Biomass Conversion and Biorefinery

https://doi.org/10.1007/s13399-020-00816-9

ORIGINAL ARTICLE

Contributions of hemicellulose, cellulose, and lignin to the mass

and the porous characteristics of activated carbons produced
from biomass residues by phosphoric acid activation
Henriette Moussounda Boundzanga 1 & Benoît Cagnon 1 & Marjorie Roulet 1 & Stéphanie de Persis 2 &
Christine Vautrin-Ul 1 & Sylvie Bonnamy 1

Received: 7 April 2020 / Revised: 8 June 2020 / Accepted: 10 June 2020

# Springer-Verlag GmbH Germany, part of Springer Nature 2020

Abstract
This paper investigates on the contribution of hemicelluloses, cellulose, and lignin to the carbon mass and the textural properties
of activated carbons produced from lignocellulosic precursors by phosphoric acid activation. Four raw materials (olive pomace,
miscanthus, tomato plants, and poplar wood) were tested. Nitrogen adsorption-desorption at 77 K was used to determine the
porous properties of chars and activated carbons produced from the biomass residues studied. A predictive calculation, based on
the biochemical composition of the raw materials, was studied to evaluate the heat treatment yields without and with the
activating agent and the respective contributions of hemicelluloses, cellulose, and lignin to the chars and to the subsequent
activated carbons of various precursors in terms of carbon weight fraction. The results of this calculation were compared with the
experimental ones. This study shows that the contribution (in carbon mass %) of hemicellulose, cellulose, and lignin in the final
activated carbons after a phosphoric acid activation is very close to the biochemical composition of the lignocellulosic precursor.
It was also found that lignin is responsible for the microporous domain in the activated carbon in contrast with hemicelluloses and
cellulose which are responsible for the formation of the mesoporous domain.

Keywords Lignocellulosic biomass . Chemical activation . Carbon content . Microporosity . Predictive calculation

Statement of novelty
This study forms part of our work on the elaboration of activated carbons
(AC) from different farming biomass residues with a phosphoric acid
activation. The originality of the paper is focused on the predictive cal-
culation, based on the biochemical composition of the raw materials,
which permits to evaluate the heat treatment yields without and with the
activating agent and the respective contributions of hemicelluloses, cel-
lulose, and lignin to the chars and the subsequent AC of various precur-
sors in terms of carbon weight fraction. The results are of interest in the
context of biomass valorization to produce AC by chemical activation
(phosphoric acid) of different types of biomass residues in limiting the
number of experiments thanks to the predictive calculation.
Electronic supplementary material The online version of this article
(https://doi.org/10.1007/s13399-020-00816-9) contains supplementary
material, which is available to authorized users.

* Benoît Cagnon 2
Institut de Combustion Aérothermique Réactivité et Environnement,
benoit.cagnon@univ-orleans.fr ICARE, UPR 3021-CNRS, 1C Avenue de la Recherche Scientifique
CS 50060, 45071 Orléans, Cedex 2, France
1
ICMN (Interfaces Confinement Matériaux Nanostructures) – CNRS
(UMR 7374), Université d’Orléans, 1B Rue de la Ferollerie CS
40059, 45071 Orléans, Cedex 2, France

1 Introduction
The valorization of biomass, in particular residues and/or
wastes from agriculture, represents a very important research
activity in many countries, not only for energy use
(methanization, hydrogen production, ethanol production,
combustion) [1–5] but also for environmental protection with
the development of adsorbent carbonaceous materials [6–10].
The demand and the use of activated carbons (AC) are in-
creasing by more than 10% each year, and it is therefore essential
to find new raw materials to meet this demand by producing
carbonaceous materials with excellent adsorbent properties [7,
11]. Commercial activated carbons are produced from a wide
variety of precursors available in different forms: 55% of the total
production is in powder form (powder), 35% in granular form,
and 10% in the form of rods (or pellets). According to Bansal
et al. [12], 80% of the total production of activated carbons is
used for liquid adsorption applications (decoloration and
depollution of industrial waste, treatment of drinking and indus-
trial water) and 20% for gas adsorption applications (dechlorina-
tion, air purification, gas purification and separation, military
applications for protection against chemical warfare), which re-
quire a wide spectrum of materials with different porous proper-
ties. The most commonly used precursors in industry are wood,
coal, lignite, and coconut, but it is important to valorize new
lignocellulosic materials in order to be able to develop activated
carbons with new textural properties.
Non-hazardous, vegetable waste represents large quantities
of material to be managed [3, 6, 11]. This growing demand is
also reflected in the literature with the increase in numerous
studies and publications devoted to the development of acti-
vated carbons particularly from lignocellulosic materials [11].
The fabrication of activated carbons is carried out accord-
ing to two types of processes (physical and chemical activa-
tions) [12]. As demonstrated as early as 1982 by Mackay and
Roberts [13, 14], the yield and final textural characteristics as
well as the chemical properties of activated carbons depend on
not only the nature and the composition of the precursor but
also on the operating parameters of the activation process
used. In the literature, there are numerous parametric studies,
leading or not to the improvement in the adsorbent properties
of the final activated carbon, that describe the experimental
procedures according to the parameters used [6, 7, 11] and the
different stages of the processes [9, 11, 15, 16].
Hemicellulose, cellulose, and lignin are the main compo-
nents of the biomass which are very studied [17–20]. There
are also many studies on lignocellulosic precursors of different
biochemical compositions in hemicellulose, cellulose, and lig-
nin [1, 17–19] of different kinds. Only a few of them empha-
size the importance of biochemical composition on the final
mass of activated carbon obtained [20] and on the final prop-
erties of the adsorbent material [11, 14, 17, 21] in contrast with
others which only use lignocellulosic material to produce
Biomass Conv. Bioref.
activated carbon without necessarily indicating the biochemi-
cal compositions of the raw materials tested and without con-
sidering the potential activability of the precursor and the final
yield [9, 16, 22–24].
However, knowledge of the biochemical composition of lig-
nocellulosic precursors for the production of activated carbons is
essential in order to try to control the resulting yield of activated
carbons obtained and their final porous characteristics [17]. The
possibility of “optimizing” the precursor composition (identifica-
tion of “ideal” compositions of plant materials) is an original
approach aimed at rapidly orienting the choice of plant resources
and associated treatments (carbonization, physical, or chemical
activations) to control their porosity characteristics. The lack of
data and knowledge on the behavior of various lignocellulosic
biomasses justifies the aim of this study, which consists in sys-
tematically comparing the contribution of each component of a
raw lignocellulosic material (hemicellulose, cellulose, and lignin)
to the thermal treatment yield and porous texture of the activated
carbons produced after chemical activation. For this purpose,
four raw materials were selected: olive pomace (OP), miscanthus
X giganteus (MIS), tomato plants (TOM), and poplar wood
(PW) as well as the three reference lignocellulosic compounds
(hemicellulose, cellulose, and lignin).
These biomasses and compounds were heat-treated without
and with phosphoric acid using the chemical activation pro-
cedure developed by Goncalves Pereira et al. [25] to produce
activated carbons. The porous characteristics of the chars and
activated carbons elaborated from lignocellulosic materials,
obtained from N2 adsorption-desorption isotherms at 77 K,
were compared with those of the materials produced from
hemicellulose, cellulose, and lignin. The objective was to cor-
relate the biochemical composition of the lignocellulosic pre-
cursors with the carbon mass and textural characteristics of the
final activated carbons produced. To achieve this purpose,
predictive calculation, previously developed for the physical
activation of biomasses with water vapor [17], was applied
here to chemical activation with phosphoric acid to predict
the yield of heat treatment (HT) without activating agent and
the burn-off of the activation with activating agent. In this
study, the predictive calculation is based on the use of the
biochemical composition of the lignocellulosic precursors
and on the activation of the main compounds of the biomass
residues (hemicelluloses, cellulose, and lignin) to predict the
contribution of each one to the carbon mass and porosity of
the activated carbons produced.
2 Materials and methods
2.1 Raw materials
A series of activated carbons were prepared using different
lignocellulosic materials coming from different agricultural
Biomass Conv. Bioref.
biomasses and different phosphoric acid mass/raw materials
mass ratios: olive pomace (OP), miscanthus X giganteus
(MIS), tomato plants (TOM), and poplar wood (PW). Olive
pomace came from the Fès-Mèknes-Region in Morocco,
which contributes 25 to 30% of Moroccan production
(250,000 t per year). Miscanthus X giganteus (MIS) came
from a cultivation field in the Centre-Val de Loire region,
whose production covers nearly 200 ha, with an average yield
of 16 t of dry matter per hectare per year. The tomato plants
(TOM) were supplied by a farmer from Centre-Val de Loire
region. Finally, poplar wood (PW) was supplied by the
National Institute of Agronomic Research INRA, Ardon
(France). Poplar is the fourth most harvested species in the
Centre-Val de Loire region.
The three reference compounds of biomass: hemicellulose
(xylan from beech wood (Serva)), cellulose, and alkali lignin
(provided by Sigma Aldrich) were also studied.
2.2 Activation procedure used to produce activated
carbons
The use of acidic activating agents is of particular interest
because the acids lead to a targeted hydrolysis of hemicellu-
lose and cellulose, leaving in the final material a high yield of
carbon coming from lignin [16]. The acidic activating agents
commonly used for chemical activation are sulfuric acid
(H2SO4) [11, 26, 27], nitric acid (HNO3) [11, 28, 29], and
phosphoric acid (H3PO4) [6, 7, 11, 25, 30]. These mineral
acids are also of interest because they are non-toxic to the
environment and therefore usable in an industrial environ-
ment, unlike ZnCl2 [6, 11].
Chemical activation is usually carried out in several stages
but only involves a single heat treatment. The steps are as
follows:
– bringing the activating agent into contact with the raw
material,
– heat treatment,
– rinsing and washing steps.
In the first stage, chemical activation involves the reaction
between the raw material and an activating chemical agent.
The mixing of the precursor and the activating agent can be
carried out in different ways. The powder mixing method [31,
32] consists of grinding the two powders (activating agent and
precursor) and mixing them. The raw material and the activat-
ing agent must have the same granulometry in order to have a
homogeneous activation in terms of porosity (which is diffi-
cult with vegetable raw materials). The burn-off is the function
of the proportion of the activating agent. The difficulty lies in
the efficiency of mixing to obtain a homogeneous powder.
In the case of the impregnation method [31, 32], the crude
precursor is brought into contact with a concentrated solution
of the activating agent. The mix is heated under agitation to a
temperature of 80 °C for several minutes or more without
allowing the solution to evaporate. The longer the stirring
and heating time, the more the activating agent becomes in-
corporated into the core of the precursor particle. The whole is
then filtered and only the solid is recovered. For a given com-
position, the burn-off of the method depends mainly on the
impregnation time. The method of chemical activation by im-
pregnation generally makes it possible to obtain activated car-
bons that are relatively more homogeneous, in terms of chem-
ical composition and adsorbent properties of the material, than
the previous method regardless of the raw material and its
particle size.
Finally, the coating method [33] is carried out under the
same conditions as the previous method, only the heating step
is different. The precursor-concentrated solution of the acti-
vating agent is heated to a temperature of 80 °C. It is then
dehydrated so that the salt of the activating agent crystallizes
around the particles of the precursor. For a given composition,
the burn-off depends on the relative amount of activating
agent and particle size. The coating chemical activation meth-
od does not allow uniform activation of the particle all the way
to the core.
Solid mixtures obtained by any mixing method shall be
heat-treated under a flow of inert gas (nitrogen) from room
temperature to temperatures between 500 and 900 °C. The
heat treatment conditions depend on the precursor and activat-
ing agent used. During the heat treatment, the activating agent
dehydrates the material. The resulting activated carbon can
then be washed with acid and rinsed with distilled water until
a neutral filtrate is obtained. In all cases, the activation levels
depend on the mass ratios between the activating agent and the
precursor. Each mixing method results in activated carbons
with different adsorbent properties.
The processes of action of chemical activating agents dur-
ing chemical activation are complex and still poorly controlled
despite the existence of several studies. One of the major
problems encountered in processes based on chemical activa-
tion is the use of polluting chemical agents. Nevertheless, it
can be said that the action of phosphoric acid on lignocellu-
losic materials is today well-controlled from a mechanistic and
kinetic point of view. Moreover, phosphoric acid has the ad-
vantage of being totally recyclable. In all cases, whatever the
chemical agent used, chemical activation produces high-
performance materials [34].
Thus, for this study, impregnation method and phosphoric
acid were chosen because the specific surface area values of
the activated carbons produced are higher, which is an impor-
tant criterion for the use of activated carbons in a liquid phase
adsorption process [6, 7, 11, 25, 30]. After a comparison of the
various chemical carbon activation procedures found in the
literature in terms of yield and specific surface area, activating
agent, and viability of the experimental conditions, the

experimental conditions used by Gonçalves Pereira et al. [25]
were chosen.
First, the raw material was ground, which ensures a homo-
geneous impregnation of the sample by the activating agent.
The activating agent was phosphoric acid at 85% (wt.%), and
the ratio of raw material to acid was 1:1 or 1:2 (w:w). The
mixture was heated to 80 °C and stirred on a hot plate for
30 min. The resulting material was dried in an oven, under
air, at 110 °C for 15 h. This step allows the sample to be
dehydrated as much as possible. The impregnated material
was then placed in an oven for thermal treatment. The tem-
perature programming was as follows: temperature rise from
room temperature to 500 °C at a rate of 20 °C min−1, under
argon (160 mL min−1) followed by a 40 min interval at 500 °C
and then cooling the sample to room temperature. Generally,
heat treatments in chemical activation take place in a temper-
ature domain of 300–500 °C [6] and the value of 500 °C was
chosen according to our TGA results. In our study, heat treat-
ments with the activating agent were carried out both in a
thermobalance and in an oven.
Thermogravimetric analyses were performed using a TGA
92 thermobalance (Setaram). A mass of approximately
0.040 g of sample was placed in the thermobalance under a
160 mL min−1 argon flow. Systematically, a blank experiment
was carried out, under the same conditions, in order to deter-
mine the correction required for the base-line. The procedure
consisted of a temperature increase at a 20 °C min−1 heating
ramp from ambient temperature to 800 °C (to study a larger
temperature domain), followed by a 1-h interval at this final
temperature and a cooling to room temperature at a cooling
rate of 10 °C min−1.
In order to have a sufficient quantity of material for the
porosity characterization, the same experiments were carried
out with a mass of 10 g in a conventional horizontal furnace,
under a nitrogen flow at a volume rate of 160 mL min−1. The
heat treatment with the activating agent followed the same
procedure as that of the thermogravimetric study but with a
final temperature of 500 °C.
Following these experimental conditions, the sample was
washed with 37% (wt.%) hydrochloric acid. This step elimi-
nates the remaining impurities in the activated carbon obtain-
ed after the heat treatment. The sample was then washed with
distilled water to adjust the pH between 6.5 and 7. Finally, the
activated carbon produced was placed in a vacuum oven at a
temperature of 50 °C for 15 h to ensure complete evaporation
of the water.
In order to compare the thermal behavior of the reference
components (hemicellulose, cellulose, and lignin) with the
raw materials with and without a chemical activation agent,
the usual heat treatment (under nitrogen flow) was carried out.
Then, thermogravimetric analyses were also carried out on the
reference components under the same conditions as described
above. From TGA analyses, the degradation rate and
Biomass Conv. Bioref.
temperature range of each reference compound (hemicellu-
lose, cellulose, and lignin) and of the four lignocellulosic pre-
cursors were determined.
2.3 Material characterization
The quantification of the biochemical composition in hemi-
cellulose, cellulose, and lignin of the raw lignocellulosic ma-
terials was carried out by the Forest Improvement, Genetics,
and Physiology Unit (AGPF) of the INRA Ardon’s GénoBois
Technical Plateau according to the procedure described by
Rabemanolonstoa et al. [35].
Elemental chemical analyses were performed on the three
reference compounds (hemicellulose, cellulose, and lignin)
and the four raw precursors using a Thermo Scientific
CHONS flash 2000 elemental analyzer. The samples were
preconditioned in tin capsules (for C, H, N, and S analyses)
and silver capsules (for O). The capsule must contain a mass
between 0.8 and 1.1 mg of material. To determine the sulfur
content, an amount between 0.8 and 1.1 mg of vanadium
oxide (V2O5) must be added to the tin capsule. The analysis
consists of a flash combustion under He. The detector is a
catharometer with a temperature-controlled gas flow system,
and the gas separation is carried out by elution chromatogra-
phy. For the repeatability of the experiment, three analyses
were performed for each sample.
The porous characteristics of the materials, chars, i.e., when
thermal treatment is performed without the activating agent
and activated carbon, were determined from the conventional
nitrogen adsorption isotherms at − 196 °C obtained by using
an ASAP 2020 Micromeritics apparatus. Beforehand, the
samples were degassed at 250 °C for at least 24 h under a
residual vacuum of at least 6 μm Hg.
From the nitrogen adsorption and desorption isotherms at
− 196 °C, the specific total volume of the porosity (Wt) was
determined, and the specific microporous volume (Wo) and the
average micropore size (Lo) were calculated by applying the
Dubinin-Radushkevich equation [12, 36, 37]. The micropore
size distributions of the different activated materials were de-
termined from the device software implementing the DFT
(Density Functional Theory) method. The specific external
surface area (Sext) was determined from the alpha S method,
and the specific microporous surface area was calculated from
the Stoeckli equation [36].
3 Results and discussion
3.1 Biochemical composition of the raw materials
The mass fractions of hemicellulose, cellulose, and lignin
present in the raw lignocellulosic precursors are reported in
Fig. 1.
Biomass Conv. Bioref.
Fig. 1 Biochemical composition
(in wt.%) in hemicellulose (H.),
cellulose (C.), and lignin (L.) of
the raw lignocellulosic
precursors: olive pomace (OP),
miscanthus (MIS), tomato plants
(TOM), and poplar wood (PW)
Olive Pomace
L.
43.75
Tomato plants
L.
23.20
C.
37.20
As shown in Fig. 1, the three raw lignocellulosic materials
(miscanthus (MIS), tomato plants (TOM), and poplar wood
(PW)) have very similar biochemical compositions (hemicel-
luloses, cellulose, and lignin amounts respectively ranging
from 39.60 to 40.90%, from 35.85 to 38.65%, and from
20.55 to 23.23%). On the other hand, olive pomace (OP) has
a higher quantity of lignin (43.75%) and lower quantity of
hemicelluloses and cellulose (respectively 33.20% and
23.05%) compared with the other three precursors. From a
morphological point of view, as shown in Fig. 1, the precur-
sors are different which should lead to differences in behavior
during the contact with the activating agent and during the
thermal degradation after impregnation with phosphoric acid
and consequently have an influence on the final textural char-
acteristics of the activated carbons obtained.
The elemental compositions of the three reference compo-
nents and the raw lignocellulosic materials are given in
Table 1.
Table 1 shows that the hemicellulose and cellulose used
in this study have similar elemental compositions with
about 41–42 wt.% carbon, 6 wt.% hydrogen, and
Miscanthus
L.
20.55 H.
H. 40.80
33.20
C.
38.65
C.
23.05
Poplar Wood
L.
H. 23.25 H.
39.60 40.90
C.
35.85
50 wt.% oxygen. In contrast, lignin has about 48 wt.%
carbon, 5 wt.% hydrogen, 33 wt.% oxygen, and 4.1 wt.%
sulfur. These results are close to those obtained by Cagnon
et al. [17] on the elemental compositions of hemicellu-
loses, cellulose, and lignin. The elemental composition de-
pends on the origin of the compounds used. Miscanthus
and poplar wood have a similar composition (48–
49 wt.% of carbon, 6 wt.% of hydrogen, 43 wt.% of oxy-
gen, and 2.3–3.3 wt.% of water and ashes). In contrast,
olive pomace contains about 40 wt.% carbon, 6.2 wt.%
hydrogen, 1.7 wt.% nitrogen, 29.4 wt.% oxygen, and
21.8 wt.% water and residues. Tomato plants, which have
a hemicellulose, cellulose and lignin composition similar
to that of miscanthus and poplar wood, have nevertheless
much less carbon (28.2 wt.%), less hydrogen (3.6 wt.%),
and less oxygen (39.8 wt.%) and contain more water and
residues (22.4 wt.%) and nitrogen (5.5 wt.%). It is impor-
tant to know these compositions to develop activated car-
bons from lignocellulosic materials because sometimes this
composition for the same lignocellulosic precursor de-
pends on the geographical location of the culture.

Table 1 Elementary analyses of
the three main components C (%)
(hemicellulose, cellulose, and
lignin) and raw lignocellulosic Hemicellulose H. 41.2
materials Cellulose C. 42.3
Lignin L. 47.8
Olive pomace OP 40.4
Miscanthus MIS 47.8
Tomato plants TOM 28.2
Poplar wood PW 48.6
3.2 Thermogravimetric analysis
In order to understand the role of the activating agent during
the thermal activation step, the thermograms performed with-
out and with activating agent were analyzed and compared.
3.3 Heat treatment without the activating agent
Figure 2 shows the relative mass loss (in %) and the instanta-
neous rate of mass loss (in mg °C−1) as a function of temper-
ature during heat treatment without activating agent per-
formed at 20 °C min−1 under argon flow for hemicellulose
(H.), cellulose (C.), and lignin (L.) compounds.
During heat treatment without the activating agent, hemi-
cellulose (H.), cellulose (C.), and lignin (L.) decompose, vol-
atilize, and polymerize at different rates and temperature
ranges. The TGA mass losses, from ambient temperature to
800 °C, of the hemicellulose (H.), cellulose (C.), and lignin
(L.) are 76.5%, 80.9%, and 55.1% respectively which corre-
spond to heat treatment yield values of 23.5%, 19.1%, and
45.9% respectively. The first loss of mass between 80 and
120 °C corresponds, for these three compounds, to the loss
of water. It represents about 10% of the initial mass for each
compound. The characteristic peaks in DTG correspond to the
most important mass loss, at 354 °C (over a range of 277 to
410 °C) for cellulose and 375 °C (over a range of 203 to
507 °C) for lignin. Hemicellulose displays two peaks at
249 °C and a shoulder at 287 °C (over a range of 203 to
344 °C) unlike what can be found in the literature with only
one peak [17]; this depends on the nature of the pure com-
pound. Unlike hemicellulose (H.) or cellulose (C.), lignin (L.)
decomposes over a wider temperature range, showing that
degradation is much slower. These results are similar to those
of Slopiecka et al. [38] for hemicellulose (characteristic peak
at 287 °C over a range of 200 to 380 °C) and for cellulose
(characteristic peak at 352 °C over a range of 250 to 380 °C).
Figure 3 shows the relative mass (mass loss curves in %)
and the instantaneous mass loss rate variations (in mg °C−1) as
a function of temperature during heat treatment at a
20 °C min−1 heating rate under argon flow, for olive pomace
Biomass Conv. Bioref.
H (%) N (%) S (%) O (%) H2O + ash (%)
5.9 0 0 50.0 2.9
6.4 0 0 50.6 0.7
4.9 0 4.1 33.3 9.9
6.2 1.7 0 29.4 21.8
6.2 0 0 42.7 3.3
3.6 5.5 0.4 39.8 22.4
6.1 0 0 43.0 2.3
(OP), miscanthus (MIS), tomato plants (TOM), and poplar
wood (PW).
On all the thermograms, the water loss occurs between 80
and 120 °C and corresponds to about 10% of the mass loss.
On the other hand, each lignocellulosic precursor has a differ-
ent thermal behavior even if the raw materials have similar
biochemical compositions (see Fig. 1). This is the case for
miscanthus (MIS), tomato plants (TOM), and poplar wood
(PW). Olive pomace (OP) (Fig. 3a) has a well-defined peak
at 280 °C corresponding to hemicellulose and a peak at 340 °C
corresponding to cellulose. Miscanthus (MIS) (Fig. 3b) has
instantaneous rate variations in mass loss similar in shape to
olive pomace (OP) but presents a thermogram with a natural
deconvolution corresponding to hemicellulose (300 °C) and
cellulose (358 °C) peaks. Tomato plants (TOM) (Fig. 3c) and
poplar wood (PW) (Fig. 3d) show similar instantaneous rates
of mass loss variations with a shoulder corresponding to hemi-
cellulose at 250 and 290 °C, respectively, and a peak corre-
sponding to cellulose degradation at 315 and 350 °C, respec-
tively. For the four lignocellulosic precursors, the characteris-
tic peak of lignin is not visible; it is masked by the decompo-
sition peaks of hemicellulose and cellulose, which may ex-
plain why the peak of the cellulose is higher. The respective
TGA mass losses of each of these raw materials, olive pom-
ace, miscanthus, tomato plant, and poplar wood are 72.2, 78.5,
74.8, and 75.7%, which correspond to heat treatment yield
values of 27.8%, 21.5%, 25.2%, and 24.3% respectively at
800 °C. The thermal degradation of each constituent within
the raw material is highly dependent on the experimental car-
bonization conditions and their proportion at the end of car-
bonization, and their structural rearrangement in the final char
may also play an important role in the adsorbent properties of
the resulting activated carbon [14]. It is important to note that
the heat treatment yields obtained in TG and in the furnace
under the same operating conditions, but with a higher initial
mass of precursor for the furnace, are similar.
3.4 Heat treatment with the activating agent
Thermogravimetric analyses were also performed on the ref-
erence compounds and precursors after their impregnation by
Biomass Conv. Bioref.

a 0.7 b 0.7

Hemicellulose 100 354°C Cellulose 100

0.6 0.6

249°C
0.5 80
0.5 80

-dm/dT (mg.°C )
-1
0.4

Mass loss (%)

-dm/dT (mg.°C )
-1

Mass loss (%)

0.4 60
60
0.3
0.3 287°C
40
40 0.2
0.2
0.1 20
0.1 20
0.0
0.0 0
0 0 100 200 300 400 500 600 700 800 900
0 200 400 600 800 X Axis Title
Temperature (°C)

c 0.7
Lignin 100
0.6

0.5 80
-dm/dT (mg.°C )
-1

Mass loss (%)

0.4
60
0.3

40
0.2

375°C
0.1 20

0.0
0
0 200 400 600 800

Temperature (°C)
Fig. 2 (a) Hemicellulose (H.), (b) Cellulose (C.), and (c) Lignin (L.). TGA-DTG experimental curves at 20 °C min−1 under argon

the activating agent to determine the degradation rates and
temperature ranges during the chemical activation step. The
same equipment, quantities, and operating conditions as be-
fore were used.
Figure 4 shows the relative mass (loss curves in %) and the
instantaneous rate variations of mass loss (in mg °C−1) as a
function of temperature during heat treatment at a 20 °C min−1
heating rate under argon flow for impregnated hemicellulose
H., cellulose C., and lignin L. with phosphoric acid in a 1:2
ratio (Fig. 4a, b, c, d).
Figure 4 a shows that cellulose and lignin impregnated with
phosphoric acid have a similar thermal behavior, with a first
peak at 140 °C corresponding to water loss and a second peak
at 230 °C corresponding to the thermal degradation of phos-
phoric acid which probably did not react with the raw materi-
al. At 665–670 °C (temperature higher than the chemical ac-
tivation procedure used in this study), cellulose and lignin
have a significant peak corresponding to the reaction products
between the acid and the raw material. The heat treatment
yield for cellulose and lignin is 64.7% and 71.3% respectively
at 500 °C and 14.0% and 27.2% at 800 °C. On the other hand,
hemicellulose has a different thermal behavior, with a first
peak at 80 °C, corresponding to water loss, and a second peak
at 180 °C, corresponding to the thermal degradation of phos-
phoric acid. After 500 °C, the loss of mass is much lower than
the other two isolated compounds with a very small peak at
610 °C. The heat treatment yield for hemicellulose is 66.9% at
500 °C and 40% at 800 °C. These differences in thermal
degradation are due to the differences in compound/
activating agent reactivity [11].
Figure 4 b shows the superposition of the instantaneous
rate variations of mass loss as a function of the temperature
of the hemicellulose and the hemicellulose impregnated with
phosphoric acid during the activation step. For the impregnat-
ed sample, these results show the disappearance of the char-
acteristic thermal degradation peak of hemicellulose at 249 °C
and 287 °C indicating the reaction between the activating
agent and the hemicellulose. The disappearance of the charac-
teristic thermal degradation peaks of cellulose and lignin were
also observed during the heat treatment of the impregnated
 Biomass Conv. Bioref.

a 0.5 b 0.5

Olive Pomace 100 Miscanthus 100

0.4 0.4

80 80

-dm/dT (mg.°C )
-dm/dT (mg.°C )

-1

M a ss lo ss ( %)
0.3
-1

M a ss lo ss ( %)
0.3
60 60
340°C
280°C
0.2 0.2
40
40

0.1 358°C
0.1 300°C 20
20

0.0 0
0.0 0
0 200 400 600 800
0 200 400 600 800
Temperature (°C)
Temperature (°C)

c 0.5 d 0.5
Tomato Plants 100 100
Poplar Wood
0.4 0.4
80 80

-dm/dT (mg.°C )
-dm/dT (mg.°C )

-1
-1

M a ss lo ss ( % )
M a ss lo ss ( %)

0.3 0.3
60 60

0.2 0.2
40 350°C 40

0.1 315°C 0.1

20 20
290°C
250°C

0.0 0 0.0 0
0 200 400 600 800 0 200 400 600 800

Temperature (°C) Temperature (°C)

Fig. 3 Experimental TG-DSC curves of (a) olive pomace (OP). (b) miscanthus (MIS). (c) tomato plants (TOM) and (d) poplar wood (PW) at a
20 °C min−1 heating rate under argon flow

samples (Fig. 4 c and d). Phosphoric acid activates each of the pomace, miscanthus, tomato plants and poplar wood. After
main compounds in the biomass. The yields obtained for 500 °C, lignocellulosic precursors with a high cellulose mass
phosphoric acid impregnation at a 1:1 ratio (TGA not shown fraction (miscanthus, tomato plants, and poplar wood) have a
here) are 62.6% for hemicellulose, 65.0% for cellulose, and high mass loss, as cellulose is easily degraded by acids. The
60.0% for lignin. disappearance of the characteristic thermal degradation peaks
Figure 5 shows the instantaneous rate variations of mass of hemicellulose, cellulose, and lignin was also observed dur-
loss (in mg °C−1) as a function of temperature during heat ing the heat treatment of each sample of impregnated raw
treatment at a 20 °C min−1 heating rate under argon flow for material (Fig. 5b, c, d and e).
impregnated olive pomace, miscanthus, tomato plants, and
poplar wood.
Figure 5 a shows that the four precursors impregnated with 3.5 Predictive calculations
phosphoric acid have a similar thermal behavior, with a first
peak at 150 °C corresponding to the loss of water, a second The predictive calculation developed by Cagnon et al. [17] for
peak at 250 °C corresponding to the thermal degradation of water vapor activation was transposed in this study to evaluate
phosphoric acid that has not reacted with the raw material and the respective contribution of each component (hemicellulose,
a last peak between 620 and 700 °C corresponding to the cellulose, and lignin) to the mass and porosity of the chemi-
reaction products between the phosphoric acid and the raw cally activated carbon with phosphoric acid. The knowledge
material. At 500 °C (final temperature of the procedure used of the biochemical composition of lignocellulosic precursors
in this study), the heat treatment yield is 68.9, 71.4, 74.9, and for activated carbon production is essential in order to try to
73.2% for olive pomace, miscanthus, tomato plants, and pop- control the resulting masses of activated carbons obtained and
lar wood respectively. At 800 °C, the heat treatment yield is their final porous characteristics. The aim of this calculation is
27.7, 14.5, 19.9, and 9.1% respectively for impregnated olive also to estimate the burn-off of a raw lignocellulosic material,
Biomass Conv. Bioref.

a 0.7 b 0.7
H. HT with H3PO4
H. HT without H3PO4
0.6 C. HT with H3PO4
0.6 H. HT with H3PO4
L. HT with H3PO4
249°C
0.5 0.5
-dm/dT (mg °C )

-dm/dT (mg.°C )
-1

-1
0.4 0.4

0.3 0.3 287°C

0.2 0.2

0.1 0.1 122°C

80°C
610°C
0.0 0.0
0 200 400 600 800 0 200 400 600 800

Temperature (°C) Temperature (°C)

c d 0.7
0.7
C. HT without H3PO4 L. HT without H3PO4
354°C C. HT with H3PO4 0.6 L. HT with H3PO4
0.6

0.5
0.5 -dm/dT (mg.°C )
-1
-dm/dT (mg °C )
-1

0.4
0.4

0.3
0.3
670°C
140°C 0.2
0.2 665°C

140°C 230°C 375°C

230°C 0.1
0.1
100°C
0.0 0.0
0 200 400 600 800 0 200 400 600 800

Temperature (°C) Temperature (°C)

Fig. 4 TGA experimental curves. (a) Hemicellulose H.. cellulose C., and lignin L. activated with a phosphoric acid ratio 1:2; (b) Heat treatment of
hemicellulose, (c) heat treatment of cellulose, and (d) heat treatment of lignin with and without phosphoric acid at 20 °C min−1 under argon flow

knowing its biochemical composition in hemicellulose, cellu-
lose, and lignin, without even performing experiments.
3.6 Predictive calculation: contribution of each
component to the chars after heat treatment without
the activation agent
The predictive calculation is based on the biochemical
composition shown in Fig. 1 and the yields obtained during
the heat treatment of isolated hemicellulose, cellulose, and
lignin. First, based on the experimental results, the contri-
bution of each compound (hemicelluloses, cellulose, and
lignin in Fig. 1) to the formation of the carbonaceous mass
of the char (heat treatment at 800 °C of 10 g of lignocel-
lulosic precursor (olive pomace, miscanthus, tomato
plants, and poplar wood) without the activating agent was
estimated. Table 2 shows the results of the predictive cal-
culation applied to the different natural lignocellulosic
precursors studied; the experimental yields correspond to
the experiments carried out in the furnace at 800 °C.
As described by Cagnon et al. [17], under those experimen-
tal conditions, the yield Y (in %) of char is calculated using the
following equation:
Y ð%wt:Þ ¼ 100−½ð1−xÞ  100 ð1Þ
with,
x ¼ H  yc;H þ C  yc;C þ L  yc;L ð2Þ
Y corresponds to the calculated char mass after heat treat-
ment without the activating agent where H, C, and L are re-
spectively the percentage of compounds in the precursor (in
%) and yc,i are the heat treatment yields of each individual
component (in %).
By taking into account the raw material initial mass, the
contribution of each component can be calculated by the fol-
lowing equation (lignin is given as an example):
 Biomass Conv. Bioref.

a b
0.4 OP HT with H3PO4 0.4 OP HT without H3PO4
MIS HT with H3PO4 OP HT with H3PO4
TOM HT with H3PO4
PW HT with H3PO4
0.3 0.3

-dm/dT (mg.°C )
-dm/dT (mg °C )

-1
-1

0.2 0.2

0.1 0.1

0.0 0.0
0 200 400 600 800 0 200 400 600 800

Temperature (°C) Temperature (°C)

c d
MIS HT without H3PO4 0.4 TOM HT without H3PO4
0.4
MIS HT with H3PO4 TOM HT with H3PO4

0.3 0.3
-dm/dT (mg.°C )
-dm/dT (mg.°C )

-1
-1

0.2 0.2

0.1 0.1

0.0 0.0
0 200 400 600 800 0 200 400 600 800

Temperature (°C) Temperature (°C)

e
PW HT without H3PO4
0.4 PW HT with H3PO4

0.3
-dm/dT (mg.°C )
-1

0.2

0.1

0.0
0 200 400 600 800

Temperature (°C)
Fig. 5 TGA experimental curves. a Olive pomace OP, miscanthus MIS, poplar wood with and without phosphoric acid impregnation, ratio 1:2, at
tomato plants TOM, and poplar wood PW impregnated with a phosphoric a 20 °C min−1 heating rate under argon flow
acid ratio 1:2; (b) olive pomace, (c) miscanthus, (d) tomato plant, and (e)

# " where Lc is the production of the char mass from lignin after heat
x− L  yc;L treatment (in %), x is the calculated char mass after heat treat-
Lca ¼ 1−  100 ð3Þ
x ment, and yc,L are the heat treatment yields of lignin (in %).
Biomass Conv. Bioref.
Table 2 Contribution of each
hemicellulose, cellulose, and Production Production
lignin compound to the H. (HC %) C. (CC %)
composition of chars (after HT
without H3PO4) estimated by OP 36.9 18.5
predictive calculation MIS 37.7 25.7
TOM 35.6 24.1
PW 36.7 23.2
Nevertheless, the calculated yields do not take into account
the amount of residue.
As shown in Table 2, for all the lignocellulosic precursors
studied, the mass contribution of hemicellulose is between
35.6 and 37.7%, that of cellulose between 18.5 and 25.7%,
and that of lignin between 36.6 and 44.6% after the heat treat-
ment without the activating agent. According to these results
and contrary to the previous study [17], lignin can no longer
be considered the majority compound in terms of mass for any
of the chars considered, as this depends strongly on the nature
of the raw precursors and the kind of activation used.
Cellulose and hemicellulose have a significant mass con-
tribution contrary to what some authors describe [39]. This
mass contribution of hemicellulose, cellulose, and lignin in
char is inherent to the biochemical composition of the raw
material. The lignocellulosic precursors studied in this work
have a higher hemicellulose and cellulose content by weight
than the raw materials analyzed in a previous study [17]. This
shows the importance of knowing the biochemical composi-
tion of the raw material to be recovered in the activated car-
bon. Since the mean deviations for each lignocellulosic pre-
cursor are close to 5%, the experimental and calculated results
are consistent, which confirms the validation of this approach.
This difference is greater in the case of poplar wood. This can
be attributed mainly to the fact that the amount of water and
the amount of residue were neglected.
In terms of mass production in the heat treatment step with-
out the activating agent, these results confirm our initial hy-
pothesis: the hemicellulose, cellulose, and lignin compounds
behave within the raw material in the same way as when they
are individually pyrolyzed.
3.7 Predictive calculation: contribution of each
component to the activated carbon after chemical
activation
The same approach was applied for chemical activation in
order to estimate the burn-off rates of each lignocellulosic
precursor and to estimate the respective contribution of each
hemicellulose, cellulose, and lignin compound to the mass of
the final activated carbon. The theoretical activated carbon
mass is calculated according to the following equation:
Production Calculated Experimental Deviation from the
L. (LC %) yield (%) yield (%) average (%)
44.6 20.9 22.4 3.5
36.6 25.2 25.7 0.9
40.2 25.9 26.9 1.9
40.2 26.0 21.9 7.9
x ¼ H  ya;H þ C  ya;C þ L  ya;L ð4Þ
with H., C., and L.; the mass of hemicellulose, cellulose,
and lignin within 10 g of raw material (by applying the mass
% of each compound within the raw material) (Fig. 1); and ya,i
the phosphoric acid chemical activation yields in our case of
each compound alone (in %). The terms H × ya,H, C × ya,C
and L × ya,L indicate the mass of activated carbon produced
by each major compound within the lignocellulosic precursor
(Table 3).
The yield of the theoretical activation (Rcalc) of the raw
material is calculated according to Eq. 5:
Rcalc ð%weightÞ ¼ 100−½ð1−xÞ  100 ð5Þ
The burn-off is estimated according to the following
equation:
Burn−off ð%Þ ¼ 100−Rcal ð6Þ
The results of the predictive calculation on the chemical
activation step applied to the different natural lignocellulosic
precursors studied are summarized in Table 3.
The results presented in Table 3 make it possible to esti-
mate the mass contribution of hemicellulose (between 32.7
and 41.2%), cellulose (between 21.2 and 37.4%), and lignin
(between 22.0 and 46.1%) to the production of carbon for the
lignocellulosic precursors activated with phosphoric acid,
whatever the mass ratio of the raw material to the activating
agent mass. Whatever the impregnation ratio used in the phos-
phoric acid activation process, the carbon contribution of
hemicellulose, cellulose, and lignin remains the same between
the two protocols used. By comparing these results with those
obtained for the heat treatment without the activating agent,
the deviations from the average are close to 5%. The experi-
mental and calculated results are in good agreement and the
predictive calculation can also be considered consistent in the
case of chemical activation with phosphoric acid. Compared
with the physical activation and the results of Cagnon et al.
[16], lignin is not systematically the compound that contrib-
utes the most in the final activated carbon. In this study, it is
shown that, by performing chemical activation with
 Biomass Conv. Bioref.

Table 3 Contribution of each

hemicellulose, cellulose, and Production Production Production Calculated Experimental Deviation from
lignin compound to the H. (HC %) C. (CC %) L. (LC %) yield (%) yield (%) the average (%)
composition of activated carbons
after activation with phosphoric Ratio
acid in a 1:1 and 1:2 ratio 1:1
estimated by the predictive OP 32.7 21.2 46.1 62.0 60.0 1.0
calculation MIS 41.2 36.6 22.2 63.0 63.0 0.0
TOM 39.9 35.1 25.0 62.9 64.7 0.9
PW 41.2 33.8 25.0 62.9 60.0 1.4
Ratio
1:2
OP 32.7 21.9 45.8 68.2 68.9 0.6
MIS 40.6 37.4 22.0 66.7 71.4 3.5
TOM 39.4 35.9 24.7 66.9 74.9 6.0
PW 40.6 34.6 24.8 66.9 73.2 4.7

phosphoric acid, the contribution (in mass %) of hemicellu- thermogravimetry (shown previously in Fig. 3). These precur-
lose, cellulose, and lignin in the final activated carbons is very sors are therefore potentially activatable.
close to the initial mass % of hemicellulose, cellulose, and The porous properties of the corresponding chars are
lignin present in the lignocellulosic precursor. different. Indeed, each char has a low BET surface area
value of 144, 68, 40, and 483 m2 g−1 respectively for
3.8 Porous characteristics of chars and activated olive pomace, miscanthus, tomato plants, and poplar
carbons wood. Owing to the very low values of the BET surface
area of the chars, isotherms were not performed for
Initially, lignocellulosic precursors (olive pomace, these samples. On the other hand, hemicellulose, cellu-
miscanthus, tomato plants, poplar wood) and the reference lose, and lignin chars already have a developed porosity.
compounds (hemicellulose, cellulose, and lignin) were treated This difference is probably due to the morphology and
thermally without the activating agent according to the proce- arrangement of the three compounds within the plant
dure described above. The yields after heat treatment at raw material.
800 °C and the porous characteristics of the different chars In a second step, the three compounds and the four ligno-
obtained are summarized in Table 4. cellulosic precursors were chemically activated according to
Table 4 shows that during heat treatment without activating the procedure described above.
agent, the four lignocellulosic precursors have similar yields Figure 6 shows the adsorption and desorption isotherms of
that are also close to the precursors of the previous study [16], nitrogen at 77 K and the micropore size distributions (accord-
namely 27.8, 21.5, 25.2, and 24.3% respectively for olive ing to DFT theory) of the activated carbons obtained from
pomace, miscanthus, tomato plants, and poplar wood. These hemicellulose, cellulose and lignin with a 1:2 ratio and obtain-
results are in perfect agreement with the results obtained by ed from olive pomace, miscanthus, tomato plants, and poplar
wood with a 1:2 ratio (results of ratio 1:1 not shown here).
Figure 6 a shows that the three activated carbons have
Table 4 Porous characteristics and yields of the various chars (after HT a microporous texture (in the low p/p0 range). The hys-
without H3PO4) obtained from hemicellulose H., cellulose C., lignin L.,
olive pomace (OP), miscanthus (MIS), tomato plants (TOM), and poplar teresis loops of the three isotherms clearly indicate the
wood (PW) presence of mesopores in the final activated carbons, par-
ticularly for cellulose and hemicellulose. The shape of the
SBET (m2 g−1) Yield (%)
isotherm of activated carbon produced from lignin indi-
H. 454 77.8 cates that this material is the most microporous with a low
C. 613 92.2 external specific surface area, while cellulose appears to
L. 108 58.3 be more mesoporous with a high external specific surface
OP 144 27.8
area. Figure 6 b shows that the micropore size distribu-
MIS 68 21.5
tions have two microporous domains for the three sam-
TOM 40 25.2
ples: a first domain centered on 0.55 nm and a second,
wider domain between 1.2 and 2.0 nm, a value at the
PW 483 24.3
boundary of the mesoporous domain.
Biomass Conv. Bioref.

a 1400 b 2.5
AC H. AC H.
1200 AC C.
AC C.

Differential pore volume (cm g )

Adsorbed Volume (STP cm g ) AC L. 2.0

-1
-1
AC L.

3
3

1000

1.5
800

600
1.0

400
0.5
200

0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
p/p0 Pore width (nm)

c 1200
d 2.0
AC OP
AC OP
AC MIS
AC MIS
AC TOM

Differential pore volume (cm g )

1000

-1
AC TOM
Adsorbed Volume (STP cm g )
-1

1.5 AC PW

3
AC PW
3

800

1.0
600

400
0.5

200

0.0
0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
p/p0 Pore width (nm)

Fig. 6 (a) Isotherms of adsorption and desorption of N2 to 77 K and (b) (DFT) of activated carbons made from olive pomace (OP), miscanthus
distribution of micropore sizes (DFT) of activated carbons made from (MIS), tomato plants (TOM), and poplar wood (PW) with a phosphoric
hemicellulose, cellulose, and lignin (ratio 1:2), (c) Isotherms of adsorp- acid (ratio 1:2)
tion and desorption of N2 to 77 K and distribution of micropore sizes

These results show that the chemical activation with
phosphoric acid of the hemicellulose, cellulose, and lignin
compounds allowed the development of activated meso-
porous carbon with a low microporous domain.
Figure 6 c shows that the isotherms of the four activated
carbons have hysteresis loops characteristic of the presence of
mesopores. The shape of the isotherms of activated carbons
from poplar wood and miscanthus is similar to that of the
isotherm of activated carbon from cellulose. On the other
hand, the shape of the isotherms of activated carbons from
tomato plants and olive pomace is similar to that of the iso-
therms of activated carbons from hemicellulose and lignin.
These results are consistent with the biochemical composi-
tions of the raw lignocellulosic compounds (olive pomace
having a higher lignin content than the other three raw
materials).
Figure 6 d shows that micropore size distributions have two
domains: a first one between 0.58 and 0.68 nm and a second,
larger, and wider domain between 1.26 and 2.0 nm, a value at
the boundary of the mesoporous domain. The results show
that the four activated carbons chemically activated with
phosphoric acid have a larger mesoporous texture domain
than the microporous domain.
The yields after the activation step at 500 °C and the porous
characteristics of the different chars and activated carbons
obtained from components (hemicellulose, cellulose, and lig-
nin), olive pomace, miscanthus, tomato plants, and poplar
wood are collected in Table 5.
Table 5 shows that after chemical activation with phospho-
ric acid, hemicellulose, cellulose, and lignin have yields close
to 66.9, 64.7, and 71.3% respectively. These results are in
agreement with the results obtained by thermogravimetry
(Fig. 4).
The porous properties of the corresponding activated car-
bons are different. Activated carbons obtained from hemicellu-
lose, cellulose, and lignin have different specific microporous
volume values of 0.47, 0.40, and 0.30 cm3 g−1 respectively. The
mean micropore size of the activated carbons obtained from
hemicellulose and cellulose are higher and at the mesoporosity
limit of 2.52 and 3.22 nm respectively. These values, up to
2.50 nm, obtained by the Dubininin-Raduskevich equation,
show that the microporous volumes of these activated carbons
 Biomass Conv. Bioref.

Table 5 Yields and porous

characteristics of the various chars Activation yield (%) W0 (cm3 g−1) L0 (nm) Sext (m2 g−1) Smicro (m2 g−1) Stot (m2 g−1)
and activated carbons obtained
from hemicellulose (H.), cellulose H. 66.9 0.47 2.52 321 373 694
(C.), lignin (L.), olive pomace C. 64.7 0.40 3.22 1122 248 1370
(OP), miscanthus (MIS), tomato L. 71.3 0.30 1.60 225 375 600
plants (TOM), and poplar wood
(PW) with a ratio 1:2 OP 68.9 0.29 1.88 396 309 705
MIS 71.4 0.32 2.62 743 244 987
TOM 74.9 0.38 2.21 404 344 748
PW 73.2 0.47 3.01 1009 312 1321

are overestimated. On the other hand, the activated carbon ob-
tained from lignin has an average micropore width of 1.60 nm,
which is representative of a microporous domain. The propor-
tion between the values of the specific external and micropo-
rous surface area indicates a high presence of mesopores in the
activated carbon obtained from cellulose: mesopores represent
82% of the total porosity (taking into account that the calculated
microporosity is overestimated for this activated carbon). The
activated carbon of hemicellulose has equivalent microporous
and mesoporous domains (respectively 54 and 45%) unlike the
activated carbon of lignin which is more microporous (63%
microporosity) as shown by the shapes of the adsorption iso-
therms and the micropore size distribution graph obtained by
the DFT method.
Table 5 shows that after chemical activation with phos-
phoric acid, olive pomace, miscanthus, tomato plants, and
poplar wood have yields close to 68.9, 71.4, 74.9, and
73.2% respectively. These results are also in agreement
with the results obtained by thermogravimetry (Fig. 5).
Concerning their porosity, the activated carbon of olive
pomace has textural characteristics very similar to those
of lignin, which is consistent with the biochemical compo-
sition of this precursor which consists of 43.75% lignin. It
has a significant microporous domain compared with the
others but its mesoporous domain remains nevertheless
larger, representing 56% of the total porosity of the adsor-
bent material. The activated carbon obtained from tomato
plants has textural properties very similar to those of hemi-
cellulose with an average micropore width of 2.21 nm (in
the microporous range). Microporous and mesoporous sys-
tems represent respectively 46 and 54% of the total poros-
ity. The activated carbons of miscanthus and poplar wood
have textural properties similar to those of cellulose with
average micropore widths greater than 2.50 nm: their mi-
cropores are wide at the limit of the mesoporosity. Their
mesoporous network represents 75 and 76% of the total
porosity respectively. Miscanthus and poplar wood have a
significant amount of hemicellulose (40.80% and 40.90%
respectively) and cellulose (38.65% and 35.85% respec-
tively) responsible for mesoporosity within the final acti-
vated carbon.
Predictive calculation is an innovative approach that offers
the possibility of optimizing the choice of raw material (iden-
tification of the “ideal” compositions of plant matter) and the
treatments applied to it in order to rapidly guide the choice of
plant resources and associated treatments (carbonization, acti-
vation) for a given type of application. This should make it
possible to adapt the activation process according to the nature
of the raw material and the proportions of hemicellulose, cel-
lulose, and lignin in the biomass.
4 Conclusions
This study showed that the four lignocellulosic agricultural
residues used (olive pomace, miscanthus X giganteus, to-
mato plants, and poplar wood), activated according to the
same chemical activation protocol with phosphoric acid,
are potentially activatable to produce activated carbon that
are well-developed. This result shows the possibility of
recovery of this agricultural waste. This work has also
clearly established that hemicellulose and lignin are the
major compounds in all activated carbons of the lignocel-
lulosic precursors studied. The proposed predictive calcu-
lation makes it possible, from the biochemical composition
of a lignocellulosic precursor, to estimate the contribution
of hemicellulose, cellulose, and lignin to the yield and the
porosity of the corresponding activated carbon. The com-
pound responsible for the formation of micropores in the
final activated is lignin. In contrast, hemicellulose and cel-
lulose are responsible for the formation of mesopores. The
results are of interest in the context of biomass valorization
to produce activated carbon by chemical activation (here
with phosphoric acid) of different types of biomass. The
predictive calculation makes it possible to estimate, from a
mass of agricultural residues, the mass of activated carbon
likely to be obtained for a given activation process, by
limiting the number of experiments. It also makes it possi-
ble to select the activatable lignocellulosic raw materials
(based on their biochemical composition) in terms of mass
and therefore yield.
Biomass Conv. Bioref.
Acknowledgments The authors thank Jacobi Carbons for gratuitously
supplying ACs: Chambre d’Agriculture du Loiret, PIVOTS, Martin
Pajot and Jean-Paul Charpentier of Institut National de la Recherche
Agronomique (INRA).
Funding information This operation was co-financed by the European
Union and the Conseil Regional du Centre-Val de Loire region through
the European Regional Development Fund. We also acknowledge the
financial support provided by the PIVOTS project and the Conseil
Regional du Centre-Val de Loire (ARD 2020 program and CPER
2015–2020), the French Ministry of Higher Education and Research
(CPER 2015–2020), and subsidy funds from CNRS and University of
Orleans and the “Conseil Général du Loiret”.
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