Fuel 254 (2019) 115689

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Renewable antioxidant additive for biodiesel obtained from black liquor T

a a a b b
Jean-Michel Lavoie , Thierry Ghislain , Emmanuelle Bahl , Jesús Arauzo , Alberto Gonzalo ,
⁎
Noemí Gil-Lalagunab, José Luis Sánchezb,
a
Biomass Technology Laboratory (BTL), Université de Sherbrooke, Centre de mise à l’échelle – CME, 3000 Boul. de l'Université (P3 pavillon), Sherbrooke, Québec J1K
0A5, Canada
b
Thermochemical Research Group (GPT), Aragón Institute of Engineering Research, University of Zaragoza, Mariano Esquillor s/n, 50018 Zaragoza, Spain

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

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

Keywords: Black liquor obtained from semichemical pulping of barley straw was depolymerized in a stirred autoclave
Black liquor reactor, at temperature in the range of 250–300 °C while varying the amount of catalyst (zeolite Y). Three
Lignin fractions were obtained from the depolymerized liquor: a fraction directly extracted from the liquid with iso-
Depolymerization propyl acetate (Lα), a second one which contains the heaviest compounds precipitated from the liquid at pH 1
Biodiesel
(Lβ) and a third one obtained by extraction of the acidified liquid (Lγ). The three fractions were tested as
Antioxidants
antioxidant additives for biodiesel, blending them individually at a dosage of 1 wt%. The antioxidant activity
was Lα > Lγ > Lβ. The Lα fraction showed the highest antioxidant activity, increasing the oxidation stability
time over neat biodiesel from 150 to 250%. The phenolic volatile content of the fractions (measured by GC/MS)
decreased in the same rank (Lα > Lγ > Lβ), so there doesn’t seem to be correlation between the volatile
content and the increase of antioxidant activity. Depolymerizarion temperature was the most influential para-
meter, showing a clear positive effect on the antioxidant activity for the three fractions.

1. Introduction chemical functional groups in lignin. Monomers, heterogeneous in

Lignin is often referred to as a valuable source of renewable phe-
nolic compounds, although its valorization is difficult due to its com-
plex structure, involving different types of bonds [1]. The hydroxyl,
methoxyl, carbonyl and carboxyl groups are the most important
nature, are mainly linked via two types of linkages: condensed linkages
(e.g., 5–5 and β-1 linkages) and ether linkages (e.g., α-O-4 and β-O-4).
Many different technologies have been studied and implemented in
order to cleave these stable bonds and obtain useful products [2], such
as pyrolysis [3], gasification [4], oxidation [5], hydrothermal treatment

⁎
Corresponding author.
E-mail address: jlsance@unizar.es (J.L. Sánchez).

https://doi.org/10.1016/j.fuel.2019.115689
Received 20 February 2019; Received in revised form 22 May 2019; Accepted 20 June 2019
Available online 01 July 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
J.-M. Lavoie, et al.
[6], or ionic liquids-assisted depolymerization [7], to name a few.
In this work, the valorization of semichemical pulping black liquor
from straw was investigated. Black liquor (BL), a by-product from the
pulp and paper industry, could represent a significant source of lignin,
as it comes from a mature industry and it is readily available [8]. Straw
is a residue that can represent a feedstock for the pulp and paper in-
dustry, especially for the boardmaking industry [9] using a semi-
chemical process, where only sodium hydroxide would be used as re-
agent. BL contains dissolved lignin, hemicelluloses and mineral
components from the straw, as well as the cooking chemicals. The re-
covery of straw BL cannot be accomplished using the same combustion
process as wood kraft BL mainly due to its silica content, which causes
high viscosity and fouling problems in evaporators and burning
chambers [10]. Nevertheless, in spite of BL management issues, the use
of this kind of raw materials (straw) in the boardmaking industry is still
justified because of the improvement of mechanical properties related
to the use of cellulose from such raw materials, making it possible to
reduce or eliminate the use of additives, as starch. The latter is added to
the paper to enhance the mechanical properties needed for cardboard
production [11,12].
The water content in the “as produced” BL is very high, thus its
direct treatment (benefiting from water content) has some advantages,
such as avoiding an energy-costly predrying step required, for example,
in a combustion process. Developing other direct valorization processes
different from combustion could avoid the release of S and N (if pre-
sent) to the atmosphere, without forgetting the potential of water to act
as a hydrogen source [6,13]. Moreover, as is the case of semichemical
BL, sodium hydroxide, which is a base catalyst for lignin depolymer-
ization [14,15], is already present. The depolymerization of lignin has
also been studied with a wide range of catalysts, as Fe limonite [16], Ni
Raney [17,18], or noble metals as Ru [19] or Pt [20,21]. Less frequent
is the use of acidic catalysts as zeolites, as in the works developed by
Deepa & Dhepe [22,23] and Chaudhary & Dhepe [24].
Lignin depolymerization aims at producing aromatic (phenolic)
chemicals in a sustainable way. Phenolic compounds are commonly
used as antioxidants for biodiesel [25], as oxidation is a radical driven
reaction [26] and phenolic compounds can release a H radical that
quenches the oxidation pathway. Based on previous works, the use of
lignin-derived fractions from bio oil increases the oxidation stability of
biodiesel [27–29]. Recent works point out at the role of different phe-
nolic compounds of bio oil on the increase of biodiesel oxidation sta-
bility [30,31]. In these works, the authors have identified the presence
of phenolic dimers, which seems to be responsible for the enhancement
of these properties.
Thus, the objective of this work is to study the hydrothermal
treatment of straw semichemical black liquor and the application of the
obtained lignin fractions as antioxidant additive. With this aim, the
effects of reaction temperature and catalyst addition (zeolite) were in-
vestigated. Reactions were performed in a stirred batch reactor, and
product distribution and characteristics were investigated as well.
Extracted fractions from the treated BL were used as biodiesel additives
(dosage of 1 wt%) and the change in the biodiesel oxidation stability
was also evaluated.
2. Materials and methods
2.1. Black liquor production
Barley straw, collected at Sabiñánigo (north of Spain; W0°21′57.85″,
N42°31′9.26″), was digested with sodium hydroxide (PA purity,
Panreac) in tap water. Prior to the digestion, straws were washed with
water (liquid/solid mass ratio equal to 15) to remove dirt and particles.
The feedstock was then digested for 3 h using an aqueous solution of
sodium hydroxide (9.5 wt% of NaOH with respect to the dry weight of
straw; liquid/solid mass ratio of 10). Such experimental conditions
were selected according to a semichemical pulping protocol reported
2
Fuel 254 (2019) 115689
Table 1
BLS analysis.
Parameter Average value
a
C (%) 38.62 ± 0.01
H (%)a 4.22 ± 0.06
N (%)a 0.93 ± 0.01
S (%)a 0.35 ± 0.03
Ash (%)a 33.11 ± 0.09
O (%)a,b 22.78
Na (mg/g) 99.8
K (mg/g) 22.8
Ca (mg/g) 2.0
HHV (kJ/kg, dry basis) 14760 ± 10
a
Mass percentage dry basis.
b
by difference.
previously [12].
The resulting cellulose pulp was discarded, whereas the black liquor
(BL) was centrifuged and dried at 105 °C to obtain the black liquor solid
(BLS) that was used for the following depolymerization experiments.
Table 1 shows the elemental analysis of the BLS (LECO 628 series). The
HHV was measured using a calorimetric pump (IKA C2000 basic), while
the Na, K and Ca content was obtained from ICP-MS analysis (Elan
DRC-e, Perkin Elmer).
2.2. Depolymerization process
Depolymerization was carried out in a 300 mL stainless steel stirred
reactor (Parker Inc. USA). For each experiment, 200 g of a 7 wt% BLS
aqueous solution was prepared. The selected amount of catalyst
(Zeolyst CVB 720, SiO2/Al2O3), varying from 7 to 14 g, was added to
the reactor. It must be taken into account that although the acidic sites
of this kind of materials can get solvated in an aqueous environment
[22], there is also evidence that they can retain catalytic activity [32].
The reactor was then properly closed, purged with N2 and heated (at
about 5 °C/min) to the desired temperature (ranging from 250 to
300 °C). Once the desired temperature was reached, it was maintained
for one hour, after which the reactor was cooled and purged once more
with nitrogen before venting all residual gas.
The experiments have been planned according to a factorial ex-
perimental design of two factors (reaction temperature and amount of
zeolite used) and two levels (250–300 °C and 7–14 g of zeolite, re-
spectively), with four replicates of the central point (275 °C and 10.5 g
of zeolite). Such approach allows easily selecting the significant factors,
avoiding the occurrence of higher order influences. Analysis of variance
(ANOVA) was used to calculate the experimental error of each response
measured and to determine the effect of the factors.
Both the liquid and the solid generated during the experiments were
recovered from the reactor. Methanol was used to remove remaining
organic matter sticking to the reactor, after which both liquid mixtures
(liquid product and washing methanol) were combined. The mixture
was filtered to recover the solid (both the zeolite as well as the carbon-
based insoluble solid formed in/on it), which was weighted after drying
overnight at 105 °C.
2.3. Lignin-derived additives production
The experimental procedure for obtaining the lignin-derived ad-
ditives is plotted in Fig. 1 and can be summarized as follows. A given
amount (about 40 g) of the filtered mixture obtained from the reactor
was extracted using twice the weight (about 80 g) of isopropyl acetate,
vigorously shaking and keeping in a decantation funnel at room tem-
perature for 10 min. After decantation and separation of the aqueous
phase, the organic phase was filtered and the solvent was removed
using a rotary evaporator under vacuum. This solvent-free portion was
then used as antioxidant additive (referred to as fraction Lα in the
J.-M. Lavoie, et al.
Fig. 1. Experimental procedure used to produce Lα, Lβ and Lγ additives.
following discussion) and was blended with the prepared biodiesel.
A second part of the obtained liquid (about 60 mL) was acidified to
pH 1 using a 1 M aqueous HCl solution and maintained at 70 °C for
15 min in order to induce the precipitation of phenolic oligomers,
modified lignin and other condensed products [33]. The precipitated
solid was separated by centrifugation, recovered from the centrifuge
tube with methanol and dried at 40 °C prior to be weighted. This por-
tion (referred to as Lβ fraction) was also used as additive by blending it
in the biodiesel.
As not all the phenolic compounds precipitated, the acidified liquid
separated from the aforementioned solid by centrifugation, was ex-
tracted according to the same procedure as described above (twice the
weight of isopropyl acetate over the weight of liquid), obtaining an-
other fraction (noted as Lγ) that was also used as biodiesel additive.
2.4. Biodiesel production
Biodiesel was produced at laboratory scale using sunflower oil
purchased at a local store. The oil was reacted with methanol (> 99.8%
purity, Panreac) using potassium hydroxide (85% purity, Carlo Erba
Reagents) as catalyst (1 wt% of catalyst with respect to oil mass; 6/1
methanol/oil molar ratio). Reaction temperature was set at 60 °C under
reflux at atmospheric pressure for 3 h. After the reaction, the glycerine
was separated. The biodiesel produced was washed with a mildly acidic
water (1 mL of H2SO4 98 wt. % per 400 g of distilled water). The re-
sulting mixture was separated by decantation, and moisture from bio-
diesel phase was removed in a rotary evaporator. More details about the
biodiesel production protocol used in this work has been published
previously [29].
3
Fuel 254 (2019) 115689
2.5. Testing of the lignin-derived fractions antioxidant activity
A given amount of each lignin fraction (Lα, Lβ and Lγ) was in-
dividually mixed with biodiesel at a 1 wt% concentration. Isopropyl
acetate was added to the mixture (approximately the same weight as
biodiesel), acting as a co-solvent to enhance the dissolution of lignin-
derived additives in the biodiesel. The mixture was sonicated in an
ultrasound bath (ATU, Spain, model ATM6L) at room temperature for
15 min, in order to ease the mixing. Isopropyl acetate was then removed
in a rotary evaporator, and the lignin-doped biodiesel was centrifuged
to remove the non-soluble matter.
Biodiesel oxidation stability, both prior and after adding the lignin-
derived compounds, was measured using a PetroOXY device (Petrotest
Instruments GmbH & Co.) according to EN 16091 and ASTM D7545 test
methods.
2.6. Mass balance and characterization of the lignin fractions
After the reaction and filtration of the liquid recovered from the
reactor, the following parameters were determined:
- Yield of insoluble carbon-based solid product (%): From weight data
of zeolite used in each experiment and total amount of solid re-
covered after filtration, the amount of carbon-based insoluble solid
produced during the reaction could be deduced by difference. This
was reported as a percentage of the BLS used, Eq. (1).
J.-M. Lavoie, et al. Fuel 254 (2019) 115689

Insoluble carbonaceous solid yield (%) Lγ yield (%)

Filtered solid (g ) − zeolite weight (g )
= ·100
BLS weight (g )
- Yield of solid dissolved in the treated BL (%): The solid content in
the treated BL was determined by drying the filtered liquid (three
replicates of 5–10 g each) at 105 °C and its yield was calculated with
respect to the BLS used, Eq. (2).
Dissolved solid yield (%)
Content of dry solids in filtered liquid (%)· Weight of liquid (g )
= ·100
BLS weight (g )
- Distribution (or conversion) of C, H and N into insoluble solid (%).
An ultimate analysis of the recovered filtered solid was performed in
order to determine the fraction of C, H and N initially present in BLS
which ended in the insoluble solid formed after the hydrothermal
treatment, Eq. (3).
C / H / N in BLS converted to solid (%)
Content of C / H / N in filtered solid (%)· Filtered solid weight (g )
= ·100
Content of C / H / N in BLS (%)· BLS weight (g )
- Yield to Lα: Yield of the isopropyl acetate-soluble fraction extracted
from the filtered liquid, reported as weight percentage with regards
to the BLS used, Eq. (4).
Lα yield (%)
Weight of extract (g )·Weight of total filtered liquid obtained
from reactor (g )
= ·100
Weight of filtered liquid used for extraction (g )·BLS weight (g )
- Yield to Lβ: Yield of oligomers precipitated at pH 1, reported as
weight percentage with regards to the BLS used, Eq. (5).
Lβ yield (%)
Weight of solid precipitated (g )·Weight of total filtered
liquid obtained from reactor (g )
=
Weight of filtered liquid used for acidification (g )·BLS weight (g )
·100
- Yield to Lγ: Yield of the organic fraction extracted with isopropyl
acetate from the acidified liquid, i.e., following the acidification of
the liquid and after the precipitation of the Lβ fraction, calculated as
weight percentage with respect to BLS used, Eq. (6).
Weight of extract from acidified liquid (g )·Total weight of
(1)
acidified liquid that could be obtained (g )
=
Weight of acidified liquid used for extraction (g )· BLS weight (g )
·100 (6)
Other characterization results included the molecular weight dis-
tribution of the solid taking part of the three fractions of depolymerized
lignin (Lα, Lβ and Lγ), that was measured by GPC using a HPLC Agilent
1200 with two columns (GFC-P2000 and GFC P-linear), a UV–Vis de-
tector (280 nm) and 1 mL/min of water/methanol (50 vol%) with
0.1 vol% NH3 as mobile phase. The average molecular weight in
(2) number (Mn) and in weight (Mw), as well as polydispersity, were cal-
culated for each experimental condition tested, using polystyrene
standards (Agilent) for calibration.
The volatile content (compounds soluble in isopropyl acetate and
detected by GC/MS/FID) of Lα and Lγ was analyzed. Moreover, an
aliquot of Lβ, the solid precipitated after acidification, was also dis-
solved in isopropyl acetate, after which it was also analyzed. An Agilent
GC/MS/FID (7890A/5975C) equipped with an Agilent DB-17MS
column (60 m long, 0.250 mm diameter and 0.25 μm film thickness)
was used. Samples were injected at 1 μL (splitless), and the GC followed
a temperature program starting at 50 °C (maintained for 2 min), after
(3) which the column was heated at 280 °C (10 °C/min), which was held for
10 min. Phenolic compounds identification was performed using the
NIST14 library. Quantification was achieved with external standards:
FID calibration curves were generated using phenol (99.5% purity),
guaiacol (98%), 4-ethylphenol (97%), creosol (98%), catechol (99%),
and 2,6-dimethoxyphenol (99%), all supplied by Sigma Aldrich.
Phenolic compounds that were not calibrated using external standards
were quantified using the guaiacol response, correcting its response
factor according to the Effective Carbon Number contribution of each
specific phenolic compound [34].
(4)
3. Results and discussion
3.1. Solid product: Yield and characterization
Table 2 reports on the yield of insoluble carbon-based solid formed
during the hydrothermal treatment at the different experimental con-
ditions tested, as well as the ultimate analysis of the filtered product
solid, which includes both zeolite and insoluble carbon-based solid
(5) formed. The conversion (distribution) of C, H and N initially present in
BLS into insoluble carbon-based solid (calculated from data of weights
and elemental analyses of both the raw BLS and the filtered solids re-
covered after each reaction) are also shown in Table 2. Elemental
analysis was performed on the filtered solid (involving both the zeolite
as well as any carbon-based insoluble solid formed in/on it), thus the C,
H and N content (%) in the solid was directly influenced by the weight
of zeolite used.

Table 2
Insoluble carbon-based solid yield, elemental analyses and conversion of C, H and N into the insoluble solid product in the catalytic depolymerization of BLS.
Exp.# Temp. (°C) Zeolite weight (g) Insoluble solid yield (wt Elemental analysis of the filtered solid (wt%) Distribution of C, H and N:
%)
%C %H %N % C in BLS to % H in BLS to % N in BLS to
solid solid solid

1 250 7 10.1 14.61 1.83 0.41 23.1 25.5 27.0

2 300 7 12.2 15.57 1.87 0.47 25.4 26.9 31.9
3 250 14 11.7 9.38 1.41 0.35 27.5 36.3 43.1
4 300 14 9.4 10.28 1.45 0.38 29.6 36.8 45.0
5 275 10.5 13.6 11.84 1.60 0.42 27.6 32.8 40.4
6 275 10.5 17.1 12.30 1.68 0.36 29.8 35.8 36.7
7 275 10.5 14.1 12.05 1.69 0.37 28.2 34.8 36.0
8 275 10.5 14.1 12.23 1.68 0.39 28.6 34.7 38.4

4
J.-M. Lavoie, et al.
16
15
Content of C in the filtered solid (%)
14
13
12
11
10
9
250 275
Temperature (ºC)
Fig. 2. Effect of temperature and weight of zeolite used in the depolymerization
experiments on the content (%) of C in the filtered solid [■7 g zeolite (mean
value from ANOVA), 14 g zeolite (mean value from ANOVA), experimental
points].
Data in Table 2 does not depict any correlation between the ex-
perimental conditions and the yield of insoluble carbon-based solid.
The variability at the central point is rather high, ranging from 13 to
17 wt% when working at the same replicated conditions, while chan-
ging the temperature and the amount of zeolite leads the insoluble
carbon-based solid yield to range between 9 and 12 wt%. The elemental
composition of the filtered solid (involving both the zeolite as well as
any carbon-based insoluble solid formed in/on it) shows that the con-
tent of C in the solid increases with regards to temperature and de-
creases with the amount of zeolite used in the process (Fig. 2). Katahira
et al. [35] observed a completely opposite trend when temperature was
increased for base-catalyzed depolymerization of several types of lignin.
The downward trend observed with the increased amount of zeolite is
probably due to a dilution effect.
The ANOVA statistical analysis shows that both the temperature and
the amount of zeolite have a significant effect on the conversion of C
into insoluble solid (Fig. 3). Both operational factors have the same
positive effect (the higher the temperature or the zeolite weight, the
higher the fraction of C in BLS which is converted into insoluble carbon-
based solid), which can be summarized as a direct correlation between
32
Conversion of C into insoluble solid (%)
30
28
26
24
22
250 275
Temperature (ºC)
Fig. 3. Effect of temperature and weight of zeolite used in the depolymerization
experiments on the conversion of C into insoluble solid [■ 7 g zeolite (mean
value from ANOVA), 14 g zeolite (mean value from ANOVA), experimental
points].
Fuel 254 (2019) 115689
the observed yields and the experimental factors. As for the conversion
of H and N into insoluble solid, only the amount of zeolite seems to
have a significant positive effect (Fig. 4). Thus, it seems that the in-
crease of both factors, temperature and zeolite weight, is detrimental
for the product distribution, considering that this insoluble solid may
probably be a valueless residue for the applications targeted in this
work. As the global yield of insoluble solid formed is not significantly
affected by the operational effects, this means that the insoluble solid
product is enriched on C, H and N with the use of more amount of
zeolite.
3.2. Liquid product: Yields and characterization
Table 3 shows the conversion data of BLS into the soluble solid
remaining in the liquid after the reaction, as well as the yields of the
300 three fractions of depolymerized lignin produced (Lα, Lγ, Lβ).
The yield of soluble solid remaining in the recovered filtered liquid
ranges from 50 to 70 wt% of the initial BLS. The ANOVA performed on
the results shows that increasing the temperature, as well as the amount
of zeolite used, leads to a reduction of the dissolved solid yield, as it is
reported in Fig. 5.
Table 3 shows that Lα yield, the fraction directly extracted from the
reaction filtered liquid, ranges between 4 and 8 wt% of the BLS fed,
while the fraction extracted from the acidified liquid (Lγ) is higher (15
to 25 wt%), showing that the acidification step helps to increase the
fraction of additive after the extraction step. The reported yields cor-
responding to the central point experiments show a variability of 5.8 to
8.3% for Lα and 15.8 to 20.5% for Lγ. Such results are high enough to
avoid classifying the effect as significant at a 95% confidence level.
Thus, the ANOVA of the results shows that neither Lα nor Lγ yields
seems to be affected by the experimental conditions. On the other hand,
Lβ is the fraction with the lowest recovery yield (1–5 wt% of BLS). For
this fraction, the ANOVA shows that the highest temperatures con-
sidered in this work have a negative impact on the Lβ yield (see
Table 3). It is noteworthy to observe this effect in Fig. 6, as similar yield
values were obtained both at 275 and 300 °C.
Variations of the molecular weight (both Mn and Mw) were analyzed
using GPC. The results are reported in Tables 4 (Lα), 5 (Lβ) and 6 (Lγ).
These data have to be considered keeping in mind that the obtained
values of the molecular weight are linked to the calibration of a stan-
dard that may not have the same properties of the lignin fractions.
Nevertheless, literature shows that lignin is a rather complex and very
variable molecule, hence, utilization of standards such as polystyrene is
a common approach permitting the evaluation of an average value of
molecular weight [36]. Assuming a possible constant bias related to
calibration, the results are still valuable since they can provide in-
formation on the variation of the molecular weight of the different
fractions obtained from different treatments. The GPC of the original
BLS before the reaction gave a value of 3750 for Mn and 11,690 for Mw.
Results in Tables 4, 5 and 6 show that the lignin derived Lα and Lγ
fractions have a lower molecular weight as compared to the original
black liquor. Only the Lβ fraction obtained at 300 °C and 7 g of zeolite
showed a slightly higher Mw than the original lignin used in the process.
Regarding the effect of the experimental conditions on the measured
molecular weight for the Lα samples, both the temperature and the
amount of zeolite used are shown to have an effect on Mw, Mn and
polydispersity. These are statistically analyzed in Fig. 7. Increasing both
the temperature and the amount of zeolite leads to smaller molecular
weight. A significant interaction between the two experimental factors
300 has been observed, showing that the difference between using 7 or 14 g
of zeolite is bigger at 300 °C than at 250 °C. The effect of this interaction
is stronger in the case of Mw, as the amount of zeolite is not a statisti-
cally significant factor at the lowest temperature. Thus, the depoly-
merization of lignin is more intense, in terms of molecular weight of the
lignin, due to the presence of zeolite Y. As a result of these changes,
polydispersity of Lα varies following a different trend, since when using
5
J.-M. Lavoie, et al. Fuel 254 (2019) 115689

46
38

Conversion of N into insoluble solid (%)

44
Conversion of H into insoluble solid (%)
36 42

34 40

38
32
36
30
34
28 32

26 30

28
24
26
7.0 10.5 14.0 7.0 10.5 14.0
Weight of zeolite Y (g) Weight of zeolite Y (g)

Fig. 4. Effect of zeolite weight used in the depolymerization experiments on the conversion of H into insoluble solid (left) and conversion of N into insoluble solid
(right) [■ mean value from ANOVA, experimental points].

Table 3 6
Yield of solid soluble in the filtered liquid and yields of Lα, Lβ and Lγ fractions
(reported as wt% of BLS used).
5
Temp. (°C) Zeolite Yield of dissolved Lα yield Lβ yield Lγ yield
weight (g) solids (wt. %) (wt. %) (wt. %) (wt. %)
Yield to L (%) 4
250 7 67.2 5.45 5.68 24.86
300 7 57.3 8.35 1.61 21.59
250 14 62.4 7.38 4.71 20.12
300 14 52.5 4.09 2.20 18.37 3
275 10.5 57.8 5.48 – –
275 10.5 59.4 6.65 2.33 20.46
275 10.5 57.8 8.31 2.00 16.21 2
275 10.5 57.9 5.77 1.47 15.82

1
70

250 275 300

BLS yield to dissolved solids (%)

Temperature (ºC)
65
Fig. 6. Effect of temperature on Lβ yield expressed as wt. % of BLS [■ mean
value from ANOVA, experimental points].

60
Table 4
Molecular weight of the Lα fraction determined by GPC.
Temp. (°C) Zeolite weight (g) Mn (Da) Mw (Da) Polydispersity
55
250 7 3200 8220 2.56
300 7 2880 8650 3.00
250 14 2930 7420 2.53
300 14 2220 5400 2.43
50
275 10.5 2490 6360 2.55
250 275 300
275 10.5 2550 6500 2.54
Temperature (ºC) 275 10.5 2480 6390 2.57
275 10.5 2600 6930 2.66
Fig. 5. Effect of temperature and amount of zeolite on the soluble solid yield [■
7 g zeolite (mean value from ANOVA), 14 g zeolite (mean value from
ANOVA), experimental points].
Table 5
Molecular weight of the Lβ fraction determined by GPC.
7 g of zeolite, polydispersity increases with the temperature (wider Temp. (°C) Zeolite weight (g) Mn (Da) Mw (Da) Polydispersity
molecular weight distribution), while when 14 g of zeolite are used,
polydispersity does not change significantly with the temperature. 250 7 5950 11,150 1.87
As for the Lγ fraction, the experimental conditions do not seem to 300 7 5900 12,490 2.12
250 14 6670 11,580 1.74
have an impact neither on Mn and Mw nor on the polydispersity. 300 14 5460 10,580 1.94
Comparable observations could be made on the Lβ fraction. 275 10.5 5620 10,610 1.89
275 10.5 5410 9810 1.81
275 10.5 5510 10,030 1.82
3.3. GC/MS/FID analysis of the extracted fractions. 275 10.5 5990 11,240 1.87

The number of identified phenolic compounds in the different

6
J.-M. Lavoie, et al. Fuel 254 (2019) 115689

Table 6 ethyl-phenol concentrations in Lα are also affected positively by the

Molecular weight of the Lγ fraction determined by GPC. temperature, whereas guaiacol and 2,6-dimethoxy-phenol concentra-
Temp. (°C) Zeolite weight (g) Mn (Da) Mw (Da) Polydispersity tions decrease when the temperature is increased. 4-ethyl-guaicol in Lα
is affected by neither the temperature nor the amount of zeolite. Trends
250 7 1700 4650 2.74 on phenol and 2,6-dimethoxy-phenol concentration are depicted in
300 7 2250 7750 3.45
Fig. 9.
250 14 1590 4240 2.67
300 14 1580 4720 2.99
For the total concentration of phenolic volatiles in Lγ fraction,
275 10.5 1480 3990 2.69 ANOVA shows a significant effect of both operational factors. As it can
275 10.5 1750 5230 2.99 be observed in Fig. 10, the same amount of volatiles are produced at
275 10.5 1750 5250 3.00 250 °C in spite of the zeolite weight used, but lower content of volatiles
275 10.5 1980 6100 3.09
is detected in Lγ when using more zeolite at 300 °C.
Phenol, guaiacol, 4-ethyl-guaiacol and 2,6-dimethoxy-phenol are
samples ranges from 10 to 19, Lα being the fraction with the highest detected in all the Lγ samples. As it was observed in the Lα samples, the
number of compounds detected, as well as the highest concentrations. ANOVA shows that the strongest significant effect is caused by tem-
Tables 7, 8 and 9 show the content of each phenolic compound in perature, as it has already been reported in literature [13]. The increase
terms of mg per g of Lα, Lβ and Lγ, respectively. in phenol content and decrease of 2,6-dimethoxy-phenol and guaiacol
Overall, the most abundant phenolic compounds identified are contents (Fig. 11) are probably a consequence of demethoxylation re-
phenol, guaiacol, 2,6-dimethoxy-phenol, catechol, creosol, 4-ethyl- actions at higher temperatures, which may also cause the observed
phenol, 4-ethyl-guaiacol, and 1-(4-hydroxy-3,5-dimethoxyphenyl)- increase in the production of catechol with temperature.
ethanone. Regarding the phenolic volatile concentration in the fraction Lβ, no
The Lβ samples (Table 8) show a significantly smaller variety and significant effects have been found with ANOVA.
quantity of phenolic compounds, with less than 130 mg of total phe-
nolic compounds per g of solid Lβ. This lower content could be expected 3.4. Effect of Lα, Lγ and Lβ addition on the oxidation stability of biodiesel
as Lβ is mainly composed of oligomeric phenolic compounds that pre-
cipitate at low pH, and probably the small concentration of volatiles The three fractions obtained from the catalytic conversion of BLS
detected in this fraction comes from the liquid fraction Lγ that could not (Lα, Lγ and Lβ) were individually mixed with sunflower biodiesel at a
be properly separated. dosage of 1 wt% (see Section 2.5). The impact of the different depoly-
Whether volatile compounds are considered individually or collec- merized lignin fractions on the biodiesel oxidation stability are reported
tively, Lα is more concentrated in such compounds than Lγ (Table 9). in Table 10. The oxidation stability time (OXY) of neat biodiesel (prior
This is somehow an unexpected result as if volatiles are not in fraction to the addition of Lα, Lγ or Lβ fractions) was 17.50 ± 0.53 min, thus
Lβ, they should be in fraction Lγ. This behavior could be due to a dif- the addition of all the lignin fractions significantly improved this im-
ferent efficiency in the extraction step because of the lower pH of the portant biodiesel property.
acidified liquid, which promotes the extraction of more compounds Results from Table 10 show that the oxidation stability time is
(not detectable by GC/MS) as compared to the extraction of the Lα higher when adding the Lα fraction, followed by Lγ and Lβ, respec-
fraction, thus causing a dilution effect in the detectable phenolic vo- tively. Adding 1 wt% of the Lα fraction improves the biodiesel oxida-
latile content. tion stability time by 150–250%, the addition of Lγ increases the oxi-
Regarding the total amount of volatiles determined in the Lα frac- dation stability time by 90–200%, whereas 1 wt% of Lβ in biodiesel
tions, a negative effect of temperature has been found, as shown in causes an increase of the oxidation stability time that ranges from 30%
Fig. 8. Increasing the reaction temperature from 250 to 300 °C de- to 100%. The ANOVA shows that temperature is the only significant
creases the phenolic volatile content determined in Lα from around factor impacting on the oxidation stability time when Lα and Lγ are
900 mg/g to 550 mg/g. added to biodiesel (Fig. 12). The only statistical difference between the
Among the 19 phenolic compounds identified in Lα samples, seven behavior of Lα and Lγ is that the former shows a strong curvature with
of them are present in all the samples: phenol, guaiacol, 4-ethyl-phenol, regards to temperature, meaning that the antioxidant character of Lα is
creosol, 4-ethyl-guaiacol, 2,6-dimethoxy-phenol and 1-(4-hydroxy-3,5- similar when being produced at 275 or 300 °C. On the other hand, there
dimethoxyphenyl)-ethanone. Of those, phenol is the only compound seems to be a linear increment of the biodiesel oxidation stability with
which is affected by both the temperature and the zeolite amount used. regards to temperature at which the Lγ fraction is generated.
The two factors exert a positive effect on the phenol concentration (the The experimental conditions related to the production of the Lβ
higher the factor level, the higher the phenol concentration in Lα), fraction show a small effect when it comes to the depolymerization
although the effect of zeolite is only noticeable at 300 °C. Creosol and 4- temperature and the amount of zeolite used. As shown in Fig. 13, using
more zeolite leads to an increase in the biodiesel oxidation stability

3400 9500
3,1
9000
3200
3,0
8500

3000 8000 2,9

Polydispersity (-)

7500 2,8
Mw (Da)

2800
Mn (Da)

7000 2,7
2600 6500 2,6

6000
2400 2,5
5500
2,4
2200
5000
2,3
250 275 300 250 275 3 00 250 275 300
Temperature (ºC) Temperature (ºC) Temperature (ºC)

Fig. 7. Effect of temperature and amount of zeolite on Mn (left), Mw (center) and polydispersity (right) of the Lα lignin fraction [■ 7 g zeolite (mean value from
ANOVA), 14 g zeolite (mean value from ANOVA), experimental points].

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J.-M. Lavoie, et al. Fuel 254 (2019) 115689

Table 7
Phenolic compounds (identified by GC/MS) found in the Lα fraction (mg/g of Lα).
T = 250 °C, 7 g T = 300 °C, 7 g T = 250 °C, 14 g T = 300 °C, 14 g T = 275 °C, 10.5 g zeolite
zeolite zeolite zeolite zeolite

Phenol 53 89 66 138 94 83 79 100

Phenol, 2-methyl- 10 9 – – 5 – – 7
p-Cresol – 11 – 15 4 4 – 4
Phenol, 2-methoxy- 216 86 279 118 282 238 239 297
Phenol, 4-ethyl- 5 8 5 13 8 6 6 8
2-Methoxy-6-methylphenol – 9 – – 8 5 6 8
Phenol, 4-methoxy-3-methyl- – 8 – – – – – –
Creosol 8 19 8 23 23 18 18 23
Catechol – 185 – 247 134 – – –
Phenol, 4-ethyl-2-methoxy- 14 10 18 13 25 17 18 23
1,2-Benzenediol, 3-methoxy- – 63 11 15 83 47 37 48
Phenol, 2,6-dimethoxy- 179 12 228 15 144 130 113 147
Vanillin 17 – 11 – – – – –
3,5-Dimethoxy-4-hydroxytoluene 27 – 30 – 50 42 42 52
Ethanone, 1-(2-hydroxyphenyl)- 6 – – – 8 6 – –
5-tert-Butylpyrogallol 27 – 34 – 31 24 25 30
Apocynin 22 – 22 1 19 18 15 19
Benzaldehyde, 4-hydroxy-3,5-dimethoxy- 13 – – – – 8 – –
Ethanone, 1-(4-hydroxy-3,5- 226 9 240 – 101 92 79 102
dimethoxyphenyl)-
Total mg/g Lα 823 517 952 598 1018 738 676 868

Table 8
Phenolic compounds (identified by GC/MS) found in the Lβ fraction (mg/g of Lβ).
T = 250 °C, 7 g zeolite T = 300 °C, 7 g zeolite T = 250 °C, 14 g T = 300 °C, 14 g T = 275 °C, 10.5 g zeolite
zeolite zeolite

Phenol 3 – 3 5 – 3 4
Phenol, 2-methoxy- 3 – 4 – – 3 0
Phenol, 4-ethyl- – – – 4 – – –
Creosol 2 – 3 3 2 4
Phenol, 4-ethyl-2-methoxy- 2 – 1 2 2 3 4
Phenol, 2,6-dimethoxy- 11 – 11 – 8 7 11
3,5-Dimethoxy-4-hydroxytoluene 7 – 8 – 9 8 19
5-tert-Butylpyrogallol 14 – 12 – 10 7 22
Apocynin 5 – 6 – 4 2 9
Ethanone, 1-(4-hydroxy-3,5- 50 – 58 – 23 15 59
dimethoxyphenyl)-
Total mg/g Lβ 97 – 103 14 57 51 131

Table 9
Phenolic compounds (identified by GC/MS) found in the Lγ fraction (mg/g of Lγ).
T = 250 °C, 7 g T = 300 °C, 7 g T = 250 °C, 14 g T = 300 °C, 14 g T = 275 °C, 10.5 g zeolite
zeolite zeolite zeolite zeolite

Phenol 20 55 22 54 27 34 31 34
Phenol, 2-methyl- 8 – – 6 4 – 5 4
p-Cresol – 8 – 11 – – – –
Phenol, 2-methoxy- 78 50 87 46 79 95 88 93
Phenol, 4-ethyl- 3 8 – 9 3 – 4 –
Creosol – 14 – – 8 8 9 9
Catechol 132 – 51 40 – – –
Phenol, 4-ethyl-2-methoxy- 4 6 5 4 6 6 7 7
1,2-Benzenediol, 3-methoxy- 2 26 – 9 23 27 11 15
Phenol, 3,4-dimethoxy- – 1 – – – – – –
Phenol, 2,6-dimethoxy- 66 8 72 5 40 55 49 51
3,5-Dimethoxy-4-hydroxytoluene 12 – – – 17 16 16 18
Ethanone, 1-(2-hydroxyphenyl)- 2 – – – 3 – – –
5-tert-Butylpyrogallol 9 – 10 – 8 – 9 9
Apocynin 10 5 8 – 7 – 8 8
Ethanone, 1-(4-hydroxy-3,5- 88 7 77 – 32 42 37 38
dimethoxyphenyl)-
Total mg/g Lγ 302 320 280 197 299 283 274 285

time achieved with the addition of Lβ fraction. Increasing the reaction the additive was produced) on the improvement of the biodiesel oxi-
temperature from 250 to 300 °C is also shown to have a positive impact dation time agrees with the results published in other studies related to
on the biodiesel oxidation stability time. lignosulphonates [37] and organosolv lignin [38], where it was found
The positive effect of the depolymerization temperature (at which that increasing the depolymerization temperature, and using NaOH as

8
J.-M. Lavoie, et al. Fuel 254 (2019) 115689

1100
340

1000 320

900 300

Volatiles (mg/g L )
Volatiles (mg/g L )

280
800
260
700
240

600 220

500 200

180
400
160
250 275 300 250 275 300

Temperature (ºC) Temperature (ºC)

Fig. 8. Effect of temperature on the total phenolic volatiles content of Lα, mg/g Fig. 10. Effect of temperature and amount of zeolite on the total phenolic vo-
Lα [■ mean value from ANOVA, experimental points]. latiles content in Lγ fraction, mg/g Lγ [■ 7 g zeolite (mean value from ANOVA),
14 g zeolite (mean value from ANOVA), experimental points].

catalyst, led to a higher production of phenolic groups, thus increasing

the amount on labile H that can power up the antioxidant effect of
depolymerized lignin.
As it has been recently reported, when using fractions of bio oil from
pyrolysis of lignin as additives for biodiesel, its antioxidant effect does
not seem to be caused mainly by monomeric phenols, detectable and
identifiable by GC/MS, but probably by compounds as dicatechols, di-
guaiacols or diapocynin-derived dimers [30]. Although our GC analyses
did not permit to detect such heavier compounds, the experimental data
tend to show that the biodiesel oxidation stability measured after the
addition of 1 wt% of any of the three lignin fractions is not related to
the volatile content of such fractions, as depicted in Fig. 14.
In order to complete the study about the relation between the OXY
improvement and the content of volatile phenolics, the compounds
used as external standards for the GC/FID analysis in this work, as well
as 3-methoxycatechol, were individually tested as additives for bio-
diesel. Only catechol and 3-methoxycatechol showed antioxidant ac-
tivity, as already observed in the previously cited work [30], where
catechol was the only volatile product detected by GC/MS in the pyr-
olysis bio oil that had a noticeable antioxidant effect.
4. Conclusions
The production of antioxidant additives from the lignin contained in
a stream of black liquor (BL) obtained from semichemical pulping of
barley straw has been studied by catalytic depolymerization, followed
by liquid/liquid extraction with an organic solvent (isopropyl acetate).
Three depolymerized lignin fractions have been produced and tested:
(i) Lα fraction, directly obtained by extraction from the depolymerized
BL resulting after the reaction; (ii) Lβ fraction, consisting of the solid
precipitated from the depolymerized BL after acidification; and (iii) Lγ
fraction, which was the extracted fraction from the acidified liquid. The
impact of the temperature (250–300 °C) and the addition of zeolite Y
(zeolite to black liquor solid ratio of 0.5 to 1) was studied on the
characteristics of the degraded lignin fractions and their effect as an-
tioxidant additives. To determine this effect, 1 wt% of each fraction was
added to biodiesel.
Overall, the effect of the temperature was more noticeable that the
impact of the amount of zeolite used. Temperature was detrimental for
the process in terms of increasing the conversion of the C and H initially
present in the BL into insoluble carbon-based solid formed during de-
polymerization, thus reducing the fraction of lignin that remained
dissolved in the liquid after the reaction (which is the intermediate

160 250

140
mg 2,6-dimethoxy-phenol/g L

200

120
mg phenol/g L

150
100

80
100

60

50
40

20 0
250 275 300 250 275 300

Temperature (ºC) Temperature (ºC)

Fig. 9. Effect of experimental conditions on the concentration of phenol (left) and 2,6-dimethoxy-phenol (right) in Lα [■ 7 g zeolite (mean value from ANOVA),
14 g zeolite (mean value from ANOVA), experimental points].

9
J.-M. Lavoie, et al. Fuel 254 (2019) 115689

100
70

90
60

mg 2,6-dimethoxyphenol/g L
mg guaiacol/g L

80 50

40
70

30

60
20

50
10

40 0
250 275 300 250 275 300

Temperature (ºC) Temperature (ºC)

Fig. 11. Effect of temperature on the concentration of guaiacol (left) and 2,6-dimethoxy-phenol (right) in Lγ, mg/g Lγ [■ mean value from ANOVA, experimental
points].

Table 10 40
Oxidation stability time of biodiesel after the addition of 1 wt% of the fractions
Lα, Lγ or Lβ obtained from the catalytic depolymerization of barley straw black
Oxy time (min), biodiesel with L

liquor. 35
Temp (°C) Zeolite (g) Biodiesel OXY Biodiesel OXY Biodiesel OXY
with Lα (min) with Lγ (min) with Lβ (min)
30
250 7 41.61 32.95 21.6
300 7 60.26 50.65 29.61
250 14 44.88 32.76 26.81
300 14 60.96 54.46 34.85 25
275 10.5 57.86 45.36 36.41
275 10.5 62.31 41.86 34.35
275 10.5 60.20 46.88 32.71
275 10.5 55.70 47.10 – 20

250 275 300

product for obtaining the additives). The composition of the volatile
compounds analyzed by GC/MS changed with the depolymerization Temperature (ºC)
temperature, with an upward trend in the concentration of phenol and
Fig. 13. Effect of temperature on the oxidation stability of biodiesel doped with
catechol while decreasing guaicacol and other methoxy phenols when 1 wt% of Lβ [■ 7 g zeolite (mean value from ANOVA), 14 g zeolite (mean
temperature was increased. The most important effect of temperature value from ANOVA), experimental points].
was to increase the antioxidant effect of the three lignin fractions ob-
tained. The Lα fraction was the one that showed the highest antioxidant

65 55

60 50
Oxy time (min), biodiesel with L
Oxy time (min), biodiesel with L

55 45

50 40

45 35

40 30
250 275 300 250 275 300
Temperature (ºC) Temperature (ºC)

Fig. 12. Effect of temperature on the oxidation stability of biodiesel doped with 1% of Lα (left) or Lγ (right) [■ mean value from ANOVA, experimental points].

10
J.-M. Lavoie, et al. Fuel 254 (2019) 115689

70 60 40

60
50

Oxy time (min), biodiesel with L

Oxy time (min), biodiesel with L

Oxy time (min), biodiesel with L

30
50
40

40 20

30
30
10
20
20

10 10 0
500 600 700 800 900 1000 1100 180 200 220 240 260 280 300 320 0 20 40 60 80 100 120 140

Phenolic volatiles (mg/g L Phenolic volatiles (mg/g L ) Phenolic volatiles (mg/g L )

Fig. 14. Oxidation stability of biodiesel with 1 wt% of Lα, Lγ or Lβ vs. GC/MS volatile content of the fractions (left: Lα, center: Lγ, right: Lβ).

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