DOI: 10.1002/cctc.
201500840 Full Papers
Simultaneous Liquefaction and Hydrodeoxygenation of
Lignocellulosic Biomass over NiMo/Al2O3, Pd/Al2O3, and
Zeolite Y Catalysts in Hydrogen Donor Solvents
Miha Grilc, Blaž Likozar,* and Janez Levec[a]
The one-step solvolysis and hydro-treatment of oak, fir and
beech sawdust was studied in a slurry reactor using tetralin,
phenol and glycerol as solvents and representative heteroge-
neous catalysts used in the petrochemical industry for hydro-
genolysis (the sulfide form of NiMo/Al2O3), hydrogenation (Pd/
Al2O3) or fluid catalytic cracking (zeolite Y). Deoxyliquefaction
products of cellulose, hemicellulose and lignin were character-
ised in terms of solvent fractionation, FTIR and diffuse reflec-
tance infrared Fourier transform spectroscopy, elemental analy-
Introduction
The valorisation of waste lignocellulosic (LC) biomass by its
conversion into higher-value chemicals or liquid transportation
fuels has attracted great attention in recent years. A typical
thermochemical approach to convert the LC biomass into
liquid transportation fuel involves a two-step process, in which
solid biomass or its components are de-polymerised in the first
step by pyrolysis, dissolution/liquefaction (LIQ) or gasification,
and low-value intermediates (i.e., pyrolysis oil, liquefaction oil
or synthesis gas) are subsequently upgraded by catalytic
hydro-treatment or Fischer–Tropsch synthesis to obtain a com-
petitive-quality liquid fuel.[1] In contrast to pyrolysis or gasifica-
tion that both require high operating temperatures, direct liq-
uefaction is performed at a significantly lower temperature in
the presence of solvents that may serve as reactants and heat
carriers, whereas the use of hydrogen donor solvents, accom-
panied by a moderate H2 pressure, is known to promote C¢C
and C¢O bond cleavage, to reduce coke formation and inhibit
re-polymerisation reactions.[2] A higher temperature is expect-
ed to be required for the biomass liquefaction using tetralin in
comparison to phenol, glycerol or other polyhydroxyl alcohols,
therefore, liquefaction conditions might already overlap with
pyrolysis, whereas the absence of the chemically bonded
oxygen in this solvent avoids its removal in the hydrodeoxyge-
nation (HDO) step.[3] However, the hydro-treatment of bio-
mass-derived oils also requires temperatures above 300 8C,
high hydrogen pressure and the presence of a heterogeneous
[a] Dr. M. Grilc, Assist. Prof. Dr. B. Likozar, Prof. Dr. J. Levec
Laboratory of Catalysis and Chemical Reaction Engineering
National Institute of Chemistry
Hajdrihova 19, SI-1001 Ljubljana (Slovenia)
E-mail: blaz.likozar@ki.si
Supporting Information for this article is available on the WWW under
http://dx.doi.org/10.1002/cctc.201500840.
ChemCatChem 2016, 8, 180 – 191
sis and an innovative method for particle size distribution and
mean grain size determination by SEM image processing. A
new lumped kinetic model was developed according to the re-
action mechanisms, which contain wood de-polymerisation,
decarbonylation, decarboxylation and demethanation, tar
phase hydrodeoxygenation by molecular and in situ generated
hydrogen, as well as charring inhibition by free-radical stabili-
sation hydrogen transfer.
catalyst with an active phase (e.g., MoS2, WS2, Ni, Ru, Pt or Pd)
that is responsible for HDO and hydrogenation, whereas an
acidic support (Al2O3, SiO2, etc.) is responsible for bond cleav-
age, required for heteroatom removal and catalytic cracking re-
actions.[4] The addition of a hydrogen donor solvent is also de-
sirable to improve hydrogen transfer and stabilise free radicals
formed during catalytic cracking.[4a, 5] The similarity of the reac-
tion conditions for direct liquefaction and HDO, which include
the reaction temperatures in the range of 250–400 8C, elevated
hydrogen pressure and a beneficial influence of hydrogen
donor solvent, makes the integration of liquefaction processes
possible and presumably feasible. Rocha et al.[6] investigated
the solvent-free pyrolysis and HDO of cellulose under an ele-
vated H2 pressure in the single- and two-stage process by
using dispersed iron sulfide or the sulfide form of NiMo/Al2O3
and reported an increased semi-solid tar yield from 8 to
32 wt % by increasing the reaction temperature from 300 to
350 8C. A further temperature increase to 520 8C only affected
the char and gas yield, and the tar fraction remained more or
less unchanged.[6] Vasilakos and Austgen[2a] also investigated si-
multaneous cellulose liquefaction and HDO under H2 or an
inert atmosphere, and tetralin was used as a solvent. Oil-phase
yields as high as 52 wt % were reported without the use of
a catalyst, and the addition of Pd/Al2O3 increased the yield.
Little solid residue indicates that cellulose might not be re-
sponsible for potential char formation during the deoxylique-
faction of wood.[2a] The influence of temperature, pressure and
reaction time on the direct liquefaction of sawdust in tetralin
at an elevated hydrogen pressure but without a catalyst was
investigated by Wang et al. and Yan et al. in the temperature
range of 150–450 and 200–350 8C, respectively.[7] Araya et al. in-
vestigated the direct liquefaction of pine sawdust, cellulose
and lignin in tetralin using CoMo/Al2O3, Pt/Al2O3 and Raney Ni
180 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

catalysts and described the influence of feedstock, catalyst
type, solvent and atmosphere.[8] However, no reaction mecha-
nism or kinetic model was proposed as no temperature- or
time-dependent results were obtained. However, Beuchet et al.
used a mixture of lignocellulosic wastes and Raney Ni to inves-
tigate hydroliquefaction in tetralin under H2 pressure and pro-
posed a schematic pathway for hydroliquefaction that involves
two steps: non-catalytic solvolysis by thermal degradation of
biomass as the first, and the catalytic hydrogenation and HDO
enhanced by hydrogen transfer as the second step.[9]
In this work, the simultaneous biomass liquefaction and
hydro-treatment of LC biomass was investigated in hydrogen
donor solvents under an inert or H2 atmosphere in the pres-
ence of a typical HDO, hydrogenation or fluid catalytic cracking
(FCC) heterogeneous catalyst. The influence of the reaction
time, temperature, pressure, process gas, catalyst, wood and
solvent type on the yield and composition of products was es-
tablished and a new lumped kinetic model that considers LC
biomass liquefaction, decarboxylation, decarbonylation, HDO
and char formation was developed based on the reaction
mechanisms proposed from the experimental results.
Full Papers
According to the SEM image (Figure S1), zeolite Y comprises
uniform octahedral crystals with an edge length of 600–
800 nm. It exhibits a superior specific area because of its
micro-porosity and relatively high pore volume. However,
a high specific surface area determined by BET might not cor-
respond to the actual surface area available for reactions as
pores with a diameter below 10 æ might not be accessible for
the rather large molecules present in liquefied biomass. More-
over, micro-porous material might also be more sensitive to
physical deactivation because of pore plugging, which is quite
possible if a slurry bulk that contains the biomass particles and
real biomass-derived oils is processed. The actual reactive sur-
face area during the process is, therefore, expected to be
lower than that determined by the N2 physisorption method.
Biomass characterisation
The chemical and morphological characteristics of the dried
sawdust samples used in this study are presented in Table 2.
Table 2. Properties of biomass feedstock before LIQ-HT

Sample Elemental analysis GCV[b] d50[c] SBET[d]

Results and Discussion [wt %] [MJ kg¢1] [mm] [m2 g¢1]
C H S O[a]
Catalyst characterisation
[e]
Beech 48.1 6.4 0.16 45.3 17.9 31, 191 0.54, 0.28
The characteristics of the pre-treated catalysts, tested in this Fir 47.4 6.0 < LOD[f] 46.6 16.9 173 0.21
work, are summarised in Table 1. NiMo/Al2O3 is a typical bi- Oak 49.1 6.2 < LOD[f] 44.7 18.1 180 0.31
functional catalyst with heteroatom-removal and hydrocrack- [a] Calculated as balance. [b] Gross calorific value calculated using the
ing functionality. The tested catalyst type and off-site sulfide Dulong formula. [c] According to the particle size distribution determined
form pre-rendering method are the same as those used in the by SEM. [d] BET surface area. [e] Two particle size fractions of beech wood
were tested. [f] Limit of detection.
petrochemical industry, and hence, such a catalyst, with equal
performance and physical properties, which include metal
loading and specific surface area, is potentially available (and
feasible) for use on a larger scale. Pd/Al2O3 was chosen as a dis- Elemental analysis showed that all sawdust samples contained
tinct representative of hydrogenation catalysts in the petrole- relatively similar C, H and O amounts and possessed a compara-
um industry. NiMo/Al2O3 and Pd/Al2O3 are both alumina-sup- ble calorific value. The particle size distribution of the sawdust
ported meso-porous materials (the morphology of both mate- samples used in this work is shown in Figure 1, and the SEM
rials is depicted in Figure S1) with similar pore volumes, where- images of some representative sawdust particles are shown in
as the average pore diameter of the latter is somewhat higher. Figure S2. According to the analysis of 1039 fine beech saw-
This might be, along with the larger particle size, the main dust particles, the sample only contained biomass pieces (with
reason for the significantly lower specific surface area of Pd/ the minimal Feret diameter) smaller than 75 mm, whereas the
Al2O3 than that of NiMo/Al2O3. Zeolite Y represents the group other sawdust sample dimensions were significantly larger. To
of FCC catalysts. As it was used in a powder form, the SEM reduce the influence of the eventual mass transfer limitations
technique was used to approximate the crystal size. within the pores of the particles during liquefaction, most of

Table 1. Catalysts used for simultaneous liquefaction and hydro-treatment.

Catalyst Form[a] Pre-treatment Active phase SBET[b] VP[c] DP[d]

[wt %] [m2 g¢1] [cm3 g¢1] [æ]
NiMo/Al2O3 1 mm sulfide formation > 4.5 (NiS), > 22 (MoS2) > 200 > 0.40 < 100
Q
Pd/Al2O3 2–4 mm reduction 0.3 (Pd) 118 0.48 160
S
Zeolite Y 0.6–0.8 mm calcination 73 (SiO2), 24 (Al2O3) 549 0.26 9.4
P

[a] Q = quadri-lobe particles; S = spheres; P = powder. [b] BET surface area. [c] Pore volume. [d] Pore diameter.

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 Full Papers

Figure 1. Particle size distribution of a) fine beech, b) coarse beech, c) fir, and d) oak sawdust.

the experiments were performed by using the fine beech

wood powder with a median grain size (d50) of only 33 mm.
A small particle size and correspondingly high reactive sur-
face area is expected to have a crucial effect on the solid–
liquid reactions of liquefaction. For this reason the influence of
the wood type on the progress of the reactions involved in
the simultaneous liquefaction and hydro-treatment (LIQ-HT)
was investigated using the beech, fir and oak samples with
comparable particle size distributions and similar specific sur-
face areas.

Effect of the processing time

The influence of the process time on the reactions involved in
LIQ-HT was investigated by conducting the experiments with
the fine beech sawdust in tetralin for 30, 60 and 90 min at the
temperature of 350 8C, the hydrogen pressure of 5 MPa and
using the NiMo/Al2O3 catalyst. Biomass was to a great extent
already liquefied within the first 30 min at the plateau temper-
ature (Tp) to result in the formation of the polar tar phase in
the first step and its subsequent HDO in the second (Figure 2).
The amount of insoluble residue decreased to 21 wt % at
75 min (30 min after TP was reached) but it apparently con-
tained some char as the resulting solid powder was completely
black. The char content increased during the process time as
the solid residue content reached its minimal value of
0.17 wt % after … 60 min at Tp, whereas a longer hydro-process-
ing time caused its substantial increase. An increase of insolu-
ble residue content corresponded to the decrease of liquid
HDO products, which indicates that the hydrodeoxygenated
oil phase is the predominant precursor for char formation.
Figure 2. Experimental (symbols) and modelling (lines) results for the simul-
taneous direct liquefaction and hydrodeoxygenation of beech sawdust over
the sulfide form of NiMo/Al2O3 at 350 8C, heating rate of 7.5 K min¢1, total
pressure of 5 MPa, stirring speed of 500 rpm, sawdust-to-tetralin mass ratio
of 1:4 and catalyst-to-sawdust mass ratio of 0.10.
Gas formation (Figure 3) can be attributed to the biomass
de-polymerisation by either direct liquefaction or pyrolysis as
the rate of (CO2, CO and CH4) gas formation showed a straight-
forward proportional dependency on the time profile of the
unconverted wood content. CO and CO2 could also have been
formed from the oxygen-containing tar phase, but in that case,
their evolution rates would not be completely diminished after
100 min when the tar phase content is still relatively high. As
kinetic modelling could not have provided a satisfactory agree-
ment between the calculated and measured values, if we ac-
knowledge the latter reaction mechanism, it was concluded

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Figure 3. Experimental (symbols) and modelling (solid lines for best fit, and
dashed lines for 95 % confidence intervals) results for gas formation during
the simultaneous direct liquefaction and hydrodeoxygenation of beech saw-
dust over the sulfide form of NiMo/Al2O3 at 350 8C, heating rate of
7.5 K min¢1, total pressure of 5 MPa, stirring speed of 500 rpm, sawdust-to-
tetralin mass ratio of 1:4 and mass of catalyst divided by the initial mass of
sawdust of 0.10.
that solid sawdust is the main precursor for CO2, CO and CH4
formation. CO2 is the primary gaseous product that is formed,
which is advantageous in terms of deoxygenation and higher
product quality and yield, as two oxygen atoms are removed
by each gas molecule. The mass yields of CO and CH4 are 8.2
and 12.5 times lower, respectively, which is in relatively good
agreement with the non-catalysed runs reported by Beauchet
et al.[9]
The lumping reaction mechanism of the LIQ-HT in tetralin is
shown in Scheme 1 and was proposed according to the inter-
pretation of the experimental results. Sawdust de-polymeri-
sation results in gas (CO2, CO and CH4) and tar formation,
whereas the liquefied tar phase is further hydrodeoxygenated
to water and oil (liquid HDO products) by two possible hydro-
gen sources: tetralin and H2. The mechanism of the char for-
mation from the oil phase is explained in detail in the follow-
ing sections.
Scheme 1. Reaction mechanism of the simultaneous liquefaction and hydro-
treatment of lignocellulosic biomass.
Effect of the process temperature
The reaction temperature variation between 300 and 350 8C in-
fluenced the product distribution after 60 min for the fine
beech liquefaction and hydro-treatment in tetralin at various
(plateau) temperatures, a hydrogen pressure of 5 MPa and
using the sulfide form of the NiMo/Al2O3 catalyst (Figure 4). In
accordance with the Arrhenius law, the reaction rates of lique-
faction, HDO and gas and char formation increased with ele-
vating temperature; specifically, the solid- and tar-phase yields
decreased, whereas the fraction of gas-phase and HDO prod-
ucts increased noticeably at elevated temperatures.
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Full Papers
Figure 4. Influence of the plateau temperature on the product distribution
after 60 min of simultaneous liquefaction and HDO of fine beech sawdust in
tetralin under 5 MPa hydrogen pressure over the sulfide form of NiMo/Al2O3,
total hydrogen pressure of 5 MPa, heating rate of 7.5 K min¢1, stirring speed
of 500 rpm, sawdust-to-tetralin mass ratio of 1:4 and mass of catalyst divid-
ed by the initial mass of sawdust of 0.10.
By elevating the reaction temperature from 300 to 350 8C,
the rate of sawdust liquefaction apparently increased faster in
comparison to char formation as the cumulative yield of solid
residue decreased from 28 to 17 wt %, whereas the char con-
tent in the solid residue increased from 12 to 70 wt %. Even
though the increase of the reaction temperature resulted in
higher rates of biomass liquefaction, a lower fraction of tar
phase was obtained in the product because the HDO rates in-
crease even faster if we apply a higher temperature, which
thus consumes more of the tar phase and results in significant-
ly higher yields of the oil phase and water. The optimised reac-
tion rate constants (Table 3) confirm that Ea2 and Ea3 are signifi-
cantly higher than Ea1 (i.e., the reaction temperature has
a greater influence on HDO rate constants (k2 and k3) in com-
parison to that of liquefaction (k1)). The activation energies of
tar-phase HDO (Ea2 and Ea3) are in the same range as the activa-
tion energy reported for the catalytic HDO of the ¢OH group
in the liquefied biomass over NiMo/Al2O3 in our previous
work.[10]
Table 3. Activation energies and apparent reaction rate constants at
350 8C for LIQ-HT.
Reaction Ean [J mol¢1] kn(350 8C) [min¢1]
1 (4.3 œ 0.1) Õ 10 4
(3.34 œ 0.03) Õ 10¢2
2 (7.0 œ 0.8) Õ 104 (1.83 œ 0.02) Õ 10¢2
3 (7.9 œ 0.6) Õ 104 (1.24 œ 0.01) Õ 10¢2[a]
4 (1.5 œ 0.7) Õ 104 (3.1 œ 0.1) Õ 10¢2
4C n.a.[b] > 103
4T n.a.[b] (3.9 œ 0.2) Õ 10¢2 Õ k4T[c]
5 (5 œ 2) Õ 104 (7.8 œ 0.2) Õ 10¢3
6 (5 œ 1) Õ 104 (9.1 œ 0.9) Õ 10¢4
7 (7 œ 3) Õ 104 (7.0 œ 0.8) Õ 10¢4
[a] Actual unit is min¢1 bar¢0.3 as m = 0.3 (the value of 0.297 was deter-
mined by regression analysis). [b] Within the error of estimation for all
model predictions but determined as approximately the same for reac-
tions 4T and 4C. [c] Actual unit is min¢1 bar¢1.
183 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Full Papers
The influence of the reaction temperature on the particle
size distribution of the solid residue is shown in Figure 5. A
comparison with the particle size distribution of the feedstock
(Figure 1) shows that the mean grain size is reduced during
LIQ-HT at 300 8C from 33 to 21 mm, whereas an increase in the
reaction temperature leads not only to a lower mass of the res-
idue but also to a smaller mean grain size of only 16 mm. The
particle size distribution also shows that the largest particles of
fine beech sawdust (up to 75 mm) were reduced as well as the
biggest bits that remained in solid residue were approximately
two times smaller.
The Van Krevelen diagram (Figure 6) shows that the insolu-
ble residue obtained after simultaneous liquefaction and
hydro-treatment contained a significantly lower hydrogen and Figure 6. Van Krevelen diagram for the feedstock and insoluble residue ob-
especially oxygen content in comparison to the original feed- tained after LIQ-HT at noted temperatures under 5 MPa pressure and with
the NiMo/Al2O3 catalyst.
stock as the residue is located in the area of the diagram that
is characteristic for bituminous coal and biomass-derived char
obtained after pyrolysis.[11] The process temperature does not also agree quite well with the spectrum of commercially avail-
have a remarkable influence on the O/C ratio of the solid resi- able alkali lignin (Figure S3 a), and hence, it may be concluded
due, whereas it affects the dehydrogenation slightly as the H/C that char is formed during the LIQ-HT from the chemically un-
ratio is decreased as the temperature is increased. Diffuse re- stable compounds that constitute the oil phase. These compo-
flectance infrared Fourier transform (DRIFT) spectra (Support- nents are most probably the aromatics from lignin, as the
ing Information, Figure S3) also confirm that the chemical com- latter were reported to be responsible for char formation even
position of the solid residue differs from the input feedstock at significantly lower temperatures, although in the presence
and matches well to DRIFT spectra of the bio-char obtained by of hydrogen donor solvents.[3a]
Azargohar et al. during pyrolysis at 400–475 8C.[11b] The spectra

Figure 5. Particle size distribution of solid residue after 60 min of LIQ-HT at a) 300 8C and 5 MPa, b) 325 8C and 5 MPa, c) 350 8C and 5 MPa and d) 350 8C and
8 MPa.

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The mass balance for the carbon source distributed among
the LIQ-HT products for all three reaction temperatures is
shown in Table S1. Values are based on experimental data,
whereas the carbon content for the tar phase and HDO prod-
ucts was calculated by assuming the same elemental composi-
tion for the solid and de-polymerised biomass fraction, that is,
tar phase, and the stoichiometric reaction progression of tar-
based phase HDO as explained in the description of the kinetic
model. An increase of the temperature from 300 to 350 8C re-
sulted in a higher conversion of the carbon-based components
from the solid phase into HDO products, whereas the carbon
content of the undesired products (i.e., the sum of the gas
phase and solid residue) decreased at a higher temperature,
which confirmed that the operation at temperatures up to
350 8C can be considered to be feasible because the process
was still not considerably compromised with the (undesired)
conversion of the carbon energy carriers into the carbon-con-
taining side products in this range.
Effect of the process pressure and gas
A variation of the hydrogen pressure from 0 to 8 MPa had
a noteworthy influence on the course of the HDO and char for-
mation at 350 8C. Therefore, hydrogen pressure or its absence
affected char, tar and HDO product yields and ratio, and practi-
cally no effect on gas formation (Figure 7). There was also no
noticeable difference in the particle size distributions of solid
residues for the experiments performed at 5 or 8 MPa
(Figure 5).
Figure 7. Influence of process gas and hydrogen pressure on the product
distribution after 60 min of simultaneous liquefaction and HDO of fine
beech sawdust in tetralin at 350 8C with NiMo/Al2O3.
Molecular (gaseous) hydrogen and the hydrogen radicals
generated from tetralin are a possible hydrogen source for
HDO. Although it is well known that H2 can re-hydrogenate
naphthalene into tetralin and, therefore, enhance the HDO ac-
tivity of tetralin, those two mechanisms were considered inde-
pendent for the sake of dissimilarity, in which k2 governs the
HDO reaction with tetralin in the absence of molecular hydro-
gen, whereas reaction 3 controls the influence of H2 pressure
to enhance the HDO by reaction between tar and dissolved
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(and in turn dissociated) H2 on catalyst surface or also by im-
proving hydrogen transfer (the effect included implicitly in k3).
Further exposure of the deoxygenated oil phase to harsh
hydro-processing conditions causes the formation of free radi-
cals (reaction 4) as a result of C¢C or C¢H bond cleavage on
a catalyst surface. These free radicals seek a stabilisation route
among the competing possibilities and can be saturated by
hydrogen radicals (reaction 4T) released by the hydrogen
donor solvent assisted by a high hydrogen pressure, which
causes free radical stabilisation and prevents the recombina-
tion that leads to the undesired char formation (reac-
tion 4C).[2, 12]
The experiment under N2 revealed the rate of the HDO dic-
tated by the hydrogen radicals from tetralin in the absence H2 ;
HDO was slow and only comparable to the reaction at 300 8C
under 5 MPa of H2, whereas the lack of H2 lowered the selectiv-
ity towards free-radical stabilisation in comparison to re-combi-
nation, and hence, the apparent rate of char formation was
high despite a significantly lower presence of oil phase (the
precursor for char). However, the char yield was still nearly two
times lower with respect to the non-catalytic reaction at 350 8C
by using a hydrocarbon solvent without the hydrogen donor
activity reported by Schwaiger et al.[13] The reactions under
only 2 MPa H2 showed a considerably increased overall HDO
rate (in comparison to the reactions performed under N2),
which resulted in a three-times lower yield of tar and a notably
higher yield of HDO products. A subsequent increase of the H2
pressure has a direct effect on the HDO rate (reaction 4); spe-
cifically, the reaction order with respect to H2 pressure was de-
termined to be 0.3 according to regression analysis. The influ-
ence of H2 pressure to prevent char (solid phase) formation is
seen clearly in Figure 7 and this aspect is described well by the
kinetic model. Operation in the absence of H2 led to a carbon-
rich solid phase as a result of char formation and nearly a two-
times lower conversion of the carbon source into the HDO
products in comparison to the reaction under the H2 atmos-
phere within the same time period, whereas the gas-phase
yield was not affected significantly (Table S1).
Experiments at various pressures of H2 or its absence
showed no significant effect on the gas formation rate or se-
lectivity. This indicates that decarboxylation (DCX) and decar-
bonylation (DCN) reactions can be considered mainly as the
side reactions of the thermal de-polymerisation (liquid-phase
pyrolysis) of solid biomass (clearly also independent of H2 pres-
sure) rather than the oxygen-containing tar phase deoxygena-
tion reactions. In the latter case, DCX and DCN reactions would
compete against catalytic HDO, and therefore, a variable H2
pressure or its absence would affect HDO/DCX and HDO/DCN
selectivity significantly, and consequently, the CO and CO2
yields, which was not the case. Nevertheless, the DCX and DCN
of the tar-based phase cannot be excluded completely, but
this mechanism was clearly not dominant for CO and CO2 for-
mation in this work. Our results are in accordance with the
work of Wang et al. who reported a negligible effect (even
with a negative trend) of the elevated H2 pressure on the gas
formation during the sawdust decomposition process in tetra-
lin without any heterogeneous catalyst.[7a]
185 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Effect of the catalyst type
The effect of the catalyst type on the product distribution is
shown in Figure 8. Experiments were conducted in tetralin at
Figure 8. Influence of catalyst type on the product distribution after 60 min
of simultaneous liquefaction and HDO of fine beech sawdust in tetralin at
350 8C, and under 5 MPa of H2 pressure.
350 8C for 60 min under 5 MPa of H2 with a catalyst loading of
10 wt % with regard to the mass of fine beech sawdust.
Among all reactions involved in LIQ-HT, the catalyst type af-
fects only the rates of HDO and cracking, whereas gas forma-
tion is completely independent (Figure S4). The gas yield and
CO/CO2 ratio also corresponded well to the non-catalysed bio-
mass liquefaction in tetralin reported by Wang et al.,[7a] which
confirms that gas formation can be attributed predominantly
to the thermal de-polymerisation of biomass and not to the re-
actions promoted by heterogeneous catalysts. Therefore, the
presence of these catalysts neither promotes nor inhibits CO2
or CO formation as the probability of the precursor (biomass
particles) to be in physical contact with the catalyst surface is
insignificant. However, the catalyst type had some influence on
CH4 yield (Figure S4), which was the highest (but still as low as
1.5 wt %) if the HDO catalyst NiMo/Al2O3 was used and the
lowest with zeolite Y with no HDO active sites. The difference
in CH4 yield might be caused by the HDO of components such
as methanol, formaldehyde, formic acid, methyl ethers or
esters or methane formation from CO and CO2 as suggested
by Beauchet et al. who measured a similar selectivity for CO2,
CO and CH4 in the non-catalysed process at 330 8C but pointed
out that the presence of Raney Ni had a significant effect on
the selectivity of gas formation (CH4 selectivity increased from
a few to nearly 50 %) but not on the global yield as a result of
methane formation from the evolving CO and CO2 gases and
not hydrogenolysis.[9] The catalysts tested in this work were
clearly much less active for the methane formation reactions.
As the catalysts primarily only promoted HDO reactions, it is
of no surprise that the highest yield of HDO products was ob-
tained by NiMo/Al2O3, a catalyst developed for hydro-treat-
ment. Zeolite Y showed an insignificant HDO activity, and con-
sequently, the yield of the polar tar phase was the highest and
that of the HDO products was the lowest. Zeolite Y was also
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Full Papers
tested in a mixture with the same mass of NiMo/Al2O3 to eval-
uate whether a synergetic effect of the catalytic cracking and
HDO can cause a lower amount of insoluble residue, yet this
was not the case. Pd/Al2O3 showed some HDO activity; never-
theless, it was significantly lower in comparison to that of
NiMo/Al2O3. Although HDO activity could have been included
in the kinetic model for each catalyst individually, additional
experiments would have been required to obtain reliable ki-
netic parameters (i.e., activation energy).
Effect of the biomass type and granulation
The influence of the wood type with respect to the product
yield and distribution was investigated by using oak, fir and
coarse beech sawdust, which all had a relatively similar particle
size distribution and specific surface area, and the effect of par-
ticle size was evaluated by comparing the fine and coarse
beech sawdust LIQ-HT in tetralin at 350 8C under 5 MPa H2 and
with the NiMo/Al2O3 catalyst.
Clearly, the particle size distribution affected the rate of liq-
uefaction as the higher yields of solid and tar phase reveal that
the liquefaction of biomass is still taking place after 60 min if
coarse beech sawdust is used (in comparison to the fine beech
counterpart; Figure 9). A nearly two-times lower specific sur-
Figure 9. Influence of wood type and its particle size on the product distri-
bution after 60 min of simultaneous liquefaction and HDO in tetralin at
350 8C under 5 MPa of H2 pressure with NiMo/Al2O3.
face area of coarse beech sawdust in comparison to the finer
fraction affects the rate of the solid–liquid interface reaction of
liquefaction directly. A lower biomass conversion is also reflect-
ed in a decreased yield of HDO products, although the experi-
mental content values for tar and HDO products might not be
very precise as a result of fractionating (method), whereas the
absolute experimental errors for the solid- and gas-phase
yields are expected to be much lower (below 2 wt %).
A very similar conversion of sawdust into HDO products was
obtained with the use of fine beech, coarse oak and fir saw-
dust (Figure 9). In contrast to catalyst or H2 pressure variation,
a difference in wood type had little, but still noticeable, effect
on the gas-phase composition formed during the LIQ-HT in
tetralin, which proves once again that gas was formed directly
186 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 10. Influence of sawdust type and reaction temperature on the gas-
phase composition in the reactor at a particular time (other characteristics
noted in the caption of Figure 9).
from biomass during the non-catalytic thermal de-polymeri-
sation (Figure 10). The differences in the gas-phase composi-
tion were probably low because of the similar cellulose, hemi-
cellulose and lignin content in the tested wood samples. In the
LIQ-HT of the pure lignin in tetralin at 400 8C under H2 pressure
and in the presence of CoMo/Al2O3, Araya et al. reported
a 2.5 times lower gas yield in comparison to pure cellulose,
whereas the selectivity towards gaseous hydrocarbons was
50.3 wt % for lignin and only 15.3 wt % for cellulose.[8]
Effect of the solvent
The influence of the solvent type was compared directly in
terms of solid residue as the solubility of de-polymerised or hy-
drodeoxygenated components in solvents is significantly differ-
ent for non-polar tetralin, semi-polar phenol and polar glycer-
ol; in addition, CO and CO2 can also be formed from an
oxygen-containing solvent. Liquefaction in glycerol is slower in
comparison to that in tetralin, whereas the addition of a homo-
geneous acidic catalyst (p-toluenesulfonic acid; p-TSA) im-
proves liquefaction significantly as the remaining solid residue
was only 1 wt % of the initial sawdust mass (Figure S5). The
acidic nature of phenol does not require an additional homo-
geneous catalyst for a relatively high biomass conversion, and
the amount of gases formed is lower in comparison to that in
the reaction with tetralin, which is mostly in the form of CO2.
Therefore, the formed gases result from biomass decomposi-
tion and not from the phenolic hydroxyl group. In contrast,
the use of glycerol results in extensive gas formation, which is
more than that generated from the decarboxylation and decar-
bonylation of the solvent. A higher liquefaction activity of the
ChemCatChem 2016, 8, 180 – 191 www.chemcatchem.org
Full Papers
acidified polyol in comparison to phenol and especially tetralin
is in accordance with previous reports.[3b]
The progression of solvolysis and HDO in glycerol can be fol-
lowed by the FTIR spectroscopy of liquid samples as the prod-
ucts of biomass de-polymerisation were soluble in the liquid
phase. The FTIR spectra shown in Figure 11 correspond to the
Figure 11. FTIR spectra of the liquid phase during LIQ-HDO in glycerol and
glycerol, acidified by p-TSA, at 350 8C and 5 MPa hydrogen pressure over
NiMo/Al2O3.
mechanism of the biomass solvolysis by polyhydroxyl alcohols
reported previously,[14] in which the glycoside bond of cellulose
or hemicellulose is de-polymerised followed by furanose or
pyranose ring opening and the formation of levulinates with
the characteristic peaks located at ñ = 1715–1720 cm¢1, where-
as carbonyl groups conjugated to aromatic rings showed char-
acteristic signals at ñ = 1640 cm¢1. Evidence of deoxygenation
is also noticeable in the spectra shown in Figure 11 by the di-
minishing areas of the peaks at ñ = 3300 and 1040–1117 cm¢1
that represent O¢H and C¢O groups, respectively. The FTIR
spectra of liquid-phase samples collected during LIQ-HT with
the use of phenol or especially tetralin do not reveal much in-
formation about the reactions for two reasons: i) an intense
signal of aromatics masks the FTIR spectra and ii) the insolubili-
ty of the polar tar phase in non-polar tetralin causes most of
the polar phase to be adsorbed physically or chemically on the
solid residue, polar alumina or zeolite, and only the completely
deoxygenated components have a low enough polarity to be
extracted by a non-polar solvent; however, the C¢C and C¢H
signals of those components are clearly not dominant enough
to be seen in the spectra or are masked by the C¢C and C¢H
signal of the solvent (Figure S6).
Conclusions
Simultaneous direct liquefaction and hydrodeoxygenation of
lignocellulosic biomass in hydrogen donor solvents involves
several reaction steps, which include biomass de-polymeri-
sation, decarboxylation or decarbonylation, char formation and
hydrodeoxygenation (HDO), governed by hydrogen supplied
in gaseous form or generated in situ. A reaction mechanism
was proposed, and a new lumped kinetic model was devel-
187 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

oped according to the results obtained by varying the reaction
time, temperature, pressure, process gas, catalyst type, wood
type and solvent. Temperature affected all of the investigated
reactions according to the Arrhenius law, and a temperature
increase from 300 to 350 8C resulted in an approximately
2.5 times higher yield of HDO products, whereas the mass of
solid residue decreased by 39 %. The significantly higher activa-
tion energy of the HDO reactions in comparison to biomass
liquefaction caused the lower yields of the tar phase at higher
temperatures, for which the latter is the product of liquefac-
tion and the precursor for HDO, as well as higher correspond-
ing oil yields. However, an increase of the temperature to over
350 8C might result in lower oil yields because of char forma-
tion, especially at reaction times longer than 60 min. This study
also showed that hydrogen pressure affected the HDO rate
positively (with an apparent reaction order of 0.3) and it also
inhibited char formation considerably, presumably by saturat-
ing the free radicals formed during catalytic cracking, and thus
prevented their polymerisation. As the formation of the polar
tar and gas phase is a process caused by the thermal degrada-
tion and de-polymerisation of lignocellulosic biomass, the cata-
lyst type did not affect the rate of tar formation and the com-
position of the latter, whereas it has a considerable effect on
HDO, and hence the highest oil and the lowest tar yields were
obtained by using the sulfide form of NiMo/Al2O3 followed by
Pd/Al2O3, which also showed some HDO activity. The insignifi-
cant HDO activity of zeolite Y resulted in the highest solid-
phase conversion and tar-phase yield, whereas the fraction of
HDO products was the lowest. As already mentioned in the lit-
erature and confirmed in this study, there are other solvents
available for the even more efficient biomass liquefaction and
further hydro-processing in comparison to rather expensive
tetralin; nonetheless, most of them contain the undesired
chemically bonded oxygen atom that reduces the gross calorif-
ic value of the resulting product and its applicability and po-
tential use as a transportation fuel.
Experimental Section
Catalyst activation and characterisation
Three catalyst types that are used commonly on an industrial scale
were tested in this study (Table 1). Commercially available NiMo/
Al2O3 (quadri-lobe-shaped) catalyst was received in oxide form and
was sent to Eurecat France (La Voulte-sur-Rhúne, France) for the
sulfide form rendition by the Totsucat process using H2S/H2 sulfide
agent. Palladium supported on 2–4 mm Al2O3 spheres (G-68 C,
Sìd-Chemie, Munich, Germany), was dried under N2 at 250 8C for
60 min and reduced subsequently under 500 mL min¢1 H2 flow in
a tube furnace before use. The initial reduction temperature was
set to 150 8C and kept constant for 1 h followed by gradual heat-
ing (0.25 K min¢1) to 350 8C, at which the Pd-containing catalyst
was reduced for an additional 7 h. Zeolite Y (CBV 300, Zeolyst, Con-
shohocken, PA, USA) was used in powder form and was activated
by calcination in air by using a ventilated furnace at 500 8C for 5 h
to substitute ammonium cations with H+.
The specific surface area of the catalysts (as well as sawdust sam-
ples) was determined by the BET N2 physisorption method by
using an ASAP 2020 (Micrometrics, Norcross, GA, USA) instrument.
ChemCatChem 2016, 8, 180 – 191 www.chemcatchem.org
Full Papers
The total pore volume was determined by estimating the amount
of N2 adsorbed at the relative pressure (P/P0) of 0.95, and the Hor-
vath–Kawazoe method was used to determine the pore size and
pore volume determination for micro-porous zeolite Y. Information
about the catalyst compositions is given according to the data pro-
vided by the suppliers.
Materials
Sawdust samples from debarked European beech (Fagus sylvatica),
European silver fir (Abies alba) and sessile oak (Quercus petrea) cut
down in the forests near Postojna, Slovenia (458 41’ N, 148 12’ E)
were dried on a metal tray (the layer thickness below 3 mm) at
80 8C under a N2 flow for 24 h and kept in a desiccator at RT
before use. Two different particle size fractions of European beech
were tested. The dried wood samples were characterised by field
emission scanning electron microscopy (FE-SEM), BET, DRIFTS and
Pregl–Dumas (CHNS-O) methods.
All solvents and gases were obtained from commercial suppliers.
Tetralin (Š 97 wt %), phenol (Š 99 wt %) and p-toluenesulfonic acid
(Š 98 wt %) were from Sigma–Aldrich (St. Louis, MO, USA). Glycerol
(Š 99 wt %) was from Pharmachem Sušnik (Ljubljana, Slovenia). H2
(5.0) and N2 (5.0) were from Messer (Bad Soden am Taunus, Germa-
ny).
Simultaneous liquefaction and hydro-treatment
The simultaneous liquefaction and catalytic hydro-treatment of
sawdust was investigated by using a 300 mL cylindrical stainless-
steel slurry reactor (Parker Autoclave Engineers, Erie, PA, USA). The
same reactor configuration was used as reported previously,[4b, c] in
which further details about the experimental setup can be found
(Figure S7).
The reaction mixture contained a dried sawdust sample (20 g) and
a solvent (tetralin, phenol or glycerol) in a 1:4 mass ratio, and the
catalyst mass (after activation) was set to 10 wt % with regard to
the initial mass of dry wood. After the reactor vessel was attached
to its casing, the headspace was pressurised and depressurised
with H2 (or N2 if it was used as the process gas) twice to displace
air before the final pressure was set to 2, 5 or 8 MPa at a constant
gas flow through the reactor (1000 mLN min¢1). The reactor was op-
erated in a batch regime if we consider the solid and liquid phase,
and a continuous H2 flow was established to ensure sufficient and
constant H2 availability throughout the process and to enable
online gas-phase analysis. The agitation speed was set to
500 min¢1, and the reactor content was heated (7.5 K min¢1) to the
desired temperature (300, 325 or 350 8C), which was kept constant
for 60 min except if noted otherwise, followed by H2 supply shut-
down and rapid reactor cooling below 30 8C. After depressurisa-
tion, the reactor was flushed with N2, opened and weighed.
Gas-, liquid- and solid-phase analysis
The cooled and decompressed gas from the reactor was analysed
on-line by FTIR spectroscopy (Spectrum 100, PerkinElmer, Waltham,
MA, USA) in the range of 450–4000 cm¢1, and the detected compo-
nents were quantified. Six liquid samples of 0.5 mL were with-
drawn and stored during the LIQ-HT experiments, subsequently ap-
plied to a silicon wafer and analysed off-line. Liquid- and gas-phase
analyses, as well as the component or functional group quantifica-
188 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

tion methodology by FTIR is described in detail in our previous
studies.[4a, 10]
After each run with tetralin, the LIQ-HT products were determined
and quantified according to the sequence shown in Scheme 2. The
liquid phase was separated from the solid and tar counterparts by
Scheme 2. Separation and analysis of LIQ-HT products.
filtration, and the reactor vessel and filter cake were rinsed with
toluene several times; subsequently, the residue (insoluble in non-
polar solvent) was dried at 110 8C overnight (16 h) and weighed,
and the filtrate, which contained solvent and the oil phase, was
centrifuged for 10 min at 7500 rpm and examined visually for the
potential presence of a polar phase. Polar tarry components (T)
were extracted from the filter cake with absolute ethanol. The in-
soluble residue (S) and solid catalyst were separated from the dilut-
ed tar phase by two-step filtration (0.8 mm mesh to separate cata-
lyst particles and a black ribbon filter paper for the remaining solid
phase), rinsed thoroughly with absolute ethanol, and dried over-
night (16 h) at 80 8C. If the catalyst could not be separated from
the insoluble residue (i.e., if zeolite powder was used), the mass of
the latter was calculated by the subtraction of the initial catalyst
mass from the mass of the dried filter cake after extraction
[Eqs. (1)–(5)].
wS ¼ mS =m0 ð1Þ
wT ¼ mT =m0 ð2Þ
X
L dwCO2 ðtÞ
wG ¼ mG =m0 ¼ ðni ¡ Mi Þ=m0 ð3Þ
l¼1
wHDO ¼ 1¢wS ¢wT ¢w G ð4Þ
wOIL ¼ wHDO ¢wH2 O ¼ wHDO ¢mH2 O =m0 ð5Þ
The yield of solid residue (wS) or tar phase (wT) was calculated by
dividing the mass of the solid residue (mS) or tar phase (mT) by the
initial mass of sawdust (m0). The yield and mass of the formed per-
manent gases (wG and mG) was calculated according to the on-line
analysis of the main components (l), in which L is their number, de-
tected in the gas phase during reactions and depressurisation. If
we consider that the tar phase is the main product of liquefaction
and that it is subsequently hydrodeoxygenated, then the HDO
product yield (wHDO) can be calculated as the balance [Eq. (4)], and
this fraction contains the completely deoxygenated oil phase (mOIL)
dissolved in a non-polar solvent (only C¢H and C¢C bonds were
present in the liquid phase after the HDO with tetralin as the sol-
vent) and water (mH2 O ) [Eq. (5)] that is separated from the gas
phase and collected in a condenser.
The particle size distribution for all sawdust samples (and the solid
residue after reactions) was determined by FE-SEM (SUPRA 35 VP,
Carl Zeiss, Jena, Germany) operated at a high acceleration voltage
(20 kV) to ensure a sufficient contrast of bright (non-conductive)
ChemCatChem 2016, 8, 180 – 191 www.chemcatchem.org
Full Papers
wood particles spread over dark (conductive) graphite tape. The
particle sizes were subsequently determined by using image pro-
cessing and analysis software (ImageJ, Bethesda, MA, USA), in
which 400–1000 particles were digitally characterised in the SEM
images for each sample. The minimal Feret diameter was consid-
ered as the most relevant particle characteristic to simulate sieve
analysis, and we assumed that the observed particles are isotropic
and similar to the solid of revolution obtained by rotating the par-
ticles’ 2 D projection around the Feret axis. The solid of revolution,
the 2 D projection of which has a minimal Feret diameter lower
than the mesh opening, can theoretically pass through the respec-
tive sieve.
The FTIR spectra of sawdust and insoluble residue were recorded
using the DRIFTS method by averaging 16 scans with the resolu-
tion of 4 cm¢1 by using a DiffusIR (Pike Technologies, Madison, WI,
USA) environmental chamber flushed with nitrogen installed in the
spectrometer. The KBr background was recorded before the solid
samples were diluted with KBr in a 1:2 mass ratio, placed in
a sample cup (10 mm diameter, 2.3 mm deep) and analysed. The
elemental (CHNS-O) composition of insoluble residue was deter-
mined by the Pregl–Dumas method by using a vario EL cube (Ele-
mentar, Hanau, Germany) analyser.
Kinetic model of simultaneous liquefaction and hydro-treat-
ment in tetralin
The lumped kinetic model was based on the reaction mechanism
(Scheme 1) developed according to the experimental results and
modelling responses for various reaction pathways.
The reaction mechanism includes the reactions of liquefaction and
liquid-phase pyrolysis to partly de-polymerised lignocellulosic
macro-molecules (k1), accompanied by gas formation (k6–k8), which
became extensive if temperatures exceeded 280 8C [Eqs. (6)–(10)].
dww ðtÞ
¼ ¢k1 ¡ ww ðtÞ¢k 5 ¡ ww ðtÞ¢k 6 ¡ ww ðtÞ¢k7 ¡ w w ðtÞ ð6Þ
dt
¼ k 5 ¡ ww ðtÞ ð7Þ
dt
dwCO ðtÞ
¼ k 6 ¡ w w ðtÞ ð8Þ
dt
dwCH4 ðtÞ
¼ k 7 ¡ ww ðtÞ ð9Þ
dt
w G ðtÞ ¼ wCO2 ðtÞ þ wCO ðtÞ þ w CH4 ðtÞ ð10Þ
The hydrodeoxygenation of the liquefied (tarlike) biomass phase
proceeded through two different mechanisms: i) transfer hydro-
(deoxy)genation caused by the hydrogen radicals formed by tetra-
lin (extent of this effect being determined by the reaction under N2
pressure) and ii) hydrogenolysis caused by H2. The experiments at
different hydrogen pressures (PH2 ) showed that its impact on reac-
tion rate was lower than that encompassed by the reaction order
of unity; therefore, the reaction order (m) with respect to pressure
was determined by regression analysis [Eq. (11)].
dwT ðtÞ
¼ k1 ¡ ww ðtÞ¢k2 ¡ wT ðtÞ¢k3 ¡ wT ðtÞ ¡ Pm ð11Þ
dt H2
During HDO, water and the deoxygenated oil phase were consid-
ered to be formed in the mass ratio of 2:3 according to the gener-
alised stoichiometry. If we assumed that the de-polymerised tar
189 Ó 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

phase had the same elemental composition as sawdust, the stoi-
chiometric ratio of 0.417:0.583 was determined for the hydrodeox-
ygenation of the treated feedstock. Water-to-oil mass ratios be-
tween 0.40:0.60 and 0.45:0.55 were tested, and it was determined
that the latter also allowed for the carbon and oxygen mass bal-
ance closure for the LIQ-HDO process. As a result of the experi-
mental uncertainty and non-ideal stoichiometry of actual deoxyge-
nation reactions, this ratio can only be given as accurately as
0.4:0.6, whereas the balances for water and oil may thus be formu-
lated as according to Equations (12) and (13).
dwH2 O ðtÞ
¼ 0:4 ¡ ðk2 ¡ w T ðtÞ þ k3 ¡ wT ðtÞ ¡ Pm Þ
dt H 2
dwOIL ðtÞ
¼ 0:6 ¡ ðk2 ¡ wT ðtÞ þ k 3 ¡ wT ðtÞ ¡ Pm Þ¢k4 ¡ wOIL ðtÞþ
dt H 2
ðk4T ¡ PH2 Þ ¡ w OIL*
Char formation is triggered by the free radical (OIL*) formation (re-
action 4) after the compounds that constitute oil are cracked on
acidic catalyst support. Free radicals can either re-combine to form
high-molecular-weight compounds (char; reaction 4C) or can be
stabilised by a radical scavenger that saturates free radicals and
prevents the re-combination [reaction 4T; Eqs. (14) and (15)].
dwOIL* ðtÞ
¼ k4 ¡ wOIL ðtÞ¢k 4C ¡ w OIL* ðtÞ¢ðk 4T ¡ PH2 Þ ¡ w OIL* ðtÞ
dt
dwCHAR ðtÞ
¼ k4C ¡ w OIL* ðtÞ
dt
The rates of the reactions between free radicals (reaction 4T and
4C) are orders of magnitude higher than the rate of free radicals
formation (reaction 4), therefore, the following applies: i) The con-
centration of free radicals is negligible. ii) The constant k4 is the
rate-determining step parameter for charring, and the k4C/(k4T·PH2 +
k4C) and k4T·PH2 /(k4T·PH2 + k4C) ratios determine the selectivity to-
wards either char formation or radical stabilisation. In this work,
the selectivity was considered to be temperature independent as
indicated by the measured data. As the experimental results
showed a positive influence of higher hydrogen pressure to pre-
vent char formation, the effect of hydrogen pressure (PH2 ) was also
considered in the respective backward reaction.
This simplified the balance for oil and char and eliminated the bal-
ance for free radicals [OIL*; Eqs. (16)–(18)].
dwOIL ðtÞ
¼ 0:6 ¡ ðk2 ¡ wT ðtÞ þ k 3 ¡ wT ðtÞ ¡ Pm Þ¢
dt H2
k4 ¡ ðk 4C =ðk4T ¡ PH2 þ k4C ÞÞ ¡ wOIL ðtÞ
dwCHAR ðtÞ
¼ k4 ¡ ðk4C =ðk4T ¡ PH2 þ k4C ÞÞ ¡ wOIL ðtÞ
dt
wS ðtÞ ¼ w W ðtÞþwCHAR ðtÞ
Apparent reaction rate constants were for the corresponding tem-
perature at each time increment calculated according to the modi-
fied Arrhenius equation [Eq. (19)]:
  ŒŒ
E 1 1
k n ðTðtÞÞ ¼ k n ðT P Þ ¡ exp ¢ a n ¢ ð19Þ
R TðtÞ T P
in which kn(TP) is the apparent rate constant for reaction n at the
temperature of 623 K (TP), which was chosen as the temperature of
plateau set for the most of experiments. The Arrhenius equation
ChemCatChem 2016, 8, 180 – 191 www.chemcatchem.org
Full Papers
was modified to minimise the mutual correlation between the acti-
vation energy and pre-exponential factor during regression analy-
sis.
Regression analysis and modelling in general was performed by
using Matlab 7.12.0. For optimisation purposes, the Nelder–Mead
method was applied for the initial optimisation of the apparent re-
action rate constants followed by the Levenberg–Marquardt
method for the final Ean and kn(TP) optimisation [the minimisation
of the objective function given by Eq. (20)] and the Jacobian
matrix computation required for the subsequent determination of
the 95 % confidence intervals for non-linear least squares kinetic
ð12Þ parameter estimation.
f ðE a1 ,k1 ðT p Þ, . . . ,E a7 ,k 7 ðT p Þ,k4C =k4T , mÞ ¼
ð13Þ
X
J XI
ðwi,j meas ¢w i,j calc ðE a1 ,k1 ðT P Þ, . . . ,E a7 ,k 7 ðT P Þ,k4C =k4T , mÞÞ2
j¼1 i¼1
ð20Þ
The measured mass yields (wi,jmeas) of each component i (I is their
number) were fitted to modelled values (wi,jcalc) simultaneously for
all LIQ-HT runs (j; J is their number) that were included in model-
ling study to obtain the apparent kinetic parameters for liquefac-
tion, HDO, char and gas formation during the LIQ-HT of beech
ð14Þ wood in tetralin over NiMo/Al2O3.
ð15Þ
Acknowledgements
The authors gratefully acknowledge the financial support of the
Slovenian Research Agency (ARRS) through the Programme P2-
0152. The authors also acknowledge Gozdno Gospodarstvo Post-
ojna for wood samples and Eva Kovič for her excellent laboratory
work. Special thanks go to Eurecat for the catalyst sulfide from
rendition by the Totsucat process.
Keywords: biomass · kinetics · reaction mechanisms ·
solvolysis · supported catalysts
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