Reproduced from reference [121] with permission
from John Wiley and Sons.
Catalysts 2018, 8, x FOR PEER REVIEW 16 of 31

colors are used to facilitate the reading of the figure. Reproduced from reference [121] with
Catalysts 2019, 9, 43 16 of 31
permission from John Wiley and Sons.

Figure 10. Possible reaction routes during lignin depolymerization in ethanol in the presence of catalyst.
Figure 10. Possible reaction routes during lignin depolymerization in ethanol in the presence of
Reproduced from reference [121] with permission from John Wiley and sons.
catalyst. Reproduced from reference [121] with permission from John Wiley and sons.
Soda lignin depolymerization was performed over metals catalysts supported on ZSM-5 zeolite in
Soda lignin depolymerization was performed over metals catalysts supported on ZSM-5 zeolite
supercritical ethanol at 440 ◦ C [125]. When comparing the transition metals Ni, Co and Cu at 10 wt.%
in supercritical ethanol at 440 °C [125]. When comparing the transition metals Ni, Co and Cu at 10
loading on ZSM-5 with Si/Al2 of 200, the 10% Cu/ZSM-5(200) catalyst showed the highest yield of
wt.% loading on ZSM-5 with Si/Al2 of 200, the 10% Cu/ZSM-5(200) catalyst showed the highest yield
monoaromatic compounds (15.3 wt.%). Changing the metal loading from 10% to 5 and 30% a small
of monoaromatic compounds (15.3 wt.%). Changing the metal loading from 10% to 5 and 30% a small
decrease in monoaromatic compounds was observed. In order to find the optimum Si/Al2 ratio of
decrease in monoaromatic compounds was observed. In order to find the optimum Si/Al2 ratio of
ZSM-5, Si/Al2 was varied from 30 to 200. The highest yield 98.2 wt.% of monoaromatic compounds
ZSM-5, Si/Al2 was varied from 30 to 200. The highest yield 98.2 wt.% of monoaromatic compounds
was obtained over 10 wt.% Cu/ZSM-5(30) due to the higher acid density. The beneficial effect of Cu
was obtained over 10 wt.% Cu/ZSM-5(30) due to the higher acid density. The beneficial effect of Cu
in the depolymerization was confirmed by the experiment conducted in Cu-free ZSM-5 (30) which
in the depolymerization was confirmed by the experiment conducted in Cu-free ZSM-5 (30) which
resulted in 89.4 wt.% monoaromatic compounds. The authors suggested that the in situ produced
resulted in 89.4 wt.% monoaromatic compounds. The authors suggested that the in situ produced
hydrogen atoms were adsorbed onto the surface of Cu leading to cleavage of ether bonds and thus
hydrogen atoms were adsorbed onto the surface of Cu leading to cleavage of ether bonds and thus
promoting the depolymerization.
promoting the depolymerization.
4.3. Alkali Lignins
4.3. Alkali Lignins
In the hydrogenolysis of alkali lignin in supercritical ethanol, Zhou et al. found that
In the hydrogenolysis
CuNiAl-hydrotalcite was moreof alkali
activelignin in than
catalyst supercritical
Ni/ZSM-5 ethanol, Zhou
or Ru/C, et al. found
resulting in 49.5that
wt.%CuNiAl-
bio-oil
hydrotalcite
yield at 290 ◦was more
C [126]. active
The strongcatalyst than of
basic sites Ni/ZSM-5 or Ru/C,
hydrotalcite, resulting
compared in 49.5
to the acidicwt.% bio-oil
ZSM-5 andyield at
carbon,
290 °C [126]. The strong basic sites of hydrotalcite, compared to the acidic ZSM-5
inhibited the recondensation of reactive compounds of bio-oil. The addition of phenol as co-solvent to and carbon,
inhibited the recondensation increased
ethanol (phenol/lignin=0.8), of reactivebio-oil
compounds
yield toof72.3
bio-oil.
wt.%.The addition
Phenol of phenoltoas
is suggested co-solvent
promote the
to ethanol (phenol/lignin=0.8), increased bio-oil yield to 72.3 wt.%. Phenol is
hydrogenolysis due to the enhanced solubilization of lignin and the capping agent action favoring suggested to promote
the
the hydrogenolysis due to the enhanced
formation of mono-phenolics compoundssolubilization of lignin and
and suppressing the capping agent
repolymerization. action
Higher favoring
amounts of
the formation of mono-phenolics compounds and suppressing repolymerization.
phenol resulted in lower bio-oil yields and increased molecular weights, phenomena which attributed Higher amounts of
phenol resulted
to secondary in lower bio-oil
repolymerization yields Also,
reactions. and theincreased
addition molecular
of hydrogenweights,
gas did phenomena
not enhanced which
the
attributed to secondary repolymerization reactions. Also, the addition
bio-oil yield (70.3 wt.%). The optimum temperature and time considering the bio-oil yield wereof hydrogen gas did not
enhanced
determined theto bio-oil
be 290 yield
◦ C and(70.3
3 h.wt.%). The optimum temperature and time considering the bio-oil
yieldThe
were determined to be 290 °C and 3 h.catalysts was also reported by Li et al., in the hydrogen
effective activity of nickel-based
The effective activity of nickel-based catalysts was alsosolvent
transfer conversion of alkali lignin using isopropanol/water reported by Alkali
[127]. Li et al., in the
lignin hydrogen
showed high
transfer conversion of alkali lignin using isopropanol/water
◦ solvent [127]. Alkali
conversion (93%) over Raney Ni catalysts at 180 C, superior than with Pd/C catalyst which led to low lignin showed high
conversion
conversion and (93%) over Raneyrates.
liquefaction Ni catalysts at 180 °C, was
Lower conversion superior than for
observed with Pd/C lignin
Klason catalystduewhich
to itsled
moreto
low conversion and liquefaction rates. Lower conversion was observed for Klason
condensed nature, attributed to the high acid concentrations in the Klason lignin preparation process. lignin due to its
moreThecondensed
synergistic nature, attributed
activity of formic toacid
the high acid concentrations
and Pd/C was examined in the catalytic
in the Klason lignin preparation
depolymerization
process.
of alkali lignin in subcritical water [128]. When the reaction was contacted without formic acid and
Pd/C at 265 ◦ C for 1 h, the liquid products yield was 58.2 wt.% and the solid residue 30.6 wt.%.
Catalysts 2019, 9, 43 17 of 31

The addition of formic acid slightly increased the liquid products to 61.6 wt.% but extremely decreased
the solid residue to 0.64 wt.%. The addition of Pd/C catalyst either in the presence of formic acid
or not, resulted in lower liquid products (45.8 and 41.3 wt.%) and higher solid residues (16.3 and
54.4 wt.%). The products yields from lignin depolymerization in all reaction systems are shown in
Table 3. The catalyst favored the conversion of formic acid and production of H2 via reforming and
water–gas shift reactions and promoted the repolymerization reactions. Significant differences are
observed in the composition of liquid products. In the absence of formic acid and Pd/C, the main
compound was guaiacol, while in the presence of formic acid or both formic acid and Pd/C, catechol
was the main compound. Pd/C can catalyze the hydrogenolysis of the aryl–O ether bond resulting in
significant yield of phenol and char formation.

Table 3. Product yields from lignin depolymerization with additives at 265 ◦ C, 6.5 MPa from 1–6 h
hold time. Reproduced from reference [128] by permission of The Royal Society of Chemistry.

Hold Time Liquid Solid Residue Gas

Sample % Balance
(h) (wt.%) (wt.%) (wt.%)
Lignin 1.0 58.2 30.6 5.56 94.4
Lignin 3.0 51.6 35.9 9.12 96.6
Lignin 6.0 33.3 46.0 17.0 96.3
Lignin/FA 1.0 61.6 0.64 36.5 98.7
Lignin/FA 3.0 52.3 0.19 46.1 98.6
Lignin/FA 6.0 41.1 1.12 58.3 101
Lignin/Pd/C 1.0 41.3 54.4 0.84 96.5
Lignin/Pd/C 3.0 36.1 57.3 1.25 94.7
Lignin/Pd/C 6.0 35.6 59.1 2.25 97.0
Lignin/FA-Pd/C 1.0 45.8 16.3 38.7 101
Lignin/FA-Pd/C 3.0 38.5 18.3 49.8 107
Lignin/FA-Pd/C 6.0 31.6 22.9 53.4 108
Pd/C 6.0 - 98.5 - 98.5

4.4. Organosolv Lignins

Toledano et al. studied the hydrogenolysis of organosolv lignin from olive tree prunings under
microwave irradiation, using a variety of hydrogen donor solvents without any H2 addition [129,130].
In a first paper, they examined the activity of metallic (Ni, Ru, Pd, Pt) catalysts supported on Al-SBA-15
and found that 10% Ni/Al-SBA-15 with tetralin as solvent provided improved bio-oils with 17 wt.%
yield, consisting of simple phenolics, including mesitol and syningaldehyde, as well as, a small amount
of esters. The product distribution obtained over Ni, Ru, Pd, Pt catalysts supported on Al-SBA-15
can be seen in Table 4. The other metals exhibited lower activity with high remaining lignin due to
repolymerization phenomena [129]. In a further work, the same group carried out detailed research
on the solvent effect on the hydrogenolysis of organosolv lignin from olive tree prunings with 10%
Ni/Al-SBA-15 at 150 ◦ C [130]. The most effective solvent, as shown in Figure 11, was proved to be
formic acid resulting in high bio-oil yield (28.89 wt.%), no biochar and a wide variety of phenolics
compounds. Formic acid was noted to exhibit additional acidolytic properties for the depolymerization
of lignin. Less efficient solvents were glycerol and tetralin with the later leading mainly to phthalates.
The authors highlighted the unexpected behavior of isopropanol which in the case of the catalytic
experiment, it was proven less efficient compared to the blank experiment due to the dehydrogenation
of isopropanol to acetone over the Ni/Al-SBA-15 catalyst.
Catalysts 2019, 9, 43 18 of 31

4. Compounds
Table 2018,
Catalysts identified
8, x FOR PEER REVIEW in appreciable quantities in lignin bio-oils obtained by the hydrogenolysis
18 of 31
of organsolv lignin from olive tree prunings under microwave irradiation using Ni, Pd, Pt, Ru catalysts
Pd, Pt, Ru
supported oncatalysts supported
Al-SBA-15. on Al-SBA-15.
Compounds yields Compounds
expressed asyields
mg ofexpressed as mg of each
each compound compound
per gram of lignin.
per gram of lignin. Reproduced from ref. [129] with
Reproduced from ref. [129] with permission from Elsevier. permission from Elsevier.

Ni2% Ni5% Ni10% Pd2% Pt2% Ru2%

Blank Ni2% Ni5% Ni10% Pd2% Pt2% Ru2%
Blank AlSBA AlSBA AlSBA AlSBA AlSBA AlSBA
AlSBA AlSBA AlSBA AlSBA AlSBA AlSBA
Mesitol (2) 0.56 2.26 1.19 1.13 0.49 1.67 1.40
Mesitol (2)
2,3,6-Trimehtylphenol (3) 0.560.19 2.26
0.76 1.19
0.22 0.281.13 0.18 0.49 0.17 1.67 0.45 1.40
2,3,6-Trimehtylphenol
6-Ethyl-o-cresol(3)(5) 0.190.13 0.76
0.14 0.22
0.04 - 0.28 - 0.18 0.32 0.17 0.19 0.45
6-Ethyl-o-cresol (5) (6)
4-Ethyl-m-cresol 0.13 - 0.14
0.11 0.04
0.04 - - - - 0.08 0.32 - 0.19
4-Ethyl-m-cresol
Vanillin(6)
(7) - 0.20 0.11
0.20 0.04
0.19 0.20 - - - 0.13 0.08 0.11 -
Vanillin (7)
Diethylphthalate (10) 0.202.34 0.20
10.10 0.19
1.67 1.690.20 10.93 - 10.66 0.13 7.44 0.11
Diethylphthalate (10)
3,4-Dimethoxyphenol (11) 2.340.05 10.10
0.12 1.67
0.05 0.151.69 0.24 10.93 0.09 10.660.09 7.44
3,4-Dimethoxyphenol (11) 0.05 0.12 0.05 0.15 0.24 0.09 0.09
Syringaldehyde (12) 0.47 0.68 0.57 0.56 0.15 0.43 0.43
Syringaldehyde (12) 0.47 0.68 0.57 0.56 0.15 0.43 0.43
Butyl-octyl ester phthalic acid (16) 0.21 0.36 0.30 0.19 0.34 0.36 0.37
Butyl-octyl ester phthalic acid (16) 0.21 0.36 0.30 0.19 0.34 0.36 0.37
a Reaction conditions: 0.5 g lignin, 0.5 g catalyst, 12.5 mL tetralin, microwaves, 400 W, average temperature 140 °C,
a Reaction conditions: 0.5 g lignin, 0.5 g catalyst, 12.5 mL tetralin, microwaves, 400 W, average temperature 140 ◦ C,
30 min reaction.
30 min reaction.

Figure
Figure 11. 11. Products
Products yields
yields (%, (%,
w/w)w/w) referenced
referenced to initial
to initial lignin
lignin weight
weight of bio-oil
of bio-oil (black),
(black), biochar
biochar (white)
and(white)
residualand residual
lignin lignin
(grey) (grey)
derived byderived by hydrogenolysis
hydrogenolysis of lignin
of lignin under under
mild, mild, microwave- H2
microwave-assisted,
freeassisted, H2 free
conditions, conditions,
using varioususing various
solvents: solvents:
tetralin (TL),tetralin (TL),
glycerol glycerol
(GLY), (GLY),
formic acid formic
(FA) acid
and (FA) and
isopropanol
isopropanol (IP). Reaction conditions: 0.5 g lignin, 0.5 g catalyst, 12.5 mL solvent,
(IP). Reaction conditions: 0.5 g lignin, 0.5 g catalyst, 12.5 mL solvent, microwaves, Taverage = 423 K, microwaves,
Taverage=423
t = 30 K, t=30 min.
min. Reproduced fromReproduced fromwith
reference [130] reference [130] with
permission frompermission
John Wileyfrom and John
sons.Wiley and
sons.
Organosolv lignin from switchgrass had been successfully depolymerized in ethanol, 20 wt.%
Pt/C and Organosolv
formic acid lignin
asfrom switchgrass
hydrogen donorhad been successfully
molecule at 350 ◦ Cdepolymerized
for the productionin ethanol, 20 wt.%and
of phenol
Pt/C and formic acid as hydrogen donor molecule at 350 °C for the production
substituted phenols with higher H/C and lower O/C molar ratios [131]. In a similar reaction system, of phenol and
substituted phenols with higher H/C and lower O/C molar ratios [131]. In a similar reaction system,
organosolv lignin was depolymerized using isopropanol as solvent, Ru/C as catalyst and formic acid
organosolv lignin was depolymerized using isopropanol as solvent, Ru/C as catalyst and formic acid
as hydrogen donor at 400 ◦ C [132]. The catalytic experiments resulted in 71.2 wt.% lignin oil, negligible
as hydrogen donor at 400 °C [132]. The catalytic experiments resulted in 71.2 wt.% lignin oil,
solids formation and significant amount of water (9.6%) due to the decomposition of formic acid.
negligible solids formation and significant amount of water (9.6%) due to the decomposition of formic
Theacid.
activity
The of the catalyst
activity was confirmed
of the catalyst by the by
was confirmed experiment conducted
the experiment in theinabsence
conducted of Ru/C
the absence which
of Ru/C
led which
to onlyled18 to
wt.% conversion and a large amount of solids derived either
only 18 wt.% conversion and a large amount of solids derived either from the from the unconverted
lignin or repolymerization
unconverted reactions. The reactions.
lignin or repolymerization effective conversion
The effective ofconversion
lignin wasof further
lignin compared
was further with
the compared
hydrotreatment
with the experiment,
hydrotreatmentconducted in theconducted
experiment, absence ofinsolvent (onlyofRu/C
the absence solvent+H 2 gas),
(only Ru/Cexhibiting
+ H2
lower oilexhibiting
gas), yield (63.1 wt.%)
lower compared
oil yield to the
(63.1 wt.%) use of isopropanol
compared to the use of as solvent. Considering
isopropanol the chemical
as solvent. Considering
composition
the chemical of composition
derived oils,ofthe majoroils,
derived products were
the major ketones
products (methyl
were ketonesisobutylketone) followed by
(methyl isobutylketone)
followedcatechols
aromatics, by aromatics, andcatechols and alkylphenolics.
alkylphenolics. In an to
In an attempt attempt
improve to improve the catalytic
the catalytic reaction
reaction system,
Catalysts 2019, 9, 43 19 of 31

methanol and ethanol were also tested as solvents. Methanol gave almost similar yield (68.4 wt.%)
with isopropanol but higher amounts of alkylphenolics and aromatics whereas ethanol resulted in
lower yield (63.4 wt.%).
The effect of biomass feedstock and isolation method of lignin on the depolymerization in
supercritical ethanol and formic acid, in absence of catalyst, at 250–350 ◦ C was also investigated [133].
The reaction was performed in lignin derived from oak (hardwood) and pine (softwood), isolated
as ethanosolv, formasolv and Klason types. Regardless the isolation method, all lignins exhibited
bio-oil and conversion yields above 90 wt.% with low solid residue <2.5 wt.% at 350 ◦ C. At this
temperature, the combination of ethanol with formic acid facilitated the hydrogen production which
quenched the radicals, suppressing the repolymerization. For the hardwood type biomass, at lower
reaction temperature (250 ◦ C), the ethanosolv and the formasolv lignin exhibited lower bio-oil
yield, 68.0 and 77.5 wt.%, respectively, while Klason lignin bio-oil yield dramatically decreased
to 19.3 wt.% due to the abundance of C-C recalcitrant bonds formed in the Klason process. With regard
to bio-oil composition, at 350 ◦ C, linear and branched short-chain oxygenated species from the
decomposition of ethanol and formic acid, monoaromatic species and long chain fatty acid alkyl esters
from the esterification of woody biomass with ethanol were produced. At lower reaction temperature,
where the deoxygenation/hydrogenation reactions are limited, carbonyl or double bond-containing
monoaromatics were formed. With regard to softwood biomass, the ethanosolv and formasolv lignins
exhibited 97.1 and 99.4 wt.% conversion and 88.1 and 90.7 wt.% bio-oil yield. Again, the Klason lignin
depolymerization resulted in lower conversion (95.1 wt.%) and bio-oil yield (81.7 wt.%). At the low
temperatures of 250–300 ◦ C, the most important parameter was suggested to be the relative abundance
of ether linkages in the lignin structure.
The catalytic activity of Cu based porous metal oxides towards the depolymerization of organosolv
lignin extracted from candlenuts was examined in supercritical methanol at 310 ◦ C [134]. Taking
into consideration lignin conversion, the following rank was determined: Cu20 PMO > Cu20 PMO
Cu20 Cr20 PMO > Cu20 La20 PMO (PMO stands for porous metal oxide). For the best catalyst Cu20 PMO,
lignin conversion reached 48.3% after 1 h reaction. Due to the lower methanol reforming ability
of lanthanum, the reaction was also carried out for higher times and the conversion reached 98%
after 6 h. Under the same reaction conditions, the activity Cu-free porous metal oxides were also
examined. [Mg/Al]PMO exhibited the highest lignin conversion of 74.6% for 5 h reaction. Comparison
of CuPMOs to Cu-free analogs showed that Cu promotes higher yields of methanol-soluble products
and suppresses re-condensation reactions. The Cu20 La20 PMO variant was suggested as the most
effective catalyst in terms of limiting over-reduction of aromatic intermediates due to the lower
methanol-reforming of lanthanum, thus regulating the in situ production of hydrogen.
Organosolv lignin isolated from eucalyptus was depolymerized in water to syringol monomers
over β-CaP2 O6 and CoP2 O6 [135]. Despite that eucalyptus is a hardwood feedstock, the use of
phosphate catalysts selectively produced only syringol with yield of 8.47% over β-CaP2 O6 and
6.67 % over CoP2 O6 . The hydrogenolysis of organosolv lignin from hybrid poplar in supercritical
ethanol at 320 ◦ C, by the use of amorphous B-containing FeNi alloyed catalysts, resulted in lignin
depolymerization and the production of deoxygenated aliphatic side chains [136].

4.5. Lignosulfonate
Lignosulfonate depolymerization via hydrogen transfer reactions was investigated over Raney
Ni at 200 ◦ C and a solvent mixture composed of water, isopropanol, butanol and hexane, introducing
the concept of an emulsion microreactor [137]. Isopropanol was considered to be the hydrogen donor
solvent for the hydrogenolysis of lignolsulfonate while the combination of the above three solvents
provided higher monomer yields, compared to the more classical water, alcohol or water-alcohol
mixtures, as can be seen in Table 5. The higher yield of phenolic monomers was observed for the
solvent mixture water: butanol: isopropanol: hexane = 1:1:3:0.1, with 4-ethyl guaiacol being the most
abundant compound. The facile phase separation after the hydrogenolysis reaction was suggested as
an important advantage of the described emulsion microreactor.
Catalysts 2019, 9, 43 20 of 31

Table 5. Catalytic depolymerization of sodium lignosulfonate in emulsion microreactor. Reproduced

from reference [137] with permission from Elsevier.
Catalysts 2018, 8, x FOR PEER REVIEW 20 of 31
Solvent (mL) Yield of Phenolic Monomers (mg·g−1 )
TableH5.2Catalytic
O depolymerization
n-BuOH i-PrOH of sodium lignosulfonate
4-Ethyl Guaiacol in emulsion
Othersmicroreactor. Reproduced
Total
from reference [137] with permission from Elsevier.
25 / / 18.8 ± 0.3 37.3 ± 0.5 56.1 ± 0.7
20 5.0 Solvent (mL)
/ 22.0 ±
Yield 0.4
of Phenolic 39.8 ±(mg∙g
Monomers 0.6 −1) 61.8 ± 0.8
15 H210
O n-BuOH / i-PrOH ± 0.2
23.5 Guaiacol
4-Ethyl 41.9 ± 0.5
Others Total 65.4 ± 0.7
10 15
25 / / / 18.8 ±
22.3 0.3
± 0.3 0.5 ±56.1
37.3 ±40.2 0.6± 0.7 62.5 ± 0.8
20 20/ 5.0 5.0 / 22.0 ±
21.3 ± 0.4
0.5 39.8 ±32.1
0.6 ±61.8
0.6± 0.8 53.4 ± 1.1
15 10
15 5.0 5.0 / 23.5 ± 0.2
24.8 ± 0.4 41.9 ± 0.5
50.2 ±65.4
1.9± 0.7 75.0 ± 2.2
10 15 / 22.3 ± 0.3 40.2 ± 0.6 62.5 ± 0.8
10 5.0 10 33.8 ± 0.3 50.3 ± 2.5 84.1 ± 2.8
20 / 5.0 21.3 ± 0.5 32.1 ± 0.6 53.4 ± 1.1
10 10
15 5.0 5.0 5.0 24.8 ±
27.7 0.1
± 0.4 1.9 ±75.0
50.2 ±52.8 3.0± 2.2 80.5 ± 3.0
5.0 15
10 5.0 5.0 10 33.8 ±
27.2 0.5
± 0.3 2.5 ±84.1
50.3 ±55.5 2.4± 2.8 82.7 ± 2.8
5.0 10
10 10 10 5.0 27.7 ±
29.9 0.6
± 0.1 3.0 ±80.5
52.8 ±65.5 3.1± 3.0 95.4 ± 3.5
5.0 5.0
5.0 15 15 5.0 27.2 ±
39.3 0.7
± 0.5 2.4 ±82.7
55.5 ±76.8 2.3± 2.8 116.1 ± 2.8
5.0 10 10 29.9 ± 0.6 65.5 ± 3.1 95.4 ± 3.5
Condition: sodium lignosulfonate 0.5 g, Raney Ni 2.0 g, hexane 0.5 mL, 473 K for 2.0 h.
5.0 5.0 15 39.3 ± 0.7 76.8 ± 2.3 116.1 ± 2.8
Condition: sodium lignosulfonate 0.5 g, Raney Ni 2.0 g, hexane 0.5 mL, 473 K for 2.0 h
4.6. Enzymatic and Acid Hydrolysis Lignins
4.6. Enzymatic
The and Acid
role of formic acidHydrolysis Lignins depolymerization of lignin has been studied in the work of
in the reductive
Oregui-Bengoechea et al. [138].
The role of formic acid inInthe
the hydrogenolysis
reductive of enzymatic
depolymerization hydrolysis
of lignin eucalyptus
has been studied in thelignin
work over
NiMo/sulfated alumina and
of Oregui-Bengoechea ethanol
et al. atthe
[138]. In ◦ C, the synergistic
320hydrogenolysis action of
of enzymatic formic acid
hydrolysis and catalyst
eucalyptus lignin was
shown over
byNiMo/sulfated
the increasedalumina
oil yieldand ethanol
(38.4 wt.%) at compared
320 °C, the synergistic action of formic
to the uncatalyzed acid and
experiment (23catalyst
wt.%) and
was shown by the increased oil yield (38.4 wt.%) compared to the uncatalyzed
the experiment where gaseous H2 had been used instead of formic acid (19.7 wt.%). All the experiment (23derived
wt.%) oils
and the experiment where gaseous H 2 had been used instead of formic acid (19.7 wt.%). All the
contained methoxy-, hydroxyl- and alkyl- substituted benzenes. The authors suggested that the formic
derived oils contained methoxy-, hydroxyl- and alkyl- substituted benzenes. The authors suggested
acid is involved in lignin depolymerization via a formylation-elimination-hydrogenolysis mechanism,
that the formic acid is involved in lignin depolymerization via a formylation-elimination-
which includes also the catalytic decomposition of formic acid that provides molecular H2 for the
hydrogenolysis mechanism, which includes also the catalytic decomposition of formic acid that
hydrogenolysis reaction
provides molecular H2(Figure 12). The important
for the hydrogenolysis reactionrole of the
(Figure 12).solvent was discussed
The important role of theand ethanol
solvent
proved to be more effective (oil yield 38.4 wt.%) than methanol (23.8 wt.%) or isopropanol
was discussed and ethanol proved to be more effective (oil yield 38.4 wt.%) than methanol (23.8 wt.%) (21.7 wt.%),
as suggested in similar studies [130].
or isopropanol (21.7 wt.%), as suggested in similar studies [130].

Figure 12. Proposed mechanism for formic acid-aided depolymerization of lignin through formylation,
elimination, and hydrogenolysis. Reproduced from reference [138] with permission from John Wiley
and sons.
Catalysts 2019, 9, 43 21 of 31

Similar observations about the enhanced depolymerization in the presence of formic acid and
ethanol had been reported also by Kristianto et al. for the concentrated acid hydrolysis lignin from fruit
bunch palm oil [139]. From the catalytic activity screening of 5% Pd/C, 5% Ru/Al2 O3 , 5% Ru/C and
10% Ni/C at 300 ◦ C it was shown that the most active catalyst was 5% Ru/C with 31 wt.% bio-oil yield
and 47.1 wt.% solid residue. The addition of formic acid increased the bio-oil yield to 62.9 wt.% and
decreased the solid residue to 19.8 wt.%, making formic acid better hydrogen donor than the external
gas. The products obtained from the reaction were phenol and its derivatives whose amount increased
with increase in formic acid/lignin ratio and reaction time. Small amounts of phenolic compounds
with ethyl and ester groups were observed due to alkylation and esterification reactions of phenol
intermediates with ethanol.
The synergistic effect of Raney Ni and zeolites catalysts had been investigated in the
depolymerization of enzymatic hydrolysis lignin from bamboo residues [140]. In a methanol/water
reaction mixture at 250 ◦ C, when Raney Ni was combined with zeolite catalysts, the yield of
mono-phenols significantly increased from 12.9 wt.% (Raney Ni) and 5 wt.% (zeolite) to 27.9 wt.%
(HUSY and Raney Ni). The optimum ratio of zeolite: Raney Ni was determined to be 8:4. The authors
proposed that Raney Ni could act as lignin cracking and methanol reforming catalyst and zeolite
as Brønsted and/or Lewis solid acid essential for ether solvolysis and dehydration. Furthermore,
zeolites can act as a blocking agent to prevent reactions between the original lignin and the unstable
lignin fragments.

4.7. Lignins Extracted by Deep Eutectic Solvents

Das et al. studied the hydrogenolysis of deep eutectic solvent extracted lignin by the use of Ru/C,
Pd/C and Pt/C at 270 ◦ C with isopropanol as hydrogen donor solvent [141]. The most effective catalyst
was Ru/C resulting in the highest oil yield 36.28 wt.% and the lowest char formation 46.43 wt.%.
The main products were phenol, substituted phenols and long chain fatty acids derived by the reductive
couple reaction of lignin. Increase in catalyst loading from 2 wt.% to 15 wt.% resulted in increase in oil
yield but further increase (20 wt.%), decreased the oil yield due to side chain reactions, hindering the
production of monomeric phenolic compounds. Higher reaction temperature (300 ◦ C) did not enhance
lignin depolymerization, resulting in decrease in oil yield and increase of gas products yield due to
the further decomposition of lignin-derived compounds to gaseous products or condensation to char
formation. Similar results was obtained by changing the reaction time. Gradual increase from 30 to
60 min, increased the oil yield but further increase to 180 min, resulted in decrease of oil yield and
increase of gas products yield.

4.8. Selection and Design Criteria for an Effective Catalyst in Reductive Depolymerization of Lignin Using
Hydrogen Donors
As discussed in the previous sections, the catalysts which have been widely studied in the
reductive depolymerization of lignin by the use of hydrogen donors are based on noble (Pd, Ru, Pt)
or transition metals (Ni, Cu) supported on carbon, zeolites and silica materials due to their known
ability to catalyse the cleavage (hydrogenolysis) of C-O and C-C bonds, the hydrodeoxygenation of
oxygenated compounds and the hydrogenation of aromatic double bonds. A summary of the most
representative catalytic systems is shown in Table 6. However, the specific mechanisms of the in situ
hydrogen production has been scarcely discussed with general reference to reforming of alcohols
and related water gas shift reaction as well as decomposition of formic acid. Furthermore, while the
terms “transfer hydrogenation” or “hydrogen transfer” have been used in some cases, there was no
systematic effort to elucidate the reaction pathways involved in relation to the catalyst properties and
the experimental conditions.
Catalysts 2019, 9, 43 22 of 31

Table 6. Representative optimum results on catalytic hydrogenolysis of various lignins using small alcohols or formic acid as hydrogen donors.

Lignin Catalyst & Reaction Conditions Conversion/Yields a (wt.%) Main Products Reference
Kraft α-MoC1−x /AC, EtOH, 280 ◦C 100/-/- Esters, alcohols, aromatics [110]
Kraft Cu/Mo-ZSM-5, H2 O:MeOH=1:1, 220 ◦ C, NaOH 95.7/-/19.9 Phenolics [113]
Kraft 10% Ni/Zeolite, H2 O:EtOH=1:1, HCOOH, 200 ◦ C 93.5 b Aromatics [114]
Kraft Pd-Nafion SAC-13, H2 O, HCOOH, 300 ◦ C -/-/10.5 Phenolics [116]
Kraft MgO/ZrO2 , EtOH, 350 ◦ C -/47.5/4.22 Phenolics [117]
Kraft Ru/C+ MgO/ZrO2 , EtOH, 350 ◦ C -/82.7/6.10 Phenolics, higher alcohols, aliphatic esters [117]
Kraft HZSM-5, MeOH, 220 ◦ C 85.1/-/4.2 Phenolics [120]
Kraft Iron turnings, MeOH, 220 ◦ C 44.4/-/1.7 Phenolics [120]
Soda CuMgAlOx , EtOH, 300 ◦ C -/-/17 Aromatics, furans, hydrogenated cyclics [121–124]
Soda 10 wt.% Cu/ZSM-5(30), EtOH, 440 ◦ C -/-/98.2 Aromatics [125]
Alkali CuNiAl-HT, EtOH, Phenol:lignin=0.8, 290 ◦ C -/72.3/- - [126]
Alkali Raney Ni, i-PrOH/H2 O, 180 ◦ C 93.5/-/- Phenolics-aromatics [127]
Alkali Pd/C, H2 O, HCOOH, 265 ◦ C -/45.8/- Phenolics [128]
Organosolv 10% Ni/Al-SBA-15, Tetralin, 140 ◦ C c -/16.94/- Phenolics, esters [129]
Organosolv 10% Ni/Al-SBA-15, HCOOH, 150 ◦ C c -/28.89/- Phenolics [130]
Organosolv 20 wt.% Pt/C, EtOH, HCOOH, 350 ◦ C -/-/21 Phenolics [131]
Organosolv Ru/C, i-PrOH, HCOOH, 400 ◦ C -/71.2/- ketones aromatics, phenolics [132]
Organosolv Cu20 PMO, MeOH, 310 ◦ C 48.3/-/- Phenolics, aromatics [134]
Organosolv FeNiB alloys, EtOH, 320 ◦ C -/-/- Phenolics [136]
Enzymatic hydrolysis NiMo/sulfated alumina, EtOH, HCOOH, 320 ◦ C -/38.4/- methoxy, hydroxyl, alkyl benzenes [138]
Acid hydrolysis 5% Ru/C, EtOH, HCOOH, 300 ◦ C -/62.9/- Phenolics, esters [139]
Enzymatic hydrolysis HUSY+Raney Ni, MeOH/H2 O, 250 ◦ C -/-/27.9 Phenolics [140]
DES Extracted Ru/C, i-PrOH, 270 ◦ C -/36.28/- Phenolics, acids [141]
a Conversion/Bio-oil/ Monomers, b depolymerized lignin, c Microwave irradiation.
Catalysts 2019, 9, 43 23 of 31

Supercritical alcohols can donate hydrogen in the form of molecular hydrogen, hydride, or protons,
with the hydride deriving from α-hydrogen and the proton from the alcohol hydroxyl, forming
simultaneously electron-deficient hydroxylalkylation species, alkoxide ions and aldehydes [142].
Similarly, decomposition of formic acid in supercritical water conditions leads to in situ H2 formation.
However, the relatively high temperatures, e.g., >280 ◦ C, at which most of the lignin hydrogenolysis
studies in supercritical solvents have been conducted, may also induce repolymerization-condensation
reactions of the initially formed monomer phenolics, especially in the presence of acidic catalysts.
Thus, optimization of the overall system, i.e., type of solvent/hydrogen donor—reaction temperature—
catalyst properties, is required in order to achieve high yields of liquid products enriched in monomers.
With regard to the catalyst properties, three main interactive criteria should be considered:
(i) effect on the in situ hydrogen production mechanism, (ii) high hydrogenation reactivity and
facilitated activation of the lignin C-O or C-C bonds, and (iii) stabilization of reactive intermediates via
alkylation or other reactions. The first criterion is related with the catalyst properties that should be
tailored towards enhanced reforming and WGS reaction activity and/or transfer and stabilization via
surface intermediates of hydride (H:) or protons (H+ ) by selecting appropriate metals and supports.
In this latter case, which is less discussed in the literature, an effective catalyst or catalyst support
surface would comprise of Lewis acid sites and Brønsted or Lewis basic sites that can attract H: and
H+ from alcohols, respectively, thus initiating the steps of hydrogen transfer and lowering the overall
reaction required temperature. Materials with such properties can be various transition metal oxides
or mixed oxides, such as ZrO2 , TiO2 , MgO, etc and their modified/doped analogues, as well as
metal-modified zeolites and other aluminosilicates. The surface acid-base properties of these materials
can be tuned by selecting the appropriate composition. The second criterion refers to the intrinsic
(de)hydrogenation and redox activity of noble or transition metals which includes the dissociative
adsorption of molecular H2 , as two hydrogen atoms, which are available to participate in the various
hydrogenation or hydrogenolysis pathways. The hydrogen atoms on the noble/transition metals
may interact directly with the abundant ether bonds in the lignin fragments or with a double bond
(at deeper hydrogenation conditions) or they can interact via spill-over phenomena with a nearby
sorbed intermediate, such as an ether bond reacting with the Brønsted acid sites of the support of
the hydrogenating metal. Thus, the synergistic action of the metal with the support could also lead
to facile hydrogenation/hydrogenolysis reaction reducing further the required reaction temperature.
The third criterion is related with the effect of the catalyst on the reactions occurring between the
alcohol solvent and the formed reactive intermediates in lignin hydrogenolysis with the aim to inhibit
their repolymerization, one representative example being that of favoring their alkylation with methyl
or ethyl moieties (from methanol or ethanol respectively) in the presence of metal oxides such as
SiO2 -Al2 O3 , CuO, TiO2 , etc. A balance between hydrogenation and alkylation may also be desirable,
in order to limit repolymerization and not lose the aromatic nature of the obtained monomers, thus
pointing to metal oxides (mainly being used as supports) that cannot be easily reduced in situ in the
presence of hydrogen.
Along these lines and in addition to the more classical hydrogenation catalysts, e.g., noble
or transition metals on carbon, zeolites, silica, etc., more “sophisticated” multifunctional catalytic
formulation have been recently reported, as described in the sections above, including TiN-Ni and
TiO2 -Ni, FeNiB alloys, Cu based materials such as Cu20 La20 PMO (porous metal oxides) and CuMgAlOx ,
Fe on Rh/La2 O3 /CeO2 -ZrO2 , β-CaP2 O6 and CoP2 O6 , and others. With regard to catalyst recovery
from batch reactor systems, new magneticcatalytic formulations with weakly acidic Brønsted-type
centers, such as Fe3 O4 @SiO2 @Re and Co@Nb2 O5 @Fe3 O4 which exhibited promising behavior in the
reductive depolymerization of lignin using gaseous H2 , could be also effectively used in catalytic
transfer hdyrogenolysis reactions [143,144].

5. Conclusions and Outlook

The valorization of lignin, being the most abundant natural phenolic/aromatic polymer,
has tremendous potential provided that efficient depolymerization processes will be developed.
Catalysts 2019, 9, 43 24 of 31

The reductive depolymerization via catalytic hydrogenation/hydrogenolysis reactions utilizing

hydrogen donors offers a possible route with minimum requirements of molecular (gaseous) hydrogen.
Small alcohols and water may act both as solvents and hydrogen donors, under sub- or supercritical
conditions, providing the necessary hydrogen for breaking the primary ether bonds of the lignin
macromolecule and leading to deeper C-C bond hydrogenolysis and hydrogenation of the derived
alkoxy-phenols depending on process parameters and catalysts used. Methanol, ethanol, isopropanol
or mixtures of these alcohols with water, can lead to high degrees of lignin depolymerization and
monomers yield, with ethanol being the most promising candidate. Apart from the alcohol-based
solvents, formic acid can also act as hydrogen donor, in cooperation with alcohols or water, thus
leading to enhanced depolymerization and increased bio-oil production.
Although the selection of the most appropriate solvent is crucial for inducing transfer
hydrogenolysis/hydrogenation reactions in lignin depolymerization, still the major role is being played
by the catalyst type and its properties, especially when relatively low/moderate temperatures are aimed
that do not favor undesirable hydrogenation of the aromatic ring and repolymerization/condensation
reactions. As discussed in Section 4.8, an effective catalyst in reductive depolymerization of lignin using
hydrogen donors should promote the in situ generation of hydrogen via alcohol reforming, WGS or
dehydrogenation (via H: and H+ abstraction) reactions or formic acid decomposition, should exhibit
high hydrogenation reactivity and favor activation of the lignin aryl-ether bonds, and should be able
to contribute to stabilization of reactive intermediates, for example, via alkylation reactions leading to
increased bio-oil yield and minimum solid residues.
Finally, towards the potential upscaling of lignin depolymerization via catalytic transfer
hydrogenolysis using hydrogen donors, continuous flow reactors and processes need to be developed
by considering important parameters such as the effective solubilization of lignin as feedstock, increased
catalyst reactivity to balance the relatively short contact times and low rate of catalyst deactivation.
The lignin bio-oils rich in alkoxy- or alkyl-phenols, derived either from reductive depolymerization
or from thermal/catalytic fast pyrolysis, could be used without or after further upgrading
(e.g., glycidilation) in the production of epoxy or phenol-formaldehyde resins and related polymers
and composites, while specific components such as vanillin will find application in the food industry,
cosmetics, and pharmaceuticals. Furthermore, the lignin bio-oil can be upgraded via hydrodeoxygation
(HDO) reactions to hydrocarbon (alkanes) fuels.

Acknowledgments: We acknowledge support of this work by the project “INVALOR: Research Infrastructure
for Waste Valorization and Sustainable Management” (MIS 5002495) which is implemented under the Action
“Reinforcement of the Research and Innovation Infrastructure”, funded by the Operational Programme
“Competitiveness, Entrepreneurship and Innovation” (NSRF 2014–2020) and co-financed by Greece and the
European Union (European Regional Development Fund). We would also like to acknowledge COST Action
CA17128 (LignoCOST) for promoting exchange and dissemination of knowledge and expertise in the field of
lignin valorization.
Conflicts of Interest: The authors declare no conflict of interest. The funders had no role in the design of the
study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to
publish the results.

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