Applied Catalysis A, General 623 (2021) 118298

Contents lists available at ScienceDirect

Applied Catalysis A, General

journal homepage: www.elsevier.com/locate/apcata

Catalytic fast pyrolysis of beech wood lignin isolated by different biomass

(pre)treatment processes: Organosolv, hydrothermal and
enzymatic hydrolysis
A.G. Margellou a, P.A. Lazaridis a, I.D. Charisteidis a, C.K. Nitsos a, C.P. Pappa a, A.P. Fotopoulos a,
S. Van den Bosch b, B.F. Sels b, K.S. Triantafyllidis a, c, *
a
Department of Chemistry, Aristotle University of Thessaloniki, Thessaloniki, 54124, Greece
b
Center for Sustainable Catalysis and Engineering, KU Leuven, Celestijnenlaan 200F, Heverlee, 3001, Belgium
c
Chemical Process & Energy Resources Institute, Centre for Research and Technology-Hellas, Thermi, Thessaloniki, 57001, Greece

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

Keywords: Lignin is one of the three main structural components of lignocellulosic biomass and is considered as the most
Hardwood lignin abundant source of aromatic and phenolic compounds. Lignin is produced as side-stream in the pulp/paper
Organosolv industry or as residue in the production of second-generation bioethanol. More recently, novel biomass frac­
Enzymatic hydrolysis
tionation processes in biorefineries have been developed aiming at the production of high quality/purity lignin
Surface lignin
towards its more efficient down-stream catalytic conversion to chemicals, monomers, and fuels. Within this
Catalytic fast pyrolysis
Bio-oil upgrading context, in this work, we studied the thermal (non-catalytic) and catalytic fast pyrolysis on a Py/GC–MS system
deoxygenation/aromatization and a fixed-bed reactor unit of three types of lignin, all originating from the same biomass (beech wood sawdust)
Microporous and mesoporous ZSM-5 but with different isolation processes: organosolv lignin derived by the organosolv pretreatment/fractionation of
BTX aromatics biomass, surface extracted lignin derived by the mild Soxhlet extraction (with ethanol or acetone) from the hy­
drothermally (HT) in pure water pretreated biomass, and the enzymatic hydrolysis lignin derived as a lignin-rich
solid residue from the enzymatic hydrolysis of the HT pretreated biomass. Conventional microporous ZSM-5 and
mesoporous ZSM-5 zeolites (with intracrystal mesopores, ̃9 nm) were used as catalysts in the pyrolysis exper­
iments. Both zeolites were very active in converting the initially produced via thermal pyrolysis methoxy-
substituted phenols, benzenes and benzaldehydes mainly towards BTX mono-aromatics, such as 1,3-dimethyl­
benzene/p- and o-xylenes, toluene and trimethylbenzenes, as well as polycyclic aromatic hydrocarbons (PAHs,
mainly naphthalenes). The mesoporous ZSM-5 induced higher dealkoxylation reactivity compared to the
microporous ZSM-5 leading to higher concentration of BTX aromatics without a consequent increase of PAHs.
The pronounced dealkoxylation/aromatization reactivity of both ZSM-5 zeolites resulted to lower yields (but
highly aromatic) organic bio-oils (e.g. from 32− 35 wt.% to 15− 22 wt.%) compared to thermal pyrolysis,
increased non-condensable gases (mainly CO, CO2, methane, ethylene and propylene) and formation of relatively
low amounts of coke on catalysts (e.g. 3− 5 wt.% on lignin) in addition to thermal pyrolysis char. The observed
moderate variations in the characteristics of the three types of beech wood lignin, i.e. molecular weight (GPC), S/
G ratio, inter-unit linkages (2D HSQC NMR) and elemental composition, did not induce a systematic/substantial
differentiation in the thermal and catalytic fast pyrolysis product yields and composition.

1. Introduction
Lignocellulosic biomass is considered as a promising alternative
renewable source of petroleum-based fuels and chemicals. Lignocellu­
losic feedstocks consist of cellulose, a linear polymer of glucose, hemi­
cellulose, a branched polymer of C5/C6 sugars and lignin, an amorphous
phenolic polymer. The primary building blocks of lignin are p-coumaryl
(H units), coniferyl (guaiacyl, G units) and sinapyl (syringyl, S units)
alcohols which are linked via C–O ether and C–C bonds [1]. The most
abundant types of bonds in lignin structure are ether type linkages, like
β-O-4 (40–50 %) while carbon-carbon bonds (β-β, β-5, β-1, 5-5) appear at
lower percentage [2]. The nature of lignocellulosic biomass determines

* Corresponding author at: Department of Chemistry, Aristotle University of Thessaloniki, Thessaloniki, 54124, Greece.
E-mail address: ktrianta@chem.auth.gr (K.S. Triantafyllidis).

https://doi.org/10.1016/j.apcata.2021.118298
Received 11 May 2021; Received in revised form 22 July 2021; Accepted 29 July 2021
Available online 4 August 2021
0926-860X/© 2021 Elsevier B.V. All rights reserved.
A.G. Margellou et al.
the lignin content and its composition and type of linkages. Softwood
biomass (i.e. spruce, pine, etc.) contains relatively higher amounts of
lignin (20− 30 wt.%) than hardwood biomass (i.e., beech, birch, poplar,
etc.; 15− 25 wt.%) or grasses (10− 20 wt.%) [1,3]. With regard to
composition, softwood lignins are composed mainly of coniferyl alcohol
(guaiacyl) units while hardwood lignins contain both coniferyl and
sinapyl (syringyl) alcohol units [1,2]. Furthermore, softwood lignins
exhibit relatively higher percentage of C–C bonds while in hardwood
lignins, ether β–O–4 linkages are more abundant [1,3,4]. Lignin was
initially considered as a low-value by-product, used for heat and power
production or as antioxidant, adsorbent, emulsifier, dispersant, binder,
co-polymer component, and only until recently it has attracted increased
interest for its utilization as a source of high added value chemicals and
materials (aromatics, phenolics, vanillin, DMSO, carbon fibers, etc.)
[5–7].
In addition to the more traditional kraft lignin and lignosulfonates
produced by the pulp and paper industry, the development of new in­
tegrated biorefinery schemes and advanced biomass pretreatment/
fractionation methods has offered new types of technical lignins, such as
the enzymatic hydrolysis lignin and the organosolv lignin [8–10]. The
former is recovered as the lignin-rich solid residue after enzymatic hy­
drolysis of the hydrothermally (in neat water or dilute acid) pretreated
biomass [11–16] towards glucose which is further used for the pro­
duction of bioethanol or other sugar derived chemicals, such as
hydroxymethylfurfural (HMF), lactic, succinic and levulinic acids, etc.
[17–21]. The latter is isolated by the organosolv pretreatment/fractio­
nation method of biomass which is performed under hydrothermal
conditions but with the use of water/alcohol (usually ethanol) solvent
that induces simultaneous hemicellulose and lignin solubilization, thus
facilitating the recovery of lignin at the initial stages and prior to hy­
drolysis [22–24]. Organosolv lignins are usually characterized by high
purity compared to kraft or hydrolysis lignin which contain sulfur or
carbohydrate residuals, respectively [22]. Recently, it was shown that
following the hydrothermal pretreatment of biomass in neat water, the
removal of “surface” lignin, which is formed by partial sol­
ubilization/depolymerization of native lignin and recondensation/re­
polymerization on the surface of biomass particles, by mild extraction
with green solvents (e.g. acetone or ethanol), leads to enhanced enzy­
matic hydrolysis of cellulose [13]. Preliminary characterization of the
surface lignin, recovered from hydrothermally pretreated beechwood at
190 ◦ C and 220 ◦ C in neat water has indicated its high purity, low mo­
lecular weight, and features suggesting that it consists mainly of frag­
ments of the native wood lignin [13]. Additional characterization by 2D
HSQC NMR, which enables detailed structural identification [25], of the
surface lignin performed in the present study has further verified its
similarity to the native lignin. The partial depolymerization and repo­
lymerization/redeposition of lignin has been also clearly identified and
described in other previous works [26], regarding the hydrothermal
pretreatment of poplar wood [27] and corn stover [28]. In addition to
the surface/recondensed lignin, “pseudo-lignin” can be also formed,
especially when dilute acid hydrothermal pretreatment is applied which
may be derived by biomass carbohydrates and more specifically from
the rearrangement of HMF or furfural towards aromatic type compounds
which can be further polymerized to polyphenols [29,30].
Lignin depolymerization into aromatic/phenolic monomers is per­
formed via thermo-, chemo-, or bio-catalytic processes. The main ther­
mochemical processes for lignin depolymerization can be divided into
three groups: fast pyrolysis, hydrotreatment or hydroprocessing in the
absence of solvents and liquid phase depolymerization using various
acids/bases under reductive/oxidative reaction conditions [1–3,7,8,
31–34]. More recently, “lignin-first” approaches that aim at the in situ
catalytic depolymerization and stabilization of native lignin and its in­
termediate products during biomass pretreatment have been also shown
to be very effective [35–37]. In fast pyrolysis, lignin is heated to rela­
tively moderate/high temperatures (400− 700 ◦ C) with high hea­
ting/cooling rates under inert atmosphere in the absence of oxygen,
2
Applied Catalysis A, General 623 (2021) 118298
leading to the production of pyrolysis oil (bio-oil) rich in alkoxy-phenols
and alkoxy-aromatics (30− 40 wt.% based on initial lignin), as well as
few gaseous products (10− 15 wt.%; CH4, CO2, CO) and char (40− 45 wt.
%) [38–42].The produced bio-oil can be further upgraded via hydro­
deoxygenation to produce aromatics and (cyclo)alkanes [43–45].
Alternatively, the bio-oil can be in situ deoxygenated during the catalytic
fast pyrolysis of lignin, similar to the catalytic fast pyrolysis of biomass
where the initially formed thermal pyrolysis vapors are converted to
aromatics on the catalyst active acid sites [46–51]. The most widely
studied catalysts in lignin pyrolysis are zeolites, such as ZSM-5, beta,
mordenite, ferrierite and USY, which can induce deoxygenation via
enhanced dehydration, decarbonylation and decarboxylation reactions
[38–41,52–60]. ZSM-5 zeolite has been proven to be very active in
converting the intermediate pyrolysis products via cracking,
de-alkoxylation, (de)alkylation, aromatization, condensation and olig­
omerization reactions towards the production of a highly deoxygenated
bio-oil, consisting mainly of monocyclic aromatic hydrocarbons (BTX)
and naphthalenes [38,39,52,61]. The deep deoxygenation and aroma­
tization of the bio-oil leads to substantial decrease of the organic fraction
which is accompanied by increase of water and non-condensable gases
(mainly of the highly valuable ethylene and propylene), as well as for­
mation of coke on catalyst [38–41,53].
The beneficial use of hierarchical zeolites and aluminosilicates as
catalysts [62] has been also recently demonstrated in biomass and lignin
fast pyrolysis, leading to enhanced production of alkyl-phenols and ar­
omatics, as well as lower coke formation [38,39,48,49,61,63–65].
Furthermore, we have shown in our previous works that the effects of
intracrystalline mesoporosity as well as of the higher external surface
area of nano-crystalline ZSM-5 zeolites, depend on the type and nature
of lignin [38,39]. For example, the enhancement of mono-aromatics by
the use of mesoporous ZSM-5, compared to classical microporous
ZSM-5, was clearly identified in the fast pyrolysis of organosolv birch
and spruce derived lignin compared to the pyrolysis of kraft lignin from
spruce where the effect was marginal [38,39].
Within this context, in the present work we studied the catalytic fast
pyrolysis of three types of lignin derived from the same lignocellulosic
biomass (beechwood sawdust) that have been obtained by a) organosolv
pretreatment, b) hydrothermal (HT) pretreatment in neat water fol­
lowed by mild extraction of surface lignin with ethanol and acetone, and
c) enzymatic hydrolysis of the above HT pretreated biomass in the form
of lignin-rich residue (enzymatic hydrolysis lignin). The catalysts used
were a conventional microporous ZSM-5 zeolite (Si/Al = 40) and the
corresponding zeolite with intracrystal mesoporosity prepared by mild
alkaline treatment of the parent ZSM-5. The pyrolysis experiments were
carried out on a Py/GC–MS setup and on bench scale fixed bed fast
pyrolysis reactor. The effect of catalyst acidity and micro/mesoporosity
on product yields (bio-oil, gases, char/coke) and bio-oil composition has
been discussed considering the characteristics of the three types of
lignin.
2. Experimental
2.1. Catalyst preparation
Two zeolite materials were used as catalysts in the pyrolysis exper­
iments. Commercial ZSM-5 zeolite CBV 8014 with Si/Al = 40 (provided
by Zeolyst) was received in ammonium form and was converted to
proton form via calcination at 500 ◦ C for 3 h in air flow (ZSM-5 (40)).
Mesoporous ZSM-5 (Meso-ZSM-5) was prepared by mild alkaline treat­
ment of the commercial H-CBV8014 (Si/Al = 40) zeolite with 0.2 M
NaOH aq. solution for 30 min at 65 ◦ C, under stirring. The alkaline
treated zeolite was recovered by vacuum filtration followed by washing
with deionized water until pH̃8 and drying overnight at 100 ◦ C. The
desilicated zeolite sample was then treated with 0.1 N HCl aqueous
solution for 6 h at 65 ◦ C to remove the generated extra-framework Al
species as well as the sodium ions, thus producing again the proton form
A.G. Margellou et al.
of the desilicated ZSM-5 zeolite. The zeolite was recovered by filtration,
washing with deionized water until pH̃6 and drying overnight at 100 ◦ C.
All zeolite powders were pelletized, crushed and sieved to a particle size
range of 180− 500 μm before use in the lignin pyrolysis experiments.
2.2. Lignin isolation procedures
The three lignin variables were isolated from the same lignocellu­
losic biomass feedstock (beech wood sawdust; Lignocel HBS 150–500)
with different procedures.
The enzymatic hydrolysis lignin and the extracted surface lignin were
obtained from beech wood after hydrothermal pretreatment in neat
waster. Briefly, experiments were performed in a 600 mL stirred auto­
clave batch reactor (Parr, Model 4563), as described in detail in our
previous works [11,13]. Biomass and deionized H2O were added at a
liquid to solid (LSR) ratio of 15 and the hydrothermal pretreatment was
carried out at 220 ◦ C for 15 min, with heating ratẽ7 ◦ C/min and stirring
speed 150 rpm. After the isothermal treatment, the reactor was imme­
diately quenched in cold water and the resulting slurry was vacuum
filtrated. The recovered solids were washed with deionized H2O until
neutral pH of the filtrate, air dried, and used for further experiments.
The liquid product was passed through 0.2 μm filters and stored at − 20
◦
C for analysis. Subsequently, the surface lignin isolation was performed
with exhaustive extraction (̃ 6 h) in a Soxhlet apparatus with either
ethanol or acetone as the solvent [13]. In a typical experiment, about 4 g
of pretreated biomass was extracted with continuous recirculation of
250 mL of solvent, until the extract flow was colorless. The recovered
biomass solid after extraction was air-dried to evaporate solvent traces
and used for further analysis. The extracted solubilized lignin was
recovered by solvent removal in a rotary evaporator and air dried
(denoted as HT-extr. Ac and HT-extr. EtOH).
Enzymatic hydrolysis lignin (EHL) was obtained from the hydrolysis of
the above described hydrothermally pretreated biomass at 220 ◦ C for 15
min. In brief, pre-estimated amount of treated biomass containing 100
mg cellulose was placed in 25 mL conical flasks and mixed with 0.1 M
sodium citrate buffer (pH 4.8) at a solids concentration 10 % (w/v). The
flasks were heated to 50 ◦ C in a shaking incubator and 60 FPU cellulase
g− 1 cellulose was added to the suspension. The cellulase used was the
commercial cocktail Cellic® CTec2. The samples were hydrolyzed for 72
h at 50 ◦ C and at 150 rpm mixing speed. At the end of the 72 h period the
suspensions were centrifuged at 10000 rpm for 10 min to separate the
solids from the liquids. The solids were then resuspended in dilute hy­
drochloric acid (0.1 M) followed by centrifugation to remove any
adsorbed enzyme. It was further washed three times with 0.1 M sodium
citrate buffer (pH 4.8) to remove any residual enzyme, water-soluble
lignin molecules and free sugars, and finally three times with deion­
ized water. The recovered lignin-rich solid represents the enzymatic
hydrolysis lignin.
Organosolv lignin (Org-lignin) was isolated by hydrothermal pre­
treatment of beech wood in ethanol/water mixture. Briefly, 20 g of
beechwood were mixed with a solution of ethanol and deionized H2O
(60:40 v/v) in a 600 mL stirred autoclave batch reactor and the orga­
nosolv pretreatment was performed at 190 ◦ C for 60 min, with heating
rate ̃7 ◦ C/min and stirring speed 200 rpm. Afterwards, the reactor was
quenched, and the resulting slurry was vacuum filtrated. The recovered
solids were washed with 200 mL deionized H2O. The lignin was
precipitated from the liquid mixture with the addition of 200 mL
deionized H2O, inside an ice bath, for 60 min and was then separated
from the liquid with centrifugation. The recovered organosolv lignin
was dried at 80 ◦ C under vacuum.
2.3. Catalyst characterization
The chemical composition (wt.% Al and Na) of the zeolitic catalysts
was determined by inductively coupled plasma-atomic emission spec­
troscopy (ICP-AES) using a Plasma 400 (Perkin Elmer) spectrometer,
3
Applied Catalysis A, General 623 (2021) 118298
equipped with Cetac6000AT + ultrasonic nebulizer.
Powder X-ray diffraction (XRD) was used for the determination of
zeolites’ crystallinity using a Rigaku Rotaflex 200B diffractometer
equipped with Cu Ka X-ray radiation and a curved crystal graphite
monochromator operating at 45 kV and 100 mA; counts were accumu­
lated in the range of 2θ = 5− 75 ◦ every 0.02 ◦ with counting time 2 s per
step.
Nitrogen adsorption/desorption experiments at − 196 ◦ C were per­
formed on an Automatic Volumetric Sorption Analyzer (Autosorb-1 MP,
Quantachrome). The samples were previously outgassed at 350 ◦ C for 16
h under 5 × 10− 9 Torr vacuum. The BET area (total surface area) of the
catalysts was determined by the multi-point BET method, the mesopore
size distribution and average size by the BJH analysis of adsorption data,
and the micropore volume and area by the t-plot method.
Transmission electron microscopy (TEM and HRTEM) experiments
were carried out on a JEOL 2011 high resolution transmission electron
microscope operating at 200 kV, with a point resolution of 0.23 nm and
Cs = 1.0 mm. Samples were prepared by grinding the catalyst in high-
purity ethanol using an agate pestle and mortar. A drop of the suspen­
sion was then deposited onto a lacey carbon-film supported on Cu grid
and was allowed to evaporate under ambient conditions.
The determination of the amount and relative strength of Brønsted
and Lewis acid sites of the catalysts was performed by Fourier transform-
infrared (FT-IR) spectroscopy combined with in situ adsorption of pyr­
idine. The FT-IR spectra were recorded on a Nicolet 5700 FTIR spec­
trometer (resolution 4 cm− 1) using the OMNIC software and a specially
designed heated, high-vacuum IR cell with CaF2 windows. All samples
were finely ground in a mortar and pressed in self-supported wafers (15
mg/cm2). The wafers were outgassed in situ at 450 ◦ C for 1 h under high
vacuum (10-6 mbar) and a background spectrum was recorded at 150 ◦ C.
Adsorption/equilibration with pyridine vapors was then conducted at
150 ◦ C, by adding pulses of pyridine for 1 h at a total cell pressure of 1
mbar. Spectra were recorded at 150 ◦ C, after equilibration with pyridine
at that temperature and after outgassing for 30 min at higher tempera­
tures, i.e., 250, 350, and 450 ◦ C, in order to evaluate the strength of the
acid sites. The bands at 1545 cm− 1 (pyridinium ions) and 1450 cm− 1
(coordinated pyridine) were used to identify and quantify the Brønsted
and Lewis acid sites, respectively, by adopting the molar extinction
coefficients provided by Emeis et al. [66].
2.4. Characterization of lignins
Lignin isolated from beech wood sawdust was characterized by
elemental analysis, which was performed on a C/H/N/S elemental
analyzer (LECO 628 and LECO 932, USA). Oxygen content was calcu­
lated by difference. Thermogravimetric analysis (TGA, NETZSCH STA
449 F5 Jupiter) of lignin samples was carried out using N2 as carrier gas
(> 99.99 vol %) at a flow rate of 50 mL/min. The samples were heated
from room temperature to 950 ◦ C at heating rate of 10 ◦ C/min. FTIR
spectra were obtained on a Perkin-Elmer FTIR spectrometer, model
SPECTRUM 1000, using the KBr method. Measurements were carried
out using thin disks prepared with a hydraulic press and spectra were
recorded over the range of 4000 to 400 cm− 1 at a resolution of 2 cm− 1
(64 scans were averaged to reduce noise). The spectra presented were
baseline-corrected.
The molecular weight distribution (MWD) and the average molecu­
lar weight of lignin were determined by Gel Permeation Chromatog­
raphy (GPC) using a Polymer Laboratories, model PL-GPC 50 Plus
instrument, comprised of an isocratic pump, a differential refractive
index detector, and three PLgel 5 l MIXED-C columns in series. Prior to
the measurements, the acetyl bromide treatment was applied to all
samples: Approximately 5 mg of lignin were suspended in 1 mL glacial
acetic acid/acetyl bromide (9:1 v/v) for ~2 h [67]. Afterwards, the
solvent was fully removed in vacuum evaporator, and the residue
sample was dissolved in THF at a constant concentration of 1 mg/mL
and sonicated overnight. After filtration with PTFE-L 0.45 μm, 200 μL of
A.G. Margellou et al.
sample was injected into the chromatograph. The elution solvent was
THF (HPLC grade) at a constant flow rate of 1 mL/min, and the entire
system was kept at a constant temperature of 30 ◦ C. Calibration of GPC
was carried out with standard polystyrene samples (Polymer
Laboratories).
The 2D HSQC NMR spectra were obtained on a Varian (Agilent
Technologies, California, CA, USA) 500 MHz DD2 spectrometer.
100− 200 mg of the lignin samples were dissolved in 0.45 mL of DMSO-
d6 (dimethylsulfoxide-d6), 99.8 % (Deutero GmbH, Kastellaun, Ger­
many) and stirred overnight before the analysis. The chemical shifts
were referenced to the solvent signal (2.500/39.520 ppm). The relaxa­
tion delay was set to 5 s, which has been found to be a sufficient time for
full relaxation of the signals [68]. The spectral widths were from 13 to -1
ppm and from 160 to 0 ppm for the 1H and 13C dimensions, respectively.
The number of transients was 16 or 32, and 256 time increments were
recorded in the 13C dimension. The spectra were processed using the
MestReNova software. Prior to Fourier transformation, FID (free in­
duction decay) signals were apodized with a π/2 sine squared bell
function in both dimensions. The relative abundance of each aromatic
unit, linkage and end-group was calculated as
∫ periments (char formation is not affected by the presence of the cata­
X
X% =
100 Ar
For the linkages, the Cα-Hα correlation peak was used for the above
calculation. In the case of S2,6, S’2,6 and H2,6 type of aromatic units the
half sum of the areas of C2-H2 and C6-H6 correlation peaks were used for
the calculation of the abundance of each aromatic unit. The ratio of the
S, G, H type of units was calculated using the respective relative abun­
dance of the S2,6+S’2,6, G + G’2, H2,6 correlations. The abundance of J
structure was calculated as the mean value of the areas of Jβ cross peaks.
The 2D HSQC NMR spectra of the bio-oils are collected under the
same conditions, using the appropriate amount of bio-oil.
2.5. Fast pyrolysis experiments using the Py/GC–MS system
The thermal and the catalytic fast pyrolysis experiments of lignins
were performed on a Multi-Shot Micro-Pyrolyzer (EGA/PY-3030D,
Frontier Laboratories, Japan) connected to a gas chromatograph-mass
spectrometer system (GCMSQP2010, Shimadzu) which is shown in
Fig. SI-1. In a typical thermal (non-catalytic) run, a dried (80 ◦ C under
vacuum for 6 h) mixture of 1 mg lignin and 4 mg silica sand (as inert heat
carrier material) were loaded in a stainless steel cup which was
instantaneously dropped in the hot reactor/furnace and pyrolysis was
conducted at the preset temperatures of 400, 500, and 600 ◦ C, for 12 s.
In the catalytic fast pyrolysis (CFP) experiments, 1 mg of dried lignin
was mixed with 4 mg of the dried catalyst (catalyst to lignin ratio 4:1).
Identification of mass spectra peaks was achieved using the scientific
library NIST11 s. The derived compounds were classified and catego­
rized in the following 16 groups-families: mono-aromatics (AR), ali­
phatics (ALI), phenols (PH), acids (AC), esters (EST), alcohols (AL),
ethers (ETH), aldehydes (ALD), ketones (KET), polycyclic aromatic hy­
drocarbons (PAH’s), sugars (SUG) nitrogen compounds (NIT), sulfur
compounds (SUL), oxygenated aromatics (OxyAR), oxygenated phenols
(OxyPH) and unidentified compounds (UN). At least three experiments
were performed for each lignin/catalyst sample and the reported data
are the mean values with a standard deviation being below 10 % in all
cases.
2.6. Fast pyrolysis experiments in fixed-bed reactor
Fast pyrolysis tests were also carried out on a bench-scale, fixed-bed
tubular reactor made of stainless-steel 316 and heated by a 3-zone
furnace (Fig. SI-2). A specially designed piston system was used to
introduce lignin into the reactor. The amount of lignin (dried at 80 ◦ C
under vacuum for 6 h) used in all experiments was 0.5 g and the amount
of silica sand (thermal pyrolysis experiments, non-catalytic) or catalyst
4
Applied Catalysis A, General 623 (2021) 118298
(in the catalytic experiments) was also 0.5 g. In a typical experiment, the
solid lignin was inserted from the top of the reactor and was pushed
down instantaneously with the aid of the piston in the hot reactor zone,
where it was vaporized at 600 ◦ C. The pyrolysis vapors produced were
driven downwards through the catalyst bed with the aid of a constant N2
flow (100 cm3/min), for 20 min. The product vapors were condensed in
pre-weighted spiral glass receivers that were immersed in a cooling bath
(− 20 ◦ C). Bio-oil was collected with 1 mL of methanol and was analyzed
by GC–MS (GC–MS-QP2010, Shimadzu). For the identification of the
relative abundance of the produced compounds in bio-oil, the NIST11 s
mass spectral library was used and the derived compounds were clas­
sified and categorized in the 16 groups and families, as in the case of the
Py/GC–MS experiments. The water content of bio-oil was determined
by Karl-Fischer titration (ASTM E203-08).
The solid products, which comprised of char in the non-catalytic
pyrolysis experiments and char plus coke-on-catalyst in the catalytic
pyrolysis experiments, were determined by direct weighting. An indirect
estimation of the coke formed on the catalyst, as wt.% on initial lignin,
was performed by subtracting the measured char content of the non-
catalytic experiment from the char + coke content of the catalytic ex­
lysts, as lignin and catalysts do not come in contact in this experimental
set-up). The non-condensable gases in the pyrolysis experiments were
measured by the liquid displacement method and were analyzed by GC
equipped with TCD and FID (HP5890 Series II) (Agilent Technologies.
Santa Clara, CA, USA). The standard deviation of the product yield
values reported, at all cases, is below 5%.
3. Results and discussion
3.1. Physicochemical characterization of zeolite catalysts
The XRD patterns (Fig. 1A) of the conventional microporous and
mesoporous ZSM-5 zeolites (the latter being prepared from the parent
microporous ZSM-5 by desilication and mild acid washing) show the
high crystallinity of both materials, comprising of diffraction peaks
which are characteristic of the MFI structure, as also reported in previ­
ous publications [38,39]. The intensity of the peaks of the meso-ZSM-5
zeolite was slightly lower compared to those of the parent ZSM-5, which
is consistent with the related reduction in the intrinsic density and
scattering power of the crystals [38,69]. The N2 isotherms and the BJH
mesopore size distribution curves of the catalysts can be seen in Fig. 1B.
The conventional ZSM-5 zeolite exhibits typical adsorption isotherm of
Type I(a) according to the IUPAC classification, corresponding to
microporous materials without significant crystal and textural imper­
fections which may induce meso/macroporosity [70]. The well-formed
crystals with a parallelepiped shape, typical of ZSM-5 crystals, can be
seen in the TEM image of Fig. 1C. The BET surface area of conventional
ZSM-5 is equal to 437 m2/g with about 332 m2/g being attributed to
microporous area (t-plot method), as can be seen in Table 1. The
meso-ZSM-5 exhibits a combined Type I(a) and II adsorption isotherm,
indicating the presence of both micropores and intracrystal mesopores.
The steep increase of adsorbed nitrogen at P/Po> 0.9 reveals also the
presence of high macropore and/or external surface area. The BET
surface area of meso-ZSM-5 is 576 m2/g with about 259 m2/g being
attributed to microporous area. It has to be noted that the total (BET)
surface area of the mesoporous ZSM-5 has been substantially increased
compared to that of the conventional ZSM-5, due to the significant in­
crease of the meso/macropore area and despite the decrease of the
micropore area (Table 1). The BJH curves showed a relatively broad
mesopore size distribution from 2.5–30 nm, with the maximum at about
9 nm, as shown in the inserted graph in Fig. 1B. The mesoporous
structure of meso-ZSM-5 zeolite can be also confirmed by the TEM image
shown in Fig. 1D, where the evenly distributed light contrast spots
correspond to the intracrystal meso/macropores.
The relatively strong acidity and unique medium-size tubular
A.G. Margellou et al. Applied Catalysis A, General 623 (2021) 118298

Fig. 1. (A) X-ray diffraction patterns, (B) N2 adsorption-desorption isotherms and BJH pore size distribution curves (insert graph) and Transmission Electron Mi­
croscopy (TEM) images of (C) ZSM-5 and (D) Meso-ZSM-5.

Table 1
Textural characteristics, chemical composition and acidity of conventional microporous and mesoporous ZSM-5 zeolite catalysts.
Chemical Acidity
compositione FTIR/pyridinef
BET area a (m2/ Micropore area b (m2/ Meso/macro pore & external areac Average mesopore diameterd (wt.%) (μmol Pyr/g)
Catalyst
g) g) (m2/g) (nm)
Al Na B L B/
L

ZSM-5 437 332 105 – 0.91 0.03 161 21 7.6

Meso-ZSM-5 (9 576 259 317 9.0 0.86 0.04 172 20 8.4
nm)
a
BET area from N2 sorption at − 196 ◦ C, Multipoint BET method.
b
t-plot method.
c
Difference of BET area minus micropore area.
d
BJH analysis using adsorption data.
e
ICP-AES chemical analysis data.
f
Determination of the amount of Brønsted and Lewis acid sites performed by Fourier transform-infrared (FT-IR) spectroscopy combined with in situ adsorption of
pyridine.

micropores of ZSM-5 zeolite has render it as one of the most suitable
catalyst for producing aromatic hydrocarbons (BTX) in the pyrolysis of
bio-feedstocks, such as lignocellulosic biomass, lignin, bio-waxes and
others [38,39,48,49,71,72]. ZSM-5 zeolites possess mainly Brønsted
acid sites of high strength originating from the framework aluminum
atoms, while Lewis acid sites may also be present due to the formation of
Si-Al extra-framework phases upon (hydro)thermal or chemical pro­
cessing and pretreatment of the as-synthesized zeolite [73,74].
As can be seen in Table 1, the amount of Brønsted sites and the
Brønsted to Lewis (B/L) sites ratio of the meso-ZSM-5 remained high and
similar to those of the parent ZSM-5, proving that the mild alkaline
treatment and the subsequent mild acid “washing” to remove Na+ cat­
ions and extra-framework species did not significantly alter the acidic
properties of ZSM-5 zeolite. Furthermore, the Brønsted acid sites of both
zeolites are of similar strength, as it is revealed by FT-IR/pyridine
measurements by comparing the amount of pyridine that remains sor­
bed at increasing outgassing temperatures (Fig. SI-3), in accordance
with previous works on conventional and mesoporous ZSM-5 zeolites
[38].
3.2. Lignin isolation and characterization
The three types of lignin that were used in the present fast pyrolysis
study originated from the same lignocellulosic biomass (beech wood
sawdust) by different pretreatment methods, i.e., organosolv, hydro­
thermal followed by enzymatic hydrolysis, and hydrothermal followed
by mild extraction of lignin with ethanol or acetone, as it is described in
the experimental section. The isolation and properties of organosolv
lignin [22–24,75] and enzymatic hydrolysis lignin, i.e. the lignin-rich
solid residue after biomass pretreatment and enzymatic hydrolysis,
respectively, have been widely described previously [14,15]. More
recently, we have described the isolation of surface lignin which can be
recovered by mild Soxhlet extraction with ethanol or acetone from
biomass that has been hydrothermally treated in neat water at ca.
190− 220 ◦ C for 15 min, leading also to substantially enhanced enzy­
matic hydrolysis of the remaining cellulose-rich biomass [13]. Pre­
liminary characterization of the recovered surface lignin have indicated
to exhibit similar composition and structural characteristics with those
of the native lignin, with high purity and low molecular weight, while
further characterization with 2D HSQC NMR and other complementary
methods is presented in this study. The Soxhlet extraction with acetone

5
A.G. Margellou et al. Applied Catalysis A, General 623 (2021) 118298

or ethanol, of the biomass that was hydrothermally pretreated at 220

◦
C-15 min, resulted in 76.2 and 59.4 % lignin recovery, respectively.
These values correspond to 56.9 and 44.3 % lignin recovery based on the
initial lignin content of parent biomass, as is described in more detail in
Supporting Information (Table SI-1).
The elemental composition and the properties of obtained lignins are
shown in Table 2. All lignin samples exhibit similar elemental compo­
sition except from the EHL which exhibits lower carbon and higher
oxygen content due to carbohydrate remainings after the enzymatic
hydrolysis process. Considering the molecular weights of isolated lig­
nins, Org-lignin exhibits relatively higher molecular weight (Mw) of
2350 g/mol and higher PD of 3.67, whereas the HT-extracted (surface)
and EHL lignins exhibit significantly lower molecular weights (ca.
890− 1140 g/mol) and PDs which can be attributed to the hydrothermal
pretreatment of biomass prior to the extraction of lignin or the enzy­
matic hydrolysis. More specifically, the relatively intense hydrothermal
conditions (220 ◦ C, 15 min) led to solubilization and hydrolysis of
hemicellulose and the formation of acetic acid. The acidity of
hydroxonium ions, formed by the protonation of water molecules as well
as the in situ released acetic acid, induced a partial cleavage of β-O-4
bonds (as is described below based on the 2D HSQC NMR data) of lignin
and the formation of oligomers, which are solubilized during the
extraction with EtOH/acetone or recovered as EHL after enzymatic
hydrolysis.
The FTIR spectra of all lignin samples are presented in Fig. 2A. The
broad and intense peak at 3450 cm− 1 is assigned to stretching vibrations
of -OH in alcoholic and phenolic hydroxyl groups. The peaks at 2935 and
2845 cm− 1 are attributed to C–H asymmetric stretching vibrations in
methoxy groups (− OCH3) and to symmetrical vibrations of − CH2- in the Fig. 2. (A) FTIR spectra and (B) TGA/DTG curves of lignin samples.
side chains of lignin moieties, respectively. The peaks in the range
1604− 1400 cm− 1 are assigned to the vibrations of the aromatic rings
suggesting that the aromatic nature of the lignin samples was not Table 3
deteriorated during the biomass hydrothermal or organosolv pretreat­ Percentages of aromatic units (S, G, H) and inter-unit linkages (β-O-4, β-β, β-5) of
the different isolated beech wood lignin samples.
ment and the lignin isolation processes (mild Soxhlet extraction or
enzymatic hydrolysis of cellulose). The peak at 1703 cm− 1 can be Lignin samples S (%) G (%) H (%) β-O-4 β-β β-5
assigned to the stretching vibration of C– – O bonds of carboxylic esters, /100 Ar /100 Ar /100 Ar

conjugated aldehydes or non-conjugated ketones in the aromatic ring Org 64.3 34.5 1.2 57.0 17.2 8.4
and proved to be more intense for the HT-extr. Ac and HT-extr. EtOH HT-extr.Ac 65.9 27.2 6.9 6.3 10.1 5.1
HT-extr. EtOH 72.4 27.3 0.3 2.7 4.8 4.2
lignins compared to organosolv lignin. This is indicative of the forma­
EHL 90.2 9.8 – – 8.9 –
tion of carbonyl groups in the two surface lignins and can be attributed
to the cleavage of β-O-4′ linkages (as can be seen below in Table 3, 2D
HSQC NMR data) that occur under the relative intense hydrothermal evaporation. A sharp and intense weight loss (40–60 %) is observed in
pretreatment conditions applied (220 ◦ C, 15 min) [13]. The peak at the temperature range of 170− 550 ◦ C with maximum DTG peak tem­
1326 cm− 1 is assigned to C–O in alcohols, ethers or carboxylic esters perature of 360 ◦ C, corresponding to the decomposition of lignin. A
and is related with syringyl units, as well as the peak at 1116 cm− 1, progressive weight loss is observed at higher temperatures, 600− 950 ◦ C,
which is also typical for syringyl units and is attributed to aromatic C–H which is attributed to further condensation of the initially formed
in plane bending. The peak at 1031 cm− 1 is characteristic of the aro­ carbonaceous material leading to residual char at 950 ◦ C of about 25–35
matic C–H in-plain deformation mainly in G aromatic units of lignin. %.
The peak at 911 cm− 1 corresponds to the C–H out of plane vibrations in Inter-unit linkages and the types of aromatic units are determined by
aromatic units [76] and the peak at 831 cm− 1 corresponds to the vi­ the 2D HSQC NMR. The HSQC cross peaks were attributed to specific
brations of C–H located at 2 or 6 sites of S aromatic units [77]. aromatic units and linkages using previously reported data [38,78–81].
Considering the thermal degradation of lignin, TGA curves were The assigned peaks are listed in Table SI-2 and the specific types of ar­
obtained under nitrogen atmosphere and are shown in Fig. 2B. All lignin omatic units (S, S’, G, G’, H, J) and inter-unit linkages (A, B, C, I, J, FA)
types exhibit a small weight loss < 3% up to 120 ◦ C, due to humidity are shown in Fig. 3, indicatively for the surface lignin recovered by

Table 2
Physicochemical characteristics of the beech wood lignins isolated by different methods (Organosolv, hydrothermal followed by mild extraction with ethanol or
acetone, hydrothermal followed by enzymatic hydrolysis).
Lignins C H S Oa Ash Moisture Mw Mn PDb
(wt%) (wt%) (wt%) (wt%) (wt%) (wt%) (g/mol) (g/mol)

Org 60.55 6.11 – 33.34 0.46 7.14 2350 640 3.67

HT-extr. Ac 66.71 5.73 – 27.56 0.71 2.93 1138 592 1.92
HT-extr. EtOH 65.21 5.51 – 29.28 0.86 2.49 986 621 1.59
EHL 56.44 5.90 – 37.66 0.65 2.46 887 482 1.84
a
O% = 100-%C-%H-%S.
b
Polydispersity index (PD) = Mw (average molecular weight per weight)/Mn (average molecular weight per number).

6
A.G. Margellou et al.
Fig. 3. 2D HSQC NMR spectra of surface lignin recovered by Soxhlet extraction with ethanol of the hydrothermally pretreated beech wood biomass. The types of
aromatic units and the types of linkages are shown in the upper and lower inset frame.
Soxhlet extraction with ethanol of the hydrothermally pretreated
biomass (HT-extr. EtOH lignin). The HSQC spectra of the rest of lignins
are provided in Fig. SI-4. The cross-peaks in the aromatic region (δC/δH
= 100–135/6− 8) clearly shows that lignin consists mainly of syringyl
units (S) corresponding to C2,6-H2,6 correlation peaks of either S2,6 at
δC/δH = 105.2/6.6 or S’2,6 in oxidized Ca = O at δC/δH = 105.8/7.3.
Lesser amount of guaiacyl units (G) are also observed corresponding to
C2-H2 correlation peaks of G2 (δC/δH = 111.2/6.9) or G’2 in oxidized Ca
= O guaiacyl units at δC/δH = 112.1/7.45, C5-H5 of G5 (δC/δH =
115.3/6.7) and C6-H6 of G6 (δC/δH = 118.9/6.77). Cross peaks of lower
intensity at δC/δH = 127.5/7.1 and δC/δH = 124.9–127.1/7.1–6.7 are
attributed to C2-H2 and C6-H6 in p-hydroxyphenyl units (H2,6) and JB in
aldehyde end-group, respectively. In the case of HT-extr. Ac lignin, an
additional peak is observed at δC/δH = 128–130/6.9− 7.3 ppm, corre­
sponding to p-hydroxyphenyl (H) aromatic units. In the spectra of
organosolv lignin, small amounts of xylan were also observed at δC/δH =
72.5− 75.3/3.0–3.0 ppm for X2, X3 and X4 xylan structure. Integrating
the respective cross-peaks, the molar ratio of S, G and H units are
determined and shown in Table 3. The EHL exhibited the highest portion
of S aromatic units (90 %) while all the rest of lignins exhibit also
high/moderate ratio of S/G 64–72 %/27− 34 %, with low percentage of
H units. The observed moderate/high S/G ratios of the recovered lignins
were expected due to the nature of beechwood, a hardwood type
biomass. Similar results have been previously reported for different
hardwood species [38,78,82].
The part of the 2D HSQC spectrum assigned to the inter-unit linkages
at δC/δH = 50–90/2.5–6.0 ppm, is mostly dominated by signals of β-Aryl
ethers (β-O-4, type A linkage, δC/δH = 71.5/48 ppm and δC/δH =
87.1− 82.5/4.3–4.7 ppm), β-5′ of phenylcoumaran structures (type Ca,
δC/δH = 87.9/5.5 ppm) and resinol type linkages (β-β, type B, δC/δH =
85.5-/4.7 ppm, for Bα and δC/δH = 70.7-/4.1 ppm, for Bβ). The relative
7
Applied Catalysis A, General 623 (2021) 118298
abundance of each type of linkages is shown in Table 3. From the data it
can be observed that the main inter-unit linkages in the HT-extr. EtOH
and HT-extr. Ac lignins, as well as in the EHL, are β-β and β-5 whereas in
Org-lignin, the main type of inter-unit linkages is the β-O-4. The lower
portion of β-O-4 linkages in HT-extr. EtOH, HT-extr. Ac and EHL lignins
is in accordance with their lower molecular weights (Table 2) and can be
attributed to the hydrothermal pretreatment of biomass efficiently
cleaving the β-O-4 interlinakges, as is also discussed above.
3.3. Non-catalytic and catalytic fast pyrolysis of lignin in Py/GC–MS
system
The non-catalytic pyrolysis of the isolated lignin samples was studied
at three different pyrolysis temperatures, ca. 400, 500 and 600 ◦ C.
Representative Py/GC–MS spectra at 400 and 600 ◦ C of Org-lignin
pyrolysis vapors are shown in Fig. 4, together with the most abundant
identified compounds. The distribution of the compounds among the
various groups, i.e., AR, PH, OxyPH, AC, etc. (see the experimental
section), derived from the non-catalytic pyrolysis of all the beech wood
lignin samples, prepared and studied in this work, is shown in Fig. 5. In
addition, the most abundant compounds derived from all lignin samples
at 600 ◦ C are listed in Table 4 (full product lists are provided in Tables SI-
3 to SI-6; Supporting Information). Alkoxy-phenols were the predomi­
nant compounds identified in all lignin non-catalytic pyrolysis vapors,
substituted mainly with two methoxy groups (–OCH3) representing the
S-type compounds, such as syringol (2,6-dimethoxyphenol) and 2,6-
dimethoxy-4-(2-propenyl)phenol, while G-type compounds were are
also present in lower concentrations, e.g. creosol (2-methoxy-4-meth­
ylphenol) and 2-methoxy-4-vinylpenol. Similar bio-oil compositions
were observed in the thermal (non-catalytic) fast pyrolysis of other
hardwood lignins [38,83]. The S/G units ratio determined in the
A.G. Margellou et al.
Fig. 4. Representative Py/GC–MS spectra of the non-catalytic (thermal) fast
pyrolysis of beech wood organosolv lignin at 400 and 600 ◦ C.
Py/GC–MS pyrolysis vapors of the lignin samples were as follows:
81/19 (400 ◦ C), 75/25 (500 ◦ C) and 61/39 (600 ◦ C) for Org-lignin;
73/27 (400 ◦ C), 70/30 (500 ◦ C) and 64/36 (600 ◦ C) for HT-extr. Ac;
74/26 (400 ◦ C), 71/29 (500 ◦ C) and 67/33 (600 ◦ C) for HT-extr. EtOH;
74/26 (400 ◦ C), 71/29 (500 ◦ C) and 68/32 (600 ◦ C) for EHL. It is clear
that the increase of pyrolysis temperature from 400 to 500 and 600 ◦ C,
resulted in a progressive decrease in relative concentration of S-type
compounds and increase of G-type compounds, possibly due to
enhanced non-catalytic (thermal) dealkoxylation of syringol type in­
termediates. When comparing the four lignin variants, all derived from
beech wood with different isolation method, no significant variations
can be observed in the S/G ratios, at all pyrolysis temperatures. In
general, from the above results it is shown that the non-catalytic (ther­
mal) fast pyrolysis oil from all different types (in terms of isolation
method) of beech wood lignin, has a similar composition profile in terms
of S/G units with that identified in the respective solid lignin samples by
2D HSQC NMR. These results are in accordance with our previous works
on the thermal pyrolysis of softwood kraft and softwood and hardwood
organosolv lignins [38,39].
In addition to alkoxy-phenols, oxygenated aromatics (1,2,3-or 1,2,4-
Fig. 5. Relative concentration of the various groups of compounds in the fast pyrolysis vapors derived by the non-catalytic fast pyrolysis of the four lignin samples at
400-600 ◦ C, in Py/GC–MS system.
8
Applied Catalysis A, General 623 (2021) 118298
trimethoxybenzene), aldehydes (e.g. 4-hydroxy-3,5-dimethoxybenzal­
dehyde), ketones (e.g. 3′ ,5′ -dimethoxyacetophenone) and acids
(mainly acetic acid) were also produced, as well as alkyl-phenols (not
oxygenated), furans, esters, aliphatic alcohols and nitrogen-containing
compounds in much lower portions, as can be seen in Fig. 4, and Ta­
bles 4, SI-3 to SI-6. Furthermore, thermal pyrolysis of EHL at 400 ◦ C
resulted in significant concentration of D-allose in the vapors (̃ 10 %
GC–MS relative abundance), derived by the thermal degradation of
cellulose remained after enzymatic hydrolysis of the hydrothermally
pretreated treated biomass, in accordance with the above discussion of
the elemental analysis of EHL. At higher pyrolysis temperatures, the
carbohydrate derived compounds are converted to substituted furans via
dehydration of sugars, as also previously mentioned for the fast pyrolysis
of hydrolysis lignin [84].
Catalytic fast pyrolysis experiments of the various beech wood lignin
samples were carried out at 600 ◦ C by the use of the conventional
microporous ZSM-5 and the mesoporous ZSM-5 zeolites. The results
from the catalytic experiments are interpreted in correlation with the
lignin properties and isolation procedure, catalyst characteristics and
catalyst to lignin ratio (C/L). The distribution of the compounds among
the various product groups is shown in Fig. 6 and the most abundant
compounds are listed in Table 4 (full product lists are provided in
Tables SI-3 to SI-6; Supporting Information). The general trend for all
lignin samples tested by the use of the microporous ZSM-5 zeolite was
the conversion of the initially formed (by thermal pyrolysis) alkoxy-
phenols into BTX mono-aromatics (e.g. 1,3-dimethyl-benzene, toluene,
p-xylene, etc.) and polycyclic aromatic hydrocarbons (mainly naph­
thalene and substituted naphthalenes, e.g. such as 1- or 2-methyl-naph­
thalene), in accordance with our previous works on birch/spruce
organosolv lignin and spruce kraft lignin pyrolysis [38,39] as well as
other relevant studies [54,56,58,65]. These effects were more pro­
nounced when the catalyst to lignin ratio (C/L) was increased from 2 to 4
(Fig. SI-5, Supporting Information). ZSM-5 zeolite is known for the high
deoxygenation activity of lignin pyrolysis intermediates and increased
production of BTX aromatics due to its strong Brønsted acidity and
unique porous structure with tubular micropores of moderate size (̃5.5 Å
diameter) and slightly wider spherical intersections (̃10 Å diameter).
These characteristics favor decarbonylation, decarboxylation, dehydra­
tion and C–O/C–C bond cleavage reactions, as well as the formation of
A.G. Margellou et al. Applied Catalysis A, General 623 (2021) 118298

Table 4 mono-aromatics via deoxygenation of the initially formed phenolics or

Most abundant compounds derived from non-catalytic and catalytic fast pyrol­ via aromatization of small olefins (ethylene/propylene) that can be
ysis at 600 ◦ C of the 4 beech wood lignins in the Py/GC–MS system (GC–MS peak produced by cracking or dealkylation of ethyl/propyl-phenolics or via
area, %). dehydration of small intermediate alcohols [38,39,54,55,57,58,85].
Compound Non- ZSM- Meso-ZSM- Dealkylation of alkylphenols over ZSM-5 zeolite towards phenol and
catalytic 5 5 ethylene/propylene has been also previously shown based on model
Organosolv lignin phenolics studies [86,87]. In these studies, in addition to dealkylation,
Phenol, 2,6-dimethoxy-4-(2-propenyl)- 14.99 4.49 1.58 intermediate reactions such as transalkylation and disproportionation
1,2,3-Trimethoxybenzene 14.80 – – have been also proposed which may lead to the formation of dialkyl
Phenol, 2,6-dimethoxy- 7.82 1.87
aromatics and eventually to dimethyl aromatics via cracking of the alkyl
–
6-Methoxycoumaran-7-ol-3-one 7.82 – –
Creosol 5.10 0.36 – side chain. Indeed, 1,3- or 1,4- dimethyl benzene (p-xylene) were the
2-Methoxy-4-vinylphenol 4.38 0.13 – most abundant mono-aromatics identified in the pyrolysis products with
Benzaldehyde, 4-hydroxy-3,5- 4.14 0.65 – ZSM-5 zeolite, as can be seen in Table 4. Further condensation and
dimethoxy-
polymerization of the mono-aromatics on the zeolite acid sites leads to
1,2,4-Trimethoxybenzene – 7.19 0.51
Benzene, 1,3-dimethyl-/p-xylene – 15.22 12.57 the formation of PAHs, mainly naphthalenes. The possible reaction
Toluene – 6.70 14.18 pathways in non-catalytic and catalytic fast pyrolysis of lignin over
o-Xylene – 1.83 7.90 ZSM-5 zeolite catalysts are described in more detailed in our previous
Benzene, 1,2,3-trimethyl- – 4.33 8.57 work [39].
Naphthalene, 1-methyl- 6.11 1.63
The use of hierarchical ZSM-5 zeolite with combined micro- and
–
Naphthalene, 2,6-dimethyl- – 5.80 5.03
Naphthalene, 2-methyl- – 4.21 9.69 meso/macroporosity induced a pronounced enhancement of the con­
Naphthalene – 3.92 11.26 version of alkoxy-phenols and oxygenated aromatics towards the for­
mation of BTX mono-aromatic compounds for all lignins tested,
Enzymatic hydrolysis lignin compared to the conventional ZSM-5, as can be seen in Fig. 6 and Table 4
Phenol, 2,6-dimethoxy- 19.57 4.71 1.33
(full product lists are provided in Tables SI-3 to SI-6; Supporting Infor­
1,2,4-Trimethoxybenzene 9.78 7.66 1.86
Creosol 6.97 1.52 0.52 mation). PAHs (mainly naphthalenes) were similar or slightly higher
3′ ,5′ -Dimethoxyacetophenone 6.82 1.72 0.49 depending on the lignin type. It should be noted that the meso-ZSM-5
Phenol, 2-methoxy- 6.81 0.92 0.68 zeolite has similar acidic characteristics with those of the parent
2-Methoxy-4-vinylphenol 6.26 0.64 – microporous ZSM-5 (Table 1, Fig. SI-3), thus attributing it’s increased
Phenol, 2,6-dimethoxy-4-(2-propenyl)- 4.97 1.95 0.31
Benzene, 1,3-dimethyl-/p-xylene – 18.00 18.54
reactivity mainly to the intracrystal mesopores and the improved
o-Xylene – 15.87 4.78 diffusion, as the average critical diameter of the alkoxy-phenolics (at
Toluene 0.23 14.62 12.61 least the monomeric compounds formed by the initial thermal pyrolysis
Benzene, 1,2,3-trimethyl- – 6.36 9.81 of lignin) ranges from ̃ 7.5–10 Å [88]. The positive effect of intra­
Naphthalene, 1-methyl- 4.80 6.46
–
crystalline mesoporosity was also depicted in the relative higher con­
centration of mono-aromatics compared to PAHs, indicating the
HT- acetone extracted lignin
Phenol, 2,6-dimethoxy- 11.94 3.08 – suppressed condensation of the former to larger polycyclic aromatic
1,2,4-Trimethoxybenzene 8.84 11.80 1.52 compounds due to their facilitated diffusion out of the zeolitic crystal. It
Creosol 6.28 0.28 – is also interesting to note that with the use of the meso-ZSM-5 the
Benzaldehyde, 4-hydroxy-3,5- 6.13 4.07 –
concentration of 1,2,3- or 1,24-trimethylbenzene was substantially
dimethoxy-
1,2,3-Trimethoxybenzene 5.73 0.29 –
increased compared to ZSM-5 for all lignin samples, supporting further
Phenol, 2-methoxy- 4.28 0.02 – the occurrence of bimolecular reactions, such as transalkylation or
Cyclopentene, 1-ethenyl-3-methylene- 8.29 – – disproportionation, that are favored by the intracrystalline mesopores.
Cyclobutane, methoxy- – 3.56 7.40 Similar results and trends were observed in our previous work,
Benzene, 1,3-dimethyl-/p-xylene 17.01 16.81
regarding the use of mesoporous ZSM-5 in fast pyrolysis of spruce and
–
Toluene 0.44 8.79 11.11
o-Xylene – – 4.96 birch organosolv lignins [38].
Benzene, 1,2,3-trimethyl- – 2.11 10.18 Considering the lignin isolation procedure, no significant effect could
Naphthalene, 1-methyl- – 6.19 1.01 be identified on the changes induced by the use of ZSM-5 zeolites. The
Naphthalene 4.89 5.67
–
alkoxy-phenols and oxy-aromatics were almost completely converted
Naphthalene, 2-methyl- – 0.15 6.54
especially by the meso-ZSM-5 and the BTX mono-aromatics for all lignin
HT- EtOH extracted lignin samples reached a relative concentration of ̃60 % (Fig. 6). Perhaps a
1,2,4-Trimethoxybenzene 13.67 6.94 3.85 slightly higher abundance of PAHs (naphthalenes) could be observed for
Phenol, 2,6-dimethoxy- 12.82 1.36 0.39 the organosolv derived lignin but this needs further systematic investi­
Benzaldehyde, 4-hydroxy-3,5- 7.78 1.37 – gation. There is also no systematic differentiation with regard to the
dimethoxy-
Creosol 6.41 – –
selectivity of individual mono-aromatic compounds, as for all lignin
3 ,5 -Dimethoxyacetophenone
′ ′
4.04 0.83 0.29 samples the most abundant BTX aromatics were toluene and 1,3- or 1,4-
Cyclobutane, methoxy- – – 5.04 dimethyl-benzene (m-xylene/p-xylene), followed by 1,2,3- or 1,2,4-tri­
Benzene, 1,3-dimethyl-/p-xylene – 15.82 20.95 methyl-benzene and benzene. Similarly, naphthalene, 1- or 2-methyl-
Toluene 10.95 10.98
–
naphthalene and 2,6-dimethyl-naphthalene were the most abundant
Benzene, 1,2,4-trimethyl- – 2.63 12.06
Benzene, 1-ethyl-2-methyl- – 0.91 4.18 PAHs for all lignin samples. Similar results were obtained in our previ­
Naphthalene, 2-methyl- 0.77 6.23 0.69 ous work on the catalytic fast pyrolysis of organosolv lignin derived from
Naphthalene, 2,6-dimethyl- – 5.44 3.24 birch being also a hardwood as beech [38]. Although there are few
Naphthalene – 4.52 3.95 studies available in the literature that have investigated the catalytic fast
pyrolysis of different types of lignin, e.g. from different industrial
sources or from different types of biomass (even mixtures of two types of
biomasses) [41,55], the present work investigates four differently iso­
lated lignin samples produced from the same beech wood, as described
above, thus aiming to elucidate the possible effect of the isolation

9
A.G. Margellou et al. Applied Catalysis A, General 623 (2021) 118298

Fig. 6. Relative concentration of the various groups of compounds in the bio-oil derived by the catalytic fast pyrolysis of four lignin samples at 600 ◦ C, over zeolite
catalysts (C/L = 4), in Py/GC–MS system.

process, excluding the changes induced by the origin and composition of

lignin in parent biomass. Furthermore, two of the four samples, the
surface lignin recovered by ethanol and acetone Soxhlet extraction of
the hydrothermally pretreated biomass, are investigated for the first
time as feedstocks in fast (catalytic) pyrolysis.

3.4. Non-catalytic and catalytic fast pyrolysis of lignins on fixed bed

reactor

The pyrolysis experiments were carried out at 600 ◦ C in the absence

(using sand; non-catalytic) or presence of parent microporous and meso-
ZSM-5 in order to determine the yield of total liquids, including organic
bio-oil and water, non-condensable gases, and solids (char/coke on
catalyst). In the non-catalytic experiments, the total liquid products for
all lignin samples were ̃40− 44 wt.% (organic phase 33− 35 wt.% and
aqueous phase 6− 9 wt.%), gases were in the range of 11− 14 wt.% and
solids exhibited higher yields of 40− 45 wt.%, as can be seen in Fig. 7A
(and in Tables SI-7 to SI-10, Supporting Information). The organic
fraction of the bio-oils was substantially decreased by the use of the
ZSM-5 zeolite to ca. 19− 30 wt.%, with a subsequent increase of water to
ca. 12− 17 wt.%, resulting to an overall similar or slightly lower yields of
total liquid products (ca. 35–42 wt.%) for all lignin samples tested. The
non-condensable gases were increased to ca. 16− 19 wt.%. These
changes in the product yields are the direct consequence of the acid
catalytic function of ZSM-5 zeolite via the pathways described in the
previous section, i.e. conversion of the initially (via thermal pyrolysis)
produced alkoxy-phenolics and alkoxy-aromatics to water (via dehy­
dration/dehydroxylation), CO/CO2 gases (via decarbonylation/decar­
boxylation), BTX aromatics (via complete deoxygenation of oxygenated
phenolics/aromatics or aromatization of small alkenes), PAHs (via
condensation of mono-aromatics) and coke (via polymerization of PAHs
and alkylphenols on the zeolitic acid sites). The above changes in liquid
and gas product yields were enhanced further, with the use of the
mesoporous meso-ZSM-5 zeolite, in accordance with the observed in the
Py/GC–MS experiments higher reactivity of the mesoporous zeolite in Fig. 7. (A) Product yield distribution and (B) non-condensable gases yields
obtained in the thermal and catalytic fast pyrolysis of lignin samples, with the
converting the alkoxy-compounds to BTX aromatics. The changes
fixed-bed reactor at 600 ◦ C.
induced in the composition of the catalytic bio-oils compared to the non-
catalytic ones were similar to those described above for the Py/GC–MS
experiments (data not shown for brevity). These results are in agreement

10
A.G. Margellou et al.
with our previous studies on spruce and birch derived lignins [38,39] as
well as other previously reported works with microporous or meso­
porous ZSM-5 zeolites on biomass or lignin pyrolysis using similar
experimental set-up that utilizes a catalytic fixed-bed reactor for the
upgrading of in situ produced pyrolysis vapors [40,41,89–91].
The solids (char and coke on catalyst) were similar or slightly
decreased by the use of the microporous ZSM-5 zeolite to ca. 39− 45 wt.
% and as it can be seen from the data in Tables SI-7 to SI-10 (Supporting
Information) and the coke that was formed on ZSM-5 (determined by
TGA) was 3− 5 wt.% on lignin (via acid catalyzed polymerization of the
initially formed aromatics), with small variations between the different
lignins. Similar results regarding coke formation on ZSM-5 based cata­
lysts were previously observed in the pyrolysis of lignins from different
biomass/origin, i.e. spruce kraft lignin [39], spruce and birch organo­
solv lignins [38], and mixtures of birch, aspen, pine and spruce lignins
isolated by the LignoBoost process [41]. The effect of intracrystalline
mesoporosity of meso-ZSM-5 identified in the increased concentration of
monomeric BTX aromatics compared to that of PAHs, is also depicted on
the formation of reaction coke which is like that in the case of micro­
porous ZSM-5, not exceeding 5 wt.% on lignin (Tables SI-7 to SI-10,
Supporting information).
The composition analysis of the non-condensable gases is shown in
Fig. 7B. Non-catalytic pyrolysis gases consisted mainly of carbon mon­
oxide and dioxide, as well as methane, for all lignins tested. Higher
yields of CO and CO2 were observed in the catalytic experiments due to
the decarbonylation and decarboxylation reactions, promoted by both
ZSM-5 and meso-ZSM-5 zeolites. In addition, gaseous hydrocarbons,
mainly ethylene and propylene, were produced via the cracking and
dealkylation reactions of the primary alkylated alkoxy-phenols. As dis­
cussed above and in accordance with the suggested reaction
Fig. 8. 2D HSQC NMR spectrum of the HT-extr. EtOH lignin and the correspond bio-oil obtained by the non-catalytic pyrolysis at 600 ◦ C, separated in three regions:
(A) aliphatic, (B) inter-unit linkages and (C) aromatic region.
11
Applied Catalysis A, General 623 (2021) 118298
mechanisms in the literature, these small alkenes are precursors of BTX
aromatics via the known aromatization activity of ZSM-5 [38,39,55].
The bio-oils derived by the non-catalytic (thermal) and the catalytic
fast pyrolysis of HT-extr. EtOH lignin in the fixed bed reactor at 600 ◦ C,
were analyzed by 2D HSQC NMR. The HSQC NMR spectra of the non-
catalytic bio-oil are shown in Fig. 8, in comparison with those of the
parent HT-extr. EtOH lignin, while the analysis of the catalytic bio-oils
are presented in Fig. 9. The assignment of the peaks was based on pre­
viously reported data [58,80,92–98].
The aliphatic part of the HSQC NMR spectra (Fig. 8A) demonstrates
the structural differences between the HT-extr. EtOH lignin and the bio-
oil derived from the non-catalytic (thermal) fast pyrolysis, due to the
breaking of the inter-unit linkages. The lignin sample consists of longer
aliphatic chains and exhibit more β, γ C atoms than the non-catalytic bio-
oil whereas the latter exhibit mainly cross-peaks that correspond to
methyl-Ar (Ar = oxyphenols or oxyaromatic) structures. From Fig. 8B, it
can be seen that the bio-oil derived by the non-catalytic pyrolysis does
not have the inter-unit linkages (such as β-O-4, β-β, β-5) that existed in
lignin and this indicates that these bonds have been cleaved to a great
extent during thermal fast pyrolysis. From this part of the spectrum, it
can also be seen that the bio-oil still exhibits a relatively strong methoxy
signal, indicating the presence of S, G types of aromatic rings.
Fig. 8C clearly shows the signals assigned to S and G aromatic units in
the thermal bio-oil, to be of lower intensity compared to those for the
initial lignin. The S/G ratio of the bio-oil was estimated to 63/36, being
slightly lower compared to that in the parent lignin (72/27; Table 3).
This finding is in accordance with the ratio estimated by the non-
catalytic Py/GC–MS experiment at 600 ◦ C (67/33), as described
above. The demethoxylation of S, G units indicates the presence of
(methyl)catechols and/or hydroxyphenyl (H) units. The bio-oil exhibits
A.G. Margellou et al.
Fig. 9. 2D HSQC NMR spectrum of the HT-extr. EtOH lignin and the correspond bio-oil obtained by the catalytic fast pyrolysis at 600 ◦ C, separated in three regions:
(A) aliphatic, (B) methoxy-signals and (C) aromatic region.
some cross-peaks in the region of 108–110/6.2–6.5 that do not exist in
the initial lignin. These signals could be ascribed to dimer structures
with two phenolic rings connected with a bridged oxygen [80]. The
bio-oil also exhibits cross-peaks in the region of 120–122/6.25− 6.4 ppm
that correspond probably to the β-atom of conjugated double bond.
More specifically β-atom of propylene end group or ferulic type esters
have been reported to exhibit signals in this region [80]. The ester
structure could be formed in the non-catalytic bio-oil by re-arrangement
of monomers that originated from inter-unit linkages scission or lignin
end groups with a conjugated double bond (Jβ/stilbene structures) that
they indeed existed in the initial ethanol-extracted lignin.
The bio-oils obtained from the catalytic fast pyrolysis of HT-extr.
EtOH lignin in the presence of microporous and meso-ZSM-5 zeolites
are shown in Fig. 9. In Fig. 9A, for the aliphatic region, it is observed that
both bio-oils exhibit strong signals that correspond to methyl-Ar struc­
tures, resulted from the bond dissociation between the aromatic rings.
The strong signals at the region of 15–17/2.0–2.2 ppm corresponds to
ortho-substituted methyl-oxyAr [97,98] and dictates the presence of
cresols/methyl catechols or methylanisoles in both bio-oils. The signals
at 19–21.6/2.1–2.5 ppm may indicate the presence of m,p-substituted
methyl-oxyAr, as well as non-oxygenated methyl-Ar (i.e. xylenes,
toluene) in accordance with Py/GC–MS catalytic experiments.
Furthermore, the bio-oil obtained with microporous ZSM-5 seems to
retain more long chains than the bio-oil obtained with meso-ZSM-5
(being substantially less in both catalytic bio-oils compared to the
non-catalytic one, Fig. 8A), since more signals are observed at the right
part of the spectrum. There are no signals of the typical inter-unit
linkages of lignin since the bonds between the aromatic rings have
been cleaved already to a great extent at the non-catalytic (thermal)
pyrolysis stage, prior to the catalytic upgrading of the vapors; thus
12
Applied Catalysis A, General 623 (2021) 118298
Fig. 9B is focused on the methoxy signal. This signal is divided in two
parts with the left corresponding to methoxy signal with adjacent
OH/OR group while the right part corresponds to methoxy signal with
methyl or without any group in o-position [94,97]. In both catalytic
bio-oils, this methoxy signal has been shifted towards lower chemical
shift values whereas the initial lignin and the non-catalytic bio-oil had
about equal signals of the two parts. This dictates that dehydroxylation
occurs to a considerable degree during the catalytic process and
(methyl)anisoles possibly were produced as a result of dehydroxylation.
Fig. 9C shows the possible single compounds that could be assigned
to the signals of the aromatic part of the HSQC NMR spectra of the
catalytic bio-oils. In the region of 112–122/6.3–6.8 ppm (usually
assigned to G units in parent lignin or non-catalytic bio-oil), the iden­
tified signals were mostly assigned to non-methoxylated phenolic units,
such cresols, (methyl)anisoles and (methyl)catechols, for both micro­
porous and meso-ZSM-5 zeolites. The bio-oil obtained with the ZSM-5
catalyst still retains few S aromatic units of the initial lignin or non-
catalytic bio-oil, whereas these are minimized with the meso-ZSM-5,
thus implying that demethoxylation has occurred to a large extend in
this catalytic bio-oil during the upgrading of the thermal pyrolysis va­
pors. As a result, the bio-oil derived from meso-ZSM-5 exhibits more
cross-peaks in the region 127–131/6.7–7.1 ppm corresponding to alkyl-
benzenes (and/or cresols), in accordance with the Py/GC–MS catalytic
data. Furthermore, the bio-oil obtained with meso-ZSM-5 shows more
signals of PAHs than this with ZSM-5.
4. Conclusions
In this study, the thermal (non-catalytic) and the catalytic fast py­
rolysis (or catalytic upgrading of thermal pyrolysis vapors) of beech
A.G. Margellou et al.
wood lignin samples isolated by different processes was studied in a Py-
GC/MS system and a fixed-bed reactor, with conventional microporous
ZSM-5 and mesoporous ZSM-5 catalysts. The non-catalytic pyrolysis
vapors in the Py/GC–MS study, consisted mainly of alkoxy-substituted
phenols, benzenes and benzaldehydes, such as 2,6-dimethoxyphenol
(syringol), 2,6-dimethoxy-4-(2-propenyl)phenol, 2-methoxy-4-methyl­
phenol (creosol), trimethoxybenzenes and 4-hydroxy-3,5-dimethoxy­
benzaldehyde. The estimated S/G ratios in the pyrolysis vapors were
60–80/40− 20, being in the same range (65–90/35− 10) obtained by 2D
HSQC NMR of the solid lignins, thus verifying previously reported re­
sults showing that the main composition profile of the lignin feedstock,
in terms of phenylpropane units, is being “transferred” to the bio-oil.
The microporous ZSM-5 zeolite was very active in converting the
initially produced via thermal pyrolysis methoxy-compounds towards
BTX mono-aromatics, such as 1,3-dimethylbenzene/p- and o-xylenes,
toluene and trimethylbenzenes, as well as polycyclic aromatic hydro­
carbons (PAHs, mainly naphthalenes). The mesoporous ZSM-5 (with
intracrystal mesopores of ̃9 nm and with similar acidic properties with
those of the microporous ZSM-5) exhibited higher dealkoxylation ac­
tivity leading to higher concentration of BTX aromatics, which was not
followed by a consequent increase of PAHs, thanks to the enhanced
diffusion of reactants (alkoxy-compounds formed from initial thermal
pyrolysis) and primary aromatization products (formed in ZSM-5
microporous channels).
The changes observed in the product yields, i.e. decrease of organic
bio-oil, increase of aqueous phase/water, increase of non-condensable
gases (mainly of CO, ethylene and propylene), formation of reaction
coke on catalysts (in addition to the thermal pyrolysis char) by the use of
both zeolites were the expected ones, based on previous studies on
biomass and lignin catalytic fast pyrolysis. These changes arise from the
strong acidity and narrow microporous channels of ZSM-5 zeolite which
favor decarbonylation, decarboxylation, dehydration/dehydroxylation,
cracking and dealkylation reactions of the primary oxygenated com­
pounds, as well as aromatization of in situ formed small olefins
(ethylene/propylene) followed by (trans)alkylation and disproportion­
ation towards dimethyl-aromatics, and further condensation and poly­
merization of the mono-aromatics towards PAHs, and eventually coke
on catalyst.
The detailed characterization of the three lignin types originated
from the same beech wood biomass, i.e. organosolv lignin, surface lignin
derived by mild Soxhlet extraction (with ethanol or acetone) from the
hydrothermally (HT) pretreated biomass, and the enzymatic hydrolysis
lignin, revealed moderate differences in their properties, such as mo­
lecular weight, S/G ratio and inter-unit linkages, and elemental
composition. However, these differences were not capable to induce
systematic/substantial variations in the thermal and catalytic fast py­
rolysis product yields and composition. It was also shown that the less
studied, so called surface lignin, being an easily recovered by-product
whose removal facilitates the enzymatic/acidic hydrolysis of the
remaining pretreated biomass [13], can offer high quality phenolic and
aromatic pyrolysis oils, similar to those provided by the more classical
organosolv and enzymatic hydrolysis lignin.
CRediT authorship contribution statement
A. G. Margellou: Lignin samples production and characterization;
Bio-oil analytics; Writing-draft preparation; P. A. Lazaridis: Catalysts
preparation and characterization; pyrolysis experiments; bio-oil ana­
lytics; I. D. Charisteidis: pyrolysis experiments; bio-oil analytics; C. K.
Nitsos: Lignin samples production and characterization; C. P. Pappa:
Lignin samples production and characterization; A. P. Fotopoulos:
Lignin samples characterization; S. Van den Bosch: Lignin samples
characterization and draft reviewing; B. F. Sels: Reviewing and editing;
K. S. Triantafyllidis: Writing-reviewing and editing
13
Applied Catalysis A, General 623 (2021) 118298
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This research has been co-financed by the European Regional
Development Fund of the European Union and Greek national funds
through the Operational Program Competitiveness, Entrepreneurship
and Innovation (EPAnEK 2014-2020), under the Action “RESEARCH –
CREATE – INNOVATE” B’ CALL (project code: T2EDK-01243). 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.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.apcata.2021.118298.
References
[1] P. Azadi, O.R. Inderwildi, R. Farnood, D.A. King, Renew. Sustain. Energy Rev. 21
(2013) 506–523.
[2] J. Zakzeski, P.C.A. Bruijnincx, A.L. Jongerius, B.M. Weckhuysen, Chem. Rev. 110
(2010) 3552–3599.
[3] C. Li, X. Zhao, A. Wang, G.W. Huber, T. Zhang, Chem. Rev. 115 (2015)
11559–11624.
[4] M.P. Pandey, C.S. Kim, Chem. Eng. Tech. 34 (2011) 29–41.
[5] F.G. Calvo-Flores, J.A. Dobado, ChemSusChem 3 (2010) 1227–1235.
[6] K. Kohli, R. Prajapati, B.K. Sharma, Energies 12 (2019) 233.
[7] W. Schutyser, T. Renders, S. Van den Bosch, S.F. Koelewijn, G.T. Beckham, B.
F. Sels, Chem. Soc. Rev. 47 (2018) 852–908.
[8] R. Rinaldi, R. Jastrzebski, M.T. Clough, J. Ralph, M. Kennema, P.C.A. Bruijnincx, B.
M. Weckhuysen, Biorefin. Catal. 55 (2016) 8164–8215.
[9] L.A. Zevallos Torres, A. Lorenci Woiciechowski, V.O. de Andrade Tanobe, S.
G. Karp, L.C. Guimarães Lorenci, C. Faulds, C.R. Soccol, J. Clean. Prod. 263 (2020)
121499.
[10] J. Lora, in: M.N. Belgacem, A. Gandini (Eds.), Monomers, Polymers and Composites
from Renewable Resources, Elsevier, Amsterdam, 2008, pp. 225–241.
[11] C.K. Nitsos, K.A. Matis, K.S. Triantafyllidis, ChemSusChem 6 (2013) 110–122.
[12] C.K. Nitsos, T. Choli-Papadopoulou, K.A. Matis, K.S. Triantafyllidis, ACS Sustain.
Chem. Eng. 4 (2016) 4529–4544.
[13] C.K. Nitsos, P.A. Lazaridis, A. Mach-Aigner, K.A. Matis, K.S. Triantafyllidis,
ChemSusChem 12 (2019) 1179–1195.
[14] J.I. Santos, R. Martín-Sampedro, Ú. Fillat, J.M. Oliva, M.J. Negro, M. Ballesteros,
M.E. Eugenio, D. Ibarra, Int. J. Polym. Sci. (2015) 314891.
[15] M.M. Jensen, D.T. Djajadi, C. Torri, H.B. Rasmussen, R.B. Madsen, E. Venturini,
I. Vassura, J. Becker, B.B. Iversen, A.S. Meyer, H. Jørgensen, D. Fabbri, M. Glasius,
ACS Sustain. Chem. Eng. 6 (2018) 5940–5949.
[16] C. Nitsos, L. Matsakas, K. Triantafyllidis, U. Rova, P. Christakopoulos, Biofuels 9
(2018) 545–558.
[17] R.-J. van Putten, J.C. van der Waal, E. de Jong, C.B. Rasrendra, H.J. Heeres, J.G. de
Vries, Chem. Rev. 113 (2013) 1499–1597.
[18] D. Steinbach, A. Kruse, J. Sauer, Biomass Convers. Biorefinery 7 (2017) 247–274.
[19] D.L. Aguilar, R.M. Rodríguez-Jasso, E. Zanuso, D.J. de Rodríguez, L. Amaya-
Delgado, A. Sanchez, H.A. Ruiz, Bioresour. Technol. 263 (2018) 112–119.
[20] J.K. Saini, R. Saini, L. Tewari, 3 Biotech 5 (2015) 337–353.
[21] The Role of Catalysis for the Sustainable Production of Bio-fuels and Bio-chemicals,
Elsevier, Amsterdam, 2013.
[22] C. Nitsos, U. Rova, P. Christakopoulos, IDEAS 11 (2018) 50.
[23] C. Nitsos, R. Stoklosa, A. Karnaouri, D. Vörös, H. Lange, D. Hodge, C. Crestini,
U. Rova, P. Christakopoulos, ACS Sustain. Chem. Eng. 4 (2016) 5181–5193.
[24] D. Wei Kit Chin, S. Lim, Y.L. Pang, M.K. Lam, Biofuels Bioprod. Biorefin. 14 (2020)
808–829.
[25] K. Van Aelst, E. Van Sinay, T. Vangeel, E. Cooreman, G. Van den Bossche,
T. Renders, J. Van Aelst, S. Van den Bosch, B.F. Sels, Chem. Sci. 11 (2020)
11498–11508.
[26] C.G. Yoo, X. Meng, Y. Pu, A.J. Ragauskas, Bioresour. Technol. 301 (2020) 122784.
[27] H.L. Trajano, N.L. Engle, M. Foston, A.J. Ragauskas, T.J. Tschaplinski, C.
E. Wyman, Biotechnol. Biofuels 6 (2013) 110.
[28] B.S. Donohoe, S.R. Decker, M.P. Tucker, M.E. Himmel, T.B. Vinzant, Biotechnol.
Bioeng. 101 (2008) 913–925.
[29] F. Hu, S. Jung, A. Ragauskas, Bioresour. Technol. 117 (2012) 7–12.
[30] X. Meng, A. Ragauskas, Recent. Adv. Petrochem. Sci. 1 (2017) 1–5.
[31] A. Margellou, K.S. Triantafyllidis, Catalysts 9 (2019) 43.
[32] C. Cheng, D. Shen, S. Gu, K.H. Luo, Catal. Sci. Technol. 8 (2018) 6275–6296.
A.G. Margellou et al.
[33] R.K. Chowdari, S. Agarwal, H.J. Heeres, ACS Sustain. Chem. Eng. 7 (2019)
2044–2055.
[34] Y. Zhu, Y. Liao, W. Lv, J. Liu, X. Song, L. Chen, C. Wang, B.F. Sels, L. Ma, ACS
Sustain. Chem. Eng. 8 (2020) 2361–2374.
[35] T.I. Korányi, B. Fridrich, A. Pineda, K. Barta, Molecules 25 (2020) 2815.
[36] T. Renders, G. Van den Bossche, T. Vangeel, K. Van Aelst, B. Sels, Curr. Opin.
Biotechnol. 56 (2019) 193–201.
[37] W. Arts, D. Ruijten, K. Van Aelst, L. Trullemans, B. Sels, in: P.C. Ford, R. van Eldik
(Eds.), Advances in Inorganic Chemistry, Academic Press, 2021, pp. 241–297.
[38] I. Charisteidis, P. Lazaridis, A. Fotopoulos, E. Pachatouridou, L. Matsakas, U. Rova,
P. Christakopoulos, K. Triantafyllidis, Catalysts 9 (2019) 935.
[39] P.A. Lazaridis, A.P. Fotopoulos, S.A. Karakoulia, K.S. Triantafyllidis, Front. Chem.
6 (2018).
[40] K.G. Kalogiannis, L. Matsakas, A.A. Lappas, U. Rova, P. Christakopoulos, Energies
12 (2019) 1606.
[41] K.G. Kalogiannis, S.D. Stefanidis, C.M. Michailof, A.A. Lappas, E. Sjöholm, J. Anal.
Appl. Pyrolysis 115 (2015) 410–418.
[42] A.K. Mondal, C. Qin, A.J. Ragauskas, Y. Ni, F. Huang, Ind. Eng. Chem. Res. 59
(2020) 3310–3320.
[43] Z. Si, X. Zhang, C. Wang, L. Ma, R. Dong, Catalysts 7 (2017) 169.
[44] R. Shu, R. Li, B. Lin, C. Wang, Z. Cheng, Y. Chen, Biomass Bioenergy 132 (2020)
105432.
[45] C. Zerva, S.A. Karakoulia, K.G. Kalogiannis, A. Margellou, E.F. Iliopoulou, A.
A. Lappas, N. Papayannakos, K.S. Triantafyllidis, Catal. Today (2020).
[46] C. Liu, H. Wang, A.M. Karim, J. Sun, Y. Wang, Chem. Soc. Rev. 43 (2014)
7594–7623.
[47] A. Imran, E.A. Bramer, K. Seshan, G. Brem, J. Biofuel Res. J. 5 (2018) 872–885.
[48] E.F. Iliopoulou, P.A. Lazaridis, K.S. Triantafyllidis, Nanotechnol. Catal. (2017)
655–714.
[49] E.F. Iliopoulou, K.S. Triantafyllidis, A.A. Lappas, WIREs Energy Environ. 8 (2019)
e322.
[50] K.S. Triantafyllidis, S.A. Karakoulia, A. Pineda, A. Margellou, K.G. Kalogiannis, E.
F. Iliopoulou, A.A. Lappas, in: A.M. Balu, A.G. Nuñez (Eds.), Biomass and Biowaste,
De Gruyter, 2020, pp. 113–144.
[51] M.M. Rahman, R. Liu, J. Cai, Fuel Process. Technol. 180 (2018) 32–46.
[52] J.-Y. Kim, J. Moon, J.H. Lee, X. Jin, J.W. Choi, Fuel 279 (2020) 118484.
[53] D.J. Mihalcik, C.A. Mullen, A.A. Boateng, J. Anal. Appl. Pyrolysis 92 (2011)
224–232.
[54] M.A. Jackson, D.L. Compton, A.A. Boateng, J. Anal. Appl. Pyrolysis 85 (2009)
226–230.
[55] C.A. Mullen, A.A. Boateng, Fuel Process. Technol. 91 (2010) 1446–1458.
[56] X.Y. Li, L. Su, Y.J. Wang, Y.Q. Yu, C.W. Wang, X.L. Li, Z.H. Wang, Front. Environ.
Sci. Eng. 6 (2012) 295–303.
[57] Z. Ma, E. Troussard, J.A. van Bokhoven, Appl. Catal. A Gen. 423-424 (2012)
130–136.
[58] H. Ben, A.J. Ragauskas, ACS Sustain. Chem. Eng. 1 (2013) 316–324.
[59] M. Zhang, F.L.P. Resende, A. Moutsoglou, Fuel 116 (2014) 358–369.
[60] T. Ohra-aho, J. Linnekoski, J. Anal. Appl. Pyrolysis 113 (2015) 186–192.
[61] J. Li, X. Li, G. Zhou, W. Wang, C. Wang, S. Komarneni, Y. Wang, Appl. Catal. A Gen.
470 (2014) 115–122.
[62] D. Kerstens, B. Smeyers, J. Van Waeyenberg, Q. Zhang, J. Yu, B.F. Sels, Adv. Mater.
32 (2020), 2004690.
[63] H.W. Lee, T.H. Kim, S.H. Park, J.-K. Jeon, D.J. Suh, Y.-K. Park, J. Nanosci.
Nanotechnol. 13 (2013) 2640–2646.
[64] S.-S. Kim, H.W. Lee, R. Ryoo, W. Kim, S.H. Park, J.-K. Jeon, Y.-K. Park, J. Nanosci.
Nanotechnol. 14 (2014) 2414–2418.
[65] V.B.F. Custodis, S.A. Karakoulia, K.S. Triantafyllidis, J.A. van Bokhoven,
ChemSusChem 9 (2016) 1134–1145.
[66] C.A. Emeis, J. Catal. 141 (1993) 347–354.
14
Applied Catalysis A, General 623 (2021) 118298
[67] J. Asikkala, T. Tamminen, D.S. Argyropoulos, J. Agric. Food Chem. 60 (2012)
8968–8973.
[68] S. Heikkinen, M.M. Toikka, P.T. Karhunen, I.A. Kilpeläinen, J. Am. Chem. Soc. 125
(2003) 4362–4367.
[69] D.H. Park, S.S. Kim, H. Wang, T.J. Pinnavaia, M.C. Papapetrou, A.A. Lappas, K.
S. Triantafyllidis, Angew. Chem. Int. Ed. Engl. 48 (2009) 7645–7648.
[70] M. Thommes, K. Kaneko, A.V. Neimark, J.P. Olivier, F. Rodriguez-Reinoso,
J. Rouquerol, K.S.W. Sing, J. Pure Appl. Chem. Res. 87 (2015) 1051.
[71] A.C. Psarras, C.M. Michailof, E.F. Iliopoulou, K.G. Kalogiannis, A.A. Lappas,
E. Heracleous, K.S. Triantafyllidis, Mol. Catal. 465 (2019) 33–42.
[72] V.G. Komvokis, S. Karakoulia, E.F. Iliopoulou, M.C. Papapetrou, I.A. Vasalos, A.
A. Lappas, K.S. Triantafyllidis, Catal. Today 196 (2012) 42–55.
[73] C.S. Triantafillidis, A.G. Vlessidis, L. Nalbandian, N.P. Evmiridis, Microporous
Mesoporous Mater. 47 (2001) 369–388.
[74] K.S. Triantafyllidis, L. Nalbandian, P.N. Trikalitis, A.K. Ladavos,
T. Mavromoustakos, C.P. Nicolaides, Microporous Mesoporous Mater. 75 (2004)
89–100.
[75] K.G. Kalogiannis, L. Matsakas, J. Aspden, A.A. Lappas, U. Rova, P. Christakopoulos,
Molecules 23 (2018) 1647.
[76] M. Yáñez-S, B. Matsuhiro, C. Nuñez, S. Pan, C.A. Hubbell, P. Sannigrahi, A.
J. Ragauskas, Polym. Degrad. Stab. 110 (2014) 184–194.
[77] W. Mu, H. Ben, A. Ragauskas, Y. Deng, Bioenergy Res. 6 (2013) 1183–1204.
[78] S. Constant, H.L.J. Wienk, A.E. Frissen, Pd. Peinder, R. Boelens, D.S. van Es, R.J.
H. Grisel, B.M. Weckhuysen, W.J.J. Huijgen, R.J.A. Gosselink, P.C.A. Bruijnincx,
Green Chem. 18 (2016) 2651–2665.
[79] C. Crestini, H. Lange, M. Sette, D.S. Argyropoulos, Green Chem. 19 (2017)
4104–4121.
[80] S.A. Ralph, J. Ralph, L.L. Landucci, NMR Database of Lignin and Cell Wall Model
Compounds, 2009.
[81] T.-Q. Yuan, S.-N. Sun, F. Xu, R.-C. Sun, J. Agric. Food Chem. 59 (2011)
10604–10614.
[82] C. Zhang, L.-H. Xu, C.-Y. Ma, H.-M. Wang, Y.-Y. Zhao, Y.-Y. Wu, J.-L. Wen, Front.
Energy Res. 8 (2020).
[83] V.B.F. Custodis, C. Bährle, F. Vogel, J.A. van Bokhoven, J. Anal. Appl. Pyrolysis
115 (2015) 214–223.
[84] H. Paysepar, K.T. Venkateswara Rao, Z. Yuan, H. Shui, C. Xu, J. Anal. Appl.
Pyrolysis 149 (2020) 104842.
[85] K. Wang, K.H. Kim, R.C. Brown, Green Chem. 16 (2014) 727–735.
[86] Y. Liao, R. Zhong, M. d’Halluin, D. Verboekend, B.F. Sels, ACS Sustain. Chem. Eng.
8 (2020) 8713–8722.
[87] Y. Liao, M. d’Halluin, E. Makshina, D. Verboekend, B.F. Sels, Appl. Catal. B 234
(2018) 117–129.
[88] Y. Yu, X. Li, L. Su, Y. Zhang, Y. Wang, H. Zhang, Appl. Catal. A Gen. 447-448
(2012) 115–123.
[89] G. Zhou, P.A. Jensen, D.M. Le, N.O. Knudsen, A.D. Jensen, Green Chem. 18 (2016)
1965–1975.
[90] S. Stephanidis, C. Nitsos, K. Kalogiannis, E.F. Iliopoulou, A.A. Lappas, K.
S. Triantafyllidis, Catal. Today 167 (2011) 37–45.
[91] H.J. Park, H.S. Heo, J.-K. Jeon, J. Kim, R. Ryoo, K.-E. Jeong, Y.-K. Park, Appl.
Catal. B 95 (2010) 365–373.
[92] C.A. Mullen, G.D. Strahan, A.A. Boateng, Energy Fuels 23 (2009) 2707–2718.
[93] J. Joseph, C. Baker, S. Mukkamala, S.H. Beis, M.C. Wheeler, W.J. DeSisto, B.
L. Jensen, B.G. Frederick, Energy Fuels 24 (2010) 5153–5162.
[94] H. Ben, A.J. Ragauskas, Energy Fuels 25 (2011) 5791–5801.
[95] H. Ben, A.J. Ragauskas, ChemSusChem 5 (2012) 1687–1693.
[96] F. Huang, H. Ben, S. Pan, Y. Pu, A. Ragauskas, Sustain. Chem. Process. 2 (2014) 7.
[97] N. Hao, H. Ben, C.G. Yoo, S. Adhikari, A.J. Ragauskas, Energy Fuels 30 (2016)
6863–6880.
[98] C. Mattsson, S.-I. Andersson, T. Belkheiri, L.-E. Åmand, L. Olausson, L. Vamling,
H. Theliander, Biomass Bioenergy 95 (2016) 364–377.