Bioresource Technology 298 (2020) 122432

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

Review

A review on high catalytic efficiency of solid acid catalysts for lignin T

valorization
Weixiang Guana, Chi-Wing Tsangb, Carol Sze Ki Linc, Christophe Lend, Haoquan Hua,
⁎
Changhai Lianga,
a
State Key Laboratory of Fine Chemicals, Laboratory of Advanced Materials and Catalytic Engineering, School of Chemical Engineering, Dalian University of Technology,
Dalian 116024, China
b
Faculty of Science and Technology, Technological and Higher Education Institute of Hong Kong, 20A Tsing Yi Road, Tsing Yi, Hong Kong China
c
School of Energy and Environment, City University of Hong Kong, Kowloon Tong, Hong Kong China
d
Chimie ParisTech, PSL Research University, CNRS, Institute of Chemistry for Life and Health Sciences, 11 rue Pierre et Marie Curie, F-75005 Paris, France

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

Catalytic valorization of lignin over solid acid catalysts including zeolites, heteropolyacids, metal oxides and phosphates, Lewis acid and metal organic frameworks
were reviewed in this work, which not only summarizes the application of solid acid catalysts, but also provides prospects for design of more efficient solid acid
catalysts in conversions of lignin in the future.

A R T I C LE I N FO A B S T R A C T

Keywords: It is imminent to develop renewable resources to replace fossil-derived energies as fossil resources are on the
Lignin brink of exhaustion. Lignin is one of the major components of lignocellulosic biomass, which is a natural
Solid acid catalysts amorphous three-dimensional polymer with abundant C–O bonds and aromatic structure. Hence, valorization of
C-O bonds lignin into high value-added liquid fuels and chemicals is regarded as a promising strategy to mitigate fossil
Valorization
resource shortages. Solid acid catalysts are extensively studied due to environmentally friendly in terms of the
ease of separation, recovery and reduced amount of wastes. Hence, this review focuses on summarizing the
recent progress of catalytic valorization of lignin over different kinds of solid acid catalysts including zeolites,
heteropolyacids, metal oxides, amorphous SiO2-Al2O3, metal phosphates, and Lewis acid. Based on reviewing of
current progress of lignin conversion, the challenges and future prospects are emphasized.

⁎
Corresponding author.
E-mail address: [email protected] (C. Liang).

https://doi.org/10.1016/j.biortech.2019.122432
Received 13 September 2019; Received in revised form 10 November 2019; Accepted 12 November 2019
Available online 14 November 2019
0960-8524/ © 2019 Elsevier Ltd. All rights reserved.
W. Guan, et al. Bioresource Technology 298 (2020) 122432

1. Introduction industrial practices and laboratory studies. Considering the advantages

of zeolite mentioned above, it was widely used as the metal support in
Energy depletion becomes a worldwide crisis and never been higher upgrading of lignin and lignin derivatives. In this section, we sum-
than it is today because of the way of our living and the ever-increasing marize the role of zeolites played in the conversion of lignin and lignin
population (Mortensen et al., 2011). As the fossil resources would ex- model compounds.
haust in the near future, it is urgent to develop renewable energies to Owing to the complex structure of lignin macromolecule, therefore,
replace fossil fuels. most researchers first focused on lignin model compounds over zeolites.
Biomass is the only renewable organic carbon resource in nature, Li et al. (2017a) has already reviewed the hydrodeoxygenation of
which makes it the great candidate in producing high value-added lignin-derived bio-oil over molecular sieves supported metal catalysts.
products (Li et al., 2015). Lignocellulose is the most abundant compo- There is no doubt that zeolites exhibited excellent deoxygenation
nent of biomass with a production of ~170 billion metric tons per year ability towards lignin-derived model compounds due to the cooperative
(Li et al., 2015). Lignin, which is the main component of lignocellulose, effect between abundant acid sites and metal active sites.
accounts for 10–25 wt% depending on the plant species and has higher Apart from lignin model compounds, zeolite catalysts were also
energy density than the other two components which are cellulose and used in conversion of lignin macromolecule through pyrolysis and hy-
hemicellulose (Han et al., 2019). At present, most of the commercial drotreating methods (Adhikari et al., 2014; Bi et al., 2018; Ma et al.,
biorefinery process concentrate on the exploitation of the cellulose and 2012; Xue et al., 2016). Adhikari et al. (2014) investigated the effect of
hemicellulose, while the lignin fraction is always treated as waste temperature and shape-selective zeolite catalyst with different acidity
(Wang et al., 2019). Moreover, the lignin is also a by-product produced in lignin pyrolysis. Catalytic fast pyrolysis was carried out with different
from paper and pulp manufacturing (Hossain et al., 2019). Hence, the Si/Al ratio (SiO2/Al2O3: 30, 50, 80, and 280) at 500, 550, and 600 °C,
huge quantities of wasted lignin could have potential economic value respectively. These four ZSM-5 zeolites bearing different Si/Al ratio
upon its conversion. Lignin is a natural amorphous three dimensional were characterized with isopropylamine absorption and NH3-TPD
polymers which is cross-linked via C–C bonds and C-O bonds (Shao technique. It was found that SiO2/Al2O3 = 30 has the most Brønsted
et al., 2017), and has great potential to produce fuels and aromatics. acid sites and amount of acid sites. After discussing the effect of pyr-
However, the high oxygen content and complex structure render the olysis temperature and catalyst acidity in raw lignin and torrefied
direct utilization of lignin infeasible due to several shortcomings such lignin, it was concluded that acid sites acted an essential role in removal
as low heating value, and low thermal stability. Hence, it is necessary to of oxygen in oxygenates and promoting hydrocarbons production.
remove the oxygen from lignin and improve the energy density of the Thereinto, the highest aromatic hydrocarbons (~35 wt% C) was
lignin-derived products (Guan et al., 2017). Based on above con- achieved over ZSM-5 zeolite with Si/Al = 30 catalyst at 600 °C in
sideration, catalytic conversion of lignin into aromatics over solid acid pyrolysis of torrefied lignin. From this work we can conclude that
catalysts have attracted interests (Adhikari et al., 2014; Güvenatam acidity of zeolites and pyrolysis temperature mainly affected the con-
et al., 2015; Hita et al., 2018; Hong et al., 2014). version of lignin into aromatic hydrocarbons. However, the influence of
Extensive works have been carried out to depolymerize lignin by surface area and pore structure in depolymerization of lignin were not
using various base catalysts and liquid acid catalysts. KOH, NaOH, and discussed in detail due to the fact that physical structure of zeolite is
CsOH were introduced in depolymerization of Kraft and organsolv important for the diffusion of lignin and its degradation products.
lignin under supercritical conditions (Okuda et al., 2004). However, Ma et al. (2012) also investigated catalytic fast pyrolysis of alkaline
high temperature and pressure are required for the reaction conditions. lignin over zeolite catalysts with different acidity and pore size. The
Moreover, a series of Rh/C, and Pt/C with H3PO4 were employed in yield of desired products can be controlled via tuning the acidity and
conversion of birch wood lignin into monomers and dimers (Yan et al., pore size of the catalyst, and the highest yield of liquid was obtained
2008). The results illustrated that with addition of extra H3PO4, the over H-USY (75 wt%) due to the largest pore size (0.74 nm) and highest
yield of monomers and dimers were increased. However, these base and number of acid sites (1.2 mmol/g, determined by NH3 desorption). The
homogenous catalysts could cause serious corrosion to equipment. Solid author emphasized that the number of acid sites, and large pore size are
acid catalysts are environment-friendly, less corrosive and waste, and important to conversion of lignin into aromatics. Because acid sites of
much safety than homogenous catalysts. Moreover, they are relative zeolite have the ability to cleave of C–O and C–C bonds, hence dehy-
much easier to be separated and recovered than homogenous catalysts dration, decarboxylation, dealkylation, cracking, etc. were resulted.
(Okuhara, 2002; Zabeti et al., 2009). Hence, in this work, the conver- Meanwhile, large pore size allows larger species to fit in and undergo
sions of lignin over solid acid catalysts including zeolite catalysts consecutive reaction, leading to the high yield of aromatics hydro-
(Adhikari et al., 2014; Kasakov et al., 2015; Kong et al., 2019), het- carbons (~40 wt%).
eropolyacids (Sonnen et al., 1997; Weinslock et al., 1998; Weinstock It should be emphasized that lignin derived phenolic compounds
et al., 2001; Yokoyama et al., 2004), metal oxides (Custodis et al., 2016; were formed during the catalytic fast pyrolysis, however these phenolic
Dong et al., 2018; Hita et al., 2018; Leal et al., 2019; Mai et al., 2019), compounds were strongly adsorbed on acidic sites, which could result
amorphous SiO2-Al2O3 (Sui and Wu, 2011; Zabeti et al., 2016), metal in cokes formation. Consequently, the zeolite pores were blocked and
phosphides (Koranyi et al., 2017; Lan et al., 2018; Li et al., 2017b), and then the catalytic efficiency was decreased. Hence, the introduced
Lewis acid catalysts (Güvenatam et al., 2016; Robin Jastrzebski et al., hierarchical zeolite is a promising approach for enhancement of diffu-
2016; Yang et al., 2014) are briefly reviewed. All these works illustrated sion and mass transfer. Based on the above consideration, Bi et al.
that solid acid are highly efficient in depolymerization of lignin into (2018) investigated catalytic fast pyrolysis of Kraft lignin over hier-
high value-added products. archical HZSM-5 and H-Beta. Different kinds of alkaline were used to
treat zeolite to increase the surface area of mesoporosity. As expected,
2. Zeolites nitrogen physisorption demonstrated that the mesoporous surface area
and volume of mesoporous of treated HZSM-5 all increased to about
Zeolites are widely used as solid acid catalysts due to variable pore 34 m2/g and 0.08 cm3/g, respectively, while microporous surface area
structures and adjustable strong acidity of Brønsted and Lewis acid sites decreased synchronously. Similar phenomenon was observed over al-
(Li et al., 2017a). Moreover, the large surface area, unique topological kaline treated Hβ zeolites. The larger mesopores created was mainly
structure and morphology catch researchers’ attention. Furthermore, attributed to amorphization and skeleton atom leaching · NH3-TPD
zeolites exhibited favorable hydrothermal stability, strong adsorption results illustrated that alkaline treatment has tiny effect on the strength
ability, electric fields characteristics and limiting effects in the pores (Li of the Brønsted acid sites. The oxygen content was effectively decreased
et al., 2017a). Therefore, zeolites were extensively employed in both from 27.2% (original HZSM-5) to 3.3% (A sequential mild acid

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W. Guan, et al. Bioresource Technology 298 (2020) 122432

treatment with HCl after desilication of HZSM-5 with NaOH) without transfer and diffusion of lignin products and therefore reduce the for-
extra coke formation over hierarchical HZSM-5, while the yield of mation of char and coke; meanwhile abundant acid sites promotes the
condensable volatiles was gradually increased over hierarchical H-Beta. breakage of C–O bonds in phenolic compounds. Generally, zeolites
Indeed, acid sites and pore structure properties are regarded as two supported metal active sites acted as bifunctional catalysts in conver-
main factors to cleave of C–O bonds and prevent the formation of coke sion of lignin macromolecules.
and char in the deoplymerization of lignin over zeolites. In addition to
its wide application in pyrolysis of lignin, zeolite catalysts have at- 3. Heteropolyacids
tracted many researchers' attention in hydrotreating process. Generally,
pyrolysis of lignin requires higher reaction temperature (> 400 °C), Polyoxometalate (POM) anion is a type of stable oxidative meta-
while hydrotreating of lignin needs relative lower temperature and the l–organic catalyst. It is also a type of reversible oxidant which is capable
participation of hydrogen or H-donor solvents. Kasakov et al. (2015) of undergoing repeated cycles of re-oxidation and reduction (Neumann,
focused on deconstruction and hydrodeoxygenation of organosolv 1998). It has the ability to convert O2 to O2– and subsequently to H2O2.
lignin using Ni/HZSM-5, Ni/HBEA, and Ni/SiO2 catalysts. Many char- To be qualified as a heteropoly acid, the compounds should consist of
acterizations were used to analyze lignin and products, such as ATR-IR, an addenda atom such as vanadium, tungsten, molybdenum and nio-
2D HSQC NMR, MALDI-TOF MS, Elemental analysis, GPC, SEM-EDX. bium being arranged in MO6 octahedral units, acidic hydrogen and
All these techniques illustrated that the Beech extracted organosolv oxygen atoms, and a p-block element such as aluminium, silicon or
lignin structure approximately consisted seven interconnected mono- phosphorus to form closed 3D frameworks. Several POM ions, such as
lignols. After catalyzed lignin depolymerization, the products were [AlVVW11O40]6– (Weinstock et al., 2001), [SiVVW11O40]5− (Weinslock
analyzed and compared. The higher yields of hydrocarbons over Ni/ et al., 1998; Weinstock et al., 2001), Na8H[PW9O34] · 19H2O
HZSM-5 and Ni/HBEA are ascribed to the presence of Brønsted acid (Egusquiza et al., 2008) and H3PMo12O40 (Voitl et al., 2010), had been
sites. Moreover, the yield of gas phase and liquid phase products were demonstrated to oxidatively cleave lignin and lignin derived model
summarized and the components of liquid mix were identified. The compounds in aqueous solutions under mild conditions. Different from
highest yield of gas products was obtained over Ni/HBEA, as well as other types of solid acid catalysts mentioned above, except various
liquid products, however, bicyclic products were also formed and se- phenolic fragments, p- and o-benzoquinone were also produced, which
lectivity up to 17%. Finally, the authors proposed that the decon- can be further oxidized and ring-opened to produce dicarboxylic acids
struction of lignin proceeds through the hydrogenolysis of the C–O (DCAs). Thus, oxidative cleavage could be a strategy to further expand
ether bonds followed by hydrogenation of aromatic rings, as well as the products scope in lignin depolymerization.
alkylation between lignin monomers and substituted phenols. POMs have been particular useful in the cleavage of both inter-units
Recently, catalytic transfer hydrogenlysis has been regarded as a and aromatic ring. Na5[PV2Mo10O40] can act as a direct oxidant of
promising method based on the consideration of safety and reduction in lignin during the bleaching of wood-pulp fibers (delignification)
hydrogen consumption. Generally, alcohols were widely used as H- (Sonnen et al., 1997). Later, the same group investigated the oxidative
donor sources in conversion of lignin without external hydrogen. In cleavage of a series of lignin-derived dimeric model compound using
addition, the solubility of the lignin in the alcohol solvent is higher than [SiVVW11O40]5− and quinone species were observed (Grigoriev et al.,
that of the non-polar solvent, such as n-decane. Kong et al. (2019) in- 2001). 2,6-dimethoxy-4-(3,4,5-trimethoxybenzyl) phenol, a compound
vestigated alcoholysis of Kraft lignin by Ni-Cu supported on H-Beta, commonly found under alkaline pulping conditions, reacts rapidly with
HZSM-5, MAS-7, MCM-41 and SAPO-11 zeolite with isopropanol as [SiVVW11O40]5− to form phenolic aldehyde and quinone under mild
solvent. The best results were obtained over Ni-Cu/H-Beta catalyst with conditions. A close analogue of this is the [AlVVW11O40]6–, which can
98.8 wt% yield of bio-oil and 50.8% yield of monomers at 330 °C due to oxidatively depolymerize 75% of lignin in unbleached pulp fibers
the Ni-Cu/H-Beta catalyst has the highest acidity, surface area, pore yielding water soluble fragments (Weinstock et al., 2001). The me-
volume, and pore size. After screening different catalysts, Kong found chanism for the cleavage is first the oxidation of the benzylic position,
that the Ni-Cu/H-beta showed the highest yield of monomers and bio- then the formation of phenoxy radical, followed by further oxidation to
oil. The order the yield of bio-oil is as follow: Ni-Cu/H-Beta (98.8 wt cyclohexdienyl cation and finally to depolymerized products.
%) > Ni-Cu/MAS-7 (95.2 wt%) > Ni-Cu/MCM-41(93.3 wt%) > Ni- It was not until the discovery of Keggin’s HPA-5 POM such as
Cu/HZSM-5 (88.8 wt%) > Ni-Cu/SAPO-11(85.7 wt%). The composi- [PMo7V5O40]8− can catalytically cleave lignin instead of stoichiome-
tion of products was influenced by the acidity and pore structure of trically. Heteropoly acid (HPA), also known as Keggin compounds, is a
catalyst, consequently, the highest yield of cycloalkanes was achieved sub-class of POM with slightly different structure, in which quasi-
over Ni-Cu/H-Beta with large pore size and higher acidity, while cy- spherical structures are derived from assemblies of twelve MO6 octa-
clicketones/alcohols and alkanes preferred to be formed over smaller hedra around a tetrahedron containing a heteroatom (P, B, Si, etc.) and
pore size and less acidity zeolites. Moreover, the gaseous product dis- the number 5 refers to the number of V atoms (Evtuguin et al., 2000a).
tribution was also discussed and found that acid sites of catalysts have Lignin macromolecule is almost completely oxidized to carbon dioxide
an important effect on the production of H2 from isopropanol solvent. at 100 °C and 0.7 MPa (Evtuguin et al., 2000b), with small amount of
Wang et al. (2017) studied the hydrodeoxygenation of lignin to low-molecular weight residual aromatic products. Using vanillyl and
alkanes using Ru-based bimetallic catalysts supported on HY zeolite. veratryl alcohols as lignin model compounds, under heterolytic clea-
Ru-M/HY (M = Fe, Ni, Cu, Zn) catalysts were tested in conversion of vage, methoxy-substituted phenolics and phenol-ether-substituted acids
softwood lignin, and it was found that conversion was similar, while the were formed. It was suggested that the catalyst is more reactive towards
Ru-Cu/HY catalyst showed a little higher selectivity of alkanes than hydroxybenzyl group than benzylether and α-carbonyl group. On the
others, which could be attributed to the smaller activation energy for other hand, non-phenolic units are more stable towards the catalyst.
hydrogen diffusion over Cu metal than those of Fe, Ni, and Zn. As a VO2+ ions present in HPA-5 acidic solutions are responsible for the
result, the advantage of Ru-based bimetallic catalysts is that the tran- homolytic cleavage of β-O-4 and Cα-Cβ linkages. Similar POM such as
sition metals can modulate the hydrogenolysis activity of Ru and pre- H3PMo12O40 effectively converts kraft lignin and lignosulfonates into
vent the hydrocarbons over-hydrogenolysis to gas products. vanillin and methyl vanillate in moderate yield (Voitl et al., 2010). Size-
Table 1 summarizes recent works on the depolymerization of lignin exclusion chromatography (SEC) method was employed to observe
over zeolite catalysts. To sum up, zeolite catalysts are promising solid acidic condensation of lignin intermediates, while polymerization re-
acid catalysts for catalytic upgrading of lignin into monomers and di- actions were prevented by addition of methanol. In both case, alcohol
mers due to the large specific surface area and abundant Lewis acid solvent can effectively suppress lignin repolymerization. Further de-
sites and Brønsted acid sites. The large surface area guarantees the mass velopment in this field includes the use of manganese-substituted POM

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W. Guan, et al. Bioresource Technology 298 (2020) 122432

Table 1
Conversion of lignin over zeolite catalysts.
Catalyst Feed Reaction conditions Major Product Major Product yield (%) Ref.

Temperature (°C) Pressure (MPa)

H-ZSM5(2 1 0) Alkaline lignin 650 – Phenol alkoxy 19.0 (Ma et al., 2012)
H-USY Alkaline lignin 650 – Hydrocarbons ~40.0 (Ma et al., 2012)
ZSM-5 Organosolv lignin 600 – Aromatic hydrocarbons ~35.0 (Adhikari et al., 2014)
Ni/HZSM-5 Organosolv lignin 320 2.0 Alkanes 28.0 ± 2.0 (Kasakov et al., 2015)
Ni/HBEA Organosolv lignin 320 2.0 Alkanes 35.0 ± 4.0 (Kasakov et al., 2015)
HY Corn stover-derived lignin 600 – Aromatic hydrocarbon 66.2 (Xue et al., 2016)
HZSM-5 Corn stover-derived lignin 600 – Aromatic hydrocarbon 35.9 (Xue et al., 2016)
Ru-Cu/HY Soft wood lignin 250 4.0 Hydrocarbons ~32.0 (Wang et al., 2017)
HZSM-5 Kraft lignin 500 – Naphthalene Selectivity > 50 (Bi et al., 2018)
Hβ Kraft lignin 500 – Naphthalene Selectivity > 40 (Bi et al., 2018)
Ni-Cu/H-Beta Kraft lignin 330 – Cyclohexanes 40.4 (Kong et al., 2019)
Ni-Cu/MAS-7 Kraft lignin 330 – Cyclic ketones/alcohols 26.2 (Kong et al., 2019)
Ni-Cu/MCM-41 Kraft lignin 330 – Cyclic ketones/alcohols 25.2 (Kong et al., 2019)
Raney Ni/H-USY Cellulolytic enzyme lignin 250 – Mono-phenols 21.0–27.9 (Jiang et al., 2015)
Cu-Mo/ZSM-5 Hardwood lignin 220 – 3-methoxy,2,5,6-trimethylphenol 67.3 (Singh and Ekhe, 2015)
Ni/ZSM-5 Kraft lignin 220 – Alkyl substituted phenols 15.4 (Singh and Ekhe, 2014)

derived from Keggin anions, such as the [SiMnIII(OH2)-W11O39]5−, 4. Metal oxides

which can promote one-electron lignin oxidation when Mn(III) was
reduced to Mn(II) (Gaspar et al., 2003). However, most of these studies Metal oxides include positive metal ions (cations), which possess
focus on delignification, and not to produce specific chemicals or fuels. Lewis acid and negative oxygen ions (anions) which possess Brønsted
Compared with other type of oxidative cleavage catalysts such as base (Zabeti et al., 2009). Metal oxides, such as: Al2O3, ZrO2, WO3, and
CuFeS2 where further oxidized product such as dicarboxylic acid was Nb2O5 have attracted much attention for upgrading of lignin. Here, we
observed, both the selectivity and product variety of POM towards briefly summarize the utilization of these solid acid metal oxides cat-
lignin are lower and should be improved. alysts and supported metal oxides in conversion of lignin to produce
Apart from the oxidation of lignin, the liquefaction processes of value-added products. Table 3 lists recent efforts on conversion of lignin
lignin with heterpolyacid salts were also investigated. Du et al. (2019) over metal oxides mentioned above.
discussed the effect of liquefaction solvents on chemical compositions
of bio-oils with CePW12O40 · xH2O and found that the 73.4% of lignin 4.1. γ-Al2O3
can be converted in the presence of isopropanol at 300 °C. The main
composition of products consisted of aldehydes and phenols, which Al2O3 can serve as a catalyst and a carrier for metals and metal
accounted for 29.17% and 26.33% of total integral area, respectively. oxides for various reactions. Due to its good mechanical strength and
Lignin was degraded into various monomers via the cleavage of C–C strong interaction with metals and metal oxides, the supported com-
and C–O bonds followed by dehydration, dealkylation, and demethox- pounds can be highly dispersed and widely used in industrial catalyst
ylation reactions of monomeric species. These results revealed that it is supports. Generally, Al2O3 is prepared by hydration of Al(OH)3 and AlO
a promising strategy for production of bio-oils from depolymerization (OH) at high temperature. γ-Al2O3 has a large surface area, high
of lignin over heterpolyacid catalysts. The recent works on conversion thermal resistance and abundant surface acid sites. Because of the ad-
of lignin over different heteropolyacid catalysts are listed in Table 2. vantages mentioned above over γ-Al2O3 it was widely used as a catalyst
The acid strength of heteropolyacid catalysts is stronger than the support in catalytic conversion of lignin and lignin model compounds.
conventional solid acid catalysts. Therefore, it is a promising solid acid In addition, some auxiliary agents were added to enhance the acidity of
catalysts in conversion of lignin into value-added bio-oils. However, the catalysts, thereby increasing the ability of C-O bond scission of the re-
reaction solvent usually exhibits high acidity, thus the reactor need to fractory lignin model compounds, such as WOx (Hong et al., 2014),
be acid resistance. ZrO2, CeO2, CeO2-ZrO2 (Wang et al., 2016). With respect to lignin
macromolecules, Hita et al. (2018) investigated the catalytic depoly-
merization of Kraft lignin over noble metals (Pt, Pd, Rh, Ru) supported

Table 2
Conversion of lignin over heteropolyacid catalysts.
Catalyst Feed Reaction conditions Major Product Major Product Ref.
yield (%)
Temperature (°C) Pressure
(MPa)

H3PMo12O40 Kraft lignin 170 1.0 vanillin 6.5 (Voitl et al., 2010)
H3PMo12O40 Kraft lignin 170 1.0 Vanillin Methyl 3.5 (Voitl and von Rohr,
vanillate 3.5 2010)
H3PMo12O40 Kraft lignin 170 0.5 Vanillin 4.5 (Voitl and von Rohr,
2008)
[AlMnIII(OH2) W11O39]6− unbleached softwood 25 N.R. N.R. N.R. (Ruuttunen and
[SiMnIII(OH2)-W11O39]5− kraft pulp Vuorinen, 2005)
H5PMo10V2O40 Various lignin 190 2.5 Oil liquid products 65.2 (Zhao et al., 2013)
H3PW12O40 Alkali lignin 175 – Carboxylic acids 20.0 (Demesa et al., 2017)
H3PMO12O40 Alkali lignin 200 – Carboxylic acids 45.0 (Demesa et al., 2017)

N.R. = not reported

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Table 3
Conversion of lignin over metal oxides.
Catalyst Feed Reaction conditions Major Product Major Product yield (%) Ref.

Temperature (°C) Pressure (MPa)

Rh/Al2O3 Kraft lignin 450 10.0 Alkylphenolic 15.3 (Hita et al., 2018)
Mo2N/γ-Al2O3 Alkaline lignin 700 – Aromatic hydrocarbon 17.5 (Zheng et al., 2013)
Mo2N/γ-Al2O3 Alkaline lignin 850 – Benzene 70.1 (Zheng et al., 2013)
Ru/Al2O3 Acid hydrolysis lignin 340 Phenolics 91.2 (Oregui Bengoechea et al., 2015)
CuO/SO42−/ZrO2 Soda lignin 100 3.0 Phenolic hydroxyl 29.4 (Zhang et al., 2015a)
SO42−/ZrO2 Soda lignin 100 3.0 Phenolic hydroxyl 26.6 (Zhang et al., 2015b)
Rh/La2O3/CeO2-ZrO2 Kraft lignin 350 – Aromatic alcohols 57.0 (Yang et al., 2016)
WO3 Beech dioxasolv lignin 200 1.0 Monomers 6.3 (Guo et al., 2019)
WO3/γ-Al2O3 Enzymatic hydrolysis lignin 320 – Alkylphenols 67.5 (Mai et al., 2019)
Ru/Nb2O5 Birch lignin 250 0.7 C7–C9 hydrocarbons 35.5 (Shao et al., 2017)
Pd/Nb2O5 Birch lignin 250 0.7 C7–C9 hydrocarbons 31.9 (Dong et al., 2018)
Pt/Nb2O5 Birch lignin 250 0.7 C7–C9 hydrocarbons 34.7 (Dong et al., 2018)

on Al2O3. The Al2O3 supported catalysts were characterized by NH3- isomerization (Lukinskas et al., 2007), dehydration and other acid-
TPD technique and it was found that weaker sites (297–367 °C) are catalyzed reactions (Baertsch et al., 2002). However, few literatures
predominant in the Pt/Al2O3 and Rh/Al2O3, while stronger sites focused on the degradation of lignin. WO3/γ-Al2O3 exhibited excellent
(420–491 °C) prevail in the Pd/Al2O3.The roles of support and metal performance in conversion of enzymatic hydrolysis lignin into alkyl-
were discussed via the depolymerization of Kraft lignin at 450 °C, and phenols in supercritical ethanol with a total yield of 363.4 mg aliphatic
10 MPa H2 pressure. Apparently, the products can be classified into four and aromatics/g lignin (Mai et al., 2019). After WO3 was supported, the
types: alkylphenolics, aromatics, oxygenated compounds, and alkanes, specific surface area of γ-Al2O3 was increased from 145 to 174 m2/g,
while the alkylphenolics are the dominant component. The total yield while the average pore diameter was slightly decreased from 7.19 to
of monomer is the highest and reached 30 wt% over Rh/Al2O3. This is 6.98 nm. However, the weak acid sites of γ-Al2O3 was significantly
attributed to the cooperation of Rh metal and Al2O3, which has higher enhanced after WO3 modified, as determined by NH3-TPD results.
total acidity and especially a large number of weaker acid sites. Catalytic depolymerization of enzymatic hydrolysis lignin over WO3,
Moreover, an oxidative treatment at 550 °C has been carried out for Rh/ H2WO4, γ-Al2O3, and WO3/γ-Al2O3 were performed and WO3/γ-Al2O3
Al2O3 in order to remove deposited solid carbon. As expected, the total gave the highest total product yield (363.4 mg/g lignin) with selectivity
acidity, surface area, pore volume decreased, while the average metal of alkylphenols (245.2 g/g lignin). Specifically, alkylphenols included
particle size increased. XRD results proved that a proportional γ-Al2O3 methyphenols, ethylphenols, isopropylphenols, and tert-butylphenols.
and α-Al2O3 formed boehmite (AlOOH) due to the presence of water Thereinto, the methylphenols were the most abundant products with a
which was produced form dehydration of lignin. selectivity of 45.8% in depolymerization of enzymatic hydrolysis lignin.
It was also found that the stability of γ-Al2O3 is not ideal in hy- Meanwhile, the yield of 5-methoxy-2,3-4-trimethyl-phenol is 89.3 mg/g
drothermal conditions due to the ease of formation of hydrated boeh- lignin, which was dominant of overall product. The high yield of al-
mite and hence result in reduction of surface area and Lewis acid sites kylphenols may be ascribed to a synergistic effect existed between WO3
(Guan et al., 2017; Jongerius et al., 2013a). and γ-Al2O3. Moreover, the effect of solvent was also explored and the
highest total yield of product was obtained under ethanol. Ethanol not
4.2. ZrO2 only acted as the solvent but also as stabilizing agent via alkylating the
active lignin fragments. Three cycle tests demonstrated that the partial
ZrO2 is an amphoteric solid oxide which was widely used in various reduction of W6+, carbon deposit, decreasing of acidity, and change of
acid and base catalyzed reactions (Liu et al., 2008; Lu et al., 2014). pore structure are responsible for the decrease of catalytic activity.
Owing to the amphoteric nature of ZrO2, hence, after combination with However, Guo et al. (2019) investigated the tungsten-based catalysts
SO42−, the acid strength of ZrO2 was greatly improved (measured by for conversion of lignin and declared that WO3 showed a lower catalytic
Hammett indicator and H0 = 14.06) (Zhang et al., 2015a,b). In order to performance with respect to the co-existence of WO3 and W2C in de-
reduce the degree of polymerization of lignin, degradation of hydro- polymerization of lignin model compound and real lignin, which may
genolysis of soda lignin over CuO/SO42−/ZrO2 was examined (Zhang be ascribed to the better balanced amount of acidity and metallicity.
et al., 2015a,b). The results indicated that the content of hydroxyl and This study may provide a more promising strategy for the conversion of
phenolic hydroxyl group were increased by 62.9% and 29.4%, respec- lignin over carbonized material.
tively, while the oxygen content was sharply declined by 10.2% after
degradation of soda lignin. Meanwhile, the weight-average molecular 4.4. Nb2O5
weight (Mw) was significantly decreased from 7700 g/mol to 5500 g/
mol. All these results illustrated that the cleavage of β-O-4 and methoxy Niobia (Nb2O5) has drawn a great deal of attention for catalytic
group occurred via the catalyzed by SO42−/ZrO2 and CuO, respectively. applications due to the water-tolerant nature of the Lewis acid sites
In addition to SO42− modified ZrO2, WO3 modified ZrO2 is also re- (Guan et al., 2017; Leal et al., 2019; Nakajima et al., 2011). Extensive
garded as a solid acid catalyst (Baertsch et al., 2002; Chai et al., 2014). research focused on the deoxygenation of lignin and its derivatives
Usually these modified ZrO2 catalysts are combine with SiO2 to increase using Nb2O5 as solid acid catalyst (Dong et al., 2018; Guo et al., 2017;
the specific surface area of the catalysts. However, few works related to Shao et al., 2017; Xin et al., 2019). As expected, favorable results were
depolymerize of lignin macromolecules over ZrO2-based solid acid also achieved, which may be attributed to the co-operative effect be-
catalysts. tween remarkably promotion of the NbOx species on breaking of C–O
bonds and suitable transfer hydrogenation activity of Ru particles.
4.3. WO3 Barrios et al. (2018) also suggested that surface of Pd was partially
covered by NbOx during the reduction, leading to the stronger inter-
Owning to the abundant acid sites, WO3 was widely used in action between oxygen form phenol substrate and Nb5+/Nb4+ cations

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W. Guan, et al. Bioresource Technology 298 (2020) 122432

derived from NbOx. However, with increasing the reduction tempera- 5. Amorphous SiO2-Al2O3
ture, the reaction rate was significantly declined over Pd/Nb2O5 due to
the over-coverage of Pd particles by reduced NbOx species, while the Before the advent of zeolite catalysts, amorphous SiO2-Al2O3 is the
reaction rate remains unchanged over Pd/SiO2. most common solid acid catalyst. In many cases, SiO2-Al2O3 is less
Leal et al. (2019) designed Ni/Nb2O5 catalyst and firstly used it in active than zeolites for various acid-catalyzed reactions. However, SiO2-
hydrodeoxygenation of diphenyl ether. As expected, a good result was Al2O3 has various sizes of pores and can be applied to macromolecular
achieved after optimizing the balance between acidity and hydro- reactions. Therefore, the investigation of the conversion of lignin over
genation property. After that, hydrotreating of lignin oil was examined SiO2-Al2O3 was quite popular (Custodis et al., 2016; Kong et al., 2016;
over 15%Ni/Nb2O5 under 300 °C and at the H2 pressure of 7 MPa. Liu et al., 2017).
Throughout the catalytic tests, the conversion of lignin was increased With respect to conversion of lignin, catalysts with large surface
from 68% (without catalyst, thermal processes) to 89% after catalyst area and pore size are beneficial to reduce the degree of carbon de-
added. And the H/C ration was increased to 1.80 ± 0.01, which was positions. Moreover, the acidity of catalysts also plays a vital role in
higher than thermal processes (1.74 ± 0.02). In the meantime, the O/ catalytic fast pyrolysis. Based on the above consideration, Custodis
C ration was dropped down to 0.006 ± 0.004, which was significantly et al. (2016) prepared high specific surface area of Al-MCM-41 alumi-
lower than the experiment performed without catalyst (0.23 ± 0.01). nosilicates and discussed the effect of porosity and acidity of catalyst.
Hence, these results clearly demonstrate that the Ni/Nb2O5 is an ex- The influence of acidity to liquid yield and aromatic hydrocarbons was
cellent catalyst to hydrogenation liquid products and removal of discussed and found that differ from zeolite catalysts that a correlation
oxygen. The stability of catalyst was also evaluated in three runs. The between the yield of aromatics and aluminum weight, it is difficult to
author proposed that the ratio of O/C and H/C of liquid products and find out the correlation over aluminosilicate catalysts. The moderate
residues indicated that the degradation of hydrogenation activity of acidity, small grain size, and large pore volume may facilitate the high
catalyst was less than that of deoxygenation ability. The decrease of yield of aromatics. At the same time, a relatively small number of Lewis
acidity after stability tests may be ascribed to the blocking of the Lewis acid sites and weak Brønsted acid sites could reduce deactivation.
acid sites. However, the condensation of lignin occurred even under the Kong et al. (2016) investigated the silica-alumina (Ni/ASA) sup-
reductive process, hence, carbonaceous species were formed, which in ported Ni catalyst for liquefaction and hydrodeoxygenation of lignin
turns blocked the Lewis acid sites. into alkanes at 300 °C and 6.0 MPa H2 pressure. The nonpolar solvent
Dong et al. (2018) prepared Pd/Nb2O5 and Pt/Nb2O5 and used them dodecane was regarded as the best solvent when compared with other
in one-pot hydrodeoxygenation of lignin to value-added feedstock. polar solvents including ethylene glycol, ethanol, and 1,4-dioxane,
Model compound phenol was first examined over Nb2O5 supported Pd which is attributed to the fact that catalytic performance of Ni is the
and Pt catalysts. In situ Inelastic Neutron Scattering (INS) was employed best to other solvents. Besides, high specific surface area ensures the
to analyze the dynamics of hydrogen in-host-guest systems. In situ INS fully exposed to lignin molecules. Thereinto, Ni/ASA shows the highest
revealed that phenol undergoes different reaction pathways over dif- surface area as well as Brønsted and Lewis acid concentrations than
ferent catalysts. In more details, the selectivity of hydrogenation of other supported Ni catalysts. The C–O bonds cleavage yields highly
phenol rings products was higher than that of the cleavage of C–O depended on the Brønsted acid densities. Therefore, the acidity of the
bonds because of stronger adsorption of phenyl rings to catalyst and the ASA support promoted the capability of Ni to break the C–O bonds. As a
high hydrogenation activity of Pd over Pd/Nb2O5, while Pt/Nb2O5 result, approximately 80% conversion of lignin with 50 wt% liquid
catalyst leads to a higher selectivity of arenes. However, this phenom- yield as well as 100% hydrocarbon were achieved. This work elabo-
enon was not obvious in the degradation of lignin macromolecules. The rated the cooperation of Ni active sites and ASA support, which provide
yields of liquid hydrocarbons over Pd/Nb2O5 and Pt/Nb2O5 are 31.9 wt a promising way in hydrodeoxygenation of lignin. Indeed, the surface
% and 34.7 wt%, respectively, which were comparable to that 35.5 wt% area, pore structure, and acid sites of amorphous SiO2-Al2O3 paly vital
over Ru/Nb2O5 reported by Shao et al. (2017). The main product roles in conversion of lignin, which is similar with zeolite catalysts.
components were C7-C9 hydrocarbons, and the relative contents were Hence, design a larger surface, pore volume, and abundant acid sites of
similar in both two catalysts. These results obtained from hydro- amorphous SiO2-Al2O3 is needed to conversion of lignin into chemicals
deoxygenation of raw lignin demonstrated that Nb2O5 was an excellent and fuels.
solid acid support to remove oxygen. Raman results reveal that a re-
lative weak peak located around 930 cm−1 was assigned as the dis- 6. Metal phosphides
torted octahedral with unsaturated Nb = O surface groups. Moreover,
Xin et al. (2019) regarded unsaturated NbOx species as responsible for Transition metal phosphide compounds (MxPy) can be classified into
cleaving of C–O bonds. three categories according to the M: P ratio, namely, the monopho-
Xin et al. (2019) prepared catalysts with different morphologies for sphides (x = y), the metal-rich phosphide (x > y) and the P-rich
Nb2O5 supported Ru catalysts and then used them in hydro- phosphides (x < y). The six-coordinated phosphorus in monopho-
deoxygenation of 4-methylphenol. The result revealed that layered sphides and nine-coordinated phosphorus in metal-rich phosphide
Nb2O5 supported Ru exhibited more unsaturated NbOx sites and the compounds have bifunctional properties (both acidic and metallic) and
highest Ru dispersion, leading to the highest catalytic activity and to- are potential materials for catalysis applications (Corbridge, 1990). The
luene selectivity. Owing to the best results obtained over Ru/L1-Nb2O5, metal site of metal phosphide could facilitate the hydrogenolysis of
hydrodeoxygenation of enzymatic lignin was also evaluated over Ru/ Caryl-O bond and the hydrogenation of aromatic ring, while the acidic
L1-Nb2O5 at 250 °C and 0.7 MPa H2 in water. The selectivity of arenes nature of the Brønsted acidic phosphorus could promote dehydration
reached at 94.8% with the yield of hydrocarbons of 99.6%, indicating and transalkylation (Jongerius et al., 2013b; Sullivan et al., 2016).
that Ru/L1-Nb2O5 was a promising candidate catalysts for conversion Catalysts such as Ni2P and MoP, were recently found in many hydro-
of lignin into high value-added products. The results obtained in this deoxygenation reaction because of their effectiveness in analogue re-
work are better than those reported in most of the literatures. More actions like hydrodesulfurization (Shu et al., 2005) and hydro-
strikingly, no obviously coke formation was observed under the milder denitrogenation (Oyama, 2003). They had been found effective in the
reaction conditions. This result is encouraging because it provides an hydrodeoxygention of biomass-derived 2-MTHF (Bui et al., 2012) and
efficient method for valorization of lignin into aromatics over Nb2O5 in the conversion of waste oil to green diesel (Alvarez-Galvan et al.,
under milder conditions with high atomic economy. 2019). The hydrodeoxygenation of lignin reported for the past decade
will be briefly accounted in this section.
Real lignin depolymerization has been attempted using Ni2P/SiO2

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W. Guan, et al. Bioresource Technology 298 (2020) 122432

catalysts (Koranyi and Hensen, 2017; Koranyi et al., 2017). However, and a polarization reagent for C–O bonds. Moreover, the impact of
only 8 wt% total yield of lignin monomer was obtained. Combing with metal cation was examined and found that the valence of metal cation
an ethanolysis catalyst CuMgAlOx, soda lignin can then be effectively played an important role in lignin liquefaction: the higher the valence
depolymerized in ethanol at 340 °C, obtaining more than 50 wt% lignin of metal cation, the higher the degree of lignin liquefaction. This could
monomers with high degree of hydrodeoxygenation. be explained by the fact that higher valence cations produce more
Besides oxide supports, activated carbon support has also been acidic centers and increase the acidic strength of the catalyst. The effect
employed for the conversion of phenol using Ni2P catalysts (Moon and of alcohols was also considered and the results illustrated that with the
Lee, 2015). Compared with SiO2, where water or phenol was found to length of carbon chain increased, the degree of lignin liquefaction de-
slightly oxidize the local structure of Ni2P over the support which could creased, which may be attributed to the fact that Lewis basicity in-
facilitate the hydration of the catalyst during the hydrodeoxygenation, creased with the chain of alcohols increased. After optimizing the re-
the less hydrophilic ZrO2 and AC are more stable towards the oxidation. action conditions, the best results could be obtained over Pd/C and
Thus, although the Ni2P/ZrO2 and Ni2P/AC are less active, they are CrCl3 at 280 °C with 85.6% lignin conversion and 35.4% phenolic
more stable catalysts. Due to their stability, various mono- and bime- monomer yield.
tallic Ni, Mo and W phosphides supported on AC have been employed Although good results were obtained under the synergistic catalytic
to depolymerize Kraft lignin without external solvent (Chowdari et al., effect of Pd/C and CrCl3, controllable products were difficult to achieve.
2019). After screening, the bimetallic 20NiMoP/AC was found to obtain Based on previous works, Shu et al. (2018) found that hydrogenolysis of
the highest monomer yields (45.7%), including 25% alkylphenolics, lignin into guaiacols occurred over Pd/C and ZnCl2, while phenols were
8.7% aromatics and 9.9% alkanes, which was outperforming than the obtained over Pd/C and CrCl3. To figure out the details of the reaction
sulfided NiMo catalysts (monomer yields < 30%). In addition, this pathways, model compound was tested. As a result, guaiacols were
NiMo phosphides are superior to sulfide NiMo/Al2O3 catalysts, in which formed at the initial stage, while the stronger Lewis acid CrCl3 pro-
does not need an additional of sulfiding agent. However, the specific moted the tandem reaction and catalyzed guaiacols via demethoxyla-
role of the metal phosphide catalysts played in the depolymerization of tion and alkylation into phenols. This work provided a strategy to
lignin has not been explicitly. produce controllable products with optimized Lewis acidity.
Güvenatam et al. (2016) investigated the decomposition of proto-
7. Lewis acid bind lignin (obtained from wheat straw) in supercritical water and
ethanol at 400 °C. The effect of solvent was discussed and the formation
Bifunctional catalysts have been extensively used for conversion of of char was inevitable and resulted in low yield of monomeric products.
lignin into chemicals and fuels with promising performance. Lewis However, the char formation was prohibited and higher yield of low
acids can activate specific functional groups and cleave C–O bonds molecular-weight products were achieved in ethanol. Three kinds of
during the depolymerization processes. Thus, Lewis acid salts have been Lewis acid MCln, M(OAc)n, and M(OTf)n were introduced in depoly-
rarely reported compared with other depolymerization of lignin and merization of lignin. The total yield of organics was slightly lower over
lignin model compounds approaches (Güvenatam et al., 2016; Robin MCln catalyst than M(OAc)n, and the solvent ethanol was partially
Jastrzebski et al., 2016; Shu et al., 2018; Wang et al., 2018). Lewis acid converted into higher hydrocarbons, mainly paraffins. CuCl2 showed
including metal chlorides, metal acetates, and metal triflates, such as, the highest yield of organics yields (368 mg) and alkylated mono-aro-
NiCl2, FeCl3, ZnCl2, AlCl3, CuCl2, Fe(OAc)2, Cu(OAc)2, Co(OAc)2, Ni matics (81 mg). Besides, lower yields of ketones and carboxylic acids,
(OAc)2, Al(OTf)3, Sc(OTf)3, etc. have been widely used in degradation and higher alkylated mono-aromatics were obtained over MCln than M
of lignin (Güvenatam et al., 2015; Shu et al., 2015; Shu et al., 2018; (OAc)n. However, M(OTf)n exhibited higher total yields of organics
Wang et al., 2018). For the sake of clarity, the representative reports on than MCln and M(OAc)n, and Al(OTf)3 is the best metal triflates among
conversion of lignin over Lewis acid were summarized, as listed in all M(OTf)n with the highest total yield of organics, aliphatics, and
Table 4. mono-aromatics. GPC results demonstrated that the order of the degree
It is well known that chloride atom Cl is a high electronegativity of lignin decomposition was as follows: M(OTf)n > MCln > M(OAc)n.
element. As an excellent hydrogen bond acceptor and nucleophile, Cl The selection of metal cation has little effect on product distribution.
has been widely used in biomass dissolution transformation (Long et al., Moreover, the conversion of ethanol was also analyzed, it was found
2011). Shu et al. (2015) has explored the effect of metal chlorides that ethanol converted into alkanes, alkenes, and a small amount of
combined with Pd/C catalyst in depolymerization of lignin. The co- aromatics probably through dehydration, oligomerization, and hy-
operation with Pd/C obviously increased the degree of the lignin li- drogen transfer catalyzed by Lewis acid. Additionally, lignin degrada-
quefaction. CrCl3 combined with Pd/C exhibited the highest total yield tion products were alkylated by ethanol.
of 28.5% the phenolic monomer, which was the highest among all Robin Jastrzebski et al. (2016) described a tandem catalysis which
Lewis acid. Throughout the screening of Lewis acid catalysts, it was can break the C–O bonds within lignin through water-tolerant Lewis
concluded that Cl anion can acted as hydrogen bond acceptor for lignin acids (metal triflates) followed by aldehyde decarbonylation by Rh

Table 4
Conversion of lignin over Lewis acid catalysts.
Catalyst Feed Reaction conditions Major Product Major Product yield (%) Ref.

Temperature (°C) Pressure (MPa)

FeCl3 Solvolysis lignin 305 – Ether solubles 14.1 (Hepditch and Thring, 2000)
NiCl2 Solvolysis lignin 305 – Ether solubles 17.5 (Hepditch and Thring, 2000)
CrCl3 + Pd/C Alkali lignin 280 4.0 Phenolic monomer 35.4 (Shu et al., 2015)
ZnCl2 + Pd/C Alkali lignin 260 4.0 Phenolic monomer 13.0 (Shu et al., 2018)
ZnCl2 Alkali lignin 300 – Volatile fraction 38.1 (Zhang et al., 2014)
CuCl2 Protobind lignin 400 – Mono-aromatics 22.0 (Güvenatam et al., 2016)
Cu(OAc)2 Protobind lignin 400 – Ketones 59.0 (Güvenatam et al., 2016)
Al(OTf)3 Protobind lignin 400 – Aliphatics 75.0 (Güvenatam et al., 2016)
Yb(OTf)3 + [Rh(cod)Cl]2 Poplar dioxasolv lignin 175 – Monmers 12.4 (Robin Jastrzebski et al., 2016)
Hf(OTf)4 + Ru/Al2O3 Lignin 250 4.0 Hydrocarbons > 30.0 (Wang et al., 2018)

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W. Guan, et al. Bioresource Technology 298 (2020) 122432

complex. The author tested β-O-4 model compound over Sc(OTf)3/In 1. Several conversion methods could be combined to improve the
(OTf)3 and [Rh(cod)Cl]2 and a tandem mechanism of cleavage of model quality of products. For example, catalytic pyrolysis followed with
compound was proposed at the beginning. After that, actual lignin was hydrodeoxygenation could efficiently remove oxygen from bio oil to
carried out over Sc(OTf)3 and [Rh(cod)Cl]2, no char formation was produce hydrocarbons.
detected with limited volatile products. 4-methylguaiacol and 4-me- 2. Robust and highly efficient and water resistant solid acid catalysts
thylsyringol derived from S(syringyl) and G(guaiacyl) units were re- should be designed due to the complex structure and high oxygen
garded as decarbonylation products, which confirmed that model content of lignin.
compound chemistry translated well to actual lignin. The Lewis acid Yb 3. The reactor should be designed specifically to meet the conversion
(OTf)3, In(OTf)3, and Ga(OTf)3 were also explored. With more Lewis methods over different solid acid catalysts. For example, when
acid or stronger Lewis acid, the rate of enol ether hydrolysis was in- heteropolyacids are used to catalyze the depolymerization of lignin,
creased followed by increased decarbonylation activity. Hence, max- the reactor is required to be acid resistant.
imum yields of decarbonylation products were obtained over Ga(OTf)3 4. New valorization of lignin strategy should be developed such as
(5.1 wt%). Meanwhile, the highest yield of 4-(1-propenyl) phenols (iso- photocatalytic conversion of lignin and can be combined with solid
eugenol and 4-(1-propenyl) syringol, total yield of 9.2 wt%) as well as acid catalysts.
the highest total monomer yield (12.4 wt%) was obtained over weak
Lewis acid Yb(OTf)3. This work employed a strategy to use a lignin with 9. Conclusion
an appropriate syringyl/guaiacyl ratio and Lewis acid, as a result dif-
ferent products can be specifically targeted. Lignin is a natural amorphous three-dimensional polymer with
Wang et al. (2018) also explored the super Lewis acids metal triflate abundant C–O bonds and aromatics structure. Therefore, valorization of
such as, Hf(OTf)4, Ln(OTf)3, In(OTf)3, and Al(OTf)3 combined with Ru/ lignin into high value-added aromatic chemicals and fuels is regarded
C, Ru/Al2O3 in hydrodeoxygenation of lignin. Throughout the discus- as a promising strategy. In this review, the conversion of lignin over
sion of the influence of metal triflates, solvents effect, and lignin model different kinds of solid acid catalysts including zeolites, hetero-
compounds, the best results with > 30 wt% of hydrocarbon products polyacids, metal oxides, amorphous SiO2-Al2O3, metal phosphates, and
were obtained over Hf(OTf)4 and Ru/Al2O3 using n-octane as solvent. Lewis acid catalysts are briefly summarized. Despite all these solid acid
Furthermore, a synergistic effect existed between strong Lewis acid and catalysts exhibited favorable results in valorization of lignin, com-
Ru/Al2O3. The major products are mainly in the range of C9-C18 hy- pletely unsealing lignin’s potential for producing value-added fuels and
drocarbons. Moreover, conversion of biomass into chemicals and fuels chemicals need further efforts.
through the selective cleavage of etheric C–O bonds catalyzed over Ln
(OTf)3 (Ln = La, Ce, Sm, Gd, Yb, and Lu) were investigated based on Declaration of Competing Interest
the DFT (Density Functional Theory) method. The results indicate that
the reaction pathway for C–O cleavage by the proton transfer of C–H → The authors declare that they have no known competing financial
O–H, which weakens the C–O bond of the coordination ether and finally interests or personal relationships that could have appeared to influ-
produces the substrate of the coordinated alkenol (Assary et al., 2013). ence the work reported in this paper.
In this section, we discuss the performance of Lewis acid catalysts
including metal chlorides, metal acetates, and metal triflate in the de- Acknowledgements
polymerization of lignin. Generally, the Lewis acid catalysts are used
together with Pd/C, Ru/Al2O3, etc. supported metal catalysts. This work was supported by a grant from the National Key Research
Moreover, the conversion of lignin into hydrocarbons over Hf(OTf)4 & Development Program of China (2016YFB0600305). Chi-Wing Tsang
and Ru/Al2O3 may provide a promising strategy to combine different acknowledges the Research Grants Council of the Hong Kong Special
solid acid catalysts. Therefore, the controllable products may be ob- Administrative Region, China (UGC/FDS25/E09/17). Carol Sze Ki Lin
tained with optimized cooperation of solid acid catalysts. acknowledges the Strategy Research Grant from City University of
Hong Kong, China [Project No. SRG 7004922].
8. Challenges and prospects
References
At present, commercial aromatic chemicals are mainly derived from
petrochemical feedstocks. Lignin is a major component of biomass with Adhikari, S., Srinivasan, V., Fasina, O., 2014. Catalytic pyrolysis of raw and thermally
similar chemically structurally with petroleum resources but with much treated lignin using different acidic zeolites. Energ. Fuels 28 (7), 4532–4538.
Alvarez-Galvan, M.C., Campos-Martin, J.M., Fierro, J.L.G., 2019. Transition metal phos-
higher oxygen content. Hence, removal of oxygen from lignin offers a phides for the catalytic hydrodeoxygenation of waste oils into green diesel. Catalysts
promising prospect to produce renewable chemicals and energy. 9 (293).
Considerable efforts have been devoted to valorization of lignin, while a Assary, R.S., Atesin, A.C., Li, Z., Curtiss, L.A., Marks, T.J., 2013. Reaction pathways and
energetics of etheric C-O bond cleavage catalyzed by lanthanide triflates. ACS Catal. 3
great deal of challenges is brought in producing high value-added (9), 1908–1914.
products cost-effectively. At first, lignin isolation and purification Baertsch, C.D., Komala, K.T., Chua, Y.-H., Iglesia, E., 2002. Genesis of Brønsted acid sites
strategies result in structural modification of lignin matrix which makes during dehydration of 2-butanol on tungsten oxide catalysts. J. Catal. 205 (1), 44–57.
Barrios, A.M., Teles, C.A., de Souza, P.M., Rabelo-Neto, R.C., Jacobs, G., Davis, B.H.,
unclear of native lignin. Besides, the transformation mechanisms of Borges, L.E.P., Noronha, F.B., 2018. Hydrodeoxygenation of phenol over niobia
lignin conversion such as pyrolysis, hydrodeoxygenation, hydro- supported Pd catalyst. Catal. Today 302, 115–124.
genolysis, and oxidation is not fully understanding. Also, the biopo- Bi, Y., Lei, X., Xu, G., Chen, H., Hu, J., 2018. Catalytic fast pyrolysis of kraft lignin over
hierarchical HZSM-5 and Hβ zeolites. Catalysts 8 (2), 82.
lymer nature of lignin leads to the low solubility in solvents. Moreover,
Bui, P., Cecilia, J.A., Oyama, S.T., Takagaki, A., Infantes-Molina, A., Zhao, H., Li, D.,
the product is usually mixed including alkanes, phenolics, etc. Hence, Rodríguez-Castellón, E., Jiménez López, A., 2012. Studies of the synthesis of transi-
how to improve the selectivity for one type of product or even a single tion metal phosphides and their activity in the hydrodeoxygenation of a biofuel
product is needed. The most important challenge is to design variety of model compound. J. Catal. 294, 184–198.
Chai, S.-H., Yan, B., Tao, L.-Z., Liang, Y., Xu, B.-Q., 2014. Sustainable production of ac-
catalysts for conversion of lignin into valuable products, especially solid rolein: catalytic gas-phase dehydration of glycerol over dispersed tungsten oxides on
acid catalysts. To produce economically competitive products, con- alumina, zirconia and silica. Catal. Today 234, 215–222.
tinuously efforts should be paid on upgrading of lignin into high quality Chowdari, R.K., Agarwal, S., Heeres, H.J., 2019. Hydrotreatment of Kraft lignin to al-
kylphenolics and aromatics using Ni, Mo, and w phosphides supported on activated
products and developing efficient and economical solid acid catalysts. carbon. ACS Sustain. Chem. Eng. 7 (2), 2044–2055.
Here are several suggestions for further conversion of lignin into useful Corbridge, D.E.C., 1990. Phosphorus: an outline of its chemistry, biochemistry, and
chemicals and fuels. technology. Elsevier, New York.

8
W. Guan, et al. Bioresource Technology 298 (2020) 122432

Custodis, V.B., Karakoulia, S.A., Triantafyllidis, K.S., van Bokhoven, J.A., 2016. Catalytic Renew. Sustain. Energ. Rev. 71, 296–308.
fast pyrolysis of lignin over high-surface-area mesoporous aluminosilicates: effect of Li, Y., Fu, J., Chen, B., 2017b. Highly selective hydrodeoxygenation of anisole, phenol and
porosity and acidity. ChemSusChem 9 (10), 1134–1145. guaiacol to benzene over nickel phosphide. RSC Adv. 7 (25), 15272–15277.
Demesa, A.G., Laari, A., Sillanpaa, M., Koiranen, T., 2017. Valorization of lignin by partial Li, C., Zhao, X., Wang, A., Huber, G.W., Zhang, T., 2015. Catalytic transformation of
wet oxidation using sustainable heteropoly acid catalysts. Molecules 22 (10). lignin for the production of chemicals and fuels. Chem. Rev. 115 (21), 11559–11624.
Dong, L., Shao, Y., Han, X., Liu, X., Xia, Q., Parker, S.F., Cheng, Y., Daemen, L.L., Ramirez- Liu, L.J., Liu, Y.G., Gao, X., Zhang, R.Q., Zhai, Y.P., 2017. Hydrodeoxygenation of bio-oil
Cuesta, A.J., Wang, Y., Yang, S., 2018. Comparison of two multifunctional catalysts model compounds over amorphous NiB/SiO2-Al2O3 catalyst in oil-water biphasic
[M/Nb2O5 (M= Pd, Pt)] for one-pot hydrodeoxygenation of lignin. Catal. Sci. system. J. Fuel Chem. Technol. 45 (8), 932–938.
Technol. 8 (23), 6129–6136. Liu, S., Zhang, X., Li, J., Zhao, N., Wei, W., Sun, Y., 2008. Preparation and application of
Du, F., Li, Y., Xian, X., Li, B., Tang, P., Lu, B., Lai, J., 2019. Liquefaction Behavior of Lignin stabilized mesoporous MgO–ZrO2 solid base. Catal. Commun. 9 (7), 1527–1532.
in Different Alcohol Solvents under the Catalysis of Heteropolyacid Salt. Energ. Fuels Long, J., Guo, B., Li, X., Jiang, Y., Wang, F., Tsang, S.C., Wang, L., Yu, K.M.K., 2011. One
33 (8), 7366–7376. step catalytic conversion of cellulose to sustainable chemicals utilizing cooperative
Egusquiza, M.G., Romanelli, G.P., Cabello, C.I., Botto, I.L., Thomas, H.J., 2008. Arene and ionic liquid pairs. Green Chem. 13 (9), 2334.
Phenol oxidation with hydrogen peroxide using ‘sandwich’ type substituted poly- Lu, Q., Zhang, Z.B., Wang, X.Q., Dong, C.Q., Liu, Y.Q., 2014. Catalytic Upgrading of
oxometalates as catalysts. Catal. Commun. 9 (1), 45–50. Biomass Fast Pyrolysis Vapors Using Ordered Mesoporous ZrO2, TiO2 and SiO2.
Evtuguin, D.V., Daniel, A.I.D., Silvestre, A.J.D., Amado, F.M.L., Neto, C.P., 2000a. Lignin Energ. Procedia 61, 1937–1941.
aerobic oxidation promoted by molybdovanadophosphate polyanion [PMo7V5O40]8-. Lukinskas, P., Kuba, S., Grasselli, R.K., Knözinger, H., 2007. Chromium promotion of
Study on the oxidative cleavage of b-O-4 aryl ether structures using model com- tungstated zirconia catalysts for the isomerization of n-alkanes. Top. Catal. 46 (1–2),
pounds. J. Mol. Catal. A: Chem. 154, 217–224. 87–92.
Evtuguin, D.V., Neto, C.P., Rocha, J., 2000b. Lignin degradation in oxygen delignification Ma, Z., Troussard, E., van Bokhoven, J.A., 2012. Controlling the selectivity to chemicals
catalysed by [PMo7V5O40]8- polyanion. Part I. Study on wood lignin. Holzforschung from lignin via catalytic fast pyrolysis. Appl. Catal. A: Gen. 423–424, 130–136.
54, 381–389. Mai, F., Wen, Z., Bai, Y., Ma, Z., Cui, K., Wu, K., Yan, F., Chen, H., Li, Y., 2019. Selective
Gaspar, A., Evtuguin, D.V., Neto, C.P., 2003. Oxygen bleaching of kraft pulp catalysed by conversion of enzymatic hydrolysis lignin into alkylphenols in supercritical ethanol
Mn(III)-substituted polyoxometalates. Appl. Catal. A: Gen. 239, 157–168. over a WO3/γ-Al2O3 catalyst. Ind. Eng. Chem. Res. 58 (24), 10255–10263.
Grigoriev, V.A., Hill, C.L., Weinstock, I.A., 2001. Polyoxometalate Oxidation of Phenolic Moon, J.S., Lee, Y.K., 2015. Support effects of Ni2P catalysts on the hydrodeoxygenation
Lignin Models. Oxidative Delignification Chemistry 297–312. of guaiacol Situ XAFS Studies. Top. Catal. 58 (4–6), 211–218.
Guan, W., Chen, X., Jin, S., Li, C., Tsang, C.W., Liang, C., 2017. Highly Stable Mortensen, P.M., Grunwaldt, J.D., Jensen, P.A., Knudsen, K.G., Jensen, A.D., 2011. A
Nb2O5–Al2O3 composites supported Pt Catalysts for hydrodeoxygenation of diphenyl review of catalytic upgrading of bio-oil to engine fuels. Appl. Catal. A: Gen. 407
Ether. Ind. Eng. Chem. Res. 56 (47), 14034–14042. (1–2), 1–19.
Guo, H., Qi, Z., Liu, Y., Xia, H., Li, L., Huang, Q., Wang, A., Li, C., 2019. Tungsten-based Nakajima, K., Baba, Y., Noma, R., Kitano, M., Kondo, J.N., Hayashi, S., Hara, M., 2011.
catalysts for lignin depolymerization: the role of tungsten species in C-O bond clea- Nb2O5.nH2O as a heterogeneous catalyst with water-tolerant Lewis acid sites. J. Am.
vage. Catal. Sci. Technol. 9 (9), 2144–2151. Chem. Soc. 133 (12), 4224–4227.
Guo, T., Xia, Q., Shao, Y., Liu, X., Wang, Y., 2017. Direct deoxygenation of lignin model Neumann, R., 1998. Poly oxlometalate Complexes in Organic Oxidation Chemistry. Prog.
compounds into aromatic hydrocarbons through hydrogen transfer reaction. Appl. Inorg. Chem. 47, 317–370.
Catal. A: Gen. 547, 30–36. Okuda, K., Man, X., Umetsu, M., Takami, S., Adschiri, T., 2004. Efficient conversion of
Güvenatam, B., Heeres, E.H.J., Pidko, E.A., Hensen, E.J.M., 2015. Decomposition of lignin lignin into single chemical species by solvothermal reaction in water–p-cresol sol-
model compounds by Lewis acid catalysts in water and ethanol. J. Mol. Catal. A: vent. J. Phys: Condens. Mater. 16 (14), S1325–S1330.
Chem. 410, 89–99. Okuhara, T., 2002. Water-tolerant solid acid catalysts. Chem. Rev. 102, 3641–3666.
Güvenatam, B., Heeres, E.H.J., Pidko, E.A., Hensen, E.J.M., 2016. Lewis-acid catalyzed Oregui Bengoechea, M., Hertzberg, A., Miletić, N., Arias, P.L., Barth, T., 2015.
depolymerization of Protobind lignin in supercritical water and ethanol. Catal. Today Simultaneous catalytic de-polymerization and hydrodeoxygenation of lignin in
259, 460–466. water/formic acid media with Rh/Al2O3, Ru/Al2O3 and Pd/Al2O3 as bifunctional
Han, X., Guo, Y., Liu, X., Xia, Q., Wang, Y., 2019. Catalytic conversion of lignocellulosic catalysts. J. Anal. Appl. Pyrol. 113, 713–722.
biomass into hydrocarbons: A mini review. Catal. Today 319, 2–13. Oyama, S.T., 2003. Novel catalysts for advanced hydroprocessing: transition metal
Hepditch, M.M., Thring, R.W., 2000. Degradation of solvolysis lignin using lewis acid phosphides. J. Catal. 216 (1–2), 343–352.
catalysts. Can. J. Chem. Eng. 78, 226–231. Robin Jastrzebski, R., Lancefield, C.S., Westwood, N.J., Weckhuysen, B.M., Bruijnincx,
Hita, I., Deuss, P.J., Bonura, G., Frusteri, F., Heeres, H.J., 2018. Biobased chemicals from P.C.A., 2016. Tandem catalytic depolymerization of lignin by water-tolerant lewis
the catalytic depolymerization of Kraft lignin using supported noble metal-based acids and rhodium complexes. ChemSusChem 9, 2074–2079.
catalysts. Fuel Process. Technol. 179, 143–153. Ruuttunen, K.S., Vuorinen, T., 2005. Developing catalytic oxygen delignification for kraft
Hong, Y.-K., Lee, D.-W., Eom, H.-J., Lee, K.-Y., 2014. The catalytic activity of Pd/WOx/γ- pulp: kinetic study of lignin oxidation with polyoxometalate anions. Ind. Eng. Chem.
Al2O3 for hydrodeoxygenation of guaiacol. Appl. Catal. B: Environ. 150–151, Res. 44, 4284–4291.
438–445. Shao, Y., Xia, Q., Dong, L., Liu, X., Han, X., Parker, S.F., Cheng, Y., Daemen, L.L., Ramirez-
Hossain, M.A., Phung, T.K., Rahaman, M.S., Tulaphol, S., Jasinski, J.B., Sathitsuksanoh, Cuesta, A.J., Yang, S., Wang, Y., 2017. Selective production of arenes via direct lignin
N., 2019. Catalytic cleavage of the β-O-4 aryl ether bonds of lignin model compounds upgrading over a niobium-based catalyst. Nature Commun. 8, 16104.
by Ru/C catalyst. Appl. Catal. A: Gen. 582, 117100. Shu, Y., Lee, Y., Oyama, S.T., 2005. Structure-sensitivity of hydrodesulfurization of 4,6-
Jiang, Y., Li, Z., Tang, X., Sun, Y., Zeng, X., Liu, S., Lin, L., 2015. Depolymerization of dimethyldibenzothiophene over silica-supported nickel phosphide catalysts. J. Catal.
cellulolytic enzyme lignin for the production of monomeric phenols over Raney Ni 236 (1), 112–121.
and acidic zeolite catalysts. Energ. Fuels 29 (3), 1662–1668. Shu, R., Long, J., Yuan, Z., Zhang, Q., Wang, T., Wang, C., Ma, L., 2015. Efficient and
Jongerius, A.L., Copeland, J.R., Foo, G.S., Hofmann, J.P., Bruijnincx, P.C.A., Sievers, C., product-controlled depolymerization of lignin oriented by metal chloride cooperated
Weckhuysen, B.M., 2013a. Stability of Pt/γ-Al2O3 catalysts in lignin and lignin model with Pd/C. Bioresour. Technol. 179, 84–90.
compound solutions under liquid phase reforming reaction conditions. ACS Catal. 3 Shu, R., Xu, Y., Ma, L., Zhang, Q., Wang, C., Chen, Y., 2018. Controllable production of
(3), 464–473. guaiacols and phenols from lignin depolymerization using Pd/C catalyst cooperated
Jongerius, A.L., Gosselink, R.W., Dijkstra, J., Bitter, J.H., Bruijnincx, P.C.A., Weckhuysen, with metal chloride. Chem. Eng. J. 338, 457–464.
B.M., 2013b. Carbon nanofiber supported transition-metal carbide catalysts for the Singh, S.K., Ekhe, J.D., 2014. Towards effective lignin conversion: HZSM-5 catalyzed one-
hydrodeoxygenation of guaiacol. ChemCatChem 5 (10), 2964–2972. pot solvolytic depolymerization/hydrodeoxygenation of lignin into value added
Kasakov, S., Shi, H., Camaioni, D.M., Zhao, C., Baráth, E., Jentys, A., Lercher, J.A., 2015. compounds. RSC Adv. 4 (53), 27971.
Reductive deconstruction of organosolv lignin catalyzed by zeolite supported nickel Singh, S.K., Ekhe, J.D., 2015. Cu–Mo doped zeolite ZSM-5 catalyzed conversion of lignin
nanoparticles. Green Chem. 17 (11), 5079–5090. to alkyl phenols with high selectivity. Catal. Sci. Technol. 5 (4), 2117–2124.
Kong, J., Li, B., Zhao, C., 2016. Tuning Ni nanoparticles and the acid sites of silica-alu- Sonnen, D.M., Reiner, R.S., Atalla, R.H., Weinstock, I.A., 1997. Degradation of pulp-mill
mina for liquefaction and hydrodeoxygenation of lignin to cyclic alkanes. RSC Adv. 6 effluent by oxygen and Na5[PV2Mo10O40], a multipurpose delignification and wet air
(76), 71940–71951. oxidation catalyst. Ind. Eng. Chem. Res. 36, 4134–4142.
Kong, L., Liu, C., Gao, J., Wang, Y., Dai, L., 2019. Efficient and controllable alcoholysis of Sui, X.J., Wu, S.B., 2011. Study on mechanism of action of catalysts on liquefaction of
Kraft lignin catalyzed by porous zeolite-supported nickel-copper catalyst. Bioresour. bagasse alkali lignin. Adv. Mater. Res. 383–390, 6145–6150.
Technol. 276, 310–317. Sullivan, M.M., Chen, C.J., Bhan, A., 2016. Catalytic deoxygenation on transition metal
Koranyi, T.I., Hensen, E.J.M., 2017. Preparative aspects of supported Ni2P catalysts for carbide catalysts. Catal. Sci. Technol. 6 (3), 602–616.
reductive upgrading of technical lignin to aromatics. Catal. Lett. 147 (7), 1722–1731. Voitl, T., Nagel, M.V., von Rohr, P.R., 2010. Analysis of products from the oxidation of
Koranyi, T.I., Huang, X., Coumans, A.E., Hensen, E.J.M., 2017. Synergy in lignin up- technical lignins by oxygen and H3PMo12O40 in water and aqueous methanol by size-
grading by a combination of Cu-based mixed oxide and Ni-phosphide catalysts in exclusion chromatography. Holzforschung 64 (1), 13–19.
supercritical ethanol. ACS Sustain. Chem. Eng. 5 (4), 3535–3543. Voitl, T., von Rohr, P.R., 2008. Oxidation of lignin using aqueous polyoxometalates in the
Lan, X., Hensen, E.J.M., Weber, T., 2018. Hydrodeoxygenation of guaiacol over Ni2P/ presence of alcohols. ChemSusChem 1 (8–9), 763–769.
SiO2–reaction mechanism and catalyst deactivation. Appl. Catal. A: Gen. 550, 57–66. Voitl, T., von Rohr, P.R., 2010. Demonstration of a process for the conversion of Kraft
Leal, G.F., Lima, S., Graca, I., Carrer, H., Barrett, D.H., Teixeira-Neto, E., Curvelo, A.A.S., lignin into vanillin and methyl vanillate by acidic oxidation in aqueous methanol.
Rodella, C.B., Rinaldi, R., 2019. Design of nickel supported on water-tolerant Nb2O5 Ind. Eng. Chem. Res. 49, 520–525.
catalysts for the hydrotreating of lignin streams obtained from lignin-first biorefining. Wang, H., Ruan, H., Feng, M., Qin, Y., Job, H., Luo, L., Wang, C., Engelhard, M.H., Kuhn,
iScience 15, 467–488. E., Chen, X., Tucker, M.P., Yang, B., 2017. One-pot process for hydrodeoxygenation
Li, X., Chen, G., Liu, C., Ma, W., Yan, B., Zhang, J., 2017a. Hydrodeoxygenation of lignin- of lignin to alkanes using Ru-based bimetallic and bifunctional catalysts supported on
derived bio-oil using molecular sieves supported metal catalysts: a critical review. zeolite Y. ChemSusChem 10 (8), 1846–1856.

9
W. Guan, et al. Bioresource Technology 298 (2020) 122432

Wang, H., Wang, H., Kuhn, E., Tucker, M.P., Yang, B., 2018. Production of jet fuel-range 2633–2639.
hydrocarbons from hydrodeoxygenation of lignin over super lewis acid combined Yang, J., Zhao, L., Liu, C., Wang, Y., Dai, L., 2016. Catalytic ethanolysis and gasification of
with metal catalysts. ChemSusChem 11 (1), 285–291. kraft lignin into aromatic alcohols and H2-rich gas over Rh supported on La2O3/
Wang, H., Pu, Y., Ragauskas, A., Yang, B., 2019. From lignin to valuable products-stra- CeO2–ZrO2. Bioresour. Technol. 218, 926–933.
tegies, challenges, and prospects. Bioresour. Technol. 271, 449–461. Yokoyama, T., Chang, H.M., Reiner, R.S., Atalla, R.H., Weinstock, I.A., Kadla, J.F., 2004.
Wang, W., Wu, K., Liu, P., Li, L., Yang, Y., Wang, Y., 2016. Hydrodeoxygenation of p- Polyoxometalate oxidation of non-phenolic lignin subunits in water: effect of sub-
Cresol over Pt/Al2O3 catalyst promoted by ZrO2, CeO2, and CeO2–ZrO2. Ind. Eng. strate structure on reaction kinetics. Holzforschung 58, 116–121.
Chem. Res. 55 (28), 7598–7603. Zabeti, M., Wan Daud, W.M.A., Aroua, M.K., 2009. Activity of solid catalysts for biodiesel
Weinslock, I.A., Hammel, K.E., Moen, M.A., Landucci, L.L., Ralph, S., Sullivan, C.E., production: a review. Fuel Process. Technol. 90 (6), 770–777.
Reiner, R.S., 1998. Selective transition-metal catalysis of oxygen delignification using Zabeti, M., Baltrusaitis, J., Seshan, K., 2016. Chemical routes to hydrocarbons from
water-soluble salts of polyoxometalate (POM) anions. Holzforschung 52, 311–318. pyrolysis of lignocellulose using Cs promoted amorphous silica alumina catalyst.
Weinstock, I.A., Barbuzzi, E.M.G., Wemple, M.W., Cowan, J.J., Reiner, R.S., Sonnen, Catal. Today 269, 156–165.
D.M., Heintz, R.A., Bond, J.S., Hill, C.L., 2001. Equilibrating metal-oxide cluster Zhang, S., Su, L., Liu, L., Fang, G., 2015a. Degradation on hydrogenolysis of soda lignin
ensembles for oxidation reactions using oxygen in water. Nature 414, 191–195. using CuO/SO42−/ZrO2 as catalyst. Ind. Crop. Prod. 77, 451–457.
Xin, Y., Dong, L., Guo, Y., Liu, X., Hu, Y., Wang, Y., 2019. Correlation of the catalytic Zhang, S., Yan, Z., Liu, L., Fang, G., 2015b. Antioxidant activity of organosolv lignin
performance with Nb2O5 surface properties in the hydrodeoxygenation of lignin degraded using SO42-/ZrO2 as Catalyst. Bioresour. 10 (4), 6819–6829.
model compound. J. Catal. 375, 202–212. Zhang, X., Zhang, Q., Long, J., Xu, Y., Wang, T., Ma, L., Li, Y., 2014. Phenolics production
Xue, Y., Zhou, S., Bai, X., 2016. Role of hydrogen transfer during catalytic copyrolysis of through catalytic depolymerization of alkali lignin with metal chlorides. Bioresour. 9
lignin and tetralin over HZSM-5 and HY zeolite catalysts. ACS Sustain. Chem. Eng. 4 (2), 3347–3360.
(8), 4237–4250. Zhao, Y., Xu, Q., Pan, T., Zuo, Y., Fu, Y., Guo, Q.X., 2013. Depolymerization of lignin by
Yan, N., Zhao, C., Dyson, P.J., Wang, C., Liu, L.T., Kou, Y., 2008. Selective degradation of catalytic oxidation with aqueous polyoxometalates. Appl. Catal. A: Gen. 467,
wood lignin over noble-metal catalysts in a two-step process. ChemSusChem 1 (7), 504–508.
626–629. Zheng, Y., Chen, D., Zhu, X., 2013. Aromatic hydrocarbon production by the online
Yang, L., Li, Y., Savage, P.E., 2014. Hydrolytic cleavage of C-O linkages in lignin model catalytic cracking of lignin fast pyrolysis vapors using Mo2N/γ-Al2O3. J. Anal. Appl.
compounds catalyzed by water-tolerant lewis acids. Ind. Eng. Chem. Res. 53 (7), Pyrol. 104, 514–520.

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