Biomass Conversion and Biorefinery (2023) 13:13163–13179

[Link]

ORIGINAL ARTICLE

Production and characterization of adsorbents from a hydrothermal

char by pyrolysis, carbon dioxide and steam activation
Ghazaleh Chegini1 · Cedric Briens1 · Dominic Pjontek1

Received: 18 August 2021 / Revised: 23 January 2022 / Accepted: 3 February 2022 / Published online: 24 February 2022
© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2022

Abstract
Adsorbents for wastewater treatment were produced from industrially obtained hydrochars using pyrolysis, C ­ O2, and steam
activation. Both pyrolysis and CO2 activation were studied between 400 to 900 °C, with a holding time of 1 or 2 h. Steam
activation was carried out between 600 to 900 °C for a holding time of 2 h. Pyrolysis, C
­ O2, and steam activation yields were
in the ranges of 44–72, 26–51, and 14–59 wt.%, respectively. The best performing adsorbents based on phenol and methylene
blue removal were obtained at 800 °C and a 2-h holding time with the three gases (­ N2, ­CO2, steam). Steam activation of
hydrochar provided the best adsorbent with maximum capacities of 179 and 167 mg ­g−1 toward methylene blue and phenol.
The maximum Brunauer–Emmett–Teller (BET) surface area of the product was 593 ­m2 ­g−1 with an average pore size diameter
of 4.38 nm and a total pore volume of 0.651 c­ m3 ­g−1. This study shows that adsorbents derived from hydrochar can be used
for wastewater remediation, offering a valorization pathway of a waste stream from hydrothermal processes.

Keywords Hydrochar · Activated carbon · Pyrolysis · CO2 activation · Steam activation · Contaminant adsorption

1 Introduction HTC [3]. Hydrochar applications are generally similar to

those of biochar, a carbon-rich residue from dry pyrolysis,
In recent years, hydrothermal carbonization (HTC), also such as soil amendment for carbon sequestration or fertility
known as wet torrefaction, has received much attention enhancement [4–6], fuel and energy storage [7–9], adsorp-
due to its energy efficiency and higher product yield when tion of contaminants from water [10–13], and catalysis [14].
compared to conventional dry pyrolysis [1]. HTC is a tech- Compared to biochar produced by dry pyrolysis, however,
nology through which wet biomass, such as organic and hydrochar has a higher volatile organic compound (VOC)
agricultural wastes, is heated and decomposed under rela- content, which may leach into water and contribute to its
tively low temperatures (180–350 °C) and elevated pres- contamination. Although some VOCs are water-soluble,
sures (1–5 MPa) in the presence of water [2]. Hydrochar, a washing the hydrochar may not entirely remove them [15].
carbon-rich and lignite-like solid, is one of the products of Hydrochar also generally has a lower surface area and pore
volume when compared to biochar, providing fewer sorption
sites for contaminants [3]. Modifying the hydrochar via acti-
Highlights vation may therefore provide the desired characteristics for
• Activation study for hydrothermal chars obtained from an
industrial process.
contaminant remediation. Moreover, the lower ash content
• Pyrolysis, ­CO2, and steam activation compared at varying of hydrochars makes them a more attractive precursor than
temperature and holding time. biochar to produce activated carbon since inorganic elements
• Products characterized based on aqueous phenol and methylene may hinder the pore and surface area development, weaken-
blue adsorption.
• Steam activation at 800 °C and 2-h holding time produced best
ing their structure and causing pore collapse in the carbon
adsorbents. matrix [16].
Activated carbons are generally produced from coal-
* Dominic Pjontek derived materials using physical or chemical processes that
dpjontek@[Link]
have been widely studied [17, 18]. Since coal is not a sus-
1
Institute for Chemicals and Fuels From Alternative tainable precursor, the focus has thus shifted toward produc-
Resources (ICFAR), Western University, London, Canada ing activated carbons from lignocellulosic biomass, which

13
Vol.:(0123456789)
13164 Biomass Conversion and Biorefinery (2023) 13:13163–13179

has drawbacks due to their lower yields and porosity devel- materials from an industrial hydrochar by-product via
opment from excessive degradation of organic matters [19, pyrolysis (heating under N
­ 2 environment), carbon dioxide,
20]. From this perspective, the lignite (i.e., low-grade coal) and steam activation using a lab-scale fluidized bed as the
structure of hydrothermally treated biomass may represent activation reactor to provide good mixing, heat transfer,
a more suitable precursor for activated carbons. Therefore, and mass transfer [39].
recent studies have investigated the production of activated
carbons from hydrochars obtained from lignocellulosic bio-
mass [21–25]. Compared to pristine hydrochar, the derived 2 Materials and methods
activated carbons showed improved performance as liquid-
phase adsorbents [3]. 2.1 Hydrochars
Liquid-phase adsorption performance can be expressed in
terms of surface area and adsorption efficiency toward model The hydrochar-like materials were provided by Origin Mate-
compounds, such as phenol and methylene blue [26–28]. rials and were generated from a patented process using wood
The choice of these molecules is justified by their physico- feedstocks. Initial experiments were completed using the
chemical characteristics and their role in wastewater pollu- first batch of hydrochar material, referred to as “batch 1.”
tion. Phenol and its derivatives are considered priority pol- Origin then provided a second feedstock batch once the ini-
lutants in water by US Environmental and Pollution Agency tial material was depleted, which was observed to produce
(EPA) [29] as they exist in industrial wastewater discharges different results due to different hydrothermal conditions.
such as petrochemical plants, textile processing, oil refining, Batches are thus referred to as batch 1 and batch 2 in the
pharmaceutical manufacturing, and insecticide production. following sections. Table 2 compares the textural and phys-
The EPA limit for phenol concentration is 0.1 and 0.002 mg icochemical properties of the two batches. Batch 2 was used
­L−1 for wastewater and drinking water, respectively [30]. to reproduce some of the pyrolysis and activation hydrochars
Even at low concentrations, phenol is considered highly to compare based on one feedstock. The main difference
toxic to aquatic life and humans [31]. Methylene blue is a between the feedstocks, as shown in Table 2, is the ash con-
commonly used dye in textile industries and is thus present tent. An advantage of using two different batches was to
in some industrial effluents. Both phenol and methylene blue confirm that high value activated carbon could be obtained
represent other organic contaminants: phenol represents low- from hydrochar, independently of the minor variations that
molecular-weight organic micropollutants in water, while can be expected with natural feedstocks and industrial pro-
methylene blue is widely used as one of the model com- cesses. It should be noted that the hydrochar material was
pounds for larger organic contaminants [32–34]. used in the same condition as received and no additional
Several studies have examined the adsorptive properties chemical or mechanical treatment was performed before
for various contaminants on hydrochars and their derived each experiment.
activated carbons [27, 35–38]. These studies generally
focus on tuning the hydrothermal carbonization process 2.2 Commercial activated carbons
conditions to optimize the final activated adsorbents;
however, industrial hydrochars, typically considered HTC Two types of commercial activated carbons (AC) were
by-products, are obtained at conditions optimized based purchased from General Carbon Corporation to represent
on the production of other value-added chemicals. In the available activated carbons proposed by the manufacturer
latter case, the activated adsorbent properties would thus for removing organic compounds from wastewater streams.
benefit from optimizing the activation process parameters. GC 20 × 50 is a granular AC made from bituminous coal,
To our knowledge, this approach has not yet been estab- and GC 12 × 40 is made from coconut shells.
lished. Table 1 provides a summary of previous studies
on pyrolysis, ­CO 2, and steam activation of hydrochars. 2.3 Reactor
Specifically, the impacts of the temperature and holding
time on the performance of the produced adsorbents are The reactor used for pyrolysis and activation is the Jiggle
expressed in terms of methylene blue and phenol adsorp- Bed Reactor (JBR), developed at the Institute for Chemi-
tive capacity and the Brunauer–Emmett–Teller (BET) cals and Fuels from Alternative Resources (ICFAR) for
surface area and Barrett-Joyner-Halenda (BJH) pore size studies on endothermic reactions. Schematics of the reactor
distribution. Furthermore, most lab-scale activation units configurations for pyrolysis/CO2 and steam activations can
are fixed-bed configurations with mass and heat transfer be found in Fig. 1, respectively. The JBR is a semi-batch
limitations along the reaction zone, suggesting that the fluidized reactor made of Inconel with an inner volume of
activation does not occur under a uniform atmosphere. 80 mL, agitated by a pneumatic actuator. The frequency
This work thus focuses on the production of porous carbon and amplitude of the agitation are controlled by a solenoid

13
Biomass Conversion and Biorefinery (2023) 13:13163–13179 13165

Table 1  Comparison of activated hydrothermal char characteristics from different feedstocks

Hydrochar Activation gas Temp (°C) Time (h) Yield (%) SBET ­(m2 ­g−1) Adsorbate Capacity (mg Reactor Type Reference
source ­g−1)

Orange peels CO2 750 1.5 47 301 Diclofenac 5.7 Tubular reac- [35]
Salicylic acid 17.5 tor
Flurbiprofen 136.8
Air 300 1.5 31 499 Diclofenac 52.2
Salicylic acid 108.8
Flurbiprofen 158.8
Salix psam- N2 700 1 21.1 350 – – – [27]
mophila
wood
Rice husk CO2 800 0.5 89.7 292 – –
1 80.5 358 Cu (II), Phenol 22.62, 39.3
1.5 73.8 419 – –
2 73.4 446 – –
Walnut shell CO2 850 0.5 48 379 – – Tubular reac- [36]
Sunflower stem CO2 850 0.5 44 438 – – tor
Olive stone CO2 850 0.5 49 438 – –
Walnut shell Air 250 0.5 29 213 – –
Sunflower stem Air 250 0.5 59 434 – –
Olive stone Air 250 0.5 23 204 – –
Hickory CO2 600 1 50 445 Methylene 80, 1.7 Quartz reactor [37]
2 48 453 blue, Cu 80, 1.4
CO2 700 1 46 441 Methylene 80, 1.5
2 46 465 blue, Cu 80, 1.8
CO2 800 1 44 474 Methylene 77, 1.3
2 30 667 blue, Cu 70, 3.4
CO2 900 1 34 703 Methylene 128, 3.2
2 28 928 blue, Cu 144, 4.6
Peanut hull CO2 600 1 54 310 Methylene 48, 1.3
2 52 353 blue, Cu 48, 1.1
CO2 700 1 52 349 Methylene 48, 2.1
2 54 365 blue, Cu 70, 2.6
CO2 800 1 52 345 Methylene 70, 3.2
2 42 488 blue, Cu 70, 3.2
CO2 900 1 34 988 Methylene 192, 3.8
2 38 1308 blue, Cu 160, 4.3
Beer waste CO2 800 2 24.1 570 – – – [38]
Horse manure CO2 800 2 13.1 749 – –
Grass cutting CO2 800 2 31 841 – –
Biosludge CO2 800 2 14.9 326 – –

valve programmed with an Arduino, using values found to 2.4 Pyrolysis

ensure excellent particle mixing and heat transfer [39]. An
induction unit with a 9 kW power capacity is used as the Nitrogen gas was used to pyrolyze hydrochars under dif-
heating source. A proportional-integral-derivative (PID) ferent temperatures (400–900 °C) and holding times (1
temperature controller was used to set the heating rate and 2 h). The reaction setup is presented in Fig. 1. In addi-
(50 °C ­min−1), the final activation temperature, and the tion, the batch number and process conditions (i.e., gas
holding time at the final temperature. After each run, prod- flowrate, heating rate, temperature, and holding time) are
ucts were cooled to room temperature (~ 125 °C ­min−1) provided in Table 3. During initial runs, challenges with
under a nitrogen environment and were stored in an airtight clogging and bed agglomeration were observed with the
container before characterization. All runs were performed feedstock due to the fine and soft nature of the hydrochar
at atmospheric pressure. preventing a uniform formation of products. As a result,

13
13166 Biomass Conversion and Biorefinery (2023) 13:13163–13179

Table 2  Proximate, ultimate analysis, surface area, and porosity char- from the surface at elevated temperatures to develop the
acteristics of hydrochar batches presented as mean ± standard devia- pore structure (reaction 3). However, the gaseous CO in
tion (triplicates)
the vicinity of the carbon surface can be re-adsorbed on the
Batch 1 Batch 2 surface to retard further reactions (reaction 4). Note that in
Proximate (wt% dry basis)
all following reactions ­Cf, C(O), and C (CO) are the free
Moisturea 2 ± 0.1 1 ± 0.1
active carbon site, carbon–oxygen complex, and adsorbed
Volatile matter 55.5 ± 0.3 54.5 ± 0.2
CO respectively [18].
Ash 0.6 ± 0.1 1.7 ± 0.1 Cf + CO2 → C(O) + CO ΔH = +172 kJ mol−1 (2)
Fixed carbon 43.9 ± 0.2 43.8 ± 0.3
Ultimate (wt% dry basis)
N 0.2 ± 0.1 0.2 ± 0.1
C(O) → CO + Cf (3)
C 62.9 ± 0.1 62.7 ± 0.1
H 4.3 ± 0.0 4.4 ± 0.0 Cf + CO → C(CO) (4)
S 0.4 ± 0.0 0.4 ± 0.0
The most commonly reported temperatures used in prior
Ob 32.3 ± 0.1 32.4 ± 0.3
studies are in the range of 700 to 900 °C, with typical hold-
pHc 3.10 3.05
ing times of 1–2 h [18]. Therefore, hydrochar activation
Porosity characterization
using ­CO2 was conducted under temperatures ranging from
SBET ­(m2 ­g−1) 116 109
700 to 850 °C and holding times of 1, 2, or 3 h. Table 3
Smeso ­(m2 ­g−1) 116 109
provides all studied CO2 activation conditions. Hydrochar
Smicro ­(m2 ­g−1) 0 0
(2.5 g) was placed in the reactor, and the reaction chamber
Dp (nm) 16.98 19.10
was sealed and flushed with C ­ O2 before the run. However,
Vmicro ­(cm3 ­g−1) 0 0
at the end of the run, the sample was cooled down under ­N2
Vtotal ­(cm3 ­g−1) 0.33 0.4
flow to prevent further reaction.
Vmeso ­(cm3 ­g−1) 0.33 0.4
a
After drying at 80 °C for 24 h 2.6 Steam activation
b
Calculated by difference
c
Measured following IBI procedure[96] Steam can be a lower cost activation agent than carbon diox-
ide [41, 42]. The heterogeneous water–gas shift reaction is
the sample size had to be reduced to 2.5 g. Therefore, the primary path for carbon conversion and pore creation
before each experiment, 2.5 g of batch 1 hydrochar was during steam activation [43, 44]. Similar to C­ O2 activation,
placed in the reactor, and the reaction chamber was sealed the forward reaction is facilitated at elevated temperatures
and flushed with nitrogen before each run. The conditions (> 600 °C) [45].
were then set to those summarized in Table 3 to obtain the
products, which will be referred as pyrolytic hydrochars
C + H2 O(g) ⇌ CO(g) + H2 (g) (5)
in this study. The reaction starts with the dissociative chemisorption
of water on the carbon surface to form carbon–oxygen com-
plex, C(O), and releases hydrogen (reaction 6). The C(O)
2.5 CO2 activation
complex can further decompose to yield carbon monoxide
and a new free carbon active site (reaction 7). The back-
Carbon reacts with C ­ O2 via the endothermic Boudouard
ground CO can increase the gasification rate by scavenging
reaction (1). Due to large positive enthalpy (+ 172 kJ ­mol−1),
­ O2 (reac-
of the adsorbed oxygen (in form of C(O)) to form C
the forward reaction is thermodynamically favored at tem-
tion 8). At high temperatures, the water–gas shift reaction
peratures greater than 700 °C [40]. The reaction rate is tem-
can be catalyzed on the surface of carbon as reaction (9).
perature-dependent, and an increase in the temperature facil-
Activation of the carbon surface takes place by the resultant
itates the bulk diffusion of C­ O2 molecules into the pores,
­CO2 and ­H2 gas (reactions 10 and 11) [18, 46].
removing carbon atoms and resulting in a higher degree of
burn-off. Cf + H2 O → C(O) + H2 ΔH = +131 kJ mol−1 (6)
C + CO2 (g) ⇌ 2CO(g) (1)
C(O) → CO + Cf (7)
In this process, C
­ O2 dissociates on the carbon surface
to form surface oxides and carbon monoxide as shown in
CO + C(O) → CO2 + Cf (8)
reaction (2). Subsequently, the surface oxide is desorbed

13
Biomass Conversion and Biorefinery (2023) 13:13163–13179 13167

Fig. 1  Schematic of the JBR used for pyrolysis and activation of hydrochar

Table 3  Studied hydrochar pyrolysis and activation operating conditions

Batch number Gas Temperature (°C) Heating rate (°C Gas flowrate, STP Hold-
­min−1) (mol ­h−1) ing time
(min)

Pyrolysis
Batch 1 N2 550, 600,650, 700, 750, 800, 850, 900 50 0.4 60
Batch 1 N2 400, 450, 500, 550, 650, 750, 800, 850 50 0.4 120
Batch 2 N2 500, 800 50 0.4 120
Batch 2 N2 850 50 0.4 60
Activation
Batch 1 CO2 750, 800, 850 50 0.4 60
Batch 1 CO2 750, 800 50 0.4 120
Batch 1 CO2 700, 750 50 0.4 180
Batch 2 CO2 800 50 0.4 120
Batch 2 Steam-N2 500, 600, 700, 800, 900 50 0.4 120
(70:30 mol%)

CO + H2 O → CO2 + H2 ΔH = −41 kJ mol−1 (9) Hydrogen can inhibit the activation reaction by for-
mation of C(H) or C(H)2 complexes as a result of disso-
ciative adsorption (12), associative adsorption (13), and
Cf + CO2 → 2CO ΔH = +171 kJ mol−1 (10) reverse oxygen exchange reaction (13) which ultimately
block the carbon active site for sequential activating
Cf + 2H2 → CH4 ΔH = −74.5 kJ mol−1 (11) mediums [47].

13
13168 Biomass Conversion and Biorefinery (2023) 13:13163–13179

1 Where ­mhydrochar and ­mproduct are the masses of the raw

Cf + H2 ⇌ C(H) (12)
2 hydrochar and the resulting product, respectively, on a
dry basis. All samples were dried overnight in an oven at
Cf + H2 ⇌ C(H)2 (13) 107 °C before weighing.

2.7.2 Surface area and pore volume

C(O) + H2 → Cf + H2 O (14)
The rate of the carbon-steam reaction (15) is about The specific surface area ­(SBET) was determined from nitro-
two to five times faster than that of the Boudouard reac- gen adsorption–desorption isotherms in the relative pres-
tion (16), which is attributed to the higher diffusion sure range of 0.3. The samples were measured using the
rate of steam into the pores due to its smaller molecu- Brunauer–Emmett–Teller (BET) method by ­N2 physisorp-
lar size [46]. Moreover, compared to CO2 activation, tion at 77 K with a NOVA 1200e (Quantachrome Instru-
steam-activated carbons have shown higher presence of ment, Florida, US). Pore volumes were calculated from the
O-containing functional groups (responsible for carbon desorption branch of N ­ 2 isotherms using Barrett-Joyner-
surface charge), wider range of pore size distribution, Halenda (BJH) theory.
and larger surface area. A detailed discussion about
effect of physical activation and pyrolysis processes on
2.7.3 Batch adsorption measurement
the chemical and morphological properties of carbona-
ceous material are available in reviews by Sajjadi et al.
Methylene blue and phenol were used in batch adsorption
[17, 18]
measurements to compare the performance of activated
According to the same reviews, it is believed that acti-
hydrochars for the removal of organic contaminants from
vation at temperatures between 700 and 800 °C and a
water. Table 4 shows the physicochemical properties of
holding time close to 2 h results in products with higher
both adsorbates. All solutions were prepared by dilution
surface area and porosity [18]. Therefore, hydrochar acti-
in DI water of known masses of methylene blue (MB) or
vation was carried out in the JBR using 2.5 g of batch 2
phenol in crystalline forms. The pyrolytic and activated
at temperatures between 500 and 900 °C with a holding
hydrochars were rinsed by submersion in DI water and
time of 2 h.
sonicated for one hour to remove submicron particles along
The modifications to the reactor setup required for
with some impurities. The products were then oven-dried
steam activation are presented in Fig. 1. A quartz bub-
for 24 h at 107 °C. Batch adsorption experiments were car-
bler was filled with deionized (DI) water and placed
ried out by placing 0.02 g of pyrolytic or activated hydro-
inside a container filled with boiling water to generate a
char in contact with 15 mL of 1000 mg L ­ −1 methylene blue
mixture of steam and nitrogen. Nitrogen gas flowing at −1
or 800 mg ­L phenol solutions inside 25 mL glass tubes.
0.4 mol ­h−1 was bubbled through the DI water, and steam-
The mixtures were then agitated using an incubator shaker
saturated gas was obtained at the exit with a temperature
at 1000 rpm for 48 h at 30 °C. The solutions were then
of approximately 90 °C at nearly atmospheric pressure.
centrifuged, and the final concentration of methylene blue
The molar percentage of steam can be estimated as 70%
or phenol was measured with a UV–Vis spectrophotometer
to 30% based on the water vapor pressure. A coil heater
(Thermo Scientific EVO 220) at wavelengths of 664 or
immediately downstream from the bubbler prevented
270 nm, respectively. The batch adsorption capacities were
condensation in the feed line by superheating the gas to
calculated as follows:
200 °C before entering the reactor.
C0 − Ct
qt = ×V (16)
mChar
2.7 Product characterization
Where ­C0 (mg ­L−1) is the initial contaminant concen-
2.7.1 Yield tration, V (L) is the volume of contaminated solution, C ­t
(mg ­L−1), and ­qt (mg ­g−1) are the contaminant concentration
The product yield for each experiment was measured as a and the amount of contaminant adsorbed on the solid phase,
weight percentage using the following equation: respectively, at the end of the adsorption measurement. The
adsorption capacity of each hydrochar product for 800 mg
m product
Product yield (wt%) = × 100% (15) ­L−1 methylene blue and 1000 mg ­L−1 phenol after 48 h is
m hydrochar referred to as ­q800 and ­q1000, respectively.

13
Biomass Conversion and Biorefinery (2023) 13:13163–13179 13169

Table 4  Physicochemical
characteristics of phenol and Properties Phenol Methylene blue (MB)
methylene blue [97–100]

Chemical formula C6H5OH C16H18ClN3S

Molecular weight
94.11 319.85
(g mol-1)

pKa 9.9 3.8

Acid-base properties Acidic Basic

Molecular structure

Water solubility
87 43.6
(g L-1)

λ (nm) 270 664

2.7.4 Adsorption isotherm 3 Results and discussion

Adsorption isotherms were measured for pyrolytic and acti- 3.1 Hydrochar pyrolysis
vated hydrochars with high methylene blue and phenol batch
adsorption capacities. Solutions with a volume of 15 mL 3.1.1 Yield
with varying initial concentrations of methylene blue (100 to
1000 mg ­L−1) and phenol (50 to 1000 mg L ­ −1) were placed in Nitrogen pyrolysis of hydrochars was carried out using the
25 mL test tubes. Approximately 0.02 g of solids were added batch 1 feedstock. The pyrolytic hydrochar yield consist-
to the solution and agitated at 1000 rpm in a shaker at 30 °C ently dropped as the temperature was increased from 400
for 48 h. Preliminary studies had shown 48 h to be enough to to 900 °C, and as the holding time was increased from 1 to
reach equilibrium under adsorption conditions used. Langmuir 2 h (Fig. 2). Increasing the temperature and holding time
(Eq. 3) and Freundlich (Eq. 4) models were used to describe facilitates the removal of chemically bound moisture and the
the adsorptive behavior of contaminants onto pyrolytic and
activated hydrochars produced under optimum conditions.
Linear forms of these isotherms were used in our calculations:
Ce 1 1
Langmuir isotherm ∶ = + ∙ Ce (17)
qe KL qm qm

Freundlich isotherm ∶ log(qe ) = log(KF ) + nlog(Ce ) (18)

where ­Ce (mg L ­ −1) is the contaminant concentration at equi-
librium, ­qe (mg ­g−1) is contaminant adsorbed on the solid
phase at equilibrium (calculated from Eq. 2 when ­Ct = ­Ce),
­qm (mg g­ −1) is the maximum monolayer adsorption capac-
ity of the adsorbent, ­KL (L ­mg−1) is the Langmuir constant
related to the affinity between the adsorbent and contami-
nant, ­KF ((mg ­g−1) (mg ­L−1)n)) is the Freundlich constant,
and n is the Freundlich intensity parameter that reflects the
Fig. 2  Effect of temperature and holding time on the yield of pyro-
magnitude of the adsorption driving force. lytic hydrochars from batch 1

13
13170 Biomass Conversion and Biorefinery (2023) 13:13163–13179

decarboxylation reactions and eliminate surface groups that

can participate in the efficient adsorption of contaminants
[52, 53].
Figure 4 presents an increasing phenol adsorption capac-
ity as a function of the pyrolysis temperature. A longer hold-
ing time of 2 h compared to 1 h generally increased the
adsorption capacity, though its impact was lower than the
pyrolysis temperature. Prior studies have suggested that
micropores (< 2 nm) and narrow mesopores (2–10 nm)
are the main contributors to adsorption of phenol in the
pores. Adsorbate-adsorbent intermolecular interactions
are reinforced in micropores due to the enhanced adsorp-
tion potential occurring from the opposite graphene walls.
However, adsorption of phenol trough complexation with
surface mostly occurs in mesopores. It should be noted that
Fig. 3  Effect of pyrolysis temperature and holding time on methylene
blue adsorption capacity of pyrolytic hydrochars from batch 1. Ini-
macropores are believed to mainly facilitate the diffusion
tial methylene blue concentration of 800 mg L ­ −1 and temperature of of contaminant molecule to the adsorption sites [54, 55].
30 °C Besides porosity, since phenol is considered a weak acid,
its adsorption can be enhanced in carbons with higher sur-
face basicity [56]. It is believed that the increase in phenol
decomposition of organic materials. Past studies observed adsorptive capacity with an increase in pyrolysis temper-
the same trend for pyrolysis of bamboo shoot shells [48], ature and holding time is due to higher surface area and
pine needles, and other biomass [27]. micropore volume and stronger aromatic structure and thus
surface basicity [57–59].
3.1.2 Contaminant adsorption
3.2 Hydrochar ­CO2 and steam activation
Figure 3 shows that the methylene blue adsorption capacity
for pyrolytic hydrochars did not significantly change when 3.2.1 Yield
varying the pyrolysis temperature under both studied holding
times. Nonetheless, increasing the holding time from 1 to 2 h Figure 5 provides the product yields obtained when varying
increased the adsorption capacity of pyrolyzed hydrochars the holding times and activation gases. The product yield is
from approximately 40 to 70 mg ­g−1. The reduced impact consistently reduced when increasing the holding time and
of pyrolysis temperature on methylene blue adsorption was the activation temperature between 700 and 850 °C. Hydro-
unexpected but may be explained by a synergistic effect of char from batch 2 was used for the steam activation runs
surface textural properties and surface chemical structure.
Thermal carbonization under nitrogen not only modifies the
carbon structure and porosity but can also change the nature
of surface functional groups by eliminating heteroatoms
such as hydrogen and oxygen, reducing surface polarity,
and lowering O-containing functional groups [49]. Increas-
ing pyrolysis temperature has been shown to increase the
porosity and surface area by removing higher volumes of
VOCs, improving contaminant adsorption [50]. Adsorbents
remove contaminants (adsorbate) from water by two distinct
mechanisms: physical and chemical adsorption. Physical
adsorption (physisorption) occurs when the intermolecular
interactions (Van der Waals forces) between the adsorbate-
adsorbent are stronger than those of adsorbate-water. On the
other hand, chemical adsorption (chemisorption) involves
chemical bonding (shared electron) between the adsorbate
and active sites on the adsorbents. These active sites mainly
Fig. 4  Effect of pyrolysis temperature and holding time on phenol
include O-containing functional groups [51]. Higher tem- adsorption capacity of pyrolytic hydrochars from batch 1. Initial phe-
peratures during pyrolysis can promote dehydration and nol concentration of 1000 mg ­L−1 and temperature of 30 °C

13
Biomass Conversion and Biorefinery (2023) 13:13163–13179 13171

temperature and holding time. The activated hydrochars

obtained with 2 or 3 h holding times at 750 °C have similar
adsorption capacities. Figure 5 demonstrates similar yields
at the conditions mentioned above, suggesting a relationship
between yield and adsorption capacities. The 1-h activation
at 850 °C with C ­ O2 showed the highest methylene adsorp-
tion capacity. Hydrochar steam activation showed minimal
improvement up to 600 °C, followed by an increase in meth-
ylene adsorption up to 800 °C with a slight drop at 900 °C,
which seems to be within the error of the experiment. Previous
literature showed an increase in surface area and dye adsorp-
tion capacity, increasing activation temperature [60–63].
Increasing the activation temperature under ­CO2 and
steam increased phenol adsorption capacity, as shown in
Fig. 7. Similar to ­N2 pyrolysis, the activation temperature
Fig. 5  Effect of activation temperature and holding time on yield of
­CO2 activated hydrochars from batch 1 and steam activated hydrochar significantly impacts the phenol adsorptive capacity com-
from batch 2 pared to the holding time, likely because of the higher sur-
face area and microporosity created at elevated temperature,
as observed in prior work [62, 64–66]. Moreover, methylene
within an activation temperature range of 500–900 °C. The blue and phenol capacities of the steam-activated hydro-
steam activation product yields also dropped as the tempera- char appear to reach a plateau above 700 °C, with a slight
ture was increased. Since the hydrochars used for ­CO2 and increase at 800 °C. Although results from prior studies indi-
steam activation are not from identical batches, it is difficult cate a drop in the surface area at temperatures higher than
to directly compare the product yields (refer to Sect. 3.3 for 800 °C [67, 68], more data would be required to confirm the
more information). However, past studies have observed a trend in this study.
higher reactivity for activation using steam, corroborating
the lower product yield obtained when compared to C ­ O2 3.3 Impact of hydrochar
activation under the same operating conditions [40].
At the end of pyrolysis runs, there was not enough hydrochar
3.2.2 Contaminant adsorption left to conduct additional ­CO2 and steam activation experi-
ments. Therefore, a second batch of hydrochar material
Figure 6 shows that the methylene blue adsorption capac- (batch 2) was used, which resulted in different adsorption
ity of C
­ O2-activated chars both increased with activation capabilities compared to batch 1. We reproduced 1-h ­CO2

Fig. 6  Effect of activation temperature and holding time on methyl- Fig. 7  Effect of activation temperature and holding time on phenol
ene blue adsorption capacity of ­CO2 activated hydrochars from batch adsorption capacity of C ­ O2 activated hydrochars from batch 1 and
1 and Steam/N2 activated hydrochars from batch 2. Initial methylene steam activated hydrochars from batch 2. Initial phenol concentration
blue concentration of 800 mg ­L−1 and temperature of 30 °C of 1000 mg ­L−1 and temperature of 30 °C

13
13172 Biomass Conversion and Biorefinery (2023) 13:13163–13179

activation at 850 °C which indicated high MB and phenol

capacity and continued with 2-h ­CO2 activation of batch 2
at 800 °C. The results showed a higher adsorptive capacity.
To confirm that pyrolytic hydrochars from batch 2 behave
in the same way as batch 1, which showed low sensitivity
of MB adsorption capacity to production temperature, some
runs were repeated using batch 2 (Table 5). The results con-
firmed that the insensitivity of MB adsorptive capacity to
the product production temperature during pyrolysis can be
expected for hydrochars from a different batch.
Batch 2 hydrochar was thus used to compare the best per-
formed pyrolytic and activated hydrochar conditions. The
methylene blue adsorptive capacity of batch 2 hydrochar
increased by 68% after ­N2 pyrolysis at 800 °C (2 h), 350%
after ­CO2 activation at 800 °C (2 h), and 475% after steam
activation at 800 °C (2 h). A similar trend can be observed
for hydrochar phenol adsorptive capacity, which increased
by 15% after ­N2 pyrolysis, 111% after ­CO2 activation, and
146% after steam activation at 800 °C and 2-h holding time.

3.4 Reproducibility

Due to the limited quantity of hydrothermal char available

and many process conditions of interest (i.e., temperature,
holding time, and gasifying agent), only selected experimen-
tal were carried out in triplicates (refer to Table 5). We thus
opted to carry out experiments over a wider range of activa-
tion conditions, where consistent trends can provide some
insights on reproducibility. Figure 8 provides the general
trend of methylene blue and phenol adsorption capacities as Fig. 8  Relationship between adsorption capacities with char yield for
batches 1 and 2
a function of the product yields for both feedstock batches.
In general, batch 1 hydrochar has shown higher reactivity
to the thermal treatment, corresponding with lower product adsorption capacities for chars produced from both batches
yields than batch 2. Conversely, batch 1 derived products show similar trends, with higher adsorption capacities asso-
have shown higher adsorptive capacities. Nonetheless, the ciated with lower product yields.

Table 5  Comparison of Batch Gas Temperature Holding Yield (%) Methylene blue Phenol
pyrolytic and activated number (°C) time (h) ­q800 (mg ­g−1) ­q1000 (mg
hydrochar produced from batch ­g−1)
1 and 2 hydrochars. Results
with standard deviations 1 N2 850 1 50 ± 0 37 ± 3 138 ± 4
indicate that triplicates were
2 N2 850 1 66 22 63
carried out for these conditions
1 N2 500 2 63 ± 0 71 ± 1 91 ± 3
2 N2 500 2 75 50 42
1 N2 800 2 46 ± 1 65 ± 1 146 ± 2
2 N2 800 2 62 ± 1 47 ± 2 75 ± 1
2 CO2 800 2 42 ± 1 126 ± 3 137 ± 2
1 CO2 850 1 38 135 154
2 CO2 850 1 52 52 100
2 Steam/N2 800 2 30.5 ± 0.4 161 ± 2.2 160 ± 1.2

13
Biomass Conversion and Biorefinery (2023) 13:13163–13179 13173

3.5.1 BET surface area and pore size distribution

The ­N2 adsorption isotherms of hydrochar and its derivative

pyrolytic and activated carbons, shown in Fig. 9, indicate a
type-IV isotherm with an H3 hysteresis loop. The presence
of a hysteresis loop is an indication of nitrogen condensa-
tion in mesopores, which starts at a relative pressure range
from 0.4 [69]. The height of the hysteresis loop indicates
mesopore volume, while the relative pressure at which it
starts indicates the size of the pores [70]. For example,
the original hydrochar isotherm shows mesopores with a
larger diameter than steam-activated hydrochars. Type-H3
hysteresis loop generally occurs in disordered mesoporous
structures with a combination of parallel plate-shaped and
cylindrical pores [69, 71, 72]. A steep increase in adsorption
Fig. 9  Nitrogen adsorption isotherms for optimal hydrochars using volume of N ­ 2 at lower relative pressure (P/P0 < 0.1) could
­N2, ­CO2, and Steam activation. Filled and hollow symbols represent reflect the existence of micropores. Herein, all the adsorp-
adsorption and desorption branches, respectively
tion isotherms show a broad inflection point, suggesting low
microporosity and higher mesopore volume with small pore
3.5 Optimal activated hydrochar characterization widths (2–10 nm) (Table 6).
Table 7 provides the surface area, pore volume, and
The best performing pyrolytic and activated hydrochars average pore diameter for each sample. The raw hydrochar
based on the batch adsorption measurements were further used in this study has a higher surface area compared to
characterized. Pyrolysis and activation at a temperature of other hydrochars obtained from feedstocks such as waste
800 °C and a holding time of 2 h was observed as the opti- biomass (8 m ­ 2 ­g−1), digestate (9–14 m
­ 2 ­g−1), sawdust (1.7
2 −1
mal pyrolysis, C
­ O2, and steam activations. All subsequent ­m ­g ) reported by others [73–77]. The BET specific sur-
characterization measurements are based on the batch 2 face areas and micro-porosity increased in the following
feedstock. order: Steam-800 °C (2 h) > ­CO2-800 °C (2 h) > ­N2-800 °C

Table 6  Porous texture Sample SBET ­(m2 ­g−1) Porosity properties

properties of pristine pyrolytic
and activated hydrochars Vta ­(cm3 ­g−1) Vmicrob ­(cm3 ­g−1) Micro-porosity DPc (nm)
­(Vmicro/Vt,%)

Hydrochar 116.4 0.328 0 0 11.26

N2-800 °C (2 h) 291.2 0.376 0.071 19 5.16
CO2-800 °C (2 h) 454.6 0.528 0.127 24 4.68
Steam-800 °C (2 h) 593.4 0.651 0.174 27 4.38
a
Vt—total pore volume (P/P0 = 0.99)
b
Vmicro—micro-pore volume (determine by the t-plot method) (pore width < 2 nm)
c
Dp—average pore diameter

Table 7  Adsorption parameters Sample Langmuir parameters Freundlich parameters

of methylene blue on raw,
pyrolytic, and activated KL (L ­mg−1) qm (mg ­g−1) R2 KF 1/n R2
hydrochars for Langmuir and
Freundlich models Hydrochar 0.015 28 0.99 1.416 0.462 0.92
N2-800 °C (2 h) 0.026 52 0.99 7.649 0.295 0.87
CO2-800 °C (2 h) 0.047 141 0.99 42.092 0.188 0.85
Steam-800 °C (2 h) 0.064 179 0.99 48.955 0.211 0.86
Coal-based AC 0.875 357 0.99 251.19 0.039 0.81
Coconut-based AC 0.063 286 0.99 96.450 0.182 0.98

The units of ­KF being (mg ­g−1) (mg ­L−1)n

13
13174 Biomass Conversion and Biorefinery (2023) 13:13163–13179

(2 h) > Hydrochar. The higher microporosity for steam Langmuir model provided the best fits for the methylene
activation is associated with the smaller size of water mol- blue adsorption onto all samples, suggesting monolayer
ecules that facilitates their penetration inside the carbon coverage rather than multi-layer adsorption. The Langmuir
structure [78–80]. Hydrochar pyrolysis using N ­ 2 removes isotherm parameters are summarized in Table 8. The K ­ L
trapped products (e.g., acids, aldehydes, ketones, or par- values for the hydrochar samples increase in the order of
ticular constituents of the biomass) from the pores due to steam > ­CO2 > ­N2 > hydrochar. Comparing the K ­ L of the two
incomplete pyrolysis [81], increasing the surface area and CACs, the higher Langmuir adsorption and constant during
micro-porosity. Adding steam to N ­ 2 during steam activa- MB adsorption belongs to coal-based AC. Methylene blue
tion further increased the porosity of activated hydrochars adsorptive capacities of ­N2-800 °C (2 h), ­CO2-800 °C (2 h),
by developing new pores. C ­ O2 activation of hydrochars and Steam-800 °C (2 h) range between 15–18%, 39–49%,
similarly increased the micropore fraction, and the larger and 50–63% of that of coal and coconut-based activated
molecular size of carbon dioxide produced slightly larger carbons, respectively. The adsorption capacities compared
pores than steam [82, 83]. Also, the higher total pore vol- well and even favorably with those reported in the litera-
ume of steam-activated carbon compared to ­CO2 carbon ture of some other adsorbents. For example, methylene blue
can be associated with higher reactivity of steam toward capacity was reported to be 55 mg ­g−1 for almond peels
carbon material and the fact that its smaller size molecules [86], 60 mg ­g−1 for Banana trunk activated carbons [87], and
have higher accessibility to tiny pores [84, 85]. 51 mg ­g−1 for nutshells [88]. A recent review [89] provides
methylene blue adsorptive capacities for various adsorbents
3.5.2 Methylene blue adsorption isotherms and suggests that the adsorption capacity of adsorbents
improves with surface area enhancement but shows little
Figure 10 compares the methylene blue adsorption isotherms influence of pore volume.
for commercial activated carbons (CAC) and pyrolytic/
activated hydrochar at 800 °C and 2-h holding time. The 3.5.3 Phenol adsorption isotherms

Figure 11 provides the phenol adsorption isotherms for

the previous samples. Again, the experimental data for all
samples was best fitted by the Langmuir isotherm. Com-
paring the ­KL of each adsorbent, the forces between phe-
nol and carbon surface get stronger in the order of hydro-
char < ­N2 < ­CO2 < steam. Since phenol exists predominantly
in its molecular form, the increase in attraction of phenol to
the carbon surface can result from higher microporosity in
order of steam > ­CO2 > ­N2. The hydrochar derived adsor-
bents produced under N ­ 2, ­CO2, and steam have 34–37%,
58–64%, and 70–77% of the coconut and coal-based capac-
ities. Other researches have reported phenol adsorption
capacity to be 0.18 mg/ ­g-1 for coal and 7.9 mg g­ -1 for rice
husk biochar [90], 75.5–158 mg ­g-1 for coal-activated car-
bons [91], 12–19.5 mg ­g-1 for bagasse and rice husk-acti-
Fig. 10  Methylene blue adsorption isotherms for the raw, pyrolytic vated carbons [92], 110.2 mg g-1 for activated carbon fibers
and activated hydrochars. Lines indicate fitted Langmuir model [93], and 49.72 mg ­g-1 for commercial activated carbon [94].

Table 8  Adsorption parameters Sample Langmuir parameters Freundlich parameters

of phenol on pyrolytic and
activated hydrochars for KL (L ­mg−1) qm (mg ­g−1) R2 KF 1/n R2
Langmuir and Freundlich
models Hydrochar 0.005 63 0.99 2.89 0.374 0.93
N2-800 °C (2 h) 0.023 80 0.99 15.99 0.239 0.86
CO2-800 °C (2 h) 0.046 139 0.99 29.95 0.240 0.86
Steam-800 °C (2 h) 0.061 167 0.99 37.87 0.234 0.83
Coal-based AC 0.037 217 0.99 37.60 0.275 0.92
Coconut-based AC 0.143 238 0.99 58.01 0.229 0.90

The units of ­KF being (mg ­g−1) (mg ­L−1)n

13
Biomass Conversion and Biorefinery (2023) 13:13163–13179 13175

[95]. The phenol (0.58 × 0.45 nm) used would thus require
pores with diameters larger than 0.78 nm to effectively
participate in the adsorption process, while pores with a
diameter larger than 0.94 nm are required for methylene
blue (1.41 × 0.55 nm).
Activated carbons derived from hydrochar as an indus-
trial by-product have several economic and environmen-
tal advantages when compared to commercial activated
carbons derived from coal and coconut shell. Unlike coal,
hydrochar in our study is derived from wood, which is a
sustainable resource. It is also a by-product of another
bioprocess, which makes downstream activation a means
of waste-to-value process for the industrial plants. Unlike
coconut shells derived activated carbons, the hydrochar
does not require initial carbonization process as it has low
ash content and high C to H atomic ratio (Table 2) as a
Fig. 11  Phenol adsorption isotherms for the raw, pyrolytic and acti-
vated hydrochars. Lines indicate fitted Langmuir model result of the hydrothermal carbonization process. There-
fore, we believe our study demonstrated that a hydrochar
which was not intentionally optimized for production of
Figure 12 demonstrates the effects of BET surface area activated carbon can be a suitable low-cost precursor to
and pore volumes on the methylene blue and phenol aque- produce adsorbents for wastewater treatment.
ous adsorptive capacities. Both adsorption capacities of
phenol and methylene blue increased with both surface
area and total pore volume in the order of steam-800 °C 4 Conclusions
(2 h) > ­CO2-800 °C (2 h) > ­N2-800 °C (2 h) > hydrochar.
It has been suggested that only pores with a diameter at Pyrolyzed, ­CO2, and steam activated hydrochars from an
least 1.7 times larger than the second widest dimension industrial hydrothermal carbonization process were stud-
of the adsorbate can participate in the adsorption process ied to produce adsorbents for phenol and methylene blue

Fig. 12  Relationship between

adsorptive capacity of phenol
(filled symbols) and methylene
blue (hollow symbols) with a
surface area, b micropore vol-
ume, c total pore volume, and d
mesopore volume

13
13176 Biomass Conversion and Biorefinery (2023) 13:13163–13179

removal from aqueous solutions. The following conclusions Data availability Available upon request.
can be drawn based on the obtained results:
Code availability N/A.
1. Pyrolysis temperatures between 400 and 900 °C had a
minimal effect (less than 5% relative change) on meth- Declarations
ylene blue adsorption; however, increasing the holding
Conflict of interest The authors declare no conflict of interest.
time from 1 to 2 h approximately doubled the methylene
blue adsorptive capacity. Conversely, phenol adsorptive Additional declarations The authors have no additional declarations
capacity was improved by increasing the pyrolysis tem- to provide.
perature, while increasing the holding time had a mini-
mal impact on the adsorptive performance.
2. Increasing temperature and holding time for ­CO2 and
steam activation improved the methylene blue and phe- References
nol adsorption capacities until reaching a plateau at
1. Khan TA, Saud AS, Jamari SS et al (2019) Hydrothermal car-
approximately 800 °C for both activation gases. bonization of lignocellulosic biomass for carbon rich material
3. Pyrolytic, ­CO2, and steam-activated hydrochars pro- preparation: a review. Biomass Bioenerg 130:105384. [Link]
duced at 800 °C with a 2-h holding time showed the doi.​org/​10.​1016/j.​biomb​ioe.​2019.​105384
2. Saha P, McGaughy K, Hasan MR, Reza MT (2019) Pyrolysis and
best methylene blue and phenol adsorption capacities.
carbon dioxide gasification kinetics of hydrochar produced from
4. When using an activation temperature of 800 °C and a cow manure. Environ Prog Sustain Energy 38:154–162. [Link]
2-h holding time, the methylene blue and phenol adsorp- doi.​org/​10.​1002/​ep.​12907
tion capacities of the batch 2 hydrochar (initial capaci- 3. Fang J, Zhan L, Ok YS, Gao B (2018) Minireview of potential
applications of hydrochar derived from hydrothermal carboniza-
ties of 28 and 65 mg ­g−1) increased to 47 and 75 mg ­g−1
tion of biomass. J Ind Eng Chem 57:15–21. [Link]
after pyrolysis, 126 and 147 mg ­g−1 after CO2 activa- 1016/J.​JIEC.​2017.​08.​026
tion, and 161 and 160 mg ­g−1 after steam activation, 4. Reza MT, Andert J, Wirth B et al (2014) Hydrothermal carboni-
respectively. zation of biomass for energy and crop production. Appl Bioen-
ergy 1:11–29. [Link]
5. Steam-activated hydrochars at 800 °C and 2-h holding
5. Gronwald M, Vos C, Helfrich M, Don A (2016) Stability of pyro-
times showed the highest BET surface area, phenol, and char and hydrochar in agricultural soil—a new field incubation
methylene blue adsorptive capacities. method. Geoderma 284:85–92. [Link]
rma.​2016.​08.​019
6. Paneque M, Knicker H, Kern J, De la Rosa JM (2019) Hydro-
thermal carbonization and pyrolysis of sewage sludge: effects
Nomenclatures ΔH: Enthalpy of the reaction (kJ ­mol−1); C0: The ini-
on Lolium perenne Germination and Growth. Agronomy 9:363.
tial concentration of adsorbate in the liquid phase (mg L­ −1); Ce: The
[Link]
concentration of adsorbate in the liquid phase at the equilibrium (mg
7. Wang Y, Qiu L, Zhu M et al (2019) Comparative evaluation of
­L−1); Ct: The concentration of adsorbate in the liquid phase at time = t
hydrothermal carbonization and low temperature pyrolysis of
(mg ­L−1); Dp: Average pore diameter (nm); Kf: The Freundlich constant
eucommia ulmoides oliver for the production of solid biofuel.
((mg ­g−1) (mg ­L−1)n)); KL: The Langmuir constant (L m­ g−1); M: Molar
−1 Sci Rep 9:1–11. [Link]
concentration (mol L ­ ); m: Mass (g); pKa: Acid dissociation con-
8. Volpe M, Fiori L, Volpe R, Messineo A (2016) Upgrading of
stant; qe: The amount of adsorbate adsorbed on the solid phase at the
olive tree trimmings residue as biofuel by hydrothermal carboni-
equilibrium (mg ­g−1); qm: The maximum monolayer adsorption capac-
zation and torrefaction: a comparative study. Chem Eng Trans
ity of the adsorbent (mg g­ −1); qt: Adsorbate concentration adsorbed
50:3–18. [Link]
on the solid at time = t (mmol ­g−1); SBET: Brunauer–Emmett–Teller
9. Liu Z, Balasubramanian R (2014) Upgrading of waste biomass by
(BET) specific surface area (­ m2 ­g−1); Smicro: The micopores surface
hydrothermal carbonization (HTC) and low temperature pyroly-
area ­(m2 ­g−1); V: Volume (L); Vmeso: Mesopores volume (­ cm3 ­g−1);
sis (LTP): a comparative evaluation. Appl Energy 114:857–864.
Vmicro: Micropores volume ­(cm3 ­g−1); Vtotal: Total pore volume ­(cm3
[Link]
­g−1); λ: Wavelength of maximum absorbance (nm
10. Hu B, Wang K, Wu L et al (2010) Engineering carbon materials
from the hydrothermal carbonization process of biomass. Adv
Acknowledgements The authors would like to acknowledge MITACS Mater 22:813–828
Canada (Grant number IT12425), Origin Materials, and the Faculty of 11. Liu Z, Zhang F-S (2009) Removal of lead from water using
Engineering at the University of Western Ontario for financial support biochars prepared from hydrothermal liquefaction of biomass. J
of this study. Hazard Mater 167:933–939. [Link]
2009.​01.​085
Author contribution Available upon request. 12. Mochidzuki K, Sato N, Sakoda A (2005) Production and charac-
terization of carbonaceous adsorbents from biomass wastes by
Funding Financial support for this study was obtained from MITACS aqueous phase carbonization. Adsorption 11:669–673. [Link]
Canada (Grant number IT12425), Origin Materials, and the Faculty of doi.​org/​10.​1007/​s10450-​005-​6004-6
Engineering at the University of Western Ontario. 13. Saetea P, Tippayawong N (2013) Characterization of adsorbent
from hydrothermally carbonized and steam activated sewage
sludge. Lect Notes Eng Comput Sci 3:1909–1912

13
Biomass Conversion and Biorefinery (2023) 13:13163–13179 13177

14. Titirici M-M, Thomas A, Antonietti M (2007) Back in the 29. Kundu S, Chowdhury IH, Naskar MK (2018) Hierarchical
black: hydrothermal carbonization of plant material as an effi- porous carbon nanospheres for efficient removal of toxic
cient chemical process to treat the CO2 problem? New J Chem organic water contaminants of phenol and methylene blue.
31:787–789. [Link] J Chem Eng Data 63:559–573. [Link] oi.​o rg/​1 0.​1 021/​a cs.​
15. Buss W, Mašek O (2014) Mobile organic compounds in bio- jced.​7b007​45
char—a potential source ofcontamination - Phytotoxic effects 30. Xiaoxia Ou (2017) Developing hierarchically structured catalysts
on cress seed (Lepidiumsativum) germination. J Environ Man- on cellular foams for continuous flow catalysis. The University
age 137:111–119. [Link] of Manchester, Manchester
045 31. Yadav LS, Mishra BK, Kumar A (2019) Adsorption of phenol
16. Chang C-F, Chang C-Y, Tsai W-T (2000) Effects of burn-off and from aqueous solutions by bael furit shell activated carbon:
activation temperature on preparation of activated carbon from kinetic, equilibrium, and mass transfer studies. Theor Found
corn cob agrowaste by CO2 and steam. J Colloid Interface Sci Chem Eng 53:122–131. [Link]
232:45–49. [Link] 90101​84
17. Sajjadi B, Zubatiuk T, Leszczynska D et al (2019) Chemical 32. Rafatullah M, Sulaiman O, Hashim R, Ahmad A (2010) Adsorp-
activation of biochar for energy and environmental applications: tion of methylene blue on low-cost adsorbents: A review. J Haz-
a comprehensive review. Rev Chem Eng 35:777–815. [Link] oi.​ ard Mater 177:70–80. [Link] oi.o​ rg/1​ 0.1​ 016/J.J​ HAZMA
​ T.2​ 009.​
org/​10.​1515/​revce-​2018-​0003 12.​047
18. Sajjadi B, Chen WY, Egiebor NO (2019) A comprehensive 33. Sun J, Liu X, Zhang F et al (2019) Insight into the mechanism
review on physical activation of biochar for energy and environ- of adsorption of phenol and resorcinol on activated carbons with
mental applications. Rev Chem Eng 35:735–776. [Link] oi.o​ rg/​ different oxidation degrees. Colloids Surfaces A Physicochem
10.​1515/​revce-​2017-​0113 Eng Asp 563:22–30. [Link]
19 Khezami L, Ould-Dris A, Capart R (2007) Activated carbon from 042
thermo-compressed wood and other lignocellulosic precursors. 34. Fierro V, Torné-Fernández V, Montané D, Celzard A (2008)
BioResources 2:193–209. [Link] Adsorption of phenol onto activated carbons having differ-
193-​209 ent textural and surface properties. Microporous Mesoporous
20. Mohamad Nor N, Lau LC, Lee KT, Mohamed AR (2013) Syn- Mater 111:276–284. [Link] oi.​o rg/​1 0.​1 016/j.​m icro​m eso.​
thesis of activated carbon from lignocellulosic biomass and its 2007.​08.​002
applications in air pollution control—a review. J Environ Chem 35. Fernandez ME, Ledesma B, Román S et al (2015) Development
Eng 1:658–666. [Link] and characterization of activated hydrochars from orange peels as
21. Falco C, Marco-Lozar JP, Salinas-Torres D et al (2013) Tailoring potential adsorbents for emerging organic contaminants. Biore-
the porosity of chemically activated hydrothermal carbons: influ- sour Technol 183:221–228. [Link]
ence of the precursor and hydrothermal carbonization tempera- ECH.​2015.​02.​035
ture. Carbon N Y 62:346–355. [Link] 36. Román S, Valente Nabais JM, Ledesma B et al (2013) Production
2013.​06.​017 of low-cost adsorbents with tunable surface chemistry by con-
22. Zhao X, Becker GC, Faweya N et al (2018) Fertilizer and acti- junction of hydrothermal carbonization and activation processes.
vated carbon production by hydrothermal carbonization of diges- Microporous Mesoporous Mater 165:127–133. [Link] oi.o​ rg/1​ 0.​
tate. Biomass Convers Biorefinery 8:423–436. [Link] oi.o​ rg/1​ 0.​ 1016/J.​MICRO​MESO.​2012.​08.​006
1007/​s13399-​017-​0291-5 37. Fang J, Gao B, Zimmerman AR et al (2016) Physically (CO2)
23. Rodríguez Correa C, Ngamying C, Klank D, Kruse A (2018) activated hydrochars from hickory and peanut hull: preparation,
Investigation of the textural and adsorption properties of acti- characterization, and sorption of methylene blue, lead, copper,
vated carbon from HTC and pyrolysis carbonizates. Biomass and cadmium. RSC Adv 6:24906–24911. [Link]
Convers Biorefinery 8:317–328. https:// ​ d oi. ​ o rg/ ​ 1 0. ​ 1 007/​ 1039/​c6ra0​1644h
s13399-​017-​0280-8 38. Hao W, Björkman E, Lilliestråle M, Hedin N (2013) Activated
24. Rodriguez Correa C, Bernardo M, Ribeiro RPPL et al (2017) carbons prepared from hydrothermally carbonized waste biomass
Evaluation of hydrothermal carbonization as a preliminary step used as adsorbents for CO2. Appl Energy 112:526–532. [Link]
for the production of functional materials from biogas digestate. doi.​org/​10.​1016/j.​apene​rgy.​2013.​02.​028
J Anal Appl Pyrolysis 124:461–474. [Link] 39. Latifi M, Berruti F, Briens C (2014) A novel fluidized and induc-
jaap.​2017.​02.​014 tion heated microreactor for catalyst testing. AIChE J 60:3107–
25. Unur E (2013) Functional nanoporous carbons from hydrother- 3122. [Link]
mally treated biomass for environmental purification. Micropo- 40. Jung S-H, Kim J-S (2014) Production of biochars by intermedi-
rous Mesoporous Mater 168:92–101. [Link] ate pyrolysis and activated carbons from oak by three activation
micro​meso.​2012.​09.​027 methods using CO2. J Anal Appl Pyrolysis 107:116–122. [Link]
26. Baccar R (2013) Removal of some water contaminants by doi.​org/​10.​1016/j.​jaap.​2014.​02.​011
adsorption on activated carbon prepared from olive-waste cakes 41. Reshadi MAM, Bazargan A, McKay G (2020) A review of the
and biological treatment using fungi. Dissertation, Universitat application of adsorbents for landfill leachate treatment: Focus
Autònoma de Barcelona on magnetic adsorption. Sci Total Environ 731:138863. [Link]
27. Zhu X, Liu Y, Qian F et al (2015) Investigation on the physical doi.​org/​10.​1016/j.​scito​tenv.​2020.​138863
and chemical properties of hydrochar and its derived pyrolysis 42. Toles CA, Marshall WE, Wartelle LH, McAloon A (2000)
char for their potential application: influence of hydrothermal Steam- or carbon dioxide-activated carbons from almond shells:
carbonization conditions. Energy Fuels 29:5222–5230. [Link] physical, chemical and adsorptive properties and estimated cost
doi.​org/​10.​1021/​acs.​energ​yfuels.​5b005​12 of production. Bioresour Technol 75:197–203. [Link]
28. Jain A, Balasubramanian R, Srinivasan MP (2015) Production of 10.​1016/​S0960-​8524(00)​00058-4
high surface area mesoporous activated carbons from waste bio- 43. Rajapaksha AU, Vithanage M, Ahmad M et al (2015) Enhanced
mass using hydrogen peroxide-mediated hydrothermal treatment sulfamethazine removal by steam-activated invasive plant-
for adsorption applications. Chem Eng J 273:622–629. [Link] derived biochar. J Hazard Mater 290:43–50. [Link]
doi.​org/​10.​1016/j.​cej.​2015.​03.​111 1016/j.​jhazm​at.​2015.​02.​046

13
13178 Biomass Conversion and Biorefinery (2023) 13:13163–13179

44. Azargohar R (2009) Production of activated carbon and its cata- thermodynamic studies. Bioresour Technol 200:350–359. [Link]
lytic application for oxidation of hydrogen sulphide. University doi.​org/​10.​1016/j.​biort​ech.​2015.​10.​047
of Saskatchewan, Saskatoon 62. Zhou J, Luo A, Zhao Y (2018) Preparation and characterisation
45. Daza YA, Kuhn JN (2016) CO2 conversion by reverse water gas of activated carbon from waste tea by physical activation using
shift catalysis: comparison of catalysts, mechanisms and their steam. J Air Waste Manage Assoc 68:1269–1277. [Link] oi.o​ rg/​
consequences for CO2 conversion to liquid fuels. RSC Adv 10.​1080/​10962​247.​2018.​14602​82
6:49675–49691. [Link] 63. Zhang YJ, Xing ZJ, Duan ZK et al (2014) Effects of steam acti-
46 Basu P (2010) Gasification Theory and modeling of gasifiers. vation on the pore structure and surface chemistry of activated
Biomass Gasification Design Handbook. Academic Press, Cam- carbon derived from bamboo waste. Appl Surf Sci 315:279–286.
bridge, pp 117–165 [Link]
47. Lussier MG, Zhang Z, Miller DJ (1998) Characterizing rate inhi- 64. Guo S, Peng J, Li W et al (2009) Effects of CO 2 activation on
bition in steam/hydrogen gasification via analysis of adsorbed porous structures of coconut shell-based activated carbons. Appl
hydrogen. Carbon N Y 36:1361–1369. [Link] Surf Sci 255:8443–8449
S0008-​6223(98)​00123-7 65. Zhang T, Walawender WP, Fan LT et al (2004) Preparation of
48. Guo S, Dong X, Zhu C et al (2017) Pyrolysis behaviors and activated carbon from forest and agricultural residues through
thermodynamics properties of hydrochar from bamboo (Phyllos- CO2 activation. Chem Eng J 105:53–59. [Link]
tachys heterocycla cv. pubescens) shoot shell. Bioresour Technol 1016/j.​cej.​2004.​06.​011
233:92–98. [Link] 66. Carrier M, Hardie AG, Uras Ü et al (2012) Production of char
49. Park CM, Han J, Chu KH et al (2017) Influence of solution pH, from vacuum pyrolysis of South-African sugar cane bagasse and
ionic strength, and humic acid on cadmium adsorption onto its characterization as activated carbon and biochar. J Anal Appl
activated biochar: Experiment and modeling. J Ind Eng Chem Pyrolysis 96:24–32. [Link]
48:186–193. [Link] 67. Demiral H, Demiral İ, Karabacakoğlu B, Tümsek F (2011)
50. Zhang X, Gao B, Zheng Y et al (2017) Biochar for volatile Production of activated carbon from olive bagasse by physical
organic compound (VOC) removal: sorption performance and activation. Chem Eng Res Des 89:206–213. [Link]
governing mechanisms. Bioresour Technol 245:606–614. [Link] 1016/j.​cherd.​2010.​05.​005
doi.​org/​10.​1016/j.​biort​ech.​2017.​09.​025 68. Petrov N, Budinova T, Razvigorova M et al (2008) Conversion
51. Koehlert K (2017) Activated carbon: fundamentals and new of olive wastes to volatiles and carbon adsorbents. Biomass Bio-
applications. Chem Eng (United States) 124:32–40 energ 32:1303–1310. [Link]
52. Kinoshita K (1988) Carbon: electrochemical and physicochemi- 03.​009
cal properties. Wiley-Interscience, Hoboken 69 Lowell S, Shields JE, Thomas MA, Thommes M (2005) Charac-
53. Chiang H-L, Chiang PC, Huang CP (2002) Ozonation of acti- terization of porous solids and powders: surface area, pore size,
vated carbon and its effects on the adsorption of VOCs exempli- and density. Choice Rev Online 42:42–5288. [Link]
fied by methylethylketone and benzene. Chemosphere 47:267– 5860/​choice.​42-​5288
275. [Link] 70. Thommes M (2010) Physical Adsorption characterization of
54. Lorenc-Grabowska E (2016) Effect of micropore size distribution nanoporous materials. Chemie Ing Tech 82:1059–1073. [Link]
on phenol adsorption on steam activated carbons. Adsorption doi.​org/​10.​1002/​cite.​20100​0064
22:599–607. [Link] 71 Celzard A, Fierro V, Amaral-Labat G (2012) Adsorption by car-
55. Mohan D, Sarswat A, Ok YS, Pittman CU (2014) Organic and bon gels. In: Tascón JMDBT-NCA (ed) Novel Carbon Adsor-
inorganic contaminants removal from water with biochar, a bents. Elsevier, Oxford, pp 207–244
renewable, low cost and sustainable adsorbent—a critical review. 72. Khanday WA, Kabir G, Hameed BH (2016) Catalytic pyrolysis
Bioresour Technol 160:191–202. [Link] of oil palm mesocarp fibre on a zeolite derived from low-cost oil
ech.​2014.​01.​120 palm ash. Energy Convers Manag 127:265–272. [Link]
56. Stavropoulos GG, Samaras P, Sakellaropoulos GP (2008) Effect 10.​1016/j.​encon​man.​2016.​08.​093
of activated carbons modification on porosity, surface structure 73. Chen SQ, Chen YL, Jiang H (2017) Slow pyrolysis magnetization
and phenol adsorption. J Hazard Mater 151:414–421. [Link] oi.​ of hydrochar for effective and highly stable removal of tetracy-
org/​10.​1016/j.​jhazm​at.​2007.​06.​005 cline from aqueous solution. Ind Eng Chem Res 56:3059–3066.
57. Zhou Z, Xu Z, Feng Q et al (2018) Effect of pyrolysis condition [Link]
on the adsorption mechanism of lead, cadmium and copper on 74. Zhu X, Liu Y, Zhou C et al (2014) A novel porous carbon derived
tobacco stem biochar. J Clean Prod 187:996–1005. [Link] oi.​ from hydrothermal carbon for efficient adsorption of tetracycline.
org/​10.​1016/j.​jclep​ro.​2018.​03.​268 Carbon N Y 77:627–636. [Link]
58. Shaaban A, Se S-M, Dimin MF et al (2014) Influence of heating 05.​067
temperature and holding time on biochars derived from rubber 75. Bernardo M, Correa CR, Ringelspacher Y et al (2020) Porous
wood sawdust via slow pyrolysis. J Anal Appl Pyrolysis 107:31– carbons derived from hydrothermally treated biogas digestate.
39. [Link] Waste Manag 105:170–179. [Link]
59. Saha N, Xin D, Chiu PC, Reza MT (2019) Effect of pyrolysis 2020.​02.​011
temperature on acidic oxygen-containing functional groups and 76. Hou Y, Huang G, Li J et al (2019) Hydrothermal conversion of
electron storage capacities of pyrolyzed hydrochars. ACS Sustain bamboo shoot shell to biochar: Preliminary studies of adsorp-
Chem Eng 7:8387–8396. [Link] oi.o​ rg/1​ 0.1​ 021/a​ cssus​ cheme​ ng.​ tion equilibrium and kinetics for rhodamine B removal. J Anal
9b000​24 Appl Pyrolysis 143:104694. [Link]
60. Islam MS, Rouf MA, Fujimoto S, Minowa T (2012) Preparation 104694
and characterization of activated carbon from bio-diesel by-prod- 77. Bahcivanji L, Gascó G, Paz-Ferreiro J, Méndez A (2020) The
ucts (Jatropha seedcake) by steam activation. Bangladesh J Sci effect of post-pyrolysis treatment on waste biomass derived
Ind Res 47:257–264. [Link] hydrochar. Waste Manag 106:55–61. [Link]
61. Maneerung T, Liew J, Dai Y et al (2016) Activated carbon wasman.​2020.​03.​007
derived from carbon residue from biomass gasification and 78. Kühl H, Kashani-Motlagh MM, Mühlen HJ, van Heek KH
its application for dye adsorption: Kinetics, isotherms and (1992) Controlled gasification of different carbon materials and

13
Biomass Conversion and Biorefinery (2023) 13:13163–13179 13179

development of pore structure. Fuel 71:879–882. [Link] from waste water. Mater Today Chem 16:100233. [Link] oi.o​ rg/​
10.​1016/​0016-​2361(92)​90236-H 10.​1016/j.​mtchem.​2019.​100233
79. Wigmans T (1989) Industrial aspects of production and use of 90. Ahmaruzzaman M, Sharma DK (2005) Adsorption of phenols
activated carbons. Carbon N Y 27:13–22. [Link] from wastewater. J Colloid Interface Sci 287:14–24. [Link]
1016/​0008-​6223(89)​90152-8 org/​10.​1016/j.​jcis.​2005.​01.​075
80. Linares-Solano A, Salinas-Martínez De Lecea C, Cazorla- 91 Dąbrowski A, Podkościelny P, Hubicki Z, Barczak M (2005)
Amorós D, Martín-Gullón I (2000) Porosity development dur- Adsorption of phenolic compounds by activated carbon—a
ing CO2 and steam activation in a fluidized bed reactor. Energy critical review. Chemosphere 58:1049–1070. [Link]
Fuels 14:142–149. [Link] 1016/j.​chemo​sphere.​2004.​09.​067
81. Santos RM, Santos AO, Sussuchi EM et al (2015) Pyrolysis of 92. Kalderis D, Koutoulakis D, Paraskeva P et al (2008) Adsorption
mangaba seed: production and characterization of bio-oil. Biore- of polluting substances on activated carbons prepared from rice
sour Technol 196:43–48. [Link] oi.o​ rg/1​ 0.1​ 016/j.b​ iorte​ ch.2​ 015.​ husk and sugarcane bagasse. Chem Eng J 144:42–50. [Link] oi.​
07.​060 org/​10.​1016/j.​cej.​2008.​01.​007
82. Choi G-G, Oh S-J, Lee S-J, Kim J-S (2015) Production of bio- 93. Liu QS, Zheng T, Wang P et al (2010) Adsorption isotherm,
based phenolic resin and activated carbon from bio-oil and bio- kinetic and mechanism studies of some substituted phenols on
char derived from fast pyrolysis of palm kernel shells. Bioresour activated carbon fibers. Chem Eng J 157:348–356. [Link]
Technol 178:99–107. [Link] oi.o​ rg/1​ 0.1​ 016/j.b​ iorte​ ch.2​ 014.0​ 8.​ org/​10.​1016/j.​cej.​2009.​11.​013
053 94. OZKAYA B, (2006) Adsorption and desorption of phenol on acti-
83. Kołtowski M, Hilber I, Bucheli TD et al (2017) Activated bio- vated carbon and a comparison of isotherm models. J Hazard Mater
chars reduce the exposure of polycyclic aromatic hydrocarbons in 129:158–163. [Link]
industrially contaminated soils. Chem Eng J 310:33–40. [Link] 95. Peiris C, Nayanathara O, Navarathna CM et al (2019) The influ-
doi.​org/​10.​1016/J.​CEJ.​2016.​10.​065 ence of three acid modifications on the physicochemical charac-
84. Dalai AK, Azargohar R (2007) Production of activated carbon teristics of tea-waste biochar pyrolyzed at different temperatures:
from biochar using chemical and physical activation: mechanism a comparative study. RSC Adv 9:17612–17622. [Link]
and modeling. Materials, Chemicals, and Energy from Forest 10.​1039/​c9ra0​2729g
Biomass. American Chemical Society, Washington, pp 29–463 96 Singh B, Camps-Arbestain M, Lehmann J (2017) Biochar: a
85. Feng D, Zhang Y, Zhao Y et al (2018) Improvement and mainte- guide to analytical methods. CSIRO Publishing, Clayton
nance of biochar catalytic activity for in-situ biomass tar reform- 97. Ma Y, Gao N, Chu W, Li C (2013) Removal of phenol by pow-
ing during pyrolysis and H2O/CO2 gasification. Fuel Process dered activated carbon adsorption. Front Environ Sci Eng 7:158–
Technol 172:106–114. [Link] 165. [Link]
011 98. Rakass S, Hassani HO, Abboudi M et al (2018) Molybdenum
86. Benaïssa H (2009) Effect of temperature on methylene blue sorp- trioxide: efficient nanosorbent for removal of methylene blue dye
tion from aqueous solutions by almond peel: experimental stud- from aqueous solutions. Molecules 23:2295. [Link]
ies and modelling. Thirteenth International Water Technology 3390/​molec​ules2​30922​95
Conference, IWTC 13:377–393 99. Kang S, Fu J, Deng Z et al (2018) Valorization of biomass
87. Danish M, Ahmad T, Nadhari WNAW et al (2018) Optimization hydrolysis waste: activated carbon from humins as exceptional
of banana trunk-activated carbon production for methylene blue- sorbent for wastewater treatment. Sustainability 10:1795. [Link]
contaminated water treatment. Appl Water Sci 8:9. [Link] doi.​org/​10.​3390/​su100​61795
org/​10.​1007/​s13201-​018-​0644-7 100. Phan NH, Rio S, Faur C et al (2006) Production of fibrous acti-
88. Doğan M, Abak H, Alkan M (2009) Adsorption of methylene vated carbons from natural cellulose (jute, coconut) fibers for
blue onto hazelnut shell: Kinetics, mechanism and activation water treatment applications. Carbon N Y 44:2569–2577. [Link]
parameters. J Hazard Mater 164:172–181. [Link] doi.​org/​10.​1016/J.​CARBON.​2006.​05.​048
1016/j.​jhazm​at.​2008.​07.​155
89. Santoso E, Ediati R, Kusumawati Y et al (2020) Review on recent Publisher's note Springer Nature remains neutral with regard to
advances of carbon based adsorbent for methylene blue removal jurisdictional claims in published maps and institutional affiliations.

13