Bioresource Technology 284 (2019) 105–114

Contents lists available at ScienceDirect

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

Production of carboxylic acids from the non-lignin residue of black liquor by T

hydrothermal treatments
⁎
Lucía Pola, Sergio Collado, Paula Oulego, Mario Díaz
Department of Chemical and Environmental Engineering, University of Oviedo, 33071 Oviedo, 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: The present study assesses, for the first time, the use of the non-lignin residue from Kraft black liquor as a
Black liquor renewable source of carboxylic acids. For this purpose, the liquid fraction obtained after separating the lignin
Carboxylic acids from the black liquor by acid precipitation was subjected to different hydrothermal treatments. It was found that
Non-lignin residue the formation of carboxylic acids can be maximized at 190 °C, 70 bar and under an inert atmosphere, with
Partial wet oxidation
concentrations after 2 h of 29.0 g/l of oxalic acid, 1.8 g/L of malic acid, 10.0 g/L of lactic acid, 4.1 g/L of formic
Thermal hydrolysis
acid, 11.8 g/L of acetic acid and 3.4 g/L of propionic acid. The presence of an oxidizing atmosphere generated a
less concentrated, but more purified, stream of acids than that obtained by thermal hydrolysis, simplifying the
subsequent downstream processing.

1. Introduction
During the cooking step of the Kraft process, the method used most
widely by pulp mills, wood chips react with white liquor (a solution of
sodium hydroxide and sodium sulphide) in order to disassociate cellu-
lose fibres from lignin. After washing, the pulp continues through the
process, whereas the liquid residue forms a toxic waste stream, called
black liquor, which is an aqueous solution that contains a complex
mixture including polysaccharides, lignocellulosic compounds, resins,
soluble salt ions and carboxylic acids (Mateos-Espejel et al., 2011).
Taking into account the high volumes generated and the fact that its pH
is higher than 11, with Chemical Oxygen Demand (COD) values of
around 70 g/L and roughly 15% of suspended solids, its correct man-
agement represents an environmental issue of high priority (Cardoso
et al., 2009; Garg et al., 2007).
Traditionally, black liquor has been concentrated and afterwards
incinerated to recover heat energy and chemicals. Although this alter-
native is very widespread, other methods have been studied in order to

⁎
Corresponding author at: Department of Chemical and Environmental Engineering, University of Oviedo, C/ Julián Clavería s/n Oviedo, Asturias ES E-33071,
Spain.
E-mail address: mariodiaz@uniovi.es (M. Díaz).

https://doi.org/10.1016/j.biortech.2019.03.066
Received 9 January 2019; Received in revised form 12 March 2019; Accepted 13 March 2019
Available online 14 March 2019
0960-8524/ © 2019 Elsevier Ltd. All rights reserved.
L. Pola, et al. Bioresource Technology 284 (2019) 105–114

remove the pollutants and organic matter, such as electrochemical Table 1

methods, membrane filtration or adsorption, among others (a more Characterization of Kraft black liquor and its non-lignin fraction.
detailed description of these methods can be found in Kamali and Parameters Kraft black liquor Non-lignin fraction
Khodaparast (2015)). Currently, the trend is to reduce operating pro-
blems, such as incrustation and corrosion, and environmental problems, pH 12.8 ± 0.1 12.8 ± 0.1
Colour Number (CN) 147 ± 7 12 ± 3
principally air pollution, whilst employing techniques to obtain other
Chemical Oxygen Demand (COD) (g 140 ± 7 37 ± 6
products of higher added value (Debellefontaine and Foussard, 2000). O2/L)
In this regard, more attention has been devoted in recent years to the Total Organic Carbon (TOC) (g C/L) 59 ± 1 18 ± 1
use of the Kraft black liquor as a cheap and renewable source for lignin, Oxalic acid (g/L) 62.2 ± 0.8 29 ± 3
due to the multiple applications and high value of this biopolymer. In Malic acid (g/L) 0.6 ± 0.3 0.6 ± 0.1
Lactic acid (g/L) 9±1 7.1 ± 0.5
fact, Kraft lignin biorefineries are becoming increasingly important as a
Formic acid (g/L) 2.3 ± 0.3 1.9 ± 0.3
source of value-added products such as aromatic compounds, which is Acetic acid (g/L) 8.2 ± 0.8 6.4 ± 0.4
not surprising, bearing in mind that about 40 million tons of lignin per Propionic acid (g/L) 4.2 ± 0.1 1.7 ± 0.4
year are produced by the Kraft process (Hu et al., 2018). Acids (% Initial COD) 27 ± 7 62 ± 7
Lignin can easily be separated from black liquor by precipitation
with acid and subsequent centrifugation (Mussatto et al., 2007).
Nevertheless, after this separation, the liquid fraction, that is to say, the closed equipment (Debellefontaine and Foussard, 2000).
non-lignin residue, still has to be properly managed. One of the most Therefore, the aim of this study is to assess, for the first time, the
important compounds in this stream is hemicellulose, a naturally syn- non-lignin fraction as a cheap renewable source of carboxylic acids by
thesized biopolymer, which is a promising sustainable raw material hydrothermal treatments. This information may well make it possible to
with a wide range of attractive properties, such as biodegradability and achieve a more efficient recovery of resources from the black liquor,
bioactivity (Luo et al., 2019; Mendes et al., 2017). Nevertheless, obtaining lignin in parallel with other higher added-value products.
hemicelluloses are generally depolymerised and degraded during con-
ventional pulping processes (Gallina et al., 2018) and their industrial 2. Materials and methods
applications are limited by the practical difficulties involved in pro-
cessing them (Farhat et al., 2018). These characteristics make the se- 2.1. Materials
paration and revalorization of hemicelluloses from the non-lignin re-
sidue, or directly from the black liquor, an inefficient alternative. The non-lignin liquid waste was obtained from the Kraft black li-
In addition to hemicelluloses, other components present in the non- quor of Eucalyptus wood, provided by a paper mill in Asturias (Spain).
lignin residue are the carboxylic acids. There are two groups of car- With the aim of maintaining its characteristics, the samples were stored
boxylic acids that are present in the black liquor: volatile (mono- at 4 °C until use.
carboxylic acids) and non-volatile hydroxy acids (Käkölä et al., 2007). The lignin fraction was precipitated by means of the addition of
Traditionally, they have been produced from fossil resources sulphuric acid until pH 3 and subsequent separation by centrifugation
(Bermúdez-Penabad et al., 2017). However, given the growing demand at 10,000 g for 20 min. Afterwards, the supernatant (non-lignin residue)
(18,500 kilotons will be required in 2020, approximately) and the was returned to the initial pH and stored until the corresponding hy-
tendency towards the creation of a circular and green economy, new, drothermal treatment.
more ecologically acceptable production methods are being in- Table 1 shows the main physicochemical characteristics of both the
vestigated (Atasoy et al., 2018; Djas and Henczka, 2018). In this regard, raw black liquor and the non-lignin fraction.
the non-lignin residue could have a great potential as renewable feed-
stock for these carboxylic acids. 2.2. Experimental setup
There are already some studies dealing with the purification of
carboxylic acids directly from the black liquor. Although some re- The hydrothermal reactions were carried out in a 1 L 316 SS semi-
searchers have focused on their extraction by means of different sol- batch reactor (Parr Instrument Co., Moline, IL.) which was stirred by
vents (Kim et al., 2016; Magnin et al., 2018), the preferred method of two six-bladed magnetically driven turbine agitators. In addition, it had
separation is membrane filtration (Hellstén et al., 2013; Mänttäri et al., safety systems to prevent the pressure from exceeding 120 bar. Besides
2015; Niemi et al., 2011). In this regard, it should be pointed out that, the reactor, the experimental setup was composed of temperature and
besides lignin recovery, the use of the non-lignin residue instead of the pressure controllers with the corresponding indicators, a sampling
raw black liquor would improve the separation of the carboxylic acids system and a heating blanket. Specifically, pressure was adjusted by a
because the membrane fouling caused by lignin disappears. Ad- back-pressure control valve located at the gas outlet. Finally, a 2 L
ditionally, after lignin recovery and before carboxylic acid separation, stainless steel water reservoir preceded the reactor in order to saturate
the implementation of a hydrothermal treatment in order to promote an the gas flow (N2 for thermal hydrolysis or O2 for partial wet oxidation),
increase in the concentration of these acids, which has already been which was provided by a compressed bottle. The loaded volume in each
addressed by a few researchers in recent years (Zhu et al., 2013; vessel was about 70% of the total to ensure safe operating conditions.
Muddassar et al., 2015a,b), might be of great interest. Nevertheless, to Temperatures chosen for the experiments were 170 °C, 190 °C and
the best of our knowledge, the recovery of carboxylic acids from the 210 °C, whereas pressure was maintained constant at 70 bar. The stirrer
non-lignin residue after applying hydrothermal treatments has not been speed and the flow rate were adjusted to 150 rpm and 1800 mL/min,
studied, even when the advantages of this option over the black liquor respectively. Thus, the reactor was pressurized and heated up to the
as raw material seem to be, at least, substantial. desired conditions, which were maintained constant during the course
Hydrothermal processes, which are the reactions that take place in of each experiment. Throughout the experiment, including the heating
an aqueous medium at elevated temperature and pressure, can be non- period, samples were periodically withdrawn and analysed.
oxidative when the atmosphere is inert (for example, thermal hydro-
lysis) or oxidative when it contains oxygen (wet oxidation) (Suárez- 2.3. Analysis of feedstock and samples
Iglesias et al., 2017; Urrea et al., 2018; Vallejos, 2017). These techni-
ques are especially environmentally friendly because they do not re- The pH was measured at atmospheric pressure and room tempera-
quire the addition of chemical reagents (Liu et al., 2018), generate few, ture using a Basic 20 Crison pH-meter.
low-hazard gaseous products (Zhao et al., 2018) and are carried out in The Colour Number (CN) was calculated by measuring the

106
L. Pola, et al.
absorbance at three wavelengths (436 nm, 525 nm and 620 nm) using a
spectrophotometer (T80 UV/VIS PG Instruments Ltd). The following
equation was applied (Eq. (1)) (Urrea et al., 2017):
2 2 2
ABS436 + ABS525 + ABS620
C. N =
ABS436 + ABS525 + ABS620 (1)
where ABSi is the value of the absorbance at the specific wavelength i.
The Chemical Oxygen Demand was determined following the
Standard Methods, according to which the samples are oxidized with
dichromate and the results are given by colorimetric measures at
600 nm (APHA et al., 2005).
Regarding the concentrations of the carboxylic acids, they were
determined by High Performance Liquid Chromatography (HPLC). The
system (Agilent 1200, Agilent Technologies, CA, USA) was equipped
with an ICSep ICE-ION-300 column (Transgenomic, CA, USA) and a
refractive index detector. The mobile phase was a solution of sulphuric
acid 0.45 mM (3.2 < pH < 3.3) at a flow rate of 0.3 mL/min. The
temperature of the column was 75 °C.
Although this column enables the detection of sugars and organic
acids, only three non-volatile hydroxy (oxalic, malic and lactic acids)
and three volatile acids (formic, acetic and propionic acids) were de-
tected and subsequently monitored in the reaction medium (Käkölä
et al., 2007).
The majority of experiments were carried out at least in duplicate
and as separate, independent experiments. The reproducibility was high
in all cases, the standard deviation being 10% as maximum.
3. Results and discussion
3.1. Preliminary study
Before beginning to study the formation of carboxylic acids from the
non-lignin residue, a comparison between the effects of the thermal
treatments on the main physicochemical parameters of black liquor and
non-lignin residue was made.
Fig. 1 shows the changes in these properties in black liquor or non-
lignin residue before and after being subjected to hydrothermal treat-
ments in absence or presence of an oxidizing atmosphere.
First of all, it should be noted that lignin is the main cause of the
black colour and high organic load of the black liquor. Indeed, the
previous separation of the lignin reduces by 69% the total COD and by
90% the Colour Number of the black liquor. The non-lignin residue
obtained is a dark brown liquid with only 31% of the initial organic
matter.
Despite these differences, the behaviour of the two feedstocks
during the hydrothermal treatments was quite similar. For example,
thermal hydrolysis did not have a significant effect on the COD. On the
other hand, the presence of an oxidizing atmosphere improved COD
removal in both cases, although the non-lignin residue turned out to be
less refractory to oxidation than the black liquor, with COD reductions
of around 60 and 47%, respectively. This suggests that lignin is one of
the more refractory compounds present in the black liquor. Wet oxi-
dation also had a positive effect on the colour reduction for both the
raw black liquor and, in particular, the non-lignin fraction, with re-
ductions in the Colour Numbers of 17 and 92%, respectively. It is in-
teresting to point out here that the colour did not change significantly
during the thermal hydrolysis of the non-lignin fraction, but it increased
by 48% in the case of the black liquor. It seems reasonable to attribute
this to the formation of highly coloured intermediates during the hy-
drolysis of lignin. In this regard, Fang et al. (2008) reported the de-
velopment of a reddish colour for lignin solutions in supercritical water
at high temperature.
Finally, thermal hydrolysis did not have any effect on the pH of the
non-lignin residue, but it decreased in the case of black liquor, sug-
gesting that intermediates from lignin hydrolysis, as well as being
107
Bioresource Technology 284 (2019) 105–114
coloured, have an acid nature. Fang et al. (2008) also measured the
formation of acids during the supercritical hydrolysis of lignin. This
acidification of the medium was greater for the black liquor than for the
non-lignin residue, probably due to the contribution of the inter-
mediates generated from the lignin.
3.2. Chemical oxygen Demand
Once the differences between black liquor and non-lignin residue
have been discussed, the hydrothermal treatment of the latter will be
studied in more detail. The evolution of the Chemical Oxygen Demand
during the partial wet oxidation and the thermal hydrolysis of the non-
lignin fraction at 70 bar and different temperatures are shown in Fig. 2.
It should be noted that only a slight fraction of the total COD is
removed after treatment under the inert atmosphere, whereas the major
part is present in the effluent, showing that the thermal treatment
partially breaks down the organic matter (lignin depolymerization) but
does not completely mineralize it into water and carbon dioxide. In this
sense, Huet et al. (2016) observed a more significant COD reduction
during the hydrothermal treatment of black liquor than in our case,
although at higher temperatures (250–310 °C) and pressures
(5–10 MPa) than the ones used in this study. Although the results show
that the organic load decreased during the whole reaction time, even
during the first 100 min, when the working conditions had not yet been
reached. This reduction was highly dependent on the presence of an
oxidizing atmosphere. For example, after 210 min at 210 °C, COD re-
moval by wet oxidation was 50% higher than that obtained by thermal
hydrolysis.
As expected, increasing the reaction temperature also causes a
higher degradation, by both hydrolysis and oxidation reactions. The
COD reductions at the end of the partial wet oxidation were 35% at
170 °C, 60% at 190 °C and 74% at 210 °C. By contrast, the removals
were only 0%, 10% and 24%, respectively, after thermal hydrolysis.
Similar behaviour was observed in other studies using black liquor:
the reduction of the organic matter increases if higher temperatures are
used, even during the pre-heating phase (Garg et al., 2007; Muddassar
et al., 2015b). For example, using a partial pressure of oxygen of
0.6 MPa and a stirring speed of 800 rpm, Muddassar et al. (2015b) re-
ported COD reductions of 34% after 60 min at 230 °C and 49% at 260 °C
during 80 min after being preheated. In comparison with those values,
and although the working conditions are quite different, the degrada-
tions observed in our case were higher due to the absence of lignin,
which is refractory, mainly due to its structural compactness and sta-
bility (Ma et al., 2018). The COD reductions observed here were 4% at
170 °C, 29% at 190 °C and 43% at 210 °C.
3.3. pH and colour Number
Fig. 3 shows the evolution of pH and Colour Number during the
partial wet oxidation and the thermal hydrolysis of the non-lignin re-
sidue at 70 bar and different temperatures.
The results reveal a lower effect of temperature on both pH and
colour during the thermal hydrolysis than during the wet oxidation. For
example, pH remained approximately constant for all the temperatures
tested in an inert atmosphere, which suggests the hydrolysis reactions
do not generate a significant amount of acid compounds, although the
COD is reduced. In the case of raw black liquor, Zhu et al. (2013)
proposed that thermal hydrolysis converts hemicellulose into organic
acids and the residual lignin into small molecular aromatics without the
appearance of oxidation products such as carbon dioxide, so that nei-
ther the pH nor the colour number drop substantially. As can be seen in
Fig. 3b.2, the decrease in the colour in absence of oxygen is clearly less
pronounced, especially at the lowest temperature tested, which sug-
gests that the explanation of Zhu et al. (2013) may also be valid in the
case of the non-lignin residue. Comparing COD and colour evolution
(Figs. 2 and 3), it can also be concluded that the initial COD removal
L. Pola, et al. Bioresource Technology 284 (2019) 105–114

Fig. 1. Values of pH (a), Colour Number (b)

and COD (c) before ( ) and after applying
wet oxidation ( ) and thermal hydrolysis
(■) to black liquor (BL) and non-lignin re-
sidue (NLR). In all cases: 190 °C, 70 bar and
210 min.

Fig. 2. Chemical Oxygen Demand evolution

at 70 bar and 170 °C ( ), 190 °C ( ) and
210 °C (▲) during the partial wet oxidation
(a) or thermal hydrolysis (b) of the non-
lignin fraction and evolution of temperature
(c) and pressure (d) during the hydro-
thermal treatments.

108
L. Pola, et al.
observed during the first minutes of thermal hydrolysis did not involve
the degradation of coloured compounds in the non-lignin fraction.
On the other hand, the acidification of the medium observed during
the wet oxidation can be linked to the generation of acid compounds. In
this case, an almost complete decolourization is also obtained due to the
oxidation reactions, with a change in the colour of the reaction mixture
from dark brown to pale yellowish after being treated. Muddassar et al.
(2015a), who reported similar behaviour during the wet oxidation of a
raw black liquor, proposed that alkalis were consumed, while the or-
ganic compounds and the sugars were oxidized into short chain car-
boxylic acids and, simultaneously, the coloured intermediates such as
quinone-like compounds were degraded.
In the case of wet oxidation, it can also be pointed out that no
changes in the pH were observed during the first minutes of reaction,
although the COD decreased significantly. Nevertheless, after a fast
decline in the pH between minutes 30 and 90, this parameter reached a
minimum of around 8 and then slightly increased until the end of the
reaction. On the other hand, the COD was continuously reduced during
the reaction period. This suggests that acids are probably formed as
reaction intermediates and not as final products or, in other words, that
there will be a reaction time at which the highest overall concentrations
of acids are achieved. For higher reaction times, both COD and acid
concentrations decrease, although the COD reduction is sharper, and
these changes lead to a rise in pH (Garg et al., 2007). Therefore, it
seems reasonable to propose that the total amount of acids in the
medium decreases as the wet oxidation treatment is carried out, but
also that they will be more easily separated from other compounds of
the non-lignin fraction because the ratio between total acids and COD
concentrations increases. Anyway, this proposal will be discussed in
more detail in the following sections.
109
Bioresource Technology 284 (2019) 105–114
Fig. 3. Evolution of the pH (a) and the
Colour Number (b) at 70 bar and 170 °C ( ),
190 °C ( ) and 210 °C (▲) during the par-
tial wet oxidation (1) and the thermal hy-
drolysis (2) of the non-lignin residue.
3.4. Non-volatile hydroxy acids
Fig. 4 shows the effect of temperature on the evolution of the non-
volatile hydroxy acids during the partial wet oxidation and the thermal
hydrolysis of the non-lignin residue at 70 bar and different tempera-
tures.
Initially, oxalic acid is the main non-volatile hydroxy acid in the
non-lignin residue (29 ± 3 g/L), followed by lactic acid (7.1 ± 0.5 g/
L) and, finally, malic acid (0.6 ± 0.1 g/L). When these values are
compared with those measured in the raw liquor, it can be concluded
that half of the total amount of these types of acids remain in the lignin
fraction (see Table 1).
As can be deduced from the Fig. 4, the evolution of the non-volatile
hydroxy acids with time depends on the specific acid studied, it not
being possible to distinguish a general trend for all of them at first
glance. However, the effect of the temperature and the oxidizing at-
mosphere on their formation and degradation is quite similar. The
findings suggest that the presence of oxygen during the hydrothermal
treatment accelerates the degradation of these types of acids. Mean-
while, the degradation rate of these acids depends on the temperature,
as does their formation rate, obtaining maximum concentrations of
acids at the intermediate temperature of 190 °C. This behaviour could
be explained by assuming that the activation energy of formation is
lower than that of degradation. In such a way, when the temperature
was 170 °C, the formation rate was higher than the removal rate, but it
was still very low to cause an increase in the acid concentration.
However, this formation rate became significant when the temperature
was set at 190 °C, giving place to a higher concentration. Finally, at the
highest temperature, the reaction with the highest activation energy
prevailed and the removal rate became increasingly more predominant.
Focusing now on each non-volatile hydroxy acid, in the case of
oxalic acid, increasing the temperature seems to have a slight negative
L. Pola, et al.
effect on the concentration of the acid during the wet oxidation of the
non-lignin residue. The concentration of this acid decreased by 7% after
210 min at 190 °C using the non-lignin fraction. However, working at
210 °C, at the end of the reaction a 25% reduction in the oxalic acid was
observed, again in the presence of oxygen. Nevertheless, when the same
experiment was carried out in an inert atmosphere, the oxalic acid
concentration remained constant during the whole experiment. What is
more, at 190 °C, a significant formation of oxalic acid was obtained by
thermal hydrolysis, with a final concentration 9% higher than the initial
one. According to Muddassar et al. (2015b), after 120 min of partial wet
oxidation at 270 °C, using a partial pressure of oxygen of 0.5 MPa and
an impeller speed of 800 rpm, the oxalic acid increased a 91% in
comparison with its initial concentration in the black liquor. However,
in our case the concentration of this acid decreased by 5% after 120 min
at 190 °C using the non-lignin fraction.
Malic acid behaved in a similar way to oxalic acid during the
thermal hydrolysis of the non-lignin residue at different temperatures.
Once again, the maximum concentration was detected at 190 °C. After
2 h of reaction, it increased threefold, from 0.6 g/L to 1.8 g/L, but it
started to decline after this time, reaching a final value of 0.9 g/L. This
tendency for the concentration to rise and then begin to decline was
similar, although less marked, at 170 °C. Nevertheless, when the tem-
perature was 210 °C, the concentration of malic acid decreased gently at
110
Bioresource Technology 284 (2019) 105–114
Fig. 4. Evolution of oxalic, malic and lactic
acid concentrations during the partial wet
oxidation and the thermal hydrolysis of the
non-lignin residue at 70 bar and 170 °C ( ),
190 °C ( ) and 210 °C (▲).
the beginning of the reaction and then it remained stable after the first
hour. Therefore, the aforementioned proposal of a higher activation
energy for the removal of the malic acid than for its formation is con-
sistent with the results obtained. Regarding the wet oxidation experi-
ments, the results also corroborate the negative impact of oxygen on the
concentration of malic acid, speeding up its degradation. For example,
although the maximum concentration of malic acid in presence of
oxygen was also achieved at 190 °C, after two hours its value was 0.2 g/
L lower than that obtained during thermal hydrolysis. Moreover, at the
other experimental temperatures employed for wet oxidation, the
concentrations of malic acid were also lower than those reported for
thermal hydrolysis, due to the higher degradation rates caused by the
presence of oxygen. Muddassar et al. (2015b) reported a decrease in the
initial concentration of malic acid of around 28% after 120 min of wet
oxidation at 270 °C; however, using the non-lignin residue, the max-
imum concentration in our case was observed at this time (120 min)
and at 190 °C, registering an increase of 165% in absence of lignin.
Finally, most of the previous comments can also be applied to the
evolution of the concentration of lactic acid, which is shown in Fig. 4.
The maximum levels of lactic acid were also obtained at 190 °C. Like-
wise, the presence of oxygen also improved the degradation of this non-
volatile hydroxy acid, as did high temperatures. However, in the ab-
sence of oxygen there was an initial accumulation of lactic acid that
L. Pola, et al.
stopped after 60 min, and after this time the concentration was main-
tained. The results at 190 °C after 120 min of wet oxidation of the non-
lignin fraction were quite similar to those obtained by Muddassar et al.
(2015b) at 270 °C using black liquor, with an increase in the con-
centration of lactic acid of 32% when the non-lignin residue was oxi-
dized and a 25% increase when the feedstock was the black liquor.
Aside from this, it is interesting to point out that there is a re-
lationship between the structure of the non-volatile hydroxy acids and
their changing concentrations during the hydrothermal treatments. It
appears that the longer the chain is, the lower is the initial concentra-
tion and the higher the reactivity of the acid. Hence, malic acid, which
has the longest structure, has pronounced formation and degradation
rates, while the concentration of oxalic acid, which is the shortest
molecule, hardly changes during the treatment.
3.5. Volatile acids
The evolution of the concentration of the three main volatile acids
detected (formic, acetic and propionic) during the wet oxidation and
the thermal hydrolysis of the non-lignin fraction at 70 bar and at dif-
ferent temperatures is shown in Fig. 5.
Before starting the hydrothermal treatment, acetic acid is the main
volatile acid present in the non-lignin residue, with a concentration of
111
Bioresource Technology 284 (2019) 105–114
Fig. 5. Evolution of formic, acetic and pro-
pionic acid concentrations during the partial
wet oxidation and the thermal hydrolysis of
the non-lignin residue at 70 bar and 170 °C
( ), 190 °C ( ) and 210 °C (▲).
6.4 ± 0.4 g/L, whereas formic and propionic acids had lower, but si-
milar concentrations (1.9 ± 0.3 and 1.7 ± 0.4 g/L, respectively).
Comparison of these values with those seen in the original black liquor
shows that 39% of the total amount of the volatile acids were lost with
the lignin fraction.
Once the hydrothermal treatment has begun, the behaviour of the
volatile acids with respect to temperature and oxygen has much in
common with that of the non-volatile ones. Thus, the maximum con-
centrations of volatile acids were also obtained when the temperature
was fixed at 190 °C and the presence of an oxidizing atmosphere had a
negative effect on their formation.
Thus, focusing on formic acid, the highest concentration was ob-
served after one hour of thermal hydrolysis at 190 °C, with a value of
4.6 g/L, 143% higher than the initial one. After this time, this con-
centration gradually fell until the end of the reaction time, reaching a
final value of 2.8 g/L. Nevertheless, if temperature was increased or
decreased, the formation rate of formic acid dropped. The same beha-
viour was observed when the experiments were carried out under an
oxidizing atmosphere, but the concentration values were lower than
those obtained with thermal hydrolysis at all temperatures. For ex-
ample, by wet oxidation, the maximum concentration of formic acid
was 3.0 g/L, that is to say, 1.6 g/L lower than the maximum under a
non-oxidative atmosphere. Returning to the results achieved by
L. Pola, et al.
Muddassar et al. (2015b), formic acid remained almost constant (with
just a 3% reduction) after 120 min of partial wet oxidation of black
liquor at 270 °C, 0.5 MPa partial pressure of oxygen and 800 rpm im-
peller speed. Similarly, in this study, after 120 min of wet oxidation of
the non-lignin residue at 190 °C and 70 bar, its concentration increased
slightly (5%).
It was seen that the changes in the concentration of acetic acid
followed the same general pattern described above. With thermal hy-
drolysis at 190 °C, the initial concentration of acetic acid almost dou-
bled after two hours of reaction, from 6.4 g/L to 11.8 g/L, although it
slightly decreased after this time. On the contrary, there was no sig-
nificant change in the concentration of this acid when higher or lower
temperatures were used. For wet oxidation experiments, acetic acid
concentrations were lower, as was seen in other cases. For example,
8.9 g/L was the maximum concentration achieved under an oxidizing
atmosphere, which is 2.9 g/L less than the obtained under an inert one.
In the research of Muddassar et al. (2015b) acetic acid increased by
88%; nevertheless, here the increase observed was 37%.
Likewise, propionic acid concentration increased from 1.7 g/L to
3.5 g/L, 111% more, by thermal hydrolysis of the non-lignin fraction
after less than an hour at 190 °C. Surprisingly, this concentration did
not decrease after this time and it remained constant until the end of the
treatment (210 min). The evolution of propionic acid during this
treatment at 210 °C is quite similar to that reported at 190 °C but with a
112
Bioresource Technology 284 (2019) 105–114
Fig. 6. Evolution of the non-volatile ( ) and
volatile ( ) acids in terms of Chemical
Oxygen Demand, their sum ( ) and the
total Chemical Oxygen Demand (●) during
the partial wet oxidation and the thermal
hydrolysis of the non-lignin residue at
70 bar and 170 °C, 190 °C and 210 °C.
lower final concentration (2.7 g/L), whereas no changes in the con-
centration were observed at 170 °C. On the other hand, propionic acid
seems to be less stable under oxidizing conditions.
Curiously, and in contrast to the relation between the chain length
of the non-volatile acids and the evolution of their concentrations, it
seems that the longer the chain of volatile acids, the less is their re-
activity. This is probably due to the fact that acetic and propionic acids
are highly refractory to oxidation (Debellefontaine and Foussard,
2000).
3.6. Comparison
Finally, due to the fact that the purpose of this research is to pro-
duce high added-value products, the changing concentrations of the
different types of acids and the total organic load at the different
temperatures and treatments are shown in Fig. 6.
When comparing the evolution of the acids during hydrothermal
treatment, it is noteworthy that the concentration of non-volatile acids
was always above that of the volatile ones, regardless of the time, the
temperature or the type of atmosphere tested. Fig. 6 also confirms that
the maximum concentration of acids was obtained after two hours of
thermal hydrolysis at 190 °C, with 29.0 g/L of oxalic acid, 1.8 g/L of
malic acid, 10.0 g/L of lactic acid, 4.1 g/L of formic acid, 11.8 g/L of
acetic acid and 3.4 g/L of propionic acid. If yields for hydrothermal and
L. Pola, et al.
fermentation processes are compared with each other, the concentra-
tions of acids obtained by the former are lower. For example, Aspergillus
niger is able to produce more than 100 g/L of oxalic acid after a week
(Emeko et al., 2015) and the productivities of malic and propionic acids
are lower than 0.59 g/L·h (Zelle et al., 2008) and 1 g/L·h (Ahmadi et al.,
2017), respectively. Nevertheless, thermal treatments do possess other
advantages such as a much faster production of acids, easier down-
stream processing and the use of non-biodegradable wastes as raw
material.
As stated above for each acid, the presence of oxygen during hy-
drothermal treatment has a negative impact on the production of both
non-volatile and volatile acids due to the degradation of the acid by
oxidation reactions. For example, the final total acid concentrations
after 210 min of thermal hydrolysis at 170, 190 and 210 °C were, re-
spectively, 20.4, 27.9 and 23.7 g/L. Nevertheless, when experiments
were carried out under the same conditions but with an oxidizing at-
mosphere, the concentrations were 18.4, 22.1 and 13.4 g/L. That is to
say, the presence of oxygen caused a reduction in the final production
of acid of 9.7, 20.7 and 43.4% at 170, 190 and 210 °C. These results
further reveal that the higher the temperature, the more negative the
impact of oxygen on the production of acids from the non-lignin frac-
tion. Nonetheless, although the oxidation reactions reduce the pro-
duction yield of acids, the presence of oxygen during the hydrothermal
treatment does provide a competitive advantage over the thermal hy-
drolysis: a significantly higher ratio of COD due to the acids to total
COD. Thus, around 65–70% of the final COD of non-lignin residue after
being treated by thermal hydrolysis corresponded to acids. On the
contrary, more than 95% of the final COD was generated by the car-
boxylic acids present in the oxidized non-lignin fraction. It should be
here taken into account that the latter term of this ratio, the total COD,
remained almost constant during thermal hydrolysis but decreased in
the case of wet oxidation, whereas the former, the COD due to acids,
increased during both treatments. From an operational point of view,
these results lead to a cheaper and easier downstream processing for
separating the acids from each other and from the other compounds
present in the non-lignin matrix. Therefore, to summarize, the wet
oxidation of the non-lignin fraction generated a less concentrated but
more purified stream of acids than that obtained by thermal hydrolysis.
However, it should be here pointed out that these explanations are
focused on obtaining the maximum total concentration of acids, not
taking into account the specific market value for each of them.
Although mixtures of these organic acids in different concentrations are
being sold currently, for example, for animal feed (Atasoy et al., 2018;
Mänttäri et al., 2015), the further purification of this mixture towards
the pure acids will determine to a large extent the profitability of the
overall process. This fact, however, is beyond the scope of this article,
and would require a deeper discussion.
4. Conclusions
It was found that the optimal conditions were 2 h of reaction, 190 °C
and 70 bar under an inert atmosphere. The maximum concentrations
reached were 29.0 g/L of oxalic acid, 1.8 g/L of malic acid, 10.0 g/L of
lactic acid, 4.1 g/L of formic acid, 11.8 g/L of acetic acid and 3.4 g/L of
propionic acid. However, although wet oxidation reduced the forma-
tion of acids, it generated a more purified stream than that obtained by
thermal hydrolysis or by fermentation. The findings suggest the possi-
bility of obtaining lignin in parallel with other higher added-value
products from the black liquor.
Acknowledgements
The authors are grateful for the financial support from the
Employment, Industry and Tourism Office of Principality of Asturias
(Spain) through project GRUPIN IDI/2018/000127. Authors also ac-
knowledge the financial support from the Spanish Ministry of Economy
113
Bioresource Technology 284 (2019) 105–114
and Competitiveness (MINECO) through Project CTM2015-63864-R
and FEDER funds from European Union.
References
Ahmadi, N., Khosravi-Darani, K., Mortazavian, A.M., 2017. An overview of biotechno-
logical production of propionic acid: from upstream to downstream processes.
Electron. J. Biotechnol. 28, 67–75.
APHA, Awwa, WEF, 2005. Standard Methods for the Examination of Water and
Wastewater. APHA, Washintong, D.C.
Atasoy, M., Owusu-Agyeman, I., Plaza, E., Cetecioglu, Z., 2018. Bio-based volatile fatty
acid production and recovery from waste streams: current status and future chal-
lenges. Bioresour. Technol. 268, 773–786.
Bermúdez-Penabad, N., Kennes, C., Veiga, M.C., 2017. Anaerobic digestion of tuna waste
for the production of volatile fatty acids. Waste Manag. 68, 96–102.
Cardoso, M., de Oliveira, É.D., Passos, M.L., 2009. Chemical composition and physical
properties of black liquors and their effects on liquor recovery operation in Brazilian
pulp mills. Fuel 88, 756–763.
Debellefontaine, H., Foussard, J.N., 2000. Wet air oxidation for the treatment of industrial
wastes. Chemical aspects, reactor design and industrial applications in Europe. Waste
Manag. 20, 15–25.
Djas, M., Henczka, M., 2018. Reactive extraction of carboxylic acids using organic sol-
vents and supercritical fluids: a review. Sep. Purif. Technol. 201, 106–119.
Emeko, H.A., Olugbogi, A.O., Betiku, E., 2015. Appraisal of artificial neural network and
response surface methodology in modeling and process variable optimization of
oxalic acid production from cashew apple juice: a case of surface fermentation.
BioResources 10, 2067–2082.
Fang, Z., Sato, T., Smith, R.L., Inomata, H., Arai, K., Kozinski, J.A., 2008. Reaction
chemistry and phase behavior of lignin in high-temperature and supercritical water.
Bioresour. Technol. 99, 3424–3430.
Farhat, W., Venditti, R., Ayoub, A., Prochazka, F., Fernández-de-Alba, C., Mignard, N.,
Taha, M., Becquart, F., 2018. Towards thermoplastic hemicellulose: chemistry and
characteristics of poly-(ε-caprolactone) grafting onto hemicellulose backbones.
Mater. Des. 153, 298–307.
Gallina, G., Alfageme, E.R., Biasi, P., García-Serna, J., 2018. Hydrothermal extraction of
hemicellulose: from lab to pilot scale. Bioresour. Technol. 247, 980–991.
Garg, A., Mishra, I.M., Chand, S., 2007. Catalytic wet oxidation of the pretreated synthetic
pulp and paper mill effluent under moderate conditions. Chemosphere 66,
1799–1805.
Hellstén, S., Lahti, J., Heinonen, J., Kallioinen, M., Mänttäri, M., Sainio, T., 2013.
Purification process for recovering hydroxy acids from soda black liquor. Chem. Eng.
Res. Des. 91, 2765–2774.
Hu, J., Zhang, Q., Lee, D.J., 2018. Kraft lignin biorefinery: a perspective. Bioresour.
Technol. 247, 1181–1183.
Huet, M., Roubaud, A., Chirat, C., Lachenal, D., 2016. Hydrothermal treatment of black
liquor for energy and phenolic platform molecules recovery in a pulp mill. Biomass
Bioenergy 89, 105–112.
Käkölä, J., Alén, R., Pakkanen, H., Matilainen, R., Lahti, K., 2007. Quantitative de-
termination of the main aliphatic carboxylic acids in wood kraft black liquors by
high-performance liquid chromatography-mass spectrometry. J. Chromatogr. A 1139,
263–270.
Kamali, M., Khodaparast, Z., 2015. Review on recent developments on pulp and paper
mill wastewater treatment. Ecotoxicol. Environ. Saf. 114, 326–342.
Kim, G.H., Park, S.J., Um, B.H., 2016. Response surface methodology for optimization of
solvent extraction to recovery of acetic acid from black liquor derived from Typha
latifolia pulping process. Ind. Crops Prod. 89, 34–44.
Liu, H.M., Li, Y.R., Wu, M., Yin, H.S., De, Wang X., 2018. Two-step isolation of hemi-
celluloses from Chinese quince fruit: effect of hydrothermal treatment on structural
features. Ind. Crops Prod. 111, 615–624.
Luo, Y., Li, Z., Li, X., Liu, X., Fan, J., Clark, J.H., Hu, C., 2019. The production of furfural
directly from hemicellulose in lignocellulosic biomass: a review. Catal. Today 319,
14–24.
Ma, R., Guo, M., Zhang, X., 2018. Recent advances in oxidative valorization of lignin.
Catal. Today 302, 50–60.
Magnin, J.P., Papaiconomou, N., Billard, I., 2018. Polyphenol, polysaccharide and lactate
extraction from pulping factory black liquor by ionic liquids. Sep. Purif. Technol. 196,
140–148.
Mänttäri, M., Lahti, J., Hatakka, H., Louhi-Kultanen, M., Kallioinen, M., 2015. Separation
phenomena in UF and NF in the recovery of organic acids from kraft black liquor. J.
Memb. Sci. 490, 84–91.
Mateos-Espejel, E., Savulescu, L., Maréchal, F., Paris, J., 2011. Unified methodology for
thermal energy efficiency improvement: application to Kraft process. Chem. Eng. Sci.
66, 135–151.
Mendes, F.R.S., Bastos, M.S.R., Mendes, L.G., Silva, A.R.A., Sousa, F.D., Monteiro-
Moreira, A.C.O., Cheng, H.N., Biswas, A., Moreira, R.A., 2017. Preparation and
evaluation of hemicellulose films and their blends. Food Hydrocoll. 70, 181–190.
Muddassar, H.R., Melin, K., De Villalba Kokkonen, D., Riera, G.V., Golam, S., Koskinen, J.,
2015a. Green chemicals from pulp production black liquor by partial wet oxidation.
Waste Manag. Res. 33, 1015–1021.
Mussatto, S.I., Fernandes, M., Roberto, I.C., 2007. Lignin recovery from brewer’s spent
grain black liquor. Carbohydr. Polym. 70, 218–223.
Niemi, H., Lahti, J., Hatakka, H., Kärki, S., Rovio, S., Kallioinen, M., Mänttäri, M., Louhi-
Kultanen, M., 2011. Fractionation of organic and inorganic compounds from black
liquor by combining membrane separation and crystallization. Chem. Eng. Technol.
L. Pola, et al.
34, 593–598.
Muddassar, H.R., Melin, K., Kuppa, S., Koskinen, J., Hurme, M., DE Kokkonen, D., Kallas,
J., 2015b. Novel treatment method for black liquor and biomass hydrolysate with
partial wet oxidation. Cell. Chem. Technol. Cell. Chem. Technol 49, 3–4.
Suárez-Iglesias, O., Urrea, J.L., Oulego, P., Collado, S., Díaz, M., 2017. Valuable com-
pounds from sewage sludge by thermal hydrolysis and wet oxidation. A review. . Sci.
Total Environ. 584–585, 921–934.
Urrea, J.L., Collado, S., Oulego, P., Díaz, M., 2017. Wet oxidation of the structural sludge
fractions. J. Clean. Prod. 168, 1163–1170.
Urrea, J.L., García, M., Collado, S., Oulego, P., Díaz, M., 2018. Sludge hydrothermal
treatments. Oxidising atmosphere effects on biopolymers and physical properties. J.
Environ. Manage. 206, 284–290.
114
Bioresource Technology 284 (2019) 105–114
Vallejos, E., 2017. Hydrothermal treatments applied to agro-and forest- industrial waste
to produce high added-value compounds. BioResources 12, 1–23.
Zelle, R.M., De Hulster, E., Van Winden, W.A., De Waard, P., Dijkema, C., Winkler, A.A.,
Geertman, J.M.A., Van Dijken, J.P., Pronk, J.T., Van Maris, A.J.A., 2008. Malic acid
production by Saccharomyces cerevisiae: engineering of pyruvate carboxylation,
oxaloacetate reduction, and malate export. Appl. Environ. Microbiol. 74, 2766–2777.
Zhao, X., Zhan, L., Xie, B., Gao, B., 2018. Products derived from waste plastics (PC, HIPS,
ABS, PP and PA6) via hydrothermal treatment: characterization and potential ap-
plications. Chemosphere 207, 742–752.
Zhu, Z., Sun, M.M., Su, C., Zhao, H., Ma, X., Zhu, Z., Shi, X., Gu, K., 2013. One-pot
quantitative hydrolysis of lignocelluloses mediated by black liquor. Bioresour.
Technol. 128, 229–234.